functionalized dye, hair coloring method, kit and dye composition

专利摘要:
FUNCTIONAL DYE, METHOD FOR COLORING HAIR, KIT AND DYE COMPOSITION. The present invention relates to dyes, compositions comprising dyes and methods for using them.
公开号:BR112012018329B1
申请号:R112012018329-0
申请日:2010-12-21
公开日:2020-11-24
发明作者:David Puerta；Lorna Nagamoottoo-Casse；Jana Lewis
申请人:Living Proof, Inc.；
IPC主号:

专利说明:

RELATED REQUESTS
[001] This application claims priority to United States Provisional Patent Application No. 61 / 288,668, filed on December 21, 2009, United States Provisional Patent Application No. 61 / 288,676, filed on December 21, 2009, and United States Provisional Patent Application No. 61 / 415,251, filed on November 18, 2010. The total contents of the preceding applications are therefore incorporated by reference. BACKGROUND
[002] According to the International Cosmetic Ingredient Dictionary and Handbook, Decima Ed., 2004 (here incorporated by reference in its entirety), hair dyes (for example, materials that give hair color) are classified as temporary, semi-permanent, permanent, or progressive.
[003] Temporary hair dyes include color rinses, which provide color that lasts until the first shampoo application. The ingredients that give temporary color can have a positively high molecular weight and are not able to penetrate the hair shaft. These materials are simply deposited on the hair fiber, and are removed by applying subsequent shampoo.
[004] Direct dyes generally provide color through shampoo application. These materials are either pre-formed colored compounds of low molecular weight that can penetrate the hair shaft to some extent, or colored compounds of great molecular weight that interact with the surface of the hair fiber, via non-covalent interactions.
[005] Oxidizing dyes are considered permanent hair coloring preparations, as they provide color that is not substantially removed by shampoo application. The oxidizing Colorado involves the deposition of an essentially colorless intermediate, and of a coupling agent within the hair fiber. In the presence of an oxidizing agent, usually hydrogen peroxide, these chemicals form a series of complex colored dyestuffs within the hair fiber. Colorado progressive hair preparations are oxidizing hair colors that develop gradually through repeated applications.
[006] While oxidizing dyes may be preferred due to their long-lasting Colorado, they do have some disadvantages in targeting coloring preparations. For example, direct dyes are more vibrant and provide a more "pure" color than oxidizing dyes. It will be appreciated by those skilled in the art that the "pure" color of direct dyes is due to the generally higher extinguishing coefficients and narrower peak widths at half height than oxidizing dyes. Oxidizing dyes can also participate in later reactions during the application process which can affect the final color of the hair, and act less well on damaged hair. Therefore, it would be desirable to develop non-oxidizing dyes with the color and vibration of a direct dye and the long-lasting color fastness of an oxidizing dye that optionally acts better on damaged hair than on undamaged hair. SUMMARY OF THE INVENTION
[007] The present invention is based, at least in part, on the discovery that certain functionalized non-oxidizing dyes exhibit enhanced color fastness and vibration compared to other dyes (for example, oxidizing dyes and / or direct dyes). Therefore, it is an object of the present invention to provide such dyes and compositions thereof, as well as methods of using such dyes and kits comprising them.
[008] Consequently, in one aspect, the present invention provides a functionalized dye comprising at least one chromophor and a color fastness portion, wherein the chromophor is attached to the color fastness portion by a binder, wherein said functionalized dye they have an enhanced color fastness compared to a non-functionalized direct dye.
[009] In some embodiments, the dye is a compound of formula la: C-L-F (la)
[0010] when
[0011] C and a chromophor; Lea binder; and
[0012] F is a portion of color fastness, or a cosmetically acceptable salt thereof.
[0013] In some embodiments, the color fastness portion comprises at least one hydrogen bond donor and at least one hydrogen bond acceptor.
[0014] In some embodiments, the binder and the color fastness portion comprise two or more hydrogen bond donors and at least one hydrogen bond acceptor.
[0015] In some embodiments, the hydrogen bond acceptor is a tertiary amine.
[0016] In some embodiments, the hydrogen bond donor is a secondary amine.
[0017] In some embodiments, C and formula Hz:

[0018] wherein R26a is attached to a ligand L; and
[0019] R26b, R26c, R26d, R26e and R26f are each independently hydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO2, CF3, SO3H, CN, carbonyl, carbonyl, alkoxycarbonyl, or a portion of arildiazene.
[0020] In some embodiments, L and of formula (III):

[0021] where
[0022] L covalently binds chromophore C, via the left side of formula III to the portion of color fastness F, via the right side of formula HI;
[0023] a, b, c, d, e, and f are each independently an integer from 0-2, with the proviso that at least one of a, b, c, d, e and f is different from 0;
[0024] R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50 and R51 are each independently absent or hydrogen;
[0025] E and NR52 or NR53C = 0;
[0026] R52 and R53 are each independently hydrogen or there.
[0027] In some embodiments, R26b and -NO2; R26c, R26e and R26f are hydrogen; R26d and hydrogen.
[0028] In some embodiments, the amount of color fastness and formula (V):

[0029] m, n, o, p, q and r are each independently an integer from 0-2, with the proviso that at least one of m, n, o, p, q and r is different from 0;
[0030] R78, R79, R80, R81, R82, R83, R84, R85, R87, R88 and R89 are each independently hydrogen or absent;
[0031] R86 is absent, hydrogen or hydroxyl;
[0032] K and NR90, C (= O) NR92 or OC = O;
[0033] W and NR95R96, CR97R98R "or OR100;
[0034] R90 and R92 are each independently hydrogen or there;
[0035] R95 and alkyl and R96 and hydrogen or alkyl, or R95 and R96, together with the nitrogen to which they are attached are attached to form a 4-8 membered heterocyclic ring comprising 1 -3 heteroatoms;
[0036] R97, R98 and R "are hydrogen, alkyl, alkoxy or heteroaryl; and
[0037] R100 is hydrogen or alkyl, or a cosmetically acceptable salt thereof, with the proviso that when m, n, o and p are 0; q and r are 1, R86, R87, R88 and R89 are each hydrogen; W and OR100, K and NR90 and R100 are hydrogen, so R90 is not methyl.
[0038] In some embodiments, m, n and o are 0; p, q and r are each I; R84, R85, R86, R87; R88 and R89 are each hydrogen; K and NR90; R90 and hydrogen; W and NR95NR96, and R95 and R9 are each alkyl.
[0039] In some embodiments, the dye is a compound of formula Xa:

[0040] where
[0041] Ra, Rb, Rc, Rd and Re are each independently hydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO2, CF3, SO3H, CN, aminocarbonyl, carbonyl, alkoxycarbonyl or a portion of arildiazene;
[0042] aa and bb are each 1-5 integers;
[0043] A and NRf or NRfCO; D and O (CO), NR9 or CONR9; Rf, R9 and Rh are each independently hydrogen or alkyl;
[0044] R 'and alkyl; or Rh and R 'are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; or a cosmetically acceptable salt thereof.
[0045] In some embodiments, Ra and -NO2; Rb, Rd and Re are each hydrogen; Rc and hydrogen or NH2; A and NR; D and NR9; R and R9 are each hydrogen; and Rh and R 'are each alkyl. In some embodiments, alkyl is methyl, ethyl or hydroxyethyl.
[0046] In some embodiments, Ra and -NO2; Rb, Rd and Re are each hydrogen; Rc and hydrogen or NH2; A and NR; D and NR9; R and R9 are each hydrogen; and Rh and R 'are linked to form a 6-membered heterocyclic ring. In some embodiments, the ring is a piperidine or morpholine ring.
[0047] In some embodiments, the dye is a compound of formula (Xia):

[0048] Rj and Rk are each independently hydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO2, CF3, SO3H, CN, aminocarbonyl, carbonyl, alkoxycarbonyl, or a portion of arildiazene;
[0049] cc and dd are each an integer from 1-5;
[0050] TeNR'orNR’O;
[0051] M and NRm or CONRm;
[0052] Q and NRnR °;
[0053] R1, Rm and Rn are each independently hydrogen or alkyl;
[0054] R ° and alkyl; or Rn and R ° are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; and cosmetically acceptable salts thereof.
[0055] In some embodiments, T and NR1; M and NRm; R1 and Rm are each hydrogen; cc and 2 and dd and 3; Rj and NO2; Rk and hydrogen or NH2; Rn and R ° are each alkyl. In some embodiments, the alkyl is methyl, ethyl or hydroxyethyl.
[0056] In some embodiments, T and NR1; M and NRm; R1 and Rm are each hydrogen; cc and 2 and dd and 3; Rj and NO2; Rk and hydrogen or NH2; Rn and R ° are linked to form a 6-membered heterocyclic ring. In some embodiments, the ring is a piperidine or morpholine ring.
[0057] In some embodiments, the dye is a compound of formula XII:

[0058] where
[0059] Rp and hydrogen or amino;
[0060] Rq and Rr are each independently hydrogen or alkyl;
[0061] ee and ff are each independently an integer from 1-5; and Rs and R 'are each alkyl, or together with the atom to which they are attached to form a 4-8 membered heterocyclic ring with 1 or 2 heteroatoms, and cosmetically acceptable salts thereof.
[0062] In some embodiments, Rq and Rr are each hydrogen; ee e 2 and ff e 3; and Rse R ‘are each alkyl. In some embodiments, the alkyl is methyl, ethyl or hydroxyethyl. In some embodiments, Rp and hydrogen or NH2.
[0063] In some embodiments, Rq and Rr are each hydrogen; ee e 2 and ff e 3; and Rs and Rf are linked to form a 6-membered heterocyclic ring. In some embodiments, the ring is a ring of piperidine or morpholine. In some embodiments, Rp and hydrogen or NH2.
[0064] In some embodiments, the dye and compound of formula XIII:

[0065] where
[0066] Ru and hydrogen or NH2, and
[0067] Rv and Rw are alkyl, and cosmetically acceptable salts thereof.
[0068] In some embodiments, Rv and Rw are each methyl, ethyl or hydroxyethyl. In some embodiments, the dye is a compound selected from Table 2, or a cosmetically acceptable salt thereof.
[0069] In some respects, the present invention provides a dye composition comprising at least one dye disclosed herein, and a suitable medium for coloring keratin fibers.
[0070] In some embodiments, the medium additionally includes one or more of surfactants, thickeners, direct dyes, fragrances, sequestering agents, UV sorting agents, waxes, silicones, preserving agents, couplers, primaries, alkalinizing agents, ceramides , oils, vitamins, pro-vitamins, opacity builders, reducing agents, antioxidants, emulsifiers, chelating agents, color retardants, solvents and buffers.
[0071] In some aspects, the invention provides methods for coloring hair comprising applying to said hair a dye composition comprising at least one dye disclosed herein, or a cosmetically acceptable salt thereof.
[0072] In some embodiments, hair coloring is to realign hair or touch up the roots.
[0073] In some respects, the present invention provides a kit comprising a dye composition comprising at least one dye disclosed herein and instructions for use.
[0074] In some embodiments, the kit additionally comprises at least one or more direct dyes, a developer bottle, gloves or a conditioning rinse. BRIEF DESCRIPTION OF THE DRAWINGS
[0075] Figures la and lb compare the color fastness of a commercially available red dye (figure la) with the color fastness of compound A (figure lb) immediately after application to the hair (la and lb; left strands) and after 15 cycles of shampoo (la and lb; straight straps).
[0076] Figures 2a and 2b compare the color fastness of a commercially available red dye applied to heavily damaged hair (figure 2a) with the color fastness of compound A applied to strips having the same damage (figure 2b) immediately after application to the hair and after 15 cycles of shampoo. The left side of each pair is the starting color, while the right side of each pair is the result after shampooing. The last lock in both 2a and b does not have a pair of shampoo application (only the initial color has been examined). DETAILED DESCRIPTION OF THE INVENTION
[0077] In order to describe more clearly and precisely the subject matter of the claims, the following definitions are intended to provide guidance for the meaning of the terms used here.
[0078] As used herein, the articles "o" and "one" mean "one or more", or "at least one", unless otherwise indicated. That is, referring to any element of the present invention by indefinite articles "o" or "one" does not exclude the possibility that more than one of the element is present. L COLORING
[0079] It should be noted that the term "dye" and "compound" can be used interchangeably.
[0080] In some aspects, the present invention provides functionalized dyes. The "functionalized dye" language includes dyes having at least one chromophor that has been chemically modified. The "non-functionalized dye" language includes dyes that have at least one chromophor that has not been chemically modified. In some embodiments, the non-functionalized dye is a chromophor, C, as defined below.
[0081] In other respects, the present invention provides selective damage dyes. The language "selective damage dye" includes dyes that work better on damaged hair than on normal hair (for example, undamaged hair). The term "damaged hair" includes hair that is more porous than normal hair due to chemical exposure (for example, bleaching or over-coloring of hair, exposure to chemicals in swimming pools or minerals in groundwater), prolonged or repeated exposure to heat (for example, through the use of heat styling tools or excessive exposure to the sun), prolonged exposure to UV, excessive permeation and hair styling, or a genetic predisposition to having more porous hair. In one embodiment, damaged hair includes hair with split ends. The language "normal hair" includes hair that is of normal porosity (for example, undamaged hair), and may include non-bleached or colored hair.
[0082] In some aspects, the invention provides non-oxidizing dyes. The language "non-oxidizing dye" includes dyes that are preformed before application to the hair and do not require a coupling agent or an oxidizing agent to form the dye after depositing on the hair. In contrast, the language "oxidizing dye" includes dyes that are formed by applying an intermediate, a coupling agent and an oxidizing agent to the hair so that the intermediary and coupling agent penetrate the hair and withstand chemical reaction to form a dye colored inside the hair.
[0083] In some embodiments, the dyes of the invention have greater color fastness than a semipermanent dye (for example, a level 2 dye, or a dye that lasts for about 5-8 shampoos). In some embodiments, the dyes of the invention have greater color fastness than a permanent dye (for example, a level 3 dye, or a dye that lasts for about 9 or more shampoos). The language "greater color fastness" includes the ability of the dye to have an improved resistance to color change, or color fading after application to the hair when compared to a direct dye or an oxidizing dye of substantially the same color.
[0084] In some embodiments, the dye is retained and gives color to the hair after application to the hair. The "retained and colored" language includes the ability of the dye to remain in the hair and provides the desired color with substantially no change in color, or color fading after a period of time compared to a direct dye or an oxidizing dye of substantially the same color, and after substantially the same period of time, as measured by the visual inspiration test described in Example 4. In some embodiments, the dye is retained and colors the hair after application to at least about 5%, about 10 %, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or about 100% longer than a direct dye or an oxidizing dye of substantially the same color.
[0085] In other embodiments, the dye has greater vibration after application to the hair. The language "greater vibration" includes the ability of the dye to provide a brighter color after application to the hair, compared to an oxidizing dye, as measured, for example, by the visual inspiration test described in Example 4, or by a colorimeter. In some embodiments, the dye provides vibration which is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or about 100% greater than an oxidizing dye of substantially the same color.
[0086] In other embodiments, the dye maintains its vibration after application to the hair. The language "maintains vibration" includes the ability of the dye to retain its luster after a period of time compared to an oxidizing dye of substantially the same color after substantially the same period of time, as measured by the visual inspection test described in Example 4. In some embodiments, the dye maintains its vibration for about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90% , about 95% or about 100% longer than an oxidizing dye of substantially the same color.
[0087] In some embodiments, the dyes of the invention are non-ionic (for example, the dyes do not have a positive charge (for example, non-cationic), or negative charge (for example, non-anionic).
[0088] Examples of anionic and cationic dyes include, but are not limited to, those in Table 1.
[0089] In some embodiments, the dye is fluorescent.
[0090] In other embodiments, the dye is an unnatural dye (for example, a dye obtained from a natural source, for example, a plant, animal or mineral). Examples of dyes obtained from natural sources include, for example, indigo, carminic acid, lawsone (e.g., henna), lycopene, madder, monascus derivatives, santalin, annatto, apigenin, canthaxanthin, capsantin, capsorubin, carotenes, cartamin, crocin , crocetin, curcumin, lutein, luteolin, pratol, caramel, coconut, chlorophyll and indigo.
[0091] In still other embodiments, and without being bound by theory, the dye interacts with the hair through non-covalent interactions after application to the hair. Examples of non-covalent interactions include, for example, hydrogen bonding, pi stacking, Ovan der Waals interactions, hydrophobic interactions, and dipole-dipole interactions.
[0092] In some embodiments, the dye is a functionalized or intermediate oxidant dye precursor that is capable of additionally reacting chemically within the typical hair fiber of oxidizing dyes (e.g., functionalized para-phenylene diamine) so that the reacted dye final has a longer color duration than the non-functionalized dye.
[0093] In one embodiment, the dye is of formula la: C-L-F (la)
[0094] where
[0095] C and a chromophor, L and a ligand e;
[0096] F is a portion of color fastness, and cosmetically acceptable salts thereof.
[0097] In other embodiments, the dye and formula lb: C-L-F-L * -C * (lb)
[0098] where
[0099] C and C * are each the same or different chromophores;
[00100] L and L * are binders, and
[00101] F is a portion of color fastness, and cosmetically acceptable salts thereof.
[00102] The term "chromophore" includes chemical portions that are capable of providing color to the dyes of the invention. In some embodiments, the chromophore is a colored portion before being covalently bound to L and / or L * and / or F. In other embodiments, the dye resulting from covalently bonding L and / or L * and / or F to C or C * when CouC * and a colored portion provide a molecule with the same or a different color than C or C *. In some embodiments, when C or C * are non-colored molecules, covalent attachment of C or C * to L and / or L * and / or F results in a colored molecule.
[00103] In some embodiments, the chromophor (for example, C or C *) is selected from the group consisting of an anthraquinone chromophor, an arylmethane chromophor, a diarylmethane chromophor, a dimethyl methane chromophor, a triarylmethane chromophore, an azo chromophor, a cyanine chromophor, a diazonium chromophor, a nitro chromophor, a nitrous chromophor, a phthalocyanine chromophor, an quinine imine chromophor, an azin chromophor, a eurodin chromophore, a safranin chromophore, a safranin chromophore chromophor of indamin, chromophor of indophenol, chromophor of oxazin, chromophor of oxazone, chromophor of thiazine, chromophor of thiazole, chromophor of fluorine, chromophore of fluorine, chromophore of pironin, chromophore of fluorine, chromophore of fluorine rhodamine chromophor, a substituted benzene or derivative, or cosmetically acceptable salts thereof. Examples of the preceding chromophores include, but are not limited to, those compounds found in Table 1.
[00104] In at least one embodiment, the present invention includes dyes wherein the "C" or "C *" substituent of formulas la and lb and a known chromophor, for example, including, but not limited to, a chromophor listed in Table 1 below. In this embodiment, the dyes of the invention include an "L" or "L *" substituent and / or and "F" substituent, which are defined above, in addition to the chromophores. In another embodiment, the dye of the invention is not a compound of Table 1.
[00105] In other embodiments, chromophore is a compound of formula Ila:

[00106] wherein Rla, Rlb, Rlc, Rld, Rle, Rlf, R'9, Rlh, R11, R'J Rlk, R11, Rlm, Rln, R '° and Rlp are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic or thioether moiety, or are attached to an L or L * linker , and cosmetically acceptable salts thereof.
[00107] Rla, Rlb, Rlc, Rld, Rle, Rlf, R's, Rlh, R11, Rlj Rlk, R11, Rlm, Rln, R '° and Rlp are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic or thioether moiety, or are attached to an L or L * linker, and cosmetically acceptable salts of the themselves.
[00108] In other embodiments, chromophore is a compound of formula lib:

[00109] where
[00110] R2a, R2b, R2c, R2d, R2e, R2f, R29, R2h, R2i, R2 R2k, R21, R2m and R2n are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl , carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to the L or L * ligand, and cosmetically acceptable salts thereof.
[00111] In other embodiments, chromophore and a compound of formula He:

[00112] where ^ 3a p3b p3c f ^ 3d f ^ 3e f ^ 3f p3g p3h f ^ 3i f ^ 3j p3k p3l f ^ 3m R3n, R3 ° and R3p are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl , amino, alkylammonium, sulfonyl, carbo nils, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts of the same.
[00113] R3a, R3b, R3c, R3d, R3e, R3f, R3q, R3h, R3i, R3 ', R3k, R3', R3m, R3n, R3 ° and R3p are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl , aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -N02, CN, a heterocyclic or thioether moiety, or are attached to an L or L * linker, and cosmetically salts acceptable values.
[00114] In other embodiments, chromophore is a compound of formula lid:

[00115] where
[00116] | ^ 4a p4b p4c f ^ 4d f ^ 4e | ^ 4f p4g p4h ^ 4i ^ 4j f ^ 4k p4l f ^ 4m R4n, R4 °, R4p, R4q and Rrsoo each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, N02, -CN, a heterocyclic moiety or uncle or thioether, or are attached to an L or L * linker. and cosmetically acceptable salts thereof.
[00117] In other embodiments, chromophor is a compound of formula He:

[00118] wherein R5n, R5 °, R5p, R4q, Rr, R5s, R5t, R5u, R5we R5x are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy , halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00119] R5a, R5b, R5c, R5d, R5e, R5f, R59, R5h, R5i, R5J, R5k, R5 ', R5m, R5n, R5 °, R5p, R4q, Rr, R5s, R5t, R5u, R5we R5x are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -N02, -CN, a heterocyclic portion or thioether, or are attached to an L or L * ligand; and
[00120] R5j and R5v are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to the L or L * linker, and cosmetically acceptable salts thereof.
[00121] In other embodiments, chromophore is a compound of formula Ilf:

[00122] where
[00123] f ^ 6a p6b R6C R6d f ^ 6e | ^ 6f f ^ 6g f ^ 6h | ^ 6i f ^ 6j p6k R61 p6m g R6n are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium , sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand, and cosmetically acceptable salts thereof.
[00124] In other embodiments, chromophore and a compound of formula llg:

[00125] where
[00126] R7a, R7b, R7c, R7d, R7e, R7f, R7a, R7h, R7i and R7j are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy , aryloxy, halogen, acyl, oxy, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00127] In other embodiments, chromophore and a compound of

[00128] when
[00129] R8a, R8b, R8c, R8d, R8e, R8f, R89, R8h, R8i, R8j, R8k and R81 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy , alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00130] In other embodiments, chromophore is a compound of formula Hi:

[00131] where
[00132] R9a, R9b, R9c, R9d, R9e, R9f, R ", R9h, R9i, R9j, R9k and R91 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxy, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00133] In other embodiments, chromophor is a compound of formula llj:

[00134] where
[00135] RlOa ^ 10b R10C RlOd j ^ 10e p ^ 10f R10g R1®h R1® 'RlOj R10k Ri ° i, R10m and R10n are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylamonia, sulfonyl , carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00136] In other embodiments, chromophore is a compound of formula Ilk:

[00137] where
[00138] R11a, R11b, R11c, R11d, R11e, R11f, R11g, R11h, R11i, R11 R111 and R11m are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkyladnia, sulfonyl, carbonyl, carboxy , alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00139] R is hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or is attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00140] In other embodiments, chromophore and a compound of formula III:

[00141] where
[00142] R12b, R12c, R12e, R12f, R12g, R12h and R12i are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00143] R 12a and R 12d are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00144] In other embodiments, chromophor is a compound of formula I Im:

[00145] where
[00146] Rl3a p13b R13C f ^ 13d ^ 13e p13f ^ 13g ^ 13h ^ 13i R13J ^ 13k g R131 are each independently hydrogen, hydroxyl, alkyl, alkyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy , aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00147] In other embodiments, chromophore is a compound of formula I In:

[00148] where
[00149] ^ i4a ^ i4b R14c R14d R14e R14f R14g R14j R14k R141 R14m R14n, R14 ° and R14p are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, aroxy, alkoxy, carboxy, alkoxy , halogen, acyl, oximyl, hydrazinyl, -NO2, CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00150] R14h and R14i are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00151] In other embodiments, chromophore is a compound of formula Ho:

[00152] where
[00153] Ri5a ^ i5b R15c R15d R15e R15f R159 R15J R15k R151 Risn, R15 °, R15p, R15ci and R15r, are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00154] R15h and R15i are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00155] In other embodiments, chromophore is a compound of formula lip:

[00156] when
[00157] R16a, R16b, R16c, R16d, R16e and R16f are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00158] In other embodiments, chromophore and a compound of formula llq:

[00159] where
[00160] R17a, R17b, R17c, R17d, R17e, R17f, R17a and R17h are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to the L or L * ligand, and cosmetically acceptable salts thereof.
[00161] In other embodiments, the chromophore and a compound of formula Hr:

[00162] where
[00163] Ri8a pi8b R18c R18d R18e R18f R189 R18h R18i R18J R18k Ri8ie R18m, are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, acyl, aryloxy oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00164] R18g and R18n are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to the L or L * linker, and cosmetically acceptable salts thereof.
[00165] In other embodiments, chromophore and a compound of formula Ils:

[00166] when
[00167] R19a, R19b, R19c, R19d, R19e, R19g, R19h, R19j, R19k, R191, R19m, R19O Rl9p R19r R19s R19t R19u R19v R19x R19y R19z R19a * Rl9b * R19C are each G19 hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymetry, hydrazinyl, -NO2, -CN, a heterocyclic porpium or thioether, or are attached to a linker L or L *; and
[00168] R19f, R19i, R19n and R19q are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to an L or L * linker, and cosmetically acceptable salts thereof .
[00169] In other embodiments, chromophor is a compound of formula II:

[00170] when
[00171] R20a f ^ 20b R20C f ^ 20d f ^ 20e p20g f ^ 20h R20j p20k p20l R20m R20n, R20 ° and R20p, are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00172] R20f and R20i are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00173] In other embodiments, chromophor is a compound of formula Hu:

[00174] when
[00175] R21a, R21b, R21c, R21d, R21e, R21f, R219, R21h, R21i, R21j, R21k and R211 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy , alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether or are attached to an L or L * ligand;
[00176] PeOouNR21m; and
[00177] R2 m is hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or is attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00178] In other embodiments, chromophore and a compound of formula llv:

[00179] when
[00180] R22a, R22b, R22c, R22d, R22e, R22s, R22h, R22i, R22j, R22k and R221 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy , aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; and
[00181] R22f and hydrogen, alkyl, alkenyl, alkynyl, aryl, carbonyl, acyl, or a heterocyclic moiety, or is attached to L or L *, and cosmetically acceptable salts thereof.
[00182] In other embodiments, chromophore and a compound of formula llw: (JIw)

[00183] where
[00184] R23a, R23b, R23c, R23d, R23f, R23g, R23h and R23i are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand;
[00185] QeS.OouN;
[00186] T and N + R23e or N when R23e is absent; and
[00187] R23e is absent, hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or is attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00188] In other embodiments, chromophore and a compound of formula I lx:

[00189] where
[00190] R24a, R24b, R24c, R24d, R24e, R24f, R24h, R24i, R24j and R24k are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy , halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to an L or L * ligand; U and N + R24g or O when R24g is absent; and
[00191] R24g is absent, hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or is attached to an L or L * linker, and cosmetically acceptable salts thereof.
[00192] In other embodiments, chromophore is a compound of

[00193] when
[00194] R25a, R25b, R25c, R25d, R25e, R25f, R25h, R25i and R25j are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen , acyl, oxymyl, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or are attached to the L or L * ligand;
[00195] V and CR25iR25j or NR25k; and
[00196] R25g and R25k are each independently hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl, or are fixed to L or L *, and cosmetically acceptable salts thereof.
[00197] In other embodiments, chromophor is a compound of formula Hz:

[00198] when
[00199] R26a, R26b, R26c, R26d, R26e and R26f are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, sulfonic acid, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl , oximyl, hydrazinyl, -NO2, -CN, -CF3, SO3H, aminocarbonyl, alkoxycarbonyl, a heterocyclic moiety, a diazene or thioether, or are attached to the L or L * ligand, and cosmetically acceptable salts thereof.
[00200] In some embodiments, oCede formulates Hz:

[00201] where
[00202] R26a and attached to a ligand L; and
[00203] R26b, R26c, R26d, R26e and R26f are each independently hydrogen, hydroxy, amino, alkoxy, alkyl, CF3, CN, halogen, NO2, SO3H, aminocarbonyl, carbonyl, alkoxycarbonyl, or a portion of arildiazene.
[00204] In some embodiments, R26b and -NO2.
[00205] In some embodiments, R26c, R26e and R26f are hydrogen.
[00206] In some embodiments, R26d and hydrogen or NH2.
[00207] In still other embodiments, chromophore (for example, C or C *) includes, but is not limited to, Acid Blue 1, Acid Blue 3, Acid Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue 62, Acid Blue 104, Acid Marram 13, Acid Orange 3, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 33, Acid Red 35, Acid Red 41, Acid Red 50, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 94, Acid Red 95, Acid Red 98, Acid Red 184, Acid Green 1, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Yellow 1, Acid Yellow 9, Acid Yellow 73, Acid Violet 9, Acid Violet 50, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 99, Basic Marram 4, Basic Marram 16, Basic Marram 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 40, Basic Yellow 57, Basic Yellow 87, Direct Black 51, Direct Red 23, Direct Red 80, Direct Red 81, Direct Violet 48, Direct Yellow 12, Black Disperse 9, Blue Disperse 1, Blue Disperse 3, Blue Disperse 7, Blue Disperse 72, Marram Disperse 1, Orange Disperse 3, Red Disperse 1, Red Disperse 3, Red Disperse 11, Red Disperse 13, Red Disperse 14, Red Disperse 15, Red Disperse 17, Red Disperse 19, Violet Disperse 1, Violet Disperse 4, Violet Disperse 15, Violet Disperse 27, HC Blue 2, HC Blue 4, HC Blue 5, HC Blue 6, HC Blue 8, HC Blue 9, HC Blue 10, HC Blue 11, HC Blue 1 2, HC Blue 13, HCAzul 14, HCAzul 15, HC Marram 1, HC Marram 2, HC Green 1, HC Orange 1, HC Orange 2, HC Orange 3, HC Orange 5, HC Red 1, HC Red 3, HC Red 7, HC Red 8, HC Red 9, HC Red 10, HC Red 11, HC Red 13, HC Red 14, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 8, HC Yellow 9, HC Yellow 10, HC Yellow 11, HC Yellow 12, HC Yellow 13, HC Yellow 14, HC Yellow 15, Dispersed Red 3, Disperse Red 19, Acid Black 1, Acid Red 1, Acid Red 73, Solvent Red 23, Scarlet Red, Bright Black, Black 1, Mattom 1, Cl 20040, Cl 21100, Cl 21108, Cl 21230, Cl 27755, Cl 28440, Acid Black 52, Acid Red 18, Acid Red 27, Lithol Rubin B, Betanina, Lithol, Cl 15800, Cl 15880, red Hansa B, Cl 12085, Pigment Red 22, Cl 15865: 2, Cl 16155, Acid Red 26, Cl 14700, Solvent Orange 7, Acid Red 88, Cl 11680, Cl 11710, Cl 11725, Cl 11 920, Cl 12010, Cl 12085, Cl 12120, Cl 12150, Cl 12370, Cl 12420, Cl 12480, Cl 12490, Acid Yellow 23, Acid Red 195, Cl 12700, Cl 14700, Cl 14815, Cl 15525, Cl 15580, Cl 15630, Cl 15850, Cl 15980, Cl 15985, Cl 16035, Acid Red 155, Acid Yellow 121, Acid Red 180, Acid Yellow 11, Cl 12075, Cl 12100, Cl 42053, Acid Violet 43, Cl 69825, Solvent Blue 63, Cl 58000, Cl 61565, Acid Blue 80, Cl 69800, Cl 10006, Rhodamine B, Japan Red 104, Japan Red 223, Acid Yellow 73, Cl 45396, Cl 45410, Cl 45370, Cl 51319 and a compound disclosed in Table 1, and / or derivatives and cosmetically acceptable salts thereof. TABLE 1














[00208] and cosmetically acceptable salts thereof.
[00209] In one embodiment, the portion of color fastness (for example, F) of formulas la and lb is linked (for example, covalently linked) to the chromophor (for example, C and C *), via a binder (for example, L and L *, respectively). The term "binder" includes chemical portions that are capable of binding (for example, by a covalent bond) the chromophor to the color fastening portion.
[00210] In some embodiments, the linker will have at least one portion of hydrogen bond donor. In some embodiments, the color fastness portion will have at least one hydrogen bond donor portion and at least one hydrogen bond acceptor portion. In some embodiments, the portion of color fastness together with the binder comprises at least one hydrogen bond donor and at least one hydrogen bond acceptor. In some embodiments, the color fastness portion together with the binder comprises at least 2 hydrogen bond donors and at least one hydrogen bond acceptor.
[00211] The language "hydrogen bond donor portion" includes those chemical groups that have a hydrogen covalently linked to an electronegative atom, for example, oxygen, nitrogen, fluorine, and the like. In some embodiments, the hydrogen bonding donor moiety is a hydroxyl or amine moiety primary (e.g., -NH2) or secondary (e.g., -NHR).
[00212] The language "hydrogen bond acceptor moiety" includes electronegative atoms that have only one electron pair with which it interacts non-covalently with the hydrogen of the hydrogen bond donor. Examples of hydrogen bond acceptor portions include oxygen, nitrogen and fluorine. In some embodiments, the hydrogen bond acceptor moiety is a primary, secondary outer amine moiety (eg, -NR2), a hydroxyl moiety, an ether moiety (eg -RO-R) or CF3 .
[00213] In some embodiments, the binder and the amount of color fastness together have at least three amine portions. In some embodiments, at least one of the amine moieties is a tertiary amine.
[00214] In other embodiments, ligand L and formula III:

[00215] where
[00216] L covalently bonds C, via the left portion of formula III to F via, the right side of formula III;
[00217] E and NR52, O, S, S02, S03, C = A, NR53C = A, C (= A) NR54, NR55C (= A) NR56,

[00218] A, A * and A ** are each independently oxygen or sulfur;
[00219] Y and NR125, O, S, SO2, SO3, C = A *, NR126C = A *, C (= A *) NR127, NR128C (= A *) NR129, (C = A *) I or OC = A *;
[00220] Z and NR130, O, S, SO2, SO3, C = A **, NR131C = A **, C (= A **) NR132, NR133C (= A **) NR134, (C = A * *) O or OC = A **;
[00221] a, b, c, d, e, f, v, w and x are each independently an integer between 0 and 5, with the proviso that at least one of a, b, c, d, e, f, v , w and x is different from 0;
[00222] R40 and R4 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymetry, hydrazinyl, -NO2, -CN, a heterocyclic moiety or thioether, or R40 and R4 are absent when a and 0;
[00223] R42 and R43 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R42 and R43 are absent when b and 0;
[00224] R44 and R45 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R44 and R4 are absent when ce 0;
[00225] R46 and R47 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R4 and R47 are absent when 0;
[00226] R48 and R49 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R48 and R49 are absent when ee 0;
[00227] R50 and R51 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R50 and R51 are absent when fe 0;
[00228] R119 and R120 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R119 and R120 are absent when ve 0;
[00229] R121 and R122 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R121 and R122 are absent when we 0;
[00230] R123 and R124 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxymyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R123 and R124 are absent when x and 0; or
[00231] R40 and R41 or R41 and R42 or R42 and R43 or R43 and R44 or R44 and R45or R45
[00232] and R46 or R46 and R47 or R47 and R48 or R48 and R49 or R49 and R50 or R50 and R51 or
[00233] R119 and R120 or R120 and R121 or R121 and R122 or R123 and R124, together with the carbon atoms to which they are attached are attached to form a 3 to 10 membered carbocyclic or heterocyclic ring;
[00234] R52 R53 R54 R55R56 R125 R126 R127 R128R129R130 R131 R132 R133 and R134 are each independently hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR57 R58;
[00235] R57 and R58 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a heterocyclic or carbonyl moiety.
[00236] In some embodiments, the ligand L and formula Illa:

[00237] where
[00238] covalently bonds C, via the left side of formula Illi to F, via the right side of formula Illa;
[00239] a, b, c, d, e, and f are each independently an integer from 0-2, with the proviso that at least one of a, b, c, d, e and f is different from 0;
[00240] R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50 and R51 are each independently absent or hydrogen;
[00241] E and NR52 or NR53C = O;
[00242] R52 and R53 are each independently hydrogen or there.
[00243] In some embodiments, a, b, c and d are each 0.
[00244] In some embodiments, e and f are each 1.
[00245] In some embodiments, E and NR52.
[00246] In some embodiments, R52 is hydrogen.
[00247] In some embodiments, R52 and alkyl (for example, ethyl).
[00248] In other embodiments, L * and formula IV:

[00249] where
[00250] L * and covalently linked to C *, via the left side of formula IV;
[00251] G and NR71, O, S, SO2> SO3, C = J, NR72C = J, C (= J) NR73, NR74C (= J) NR75, (C = J) O,
[00252] OC = L, or

[00253] J, J * and J ** and oxygen or sulfur;
[00254] Y * and NR141, O, S, SO2> SO3, C = J *, NR142C = P, C (= J *) NR143, NR144C (= J *) NR145, (C = J *) O or OC = P;
[00255] Z * and NR146, O, S, SO2, SO3> C = J **, NR147C = J **, C (= P *) NR148, NR149C (= P *) NR150, (C = P *) 0, OC = J ** or
[00256] g, h, i, j, k, 1, v *, w * and x * are each independently an integer between 0 and 5, with the proviso that at least one of g, h, I, j, k , 1, v *, w * and x * are different from 0;
[00257] R59 and R60 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, hydrazinyl, -NO2, -CN, a he-terocyclic or thioether moiety, or R59 and R60 are absent when g and 0,
[00258] aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, when g is 0;
[00259] R61 and R62 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxy, hydrazinyl, when h and 0;
[00260] R63 and R64 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxy, hydrazinyl, when i and 0;
[00261] R65 and R66 are each independently hydrogen, hydroxy, alkyl, alkenol, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxy, hydrazinyl, 25 when j and 0;
[00262] R67 and R68 are each independently hydrogen, hydroxy, alkyl, alkenyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oxy, hydrazinyl, when k is 0;
[00263] R69 and R70 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R 9 and R70 are absent when 1 and 0;
[00264] R135 and R136 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R135 and R136 are absent when v * and 0;
[00265] R137 to R138 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R137 and R138 are absent when w * and 0;
[00266] R139 and R140 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R139 and R140 are absent when x * and 0; or
[00267] R59 and R60 or R60 and R61 or R61 and R62 or R62 and R63 or R63 and R64 or R64
[00268] and R65 or R65 and R66 or R66 and R67 or R67 and R68 or R68 and R69 or R69 and R70 or
[00269] R135 and R136 or R136 and R137 or R137 and R138 or R138 and R139 or R139 and R140, together with the carbon atoms to which they are attached are attached to form a 3 to 10 membered carbocyclic or heterocyclic ring;
[00270] R71, R72, R73, R74, R75, R141, R142, R143, R144, R145, R146 R147,
[00271] are each independently hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR7 R77; and
[00272] R76 and R77 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a heterocyclic or carbonyl moiety.
[00273] The language, "portion of color fastness" includes chemical groups that cause the dye to resist color change, for example, a chemical group that increases the retention and / or capacity of the dye in the substance to which it is applied.
[00274] In one embodiment, the portion of color fastness and formula V:

[00275] where
[00276] K and NR90, O, S, S02, S03, C = M, NR91C = M, C (= M) NR92, NR93C (= M) NR94 or (C = M) O, OC = M when the dye and to formulate it; or K and NL *, NL * C = M, C (= M) NL *, NL * C (= M) NR94 or NR93C (= M) NL * when the dye is of formula lb;
[00277] W and NR95R96, CR97R98R ", OR100, SR101 or halogen,
[00278] M and oxygen or sulfur
[00279] m, n, o, p, q and r are independently an integer between 0 and 5, with the proviso that at least one of m, n, o, p, q, and r is different from 0;
[00280] R78 and R79 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R78 and R79 are absent when me 0;
[00281] R80 and R81 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R80 and R81 are absent when ne 0;
[00282] R82 and R83 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R82 and R83 are absent when oe 0;
[00283] R84 and R85 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R84 and R85 are absent when p 0.
[00284] R86 and R87 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R86 and R87 are absent when q and 0;
[00285] R88 and R89 are each independently hydrogen, hydroxy, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R88 and R89 are absent when ee 0;
[00286] R78 and R79 or R79 and R80 or R80 and R81 or R81 and R82 or R82 and R83 or R83
[00287] and R84 or R84 and R85 or R85 and R86 or R86 and R87 or R87 and R88 or RSS E R89, together with the carbon atoms to which they are attached are attached to form a 3 to 10 carbocyclic or heterocyclic ring members;
[00288] R90, R91, R92, R93 and R94 are each independently hydro genio, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy or acyl;
[00289] R95 and R96 are each independently hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR102R103, or R95 and R96 together with the nitrogen to which they are attached are linked to form a ring 3 to 10 membered aliphatic, heterocyclic or aromatic;
[00290] R97, R98 and R "are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN , a heterocyclic moiety or thioether, or R97 and R98 together with the carbon to which they are attached are attached to form a 3 to 10 membered carbocyclic or heterocyclic ring; or R "is absent and R97 and R98 together with the carbon to which they are attached. fixed are linked to form aromatic ring with 4 to 10 members;
[00291] R100 and R101 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, carbonyl, acyl, or a heterocyclic moiety; and
[00292] R102 and R103 are each independently hydrogen, hydro xi, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy or acyl, or R102 and R103 together with the nitrogen to which they are attached are linked to form an aliphatic ring , 3 to 10 membered heterocyclic or aromatic.
[00293] In some embodiments, the amount of color fastness and formula (Va):

[00294] in, n, o, p, q and r are each independently an integer from 0-2, with the proviso that at least one of m, n, o, p, q and r is different from 0;
[00295] R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88 and R89 are each independently hydrogen, or absent;
[00296] R86 is absent, hydrogen or hydroxyl;
[00297] K and NR90, C (= O) NR92 or OC = O;
[00298] W and NR95R96, CR97R98R "or OR100;
[00299] R90 and R92 are each independently hydrogen or there;
[00300] R95 and alkyl and R96 and hydrogen or alkyl, or R95 and R96, together with the nitrogen to which they are attached are attached to form a 4-8 membered heterocyclic ring comprising 1-3 heteroatoms;
[00301] R97, R98 and R "are hydrogen, alkyl, alkoxy or heteroaryl; and
[00302] R100 and hydrogen or alkyl,
[00303] with the proviso that when m, n, o and p are 0; q and r are 1, R86, R87, R88 and R89 are each hydrogen; W and OR100, K and NR90 and R100 are hydrogen, so R90 is not methyl.
[00304] In some embodiments, m, n and o are 0.
[00305] In some embodiments, p, q and r are each 1.
[00306] In some embodiments, R84, R85, R86, R87; R88 and R89 are each hydrogen.
[00307] In some embodiments, K and NR90.
[00308] In some embodiments, R90 and hydrogen.
[00309] In some embodiments, W and NR95NR96, and R95 and R96 are each alkyl.
[00310] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl (for example, ethyl); f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; Ke C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and NR95R96; R95 and R96 are each alkyl (for example, substituted or unsubstituted alkyl, for example, ethyl or hydroxyl substituted alkyl, as well as hydroxyethyl).
[00311] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl (for example, ethyl); f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; Ke C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and NR95R96; R95 and R96 are linked to form a ring (for example, a 6-membered heterocyclic ring, for example, a morpholinyl ring).
[00312] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl (for example, ethyl); f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; Ke C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and CR97R98R "; R97 hydrogen and R98 and R" are each alkoxy (e.g., ethoxy).
[00313] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl (for example, ethyl); f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; Ke C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and CR97R98R "; R97 and R98 are each hydrogen and R" is hydroxyl.
[00314] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl (for example, ethyl); f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; Ke C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R87, R88, R89 and R92 are each hydrogen; R8 and hydroxyl; W and OU 00 and R °° and hydrogen.
[00315] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7ce fixed to L; a, b, c and d are each 0;
[00316] Ee

[00317] Y is NR125, R125 is alkyl (for example, ethyl); v and w are ca da
[00318] 1; x is 0; R119, R120, R121 and R122 are each hydrogen; Z is OC = A **; A ** and oxygen; e and f are each 1; R48, R49, R50 and R51 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R90 are each hydrogen; W and NR95R96; R95 and R96 are each alkyl (for example, substituted or unsubstituted alkyl, for example ethyl or hydroxyl substituted alkyl, as well as hydroxyethyl).
[00319] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c and d are each 0;
[00320] E and

[00321] Y and NR125, R125 and alkyl (for example, ethyl); v and w are each
[00322] 1; x and 0; R119, R120, R121 and R122 are each hydrogen; Z and OC = A **; A ** and oxygen; e and f are each 1; R48, R49, R50 and R51 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85 „R87, R88, R89 and R90 are each hydrogen; R86 and hydroxyl; W and OR100; and R100 is hydrogen.
[00323] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine) and R7c is fixed to L; a, b, c and d are each 0;
[00324] And and

[00325] Y and NR125, R125 and alkyl (for example, ethyl); v and w are each
[00326] 1; x and 0; R119, R120, R121 and R122 are each hydrogen; Z and OC = A **; A ** and oxygen; e and f are each 1; R48, R49, R50 and R51 are each hydrogen; m, n and o are each 0; K and NR90; pe1; qe1; re0; R84, R85, R86, R87 and R90 are each hydrogen; W and NR95R96; R9 and R9 are each hydrogen.
[00327] In one embodiment, the dye is of formula la, and C is an azo dye. In yet another embodiment, C is of formula llg; R7a, R7b, R7d, R7e, R7f, R79 and R7i are each hydrogen; Rh and -NO2; R7j is halogen (e.g. chlorine) and Rce is fixed to L; a, b, c and d are each 0;
[00328] E and

[00329] Y and NR125, R125 and alkyl (for example, ethyl); v and w are each
[00330] 1; x and 0; R119, R120, R121 and R122 are each hydrogen; Z and OC = A **; A ** and oxygen; e and f are each 1; R48, R49, R50 and R51 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R90 are each hydrogen; W and CR97R98R "; R97 and hydrogen and R98 and R" are each alkoxy (e.g., ethoxy).
[00331] In one embodiment, the dye is of formula lb in which C and C * are the same chromophores; C and of formula llg, R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine); R7c and attached to a ligand L; a, b and c are 0;
[00332] E and

[00333] 125 and alkyl (for example, ethyl); v and w are each
[00334] Y and NR125; R125 and alkyl (for example, ethyl); v and w are each 1, x and 0; R119, R120, R121 and R122 are each hydrogen; Z and oxygen; d, e and f are each 1; R46, R47, R48, R50 and R51 are each hydrogen; R49 and hydroxyl; m, n and o are each 0; Ke NL *; g, h and i are each 1; R59, R60, R61, R63 and R64 are each hydrogen; R62 and hydroxyl;
[00335] G e

[00336] Y * and oxygen; v * and 1; w * and 1; x * and 0; R135, R136, R137 and R138 are each hydrogen; Z * and NR146; R146 and alkyl (for example, ethyl); j, k and 1 are each 0; C * is of formula llg in which R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7he -NO2; R7j and halogen (for example, chlorine); R7c and attached to a L * linker; p, q and r are each 1; R84, R85, R86, R87, R88 and R89 are each hydrogen; W and NR95R96; and R95 and R96 are each alkyl (for example, hydroxyl substituted alkyl, for example, hydroxyethyl).
[00337] In one embodiment, the dye is of formula lb in which C and C * are the same chromophores; C and of formula llg, R7a, R7b, R7d, R7e, R7f, R79 and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine); R7c and attached to a ligand L; a, b and c are 0;
[00338] E and

[00339] v and 1; w and 1; x and 0; R119, R120, R121 and R122 are each hydrogen; Y and NR125; R125 and alkyl (for example, ethyl); Z and oxygen; d, e and f are each 1; R46, R47, R48, R50 and R51 are each hydrogen; R49 and hydroxyl; m, n and o are each 0; Ke NL *; g, h and i are each 1; R59, R60, R61, R63 and R64 are each hydrogen; R62 and hydroxyl;
[00340] G e

[00341] Y * and oxygen; v * e 1, w * e 1; x * and 0; R135, R136, R137 and R138 are each hydrogen; Z * and NR146; R146 and alkyl (for example, ethyl); j, k and 1 are each 0; C * is of formula llg in which R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7he -NO2; R7j and halogen (for example, chlorine); R7c and attached to a L * linker; p, q and r are each 1; R84, R85, R86, R88 and R89 are each hydrogen; R87 and hydroxyl; W and OR100 and R100 and hydrogen.
[00342] In one embodiment, the dye is of formula lb in which C and C * are the same chromophores; C and of formula llg, R7a, R7b, R7d, R7e, R7f, R79 and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine); R7c and attached to a ligand L; a, b, c and d are 0;
[00343] E and

[00344] V and 1; we 1; x and 0; R119, R120, R121 and R122 are each hydrogen; Y and NR125; R125 and alkyl (for example, ethyl); Z and OC = A **; A ** and oxygen; and e are each 1; R48, R49, R50 and R51 are each hydrogen; m, neo are each 0; Ke NL *; g, eh are each 1; ie 0; R59, R60, R61 and R62 are each hydrogen; G e

[00345] Y * e (C = J *) O; J * and oxygen; v * and 1; w * and 1; x * and 0; R135, R136, R137 and R138 are each hydrogen; Z * and NR146; R146 and alkyl (for example, ethyl); j, k and 1 are each 0; C * is of formula llg in which R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j and halogen (for example, chlorine); R7c and attached to a L * linker; p, q and r are each 1; R84, R85, R86, R87, R88 and R89 are each hydrogen; W and NR95R96; and R95 and R96 are each alkyl (for example, ethyl or hydroxyethyl).
[00346] In one embodiment, the dye is formulated therein; C and formula IIz; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26c and NO2; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and o are each 0; K and NR90; p and 0; q and r are each 1; R87, R88, R89 and R90 are each hydrogen; W and OR100; R 00 and hydrogen; and R8 and alkyl (for example, hydroxymethyl).
[00347] In one embodiment, the dye is formulated therein; C and formula II; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26c and NO2; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and o are each 0; Ke NR90; pe1; qe1; re0; R84, R85, R86, R87 and R90 are each hydrogen; W and NR9 R9; R9 and R9 are each hydrogen or alkyl (for example, hydroxyethyl).
[00348] In one embodiment, the dye is formulated therein; C and formula II; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26ce N02; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85, R87, R88, R89 and R90 are each hydrogen; R8 and hydroxyl; W and OR100 and R100 and hydrogen.
[00349] In one embodiment, the dye is formulated therein; C and formula II; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26ce N02; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R90 are each hydrogen; W and NR95 R96; R95 and R96 are each alkyl (for example, ethyl or hydroxyethyl).
[00350] In one embodiment, the dye is formulated therein; C and formula II; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26ce N02; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and o are each 0; Ke NR90; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R90 are each hydrogen; W and CR97R98R "; R97 and hydrogen; R98 and R" are each alkoxy (e.g., ethoxy).
[00351] In one embodiment, the dye is formulated therein; Yield formula llz; R26b, R26e and R26f are each hydrogen; R26d and amine (for example, arylamino, for example, phenylamino); R26ce N02; R26a and attached to a ligand L; a, b, c, and d are each 0; E and NR53C = A; A and oxygen; e and f are each 1; R48, R49, R50, R51 and R53 are each hydrogen; m, n and 0 are each 0; Ke NR90; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R90 are each hydrogen; W and CR97R98R "; R97 and R98 are each hydrogen; R" is alkyl (e.g., n-butyl).
[00352] In some embodiments, C and formula llz; R26a and attached to a ligand L; R26b and -N02; R26c, R26d, R26e and R26f are hydrogen; a, b, c and d are each 0; E and NR52; e and f are each 1; R48, R49, R50, R51 and R52 are each hydrogen; m, n and o are 0; K and NR90; p, q and r are each 1; W and NR95 R96; R95 and R96 are each alkyl (for example, methyl, ethyl or hydroxyethyl); and R84, R85, R86, R87; R88, R89 and R90 are each hydrogen.
[00353] In some embodiments, C and formula Hz, R26a is attached to a ligand L; R2 and -NO2; R26c, R26e and R26f are hydrogen; R26d and -NH2; a, b, c and d are each 0; E and NR52; e and f are each 1; R48, R49, R50, R51 and R52 are each hydrogen; m, n and o are 0; Ke NR90; p, q and r are each 1; W and NR95R96; R95 and R96 are each alkyl (for example, methyl, ethyl or hydroxyethyl); and R84, R85, R86, R87; R88, R89 and R90 are each hydrogen.
[00354] In some embodiments, C and formula II; R26a and attached to a ligand L; R26b and -NO2; R26c, R26d, R26e and R26f are hydrogen; a, b, c and d are each 0; E and NR52; e and f are each 1; R48, R49, R50, R51 and R52 are each hydrogen; m, n and o are 0; K and NR90; p, q and r are each 1; W and NR95R96; R95 and R96 are linked to form a 6-membered heterocyclic ring (for example, piperidine or morpholine ring); and R84, R85, R86, R87; R88, R89 and R90 are each hydrogen.
[00355] In some embodiments, C and formula Hz, R26a is attached to a ligand L; R26d and -NO2; R26c, R26e and R26f are hydrogen; R26d and NH2; a, b, c and d are each 0; E and NR52; e and f are each 1; R48, R49, R50, R51 and R52 are each hydrogen; m, n and o are 0; K and NR90; p, q and r are each 1; We NR95R96; R95 and R96 are linked to form a 6-membered heterocyclic ring (for example, piperidine or morpholine ring); and R84, R85, R86, R87; R88, R89 and R90 are each hydrogen.
[00356] In some embodiments, the dye is a compound of formula X:

[00357] where
[00358] Ra, Rb, Rc, R and Re are each independently hydrogen, hydroxy, amino, alkoxy, alkyl, CF3, CN, halogen, NO2, CF3, SO3H, CN, aminocarbonyl, carbonyl, alkoxycarbonyl, or an arildiazene moiety ;
[00359] aa and bb are each 1-5 integers;
[00360] A and O, S, CO, NRf, NRfCO or CONRf;
[00361] D and O, S, CO, O (CO), NR9, NR9CO or CONR9;
[00362] J and ORh, SRh or NRhR :;
[00363] Rf, R9, and Rh are each independently hydrogen or alkyl;
[00364] R 'and alkyl; or Rh and R 'are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; and cosmetically acceptable salts thereof, and
[00365] with the proviso that when A and NRf; D and NR9; J and ORh; Ra, Rb, Re, Rf and Rh are each hydrogen; Rc and methylamino; R and -NO2; aa is 3 and bb is 2, so R9 is not methyl.
[00366] In some embodiments, Ra and -NO2, Rb, Rd and Re are each hydrogen; Rc and amine (for example, -NH2); A and NRf, Rf and hydrogen, aa and 2, D and NRg, R9 and hydrogen; bb and 3; J and NRhR '; and Rh and R 'are each alkyl (for example, ethyl).
[00367] In some embodiments, Ra and -NO2, Rb, Rc, Rd and Re are each hydrogen; A and NRf, Rf and hydrogen, aa and 2, D and NR9, R9 and hydrogen; bb and 3; J and NRhR '; and Rh and R 'are each alkyl (for example, ethyl or hydroxyethyl).
[00368] In some embodiments, the dye and formula Xa:

[00369] where
[00370] Ra, Rb, Rc, Rd and Re are each independently hydrogen, hydroxyl, amino, alkoxy, alkyl, CF3, CN, halogen, NO2, CF3, SO33H, CN, aminocarbonyl, carbonyl, alkoxycarbonyl or a portion of arildiazene;
[00371] aa and bb are each 1-5 integers;
[00372] Ae NRfouNRfCO;
[00373] D and O (CO), NRg or CONRg;
[00374] Rf, Rg and Rh are each independently hydrogen or alkyl; R 'and alkyl; or Rh and R 'are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 13 heteroatoms; or the cosmetically acceptable salt thereof.
[00375] In some embodiments, Ra and -NO2.
[00376] In some embodiments, Rb, Rd and Re are each hydrogen.
[00377] In some embodiments, Rc and hydrogen or NH2.
[00378] In some embodiments, A and NRf.
[00379] In some embodiments, D and NR9.
[00380] In some embodiments, Rf and Rg are each hydrogen.
[00381] In some embodiments, Rh and R 'are each alkyl (for example, methyl, ethyl or hydroxyethyl).
[00382] In some embodiments, Rh and R 'are linked to form a 6-membered heterocyclic ring (e.g., a piperidine or morpholine ring).
[00383] In some embodiments, the dye is a compound of formula XI:

[00384] Rj and R are each independently hydrogen, hydroxyl, amino, alkoxy, alkyl, CF3, CN, halogen, NO2, CF3, SO3H, CN, aminocarbonyl, carbonyl, alkoxycarbonyl or a portion of arildiazene;
[00385] cc and dd are each an integer from 1-5;
[00386] T and O, S, CO, NR1, NR1 CO or CONR1;
[00387] M and O, S, CO, OC (O), NRm, NRmCO or CONRm;
[00388] Q and ORn, SRn or NRnR °;
[00389] R1, Rm and Rn are each independently hydrogen or alkyl;
[00390] R ° and alkyl; or Rn and R ° are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; and cosmetically acceptable salts thereof.
[00391] In some embodiments, Rj and -NO2, Rk and hydrogen; T and NR1, R1 and hydrogen; cc and 2; M and NRm, Rm and hydrogen; dd and 3; Q and NRnR ° and Rn and R ° are each alkyl (for example, ethyl or hydroxyethyl).
[00392] In some embodiments, Rj and -NO2, Rk and amine (for example, -NH2); T and NR1, R1 and hydrogen; cc and 2; M and NRm, Rm and hydrogen; dd and 3; Q and NRnR ° and Rn and R ° are each alkyl (for example, ethyl).
[00393] In some embodiments, the dye and formula Xia:

[00394] where
[00395] Rj and Rk are each independently hydrogen, hydroxyl, amino, alkoxy, alkyl, CN, halogen, NO2, CF3, SO3H, aminocarbonyl, carbonyl, alkoxycarbonyl or a portion of arildiazene;
[00396] cc and dd are each an integer from 1-5;
[00397] T and NR1 or NR'CO;
[00398] M and NRm or CONRm;
[00399] Q and NRnR °;
[00400] R1, Rm and Rn are each independently hydrogen or alkyl;
[00401] R ° and alkyl; or Rn and R ° are linked together with the atom to which they are attached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; and cosmetically acceptable salts thereof.
[00402] In some embodiments, T and NR1.
[00403] In some embodiments, M and NRm.
[00404] In some embodiments, R1 and Rm are each hydrogen.
[00405] In some embodiments, cc and 2 and dd and 3.
[00406] In some embodiments, RJ and NO2.
[00407] In some embodiments, Rk and hydrogen or NH2.
[00408] In some embodiments, Rn and R ° are each alkyl (for example, methyl, ethyl or hydroxyethyl).
[00409] In some embodiments, Rn and R ° are linked to form a 6-membered heterocyclic ring (for example, a piperidine or morpholine ring).
[00410] In some embodiments, the dye is a compound of formula XII:

[00411] when
[00412] Rp and hydrogen or amino;
[00413] Rq and Rr are each independently hydrogen or alkyl;
[00414] ee and ff are each independently an integer from 1-5; and
[00415] Rs and R 'are each alkyl or together with the atom to which they are attached to form a 4-8 membered heterocyclic ring with 1 or 2 heteroatom, and cosmetically acceptable salts thereof.
[00416] In some embodiments, Rp and amine (for example, NH2); Rq and Rr are each hydrogen; ee e 2; ff and 3; and Rs and R 'are each alkyl (for example, ethyl).
[00417] In some embodiments, Rp, Rq and Rr are each hydrogen; ee e 2; ff and 3; and Rs and R £ are each alkyl (for example, ethyl or hydroxyethyl).
[00418] In some embodiments, Rr and hydrogen.
[00419] In some embodiments, ee and 2.
[00420] In some embodiments, ff and 3.
[00421] In some embodiments, Rs and R 'are each alkyl (for example, methyl, ethyl or hydroxyethyl).
[00422] In some embodiments, Rs and R 'are linked to form a 6-membered heterocyclic ring (e.g., piperidine or morpholine ring).
[00423] In some embodiments, Rp and hydrogen.
[00424] In some embodiments, Rp and NH2.
[00425] In some embodiments, the dye is a compound of formula XIII:

[00426] where
[00427] Ru and hydrogen or NH2 and
[00428] Rv and Rw are alkyl, and cosmetically acceptable salts thereof.
[00429] In some embodiments, Ru is hydrogen and Rv and Rw are each ethyl.
[00430] In some embodiments, Ru and amine and Rv and Rw are each ethyl.
[00431] In some embodiments, Ru and hydrogen, Rv and Rw are methyl.
[00432] In some embodiments, Ru and NH2, Rv and Rw are methyl.
[00433] In some embodiments, Ru and hydrogen, Rv and Rw are hydroxyethyl.
[00434] In some embodiments, Ru and NH2, Rv and Rw are hydroxyethyl.
[00435] In some embodiments, the dye is selected from a compound in Table 2: TABLE 2








[00436] or a cosmetically acceptable salt thereof.
[00437] In some embodiments, the dyes of the invention are not:

[00438] In some embodiments, the dyes of the invention are not those compounds disclosed in United States Patent Nos. 2,750,326; 3,632,582; 3,665,036; 3,867,456; 3,904,690; 4,845,293; 4,797,129; French Patent No. 2870727; Published Dutch Patent Application No. 6610759; and Great Britain Patent Publications Nos. 1150445; 1159557; 1164824 and 1164825.
[00439] The term "alkyl" includes saturated aliphatic groups, including straight chain alkyl groups (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), alkyl groups of branched chain (isopropyl, tert-butyl, isobutyl, etc.), cycloalkyl (alicyclic) groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl), cycloalkyl substituted alkyl groups, and substituted cycloalkyl alkyl groups. alkyl groups that may include oxygen, nitrogen, sulfur or phosphorus atoms replacing one or more carbons of the hydrocarbon support In certain embodiments, a straight or branched chain alkyl has 6 or less carbon atoms in its support (for example , Ci-Ce for straight chain, C3-C6 for branched chain) Likewise, cycloalkyls can have 3-8 carbon atoms in their ring structure. The term "Ci-Ce" includes alkyl groups containing © 1 to 6 carbon atoms.
[00440] In addition, the term alkyl includes both "unsubstituted alkis" and "substituted alkyls", the latter of which refer to portions of alkyl having substituting hydrogen on one or more carbons of the hydrocarbon support. Such substituents may include, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl. , phosphinate, cyano, amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, sulfonylsulfonates, thiocarboxylate , sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. Cycloalkyls can be additionally substituted, for example, with the substituents described above. An "alkylaryl" moiety or an "arylalkyl" moiety and an alkyl substituted with an aryl (e.g., phenylmethyl (benzyl)). The term "alkyl" also includes the natural and unnatural acid side chains of amine. In one embodiment, an alkyl group may have the structure of formula VI:

[00441] R104 and R105 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R104 and R105 are absent when 0;
[00442] R106 and R107 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R106 and R107 are absent when te 0;
[00443] R108 and R109 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one portion heterocyclic or thioether, or R108 and R109 are absent when u and 0; or
[00444] R104 and R105 or R105 and R106 or R106 and R107 or R107 and R108 or R108 and R109 together with the carbon atoms to which they are attached are attached to form a 3 to 10 membered carbocyclic or heterocyclic ring;
[00445] s, t and u are integers from 0 to 5;
[00446] X and NR11OR1U, CR112R113R114, OR115, SR116 or halogen;
[00447] R110 and R111 are each independently hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR117R118, or R109 and R110 together with the nitrogen to which they are attached are linked to form an aliphatic ring , 3 to 10 membered heterocyclic or aromatic;
[00448] R112, R113 and R114 are each independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, -NO2, -CN, one heterocyclic or thioether moiety, or R112 and R113 together with the carbon to which they are attached are attached to form a 3 to 10 membered carbocyclic or heterocyclic ring; or R112 is absent and R113 and R114 together with the carbon to which they are attached are attached to form an aromatic ring with 4 to 10 members;
[00449] R115 and R116 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, carbonyl, acyl or a heterocyclic moiety; and
[00450] R117 and 118 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, carbonyl, acyl or a heterocyclic moiety.
[00451] The term "aryl" includes groups, for example, 5- and 6-membered single ring aromatic groups, which may include from zero to four heteroatoms, for example, benzene, phenyl, pyrrole, furan, thiophene, thiazole, isothiaozole , imidazole, triazole, tetrazole, pyrazole, oxazole, isooxazole, pyridine, pyrazine, pyridazine, and the like In addition, the term "aryl" includes multicyclic aryl groups, for example, tricyclic, bicyclic, for example, naphthalene, benzoxazole, benzodioxazole, benzothiazole, benzoimidazole, benzothiophene, methylenedioxiphenyl, quinoline, isoquinoline, naptridine, indole, benzofuran, purine, benzofuran, deazapurine, or indolizine. Those aryl groups having hetero atoms in the ring structure can also be referred to as "aryl heterocycles", "heteroaryls" or "heteroaromatics". The aromatic ring can be substituted at one or more ring positions with such substituents as described above, such as, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkoxy, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, alkylaminoacarbonyl, arylalkyl amine no carbonyl, alkenylaminocarbonyl, alkylcarbonyl, arylcarbonyl, arylalkylcarbonyl, alkenylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, alkylaminoamino, aminoamino, alkylamino, amino, diamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azide, an aromatic or heterocyclyl heteroaromatic. The aryl groups can also be fused into bridged with alicyclic or heterocyclic rings that are not aromatic in order to form a polycyclic (for example, tetralin). The term heteroaryl includes unsaturated cyclic compounds such as azirine, oxirene, dithete, pyrroline, pyrrole, furan, dihydrofuran, dihydrothiophene, thiophene, pyrazole, imidazole, oxazole, thiazole, isothiazole, 12,2,3-triazole, 1,2 , 4, triazole, dithiazole, tetrazole, pyridine, pyran, pyrimidine, pyran, thiapyrane, diazine, thiazine, dioxin, triazine and tetrazene.
[00452] The term "heterocyclic moiety" includes saturated cyclic moieties having a closed ring of atoms in which at least one atom is not a carbon. As used herein, heterocyclic moieties do not include heteroaryl moieties, where the closed ring of atoms is both heterocyclic and aromatic and / or unsaturated. Examples of heterocyclic moieties include aziridine, ethylene oxide, thyrane, dioxirane, azetidine, oxetane, tiethane, dioxietane, dithietane, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, imidazolidine, oxazolidine, thiazolidine, dioxolane, tyrolane, ditiolane, ditiolane, pyridine, tyrolane, tyrolane, dithiolane, tyrolane, tyrolane, tyrolane, tyrolane, dithiolane, tyrolane, tyrolane, tyrolane, tyrolane, tyrolane, tetrahydrate. , piperzine, pxazine, dithian, dioxane and trioxane.
[00453] The term "heterocyclic moiety" includes both "unsubstituted heterocyclic moieties" and "substituted heterocyclic moieties", the latter of which include portions having substituents that replace a hydrogen in one or more of the atoms in the closed ring. Such substituents may include , for example, alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl alkylcarbonyloxy, arylcarbonylbxi, alkoxycarbonyl oxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, phosphineaminocarbonyl, phosphylaminocarbonyl, phosphylaminocarbonyl, fosylaminocarbonyl, phosphate , amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ure (do), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl , sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic portion.
[00454] The term "alkenyl" includes unsaturated aliphatic groups analogous in length and possible substitution for the alkyls described above, but which contains at least a double bond. For example, the term "alkenyl" includes straight chain alkenyl groups (for example, ethylenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc.), branched chain alkenyl groups, cycloalkenyl (alicyclic) groups (cyclopropentyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclohexyl) substituted alkenyl cycloalkenyl, and cycloalkyl or cycloalkenyl groups substituted alkenyl. The term "alkenyl" additionally includes alkenyl groups that include oxygen, nitrogen, sulfur or phosphorus atoms that replace one or more carbons of the hydrocarbon support. In certain embodiments, a straight and branched chain alkenyl group has 6 or less atoms of carbon in its support (for example, C2-C6 for straight chain, C3-C6 for branched chain). Similarly, cycloalkenyl groups can have 3-8 carbon atoms in their ring structure. The term C2-C6 includes alkenyl groups containing 2 to 6 carbon atoms.
[00455] In addition, the term "alkenyl" includes both "unsubstituted alkenyls" and "substituted alkenyls", the latter of which refer to portions of alkenyl having substituents that replace a hydrogen in one or more carbons of the hydrocarbon support Such substituents may include, for example, alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl oxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl. phosphonate, phosphinate, cyano, amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, arylthioates, arylthio, arylthio, arylthio, arylthio, arylthio, arylthio, aryl, sulfate, aryl, sulfate, aryl, sulfate, aryl, sulphate, aryl, sulphate. sulfonate, sulfamoyl, sulfoamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alk uilaryl, or an aromatic or heteroaromatic portion.
[00456] The term "alkynyl" includes unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but which contains at least a triple bond. For example, the term "alkynyl" includes straight-chain alkynyl groups (for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptinyl, octinyl, noninyl, decynyl, etc.), branched chain alkynyl group, and substituted cycloalkyl or cycloalkenyl groups. The term "alkynyl" additionally includes alkynyl groups that include oxygen, nitrogen, sulfur or phosphorus atoms that replace one or more carbons of the hydrocarbon support. In certain embodiments, a straight-chain or heavy-chain alkynyl group has 6 or less atoms of carbon in its support (for example, C2-C6 for straight chain, C3-C6 for branched chain) The term C2-C6 includes alkynyl groups containing 2 to 6 carbon atoms.
[00457] Furthermore, the term "alkynyl" includes both "unsubstituted alkynyls" and "substituted alkynyls", the latter of which refer to alkynyl portions having substituents that replace a hydrogen in one or more carbons of the hydrocarbon support. Such substituents may include, for example, alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl. , phosphinate, cyano, amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, sulfonylsulfonates, thiocarboxylate , sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety.
[00458] The term "acyl" includes compounds and moieties containing the acyl radical (CH3CO-). It also includes substituted acyl portions. The term "substituted acyl" includes acyl groups where one or more of the hydrogen atoms are replaced by, for example, alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, -COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, alkylaminocarbonyl, fosylaminocarbonyl, fosylaminocarbonyl, fosylaminocarbonyl, fosylaminocarbonyl, phosphate amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety.
[00459] The term "acylamino" includes portions where: an acyl moiety is attached to an amino group. For example, the term includes alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido groups.
[00460] The terms "alkoxyalkyl," "alkylaminoalkyl" and "thioalkoxyalkyl" include alkyl groups, as described above, which additionally include oxygen, nitrogen or sulfur atoms that replace one or more carbons of the hydrocarbon support, for example, atoms of oxygen, nitrogen or sulfur.
[00461] The term "alkoxy" includes substituted and unsubstituted alkyl, alkenyl, and alkynyl groups covalently attached to an oxygen atom. Examples of alkoxy groups include methoxy, ethoxy, isopropyloxy, propoxy, butoxy, and pentoxy groups.
[00462] Examples of substituted alkoxy groups include halogenated alkoxy groups. The alkoxy groups can be substituted with groups such as alkyl, alkenyl, alkynyl, halogen, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl, alkylcarbonyl. phosphonate, phosphinate, cyano, amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamine (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, sulfate, allylates, thiylboxyl sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or aromatic or heteroaromatic portions. Examples of halogen-substituted alkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, etc.
[00463] The term "amine" or "amino" includes unsubstituted and substituted compounds where an atom of is covalently bonded to at least one carbon or heteroatom including, but not limited to, amino alkyl, amino dialkyl, amino aryl, diarylamino, and alkylarylamine. The term includes "amino alkyl" which comprises groups and compounds in which: nitrogen is attached to at least one additional alkyl group. The term "amino dialkyl" includes groups in which: the nitrogen atom is attached to at least two additional alkyl groups. The term "arylamino" "and" diarylamino "include groups in which nitrogen is attached to at least one or two aryl groups, respectively. The term" alkylarylamino "," alkylaminoaryl "or" arylaminoalkyl "refer to an amino group that is attached to at least one alkyl group and at least one aryl group The term "alkaminoalkyl" refers to an alkyl, alkenyl or alkynyl group attached to a nitrogen atom which is also attached to an alkyl group.
[00464] The term "amide", "starch" or "aminocarbonyl" includes compounds or moieties that contain a nitrogen atom that is attached to the carbon of a carbonyl group or a thiocarbonyl group. The term includes "alkaminocarbonyl" or "alkylaminocarbonyl groups. "Which include alkyl, alkenyl, aryl or alkynyl groups attached to an amine group attached to a carbonyl group. It includes arylaminocarbonyl and arylcarbonylamino groups, which include all aryl or heteroaryl moieties attached to an amino group that is attached to the carbon of a group carbonyl or thiocarbonyl. The terms "alkylaminocarbonyl", "alkenylaminocarbonyl", "alkynylaminocarbonyl", "arylaminocarbonyl", "alkylcarbonylamino", "carbonylamino alkenyl", "alkynylcarbonylamino", and "arylcarbonylamino" are also included in the term "amyl". include groups of urea (aminocarbonylamino) and carbamates (oxycarbonylamino).
[00465] The term "carbonyl" or "carboxy" includes compounds and portions that contain a carbon bonded with a double bond to an oxygen atom. The carbonyl can be additionally substituted with any portion that allows the compounds of the invention to perform their function For example, portions of carbonyl may be substituted with alkyls, alkenyls, alkynyls, aryls, alkoxy, amines, etc. Examples of portions containing a carbonyl include aldehydes, ketones, carboxylic acids, amides, esters, anhydrides, etc. The term "carboxy" additionally includes the structure of -COOH and -COO.
[00466] The term "oxymyl" includes compounds and portions that contain a carbon bonded with a double bond to a nitrogen atom, which is in turn bonded to a hydroxyl group or an alkoxyl group. The term "hydrazinyl" includes compounds and portions that contain a carbon bonded with a double bond to a nitrogen atom, which is in turn bonded to an amino group.
[00467] The term "thiocarbonyl" or "thiocarboxy" includes compounds and moieties that contain a carbon bonded with a double bond to a sulfur atom.
[00468] The term "ether" includes compounds or moieties that contain an oxygen attached to two different carbon atoms or hetero atoms. For example, the term includes "alkoxyalkyl" which refers to an alkyl, alkenyl, or alkynyl group covalently attached to an oxygen atom which is covalently attached to another alkyl group.
[00469] The term "thioether" includes compounds and moieties that contain a sulfur atom attached to two different carbon atoms or hetero atoms. Examples of thioethers include, but are not limited to, alktioalkenis, alktioalkenis, and alktioalquinis. The term "alktylalkyls" includes compounds with an alkyl, alkenyl, or alkynyl group attached to a sulfur atom which is attached to an alkyl group Similarly, the term "alktylalkyls" and "alktylalkini" refers to compounds or portions in which a group alkyl, alkenyl or alkynyl and attached to a sulfur atom which is covalently attached to an alkenyl or alkynyl group, respectively.
[00470] The term "sulfonyl" includes portions containing a sulfonyl functional group (for example, SO2) attached to two carbons, via a covalent bond to the sulfur atom of the sulfonyl functional group.
[00471] The term "sulfonic acid" includes moieties containing a sulfonyl functional group (e.g., SO2) attached to a carbon and oxygen, via covalent bonds.
[00472] The term "diazene" and "diazo" include portions containing two nitrogen atom covalently doubly bonded to each other (for example, N = N). Nitrogen atoms can be covalently linked to hydrogen, alkyl, alkenyl, alkynyl, hydroxyl or aryl. In some embodiments, the diazene moiety is an arildiazene, for example, the diazene phenyl, which can be replaced with alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyloxy, -COOH, -COOH , alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, alkoxy, phosphate, phosphonate, phosphinate, cyano, amine (including amino alkyl, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoamide. , imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic portion.
[00473] The term "hydroxy" or "hydroxyl" includes groups with an -OH or -O ".
[00474] The term "halogen" includes fluorine, bromine, chlorine, iodine, etc.
[00475] The term "heteroatom" includes atoms of any element other than carbon or hydrogen. Preferred heteroatom are nitrogen, oxygen, sulfur and phosphorus.
[00476] The language "cosmetically acceptable salts" includes those salts of the dyes of the invention that are acceptable for cosmetic application. A person skilled in the art would be able to readily determine salts that are cosmetically acceptable because they refer to, for example, the ntemational Cosmetic Ingredient Dictionary and Handbook, Tenth Ed., 2004 (hereby incorporated by reference in its entirety).
[00477] The dyes of the invention that are basic in nature are capable of forming a wide variety of cosmetically acceptable acid adipation salts of the dyes of the invention that are basic in nature are those that form non-toxic acid adipation salts, i.e., salts contains cosmetically acceptable anions, such as hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate , maleate, gentisinate, fumarate, gluconate, glucaronate, saccharate, format, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and palmoate (/ sto e, l, l'methylene-bis- (2-hydroxy-3-) acid adipation salts of base dyes are readily prepared by treating the base compound with a substantially equivalent amount of the mineral or organic acid chosen in a medium aqueous solvent in a suitable organic solvent, such as methanol or ethanol. After careful evaporation of the solvent, the desired solid salt is readily obtained. The preparation of other dyes of the invention not specifically described in the experimental section can be carried out using combinations of the described reps that will be apparent to a person skilled in the art.
[00478] Invention dyes that are acidic in nature are capable of forming a wide variety of base salts. The chemical bases that can be used as reagents to prepare cosmetically acceptable base salts of the dyes of the invention that are acidic in nature are those that form non-toxic base salts with such compounds. Such non-toxic base salts include, but are not limited to, those derived from such cosmetically acceptable cations such as alkali metal cations (for example, potassium and sodium) and alkaline earth metal cations (for example, calcium and magnesium), salts of water-soluble amine ammonia addition such as N-methylglucamine- (meglumine), and the lower alkanolammoniums and other cosmetically acceptable organic amine based salts. The cosmetically acceptable acidic additive salts of the dyes of the invention that are acidic in nature can be formed with cosmetically acceptable cations by conventional methods. In this way, these salts can be readily prepared by treating the dyes of the invention with an aqueous solution of the desired cosmetically acceptable cation and evaporating the resulting solution on drying, preferably under reduced pressure. Alternatively, a lower alkyl alcohol solution of the dyes of the invention can be mixed with a desired metal alkoxide and the solution subsequently evaporated to dryness. II. DYE COMPOSIGNS
[00479] In some aspects, the present invention provides dye composition containing at least one dye of the invention and a suitable medium for coloring keratin fibers (for example, hair). The language "suitable medium for coloring keratin fibers" includes media that are capable of containing at least one dye of the invention and include, for example, solutions, sprays, rinsers, mousses, gels, powders, shampoos and creams.
[00480] In some embodiments, the dye compositions contain one or more direct dyes or oxidizing dyes in addition to those containing at least one dye of the invention. Where the dye composition contains one or more oxidizing dyes, the dye or dyes of the invention in the composition can act as a spectator dye. The language "spectator dye" includes the dye of the invention being present in the dye solution or composition, but not participating in the oxidative reaction required by the oxidizing dyes to provide color.
[00481] In other embodiments, the dyes of the invention are formulated as a color developer. The "color enhancer" language includes dye compositions comprising at least one dye of the invention that can be added to a dye composition containing one or more direct dyes or oxidizing dyes in order to increase the color and / or increase the vibration of the composition of dye after application to the hair. In some embodiments, the color enhancer can be applied to hair in the same compositions as the dye composition containing one or more direct dyes or oxidizing dyes. In other embodiments, the color enhancer may be applied to the hair in a composition separate from that of the composition containing one or more direct dyes or oxidizing dyes, and may be added before, substantially at the same time, or after application of the composition containing one or more direct or oxidizing dyes.
[00482] In other embodiments, the medium is an aqueous medium. The language "aqueous medium" includes a medium that contains about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40% , about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90% or about 95% water.
[00483] In still other embodiments, the medium additionally includes one or more of surfactants, thickeners, fragrances, sequestering agents, UV classifying agents, waxes, silicones, preservative agents, ceramides, oils, vitamins, pro-vitamins, opacity builders , couplers, primary intermediates, alkalizing agents, direct dyes, reducing agents, antioxidants, emulsifiers, chelating agents, color retardants, solvents and buffers (for example, phosphate buffers). Examples of the preceding agents can be found in the International Cosmetic Ingredient Dictionary and Handbook, Tenth Ed., 2004 (hereby incorporated by reference in its entirety).
[00484] Examples of surfactants include, but are not limited to, oleth 5, oleic acid and sodium lauryl sulfate.
[00485] Examples of thickeners include, but are not limited to, fatty alcohols (for example, oleyl alcohol), etixylated phenols (for example, octoxynol-1, nonoxynol-4, and nonoxynol-9), and polymers (for example, hydroxyethylcellulose).
[00486] Examples of couplers include, but are not limited to, 3-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, 2-methyl-5aminoenol, and 4-amino-2-hydroxytoluene.
[00487] An example of a primary intermediate includes, but is not limited to, paraeinylenediamine and 4-aminophenol.
[00488] Examples of antioxidants include, but are not limited to, sodium sulfite and erythorbic acid.
[00489] Examples of emulsifiers include, but are not limited to, Pluracare L64® and Inconam 30®.
[00490] An example of a chelating agent includes, but is not limited to, EDTA.
[00491] Examples of solvents include, but are not limited to, water, Ci to C4 lower alcohols (for example, ethanol, 2-propanol and isopropanol), acetone, methyl ethyl ketone, ethyl acetate, methyl acetate, butyl acetate, diethoxyethane , dimethoxyethane, Ce to C10 alkanes, dimethyl isosorbide, ethoxydiglycol propylene glycol.
[00492] Examples of alkalizing agents include, ammonium hydroxide, ammonia, alkylamines (e.g., ethylamine; dipropylamine; triethylamine; n-propylamine, isobutylamine, 2-ethylbutylamine, diethylamine), alkanodiamines (e.g., 1,3-diaminopropane ; ethylenediamine; 1,2-diaminopropane; diethylenetriamine; triethylonetriamine; 2,2'minodipropylamine; 3,3-iminodipropylamine; and bishexamethylenetriamine), alkanolamines (for example, ethanolamine, diethanolamine, isopropanolamine; di-isopropanolamine-mine; isopropanolamine; N-methylldiethanolamine; diisopropylethanolamine; dimethylisopropanolamine; 2-amino-2-methylpropane-1,3-diol; tris (hydroxymethyl) methylamine; N- (2-hydroxyethyl) aniline; N-methyl-N (2hydroxyethyl) aniline; N , N-bis (2-hydroxyethyl) aniline), polyalkylene polyamines, (e.g., diethylene triamine), heterocyclic amines (e.g., morpholine; N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-phenylmorpholine, piperidine, N-hydroxy pip erazine), alkaline earth hydroxides (for example, calcium hydroxide or magnesium hydroxide), alkali metal hydroxide (for example, sodium hydroxide or potassium hydroxide), or carbonates (for example, carbonate and sodium bicarbonate).
[00493] In particular embodiments, the alkalizing agent is present in the composition between about 0.05% to about 10%, between about 0.1% and about 5%, or between about 1.5% to about 3.5%.
[00494] In some embodiments, the dye composition is formulated into a cosmetically acceptable composition. The language "cosmetically acceptable composition" includes dye compositions that comprise at least one dye of the invention and are suitable for cosmetic application. A person skilled in the art would be able to readily determine formulations and compositions that are cosmetically acceptable by reference to, for example, the International Cosmetic Ingredient Dictionary and Handbook, Tenth Ed., 2004 (hereby incorporated by reference in its entirety).
[00495] In some embodiments, the dye composition comprises about 3% of the invention's dye, about 15% of an emulsifier (for example, Pluracare L64® or Incronam 30®), about 25% of a solvent (for example example, dimethyl isosorbide), and about 53% aqueous phosphate buffer.
[00496] In other embodiments, the dye composition comprises about 0.1% to 3% of the dye of the invention, about 50% of solvent (e.g., ethanol), and the remaining solution of a phosphate buffer.
[00497] In still other embodiments, the dye composition comprises about 0.1-3% dye of the invention, between about 1.5% to about 3.5% ammonia, about 0.05% stabilizer (for example, EDTA), about 0.4% of antioxidant (for example, sodium sulfite and / or isoascorbic acid), between about 20% and about 25% of solvent (for example, ethoxydiglycol) and about 30% surfactant (e.g., oleth-5 and / or oleic acid) with the remaining solution comprising water.
[00498] In still other embodiments, the dye composition comprises about 0.1-3% dye of the invention, between about 1.5% to about 3.5% ammonia, about 0.05% stabilizer (for example, EDTA), about 0.2% of antioxidant (for example, sodium sulfite), between about 8% and about 25% of solvent (for example, propylene glycol and / or 2-propanol) , about 2% surfactant (for example, sodium lauryl sulfate), about 21% of buffer (for example, oleic acid), about 10% of thickener (for example, oleyl alcohol) with the remaining solution comprising water.
[00499] In some embodiments, the dyes of the invention are formulated in a conditioner after dyeing (for example, L'Oreal Superior Preference Care Supreme Color-Saving Conditioner) and similar formulations for application during conditioning. III. METHODS
[00500] In some respects, the present invention provides methods for dyeing keratin fibers by applying to the keratin fibers a Dye Composition comprising at least one dye of the invention. The term "keratin fibers" includes human hair and animal hair.
[00501] In some respects, the present invention provides methods for dyeing synthetic hair by applying to the synthetic hair a Dye Composition comprising at least one dye of the invention. The term "synthetic hair" includes hair or hair produced from unnatural fibers, for example, adulterated or "fake" hair and synthetic hair wigs.
[00502] In some respects, the present invention provides methods for coloring hair by applying to the hair a Dye Composition comprising at least one dye of the invention. The language "hair coloring" includes treating substantially all of the hair on a person's head, or some of the hair on a person's head.
[00503] In some respects, the present invention provides methods for dyeing damaged hair by applying to the hair a dye composition comprising at least one dye of the invention. The language "dyeing damaged hair" includes treating all hair on a person's head or some of the hair on a person's head, where hair is more porous than normal hair.
[00504] In some respects, the present invention provides methods for lightening hair by applying to the hair a Dye Composition comprising at least one dye of the invention. The language "lighten hair" includes treating some of the hair on a person's head.
[00505] In other respects, the present invention provides methods for retouching hair roots by applying the roots of a dye composition comprising at least one dye of the invention. The "touch-up" language of hair roots "includes treating the hair on the head of a person who is closest to the scalp.
[00506] In some embodiments, the dye composition comprising at least one dye of the invention is applied to wet or dry hair.
[00507] In other embodiments, the methods include the step of leaving the composition comprising at least one dye of the invention in the hair for between about 1 and 60 minutes.
[00508] In some other embodiments, the methods include the steps of a) treating the hair with an oxidizing dye in the presence of ammonia and, optionally, hydrogen peroxide for between about 1 and about 60 minutes; b) optionally rinse the hair; and, optionally, partially drying the hair; c) treating the hair with a dye composition comprising at least one dye of the invention for between about 1 and about 60 minutes; and d) rinse the hair. The methods may also include the steps of e) washing the hair with shampoo and / or conditioning the hair with conditioner after rinsing the hair; f) rinse the hair; and g) optionally drying the hair.
[00509] In some embodiments, the methods additionally comprise the steps of a) treating the hair with a dye composition comprising at least one dye of the invention optionally containing one or more oxidizing precursor dye and / or one or more direct dyes with one or more more alkalinizing agents and, optionally, hydrogen peroxide for between about 1 and about 60 minutes; b) rinse the hair; c) wash your hair with shampoo and / or condition your hair with conditioner; d) rinse the hair; and e) optionally drying the hair. IV. KITS
[00510] In some aspects, the present invention provides kits comprising a dye composition comprising at least one dye of the invention with instructions for use. In some embodiments, the dye is formulated as a cosmetically acceptable formulation. In some embodiments, the cosmologically acceptable formulation may additionally comprise ammonia.
[00511] In other embodiments, the kit can confer, for example, a return bottle, gloves or a conditioning rinse. In some other embodiments, the return bottle contains a solution comprising hydrogen peroxide. In still other embodiments, one or more dyes of the invention are packaged separately from the dye composition. FICACAQ EXAMPLE OF THE INVENTION
[00512] The methods of this invention can be further understood by the following examples. It will be appreciated, however, that these examples do not limit the invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the present invention as described herein and hereinafter claimed. Example 1: Synthesis of Selected Dyes of the Invention Synthesis of AF Compounds: The synthesis of the AF compounds was synthesized as shown below in Scheme 1.
Layout 1
[00513] N-Ethylaniline (1.50.00 g, 0.412 mol) was added to a stirred solution of NaH (1.2 eq, 11.86 g, 0.495 mol) in THF (300 ml) at 0 ° C, followed by ethyl bromoacetate (2, 1.2 eq, 82.69 g, 0.495 mol). The reaction mixture was warmed to room temperature and continued stirring for 30 minutes. The temperature of the reaction mixture was raised to 55 ° C and stirred for 14 hours. The reaction mixture was brought to room temperature, quenched with ice water and extracted with EtOAc (3 x 300 ml). The resulting extracted EtOAc was washed with water (2 x 300 ml), dried over Na2SO4, and concentrated. The concentrated product was purified by column chromatography using 5% EtOAc in petroleum ether to provide compound 3 as a marram liquid (80 g, 93.5%). Rf: 0.8 (petroleum ether: EtOAc, 9: 1). 1 H NMR (300 MHz, CDCl 3): 6 121-120 (m, 2H), 6.75-6.65 (m, 3H), 4.21 (q, 7 = 7.1 Hz, 2H), 4 , 02 (s, 2H), 3.99 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3), 1.22 (t, 7 = 7, 1 Hz, 3H). LCMS, single peak, 4.188 min, ESAPCI: n / Z 208.2 [M + H] +.
[00514] To a stirred solution of 2-chloro-4-nitroaniline (4, 1.5 eq, 50.00 g, 0.289 mol) in acetonitrile (715 ml) and HC11.0 N (1.285 L) was added now at drop NaNCh (1.5 eq, 20.00 g, 0.289 mol) in water (150 ml) at 0 ° C over a period of 30 minutes and continued agitation for 1.5 hours. The resulting reaction mixture was added to 3 (1.0 eq, 38.25 g, 0.185 mol) with sulfamic acid (0.1 eq, 1.80 g, 18.5 mmol) in acetonitrile (1.150 L) and HC11 M (1,150 L) at 0 ° C over i, 45 minute period with continued agitation for 60 minutes. Saturated sodium bicarbonate was then added to the resulting reaction mixture at 0 ° C to adjust to a pH of about 1 and the mixture was stirred for 1.2 hours at the same temperature. Then, the reaction mixture was extracted with dichloromethane (4x1 L), dried over Na2SO4, and concentrated. The concentrated product was stirred with methyl t-butyl ether (500 ml) for 30 minutes and filtered to provide 5 as a dry red solid (35 g, 48.5%). Rf: 0.6 (pet. Ether: EtOAc, 9: 1). 1 H NMR (400 MHz, DMSO-d6): 5 8.46 (bs, 1H), 8.28-8.25 (m, 1H), 7.88 (d, J = 9.0 Hz, 2H) , 7.79 (d, 7 = 8.9 Hz, 1H), 6.84 (d, J = Hz, 2H), 4.38 (s, 2H), 4.16 (q, J = 7.1 Hz, 2H), 3.58 (q, J = 7.1 Hz, 2H), 1.22 (t, J = Hz, 3H), 1.82 (t, 7 = 7.1 Hz, 3H). LCMS, single peak, 4.965 min, ES-APCI: m / z 390.9 [M + H] +.
[00515] Lithium hydroxide (2.6 eq, 3.23 g, 0.135 mol) in H2 O (20 ml) was added to a stirred solution of 5 (1.0 eq, 20.00 g, 0.051 mol) in tetra -hydrofuran (120 mL) and water (120 mL) at 0 ° C, which was allowed to stir at room temperature for 1.5 hours. The tetrahydrofuran was evaporated in vacuo and the pH adjusted to approximately 7 using citric acid solution. The resulting reaction mixture was extracted with ethyl acetate (2 x 200 ml). The organic layer was dried over Na2SO4 and concentrated. The concentrated product was triturated with 100 ml of Et2O-EtOAc (8: 2) to provide 6 as a dark shallow solid (14 g, 75.4%). Rf 0.2 (CHCh: MeOH, 9: 1). 'H NMR (300 MHz, CDC13): 6 8.35 (s, 1H), 8.12 (d, J = 9.0 Hz, 1H), 7.90 (d, J = 9.3 Hz), 7.73 (d, 7 = 9.0 Hz, 1H), 6.70 (d, 7 = 9.3 Hz, 2H), 4.10 (s, 2H), 3.55 (q, J = 7 , 1 Hz, 2H), 1.26 (t, 7 = 7.2 Hz, 3H). LCMS, single peak, 4.729 min, ES-APCI: m / z 362.9 [M + H] +. HPLC purity: 97.6%.
[00516] Compound A: N- (3-aminopropyl) diethanolamine (1 eq, 298 mg, 1.84 mmol, CAS # 4985-85-7) was dissolved in 10 ml of 9: 1 CH2Cl2: DMF. An amount of 1-ethyl-3- (3dimethylaminopropyl) carbodiimide hydrochloride (EDC, 2.0 eq, 571 mg, 3.68 mmol), 1-hydroxybenzotriazole hydrate (HOBt, 1.5 eq, 422 mg, 2.76 mmol ), and N, N-diisopropylatylamine (DIPEA, 2.0 eq, 640 (pL, 3.68 mmol) were added therein to the amine stirring solution. Compound 6 (1.2 eq, 1.00 g, 2 , 76 mmol) was dissolved in 5 ml of 9: 1 CH2Cb: DMF and added to the reaction vessel The mixture was stirred at room temperature overnight and was subsequently diluted with 30 ml of CH2 Cl2 and washed with saturated sodium bicarbonate ( 2 x 30 ml) and brine (1 x 30mL), dried over Na2SO4 and concentrated by rotary evaporation After column chromatography (2X), the yield was 47%. 'H NMR (300 MHz, CDCl3): 6 8.25 (s, 1H), 8.04 (d, J = 9.0 Hz, 1H), 7.85 (d, J = 9.0 Hz, 2H), 7.67 (d, J = 9.0 Hz , 1H), 6.89 (bt, J = 5.9 Hz, 1H, NH), 6.72 (d, J = 9.0 Hz, 2H), 3.98 (s, 2H), 3.54 (m, 6H), 3.40 (q, J = 6.7 Hz, 2H), 2.53 (t, J = 5.0 Hz, 4H), 2.46 (t, J = 6.2 Hz , 2H), 1.65 (quin ceiling, J = 6.3 Hz, 2H), 1.27 (t, J = 6.7 Hz, 3H). LCMS, single peak, 2.554 min, ES-APCI: m / z507.2 [M + H] +.
[00517] Compound B: Using a similar procedure as outlined for compound A, an amount of 6 (1.2 eq, 435 mg, 1.20 mmol) was reacted with 3- (diethylamino) polyamine (1.0 eq, 130 mg, 158 pL, 1.00 mmol, CAS # 104-78-9). In addition to the washes, the organic fractions were removed in CH2CI2 and loaded into a Thermo Scientific 5 g HyperSep SCX cartridge. The cartridge was washed with 25 ml each of CH2 Cl2, then MeOH, and was then eluted with 2 M NH3 in MeOH to produce dark red / purple solid. Yield: 78%. 1H NMR (300 MHz, CDCl3): 5 8.40 (s, 1H), 8.16 (d, J = 9.0 Hz, 1H), 7.95 (d, J = 9.0 Hz, 2H) , 7.78 (d, J = 9.0 Hz, 1H), 7.67 (bt, 1H, NH), 6.77 (d, J = 9.0 Hz, 2H), 3.99 (s, 2H) , 3.57 (q, J = 7.1 Hz, 2H), 3.38 (q, J = 6.1 Hz, 2H), 2.41 (t, J = 6.1 Hz, 2H), 2.34 (q, 7 = 7.1 Hz, 4H), 1.59 (quintet, 7 = 6.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H), 0.84 (t, J = 7.1 Hz, 6H). LCMS, single peak, 3.257 min, ES-APCI: m / z 475.2 [M + H] +.
[00518] Compound C: Compound C was synthesized in a similar manner as compound A above. Partitioning with compound 6 (1.2 eq, 268 mg, 0.739 mmol) and reacting with N- (3-aminopropyl) morpholine (1.0 eq, 88.8 mg, 89.7 pL, 0.616 mmol, CAS # 123-00-2) produced a dark red / purple residue. Yield: 90%. 'H NMR (400MHz, CDC13): 5 8.41 (d, 1H, J = 2.4 Hz), 8.17 (dd, 1H, J = 2.4 Hz, and 8.9 Hz), 7, 97 (d, 2H, J = 9.1 Hz), 7.78 (d, 1H, J = 8.9 Hz), 7.0 (brs, 1H), 6.81 (d, 2H, J = 9 , 1 Hz), 4.01 (s, 2H), 3.62-3.59 (m, 6H), 3.38 (q, 2H, J = 6.3 Hz), 2.36 (brs, 6H ), 1.70 (t, 2H, J = 6.4 Hz), 1.30 (t, 3H, J = 7.0 Hz). LCMS, single peak, 3.935 min, ES-APCI: m / z489.2 [M + H] +. Synthesis of Compounds G and J: Compounds G and J were synthesized as shown in Scheme 2.

[00519] Compound 9 was either purchased from Polymer Source, Inc., or synthesized as follows: Red dye Disperse 13 dye (8, 13.14 g, 37.68 mmol, 1.0 eq) was dissolved in 250 mL of tetrahydrofuran (THF) and triethylamine (NEt3, 33.62 mL, 241 mmol, 6.4 eq), and the mixture was cooled in an ice bath. Acryloyl chloride (5.70 g, 5.36 ml, 65.95 mmol, 1.75 eq) was added in 55 ml of THF dropwise with a funnel adding to the stirred reaction mixture. The mixture was then allowed to warm to room temperature, and was stirred overnight. The excess of acryloyl chloride was quenched with the addition of 200 ml of saturated sodium bicarbonate, and the product was extracted with 1 x 200 ml and 2 x 100 ml of CHCl 3. The organic portion was dried over Na2SO4 and concentrated by rotary evaporation to produce a dark red / purple residue. Co-evaporation with 125 ml of a mixture of 3: 2 acetone and MeOH led to the isolation of a dark purple solid (9). Yield: 96%. 1H NMR (CDCI3, 300 MHz, 25 ° C): 5 8.38 (s, 1H), 8.14 (d, J = 9.0 Hz, 1H), 7.94 (d, J = 9.2 Hz, 2H), 7.77 (d, J = 9.0 Hz, IH), 6.81 (d, J = 9.2 Hz, 2H), 6.42 (d, 7 = 17.5 Hz, IH), 6.12 (dd, J = 17.5, 10.4 Hz, IH), 5.87 (d, J = 10.4 Hz, IH), 4.36 (t, J = 6.2 Hz, 2H), 3.74 (t, J = 6.2 Hz, 2H), 3.54 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H).
[00520] Compound J: Ethylene diamine (323 mg, 360 pL, 5.37 mmol, 1.0 eq) was dissolved in 10 ml of CHCl3 and cooled on ice. Compound 9 (2.16 g, 5.37 mmol) was dissolved in 15 ml of CHCl 3 and added dropwise via syringe to stirring and the mixture cooled. The mixture was stirred at 50-60 ° C for 2 days. 1H NMR (CDCl3, 400 MHz, 25 ° C): 5 8.37 (s, IH), 8.14 (d, J = 9.0 Hz, IH), 7.92 (d, 2H), 7, 77 (d, J = 9.0 Hz, IH), 6.79 (d, 2H), 4.31 (m, 2H), 3.69 (t, 2H), 3.53 (t, 2H), 2.87 (m, 2H), 2.75 (m, 2H), 2.65 (m, 2H), 2.51 (m, 2H), 1.26 (t, 3H). Synthesis of U-AA Compounds: U-AA compounds were synthesized as shown in Scheme 3.
Layout 3
[00521] U-AA Compounds were prepared by dissolving compound 9 in CHCh and adding compound 9 dropwise to 0.5 eq of amine dissolved in CHCl3 and cooled on ice. The mixture was stirred at 50-60 ° C for 2 days. Synthesis of AB-AH Compounds: AB-AH compounds were synthesized as shown in Scheme 4.

[00522] Using a similar procedure as outlined immediately above, the AB-AH compounds were synthesized. Compound 13 is synthesized as follows: Compound 12 (1.0 eq) is dissolved in 250 ml of tetrahydrofuran (THF) and triethylamine (NEta, 6.4 eq), and the mixture is cooled in an ice bath . Acryloyl chloride (1.75 eq) and 55 ml of THF are added dropwise with an addition funnel to the reaction mixture with stirring. The mixture is then allowed to warm to room temperature, and is stirred overnight. The excess of acryloyl chloride is quenched with the addition of 200 ml of saturated sodium bicarbonate, and the product is extracted with 1 x200 ml and 2 x 100 ml of CHCl 3. The organic portion is dried over Na2SO4 and concentrated by rotary evaporation. Co-evaporation with 125 ml of a mixture of 3: 2 acetone and MeOH led to the isolation of compound 13. Synthesis of Compounds A1 and AJ: Compounds A1 and AJ were synthesized as shown in Scheme 5.

[00523] Compound 8 (5.00 g, 14.34 mmol) was added to a stirred solution of epichlorohydrin (2.0 eq, 2.65 g, 28.65 mmol) in 50% aqueous sodium hydroxide (25 g of NaOH in 50 ml of H2O) and THF (10 ml), followed by adipation of tetrabutylammonium hydrogen sulfate (0.1 eq, 470 mg, 1.41 mmol) at room temperature. The resulting reaction mixture was stirred vigorously using a mechanical stirrer for 16 hours at room temperature. After completion of the reaction, water (20 ml) was added to the reaction mixture, and the product was extracted with dichloromethane (2 x 200 ml). The extracted dichloromethane was dried over Na2SO4 and concentrated by rotary evaporation. The resulting concentrated product was purified by column chromatography using 80% dichloromethane in pet ether to provide pure product 15 as a dark purple / black viscous liquid (3.5 g, 60%). Rf 0.4 (pet ether: ethyl acetate, 7: 3). 1H NMR (400 MHz, CDCh): 5 8.41 (s, 1H), 8.16 (d, / = 8.9 Hz, 1H), 7.96-7.93 (d, J = 9.2 Hz, 2H), 7.79 (d, J = 8.9 Hz, 1H), 6.79 (d, J = 9.2 Hz, 2H), 3.74-3.71 (m, 1H), 3.80-3.72 (m, 2H), 3.68-3.62 (m, 2H), 3.58 (q, 7 = 7.1 Hz, 2H), 3.39 (dd, J = 11.6, 6.0 Hz, 2H), 3.18-3.14 (m, 1H), 2.83-2.81 (m, 1H), 2.63-2.61 (m, 1H) , 1.27 (t, J = /. Hz, 3H). 13C NMR (100 MHz, CDCI3): 5 153.2, 152.0, 147.0, 144.2, 133.9, 127.1, 126.1, 122.7, 118.0, 111.5, 72.1, 69.0, 50.9, 50.4, 46.2, 44.1, 12.3, LCMS, single peak, 4,130 min, ES-APCI: m / z404.9 [M + H] +.
[00524] Compound AJ: Epoxide 15 (1.00 g, 2.47 mmol) was dissolved in 900 pL DMF. (±) -3-amino-1,2-propanediol (0.5 eq, 113 mg, 1.24 mmol) was added to the stirring reaction mixture. The mixture was stirred at 95 ° C overnight. The mixture was diluted in 20 ml of EtOAc and washed with saturated sodium bicarbonate (2 x 15 ml) and brine (1 x 10 ml), dried over Na2CO4 and concentrated by rotary evaporation to produce a dark red purple residue. The yield was quantitative. 1H NMR (400 MHz, CDC13): 5 8.37 (s, 2H), 8.15 (d, J = 8.9 Hz, 2H), 7.92 (d, J = 9.2 Hz, 4H) , 7.78 (d, J = 8.9 Hz, 2H), 6.77 (d, J = 9.2 Hz, 4H), 3.83 (m, 2H), 3.67 (m, 4H) , 3.63 (m, 5H), 3.53 (m, 5H), 3.45 (m, 3H), 3.38 (m, 2H), 2.65 (m, 1H), 2.60 ( m, 4H), 2.44 (m, 1H), 1.62 (s, 3H, -OH), 1.23 (t, 7 = 7.1 Hz, 6H). Synthesis of AK and AL Compounds: AK and AL compounds were synthesized as shown in Scheme 6.
Layout 6
[00525] 2-Chlorethylamine hydrochloride (14.32 g, 123.5 mmol, 3.3 eq) was dissolved in 100 ml of chloroform and N, N-diisopropylatylamine (DIPEA, 32.59 ml, 24.18 g, 187 , 1 mmol, 5.0 eq). 1-Fluoro-2-nitrobenzene (17, 5.28 g, 3.97 mL, 37.42 mmol, 1.0 eq) was slowly added to the stirring mixture at room temperature. The mixture was then heated to reflux under a condenser for 2 hours. The reaction mixture was diluted with 100 ml of water, and the product was extracted with 1 x 50 ml and 1 x 25 ml of CHCh. The organic portion was washed with 1 x 100 ml and 1 x 50 ml of brine, dried over Na 2 SO 4, and concentrated by rotary evaporation to produce product 18 as an orange residue. Yield: 22%. 1 H NMR (CDCl 3, 400 MHz, 25 ° C): 5 8.25 (s, IH, NH), 8.19 (dd, J = 8.6, 1.5 Hz, IH), 7.50 7 , 43 (m, IH), 6.86 (d, J = 8.6 Hz, IH), 6.70 (ddd, J = 10.6, 5.9, 2.4 Hz, IH), 3, 80 3.74 (m, 2H), 3.74 3.67 (m, 2H).
[00526] Compound AK: Compound 18 (1.26 g, 6.28 mmol) was dissolved in 15 ml of CHCl3 and DIPEA (5.47 ml, 4.06 g, 31.40 mmol, 5.0 eq). N- (3-aminopropyl) diethanolamine (3.06 g, 3.70 mL, 18.84 mmol, 3.0 eq) was dissolved in 10 mL of CHCh and the stirring reaction mixture was added along with approximately 5 mL rinse with CHCl3. The mixture was heated to reflux for 2 days. The product was purified by column chromatography eluting with 0.5% triethylamine and 4% methanol in chloroform. Yield: 23%. 1 H NMR (CDCl 3, 400 MHz, 25 ° C): 5 8.15 (bs, IH, NH), 8.12 (dd, J = 8.6, 1.6 Hz, IH), 7.41 ( ddd, J = 8.5, 7.0, 1.2 Hz, IH), 6.85 (dd, J = 6.7, 1.9 Hz, IH), 6.61 (ddd, J = 8, 4, 5.6, 1.2 Hz, IH), 3.63 (dd, J = 6.8, 3.7 Hz, 4H), 3.45 (s, IH, NH), 3.38 (dd , J = 12.1, 6.7 Hz, 2H), 3.10 2.46 (m, 10H), 1.88 (p, J = 6.8 Hz, 2H). Synthesis of Compound AN: Compound AN was synthesized as shown in Scheme 7.
Layout 7
[00527] Compound AN: 4-Fluoro-2-nitroaniline (20, 1.08 g, 6.91 mmol) was dissolved in 8 mL of methanol and DIPEA (4.61 mL, 3.42 g, 26.48 mmol , 3.8 eq). N3- (2-aminoethyl) -N, N -diethyl-1,3-propanediamine (1.73 g, 10.00 mmol, 1.4 eq) was dissolved in 5 ml of methanol and the reaction mixture was added stirring with approximately 5 ml of methanol rinsing. The mixture was heated to reflux for 2 days.
[00528] The product was purified by column chromatography eluting with 1% triethylamine and 4% methanol in chloroform. Yield: 3.8%. 1H NMR (400 MHz, MeOD) 5 7.50 (d, J = 2.7 Hz, IH), 7.09 (dd, J = 9.1, 2.8 Hz, IH), 6.92 (d , J = 9.1 Hz, IH), 3.45 (t, J = 6.3 Hz, 2H), 2.87 (t, J = 6.3 Hz, 2H), 2.65 (t, J = 7.0 Hz, 2H), 2.63 -2.49 (m, 6H), 1.76 -1.63 (m, 2H), 1.110.99 (t, J = 7.2 Hz, 6H) . Example 2: Exemplary Formulations
[00529] The formulations placed below have been prepared to test certain dyes of the invention. A person skilled in the art would be able to determine the appropriate amounts or ranges of the formulation components with no more than expert routine mentoring.








Example 3. Evaluation of Colorimetry of the Examplar Dyes of the invention
[00530] Materials: Light blond virgin hair, light brown, medium virgin brown, and medium brown bleached were purchased from International Hair Importers (Glendale, NY). Concentrated bleaching P6 BW 2000 Ultra, 20V Pure White Hydrogen Peroxide, and 40V Pure White Hydrogen Peroxide were purchased from Clairol Professional (Stamford, CT). The shampoo was a solution of 7.5% (w / w) sodium lauryl sulfate (SLS, Spectrum Chemical, Gardena, CA) in deionized water.
[00531] Bleaching: A quantity of 1 gram of virgin hair from International Hair Importers was used, which was thick enough that when laid flat on a surface, the base was not seen. The white paste was recently produced before use by mixing 5.57 grams per 10 ml of BW 2000 Ultra concentrated bleaching powder with 10 ml per 20 V pure white hydrogen peroxide solution. The thick white ruffled paste was spread quickly. on both sides of the strands of hair, and then the set time has started. The paste was then spread evenly with the fingers (gloves) on the board so that the last one was well saturated. The mat was wrapped in aluminum foil, and allowed to stand for a total of 30 minutes at room temperature after which the mat was completely rinsed with water. Shampoo was applied with a 7.5% SLS solution, rinsed and dried. For quick drying, the strips were left in the humidity chamber at 20% Relative Humidity, 50 ° C for 20 minutes. Blow drying was avoided so as not to tangle the hair and induce damage. The hair was also sometimes dried with air for at least 3-4 hours. The procedure was repeated up to 3 times if triple bleached hair was desired.
[00532] Color treatment: The batch / paste of dye should be enough to involve the hair and saturate the hair (about 5 grams of paste per 1 gram of hair). When several strands have been colored at the same time, there are delay times between the application of the dyes or shampoos that can make the tones and shadows of the dyes different for each strand. In order to minimize any discrepancy in color, the dye mixture was quickly spaced on both sides of the mat, and the set time began. The dye was then applied through each layer and sealed in foil as quickly as possible. After the color was developed (usually for 30 minutes), the cover was completely rinsed. The strips that had dye applied through them were rinsed to minimize the time difference.
[00533] Final color: The final color was determined by applying shampoo. Application of multiple shampoos can be done in a series without drying. The washing experiments were done in a consistent manner. Shampoo cycles involve the hair being foamed in a controlled manner with an SLS 7.5% (w / w) solution for 15 seconds, and rinsed for 15 seconds under hot water at 35 (+ 5) ° C. This process was done 15 -25 times to stimulate the number of shampoos for 4-6 weeks after a consumer has colored their hair.
[00534] Performance Evaluation: One gram of plain bleached hair from International Hair Importers was (a) colored with a commercial red dye, (b) treated with a commercially available non-red kit for 30 minutes at temperature environment to "elevate" the hair (for example, make the hair more porous), followed by immersion in a 0.6% (w / w) solution of compound A in a 1: 1 mixture of EtOH: phosphate buffer, pH 4.5 for 10 minutes at room temperature.
[00535] After completing the color treatment process, the strips were rinsed until the water drained clear, and shampoo was applied and rinsed once. The strips were then applied with shampoo, as described above. The results, shown in figure 1, demonstrate that colored streaks with compound A (figure 1b) significantly resist fading, have a greater solidity of core, and are brighter than colored streaks with the conduction of commercial red dye ( figure la) after the same number of washes.
[00536] In a second test to determine the effect of the dyes of the invention on damaged hair, medium blond virgin hair, single bleached (commercial), medium brown virgin hair 3X40 V, platinum (double bleached commercial), medium virgin hair 6X40 V, and medium brown virgin hair 9X40 V, were (a) colored with, or the commercially available red dye (1 of a cream dye to 1 mL of 20V peroxide) for 30 minutes at room temperature, or (b) treated with a commercial kit laurel available, such as L'Oreal Superior Preference 9Vi NB, or with a colorless base prepared on site for 30 minutes at room temperature to "elevate" the hair (for example, make the hair more porous), followed by immersion 0.6% (w / w) solution of compound A in a 1: 1 mixture of EtOH: phosphate buffer, pH 4.5 for 10 minutes at room temperature. The results, shown in figure 2, demonstrate that increased damage (moving from left to right through figure 2), the commercial red conduction dye exhibits significant fading and loss of color (figure 2a). In contrast, colored strands with compound A demonstrated a color fastness for inverse porosity property. That is, with increased damage to the hair, compound A provides greater color deposits and greater color fastness, compared to the commercially available red dye in similarly damaged hair. Example 4. Visual Inspection of Exemplary Dyes of the Invention
[00537] To determine the extent of color fastness and vibration, a number of braids are prepared as described above in Example 3. After the locks are dried, a visual inspiration comparing the locks with control locks is performed to assess vibration and color fastness of dyes. A scale of 1 to 4 is then used to rate the vibration and color fastness compared to the control locks, as shown below. In addition, the compounds of the present invention were analyzed for color fastness in hair strands using a Konica Minolta Chroma CR-400 Meter with the SpectraMagic ™ NX Lite CM-SIOOw 1.91.0002 software package, and were checked for color after cycles shampoo. Vibration scale = no vibration when compared to control 1 = little vibration when compared to control 2 = some vibration when compared to control 3 = substantially the same vibration when compared to control 4 = greater vibration when compared to the control Color fastness scale 1 = no color when compared to control 2 = little color when compared to control 3 = some color when compared to control 4 = substantially the same color when compared to control 5 = greater color when compared to control Equivalents
[00538] Those skilled in the art will recognize, or be able to determine the use of, no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be involved in the claims that follow. INCORPORATION BY REFERENCE
[00539] The contents of all references, patents and patent applications cited throughout this application are thus incorporated by reference.

权利要求:
Claims (24)
[0001]
1. Functionalized dye, characterized by the fact that it comprises at least one chromophor and a portion of color fastness, in which the chromophor is linked to the color fastness portion by a binder, in which said dye is a compound of formula la : CLF (la) where C is a chromophor of formula llg:
[0002]
2. Dye according to claim 1, characterized by the fact that: (i) C and formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j is halogen as a chlorine and R7c is linked to L; a, b, c, d and e are each 0; E and NR52; R52 and alkyl as ethyl; f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; K and C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and NR95R96; R95 and R96 are each alkyl as substituted or unsubstituted alkyl, preferably ethyl or hydroxyl substituted alkyl, as hydroxyethyl; or (ii) a, b, c and d are each 0; e and f are each 1; E and NR52; and R52 is hydrogen.
[0003]
Dye according to claim 1, characterized by the fact that m, n and o are 0; p, q and r are each 1; R84, R85, R86, R87; R88 and R89 are each hydrogen; K and NR90; and R90 and hydrogen.
[0004]
Dye according to claim 1, characterized by << CLAIMS PART >> l, Functionalized dye, characterized by the fact that it comprises at least one chromophor and a portion of color fastness, in which the chromophor is attached to the portion of fastness colored by a binder, wherein said dye is a compound of formula la: CLF (la) where C is a chromophor of formula llg:
[0005]
2. Dye according to claim 1, characterized by the fact that: (i) C and formula llg; R7a, R7b, R7d, R7e, R7f, R7g and R7i are each hydrogen; R7h and -NO2; R7j is halogen as a chlorine and R7c is linked to L; a, b, c, d and e are each 0; Ee NR52; R52 and alkyl as ethyl; f and 1; R50 and R51 are each hydrogen; m, n and o are each 0; K and C (= M) NR92; M and oxygen; p, q and r are each 1; R84, R85, R86, R87, R88, R89 and R92 are each hydrogen; W and NR95R96; R95 and R96 are each alkyl as substituted or unsubstituted alkyl, preferably ethyl or hydroxyl substituted alkyl, as hydroxyethyl; or (ii) a, b, c and d are each 0; e and f are each 1; E and NR52; and R52 is hydrogen.
[0006]
Dye according to claim 1, characterized by the fact that m, n and o are 0; p, q and r are each 1; R84, R85, R86, R87; R88 and R89 are each hydrogen; K and NR90; and R90 and hydrogen.
[0007]
4. Dye according to claim 1, characterized by the fact that the dye is a compound represented by the following structural formula:
[0008]
5. Dye according to claim 4, characterized by the fact that said dye is a compound represented by the following structural formula:
[0009]
6. Dye according to claim 4 or 5, characterized by the fact that said dye is a compound represented by the following structural formula:
[0010]
Dye according to claim 1, characterized in that C is a chromophor selected from the group of: a diarylmethane chromophor, an azo chromophor, a nitro chromophor or a substituted benzene chromophor; the ligand L and preferably of formula (Illa):
[0011]
8. Dye according to claim 7, characterized by the fact that E and NR52e K and C (= O) NR52; E and NR52 and Ke NR90; or E and NR53C = O and Ke NR90.
[0012]
Dye according to claim 7 or 8, characterized by the fact that W and NR95NR96, and R95 and R96 are each alkyl optionally substituted with hydroxyl; W and NR95R96; and R95 and R96 are linked to form a ring; W and CR97R98R "; R97 and hydrogen; and R98 and R" are each alkoxy; W and CR97R98R "; R97 and hydrogen; and R98 and R" are each alkyl optionally substituted with hydroxyl; W and CR97R98R "; R97 and R98 is hydrogen; and R" is hydroxy optionally substituted alkyl; W and CR97R98R "; R97 and R98 are hydrogen; and R" is heteroaryl; W and CR97R98R "; R97 and R98 are each hydrogen; and R" is hydroxyl; or W and OR100; and R100 is hydrogen.
[0013]
10. Dye according to claim 1, characterized by the fact that it is selected from:
[0014]
11. Dye according to claim 1, characterized by the fact that the dye has a formula:
[0015]
12. Dye according to claim 1, characterized by the fact that the dye has a formula:
[0016]
13. Dye composition, characterized in that it comprises at least one dye, as defined in any one of claims 1 to 12, or a cosmetically acceptable salt thereof, and a suitable medium for coloring keratin fibers, wherein said medium preferably includes additionally or more than surfactants, thickeners, fragrances, sequestering agents, couplers, primary intermediates, alkalizing agents, direct dyes, ceramides, oils, vitamins, pro-vitamins, opacity-forming agents, reducing agents, antioxidants, emulsifying agents UV, waxes, silicones, preservatives, stabilizers, solvents and buffers.
[0017]
14. Method for coloring hair, characterized in that it comprises applying to said hair a dye composition comprising at least one dye, as defined in any one of claims 1 to 12, or a cosmetically acceptable salt thereof, in which said The method preferably comprises the steps of: a) treating the hair with an oxidative dye in the presence of ammonia for between 1 and 60 minutes; b) treating the hair with a dye composition comprising at least one dye, as defined in any one of claims 1 to 10, for between 1 and 60 minutes; and c) rinse the hair.
[0018]
15. Method according to claim 12, characterized by the fact that said hair coloring enhances the hair or retouch the roots.
[0019]
16. Kit, characterized in that it comprises a dye composition comprising at least one dye, as defined in any one of claims 1 to 12, or a cosmetically acceptable salt thereof, and instructions for use.
[0020]
17. Method according to claim 14, characterized by the fact that step a) comprises treating the hair with an oxidative dye in the presence of ammonia or hydrogen peroxide for between 1 and 60 minutes.
[0021]
18. Method according to claim 14 or 17, characterized by the fact that it additionally comprises a step of rinsing the hair between step a) and step b).
[0022]
19. Method according to claim 14 or 17, characterized in that it additionally comprises a step of rinsing the hair and partially drying the hair between step a) and step b).
[0023]
20. Method according to any one of claims 14 and 17 to 19, characterized in that it additionally comprises one or more of the following steps: washing the hair with shampoo; and / or condition the hair with conditioner after rinsing the hair; and rinse your hair.
[0024]
21. Method according to any one of claims 14 and 17 to 20, characterized in that it additionally comprises a final step of drying the hair.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-02-12| B06T| Formal requirements before examination|

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2019-11-26| B25G| Requested change of headquarter approved|Owner name: LIVING PROOF, INC. (US) |

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2020-03-03| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-07-07| B09A| Decision: intention to grant|

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2020-11-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/12/2010, 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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US28866809P| true| 2009-12-21|2009-12-21|

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US28867609P| true| 2009-12-21|2009-12-21|

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US61/288,676|2009-12-21|

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US61/288,668|2009-12-21|

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US41525110P| true| 2010-11-18|2010-11-18|

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US61/415,251|2010-11-18|

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PCT/US2010/061578|WO2011084803A2|2009-12-21|2010-12-21|Coloring agents and methods of use thereof|

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