LU87093A1 - NOVEL UNSATURATED BENZYLIDENE-3 CAMPHOR DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS ABSORBERS OF ULTRA-PURPLE RADIATION IN COSMETICS AND AS INTERMEDIATES OF SYNTHESIS OF ORGANO-SILICON COMPOUNDS - Google Patents

Description

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New unsaturated derivatives of benzylidene-3 camphor, their preparation process and their use as absorbers of ultraviolet radiation in cosmetics and as intermediates for the synthesis of organo-silicic compounds.

5

The present invention relates to new unsaturated derivatives of benzylidene-3 camphor, to their preparation process and to their use in the cosmetic field as absorbers of ultraviolet radiation for the protection of human epidermis and hair vis-à-vis solar radiation, as well as for the stabilization of cosmetic compositions containing photosensitive constituents. The invention also relates to the use of these compounds as intermediates for the synthesis of organo-silicic compounds.

15 It is known that light radiation of wavelengths between 280 nm and 400 nm allows browning of the human epidermis and that rays of wavelengths between 280 and 320 nm, known under the name of UV -B, cause erythema and skin burns which can harm the development of the tan; this UV-B radiation must therefore be filtered.

We also know that UV-A rays, of wavelengths between 320 and 400 nm, causing browning of the skin, are capable of inducing an alteration of the latter, in particular -in the case of skin sensitive or of skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature aging. They promote the triggering of the erythematous reaction or amplify this reaction in certain 2 subjects and can even be at the origin of phototoxic or photoallergic reactions.

It is therefore advantageous to have compounds absorbing UV rays over a wide band in order to be able to filter both the 5 UV-A and UV-B rays.

We also know that the constituents used in cosmetic preparations do not always have sufficient light stability and that they degrade under the action of light radiation.

10 Consequently, it is desirable to incorporate into these preparations compounds capable of filtering UV rays and which must also have good stability and sufficient solubility in the media usually used in cosmetics, and in particular in oils and fats.

It is also desirable to provide the hair with good protection against photochemical degradation in order to avoid in particular discoloration or a change in shade.

Thus the Applicant has surprisingly discovered, during its research, that certain benzylidene-3 camphor derivatives carrying an unsaturated group have good filtering properties in a wide range of wavelengths from 280 to 360 nm. In addition to their good filtering properties, the new benzylidene-3 camphor derivatives exhibit excellent chemical and photochemical stability and have the advantage of being neither toxic nor irritant and of being perfectly harmless against skin.

They also have an excellent lipid-soluble nature, which makes them usable in fatty supports used in cosmetics and in particular in compositions intended to protect the human epidermis against UV rays, and more particularly in anti-sun compositions.

The subject of the present invention is therefore the new unsaturated derivatives of the benzylidene-3 camphor of formula: 35 A.

(I) 3 rOï in which: represents a hydrogen atom, a C ^ -Cg alkyl radical, a C ^ -Cg alkoxy radical or a - (0) n- (CE ^) ^ - (3 ^ ) = (^ 2 in which n = 0 or 1, p represents an integer between 1 and 10 10 and preferably between 1 and 4 and R ^ represents a hydrogen atom or a C ^ -C ^ alkyl radical ; R2 represents a hydrogen atom, a C ^ -C ^ alkyl radical, a 0, -0 ,, alkoxy radical or a - (CEL) -C (R,) = CEL radical in

1 ο Z p 4 Z

which p and R ^ have the meanings mentioned above; R 1 represents a hydrogen atom, a C 1 -C 4 alkyl radical or a C 1 -C 6 alkoxy radical; provided that one of the residues R ^ or R2 represents respectively a radical - (O ^ -CCI ^ -C ^ 4) = 0 ^ or a radical - (CH2) pC (R ^) = CH.2 in which n , p and R ^ have the meanings given above.

Among the preferred compounds of the invention, the following compounds may be mentioned: - 1'allyl-3'-methoxy-4'-benzylidene-3 camphor - 1'allyl-3'-dimethoxy-4 ', 5'-benzylidene -3 camphor 25 "le. methallyl-3'-methoxy-4'-benzylidene-3 camphor - methallyl-3'-dimethoxy-4 ', 5'-benzylidene-3 camphor - 1'allyloxy-3'-methoxy-4'-benzylidene-3 camphor - methalylyloxy-3'-methoxy-4'-benzylidene-3 camphor - allyl-4'-benzylidene-3 camphor 30 - methallyl-4'-benzylidene-3 camphor.

The compounds according to the invention of formula (I) can be prepared according to one of the following processes: 35 A, 4 1st process:

Preparation of the compounds of formula (I) in which represents a radical - (0) - (CH „) -G (R.) = CH„ or else R „represents an n / p 4 2 l radical - (CH) -C (R,) = CH, where R, R, n, p, R and R have the meanings “P 4 4 1 Z η · j 5 fications indicated above.

An aromatic aldehyde of formula (II) is condensed on the synthetic camphor (d, l-camphor or natural camphor (d-camphor) according to the following reaction scheme: iO fl fl 0: XX— I (II) "(I) 15

This reaction is carried out in the presence of a base, for example in the presence of an amide, a hydride or an alkali metal alcoholate, in an inert solvent such as benzene, toluene, ether, dioxane or dimethoxy-1,2-ethane, at a temperature between 0 ° C and the boiling point of the solvent.

a) The aldehyde of formula (II) in which R ^ represents a radical - (0) q- (CH2) -C (R4) = CH2 when n = 1, can be obtained by reaction of an alkenyl halide of formula (III) on an aldehyde of formula (IIA) according to the following reaction scheme: 25. OH P- (CH2) pC (R4) = CH2 I + X- (CH2) p-C (R4) = CH2-> I + Hx.

OHC OHC '^^> / AsR3 (IIA) (III) (II) 30

This reaction is carried out in the presence of a base in a solvent, for example in the presence of an alkali or alkaline earth metal carbonate or hydroxide or of an alkali metal amide, hydride or alcoholate, in a solvent compatible with nature. base such as water or an organic solvent such as dimethylformamide, â.

5 Dimethylsulfoxide, dioxane or an alcohol, at a temperature between room temperature and the boiling point of the solvent.

In the aldehyde of formula (IIA), which can be prepared according to known methods, and in the aldehyde of formula (II) in which represents a radical R2 and R3 represent a hydrogen atom, a C alkyl radical ^ -Cg or a C ^ -Cg alkoxy radical. In the compound of formula (III), X represents a halogen atom, preferably chlorine or bromine, 10 and R ^ and p have the meanings mentioned above.

b) The aldehyde of formula (II) in which R ^ represents a radical - (0) ^ - (CIL,) pC (R ^) = 011 ^ when n = 0, or in which R2 represents a radical - (CH2 ) ^ - C (R ^) = CÏÏ2, can be obtained by reaction of ethyl orthoformate on a phenyl-magnesium bromide of formula (VI), followed by hydrolysis of the acetal formed, according to the scheme following reaction: fl fl ^ V2 '> H - C-OEt X_r2

It is | 20 BrMg R3 * 0HC-- 2) H + / H20 (VI) (IIB)

This reaction can be carried out under the conditions described by QUELET (CR Acad. Science Vol. 182, p. 1285 and Bull. Soc. Chim. 25 Fr. vol. 45, p. 267), for example in an inert solvent such as ethyl ether, dioxane or dimethoxy-1,2-ethane, at a temperature between room temperature and the boiling point of the solvent.

In the compounds of formula (IIB) and (VI), one of the substituents or R2 represents a radical (CH2) ^ - C (R ^) = CH2, R ^ and p having the meaning mentioned above, and the other represents a hydrogen atom, a C 1 -C 4 alkyl radical or a C 1 -C 4 alkoxy radical (5 and ^ 3 rePr ^ setl1: e a hydrogen atom, a C 1 alkyl radical , -C, or a C, -C, alkoxy radical.

16 1 6 35

V

6 2nd Process

Preparation of the compounds of formula (I) in which R ^ represents a radical - (0) - (CEL) -C (R,) = CH9 when n is equal to 1

U Z p Z

(compounds IA) 5 These compounds can be obtained by reacting an alkenyl halide of formula (III) with a hydroxy-3'-benzylidene-3 camphor of formula (IV), in the presence of a base, for example presence of an alkali or alkaline earth metal hydroxide or carbonate or of an amide, alcoholate or alkali hydride, in a solvent compatible with the nature of the base such as water or an organic solvent such as an alcohol , dioxane, dimethylsulfoxide or dimethylformamide, at a temperature between room temperature and the boiling point of the solvent, according to the following reaction scheme: PH 0 (CH2) pC (R4) = CH2

Λ I - + - X- (CH0) -C (R,) = CH, r- ^ I + HX

2 P 4 2 (IV) (III) (IA)

In the compounds of formula (IV), (III) and (IA), R2 and R ^ represent a hydrogen atom, a C 1 -C 6 alkyl radical or a C 1 -C 6 alkoxy radical, and p have the meaning mentioned above and X represents a halogen atom, preferably chlorine or bromine.

The compounds of formula (IV) are new compounds.

The compounds of formula (IV) can be obtained by acid hydrolysis of the compounds of formula (V) in which R 1 represents a C 1 -C 6 alkyl residue, preferably a methyl residue, and R 2 and désign denote an atom of hydrogen or a C 1 -C 6 alkyl or alkoxy radical, according to the following reaction scheme: 1 o 35

K

7

or5 OH

j hydrolysis ^ X / '| J <Ca ^^ / xr3 acid - ^ CA ^^> ^ R3 (V) (IV)

This hydrolysis can be carried out in the presence of a hydrolysis agent such as, for example, pyridine hydrochloride, at a temperature close to the boiling point of the reaction mixture.

The compounds of formula (IV) can also be prepared by condensation of an aldehyde of formula (IIA) on synthetic (d, l-camphor) or natural (d-camphor) camphor, according to the following reaction scheme:

15 OH OH

r ^> rVR2 Λ r ^ SrR2 Lxl + I 1 - * L jl + h „o 0 (IIA) 0 (IV) 20 R2 and denoting a hydrogen atom, a C ^ -Cg alkyl or alkoxy radical.

This reaction is carried out in the presence of a base in a solvent, for example using sodium hydride or potassium tert-butoxide in dioxane or dimethoxy-1,2-ethane, at a temperature between room temperature and the boiling point of the solvent.

3rd process

Preparation of the compounds of formula (I) in which R ^ 30 represents a radical - (0) - (CH.) -C (R,) = CH „when n = 0 and p = 1

η Z p 4 Z

(ID compounds).

- These compounds can be obtained by CLAISEN rearrangement of a compound of formula (IB) according to the reaction scheme below: 35 * 8 ch2-c (r4) = ch2 CH2C (r4) = ch2 (IB) (IC)

In the compounds (IB) and (IC), R ^ and R ^ have the meanings mentioned above.

Compound (IB) can be prepared in a known manner, by reacting a hydroxy-4 * -benzylidene-3 camphor, of formula (VII) with an alkenyl halide of formula (III) in which p = 1 according to the scheme : I + x-ch2-c (r4) = ch2- ^ (VII) (III) 20 ^ Y ^ 0-CH2-C (R4) = CH2

R3 + HX

(IB) R 4 and R 4 having the meanings mentioned above and X being a halogen, preferably chlorine or bromine. This reaction takes place in the presence of a base, for example an alkali or alkaline earth metal carbonate or hydroxide, an amide, alkoxide or alkali hydride, in a solvent compatible with the nature of the base such as water or a organic solvent, for example an alcohol, dioxane, dimethylsulfoxide or dimethylformamide, at a temperature comprised between room temperature and the boiling point of the solvent.

The rearrangement of CLAISEN can be carried out under the conditions described by TARBELL (Organic Reactions, Vol. 2, John 35

J

9

Wiley, New York, 1944, page 1) by heating the compound of formula (IB) to at least about 170 ° C., possibly in the presence of a solvent.

The compound of formula (IC) thus obtained is transformed into compound of formula (ID) in which represents a C 6 -C 6 alkoxy radical by reaction with a C 1 -C 6 alkyl halide in the presence of a base, for example an alkali metal carbonate, in a solvent such as dimethylformamide, or else in the presence of an alkali metal hydride in dimethoxy-1,2-ethane according to the following reaction scheme: 10 CH2C (R4) = CH2 jHj -C (R4) -CH2 1S JfUX, -> jÇlXa, (IC) (ID)

In the compound (ID), represents a C ^-Cg alkoxy radical and R ^ and R ^ have the meaning mentioned above.

The compounds (IC) are new compounds which, like the compounds (I), have UV-absorbing properties.

The present invention therefore also relates to a process for the preparation of the compounds of formula (I).

The invention also relates to the new compounds of formula 25 (IV):

OH

(IV) "in which and R 1 represent a hydrogen atom or a C 1 -C 6 alkyl or alkoxy radical.

The invention also relates to the new compounds of formula (IC): ch2-c (r4) = ch2

ΓνΊ rT ° H

(IC) in which represents a hydrogen atom or a C 1 -C 4 alkyl radical and R 1 a hydrogen atom, a C 1 -C 6 alkyl or alkoxy radical thus read the use of these compounds in as UV-screening agents.

Due to their lipid-soluble nature, the unsaturated benzylidene-3 camphor derivatives of formula (I) above are distributed uniformly in conventional cosmetic carriers containing at least one fatty phase and can be applied to the skin or the hair to constitute a effective protective film.

A subject of the present invention is therefore also a cosmetic composition comprising, in a cosmetically acceptable carrier containing at least one fatty phase, an effective amount of at least one unsaturated 3-benzylidene-camphor derivative of formula (I) above.

The present invention also relates to a cosmetic composition comprising, in a cosmetically acceptable carrier containing at least one fatty phase, an effective amount of at least one unsaturated 3-benzylidene camphor derivative of formula (IC) above.

The cosmetic composition of the invention can be used as a protective composition for the human epidermis or the hair or as an anti-sun composition.

The present invention also relates to a process for protecting the skin and natural or sensitized hair with respect to solar radiation, comprising applying to the skin or the hair an effective amount of at least one compound of formula (I) contained in a cosmetically acceptable carrier containing at least one fatty phase.

The term "sensitized hair" means hair which has undergone a treatment of perm, coloring or bleaching.

) 11 The invention also relates to a colored or uncoloured cosmetic composition, stabilized in light, comprising an effective amount of at least one benzylidene-3 camphor derivative of formula (I) above.

When used as a composition intended to protect the human epidermis against ultraviolet rays, the cosmetic composition according to the invention can be in the most diverse forms usually used for this type of composition. It can in particular be in the form of oily or oleoalcoholic lotions, emulsions such as a cream or a milk, oleoalcoholic, alcoholic or hydroalcoholic gels, solid sticks, or be packaged as an aerosol.

It can contain the cosmetic adjuvants usually used in this type of composition such as thickeners, softeners, humectants, surfactants, preservatives, anti-foaming agents, perfumes, oils, waxes, lanolin , propellants, dyes and / or pigments having the function of coloring the composition itself or the skin or any other ingredient usually used in cosmetics.

The compound of formula (I) is present in proportions by weight of between 0.25 and 3% relative to the total weight of the cosmetic composition protecting the human epidermis.

As the dissolving solvent, there may be used an oil, a wax and generally any fatty substance, a monoalcohol or a lower polyol or their mixtures. The more particularly preferred monoalcohols or polyols are ethanol, isopropanol, propylene glycol, glycerin and sorbitol.

One embodiment of the invention is an emulsion in the form of a protective cream or milk comprising, in addition to the compound of formula (I), fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin, natural or synthetic oils or waxes and emulsifiers, in the presence of water.

Another embodiment consists of oily lotions based on natural or synthetic oils and waxes, (1 12 lanolin, and fatty acid esters, in particular fatty acid triglycerides, or by lotions oleoalcoholic based on a lower alcohol such as ethanol or a glycol such as propylene glycol and / or a polyol such as glycerin and oils, waxes and fatty acid esters such than fatty acid triglycerides.

The cosmetic composition of the invention can also be an alcoholic gel comprising one or more lower alcohols or polyols such as ethanol, propylene glycol or glycerin and a thickener such as silica. The oleoalcoholic gels also contain a natural or synthetic oil or wax.

Solid sticks are made of natural waxes and synthetic oils, fatty alcohols, fatty acid esters, lanolin and other fatty substances.

In the case of an aerosol-conditioned composition, conventional propellants such as alkanes, fluoro-alkanes and chlorofluoroalkanes are used.

The present invention also relates to anti-solar cometic compositions containing at least one compound of formula (I) and which may contain other UV-B and / or UV-A filters.

In this case, the total amount of filters present in the sunscreen composition, that is to say the compound of formula (I) and optionally the other filters, is between 0.5 and 15% by weight per relative to the total weight of the sunscreen composition.

These sunscreen compositions are in the forms indicated above for the compositions protecting the human epidermis.

When the cosmetic composition according to the invention is intended to protect natural or sensitized hair from UV rays, this composition may be in the form of a shampoo, lotion, gel or emulsion to be rinsed off, to be applied before or after shampooing, before or after coloring or bleaching, before or after perm, * of styling or treating lotion or gel, of lotion or gel for brushing or styling, hairspray, composition of perm, coloring or bleaching of hair . This composition can contain, in addition to the compound of the invention, various adjuvants used in this type of composition, such as surfactants, thickeners, polymers, softeners, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, anti-grease agents, dyes and / or pigments having the function of coloring the composition itself or the hair or any other ingredient usually used in the hair area.

It contains 0.25 to 3% by weight of compound of formula (I).

The present invention also relates to cosmetic compositions containing at least one compound of formula (I) as an agent for protection against ultraviolet rays constituted by hair compositions such as hair sprays, styling lotions, optionally treating. or detangling, coloring shampoos, dye compositions for hair, by make-up products such as nail varnishes, creams and oils for treatment of the epidermis, foundations, lipstick sticks, compositions for skin care such as oils or creams for the bath, as well as any other cosmetic composition which may present, because of its constituents, problems of stability to light during storage.

Such compositions contain 0.25 to 3% by weight of compound of formula (I).

The invention also relates to a process for protecting cosmetic compositions against ultraviolet rays, comprising incorporating into these compositions an effective amount of at least one compound of formula (I).

The unsaturated 3-benzylidene camphor derivatives of formula (I) according to the invention are moreover particularly advantageous as synthesis intermediates. They can for example be reacted with organosilicon compounds containing SiH groups.

The present invention therefore also relates to the use of the new unsaturated derivatives of the benzylidene-3 camphor of formula (I) as intermediates in the preparation of organo-silicic compounds.

14

The present invention will be better illustrated, without however being limited, by the following exemplary embodiments.

PREPARATION EXAMPLES

EXAMPLE 1 5 Preparation of allyl-3'-methoxy-4'-benzylidene-3 camphor 1st stage

Preparation of camphorated allyl-3'-hydroxy-4'-benzylidene-3 Heated for 24 hours, with stirring, at 185 ° C., 296 g 10 (1 mole) of camphor allyloxy-4'-benzylidene-3 obtained in accordance with Example 8 of patent FR 2 430 938. The cooled reaction mixture is recrystallized from ethyl ether. 270 g of allyl-3'-hydroxy-4'-benzylidene-3 camphor are thus obtained, having the following characteristics:

15 - melting point: 150 ° C

- 1 H NMR spectrum (CDCl 4): spectrum conforming to the expected structure - UV spectrum (ethanol) X: 327 nm 'max £: 22,600 20 Elemental analysis:

Calculated% C = 81.04 H = 8.16

Found% G = 81.11 H = 8.18 2nd stage 25 Preparation of lrallyl-3'-methoxy 4'-benzylidene camphor

9 g (0.03 mole) of allyl-3'-hydroxy-4'-benzylidene-3 3 camphor obtained in the first stage above are dissolved in 150 cm of 1,2-dimethoxy-ethane previously dried on a molecular sieve . 2.56 g of sodium hydride is added slowly and the mixture is heated to 60 ° C. 8.52 g (0.06 mole) of methyl iodide are added dropwise, followed by refluxing for 2 hours. The solvent is evaporated off and the residue is taken up in 50 cm of water and 200 cm of ethyl ether. The ethereal phase is washed twice with water, then dried over sodium sulfate. After evaporation of the solvent, 8.8 g of allyl-3'-35 methoxy-4'-benzylidene-3 camphor are recovered, in the form of blue crystals having the following characteristics:

- melting point: 37 ° C

- 1 H NMR spectrum (CDGl ^): spectrum conforming to the expected structure 5 - UV spectrum (ethanol at 95 °) Λ: 322 nm max £: 23600

Elementary analysis:

Calculate% C = 81.25 H = 8.44 0 = 10.31 10 Found% C = 81.35 H = 8.60 0 = 10.50 EXAMPLE 1

Preparation of methallyloxy-3T-methoxy-4'-banzylidene-3 camphor 15 1st stage

Preparation of hydroxy-3'-methoxy-4 '-benzylidene-3 camphor A mixture of 83.7 g (0.55 mole) of d, l-camphor is brought to 80 ° C. with stirring and under nitrogen. and 26.4 g (1.1 mole) of 3 sodium hydride in 300 cm of 1,2-dimethoxy-ethane dried over a molecular sieve. 76 g (0.5 mol) of isovanillin 3 in 200 cm of dry dimethoxy-1,2-ethane are added over 30 minutes and the mixture is heated at reflux for 4 hours. The cooled reaction mixture is carefully poured into 500 g of ice and 100 cm of concentrated hydrochloric acid. The precipitate formed is filtered, washed with water and recrystallized in isopropyl ether. 79 g (55% yield) of hydroxy-3'-methoxy-4'-benzylidene-3 camphor are obtained in the form of a pale yellow powder having the following characteristics:

- melting point: 125 ° C

- 1 H NMR spectrum (CDCl ^): spectrum conforming to the expected 3Q structure - UV spectrum (ethanol) ^: 334 nm - - g: 19650

Elementary analysis:

Calculated% C 57.50 H 7.74 35 Found% C 57.43 H 7.77 16 2nd stage

Preparation of methallyloxy-3r-methoxy-4r-benzylldene-3-camphor A mixture of 30 g (0.105 mole) of hydroxy-3'-methoxy-4'-benzylidene-3 is brought to 65-70 ° C. camphor obtained in the first stage and 21.8 g 3 5 (0.16 mole) of potassium carbonate in 100 cm of dimethyl-> 3 formamide. 17 cm (0.16 mole) of methallyl chloride are added dropwise and the mixture is kept at 70 ° C. for 3.5 hours. The reaction mixture is poured onto ice. The precipitate obtained is filtered and then washed with water. 34 g of methallyloxy-3'-methoxy-4'-benzylidene-3 camphor are obtained in the form of a pale yellow powder having the following characteristics:

- melting point: 66 ° C

- 1H HMN spectrum (CDCl ^): spectrum conforming to the expected structure 15 - UV spectrum (ethanol): X: 330 nm t 'max ζ: 19750

Elementary analysis:

Calculated% C = 77.61 H = 8.29 0 = 14.10

Found% C = 77.37 H = 8.26 0 = 14.36 The compounds (I) according to the invention can be used in the following cosmetic compositions.

17 APPLICATION EXAMPLES Example A - Sunscreen oil

Or mix the following ingredients, possibly heating 5 to 40-45 ° C to homogenize: - Cocoa butter 2.5 g - Allyl-3'-methoxy-4'-benzylidene-3 camphor 1.5 g - Butylhydroxyanisole 0.05 g - Perfume qs 10 - Vegetable oil qs 100 g EXAMPLE B - Sunscreen oil

A sunscreen oil is prepared in the same way as above from the following ingredients: 15 - Lanolin 2.5 g - Methallyloxy-3'-methoxy-4T-benzylidene- 3 camphor 3 g - Butylhydroxyanisole 0.05 g - Perfume qs 20 - Triglycerides of fatty acids in Cg-C ^ qsp 100 g EXAMPLE C - Olealcoholic sunscreen lotion - Lanolin 2.5 g - Triglycerides of fatty acids in Cg-C ^ 40 § 25 - Perfume qs - Allyl-3 ' -hydroxy-4'-benzylidene-3 camphor 2 g - Butylhydroxytoluene 0.05 g - Alcohol at 96 ° qs 100 g 30

Claims (22)

1. Unsaturated derivative of 3-benzylidene camphor, characterized in that it corresponds to the formula: - in which: 10 represents a hydrogen atom, a C 1 -C 6 alkyl radical, a C 1 -C 6 alkoxy radical or a radical - (0) n “(CH2 ^ pC ^ R4 ^ = CH2 in which n = 0 or 1, p represents an integer between 1 and 10 and preferably between 1 and 4 and R ^ represents an atom of hydrogen or a C 1 -C 4 alkyl radical; 2. Compound according to claim 1, characterized in that it is chosen from allyl-3'-methoxy-4'-benzylidene-3 camphor, 1'ally1-3'-dimethoxy-4 ', 5' -benzylidene-3 camphor, methallyl-3'-methoxy-4 * -benzylidene-3 camphor, methallyl-3'-dimethoxy-4 ', 5' - benzylidene-3 camphor, allyloxy-3'-methoxy- 4'-benzylidene-3 camphor, methallyloxy-3'-methoxy-4'-benzylidene-3 camphor, allyl-30 4'-benzylidene-3 camphor, and methallyl-4'-benzylidene-3 camphor. 3. Process for the preparation of a compound of formula (I) according to 'revèadication 1 or 2, characterized in that it consists in condensing an aromatic aldehyde of formula: 35 to 19 Jf 1 (ii) OHC 5 in which R ^, S. ^ and R3 have the meanings indicated in claim 1, on synthetic camphor (d, l-camphor) or natural camphor (d-camphor), in the presence of a base such as an amide, an alkali metal hydride or alcoholate, in an inert solvent such as benzene, toluene, ether, dioxane or ^ dimethoxy-1,2-ethane, at a temperature between 0 ° C and the point d solvent boiling. 4. Process for the preparation of a compound of formula (I) according to claim 1, in which R ^ represents a radical - ((^ - (Œ ^) -C (R ^) = CH2) when n is equal to l and represents a hydrogen atom, a C 1 -C 6 alkyl radical or a C 1 -C 6 alkoxy radical, R 4, R 4 and p having the meaning indicated in claim 1, characterized in that reacting an alkenyl halide of formula (III): X- (cH2) pc (R4) = cH2 (III) in which X represents a halogen atom, preferably chlorine or bromine and p and R ^ have the meanings indicated in claim 1, on a compound of formula (IV): OH // \ A 25 (IV) in which R ^ denotes a hydrogen atom, a C 1 -C 4 alkyl radical or a radical alkoxy in CC, and R_ has the meaning mentioned in claim 1, in the presence of a base such as an alkali or alkaline earth metal hydroxide or carbonate or an amide, alcoholate or alkali hydride, in a compatible solvent with the nature of the base such as water or an organic solvent such as an alcohol, dioxane, dimethyl sulfoxide or dimethylformamide, "at a temperature between room temperature and the boiling point of the solvent. 5. Compound of formula: OH ^ \ (IV) 10 in which represents a hydrogen atom, an alkyl radical or C 1 -C 6 alkoxy and R ^ represents a hydrogen atom or a C 1 alkyl or alkoxy radical - ^ - Cg. 6. Process for the preparation of a compound of formula (I) in which R. represents a radical - (0) - (CH0) -C (R.) = CH „when n = 0 I η Z p 2 15 and p = l, characterized in that in a first stage, a compound of formula (IB) is subjected: 0-CEL C (R,) = CH „fl (B)> in which R ^ and R ^ have the meaning indicated in claim 1, to a rearrangement of CLAISEN to obtain the compound (IC) of formula: çh2-c (r4) = ch2 "o in which R ^ and R ^ have the same meanings as above, and that in a second stage, the compound of formula (IC) thus obtained is reacted with an alkyl halide in C ^ -Cg, in the presence of an alkali metal carbonate in dimethylformamide or in the presence of an alkali metal hydride in dimethoxy-1,2-ethane, to obtain the compound of formula (ID) as follows: 35 21 H2c (r4) = ch2 I (ID) in which and have the abovementioned meanings and R2 represents a C 1 -C 6 alkoxy radical. 7. Compound of formula: CH -C (R) = CH l ° xTN, Xv ° H XI L II (ic> ΧΛΧΑ13 15 in which R ^ represents a hydrogen atom or an alkyl radical in C ^ -C ^ and R ^ represents a hydrogen atom, a C ^ -Cg alkyl or C - ^ - Cg alkoxy radical. 8. A compound according to claim 7, characterized in that it is 1’allyl-3’-hydroxy-4’-benzylidene-3 camphor. 9. Cosmetic composition, characterized in that it comprises an effective amount of at least one compound of formula (I) according to claim 1, in a cosmetically acceptable carrier containing at least one fatty phase. 10. Cosmetic composition according to claim 9, characterized in that it comprises, as compound (I), at least one of the compounds chosen from allyl-3'-methoxy-4'-benzylidene-3 camphor, 1'allyl-3'-dimethoxy-4 ', 5'-benzylidene-3 camphor, methallyl-3'-methoxy-4'-benzylidene-3 camphor, methallyl-3'-dimethoxy-4', 5 '-benzylidene-3 camphor, allyloxy-3'-methoxy-4'- benzylidene-3 camphor, methallyloxy-3'-methoxy-4'-benzylidene-3 camphor, allyl-4'-benzylidene- 3 camphor and methallyl-4'-benzylidene-3 camphor. 11. Cosmetic composition, characterized in that it comprises an effective amount of at least one compound of formula (IC) according to claim 7, in a cosmetically acceptable carrier containing at least one fatty phase. 22 12. Cosmetic composition according to claim 11, characterized in that it comprises, as compound (IC), allyl-3'-hydroxy-4'-benzylidene-3 camphor. 13. Cosmetic composition according to any one of claims 9 to 12, characterized in that it is in the form of "oily or oleoalcoholic lotion, emulsion, oleoalcoholic, alcoholic or hydroalcoholic gel, solid stick or aerosol. 14. Cosmetic composition according to claim 13, characterized in that it also contains cosmetic adjuvants 10 chosen from thickeners, softeners, humectants, surfactants, preservatives, defoamers, perfumes, oils, waxes, lanolin, monoalcohols and lower polyols, propellants, dyes and pigments. 15. Cosmetic composition according to any one of claims 9 to 14, characterized in that it constitutes a protective composition for the human epidermis and contains 0.25 to 3% by weight of compound of formula (I ) Yes c). R2 represents a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 6 alkoxy radical or a radical - (01 ^) ^ - 0 (R ^) = CH2 in which p and R ^ have the meanings mentioned above; R ^ represents a hydrogen atom, a C ^ -Cg alkyl radical or a C ^ -Cg alkoxy radical; 20 provided that one of the residues R ^ or R2 respectively represents a radical - (0) - (CH0) -C (R.) = CH_ or a radical - (CH „) - nlp 4 L 2 p C ( R ^) = CH2 in which n, p and R ^ have the meanings indicated above. 16. Cosmetic composition according to any one of claims 9 to 14, in the form of an anti-sun composition, characterized in that it contains 0.5 to 15% by weight of compound of formula (I) or (IC). 17. Anti-sun cosmetic composition according to claim 16, characterized in that it also contains an agent which filters UV-B and / or UV-A rays. 18. Cosmetic composition according to any one of claims 9 to 12, intended to be applied to the hair, characterized in that it is in the form of shampoo, lotion, gel or emulsion to be rinsed off, styling lotion or gel or treating, lotion or gel for brushing or styling, hairspray, composition of perm, bleaching or coloring and comprises 0.25 to 3% by weight of compound of formula (I) or ( IC). - - 19. Cosmetic composition according to any one of Claims 9 to 12, which is in the form of a colored cosmetic composition or not, characterized in that it consists of a hair composition, a make-up product. or a composition for the care or treatment of the skin, comprising 0.25 to 3% by weight of compound of formula (I) or (IC). 20. Protects the skin and natural or sensitized hair against ultraviolet radiation, characterized in that it consists in applying to the skin or the hair an effective amount of a cosmetic composition containing at least one derivative 3-benzylidene camphor unsaturated of formula (I) according to claim 1 or 2 or (IC) according to claim 7 or 8. 21. Method for protecting a cosmetic composition against ultraviolet rays, characterized in that it consists in incorporating into this composition an effective amount of at least one compound of formula (I) according to claim 1 or 2 or (IC) according to claim 7 or 8. 22. Use of an unsaturated 3-benzylidene-camphor derivative of formula (I) according to claim 1 or 2 or (IC) according to claim 7 or 8 as an intermediate for the preparation of organosilicon compounds by reaction of a compound of formula (I) or (IC) on an organosilicon compound containing SiH groups. 20 Drawings: —planks == jiL „.pages of which ...... A cover page description pages —h… claim pages ...... ** -“ orégô tiêscriptif Luxembourg, le ^ i ~ th representative: Mr. Alain Rukavina