cosmetic composition, compositions of formula (1), composition of formula (2), cosmetic process for

专利摘要:
cosmetic composition, compositions of formula (1), composition of formula (2), cosmetic process for controlling and / or improving skin darkening, cosmetic process for protecting keratin materials and use of merocyanins. The present invention relates to a cosmetic and / or dermatological composition comprising in a physiologically acceptable medium at least one merocyanine derivative of formula (1) or (2) and / or isomeric geometric forms thereof and, and, and, z or z, z: having specific polar groups consisting of hydroxyl and ether functionalities. The present invention also relates to a cosmetic process which allows to control and / or improve the darkening of the skin under UV radiation exposure and the color homogeneity of the complexion, which process comprises the application on the skin of a cosmetic composition as defined. above. The present invention further relates to a cosmetic process for protecting keratin materials and, in particular, the skin against photoinduced skin aging, and comprising applying a keratin material to a cosmetic composition as defined above.
公开号:BR112014001331B1
申请号:R112014001331-4
申请日:2012-07-19
公开日:2018-12-04
发明作者:Hervé Richard；Barbara Winkler；Didier Candau；Dietmar Huglin；Florence L'Alloret；Julie Grumelard；Julie Songeur-Geney；Xavier Marat
申请人:L'oreal；
IPC主号:

专利说明:

(54) Title: COSMETIC COMPOSITION, COMPOSITIONS OF FORMULA (1), COMPOSITION OF FORMULA (2), COSMETIC PROCESS TO CONTROL AND / OR IMPROVE SKIN DARKNESS, COSMETIC PROCESS TO PROTECT THE KERATINIC MATERIAL (73) : LOREAL, French company. Address: 14, Rue Royale, F-75008 Paris, FRANCE (FR) (72) Inventor: HERVÉ RICHARD; BARBARA WINKLER; DIDIER CANDAU; DIETMAR HUGLIN; FLORENCE L'ALLORET; JULIE GRUMELARD; JULIE SONGEUR-GENEY; XAVIER MARAT.
Validity Period: 20 (twenty) years from 7/19/2012, subject to legal conditions
Issued on: 12/04/2018
Digitally signed by:
Liane Elizabeth Caldeira Lage
Director of Patents, Computer Programs and Topographies of Integrated Circuits
1/100 “COSMETIC COMPOSITION, COMPOSITIONS OF FORMULA (1), COMPOSITION OF FORMULA (2), COSMETIC PROCESS TO CONTROL AND / OR IMPROVE DARK SKIN,
COSMETIC PROCESS TO PROTECT THE KERATIN MATTERS AND USE OF MEROCIANINS ”[001] The present invention deals with new cosmetic and / or dermatological compositions for topical use, designed in particular to control the darkening of the skin and / or to prevent the photoaging of keratin materials, in particular skin exposed to UV radiation which comprises, in a physiologically acceptable medium, at least one merocyanine derivative comprising specific polar groups consisting of hydroxyl and ether functionalities of formula (1) or (2) which will be detailed below.
[002] It also deals with cosmetic and / or dermatological compositions that comprise in a physiologically acceptable medium at least one merocyanine of formula (1) or (2) and also a system to filter both UVA and UVB radiation.
[003] It is a known fact that wavelengths between 280 nm and 400 nm make it possible to tan the human epidermis and that rays with wavelengths between 280 and 320 nm, which are known as UV-B rays, hinder the development of a natural tanning. This exposure is also likely to induce a change in the biomechanical properties of the epidermis, which is expressed by the appearance of wrinkles that lead to premature skin aging.
[004] It is also known that UV-A rays, with wavelengths between 320 and 400 nm, penetrate deeper into the skin than UV-B rays. UV-A rays promote an immediate and persistent darkening of the skin. Daily exposure to UVA radiation, even for a short period of time
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2/100 time, under normal conditions, it can generate a degradation of the collagen and elastin fibers that is expressed by a modification of the skin microrrelevo, the appearance of wrinkles and an irregular pigmentation (that is, dark spots, lack of homogeneity of the skin) ...).
[005] Protection against UVA and UVB radiation is therefore necessary. An efficient photoprotective product must protect against both UVA and UVB radiation.
[006] Many photoprotective cosmetic compositions for the skin have been proposed until today. They generally contain organic UV filters and inorganic UV filters that act according to their own chemical nature and according to their own physical properties by absorbing, reflecting or diffusing UV radiation. They generally contain combinations of fat-soluble organic UV filters and / or water-soluble organic UV filters associated with metal oxide pigments such as titanium dioxide (T1O2).
[007] Many cosmetic compositions designed to prevent darkening of the skin, which improve the color and homogeneity of the skin have been proposed until today. To obtain such compositions, the use of UV filters, in particular UVB filters, is well known to the technician in sun care products. Some compositions may even contain UVA filters. This filtering system needs to ensure UVB protection in order to limit and control the melanin neo-synthesis that promotes global pigmentation, but also to ensure UVA protection in order to limit and control the oxidation of the already present melanins that lead to a darkening of the skin color.
[008] But no composition contains a particular combination of UV filters that is specifically suitable for photoprotection of the skin and, in particular, for improving the quality of the skin both in terms of color and its mechanical properties of elasticity.
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3/100 [009] Advantageously, this improvement is particularly visible in already pigmented skins in order not to increase the pigment load in the melanin or the structure of the melanin that is already present in the skin.
[010] In fact, most organic UV filtering agents are aromatic compounds that absorb between 280 nm and 370 nm. In addition to their filtering power against solar radiation, the desired photoprotective compounds must also have good cosmetic properties, good solubility in the usual solvents and, in particular, in greasy substances such as oils, fats and also good photostability alone and in association with other UV filters . They must also be colorless or at least have a color that is cosmetically acceptable to the consumer.
[011] One of the main drawbacks of these known compositions to date is that these filtering agents do not provide sufficient photoprotection against UV radiation and particularly against long UVA radiation with wavelengths greater than 370nm in order to control photoinduced pigmentation and its evolution by an appropriate UV filtering system that covers the entire UV spectrum.
[012] Among all the compounds that are recommended for this purpose, the particularly interesting family of UV filters consisting of carbonated merocyanine derivatives that is disclosed in US4195999 or application W02004 / 006878 can be mentioned. These compounds have very good filtering properties in long UVA rays, but have an unsatisfactory solubility in the usual solvents and, in particular, in fatty substances such as oils and an unsatisfactory photostability for certain families of merocyanins.
[013] There remains, therefore, a need to discover new merocyanine compounds that are active in long UVAs that have good cosmetic properties, good solubility in solvents
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4/100 oily or aqueous, good compatibility with other complementary UVA filters such as dibenzoylmethane derivatives, in relation to photostability and also a cosmetically acceptable color for the consumer.
[014] However, after considerable research carried out in the aforementioned photoprotection field, the Depositor has now discovered, surprisingly, that goal could be achieved with a new family of merocyanine derivatives that comprise specific polar groups consisting of hydroxyl functionalities and ether and which correspond to formula (1) or (2) which will be detailed below.
[015] This discovery forms the basis of the present invention.
[016] A first object of the present invention concerns a cosmetic and / or dermatological composition comprising in a physiologically acceptable medium at least one merocyanine derivative of formula (1) or (2) which will be detailed below.
[017] Another object of the present invention is a cosmetic and / or dermatological composition comprising in a physiologically acceptable medium at least one merocyanine of formula (1) or (2) and also a system for filtering UVA and radiation UVB.
[018] Another object of the present invention is a cosmetic and / or dermatological composition comprising in a physiologically acceptable medium at least one merocyanine derivative of formula (1) or (2) and at least one dibenzoyl methane derivative.
[019] A third object of the present invention deals with a cosmetic process to control and / or improve the darkening of the skin under exposure to UV radiation and the homogeneity of the color of the skin comprising the application on the skin of a cosmetic composition as defined above.
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5/100 [020] Another object of the present invention is a cosmetic process to protect keratin materials and particularly skin against photoaging which comprises the application of a cosmetic composition to the keratin material as defined above.
[021] More features, aspects and advantages of the present invention will appear with the reading of the detailed description below.
[022] The term physiologically acceptable designates compatible with the skin and / or its genera, which has a pleasant color, smell and touch, and which does not cause any unacceptable discomfort (pricking, tugging or redness) liable to make the consumer not use this composition.
[023] The term keratin substances include skin, scalp, hair, eyelashes, eyebrows and nails.
[024] In the remainder of this description, the term system for filtering UVA radiation and UVB radiation is designating an agent for filtering UVA radiation with wavelengths between 320 and 400 nm and UVB radiation with wavelengths between 280 and 320 nm, consisting of a mixture of various organic compounds and / or inorganic compounds to filter said UV radiation, for example a mixture comprising a UVA filter agent and a UVB filter agent, or an organic compound to filter UVA radiation and UVB radiation.
[025] According to the present invention, merocyanine derivatives correspond to the following formula (1) or (2)
Ri and R2 independently of each other are hydrogen; alkyl
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6/100 with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R1 and R2 together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by -O- or -NH-;
R3 is a group - (C = O) OR6; or a group - (CO) NHR6;
R6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally substituted by one or more of an OH;
R4 and Rs are hydrogen; or R4 and Rs form a - (CH2) n- ring which is optionally substituted by a C1-C4 alkyl and / or interrupted by one or more of an -O- or -NH-;
n is a number from 2 to 7;
R7 and Re independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is optionally interrupted by one or more of an O and / or replaced by one or more of an OH, cycloalkyl with C3-C22 or cycloalkenyl with C3 -C22, wherein said C3-C22 cycloalkyl or C3-C22 cycloalkenyl is optionally interrupted by one or more of -O-;
or R7 and Re together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by one or more of an -O-;
R9 and R10 are hydrogen; or R9 and R10 form a - (CH2) n- ring which is optionally substituted by C1-C4 alkyl and / or interrupted by -O- or -NH-;
A is -O-; or -NH;
R11 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O; or C1-C22 alkyl or alkenyl with
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7/100
C2-C22 which is substituted by cycloalkyl with C3-C22 or cycloalkenyl with C3C22, wherein said cycloalkyl with C3-C22 or cycloalkenyl with C3-C22 is optionally interrupted by one or more of -O-;
with the proviso that (I) at least one of R1, R2 and R6 is replaced by hydroxy;
(II) if one of R1 is hydroxyethyl, R2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R1 is hydrogen, R2 is not 1-hydroxy-3-methyl-but-2-yl;
(III) if R6 is replaced by one or more of an OH; one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the bonding nitrogen form a piperidyl or morpholinyl radical;
(IV) at least one of R7 and Re, or R11 is interrupted by one or more of -O-.
[026] The compounds of formula (1) or (2) are preferred, in which
R1 and R2 independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R1 and R2 together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by -O- or -NH-;
R3 is a (C = O) OR6 group; or a group - (CO) NHR6;
R6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally substituted by one or more of an OH;
R4 and Rs are hydrogen; or R4 and Rs form a - (CH ² ) _n - ring which is optionally substituted by an alkyl with C1-C4 and / or interrupted by -Oor by -NH-;
n is a number from 2 to 7;
R7 and Re independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is
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8/100 optionally interrupted by one or more of an O and / or replaced by one or more of an OH; or R7 and Re together with the nitrogen atom that bonds them together form a - (CH2) n ring that is optionally interrupted by one or more of an -O-;
R9 and R10 are hydrogen; or R9 and R10 form a - (CH2) n- ring which is optionally substituted by a C1-C4 alkyl and / or interrupted by O- or -NH-;
A is -O-; or -NH;
R11 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O;
with the proviso that (I) at least one of R1, R2 and R6 is replaced by hydroxy;
(II) if one of R1 is hydroxyethyl, R2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R1 is hydrogen, R2 is not 1-hydroxy-3-methyl-but-2-yl;
(III) if R6 is replaced by one or more of an OH; one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the bonding nitrogen that form a piperidyl or morpholinyl radical;
(IV) at least one of R7 and Re, or R11 is interrupted by one or more of -O-.
[027] Preferred are compounds of formula (1) or (2), wherein R1 and R2 independently of each other are hydrogen; C4-12 alkyl; or hydroxyalkyl with C3-C12;
wherein at least one of R1 and R2 is hydroxyalkyl with C3-C12; and R3, R4 and Rs are as defined in claim 1.
[028] Also preferred are compounds of formula (1), in which
R6 is C1-C12 alkyl, which is optionally substituted by a
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9/100 or more of a hydroxy.
[029] More particularly preferred are also the compounds of formula (1), in which
R6 is C1-C12 alkyl which is replaced by one or more of a hydroxy;
one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the nitrogen atom that connects them form a - (CH2) n ring which is optionally interrupted by -O- and / or -NH-; and R4 and Rs and n are as defined in claim 1.
[030] The compounds of formula (2) are preferred, in which
R11 is a radical of ^- (CH2) m ^- O ^- R-12, where
R12 is C1-C12 alkyl; or C 1 -C 6 alkoxy-C 1 -C 6 alkyl; m is a number from 1 to 5; and
R7, Re, R9, R10 and A are as defined in claim 1. Even more preferred are compounds of formula (1) or (2) in which
R1 and R2 and R7 and Re respectively together with the bonding nitrogen form a piperidyl radical or a morpholinyl radical.
[031] Also preferred are compounds of formulas (1) and (2), in which R4 and Rs and R9 and R10 respectively form a carbocyclic ring containing 6 carbon atoms.
[032] More particularly preferred are compounds of formula (1), wherein
R1 and R2 independently of each other are hydrogen; or C1-C22 alkyl; or hydroxyalkyl with C1-C22; or R1 and R2 together with the nitrogen atom are linked together to form a piperidyl or morpholinyl radical;
R3 is a group - (C-O) ORe; or a group - (CO) NHRe;
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10/100
R6 is C1-C22 alkyl, which can be substituted by one or more than one -OH;
R4 and Rs are hydrogen; or R4 and Rs are linked together to form a carbocyclic ring containing 6 carbon atoms.
[033] More particularly preferred are the compounds of formula (1), wherein R1 and R2 independently of one another are hydrogen; or hydroxy-C 1 -C 22 alkyl; wherein at least one of R1 and R2 is hydroxy-C1-22 alkyl;
R3 is a group - (C = O) OR6; or a group - (C = O) NHR6;
Rô is C1-C22 alkyl; and
R4 and Rs are hydrogen; or R4 and Rs are linked together to form a carbocyclic ring containing 6 carbon atoms.
[034] More particularly preferred are the compounds of formula (2), wherein R7 and Re independently of each other are hydrogen or alkyl with Ci-Ce, which is optionally interrupted by one or more of an -O-;
A is -O-; or -NH;
R11 is C1-C22 alkyl; and
R9 and R10 are hydrogen; or R9 and R10 are linked together to form a carbocyclic ring containing 6 carbon atoms.
[035] More particularly preferred are the compounds of formula (2), wherein R7 and Re together with the nitrogen atom form a morpholinyl or piperidyl radical;
A is -O-; or -NH;
R11 is C1-C22 alkyl; that is interrupted by one or more than -O-; and
R9 and R10 are hydrogen; or R9 and R10 are linked together to form a carbocyclic ring containing 6 carbon atoms.
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11/100 [036] Even more preferred are the compounds of formula (2), where R11 is a radical of ^- (CH2) m ^- O ^- R-12, where
R12 is C1-C4 alkyl; or C 1 -C 4 alkoxy-C 1 -C 4 alkyl; m is a number from 1 to 3;
R7 and Re, independently of each other, are hydrogen; alkyl with C1-C2, which is optionally interrupted by one or more of an O; or R7 and Re together with the nitrogen atom form a morpholinyl or piperidyl radical;
R9 and R10 are hydrogen; or form a carbocyclic ring containing 6 carbon atoms; and
A is -O-; or -NH.
[037] The merocyanine compounds of the present invention can be in the geometric isomeric forms E / E-, E / Z- or Z / Z.
[038] Alkyl, cycloakyl, alkenyl, alkylidene or cycloalkylenyl can be straight or branched, monocyclic or polycyclic.
[039] C1-C22 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3pentyl, 2, 2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl or dodecyl.
[040] Substituted alkyl is, for example, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N, N-diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-tert-octyphenoxyethyl, 3- ( 2, 4di-tert-amylphenoxy) -propyl, ethoxycarbonylmethyl-2- (2-hydroxyethoxy) ethyl or 2-furylethyl.
[041] Hydroxy substituted alkyl is, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxynecyl, alkenyl with C2-C22
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12/100 is, for example, straight chain C2-C12 alkenyl or preferably branched C3-C12 alkyl, C1-C2 alkyl, such as vinyl, allyl, 2-propen-2-yl, 2buten-1-yl , 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3penten-2-yl, 2-methyl-1-buten-3 -yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,
4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, lp-menten-8-yl, 4 ( 10) -tujen-10-yl, 2-norbornen-1-yl, 2,5norbornadien-1-yl, 7,7-dimethyl-2,4,4-norcaradien-3-yl or the different isomers of hexenyl, octenyl, nonenyl , decenyl or dodecenyl.
[042] C3-C12 cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or preferably cyclohexyl.
[043] Examples of merocyanins according to the present invention are listed in Table A:
Table A Compound Structure Compound Structure 1 I% OAJ lll kN 2 I%IIN 3 I% O/ U lllN 4 N 5 o'W: jN | 6 0N 7 Oυ ϊ j 8 O 9 0 10 ⁰ f ° '^ ^j lll N
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13/100
11 I ° ^ y ^0H yi 12 O/ N 13 ^HC Y HO ^ (| L 14 15 θςγ-Νχ / '-' χ / Οχ U ^N 16 f „V- ''» »í ^ ^N yjx 17 OH Η V ^ 18 ^H % 0 N 19 ^H0 > 0, VWv.V, / N 20 N 21 O <L · 1 L _o N 22 í N 23 The yvy ^0H ^ Yv y 24 25 h ^U y ^ o- ^ - ^ Ύρ, 26 ^H0 > 0 lll N 27 0. ΟγΟ ^ Λ. u ^x 28 If, γ 29 η γ-Ό— 30 SH ° T ^O ^ O ^
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14/100
31 Η V— 32 33 S Η Υ '-' Ύ) Ύ ^aJ 34 0 35 > χ = γ7 36 d ^h Y— 37 38 S η γ-γ- 39 ¹ ° Ί _H o Υγ-χ 40 Γ[YH V 41 42 S η γ ° γ 43 XΗ V 44 OHΗ Y 45 <1 46 1 ο _γ ο''γ ^θ ·· ^ ·· ο ·· '· γ · ⁰ - · Γ 1 M 47 Ο □ Ύ'-Χ-γ ⁰ - ' ^ΗΝ γτχ
[044] The most particularly preferred merocyanine derivatives of the present invention are chosen from the group of the following compounds and their geometric isomeric forms E / E-, E / Z- or Z / Z:
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15/100
4 cn 0J 2-ethoxyethyl (2E, 4E) -2-cyano-5- (piperidin1 -yl) penta-2,4-dienoate 14 ethyl (2Z) -cyano {3 - [(3-methoxypropyl) amino] cyclohex-2-en-1-ylidene} etanoate 15 THE H (2Z) -2-cyano-N- (3-methoxypropyl) -2- {3 - [(3-methoxypropyl) amino] cyclohex-2-en-1-ilidenojetanamide 25 2-ethoxyethyl (2Z) -cyano {3 [(3-methoxypropyl) amino] cyclohex-2-en-1-ylidene} etanoate 27 2-methylpropyl (2Z) -cyano {3 - [(3methoxypropyl) amino] cyclohex-2-en-1-ylidenojetanoate 29 ° ^ ₀ -x / X 31 A _h ιΓ ^, >
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16/100
according to a preferred embodiment of the present invention, the compound 2-ethoxyethyl (2Z) -cyano {3 - [(3-methoxypropyl) amino] cyclohex2-en-1-ylidene} etanoate (25) in its geometric isomeric forms E / E and / or E / Z will be used.
[045] Its E / Z form has the following structure:
H Y “'[046] Its E / E form has the following structure:
[047] The Depositor found that these particular compounds have the following properties: better chemical stability after 2 months at 45 ° C in a 1/1 ethanol / water mixture at a concentration of 0.5%, a less yellow color.
[048] The filtering agent or merocyanins according to the present invention can be present in the compositions according to the present invention in a concentration of 0.1% to 10% and preferably of 0.2% to 5% with respect to the total weight of the composition.
[049] The compounds of formula (1) and (2) can be prepared according to known processes, as disclosed, for example, in J.Org.Chem. USSR (Engl. Transi.) 26 (8), p. 1562f (1990); J.Heterocycl.Chem.
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17/100
33 (3), ρ. 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11, p. 15371543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, p. 397-404 (1982); Chem. Heterocycl. Comp. (Trad. Inglesa) 24 (8), 914-919 (1988) and in Synthetic Communications Vol. 33, No. 3, 2003, p 367-371.
[050] The synthesis of the compounds used in the present invention is also disclosed in US2003 / 0181483A1, WO 0234710, Eur. J. Org. Chem. 2003, 2250-2253, J. Med. Chem. 1996, 39, 1112-1124 and J. Org. Chem., Vol. 37, No. 8, 1972, 1141-1145 as follows:
[051] CH-vinylogenic acid compounds are caused to react with amide acetates.
[052] In J. Heterocyclic Chem., 27, 1990, 1143-1151 esters of aminoacrylic acids or aminoacrylic nitriles are caused to react with ethoxymethyleneecanoacetates in ethanol for the corresponding compounds used in the present invention.
[053] The compounds of formula (1) and (2) in which R4 and Rs or R9 and R10 together form a carbocyclic ring containing 6 carbon atoms, respectively, which can be prepared according to the processes described in the application WO 2007/071582, IP.com Journal (2009), 9 (5A), 29-30 under the title Process for producing 3-amino-2-cyclohexan-1-ylidene compounds and in US-A-4, 749 , 643 on col, 13, line 66 -col. 14, line 57 and the references cited therein.
[054] Merocyanins of formula:
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18/100 [055] R’i and R'2 independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R'i and R'2 together with the nitrogen atom that connects them form a - (CH2) n ring which is optionally interrupted by -O- or -NH-;
R'3 is a group - (C = O) OU '; or a group - (CO) NHR'6;
R'6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally substituted by one or more of an OH;
R'4 and Rs are hydrogen; or R'4 and R's form a - (CH2) n- ring which is optionally substituted by C1-C4 alkyl and / or interrupted by -O- or NH-;
n is a number from 2 to 7;
R’7 and R’e independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is optionally interrupted by one or more of an O and / or substituted by one or more of an OH; or R’7 and R’e together with the nitrogen atom that connects them form a - (CH2) n ring which is optionally interrupted by -O-; R’9 and R’10 are hydrogen; or R'9 and R’10 form a - (CH2) n- ring which is optionally substituted by a C1-C4 alkyl and / or optionally interrupted by -O- or -NH-; A is -O-; or -NH;
R11 is C1-C22 alkyl, C2-C22 alkenyl, C2-C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O;
they are particularly suitable for protecting body care products from photolytic and oxidative degradation.
[056] Preferably, compounds of formula (1 ') or (2') are used in which at least one of R1, R2, R3 and R6, R7 and Re, or R11 is replaced by hydroxy; and / or interrupted by one or more than one -O-.
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19/100 [057] Examples of compounds of formula (1 ') and (2') are those listed in Table A and the compound
N [058] According to the present invention, the compositions may also contain one or more complementary hydrophilic, lipophilic or insoluble organic filtering agents and / or one or more inorganic filtering agents that are active against UVA and / or UVB radiation.
[059] Examples of complementary UV filters that can be used in admixture with the compounds of formulas (1) and (2) are listed in the following Tables:
Table 1: Appropriate Uv Filtering Substances that can be used
In addition With Compounds of Formula (1) and / or (2) derived from p-aminobenzoic acid, for example, 4-dimethylaminobenzoic acid 2-ethylhexyl ester;
derivatives of salicylic acid, for example, 2-ethylhexyl ester salicylic acid; benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;
diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3 (benzofuranyl) 2-cyanoacrylate;
3-imidazol-4-ylacrylic acid and esters;
benzofuran derivatives, especially 2- (paminophenyl) benzofuran derivatives, described in EP-A-582 189, US-A-5 338 539, USA-5 518 713 and EP-A-613 893;
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20/100 polymeric UV absorbers, for example benzylidene malonate derivatives described in EP-A-709 080;
camphor derivatives, for example 3- (4'-methyl) benzylidene-bornan-2-one, 3-benzyl-idenebornan-2-one, polymer of N- [2 (e 4) -2-oxyborn-3-ilidenomethyl ) -benzyl] acrylamide, 3- (4'-trimethylammonium) -benzylidenobornan-2-one methyl sulfate, 3,3'- (1,4-phenylene-dimethine) -bis (7,7-dimethyl-2- oxobicyclo [2.2.1] heptane-1-methanesulfonic) and salts, 3- (4'-sulfo) benzylidenobornan-2-one and salts; camphorbenzalkonium methosulfate;
hydroxyphenyltriazine compounds, for example 2- (4'-methoxyphenyl) -4,6-bis (2'hydroxy-4'-n-octyloxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethyl-carboxyl) -phenylamino] -1,3,5triazine; 2,4-bis {[4- (tris (trimethylsilyloxy-silylpropyloxy) -2-hydroxy] -phenyl} -6- (4methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (2 -metilpropeniloxi) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- ^(1, 1 ', ^{1, 5,} 5 ^{, 5,} -heptametiltrisilil2-methyl-propyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (3- (2-propyloxy ) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- [4-ethylcarboxy) phenylamino] -1,3,5-triazine;
benzotriazole compounds, for example, 2,2'-methylene-bis (6- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol;
trianilino-s-triazine derivatives, for example 2,4,6-trianiline- (p-carbo-2 ^, -ethyl-1-oxy) -1,3,5-triazine and the UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507 691, WO 93/17002 and EP-A-570 838;
2-phenylbenzimidazole-5-sulfonic acid and its salts;
menthyl o-aminobenzoates;
coated or uncoated physical sunscreens such as titanium dioxide, oxide
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21/100 zinc, iron oxides, mica, MnO, Fe2O3, Ce2O3, AI2O3, Ζ1Ό2. (surface coatings: polymethylmethacrylate, methicone (methylhydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone, titanium isopropyl triiso stearate as described in CAS 61417-49-0), metal soaps such as magnesium stearate (such as described in CAS 4086-70-8), perfluoroalcohol phosphate such as fluoroalcohol phosphate as C9-15 (as described in CAS 74499-44-8; JP 5-86984,
JP 4-330007)). The primary particle size is on average 15nm35nm and the dispersed particle size is in the range of 100nm- 300nm.
aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 phenyl-benzimidazole derivatives as disclosed in EP 1167358 the UV absorbers described in Sunscreens, Eds. N.J. Lowe, N.A.Shaath, Marcei Dekker, Inc., New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992) can also be used as additional UV protective substances.
Table 2. Appropriate UV filtering substances that can be used
Additionally with Merocyanins of Formula (1) and (2) (abbreviations T: Table, R: row, Comp: compound, Ex: patent example compound (s), p: page; the generic scope of UV absorbers is described in the left column; specific compounds are indicated in the right column)
DE 10013318 T 1 pp 8-9, all examples pp 10-13, T 2 pp 1314, allexamples p 14, Ex A, B, C, D, E, F pp 19-20 DE102004038485A1 Formula 1 on page 2; Ex 1-4 on page 13;
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DE102004039281A1 Formulas l-ll in p 1; Ex la-lae on pp 7-12; Ex lla-llmon pp 14-15; Ex 1-25 on pp 42-56; DE 10206562 A1 Ex1-3p 10, Ex4-7p 11, Ex8-15 pp 12-14 DE 10238144 A1 Ex on p 3-5; DE 10331804 T 1 p 4, T2 + 3p5 DE 19704990 A1 Ex 1-2 on pp 6-7; EP 613 893 Ex1-5 + 15, T 1, pp 6-8 EP 0 998 900 A1 Ex on pp 4-11 EP 1 000 950 Comp. in Table 1, pp 18-21 EP 1 005 855 T3, p 13 EP 1 008 586 Ex1-3, pp 13-15 EP 1 008 593 Ex 1-8, pp 4-5 EP 1 027 883 Compound VII, p 3 EP 1 027 883 Comp l-VI, p 3 EP 1 028 120 Ex 1-5, pp 5-13 EP 1,059,082 Ex 1; T 1, pp 9-11 EP 1 060 734 T 1-3, pp 11-14 EP 1,064 922 Compounds 1-34, pp 6-14 EP 1 077 246 A2 Ex 1-16 on pp 5-11 EP 1 081140 Ex1-9, pp 11-16 EP 1103 549 Compounds 1-76, pp 39-51 EP 1108 712 4,5-Dimorpholino-3-hydroxypyridazine EP 1123 934 T3, p 10 EP 1129 695 Ex1-7, pp 13-14 EP 1167 359 Ex 1, p 11 and Ex 2, p 12 EP 1 232 148 B1 Ex 4-17 on pp 3-5; EP 1 258 481 Ex 1, pp 7.8
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EP 1 310 492 A1 Ex 1-16 on pp 22-30 EP 1 371 654 A1 Ex on pp 5-7 EP 1 380 583 A2 Ex 1, p 6; EP 1 423 351 A2 Ex 1-16 on pp 31-37; EP 1 423 371 A1 T 1 on pp 4-8, Ex on p 9, Ex 1-9 on pp 36-42; EP 1 454 896 A1 Ex 1-5 on pp 10-13, Examples on pp 4-5; EP 1 471 059 A1 Ex 1-5 on pp 4-5; EP 1484051 A2 Formula lll-VII on pp18-19, Ex 7-14 on pp 7-9, Ex18-23 on pp 11-12, Ex 24-40 on pp 14-17; EP 1648849 A2 Formula 1 on page 4; Ex 1-2 on pp 13-17; Ex C10 e010 on pp15-16; EP420 707 B1 Ex 3, p 13 (CAS Reg. No 80142-49-0) EP 503 338 T1, pp 9-10 EP517 103 Ex 3,4,9, 10 pp 6-7 EP517 104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 EP 626 950 all compounds EP 669 323 Ex 1-3, p 5 EP 743 309 A1 Ex 1-12 on pp 18-24; EP 780 382 Ex1-11, pp 5-7 EP 823 418 Ex 1-4, pp 7-8 EP 826 361 T 1, pp 5-6 EP 832 641 Ex 5 + 6 p 7; T 2, p 8 EP 832 642 Ex22, T3, pp 10-15; T 4, p 16 EP 848944 A2 Formulas I and II on page 1; Ex on page 8; examples on page 10; EP852 137 T2, pp 41-46 EP 858 318 T1, p6
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EP863 145 Ex1-11, pp 12-18 EP 878 469 A1 T1, pp 5-7; EP 895 776 Comp. In rows 48-58, p 3; R 25 + 33, p 5 EP911 020 T2, pp 11-12 EP 916 335 T2-4, pp 19-41 EP 924 246 T 2, p 9 EP 933 376 Ex1-15, pp 10-21 EP 944 624 Ex 1 +2, pp 13-15 EP945 125 T 3 a + b, pp 14-15 EP 95 097 Ex 1, p 4 EP 967 200 Ex2; T3-5, pp 17-20 EP 969 004 Ex 5, T 1, pp 6-8 FR 2842806 A1 Exl p 10, Exll p 12 FR 2861075 A1 Ex 1-3 on pp 12-14; FR 2862641 Formula 3 at p4; Ex A-J on pp 7-9; FR 2869907 A1 Formula 1 on page 6; T 1 on page 7-8; Ex 4-39 on pp 1235; KR 2004025954 all kojil benzoate derivatives JP 06135985 A2 Formula 1 on page 2; Ex 1-8 on pp 7-8; JP 2000319629 CAS Reg Nos. 80142-49-0, 137215-83-9, 30794782-6 JP 2003081910 A Ex on p 1; JP 2005289916 A Formula I at p 1; Ex la-ld on pp 2-3; JP 2005290240 A Formulas I on p 2, Ex II on p 2; US 2003 / 0053966A 1 Ex on pp 3-6 US 2004057912 A1 Ex on page 7-9, Ex 1 on page 10; US 2004057914 A1 Ex on page 8-12, Ex 1 on page 12;
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US 2004 / 0057911A1 Formula I and II in p 1; formula ll and IV at p3; Ex 1-3atPP 5-6; US 2004 / 0071640A1 Ex 1-12 on pp 4-7; US 2004 / 0091433A1 Ex 1-6 on pp 14-16; US2004 / 0136931 A1 Ex 1-3 on page 7; US 2004 / 0258636A1 Ex 1-11 on pp 9-15; US 2005 / 0019278A1 Ex 1-9 on pp 6-8; US 2005 / 0136012A1 Formula 1 on page 2; US 2005 / 0136014A1 Formula a-c in p 2; Examples on page 3; US 2005 / 0201957A1 Formula 1 on p1; Ex A, B, C, D, E, F, G on pp 2-3; US 2005/0249681TO 1 all compounds on pp 2-3, Ex 1 on p 6; US 2005186157A1 Formula 1 on page 1; Ex 1-6 on pp 2-4; US 2005260144A1 Formula I at p1; Formula II on page 3; Ex 1-10 in pp8-11; US 2006018848A1 Ex a-p on pp 3-4; US 2006045859A1 Formula 1 on page 1; Ex 1-10 on pp 2-4; US 5 635 343 all compounds on pp 5-10 US 5,332 568 Ex 1, p 5, T 1 +2, pp 6-8 US 5 338 539 Ex 1-9, pp 3 + 4 US 5 346 691 Ex40, p 7; T 5, p 8 US 5 801 244 Ex 1-5, pp 6-7 US 6613340 Ex I, II pp 9-11, Examples in rows 28-53 p 6 US 6 800 274 B2 formulas l-VI and IX-XII on pp 14-18; US 6 890 520 B2 Ex 1-10 on pp 6-9; US 6926887 B2 Ex A on pp5 / 6; formulas I - VIII on pp 27-29;
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US 6936735 B2 Formulas 1-2 on p 2; formula 3-4 on page 6; US 6962692 B2 Formulas VII and VIII on page 6; formulas I, II, IV-VI, IX, Xon pp 14-16; Formula III on page 19; WO 0149686 Ex1-5, pp 16-21 WO 0168047 Tables on pp 85-96 WO 0181297 Ex 1-3, pp 9-11 WO 0191695 Formula I on p 4, T on p 8 WO 0202501 A1 Ex la-c, p 5 WO 02069926 A1 Ex on p 9, Ex on pp 17-23 WO 02072583 T on pp 68-70 WO 02080876 Ex 1 on pp 7-9 WO 0238537 All p 3 compounds, composed in rows 1-10p4 WO 03004557 A1 Ex A1-A29 on pp 36-57; WO 03007906 Ex l-XXIII, pp 42-48 WO 03086341 A2 Formula 2-21, pp 4-6; WO 03092643 A1 T on pp 34-35, compounds listed on p 16 WO 03097577 A1 Ex on pp 6-8; Ex 1-3 on pp 15-18; WO 03104183 A1 Formula 1-IV in p 1; Ex 1-5 on pp 27-28; WO 04000256 A1 Ex 1 -10 on pp 18-24 WO 04020398 A1 Ex 1-3 on pp 14-17 WO 04020398 A1 Formulas l-VI on pp 21-24, Formula IX on p 25; WO 04075871 Ex 1-3 on pp 17-18; Ex 7-9 on pp 21-22; WO 05009938 A2 Formula I at p 1; Ex 1-2 on pp 14-15; WO 05065154 A2 Formula a-c on pp 5-6; WO 05080341 A1 Formula 1 on page 3; examples on pp 9-13;
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WO 05107692 A1 Formula 1 on page 2; Ex 1-9 on pp 27-29; WO 05118562 A1 Formula I on page 4; Ex la-lg on page 5; WO 05121108 A1 Formula I on page 3; Formula Ia on page 5; T 1 on page 7; Ex3-22 on pp 11-23; WO 06009451 T 1 on pp 5-8; formulas III and UV0 on page 9; WO 06016806 T 1 pp 6-7; T 2 on page 10; T 3 on page 11; T 4 on page 15; WO 06032741 formulas 1-3 in p 1; Ex a-k on pp 5-7; Ex 1-4 inpp 18-20; WO 9217461 Ex1-22, pp 10-20 WO 9220690 Polymeric Comp in Examples 3-6 WO 9301164 T 1 +2, pp 13-22 WO 9714680 Ex1-3, p 10
Table 3: Appropriate Uv Filtering Substances And Adjuvants That
They should be used in addition to the Compounds of Formula (1) and / or
Í2)
At the Chemical name CAS No. 1 (+/-) - 1,7,7-trimethyl-3 - [(4-methylphenyl) methylene] bicyclo- [2.2.1] heptan-2-one;p-methyl benzylidene camphor 36861-47-9 2 1,7,7-trimethyl-3-phenylmethylene) bicycle [2.2.1 jheptan-2-one; camphor benzylidene 15087-24-8 3 (2-Hydroxy-4-methoxyphenyl) (4-methylphenyl) methanone 1641-17-4 4 2,4-dihydroxybenzophenone 131-56-6 5 2.2 ', 4.4 ^, -tetrahydroxybenzophenone 131-55-5 6 2-Hydroxy-4-methoxy benzophenone 131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5- acid 4065-45-6
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sulfonic 8 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131-54-4 9 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 10 Alpha- (2-oxoborn-3-ylidene) toluene-4- acidsulfonic and its salts; Mexoryl SL 56039-58-8 11 1 - [4- (1,1 -d i meti leti I) fe n i l] -3- (4-methoxyphenyl) propane-1,3-dione; avobenzone 70356-09-1 12 Methyl Ν, N, N-trimethyl-4 - [(4,7,7-trimethyl-3-oxobicyclo [2,2,1] hept-2-ylidene) methyl] anilíniosulfate; Mexoryl SO 52793-97-2 22 3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate;homosalate 118-56-9 27 Mentil-o-aminobenzoate 134-09-8 28 Mentile salicylate 89-46-3 29 2-Ethylhexyl2-cyano, 3,3-diphenylacrylate; Octocylene 6197-30-4 30 2- ethylhexyl 4- (dimethylamino) benzoate 21245-02-3 32 2- ethylhexyl salicylate 118-60-5 33 Benzoic Acid, 4, 4 ', 4- (1, 3, 5- triazine-2, 4,6- triyltriimino) tris-, tris (2-ethylhexyl) ester; 2.4.6-T rianilino- (p-carbo-2'-ethylhexyl-1 '-oxy) -1,3,5-triazine; octy triazone 88122-99-0 34 4- Aminobenzoic acid 150-13-0 35 Benzoic acid, 4-amino-, ethyl ester, polymerwith oxirane 113010-52-9 38 2-phenyl-1 H-benzimidazole-5-sulfonic acid; acidphenylbenzimidazolsulfonic 27503-81-7 39 2-Propenamide, N - [[4 - [(4,7,7-trimethyl-3- 147897-12-9
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oxobicyclo [2.2.1] hept-2-ylidene) methyl] phenyl] methyl] -,homopolymer 40 Triethanolamine salicylate 2174-16-5 41 3,3- (1,4-phenylenedimethylene) bis [7,7-dimethyl-2-oxo-bicyclo [2.2.1] heptane-1methanesulfonic]; Cibafast H 90457-82-2 42 Titanium dioxide 13463-67-7 44 Zinc oxide 1314-13-2 45 2,2'-Methylene-bis- [6- (2H-benzotriazol-2-yl) -4-(1,1,3,3-tetramethylbutyl) -phen]; Tinosorb M 103597-45-1 46 2,4-b i s {[4- (2-ethyl hexi loxy) -2-h id roxi] -phen i} -6- (4-methoxyphenyl 1) - (1,3,5) -triazine; Tinosorb S 187393-00-6 47 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene) bis-, disodium salt 180898-37-7 48 Benzoic acid, 4.4 '- [[6 - [[4 - [[(1,1-dimethylethyl) amino] carbonyl] phenyl] amino] 1,3,5-triazine-2,4-diyl] diimino] bis-, bis (2-ethylhexyl) ester;diethylhexyl butamido triazone; Uvasorb HEB 154702-15-5 49 Phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] disyloxanil] propyl] -;drometrizole trisiloxane; Mexoryl XL 155633-54-8 50 Dimethylodiethylbenzalmalonate; Polysilicone 15;Parsol SLX 207574-74-1 51 Benzenesulfonic acid, 3- (2H-benzotriazole-2-il) -4-hydroxy-5- (1-methylpropyl) -, monosodium salt;Tinogard HS 92484-48-5
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53 1-Dodecanamine N- [3 - [[4-(dimethylamino) benzoyl] amino] - propyl] N, N-dimethyl-,salt with 4-methylbenzenesulfonic acid (1: 1);Escalol HP610 156679-41-3 54 1- Propanamine, N, N, N-trimethyl-3 - [(1-oxo-3-phenyl-2- propenyl) amino] -, chloride 177190-98-6 55 2,2'- bis- (1,4-phenylene) 1 H-Benzimidazole-4,6-disulfonic, 170864-82-1 56 , 2,4,6-tris (4-methoxyphenyl) -1,3,5-Triazine 7753-12-0 57 1,3,5-TriazinA, 2,4,6-tris [4 - [(2-ethylhexyl) oxl] phenyl] - 208114-14-1 58 1 -Propanamino, 3 - [[3- [3- (2H-benzotriazol-2-yl) -5 (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropyl] amino] N, N-diethyl-N -methyl-, methyl sulfate (salt) 340964-15-0 59 2- 3- (1 H-imidazol-4-yl) propenoic acid 104-98-3 60 Methyl ester of acid, 2-hydroxy-, [4- (1-methylethyl) phenyl] benzoyl 94134-93-7 61 1,2,3-Propanotriol, 1- (4-aminobenzoate);glyceryl PABA 136-44-7 65 2,2'-bis (1-4-phenylene) -1 monosodium saltH-hpnyimidaynl-zl fi-rlissi ilfôninn nu Di ^ nrliiim 349580-12-7 66 1,3,5-Triazine-2,4,6-triamine, N, N'-bis [4- [5- (1,1 - 288254-16-0 68 sterols (cholesterol, lanosterol, phytosterols), such as 69 mycosporins and / or amino acidsmycosporin as described in 70 alpha lipoic acid as described in DE 71 Synthetic oranic dolimers such as
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73 silica compounds as described in 74 inorganic particles as described in 75 latex particles as described in 76 2,2'-bis- (1,4-phenylene) -1 H disodium salt 180898-37-7 77 2- [2,3-dihydro-5-methoxy-3,3-dimethyl-6 - [(2-methyl-2- 425371-15-9 78 2- (2,3-dihydro-6-hydroxy-5-methoxy-3,3-dimethyl-1 H- 425371-14-8 79 a- (2,3-dihydro-3,3,5-trimethyl-1 H-inden-1-ylidene) - 425371-11-5 80 a - (- [5- (1,1-dimethylethyl) -2,3-dihydro-3,3-dimethyl-1 H- 425371-10-4 R1 2-í6-íacetiloxh-2.3-dihydro-5-methoxy-3.3-dimethyl-1 495371-00-1 82 , 2- [2,3-d i h id ro-5-methoxy-3,3-d i methyl I-6- [2- methyl I-3- [1 .3.3.3-tetramethyl-1- 425371-08-0 83 , 2- (2,3-dihydro-5-methoxy-3,3,6-trimethyl-1 H-inden-1- 425371-07-9 84 , 4,4-d imethyl-3-oxo-2- (2, 3,7,8-tetrahydro-8,8- 425371-06-8 85 2- (2,3-dihydro-3,3,6-trimethyl-1 H-inden-1-ylidene) - 425371-05-7 86 2- (2,3-dihydro-3,3,5,6-tetramethyl-1 H-inden-1 - 425371-04-6 87 2- (2,3-dihydro-5-methoxy-3,3,4,6-tetramethyl-1H- 425371-03-5 88 2- (2,3-dihydro-5,6-dimethoxy-3,3-dimethyl-1 H- inden-1- 261356-13-2 89 Benzoic acid, 2- [4- (Diethylamino) -2- 302776-68-7 90 2-Ethylhexyl 4-methoxycinnamate -; UVINUL MC 5466-77-3 91 3- (4-Methoxyphenyl) 2-propenoic acid of 3- 71617-10-2 92 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl phenol -; 23328-53-2
[060] Of course, the person skilled in the art will take every care in choosing the additional filtering agent (s) and / or their quantities in such a way that the advantageous properties intrinsically associated with the composition according to the present invention are not, or are not. substantially, adversely affected by the additions or additions considered.
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32/100 [061] Additional organic filtering agents are most preferably chosen from derivatives of dibenzoylmethane; anthranilates; kinematic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives; derivatives of β, β-diphenylacrylate; triazine derivatives; derivatives of benzalmalonate, in particular those cited in US Patent 5,624,663; benzimidazole derivatives; imidazolines; derivatives of p-aminobenzoic acid (PABA); benzotriazole derivatives; derivatives of methylenebis (hydroxyphenylbenzotriazole), as described in patent applications US 5,237,071, US 5,166,355, GB 2,303,549, DE 197 26 184 and EP 893 119; benzoxazole derivatives, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; filter polymers and filter silicones, such as those described in particular in patent application WO 93/04665; α-alkylstyrene-derived dimers, such as those described in patent application DE 19855649; 4,4-diarlbutadienes, such as those described in patent applications EP 0 967 200, DE 19746654, DE 19755649, EP-A-1 008 586, EP 1 133 980 and EP 133 981; merocyanine derivatives such as those described in patent applications WO 04006878, WO 05058269 and WO 06032741; the indanilidene filtering agents of EP-A-0 823 418 and EP-A-1 341 752 and mixtures thereof.
[062] Examples of organic UV filtering agents may also be mentioned, which are designated with the INCI names:
Derivatives of Dibenzoylmethane [063] Butylmethoxydibenzoylmethane, sold under the trade name Parsol 1789 by DSM Nutritional Produtos.
Derivatives of Rare-Aminobenzoic Acid
PABA,
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Ethyl ΡΑΒΑ,
Ethyl Dihydroxypropyl PABA,
Ethylhexil Dimetil PABA sold privately under the name “Escalol 507” by ISP,
Glyceryl PABA,
PEG-25 PABA sold under the name “Uvinul P25” by BASF. Salicylic Derivatives [064] Homosalate sold under the name Eusolex HMS by
Merrck,
Ethylhexyl Salicylate sold under the name Neo Heliopan OS by
Symrise,
Dipropylene glycol salicylate sold under the name Dipsal by
Lubrizol,
TEA Salicilato, sold under the name Neo Heliopan TS by
Symrise
Cinânmicos Derivatives [065] Ethylhexyl Methoxycinnamate sold, in particular, under the trade name Parsol MCX by DSM Nutritional Produtos,
Isopropyl methoxycinnamate,
Isoamil Metoxicinamato sold under the trade name Neo Heliopan E 1000 by Symrise,
Cinoxate,
DEA Methoxycinnamate,
Diisopropyl methyl cinnamate,
Glyceryl Ethylhexanoate Dimethoxycinnamate
Derivatives of b, b-diphenylacrylate [066] Octocrylene sold privately under the trade name
Uvinul N539 by BASF,
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Ethylene, sold in particular under the trade name Uvinul N35 by BASF
Benzophenone Derivatives [067] Benzophenone-1, sold under the trade name Uvinul 400 by BASF,
Benzophenone-2, sold under the trade name Uvinul D50 by
BASF,
Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M40 by BASF,
Benzophenone-4, sold under the trade name Uvinul MS40 by
BASF,
Benzophenone-5,
Benzophenone-6, sold under the trade name Helisorb 11 by
Norquay,
Benzophenone-8, sold under the trade name Spectra-Sorb UV24 by Cytec,
Benzophenone-9, sold under the trade name Uvinul DS-49 by
BASF,
Benzophenone-12, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, sold under the trade name Uvinul A + or as a mixture with octyl methoxycinnamate under the trade name Uvinul A + B by BASF,
1,1 ’- (1,4-Pi perazinated i i I) bis [1 - [2- [4- (diethylamino) -2hydroxybenzoyl] phenyl] -methanone] (CAS 919803-06-8)
Derivatives of Benzylidene Camphor [068] 3-Benzylidene Camphor manufactured under the name Mexoryl SD by Chimex,
4-Methylbenzylidene Camphor sold under the name Eusolex 6300
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Benzylidene Camphor Sulfonic Acid manufactured under the name Mexoryl SL by ChimexBenzalconium Methosulfate Camphor manufactured under the name Mexoryl SO by Chimex,
Sulphonic Acid of Terephthalilidene Dicaphor made under the name Mexoryl SX by Chimex,
Polyacrylamidomethyl Benzylidene Camphor manufactured under the name Mexoryl SW by Chimex
Derivatives of Phenyl Benzimidazole [069] Phenylbenzimidazole sulfonic acid sold in particular under the trade name Eusolex 232 by Merck,
Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name Neo Heliopan AP by Symrise
Derivatives De Fenilbenzotriazol [070] Drometrizol Trisilozano sold under the name Silatrizol by Rhodia Chimie,
Methylene bis-Benzotriazolyl Tetramethylbutylphenol sold in solid form under the trade name MIXXIM BB / 100 by Fairmount Chemical or in micronized form in aqueous dispersion under the trade name Tinosorb M by BASF.
Triazine derivatives [071] - Bis (Ethylhexyloxyphenol) methoxyphenyltriazine sold under the trade name Tinosorb S by BASF,
-Ethylhexyltriazone sold privately under the trade name Uvinul T150 by BASF,
- Diethylhexylbutamidotriazone sold under the trade name Uvasorb HEB by Sigma 3V,
Silicone triazines replaced by two groups
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36/100 aminobenzoates such as those described in EP0841341 in particular the compound 2,4-Bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1,3, 3, 3-tetramethyl-1 [( trimethylsilyloxydisiloxanil} propyl) amino] -s-triazine,
2,4,6-Tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-Tris (dineopentyl 4 '-aminobenzalmalonate) -s-triazine,
2,4-Bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4'aminobenzoate) -s-triazine,
- the symmetrical triazine filters described in US patent 6 225 467, in application WO 2004/085412 (see compounds 6 and 9) or in the document "Symetrical Triazine Derivatives" IP.COM Journal, IP. COM INC West Henrietta NY, US (September 20, 2004), in particular 2,4,6-tris- (biphenyl) -1,3,5-triazines (in particular the
2,4,6-tris (biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine which is also described in patent applications from Beiersdorf WO 06/035000, WO 06/034982, WO 06/034991, WO 06/35007, WO 2006/034992, WO 2006/034985.
Anthranilic Derivatives [072] Mentil anthranilate sold under the trade name Neo Heliopan MA by Symrise
Derivatives of Imidazolines [073] Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate Benzalmalonate derivatives [074] Dineopentyl 4'-methoxybenzalmalonate,
Polyorganosiloxane comprising benzalmalonate functional groups, such as Polysilicone-15, sold under the trade name Parsol SLX by DSM Nutritional Products
4,4-Diarylbutadiene derivatives [075] 1,1-dicarboxi- (2,2'-dimethylpropyl) -4,4-diphenylbutadiene, Benzoxazole derivatives
2,4-bis- [5.1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylPetition 870180138940, from 10/8/2018, page 49/125
37/100 hexyl) -imino-1,3,5-triazine sold under the name Uvasorb K24 by Sigma 3V and its mixtures.
[076] The most particularly preferred additional organic filtering agents are chosen from:
Ethylhexyl Methoxycinnamate
Homosalate,
Ethylhexyl Salicylate,
Octocylene,
Butylmethoxydibenzoylmethane
Terephthalilidenodicanforsulfonic acid,
Disodium phenyldibenzimidazoletetrasulfonate,
Phenylbenzimidazolsulfonic acid,
Benzophenone-3, n-Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate,
4-Methylbenzylidene camphor,
Ethilhexil triazone,
Bis (ethylhexyloxyphenol) methoxyphenyltriazine,
Diethylhexyl Butamidotriazone,
2,4-Bis (n-butyl 4'-aminobenzalmalonate) -6 - [(3- {1,3,3,3-tetramethyl1- [(trimethylsilyl) -oxy] disyloxanil Ipropyl) amino] -s-triazine,
2,4,6-Tris (biphenyl-4-yl-1,3,5-triazine,
2,4,6-Tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-Tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4-Bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4 'aminobenzoate) -s-triazine,
Methylenebis (benzotriazolyl) tetramethylbutylphenol,
Drometrizole trisiloxane,
Polysilicone-15,
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Dineopentyl 4'-methoxybenzalmalonate,
1,1-Dicarboxy (2,2-dimethylpropyl) -4,4-diphenylbutadiene,
2,4-Bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2ethylhexyl) imino-1,3,5-triazine, and mixtures thereof.
[077] Additional organic UV filtering agents are preferably present in the compositions according to the present invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably 0.1 % to 15% by weight relative to the total weight of the composition.
[078] Additional mineral filtering agents are chosen from coated or uncoated metal oxide pigments in which the average size of the primary particles preferably ranges from 5 nm to 100 nm (preferably between 10 nm and 50 nm), for example, oxide titanium (amorphous or crystalline in the form of rutile and / or anatase), iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all well-known UV photoprotective agents.
[079] Coated pigments are pigments that have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105 , pp. 5364, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum fatty acid salts, metallic (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
[080] Silicones are known to be organosilicated polymers or oligomers with linear or cyclic, branched or reticulated structure, of variable molecular weight, obtained by polymerization and / or
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39/100 polycondensation of properly functionalized silanes, and basically consisting of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond), and optionally substituted hydrocarbon radicals are directly linked by means of an atom of carbon to said silicon atoms.
[081] The term silicones also includes the silanes necessary for its preparation, in particular, the alkylsilanes.
[082] The silicones used to coat the pigments suitable for the present invention are preferably chosen from the group consisting of alkylsilanes, polydialalkylsiloxanes, and polyalkylhydrogensiloxanes. Most preferably, silicones are chosen from the group consisting of octyltrimethylsilane, polydimethylsiloxanes and polymethylhydrogensiloxanes.
[083] Of course, pigments formed from metal oxides may, before being treated by silicones, have been treated by other surface agents, in particular cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or their compounds. mixtures.
[084] Such metal oxide pigments, coated or uncoated, are in particular disclosed in patent application EP-A-0 518 773. As commercial products, products sold by Sachtleben, Tayca, Merck and Evonik can be mentioned.
[085] Coated pigments are more particularly titanium oxides that have been coated:
- silica such as Ikeda's Sunveil product and Merck's Eusolex T-AVO product,
- silica and iron oxide such as Ikeda's Sunveil F product,
- silica and alumina such as the products Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA from Tayca, Tioveil from CRODA, and
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Rhodia's Mirasun TiW 60,
- alumina, such as the Tipaque TTO-55 (B) and Tipaque TTO-55 (A) products from Ishihara and UVT 14/4 from Kemira,
- alumina and aluminum stearate, such as the product Microtitanium Dioxide MT 100 TV, MT 100 TX, MT 100 Z, MT-01 from Tayca, and the products Solaveil CT-10 W, Solaveil CT 100 and Solaveil CT 200 from Croda ,
- alumina and aluminum stearate, such as the product Microtitanium Dioxide MT 100 TV, MT 100 TX, MT 100 Z and MT-01 from Tayca, and the products Solaveil CT-10 W, Solaveil CT 100 and Solaveil CT 200 from Croda ,
- silica, alumina and alginic acid, such as Tayca's MT-100 AQ product,
- alumina and aluminum laurate, such as Tayca's Microtitanium Dioxide MT 100 S product,
- iron oxide and iron stearate, such as Tayca's Microtitanium Dioxide MT 100 F product,
- zinc oxide and zinc stearate such as Tayca's BR351 product,
- silica and alumina and treated with a silicone, such as the products Microtitanium Dioxide MT 600 SAS, Microtitanium Dioxide MT 500 SAS or Microtitanium Dioxide MT 100 SAS from Tayca,
- silica, alumina, aluminum stearate and treated with silicone, such as Titan Kogyo's STT-30-DS product,
- silica and treated with silicone, such as Sachtleben's UV-Titan X 195 product or Tayca's SMT-100 WRS product,
- from alumina and treated with silicone, such as Ishihara's Tipaque TTO-55 (S) products, or Sachtleben's UV Titan M 262,
- triethanolamine, such as Titan Kogyo's STT-65-S product,
- stearic acid, such as the Tipaque TTO-55 (C) product from
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Ishihara,
- sodium hexametaphosphate, such as Tayca Microtitanium Dioxide MT 150 W,
- treated with octyl trimethyl silane such as product “T 805” from
EVONIK,
- treated with polydimethylsiloxane, such as CARDRE's product “70250 Cardre UF TÍO2SI3”,
T1O2 rutile anastase treated with a polydimethylhydrogenosiloxane, such as the product “MICROTITANIUM DIOXIDE USP GRADE HYDROPHOBIC” by COLOR TECHNIQUES.
[086] Uncoated titanium oxide pigments are sold, for example, by Tayca under the trade names “Microtitanium Dioxide MT 500 B” or “Microtitanium Dioxide MT600 B”, by EVONIK under the name P 25, by Wacker with Transparent titanium oxide PW, by Miyoshi Kasei under the name UFTR, by TOMEN under the name ITS and by Croda under the name Tioveil AQ.
[087] Uncoated zinc oxide pigments are, for example,
- those sold under the name Z-Cote by Sunsmart;
- those sold under the name Nanox by Elementis;
- those sold under the name Nanogard WCD 2025 by Nanofase Technologies;
Coated zinc oxide pigments are, for example,
- those sold under the name Z-Cote HP1 by Sunsmart (ZnO coated with dimethicone);
- those sold under the name Oxide Zinc CS-5 by Toshibi (ZnO coated with polymethylhydrogensiloxane);
- those sold under the name Nanogard Zinc Oxide FN by
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Nanofase Technologies (40% dispersion in Finsolv TN, C12-C15 alcohol benzoate);
- those sold under the name Daitopersion ZN-30 and Daitopersion Zn-50 by Daito (dispersions in oxyethylenated cyclopolymethylsiloxane / polydimethylsiloxane, which contain 30% or 50% zinc oxides coated with silica and polymethylhydrogenosiloxane);
- those sold under the name NFD Ultrafine ZnO by Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane);
- those sold under the name SPD-Z1 by Shin-Etsu (ZnO coated with acrylic polymer grafted with silicone, dispersed in cyclodimethylsiloxane);
- those sold under the name Escalol Z100 by ISP (ZnO treated with alumina and dispersed in the mixture methoxycinnamate of ethylhexyl / copolymer PVP-hexadecene / methicone);
- those sold under the name Fuji ZnO-SMS-10 by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
- those sold under the name Nanox Gel TN by Elementis (ZnO dispersed at 55% in alcohol benzoate with C12-C15 with polycondensate hydroxystearic acid).
[088] Uncoated cerium oxide pigments are sold, for example, under the name Colloldal Cerium Oxide by RHODIA.
[089] Uncoated iron oxide pigments are, for example, sold by Arnaud under the names Nanogard WCD 2002 (FE 45B), Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ, Nanogard WCD 2006 (FE 45R), or by MITSUBISHI under the name TY-220.
[090] Coated iron oxide pigments are, for example, sold by Arnaud under the names Nanogard WCD 2008 (FE 45B
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FN), Nanogard WCD 2009 (FE 45B 556), Nanogard FE 45 BL 345, Nanogard FE 45 BL, or by BASF under the name TRANSPARENT IRON OXIDE.
[091] Mixes of metal oxides, in particular titanium dioxide and cerium dioxide, such as the equiponderal mixture of titanium dioxide and silica coated cerium, sold by Ikeda under the name Sunveil A, can also be mentioned. , as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product M 261 sold by SACHTLEBEN, or coated with alumina, silica and glycerol such as the product M 211 sold by SACHTLEBEN.
[092] According to the present invention, coated or uncoated titanium oxide pigments are particularly preferred.
[093] Inorganic UV filters generally represent 0.5 to 40%, preferably 1 to 30%, by weight relative to the total weight of the composition.
[094] According to their lipophilic or hydrophilic character, more or less pronounced, inorganic UV filters can be present in the oil phase, in the aqueous phase or in both phases in an emulsion.
[095] A particular form of the present invention relates to a composition comprising in a cosmetically acceptable medium at least one merocyanine derivative of formula (1) or (2) and at least one dibenzoylmethane derivative.
[096] Among the dibenzoylmethane derivatives that can be mentioned in particular, in a non-limiting way, are:
- 2-methyldibenzoylmethane,
- 4-methyldibenzoylmethane,
- 4-isopropylbenzoylmethane,
- 4-tert-butyldibenzoylmethane,
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- 2,4-dimethyldibenzoylmethane,
- 2,5-dimethyldibenzoylmethane,
- 4,4 '-diisopropylbenzoylmethane,
- 4,4 '-dimethoxydibenzoylmethane,
- 4-tert-butyl-4'-methoxydibenzoylmethane,
- 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
- 2-methyl-5-tert-butyl-4 '-methoxydibenzoylmethane,
- 2,4-dimethyl-4'-methoxydibenzoylmethane,
- 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.
[097] It is more particularly preferred to use 4- (tert-butyl) -4'metoxidibenzoylmethane or Butyl Methoxy Dibenzoylmethane or Avobenzone, sold under the trade name Parsol 1789 by DSM Nutritional Produtos, Inc .; this filtering agent corresponds to the following formula:
[098] The dibenzoylmethane derivative or derivatives can be present in the compositions according to the present invention in levels that preferably range from 0.01% to 20% by weight, more preferably from 0.1% to 10% by weight and more preferably still 0.1% to 6% in relation to the total weight of the composition.
[099] A particular form of the present invention relates to a composition comprising in a cosmetically acceptable medium at least the compound 2-ethoxyethyl (2Z) -cyano {3- [(3-methoxypropyl) amino] cyclohex-2 -en-1 -ilidene} etanoate (25) in its geometric isomeric forms E / E and / or E / Z and a dibenzoylmethane derivative as defined above and, in particular, 4- (tert-butyl) -4 '-methoxydibenzoylmethane or Butyl Methoxy Dibenzoylmethane or Avobenzone.
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45/100 [0100] The aqueous compositions according to the present invention can also comprise classic cosmetic adjuvants chosen, in particular, among fatty substances, organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, perfumes, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, acidifying or alkalizing agents or any other ingredients commonly used in the cosmetic and / or dermatological field.
[0101] The fatty substances may consist of an oil or a wax different from the supportive waxes as defined above, or mixtures thereof. The term oil designates a compound that is liquid at room temperature. The term wax designates a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35 ° C.
[0102] As oils, mineral oils (paraffin), vegetable oils (sweet almond oil, macadamia oil, black currant seed oil or jojoba oil) can be mentioned; synthetic oils, for example perhydrosqualene, fatty alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name "Eldew SL-205" by Ajinomoto), fatty acids or fatty esters (such as alcohol benzoate with C12-C15 sold under the trade name “Finsolv TN” or “Witconol TN” by Witco, 2-ethylphenyl benzoate as the commercial product sold under the name X-Tend 226® by the ISP, octyl palmitate, lanolate of isopropyl, diisopropyl sebacate sold under the trade name Dub Dis by Stearineries Dubois and triglycerides, including triglycerides of capric / caprylic acids, and Dicaprilyl carbonate sold under the name Cetiol CC
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46/100 by Cognis, oxyethylene or oxypropylene esters and fatty ethers; silicone oils (cyclomethicone, polydimethylsiloxanes, or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimethylates such as tridecyl trimellitate.
[0103] As waxy compounds can be mentioned carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, for example, the product sold under the name Cirebelle 303 by Sasol.
[0104] Among the organic solvents, lower alcohols and polyols can be mentioned. The latter can be chosen from glycols and glycol ethers, such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, or diethylene glycol.
[0105] A particularly interesting family of solvents that can also be mentioned includes the 2-pyrrolidinone 4-carboxy ester derivatives of formula (I), alone or in mixture, and / or one of its salts and / or isomers and / or solvates :

(D in which:
- R ¹ designates a hydrogen atom or a linear alkyl with C1-C20 or branched with C3-C20;
- R2 designates a C1-C20 linear or C3-C20 branched alkyl radical which may contain a C5-C6 ring; a cycloalkyl radical with
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C5-C6 optionally substituted with one or two methyl radicals; the phenyl radical, the benzyl radical or the phenethyl radical;
- R ³ and R ⁴ designate, independently of each other, a hydrogen atom, or a linear alkyl radical with C1-C12 or branched with C3C12;
It should be clear that, when R ¹ = H, the compounds can be in their free acid form or in the form of their cosmetically acceptable salts.
[0106] In formula (I), among the alkyl groups, in particular, the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-octyl, 2-ethylhexyl , dodecyl, hexadecyl, cyclohexyl or methylcyclohexyl.
[0107] The salts of the compounds described in the present invention comprise the conventional non-toxic salts of said compounds, such as those formed from cosmetically acceptable organic or inorganic acids or bases.
[0108] Ammonium salts, alkanolamine salts such as triethanolamine salts, aminopropanediol salts, and alkali metal or alkaline earth metal salts such as sodium, potassium, magnesium and calcium can be mentioned.
[0109] Preferred compounds are those of formula (I) in which R ³ and R ⁴ are hydrogen.
[0110] Preferably, R ¹ designates a hydrogen atom or a linear alkyl with C1-C18 or branched with C3-C18; and most preferably a C2-C18 linear or C3-C10 branched alkyl radical.
[0111] Preferably, R ² designates a linear alkyl with C2-C18 or branched with C3-C18; and most preferably a C3-C16 linear or C3-C12 branched alkyl radical; or a cyclohexyl radical,
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48/100 phenyl, benzyl or phenethyl; more preferably, R ² designates a C4-C10 linear or C4-C10 branched alkyl radical; such as butyl and 2-ethylhexyl.
[0112] Among the compounds of formula (I), the following products (a) to (bx) are used more particularly:
O
Φ)
RN = 100911-23-3
The (d)
R = 428518-32-5 (a)
RN = 59S57-86-2
RN = 10080-92-9


RN = 873969-57-4
RN = 60298-19-3
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RN-593253-22 6
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ο.
Ο.
OH
Ο (ax)
RN = 52743-73-4
Ο (ay)
RN = 299920-47-1
ΌΗ

ο λ ~ οη (ba)
RN = 43094-8B-6

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[0113] The indicated counterions can be replaced by any cosmetically acceptable organic or inorganic cationic counterion, preferably chosen from the inorganic cations of alkali metals or alkaline earth metals, such as Na, Mg, K and Ca, and organic cations such as ammonium NRV, with R, which can be identical or different, representing H or a (hydroxy) alkyl with C1-C6.
[0114] The compounds still more particularly preferred are the compounds of formulas (1), (n), (o), (ac), (am), (at), (au), (av), (ba), (bg), (bl), (bm), (bp), (br), (bw) and (bx).
[0115] The compounds of formula (I) can be obtained according to the syntheses described in the following articles: J. Org. Chem., 26, pages 1519-24 (1961); Tetrahedron Asymmetric, 12 (23), pages 3241-9 (2001); J. Industrial & Engineeciclo Chem., 47, pages 1572-8 (1955); J. Am. Chem. Soc, 60, pages 402-6 (1938); and in patents EP0069512, US2811496, US2826588, US3136620, FR2290199 and FR2696744.
[0116] The compounds of formula (I) are preferably present, alone or in mixture, in the cosmetic compositions according to the present invention in an amount of 0.5% to 40% by weight.
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54/100 [0117] As hydrophilic thickeners, carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulens (Acrylate / C10-C3-alkylacrylate copolymer) can be mentioned; polyacrylamides, such as crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) ; polymers and copolymers of 2-acrylamide 2-methylpropane sulfonic acid, optionally cross-linked and / or neutralized, such as the poly (2-acrylamide 2-methylpropane sulfonic acid) marketed by Hoechst under the trade name “Hostacerin AMPS” (name CTFA: ammonium polyacryloyldimethyl taurate) or Simulgel 800 marketed by SEPPIC (CFTA name: sodium polyacryloyldimethyl taurate / polysorbate 80 / sorbitan oleate); the copolymers of 2-acrylamide 2-methylpropanesulfonic acid and hydroxyethyl acrylate such as Simulgel NS and Sepinov EMT 10 marketed by Seppic; cellulosic derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; water-soluble or hydrodispersible silicone derivatives such as acrylic silicones, polyether silicones and cationic silicones and their mixtures.
[0118] As lipophilic thickeners, synthetic polymers such as poly C10-C30 alkyl acrylates sold under the names “Intelimer IPA 13-1” and Intelimer IPA 13-6 by Landec, or modified clays such as hectorite and its derivatives, such as products marketed under the names of Bentone.
[0119] Of course, the person skilled in the art will take every care to choose the additional compound (s) mentioned above and / or their quantities so that the advantageous properties intrinsically linked to the compositions according to the present invention
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55/100 are not, or are not substantially, altered by the considered additions.
[0120] The compositions according to the present invention can be prepared according to techniques well known to the person skilled in the art. They can be presented in particular in the form of emulsion, simple or complex (O / A, W / O, O / W / O or W / O / W) such as a cream, a milk or a cream gel; in the form of an aqueous gel, in the form of a lotion; in the form of an anhydrous gel. They can optionally be aerosolized and present in the form of foam or spray.
[0121] The compositions according to the present invention are preferably in the form of an oil-in-water or water-in-oil emulsion.
[0122] The emulsification processes that can be used are the blade or propeller, rotor-stator and HHP.
[0123] It is also possible, by HHP (between 50 and 800 bars), to obtain stable dispersions with droplet sizes that can go down to 100 nm.
[0124] Emulsions generally comprise at least one emulsifying surfactant chosen from amphoteric, anionic, cationic or nonionic emulsifying surfactants, used alone or in admixture. Emulsifiers are appropriately chosen according to the emulsion to be obtained (A / O or O / A).
[0125] As emulsifying surfactants that can be used for the preparation of O / W emulsions, for example, alkyl esters or ethers of sorbitan, glycerol or sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethylone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning; or the cetyl
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56/100 dimethicone copolyol such as the product sold under the name Abil EM 90R by Evonik, and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 rols) and hexyl laurate sold under the name ABIL WE 09 by Evonik. One or more coemulsifiers can also be added to them, which can advantageously be chosen from the group comprising alkylated polyol esters.
[0126] As alkylated polyol esters, in particular polyethylene glycol esters such as PEG-30 Dipoli-hydroxystearate such as the product marketed under the name Arlacel P135 by Croda can be mentioned.
[0127] As glycerol and / or sorbitan esters, for example, polyglycerol isostearate, such as the product marketed under the name Isolan Gl 34 by Evonik; sorbitan isostearate, such as the product marketed under the name Arlacel 987 by Croda; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986 by Croda, and mixtures thereof.
[0128] The emulsifying polyoxyalkylene silicon elastomers that can be cited in particular are those disclosed in US-A-5, 236, 986, US-A-5, 412, 004, US-A-5, 837, 793, US-A-5, 811, 487. These silicone elastomers are preferably formulated as a gel in a hydrocarbon oil and / or a silicone oil. In these gels, the polyoxyalkylene silicon elastomer is often in the form of spherical particles.
[0129] As polyoxyalkylene silicon elastomers, those sold by Shin Etsu with the names:
- KSG-21 (with 27% active matter. INCI name: Dimethicone / PEG-10 Dimethicone vinyl dimethicone crosspolymer),
- KSG-20 (with 95% active matter. INCI name: PEG-10 Dimethicone Crosspolymer),
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- KSG-30 (100% active matter). INCI name: Lauryl PEG-15 Dimethicone vinyl dimethicone crosspolymer),
- KSG-31 (at 25% active matter). INCI name: Lauryl PEG-15 Dimethicone vinyl dimethicone crosspolymer),
- KSG-32 or KSG-320 or KSG-30 (at 25% active matter). INCI name: Lauryl PEG-15 Dimethicone vinyl dimethicone crosspolymer),
- KSG-33 (at 20% active matter),
- KSG-210 (with 25% active matter. INCI name: Dimethicone / PEG-10/15 crosspolymer),
- KSG-310: polyoxyethylsiloxane polyoxyethylene lauryl modified in mineral oil,
- KSG-330,
- KSG-340,
- X-22-6146 (with 32% active matter. INCI name: Dimethicone / PEG-10 Dimethicone vinyl dimethicone crosspolymer), or those sold by Dow Corning under the trade names:
- DC9010 (with 11% active matter. INCI name: PEG-12 dimethicone crosspolymer)
- DC9011 (at 11% active matter).
[0130] These products are generally in the form of oily gels that contain the silicone elastomer particles.
[0131] KSG-210 (INCI name: Dimethicone / PEG-10/15 crosspolymer) is preferably used, which is 25% active material of silicone elastomer in silicone oil.
[0132] Among the water / oil emulsifiers, polyglycerolated silicone elastomers such as those described in WO-A-2004/024798 can also be mentioned.
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58/100 [0133] As an example of polyglycerolated silicone elastomers, those sold by Shin Etsu, with the names:
KSG-710, (at 25% active matter. INCI name: Dimethicone / Polyglycerin-3 Crosspolymer),
-KSG-810,
- KSG-820,
- KSG-830,
- KSG-840.
[0134] For O / W emulsions, non-ionic emulsifiers such as oxyalkylene fatty acid and glycerol esters (more particularly polyoxyethylene) can be cited, for example, as emulsifiers; esters of oxyalkylenated fatty acids and sorbitan; oxyalkylene fatty acid esters (oxyethylene and / or oxypropylene) as the PEG-100 Stearate / Glyceryl Stearate mixture sold, for example, by Croda under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkyl polyglycosides (APG) such as decylglycoside and laurylglycoside marketed, for example, by Cognis with the respective names Plantaren 2000 and Plantaren 1200, keto-stearylglycoside optionally in admixture with ceto-stearyl alcohol , sold, for example, under the name Montanov 68 by SEPPIC, under the name Tegocare CG90 by Evonik and under the name Emulgade KE3302 by Coognis, as well as arachidyl glycoside, for example in the form of a mixture of arachidyl alcohols, beyl alcohol and arachidyl glycoside, sold under the name Montanov 202 by SEPPIC. According to a particular embodiment of the present invention, the mixture of the alkyl polyglycoside as defined above with the corresponding fatty alcohol can be in the form of a composition
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59/100 self-emulsifying, as described, for example, in WO-A-92/06778. hydrophobically modified inulins such as Lauryl Carbamate of Inulin as well as the product sold under the name INUTEC SPI by Company Beneo-ORAFTI.
[0135] According to a particular embodiment of the present invention, the composition may also contain at least one emulsifier chosen from the dimeric surfactants known as "twin surfactants" and which comprise two identical or different surfactant fractions, and consisting of a group of hydrophilic head and one lipophilic head connected to each other through the head groups, thanks to a spacer. Such surfactants are described in the patents DE19943681, DE19943668, DE 42 27 391 and DE 196 08 117; JP-A-11-60437; JP-A-8-311003; EP 0 697 244; EP0 697 245; EP0708 079; DE19622612 and JP-A 10-17593; WO 03024412, US5863 886; W096 / 25388; W096 / 14926; WO 96/16930, WO 96 / 25384WO9740124; WO9731890; DE19750246; IN
19750245; DE 19631225; DE 19647060. For a more detailed description of chemical structures and physicochemical properties, the following publications can be consulted: Milton J. Rosen, Gemini Surfactant, Proprieties of surfactant molecules with two hydrophilic groups and two hydrophobic groups, Cosmetics & Toiletries magazine, vol. 113, December 1998, pages 49 - 55, Milton J. Rosen, Recent Developments in Gemini Surfactants, Allured's Cosmetics & Toiletries magazine, July 2001, vol 116, n ° 7, pages 67 - 70, [0136] Among surfactants dimeric compounds described above, the preferred compounds of the present invention are anionic surfactants characterized by the following formula (I)
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60/100 in which
R ¹ and R ³ represent a linear alkyl group with C _s -Ci6,
R ² represents a C2-C8 alkylene group,
X and Y represent a group (C2H4C X-RF with x = 10 -15, and RF = -SO3M where M represents an alkaline atom.
[0137] A preferred twin surfactant is an anionic compound
Sodium Dicocoyl Ethylene Diamine PEG-15 Sulfate (INCI name) with formula:
[Formula] cocoil cocoil [0138] This twin surfactant can be used, for example, in commercial mixes sold by Sasol under the name CERALUTION®:
• Ceralution® H: Beenyl alcohol, Glycerol Stearate, Glyceryl Stearate Citrate and PEG-15 Ethylenediamine Sodium Sulfate.
• Ceralution® F: Sodium Lauroil Lactilate and Sodium Dicocoil Sulfate ethylene diamine PEG-15 ..
• Ceralution® C: Aqua, Capric / Caprylic Triglyceride, Glycerin, Ceteareth-25, Dicocoil Sodium Ethylenediamine Sulfate PEG-15, Sodium Lauroyl Lactylate, Beenyl Alcohol, Glyceril Stearate, Glycerol Stearate Citrate, Xanthan Gum Phenoxyethanol, Methylparaben, Ethylparaben, Butylparaben, Isobutylparaben (INCI names).
[0139] The preferred twin surfactant is the mixture of Beenyl Alcohol, Glycerol Stearate, Glyceryl Stearate Citrate and PEG-15 Ethylenediamine Sodium Sulfate PEG-15 (Ceralution® H).
[0140] Among other emulsifiers, polymers of isophthalic acid or polymers of sulfoisophthalic acid and, in particular, phthalate / sulfoisophthalate / glycol copolymers such as the diethylene glycol / phthalate / isophthalate / 1 copolymer, can be used 4-cyclohexane-dimethanol
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61/100 (INCI name: Polyester-5sol with the name “Eastman AQ polymer” (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by Eastman Chemical.
[0141] Among other emulsifiers, amphiphilic copolymers of 2-acrylamide 2-methylpropane sulfonic acid such as those described in patent EP1069142, can be used. The preferred amphiphilic AMPS copolymers are the STEARETH-25 ACRYLOYLDIMETHYLTAURATE crosslinked POLYMER STEARETH-25 sold under the name Aristoflex HMS by Clariant;
[0142] When it is an emulsion, the aqueous phase of that emulsion may comprise a non-ionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
[0143] The compositions of the present invention may also contain at least one non-emulsifying cross-linked elastomeric organopolysiloxane.
[0144] The term "non-emulsifying elastomeric organopolysiloxane" means an emulsifying elastomeric organopolysiloxane that does not contain any hydrophilic chain as polyoxyalkylene or polyglycerolated units.
[0145] Preferably, the non-emulsifying elastomeric organopolysiloxane is obtained by the reaction of adding (a) a diorganopolysiloxane containing at least two hydrogen atoms each linked to a silicon atom and (b) diorganopolysiloxanes having at least two unsaturated ethylenic groups attached to the silicon atom—, in particular in the presence (c) of a platinum catalyst as disclosed in application EP-A295886.
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62/100 [0146] In accordance with a particular form of the present invention, the emulsifying elastomeric non-organopolysiloxane is in powder form.
[0147] As examples of non-emulsifying elastomeric organopolysiloxanes in powder form, those with the INCI Name: DIMETHICONE / VINYL DIMETHICONE CROSSPOLYMER can be used such as commercial products sold under the names DOW CORNING 9505 COSMETIC POWDER, DOW CORNING POWDER 9506 by DOW CORNING.
[0148] According to a preferred embodiment of the present invention, the non-emulsifying elastomeric organopolysiloxane is mixed with at least one volatile or non-volatile hydrocarbon and / or volatile or non-volatile silicone oil to form a gel.
[0149] As examples of non-emulsifying elastomeric oil / organopolysiloxane mixtures, those having the following INCI names may be used:
DIMETHICONE AND DIMETHICONE / VINYL
DIMETHICONECROSSPOLYMER such as commercial products sold under the name "KSG6", "KSG16" by SHIN ETSU,
- CYCLOPENTASILOXANE AND DIMETHICONE / VINYL DIMETHICONE CROSSPOLYMER such as commercial products sold under the name KSG-15, KSG 24 by SHIN ETSU; “Dow Corning 9040 Silicone Elastomer Blend” by DOW CORNING;
- DIMETHICONE AND DIMETHICONE CROSSPOLYMER such as commercial products sold under the name “Dow Corning 9041 Silicone Elastomer Blend” by DOW CORNING;
- MINERAL OIL AND Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer as KSG 41 by SHIN ETSU
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- ISODODECANE AND Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer as KSG 42 sold by SHIN ETSU
TRIETHYLHEXANOIN AND VINYL DIMETHICONE / LAURYL DIMETHICONE CROSSPOLYMER as “KSG 43” sold by SHIN ETSU;
SQUALANE AND VINYL DIMETHICONE / LAURYL DIMETHICONE CROSSPOLYMER as KSG 44 sold by SHIN ETSU.
[0150] The compositions according to the present invention find their application in a large number of treatments, in particular cosmetic, skin, lips and hair treatments, including the scalp, especially for the protection and / or care of the skin , lips and / or hair, and / or for the makeup of the skin and / or lips.
[0151] Another object of the present invention consists in the use of the compositions according to the present invention as defined above for the manufacture of cosmetic products for the treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, in particular care products, sun protection products and makeup products.
[0152] The cosmetic compositions according to the present invention can be used, for example, as make-up products.
[0153] The cosmetic compositions according to the present invention can be used, for example, as care products and / or sun protection products for the face and / or body, of liquid to semi-liquid consistency, such as milks, creams more or less rich, gels-creams and pastes. They can optionally be packaged as an aerosol and can be in the form of a foam or a spray.
[0154] The compositions according to the present invention in the form of vaporisable fluid lotions according to the present invention are applied to the skin or hair in the form of fine particles by means of
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64/100 pressurization devices. The devices according to the present invention are well known to the person skilled in the art and comprise non-aerosol pumps or "atomizers, aerosol containers that comprise a propellant and aerosol pumps that use compressed air as a propellant. Such devices are described in US patents 4,077,441 and US 4,850,517.
[0155] Compositions conditioned in the aerosol form according to the present invention generally contain conventional propellants, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in amounts ranging from 15% to 50% in relation to the total weight of the composition.
[0156] The compositions according to the present invention may additionally further comprise additional cosmetic and dermatological active agents.
[0157] It will be possible, in particular, to choose additional active agents among moisturizers, desquamating agents, agents to improve barrier function, depigmenting agents, antioxidants, skin-releasing agents, anti-glycation agents, agents to stimulate the synthesis of dermal and / or epidermal macromolecules and / or to prevent their degradation, agents to stimulate the proliferation of fibroblasts or keratinocytes and / or differentiation of keratinocytes, agents to promote the maturation of the horny envelope, NO synthase inhibitors, benzodiazepine peripheral receptor antagonists (PBR), agents to stimulate sebaceous gland activity, agents to stimulate the energy metabolism of cells, tensioning agents, lipid-restructuring agents, slimming agents, agents to promote cutaneous microcirculation, soothing and / or anti-irritating agents, sebum regulators or anti-sebum astringents,
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65/100 healing agents, anti-inflammatory agents, anti-acne agents and agents that promote natural skin color.
[0158] The technician in the subject will know how to choose the active agent (s) according to the desired effect on the skin, hair, eyelashes, eyebrows or nails.
[0159] For the care and / or make-up of aged skin, he or she will preferably choose at least one active agent chosen from moisturizers, peeling agents, agents to improve barrier function, depigmenting agents, antioxidants , dermorrelaxing agents, anti-glycation agents, agents to stimulate the synthesis of dermal and / or epidermal macromolecules and / or to prevent their degradation, agents to stimulate the proliferation of fibroblasts or keratinocytes and / or differentiation of keratinocytes, agents for keratinocytes promote the maturation of the horny envelope, the NO synthase inhibitors, the antagonists of peripheral benzodiazepine receptors (PBR), the agents to increase the activity of the sebaceous glands, the agents to stimulate the energy metabolism of the cells, the lipid-restructuring agents , agents to promote skin microcirculation to the region around the eyes and agents that promote of the skin.
[0160] For the care and / or make-up of oily skin, the technician in the subject will preferably choose at least one active agent chosen from the descaling agents, the sebum regulating agents or antiseboreal and astringent.
[0161] According to a preferred embodiment, the cosmetic and / or dermatological asset is a depigmenting agent.
[0162] As depigmenting agents that can be used in accordance with the present invention, vitamin C and its derivatives, and in particular vitamin CG, vitamin CP and 3-0 ethyl, can be cited
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66/100 vitamin C; arbutin and its derivatives, such as those described in EP895779 and EP524109, for example alpha- and beta-arbutin; hydroquinone; aminophenol derivatives such as those described in WO 99/10318 and WO 99/32077, and in particular N-cholesteryloxycarbonyl-para-aminophenol and Netyloxycarbonyl-para-aminophenol; the iminophenol derivatives such as those described in WO 99/22707; L-2-oxothiazolidine-4-carboxylic acid or procysteine and also its salts or esters; ferulic acid; lucinol and its derivatives; kojic acid; resorcinol and its esters; tranexamic acid and its esters; gentisic acid, homogentisate, or methyl gentisate or homogentisate; dioic acid; calcium D-pantetein sulfonate; lipoic acid; ellagic acid; vitamin B3; linoleic acid and its derivatives; ceramides and their counterparts; plant derivatives, for example chamomile, bear grape, the aloe family (vera, ferox, bardensis), mulberry or skullcap; a kiwi juice (Actinidia chinensis) sold by Gattefosse; an extract of Paeonia suffructicosa root, such as the product sold by Ichimaru Pharcos under the name Botanpi Liquid B®, an extract of brown sugar (Saccharum officinarum), such as the molasses extract sold by Taiyo Kagaku under the name Molasses Liquid, without that this list is exhaustive. Biphenyl compounds such as magnolol, honokiol, magnolignan, etc. can also be mentioned.
[0163] Hydroxylated diphenylmethane derivatives such as those described in WO 2004/105736 and particularly the compound of structure can also be cited:
HO OH known as 4- (1-phenylethyl) -1, 3-benzenediol or 4-1-phenylethyl) -1,
3-dihydroxybenzene or also known as phenylethyl resorcinol or phenylethylbenzenediol or styryl resorcinol. This compound has a CAS number 85-27-8. This compound is sold under the name Symwhite 377® by Symrise.
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67/100 [0164] The following can be mentioned in particular:
- an anti-tanning agent, that is, an agent that, when applied to the skin, especially on the face, can produce a tanning effect that is more or less similar in appearance to what may result from prolonged exposure to the sun (natural tanning) ) or under a UV lamp;
- an additional coloring agent, that is, any compound that has a particular affinity with the skin, which allows the skin to be given a long-lasting, non-covering color (that is, that does not tend to opacify the skin) and that is not easily removed with water or using a solvent, and which resists when scrubbed and washed with a solution containing surfactants. This lasting coloring is therefore distinguished from the superficial and transitional coloring provided, for example, by a makeup pigment; and their mixtures.
[0165] Self-tanning agents can be chosen from (i) compounds that interfere with the biological melanogenesis pathway to potentiate it, such as, for example, the tyrosinase substrate, MC1R agonists;
(ii) the monocarbonyl or polycarbonyl compounds, for example, isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazoline-4,5-dione derivatives as described in patent application FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA) and 4,4-dihydroxypyrazolin-5-one derivatives as described in patent application EP 903 342. DHA will be used preferably.
[0166] DHA can be used in free and / or encapsulated form, for example, in the form of lipid vesicles such as liposomes, described in particular in patent application WO 97/25970.
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68/100 [0167] In general, the self-tanning agent is present in an amount ranging from 0.01% to 20% by weight and preferably in an amount between 0.1% and 10% of the total weight of the composition.
[0168] Other dyes that allow the modification of the color produced by the self-tanning agent can also be used.
[0169] These dyes can be chosen from direct synthetic or natural dyes.
[0170] These dyes can be chosen, for example, among the red or orange dyes of the fluorane type such as those described in patent application FR 2 840 806. For example, the following dyes can be cited:
- tetrabromofluorescein or eosin known by the name CTFA: Cl 45380 or Red 21;
- phloxin B known by the name CTFA: Cl 45410 or Red 27;
- diiodofluorescein known by the name CTFA: Cl 45425 or
Orange 10;
- dibromofluorescein known by the name CTFA: Cl 45370 or
Orange 5;
- the tetrabromofluorescein sodium salt known by the name CTFA: Cl 45380 (Na salt) or Red 22;
- the sodium salt of phloxin B known by the name CTFA: Cl 45410 (Na salt) or Red 28;
- the diiodofluorescein sodium salt known by the name CTFA: Cl 45425 (Na salt) or Orange 11;
- erythrosine known by the name CTFA: Cl 45430 or Acid Red 51;
- phloxin known by the name CTFA: Cl 45405 or Acid Red 98.
[0171] These dyes can also be chosen from anthraquinones, caramel, carmine, carbon black, azulene blue,
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69/100 methoxyalene, trioxalene, guajazulene, chamuzulene, Bengal rose, cosine 10B, cyanosine and dafinine.
[0172] These dyes can be chosen from indole derivatives, for example, monohydroxyindoles as described in FR 2 651 126 (i.e., 4-, 5-, 6- or 7-hydroxyindole) or dihydroxyindoles such as described in EP-B-0 425 324 (i.e., 5,6dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole or 2, 3dimethyl-5,6-dihydroxyindole).
[0173] The active cosmetic and / or dermatological agents will be present in one of the compositions according to the present invention in a content ranging from 0.001% to 20% in relation to the total weight of the composition, preferably from 0.01% to 10%, more preferably from 0.5 to 5% and more particularly from 0.1 to 1% in relation to the total weight of the composition.
[0174] The following photoprotective formulations were produced; the amounts are given as percentages by weight relating to the total weight of the composition.
Examples
A. Preparation Examples of UV Merocyanine Absorbers
Example A1 (D
Compound Preparation (1)
N
55.33 grams of bis (2-methoxyethyl) amine are reacted with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 21.48 grams of ethyl cyanoacetate in the presence of an organic base and a
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70/100 solvent.
[0175] The following base / solvent combinations are used:
Example Base Solvent Example A1.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A1.2 DBU (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A1.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A1.4 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylsulfoxide Example A1.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A1.6 sodium methylate dimethylacetamide Example A1.7 sodium methylate isopropanol Example A1.8 potassium t-butoxide t-butanol
[0176] The reaction temperature is between 0 ° C and the boiling point of the solvent.
[0177] The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.
[0178] After the reaction, the product (101) is obtained from the reaction mixture by isolating the normal product by liquid-liquid separation, column chromatography or crystallization by adding a poor solvent to the reaction mixture.
[0179] The desired product (1) is obtained in yields of 66% (36 grams) as a dark brownish oil that crystallizes as yellow crystals (Melting point: 76.9 ° C).
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Example A2
Preparation of Compound of Compound formula (2)
55.33 grams of bis- (2-methoxyethyl) amine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 27.18 grams of 2-methoxyethyl cyanoacetate in the presence of an organic base and a solvent.
[0180] The following base / solvent combinations are used:
Example Base Solvent Example A2.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A2.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A2.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A2.4 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylsulfoxide Example A2.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A2.6 N-methylmorpholine dimethylacetamide Example A2.7 bis- (2-methoxyethyl) amine 1-methylpyrrolidone Example A2.8 sodium methylate dimethylsulfoxide
[0181] After the reaction, the product (102) is obtained from the reaction mixture through silica gel column chromatography (eluent: toluene / acetone).
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72/100 [0182] The desired product (2) is obtained in yields of 75% (45.44 grams) as a yellow powder (melting point: 92.2 ° C).
Example A3
Compound Preparation (3)
I I
N
55.33 grams of bis- (2-methoxyethyl) amine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 29.85 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.
[0183] The following base / solvent combinations are used
Example Base Solvent Example A3.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A3.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A3.3 DBN (1,5-diazabicycle [4.3.0] non5-eno) 1-methylpyrrolidone Example A3.4 DBN (1,5-diazabicycle [4.3.0] non5-eno) dimethylsulfoxide Example A3.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A3.6 N-methylmorpholine dimethylacetamide Example A3.7 bis- (2-methoxyethyl) amine 1-methylpyrrolidone Example A3.8 sodium methylate dimethylsulfoxide
[0184] After the reaction, the product (103) is obtained from the reaction mixture by isolating the normal product by liquid-liquid separation,
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73/100 column chromatography or crystallization by adding a poor solvent to the reaction mixture.
[0185] The desired product (103) is obtained in yields of 66% (39.99 grams) as beige crystals (melting point: 58.3 ° C).
Example A4
Preparation of Compound (4) o
ΙΊ
70.67 grams of piperidine are condensed with 1,1,3,3tetramethoxypropane in acetic acid, concentrated and treated with 59.72 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.
[0186] The following base / solvent combinations are used:
Example Base Solvent Example A4.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A4.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A4.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A4.4 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylsulfoxide Example A4.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A4.6 piperidine dimethylacetamide Example A4.7 piperidine 1-methylpyrrolidone
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Example A4.8 sodium methylate dimethylsulfoxide
[0187] After silica gel column chromatography (eluent: toluene / acetone) the pure product is obtained by producing dark yellow crystals. Melting point: 66-67 ° C.
132.83 grams of piperidine are condensed with 1,1,3,3tetramethoxypropane in acetic acid, concentrated and treated with 133.38 grams of 2- (2-methoxyethoxy) -ethyl-cyanoacetate in the presence of an organic base and a solvent.
[0188] The following base / solvent combinations are used:
Example Base Solvent Example A5a1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A5a2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A5a3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A5a4 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylsulfoxide Example A55 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A5a6 piperidine dimethylacetamide Example A5a7 piperidine 1-methylpyrrolidone
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Example A5a8 sodium methylate dimethylsulfoxide
[0189] The desired product (5) is obtained in yields of 38% (82.4 grams) as an dark oil.
[0190] After column chromatography on silica gel and toluene / acetone (9: 1) as eluent the product (105) crystallizes from water as orange crystals. Melting point: 43.5-45 ° C.
Example A5b
Preparation of Compound (5) [0191] Using 5 grams of 3- (1-piperidinyl) -2-propenal and 7.39 grams of 2- (2-methoxyethoxy) ethyl-2-cyano acetic ester in the presence of the base and optionally a solvent the desired product is obtained in yields of 32% (3.5 grams) as a dark oil.
[0192] The following base / solvent combinations are used:
Example Base Solvent Example A5b1 piperidine without solvent Example A5b2 N-methylmorpholine dimethylacetamide Example A5b3 piperidine 1-methylpyrrolidone Example A5b4 piperidine dimethylsulfoxide
Example A6
Preparation of Compound (6) o
2.89 grams of piperidine are condensed with 1,1,3,3tetramethoxypropane in acetic acid, concentrated and treated with 1.22 grams of 2-cyano-N- (2-hydroxyethyl) acetamide in the presence of an organic base and a solvent .
[0193] The following base / solvent combinations are used:
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Example Base Solvent Example A6.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A6.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A6.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A6.4 ethanolamine dimethylsulfoxide Example A6.5 ethanolamine dimethylformamide Example A6.6 piperidine dimethylacetamide Example A6.7 piperidine 1-methylpyrrolidone Example A6.8 sodium methylate dimethylsulfoxide
[0194] The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.
[0195] After the reaction, the product (6) is obtained from the reaction mixture by isolating the normal product by liquid-liquid separation, column chromatography or crystallization by adding a poor solvent to the reaction mixture.
[0196] The desired product (6) is obtained as a brownish oil that crystallizes in the form of yellow crystals (0.24g, 10%).
[0197] Melting point: 139.4-141.0 ° C.
Example A7
Compound Preparation (20)
N
27.84 grams of piperidine are condensed with 1,1,3,3tetramethoxypropane in acetic acid, concentrated and treated with 56.77 grams
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77/100 ethyl (2,2-dimethyl-1,3-dioxolan-4-yl) cyanoacetate in the presence of an organic base and a solvent.
[0198] The following base / solvent combinations are used:
Example Base Solvent Example A7.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A7.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A7.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A7.4 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylsulfoxide Example A7.5 DBU (1,5-diazabicycle [5.4.0] non-7-eno) dimethylformamide Example A7.6 piperidine dimethylacetamide Example A7.7 piperidine 1-methylpyrrolidone Example A7.8 piperidine dimethylsulfoxide
[0199] 74.74 grams of the compound (20) are obtained producing yellow crystals.
Example A8
Compound Preparation (7)
{ > 0
70 ml of acid hydrochloride (1 N) is added to a solution of 74.74 grams of merocyanine compound (20) in 350 ml of ethanol. The reaction mixture is stirred for 24 hours at 40 ° C. After adding water, the product is extracted several times with ethyl acetate. The organic phases
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The combined 78/100 are dried over sodium sulfate, filtered and concentrated in vacuo to produce the crude product as a brown oil.
[0200] After crystallization, 34.44 grams of the product are produced as a yellow powder.
[0201] Melting point: 101 ° C.
Example A9
Preparation of Compound (8)
236.72 grams of piperidine are condensed with 1,1,3,3 tetramethoxypropane in acetic acid, concentrated and treated with 217.24 grams of 1- (2-hydroxy) pentyl cyanoacetate in the presence of an organic base and a solvent.
[0202] The following base / solvent combinations are used:
Example Base Solvent Example A9.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A9.2 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylacetamide Example A9.3 piperidine 1-methylpyrrolidone Example A9.4 piperidine dimethylsulfoxide Example A9.5 DBU (1,8-diazabicycle [5.4.0]undec-7-eno) dimethylformamide
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Example A9.6 DBU (1,8-diazabicycleundec-7-eno) [5.4.0] dimethylacetamide Example A9.7 DBU (1,8-diazabicycleundec-7-eno) [5.4.0] 1-methylpyrrolidone Example A9.8 DBU (1,8-diazabicycleundec-7-eno) [5.4.0] dimethylsulfoxide
500 grams of the crude product (109) are obtained by producing a dark brown oil.
[0203] After column chromatography (silica gel, eluent: toluene / ethyl acetate) and crystallization 53.09 grams (23%) of the desired product are obtained by producing yellow crystals.
[0204] Melting point: 130 ° C.
Example A10
Compound Preparation (21)
1.81 grams of morpholine are treated with 1,1,3,3tetramethoxypropane in acetic acid, concentrated and treated with 1.89 grams of ethyl (2,2-dimethyl-1,3-dioxolan-4-yl) cyanoacetate in the presence of an organic base and a solvent.
[0205] The following base / solvent combinations are used:
Example Base Solvent Example A10.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide
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Example A10.2 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylacetamide Example A10.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A10.4 morpholine dimethylsulfoxide Example A10.5 morpholine dimethylformamide Example A10.6 morpholine dimethylacetamide Example A10.7 morpholine 1-methylpyrrolidone Example A10.8 sodium methylate isopropanol
2.99 grams of the crude product (110) is obtained by producing a dark brown oil.
[0206] After column chromatography (silica gel, eluent:
toluene / acetone) and crystallization 1.17 grams (50%) of the compound (110) is obtained by producing yellowish crystals.
Example A11
Preparation of Compound (9) o
ml of acid hydrochloride (1 N) are added to a solution of 1.17 grams of merocyanine compound (21) in 5 ml of ethanol. The reaction mixture is stirred for 16 hours at room temperature.
[0207] The product is filtered and washed with small amounts of ethanol and water. After vacuum drying 0.36 grams of the product is produced as a yellowish powder.
[0208] Melting point: 144.5-146.0 ° C.
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Example A12
Compound Preparation (10)
(10) OY iliN
83.40 grams of morpholine are condensed with 1,1,3,3tetramethoxypropane in acetic acid and treated with 47.15 grams of 2ethoxyethyl cyanoacetate in the presence of the organic base and a solvent.
[0209] The following base / solvent combinations are used:
Example Base Solvent Example A12.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A12.2 DBN (1,5-diazabicycle [4.3.0] non-5-eno) dimethylacetamide Example A12.3 DBN (1,5-diazabicycle [4.3.0] non-5-eno) 1-methylpyrrolidone Example A12.4 DBN (1,5-diazabicycle [4.3.0] non-5-eno dimethylsulfoxide Example A12.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A12.6 morpholine dimethylacetamide Example A12.7 morpholine 1-methylpyrrolidone Example A12.8 sodium methylate dimethylsulfoxide
32.58 grams of the compound (10) are obtained by producing yellow crystals.
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82/100 [0210] Melting point: 81.5 ° C.
Example A13
Compound Preparation (12)
[0211] The merocyanine compound (12) is synthesized according to a method described on pages 367-371 in Synthetic Communications Vol. 33, No. 3,2003.
[0212] Using 113.00 grams of ethyl-2-hydroxyethylaminoacrolein and 102.47 grams of n-butyl cyanoacetate 123.46 grams of the crude product are obtained by producing a brown oil.
[0213] After crystallization 23.29 g of the product are obtained by producing yellowish crystals.
[0214] Melting point: 78.0 ° C.
Example A14
Compound Preparation (13) <13)

[0215] The merocyanine compound (13) is synthesized according to the merocyanine 12 synthesis producing the desired product as a brownish oil. 1H-NMR (CDC13):
δ = 7.73 (1H, d), 7.24 (1H, d), 5.5 (1H, t), 4.07A.33 (5H, m), 3.44-3.55 (2H, m ), 3.16-3.26 (2H, m), 1.67 (2H, m), 1.22-1.45 (12H, m), 0.9 (3H, m).
Example A15
Compound Preparation (14) {14)
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122.23 grams of 3- [(3-methoxypropyl) amino] -2-cyclohexen-1-one are alkylated with dimethylsulfate or diethylsulfate and treated with 75.45 grams of ethyl cyanoacetate in approximately equimolar proportions in the presence of the base and optionally a solvent.
[0216] The following base / solvent combinations are used:
Example Base Solvent Example A15.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A15.2 triethylamine isopropanol Example A15.3 3-methoxypropylamine isopropanol Example A15.4 3-methoxypropylamine tert-amyl alcohol Example A15.5 3-methoxypropylamine toluene Example A15.6 3-methoxypropylamine dimethylacetamide Example A15.7 3-methoxypropylamine no solvent Example A15.8 N-morpholine isopropanol
[0217] The completion of the alkylation reaction can be monitored, for example, by the TLC, GC or HPLC methods.
162.30 grams of the product (115) are obtained by producing a brown oil.
[0218] After crystallization the product is obtained by producing yellowish crystals.
[0219] Melting point: 92.7 ° C.
Example A16
Compound Preparation (15)
101.00 grams of 3- [(3-methoxypropyl) amino] -2-cyclohexen-1-one are alkylated with dimethyl sulfate or diethyl sulfate and treated with
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86.00 grams of 2-cyano-N- (3-methoxy-propyl) -acetamide in approximately equimolar proportions in the presence of the base and optionally a solvent.
[0220] The following base / solvent combinations are used:
Example Base Solvent Example A16.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A16.2 triethylamine isopropanol Example A16.3 3-methoxypropylamine isopropanol Example A16.4 3-methoxypropylamine tert-amyl alcohol Example A16.5 3-methoxypropylamine toluene Example A16.6 3-methoxypropylamine dimethylformamide Example A16.7 3-methoxypropylamine no solvent
[0221] The crude product (15) is obtained by producing a dark brown oil.
[0222] After silica gel column chromatography (eluent: toluene / methanol 99.1) 81.8 grams of the product are obtained by producing yellowish crystals.
[0223] Melting point: 84.7-85.3 ° C.
Example A17
Compound Preparation (16)
111.0 grams of 3- [(2-ethylhexiI) amino] -2-cyclohexen-1-one are alkylated with dimethyl sulfate or diethyl sulfate and are then treated with 64.10 grams of 2-cyano-N- (2- hydroxy-ethyl) -acetamide in the presence of
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85/100 base and optionally a solvent.
[0224] The following base / solvent combinations are used:
Example Base Solvent Example A17.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A17.2 trieti lamina isopropanol Example A17.3 ethanolamine isopropanol Example A17.4 2-ethylhexylamine tert-amyl alcohol Example A17.5 ethanolamine toluene Example A17.6 ethanolamine dimethylformamide Example A17.7 ethanolamine no solvent
[0225] The reaction temperature is between 60 to 120 ° C. [0226] The crude product is obtained by producing brownish crystals.
[0227] After recrystallization 97 grams of the product were obtained yielding yellowish crystals. Melting point: 117-119 ° C.
Example A18
Compound Preparation (17)
100.56 grams of 3- [(2-hydroxypropyl) amino] -2-cyclohexen-1-one are alkylated with dimethyl sulfate or diethyl sulfate and treated with 84.70 grams of butyl cyanoacetate in the presence of the base and optionally a solvent .
[0228] The following base / solvent combinations are used:
Example Base Solvent
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Example A18.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A18.2 triethylamine isopropanol Example A18.3 1-amino-2-propanol isopropanol Example A18.4 N-methylmorpholine tert-amyl alcohol Example A18.5 1-amino-2-propanol toluene Example A18.6 1-amino-2-propanol dimethylformamide Example A18.7 1-amino-2-propanol no solvent
15.97 grams of the crude product (17) are obtained by producing a dark brown oil.
[0229] After chromatography on silica gel (eluent:
hexane / ethyl acetate) 45.67 grams of the product were obtained by producing yellowish crystals. Melting point: 106.7 ° C.
Example A19
Compound Preparation (27)
13.09 grams of 3- [(3-methoxypropyl) amino] -2-cyclohexen-1-one are alkylated with dimethyl sulfate or diethyl sulfate and treated with 10.12 grams of butyl cyanoacetate in the presence of the base and optionally a solvent .
[0230] The following base / solvent combinations are used:
Example Base Solvent Example A19.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A19.2 triethylamine isopropanol Example A19.3 3-methoxypropylamine isopropanol
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Example A19.4 N-methylmorpholine tert-amyl alcohol Example A19.5 3-methoxypropylamine toluene Example A19.6 3-methoxypropylamine dimethylformamide Example A19.7 3-methoxypropylamine no solvent
15.97 grams of the crude product (27) are obtained by producing a dark brown oil.
[0231] After chromatography on silica gel (eluent:
toluene / acetone) 13.46 grams of the product were obtained by producing yellowish crystals. Melting point: 96.3 ° C.
Example A20
Compound Preparation (22)
222.62 grams of dipropylamine are condensed with 1,1,3,3 tetramethoxypropane in acetic acid and treated with 200,13 grams of ethyl (2,2 dimethyl-1,3-dioxolan-4-yl) cyanoacetate in the presence of organic base and a solvent as described on page 4 in US2003 / 0181483A1.
[0232] The following base / solvent combinations are used:
Example Base Solvent Example A20.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A20.2 DBN (1.5-diazabiciclo [4.3.0] non-5-eno) dimethylformamide Example A20.3 DBN (1.5-diazabiciclo [4.3.0] non- 1-methylpyrrolidone
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5-eno) Example A20.4 DBN (1.5-diazabiciclo [4.3.0] non-5-eno) dimethylsulfoxide Example A20.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A20.6 dipropylamine dimethylacetamide Example A20.7 sodium methylate 1,2-dimethoxyethane Example A20.8 N-methylmorpholine dimethylsulfoxide
327 grams of the crude product (22) are obtained by producing a brown oil.
Example A21
Compound Preparation (23)
317 ml of acid hydrochloride (1 N) is added to a solution of 327 grams of crude merocyanine (22) in 990 ml of ethanol.
[0233] The reaction mixture is stirred for 16 hours at room temperature.
[0234] After removing the ethanol in vacuo, the reaction mass was absorbed in water and the product is extracted several times with ethyl acetate.
[0235] The collected organic phases are concentrated in vacuo.
[0236] After column chromatography on silica gel (eluent: toluene / ethyl acetate) and crystallization 70 grams of the desired product are obtained by producing yellowish crystals.
[0237] Melting point: 73 ° C.
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Example A22
Compound Preparation (24)
66.43 grams of dibutylamine are condensed with 1,1,3,3tetramethoxypropane in acetic acid and treated with 46.81 grams of ethyl (2,2-dimethyl-1,3-dioxolan-4-yl) cyanoacetate in the presence of an organic base and a solvent.
[0238] The following base / solvent combinations are used:
Example Base Solvent Example A22.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A22.2 DBN (1.5-diazabiciclo [4.3.0] non-5-eno) dimethylformamide Example A22.3 DBN (1.5-diazabiciclo [4.3.0] non-5-eno) 1-methylpyrrolidone Example A22.4 DBN (1.5-diazabiciclo [4.3.0] non-5-eno) dimethylsulfoxide Example A22.5 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A22.6 dibutylamine dimethylacetamide Example N-methylmorpholine 1,2-dimethoxyethane Example A22.8 sodium methylate dimethylsulfoxide
82.49 grams of the crude product (24) are obtained by producing a
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90/100 black oil.
Example A23
Compound Preparation (11)
ml of acid hydrochloride (1 N) are added to a solution of 82.5 grams of crude merocyanine (24) in 250 ml of ethanol. The reaction mixture is stirred for 16 hours at room temperature. After removing ethanol in vacuo, the reaction mass is absorbed in water and the product is extracted several times with ethyl acetate.
[0239] The collected organic phases are concentrated in vacuo.
[0240] After silica gel column chromatography (eluent: toluene / acetone) 37.85 grams of the desired product are obtained by producing a brownish oil.
[0241] HPLC (210 nm): 99.3 A-%, 1H-NMR (CDC13): δ = 7.8 (1H, d), 7.2 (1H, d), 5.6 (1H, t ), 4.27 (2H, m), 3.98 (1H, m), 3.5-3.7 (2H, m), 3,253.33 (4H, m), 3.00 (2H, s) , 1.61 (4H, m), 1.35 (4H, m), 0.96 (6H, m).
Example A24
Preparation of Compound (25) _H
V ' ^N
148.4 grams of 3- [(3-methoxypropyl) amino] -2-cyclohexen-1-one are alkylated with dimethyl sulfate or diethyl sulfate and treated with 130.00 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.
[0242] The following base / solvent combinations are used:
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Example Base Solvent Example A24.1 DBU (1.8-diazabicycle [5.4.0] undec-7-eno) dimethylformamide Example A24.2 trieti lamina isopropanol Example A24.3 3-methoxypropylamine isopropanol Example A24.4 N-methylmorpholine tert-amyl alcohol Example A24.5 3-methoxypropylamine toluene Example A24.6 3-methoxypropylamine dimethylformamide Example A24.7 3-methoxypropylamine no solvent
UV Protection Properties [0243] The UV protection properties of merocyanine derivatives are investigated by measuring their UV spectra in ethanol. In the table below the maximum absorption investigated (Amax) together with the corresponding values A ^{o / o} 1cm listed.
[0244] All merocyanine compounds according to the present invention have extraordinarily high protection properties in the UV region as indicated by the values W ^{/ o 1} cm above 1500.
UV Protection Properties [0245] The UV protection properties of merocyanine derivatives are investigated by measuring their UV spectrum in ethanol. In the following table, the maximum absorption investigated (Amax) together with the A ^1% 1cm values listed.
Comp. n ° Maximum absorption Amax ^1% 1cm
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(1) 380 2283 (2) 380 2046 (3) 380 1965 (4) 381 2568 (5) 381 2252 (6) 380 2530 (7) 381 2467 (9) 380 2414 (12) 381 2235 (14) 385 2207 (15) 385 1644 (16) 386 1618 (17) 385 2083 (18) 385 2036 (23) 381 2230 (25) 385 1947
[0246] All merocyanine compounds according to the present invention have extraordinarily high properties in the UV region as indicated by the values A ^1% cm above 1500.
B. Examples of Cosmetic Formulations
Examples 1-3
O / A Emulsions
Ingredients 1 2 3 Caprilyl glycol 0.5 0.5 0.5 TriglycerideCaprylic / Cáprico / copolymers ofsodium acrylates (Luvigel EM - 3 3 3
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BASF) Triethanolamine 0.2 0.2 0.2 Ethylhexyl icate salt 5 5 5 Dromethizole trisoloxane 2 2 2 Carbamato Lauril Inulina(Inutec SP1 - ORAFTI) 0.3 0.3 0.3 Cyclohexasiloxane 2 2 2 Glycerin 5 5 5 Propylene glycol 10 10 10 Alkyl Benzoate with C12-C15 7 7 7 Octocylene 7 7 7 Butyl Metoxidenzoilmethane 3 3 3 Merocyanine Compound (4) 2 Merocyanine Compound (15) - 2 - Merocyanine Compound (14) - - 3 Terephthalylidene AcidSulphonic 0.5 0.5 0.5 Preservative 0.8 0.8 0.8 Disodium EDTA 0.1 0.1 0.1 Water qs 100 qs 100 qs 100
Examples 4-5
A / O Emulsions
Ingredients 4 5 Isopropyl lauroyl sarcosinate (Eldew SL-205 - Ajinomoto U.S.A., Inc.) 3 3 Triethanolamine 0.9 0.9 Dromethizole trisiloxane 7 7 Synthetic wax 2 2
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(Cirebelle 303 - SASOL) Cyclohexasiloxane 7 7 Glycerin 5 5 Dimethicone 8 8 Alkyl Benzoate with C12-C15 (Finsolv TN - INNOSPEC ACTIVE CHEMICAL) 5 5 Octocylene 7 7 Butyl methoxydibenzoylmethane 3 3 Terephthalylidene Acid 0.5 0.5 Preservatives 0.8 0.8 Disodium EDTA 0.2 0.2 Merocyanine compound (25) 3 - Merocyanine compound (27) 3 Cross-linked copolymerdimethicone; PEG10 / 15 (KSG-210 - ShinEtsu Chemical Co.) 0.2 0.2 Dimethicone crosslinked copolymer (Dow Corning 9041 Silicone Elastomer BlendDow Corning Corporation 5 5 Akzo Nobel Global Personal Care) 2 2 Water qs 100 qs 100
Examples 6-8
O / A Emulsions
Phase Ingredients 6 7 8 THE Glycerol 5 5 5 EDTA 0.1 0.1 0.1 Potassium Cetyl Phosphate 1 1 1 Deionized Water qsp 100 qsp 100 qsp 100
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Triethanolamine 0.3 0.3 0.3 Preservatives 1.2 1.2 1.2 B1 Phenethyl benzoate (e)Benzoic acid 30 30 30 Preservatives 0.25 0.25 0.5 Stearic acid 1.5 1.5 1.5 Glyceryl Stearate (e)PEG 100 Stearate 1 1 1 Cetyl alcohol 0.5 0.5 0.5 Cetearyl alcohol and cetearylglycoside 2 2 2 Polydimethylsiloxane(Viscosity: 350 CST) 0.5 0.5 0.5 Triethanolamine 0.45 0.45 0.45 Merocyanine compound 4 2 0 0 Merocyanine compound 14 0 2 0 Merocyanine compound 15 0 0 2 B2 Isohedecan 1 1 1 Cross-linked polymer / C 10-30Alkyl Acrylate 0.2 0.2 0.2 Xanthan gum 0.2 0.2 0.2 Cyclopentadimethylsiloxane 5 5 5
[0247] The effectiveness of the UV protection of these compositions was evaluated. Emulsification protocol:
[0248] The aqueous and oily phases A and B were prepared by mixing the raw materials under stirring at 80 ° C; the solutions obtained are macroscopically homogeneous. Emulsions are prepared by slowly introducing oil phase B1 into the aqueous phase under shear using a Moritz rotor / stator homogenizer at a rotation speed of 4000 rpm for 15 minutes. The temperature of the emulsion is then lowered from 80 ° C to 40 ° C with stirring. The B2 oil phase is then introduced into the emulsion under
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96/100 slow shear. The emulsion is cooled to room temperature under slow shear. The emulsion is characterized by droplets whose size is between 1 pm and 10 pm.
[0249] In vitro Evaluation Protocol for the effectiveness of UV Protection. [0250] The Persistent Pigmentation Index (PPD) is determined using the in vitro method described by BL Diffey in the article J. Soc. Cosmet. Chem. 40, 127-133, (1989) for Sun Protection Factor. Measurements are performed with a Labsphere UV-10008 spectrophotometer. The formulas are applied on a rough PPMA plate, to obtain a homogeneous film at a speed of 1 mg / cm ³ .
Results
TableI
Examples Example 6 Example 7 Example 8 In vitro PPD 6.3 +/- 0.3 4.6 +/- 0.2 5.2 +/- 0.5
Example 9
Phase Ingredients 9 THE Glycerin 5 EDTA 0.1 Potassium cetyl phosphate 1 Deionized Water qsp 100 Triethanolamine 0.3 Preservatives 1.2 B1 Phenethyl benzoate (e) benzoic acid 30 Preservatives 0.25 Stearic acid 1.5
Uv Filters Photostability Assessment Protocol [0251] The percentage of residual amount of each UV filter (merocyanine compound and dibenzoylmethane compound) caused by
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97/100 exposure to a simulator of a formula spread on a film having a thickness of approximately 20 pm was measured.
[0252] The evaluation was carried out by HPLC analysis of each UV filter in a solution after extraction of the film, comparing exposed and unexposed samples.
Material And Method [0253] Solar Simulator: Oriel 1000W device equipped with a 4 inch output, an 81017 filter and a dichroic mirror. The samples were exposed in a horizontal position.
[0254] UV meter: OSRAM CENTRA device equipped with two reading heads, one for UVA radiation and the other for UVB radiation.
[0255] The simulator and the UV meter are calibrated together annually by spectroradiometry.
[0256] Exposure measurements were performed at the beginning and at the end of the exposure by positioning the reading heads at the sample position.
[0257] UV exposure was characterized by:
- a UVB flow of 0.35 - 0.45mW / cm ²
- a UVA flow of 16 -18 mW / cm ² .
[0258] Each residual amount of each UV filter was measured by HPLC chromatography, which has a sensor with diode bars.
[0259] Each residual amount of each UV filter was measured by HPLC chromatography, which has a sensor with diode bars.
Photostability Tests [0260] About 20mg of the composition was spread over the surface of a rough melt silica disc.
[0261] 3 composition films were exposed to the solar simulator and 3 other films were used as controls.
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98/100 [0262] The samples were exposed 3 to 3 to the simulator light for a sufficient time, emitting a UVA dose of 42J / cm ² .
[0263] At the end of the exposure, the disc was placed in a 600ml container with 10ml of appropriate solvent (ie, usually ethanol). The disk and the container were placed for 5 minutes in an ultrasonic tank.
[0264] The solutions were transferred to appropriate flasks compatible with the HPLC chromatograph.
Results
Table II
Measurements ofPhotostability Example 9 % of compoundresidual merocyanin 4 afterUV exposure 85 % residual Avobenzoneafter UV exposure 91
[0265] It was observed that, in composition 9, the photostability of the merocyanine compound of the present invention and the photostability of dibenzoylmethane are both satisfactory.
Rare Stability Tests Compounds 15 And 25 [0266] The chemical stability of the compounds can be evaluated in a 1/1 water / ethanol solution with 0.5% dissolved compounds.
[0267] These solutions could be acidified to also check the stability in relation to an acidic medium, for example, 0.1 M HCl in water / ethanol / isopropanol 50/40/10 (v / v / v).
[0268] Once prepared, the solution is placed in an oven at 45 ° C for 2 months to check stability and 1 hour at 60 ° C for
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99/100 the acid tension. Then, the solution was divided into equal parts (0.005% w / v in H20 / ACN 50/50) for analysis by liquid chromatography to verify the disappearance or not.
[0269] Materials and Methods:
UPLC Acquity (Waters) with βλ diode array detector (Waters).
Column: Acquity HSS T3 (Waters), length: 50 mm, internal diameter: 2.1 mm, particle diameter 1.8 pm. Mobile phase A = 20mM ammonium acetate, B = Acetonitrile.
Linear Gradient t (minutes)% A% B
0 95 95 5 05 95 8 05 95 8.5 95 05 10 95 05 Flow speed: 0.5 mL / min
T: 20 ° C
UV detection 383 nm Analysis: 1 pL injection Compound elution time 25 Compound elution time 15 Stability in acid medium
Compounds
Stability during 2 months of storage No loss No loss
Stability in acid medium for 1 h at 60 ° C
100% loss 4% loss
Petition 870180138940, of 10/08/2018, p. 112/125
100/100 [0270] These results show the superiority of compound 25 over 15.
Petition 870180138940, of 10/08/2018, p. 113/125
1/11

权利要求:
Claims (26)
[1]
Claims
1. COSMETIC AND / or dermatological COMPOSITION, characterized by comprising in a physiologically acceptable medium at least one merocyanine derivative of formula (1) or (2) and / or its geometric isomeric forms E / E-, E / Z- or Z / Z:
where Ri and R2 independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R1 and R2 together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by -O- or -NH-;
R3 is a group - (C = O) OR6; or a group - (CO) NHR6;
R6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally substituted by one or more of an OH;
R4 and Rs are hydrogen; or R4 and Rs form a - (CH2) n- ring which is optionally substituted by a C1-C4 alkyl and / or interrupted by one or more of an -O- or -NH-;
n is a number from 2 to 7;
R7 and Re independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is optionally interrupted by one or more of an O and / or replaced by one or more of an OH, cycloalkyl with C3-C22 or cycloalkenyl with C3 -C22, wherein said C3-C22 cycloalkyl or C3-C22 cycloalkenyl is optionally interrupted by one or more than one -O-;
Petition 870180138940, of 10/08/2018, p. 114/125
[2]
2/11 or R7 and Re together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by one or more of an -O-;
R9 and R10 are hydrogen; or R9 and R10 form a - (CH2) n- ring which is optionally substituted by C1-C4 alkyl and / or interrupted by -O- or -NH-;
A is -O-; or -NH;
R11 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O; or C1-C22 alkyl or C2-C22 alkenyl which is replaced by C3-C22 cycloalkyl or C3C22 cycloalkenyl, wherein said C3-C22 cycloalkyl or C3-C22 cycloalkenyl is optionally interrupted by one or more of one -O-;
with the proviso that (I) at least one of R1, R2 and R6 is replaced by hydroxy;
(II) if one of R1 is hydroxyethyl, R2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R1 is hydrogen, R2 is not 1-hydroxy-3-methyl-but-2-yl;
(III) if R6 is replaced by one or more of an OH; one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the bonding nitrogen form a piperidyl or morpholinyl radical;
(IV) at least one of R7 and Re, or R11 is interrupted by one or more of -O-.
2. COMPOSITION, according to claim 1, characterized by
R1 and R2 independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R1 and R2 together with the nitrogen atom that connects them form an - (CH2) n- ring which is optionally
Petition 870180138940, of 10/08/2018, p. 115/125
[3]
3/11 interrupted by -O- or -NH-;
R3 is a group - (C-O) ORe; or a group - (C-O) NHRe;
R6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally substituted by one or more of an OH;
R4 and Rs are hydrogen; or R4 and Rs form a - (CH2) n- ring which is optionally substituted by an alkyl with C1-C4 and / or interrupted by -Oor by -NH-;
n is a number from 2 to 7;
R7 and Re independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is optionally interrupted by one or more of an O and / or substituted by one or more of an OH; or R7 and Re together with the nitrogen atom that bonds them together form a - (CH2) n- ring which is optionally interrupted by one or more of an -O-;
R9 and R10 are hydrogen; or R9 and R10 form a - (CH2) n- ring which is optionally substituted by C1-C4 alkyl and / or interrupted by -O- or -NH-;
A is -O-; or -NH;
R11 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O;
with the proviso that (I) at least one of R1, R2 and Rô is replaced by hydroxy;
(II) if one of R1 is hydroxyethyl, R2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R1 is hydrogen, R2 is not 1-hydroxy-3-methyl-but-2-yl;
(III) if Rô is replaced by one or more of an OH; one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the bonding nitrogen form a piperidyl or morpholinyl radical;
Petition 870180138940, of 10/08/2018, p. 116/125
[4]
4/11 (IV) at least one of R7 and Re, or R11 is interrupted by one or more of an -O-.
3. COMPOSITION OF FORMULA (1), according to any one of claims 1 to 2, characterized by
R1 and R2 independently of each other are hydrogen; alkyl with C4-12; or hydroxyalkyl with C3-C12;
wherein at least one of R1 and R2 is hydroxyalkyl with C3-C12; and
R3, R4 and Rs are as defined in claim 1.
4. COMPOSITION OF FORMULA (1), according to any one of claims 1 to 3, characterized by
R6 is C1-C12 alkyl, which is optionally substituted by one or more of a hydroxy.
[5]
5. COMPOSITION OF FORMULA (1), according to any one of claims 1 to 2, characterized by
R6 is C1-C2 alkyl which is replaced by one or more of a hydroxy;
one of R1 and R2 is C4-C22 alkyl; or R1 and R2 together with the nitrogen atom that bonds them together form a - (CH2) n ring which is optionally interrupted by -O- and / or -NH-; and R4 and Rs and n are as defined in claim 1.
[6]
6. COMPOSITION OF FORMULA (2), according to any one of claims 1 to 2, characterized by
R11 is a radical of formula (1 A) ^- (CH2) m ^- O ^- R-12, where
R12 is C1-C12 alkyl; or C 1 -C 6 alkoxy Ο-ι-Οβ; m is a number from 1 to 5; and
R7, Re, R9, R10 and A are as defined in claim 1.
[7]
7. COMPOSITION according to any one of claims 1 to 6, characterized in that in formulas (1) and (2)
Petition 870180138940, of 10/08/2018, p. 117/125
5/11
Ri and R2 and R7 and Re respectively together with the bonding nitrogen atom form a piperidyl radical or a morpholinyl radical.
[8]
COMPOSITION according to any one of claims 1 to 6, characterized in that in formulas (1) and (2):
R4 and Rs and R9 and R10 respectively form a carbocyclic ring containing 6 carbon atoms.
[9]
COMPOSITION according to any one of claims 1 to 5 and 7 to 8, characterized in that the compounds of formula (1) are chosen from those in which
R1 and R2 independently of each other are hydrogen; or C1-C22 alkyl; or hydroxyalkyl with C1-C22; or R1 and R2 together with the nitrogen atom are linked together to form a piperidyl or morpholinyl radical;
R3 is a group - (C = O) OR6; or a group - (CO) NHR6;
R6 is C1-C22 alkyl, which can be substituted by one or more than one -OH;
R4 and Rs are hydrogen; or R4 and Rs are linked together to form a carbocyclic ring containing 6 carbon atoms.
[10]
COMPOSITION according to any one of claims 1 to 9, characterized in that the compounds of formula (1) are chosen from those in which
R1 and R2 independently of each other are hydrogen; or hydroxyalkyl with C1-C22; wherein at least one of R1 and R2 is hydroxyalkyl with C1-C22;
R3 is a group - (C = O) OR6; or a group - (C = O) NHR6;
Rô is C1-C22 alkyl; and
R4 and Rs are hydrogen; or R4 and Rs are linked together to form a carbocyclic ring containing 6 carbon atoms.
Petition 870180138940, of 10/08/2018, p. 118/125
6/11
[11]
11. COMPOSITION, according to claim 1, characterized by the compounds of formula (2) being chosen among those in which
R7 and Re independently of each other are hydrogen or alkyl with Ci-Ce, which is optionally interrupted by one or more of -O-;
A is -O-; or -NH;
R11 is C1-C22 alkyl; and
R9 and R10 are hydrogen; or R9 and R10 are linked together to form a carbocyclic ring containing 6 carbon atoms.
[12]
12. COMPOSITION, according to claim 1, characterized in that the compounds of formula (2) are chosen from those in which
R7 and Re together with the nitrogen atom form a morpholinyl or piperidyl radical;
A is -O-; or -NH;
R11 is C1-C22 alkyl; that is interrupted by one or more than -O-; and
R9 and R10 are hydrogen; or R9 and R10 are linked together to form a carbocyclic ring containing 6 carbon atoms.
[13]
13. COMPOSITION, according to claim 12, characterized by the compounds of formula (2) being chosen among those, in which
R11 is a radical of ^- (CH2) m ^- O ^- R12, where
R12 is C1-C4 alkyl; or C 1 -C 4 alkoxy-C 1 -C 4 alkyl; m is a number from 1 to 3;
R7 and Re, independently of each other, are hydrogen; alkyl with C1-C12, which is optionally interrupted by one or more of an O; or R7 and Re together with the nitrogen atom form a morpholinyl radical or
Petition 870180138940, of 10/08/2018, p. 119/125
7/11 piperidyl;
R9 and R10 are hydrogen; or form a carbocyclic ring containing 6 carbon atoms; and
A is -O-; or -NH.
[14]
14. COMPOSITION according to any one of claims 1 to 13, characterized in that the merocyanine derivative is chosen from the group of the following compounds and their geometric isomeric forms E / E, E / Z or Z / Z:
O
2-ethoxyethyl (2E, 4E) -2-cyano-5- (piperidin-1-yl) penta-2,4-dienoate
N ethyl (2Z) -cyano {3 - [(3-methoxypropyl) amino] cyclohex-2-en-1ylidene} etanoate (2Z) -2-cyano-N- (3-methoxypropyl) -2- {3 - [( 3methoxypropyl) amino] cyclohex-2-en-1-ylidene} ethanamide
N
2-ethoxyethyl (2Z) -cyano {3 [(3-methoxypropyl) amino] cyclohex-2-en1-ylidene} etanoate
2-methylpropyl (2Z) -cyano {3 - [(3-methoxypropyl) amino] cyclohex-2en-1-ylidenejetanoate
Petition 870180138940, of 10/08/2018, p. 120/125
11/11
[15]
15. COMPOSITION according to claim 14, characterized in that the merocyanine derivative is the compound 2-ethoxyethyl (2Z) cyano {3 - [(3-methoxypropyl) amino] cyclohex-2-en-1-ylidene} etanoate (25 ) in its geometric E / Z isomeric form of formula:
and / or its geometric isomeric form E / E of formula:
[16]
16. COMPOSITION according to any one of claims 1 to 15, characterized in that it also contains a system for filtering both UVA and UVB radiation.
[17]
COMPOSITION according to any one of claims 1 to 16, characterized in that it also contains one or more complementary hydrophilic, lipophilic or insoluble organic filtering agents and / or one or more inorganic filtering agents that are active in UVA and / or UVB.
Petition 870180138940, of 10/08/2018, p. 121/125
9/11
[18]
18. COMPOSITION according to any one of claims 1 to 17, characterized in that it also contains at least one derivative of dibenzoylmethane and particularly Butyl Methoxy Dibenzoylmethane.
[19]
19. COMPOSITION according to any one of claims 1 to 18, characterized in that it contains at least one derivative of dibenzoylmethane and particularly Butyl Methoxy Dibenzoylmethane and the merocyanine compound the compound 2-ethoxyethyl (2Z) -cyano {3 - [(3 -methoxypropyl) amino] cyclohex-2-en-1-ylidene} etanoate (25) in its geometric isomeric E / Z form:
o and / or its geometric isomeric form E / E of formula:
J
X
[20]
20. COMPOSITION according to any one of claims 1 to 19, characterized in that it contains at least one grease substance chosen from oils and waxes.
[21]
21. COMPOSITION according to any one of claims 1 to 20, characterized in that it contains at least one hydrophilic or lipophilic thickener.
[22]
22. COMPOSITION according to any one of claims 1 to 21, characterized in that it contains at least one hydrophobically modified inulin-type emulsifier such as Inulin Lauryl Carbamate.
[23]
23. COMPOSITION, according to any of the
Petition 870180138940, of 10/08/2018, p. 122/125
10/11 claims 1 to 22, characterized in that it contains at least one depigmenting agent, and preferably at least one hydroxylated diphenylmethane derivative, and in particular the compound of structure:
HO
[24]
24. COSMETIC PROCESS TO CONTROL AND / OR IMPROVE SKIN DARKNESS under exposure to UV radiation and the homogeneity of the skin color, characterized by understanding the application on the skin of a cosmetic composition, as defined in any of claims 1 to 23 .
[25]
25. COSMETIC PROCESS TO PROTECT THE KERATIN MATTERS, and particularly the skin, against photoaging, characterized by understanding the application on the keratin matter of a cosmetic composition, as defined in any one of claims 1 to 23.
[26]
26. USE OF MEROCIANINES OF FORMULA:
R’i and R'2 independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which are optionally substituted by at least one hydroxy; or R'i and R'2 together with the nitrogen atom that connects them form a - (CH2) n ring which is optionally interrupted by -O- or -NH-;
R'3 is a group - (C = O) OR6; or a group - (CO) NHR'6;
R'6 is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally
Petition 870180138940, of 10/08/2018, p. 123/125
11/11 replaced by one or more of an OH;
R'4 and Rs are hydrogen; or R'4 and R's form a - (CH2) n- ring which is optionally substituted by C1-C4 alkyl and / or interrupted by -O- or -NH-;
n is a number from 2 to 7;
R’7 and R’e independently of each other are hydrogen; alkyl with C1-C22, alkenyl with C2-C22, alkynyl with C2-C22, which is optionally interrupted by one or more of an O and / or substituted by one or more of an OH; or R> and R'e together with the nitrogen atom that connects them form a - (CH2) n- ring which is optionally interrupted by -O-;
R'9 and R'io are hydrogen; or R'9 and R'io form a - (CH2) ring which is optionally substituted by C1-C4 alkyl and / or optionally interrupted by -O- or -NH-;
A is -O-; or -NH;
R'ii is C1-C22 alkyl, C2-C22 alkenyl, C2C22 alkynyl, C3-C22 cycloalkyl or C3-C22 cycloalkenyl, which is optionally interrupted by one or more of an O;
characterized to protect body care products from photolytic and oxidative degradation.
Petition 870180138940, of 10/08/2018, p. 124/125

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法律状态:
2017-09-05| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2017-09-19| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|

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2018-07-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2018-11-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-12-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2012, 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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PCT/EP2011/062522|WO2013010590A1|2011-07-21|2011-07-21|Cosmetic and/or dermatological composition containing a merocyanine derivative comprising specific polar groups consisting of hydroxyl- and ether-functionalities|

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IBPCT/EP2011/062522|2011-07-21|

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PCT/EP2012/064195|WO2013011094A2|2011-07-21|2012-07-19|Cosmetic and/or dermatological composition containing a merocyanine derivative comprising specific polar groups consisting of hydroxyl- and ether-functionalities|

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