FR2625195A1 - NOVEL UNSATURATED BENZYLIDENE-3 CAMPHRE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS COSMETIC ULTRA VIOLET RADIATION BEHAVIORS AND AS SYNTHETIC INTERMEDIATES OF ORGANO-SILICIC COMPOUNDS - Google Patents

Abstract

The invention relates to an unsaturated derivative of benzylidene-3 camphor, characterized in that it corresponds to the formula: (CF DRAWING IN BOPI) in which R1 represents: - a hydrogen atom, a C1 -C6 alkyl radical, a C1 -C6 alkoxy radical or a radical - (0) n - (CH2) p -C (R4) = CH2 in which n = 0 or 1, p represents an integer between 1 and 10 and preferably between 1 and 4 and R4 represents a hydrogen atom or a C1 -C4 alkyl radical; R2 represents a hydrogen atom, a C1 -C6 alkyl radical, a C1 -C6 alkoxy radical or a - (CH2) p -C (R4) = CH2 radical in which p and R4 have the meanings mentioned above ; R3 represents a hydrogen atom, a C1 -C6 alkyl radical or a C1 -C6 alkoxy radical; with the proviso that one of the radicals R1 or R2 represents respectively a radical - (0) n - (CH2) p -C (R4) = CH2 or a radical - (CH2) p -C (R4) = CH2 in which n , p and R4 have the meanings indicated above; - its preparation process and its use as a sunscreen and synthetic intermediate.

Description

Novel unsaturated derivatives of benzylidene-3 camphor, their process of

  preparation and their use as absorbers of ultraviolet radiation in cosmetics and as synthesis intermediates

of organo-silicic compounds.

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

  compounds as intermediates for the synthesis of organo-

  silicic. It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis and that the wavelength rays between 280 and 320 nm, known under the name of UV- B, provoke

  erythema and skin burns that may be detrimental to the development of

  sun tanning; this UV-B radiation must therefore be filtered.

  It is also known that UV-A rays of wavelengths between 320 and 400 nm, causing browning of the skin, are capable of inducing an alteration thereof, particularly in the case of sensitive skin. or skin continuously exposed to sunlight. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature aging. They promote the triggering of the erythematous reaction or amplify this reaction in some

2625 1 95

  subjects and may even cause phototoxic or photoallergic reactions. It is therefore advantageous to have compounds that absorb UV rays over a wide band in order to be able to filter both UV-A and UV-B rays. It is also known that the constituents entering cosmetic preparations do not always have sufficient stability to light and that they degrade under the action of

light radiation.

  Therefore, it is desirable to incorporate in these prepa-

  rations of compounds capable of filtering UV rays and which must also have good stability and sufficient solubility in the media usually used in cosmetics, and

  especially in oils and greases.

  It is also desirable to provide hair with good protection against photochemical degradation in order to avoid

  especially a discoloration or a change of shade.

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

the skin.

  They also have an excellent fat-soluble character, which makes them usable in the fatty supports used in cosmetics and in particular in compositions intended for

  protect the human skin from UV rays, and more specifically

  primarily in sunscreen compositions.

  The subject of the present invention is therefore the novel unsaturated derivatives of benzylidene-3 camphor of formula: ## STR2 ## in which R 1 represents a hydrogen atom, a C 1 -C 6 alkyl radical, a C 1 -C 6 alkoxy radical or a (C) radical. ) 7 (CH2) pC (R4) = C2 in which n = 0 or 1, p represents an integer between 1 and 10 and preferably between 1 and 4 and R4 represents a hydrogen atom or a C1-alkyl radical; C4; R2 represents a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 alkoxy radical or a - (CH2) p-C (R4) = CH2 radical in which p and R4 have the meanings mentioned above; R3 represents a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 alkoxy radical;

  provided that one of the radicals R1 or R2 represents respectively

  a radical - (O) n7 (CH2) p-C (R4) = CH2 or a radical - (CH2) p-C (R) = CH2 in which n, p and R4 have the meanings

indicated above.

  Among the preferred compounds of the invention, mention may be made of the following compounds: allyl-3'-methoxy-4'-benzylidene-3-camphor-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'-methithoxy-4', - benzylidene-3 camphor - methallyloxy-3'-methoxy-4'-benzylidene-3 camphor - allyl-4'-benzylidene3 camphor

  - methallyl-4'-benzylidene-3 camphor.

  The compounds according to the invention of formula (I) can be prepared according to one of the following processes

262 5,195

  The process: Preparation of the compounds of formula (I) in which R 1 represents a radical - (O) n - (CH 2) p - C (R 4) = CH 2 or R 2 represents a

  radical - (CH2) p-C (R4) = CH2, where R1, R2, n, p, R4 and R3 have the meanings

  mentioned above. An aromatic aldehyde of formula (II) is condensed on synthetic camphor (d, l-camphor) or natural camphor (d-camphor) according to the following reaction scheme:

R1 R1

RS O 0HC t R3 R3

(II) I

  This reaction is carried out in the presence of a base, for example in the presence of an amide, a hydride, an hydroxide 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 R1 represents a radical - (O) n- (CH2) pC (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: OH 2- (CH 2) pC (4) CH 2

R2 X R2

I + X- (CH2) -C (R4) = CH2> --- + HX

OHC 3 OHC R3

(IIA) (III) (II)

  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 an alkali metal amide, hydride or alkoxide, in a solvent compatible with the nature of the the base as

2625 1 95

  water or an organic solvent such as dimethylformamide, 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 may be prepared according to known methods, and in the aldehyde of formula (II) in which R1 represents a radical -O- (CH2) pC (R4) = CH2, R2 and R3 represents a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 alkoxy radical. In the compound of formula (III), X represents a halogen atom, preferably chlorine or bromine,

  and R4 and p have the meanings mentioned above.

  b) The aldehyde of formula (II) in which R1 represents a radical - (O) n- (CH2) pC (R4) = CH2 when n = O, or in which R2 represents a radical - (CH2) pC (R4 ) = CH2, can be obtained by

  reaction of ethyl orthoformate on a phenyl bromide

  magnesium of formula (VI), followed by hydrolysis of the acetal formed, according to the following reaction scheme: R1 DEt R1 R2 1) H-C - OEt R2 R12 OEt BrMg> R OHC 'R3

2) H / H O

(VI) (IIB)

  This reaction can be carried out under the conditions described

  by QUELET (C.R. Acad.Science Vol 182, 1285 and Bull Soc.

  Fr. 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 point

boiling solvent.

  In the compounds of formula (IIB) and (VI), one of the substituents R1 or R2 represents a radical (CH2) pC (R4) - = CH2, R4 and p having the meaning mentioned above, and the other represents a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 alkoxy radical and R3 represents a hydrogen atom, an alkyl radical or

  C1-C6 or a C1-C6 alkoxy radical.

26 2 5 1 9 5

  2nd Process Preparation of the compounds of formula (I) in which R 1 represents a radical - (O) n - (CR 2) p C (R 4) CH 2 when n is equal to 1 (compounds IA) These compounds can be obtained by reaction of a alkenyl halide of formula (III) on a 3-hydroxy-3-benzylidene camphor of formula (IV), in the presence of a base, for example in the presence of an alkali or alkaline earth metal hydroxide or carbonate or an amide, alkoxide or alkali hydride, in a solvent compatible with the nature of the base such as water or an organic solvent such as

  alcohol, dioxane, dimethylsulfoxide or dimethyl-

  formamide, at a temperature between room temperature and the boiling point of the solvent, according to the following reaction scheme: IOH O (CH 2) p-C (R 4) = CH 2

2 2

+ tX- (CH) -C (R) = CE 2 -> + ox

x H2 p- 4.

(IV) (III) (IA)

  In the compounds of formula (IV), (III) and (IA), R2 and R3 represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 alkoxy radical, R4 and p have the meaning mentioned. above and X represents a halogen atom, preferably the

chlorine or bromine.

  The compounds of formula (IV) are novel compounds.

  The compounds of formula (IV) can be obtained by acid hydrolysis of compounds of formula (V) in which R5 represents a C1-C6 alkyl residue, preferably a methyl residue, and R2 and R3 denote a hydrogen atom or an alkyl radical. or C1-C6 alkoxy, according to the following reaction scheme:

2625 1 95

OR5 I e2 acid hydrolysis R

(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) may also be prepared by condensation of an aldehyde of formula (IIA) with synthetic camphor (d, l-camphor) or natural camphor (d-camphor), according to the following reaction scheme:

1S OH OH

O + HC / 3 R3

(IIA) (IV)

  R2 and R3 denoting a hydrogen atom, an alkyl radical or

C1-C6 alkoxy.

  This reaction is carried out in the presence of a base in a

  solvent, for example by means of sodium hydride or tertiary

  potassium butoxide in dioxane or dimethyloxy-1,2-ithane at a temperature between room temperature and

boiling solvent.

  3rd method Preparation of the compounds of formula (I) in which R1 represents a radical - (O) n- (CH2) p-C (R4) = CH2 when n = O and p = 1

(ID compounds).

  These compounds can be obtained by rearrangement of Claisen with a compound of formula (IB) according to the reaction scheme below:

262 5,195

H2-C (R4) = CH2

O-CH2C (R4) CH E

>

3

(IB) (IC)

  In compounds (IB) and (It), R3 and R4 have the meanings

mentioned above.

  The compound (IB) can be prepared in a known manner by reacting a 4'-hydroxy-3-benzylidene-camphor of formula (VII) with an alkenyl halide of formula (III) in which p = 1 according to the scheme :

4 + X-CH2-C (R4) -CH2>

R

N. N. / R3

(VII) (III)

OO-CH2-C (R4) = cH2

R3 + HX

  (IB) R3 and R4 having the abovementioned meanings 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 organic solvent, for example an alcohol, dioxane, dimethylsulfoxide or dimethylformamide, at a temperature of

  between room temperature and the boiling point of the solvent.

  The CLAYEN rearrangement can be carried out under the conditions described by TARBELL (Organic Reactions, Vol.2, John Wiley, New York, 1944, page 1) by heating to at least about 170 ° C.

  of the compound of formula (IB), optionally in the presence of a solvent.

  The compound of formula (IC) thus obtained is converted into a compound of formula (ID) in which R 2 represents a C 1 -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 in the presence of an alkali metal hydride in dimethoxy-1,2-ethane according to the following reaction scheme:

V2C (R4) 21 -C (R4) = CH2

3 R 3

(IC) (ID)

  In the compound (ID), R 2 represents a C 1 -C 6 alkoxy radical

  and R3 and R4 have the meaning mentioned above.

  Compounds (ICs) are novel compounds that exhibit

  same as the compounds (I), UV absorption properties.

  The subject of the present invention is therefore also a method of

  preparation of the compounds of formula (I).

  The invention also relates to novel compounds of formula

(IV):

  OH R3 (IV) wherein R2 and R3 represent a hydrogen atom or a

C1-C6 alkyl or alkoxy radical.

262 5,195

  The invention also relates to novel compounds of formula (IC):

H2-C (R4) = CH2

  (zc) (IC) in which R4 represents a hydrogen atom or a C1-C4 alkyl radical and R3 a hydrogen atom, a C1-C6 alkyl or alkoxy radical, and the use of these compounds in as agents

filtering UV rays.

  By their liposoluble character, the unsaturated derivatives of benzylidene-3 camphor 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 skin.

  hair to form an effective protective film.

  The present invention therefore also relates to a cosmetic composition comprising, in a cosmetically acceptable support containing at least one fatty phase, an effective amount of at least

  an unsaturated derivative of benzylidene-3 camphor of formula (I) above.

  The present invention also relates to a cosmetic composition comprising, in a cosmetically acceptable support containing at least one fatty phase, an effective amount of at least one derivative

  unsaturated benzylidene-3 camphor 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 anti-solar composition.

  The present invention also relates to a method of

  protection of the skin and natural or sensitized hair

  solar radiation, comprising applying to the skin or the hair an effective amount of at least one compound of formula (I) contained in a nosmetically acceptable carrier containing at least

a fatty phase.

  The term "sensitized hair" means hair that has undergone

  permanent treatment, staining or fading.

262519.5

  The subject of the invention is also a colored or non-colored, light-stabilized cosmetic composition comprising an effective amount of at least one benzylidene-3 camphor derivative of

formula (I) above.

  When it is used as a composition intended to protect the human epidermis against ultraviolet rays, the cosmetic composition according to the invention may be in the form of

  more diverse usually used for this type of composition.

  It may especially be in the form of oily or oligoalcoholic lotions, emulsions such as cream or milk, oleoalcoholic gels, alcoholic or hydroalcoholic, rods

  solids, or be packaged as an aerosol.

  It may contain the cosmetic adjuvants conventionally used in this type of composition, such as thickeners, softeners, humectants, surfactants, preservatives, defoamers, perfumes, oils, waxes, lanolin, propellants, dyes and / or pigments whose function is to color 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

  protective cosmetic composition of the human epidermis.

  As the solubilizing solvent, it is possible to use an oil, a wax and, in general, any fatty substance, a monoalcohol or a lower polyol or their mixtures. The monoalcohols or polyols that are more particularly preferred are ethanol, isopropanol,

  propylene glycol, glycerine and sorbitol.

  An embodiment of the invention is an emulsion in the form of protective cream or milk comprising, in addition to the compound of formula (I), fatty alcohols, fatty acid esters, and especially triglycerides of fatty acids, 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,

26 2 5 1 9 5

  lanolin, and esters of fatty acids, especially triglycerides of fatty acids, or of oleoalcoholic lotions based on a lower alcohol such as ethanol or a glycol such as propylene glycol and / or a polyol such as glycerine and oils, waxes and esters of fatty acids such as triglycerides of fatty acids. The cosmetic composition of the invention may also be an alcoholic gel comprising one or more lower alcohols or polyols such as ethanol, and the like. propylene glycol or glycerine and a thickener such as silica. Oleoalcoholic gels

  also contain a natural or synthetic oil or wax.

  Solid sticks consist of synthetic natural waxes and oils, fatty alcohols, fatty acid esters,

lanolin and other fatty substances.

  In the case of a composition packaged in an aerosol,

  uses conventional propellants such as alkanes, fluoromers and

alkanes and chlorofluoroalkanes.

  The present invention also relates to the antisolar cosmetic compositions containing at least one compound of formula

  (I) and 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.

  weight relative to the total weight of the sunscreen composition.

  These sunscreen compositions are in the forms indicated above for the protective compositions of 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, to be applied before or after shampooing, before or after after coloring or discoloration, before or after permanent, lotion or gel styling or treating, lotion or gel for blow drying or setting, hair lacquer, permanent composition, coloring or bleaching hair. This composition may contain, besides 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-greasing agents, dyes and / or pigments whose function is to color the composition itself or the hair or any

  another ingredient usually used in the hair field.

  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 (1) as an agent for protection against ultraviolet rays consisting of hair compositions such as hairsprays, hair styling lotions that may be treating or detangling agents, coloring shampoos, dyeing compositions for hair, by make-up products such as nail polishes, creams and oils for treating the epidermis, foundations, lipstick sticks, compositions for skincare products such as bath oils or creams, as well as any other cosmetic composition which, due to its constituents, may have light stability problems during storage. Such compositions contain 0.25 to 3% by weight of compound

of formula (I).

  The invention also relates to a method of protecting cosmetic compositions against ultraviolet rays, comprising incorporating into these compositions an effective amount of at least one

compound of formula (I).

  The unsaturated derivatives of benzylidene-3 camphor of formula (I) according to the invention are also particularly interesting as synthesis intermediates. For example, we can do them

  react on organosilicon compounds containing SiH groups.

  The present invention therefore also relates to the use of the new unsaturated derivatives of benzylidene-3 camphor of formula

  (I) as intermediates in the preparation of organic compounds

silicic.

  The present invention will be better illustrated without being

  limited, by the following examples of embodiment.

EXAMPLES OF PREPARATION

EXAMPLE 1

  Preparation of allyl-3'-methoxy-4'-benzylidene-3 camphor 1 st stage Preparation of allyl-3'-hydroxy-4'-benzylidene-3-camphor The mixture is heated for 24 hours, with stirring, to 185 ° C. 296 g (1 mole) of 4-allyloxybenzylidene-3-camphor obtained according to Example 8 of Patent FR 2,430,938. The cooled reaction mixture is recrystallized from ethyl ether. This gives 270 g

  of allyl-3'-hydroxy-4'-benzylidene-3 camphor having the characteristics

  following factors: - melting point: 1500C - 1H NMR spectrum (CDCl3): spectrum in accordance with the expected structure - UV spectrum (ethanol): max = 327 nm

- 8 = 22600

  Elemental analysis: Calculated%: C 81.04 H 8.16 Found Z: C 81.11 H 8.18 Step 2 Preparation of allyl-3'-methoxy 4'-benzylidene-3-camphor 9 g (0 g) , 03 mole) of allyl-3'-hydroxy-4'-benzylidene-3 camphor obtained in the first stage above in 150 cm3 of dimethoxy-1,2-ethane previously dried over molecular sieves. 2.56 g of sodium hydride are added slowly and the mixture is heated to 60 ° C.. 8.52 g (0.06 mole) of methyl iodide are introduced dropwise and the mixture is refluxed for 2 hours. The solvent is evaporated and

  the residue is taken up in 50 cm3 of water and 200 cm3 of ethyl ether.

  The ethereal phase is washed twice with water and then dried over sodium sulfate.

  sodium. After evaporation of the solvent, 8.8 g of allyl-3 'are recovered.

LL'L B SE

  úLLL H E: TLD: z AnoL, '7L'LH OS' L D: ZinIoeD: alTzuamala esúv 0o961 =

mu = xmn: (iouBqlzp) An alizads -

oupueliv Where

  azniznazs and B aumoiuov vizaads: (IDO) HI Nw 7P a2vazds -

DonZT: uoTsn; ap ZuTod -

  .saiueaIns sanb sT1agzOBl sael zuupgssod elud aunup a.pnod aunp amlo; In this context, the following is an example of the above-mentioned methods of the present invention, which are described in US Pat. glTdlZ9d al * galluazuov anbTlpXlqzoltapTzp úMD 0 the t op O suvp uoTlnvBaid naAe gs: aA 7se trtolIal iauuollotea, e2lusl-gm -a * seznaq 3uspuad xnlgez nB vtnvqX UO the -as toBl-: 4i-XotlMTp p ap m OOZ suep OuTlITuvaOsTp (Viom ç) 9 9 L L L L L L L L L L L L L L L L L L L ap ap p p p p p p p p p p p p p ((((((( (Io m SS'O) 2 The 88 p a2uelgm a 'aloze snos sn uos2 snoso08 B axod uo ezlqdumz -aaTzuq, -om, çxoap, & l, l ap uoTzvavdwaza aaqdmez r-uaTXuq ^ -oza-É & oa p uoTzvavdga7a O' 0 0 0 9'8 H O 18 D: anol 18 01 O tA'7 '8E SZ18 D z galnoleg: alTzSluamgl as & leuv ooz z -?

  mu IZE = Xemy: (o 6 B IouvtqZ) An liZads -

anpuall S

  Ainlzznls Bl B amuoguov azaDads: (EIDoGD) HI NKX ap allads -

ogç: uoTsn; ap luTod -

  : greetings sanbzslagiozlvz se luupgssod souelq xnvisTiD ap amzo; Second stage of the preparation of methallyloxy-3'-methoxy-4'-benzylidene-3-camphor

  A mixture of 30 g (0.105 mol) of hydroxyl

  3'-methoxy-4'-benzylidene-3-camphor obtained in the first stage and 21.8 g (0.16 mol) of potassium carbonate in 100 cm 3 of dimethylformamide. 17 cm3 (0.16 mol) of methallyl chloride are added dropwise and the mixture is kept at 70 ° C. for 3.5 hours. The reaction mixture is poured on ice. The precipitate obtained is filtered

  then washed with water. 34 g of methallyloxy-3'-methoxy-4'-

  benzylidene-3 camphor in the form of a pale yellow powder having the following characteristics: melting point: 66 C 1H NMR spectrum (CDCl 3): spectrum in accordance with the expected structure - UV spectrum (ethanol): = 330 nm max

ú - 19750

  Elemental analysis: Calculated%: C 77.61H 8.29 0 14.10 Found%: C 77.37H 8.26 0 14.36 The compounds (I) according to the invention can be used in

  the following cosmetic compositions.

EXAMPLE 3

  Preparation of methallyl-3'-methoxy-4'-benzylidene-3 camphor 1 st stage Preparation of 1-hydroxy-4'-methallyl-3'-benzylidene-3 camphor The mixture is heated for 19 hours, with stirring, to 180 ° C. g (0.032 moles) of methallyloxy-4'-benzylidene-3 camphor. The cooled reaction mixture is taken up in dichloromethane. This organic phase is treated with 10% sodium hydroxide. An oily intermediate phase is formed at the interface. It is isolated and purified by a chromatographic column on silica 60 (eluent: CH 2 Cl 2). There is thus obtained 4.5 g of 4'-hydroxy-3'-methallyl-3-benzylidene-camphor having the following characteristics: ## EQU1 ## eznoçe uno 'awInValou slTe ans -aqzgs auinlol ap úm çS sup asswlod ap 2 ú40 Oa (-aom 6ZO'O 2 i'i) alqdmsu ap a2uvlm a' uoTlelT2e sunos' 3o098 alod no aqdumuD ú-uptizuq -'-xotumrp-, ú-pîîusi ap uoTllsadîad 17 sJim (o '01 0 69'8 H ú'18 O: z anol 98'6 0 OL'8 H 177'18 S: alnzlva: aizTvuemlî asXluY

006úZ =

mu 81u = S: (ZD 1ZHD) Al aizzds -

anpuazs

  av nzanlzs sl e amio.uoo vazaeds: (úIdao) HI NWE ap a zads -

Do-ú-ú: uoTsn; ap JuTod -

  : saluvATns senbI; sTlagZzio sal zuepgssod eqzuelq OZ aipnod aun, p amuo; a: qdmvz ú - uapT $ izugq -, - xoqzgm-, ú-ifiiqzgm ap (% 96 Zuamapuez) 2 ç'l 4ua; qo uO 'nea, e, ABI s-ud 9allT s; a nuqqo a9TdTaid a * az12 el -ap ans asaa zsa iauuoTi oe aueLIgm q 'sanagq i7 -utpuad 00 7 read, ueTuTem no 19 alqltgm ap eanpojFp (81Om 10'0) 2' 171 n; no2 B aZnOS Zono 2 u O 'pTmL-oglúqZm9p Sl ap mu OZ suBp mn; ss2lod ap alvuoqiav op (elom 10'0) 2 9'I T3 snssep-z apess ze-amad nnunazqo aqdue ú-up $ zuq-, ú- q = -, 7- úXO2p4lp (alOm o00o0) 2 ç'l Op 9agUgIm a 0017 Q alZod UO tlddm2a -auap $ lXzugq - XOqam- & úlAlleq1amu np uoTpivda.dz 9pBs amaz O [6'OT 0 8'HW 1 D: O ganoiz ú'01 0 74'8H SZs18 O:% TlnaleD: 9alTuamgI9a 9sXIBUy Xvm

  úU * XBu m (Z96 B 10uBv3, a) An azZzadS -

anpugazzl

  ainlonals el B mo: uouo ailads: (1DGD) HI NHU- ap alaDdS -

3o, úI-TlI: uo $ sn; ap luTod -

  Ll 4 hours. The water is removed by azeotropy. The reaction mixture

  cooled is poured on ice and extracted with dichloro-methane.

  The oil obtained is purified by chromatography on a silica 60 column (eluent: CH 2 Cl 2 / toluine 50:50) and recrystallized from absolute ethanol. 1.2 g (yield 25%) of allyl-3'-dimethoxy-4 ', 5'-benzylidene-3-camphor is obtained in the form of a white powder having the following characteristics:

melting point: 104-1050 ° C.

  - 1H RN spectrum (CDCl3): spectrum in accordance with the expected structure UV spectrum (96% ethanol): Amax = 312 nm

E = 18200

  - Elemental analysis: Calculated%: C 77.61 H 8.29 0 14.10 Found%: C 77, 41 H 8.33 0 14.31

262 5,195

EXAMPLES OF APPLICATION

  EXAMPLE A Sunscreen Oil The following ingredients are mixed by heating optionally 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 - Vegetable oil qs 100 g EXAMPLE B - Sunscreen oil The following ingredients are prepared in the same manner as above: - Lanolin 2.5 g

  - Methallyloxy-3'-methoxy-4'-benzylidene

  3 camphor 3 g - Butylhydroxyanisole 0.05 g - Fragrance - qs - Triglycerides of C8-C12 fatty acids qs 100 g EXAMPLE C - Oilseal Oligo-alcoholic Lotion - Lanolin 2.5 g - Triglycerides of C8-C12 fatty acids 40 g - Perfume qs - Allyl-3'-hydroxy-4'-benzylidene-3 camphor 2 g Butylhydroxytoluene 0.05 g - alcohol at 96 qs 100 g EXAMPLE D - Sunscreen oil

  - Methallyl-3'-methoxy-4'-benzylidene

  3 camphor 1.5 g - cocoa butter 2.5 g - Butylhydroxyanisole 0.05 g Sunflower oil qs 100 g

26 2 5 1 9 5

  EXAMPLE E - Sunscreen oil - Allyl-3'-dimethoxy-4 ', 5'-benzylidene-3 camphor 3 g - Lanolin 2.5 g - Preservative, perfume qs - Triglycerides of C8-C12 fatty acids qs 100 g

Claims (22)

  Unsaturated derivative of benzylidene-3 camphor characterized by the fact that it corresponds to the formula: 'R 24 I   in which: R1 represents a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 alkoxy radical or a - (O) n- (CH2) pC (R4) = CH2 radical in which n = 0 or -1, p represents an integer between 1 and preferably between 1 and 4 and R4 represents a hydrogen atom or a C1-C4 alkyl radical; R2 represents a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 alkoxy radical or a - (CH2) p-C (R4) -CH2 radical in which p and R4 have the meanings mentioned above; R3 represents a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 alkoxy radical;   provided that one of the radicals R1 or R2 respectively represents   a radical - (O) n- (CH2) p-C (R4) = CH2 or a radical - (CH2) -   C (R4) = CH2 in which n, p and R4 have the meanings given above. 2. Compound according to claim 1, characterized in that it is chosen from allyl-3'-methoxy-4'-benzylidene-3 camphor,   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 cam-   phre, methallyloxy-3'-methoxy-4'-benzylidene-3 camphor, allyl   4'-benzylidene-3 camphor, and methallyl-4'-benzylidene-3 camphor.   3. Process for the preparation of a compound of formula (I) according to claim 1 or 2, characterized in that it consists in condensing an aromatic aldehyde of formula: R1 X (II) OHC - R3   wherein R1, R2 and R3 have the meanings given in claim 1, on synthetic camphor (d, l-camphor) or natural camphor (d-camphor), in the presence of a base such as amide, hydride, an alkali metal hydroxide or alkoxide, 10 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.   4. Process for the preparation of a compound of formula (I) according to claim 1, in which R1 represents a radical - (O) n- (CH2) pC (R4) = CH2) when n is equal to 1 and R2 represents a hydrogen atom, a C 1 -C 6 alkyl radical or an alkoxy radical in   C1-C6, R3, R4 and p having the meaning indicated in the   cation 1, characterized in that a halide is reacted alkenyl of formula (III):   X- (CH2) pC (R4) = CH2 (III) wherein X represents a halogen atom, preferably chlorine or bromine and p and R4 have the meanings given in claim 1, on a compound of formula ( IV): (IV) wherein R2 denotes a hydrogen atom, a C 1 -C 6 alkyl radical or a C 1 -C 6 alkoxy radical and R 3 has the meaning given in claim 1, in the presence of a base; such as an alkali or alkaline earth metal hydroxide or carbonate or an amide, alkoxide or alkali metal 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 point boiling solvent. 5. Compound of formula: pH - <A. R2- (IV)   wherein R2 represents a hydrogen atom, a C1-C6 alkyl or C1-C6 alkoxy radical and R3 represents a hydrogen atom or   a C1-C6 alkyl or alkoxy radical.   6. A process for preparing a compound of formula (I) in   which R1 represents a radical - (O) n- (CH2) p-C (R4) = CH2 when n = 0 and p = 1, characterized in that in a first stage, a compound of formula (IB) is subjected to: O -CH (R4) = CH2 R3 (B   in which R4 and R3 have the meaning indicated in claim 1, at a CLAISEN rearrangement to obtain the compound (IC) of the formula H2C (R4) CH2   H (IC) in which R3 and R4 have the same meanings as above, and that in a second stage, the compound of formula (IC) thus obtained is reacted with a C1-C6 alkyl halide, in 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) below 2625 1 95 1H2C (R4) = CH2 4K [a- R2 I (ID)    * NR 3   wherein R3 and R4 have the aforementioned meanings and R2   represents a C1-C6 alkoxy radical. 7. Compound of formula: 2 C (R4) cH2 ! (IC)   in which R4 represents a hydrogen atom or a C1-C8 alkyl radical and R represents a hydrogen atom, a 1,4-alkyl radical and R3 C1-C6 or C1-C6 alkoxy.   8. Compound according to claim 7, characterized by the fact   that it is 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 support   containing at least one fatty phase.   10. Cosmetic composition according to claim 9, characterized in that it comprises as compound (I),   least one of the compounds selected from allyl-3'-methoxy-4'-benzyl-   lidene-3 camphor, allyl-3'-dimethoxy-4 ', 5'-benzylidene-3 camphor,   methallyl-3'-methoxy-4'-benzylidene-3-camphor, methallyl-3'-   4'-dimethoxy-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'-benzyl lidene-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 support   containing at least one fatty phase.   12. Cosmetic composition according to claim 11, characterized   because it understands as a compound (IC), the allyl-   3'-hydroxy-4'-benzylidene-3 camphor.   13. Cosmetic composition according to any one of the claims   9 to 12, characterized in that it is in the form of an oily or olioalcoholic lotion, an emulsion or an oleo-alcoholic gel,   alcoholic or hydroalcoholic, solid stick or aerosol.   14. Cosmetic composition according to claim 13, characterized   rised by the fact that it also contains cosmetic adjuvants   selected from thickeners, softeners, humectants, surfactants,   actives, preservatives, anti-foams, perfumes, oils, waxes, lanolin, monoalcohols and lower polyols, propellants, dyes and pigments.   15. Cosmetic composition according to any one of the claims   9 to 14, characterized by the fact that it constitutes a   protection of the human epidermis and contains 0.25 to 3% by weight of compound of formula (I) or (IC).   16. Cosmetic composition according to any one of the claims   9 to 14, which is in the form of an anti-solar composition, characterized in that it contains 0.5 to 15% by weight of compound of formula (I) or (IC).   17. Anti-solar cosmetic composition according to claim 16, characterized in that it additionally contains an agent   filtering UV-B and / or UV-A rays.   18. Cosmetic composition according to any one of the claims   9 to 12, intended to be applied to the hair, characterized by the fact that it is in the form of a shampoo, lotion, gel or emulsion to be rinsed, lotion or gel styling or treating, lotion or   gel for blow drying or setting, hair spray, composi-   permeation, discoloration or coloring and includes   0.25 to 3% by weight of compound of formula (I) or (IC).   19. Cosmetic composition according to any one of the claims   9 to 12, in the form of a colored cosmetic composition or not, characterized in that it is constituted by   a hair composition, a makeup product or a composition 2625 1 9 5   for the care or treatment of the skin, comprising 0.25 to 3%   by weight of compound of formula (I) or (IC).   20. Process for protecting 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 unsaturated derivative of benzylidene-3 camphor of formula (I) according to   claim 1 or 2 or (IC) according to claim 7 or 8.   21. Process 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 the Claim 7 or 8.   22. Use of an unsaturated derivative of benzylidene-3 camphor   formula (I) according to claim 1 or 2 or (IC) according to the claim   7 or 8 as an intermediate for the preparation of organosilicon compounds by reacting a compound of formula (I) or (IC) with   an organosilicon compound containing SiH groups.