PHOTOCHROMIC COMPOUND, PHOTOCHROMIC COMPOSITION AND PHOTOCHROMIC ARTICLE

专利摘要:
compound, photochromic composition and photochromic article the present invention relates to compounds represented by the formula i would follow: (i) ring a of formula i can be, for example, an aryl group, an l1, is a chiral or non-chiral group stretching. the compound represented by formula i can be a photochromic compound. the present invention also relates to photochromic compositions and photochromic articles that include one or more photochromic compounds, such as those represented by formula i.
公开号:BR112013015124B1
申请号:R112013015124-2
申请日:2011-12-01
公开日:2020-08-11
发明作者:Meng He；Sujit Mondal；Darrin R. Dabideen；Anil Kumar；Xiao-Man Dai
申请人:Transitions Optical, Inc；
IPC主号:

专利说明:

Field of invention
[0001] The present invention relates to photochromic compounds and compositions and articles that include the photochromic compounds of the present invention. Background of the invention
[0002] Conventional photochromic compounds have at least two states, a first state having a first absorption spectrum and a second state having a second absorption spectrum that differs from the first absorption spectrum, and are capable of changing between the two states in response at least actinic radiation. In addition, conventional photochromic compounds can be thermally reversible. That is, conventional photochromic compounds are capable of switching between a first state and a second state in response to at least one actinic radiation and reversion to the first state in response to thermal energy. As used herein, "actinic radiation" means electromagnetic radiation such as, but not limited to, visible and ultraviolet radiation that is capable of causing a response. More specifically, conventional photochromic compounds can undergo a transformation in response to actinic radiation, from one isomer to another, with each isomer having a characteristic absorption spectrum, and can also return to the first isomer in response to thermal energy (this is, be thermally reversible). For example, conventional thermally reversible photochromic compounds are generally able to change from a first state, for example, a "clear state" to a second state, for example, a "colored state", in response to actinic radiation and return to the "clear" state in response to thermal energy.
[0003] Dichroic compounds are compounds that are capable of absorbing one of two orthogonal components polarized in the plane of transmitted radiation more strongly than the other. Therefore, dichroic compounds are able to linearly polarize transmitted radiation. As used here, "linearly polarize" means to confine the vibrations of the electric light wave vector to a direction or plane. However, although the dichroic materials are able to preferentially absorb one of two orthogonal components polarized in the plane of transmitted radiation, if the molecules of the dichroic compound are not properly positioned or arranged, no linear polarization free of transmitted radiation will be achieved. That is, due to the random placement of the molecules of the dichroic compound, the selective absorption by individual molecules will cancel each other out so that no global or free linear polarization effect is achieved. Thus, it is generally necessary to properly position or arrange the molecules of the dichroic compound within another material to form a conventional linear polarizing element, such as a linearly polarizing filter or sunglasses lenses.
[0004] In contrast to the dichroic compound, it is generally not necessary to position or arrange the molecules of conventional photochromic compounds to form a conventional photochromic element. Thus, for example, conventional photochromic elements, such as lenses for photochromic glasses, can be formed, for example, coated by rotating a solution containing a conventional photochromic compound and a "host material" on the lens surface, and curing properly the resulting coating or layer without arranging the photochromic compound in any particular orientation. Additionally, even if the molecules of the conventional photochromic compound are properly positioned or arranged as discussed above with respect to dichroic compounds, due to the fact that conventional photochromic compounds do not demonstrate strong dichroism, the elements produced from them are generally not strongly linearly polarizing.
[0005] It would be advantageous to provide photochromic compounds, such as, but not limited to thermally reversible photochromic compounds, which may have photochromic and / or dichroic properties useful in at least one state, and which can be used in a variety of applications to transmit the photochromic and / or dichroic properties. Summary of the invention
[0006] According to the present invention, a compound represented by the following formula I is provided,

[0007] The A ring of Formula I, other related formulas described further here, is selected from the group (Ri) m_, unsubstituted aryl, substituted aryl, unsubstituted fused ring aryl, substituted fused ring aryl, unsubstituted heteroaryl substituted, and substituted heteroaryl. With some embodiments, ring A is selected from aryl, fused ring aryl, and heteroaryl.
[0008] With additional reference to formula I, and other related formulas described here, m is selected from 0 to a total number of positions for which R1 can be linked to ring A, such as 0 to 4 when ring A is a ring aromatic aroma of 6 limbs. In addition, R1 for each m is independently selected from L2 as further described below, and a chiral or non-chiral group selected from formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino, boric acid, boric acid, cycloalkoxycarbonylamino, heterocycloalkyloxycarbonylamino, heteroaryloxycarbonylamino, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, halogen, optionally substituted aryl, optionally substituted, heteroaryl, optionally substituted, optionally substituted heteroaryl, optionally substituted, optionally substituted optionally replaced.
[0009] With additional reference to Formula I, and other related formulas described further here, n is selected from 0 to 3. Additionally, R, for each n, is independently a chiral or non-chiral group selected from formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino, boric acid, optional boric acid, cycloalkoxycarbonylamino, heterocycloalkyloxycarbonylamino, alkoxyalkyl, alkylamino, heteroaryloxyalkyl substituted, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted heteroalkyl, optionally substituted heterocycloalkyl, and optionally substituted amino.
[0010] The groups R3 and R4 of the compound represented by Formula I and other related formulas described further here, are each independently selected from hydrogen, hydroxyl and a chiral or non-chiral group selected from, optionally substituted, heteroalkyl, optionally substituted alkyl , optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, halogen, optionally substituted amino, carboxy, alkylcarbonyl, optionally substituted alkoxy, and aminocarbonyl. Alternatively, one of R3 and R4 is a bond, one of R3 and R4 is oxygen, and R3 and R4 together form oxo (= 0). Furthermore, and alternatively, R3 and R4 together with any interfering atom form a group selected from optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl.
[0011] The groups B and B 'of the compound represented by Formula I and other related formulas described here, are each independently selected from hydrogen, L3 as further described here, halogen and a chiral or non-chiral group, selected from metallocenyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocycloalkyl, and optionally substituted cycloalkyl. Alternatively, B and B 'taken together with any interfering atom form a group selected from optionally substituted cycloalkyl and optionally substituted heterocycloalkyl;
[0012] The Li, L2 groups of the compound represented by Formula I and other related formulas described further here, are each independently selected from a chiral or non-chiral elongation group representing by the following formula II: “(Si ) c - (Q1 - (S2) d) d '- (Q2 _ (S3) e) e' - (Q3 - (S4) f) f '-S5 -P (II)
[0013] The groups Qi, Q2, and Q3 of Formula II are each, independently, for each occurrence, a divalent group chosen from, an unsubstituted or substituted aromatic group, an unsubstituted or substituted alicyclic group, and an unsubstituted or substituted heterocyclic group. Each substituent is independently of the group Qi, Q2, and Q3 can be independently chosen from, a group represented by P, liquid crystal mesogens, halogen, poly (Ci-Cis alkoxy), C1-8 alkoxycarbonyl, C1-8 alkylcarbonyl, alkoxycarbonyloxy Ci ~ Cie, aryloxycarbonyloxy, perfluoro (Ci ~ Cie alkoxy), perfluoro (Ci — Ci8) alkoxycarbonyl, perfluoro (Ci-Ci8) alkylcarbonyl, perfluoro (Ci-Ci8) alkylamino, di- (perfluoro (Ci ~ Ci8 alkyl) amino, perfluoro (C1-C1) alkylthio, C1-C1 alkylthio, C1-C8 alkylethyl, C1-C8 alkylthio, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, a straight-chain or branched C1-C8 alkyl group that is mono-substituted with cyano, halo, or C1- C alkoxy, or halo-substituted, and a group comprising one of the following formula: -M (T) (ti) and -M (OT) (ti ;, where M is chosen from from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organo-functional radicals, organo-functional hydrocarbon radicals, hydrocarbon radicals aliphatic arbonide and aromatic hydrocarbon radicals, and t is the valence of M.
[0014] Subscribers c, d, e, and f of Formula II are each independently an integer selected from 0 to 20, including the quoted values. The Si, S2, S3, S4, and S5 groups of Formula II are each, independently for each occurrence, a spacer unit chosen from the following categories (1), (2) and (3). Spacer units in category (1) include, - (CH2) g-, - (CF2) h-, -Si (Z) 2 (CH2) g-, - (Si (CH3) 2O) h ~ r where Z is independently chosen for each occurrence from hydrogen, C1-8 alkyl, C3-C10 cycloalkyl and aryl; g is independently chosen for each occurrence from del to 20; there is a total number from 1 to 16 inclusive.
[0015] Spacer units in category (2) include, - N (Z) -, -C (Z) = C (Z) -, -C (Z) = N-, -C (Z ') - C ( Z ') - or a simple bond, where Z is independently chosen for each occurrence from hydrogen, C1-C1 alkyl, C3-C10 cycloalkyl and aryl; and Z 'is independently chosen for each occurrence from Ci-Cie alkyl, C3-C10 cycloalkyl and aryl. The category (3) spacer unit includes -0-, -C (0) -, -C = C-, -N = N-, -S-, -S (0) -, -S (0) (0 ) -, - (0) S (0) -, - (0) S (0) 0-, -0 (0) S (0) 0-, or straight or branched chain C1-C24 alkylene residue, said C1-C24 alkylene residue being unsubstituted, mono-substituted by cyano or halo, or poly-substituted by halo. With respect to the spacer units from which Si, S2, S3, S4 and S5 can be chosen, presenting the provision that when two spacer units comprising heteroatoms are linked together, the spacer units are connected so that the heteroatoms are not directly connected to each other. With respect to the spacer units from which Si, S2, S3, S4 and S5 can be chosen, there is a provision that when Si is attached to a compound of the present invention, such as Formula I, and S5 is attached to P , Si and S2 are each linked so that two hetero atoms are not directly linked to each other.
[0016] With additional reference to Formula II, P is chosen from: hydroxy, amino, C2-C18 alkylene <C2-C18 alkynyl, azide, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl) oxy, thio, isocyanate, thioisocyanate, acryloyloxy, methacryloyloxy, 2- (acryloyloxy) ethylearbamyl, 2- (methacryloyloxy) ethylearbamyl, aziridinyl, allyoxycarbonyloxy, epoxy, carboxylic acid, alkylcarbonyl amine, alkylcarbonyl amine, acrylonylcarboxyl amine, acryloylcarbonyl amine, acryloylcarbonyl ester, (C-Cis alkyl) aminocarbonyl, C1-Cis alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C1-Cis alkyl), C1-Cis alkyl, C1-Cis alkoxy, amino (C1-Cis alkyl), C1-6 alkyl di- (Ci-Ciβ) alkylamino, Ci ~ Ci8 alkyl (Ci-Ciβ alkoxy), Ci-Ciβ alkoxy (Ci-Ciβ alkoxy), nitro, poly (Ci-Cis alkyl) ether, (Ci-Cis alkyl) alkoxy (C1-Cis) C1-8 alkyl, oxy-polyethylene, oxy-polypropylene, ethylenyl, acryloyl, acryloyloxy (C1-8 alkyl), methacryloyl, methacryloyloxy (C1-8 alkyl) r 2-chloroac ryloyl, 2-phenylacrylyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxyethanyl, glycidyl, cyano, isocyanate (C1-Cyl alkyl), itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative main chain and side chain liquid crystals, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are replaced with at least one methyl, methoxy, cyano and halogen, or monovalent or divalent chiral and non-chiral groups, substituted or unsubstituted, chosen from steroidal radicals, terpenoid radicals, alkali radicals, and mixtures thereof, where the substituents are independently chosen from C1-Cis alkyl , Ci-Ciβ alkoxy, amino, C3-C10 cycloalkyl, Ci-Ciβ alkyl alkoxy (Ci-Ci8), fluoro (Ci-Ci8) alkyl, cyano, cyano (Ci-Cis) alkyl, cyano (Ci-Ci8) alkoxy or mixtures thereof, or P is a structure having from 2 to 4 reactive groups or P is an unsubstituted or substituted open ring metastasis polymerization precursor, or P is a substituted or unsubstituted photochromic compound.
[0017] The subscripts d ', e', and f of Formula II can each be independently chosen from 0, 1, 2, 3, and 4, providing that a sum of d '+ and' + f 'is at least minus 2.
[0018] According to the present invention, a photochromic composition and articles are provided which include one or more of the compounds of the present invention. Brief description of the drawings.
[0019] Figure 1 is a graphical representation of two spectra of average differential absorption, obtained for a photochromic compound according to several non-limiting embodiments described here using METHODO CELL. Detailed description of the invention
[0020] As used herein, including the specification and the claims, the following words, phrases and symbols are generally intended to have the meaning represented below, unless the extent to which they are used indicates otherwise. Abbreviations and terms have the meaning indicated throughout the application.
[0021] A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CONH2 is linked via the carbon atom.
[0022] The term "Alkyl" alone or as part of another substituent refers to a monovalent straight or branched, saturated or unsaturated hydrocarbon radical derived by the removal of a hydrogen atom from a single carbon atom from an alkane , alkene, or original alkyne. Examples of alkyl groups include, but are not limited to, methyl; ethyl such as ethanyl, ethylene, and ethynyl; propyls such as propan-1-yl, propan-2-yl, prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), propyl 1- in-1-yl, prop-2-in-1-yl, etc .; butyl such as butan-l-yl, butan-2-yl, 2-methyl-propan-l-yl, 2-methyl-propan-2-yl, but-1-en-l-yl, but-l-en -2-yl, 2-methyl-prop-l-en-l-yl, but-2-en-l-yl, but-2-en-2-yl, buta-1,3-dien-l-yl , buta-1,3-dien- 2-yl, but-1-in-1-yl, but-1-in-3-yl, but-3-in-1-yl, etc .; and gender.
[0023] The term "alkyl" is specifically intended to include groups having any degree or level of saturation, that is, groups having exclusively single carbon-carbon bonds, groups having one or more carbon-carbon double bonds, groups having one or more carbon-carbon triple bonds, and groups having mixtures of single, double and triple carbon-carbon bonds. Where a specific level of saturation is desired, the terms "alkanyl", "alkenyl" and "alkynyl" are used. In certain embodiments, an alkyl group comprises from 1 to 20 carbon atoms, in certain embodiments, from 1 to 10 carbon atoms, in certain embodiments, from 1 to 8 or from 1 to 6 carbon atoms and, in certain embodiments, from 1 to 3 carbon atoms.
[0024] The term "acyl" alone or as part of another substituent refers to a radical -C (O) R, where R is hydrogen, alkyl, heteroalkyl, cycloalkyl, hetero cycloalkyl, cycloalkyl alkyl, hetero cycloalkyl alkyl, aryl , heteroaryl, arylalkyl, or heteroarylalkyl, which can be substituted, as defined herein. Examples of acyl groups include, but are not limited to, formyl, acetyl, cyclohexylcarbonyl, cyclohexyl methyl carbonyl, benzoyl, benzylcarbonyl, and the like.
[0025] The term "alkoxy" alone or as part of another substituent refers to a radical -OR31 where R31 is alkyl, cycloalkyl, cycloalkylalkyl, aryl, or arylalkyl, which can be substituted, as defined herein. In some embodiments, alkoxy groups have 1 to 18 carbon atoms. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.
[0026] The term "alkoxy carbonyl" alone or as part of another substituent refers to a radical -C (O) OR where R is alkyl, cycloalkyl, cycloalkylalkyl, aryl, or arylalkyl, which can be substituted as defined herein .
[0027] The term "amino" refers to the radical -NH2.
[0028] The term "amino carbonyl" alone or as part of another substituent refers to the radical of the formula -NC (O) R60 where each R60 is selected from hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, cycloalkyl substituted, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl.
[0029] The term "aryl" alone or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived by removing a hydrogen atom from a single carbon atom from an original aromatic ring system. Arila comprises aromatic carbocyclic rings of 5 and 6 members, for example, benzene; bicyclic ring systems in which at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems in which at least one ring is carbocyclic and aromatic, for example, fluorene. Arila encompasses multiple ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring. For example, aryl includes 5- and 6-membered carbocyclic aromatic rings fused to a 5- to 7-membered heterocycloalkyl ring containing one or more heteroatoms chosen from N, 0, and S. For such fused bicyclic ring systems, only one of the rings is a carbocyclic aromatic ring, the point of attachment can be in the aromatic ring or in the heterocycloalkyl ring. Examples of aryl groups include, but are not limited to dgurpso derivatives of aceantrylene, acenaftilene, acefenantrileno, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octafen, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, triphenylene, and the like. In certain embodiments, an aryl group can comprise from 5 to 20 carbon atoms, and in certain embodiments from 5 to 12 carbon atoms. However, Arila does not cover or coincide in any way with heteroaryl, defined here separately. Thus, a multiple ring system in which one or more aromatic carbocyclic rings fuse with a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein.
[0030] The term "arylalkyl" alone or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms attached to a carbon atom, typically a terminal carbon atom or sp, and replaced with a aryl group. Examples of arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-1-yl, 2-phenyleneth-1-yl, naphthylmethyl, 2-naphthylethane-1-yl, 2-naphthylethyl-1-yl, naphthobenzyl, 2- naphthophenylethane-l-ila, and the genus. Where specific alkyl parts are desired, the nomenclature arylalkanyl, arylalkenyl, or arylalkynyl is used. With some embodiments, an arylalkyl group is C7-30 arylalkyl, for example, the alkanyl, alkenyl, or alkynyl part of the arylalkyl group is Ci-10 and the aryl part is Cg-20f and in certain embodiments, an arylalkyl group is arylalkyl of C7-20, for example, the alkanyl, alkenyl, or alkynyl part of the arylalkyl group is of Ci-s and the aryl part is of C6-12 •
[0031] The term "carboxamidyl" alone or as part of another substituent refers to a radical of the formula —C (O) NR60R61, where R60 and R61, are independently hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl , substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, or substituted heteroarylalkyl, or R60 and R61 together with the nitrogen atom to which they bond form a heterocyclic ring substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl ring.
[0032] The term "compound" refers to the compounds covered by Formulas I and IA presented herein and include any specific compounds within these formulas whose structure is described herein. The compounds can be identified either by their chemical structure and / or their chemical name. When the chemical structure and the chemical name conflict, the chemical structure determines the identity of the compound. The compounds described herein can contain one or more chiral centers and / or double bonds and, therefore, can exist as stereoisomers, such as double bonded isomers (i.e., geometric isomers), enantiomers, or diastereoisomers. Consequently, any chemical structures within the protection scope of the described report, in whole or in part, with a relative configuration cover all possible enantiomers and stereoisomers of the illustrated compounds including the stereoisomerically pure form (for example, geometrically pure, enantiomerically pure, or diastereoisomerically pure) and enantiomeric and stereoisomeric mixtures. The enantiomeric and stereoisomeric mixtures can be decomposed into their enantiomeric and stereoisomeric components using separation techniques or chiral synthesis techniques well known to those skilled in the art.
[0033] The term "precursor" and related terms, such as "precursors" with respect to the various groups, for example, R1, R2, R3, R4, B and B ', of the compounds and intermediates described here, for example, the compounds represented by formulas I, Ia, and Ib, means a group that can be converted into one or more steps for the final group or the desired group. For the purpose of non-limiting illustration, a precursor to a hydroxyl group (-OH) includes, but is not limited to, a carboxylic acid ester group (-OC (O) R where R is hydrogen or an optionally substituted hydrocarbyl) ; and a precursor to a carboxylic acid ester group (-OC (O) R) includes, but is not limited to, a hydroxyl group (-OH), which can be reacted, for example, with a carboxylic acid halide , such as acetic acid chloride (or acetyl chloride).
[0034] For the purposes of this description, the term "chiral compounds" are compounds having at least one chirality center (i.e., at least one asymmetric atom, in particular at least one asymmetric C atom), having an axis of chirality, a chirality plan or a helix structure. The term "achiral compounds" refers to compounds that are not chiral.
[0035] The compounds represented by Formula I, and related formulas as further described herein, such as Formulas Ia and Ib, include, but are not limited to, optical isomers of compounds thereof, racemates thereof, and other mixtures thereof . In said embodiments, enantiomers or diastereoisomers, i.e., optically active forms, can be obtained by asymmetric synthesis or by decomposition of the racemates. The decomposition of racemic mixtures can be carried out, for example, by conventional methods such as crystallization in the presence of a decomposition agent, or chromatography, using, for example, a chiral high pressure liquid chromatography (HPLC) column. Unless otherwise stated, however, it must be admitted that the compounds represented by Formula I and related formulas cover all asymmetric variants of the compounds described herein, including isomers, racemic mixtures, enantiomers, diastereoisomers, and other mixtures thereof. In addition, the compounds represented by Formula I and related formulas include Z forms and E forms (for example, cis and trans forms) of the double bonded compounds. In embodiments in which the compounds represented by Formula I and related formulas exist in various tautomeric forms, the compounds provided by the present description include all tautomeric forms of the compound.
[0036] The compounds represented by Formula I, and related formulas as further described herein, such as Formulas Ia and Ib, can also exist in various tautomeric forms including the enol form, the ketone form, and mixtures thereof. Consequently, the chemical structures represented here encompass all possible tautomeric forms of the compounds illustrated. The compounds can exist in unsolvated forms, as well as in solvated forms, including hydrated forms and as N-oxides. In general, the compounds can be hydrated, solvated, or as N-oxides. Certain compounds can exist in a monocrystalline, multicrystalline or amorphous form. In general, all physical forms are equivalent for the uses contemplated herein and which are intended to be within the scope of protection provided by this description. In addition, when the partial structures of the compounds are illustrated, an asterisk (*) indicates the point of attachment of the partial structure with the rest of the molecule.
[0037] The term "cycloalkyl" alone or as part of another substituent refers to a saturated or unsaturated cyclic alkyl radical. Where a specific level of saturation is desired, the nomenclature "cycloalkanyl" or "cycloalkenyl" is used. Examples of cycloalkyl groups include, but are not limited to, derivatives of cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. In certain embodiments, a cycloalkyl group is C3-15 (C3-C15) cycloalkyl and, in certain embodiments, C3-12 cycloalkyl or C5-12 cycloalkyl.
[0038] The term "cycloalkylalkyl" alone or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms attached to a carbon atom, typically a terminal carbon atom or sp, and replaced with a cycloalkyl group. Where specific alkyl parts are desired, the cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynyl nomenclature is used. In certain embodiments, a cycloalkylalkyl group is C7-30 (C7-C30) cycloalkylalkyl, for example, the alkanyl, alkenyl, or alkynyl portion of the cycloalkyl group is C10 and the cycloalkyl portion is C6-20, and θ® certain embodiments , a cycloalkylalkyl group is C7-20 cycloalkylalkyl, for example, the alkanyl, alkenyl, or alkynyl portion of the cycloalkylalkyl group is Ci-s and the cycloalkyl portion is C4-20 or C6-12 •
[0039] The term "halogen" refers to a fluorine, chlorine, bromine, or iodine group.
[0040] The term "heteroalkyl" alone or as part of another substituent refers to an alkyl group in which one or more of the carbon atoms (and any associated hydrogen atoms) are independently replaced by the same or different heteroatomic groups. In some embodiments, heteroalkyl groups have 1 to 8 carbon atoms. Examples of heteroatomic groups include, but are not limited to -0-, -S-, -SS-, -NR38, = NN =, -N = N-, -N = N-NR39R40, -PR41-, - P ( 0) 2, -POR42-, -0-P (0) 2-, -S0-, -SO2-, SnR43R44- and the like, where R38, R39, R40, R41, R42, R43, and R44 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, alkyl heteroaryl or alkyl. Where a specific level of saturation is desired, the nomenclature "heteroalkanyl", "heteroalkenyl", or "heteroalkynyl" is used. With some embodiments, R38, R39, R40, R41, R42, R43, and R44 are independently chosen from hydrogen and C1-3 alkyl •
[0041] The term "heteroaryl" alone or as part of another substituent refers to a monovalent heteroaromatic radical derived from the removal of a hydrogen atom from a single atom of an original heteroaromatic ring system. The term "heteroaryl" encompasses multiple ring systems having at least one aromatic ring fused to at least one other ring, which may be aromatic or non-aromatic in which at least one ring atom is a heteroatom. The term "heteroaryl" embraces aromatic monocyclic rings of 5 to 12 members, such as 5 to 7 members, monocyclic rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3 hetero atoms chosen from N, 0, and S, with the remaining ring atoms being carbon; and bicyclic heterocycloalkyl rings containing one or more of, for example, from 1 to 4, or in certain embodiments, from 1 to 3 heteroatoms chosen from N, O, and S, with the remaining atoms being carbon and at least one heteroatom is present in an aromatic ring. For example, the heteroatom includes an aromatic ring, 5- to 7-membered heterocycloalkyl, fused to a 5- to 7-membered cycloalkyl ring. For such fused bicyclic heteroaryl ring systems, in which only one of the rings contains one or more heteroatoms, the point of attachment may be on the heteroaromatic ring or the cycloalkyl ring. In certain embodiments, when the total number of N, S, and O atoms in the heteroaryl group exceeds one, the heteroatoms are not adjacent to each other. In certain embodiments, the total number of atoms N, S, and O is not greater than two. In certain embodiments, the total number of N, S, and O atoms in the heteroaryl group is not more than one. The term "heteroaryl" does not include or overlap with aryl as defined herein.
[0042] Examples of heteroaryl groups include, but are not limited to, groups derived from acridine, arsindol, carbazole, β-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindol , isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridine, pyridine, quinoline, pyrimine, pyrimine, pyridine, quinoline , quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In certain embodiments, a heteroaryl group is a 5 to 20 membered heteroaryl, and in certain embodiments a heteroaryl is 5 to 12 members or a 5 to 10 membered heteroaryl. In certain embodiments, heteroaryl groups are those derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole, and pyrazine.
[0043] The term "heteroarylalkyl" alone or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms attached to a carbon atom, typically a terminal carbon atom or sp, and replaced by a heteroaryl group. Where specific alkyl parts are desired, the heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynyl nomenclature is used. With some embodiments, a heteroarylalkyl group is a 6 to 30 membered heteroarylalkyl group, for example, the alkanyl, alkenyl, or alkynyl part of the heteroarylalkyl is 1 to 10 members and the heteroaryl part is a 5 to 20 membered heteroaryl, and with some embodiments it is a 6 to 20 membered heteroarylalkyl, for example, the alkanyl, alkenyl, or alkynyl part of heteroarylalkyl is 1 to 8 members and the heteroaryl part is a 5 to 12 membered heteroaryl.
[0044] The term "heterocycloalkyl" alone or as part of another substituent refers to an unsaturated or partially saturated cyclic radical in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same heteroatom or a different heteroatom. Examples of heteroatoms to replace carbon atoms include, but are not limited to N, P, O, S, Si, etc. Where a specific level of saturation is desired, the nomenclature "heterocycloalkanyl", or "heterocycloalkenyl" is used. Examples of heterocycloalkyl groups include, but are not limited to, groups derived from epoxide, azirines, tyrants, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, quinuclidine, and the like.
[0045] The term "heterocycloalkylalkyl" alone or as part of another substituent refers to an acyclic alkyl radical in which one of the hydrogen atoms attached to a carbon atom, typically a terminal carbon atom or sp3, is replaced by a heterocycloalkyl group. Where specific alkyl parts are desired, the hetero cycloalkyl alkanyl, hetero cycloalkyl alkenyl, or hetero cycloalkyl alkynyl nomenclature is used. In certain embodiments, a hetero cycloalkyl alkyl group is a 6 to 30 membered hetero cycloalkyl alkyl, for example, the alkanyl, alkenyl, or alkynyl part of the hetero cycloalkyl alkyl is 1 to 10 members and the heterocycloalkyl part is a 5-membered heterocycloalkyl to 20 members, and in certain embodiments is a 6 to 20 membered heterocycloalkyl alkyl, for example, the alkanyl, alkenyl, or alkynyl part of the heterocycloalkylalkyl is 1 to 8 members and the heterocycloalkyl part is a 5 to 12 membered heterocycloalkyl.
[0046] The term "protecting group" refers to an atom or group capable of being displaced by a nucleophile and includes halogen, such as chlorine, bromine, fluorine, and iodine, alkoxycarbonyl (e.g., acetoxy), aryloxycarbonyl, mesyloxy, tosilox, trifluoromethanesulfonyloxy, aryloxy (e.g., 2,4-dinitrophenoxy), methoxy, N, O-dimethylhydroxylamino, and the like.
[0047] The term "original aromatic ring system" refers to an unsaturated cyclic or polycyclic ring system having a conjugated π (pi) electron system. Included within the definition of "original aromatic ring system" are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene , phenalene, etc. Examples of original aromatic ring systems include, but are not limited to, aceanthrene, acenaphthene, acephenanthrene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octafen, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, triphenylene, and the like.
[0048] The term "original heteroaromatic ring system" refers to an original aromatic ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced by the same or different hetero atoms. Examples of heteroatoms to replace carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Specifically included within the definition of "original heteroaromatic ring system" are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, arsindol, benzodioxane, benzofuran , chroman, chromene, indole, indoline, xanthene, etc. Examples of original heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, β-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinazoline, quinazoline, quinazoline, quinazoline thiazole, thiophene, triazole, xanthene, and the like.
[0049] The term "perhaloalkyl" is a subset of substituted alkyl where each hydrogen atom is replaced by the same halogen atom or by different halogen atoms. Examples of perhaloalkyl include, but are not limited to -CF3, -CF2CF3, and -C (CF3) 3.
[0050] The term "perhaloalkoxy" is a subset of substituted alkoxy where each hydrogen atom of R31 is replaced by the same halogen atom or by different halogen atoms. Examples of perhaloalkoxy include, but are not limited to -OCF3, -OCF2CF3, and -OC (CF3) 3.
[0051] The term "protecting group" refers to a grouping of atoms, which when attached to a reactive group in a molecule, masks, reduces or prevents that reactivity. Examples of protective groups can be found in Wuts and Greene, "Protective Groups in Organic Synthesis", John Wiley & Sons, 4th edition, 2006; Harrison et al., "Compendium of Organic Synthetic Methods", volumes 1-11, John Wiley & Sons, 1971-2003; Larock, "Comprehensive Organic Transformations", John Wiley & Sons, 2nd edition, 2000; and Paquette, "Encyclopedia of Reagents for Organic Synthesis", John Wiley & Sons, 2nd edition, 2003. Examples of amino protecting groups include, but are not limited to, formyl, acetyl, trifluoroacetyl, benzyl, benzyloxy carbonyl (CBZ), tert-butoxy carbonyl (Boc), trimethyl silyl (TMS), 2-trimethyl silyl ethane sulfonyl (SES), trityl and substituted trityl groups, allyloxy carbonyl, 9-fluorenyl methyloxy carbonyl (FMOC), nitro-veratryloxy carbonyl (NVOC) , and the like. Examples of hydroxy protecting groups include, but are not limited to those in which the hydroxy group is both acylated and alkylated such as benzyl, trityl ethers as well as alkyl ethers, tetrahydropyranyl ethers, trialkyl silyl ethers, and allyl ethers.
[0052] The term "silyl" alone or as part of another substituent refers to a radical of the formula -SiR RR where each of R30, R31, and R31 is selected independently from alkyl, alkoxy, and phenyl, which can be replaced as defined herein.
[0053] The term "siloxy" alone or as part of another substituent refers to a radical of the formula -OSiR RR where each of R30, R31, and R31 is selected independently from alkyl, alkoxy, and phenyl, which can be replaced as defined herein.
[0054] The term "substituted" refers to a group in which one or more hydrogen atoms are replaced by the same or different substituents. Examples of substituents include, but are not limited to -R64, -R60, - O ', (—OH), = 0, -OR60, -SR60, -S', = S, -NR60R61, -NR60, -CX3, -CN, -CF3, -OCN, -SCN, -NO, -NO2, = N2, -N3, -S (O) 2O ', -S (O) 2OH, - S (O) 2R60, -OS (O2 ) O ", -OS (O) 2R60, -P (O) (O ') 2, -P (O) (OR60) (O"), - OP (O) (OR60) (OR61), -C ( O) R60, -C (S) R60, -C (O) R60, -C (O) R60R61, - C (O) O ', -C (S) R60, -NR62C (0) NR60R61, -NR62C ( S) NR6OR61, NR62C (NR63) NR6OR61, -C (NR62) NR6OR61, -S (0) 2NR60R61, -NR63S (O) 2R60, - NR63C (O) R60, and -S (O) R60 where each -R64 is independently a halogen; R60 and R61 are independently hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, substituted arylalkyl, substituted arylalkyl, heteroaryl or alkyl, or and R61 together with the nitrogen atom to which they are attached form a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R62 and R63 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl , substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl, or R62 and R63 together with the atom to which they attach form one or more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, or substituted heteroaryl rings. With some embodiments, a tertiary amine or aromatic nitrogen can be replaced by one or more oxygen atoms to form the corresponding nitrogen oxide.
[0055] The term "sulfonate" alone or as part of another substituent refers to a sulfur radical of the formula - S (O) 2O ".
[0056] The term "sulfonyl" alone or as part of another substituent refers to a sulfur radical of the formula - S (O) 2R60 where R60 can be selected from hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl , substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, and substituted heteroarylalkyl.
[0057] With some configurations, substituted aryl and substituted heteroaryl include one or more of the following substituent groups: F, Cl, Br, C1-3 alkyl, substituted alkyl, C1-3 alkoxy, -S (O) 2R50R5 -NR50R51 , -CF3, -OCF3, - CN, -NR50S (O) 2R51, -NR50C (O) R51, C5-10 aryl, substituted C5-10 aryl, C5-10 heteroaryl, substituted C5-10 heteroaryl, -C ( O) OR50, -NO2, -C (O) R50, —C (O) NR50R51, -OCHF2, C1-3 acyl, - SR50, -S (O) 2OH, -S (O) 2R50, -S (O ) R50, -C (S) R50, -C (O) O ", - C (S) OR50, -NR50C (O) NR51R52, -NR5OC (S) NR51R52, and -C (NR50) NR51R52, C3- cycloalkyl 8, substituted C3-8 cycloalkyl θ, where R, R51, and R52 are each independently selected from hydrogen and C1-4 alkyl.
[0058] As used herein and in the claims, the quotations of "linear or branched" or "linear, branched or cyclic" group, such as linear or branched alkyl, or linear cyclic or branched alkyl, are understood to include: a methylene group or methyl group, groups that are linear, such as linear C2-C25 alkyl groups; groups that are suitably branched, such as branched Cs-C25 alkyl groups; and groups that are suitably cyclic, such as C3-C25 cycloalkyl groups (or cyclic C3-C25 alkyl).
[0059] As used herein and in the claims, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, are inclusive of other appropriate orientations, such as right to left orientation. For the purpose of non-limiting illustration, the left-to-right representation of the divalent link group -C (0) 0-, is even the right-to-left representation of the same group, -0 (0) C-.
[0060] As used herein and in the appended claims, the articles "one", "one", "o" and "a" include references to the plural unless expressly and unambiguously limited to one reference.
[0061] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other properties or parameters used in the report will be understood as modified in all cases by the term "about". Consequently, unless otherwise indicated, it should be understood that the numerical parameters presented below in the report and the attached claims are approximations. At least, and not as an attempt to limit the application of the doctrine of equivalents of the scope of protection of the claims, the numerical parameters should be read in the light of the number of significant figures reported and the application of conventional rounding techniques.
[0062] All numeric ranges here include all numeric values within the mentioned range of numerical values. In addition, although the numerical ranges and parameters presenting a wide scope of the invention are approximations, as discussed above, the numerical values shown in the Examples section are reported as precisely as possible. It should be understood, however, that such numerical values inherently contain certain errors resulting from the measurement equipment and / or the measurement technique. For the non-limiting purposes of the invention, a declared range or "1 to 10" ratio should be considered to include any and all sub-ranges between (and including) the minimum value of 1 and the maximum value of 10, that is, all sub-ranges or sub-proportions starting with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1; 3.5 to 7.8; and 5.5 to 10.
[0063] As used herein, the term "liquid crystal cell" refers to a structure containing a liquid crystal material that is capable of being ordered. Active liquid crystal cells are cells in which the liquid crystal material is able to change between an ordered state and a disordered state, or between two ordered states by the application of an external force, such as electric or magnetic fields. Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state. A non-limiting example of a liquid crystal cell device or element is a liquid crystal display.
[0064] The phrase "at least partial coating" means an amount of coating covering from one portion to the complete surface of the substrate. The phrase "at least partially cured coating" refers to a coating in which the curable or crosslinkable components are at least partially cured, crosslinked and / or reacted. In alternating non-limiting embodiments, the degree of reacted components can vary widely, for example, from 5% to 100% of all possible curable, crosslinkable and / or reactive components.
[0065] The phrase "abrasion-resistant film or coating at least partially" refers to a film or coating that demonstrates a Bayer abrasion resistance index of at least 1.3 to 10.0 in the standard test method ASTM F-735 for abrasion resistance of coatings and transparent plastics using the oscillating sand method. The phrase "at least partially anti-reflective coating" is a coating that improves at least partially the anti-reflective nature of the surface on which it is applied by increasing the percentage of transmittance when compared to an uncoated surface. The improvement in percentage of transmittance can vary from 1 to 9 percent above the untreated surface. In other words, the transmittance percentage of the treated surface can vary from a percentage higher than that of the untreated surface up to 99.9.
[0066] Several non-limiting configurations of the description will now be described. A non-limiting embodiment provides a thermally reversible photochromic compound comprising an elongation group Li, and optionally L2 and / or L3, also described below. Another non-limiting embodiment provides a photochromic compound adapted to have at least a first state and a second state, the thermally reversible photochromic compound having an average absorption ratio greater than 1.5 in at least one state as determined according to the CELL METHOD, which is described in detail below. In addition, according to the various non-limiting embodiments, the thermally reversible photochromic compound has an average absorption ratio greater than 1.5 in an activated state as determined according to the CELL METHOD. As used herein, in relation to photochromic compounds, the term "activated state" refers to a photochromic compound when exposed to sufficient actinic radiation to cause a change in the state of at least a portion of the photochromic compound.
[0067] In general, the CELL METHOD of measuring the average absorption ratio of a photochromic compound involves obtaining an absorption spectrum for the photochromic compound, in an activated or deactivated state, in each of the two orthogonal directions of polarization while the photochromic compound is at least partially aligned in an aligned liquid crystal medium that is contained within a cell arrangement. More specifically, the cell arrangement comprises two opposing glass substrates that are spaced by 20 microns +/- 1 micron. The substrates are sealed close to the two opposite edges to form the cell. The inner surface of each of the glass substrates is coated with a polyimide coating, the surface of which has at least been partially polished. The alignment of the photochromic compound is achieved by introducing the photochromic compound and a liquid crystal medium into the cell arrangement and allowing the alignment of the liquid crystal medium with the polished polyimide surface. Because the photochromic compound is contained within the liquid crystal medium, the alignment of the liquid crystal medium induces the alignment of the photochromic compound. It should be appreciated by those skilled in the art that the choice of liquid crystal medium and temperature used during the test can affect the proportion of measured absorption. Consequently, as shown in greater detail in the Examples, for the purposes of the CELL METHOD, the measurement of the proportion of absorption is taken at room temperature (73 ° F +/- 0.5 ° F or greater) and the liquid crystal medium is Licristal® E7 (which is reported to be a mixture of cyanobiphenyl and cyanoterphenyl liquid crystal compounds).
[0068] Once the liquid crystal medium and the photochromic compound are aligned, the cell arrangement is placed on an optical bench (which is described in more detail in the Examples). To obtain the average proportion in the activated state, the activation of the photochromic compound is achieved by exposing the photochromic compound to UV radiation for a sufficient time to reach a saturated state or a state close to saturated (that is, a state where the absorption properties of the photochromic compound do not change substantially in relation to the time interval during which measurements are made). Absorption measurements are taken over a period of time (typically 10 to 300 seconds) in a 3-second light interval that is linearly polarized in a plane perpendicular to the optical bench (referred to as 0o polarization plane or direction) and light that is linearly polarized in a plane that is parallel to the optical bench (referred to as plane or direction of polarization 90 °) in the following sequence 0 °, 90 °, 90 °, 0 ° etc. The absorbance of linearly polarized light through the cell is measured at each time interval for all wavelengths tested and the absorbance deactivated (that is, the absorbance of the cell with the liquid crystal material and the deactivated photochromic compound) during the same wavelength range that is subtracted to obtain the absorption spectrum for the photochromic compound in each of the 0o and 90 ° polarization planes to obtain an average differential absorption spectrum in each polarization plane for the photochromic compound in the saturated state or in the state close to saturated.
[0069] For example, with reference to figure 1, the average difference of the absorption spectrum (generally indicated as 10) was demonstrated in a polarization plane that was obtained by a photochromic compound according to a non-limiting embodiment described here. The average absorption spectrum (usually indicated as 11) is the average difference in the absorption spectrum obtained for the same photochromic compound in the orthogonal plane of polarization. Based on the average difference in the absorption spectrum obtained for the photochromic compound, the average absorption ratio for the photochromic compound is obtained as follows. The absorption ratio of the photochromic compound at each wavelength in a predetermined range of the corresponding wavelength for Àmax-vis + / - 5 nanometers (usually indicated as 14 in figure 1), where Àmax-vis +/- 5 is the wavelength in which the photochromic compound has the highest average absorbance in any plane, calculated according to the following equation: ARÀi = Ab1Ài / Ab2Ai (Eq.l) where, ARAÍ is the absorption property at wavelength Ài , Ab i is the average absorption in the wavelength Ài in the direction of polarization (that is, 0 ° or 90 °) having the highest absorbance, and Ab2xi is the average absorption in the wavelength Ài, in the remaining polarization direction. As previously discussed, the "absorption ratio" refers to the ratio of the absorbance of linearly polarized radiation in a foreground to absorption of the same radiation of the wavelength linearly polarized in a plane orthogonal to the foreground, the foreground being taken as the plane with the highest absorbance.
[0070] The average absorbance ratio ("AR") for the photochromic compound is then calculated by averaging the individual absorption ratios obtained for the wavelengths within the predetermined range of wavelengths (ie Àmax-vis + / - 5 nanometers) according to the following equation: AR = (ZARÀi) / ni (Eq. 2) where, AR is the average absorption ratio for the photochromic compound, ARAi are the individual absorption proportions (as determined above in Eq. 1) for each wavelength within the predetermined range of wavelengths (ie Àmax-vis + / - 5 nanometers), and n ± is the number of median individual absorption ratios.
[0071] As previously discussed, conventional thermally reversible photochromic compounds are adapted to change from a first state to a second state in response to actinic radiation, and revert back to the first state in response to thermal energy. More specifically, conventional thermally reversible photochromic compounds are able to transform from an isomeric form (eg, and without limitations, a closed form) to another isomeric form (eg, and without limitations, an open form) in response to radiation actinic, and revert back to the closed form when exposed to thermal energy. However, as previously discussed, conventional thermally reversible photochromic compounds generally do not demonstrate strong dichroism.
[0072] As discussed above, the non-limiting embodiments disclosed here provide a thermally reversible photochromic compound having an average absorption ratio greater than 1.5 in at least one state as determined according to the CELL METHOD and / or a thermally photochromic compound reversible that can be used as an intermediate in the preparation of a photochromic compound having an absorption ratio greater than 1.5. Thus, the thermally reversible photochromic compound according to this non-limiting embodiment may exhibit useful photochromic properties and / or useful photochromic and dichroic properties. That is, the thermally reversible photochromic compound can be a thermally reversible photochromic and / or photochromic-dichroic compound. As used here with respect to the photochromic compounds described here, the term "photochromic-dichroic" means to exhibit both photochromic and dichroic properties under certain conditions, whose properties are at least detectable by instrumentation.
[0073] According to other non-limiting embodiments, thermally reversible photochromic compounds can be thermally reversible photochromic-dichroic compounds having an average absorption ratio ranging from 4 to 20, from 3 to 30, or from 2.0 to 50 in at least least one state as determined according to the CELL METHOD. It will be appreciated by those skilled in the art that the higher the absorption ratio of the photochromic compound the more linearly polarizing the photochromic compound will be. Therefore, according to various non-limiting embodiments, thermally reversible photochromic compounds can have any proportion of average absorption required to achieve a desired level of linear polarization.
[0074] With some embodiments of the present invention, ring A is selected from unsubstituted aryl, substituted aryl. Ring A is selected from, in addition to a group (R1) m—, unsubstituted aryl, and substituted aryl. According to some embodiments, ring A is selected from aryl, such as a 6-membered aromatic ring (e.g., a benzene ring). Typically, ring A, in addition to the group (R1 ^ -, is selected from unsubstituted aryl, unsubstituted fused ring aryl, and unsubstituted heteroaryl (or aryl, fused ring aryl, and heteroaryl). Examples of aryl groups obtained from ring A can be selected from, but not limited to, phenyl and biphenyl Examples of fused ring aryl groups from which ring A can be selected include, but are not limited to, polycyclic aromatic hydrocarbons, such as naphthyl and anthracenyl Examples of heteroaryl groups from which ring A can be selected include, but are not limited to, furanyl, pyranyl and pyridinyl.
[0075] According to some embodiments, R1, for each m, is selected from L2, formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, optionally substituted alkyl, optionally substituted boric acid, halogen, cycloalkyl ester, optionally substituted aryl , optionally substituted alkoxy, optionally substituted heteroalkyl, optionally substituted heterocycloalkyl, and optionally substituted amino. In addition, R2, for each n, is independently selected from, formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, optionally substituted alkyl, boric acid ester, halogen, optionally substituted aryl, optionally substituted aryl, optionally substituted alkoxy, heteroalkyl optionally substituted, optionally substituted heterocycloalkyl, optionally substituted amino.
[0076] The groups R3 and R4 of the compound represented by Formula I may in some embodiments, each be independently selected from hydrogen, hydroxyl and a chiral or non-chiral group selected from optionally substituted heteroalkyl, optionally substituted alkyl, optionally substituted aryl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, optionally substituted amino, carboxy, alkylcarbonyl, alkoxycarbonyl, optionally substituted alkoxy, and aminocarbonyl. Alternatively, one of R3 and R4 is a bond, one of R3 and R4 is oxygen, and R3 and R4 together form oxo (= 0). Additionally, R3 and R4 together with any interfering atom form a group selected from optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl.
[0077] Groups B and B 'can each be independently selected, with some additional embodiments of L3, hydrogen, halogen, chiral or non-chiral groups, selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, and substituted cycloalkyl, or B and B 'taken together with any interference atom form a group selected from optionally substituted cycloalkyl and optionally substituted heterocycloalkyl.
[0078] The Li, L2 and L3 groups of the compounds according to the present invention can, in some embodiments, each be independently selected from a chiral or non-chiral prolongation group representing by formula II, in which: Qi, Q2, and Q3 are each, independently, for each occurrence a divalent group chosen from, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl. Each substituent of these groups from which Qi, Q2 and Q3 can be independently selected from, can be selected from P, liquid crystal mesogens, halogen, poly (Ci-Cie alkoxy), Ci-Ci8 alkoxycarbonyl, Ci-Ciβ alkylcarbonyl, perfluoro (C1-8 alkoxy), perfluoro (C1-8 alkoxycarbonyl), perfluoro (C1-8 alkylcarbonyl), C1-8 acetyl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, a straight chain C1- Ci2 alkyl and an alkyl Branched chain Ci ~ Ci2. The straight chain Ci-Ci2 alkyl and the branched chain Ci-Ci2 alkyl can be mono-substituted with a selected group of halogen, and Ci-Ci2 alkoxy. Alternatively, straight chain C1-C12 alkyl and branched chain C1-C12 alkyl can be poly-substituted with at least two independently selected halogen groups.
[0079] Subscribers c, d, e, and f of formula II can each be independently, and more particularly, selected from an integer chosen from 1 to 10. The groups Si, S2, S3, S4, and S5 of the Formula II can each be independently, and more particularly, for each occurrence a spacer unit chosen from the following categories (1), (2), and (3). The category (1) spacer unit including, substituted or unsubstituted alkylene, substituted or unsubstituted haloalkylene, -Si (CH2) g-, and - (Si (CH3) 2O) h-, where g for each occurrence is independently chosen of an integer from 1 to 8, and said substituent for alkylene and haloalkylene are independently selected from C1-C12 alkyl, C3-C7 cycloalkyl and phenyl. The category (2) spacer unit includes, —N (Z) -, -C (Z) = C (Z) -, and a single bond, where Z for each occurrence is independently selected from hydrogen, C1- alkyl C12, C3-C7 cycloalkyl and phenyl. The category (3) spacer unit includes -O-, -C (= 0) -, -C = C-, -N = N-, -S-, and -S (= 0) -. With respect to the spacer units whose Si, S2, S3, S4 and S5 can be more particularly chosen, there is a provision and that when two spacer units comprising heteroatoms are linked together, the spacer units are connected so that the heteroatoms of the first spacer unit are not directly linked to the hetero atoms of the second spacer unit. With respect to the spacer units from which Si, S2, S3, S4 and S5 can be more particularly chosen, there is provision and that when Si is linked to formula I and S5 is linked to P, Si and S5 are each linked in a different way that two hetero atoms are not directly linked to each other.
[0080] The P group of Formula II can, with some embodiments, be more particularly selected, for each occurrence, from: hydroxy, amino, C2-C12 alkenyl, C2-C12 alkynyl, silyl, siloxy, (tetrahydro-2H -pyran- 2-yl) oxy, isocyanate, acryloyloxy, methacryloyloxy, epoxy, carboxylic acid, carboxylic ester, C1-C12 alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C1-C12 alkyl), C1-C12 alkyl, C1- alkoxy C12, ethylene, acryloyl, acryloyloxy (C1-C12 alkyl), methacryloyl, methacryloyloxy (C1-C12 alkyl), oxyethanyl, glycidyl, vinyl ether, siloxane derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, and substituted or unsubstituted chiral or non-chiral, monovalent or divalent groups, chosen from steroidal radicals, where each substituent is independently chosen from C1-C12 alkyl, C1- alkoxy C12, amino, C cycloalkyl 3-C7, C1-C12 alkyl (C1-C12 alkoxy), or fluoro (C1-C12 alkyl), or P is a structure having 2 to 4 reactive groups.
[0081] With some additional embodiments of the invention, R1, for each m, can independently and more particularly be selected from L2, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, optionally substituted alkyl, optionally substituted boric acid, halogen, cycloalkyl ester, optionally substituted aryl , optionally substituted alkoxy, optionally substituted heterocycloalkyl, and optionally substituted amino. In addition, R2, for each n, can be independently and more particularly selected from, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, optionally substituted alkyl, boric acid ester, halogen, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted heterocycloalkyl , optionally substituted amino.
[0082] With some additional embodiments of the present invention, R3 and R4 can each independently and more particularly, be selected from hydrogen, hydroxy and selected chiral groups of optionally substituted heteroalkyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted cycloalkyl, halogen , carboxy, alkylcarbonyl, alkoxycarbonyl, optionally substituted alkoxy, and aminocarbonyl. Alternatively, one of R3 and R4 is a bond, one of R3 and R4 is oxygen, and R3 and R4 together form oxo (= 0). In addition, R3 and R4 together with any interfering atom form an optionally substituted cycloalkyl.
The groups B and B 'of the compounds of the present invention can each independently be further selected from L3, hydrogen, chiral groups selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted heteroaryl, and substituted cycloalkyl, or B and B 'taken together with any interfering atom form a selected optionally substituted cycloalkyl group.
[0084] The Li, L2 and L3 groups of the compounds according to the present invention can, in some additional embodiments, each be independently selected from a chiral or non-chiral prolongation group representing by formula II, in which: Qi , Q2, θ Q3 are each, independently and more particularly, for each occurrence a divalent group chosen from, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl. Each substituent of the groups Qi, Q2 and Q3 can be independently selected from P, C1- C alkoxycarbonyl, perfluoro (C-C6 alkoxy), C3-C7 cycloalkyl, C3-C7 cycloalkoxy, a straight-chain C-C6 alkyl and an alkyl Branched chain Ci-Cg. The straight-chain C1-Cg alkyl and the branched-chain C1-Cg alkyl are mono-substituted with a selected group of halogen, and C1-C12 alkoxy. Alternatively, straight chain Ci-Cg alkyl and branched chain Ci-Cg alkyl can be poly-substituted with at least two independently selected halogen groups.
[0085] Subscribers c, d, e, and f of formula II can each be independently selected from an integer chosen from 1 to 10. The groups II, S2, S3, S4, and S5 of Formula II can each independently, and more particularly, for each occurrence, a spacer unit chosen from the following categories (1), (2), and (3). The spacer unit of category (1) including a substituted or unsubstituted alkylene. The category (2) spacer unit including -N (Z) -, -C (Z) = C (Z) -, and a single bond, where Z for each occurrence, is independently selected from hydrogen and C 1 -C 6 alkyl . The spacer unit of category (3) includes -O-, -C (= 0) -, -C = C-, and - N = N—, -S-. With respect to the spacer units whose Si, S2, S3, S4 and S5 can be more particularly chosen, there is a provision that when two spacer units comprising heteroatoms are linked together, the spacer units are connected so that the hetero atoms of the first spacer unit are not directly linked to the hetero atoms of the second spacer unit. With respect to the spacer units from which Si, S2, S3, S4 and S5 can be more particularly chosen, there is provision and that when Si is linked to formula I and S5 is linked to P, Si and S5 are each linked in a different way that two hetero atoms are not directly linked to each other.
[0086] The P group of Formula II can, with some embodiments, be more particularly selected, for each occurrence, from: hydroxy, amino, C2-Cg alkenyl, C2-C6 alkynyl, siloxy, (tetrahydro-2H-pyran -2-yl) oxy, isocyanate, acryloyloxy, methacryloyloxy, epoxy, carboxylic acid, carboxylic ester, C1-Cg alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C1-Cg alkyl), C1-C6 alkyl, ethylene, acryloyl, acryloyl, acryloyl, acryloyl (C 1 -C 6 alkyl), oxetanil, glycidyl, vinyl ether, siloxane derivatives, and substituted and unsubstituted chiral or non-chiral divalent or monovalent groups chosen from steroidal radicals. Each substituent, from the groups from which P can be chosen, is chosen from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, amino, C 3 -C 7 cycloalkyl.
[0087] With some embodiments of the present invention, R1 is not selected from L2, θ each from B and B 'are not selected from L3. As such, with some embodiments, only the prolongation group in the compound of the present invention is Li.
The group RI of the compounds of the present invention, for example, as represented by Formula I, can be for each m, independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy and CF3. In addition, R2, for each n, is independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3. Groups R3 and R4 can each be independently selected from methyl, ethyl, propyl and butyl. Groups B and B 'can each be independently selected from substituted phenyl with one or more groups independently selected from aryl, heteroaryl, heterocycloalkyl, alkyl, alkenyl, alkynyl, alkoxy, halogen, amino, alkylcarbonyl, carboxy, and alkoxycarbonyl. The groups Li, L2 and L3 can more particularly be selected from the chiral or non-chiral prolongation group represented by Formula II, in which (i) Qi is unsubstituted aryl, Q2 for each occurrence are each independently chosen from optionally substituted aryl, and Q3 is optionally substituted cycloalkyl; (ii) and for each occurrence it is 1, f is 1, S2 for each occurrence is a single bond, S4 is a single bond, and S5 is - (CH2) g-, where g is 1 to 20; (iii) P is hydrogen, and (iv) e 'is 1 or 2, f' is 1.
[0089] The compounds of the present invention can, in some embodiments, be represented by the following Formula Ia:

[0090] The groups and subscripts of the compound represented by Formula Ia are each independently as previously described here with respect to Formula I. The subscript m of formula Ia more particularly is 0 to 3 (for example, 0, 1, 2, or 3). With some embodiments, Formula Ia's R1 is not selected from L3. For example, each R1 of the compound represented by Formula Ia, can be independently for each m, of formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino, boric acid, cycloalkyloxyalkyloxyalkyl esters, cycloalkyl acid, cycloalkyloxyalkyl esters, bicarbonate, cycloalkyloxyalkylalkyloxyalkyl esters; carbonylamino, heteroaryloxycarbonylamino, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, halogen, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroalkyl, optionally substituted heterocycloalkyl and amino optionally substituted.
[0091] The compounds of the present invention can, with some embodiments, be represented by the following formula Ib:

[0092] The groups and subscripts of the compound represented by Formula Ib are each independently as previously described here with respect to Formula I. The subscript m of formula Ib more particularly is 0 to 3 (for example, 0, 1, 2, or 3). With some embodiments, R1 of Formula Ib is not selected from L2 and each of B and B 'is not selected from L3, in which case Li is the only prolongation group present in the compound of the present invention represented by Formula Ib. For example, each R1 of the compound represented by Formula Ib, can be selected, independently for each m, of formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino, boric acid, bicarbonyl esters, cycloalkyl esters, boric acid, cycloalkyl esters; hetero cycloalkyloxy carbonylamino, heteroaryloxycarbonylamino, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, halogen, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroalkyl, optionally substituted heterocycloalkyl and optionally substituted heterocycloalkyl the optionally replaced. In addition, B and B 'of Formula Ib can each independently be selected from hydrogen, halogen, and chiral or non-chiral groups selected from metallocenyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted alkoxy optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocycloalkyl, and optionally substituted cycloalkyl, or where B and B 'are taken together with any interference atom to form a selected group of optionally substituted cycloalkyl and optionally substituted heterocycloalkyl.
[0093] With some embodiments, Li, L2 and L3 can each be independently selected from groups of extensions represented by Formulas L (a) to L (u):



[0093] According to additional embodiments of the present invention, Li of the compound represented by formula Ib can be selected from the extension groups represented by Formulas L (a) through L (u). According to the embodiments in which Li of Formula Ib is selected from extension groups represented by Formulas L (a) through L (u). R1, for each m, can be independently selected from methyl, ethyl / bromine, chlorine, fluorine, methoxy, ethoxy and CF3, R2, for each n, can be independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3. The groups R3 θ R4 can each be independently selected from methyl, ethyl, propyl and butyl, and groups B and B 'can each be independently selected from phenyl substituted with one or more groups independently selected from aryl, heteroaryl, heterocycloalkyl, alkyl, alkenyl, alkynyl, alkoxy, halogen, amino, alkylcarbonyl, carboxy, and alkoxycarbonyl.
[0095] The compounds of the present invention in which ring A is a benzene ring, as represented by Formulas Ia and Ib, can be described further with respect to the various positions, or ring positions, of the compound to which the groups can be linked, such as R1, R2, Lx, L2, R3, R4, B and B '. For non-limiting demonstration purposes, the ring positions of the compound represented by Formula Ia, can be numbered as illustrated in formula Ia 'below:

[0096] The Formula Ia 'groups are each independent as previously described here. With reference to Figure Ia ', Lx is linked to position 7, L2 is linked to position 10, R3 and R4 are each linked to position 13, and B and B' are each linked to position 3 of the compound. With additional reference to Figure la ', R' can be linked to positions, 9, 11, and / or 12, when m is greater than zero, and R2 can be linked to positions 5, 6 and / or 8, when n is greater than zero. With reference to Figure 1b, in which the same numbered positions of the Figure 1 ring are equally applicable. R1 can be linked to positions 9, 10, 11 and / or 12 when m is greater than zero.
[0097] The compounds of the present invention can be used alone, as mixtures, or in combination with other compounds, compositions, and / or materials.
[0098] The compounds of the present invention can be prepared according to a method recognized in the art. For the purposes of non-limiting illustration, the compounds of the present invention can be prepared according to the procedures described with reference to the schemes, examples and cited references described in further details below.
[0099] In the diagrams and examples described further here, the following abbreviations have the meanings below. If an abbreviation is not defined, it has its most generally recognized meaning. BINAP = 2,2'-bis (diphenylphosphino) -1,1'-binafty Bi (OTf) 3 = bismuth triflate Cul = copper iodide DHP = 3,4-dihydro-2H-pyran DCC = dicyclohexylcarbodiimide DCM = dichloromethane DBSA = dodecylbenzenesulfonic acid DIBAL = diisobutyl aluminum hydride DMAP = 4-dimethylaminopyridine DME = dimethyl ether DMF = N, N-dimethylformamide DMSO = dimethyl sulfoxide Dppf = 1,1'-bis (diphenylphosphino) ferrocene EtMgBr = bromine ethoxyl g = gram h = hour HPLC = high performance liquid chromatography (iPr) 2NH = diisopropyl amine HOAc = acetic acid LDA = diisopropylamide lithium KMnO4 = potassium permanganate M = molar (molarity) mCPBA = meta-chlorophenoxy benzoic acid MeLi = methyl lithium mg = milligram min = minutes mL = milliliters mmol = millimol mM = millimolar NatOBu = sodium tert-butoxide N = normal (normality) ng = nanogram nm = nanometer nM = nanomolar NMP = N-methyl pyrrolidone NMR = nuclear magnetic resonance Pd ( OAc) 2 = Pd2 palladium acetate (dba) 3 = tr is (dibenzyldenoacetone) dipaladium (0) PPh3 = triphenyl phosphine PPTS = pyridine p-toluenesulfonate pTSA = p-toluenesulfonic acid PdCls (PPh3) 2 = bis (triphenylphosphine) palladium (II) chloride PBS = phosphate buffered saline tetra-n-butylammonium fluoride THF = tetrahydrofuran TLC = thin layer chromatography t-BuOH = t-butanol (Tf) 20 = trifluoromethanesulfonic acid anhydride | 1L = microliter | 1M = micromolar Zn (0Ac) 2 = zinc acetate ZN (CN) 2 = zinc cyanide
[0100] As discussed in the schemes further highlighted below, compound 105 represents an intermediate that can serve as the basis for the preparation of the dichroic photochromic dyes described here. For example, it can be prepared as shown in Schemes 1, 2, 3, 4 and 5. Once prepared, the hydroxy functionality of compound 105 can be used for the formation of pyran as seen in Scheme 6. The halogen of 105 can either be conserved within a prolongation group via the Suzuki Reaction or converted to another functional group Q as illustrated with reference to Scheme 6. The chemicals that can be used for the conversion of the functional group are demonstrated with reference to Schemes 7, 8 and 9 The functional group Q can either be a prolongation group or convert to an extension group.
[0101] With the schemes described here, X can be selected from halogen, for example, F, Br, Cl and I. Each men is an integer chosen from 0 for the total number of available positions. Scheme 1 to Scheme 9, R and R for each occurrence, can be independently selected from hydrogen, halogen, and optionally substituted chiral or non-chiral groups, selected from alkyl, perfluoroalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, perfluoroalkoxy, heteroalkyl, heterocycloalkyl, alkyl, arylthiol, amino aminocarbonyl, aryloxycarbonyl, alkyloxycarbonyl, aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino, cycloalkoxycarbonylamino, heterocycloalkyloxycarbonylaminoamino.

[0102] Scheme 1 demonstrates a method by which compound 105 can be prepared. Groups R3 and R4 of scheme 1 can be selected from optionally substituted chiral or non-chiral groups, such as, heteroalkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocycloalkyl.
[0103] Aryl ketone 101 can be either purchased or prepared by "Friedel-Crafts or Grignard" or Cuperate methods known in the art. For example, see the publication "Friedel-Crafts and Related Reactions", George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis); "Regioselective Friedel-Crafts Acylation of 1, 2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size", for Ishihara, Yugi et al, J. Chem. Soc, Perkin Trans. 1, pages 3401 to 3406, 1992; "Addition of Grignard Reagents to Aryl Acid Chlorides: An efficient synthesis of aryl ketones" for Wang, Xiao-jun et al, Organic Letters, Vol. 7, No. 25, 5593- 5595, 2005, and references cited here, whose descriptions related to the synthetic methods mentioned above are hereby incorporated by reference in their entirety. A Stobbe reaction of aryl ketone 101 with dimethyl succinate in the presence of potassium t-butoxide provides the condensed product of compound 102, which undergoes a closed ring reaction in acetic anhydride followed by methanolysis to form the product of compound 103.
[0104] Compound 103 can also be prepared from an ester-mediated aromatic substitution reaction starting from compound 106 by methods known to those skilled in the art, for example, as further described in "Synthesis", January 1995, pages 41-43: "The Journal of Chemistry Society Perkin Transaction 1", 1995, pages 235-241 and in US patent No .: US 7,557,208 B2, whose description related to the said synthetic methods is incorporated herein by reference in its entirety.
[0105] Once prepared, compound 103 can be further converted to a molten indene product of compound 105 with various substitutions on the carbon bridge via various multi-step reactions that can be seen in U.S. Patent Nos .: US 5,645,767; US 5, 869, 658; US 5, 698, 141; US 5, 723, 072; US 5,961,892; US 6,113,814; US 5,955,520; US 6,555,028; 6,296, 785; US 6,555,028; US 6, 683, 709; 6, 660, 727; US 6, 736, 998; US 7,008,568; US 7,166,357; US 7,262,295; US 7,320,826 and US 7,557,208, which describe the relationship of the substituents on the carbon bridge are hereby incorporated by reference in their entirety. What is shown in scheme 1 illustrates that compound 103 reacts with the Grignard reagent followed by a ring closure reaction to provide compound 105.


[0106] Scheme 2 illustrates a second path of conversion of compound 103 to compound 105. After hydrolysis of compound 103, followed by a ring closure reaction, compound 202 was obtained. The carbonyl of compound 202 can react with a nucleophile, such as Grignard reagent, organo lithium reagent, or perfluoroalkyl trimethylsilane to form compound 203. The group R3 can be selected from optionally substituted chiral or non-chiral groups such as heteroalkyl, alkyl, perfluoroalkyl , alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and heterocycloalkyl. The hydroxyl group of compound 203 can be easily converted to R4, which can be selected from halogen and optionally substituted chiral or non-chiral groups, such as alkoxy, silanoxy, heteroaryloxy and aryloxy.

[0107] Scheme 3 illustrates a third way of converting compound 103 to compound 105. Compound 202 of scheme 2 can be reduced to 301 using a Wolff-Kishner reduction or its modified version. Examples can be seen in "Practical procedures for the preparation of N-tert-butildimethylsilyhydrozones, and their use in modified Wolff-Kishner reductions and in the synthesis of vinyl halides and germ-dihalides", for Myers, Andrew. G et al., 126, 5436-5445, 2004 and references therein, whose description related to the Wolff-Kishner reduction is incorporated here by reference. After hydroxy protection, compound 302 has a lot of nucleophilic carbon-germ, once deprotonated by the LDA-type base or by the Grignard methyl reagent. For those skilled in the art, the deprotonated compound 302 can be converted to R3 and R4 by reacting it with electrophiles such as alkyl halides, carbon dioxide, acid chlorides, nitriles and chloroformate derivatives. As a result, compound 105 can be prepared with Ri and R2 selected from hydrogen, optionally substituted chiral or non-chiral groups selected from heteroalkyl, alkyl, cycloalkyl, carboxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, or R3 and R4 can be taken together with any interfering atoms to form a selected group of oxo, optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl.
[0108] Schemes 4 and 5 summarize two new methods for preparing compound 105, which are believed not to have been previously described.

[0109] Scheme 4 starts from aryl ketone 401. R3 can be selected from optionally substituted hydrogen, chiral or non-chiral groups, such as heteroalkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and heterocycloalkyl.
[0110] After a Stobbe reaction with dimethyl succinate, compound 402 is converted to an 403 anhydride. This anhydride can be transformed into an indenone 4 04 acid with the use of aluminum chloride. A 1,4-addition reaction can be performed using nucleophiles of the type of organometallic reagent, amine, alcohol and thiol. The reaction provides the indane acid 405. R4 can be selected from optionally substituted hydrogen, chiral or non-chiral groups, such as heteroalkyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, amino, alkoxy, and thiol. Compound 405 can be reacted with a Grignard reagent 406 to form compound 407 after acid stimulation ("workup"). Compound 407 undergoes a ring closure reaction in acetic anhydride followed by methanolysis to form product 408, which can either be used directly in Scheme 6 or converted to compound 105 by hydrolysis. Layout 5


[0111] Scheme 5 departs from the Stobbe 102 product, which reacts with the Grignard reagent to provide compound 501. R3 and R4 can be selected from optionally substituted chiral or non-chiral groups such as heteroalkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and heterocycloalkyl. After treatment with bismuth triflate in toluene and then acetic anhydride, two ring closure reactions occur at the same point sequentially. The efficient reaction results in compound 408, which can be converted to compound 105.

[0112] Scheme 6 illustrates the methods for converting compounds 105 and 408 into photochromic dichroic dyes. When the Suzuki reaction is applied, the extension group is added using a 601 boronic derivative, the synthesis of which can be observed from "Palladium (0) -Catalyzed CrossCoupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters , J. Org. Chem. 60, page 7508-7519, 1995 "by Miyaura, Norio et al and references contained therein, whose descriptions related to the mentioned synthetic methods are incorporated herein by reference. The pyran ring of compound 603 is formed by coupling with propargyl alcohol 602. Compound 603 can also be obtained when the sequence of two reactions is altered. As described here, G can be -OH or O-alkyl, A 'can be selected from aryl, alkenyl, alkynyl, and heteroaryl; A "and L 'together form the group Li, L2 or L3 and B and B' can each be independently selected from L3, hydrogen, halogen, and optionally substituted chiral or non-chiral groups, such as metallocenyl, alkyl or perfluoroalkyl , alkenyl, alkynyl, heteroalkyl, alkoxy, perfluoroalkoxy, aryl, heteroaryl, heterocycloalkyl, and cycloalkyl or where B and B 'are taken together with any interference atom to form a group such as optionally substituted cycloalkyl and optionally substituted heterocycloalkyl.
[0113] Also shown in Scheme 6 as alternative ways of incorporating the extension groups, halogen X can be converted into another functional group Q, with the formation of compound 604. Compound 604 can be reacted with a propargyl alcohol to form the dye pyran 605, which can be the dichroic photochromic dye itself or can be converted to the dichroic photochromic dye of Formula I. These new functional groups Q may include:
[0114] -N3, -CN, -COOR ', -CCR', -CHCHR ', -OCOR', -OCOOR ', -SR', -OSO2R ', -OR', -OTf, -CHO, -OCHO, -OCONR ', -NR'R', - NR'CONR'R ', -NR'COR', -NR'COOR ', -CHNR', and -CONR'R ', where R' can be independently chosen from hydrogen , Li, an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkene or alkyn group having 2 to 18 carbon atoms, -CF3 and a group perfluorinated alkyl having 2 to 18 carbon atoms or two R 'can stick together with -N and form a heterocycloalkyl such as piperazinyl.
[0115] Schemes 7, 8, and 9 illustrate details of the conversion of the halogen into another functional group that can be either converted further into extension groups or into the extension groups themselves. The chemicals are conducted in a hydroxy stage starting from compound 105, which is simplified as compound 701 in Schemes 7 and 8. Each of the hydroxy products of compounds 702, 706, 708, 709, 710, 802, 803, 807, 809, 810 , 811, 812, 901, 903, 904 and 906 can be converted into photochromic pyran compounds using the propargyl alcohol chemical shown in scheme 6.



[0116] Scheme 10 demonstrates the chemicals that can be conducted with dichroic photochromic dyes. A "" is a simplified version of Formula I with one of R1 or R2 selected from halogen X. X is located in one of the positions where R1 and R2 could be located. This scheme complements what can be done from schemes 1 to 9, for R1 and R and installed groups of the cyan, aldehyde, carboxylic acid type, and optionally substituted chiral or non-chiral groups selected from imine, alkoxycarbonyl, aminocarbonyl and aryloxycarbonyl such as R1 and R2 . Cyanation and oxidation methods have been described in patent publication No. US 2009/0309076 Al, where these cyanation and oxidation methods are incorporated herein by reference. Layout 10

[0117] The compounds described here can be useful as thermally reversible photochromic compounds and / or compositions according to various non-limiting configurations described here. These compounds can be used in a variety of applications to provide photochromic properties and / or dichroic-photochromic properties.
[0118] The photochromic compositions of the present invention can comprise at least one of the compounds described herein, and optionally at least one of the other photochromic compounds. The photochromic composition can be chosen from a variety of materials. Examples of such materials can be selected from: (a) a simple photochromic compound; (b) a mixture of photochromic compounds; (c) a material comprising at least one photochromic compound such as a polymeric resin or an organic monomer solution; (d) a material such as a monomer or polymer to which at least one photochromic compound is chemically bonded; (e) material (c) or (d) additionally comprising a coating to substantially prevent contact of at least one photochromic compound with external materials; (f) a photochromic polymer; or (g) mixtures thereof.
[0119] The present invention further provides a photochromic article comprising an organic material and a photochromic composition / compound of the present description that is connected to at least a portion of the host organic material. As used here, the term "connected to" means in direct contact with an object or indirect contact with an object through one or more materials or structures, at least one of which is in direct contact with the object. In addition, the photochromic compound can be connected to at least a portion of the host through incorporation into the host material or by application on the host material, for example, as part of a coating or layer. In addition to the photochromic compound, the photochromic composition may also comprise at least one additive chosen from dyes, alignment promoters, antioxidants, kinetic improvement additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, for example, light absorbers ultraviolet light and hindered amine stabilizers, thermal stabilizers, release agents, rheology control agents, leveling agents, free radical purgers, gelators and adhesion promoters.
[0120] Examples of dyes that may be present in partial coatings according to the various configurations described here include organic dyes that are capable of imparting a desired color or other optical property to an at least partial coating.
[0121] As used here, the term "alignment promoter" means an additive that can facilitate at least one of the rates and uniformity of the alignment of a material to which it is added. Examples of alignment promoters that may be present in partial coatings according to various configurations discussed here include those described in United States patent US 6,338,808 and in patent publication No. US 2002/0039627.
[0122] Antioxidants, for example, polyphenolic antioxidants, are organic compounds used to retard oxidation. Examples of antioxidants are described in U.S. Patent Nos .: US 4,720,356; US 5,391,327 and US 5,770,115, the description of which is incorporated herein by reference.
[0123] Examples of kinetic improvement additives that may be present in at least partial coatings according to various configurations described here include compounds containing epoxy, organic polyols, and / or plasticizers. More specific examples of said kinetic enhancing additives are described in US patent 6,433,043 and in patent application publication No. US 2003/0045612.
[0124] Examples of photoinitiators that may be present, at least partially in the coatings according to the various configurations described here include cleavage-type photoinitiators and abstraction-type photoinitiators. Examples of cleavage-type photoinitiators include acetophenones, α-aminoalkyl phenonones, benoin, ethers, benzoyl, oximes, acylphosphine oxides, and bisacylphosphine oxides or mixtures of said initiators. A commercial example of said photoinitiator is DAROCURE® 4265, which is available from Ciba Chemicals, Inc .. Examples of abstraction-type photoinitiators include benzophenones, Michlers acetone, thioxanthone, anthraquinone, camphorquinone, fluorene, ketocoumarin or mixtures of said initiators.
[0125] Other examples of a photoinitiator that may be present according to the various embodiments described here is a visible light photoinitiator. Examples of suitable visible light photoinitiators are shown in column 12, line 11 to column 13, line 21 of US patent 6,602,603.
[0126] Examples of thermal initiators include organic peroxy compounds and azobis (organonitrile) compounds. Specific examples of organic peroxy compounds that are useful as thermal initiators include peroxymonocarbonate esters, such as isopropyl tertiarybutylperoxy carbonate, peroxydicarbonate esters, such as di (2-ethylhexyl) peroxydicarbonate, di (secondary butyl) peroxydicarbonate and diisopropylperoxy, disopropylperoxy, disopropylperoxy, diaisopropylperoxy, disopropylperoxy, diaisopropylperoxy, disopropylperoxy, diaisopropylperoxy, disopropylperoxy, disopropylperoxy, diisopropylperoxy, such as, 2,4-dichlorobenzoyl peroxides, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide; peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate and t-butylperoxysobutyrate; methyl ethyl ketone peroxide, and acetylcyclohexane sulfonyl peroxide. In one embodiment, the thermal initiators used are those that do not discolour the resulting polymer. Examples of azobis (organonitrile) compounds that can be used as thermal initiators include azobis (isobutyronitrile), azobis (2,4-dimethylvaleronitirla) or a mixture thereof.
[0127] Examples of polymerization inhibitors include: nitrobenzene, 1,3,5-trinitrobenzene, p-benzoquinone, chloranil, DPPH, FeCla, CuCls, oxygen, sulfur, aniline, phenol, p-dihydroxybenzene, 1,2,3- trihydroxybenzene, and 2,4,6-trimethylphenol.
[0128] Examples of solvents that may be present in the LC compositions according to various embodiments described here include those that will dissolve the solid components of the LC compositions, which are compatible with the LC compositions and the elements and substrates, and / or can guarantee the uniform coverage of a surface to which the LC composition is applied. Potential solvents include those defined below: monomethyl propylene glycol ether acetate and its derivatives (sold as DOWANOL®, industrial solvents), acetone, amyl propionates, anisol, benzene, butyl acetate, cyclohexane, ethylene dialkyl esters glycol, for example, dimethyl ether diethylene glycol and its derivatives (sold as CELLOSOLVE®, industrial solvent), diethylene glycol dibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene, ethyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone , methyl ethyl ketone, methyl isobutyl ketone, methyl propionates, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, methyl-3-propylene glycol ether, and mixtures thereof.
[0129] Examples of thermal stabilizers may include a compound containing basic nitrogen, for example, biurea, allantoin, or a metal salt thereof, a carboxylic acid hydrazide, for example, an aliphatic acid or aromatic carboxylic acid hydrazide, a salt metal of an organic carboxylic acid, an alkali or an alkaline earth metal compound, a hydrotalcite, a zeolite and an acidic compound (for example, a boric acid compound, a nitrogen-containing cyclic compound having a hydroxyl group, a compound containing the carboxyl group, a (poly) phenol, butylated hydroxytoluene, and an aminocarboxylic acid or mixtures thereof.
[0130] Examples of release agents include esters of long-chain aliphatic acids and alcohols such as pentaerythritol, guerbel alcohol, long-chain acetones, siloxane, alpha-olefin polymers, long-chain alkanes and hydrocarbons having 15 to 600 atoms of carbon.
[0131] Rheology control agents are thickeners that are typically powders that can be inorganic, such as silica, organics such as micro-crystalline cellulose or particulate polymeric materials. Gelatinizing agents or gelling agents are often organic materials that can also affect the thixotropy of the materials to which they are added. Examples of gelatinizers or gelling agents include natural gums, starches, pectins, agar-agar, and gelatin. Gelatinizing or gelling agents can often be based on polysaccharides or proteins.
[0132] In certain embodiments, one or more surfactants can be used. Surfactants include materials otherwise known as wetting agents, defoaming agents, emulsifiers, dispersing agents, leveling agents, etc. Surfactants can be anionic, cationic and non-ionic, and many surfactants of each type are commercially available. Examples of nonionic surfactants that can be used include ethoxylated alkyl phenols, such as IGEPAL® DM surfactants or octyl-phenoxypolyethoxyethanol sold as TRITON® X-100, an acetylenic diol, such as 2,4,7,9-tetramethyl-5- decina-4,7-diol sold as SURFYNOL® 104, acetylenic ethoxylated diols, such as SURFYNOL® 400 series surfactant, fluoro-surfactants, such as FLUORAD®, fluorochemical surfactant series, and capped non-ionics such as ethoxylated octyl phenol capped with benzyl, sold as TRITON® CF87, alkyl ethoxylates capped with propylene oxide, which are available as PLURAFAC® RA, series of surfactants, benzyl hexadecylethoxy octylphenoxy ether, polyether modified polyethylene dimethyl copolymer in solvents sold as BYK additive 306 by Byk Chemie and mixtures of the aforementioned surfactants.
[0133] Free radical scrubbers include synthetic pseudo-peptides resistant to hydrolysis such as carcinin hydrochloride, lipoamino acids, such as L-lysine lauroylmethionine, plant extracts containing multiple enzymes, natural tocophenol and related compounds, as well as compounds containing an active hydrogen such as -OH, -SH, or -NRH group. Additional examples of free radical scavengers are chosen from the group of sterically hindered amines (HALS - hindered amine light stabilizer) which, unlike the usual light protection agents, are not based on the absorption of irradiated light or extinction absorbed light, but essentially in the capacity to purify or replace the free radicals and hydroperoxides formed during the photodegradation of polymeric and antioxidant materials.
[0134] Adhesion promoters include adhesion promoters of organo-silane materials, such as aminoorganosilane materials, silane coupling agents, organic titanate coupling agents and organic zirconate coupling agents, described in patent publication No. US 2004/0207809, in paragraphs [0033] to [0042]. Additional examples of adhesion promoters include zirconium-aluminate adhesion promoting compounds which are commercially available from Rhone-Poulenc. The preparation of aluminum-zirconium complexes is described in U.S. Patent Nos .: US 4,539,048 and US 4,539,049. These patents describe the reaction products of the zinc-aluminate complex corresponding to the empirical formula: (Al2 (ORiO) aAbBc) x (OC (R2) 0) Y (ZrAdBe) z, where X, Y, and Z are at least 1, R2 is an alkyl, alkenyl, aminoalkyl, carboxyalkyl, mercaptoalkyl, or epoxyalkyl group, having 2 to 17 carbon atoms, and the X: Z ratio is from about 2: 1 to about 5: 1. Additional zinc-aluminate complexes are described in US patent 4,650,526.
[0135] With some embodiments, a photochromic article is provided which includes: a substrate, at least a partial coating of an alignment material, at least an additional at least a partial coating of a liquid crystal material, and at least one compound photochromic according to the present invention.
[0136] The alignment materials can be used as a coating layer, or film that has been oriented, for example, by polishing, fitting, or photo-alignment methods, and subsequently aligned such as the long geometric axis of each one of liquid crystal molecules in an orientation that is generally parallel to the general direction of the surface. Examples of photo-orientable alignment material include polymer-bound photoactive cinnamic acid derivatives, coumarin derivatives, cis / trans isomerizable azo derivatives, and photochemical decomposed polyimide derivatives.
[0137] With some embodiments, the photochromic article alignment material includes a polymer network that can be obtained by exposing at least one of, a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation and a shear force. The liquid crystal material of the photochromic article may, with some embodiments, be a liquid crystal polymer.
[0138] Non-limiting examples of organic host materials that can be used in conjunction with various non-limiting configurations of the present invention include liquid crystal materials and polymeric materials. Liquid crystal materials can be chosen from liquid crystal polymers, liquid crystal prepolymers and liquid crystal monomers. As used herein, the term "prepolymer" means partially polymerized materials. Liquid crystal polymers ("LCPs") are polymers capable of forming regions of highly ordered structures while in a liquid phase. As used herein, the term "liquid crystal monomer" means a monomeric compound that can exhibit the properties of liquid crystal in the monomeric and / or in the polymeric state. That is, the liquid crystal monomer can exhibit the properties of liquid crystal by itself and / or after it has been incorporated into a polymer or copolymer to form a liquid crystal polymer (LCP). LCPs can exhibit at least one of a nematic phase, a smectic phase, a chiral nematic phase, (ie, a cholesteric phase), a discotic phase (including a chiral discotic phase), a discontinuous cubic phase, a hexagonal phase, a bicontinuous cubic phase, a lamellar phase, a reverse hexagonal columnar phase, or a reverse cubic phase. In addition, in certain LCPs of the present invention, the LC monomers or residues thereof can transition from one phase to the next, for example, in response to thermal energy or actinic radiation.
[0139] Examples of polymeric materials include homopolymers and copolymers, prepared from monomers and mixtures of monomers, such as those described in U.S. Patent Nos .: US 5,962,617 and US 5,658,501 from column 15, line 28 for column 16, line 17, where the description of the polymeric materials in these US patents are specifically incorporated herein by reference, an oligomeric material, a monomeric material, or a mixture or combination thereof. Polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any required refractive index. Non-limiting examples of said described monomers and polymers include: polyol monomers (allyl carbonate), for example, allyl diglycol carbonates, such as bis (allyl carbonate) diethylene glycol, the monomer of which is sold under the trade name CR- 39 by PPG Industries, Inc., polyurea-polyurethane polymers (polyurea-urethane), which are prepared, for example, by the reaction of a polyurethane prepolymer and a diamine curing agent, a composition for one of said polymers being sold under the trade name TRIVEX by PPG Industries, Inc., polyol (meth) acryloyl-terminated carbonate monomer, diethylene glycol dimethacrylate monomers, ethoxylated phenol methacrylate monomers, diisopropenyl benzene monomers, trimethyl ethoxylethyl triacrylate monomers, trimethylate monoethylate. ethylene glycol bismethacrylate, poly (ethylene glycol) bismethacrylate monomers, urethane acrylate monomers; poly (ethoxylated bisphenol A dimethacrylate), poly (vinyl acetate); poly (vinyl alcohol); polyvinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; polyurethanes, polythiourethanes, thermoplastic polycarbonates, such as resin bonded to carbonate derived from bisphenol A and phosgene, one of these materials being sold under the trade name LEXAN; polyesters, such as material sold under the trade name MYLAR; poly (ethylene terephthalate); polyvinyl butyral; poly (methyl methacrylate), such as the material sold under the trade name PLEXIGLAS, and polymers prepared by the reaction of polyfunctional isocyanates with polythisulfide polyisols or monomers, both homopolymerized or co- and / or terpolymerized with polythioles, polyisocyanates, polyisothiocyanates and optionally ethylenically unsaturated monomers, or vinyl monomers containing halogenated aromatics. Additionally contemplated are copolymers of said monomers and mixtures of the described polymers and copolymers with other polymers, for example, to form block copolymers or interpenetration mesh products. Polymeric materials can also be self-arranging materials.
[0140] With some embodiments of the present invention, the polymer can be a block copolymer or a non-block copolymer. With some additional embodiments, the block copolymer can include hard blocks and mold blocks. In other configurations, the polymer can be a non-block copolymer (i.e., a copolymer that does not have large blocks of specific monomer residues), such as a random copolymer, an alternative copolymer, periodic copolymers, statistical copolymers, and gradient copolymers. . The present description is also intended to cover copolymers with more than two different types of comonomer residues.
[0141] According to further embodiments of the present invention, the organic host material is chosen from polyacrylates, polymethacrylates, poly (C1-C12 alkyl methacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl pyrrolidone) , poly ((meth) acrylamide), poly (dimethyl acrylamide), poly (hydroxy ethyl methacrylate), poly ((meth) acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly (ethylene terephthalate), polystyrene, poly (alpha-methyl-styrene), copoly (styrene / methyl methacrylate), copoli (styrene / acrylonitrile), poly (vinyl butyral) and group member polymers consisting of polyol monomers (allyl carbonate), acrylate monomers monofunctional, m monomers monofunctional ethacrylate, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, benzene diisopropenyl monomers, alkoxylated polyhydric alcohol monomers and penta diallylidene monomers.
[0142] According to another embodiment of the present invention, the host organic material is a homopolymer or copolymer of monomers chosen from acrylates, methacrylates, methyl methacrylate, ethylene glycol bis methacrylate, bisphenol A ethoxylated dimethacrylate, vinyl acetate, vinyl butyral, urethane, thiourethane, bis (allyl carbonate) diethylene glycol, diethylene glycol dimethacrylate, diisopropenyl benzene, and ethoxylated trimethylolpropane triacrylate. The most frequent polymeric material comprises liquid crystal materials, self-assembling materials, polycarbonate, polyamide, polyimide, poly (meth) acrylate, polycyclic alkene, polyurethane, poly (urea) urethane, polythiurethane, polythio (urea) urethane, polyol (allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, poly (alkylene / vinyl acetate), poly (vinyl acetate), poly (alcohol vinyl), poly (vinyl chloride), poly (formal vinyl), poly (acetal vinyl), poly (vinylidene chloride), poly (ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and / or mixtures of the same.
[0143] Furthermore, according to various non-limiting embodiments described here, the host organic material can form an optical element or portion thereof. Non-limiting examples of optical elements include ophthalmic elements, display elements, windows, and mirrors. When used herein, the term "optical" means belonging to or associated with the eye and / or vision. For example, although not limiting here, according to various non-limiting embodiments, the optical element or device can be chosen from ophthalmic devices and elements, display devices and elements, windows, mirrors, packaging materials such as transparent plastic film for packaging food, and passive and active liquid crystal cell devices and elements.
[0144] As used here, the term "ophthalmic" means belonging to or associated with the eye and vision. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including monofocal and multifocal lenses, which can be segmented or non-segmented multifocal lenses (such as, but not limited to bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or improve (cosmetically or differently) vision, including without limitation, contact lenses, intraocular lenses, magnifiers, and protective visors or lenses. When used here, the term "display" means the machine-readable or visible representation of information in words, numbers, symbols, drawings or figures. Non-limiting examples of display elements include screens, monitors, and security elements, such as security tags. As used herein, the term "window" means an opening adapted to allow the transmission of radiation through it. Non-limiting examples of windows include automotive and aircraft windshields, automotive and aircraft transparencies, filters, shutters, and optical switches. As used here, the term "mirror" means a surface that speculatively reflects a large fraction of incident light.
[0145] For example, the organic host material can be an ophthalmic element, and more particularly, an ophthalmic lens.
[0146] Furthermore, it is considered that the photochromic compounds of the present invention can be used alone or in conjunction with at least one other complementary organic photochromic compound having at least a maximum absorption activated within the range of 300 nm to 1000 nm, including ( or substances containing the same). For example, the photochromic compound described herein can be combined with at least one other conventional organic photochromic compound such that the combination of photochromic compounds, when activated, exhibits a desired color. Non-limiting examples of conventional organic photochromic compounds include the pyranes, oxazins, fulgides and fulgimides described below.
[0147] Non-limiting examples of thermally reversible photochromic pyranes include benzopyranes, naphthopyranes, for example, naphtha [1,2-b] pyranes, fused indene naphthopyranes, such as those described in US patent 5,645,767, and fused heterocyclic naphthopyranes, such as those described in patent Nos .: US 5,723,072; US 5,698,141; US 6,153,126; and US 6,022,497, which are incorporated herein by reference for the description of said naphthopyranes, spiro-9-fluorene [1,2-b] pyranes; phenanthropirans; quinopiranos; fluorantenopyranes; spiropyranes, for example, spiro [benzindoline) naphthopyranes, spiro (indoline) benzopyranes, spiro (indoline) naphthyranes, spiro (indoline) quinopyranes and spiro (indoline) pirans. More specific examples of naphthopyranes and complementary organic photochromic substances are described in US patent 5,658,501, the description of which are specifically incorporated herein by reference. Spiro (indoline) pyranes are also described in the text, "Techniques in Chemistry", Volume HI, "Photochromism", Captiluos 3, Glenn, H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971, a description of which is incorporated herein by reference.
[0148] Non-limiting examples of thermally reversible complementary photochromic oxazins include benzoxazins, naphthoxazins, and spirooxazins, for example, spiro (indoline) naphthoxazins, spiro (indoline) pyridobenzoxazines, spiro (benzindoline) pyridobenzoxazins, spiro (benzindoline) on spiro (benzindoline) (indoline) benzoxazines, spiro (indoline) fluoranthenoxazine, and spiro (indoline) quinoxazine.
[0149] Non-limiting examples of thermally reversible complementary photochromic fulgides include, fulgimides, and 3-furyl and 3-thienyl fulgides and fulgimides, which are described in US patent 4,931,220 (where the description of said fulgimides is specifically incorporated herein by reference) and mixtures of any of the aforementioned photochromic materials / compounds.
[0150] For example, it is contemplated that the photochromic compounds described here can be used alone or in conjunction with another conventional organic photochromic compound (as described above), in quantities or proportions such that the organic host material within which the photochromic compound is incorporated, or on which the organic host materials are applied, can present a desired color or colors, both in an activated state and in a "bleached" state. Thus, the amount of photochromic compounds used is not provided critically when sufficient quantity is present to produce a desired photochromic effect. As used here, the term "photochromic amount" refers to the amount of the photochromic compound needed to produce the desired photochromic effect.
[0151] The present invention also provides a photochromic article including a substrate, and at least partial coating of a coating composition having a photochromic amount of a photochromic compound of the present invention connected to at least a portion of at least one surface of the same to the substrate. Furthermore, although not limiting, at least a portion of the partial coating can be at least partially adjusted. As used herein, the term "adjusted" means fixing in a desired orientation, and includes curing the coating.
[0152] For example, according to the aforementioned non-limiting embodiment, the coating composition can be chosen, without limitation, from polymeric coating compositions, paints, and dyes. In addition, in addition, the photochromic compounds described herein, the coating compositions according to various non-limiting embodiments may further include at least other conventional organic photochromic compounds having at least a maximum activated absorption within the range of 300 nm to 1000 nm, including . The primer coating may, with some embodiments, include a polyurethane.
[0153] Non-limiting examples of suitable substrates to which the coating composition that includes a photochromic amount of the photochromic compounds can be applied include organic materials, inorganic materials, and combinations thereof. More particular examples of substrate materials include, but are not limited to, glass, joinery, textiles, ceramics, metals, wood, paper and polymeric organic materials. Non-limiting examples of suitable polymeric materials are shown above.
[0154] In addition, according to the present invention, optical elements are provided which include a substrate and at least a partial coating including at least one photochromic compound of the present invention connected to at least a portion of the substrate. Non-limiting examples of optical elements include, ophthalmic elements, display elements, windows, and mirrors. For example, the optical element can be an ophthalmic element, and the substrate can be an ophthalmic substrate chosen from corrective and non-corrective lenses, partially formed lenses, and white lens.
[0155] Although not limiting here, optical elements can comprise any amount of the photochromic compound necessary to achieve the desired optical properties, such as, but not limited to, photochromic and dichroic properties.
[0156] Other non-limiting examples of substrates that are suitable for use in conjunction with the aforementioned non-limiting embodiment include non-colored (non-colored) substrates, colored substrates, photochromic substrates, colored photochromic substrates, linearly polarizing substrates, circulating polarizing substrates, elliptically polarizing substrates, reflecting substrates, and retarding substrates and wave plates, for example, quarter wave plate or half wave plate. As used herein with reference to substrates, the term "uncolored" means substrates that are essentially free from additions of coloring agent (such as, but not limited to conventional dyes) and have an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation. In addition, with reference to substrates the term "colored" means substrates that have a coloring agent added (such as, but not limited to conventional dyes) and an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation .
[0157] As used herein, the term "linearly polarizing" with reference to substrates refers to substrates that are adapted to polarize radiation linearly (that is, they confine the vibrations of the electric light wave vector in one direction). As used herein, the term "circularly polarizing" with reference to substrates refers to substrates that are adapted to circularly polarize radiation. As used herein, the term "elliptically polarizers" with reference to substrates refers to substrates that are adapted to polarize elliptically radiation. As used herein with the term "photochromic" with reference to substrates it refers to substrates having an absorption spectrum for visible radiation that varies in response to actinic radiation and is thermally reversible. Furthermore, as used with reference to substrates the term "colored photochromic" means substrates containing addition of coloring agent as well as a photochromic compound, and having a visible radiation absorption spectrum that varies in response to actinic radiation and is thermally reversible. Thus, for example, the colored photochromic substrate may have a first color characteristic of the coloring agent and a second color characteristic of the combination of coloring agent and the photochromic compound when exposed to actinic radiation.
[0158] The present invention is also directed to an optical element comprising a substrate and an at least partial coating comprising at least one photochromic compound of the present invention connected to at least a portion of the substrate. In addition, at least one thermally reversible photochromic compound may be a photochromic-dichroic compound having an average absorption ratio greater than 1.5 in an activated state as determined according to the CELL METHOD.
[0159] As discussed above, the optical elements according to the present invention can be display elements, such as, but not limited to screens, monitors, and security elements. For example, the optical element can be a display element comprising a first substrate having a first surface, a second substrate having a second surface, the second surface of the second substrate being opposite and is spaced apart from the first surface of the first substrate so to define a gap; and a fluid material comprising at least one photochromic compound of the present description positioned within the span defined by the first surface of the first substrate and the second surface of the second substrate. In addition, at least one photochromic compound can be a photochromic-dichroic compound having an average absorption ratio greater than 1.5 in an activated state as determined according to the CELL METHOD.
[0160] Additionally, according to this non-limiting embodiment, the first and second substrates can be chosen independently from non-colored substrates, colored substrates, photochromic substrates, photochromic colored substrates, linearly polarizing substrates, circularly polarizing substrates, elliptically polarizing substrates, and reflecting substrates and retarding substrates.
[0161] The present invention also provides a security element including a substrate and at least one photochromic compound of the present description connected to at least a portion of the substrate. Non-limiting examples of security elements include security marks and authentication marks that are connected to a portion of a substrate, such as and without limitation: passes and access cards, for example, tickets, badges, identification or membership cards , debit cards, etc .; negotiable instruments and non-negotiable instruments, for example, money orders, checks, policies, money bills, certificates of deposit, etc .; government documents, for example, money, licenses, identification cards, benefit cards, visas, passports, official certificates, shares, etc .; consumer products, for example, software, compact discs ("CDs"), digital video discs ("DVDs"), furniture, consumer electronics, sports products, cars, etc .; credit cards; and labels, tags and packaging of goods.
[0162] Although not limiting here, the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, where a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, one can first apply a reflective material to at least a portion of the substrate before applying the safety mark on it . For example, an aluminum reflective coating can be applied to at least a portion of the substrate before the security element is formed thereon. In addition, the security element can be connected to at least a portion of a substrate chosen from non-colored substrates, colored substrates, photochromic substrates, colored photochromic substrates, linearly polarizing substrates, circularly polarizing substrates, and elliptically polarizing substrates.
[0163] In addition, at least one photochromic compound can be a thermally reversible photochromic-dichroic compound having an average absorption ratio greater than 1.5 in the activated state as determined according to the CELL METHOD.
[0164] In addition, the aforementioned security element may further comprise one or more other coatings or sheets to form a multi-layer reflective security element with angle-dependent characteristics as described in US patent No. 6,641,874, whose description relating to multi-reflective films here is specifically incorporated by reference.
[0165] The photochromic articles and optical elements described above can be formed according to the methods and procedures known in the art. While not limiting here, it is envisaged that the photochromic compounds of the present invention can bind to a substrate or host by incorporation into the host material or by application on the host or substrate, such as in the form of a coating.
[0166] For example, the photochromic-dichroic compound can be incorporated into an organic host material by dissolving or dispersing the photochromic compound in the host material, for example, melted in place by adding the photochromic compound in the monomeric host material prior to polymerization, to absorption of the photochromic compound in the host material by immersion of the host material in a hot solution of the photochromic compound or by thermal transfer. As used herein, the term "absorption" includes permeation of the photochromic compound alone in the host material, solvent assisted transfer of the photochromic compound in a porous polymer, vapor phase transfer, and other transfer methods. The photochromic material can be mixed with at least a portion of the polymeric material, attached to at least a portion of the polymeric material, and / or absorbed in at least a portion of the polymeric material, with some embodiments of the present invention.
[0167] In addition, the photochromic compound of the present invention can be applied to the organic host material or on another substrate as part of a coating composition (as discussed above) or a sheet comprising the photochromic compound. As used herein, the term "coating" means a supported film derived from a flowable composition, which may or may not have a uniform thickness. As used herein, the term "sheet" means a preformed film having generally uniform thickness and capable of self-supporting. In such cases, ultraviolet light absorbers may be mixed with the photochromic materials prior to their addition to the coating or sheet, or such absorbers may be superimposed, for example, super imposed, as a coating or film between the photochromic article and the incident light. .
[0168] Non-limiting methods for applying coating compositions including the photochromic compounds of the present invention include those methods known in the art for applying coatings, such as, rotating coating, spray coating, rotating and spray coating, curtain coating, flux, dip coating, injection molding, casting, lamination, wire coating, and overmoulding. The coating including the photochromic compound can be applied to a mold and the substrate can be formed on top of the coating (i.e., overmoulding). In addition or alternatively, a coating composition without the photochromic compound can first be applied to the substrate or host organic material using any of the aforementioned techniques and then embedded with the photochromic compound as described above.
[0169] Non-limiting examples of film-forming polymer coating compositions that may include photochromic materials of the present invention are as follows: dichroic / photochromic liquid crystal coatings, such as those described in US Patent No. 7,256,921, in column 2, line 60 through column 94, line 23; photochromic polyurethane coatings, such as those described in U.S. Patent No. 6,187,444 from column 3, row 4 to column 12, row 15; photochromic amine plastic resin coatings, such as those described in US patent No. 6,432,544 in column 2, line 52 through column 14, line 5 and in US patent No. 6,506,488 in column 2, line 43 through column 12, line 23; photochromic polysiloxane coatings, such as those described in U.S. Patent No. 4,556,605 in column 2, line 15 through column 7, line 27; photochromic poly (meth) acrylates coating, such as those described in US patent No. 6,602,603 in column 3, line 15 through column 7, line 50, in US patent No. 6,150,430 in column 8, lines 15- 38, and in US patent No. 6,025,026 in column 8, line 66 to column 10, line 32; photochromic polyanhydride coatings, such as those described in U.S. Patent No. 6,436,525 in column 2, line 52 through column 11, line 60; photochromic polyacrylamide coatings, such as those described in U.S. Patent No. 6,060,001 in column 2, row 6 to column 5, row 40; photochromic coatings of epoxy resins, such as those described in U.S. Patent No. 6,268,055 in column 2, line 63 to column 15, line 12; and photochromic poly (urea / urethane) coatings, such as those disclosed in US patent No. 6,531,076 in column 2, line 60 through column 10, line 49. The descriptions in the above-mentioned US patents that refer to polymer forming films are hereby incorporated by reference.
[0170] Non-limiting methods of applying slides including the photochromic compounds of the present invention to a substrate include, for example, at least one of: laminar, melt, die cast, and adhesive bond the polymeric sheet to at least a portion of the substrate. As used herein, mold casting includes a variety of casting techniques, such as, but not limited to: overmoulding, where the blade is placed in a mold and the substrate is formed (for example, by casting) on at least one substrate portion; and injection molding, in which the substrate forms around the blade. In addition, it is considered that the photochromic compound can be applied to the sheet as a coating, incorporated into the sheet by absorption or by any appropriate methods, either before or after applying the sheet to the substrate.
[0171] The polymeric sheet may include a polymeric composition of any of a wide variety of polymers, including both thermoset polymers and thermoplastic polymers. As used herein, the term "polymer" is intended to include both polymers and oligomers, as well as both, homopolymers and copolymers. Such polymers can include, for example, acrylic polymers, polyester polymers, polyurethane polymers, poly (urea) urethane polymers, polyamine polymers, polyepoxide polymers, polyamide polymer, polyether polymers, polysiloxane polymers, polysulfide polymers , copolymers thereof, and mixtures thereof. Generally, these polymers can be any polymers of these types prepared by any method known to those skilled in the art.
[0172] The polymers used to form the polymeric lamina may also include functional groups including, but not limited to, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups isocyanate (including blocked isocyanate groups), mercaptan groups, groups having ethylenic unsaturation (for example, acrylate groups), vinyl groups, and combinations thereof. Suitable mixtures of film-forming resins can also be used in the preparation of coating compositions. If the polymeric composition from which the polymeric sheet is formed comprises polymers containing functional groups (such as any of the polymers containing functional groups mentioned above), the polymeric composition may further comprise a material having functional groups reactive with those of said polymer. The reaction can be facilitated, for example, by thermal, photoinitiated, oxidative curing techniques and / or radioactive curing techniques. Mixtures of any of the foregoing polymers are also considered.
[0173] Additional non-limiting examples of polymers suitable for use in forming the polymer sheet of the present invention include the copolymers in thermoplastic blocks of poly ((meth) alkyl acrylate) and polyamide described in US patent publication 2004/0068071 in paragraphs [ 0020] - [0042], the specific portions of which are incorporated by reference; and in U.S. Patent No. 6,096,375 from column 18, line 8 to column 19, line 5, the specific portions of which are incorporated herein by reference.
[0174] In a particular embodiment of the present invention, the polymer sheet can comprise an elastomeric polymer, for example, thermoplastic elastomeric polymers. As used herein, "elastomeric polymer" means a polymer that has a high degree of resilience and elasticity such that it is capable of at least partially reversible elongation or deformation. In some cases, when stretched, the molecules of an elastomer align and can assume aspects of a crystalline arrangement; and in response to liberation, they may, to some extent, return to their natural disordered state. For the purposes of the present invention, elastomeric polymers can include thermoplastic elastomeric polymers and thermoset polymers as long as such polymers fall within the description provided above for "elastomeric polymer".
[0175] The elastomeric polymer can comprise any of a wide variety of elastomers recognized in the art including, but not limited to, copolymers of any of the aforementioned polymers. In one embodiment of the present invention, the elastomeric polymer can comprise a block copolymer having ether and / or ester bonds on the polymeric backbone. Examples of suitable block copolymers may include, but are not limited to, poly (amide-ether) block copolymers, poly (ester-ether) block copolymers, poly (ether-urethane) block copolymers, block copolymers poly (ester-urethane), and / or copolymers in poly (ether-urea) blocks. Suitable specific examples of such elastomeric polymers may include, but are not limited to, those commercially obtainable under the trade names DESMOPAN® and TEXIN® from Bayer Material Science; ARNITEL® by Royal DSM; and PEBAX® from Atofina Chemicals or Cordis Corporation.
[0176] Furthermore, as discussed above, the photochromic compounds of the present invention can be incorporated or applied alone, or in combination with at least one other conventional photochromic organic compound, which can also be applied or incorporated to the described substrates and host materials above. Additional coatings can be applied to the photochromic article including other photochromic coatings, anti-reflective coatings, linearly polarizing coatings, transition coatings, primer coatings, adhesive coatings, mirror coatings and protective coatings including anti-fog coatings, oxygen barrier coatings and oxygen-absorbing coatings UV light. With some embodiments, the transitional coating can include an acrylate polymer and / or a methacrylate polymer. With additional embodiments, the protective coating can include at least one organosilane.
[0177] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations in them will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight. EXAMPLES
[0178] Part 1 describes the preparation of Examples 1-56. Part 2 describes testing the photochromic properties of the Examples. Part 3 describes testing the dichroic properties of the Examples. The term "reaction flask" is defined here to include any suitable reaction flask such as a 3 or 4 neck flask of an appropriate size that has been pre-treated such as oven drying and has been equipped with the necessary capacities such as a reflux condenser, mechanical or magnetic stirrer, thermometer, solids addition funnel, drip funnel or other equipment to conduct the procedure described as known to a person skilled in the art.
[0179] In the examples below, the following abbreviations have a determined meaning. If the abbreviations are not defined, it has a generally acceptable meaning. BINAP = 2,2'-bis (diphenylphosphino) -1,1'-binafty Bi (OTf) 3 = bismuth triflate Cul = copper iodide DHP = 3,4-dihydro-2H-pyran DCC = dicyclohexylcarbodiimide DCM = dichloromethane DBSA = dodecylbenzenesulfonic acid DIBAL = diisobutyl aluminum hydride DMAP = 4-dimethylaminopyridine DME = dimethyl ether DMF = N, N-dimethylformamide DMSO = dimethyl sulfoxide Dppf = 1,1'-bis (diphenylphosphino) ferrocene EtMgBr = bromine ethoxyl g = gram h = hour HPLC = high performance liquid chromatography (iPr) 2NH = diisopropyl amine HOAc = acetic acid LDA = diisopropylamide lithium KMnO4 = potassium permanganate M = molar (molarity) mCPBA = meta-chlorophenoxy benzoic acid MeLi = methyl lithium mg = milligram min = minutes mL = milliliters mmol = millimol mM = millimolar NatOBu = sodium tert-butoxide N = normal (normality) ng = nanogram nm = nanometer nM = nanomolar NMP = N-methyl pyrrolidone NMR = nuclear magnetic resonance Pd ( OAc) 2 = Pd2 palladium acetate (dba) 3 = tris (dibenzyldenoacetone) dipaladium (0) PPh3 = phosphine triphenyl PPTS = pyridine p-toluenesulfonate pTSA = p-toluenesulfonic acid PdCls (PPhβ) 2 = bis (triphenylphosphine) palladium (II)) PBS = phosphate buffered fluoride tetra-n-butylammonium THE = tetrahydrofuran TLC = thin layer chromatography t-BuOH = t-butanol (Tf) 2O = trifluoromethanesulfonic acid anhydride | 1L = microliter | 1M = micromolar Zn (OAc) 2 = zinc acetate ZN ( CN) 2 = zinc cyanide Part 1 - Preparation of Examples 1-56
Step 1:
[0180] 7-ethyl-2,3-dimethoxy-7H-benzo [c] fluoro-5,7-diol (20.0) and methanol (0.4 LO were added in a reaction flask. Trimethylortoformate (32, 6 mL) and pyridinium p-toluene sulfonate (3.0 gl) were added and the mixture was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and a precipitate formed. The precipitate was collected by vacuum filtration. , washed with a minimal amount of cold methanol and dried under vacuum to provide the product (20.0 g). NMR showed that the product had a consistent structure with 7-ethyl-2,3,7-trimethoxy-7H-benzo [c] fluoren-5-ol. Step 2:
[0181] Methyl magnesium bromide (102.0 mL, 1.4M in 75:25 toluene: THF) was added to a reaction flask under nitrogen. Cis-2,6-dimethylpiperidine (11.8 ml) was added dropwise at room temperature with vigorous stirring. The reaction mixture was diluted with tetrahydrofuran (51.0 ml) to make the ratio of solvent 1: 1 to toluene. The product (10.0 g) from step 1 was added in several portions to the reaction mixture. The solution was heated to reflux for 5 hours. The reaction mixture was cooled to room temperature and carefully poured into 10 weight percent aqueous HCl solution (200 mL) at 0 ° C. The mixture was stirred for 15 minutes, diluted with ethyl acetate (100 ml) and partitioned. The organic layer was washed with saturated aqueous sodium bicarbonate (200 ml), dried with sodium sulfate and concentrated in vacuo to provide an oily residue. Dichloromethane (500 ml) was added to the residue and stirred to provide a precipitate. The precipitate was collected by vacuum filtration and dried (8.6 g). NMR demonstrated that the product had a structure consistent with 7-ethyl-3,7-dimethoxy-7H-benzo [c] fluorine-2,5-diol. This procedure was repeated to produce enough product for the next step as well as other examples. Step 3:
[0182] In a reaction flask containing a solution of chloroform (600 ml) of the product from step 2, (77.7 g) and p-toluene sulfonic acid (8.8 g), 1- (4-fluorophenyl) was added - 1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol (35.7 g). The solution was heated to reflux for 4 hours. An additional amount of 1- (4-fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol (35.7 g) was added after 4 hours and the mixture was heated to reflux for an additional 4 hours. The reaction mixture was passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with CHCl3. The fractions containing the desired material were grouped and concentrated to provide an oily residue (101.3 g) that was used directly in the next step. NMR showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7-hydroxy-3, 13-dihydro-indendo [2r, 3r: 3: 4 / naphtho [1,2-b] pyran. Step 4:
[0183] In a reaction flask containing a stirred mixture of THE (500 ml), 4'-hydroxy- (1,1'-biphenyl) -4-carboxylic acid (50 g) and dihydropyran (21.6 g), p-toluene sulfonic acid (1 g) was added. After stirring overnight, a precipitate formed and was collected by filtration, washed with diisopropyl ether (200 ml) and dried in vacuo. A white powder (59 g) was obtained as the product. NMR showed that the product had a structure consistent with 4'- ((tetrahydro-2H-pyran-2-yl) oxy) - (1,1'-biphenyl) -4-carboxylic acid. Step 5:
[0184] To a reaction flask containing a dichloromethane solution (500 mL) of the product obtained from step 3 (50.8 g), and the product from step 4 (24.1 g) were added N, N'-dicyclohexylcarbodiimide (18.3 g) DMAP (0.5 g) at room temperature. The resulting mixture was stirred for 8 hours, diluted with dichloromethane (200 ml) and filtered. The filtrate was concentrated in vacuo to provide an oily residue that was used directly in the next step. NMR showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- [iperidine-1-yl] phenyl-13-methoxy-13-ethyl-6-methoxy-7- (4- ( (tetrahydro-2H-pyran-2-yl] oxy) - [1,1'-biphenyl] -4-carbonyloxy) -3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1, 2-b] pyran. Step 6:
[0185] The product from step 5 was added in a reaction flask and dissolved in a mixture of 1,2-dichloroethane (400 ml) and ethanol (200 ml), p-toluene sulfonic acid (7.0 g) was added and the mixture was heated to reflux for 12 hours. The solvent was removed in vacuo to provide an oily residue. The residue was purified by passing it through a silica gel coating. The fractions containing the desired material were grouped and concentrated. The material was used directly for the next step. Step 7:
[0186] In a reaction flask containing a solution of dichloromethane (300 mL) of the product obtained from step 6 (21.7 g) and 4- (4-pentylcyclohexyl) benzoic acid (8.0 g) were added N, N '-dicyclohexylcarbodiimide (6.4 g) and DMAP (1.0 g) at room temperature. The resulting mixture was stirred for 12 hours, diluted with dichloromethane (200 ml), and filtered. The filtrate was concentrated in vacuo to provide an oily residue. The residue was purified by passing it through a silica gel coating and eluting with a mixture of hexane and dichloromethane with a gradient ratio of 9/1 to 1/9. The fractions containing the desired material were grouped and concentrated to provide a blue oil. The product was further purified by dissolving in dichloromethane followed by precipitation of methanol. A blue solid (22.7 g) was obtained. NMR showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- (piperidine-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4 ' - ([4- (trans-4-pentylcyclohexyl) benzoyl] oxy) - [1,1'-biphenyl) -4-carbonyloxy) -3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1, 2-b] pyran. Example 2
Step 1:
[0187] A suspension of l-bromo-4- (trans-4-pentylcyclohexyl) benzene (96 g), 4- (methoxycarbonyl) phenyl) boronic acid (56 g), K2CO3 (17 g), Pd (Pph3) 4 (1.5 g), 1,4-dioxane (400 ml), and water (12 ml) were placed in a reaction flask and stirred at 105 ° C for 10 hours. The resulting mixture was poured into water (1 L) with stirring. The solution was filtered and a gray solid was recovered, washed with water, dissolved in CH2 Cl2 (400 ml), dried over MgSO4 and filtered through an auxiliary CELITE® filter. The filtrate was concentrated and poured into methanol (600 ml) with stirring. The precipitate was collected by filtration, washed with methanol and dried. A white solid was obtained (80.4 g) as the product. NMR demonstrated that the product had a structure consistent with meti1-4- (4-pentylcyclohexyl) biphenyl-4-carboxylate. Step 2:
[0188] The product obtained from step 1 (20 g) was mixed with sodium hydroxide (6.57 g) and ethanol (500 ml) in a reaction flask. The mixture was heated to reflux for 4 hours, cooled to room temperature and acidified using concentrated HCl. The precipitate that was formed was collected by filtration, washed with water and dried. A white solid was obtained (18.2 g) as the product. NMR showed that the product had a structure consistent with 4 '- (4-pentylcyclohexyl) biphenyl-4-carboxylic acid. Step 3:
[0189] The procedure from steps 1 to 7 of Example 1 were followed except that in step 4, 4-hydroxybenzoic acid and methylene chloride were used in place of 4'-hdiroxi- (1,1'-biphenyl) -4 acid -carboxylic acid and THE and in step 7, 4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxylic acid obtained from step 2 (above) was used in place of 4- ( 4-pentylcyclohexyl) benzoic. A blue solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- [ipridin-1-yl] phenyl) -13-methoxy-13-ethyl-6-methoxy-7- [4- (4 '- (4- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy) benzoyloxy)) - 3,13-dihydro-indene [2', 3 ': 3, 4] naphtho [1,2-b] pyran. Example 3

[0190] The procedures from steps 1 to 7 of Example 1 were followed except that in step 3, 1,1-bis (4-methoxyphenyl0prop-2-in-1-ol was used in place of 1— (4— fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol. A gray solid was obtained as the product. NMR showed that the product had a structure consistent with 3,3-bis ( 4- methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4 '- ((4- (trans-4-pentylcyclohexyl) benzoyl) oxy) - [1,1'-biphenyl] -4- carbonyloxy) - 3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 4

[0191] The procedures of steps 1 to 3 of Example2 were followed except that in Step 3, based on procedures 1 to 7 of Example 1, 1,1-bis (4-methoxyphenyl) prop-2-in-l -ol was used in place of 1- (4-fluorophenyl) -1-94-piperidin-1-yl-phenyl) -prop-2-in-1-ol which was used in step 3 of Example 1. A gray solid was obtained as the product. NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4- (4'- (4 - (trans-4- pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy) benzoyloxy)) - 3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 5

[0192] The procedures in steps 1, 2, 3 and 5 of Example 1 were followed except that in step 5, 4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxylic acid was used in place of 4 '- ((tetrahydro-2H-pyran-2-yl) oxy) - [1,1'-biphenyl] -4-carboxylic. A blue solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4-fluorophenylO-3- (4- (piperidine-1-ylOphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4 '- (4 -trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy)) - 3,13-dihydro-indene [2 ', 3': 3,4] naphtho ['1, 2-b] pyran, Example 6

[0193] The procedures in steps 1, 2, 4 and 5 of Example 1 were followed except that in step 3, ol, l-bis (4-methoxyphenyl) prop-2-in-l-ol was used in place of 2 - (4-fluorophenyl) -1- (4-piperidini-1-yl-phenyl) -prop-2-in-1-ol and in step 5, (trans, trans) -4'-pentyl- [1 , 1'-bi (cyclohexane)) - 4-carboxylic acid was used in place of 4 '- (((tetrahydro-2H-pyran-2-yl-) oxy) - [1,1'-biphenyl) -4-carboxylic acid . A gray solid was obtained as the product. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- ((trans, trans) -4'-pentyl- [1, 1'-bi (cyclohexane)) - 4-carbonyloxy) -3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2- b] pyran. Example 7

[0194] The procedures from steps 1 to 7 of Example 1 were followed except that in Step 3, ol, l-bis (4-fluorophenyl) prop-2-in-l-ol was used in place of l- (4- fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol and in step 7, 4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] acid -4-carboxylic acid was used in place of 4- (4-pentylcyclohexylbenzoic acid. A yellow solid was obtained as the product. NMR demonstrated that the product had a structure consistent with 3,3-bis94-fluorophenyl) -13-methoxy-13 -ethyl-6- methoxy-7- [4 '- (4'-9trans-4-pentylcyclohexyl) - [' 1, I'-biphenyl] - 4-carbonyloxy) - [1,1'-biphenyl] -4- carbonyloxy) -3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 8

[0195] The procedures from steps 1 to 7 of Example 1 were followed except that in step 3, 1- [4-methoxyphenyl) -1- (4-piperidin-1-yl] phenyl) prop-2-in-1 -ol was used in place of 1- (4-fluorophenyl) -1- (4-piperidini-1-yl-phenyl) -prop-2-in-1-ol and in step 7, 4 '- (4 -pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxylic acid was used in place of 4— (4-pentylcyclohexyl) benzoic acid. A blue solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3- (4- [iperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4 ' - (4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy) - [1, 1' - biphenyl] 4-carbonyloxy) -3,13-dihydro-indene [2 ' , 3 ': 3,4] naphtho [1,2-b] pyran. Example 9

[0196] The procedures from steps 1 to 7 of Example 1 were followed except that in Step 3, 1- (4-methoxyphenyl) -1- [4-morpholinophenyl] prop-2-in-l-ol was used instead 1- [4-fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol and in step 7, 4 '- (4-pentylcyclohexyl) - [1 , 1'-biphenyl] 4-carboxylic acid was used in place of 4- (4-methylcyclohexyl) benzoic acid. A blue solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4-methoxyphenyl0-3- (4-morpholinophenyl) -13-methoxy-13-ethyl-6-methoxy-7- (4 '- (4' - (trans- 4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carbonyloxy) - [1,1'-biphenyl] -4-carbonyloxy) - 3,13-dihydro-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran Example 10

[0197] The procedures from steps 1 to 7 of Example 1 were followed except that in Step 3, 1— [4— (4— (4 - methoxyphenyl) piperazin-1-yl) phenyl) -l-phenylprop-2-in -l-ol was used in place of 1- (4-fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol and in step 7, 4- ( 3-hydroxyethoxy) benzoic was used in place of 4- (4-pentylcyclohexyl) benzoic acid. A blue solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4- (4-methoxyphenyl) piperazin-1-yl) -3-phenyl-13-methoxy-13-ethyl-6-methoxy-7- (4 '- ( 4- (2-hydroxyethoxy) benzoyloxy) - [1,1'-biphenyl] -4-carbonyloxy) - [1,1'-biphenyl [-4-carbonyloxy) -3,13-dihydro-indene [2 ', 3 ': 3.4] naphtho [1,2-b] pyran. Example 11

[0198] The procedures in steps 1, 2, 3 and 5 of Example 1 were followed except that in step 3, ol, l-bis (4-methoxyphenyl) prop-2-in-l-ol was used in place of l - (4-fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol and in Step 5, 3-phenylpropiolic acid was used in place of 4 '- ( (tetrahydro-2H-pyran-2-yl) oxy) - [1,1'-biphenyl] -4-carboxylic. A gray solid was obtained as the product. NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (3-phenylpropioloyloxy) -3,13-dihydro-indene [ 2 ', 3': 3,4] naphtho [1,2- b] pyran. Example 12
Step 1:
[0199] The procedures in steps 1 to 3 of Example 1 were followed except that in step 3, ol, l-bis (4-methoxyphenyl) prop-2-in-l-ol was used in place of l- (4- fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol. The NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7-hydroxy-3,13-dihydro-indendo [2 ', 3 ': 3,4] naphtho [1,2-b] pyran. Step 2;
[0200] In a reaction flask containing a dichloromethane solution (40 mL) of the product from step 1 (6.1 g), triethylamine (3 mL) was added. The resulting mixture was stirred for 5 minutes. Trifluoromethanesulfonic anhydride (2.1 ml) was added dropwise to the solution and the mixture was stirred for 1 hour at room temperature. The saturated aqueous sodium bicarbonate (200 ml) was added to the reaction mixture and stirred for 10 minutes. Dichloromethane (100 mLO was added, the solution was divided and the dichloromethane layer was collected. The organic extract was dried over sodium sulfate and concentrated in vacuo to provide an oily residue. The residue was purified by passing it through a coating silica gel and elution with a mixture of hexane: ethyl acetate (9: 1 based on volume). The fractions containing the desired material were pooled and concentrated to provide the product as a colored oil (7.1 g). NMR showed that the product had a structure consistent with 3, 3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3,13-dihydro-indene [2 ', 3': 3 , 4] naphtho [1,2-b] pyran. Step 2:
[0201] In a reaction flask containing Et3N (1.5 L), 4-bromo-3-methylaniline (144 g), 4, 4, 4 ', 4', 5.5.5 ', 5'- were added octamethyl-2,2'-bi (1,3,2-dioxaborolane) (206 g) and CH2COOK (302.3 g). The nitrogen was passed through the reaction mixture for ~ 20 minutes and PdC12 (PPha) 2 (27 g) was added. The resulting reaction mixture was heated to reflux with stirring. After ~ 4 hours of reflux, water (1 L) was added. The organic layer was extracted using EtOAc 91 L). The recovered organic phase was evaporated to dry. The remaining reaction mixture was added to a reaction flask containing 0.5 L of a mixture of hexanes: CH2 Cl2 (1: 1 based on volume) and passed through the bed of silica gel followed by a mixture of EtOAC: hexanes ( 1: 3 based on volume) used as an eluting solvent. All organic fractions were collected together and the solvents were evaporated. The recovered product was isolated as a thick pale yellow liquid (152 g). NMR showed that the product had a structure consistent with 3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline. Step 4:
[0202] Thionyl chloride [107 g (66 mL)] was added to a reaction flask containing the solid product obtained from step 2 of Example 2 the [4 '- (trans-4-pentylcyclohexyl) - [1, 1'-biphenyl] -4-carboxylic (60 g). Toluene (0.75 L0 was added and a few drops of DMF were also added. The resulting mixture was heated to ~ 80 ° C for 3 ½ hours and cooled to room temperature. The solvent was evaporated using a rotary evaporator fitted with a trap of solid NaOH. The recovered solid was washed with cold hexanes, isolated and dried in vacuo to yield the product (55 g). NMR showed that the product had a structure consistent with 4 '- (4-pentylcyclohexyl) chloride - [1 , 1'-biphenyl] -4-carbonyl. Step 5:
[0203] In a reaction flask containing 0.25 L of CH2Cl2, 3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline (25 g ). The reaction mixture was stirred under an atmosphere of N2 and EtβN [30.36 g (42 mL)] was added. The product from step 4 (40 g) was added to the reaction flask containing CH2 Cl2 (0.5 L) and the resulting solution was added dropwise to the stirred reaction mixture. After ~ 1 hour of stirring the solvent was evaporated and the recovered solid was washed with water and then acetone. The product was isolated and dried under vacuum (57 g). NMR showed that the product had a structure consistent with N- (3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4 - pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxamide.
Step 6:
[0204] In a reaction flask containing tetrahydrofuran (100 mL), the product from step 2 (97.1 g) and the product from step 5 (8.3 g) were added. An aqueous solution of potassium fluoride (6.0 g) in water (100 mL) was added to the reaction flask and the reaction mixture was degassed by bubbling with nitrogen for 15 minutes. Dichlorobis (triphenylphosphine) palladium (II) (0.7g) was added and the resulting mixture was heated to reflux for 18 hours, cooled to room temperature, diluted with ethyl acetate (100 ml) and filtered through a bed with auxiliary filter CELTITE®. The filtrate was divided and the organic layer was collected, dried with sodium sulfate and concentrated in vacuo to provide an oily residue. The residue was purified by passing a silica gel coating and eluting with a mixture of hexane and ethyl acetate. The fractions containing the desired material were grouped and concentrated to provide a purple oil. The product was dissolved in dichloromethane followed by precipitation from methanol. A gray solid (6.2 g) was obtained as the product. NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7- (2-methyl-4- (4 '- (trans-4 -pentylcyclohexyl) - [1,1'-biphenyl] -4-ylcarboxamido) phenyl) -3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 13
Step 1:
[0205] In a reaction flask, 2,3-dimethoxy-7-oxo-7H-benzo [c] fluoren-5-yl (20.7 g), trimethyl9trifluoromethyl) silane (42.2 mL) were added, potassium fluoride (0.8 g) and anhydrous tetrahydrofuran (100 mL). Potassium tert-butoxide saturated in tetrahydrofuran was added (10 grams) in portions until the solution started boiling. The reaction mixture was stirred for 1 hour, poured into a 10 weight percent solution of aqueous hydrochloric acid (500 ml) and stirred for 20 minutes. The aqueous solution was extracted with ethyl acetate (200 ml) three times. The extracts were combined, dried over sodium sulfate, filtered and concentrated to provide an oily residue. Dichloromethane (750 ml) was added to the residue to produce a precipitate. The precipitate was collected by vacuum filtration and dried. A yellow solid (13.0 g) was obtained as the product. NMR showed that the product had a structure consistent with 2,3-dimethoxy-7- (trifluoromethyl) - 7H-benzo [c] fluoren-5,7-diol Step 2:
[0206] In a reaction flask containing a chloroform solution (300 mLO of the product obtained from step 1, (10.1 g), 1,1-bis (4-methoxyphenyl) prop-2-in-l-ol was added 911.0 g), triisopropylortoformate (12.0 ml) and p-toluenesulfonate pyridinium (0.7 g). The solution was heated to reflux for 4 hours. The reaction mixture was concentrated under reduced pressure to provide an oily residue. The residue was dissolved in a minimal amount of dichloromethane and precipitated from hexanes. The precipitate was collected by vacuum filtration and dried. The red solid (13.4 g) was obtained as the product. NMR analysis of the red solid indicated that the structure was consistent with 3,3-bis (4-methoxyphenyl) -6,7-dimethoxy-13-hydroxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3 ': 3,4] naphtho [1,2-b] pyran. Step 3:
[0207] In a reaction flask containing a tetrahydrofuran solution of the product obtained from step 2. (3.9 g), iodomethane (2.0 mL) and potassium tert-butoxide (2.1 g) were added. The reaction mixture was heated to reflux for 2 hours. The reaction mixture was poured into an aqueous solution of 10 weight percent hydrochloric acid (200 ml) and stirred for 10 minutes. The aqueous solution was divided three times with ethyl acetate using (100 ml) each time. The combined ethyl acetate extracts were dried over sodium sulfate and concentrated in vacuo to provide an oily residue. The residue was passed through a silica gel coating and eluted with 4: 1 (v: v) hexane: ethyl acetate mixture. The fractions containing the desired material were pooled and concentrated to provide a solid. A white solid (3.5 g) was obtained as the product. NMR analysis of the white solid indicated a structure that was consistent with 3,3-bis- (4-methoxyphenyl0-6,7,13-trimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3.4] naphtho [1,2-b] pyran. Step 4:
[0208] In a reaction flask containing a tetrahydrofuran solution of the product obtained from step 3, (0.7 g) 4- [iperazin-l-yl] phenol (0.6 h) was added. The reaction mixture was cooled to 0 ° C and a 2 molar solution of butyl lithium in hexanes (2.0 ml) was added dropwise. The solution was stirred at 0 ° C for 10 minutes and warmed to room temperature. The reaction mixture was then poured into a 10 weight percent aqueous hydrochloric acid solution and stirred for 10 minutes. The aqueous solution was divided three times with ethyl acetate using (100 ml) each time. The ethyl acetate extracts were combined, dried with sodium sulfate and concentrated in vacuo to provide an oily residue. The residue was passed through a silica gel coating and eluted with a 4: 1 (v: v) mixture of hexane: ethyl acetate. The fractions containing the desired material were grouped and concentrated to provide an oil. A yellow colored oil (1.0 g) was obtained as the product. NMR analysis of the yellow oil indicated a structure that was consistent with 3,3-bis (4-methoxyphenylO-6,13-dimethoxy-7- (4- (4-hydroxyphenyl) piperazin-l-yl) -13-trifluoromethyl -3.13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2— b] pyran. Step 5:
[0209] In a reaction flask containing a solution of dichloromethane (20 mL) of the product obtained from step 4 (1.4 g) and the acid (trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic (0.8 g) N, N'-Dicyclohexylcarbodiimide (0.6 g) and DMA) (22.0 mg) were added at room temperature and stirred for 18 hours. The resulting mixture was diluted with dichloromethane (200 ml) and filtered. The filtrate was concentrated in vacuo to provide an oily residue. The residue was passed through a silica gel coating and eluted with a 4: 1 (v: v) mixture of hexane: ethyl acetate. The fractions containing the desired material were grouped and concentrated to provide a purple oil. The product was further purified by dissolving in dichloromethane followed by precipitation from methanol. A gray solid (0.9 g) was obtained as the product. NMR analysis of the gray solid indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl0-6,13-dimethoxy- 7 - (4 - (4-trans, trans-4'-pentyl- (1,1 '-bi (cyclohexane)] - 4-carbonyloxy) phenylOpiperazin-1-yl) -13-trifluoromethyl-3,13-dihydro-indene [2', 3 ': 3,4] naphtho [1,2-b] pyran Example 14 and Example 15


[0210] The procedures for steps 4 and 5 of Example 3 were followed except that in Step 4, the product from step 2 was used in place of the product from step 3 to produce two photochromics that were isolated using CombiFlash® Rf obtained from Teledyne ISCO. NMR analysis demonstrated that the less polar product had a structure consistent with example 14, 3,3-bis (4-methoxyphenyl0-6-methoxy-7- (4- (4- (trans, trans-4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -13-hydroxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4 ] naphtho [1,2- b] pyran The other was also suggested by NMR as having a structure consistent with example 15, 3,3-bis (4-methoxyphenyl) -6,7-di (4- (4- (trans, trans-4-pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -13-hydroxy-13-trifluoromethyl-3,13-dihydro-indene [ 2 ', 3': 3,4] naphtho [1,2-b] pyran Example 16
Step 1:
[0211] The product from step 2 of Example 13, 3,3-bis (4-methoxyphenyl) -6,7-dimethoxy-13-hydroxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3' : 3.4] naphtho [1,2-b] pyran (2.1 g) was dissolved in dichloromethane (20 mL) in a reaction flask and cooled to 0 ° C. Dimethylamino sulfur trifluoride (0.6 ml) was added dropwise via syringe. The reaction was warmed to room temperature and stirred for 1 hour. The reaction mixture was quenched with saturated aqueous sodium bicarbonate (100 ml) and diluted with dichloromethane. The layers were separated and the aqueous layer was further extracted twice with dichloromethane using (25 ml) each time. The dichloromethane extracts were combined, dried over sodium sulfate, filtered and concentrated in vacuo to provide a residue. The residue was passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with a 4: 1 (v: v) mixture of hexate: ethyl acetate. Fractions containing the desired material were pooled and concentrated to provide a yellow solid (0.8 g). NMR analysis of the yellow solid indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl0-6,7-dimethoxy-13-fluoro-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3' : 3.4] naphtho [1,2-b] pyran. Step 2:
[0212] The procedures from steps 4 and 5 of Example 13 were followed except that in Step 4, the product from step 1 (above) was used in place of the product from step 3 of Example 13. A yellow solid was obtained as the product . NMR analysis of the yellow solid indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- [4- (4- ((trans, trans) -4'-pentyl- (1 , 1'-bi (cyclohexane)] - 4-carbonyloxy) phenylOpiperazin-1-yl) -13-fluoro-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1 , 2- b] pyran Example 17

[0213] Tribromobenzene (500.0 g) and tetrahydrofuran (2.0 L) were added in a reaction flask and the mixture was stirred. The solution was cooled to ~ 10 ° C by immersing the flask in an ice bath and i-propyl magnesium chloride salt. In tetrahydrofuran (800.0 ml) was added dropwise (1 hour) to keep the solution temperature below 0 ° C. The mixture was stirred at this temperature for 40 minutes. Bis [2- [N, N-dimethylamino] -ethyl] -ether (364.0 mL) was added to the reaction mixture at ~ 10 ° C and stirred for 15 minutes. 4-Trifluoromethylbenzoyl chloride (261.0 ml) was added to the reaction mixture at ~ 10 ° C and stirred for 20 minutes. The reaction mixture was warmed to room temperature and stirred for 20 hours. The reaction mixture was poured into 10% aqueous hydrochloric acid (4.0 L) and stirred for 15 minutes. The aqueous solution was divided three times with ethyl acetate (1.0 L) each time. The ethyl acetate extracts were combined and washed three times first with brine (1.0 L), 10% aqueous solid hydroxide (1.0 L) and then brine (1.0 L) again. The recovered ethyl acetate extract was dried over sodium sulfate, filtered and concentrated to provide an oily residue. Methanol (1.0 L) was added to the residue and the flask was scraped to provide colored crystals. The crystals (347.0 g) were collected by vacuum filtration. NMR analysis of the colored crystals indicated a structure that was consistent with (3,5-dibromophenyl) (4-trifluoromethyl) phenyl) methanone. Step 2:
[0214] The product from step 1 (264, 4 g), dimethyl succinate (102.0 mL) and toluene (2 L0 were added in a reaction flask. The mixture was stirred until the solids dissolved at room temperature under protection and solid potassium tert-butoxide (110.0 g) was added followed by toluene (2.0 L) and the mixture was stirred at room temperature for 2 hours water (2.0 L) was carefully added to the stirring followed by concentrated hydrochloric acid (120.0 mL) and the mixture was stirred for 10 minutes.The aqueous solution was then divided three times with ethyl acetate (1.0 L) each time. ethyl acetate was combined, dried over sodium sulfate, filtered and concentrated in vacuo to provide an oily residue.The hexanes (1.0 L) were added to the residue to produce a cream colored precipitate. The precipitate (237.9 g) was collected by vacuum filtration.The NMR analysis of the cream colored solid indicated a consistent structure with m (E) -4- (3,5-dibromophenyl-3- (methoxycarbonyl) -4- (4- (trifluoromethyl) phenyl) but-3-enoic acid. Step 3:
[0215] The product from step 2 (7.8 g) was added to a reaction flask and dissolved in toluene (200 ml). Acetic anhydride (2.1 mLO was added and the mixture was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and the solvent was removed in vacuo to provide an oily residue. The residue was dissolved in methanol ( 200 ml) and concentrated hydrochloric acid (1 ml) was added The methanolic solution was heated to reflux for 6 hours The solution was cooled to room temperature and the solvent was removed under vacuum to provide a dark colored oil. passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with a 4: 1 (v: v) mixture of hexane: methyl acetate.The fractions containing the desired material were pooled and concentrated to provide a yellow oil, the aeol was used directly in the next step. Step 4:
[0216] The oil (5.3 g) from step 3 was added to a reaction flask and dissolved in anhydrous tetrahydrofuran (50 ml) and cooled to 0 ° C. Methylmagnesium chloride (14.1 ml) was added dropwise and the reaction mixture was warmed to room temperature and stirred for 2 hours. The reaction mixture was poured into 10 weight percent aqueous hydrochloric acid (100.0 ml) and stirred for 30 minutes. The aqueous solution was divided three times with ethyl acetate (50 ml) each time. The ethyl acetate extracts were combined, dried over sodium sulfate, filtered and concentrated to provide an oily residue. The residue was passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with a mixture of (: 1 (v: v) hexane: ethyl acetate. The fractions containing the desired material were pooled and concentrated in vacuo to provide an oily residue (0.7 g) that was used directly in the next step. Step 5:
[0217] The oil (0.7 g) from step 4 was added to a reaction flask and dissolved in toluene (20.0 ml). Bismuth triflate 910.0 mg) was added and the mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature and the solvent was removed in vacuo. The recovered residue was passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with a 4: 1 (v: v) mixture of hexane: ethyl acetate. The fractions containing the desired material were grouped and concentrated to provide an oily residue. Hexane was added to produce a precipitate. The precipitate (0.5 g) was collected by vacuum filtration. A cream colored solid was obtained as the product. NMR analysis of the cream colored solid indicated a structure consistent with 2-bromo-7,7-dimethyl-9- (trifluoromethyl) -7H-benzo [c] fluoren-5-ol. Step 6:
[0218] In a reaction flask containing a solution of chloroform (600 mL) of the product obtained from step 5, (0.5 g) and sulfonic acid p-toluene (20.0 g) was added 1— (4— fluorophenyl ) -1- (4- (piperidin-1-yl) phenyl) -prop-2-in-1-ol (0.5 g). The solution was heated to reflux for 4 hours. The reaction mixture was passed through a silica gel coating (Grade 60, 230-400 mesh) and eluted with CHCl3. The fractions containing the desired material were grouped and concentrated to provide a gray solid (0.4 g) that was used directly in the next step. NMR analysis showed that the product had a structure consistent with 3- (4-fluorophenyl) -3 (4- (piperidin-1-yl) phenyl) -7-bromo-ll-trifluoromethyl-13,13-dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4] nfate [1,2-b] pyran. Step 7:
[0219] The product obtained from step 6 (0.3 g) and N- (3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl [-4-carboxamide (0.2 g, product from step 5 of Example 12) were added in a reaction flask and dissolved in tetrahydrofuran (20, 0 mL). A solution of potassium fluoride (0.2 g) in water (20.0 ml) was added and the resulting solution was degassed by bubbles of nitrogen for 10 minutes.
[0220] Dichlorobis (triphenylphosphine) palladium (II) (0.03 g) was added and the resulting mixture was heated to reflux for 18 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (100.0 ml). The mixture was filtered through a bed of Celite and the filtrate was collected and concentrated in vacuo to provide an oily residue. The residue was purified by silica gel and eluted with a mixture of (: 1 (v: v) of hexand: acetone. The fractions containing the desired material were pooled and concentrated. The residue was dissolved with a minimal amount of dichloromethane and added dropwise. drop to methanol (25 mL) to produce a precipitate The precipitate (0.2 g) was collected by vacuum filtration The NMR analysis of the precipitate indicated a structure that was consistent with 3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl) -7- (2-methyl-4- (4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] 4-ylcarboxamido) phenyl) -11 -trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 18

[0221] The procedures from Step 1 to 7 of Example 17 were followed except that in Step 6, 1- (4-butoxyphenyl) -1- (4-methoxyphenyl) -prop-2-in-1-ol was used instead of 1— (4— fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol. A solid was obtained as the product. NMR analysis showed that the product had a structure consistent with 3- (4-butoxyphenyl0-3-94-methoxyphenyl) -7- (2-methyl-4- (4 '- (trans-4-pentylcyclohexyl) - [1, 1'-biphenyl] -4-ylcarboxamido) phenyl) -11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2r, 3r: 3,4] naphtho [1,2-b] pyran. Example 19

[0222] The procedures for slap 1 to 7 of Example 17 were followed except that in step 1, 3,5-difluorobenzoyl chloride was used instead of 4-trifluoromethylbenzoyl chloride, in step 6, 1-phenyl-l- (4-morpholinophenyl) prop-2-in-1-ol was used in place of 1— (4 - fluorophenyl) -1- (4- (piperidini-1-yl) phenyl) prop-2-in-1-ol and in step 7, N- (4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1' -biphenyl) -4- carboxamide was used in place of N- (3-methyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl) -4-carboxamide. After step 7, a photochromic blue dye was isolated using CombedyFlash® Rf from Teledyne ISCO. A bluish solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4- (N-morpholinyl) phenyl) -3-phenyl- 7- (4- (4 '- (trans-4-pentylcyclohexyl) - [1,1' -biphenyl] 4-ylcarboxamido) phenyl) -10,12-difluoro-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 20

[0223] The procedures of Example 17 were followed except that in Step 1, 3,5-difluorobenzoyl chloride was used in place of 4-trifluoromethylbenzoyl chloride and in slap 7, N- (4- (4,4,5 , 5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl) -4-carboxamide was used in place of N- (3 -methyl-4- (4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4 '- (4-penticylcohexyl) - [1,1'-biphenylO-4- carboxamide. After step 7, a photochromic dye of blue color was isolated using CombedFlash® Rf from Teledyn ISCO. A bluish solid was obtained as the product. NMR showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- (piperidini-1-yl) phenyl) -7- (4- (4 '- (trans-4-pentylcyclohexylO- [ 1,1'-biphenyl) - 4-ylababoxamido) phenyl) -10,12-difluoro-13,13-dimethyl-3, 13-dihydro-indene [2,3 ': 3,4] naphtho [1,2 b] pyran. Example 21
Step 1:
[0224] Magnesium (Mg) shavings (13.5 g) were added to a reaction flask under N2. A portion (30 ml) of a solution of 4-bromo-1,3-dimethoxybenzene [100 g (66.3 ml)] dissolved in anhydrous tetrahydrofuran (THE, 200 ml) was added to the reaction flask with stirring. Di-bromo-ethane (DBE, 1 ml) was added and the resulting mixture started boiling. The flask was placed in an ice bath and the remainder of the remaining 4-bromo-1,2-dimethoxybenzene solution was added dropwise to the reaction mixture. THF (100 ml) 2,2'-oxybis (N, N-dimethylethanomine) [82 g (98 ml)] was added dropwise and the mixture was stirred for ~ 10 minutes. Then a solution of 3,5-bis (trifluoromethyl) benzoyl chloride (141 g (92, 4 mL)) in THF (200 mL) was added dropwise with stirring and a white solid formed. After stirring overnight , the reaction mixture was added in ice water (1.5 L) with 10% by weight of NaCl, stirred for 15-20 minutes, and then acidified to pH ~ 4 using HCl The resulting mixture was extracted with EtOAc (1 L) and the recovered organic layer was passed through anhydrous MgSO4, the solvent was evaporated and the resulting thick thick sticky material was used for the next step. Step 2:
[0225] 3,4-dimethoxy-3 ', 5'-bistrifluoromethylbenzophenone (157 g) and dimethyl succinate [80 g (73 ml)] were added to the reaction flask (3 L) under N2 THF (1 L) was added. Potassium t-butoxide (52 g) was added under 0.5-1 hour to control the temperature of the reaction mixture, which was maintained at 15-20 ° C in an ice water bath. The reaction mixture was added in ice water (1.5 L) with 10% by weight of NaCl. The resulting mixture was stirred for 15-20 minutes, acidified to pH ~ 4 using HCl and then extracted with EtOAc (1 L). The recovered organic layer was passed through anhydrous MgSO4. The solvent was evaporated and the resulting thick thick sticky material was used for the next step. NMR showed that the product had a structure consistent with a mixture of E and Z isomers of 4- (3,5-bis (trifloromethyl) phenylO-4- (3,4-dimethoxyphenyl) - 3- (methoxycarbonylObut-3-enoic acid . Step 3:
[0226] The product from step 2 (197 g) and acetic anhydride (270 g [250 ml)]) were added to a reaction flask containing CH2Cl2 (1 L), bismuth triflate (18.2 g) was added and the reaction mixture was stirred at room temperature for half an hour. The solution was filtered and the solvent was evaporated to provide a dark colored product. Isopropanol (0.5 L) washed the thick sticky material yielded a yellowish white crystallized compound which was isolated and dried under vacuum (135 g). NMR analysis showed that the product had a structure consistent with methyl-4-methoxy-1- [3,5-bis (trifluoromethyl) phenyl) -6,7-dimethoxy-2-naphthoate. Step 4:
[0227] The product from step 3 (135 g) was added to a reaction flask and dissolved in THE (1 L) and then MeMgCl [525 ml (22% by weight in THF)] was added dropwise with stirring under N2 atmosphere. The reaction mixture was stirred at room temperature for ~ 3 hours. The reaction mixture was added in ice water (1.5 L) with 10% by weight of NaCl, stirred for ~ 15 minutes and then acidified to pH ~ 4 using HCl. The resulting mixture was extracted with EtOAc (1 L). The recovered organic layer was washed with 10% by weight of an aqueous NaHCO solution (0.5 L) and passed through anhydrous MgSO4. The solvent was evaporated and the resulting dark thick sticky material was solidified using a 0.5 L wash MeOH. The product was isolated and dried under vacuum (101 g). NMR showed that the product had a structure consistent with 4- (3,5-bis (trifluoromethyl) phenyl) -6,7-dimethoxy-3- (prop-1-em-2-yl) naphthalen-1-ol. Step 5:
[0228] The product obtained from step 4, (180 g) and bismuth triflate (13.12 g) were added together in a reaction flask containing xylene (1.8 L). The reaction mixture was refluxed with stirring under N2 overnight. The resulting solution was filtered and the solution and the solvent was evaporated to obtain a dark colored product. The product was passed through a silica gel coated column using a 1: 3 (v: v) EtOAc-Hexane mixture. The product was isolated after a hexane (0.5 L) washed and dried under vacuum (105 g). NMR showed that the product had a structure consistent with 2,3-dimethoxy-7,7-dimethyl-8,10-bis (trifluoromethyl) -7H-benzo [c] fluoren-5-ol. Step 6:
[0229] 1.4 (M) of MeMgBr in a mixture of toluene / THF (75/25) (860 mL) and 2,6-dimethylpiperidine [40.8 g (50 mL)] were added in a reaction flask under N2 and THF (559 ml) was added in several portions with stirring. The resulting reaction mixture was refluxed overnight. The resulting reaction mixture was added in ice water (2 L) with 10% by weight of NaCl and a precipitate was formed. The mixture was acidified with 1 (N) HCl and a light brown oil was formed. The mixture was extracted with EtOAc (1 L). The organic layer was recovered and washed with 10% by weight of the aqueous NaHCOa solution (0.5 L) and passed through anhydrous MgSO4. The solvent was evaporated and the resulting dark thick sticky material was solidified using a hexane wash. The product was isolated and dried under vacuum (64 g). NMR showed that the product had a structure consistent with 3-methoxy-7,7-dimethyl-8,10-bis (trifluoromethyl) -7H-benzo [c] fluorene-2,5-diol. Step 7:
[0230] The product obtained from step 6 (10 g) was added to a reaction flask containing (CHzJzCls (0.2 L) under nitrogen. The mixture was heated to reflux and p-toluene sulfonic acid (0.044 g) was A solution of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol (6.2 g) in (CHzJzClzíôO ml) was added slowly to the reaction mixture with stirring. The resulting reaction mixture was refluxed overnight, washed with an aqueous NaHCOa solution and dried over anhydrous MgSOí, the solvent was evaporated and the product was dissolved in the minimum volume of CH2 Cl2 and passed through a silica coating column. gel using CH2C12 as an eluent. The solvent was evaporated and the product was crystallized using diethyl ether as a solvent. The product was isolated and dried under vacuum (12 g). NMR demonstrated that the product had a structure consistent with 3.3 -bis (4-methoxyphenyl) -6-methoxy-7-hydroxy-10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro- ndeno [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 8:
[0231] The product obtained from step 7 (10 g) was added to a reaction flask and dissolved in CH2 Cl2 (200 ml) and then Et3N [4.3 g (6 ml)] was added with stirring. Trifluoromethane sulfonic anhydride [4.9 g (3.0 ml)] was added dropwise with stirring under an atmosphere of N2 at 0 ° C. When the addition was made the temperature of the reaction mixture was induced at about 23 ° C and the mixture was stirred for one hour. The reaction mixture was evaporated and the resulting residue was dissolved in CH2 Cl2 and passed through a silica gel coating column. The solvent was evaporated and the recovered precipitate was washed with hexanes. The product was isolated and dried under vacuum (10 g). NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (trifluoromethane sulfonyloxy) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13 - dihydro-indene [1 ', 3': 3,4] naphtho [1,2-b] pyran. Step 9:
[0232] The product of step 8 (5 g) and N- (3-methyl) -4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexylO- [1,1'-biphenyl] -4-carboxamide (3.8 g; obtained from step 5 of Example 12) were added to a reaction flask and dissolved in THF (0.15 L) Water (0.15 L) was added and the reaction mixture became opaque, potassium fluoride (1.8 g) was added with stirring and nitrogen was passed through the solution for ~ 15 minutes. PdC12 (PPh3 ) 2 (0.3 g) was added and the reaction was heated to reflux with stirring for ~ 2 hours. The reaction mixture was cooled to room temperature and ~ 100 ml of ethyl acetate was added. The organic layer was filtered through of an auxiliary CELITE® filter and dried with anhydrous MgSO4. The solvent was evaporated and the resulting dark colored sticky material was dissolved in CH2CI2. The solution was passed through a column using CH2CI2 as the first eluting solvent and then EtOAc : Hxane (2: 8) (v: v). o was isolated and dried in vacuo (4.7 g). NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4 '- (trans-4-pentylcyclohexylO- [1,1' - biphenyl] -4-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2- b] pyran, Example 22

[0233] The procedures obtained from step 3 to step 5 of Example 12 were followed, except that in step 5, 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline was used in place of 3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline. NMR showed that the product had a structure consistent with 4 '- (4-pentylcyclohexyl) -N- (4- (4,4,5,5-tetramethyl-1,3,3-dioxaborolan-2-yl) phenyl) - [1,1'-biphenyl] -4-carboxamide. Step 2:
[0234] The procedures obtained from step 9 of Example 21 were followed except that 4'-94-pentylcyclohexyl) -N- (4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2- ila) phenyl) - [1,1 '- biphenyl] -4-carboxamide was used instead of N- (3-methyl- 4- (4,4,5,5-tetramethyl-1-3,2-dioxaborolan- 2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-ylcarboxamido) phenyl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3.13 -dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 23
Step 1:
[0235] The procedures obtained from steps 4 and 5 of Example 2 were followed except that in Step 4, 4- (trans-4-pentylcyclohexyl) benzoic acid was used in place of 4 '- (trans-4-penti1cyclohexi1) - [1,1'-biphenyl] -4-carboxylic and in step 5, 4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline was used in place of 3-methyl-4 (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline. NMR showed that the product had a structure consistent with 4- (trans-4-pentylcyclhexyl) -N- (4- (4,4,5,5-tetramyl-1,3, 2-dioxaborolan-2-yl) phenyl) benzamide. Step 2:
[0236] The product obtained from step 1 (37 g) and 1,4-dibromo-2-methylbezene (23.34 g) were added in a reaction flask and dissolved in THE (0.37 L) and water (0 , 29 L) was added. Potassium acetate (KOAc) (76.37 g) was added to the reaction mixture with stirring. The nitrogen was passed through the solution for ~ 20 minutes. To the reaction mixture, PdCl2 (PPh3) 2) (2.73 g) was added and the reaction was heated to reflux with stirring for ~ 2 hours. The reaction mixture was cooled to room temperature and then ~ 200 ml of ethyl acetate was added. The recovered organic layer was filtered through an auxiliary CELITE® filter and dried over anhydrous MgSO4 and the solvent was evaporated in vacuo. The recovered residue was recrystallized using THF and ethanol. NMR showed that the product had a structure consistent with N- (4'-brmo-3'-methyl- [1,1'-biphenyl] - 4-yl) -4- (trans-4-pentylcyclohexyl) benzamide. Step 3:
[0237] The product obtained from step 2 (20 g) and 4,4,4 ', 4', 5, 5, 5 ', 5'-octamethyl-2,2r-bi (1,3,2-dioxaborolane) (19.59 g) were added to a reaction flask containing 2-methyl ethyl hydrofuran (0.5 L), potassium acetate (KOAc) (9.46 g) was added with stirring. The nitrogen was passed through the solution for ~ 20 minutes. To the reaction mixture, PdC12 (PPh3) 2 (5.41 g) was added and the reaction was heated to reflux with stirring for ~ 16 hours. The reaction mixture was cooled to room temperature and washed with 0.5 L of a 10% by weight aqueous NaCl solution. The recovered organic layer was dried over anhydrous MgSO4, filtered and the solvent was evaporated. The recovered residue was dissolved in CH2 Cl2 and passed through a silica gel coating column using CH2 Cl2 as the eluting solvent. The product was recrystallized from a mixture of THF and methanol. NMR analysis showed that the product had a structure consistent with N- (3'-methyl-4 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) - [1, 1'-biphenyl] -4-yl) - 4 (trans-4-pentylcyclohexyl) benzamide. Step 4:
[0238] The procedures obtained from steps 1 to 9 of Example 21 were followed except that in Step 9, the product from step 3 (above) was used in place of N- (3-methyl-4- (4.4.5 , 5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxamide. NMR analysis showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexyl) benzamido ) phenyl) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 24
Step 1:
[0239] The procedures in steps 4 and 5 of Example 12 were followed except that in Step 4, 4- (trans-4-pentylcyclohexyl) benzoic acid was used in place of 4'- (trans-4-pentylcylhexylO- [1 , 1'-biphenyl] -4-carboxylic acid and in step 4, 4-aminobenzoic acid was used in place of 3-methyl-4- (4,4,5,5-tetrametill, 3,2-dioxaborolan-2- ila) aniline NMR analysis showed that the product had a structure consistent with 4- (4- (trans-4-pentylcyclohexylObenzamido) benzoic acid). Step 2:
[0240] The procedure obtained from step 3 of Example 27 was followed except that 4- (4- (trans-4-pentylcyclohexyl) benzamido) benzoic acid was used in place of 4 - ((trans, trans) -4 'acid -pentyl- [1,1'-bi (cyclohexane)] - 4-carboxamido) benzoic. NMR analysis showed that the product had a structure consistent with N- (3-methyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl-4- (4 - (trans-4-pentylcyclohexyl) benzamido) benzamide. Step 3:
[0241] The procedures obtained from step 1 to 9 of Example 21 were followed except that in step 9, the product from step 2 (above) was used in place of N- (3-methyl-4- (4.4.5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxamide. NMR analysis showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexyl) benzamido ) benzamido) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2 -b] 1,2-b] pyran. Example 25

[0242] The procedures obtained from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-methoxyphenyl) -1-phenyl-prop-2-in-1-ol was used in place of 1, 1-bis (4-methoxyphenyl) prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-ylcarboxamido) phenyl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 26

[0243] The procedures obtained from steps 1 to 9 of Example 21 were followed except that in Step 7, l- (4-methoxyphenyl) -l-phenyl-prop-2-in-l-ol was used instead of 1 , 1-bis (4-methoxyphenyl) prop-2-in-1-ol and in step 9, N- (3'-methyl-4 '- (4,4,5,5-tetramethyl-l, 3,2 -dioxaborolan-2-yl) - [1,1'-biphenyl] -4-yl) -4- (trans-4-pentylcyclohexi1) benzamide (from step 3 of Example 23) was used in place of N- (3- methyl- 4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexylO- [1,1'-biphenyl] -4-carboxamide NMR showed that the product had a structure consistent with 3— (4 - methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (4- (4- (trans-4-pentylcyclohexylObenzamido) phenyl) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4] naphtho [1,12-b] pyran Example 27
Step 1
[0244] In a reaction flask containing CH2CH2 (100 ml) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic acid (10 g) and methyl -4-aminobenzoate (6.7 g) N, N'-dicyclohexylcarbodiimide (DCC) (10.3 g), 4- (dimethylamino) pyridine (DMAP) (2.9 g) dodecylbenzene sulfonic acid (DBSA) (6, 5 g) were added with stirring under an atmosphere of N2. After stirring for about 20 minutes, a white precipitate was formed. The white solid was filtered and washed with CH2 Cl2 three times and the solid was used during the next step without any further purification. Step 2:
[0245] Methyl 4 - ((trans, trans) -4'-poly- [1,1'- bi (cyclohexane)] - 4-carboxamido) benzoate (16.8 g) was added to a reaction flask containing MeOH (500 mL). A 50% by weight aqueous NaOH (32.8 g) was added to the reaction mixture with stirring and the mixture was refluxed for ~ 5 hours. The reaction mixture was cooled to room temperature and poured into ice-cooled water (1 L) and then acidified to pH ~ 3 with concentrated HCl. A white solid was formed and was filtered, washed with water followed by a wash with MeOH. A solid product was isolated and dried in a vacuum oven (15.4 g). NMR showed that the product had a structure consistent with 4- ((trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxamido) benzoic acid. Step 3:
[0246] The procedure of step 1 of this example was followed except that the product of step 2 and 3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) aniline were used in place of (trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic acid and methyl-4-aminobenzoate, respectively; dodecylbenzene sulfonic acid was not used; the reaction was stirred for 100 hours, instead of 20 minutes, the precipitate; and the light yellow waxy material was recovered and washed with hexanes to obtain the product. NMR demonstrated that the product had a structure consistent with (trans, trans) -N- (4 - ((3-methyl-4- (4,4,5,5, - tetramethyl) -1,3,2-dioxaborolan- 2-yl) phenyl) carbamoyl) phenyl) - 4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxamide. Step 4:
[0247] The procedures from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-methoxyphenylO-1-phenyl-prop-2-in-l-ol was used in place of l, l- bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, the product from step 3 (above) was used in place of N- (3-methyl-4- (4,4,5,5 - tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-methoxyphenyl) -3-phenyl-6-methoxy 7- (2-methyl-4- (4 - ((trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxamido) benzamido) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 28
Step 1
[0248] In a reaction flask containing 1,4-dioxane (12.5 L) water (372 mL) was added l-bromo-4- (4-pentylcyclohexyl) benzene (3000 g), 4-hydroxyphenylboronic acid (135 g), K2CO3 (5500 g) and Pd (Pph3) 4 (44.84 g) and the resulting mixture was stirred at 110 ° C for 12 hours. After the solution was cooled to room temperature, it was poured into water (65 L) with stirring. A gray solid was obtained after filtering. The solid was washed with water, dissolved in THF (12.5 L0, passed through active carbon (350 g) and filtered through an auxiliary CELITE® filter. The filtrate was concentrated and the resulting residue was poured into 4 L of methanol A white solid was obtained after filtering and it was washed with methanol and dried to yield 1840 g of the product. NMR showed that the product had a structure consistent with 4'- (trans-4-pentylcyclohexyl) - [1, 1'-biphenyl] -4-ol This procedure was repeated to produce sufficient product for the next step. Step 2:
[0249] In a reaction flask containing DMF (25.00 L), the product from step 1 (2.6 kg), trans-cyclohexane-1,4-dicarboxylic acid (2.78 kg), DBSA ( 1.31 kg) and DMAP (0.59 kg). The resulting mixture was stirred for 3 hours. DCC (1.75 kg) was added in portions and the resulting mixture was stirred for 30 hours at room temperature. A solid was formed and was filtered and washed with DMF. The recovered product was processed in three batches by means of dissolution, each batch in THF (30 L), with stirring and then filtered through an auxiliary CELITE® filter. The filtrate was concentrated and the resulting residue was poured into 4 L of ethanol with stirring. A white solid formed which was recovered by filtration, washed with ethanol and dried to provide 588 g of the product. NMR showed that the product had a structure consistent with trans-4 - (((((4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-yl) oxy) carbonyl) cyclohexanecarboxylic acid. Step 3:
[0250] The procedures of steps 4 and 5 of Example 12 were followed except that in Step 4, the product of step 2 (above) was used in place of 4 '- (trans-4-pentylcyclohexyl) - [1, 1'-biphenyl] -4-carboxylic. NMR showed that the product had a structure consistent with trans-4'- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-yl-4 - (((3-methyl- 4- (4, 4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenylOcarbamoyl) cyclohexane carboxylate. Step 4:
[0251] The procedures from steps 1 to 9 of Example2 1 were followed except that in Step 7, 1- (4-methoxyphenyl) -1- phenyl-prop-2-in-l-ol was used instead of l, l -bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, the product from step 3 (above) was used in place of N- (3-methyl-4- (4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) —4 '- [4— polycyclohexyl) - [1,1'-biphenyl [-4-carboxamide. NMR showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (trans-4 ((((4'- (trans-4- pentiylcyclohexylO- [1,1'-biphenyl] -4-yl) oxy) carbonyl) cyclohexanecarboxamido) phenyl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3 ': 3,4] naphtho [1,2-b] pyran Example 29

[0252] The procedures from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-morpholinophenyl) -1- phenylprop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3- (4-N-morpholinylphenylO-3-phenyl-6-methoxy-7- (2-methyl-4- (4 '- (trans-4-pentylcyclohexyl) - [1 , 1'-biphenyl] 4-ylcarboxamido) phenyl) -10, 12-di (trifluoromethyl) -13,13-dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4] naphthus [l, 2-b] pyran Example 30

[0253] The procedures from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-morpholinophenyl) -1- phenylprop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, trans-4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl) -4-yl-4 - (([ 3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl] phenyl) carbamolia) cyclohexanecarboxylate (obtained from step 3 of Example 28) was used in place of N- (3-methyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenylO-4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl) - 4-carboxamide NMR showed that the product had a structure consistent with 3- (4-N-morpholinophenyl) -3-phenyl-6-methoxy-7- (2-methyl-4- (trans-4 (((4 ' - (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-yl] oxy) carboxnylOcyclohexanecarboxamido) phenyl) -10, 12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro- indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 31

[0254] The procedures from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-morpholinophenyl) -1- phenylprop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol in Step 7 and Step 9, N- (4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl) -4-carboxamide (obtained from step 1 of Example 22) was used in place of N- (3-methyl- 4- (4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4'- (4-pentylcyclohexylO- [1,1'-biphenyl] -4-carboxamide. NMR showed that the product had a structure consistent with 3- (4-N-morpholinophenyl) -3-phenyl-6-methoxy-7- (4- (4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4- ilcarboxamido) phenyl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 32

[0255] The procedures of steps 1 to 9, of Example 21 were followed except that in Step 7, 1- (4-methoxyphenyl) -1- (4-morpholinophenyl) -prop-2-in-1-ol was used in 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3- (4-N-morpholinophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (2-methyl-4- (4 '- (trans-4- pentylcyclohexyl) - [1,1'-biphenyl] -4-ylcarboxamide) phenyl) - 10,12-di (trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran Example 33

[0256] The procedures from steps 1 to 9 obtained from Example 21 were followed, except that in Step 7, l- (4-methoxyphenyl) -1- (4-morpholinophenyl) -prop-2-in-l-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, 4'- (4-pentylcyclohexyl-N- (4- (4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl- [1,1'-biphenyl] -4-carboxamide (obtained from step 1 of Example 22) was used in place of N- (3-methyl-4 - (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] 4-carboxamide. NMR showed that the product had a structure consistent with 3- (4-N-morpholinophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (4- (4 '- (trans-4-pentylcyclohexyl) - [1, 1 '-biphenyl] -4-ylcarboxamide) phenyl) -10,12-di (trifluoromethyl-13, 13-dimethyl-3,13-dihydro-indene [2', 3 ': 3,4] naphtho [1,2 -b] pyran Example 34
Step 1:
[0257] The procedures obtained from steps 3 to 5 of Example 12 were followed, except that in Step 3, 4-bromo-3- (trifluoromethyl) aniline was used in place of 4-bromo-3-methylaniline and in Step 4 , 4— (4 - pentylcyclohexyl) benzoic acid was used in place of 4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxylic acid. NMR showed that the product had a structure consistent with 4- (4-pentylcyclohexyl) -N- (4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) -3- ( trifluoromethyl) phenyl) benzamide. Step 2:
[0258] The procedures from steps 1 to 9 of Example 21 were followed except that in Step 7, 1- (4-morpholinophenyl) - 1- (4-phenyl) -prop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, 4- (4- pentylcyclohexyl-N- (4- (4,4,5,5-tetramethyl-l , 3,2-dioxaborolan-2-yl) -3- (trifluoromethyl) phenyl) benzamide was used in place of N- (3-methyl-4- (4,4,5,5-tetramethyl-1, 3.2 -dioxaborolan- 2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] -4-carboxamide NMR showed that the product had a structure consistent with 3-phenyl-3- (4 -piperidin-1-yl) phenyl) -6-7- (4- (4 '- (trans-4-pentylcyclohexyl) benzamido) -2- (trifluoromethyl) phenyl) -10,12-di (trifluoromethyl) -13, 13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 35

[0259] The procedures from steps 1 to 9 of Example 21 were followed, except that in Step 7, ol, l-bis (4-fluorophenyl) prop-2-in-l-ol was used in place of 1,1- bis (4-methoxyphenyl) prop-2-in-1-ol and in Step 9, 4 '- (4-pentylcyclohexyl) -N- (4- (4,4,5,5-tetramethyl-1, 3.2 - dioxaborolan-2-yl) phenyl- [1,1'-biphenyl] -4-carboxamide was used in place of N- (3-methyl-4- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) phenyl) -4 '- (4-pentylcyclohexyl) - [1,1'-biphenyl] 4-carboxamide NMR showed that the product had a structure consistent with 3,3-bis (4- fluorophenyl) -6-methoxy-7- (4- (4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-ylcarboxamide) phenyl) -10,12-di (trifluoromethyl) -13 , 13-dimethyl-3,13-dihydro-indene [2 ', 3':, 4] naphthol [1,2-b-pyran. Example 36
Step 1:
[0260] The procedures obtained from steps 1 to 7 of Example 21 were followed except that in Step 7, ol, l-bis (4-fluorophenyl) prop-2-in-l-ol was used in place of 1,1- bis (4-methoxyphenyl) prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3,3-bis (4-fluorophenyl) -6-methoxy-7-hydroxy-10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro- indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 2:
[0261] The product from step 1 (4.0 g) was dissolved in a minimum volume of CH2C12 in a reaction flask and the following were added: 1,3-dicyclohexylcarbodiimide (DCC) 91.46 g), 4- (dimethylamino) pyridine (DMAP) (0.43 g) and dodecylbenzene sulfonic acid (DBSA) (0.96 g). The resulting mixture was stirred for a few minutes and the trans-4 - ((((4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-yl) oxy) carbonyl) cyclohexanecarboxylic acid (3 , 7 g) (obtained from step 2 of Example 28) was added. Sufficient CH2 Cl2 was added to make the mixture less viscous and stirable. The reaction mixture was stirred overnight. A white solid precipitate was formed and was removed by filtration. The filtrate was evaporated and the residue was collected as the crude product. The recovered product was dissolved in toluene and the white precipitate was removed by filtration. The toluene solution was passed through a column coated with silica gel using CH2 Cl2 as the eluent solvent. The solvent was evaporated to concentrate the solution which was added for vigorous stirring of MeOH to precipitate the solid product. The product (5 g) was recrystallized from diethyl ether. NMR analysis showed that the product had a structure consistent with 3, 3-bis (4-fluorophenylO-6-methoxy-7 (trans-4- (4 '- (trans-4-pentylcyclohexylO- [1,1' -biphenyl ] -4- yloxycarbonylOcyclohexanocarbonyloxy) -10, 12-di (trifluoromethyl) -13,13-dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 37

[0262] The procedures from steps 1 to 7 of Example 21 were followed, except that in step 7, l- (4-phenyl) -1- (4-N-piperidinylphenyl) prop-2-in-l-ol was used in place of 1,1, -bis (4-fluorophenyl) prop-2-in-1-ol. NMR demonstrated that the product had a structure consistent with 3- (4- (pipridin-1-yl) phenyl) -3-phenyl-6-methoxy-7- (trans-4- (4 '- (trans-4- pentylcyclohexi1) - [1,1'-biphenyl] -4-yloxycarbonyl) cyclohexanecarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3, 4] naphtho [1,2-b] pyran. Example 38

[0263] The procedures from steps 1 to 7 of Example 21 were followed, except that in Step 7, (4-morpholinophenyl) -1- (4-phenyl) -l-prop-2-in-1-ol was used in 1,1-bis (4-fluorophenyl) prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3- (4- (N-morpholino) phenyl) - 3-phenyl-6-methoxy-7- (trans-4- (4 '- (trans-4-pentylcyclohexyl) - [1,1'-biphenyl] -4-yloxycarboylOcyclohexanocarbonyloxy) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [l , 2-b] pyran Example 39
Step 1:
[0264] The procedures obtained from Steps 1 to 7 of Example 21 were followed except that in Step 7, (4-N-morpholinophenyl) -1- (4-phenyl) -l-prop-2-in-l-ol was used in place of 1,1-bis (4-methoxyphenyl) -prop-2-in-1-ol. NMR analysis showed that the product had a structure consistent with 3- (4- (N-morpholino) phenyl) -3-phenyl-6-methoxy-7-hydroxy-10,12-di (trifluoromethyl) -13,13 -dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 2:
[0265] The procedures obtained from steps 4, 5, 6 and 7 of Example 1 were followed, except that in Step 5, the product obtained from Step 1 (above) was used in place of 3- (4-fluorophenyl) -3 - (4- (piperidin-1-yl) phenyl) -13-methoxy-13-ethyl-6-methoxy-7-hydroxy-3,13-dihydro-indeno [2 ', 3': 3,4] naphthus [ 1,2- b] pyran and in Step 7, (trans, trans) -4'-phenyl- [1,1'-bi (cyclohexane)] - 4-carboxylic acid was used in place of 4- (4 - (trans) -pentylcyclohexyl) benzoyl. NMR showed that the product had a structure consistent with 3- (4- (N-morpholino) phenyl-3-phenyl-6-methoxy-7- (4- (4 - ((trans, trans) -4 '- pentyl- [1,1'-bi (cyclohexane)] -4-carbonyloxy) phenylObenzoyloxy) -10,12-di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3, 4] naphtho] 1,2- b] pyran EXAMPLE 40

[0266] The procedures obtained from steps 4, 5, 6 and 7 of Example 1 were followed except that in Step 1, 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol was used instead of (4-morpholinophenyl) -1-1 (4-phenyl) -1-prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4 - (((trans, trans) -4'-pentyl- [1, 1'-bi (cyclohexane)] - 4-carbonyloxy) phenylObenzoyloxy) -10,12- di (trifluoromethyl) - 13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho ] 1,2- b] pyran EXAMPLE 41

[0267] The procedures obtained from steps 4, 5, 6 and 7 of Example 39 were followed, except that in Step 1, 1— (4 - fluorophenyl) -1- (4- (piperidine-l-yl) phenyl) prop-2-in-1-ol was used in place of (4-morpholinophenyl) -1- (4-phenyl) -1-prop-2-in-ol. NMR demonstrated that the product had a consistent structure on 3- (4-fluorophnyl) -3- (4- (piperidin-1-yl) phenyl) - 6-methoxy-7- (4- (4 - (((trans, trans) -4'-pentyl- [1,1 '- bi (cyclohexane)] - 4-carbonyloxy) phenyl) benzoyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro- indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 42

[0268] The procedures obtained from steps 4, 5, 6 and 7 of Example 36 were followed except that in Step 1, l- (4-fluorophenyl) -1- (4-N-piperidinylphenyl) prop-2-in-l -ol was used in place of 1,1-bis (4-fluorophenyl) prop-2-in-1-ol. NMR demonstrated that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- (piperidini-1-yl) phenylO-6-methoxy- 7- (trans — 4- (4'-trans-4 -pentylcyclohexyl) - [1,1'-biphenyl] -4-yloxycarbonyl) cyclohexanecarbonyloxy) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 2': 3 , 4] naphtho [1,2-b] pyran. Example 43
Step 1:
[0269] The procedures obtained from steps 1 to 3, of Example 1 were followed, except that in Step 3, 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol was used in place of 1— (4— fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol of the tap 3. The NMR demonstrated that the product had a structure consistent with 3,3-bis- (4-methoxyphenyl) -13-methoxy-13-ethyl-6-methoxy-7-hydroxy-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2— b] pyran. Step 2:
[0270] The procedure of step 2 of Example 36 was followed except that the product of step 1 (above) was used in place of 3,3-bis (4-fluorophenyl) -6-methoxy-7-hydroxy-10,12 - di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6,13-dimethoxy-7- (trans-4- (4 '- (trans-4-pentylcyclohexylO- [1,1 '-biphenyl] -4-yloxycarboyl) cyclohexanocarbonyloxy) -13-ethyl-3,13-dihydro-indene [2', 3 ': 3,4] naphtho [1,2-b] pyran Example 44
Step 1:
[0271] In a reaction flask containing methylene chloride (350 ml), 2,3-dimethoxy-7,7-dimethyl-8,10-bis (trifluoromethyl) -7H-benzo [c] fluoren-5-ol (13.0 g) (product obtained from step 5 of Example 21), 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol (7.6 g) and pTSA (0.05 g) and stirred for 1 hour. The reaction mixture was washed with an aqueous solution of NaHCCb, dried over magnesium sulfate, concentrated and used directly in the next step. Step 2;
[0272] The product from step 1 (10.0 g) and 4- (piperazin-1-yl) phenol (3.02 g) was added in a reaction flask and dried in a vacuum oven at 110 ° C. THE (250 ml) was added under nitrogen protection. A solution of MeLi / ethyl ether (1.6 M, 21 ml) in 60 ml THE was added slowly over 35 minutes at 0 ° C. After TLC demonstrated that the reaction was completed, 100 ml of water was added. 2N HCl was used to adjust the pH to 5. Extraction was done using ethyl acetate. The recovered organic layer was dried over MgSO4, filtered over silica gel and concentrated. The product was used in the next step without further purification. Step 3:
[0273] A mixture of (trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic acid (2 g), the product obtained from step 2 (3 g), N , N-dicyclohexylcarbodiimide (0.9 g), 4-dimethylaminopyridine (0.3 g) and methylene chloride (30 ml) was added to a reaction flask at room temperature overnight. The solids in the reaction mixture were removed by filtration. The filtrate was washed with water several times, dried and then concentrated. The recovered residue was recrystallized from a methylene chloride / methanol mixture. The crystalline product was collected by vacuum filtration (3.01 g). NMR demonstrated that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (4 - (4- (trans, trans-4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran. Example 45
Step 1:
[0274] The procedure from step 1 of Example 44 was followed except that 1,1-bi (4 - ((tetrahydro-2H-pyran-2-yl) oxy) phenyl) prop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop-2-in-1-ol. The resulting product was not purified and used in the next step. Step 2:
[0275] The product from step 1 was mixed with ethanol (140 ml) and PTSA (0.14 g) in a reaction flask. After reflux for 4 hours, the reaction mixture was extracted using ethyl acetate and water. The organic layer was collected, dried and concentrated to provide a solid (11.9 g). The recovered solid was dissolved in THF (60 ml) in a reaction flask. Triisopropylsilyl triflate (14 g) was added. Pyridine (12 g) was added slowly. The mixture was stirred at room temperature for 16 hours. All solvents were removed and the resulting residue was dissolved in dichloromethane (100 ml), washed with 0.1 M hydrochloric acid (2 x 30 ml) and brine (3 x 50 ml), dried and concentrated. The product was recrystallized from methanol to provide crystals as the product (14.8 g). NMR showed that the product had a structure consistent with 3,3-bis (4-triisopropylsiloxyphenyl) -6,7-dimethoxy-10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [ 2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 3:
[027 6] The procedures of steps 2 and 3 of Example 44 were followed except that the product obtained from step 2 (above 9) was used in place of the product obtained from step 1 of Example 44. NMR analysis showed that the product had a structure consistent with 3,3-bis (4-triisopropylsiloxyphenyl) - 6-methoxy-7- (4- (4-9trans, trans-4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy ) phenyl) piperazin-1-yl) -10,12- di (trifloroemyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b ] pyran. Step 4:
[0277] The product from Step 3 (1.10 g), tetrabutylammonium fluoride (TBAF) (0.30 g), THF 90.30 g), THF (11 ml) and water (5.5 ml). The resulting mixture was stirred and at room temperature for 3 hours. Ethyl acetate (5 ml) was added and the resulting organic layer was collected and concentrated. The residue was purified by CombedyFlash® Rf from Teledyne ISCO followed by recrystallization from methylene chloride and hexanes. A solid (0.44 g) was obtained as the product. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-hydroxyphenyl) -6-methoxy-7- (4- (4- (trans, trans-4-pentyl- [1,1'-bi ( cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12-di (trifluoroemethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1, 2-b] pyran Example 46

[0278] The procedures obtained from steps 1 to 3 of Example 1 were followed except that in Step 3, l, l-bis (4-fluorophenyl) prop-2-in-l-ol was used in place of l- (4 - fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol. NMR showed that the product had a structure consistent with 3,3-bis (4-fluorophenyl) -6-methoxy-7- (4- (4- (trans, trans-4 '- pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12-di (trifluoromethyl) -13,13-dimethyl-3, 13-dihydro-indene [2 ', 3': 3,4 ] naphtho [1,2-b] pyran. Example 47

[0279] The procedures from steps 1 to 3 of Example 1 were followed except that 1- (4-methoxyphenyl) -1- (4-morpholinophenyl) prop-2-in-l-ol was used in place of l- (4 - fluorophenyl) -1- (4-piperidin-1-yl-phenyl) -prop-2-in-1-ol. NMR analysis demonstrated that the product had a structure consistent with 3- (4-methoxyphenyl) -3- (4-N-morpholinophenyl) -6- methoxy-7- (4- (4- (trans, trans-4'-- pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-1-yl) -10,12- di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [ 2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 48

[0280] The procedures from steps 1 to 3 of Example 1 were followed except that trans-4 - ((((4 '- (trans-4-pentylcyclohexyl) - [1,' - biphenyl] -4-yl) oxy acid ) carbonyl) cyclohexanecarboxylic acid, the product from step 2 of Example 28 was used in place of (trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic acid. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4- (trans-4- (4'- (trans-4-pentylcyclohexil) - [1,1'-biphenyl] -4-yloxycarbonyl) cyclohexanocarbonyloxy) phenyl) piperazin-1-yl) - 10,12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3 ': 3,4] naphtho [1,2-b] pyran. Example 49
. Step 2:
[0281] The procedures obtained from steps 1 and 2 of Example 28 were followed except that 4- (trans-4-pentylcyclohexyl) phenol was used in place of 4 '- [trans-4-pentylcyclohexyl) - [1, 1' - biphenyl] -4-ol. NMR demonstrated that the product had a structure consistent with trans-4- ((4- (trans-4-pentylcyclohexyl) phenoxy) carbonyl) cyclohexanecarboxylic acid. Step 2;
[0282] The procedures obtained from step 3 of Example 44 were followed, except that the product obtained from step 1 (above) was used in place of (trans, trans) -4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carboxylic. NMR analysis demonstrated that the product had a structure consistent with 3,3-bis (4-methoxyphenyl) -6-methoxy-7- (4- (4-trans-4- (4- (trans-4-pentylcyclohexyl) - phenyloxycarbonyl) - cyclohexanocarbonyloxy) phenyl) piperazin-1-yl) -10, 12-di (trifluoromethyl) -13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1 , 2-b] pyran. Example 50
Step 1:
[0283] 3-bromo-4'-methylbenzophenone (50 g), dimethyl succinate (34.5 g) and toluene (1 liter) were added in a reaction flask under a nitrogen bench. The mixture was stirred at room temperature until the solids were dissolved. Solid potassium t-butoxide (22.4 g) was added and the mixture was stirred at room temperature for 4 hours. The resulting reaction mixture was poured into 1 liter of water and the aqueous layer, which contained the product, was collected. The toluene layer was extracted with 200 ml of water. The combined water solution was washed with toluene. HCl (2N, 20 mL) was added to the water solution. The yellow oil was precipitated. The resulting mixture was extracted with ethyl acetate, dried over magnesium sulfate, concentrated and dried in vacuo. The yellow vitrified oil (55 g) was obtained as the product. It was used directly in the next step. Step 2:
[0284] The product from step 1 (55 g) and acetic anhydride 9300 ml) was mixed and refluxed in a reaction flask for 1 hour. The acetic anhydride was removed from the reaction mixture by vacuum evaporation and 55 grams of oil was obtained as the product. It was used directly in the next step. Step 3:
[0285] In a reaction flask containing 55 grams of the oil obtained from step 2, methanol (300 ml) and HCl (12 N, 1 ml) were added. The mixture was refluxed for four hours. Methanol was removed by vacuum evaporation. The recovered oil was dissolved in methylene chloride, washed with saturated sodium bicarbonate water, dried over magnesium sulfate, concentrated and dried under vacuum. The resulting oil (51 g) was used directly in the next step. Step 4:
[0286] The product (51 g) obtained from step 3 was dissolved in 50 ml of anhydrous THF in an oven-dried reaction flask. The resulting mixture was stirred at room temperature and 1.6 M of a solution of toluene / THF (1: 1) of methyl magnesium bromide (265 ml) was added dropwise. After the addition, the mixture was stirred at room temperature for about 16 hours. The reaction mixture was poured into 2 liters of ice water. The pH of the mixture was adjusted to ~ 2 using HCl (12 N). Ethyl acetate (500 ml) was added and the resulting organic layer was separated, dried over magnesium sulfate, concentrated and dried in vacuo. The recovered product (50 g of oil) was used directly in the next step. Step 5:
[0287] The product obtained from step 4 (50 g) and xylene (300 ml) were added to a reaction flask, p-toluene sulfonic acid (1 g) was added and the resulting mixture was refluxed for eight hours. The xylene was removed by vacuum evaporation and the resulting oily product was dissolved in ethyl acetate, washed with water, dried over magnesium sulfate and concentrated. A small portion of the product (50 g of the oil) contained four naphthol isomers as seen from HPLC. The product (1.8 g) was purified using a CombiFlash® Rf obtained from Teledyne ISCO. After separation, three components were obtained. NMR analysis demonstrated that the products had structures consistent with: 2,3-dimethoxy-7,7-dimethyl-7H-benzo [c] fluoren-5-ol (0.32 g); 4-bromo-7,7,9-trimethyl-7H-benzo [c] fluoren-5-ol (0.08 g) and a mixture of isomers (0.36 g) of 10-bromo-3,7,7 -trimethyl-7H-benzo [c] fluoren-5-ol and 2-bromo-7,7,9-trimethyl-7H-benzo [c] fluoren-5-ol. Step 6:
[0288] In a reaction flask containing the mixture of isomers obtained from step 5 (0.36 g) 0.26 grams of 1,1-bis (4-methoxyphenyl0prop-2-in-l-ol, a few crystals of p-toluene sulfonic acid and methylene chloride (10 ml). The mixture was stirred at room temperature for 18 hours. The formation of a blue dye and a purple dye was observed from TLC. The product was purified using a CombiFlash® RF obtained from Teledyne ISCO A product (0.5 g) with two isomers as seen from HPLC was obtained and was used directly in the next step. Step 7;
[0289] In a reaction flask containing the product obtained from step 6 (0.5 g), were added: 4- (4-trans-pentylcyclohexylOphenyl-4- (4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl) benzoate (0.39 g); potassium fluoride (0.19 g); dichlorobis (triphenylphosphine) palladium (II) (0.012 g); THF (20 ml) and water (20 ml) The mixture was degassed, protected by nitrogen and heated to reflux for 18 hours. The TLC demonstrated the formation of a gray dye and a purple dye. The mixture was extracted using methylene chloride and water. The organic layer was recovered, isolated, dried over magnesium sulfate and concentrated. The resulting product was purified using Teledyne ISCO's CombiFlash® Rf. The gray dye was obtained with a green solid (0.25 g, less polar). The purple dye was obtained as a yellowish white solid. (0.18 g, more polar). NMR analysis showed a less polar gray dye having a structure consistent with 3,3-bis (4-methoxyphenyl) -7- (4- (4- (trans-4-pentylcyclohexyl) phenoxy carbonyl) phenyl) -11-methyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Example 51
Step 1:
[0290] Magnesium (3.2 g) and THF (50 ml) were added in a reaction flask. A portion (20 mL) of a mixture of 1-bromo-4- (trifluoromethyl) benzene (30 g) and THF (200 ml) was added to a reaction flask. A few drops of dibromoethane were also added to the flask. After the solvent in the reaction flask started boiling to maintain 1-bromo-4- (trifluoromethyl) benzene and THF was added dropwise. Ice water was used occasionally to keep the reaction mixture remaining around room temperature. After the addition, the mixture was stirred at room temperature for two hours. 3-bromo-4-methylbenzonitrile (26 g) was then added to the reaction mixture. The resulting mixture was stirred at room temperature overnight. 3N HCl (200 ml) was added and the resulting mixture was stirred for 4 hours. The resulting organic layer was collected, concentrated and passed through a coated column using a mixture of 90/10 (v: v) hexanes / ethyl acetate. White crystals (19 g) were obtained as a product. NMR demonstrated that the product had a structure consistent with 3-bromo-4-methyl-4'-trifluoromethylbenzophenone. Step 2:
[0291] The procedures from steps 1 to 7 of Example 50 were followed, except that in Step 1, 3-bromo-4-methyl-4'-trifluoromethylbenzophenone was used in place of 3-bromo-4'-methylbenzophenone and in step 6, 1- (4-fluorophenyl) -1- (4- (piperidin-1-yl) phenyl) prop-2-in-1-ol was used in place of 1,1-bis (4-methoxyphenyl) prop- 2-in-1-ol and in step 7, 4 '- (4- trans-pentylcyclohexylO-N- (4- (4,4,5,5, -tetramethyl-1,3,2-dioxaborolan-2-yl ) phenyl) - [1,1'-biphenyl] -4-carboxamide was used in place of 4- (4-trans-pentylcyclohexyl) phenyl-4- (4,4,5,5-tetramethyl-1, 3.2 -dioxaborolan-2-yl] benzoate Two photochromic products were obtained The desired product was a less polar product as seen on TLC using 20/80 ethyl acetate / hexane NMR demonstrated that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4- (piperidin-1-yl) phenyl0-6-methyl-7- (4- (4 '- (trans-4-pentylcilcohexylO- [1,1'-biphenyl] -4 -ylcarboxamido) phenyl) -11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naf to [1,2-b] pyran. Example 52
Step 1:
[0292] The procedure from steps 1 to 3 of Example 50 were followed, except that in step 1, 3-bromo-4-methyl-4'-trifluoromethylbenzophenone was used in place of 3-bromo-4'-methylbenzophenone and the product oily oil was dissolved in ethyl acetate in an uncoated evaporation disc and left in the working cap during the weekend. The crystals formed were collected and washed with small amounts of ethyl acetate and then diisopropyl ether. NMR analysis demonstrated crystalline product having a structure consistent with methyl-7-bromo-4-hydroxy-6-methyl-1- (4-trifluoromethyl) phenyl) -2-naphthoate. Step 2:
[0293] The procedures from steps 4 to 5 of Example 50 were followed except that in Step 4, the product from step 1 (above) was used in place of the oil mixture. The resulting product was used directly in the next step. Step 3:
[0294] The product from step 2 (above) (1 g) was added to a reaction flask. 1,1-bis (4- (((tetrahydro-2H-pyran-2-yl) oxy) phenyl) prop-2-in-1-ol (1 g), p-toluene sulfonic acid ( a few crystals) and methylene chloride (10 ml). The mixture was stirred at room temperature for 17 hours. Methanol (20 ml) was added and the resulting mixture was refluxed for one hour. Ethyl acetate (200 ml) and water (100 ml) were added and the recovered organic layer was collected, dried over magnesium sulfate and concentrated.The product was passed through a silica gel coating column using ethyl acetate / hexanes with a gradient ratio of 2 / 8 to 5/5 A gray solid (0.93 g) was obtained as the product. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-hydroxyphenyl) -6-methyl-7-bromine -11- trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 4:
[0295] The procedure of step 7 of Example 50 was followed, except that 3,3-bis (4-hydroxyphenyl0-6-methyl-7-bromo-11-trifluoromethyl-13,13-dimethyl-3,13-dihydro- indene [2 ', 3': 3,4] naphtha [1,2-b] pyran, obtained from step 3 (above) was used in place of the dye mixture and 4 '- (4-trans-pentylcyclohexylO-N- ( 4- (4,4,5,5, -tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) - [1,1'-biphenyl] -4-carboxamide was used in place of 4- (4 -trans-pentylcyclohexyl) phenyl-4- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-2-yl) benzoate A photochromic product was obtained and collected by CombiFlash® Rf obtained from Teledyne ISCO as a gray solid. NMR demonstrated that the product had a structure consistent with 3,3-bis (4-hydroxyphenyl) -6-methyl-7- (4- (4 '- (trans-4-pentylcyclohexyl) - [1, 1'-biphenyl) -4-ylcarboxamido) phenyl) -11-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3'; 3,4] naphtho [1,2-b] pyran Example 53
Step 1:
[0296] The procedures from steps 1 to 5 of Example 21 were used, except that 4-trifluoromethylbenzoyl chloride was used in place of 3,5-bis (trifluoromethyl) benzoyl chloride. NMR demonstrated that the product had a structure consistent with 2,3-dimethoxy-7,7-dimethyl-9- (trifluoromethyl) -7H-benzo [c] fluoren-5-ol. Step 2:
[0297] The procedures of Example 44 were used except that 2,3-dimethoxy-7,7-dimethyl-9- (trifluoromethyl) -7H-benzo [c] fluoren-5-ol was used instead of 2,3- dimethoxy-7,7-dimethyl-8,10-bis (trifluoromethyl) -7H-benzo [c] fluoren-5-ol in step 1. NMR demonstrated that the product had a structure consistent with 3,3-bis (4- methoxyphenyl0-6-methoxy-7- (4- (4- (trans, trans-4'-pentyl- [1,1'-bi (cyclohexane)] - 4-carbonyloxy) phenyl) piperazin-l-yl) -11 -trifluoromethyl-13,13-dimethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 54
Step 1
[0298] The procedures from steps 2 to 8 of Example 21 were followed except that in Step 2. 3,4-dimethoxybenzophenone was used in place of 3,4-dimethoxy-3 ', 5'-bistrifluoromethylbenzophenone. NMR showed that the product had a structure consistent with 3-phenyl-3- (4- (4-methoxyphenylpiperazin-1-yl) phenyl) -13,13-dimethyl-6-methoxy-2-trifluoromethanesulfonyloxy-3, 13-dihydro - indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 2:
[0299] The product from step 1, zinc cyanide 91.71 g), zinc acetate (0.1 g), zinc (0.036 g), dimethylformamide (DMF) (40 ml), water (0.4 ml) , 1,1'-bis (diphenylphosphino) ferrocene (0.02 g) and tris (dibenzylidene acetone) dipaladium (0.013 g) were added to a degassed reaction flask and stirred under nitrogen protection. The reaction flask was kept in an oil bath maintained at a temperature of 90-100 ° C. After 12 hours, 1,1'-bis (diphenylphosphino) ferrocene (0.05 g) and tris (dibenzylidene acetone) dipaladium (0.032 g) were added. After an additional 24 hours, the reaction mixture was diluted with ethyl acetate (300 ml) filtered over a thin layer of silica gel and concentrated. The resulting product was purified by CombedyFlash® Rf from Teledyne ISCo using 2/8 (v / v) ethyl acetate / hexanes. A green solid (5.6 g) was recovered as the product. An NMR spectrum demonstrated that the product had a structure consistent with 3-phenyl-3- (4- (4-methoxyphenylpiperazin-1-yl) phenyl) -13,13-dimethyl-6-methoxy-7-cyano-3,13 dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 3:
[0300] The product from step 2 was added to a reaction flask containing methylene chloride (50 mL) and stirred at -78 ° C under the protection of dry nitrogen. Diisobutyl aluminum hydride (8.2 mL) was added to the reaction flask in one portion. The reaction was stirred at -78 ° C to -10 ° C for 2 hours and then dissipated with IM HCl (10 ml). The resulting mixture was then washed with water, dried over magnesium sulfate and concentrated. The resulting product was purified by CombedyFlash® Rf from Teledyne ISCO using 3/7 ethyl acetate / hexanes (v / v). A green solid (3.5 g) was recovered as the product. An NMR spectrum demonstrated that the product had a structure consistent with 3-phenyl-3- (4- (4-methoxyphenylpiperazin-1-yl) phenyl) -13,13-dimethyl-6-methoxy-7-formal-3,13 dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Step 4:
[0301] The product from step 3 (2.66 g), resorcinol (0.54 g), t-butanol (5 g), acetic acid (7 drops) and 1,4-dioxane (10 mLO were added to a reaction flask and kept at 80 ° C. Sodium chloride (0.69 g) in water (2 mL) was added in one portion. The reaction mixture was stirred for 10 minutes, poured into 500 ml of ice water at room temperature and the precipitated solid was collected by vacuum filtration The resulting product was purified by Teledyne ISCO's CombiFlash® Rf using 40 / 1-40 / 4 (v / v) of a methylene chloride / acetone mixture. NMR spectrum demonstrated that the recovered yellow solid (1.3 g) had a structure consistent with 3-phenyl-3- (4- (4-methoxyphenylpiperazinyl-yl) phenyl-13,13-dimethyl-6-methoxy-3, 13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran-7-carbocyclic. Step 5:
[0302] The product of step 4 (0.51 g), 4-hydroxybenzoic acid, 4- (4-pentyl-trans-cyclohexyl) phenyl ester (), 3 g), dicyclohexyl carbodiimide (0.15 g), 4- (dimethylamino) -pyridine (10 mg) and dichloromethane (5 ml) were added to a reaction flask and stirred at room temperature for 2 hours. A precipitate was formed and was removed by filtration and the filtered solution was concentrated and purified by Teledyne ISCO CombiFlash® Rf using 8/2 (v / v) hexane / ethyl acetate. An NMR spectrum demonstrated that the final product, a green solid (0.30 g) had a structure consistent with 3- (4- (4-methoxyphenyl) piperazin-1-yl) -3-phenyl-6-methoxy-7 - (4 - ((4-trans-4-propylcyclohexylOphenoxy) carbonyl) phenyloxycarbonyl) -13,13- dimethi1-3-13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b ] pyran. Example 55
Step 1:
[0303] The procedures in steps 3 and 4 of Example 13 were followed, except that in step 4, piperazine was used in place of 4- (piperazin-1-yl) phenol. NMR analysis of the product indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl) -7-piperzine-6-13-trimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3' : 3.4] naphtho [1,2- b] pyran. Step 2:
[0304] The product obtained from step 1 of Example 55, 3,3-bis (4-methoxyphenyl-7-piperazine-6,13-trimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 /, 3z: 3.4] naphtho [1,2-b] pyran (3.08 g) was dissolved in dichloromethane (40 mLO in a reaction flask. Pyridine (0.5 mL) was added followed by 4-bromophenyl chloroformate (0, 75 mLO and the resulting mixture was stirred for 4 hours at room temperature, poured into saturated sodium bicarbonate and stirred for 10 minutes.The aqueous solution was divided three times with ethyl acetate (100 ml), each time. The ethyl residue was combined, dried with sodium sulfate and concentrated in vacuo to provide an oily residue.The residue was passed through a silica gel coating and eluted with 4: 1 (v: v) of the hexane: ethyl acetate mixture The fractions containing the desired material were pooled and concentrated to provide a solid (0.8 g). NMR analysis of the solid indicated a structure that was consistent with 3,3-bis (4-me toxifenil) -7 - ((4-bromophenyloxycarbonyl) piperazine-6,13-trimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3, 4] naphtho [1,2- b] pyran . Step 3:
[0305] The product obtained from step 2, 3,3-bis (4-methoxyphenyl) -7 - ((4-bromophenyloxycarbonyl) piperazine-6,13-trimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3, 4] naphtho [1, 2-b] pyran and 4-biphenylboronic acid (0.25 g) were dissolved in 1,2-dimethoxyethane (20 mLO in a reaction flask. A solution of sodium bicarbonate (0.25 g), in water (3.5 mL) was added and the solution was degassed by nitrogen bubbles for 10 minutes, Tetrakis (triphenylphosphine) palladium (O) (0.03 g) was added and the solution was heated to reflux for 18 hours, cooled to room temperature and filtered through an auxiliary CELITE® filtrate bed.The filtrate was collected and concentrated to provide an oily residue.The residue was purified by column chromatography using 4: 1 (v: v) of a mixture of hexane: ethyl acetate as the eluent. Fractions containing the desired material were pooled and concentrated to provide an oil. The oil was dissolved in an amount minimum amount of dichloromethane and added for vigorous stirring of methanol. The resulting precipitate was collected by vacuum filtration and dried to provide a gray solid (0.45 g). NMR analysis of the gray solid indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl) - 7- (4 - ([1,1 ': 411 "-terphenyl) -4-yloxycarbonyl) piperazin-l- ila) - 6,13-dimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran Example 56

[0306] The procedures from steps 1 to 3 of Example 55 were followed, except that in step 2, 4-bromophenyl isocyanate was used in place of 4-bromophenyl chloroformate. NMR analysis of the purple solid indicated a structure that was consistent with 3,3-bis (4-methoxyphenyl) -7- (4 - ([1,1 ': 4', l "-terphenyl] -4-ylcarbamoyl) piperazin -1-yl) -6,13-dimethoxy-13-trifluoromethyl-3,13-dihydro-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran. Part 2 - Photochromic property test Part 2A - Preparation of the test square
[0307] The test was done with the compounds described in Examples 1-56, except that Examples 10, 20, 23, 38 and 48 were not tested. The test was carried out as follows: an amount of compound calculated to yield a 1.5x10-3 molar solution was added to a flask containing 50 grams of a mixture of 4 parts of ethoxylated Bisphenol A dimethacrylate (BPA 2EO DMA), 1 part of poly (ethylene glycol) 600 dimethacrylate, and 0.033 weight percent 2,2'-azobis (2-methyl propionitrile) (AIBN). Each compound was dissolved in the monomer mixture by gently stirring and heating, if necessary. After a clear solution was obtained, the sample was degassed in a vacuum oven for 5-10 minutes at 25 torr. Using a syringe, the sample was poured into a flat blade mold having an internal dimension of 2.2 mm +/- 0.3 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The mold was sealed and placed in a horizontal air flow, in a programmable oven to raise from 40 ° C to 95 ° C during an interval of 5 hours, maintained at 95 ° C for 3 hours, reduced to 60 ° C , for an interval of 2 hours and then maintained at 60 ° C for 16 hours. After curing, the mold was opened, and the polymer blade was cut into 2 inch (5.1 cm) test squares using a diamond saw blade. Part 2B - Response Test
[0308] Before the response test on the optical bench, the test squares in part 2A were conditioned for exposure to 365 nm ultraviolet light for 10 minutes at a distance of approximately 14 cm from the source, in order to pre-activate the photochromic compound in the samples. The UVA irradiation on the sample surface was measured with a Licor Model Li-1800 spectroradiometer and observed at 22.2 Watts per square meter. The samples were then placed under a halogen lamp (500 W, 120V) for about 10 minutes at a distance of about 36 cm from the lamp in order to whiten or inactivate the photochromic compounds in the samples. The illuminance in the sample was measured with the spectroradiometer and observed at 21.9 Klux. The samples were then kept in a dark medium for at least 1 hour before testing in order to cool and continue to fade to a milled state.
[0309] The optical bench was fitted with a Model # 67005 Newport 300 Watt Xenon arc lamp and a Model 69911 power supply from Vincent Associates (model VS25S2ZM0R3 with a VMM-D4 controller) and a computer controlled shutter from high-speed, a 3mm KG-2 Schott passband filter, which removed short-wavelength radiation, neutral density filters to attenuate the light from the Xenon lamp, a fused silica condensation lens for collimation beams, and a fused silica water cell / sample retainer for maintaining the sample temperature into which the test sample to be tested was inserted. The temperature in the water cell was controlled with a pumped water circulation system in which the water passes through copper springs (coil) that were placed in the reservoir of the refrigerant unit. The water cell was used to hold the test samples contained in sheets of fused silica on the front and back faces in order to eliminate the spectral change of the activation or monitoring of the light beams. The filtered water passing through the water cell was maintained at 72 ° F ± 2 ° F during the photochromic response test. A Newport Model 689456 Digital Exposure timer was used to control the intensity of the Xenon arc lamp during sample activation.
[0310] A broadband light source for monitoring response measures was positioned perpendicularly to a surface of the cell arrangement. The increased signal of the shortest visible wavelengths was obtained by collecting and combining the filtered light separately from a 100-Watt tungsten lamp (controlled via a Lambda UP60-14 constant voltage power source) with burnt tips, bifurcated with fiber optic cables. The light on one side of the tungsten halogen lamp was filtered with a Schott KG1 filter to absorb heat and a Hoya B-440 filter to allow the passage of wavelengths. The other side of the light was either filtered with a Schott KG1 filter or unfiltered. The light was collected by means of spotlight on each side of the lamp on a separate end of the burnt ends, of the bifurcated fiber optic cable, and subsequently combined in an emerging light source from the single end of the cable. A 4 "light tube was attached to the single end of the cable to ensure proper mixing. After passing through the sample, the light was refocused on a 2-inch integration and power sphere for an Ocean Optics S2000 spectrophotometer by fiber optic cables The software owned by Ocean Optics SpectraSuite and PPG were used to measure the response and control the operation of the optical bench.
[0311] The irradiation for the sample response test on the optical bench was established on the sample surface using an International Light Research Radiometer, Model IL-1700 with a detector system comprising a Model SED033 detector, filter and diffuser B. The exhibitor The radiometer output was corrected (adjustment of the factor values) against a Calibrador Licor 1800-02 Optical calibration in order to expose the exposure values representing the Watts per square meter of UVA. The irradiation at the sample point for the initial response test was adjusted to 3.0 Watts per square meter of UVA and approximately an illumination of 8.6 Klux. During the sample response test, if a sample darkened beyond an acceptable limit of detection capacity, the irradiation was decreased to 1.0 Watts per square meter of UVA or the sample was redone at half the concentration in the copolymer. The adjustment of the Xenon arc lamp output of the filtrate was accompanied by the increase or decrease of the lamp current through the controller and / or the addition or removal of neutral density filters in the light path. The test samples were exposed to light activation at 31 ° normal to their surface while perpendicular to the monitoring light.
[0312] The samples were activated at 73 ° F (22.8 ° C) controlled by the water cell for 30 minutes, then allowed to fade under ambient light conditions until the change in optical density of the faded sample activated at M of its state darker (saturated) or for a maximum of 30 minutes of fading.
[0313] The change in optical density (ΔOD) from the bleached state to the darkened state was determined by establishing the initial transmission, opening the shutter from the Xenon lamp to provide ultraviolet radiation to change the test lenses from the bleached state to an activated (that is, darkened) state. Data were collected at selected time intervals, measuring transmission in the activated state, and calculating the change in optical density according to the formula: ΔOD = log (% Tb /% Ta), where% Tb is the percentage of transmission in the bleached state,% Ta is the percentage of transmission in the activated stage and the logarithm is at base 10.
[0314] Àmax-vis in the visible light range is the wavelength in the visible spectrum in which the maximum absorption of the activated form of the photochromic compound occurs. The Xmax_vis was determined using the photochromic test square test on a Varian Cary 4000 UV-Visible spectrophotometer or comparable equipment.
[0315] ΔOD / Min, which represents the sensitivity of the photochromic compound's response to UV light, was measured over the first five (5) seconds of exposure to UV, then expressed on a per-minute basis. The optical saturation density (ΔOD in saturation) was taken under identical conditions except that the UV exposure was continued for a total of 30 minutes. Fading half-life is the time interval in seconds for ΔOD of the activated form of the photochromic compound in the square test to reach half of ΔOD measured after 30 minutes, or after saturation or near saturation has been achieved, at room temperature after removal of the light activation source, for example, by closing the shutter. The results are listed in Table 1. Table 1 Results of the photochromic performance test

Part 3 - Dichroic Property Test Part 3A - Preparation of the liquid crystal cell
[0316] The proportion of the average absorption of each of the compounds of Examples 1-56, except Examples 10, 12 and 27, was determined according to the CELL METHOD described below.
[0317] A cellular arrangement having the configuration given below was obtained from Design Concepts, Inc. Each of the cellular arrangements was formed from two opposite glass substrates that are spaced apart with a glass bubble spacer having a diameter of 20 microns +/- 1 micron. The inner surface of each of the glass substrates had a polyimide coating oriented thereon to provide the alignment of a liquid crystal material as discussed below. Two opposite edges of the glass substrates were sealed with an epoxy sealant, leaving a remainder at the two open edges for filling.
[0318] The gap between the two glass substrates of the cell arrangement was filled with a liquid crystal solution containing one of the compounds of the Examples above. The liquid crystal solution was formed by mixing the following components in the weight percentages listed below with heating, if necessary, to dissolve the test material.
Part 3B - Liquid crystal cell test
[0319] An optical bench was used to measure the optical properties of the cell and to derive the absorption ratios for each of the test materials. The filled cellular array was placed on the optical bench with an activation light source (a 300-Watt Xenon Oriel Model 66011 arc lamp purchased from Vincent Associates (model VS25S2ZM0R3 with VMM-D4 controller) high speed computer controlled shutter which closed momentarily during data collection so that wandering light would not interfere with the data collection process, a 3 mm KG-1 Schott bandpass filter, which removed short wavelength radiation, a neutral density to attenuate the intensity and a condensation lens of the collimation beam) positioned at an angle of 30 ° to 35 ° of incidence on the surface of the cell arrangement.
[0320] A broadband light source for monitoring the response measurement was positioned perpendicular to the surface of the cell arrangement. The increased signal of the shorter visible wavelengths was obtained by collecting and combining the filtered light separately from a 100-Watt tungsten halogen lamp (controlled by a Lambda UP60-14 constant voltage power source) with burnt, forked ends of fiber optic cables. The light on one side of the tungsten halogen lamp was filtered with a Schott KG1 filter to absorb heat and a Hoya B-440 filter to allow the passage of shorter wavelengths. The other side of the light was both filtered with a Schott KG1 filter and unfiltered. The light was collected by means of spotlight on each side of the lamp on a separate end of the burnt ends, of the bifurcated fiber optic cable, and subsequently combined in an emerging light source from the single end of the cable. A 4 "light tube was attached to the single end of the cable to ensure proper mixing.
[0321] The polarization of the light source was achieved by passing the light from the single end of the cable through a Moxtek Pro-Flow Polarizer, maintained in a computer-driven motorized rotation stage (Model M-061-PD from Polytech , PI). The emission monitoring was adjusted so that a polarization plane (0o) was perpendicular to the plane of the optical bench table and the second polarization plane (90 °) was parallel to the plane of the optical bench table. The samples were run in air, at room temperature (73 ° F ± 0.3 ° F, or better (22.8 ° C ± 0.1 °)) maintained by the laboratory's air conditioning system or an air cell of controlled temperature.
[0322] To conduct the measurement, the cell arrangement and coating cell were exposed to 6.7 W / m2 of UVA from the activation light source for 5 to 15 minutes to activate the test material. An International Light Research radiometer (Model IL-1700) with a detector system (Detector Model SED033, filter B, and diffuser) was used to check the exposure before each test. The light from the monitoring source that was polarized at 0o of the polarization plane was then passed through the coated sample and focused on a 1 "integration sphere, which was connected to an Ocean Optics S2000 spectrophotometer using a function fiber optic cable The spectral information, after passing through the sample, was collected using Ocean Optics SpectraSuite and PPG proprietary software. Although the photochromic-dichroic material was activated, the polarizer position was rotated back and taken to polarize the light from the monitoring light source to 90 ° from the polarization plane and back. Data were collected for approximately 10 to 300 seconds, at 5-second intervals, during activation. For each test, the rotation of the polarizers was adjusted to collect the data in the following sequence of the polarization planes: 0o, 90 °, 90 °, 0 °, etc.
[0323] The absorption spectra were obtained and analyzed for each cell arrangement using the Igor Pro software (available from WaveMetrics). The change in absorption in each polarization direction for each cell arrangement was calculated by subtracting time 0 (that is, inactivated) the absorption measure for the cell arrangement at each wavelength tested. The average absorbance values were obtained in the region of the activation profile where the response of the Examples above was saturated or close to saturated (that is, the regions where the measured absorbance did not increase or did not increase significantly in relation to time) for cellular arrangement by mean absorbance in each time interval in this region. The average absorbance values in a predetermined range of the wavelength corresponding to Àmax_vis +/- 5 nm were extracted in the 0o and 90 ° polarization planes, and the absorption ratio for each wavelength in this range was calculated by dividing the absorbance. higher mean through lower mean absorbance. For each wavelength extracted, 5 to 100 data points were averaged. The average absorption ratio for the test material was then calculated by averaging these individual absorption ratios.
[0324] For the examples listed in Table 2, the procedures described above were performed at least twice. The tabulated values for the average absorption ratio represent an average of the results obtained from the runs measured at the indicated wavelength. The results of these tests are shown in table 2 below. Table 2 Data from the Absorption Proportion (RA) Test

Part 3C - Preparation of coatings for lined liquid crystal lined substrates Part 3C-1 Preparation of the primer
[0326] In a 250 ml amber glass bottle equipped with a magnetic stir bar, the following materials were added in the order and in the quantities indicated: Polyacrylate polyol (15.2334 g) (Composition D of Example 1 in the patent US No. 6,187,444, whose description of the polyol is incorporated herein by reference); Polyalkenylenecarbonate polyol (40,0000 g) T-5652 from Asahi Kasei Chemicals; DESMODUR® PL 340 (33.7615 g) from Bayer Material Science; TRIXENE® BI 7960 (24.0734 g) from Baxenden); Polyether modified polydimethylsiloxane (0.0658 g) BYK®-333 from BYK-Chemie GmbH); King Industries' KKAT® 348 Urethane (0.8777 g) catalyst; y-Glycidoxypropyltrimethoxysilane (3,5109 g) A-187 from Momentive Performance Materials; The light stabilizer (7.8994 g) TINUVIN® 928 from Ciba Specialty Chemicals; and 1-Methyl-2-pyrrolidinone (74.8250 g) from Sigma-Aldrich.
[0327] The mixture was stirred at room temperature for 2 hours to yield a solution having 50 weight percent of final solids based on the total weight of the solution. Part 3C-2 - Preparation of the alignment of the coating components
[0328] The photoalignment coating component, Staralign 2200CP10, was purchased from Ventico and diluted in a 2% solution with cyclopentanone solvent. The rubberized alignment coating component was a 10 percent by weight solution of polyvinyl alcohol (PVA) having a molecular weight of about 61,000 g / mol in water. Part 3C-3 - Liquid Crystal Coating Components and Formulations
[0329] The liquid crystal monomers (LCM) used for solution of the monomer include the following elements:
[0330] LCM-1 is 1- (6- (6- (6- (6- (6- (6- (6- (6- (8- (4- (4- (4- (8- acryloyloxyhexilloxy)) benzoyloxy) phenyloxycarbonyl) phenoxy) octyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyloxy) -6-oxohexyl) -6-oxohexyl) ol, which was prepared according to the procedures described in Example 17, of the North American publication No .: US 2009/0323011, whose description of the liquid crystal monomer has been incorporated herein by reference.
[0331] LCM-2 is commercially available on RM257 reported as 4- (3-acryloyloxypropyloxy) -benzoic acid, 2-methyl-1,4-phenylene ester, available from EMD Chemicals, Inc., having the molecular formula of C33H32O10 .
[0332] LCM-3 is commercially available from RM105 reported as 4-methoxy-3-methylphenyl-4- (6- (acryloyloxy) hexyloxy) benzoate, available from EMD Chemicals, Inc., having the molecular formula of C23H26O6.
[0333] LCM-4 is commercially available as RM82 reported as 2-methyl-1,4-phenylene bis (4- (6- (acryloyloxy) hexyloxy) benzoate), available from EMD Chemicals, Inc., having the molecular formula of CagH ^ Oio.
[0334] The liquid crystal coating (LCCF) formulation was prepared as follows: in an appropriate vial, containing a mixture of anisole (3.4667 g) and additive BYK -346 (0.0347 g, reported to be a poly-dimethyl- polyether modified siloxian, available from BYK Chemie, USA), LCM-1 (1.3 g), LCM-2 (1.3 g), LCM-3 (1.3 g), LCM-4 (1 , 3 g), 4-methoxyphenol (0.0078 g), and IRGACURE® 819 (0.078 g, a photoinitiator, available from Ciba-Geigy Corporation) and the Example compound listed in Table 3 at a concentration of 6.3 mmol per 100 g of LCCF. When the combination of Example 1 and Example 25 were tested together, each was used at a concentration of 3.15 mmol per 100 g of LCCF. The resulting mixture was stirred for 2 hours at 80 ° C and cooled to about 26 ° C. Part 3C-4 - Transition layer coating formulation (TLCF)
[0335] The TLCF was prepared as follows:
[0336] In a 50 ml amber glass bottle equipped with a magnetic stir bar, the following materials were added: Hydroxy Methacrylate (1.242 g) from Sigma-Aldrich; Neopentyl glycol diacrylate (13.7175 g) SR247 from Sartomer; Trimethylolpropane trimethacrylate (2.5825 g) SR350 from Sartomer; DESMODUR® PL 340 (5.02 g) from Bayer Material Science; IRGACURE®-819 (0.0628 g) from Ciba Specialty Chemicals; DAROCUR® TPO (0.0628 g; from Ciba Specialty Chemicals, Polybutyl Acrylate (0.125 g), 3-Aminopropylpropyltrimethoxysilane (1.4570 g) A-1100 from Momentive Performance Materials; and Anhydrous Ethanol 200 with absolute proof (1.4570 g) from Pharmaco - Aaper.
[0337] The mixture was stirred at room temperature for 2 hours. Part 3C-5: Protective coating formulation (PCF)
[0338] The PCF (hard coating) was prepared as follows: Charge 1 was added to a dry beaker and placed in an ice bath at 5 ° C with stirring. Charge 2 was added and an exothermic raised the temperature of the reaction mixture to 50 ° C. The temperature of the resulting reaction mixture was cooled to 20-25 ° C and Charge 3 was added with stirring. Charge 4 was added to adjust the pH by about 3 to about 5.5. Charge 5 was added and the solution was mixed for half an hour. The resulting solution was filtered through a nominal 0.45 micron capsule filter and stored at 4 ° C until use. Load 1 Glycidoxypropyltrimethoxysilane 32.4 grams methyltrimethoxysilane 345.5 grams Load 2
[0339] The solution of deionized water (Dl) with nitric acid (nitric acid 1 g / 7000 g) 292 grams Charge 3 DOWANOL® PM solvent 228 grams Charge 4 TMAOH (25% tetramethylammonium hydroxide in methanol) 0.45 gram Charge 5 BYK®-306 surfactant 2.0 grams Part 3C-6 - Procedures used to prepare the coating cells reported in Table 3 Part 3C-6A - Substrate Preparation
[0340] Square substrates measuring 5.08 cm by 5.08 cm by 0.318 cm (2 inches (in.) By 2 inches by 0.125 inches) prepared from the CR-39 monomer were obtained from Homalite, Inc. Each prepared substrate of the CR-39 monomer was cleaned by drying with a tissue soaked with acetone and dried with an air stream.
[0341] Each of the aforementioned substrates was treated with a corona by passing it on a conveyor belt in a Tantec EST Series No. 020270 System, HV 2000 Power Generator series of corona treatment equipment with a high voltage transformer. The substrates were exposed to the corona generated by 53.99 KV, 500 Watts while traveling on a conveyor belt at a speed of 3 feet / minute. Part 3C-6B - Priming procedure
[0342] The primer solution was applied to the test substrates by spindle coating on a portion of the test substrate surface by dispersing approximately 1.5 mL of the solution and rotating the substrates at 500 revolutions per minute (rpm) for 3 seconds, followed by 1,500 rpm for 7 seconds, followed by 2,500 rpm for 4 seconds. A spinning processor from Laurell Technologies Corp. (WS-400B-6NPP / LITE) was used for the spin coating. Then, the coated substrates were placed in an oven maintained at 125 ° C for 60 minutes. The coated substrates were cooled to about 26 ° C. The substrate was treated with corona by passing a conveyor belt in Tantec EST Systems No. No. 020270 of the HV 2000 power generator in the series of corona treatment equipment with a high voltage transformer. The dry primer layer was exposed to the corona generated by 53.00 KV, 500 Watts while traveling on the conveyor belt at a speed of 3 feet / minute. Part 3C-6C - Coating procedure for alignment materials
[0343] The 2% by weight solutions of Staralign 2200 and the 10% by weight PVA solution prepared in part 3C-2 were individually applied to the test substrates by spin coating on a portion of the surface of the test substrates by dispersion of approximately 1.0 mL of the solution and rotation of the substrates at 800 revolutions per minute (rpm) for 3 seconds, followed by 1,000 rpm for 7 seconds, followed by 4,000 rpm for 4 seconds. A spinning processor from Laurell Technologies Corp. (WS- 400B-6NPP / LITE) was used for coating rotation. Then, the coated substrates were placed in an oven maintained at 120 ° C for 30 minutes. The coated substrates were cooled to about 26 ° C.
[0344] The dry photo-alignment layer (PAL) on each of the substrates was at least partially ordered by exposure to linearly polarized ultraviolet radiation using a DYMAX® UVC-6 UV / DYMAX® Corp. carrier system, having a source 400 Watt power. The light source was oriented so that the radiation was linearized polarized in a plane perpendicular to the substrate surface. The amount of ultraviolet radiation that each photo-alignment layer was exposed for measurement using an EIT Inc. Power Puck ™ high energy UV radiometer (Series No. 2066) and was as follows: 0.121W / cm2 UVA and 5.857 J / cm2; UVB 0.013 W / cm2 and 0.072 J / cm2; UVC 0 W / cm2 and 0 J / cm2; and UW 0.041 W / cm2 and 1.978 J / cm2. After ordering at least a portion of the photo-orientable polymer network, the substrates were cooled to about 26 ° C and kept covered. Part 3C-6D - Coating procedure for liquid crystal coating formulations
[0345] The liquid crystal coating (LCCF) formulations described in part 3C-3 were each coated by spin at a rate of 300 revolutions per minute (rpm) for 6 seconds, followed by 800 rpm for 6 seconds on at least partially ordered alignment of part 3C-6C on the test substrates. Each coated square substrate was placed in an oven at 50 ° C for 20 minutes and each coated lens was placed in an oven at 50 ° C for 30 minutes. Then, the substrates were cured under an ultraviolet lamp in the BS-03 Irradiation chamber of Dr. Grõbel UV-Elektronik GmbH in an atmosphere of nitrogen for 30 minutes at a peak intensity of 11-16 Watts / m2 of UVA. After curing, the coated substrates were completed at 105 ° C for 3 hours. Part 3C-6E - Coating procedure for the transition layer
[0346] The transition layer solution prepared in Part 3C-4 was coated by spinning at a rate of 1,400 revolutions per minute (rpm) for 7 seconds on the cured LCCF coated substrate. The lenses were then cured under an ultraviolet lamp in the BS-03 Irradiation Chamber of Dr. Grõbel UV-Elektronik GmbH in an atmosphere of nitrogen for 30 minutes at a peak intensity of 11-16 Watts / m2 of UVA. After curing, the coated substrates were completed at 105 ° C for 3 hours. Part 3C-6F - Coating procedure for protective coating (Hard coating)
[0347] The hard coating solution prepared in Part 3C-5 was coated by spinning at a rate of 2,000 revolutions per minute (rpm) for 10 seconds on the coated substrates of the cured line layer. After curing, the substrates were completed at 105 ° C for 3 hours.
[0348] The absorption rate (AR) for the different coating cells prepared with the Examples of the present invention in the liquid crystal coating formulation (LCCF) is reported in Table 3. The examples were formulated in the LCCF and applied to the layers of alignment that were either photo-aligned layers (PAL) or rubber-lined layers (R-AL). Other coatings were applied to the substrate and / or the LCCF layer. An "x" in Table 3 indicates that the coating was present in the pile of coatings on the substrates. The absorption proportions were determined for each coating stack. The low AR reported for Examples 30 having an R-AL, transition layer and hard coating may be due to poor alignment of the example in the rubber PVA coating. Table 3 Result of the absorption ratio for different piles of


[0349] The present invention has been described with reference to the specific details of the particular embodiments thereof. Such details are not intended to be related to the limitations of the scope of the invention except when extending those details which are included in the claims of the present application.

权利要求:
Claims (22)
[0001]
1. Photochromic compound, characterized by the fact that it is represented by the following formula I:
[0002]
2. Compound according to claim 1, characterized by the fact that: (A) ring A is substituted aryl; (B) (i) R1, for each m, be independently selected from, La, formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, alkyl or substituted alkyl, substituted boric acid, halogen, cycloalkyl or cycloalkyl ether, aryl or substituted aryl, substituted alkoxy or alkoxy, substituted heteroalkyl or heteroalkyl, substituted heterocycloalkyl or heterocycloalkyl and substituted amino or amino; and (ii) R2, for each n is independently selected from formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, arylcarbonyl, aryloxycarbonyl, substituted alkyl or alkyl, substituted boric acid ether, halogen, cycloalkyl or cycloalkyl, aryl or substituted aryl , substituted alkoxy or alkoxy, substituted heteroalkyl or heteroalkyl, substituted heterocycloalkyl or heterocycloalkyl and substituted amino or amino; (C) R3 and R4 are each independently selected from hydrogen, hydroxy and chiral or non-chiral groups selected from substituted heteroalkyl or heteroalkyl, substituted alkyl or alkyl, substituted aryl or aryl, substituted cycloalkyl or cycloalkyl, halogen , amino or substituted amino, carboxy, alkylcarbonyl, alkoxycarbonyl, alkoxy or alkoxy aminocarbonyl, or one of R3 and R4 is a bond, one of R3 and R4 is oxygen, and R3 and R4 together form oxo, or R3 and R4 together with any intervention atom form a group selected from substituted cycloalkyl or cycloalkyl, and substituted heterocycloalkyl or heterocycloalkyl; (D) B and B 'are each independently selected from L3, hydrogen, halogen, a chiral or non-chiral group, selected from substituted alkyl or alkyl, substituted alkenyl or alkenyl, substituted heteroalkyl or heteroalkyl, aryl or aryl substituted, substituted heteroaryl or heteroaryl, and substituted cycloalkyl or cycloalkyl, or B and B 'taken together with any intervention atom form a group selected from substituted cycloalkyl or cycloalkyl and substituted heterocycloalkyl or heterocycloalkyl; and (E) Li, La are each independently selected from a chiral or non-chiral prolongation group representing by formula II, where, (i) Qi, Q2r θ Q3 are each, independently, for each occurrence one divalent group selected from substituted aryl or aryl, substituted heteroaryl or heteroaryl, substituted cycloalkyl or cycloalkyl, and substituted heterocycloalkyl or heterocycloalkyl, each substituent being independently selected from P, liquid crystal mesogens, halogen, poly (C1-C12 alkoxy), C1-C12 alkoxycarbonyl, C1-C12 alkylcarbonyl, perfluoro (C1-12) alkoxy, perfluoro (C1-C12) alkoxycarbonyl, perfluoro (C1-12) alkylcarbonyl, C1-8 alkyl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy Straight-chain C1-C12 and branched-chain C1-C12 alkyl, said straight-chain C1-C12 alkyl and branched-chain C1-C12 alkyl are mono-substituted with a group selected from halogen, and C1 alkoxy -C12, or wherein said straight chain C1-C12 alkyl and branched chain C1-C12 alkyl are poly-substituted with at least two independently selected groups selected from halogen; (ii) c, d, e, and f are each independently an integer selected from 1 to 10; and SI, S2, S3, S4, and S5 are each independently, for each occurrence, a spacer unit chosen from: (1) substituted or unsubstituted alkylene, substituted or unsubstituted haloalkylene, -Si (CH2) g-, and - (Si [(CH3) 2] O) h_, where g for each occurrence is independently chosen from an integer from 1 to 10; h for each occurrence is independently chosen from an integer from 1 to 8; and said substituents for alkylene and haloalkylene are independently selected from C1-C12 alkyl, C3-C7 cycloalkyl and phenyl; (2) —N (Z) -, -C (Z) = C (Z) -, and a unique bond, where Z for each occurrence is independently selected from hydrogen, C1-C12 alkyl, C3-C7 cycloalkyl and phenyl; and (3) -O-, -C (= 0) -, -C = C-, -N = N-, -S-, -S (= O) -, providing that when two spacer units comprising hetero atoms are connected together, the spacer units are linked with the hetero atoms of the first spacer unit not directly linked to the hetero atoms of the second spacer unit; and providing that when Si is linked to formula I and S5 it is linked to P, Si and S5 are each linked with two heteroatoms not directly linked to each other; (iii) P for each occurrence is selected from: hydroxy, amino, C2-C12 alkenyl, silyl, siloxy, (tetrahydro-2H-pyran-2-yl) oxy, isocyanate, acryloyloxy, methacryloyloxy, epoxy, carboxylic acid, carboxylic ester , C1-2 alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C1-2C2) alkyl, C1-2 alkyl, C1-2 alkoxy, ethylene, acryloyl, C1-2 alkyl, C1-2 alkyl, methacryloyl, methacryloyloxy (C1-2) alkyl, oxyethanyl, glycidyl, vinyl ether, siloxane derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, and chiral or non-chiral monovalent or divalent groups substituted or unsubstituted, chosen from steroidal radicals, where each substituent is independently chosen from C 1 -C 2 alkyl, C 1 -C 2 alkoxy, amino, C 3 -C 7 cycloalkyl, C 1 -C 12 alkoxy (C-Ci 2) alkyl, or fluoro (C1 -C2) alkyl, or P is a structure having 2 to 4 groups the reactives; and (iv) d ', e', and f 'are each independently chosen from 0, 1, 2, 3, and 4, providing that a sum of d' + and '+ f' is at least 2.
[0003]
3. Compound according to claim 2, characterized by the fact that: (B) (i) R1, for each m, is independently selected from, L2, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, substituted alkyl or alkyl, boric acid ester , halogen, substituted cycloalkyl or cycloalkyl, substituted aryl or aryl, substituted alkoxy or alkoxy, substituted heterocycloalkyl or heterocycloalkyl and substituted amino or amino; and (ii) R2, for each n, is independently selected from alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkyl or substituted alkyl, substituted boric acid, halogen, cycloalkyl or cycloalkyl ester, substituted aryl or aryl, substituted alkoxy or alkoxy, heterocycloalkyl or substituted heterocycloalkyl and substituted amino or amino; (C) R3 and R4 are each independently selected from hydrogen, hydroxy and chiral groups selected from substituted heteroalkyl or heteroalkyl, substituted alkyl or alkyl, substituted aryl or aryl, cycloalkyl or substituted cycloalkyl, halogen, carboxy, alkylcarbonyl, alkoxycarbonyl alkoxy or alkoxy aminocarbonyl, or one of R3 and R4 is a bond, one of R3 and R4 is oxygen, and R3 and R4 together form oxo, or R3 and R4 together with any intervention atom form a substituted cycloalkyl or cycloalkyl; (D) B and B 'are each independently selected from L3, hydrogen, chiral groups selected from substituted alkyl or alkyl, substituted alkenyl or alkenyl, substituted aryl or aryl, substituted heteroaryl or heteroaryl, and substituted cycloalkyl or cycloalkyl, or B and B 'being taken together with any interfering atom to form a group selected from cycloalkyl or substituted cycloalkyl; and (E) Li, La and L3 are each independently selected from the said chiral or non-chiral prolongation group representing by formula II, where, (i) Qi, Q2, and Q3 are each, independently, for each occurrence is a divalent group selected from substituted aryl or aryl, substituted heteroaryl or heteroaryl, substituted cycloalkyl or cycloalkyl, and substituted heterocycloalkyl or heterocycloalkyl, each substituent being independently selected from P, alkoxycarbonyl Ci-Ce, perfluoro (Ci-Cg) alkoxy , C3-C7 cycloalkyl, C3-C7 cycloalkoxy, straight-chain C1-Cg alkyl and branched-chain C1-C6 alkyl, while the mentioned straight-chain C1-Cg alkyl and branched-chain alkyl are mono-substituted with a selected group of halogen and C1-C12 alkoxy, or the aforementioned straight chain Ci-Cg alkyl and branched chain Ci-Cg alkyl are poly-substituted with at least two independently selected hal groups The genius; (ii) c, d, e, and f are each independently an integer chosen from 1 to 10; and Si, S2, S3, S4, and S5 are each independently, for each occurrence, a spacer unit selected from: (1) substituted or unsubstituted alkylene; (2) —N (Z) -, -C (Z) = C (Z) -, and a single bond, where Z for each occurrence is independently selected from hydrogen, C1-Cg alkyl; and (3) -0-, -C (= 0) -, -C = C-, and -N = N-, -S-; providing that when two spacer units comprising hetero atoms are linked together, the spacer units are linked with the hetero atoms of the first spacer unit not directly linked to the hetero atoms of the second spacer unit; and providing that when Si is linked to formula I and S5 it is linked to P, Si and S5 are each linked with two heteroatoms not directly linked to each other; (iii) P for each occurrence is independently selected from: hydroxy, amino, Cs-Cg alkenyl, siloxy, (tetrahydro-2H-pyran-2-yl) oxy, isocyanate, acryloyloxy, methacryloyloxy, epoxy, carboxylic acid, ester carboxylic acid, C1-Cg alkyloxycarbonyloxy, hydrogen, aryl, hydroxy (C-Cg) alkyl, C1-Cg alkyl, ethylene, acryloyl, acryloyloxy (C1-C12) alkyl, oxyethanyl, glycidyl, vinyl ether, siloxane derivatives, and groups monovalent or divalent chiral or non-chiral substituted or unsubstituted, chosen from steroidal radicals, where each substituent is independently chosen from C1-Cε alkyl, C1-Cg alkoxy, amino, C3-C7 cycloalkyl.
[0004]
4. Compound according to claim 3, characterized by the fact that: (B) (1) R1, for each m, is independently selected from, methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3, and (ii) R2, for each n, is independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3; (C) R3 and R4 are each, independently, selected from methyl, ethyl, propyl and butyl; (D) B and B 'are each independently selected from phenyl substituted with one or more selected groups, regardless of aryl, heteroaryl, alkyl, alkenyl, alkynyl, alkoxy, halogen, amino, alkylcarbonyl, carboxy, and alkoxycarbonyl; and (E) Li is selected from said chiral or non-chiral prolongation group represented by Formula II, where: (i) Qi is unsubstituted aryl; Q2 for each occurrence is independently chosen from aryl or substituted aryl; Q3 is cycloalkyl or substituted cycloalkyl; (ii) and for each occurrence it is 1; f is 1; S3 for each occurrence is a single link; S4 is a single link; and S5 is - (CH2) g-, where g is from 1 to 20; (iii) P is hydrogen; and (iv) e 'is 1 or 2; and f 'is 1.
[0005]
5. Compound according to claim 1, characterized by the fact that said compound is represented by the following formula Ia:
[0006]
6. Compound according to claim 1, characterized by the fact that: (B) (i) R1, for each m, is independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3, and ( ii) R2, for each n, is independently selected from methyl, ethyl, bromine, chlorine, fluorine, methoxy, ethoxy and CF3; (C) R3 and R4 are each, independently, selected from methyl, ethyl, propyl and butyl; and (D) B and B 'are each independently selected from substituted phenyl with one or more selected groups, regardless of aryl, heteroaryl, heterocycloalkyl, alkyl, alkenyl, alkynyl, alkoxy, halogen, amino, alkylcarbonyl, carboxy and alkoxycarbonyl .
[0007]
7. Photochromic composition, comprising a compound, as defined in claim 1, characterized by the fact that said compound is a photochromic compound and, optionally, at least one other photochromic compound, the said composition comprising: (a) a photochromic compound single; (b) a mixture of photochromic compounds; (c) a material comprising at least one photochromic compound; (d) a material to which at least one photochromic compound is chemically bonded; (e) the material (c) or (d) further comprising a coating to prevent contact of at least one photochromic compound with the external materials; (f) a photochromic polymer; or (g) mixtures thereof.
[0008]
8. Photochromic composition, comprising at least one compound, as defined in claim 1, characterized in that said compound is a photochromic compound incorporated within at least a portion of an organic material, said organic material being a polymeric material, a material oligomeric, monomeric material or a mixture or combination thereof.
[0009]
9. Photochromic composition, according to claim 8, characterized in that said polymeric material comprises liquid crystal materials, self-shaped materials, polycarbonate, polyamide, polyamide, poly (meth) acrylate, polycyclic alkene, polyurethane, poly ( urea) urethane, polythiourethane, politic (urea) urethane, polyol (allyl carbonate), cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyalkene, polyalkylene vinyl acetate , poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinyl formal), poly (vinyl acetal), poly (vinylidene chloride), poly (ethylene terephthalate), polyester, polysulfone, polyolefin, copolymers thereof, and / or mixtures thereof.
[0010]
10. Photochromic composition, according to claim 8, characterized in that the photochromic composition also comprises at least one additive chosen from dyes, alignment promoters, antioxidants, kinetic-improving additives, photoinitiators, thermal initiators, polymerization inhibitors, solvents , light stabilizers, heat stabilizers, release agents, rheology control agents, leveling agents, free radical purifiers, gelatinizers, and adhesion promoters.
[0011]
11. Photochromic composition, according to claim 8, characterized by the fact that it comprises a coating composition chosen from liquid crystal materials, self-forming materials and film-forming materials.
[0012]
12. Photochromic article, comprising a substrate and a compound, as defined in claim 1, characterized in that said compound is a photochromic compound connected to at least a portion of a substrate.
[0013]
13. Article according to claim 12, characterized by the fact that it comprises an optical element, said optical element being at least one of an ophthalmic element, an display element, a window, a mirror, a packaging material and an element active or passive liquid crystal cell.
[0014]
14. Article according to claim 13, characterized in that the ophthalmic element comprises corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses or viewfinders.
[0015]
15. Article according to claim 12, characterized in that the substrate comprises a polymeric material and the photochromic material is incorporated within at least a portion of the polymeric material.
[0016]
16. Article according to claim 15, characterized in that the photochromic material is mixed with at least a portion of the polymeric material, bound to at least a portion of the polymeric material, and / or absorbed in at least a portion of the material polymeric, the photochromic article comprises a coating or film connected to at least a portion of the substrate, said coating or film comprising the photochromic material.
[0017]
17. Article, according to claim 16, characterized by the fact that said substrate is formed from organic materials, inorganic materials, or combinations thereof.
[0018]
18. Article according to claim 12, characterized in that it further comprises at least one addition of at least one coating chosen from photochromic coatings, anti-reflective coatings, linearly polymerized coatings, transition coatings, primer coatings, adhesive coatings, reflective coatings, anti-fog coatings, oxygen barrier coatings, ultraviolet light absorbing coatings, and protective coatings.
[0019]
19. Photochromic article, comprising at least one photochromic compound, as defined in claim 1 and characterized by the fact that it also comprises: - a substrate, at least a partial coating of an alignment material; - at least a partial coating of an alignment material; - at least an addition of at least part of the coating of a liquid crystal material.
[0020]
20. Photochromic article, according to claim 19, characterized by the fact that it also comprises at least one additive chosen from dichroic dyes, non-dichroic dyes, alignment promoters, antioxidants, kinetic-improving additives, photoinitiators, thermal initiators, polymerization inhibitors , solvents, light stabilizers, heat stabilizers, release agents, rheology control agents, leveling agents, free radical purifiers, gelatinization and adhesion promoters, or at least one primer coating, transition coating, protective coating or a combination of them.
[0021]
21. Article according to claim 20, characterized in that the transition coating comprises an acrylate polymer, the protective coating comprising at least one siloxane derivative, or the at least one primer coating comprising a polyurethane.
[0022]
22. Photochromic article, according to claim 19, characterized by the fact that the substrate is selected from glass, quartz, and polymeric organic materials, with at least one alignment material comprising a polymeric network orientable by exposure to at least one from: a magnetic field, an electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation and a shear force, or the aforementioned liquid crystal material is a liquid crystal polymer.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-03-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-08-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/928,681|2010-12-16|

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US12/928,681|US8518546B2|2003-07-01|2010-12-16|Photochromic compounds and compositions|

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PCT/US2011/062783|WO2012082383A1|2010-12-16|2011-12-01|Photochromic compounds and compositions|

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