Cosmetic and/or dermatological composition containing a merocyanine derivative comprising specific polar groups consisting of hydroxyl- and ether-functionalities

Abstract

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 its E,E-, E,Z- or Z,Z-geometrical isomer forms: comprising specific polar groups consisting of hydroxyl- and ether-functionalities. Another object of the present invention relates to a cosmetic process for controlling and/or improving the darkening of the skin under exposure to UV radiation and the homogeneity of the colour of the complexion which comprises the application onto the skin of a cosmetic composition as above defined. Another object of the present invention relates to a cosmetic process for protecting the keratinic materials and particularly the skin against photo-ageing which comprises the application onto the keratinic material of a cosmetic composition as above defined. ##STR00001##

Claims

1. A cosmetic and/or dermatological composition comprising in a physiologically acceptable medium in an amount of from 0.1% to 10% by weight based upon the weight of the composition of at least one merocyanine derivative of formula (1) or (2) and/or its E/E-, E/Z- or Z/Z geometrical isomer forms: ##STR00104## wherein R.sub.1 and R.sub.2 independently of each other are hydrogen; C.sub.4-C.sub.12alkyl; or hydroxyl-C.sub.3-C.sub.12alkyl; R.sub.3 is a —(C═O)OR6group; or a —(CO)NHR.sub.6group; R.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a —(CH.sub.2).sub.n— ring which optionally contains in its chain one or more than one —O— or by —NH—; n is a number from 2 to 7; R.sub.7 and R.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which optionally contains in its chain one or more than one O and/or substituted by one or more than one OH, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl optionally contains in its chain one or more than one —O—; or R.sub.7 and R.sub.8 together with the nitrogen atom linking them form a —(CH.sub.2).sub.n— ring which optionally contains in its chain one or more than one —O—; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 form a —(CH.sub.2).sub.n— ring which is optionally substituted by C1-C4alkyl and/or contains in its chain —O— or —NH—; A is —O—; or —NH; R.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which optionally contains in its chain one or more than one O; or C.sub.1-C.sub.22alkyl or C.sub.2-C.sub.22alkenyl which is substituted by C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, wherein said C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl optionally contains in its chain one or more than one —O—; with the proviso that (I) at least one of R.sub.1, R.sub.2 and R.sub.6 is substituted by hydroxy; with the proviso that when both R.sub.1 and R.sub.2 are hydrogen, R.sub.6 is substituted by hydroxyl; (II) if R1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; (IV) at least one of R.sub.7 and R.sub.8, or R.sub.11 contains in its chain one or more than one —O—; and at least one active agent in a content ranging from 0.001% to 20% by weight relative to the total weight of the composition selected from the group of moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, lipid restructuring agents, agents promoting the cutaneous microcirculation for the area around the eyes and agents which promote the natural colouring of the skin.

2. The cosmetic and/or dermatological composition according to claim 1, R.sub.1 and R.sub.2 independently of each other are hydrogen; C.sub.4-C.sub.12alkyl; or hydroxyl-C.sub.3-C.sub.12alkyl; R.sub.3 is a —(C═O)OR.sub.6group; or a —(CO)NHR.sub.6group; R.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 form a —(CH.sub.2).sub.n— ring which optionally contains in its chain —O— or by —NH—; n is a number from 2 to 7; R.sub.7 and R.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which is optionally interrupted by one or more than one O and/or substituted by one or more than one OH; or R.sub.7 and R.sub.8 together with the nitrogen atom linking them form a —(CH.sub.2).sub.n— ring which is optionally interrupted by one or more than one —O—; R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 form a —(CH.sub.2).sub.n— ring which is optionally substituted by C.sub.1-C.sub.4alkyl and/or interrupted by —O— or by —NH—; A is —O—; or —NH; R.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C3-C22cycloalkenyl, which is optionally interrupted by one or more than one O; with the proviso that (I) at least one of R.sub.1, R.sub.2 and R.sub.6 is substituted by hydroxy; (II) if one of R.sub.1 is hydroxyethyl, R.sub.2 is not hydrogen, methyl or ethyl or hydroxyethyl; and if R.sub.1 is hydrogen, R.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R.sub.6 is substituted by one or more than one OH; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; (IV) at least one of R.sub.7 and R.sub.8, or R.sub.11 is interrupted by one or more than one —O—; of the at least one merocyanine derivative.

3. The cosmetic and/or dermatological composition of formula (1) according to claim 1, wherein R.sub.6 is C.sub.1-C.sub.12alkyl, which is optionally substituted by one or more than one hydroxyl; of the at least one merocyanine derivative.

4. The cosmetic and/or dermatological composition of formula (1) according to claim 1, wherein R.sub.6 is C.sub.1-C.sub.12alkyl which is substituted by one or more than one hydroxy; one of R.sub.1 and R.sub.2 is C.sub.4-C.sub.22alkyl; or R.sub.1 and R.sub.2 together with the nitrogen atom linking them form a —(CH.sub.2)n-ring which is optionally interrupted by —O— and/or —NH; of the at least one merocyanine derivative.

5. The cosmetic and/or dermatological composition according to claim 1, in which the compounds of formula (1) in said composition are selected from those wherein R.sub.3 is a —(C═O)OR.sub.6group; or a —(C═O)NHR.sub.6group; R.sub.6 is C.sub.1-C.sub.22alkyl; and R.sub.4 and R.sub.5 are hydrogen; or R.sub.4 and R.sub.5 are linked together to form a carbocyclic ring which contains 6 carbon atoms.

6. The cosmetic and/or dermatological composition according to claim 1, in which the compounds of formula (2) in said composition are selected from those wherein R.sub.7 and R.sub.8 independently of each other are hydrogen or C.sub.1-C.sub.8alkyl, which optionally contains in its chain one or more than one —O—; A is —O—; or —NH; R.sub.11 is C.sub.1-C.sub.22alkyl; and R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 are linked together to form a carbocyclic ring which contains 6 carbon atoms.

7. The cosmetic and/or dermatological composition according to claim 1, in which the compounds of formula (2) in said composition are selected from those wherein R.sub.7 and R.sub.8 together with the nitrogen atom form a morpholinyl or piperidyl radical; A is —O—; or —NH; R.sub.11 is C.sub.1-C.sub.22alkyl; which is interrupted by one or more than one —O—; and R.sub.9 and R.sub.10 are hydrogen; or R.sub.9 and R.sub.10 are linked together to form a carbocyclic ring which contains 6 carbon atoms.

8. The cosmetic and/or dermatological composition according to claim 7, in which the compounds of formula (2) in said composition are selected from those, wherein R.sub.11 is a radical of —(CH.sub.2).sub.m—O—R.sub.12, wherein R.sub.12 is C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl; m is a number from 1 to 3; R.sub.7 and R.sub.8, independently of each other are hydrogen; C.sub.1-C.sub.12alkyl, which is optionally interrupted by one or more than one O; or R.sub.7 and R.sub.8 together with the nitrogen atom form a morpholinyl or piperidyl radical; R.sub.9 and R.sub.10 are hydrogen; or form a carbocyclic ring which contains 6 carbon atoms; and A is —O—; or —NH.

9. The cosmetic and/or dermatological composition according to claim 1, further containing a system for screening out both UVA radiation and UVB radiation.

10. The cosmetic and/or dermatological composition according to claim 1, further containing one or more complementary hydrophilic, lipophilic or insoluble organic screening agents and/or one or more inorganic screening agents which are active in UVA and/or UVB.

11. The cosmetic and/or dermatological composition according to claim 1, further containing at least one dibenzoylmethane derivative.

12. The cosmetic and/or dermatological composition according to claim 1, containing at least one dibenzoylmethane derivative and the merocyanine compound the compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate (25) in its E/Z geometrical isomer form of formula: ##STR00105## and/or its E/E geometrical isomer form of formula: ##STR00106##

13. The cosmetic and/or dermatological composition according to claim 1, containing at least one fatty substance selected from oils and waxes.

14. The cosmetic and/or dermatological composition according to claim 1, containing at least one hydrophilic or lipophilic thickener.

15. The cosmetic and/or dermatological composition according to claim 1, containing at least one emulsifier of the type hydrophobically modified inuline as Inuline Lauryl Carbamate.

16. The cosmetic and/or dermatological composition according to claim 1, containing at least one depigmenting agent.

17. A cosmetic and/or dermatological process for protecting the keratinic materials which comprises the application onto the keratinic material of a cosmetic composition as defined in claim 1.

18. The cosmetic and/or dermatological composition according to claim 1, wherein the at least one depigmenting agent is at least one hydroxylated diphenylmethane derivative.

19. The cosmetic and/or dermatological composition according to claim 1, which comprises at least one active agent selected from the group of moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, NO-synthase inhibitors, and agents for stimulating the energy metabolism of cells.

20. A cosmetic and/or dermatological process for controlling and/or improving the darkening of the skin under exposure to UV radiation and the homogeneity of the colour of the complexion which comprises the application onto the skin of a cosmetic composition as defined in claim 1.

21. The cosmetic and/or dermatological process according to claim 20, wherein the hydroxylated diphenylmethane derivative has the structure: ##STR00107##

22. A cosmetic and/or dermatological composition comprising in a physiologically acceptable medium in an amount of from 0.1% to 10% by weight based upon the weight of the composition of at least one merocyanine derivative selected from the group of the following compounds and their E/E, E,Z or Z/Z geometrical isomer forms: ##STR00108## ##STR00109## and at least one active agent in a content ranging from 0.001% to 20% by weight relative to the total weight of the composition selected from the group of moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, lipid restructuring agents, agents promoting the cutaneous microcirculation for the area around the eyes and agents which promote the natural colouring of the skin.

23. The cosmetic and/or dermatological composition according to claim 22, wherein the merocyanine derivative in said composition is the compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate (25) in its E/Z geometrical isomer form of formula: ##STR00110## and/or its E/E geometrical isomer form of formula: ##STR00111##

24. The cosmetic and/or dermatological composition according to claim 22, further containing at least one dibenzoylmethane derivative; at least one fatty substance selected from oils and waxes; at least one hydrophilic or lipophilic thickener; at least one emulsifier of the type hydrophobically modified inuline; and at least one hydroxylated diphenylmethane derivative.

25. A cosmetic and/or dermatological composition for improving the skin against photo-aging, comprising in a physiologically acceptable medium at least one merocyanine derivative of formula (3) and/or the E/E-, E/Z- or Z/Z geometrical isomer forms thereof: ##STR00112## wherein: A is —O— or —NH; R is a C.sub.2-C.sub.6 alkyl group, which is optionally interrupted with one or more O.

26. A method for protecting a body care product from photolytic and oxidative degradation, which comprises incorporating in the body care product at least one merocyanine derivative of formula (1′) or (2′) and/or its E/E-, E/Z- or Z/Z geometrical isomer forms: ##STR00113## R′.sub.1 and R′.sub.2 independently of each other are hydrogen; C.sub.4-C.sub.12alkyl; or hydroxyl-C.sub.3-C.sub.12alkyl; R′.sub.3 is a —(C═O)OR.sub.6group; or a —(CO)NHR′.sub.6group; R′.sub.6 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which is optionally substituted by one or more than one OH; R′.sub.4 and R′.sub.5 are hydrogen; or R′.sub.4 and R′.sub.5 form a —(CH.sub.2).sub.n— ring which is optionally contains in its chain —O— or by —NH—; n is a number from 2 to 7; R′.sub.7 and R′.sub.8 independently of each other are hydrogen; C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, which is optionally contains in its chain one or more than one O; or R′.sub.7 and R′.sub.8 together with the nitrogen atom linking them form a —(CH.sub.2).sub.n— ring which optionally contains in its chain one or more than one —O—; R′.sub.9 and R′.sub.10 are hydrogen; or R′.sub.9 and R′.sub.10 form a —(CH.sub.2).sub.n— ring which is optionally substituted by C.sub.1-C.sub.4alkyl and/or optionally contains in its chain —O— or —NH—; A is —O—; or —NH; R′.sub.11 is C.sub.1-C.sub.22alkyl, C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.22cycloalkyl or C.sub.3-C.sub.22cycloalkenyl, which optionally contains in its chain one or more than one O; with the proviso that (I) at least one of R′.sub.1, R′.sub.2 and R′.sub.6 is substituted by hydroxy; with the proviso that when both R′.sub.1 and R′.sub.2 are hydrogen, R′.sub.6 is substituted by hydroxyl; (II) if R′1 is hydrogen, R′.sub.2 is not 1-hydroxy-3-methyl-but-2-yl; (III) if R′.sub.6 is substituted by one or more than one OH; one of R′.sub.1 and R′.sub.2 is C.sub.4-C.sub.22alkyl; or R′.sub.1 and R′.sub.2 together with the linking nitrogen form a piperidyl or morpholinyl radical; (IV) at least one of R′.sub.7 and R′.sub.8, or R′.sub.11 contains in its chain one or more than one —O—; wherein the product comprises a physiologically acceptable medium and at least one active agent in a content ranging from 0.001% to 20% by weight relative to the total weight of the composition selected from the group of moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, lipid restructuring agents, agents promoting the cutaneous microcirculation for the area around the eyes and agents which promote the natural colouring of the skin; and wherein the amount of the at least one merocyanine derivative is from 0.1% to 10% by weight based upon the weight of the composition.

Description

EXAMPLES

A. Preparation Examples of Merocyanine UV Absorbers

Example A1

Preparation of the Compound (1)

(1) ##STR00080##

(2) 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 solvent.

(3) The following base/solvent combinations are used:

(4) TABLE-US-00005 Example Base Solvent Example DBU (1,8- dimethylformamide A1.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBU (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A1.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A1.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A1.4 5-ene) Example DBU (1,8- dimethylformamide A1.5 diazabicyclo[5.4.0]undec- 7-ene) Example sodium methylate dimethylacetamide A1.6 Example sodium methylate isopropanol A1.7 Example potassium t-butoxide t-butanol A1.8

(5) The reaction temperature is between 0° C. and the boiling point of the solvent.

(6) The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.

(7) After the reaction, the product (101) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(8) The desired product (1) is obtained in yields of 66% (36 grams) as a dark brownish oil which crystallized as yellow crystals (Melting point: 76.9° C.)

Example A2

Preparation of the Compound of Formula of the Compound (2)

(9) ##STR00081##

(10) 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.

(11) The following base/solvent combinations are used:

(12) TABLE-US-00006 Example Base Solvent Example DBU (1,8- dimethylformamide A2.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A2.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A2.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A2.4 5-ene) Example DBU (1,8- dimethylformamide A2.5 diazabicyclo[5.4.0]undec- 7-ene) Example N-methylmorpholine dimethylacetamide A2.6 Example bis-(2-methoxyethyl)amine 1- A2.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A2.8

(13) After the reaction, the product (102) is obtained from the reaction mixture through silica gel column chromatography (eluent: toluene/acetone).

(14) The desired product (2) is obtained in yields of 75% (45.44 grams) as a yellow powder (melting point: 92.2° C.)

Example A3

Preparation of the Compound (3)

(15) ##STR00082##

(16) 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

(17) The following base/solvent combinations are used:

(18) TABLE-US-00007 Example Base Solvent Example DBU (1,8- dimethylformamide A3.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A3.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A3.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A3.4 5-ene) Example DBU (1,8- dimethylformamide A3.5 diazabicyclo[5.4.0]undec- 7-ene) Example N-methylmorpholine dimethylacetamide A3.6 Example bis-(2-methoxyethyl)amine 1- A3.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A3.8

(19) After the reaction, the product (103) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(20) 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 the Compound (4)

(21) ##STR00083##

(22) 70.67 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 59.72 grams of 2-ethoxyethyl cyanoacetate cyanoacetate in the presence of an organic base and a solvent.

(23) The following base/solvent combinations are used:

(24) TABLE-US-00008 Example Base Solvent Example DBU (1,8- dimethylformamide A4.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A4.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A4.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A4.4 5-ene) Example DBU (1,8- dimethylformamide A4.5 diazabicyclo[5.4.0]undec- 7-ene) Example piperidine dimethylacetamide A4.6 Example piperidine 1- A4.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A4.8

(25) After silica gel column chromatography (eluent: toluene/acetone) the pure product is obtained yielding dark yellow crystals. Melting point: 66-67° C.

Example A5a

Preparation of Compound (5)

(26) ##STR00084##

(27) 132.83 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane 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.

(28) The following base/solvent combinations are used:

(29) TABLE-US-00009 Example Base Solvent Example DBU (1,8- dimethylformamide A5a.1 diazabicyclo[5.4.0]undec- 7-ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A5a.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A5a.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A5a.4 5-ene) Example DBU (1,8- dimethylformamide A5a.5 diazabicyclo[5.4.0]undec- 7-ene) Example piperidine dimethylacetamide A5a.6 Example piperidine 1- A5a.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A5a.8

(30) The desired product (5) is obtained in yields of 38% (82.4 grams) as an dark oil.

(31) After column chromatography over 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 the Compound (5)

(32) By using 5 grams of 3-(1-piperidinyl)-2-propenal and 7.39 grams of 2-(2-methoxyethoxy)ethyl-2-cyano acetic acid ester in the presence of a base and optionally a solvent the desired product is obtained in yields of 32% (3.5 grams) as an dark oil.

(33) The following base/solvent combinations are used:

(34) TABLE-US-00010 Example Base Solvent Example piperidine no solvent A5b.1 Example N-methylmorpholine dimethylacetamide A5b.2 Example piperidine 1- A5b.3 methylpyrrolidone Example piperidine dimethylsulfoxide A5b.4

Example A6

Preparation of the Compound (6)

(35) ##STR00085##

(36) 2.89 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane 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.

(37) The following base/solvent combinations are used:

(38) TABLE-US-00011 Example Base Solvent Example DBU (1,8- dimethylformamide A6.1 diazabicyclo[5.4.0]undec- 7-ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A6.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A6.3 5-ene) methylpyrrolidone Example ethanolamine dimethylsulfoxide A6.4 Example ethanolamine dimethylformamide A6.5 Example piperidine dimethylacetamide A6.6 Example piperidine 1- A6.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A6.8

(39) The reaction end point is confirmed by thin layer chromatography or high performance liquid chromatography.

(40) After the reaction, the product (6) is obtained from the reaction mixture through ordinary product isolation by liquid-liquid separation, column chromatography or crystallization by addition of a poor solvent to the reaction mixture.

(41) The desired product (6) is obtained as a brownish oil which crystallizes in form of yellow crystals (0.24 g, 10%).

(42) Melting point: 139.4-141.0° C.

Example A7

Preparation of Compound (20)

(43) ##STR00086##

(44) 27.84 grams of piperidine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 56.77 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(45) The following base/solvent combinations are used:

(46) TABLE-US-00012 Example Base Solvent Example DBU (1,8- dimethylformamide A7.1 diazabicyclo[5.4.0]undec- 7-ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A7.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A7.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A7.4 5-ene) Example DBU (1,8- dimethylformamide A7.5 diazabicyclo[5.4.0]undec- 7-ene) Example piperidine dimethylacetamide A7.6 Example piperidine 1- A7.7 methylpyrrolidone Example piperidine dimethylsulfoxide A7.8

(47) 74.74 grams of the compound (20) are obtained yielding yellow crystals.

Example A8

Preparation of Compound (7)

(48) ##STR00087##

(49) 70 ml of hydro chloride acid (1 N) are added to a solution of 74.74 grams of merocyanine compound (20) in 350 ml of ethanol. The reaction mixture is stirred for hours at 40° C. After adding water the product is extracted several times with ethyl acetate. The combined organic phases are dried with sodium sulphate, filtrated and concentrated under vacuum yielding the crude product as a brown oil.

(50) After crystallization 34.44 grams of the product is yielded as a yellow powder.

(51) Melting point: 101° C.

Example A9

Preparation of the Compound of (8)

(52) ##STR00088##

(53) 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.

(54) The following base/solvent combinations are used:

(55) TABLE-US-00013 Example Base Solvent Example DBU (1,8- dimethylformamide A9.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBU (1,8- dimethylacetamide A9.2 diazabicyclo[5.4.0]undec- 7-ene) Example piperidine 1- A9.3 methylpyrrolidone Example piperidine dimethylsulfoxide A9.4 Example DBU (1,8- dimethylformamide A9.5 diazabicyclo[5.4.0]undec- 7-ene) Example DBU (1,8- dimethylacetamide A9.6 diazabicyclo[5.4.0]undec- 7-ene) Example DBU (1,8- 1- A9.7 diazabicyclo[5.4.0]undec- methylpyrrolidone 7-ene) Example DBU (1,8- dimethylsulfoxide A9.8 diazabicyclo[5.4.0]undec- 7-ene)

(56) 500 grams of the crude product (109) are obtained yielding a dark brown oil.

(57) After column chromatography (silica gel, eluent: toluene/ethyl acetate) and crystallization 53.09 grams (23%) of the desired product are obtained yielding yellow crystals.

(58) Melting point: 130° C.

Example A10

Preparation of Compound (21)

(59) ##STR00089##

(60) 1.81 grams of morpholine are treated with 1,1,3,3-tetramethoxypropane in acetic acid, concentrated and treated with 1.89 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(61) The following base/solvent combinations are used:

(62) TABLE-US-00014 Example Base Solvent Example DBU (1,8- dimethylformamide A10.1 diazabicyclo[5.4.0]undec- 7-ene) Example DBU (1,8- dimethylacetamide A10.2 diazabicyclo[5.4.0]undec- 7-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A10.3 5-ene) methylpyrrolidone Example morpholine dimethylsulfoxide A10.4 Example morpholine dimethylformamide A10.5 Example morpholine dimethylacetamide A10.6 Example sodium methylate isopropanol A10.7 Example sodium methylate dimethylsulfoxide A10.8

(63) 2.99 grams of the crude product (110) are obtained yielding a dark brown oil.

(64) After column chromatography (silica gel, eluent: toluene/acetone) and crystallization 1.17 grams (50%) of the compound (110) are obtained yielding yellowish crystals.

Example A11

Preparation of the Compound (9)

(65) ##STR00090##

(66) 1 ml of hydro chloride acid (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.

(67) The product is filtered off and washed with small amounts of ethanol and water. After drying under vacuum 0.36 grams of the product is yielded as a yellowish powder.

(68) Melting point: 144.5-146.0° C.

Example A12

Preparation of the Compound (10)

(69) ##STR00091##

(70) 83.40 grams of morpholine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 47.15 grams of 2-ethoxyethyl cyanoacetate in the presence of the organic base and a solvent.

(71) The following base/solvent combinations are used:

(72) TABLE-US-00015 Example Base Solvent Example DBU (1,8- dimethylformamide A12.1 diazabicyclo[5.4.0]undec- 7-ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A12.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A12.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A12.4 5-ene) Example DBU (1,8- dimethylformamide A12.5 diazabicyclo[5.4.0]undec- 7-ene) Example morpholine dimethylacetamide A12.6 Example morpholine 1- A12.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A12.8

(73) 32.58 grams of the compound (10) are obtained yielding yellow crystals.

(74) Melting point: 81.5° C.

Example A13

Preparation of the Compound (12)

(75) ##STR00092##

(76) The merocyanine compound (12) is synthesized according to a method described on pages 367-371 in Synthetic Communications Vol. 33, No. 3, 2003.

(77) By 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 yielding a brown oil.

(78) After crystallization 23.29 g of the product is obtained yielding yellowish crystals.

(79) Melting point: 78.0° C.

Example A14

Preparation of the Compound (13)

(80) ##STR00093##

(81) The merocyanine compound (13) is synthesized according to the synthesis of merocyanine 12 yielding the desired product as a brownish oil. 1H-NMR (CDCl3):

(82) δ=7.73 (1H, d), 7.24 (1H, d), 5.5 (1H, t), 4.07-4.33 (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

Preparation of the Compound (14)

(83) ##STR00094##

(84) 122.23 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 75.45 grams of ethyl cyanoacetate in approximately equimolar proportions in the presence of a base and optionally a solvent.

(85) The following base/solvent combinations are used:

(86) TABLE-US-00016 Example Base Solvent Example DBU (1,8- dimethylacetamide A15.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A15.2 Example 3-methoxypropylamine isopropanol A15.3 Example 3-methoxypropylamine tert-amylalcohol A15.4 Example 3-methoxypropylamine toluene A15.5 Example 3-methoxypropylamine dimethylformamide A15.6 Example 3-methoxypropylamine no solvent A15.7 Example N-morpholine isopropanol A15.8

(87) Completion of the alkylation reaction can be monitored for example by TLC, GC or HPLC methods.

(88) 162.30 grams of the product (115) are obtained yielding a brown oil.

(89) After crystallization the product is obtained yielding yellowish crystals.

(90) Melting point: 92.7° C.

Example A16

Preparation of the Compound (15)

(91) ##STR00095##

(92) 101.00 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternative with diethylsulfate and treated with 86.00 grams of 2-cyano-N-(3-methoxy-propyl)-acetamide in approximately equimolar proportions in the presence of a base and optionally a solvent.

(93) The following base/solvent combinations are used:

(94) TABLE-US-00017 Example Base Solvent Example DBU (1,8- dimethylacetamide A16.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A16.2 Example 3-methoxypropylamine isopropanol A16.3 Example 3-methoxypropylamine tert-amylalcohol A16.4 Example 3-methoxypropylamine toluene A16.5 Example 3-methoxypropylamine dimethylformamide A16.6 Example 3-methoxypropylamine no solvent A16.7

(95) The crude product (15) is obtained yielding a dark brown oil.

(96) After silica gel column chromatography (eluent:

(97) toluene/methanol 99:1) 81.8 grams of the product are obtained yielding yellowish crystals.

(98) Melting point: 84.7-85.3° C.

Example A17

Preparation of the Compound (16)

(99) ##STR00096##

(100) 111.0 grams of 3-[(2-ethylhexyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and are then treated with 64.10 grams of 2-cyano-N-(2-hydroxy-ethyl)-acetamide in the presence of a base and optionally a solvent.

(101) The following base/solvent combinations are used:

(102) TABLE-US-00018 Example. Base Solvent Example DBU (1,8- dimethylacetamide A17.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A17.2 Example ethanolamine isopropanol A17.3 Example 2-ethylhexylamine tert-amylalcohol A17.4 Example ethanolamine toluene A17.5 Example ethanolamine dimethylformamide A17.6 Example ethanolamine no solvent A17.7

(103) The reaction temperature is between 60 to 120° C.

(104) The crude product is obtained yielding brownish crystals.

(105) After recrystallization 97 grams of the product were obtained yielding yellowish crystals. Melting point: 117-119° C.

Example A18

Preparation of the Compound (17)

(106) ##STR00097##

(107) 100.56 grams of 3-[(2-hydroxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 84.70 grams of isobutyl cyanoacetate in the presence of a base and optionally a solvent.

(108) The following base/solvent combinations are used:

(109) TABLE-US-00019 Example Base Solvent Example DBU (1,8- dimethylacetamide A18.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A18.2 Example 1-amino-2-propanol isopropanol A18.3 Example N-methylmorpholine tert-amylalcohol A18.4 Example 1-amino-2-propanol toluene A18.5 Example 1-amino-2-propanol dimethylformamide A18.6 Example 1-amino-2-propanol no solvent A18.7

(110) 15.97 grams of the crude product (17) is obtained yielding a dark brown oil.

(111) After silica gel chromatography (eluent: hexane/ethyl acetate) 45.67 grams of the product were obtained yielding yellowish crystals. Melting point: 106.7° C.

Example A19

Preparation of the Compound (27)

(112) ##STR00098##

(113) 13.09 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 10.12 grams of isobutyl cyanoacetate in the presence of a base and optionally a solvent.

(114) The following base/solvent combinations are:

(115) TABLE-US-00020 Example Base Solvent Example DBU (1,8- dimethylacetamide A19.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A19.2 Example 3-methoxypropylamine isopropanol A19.3 Example N-methylmorpholine tert-amylalcohol A19.4 Example 3-methoxypropylamine toluene A19.5 Example 3-methoxypropylamine dimethylformamide A19.6 Example 3-methoxypropylamine no solvent A19.7

(116) 15.97 grams of the crude product (27) are obtained yielding a dark brown oil.

(117) After silica gel chromatography (eluent: toluene/acetone) 13.46 grams of the product were obtained yielding yellowish crystals. Melting point: 96.3° C.

Example A20

Preparation of the Compound (22)

(118) ##STR00099##

(119) 222.62 grams of dipropylamine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 200.13 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent as described on page 4 in US2003/0181483A1.

(120) The following Base/solvent combinations are used:

(121) TABLE-US-00021 Example Base Solvent Example DBU (1,8- dimethylformamide A20.1 diazabicyclo[5.4.0]undec-7- ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A20.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A20.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A20.4 5-ene) Example DBU (1,8- dimethylformamide A20.5 diazabicyclo[5.4.0]undec-7- ene) Example dipropylamine dimethylacetamide A20.6 Example sodium methylate 1,2- A20.7 dimethoxyethane Example N-methylmorpholine dimethylsulfoxide A20.8

(122) 327 grams of the crude product (22) are obtained yielding a brown oil.

Example A21

Preparation of the Compound (23)

(123) ##STR00100##

(124) 317 ml of hydro chloride acid (1 N) are added to a solution of 327 grams of crude merocyanine (22) in 990 ml of ethanol.

(125) The reaction mixture is stirred for 16 hours at room temperature.

(126) After removal of ethanol in vacuum the reaction mass was taken up in water and the product is extracted several times with ethyl acetate.

(127) The collected organic phases are concentrated in vacuum.

(128) After silica gel column chromatography (eluent: toluene/ethyl acetate) and crystallization 70 grams of the desired product are obtained yielding yellowish crystals.

(129) Melting point: 73° C.

Example A22

Preparation of the Compound (24)

(130) ##STR00101##

(131) 66.43 grams of dibutylamine are condensed with 1,1,3,3-tetramethoxypropane in acetic acid and treated with 46.81 grams of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl cyanoacetate in the presence of an organic base and a solvent.

(132) The following Base/solvent combinations are used:

(133) TABLE-US-00022 Example Base Solvent Example DBU (1,8- dimethylformamide A22.1 diazabicyclo[5.4.0]undec- 7-ene Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylacetamide A22.2 5-ene) Example DBN (1,5-diazabicyclo[4.3.0]non- 1- A22.3 5-ene) methylpyrrolidone Example DBN (1,5-diazabicyclo[4.3.0]non- dimethylsulfoxide A22.4 5-ene) Example DBU (1,8- dimethylformamide A22.5 diazabicyclo[5.4.0]undec- 7-ene) Example dibutylamine dimethylacetamide A22.6 Example N-methylmorpholine 1- A22.7 methylpyrrolidone Example sodium methylate dimethylsulfoxide A22.8

(134) 82.49 grams of the crude product (24) are obtained yielding a black oil.

Example A23

Preparation of the Compound (11)

(135) ##STR00102##

(136) 80 ml of hydro chloride acid (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 removal of ethanol in vacuum the reaction mass is taken up in water and the product is extracted several times with ethyl acetate.

(137) The collected organic phases are concentrated in vacuum.

(138) After silica gel column chromatography (eluent: toluene/acetone) 37.85 grams of the desired product are obtained yielding a brownish oil.

(139) HPLC (210 nm): 99.3 A-%. 1H-NMR (CDCl3): 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), 3.25-3.33 (4H, m), 3.00 (2H, s), 1.61 (4H, m), 1.35 (4H, m), 0.96 (6H, m).

Example A24

Preparation of the Compound (25)

(140) ##STR00103##

(141) 148.4 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethylsulfate or alternatively with diethylsulfate and treated with 130.00 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.

(142) The following base/solvent combinations are used:

(143) TABLE-US-00023 Example Base Solvent Example DBU (1,8- dimethylacetamide A24.1 diazabicyclo[5.4.0]undec- 7-ene) Example triethylamine isopropanol A24.2 Example 3-methoxypropylamine isopropanol A24.3 Example N-methylmorpholine tert-amylalcohol A24.4 Example 3-methoxypropylamine toluene A24.5 Example 3-methoxypropylamine dimethylformamide A24.6 Example 3-methoxypropylamine no solvent A24.7
UV Shielding Properties

(144) The UV shielding properties of the merocyanine derivatives are investigated by measuring their UV spectra in ethanol. In the following table the investigated absorption maxima (Amax) together with the corresponding A.sup.1%.sub.1cm values are listed.

(145) TABLE-US-00024 Absorption maximum Comp. No. λmax A.sup.1%.sub.1 cm (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

(146) All merocyanine compounds according to the present invention possess extraordinary high shielding properties in the UV region as indicated by A.sup.1%.sub.1cm cm values above 1500.

B. Examples of Cosmetic Formulations

Examples 1-3

O/W Emulsions

(147) TABLE-US-00025 Ingredients 1 2 3 Caprylyl glycol 0.5 0.5 0.5 Caprylic/Capric Triglyceride 3 3 3 and Sodium Acrylates Copolymer (Luvigel EM-BASF) Triethanolamine 0.2 0.2 0.2 Ethylhexyl salicylate 5 5 5 Drometrizole trisiloxane 2 2 2 Inulin Lauryl Carbamate 0.3 0.3 0.3 (Inutec SP1-ORAFTI) Cyclohexasiloxane 2 2 2 Glycerin 5 5 5 Propylene glycol 10 10 10 C.sub.12-C.sub.15-Alkyl Benzoate 7 7 7 (Finsolv TN-INNOSPEC ACTIVE CHEMICAL) Octocrylene 7 7 7 Butyl methoxydibenzoylmethane 3 3 3 Merocyanine compound (4) 2 Merocyanine compound (15) — 2 — Merocyanine compound (14) — — 3 Terephthalylidene Dicamphor 0.5 0.5 0.5 Sulfonic acid 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

W/O Emulsions

(148) TABLE-US-00026 Ingredients 4 5 Isopropyl lauroyl sarcosinate 3 3 (Eldew SL-205-Ajinomoto U.S.A., Inc.) Triethanolamine 0.9 0.9 Drometrizole trisiloxane 7 7 Synthetic wax 2 2 (Cirebelle 303-SASOL) Cyclohexasiloxane 7 7 Glycerine 5 5 Dimethicone 8 8 C.sub.12-C.sub.15-Alkyl Benzoate 5 5 (Finsolv TN-INNOSPEC ACTIVE CHEMICAL) Octocrylene 7 7 Butyl methoxydibenzoylmethane 3 3 Terephthalylidene Dicamphor 0.5 0.5 Sulfonic Acid Preservatives 0.8 0.8 Disodium EDTA 0.2 0.2 Merocyanine compound (25) 3 — Merocyanine compound (27) 3 Dimethicone/PEG-10/15 4.2 4.2 crosspolymer (KSG-210-Shin- Etsu Chemical Co.) Dimethicone crosspolymer 0.2 0.2 (Dow Corning 9041 Silicone Elastomer Blend-Dow Corning Corporation) Hydrogenated Polyisobutene 5 5 Aluminium Starch Octenyl 2 2 succinate (Dry-Flo Pure- AkzoNobel Global Personal Care) Water qs 100 qs 100

Examples 6-8

W/O Emulsions

(149) TABLE-US-00027 Phase Ingredients 6 7 8 A Glycerol 5 5 5 EDTA 0.1 0.1 0.1 POTASSIUM CETYL 1 1 1 PHOSPHATE Deionized Water qsp 100 qsp 100 qsp 100 Triethanolamine 0.3 0.3 0.3 Preservatives 1.2 1.2 1.2 B1 PHENETHYL BENZOATE 30 30 30 (and) BENZOIC ACID Preservatives 0.25 0.25 0.25 STEARIC ACID 1.5 1.5 1.5 GLYCERYL STEARATE 1 1 1 (and) PEG-100 STEARATE Cetyl alcohol 0.5 0.5 0.5 Cetearyl alcohol and 2 2 2 cetearyl glucoside POLY DIMETHYLSILOXANE 0.5 0.5 0.5 (VISCOSITY: 350 CST) TRIETHANOLAMINE 0.45 0.45 0.45 Merocyanine compound 4 2 0 0 Merocyanine compound 0 2 0 14 Merocyanine compound 0 0 2 15 B2 Isohexadecane 1 1 1 ACRYLATES/C10-30 ALKYL 0.2 0.2 0.2 ACRYLATE CROSSPOLYMER Xanthan gum 0.2 0.2 0.2 Cyclopentadimethylsiloxane 5 5 5

(150) The UV protection efficacy of these compositions has been evaluated.

(151) Emulsification Protocol:

(152) Aqueous and oil Phases A and B are prepared by mixing the raw materials under stirring at 80° C.; the obtained solutions are macroscopically homogeneous. Emulsions are prepared by slow introduction of the oil phase B1 in the aqueous phase under shearing using a rotor/stator Moritz homogenizer at the rotating speed of 4000 RPM during 15 minutes. The emulsion temperature is then decreased from 80° C. down to 40° C. under stirring. Oil phase B2 is then introduced in the emulsion under low shear. The emulsion is cooled down to room temperature under low shear. The emulsion is characterized by droplets which size is between 1 μm and 10 μm.

(153) In vitro Evaluation protocol of UV protection efficacy The Persistant Pigmentation Darkening (PPD) is determined using the in vitro method described by B. L. Diffey in the paper J. Soc. Cosmet. Chem. 40, 127-133, (1989) for Sun Protection Factor (SPF). Measurements are carried out using a Labsphere UV-1000S spectrophotometer. Formulae are applied on a rough PPMA plate, to get a homogeneous film at the rate of 1 mg/cm.sup.2.

(154) Results

(155) TABLE-US-00028 TABLE I Examples Example 6 Example 7 Example 8 PPD in 6.3 +/− 0.3 4.6 +/− 0.2 5.2 +/− 0.5 vitro

Examples 9

W/O Emulsions

(156) TABLE-US-00029 Phase Ingrédients 9 A Glycerine 5 EDTA 0.1 POTASSIUM CETYL PHOSPHATE 1 Deionized Water qsp 100 Triethanolamine 0.3 Preservatives 1.2 B1 PHENETHYL BENZOATE (and) 30 BENZOIC ACID Preservatives 0.25 STEARIC ACID 1.5 GLYCERYL STEARATE (and) 1 PEG-100 STEARATE Cetyl alcohol 0.5 Cetearyl alcohol and 2 cetearyl glucoside POLY DIMETHYLSILOXANE 0.5 (VISCOSITY: 350 CST) TRIETHANOLAMINE 0.45 4-ter-butyl-4′- 2 methoxydibenzoyl méthane Merocyanine compound 4 1 B2 Isohexadecane 1 ACRYLATES/C10-30 ALKYL 0.2 ACRYLATE CROSSPOLYMER Xanthan gum 0.2 Cyclopentadimethylsiloxane 5
Protocol of Evaluation of the Photostabilty of the UV Filters

(157) The percentage of residual amount of each UV filter (merocyanine compound and dibenzoylmethane compound) caused by the exposure to a solar simulator of a formula spread in a film having a thickness of about 20 μm was measure.

(158) The evaluation was done by HPLC analysis of each UV filter in a solution after extraction of the film, by comparing exposed and non-exposed samples.

(159) Material and Method:

(160) Solar simulator: Apparatus Oriel 1000W equipped with a 4 pouces outlet, a 81017 filter and a dichroic mirror. The samples were exposed in horizontal position.

(161) UV-Meter: Apparatus OSRAM CENTRA equipped with two reading heads, one for the UVA radiation and the other one for the UVB radiation.

(162) The simulator and UV meter are together calibred annually by spectroradiometry.

(163) Exposure measurements were done at the beginning and at the end of the exposure by positioning the reading heads at the position of the sample.

(164) The UV exposure was characterized by: a UVB flux of 0.35-0.45 mW/cm.sup.2 a UVA flux 16-18 mW/cm.sup.2.

(165) Each residual amount of each UV filter was measured by HPLC chromatography with a sensor having diodes bars.

(166) Each residual amount of each UV filter was measured by HPLC chromatography with a sensor having diodes bars.

(167) Photostability Tests

(168) About 20 mg of the composition are spread on the surface of a rough melt silica disc.

(169) 3 films of composition were exposed to the solar simulator and 3 other films were used as control.

(170) The samples were exposed 3 per 3 to the light of the simulator during a sufficient time delivering an UVA dose of 42 J/cm.sup.2.

(171) At the end of the exposure, the disc was introduced in a bowl of 600 ml with 10 ml of appropriate solvent (ie generally ethanol). The disc and the bowl were then placed during 5 minutes in an ultrasonic tank.

(172) The solutions were then transferred in appropriate bottles compatibles with the HPLC chromotograph.

(173) Results

(174) TABLE-US-00030 TABLE II Measurements of Photostability Example 9 % of residual 85 merocyanine compound 4 after UV exposure % of residual 91 Avobenzone after UV exposure

(175) It was observed that, in the composition 9, the photostability of the merocyanine compound of the invention and the photostability of the dibenzoylmethane are both satisfactory.

(176) Stability Tests for Compounds 15 and 25

(177) The chemical stability of the compounds can be assessed in a water/ethanol solution 1/1 with compounds solubilized at 0.5%.

(178) These solutions could be acidified to check also stability toward acid media for example HCl 0.1M in a water/ethanol/isopropanol 50/40/10 (v/v/v).

(179) Once the solution prepared, it is placed in an oven at 45° C. for 2 months for stability and 1 h at 60° C. for acidic stress. Then the solution is aliquoted (0.005% w/v in H2O/ACN 50/50) for liquid chromatography analysis to check disappearance or not.

(180) Materials and Methods:

(181) UPLC Acquity (Waters) with diod array detector eλ (Waters).

(182) Column: Acquity HSS T3 (Waters), length: 50 mm, Inner diameter: 2.1 mm, particles diameter 1.8 μm. Mobile phase A=ammonium acetate 20 mM, B=Acetonitrile.

(183) TABLE-US-00031 Linear gradient t (minutes) % A % B 0 95 05 5 05 95 8 05 95 8.5 95 05 10 95 05 Flow rate: 0.5 mL/min T: 20° C. Detection at UV 383 nm

(184) Analysis: 1 μL injection

(185) Elution time of compound 25: 2.56 min

(186) Elution time of compound 15: 2.11 min

(187) Acid media stability

(188) TABLE-US-00032 Storage Acid media stability 2 stability Compounds months 45° C. 1 h 60° C. 15 No loss Loss 100% 25 No loss Loss 4%

(189) These results show the superiority of compound 25 versus 15.