AU630371B2

AU630371B2 - New benzylidenecyclanone derivatives, their preparation process, their use as anti-oxidants and as sunscreens, cosmetic and pharmaceutical compositions containing them

Info

Publication number: AU630371B2
Application number: AU41463/89A
Authority: AU
Inventors: Serge Forestier; Alain Lagrange; Gerard Lang; Bernadette Luppi
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1988-09-20
Filing date: 1989-09-19
Publication date: 1992-10-29
Anticipated expiration: 2009-09-19
Also published as: FR2636531A1; FR2636531B1; AU4146389A; NL8902326A; IT8967776A0; DE3931269A1; GB2222829A; GB8921224D0; JPH02160741A; BE1002236A4; LU87339A1; CH679668A5; IT1233198B; GB2222829B

Description

63C 1571 Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Application Number.

Lodged: Int. Class Complete Specification Lodged: Accepted: Published: l riority o 0 o 0 t 0 po lt o o ated Art: 0 00 0 Name of Applicant: L OPREAL 0 0 0* Address of Applicant 0 '1o 0 t) 0 o0 Artuat Inventor: Address for Service: 0 0 0 0 0 0 00v 14, Rue Royale, 75008 Paris, France ALAIN LAGRANGE, SERGE FORESTIER, GERARD LANG and BERNADETTE LUPPI AO3YM R 8:atermark Patent Trademark Attorneys 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: NEW BENZYLIDENECYCLANONE DERIVATIVES, THEIR PREPARATION PROCESS, THEIR USE AS ANTI-OXIDANTS AND AS SUNSCREENS, COSMETIC AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM The following statement is a fu!l description of this invention, including the best method of performing it known to US New benzylidenecyclanone derivatives, their preparation process, their use as antioxidants and as sunscreens, cosmetic and pharmaceutical compositions containing them.

The subject of the present invention is new benzylidenecyclanone derivatives, their preparation process and their uses as anti-oxidants as well as in acosmetic compositions for daily or sunscreen usage and in pharmaceutical compositions for the treatment of inflammations and allergies of the skin or of certain forms of cancer.

It is well known that the skin is sensitive to solar radiation which can cause trivial sunburn or 15 erythema, but also more or less accentuated burns.

0 However, solar radiation also has other harmful effects such as a loss of elasticity of the skin and the appearance of wrinkles leading to premature ageing.

Sometimes dermatoses may even also be observed. The extreme case is the appearance in certain subjects of S o .skin cancers.

It is also desirable to provide the hair with good protection against photochemical degradation in order to avoid a change in colour, bleaching or degradation of the mechanical properties.

-1 ii r~~l 11 1 1 1 -2 In addition, it is known that the constituents of cosmetic preparations do not always have sufficient i light stability and degrade under the action of light i radiation.

It is well known that the most dangerous j portion of solar radiation is constituted by the ultraviolet radiation of wavelengths less than 400 nm.

It is also known that, because of the existence of the ozone layer in the Earth's atmosphere, which absorbs a 10 portion of the solar radiation, the lower limit of the ultraviolet radiation reaching the surface of the Earth is about 280 nm.

As a consequence, it appears desirable to have available compounds capable of absorbing ultraviolet radiation in a wide band of wavelengths ranging from 280 to 400 nm, that is to say both the UV-B rays of wavelengths between 280 and 320 nm which play a i preponderant part in production of the solar erythema, and the UV-A rays of wavelengths between 320 and 400 nm which cause browning of the skin, but also its ageing, and which favour triggering of the erythematous Sreaction or amplify this reaction in certain subjects, or can even be the origin of photo-toxic or photoallergic reactions.

In the course of its research, the Applicant has just discovered new benzylidene-cyclanone derivatives having the following formula: 3

R

I

4 2 R 6 I

RR

3 in which: RI and R, which may be identical or different, represent a hydrogen atom, a hydroxyl radical, a C,-C.

S' 5 linear or branched alkyl residue or a C 1

-C

8 linear or branched alkoxy residue, with the reservation that at least one of the two radicals R, and R is other than a hydrogen atom.

R

2 and R 3 which may be identical or different, represent a hydrogen atom or a hydroxyl radical, it I t being understood that one at least of the radicals R 2 ,and R 3 represents a hydroxyl radical,

F{

R

4 Rs, R. and Ry, which may be identical or different, represent a Cl-C 1 linear or branched alkyl j 15 residue, an aralkyl residue such as benzyl which may be unsubstituted or substituted by a Cl-C 4 alkyl or

C,-C

4 alkoxy residue, an aryl residue such as phenyl which is unsubstituted or substituted by a CI-C 4 alkyl residue; the substituents R 4 and R, and/or the substituents R 6 and R 7 can form, with the carbon atom of the ring to which they are attached, a saturated ring containing from 5 to 12 carbon atoms which is

-I_-Y

4 unsubstituted or substituted by one or more Cl-C, linear or branched alkyl residues, X represents either a-CH2--, radiccJ in which n 1 or 2, or a radical in which R. represents a hydrogen atom, a Cl-C 8 linear or branched alkyl residue, an aralkyl residue such as benzyl which is unsubstituted or substituted by a C 1

-C

4 alkyl or C1-C 4 alkoxy residue, a hydroxyl radical, a residue in which R, represents a C 1

-C

8 linear or branched alkyl S 10 residue, or alternatively X represents an oxygen atom or a sulphur atom.

In addition to their good filtering properties 0 in the wavelength range between 280 and 380 nm, the above compounds also, unexpectedly, have excellent anti-oxidant properties with respect to the So peroxidation of polyunsaturated lipids and also with respect to substances which are capable of undergoing thermo- or photo-induced oxidation reactions (such as proteins, polymers and the like).

Now, it is known that the peroxidation of lipids involves the formation of intermediate free radicals which damage the cellular membranes which are composed, inter alia, of phospholipids, and are responsible, in particular, for the phenomena of ageing of the skin Tappel in "Federation Proceedings" volume 32, No. 8, August 1973).

AI

It is extremely useful to have available compounds which have at the same time wide-band filtering properties and anti-oxidant properties which potentiate the filter effect. Such compounds can, for example, make it possible more effectively to combat premature ageing of the skin due to the peroxidation of the cutaneous lipids.

They can also enable better preservation of cosmetic compositions containing a fatty phase to be 10 assured by avoiding rancidity of the unsaturated lipids CPO which are contained in it and which can be of animal S origin such as lanolin, ketin (spermaceti), beeswax, perhydrosqualene or turtle oil, or of vegetable origin Isuch as olive oil, castor oil, maize oil, sweet almond oil, avocado oil, shea oil, sunflower oil, soya oil, |jI o peanut oil, hydrogenated copra or palm oils, essential o0° *fatty acids such as vitamin F and certain essential i oils present in perfumes, such as lemon or lavender i ,oil.

s 20 The Applicant has also discovered that, in an 0I extremely surprising manner, the compounds of formula above coild be used for the treatment of inflammatioa and allergies of the skin and also in the prevention of certain cancers.

In addition to their good filtering and antioxidant properties, the compounds according to the invention have an excellent lipo-soluble character as 6 well as very good thermal stability and excellent photochemical stability.

These compounds also have the advantage of not being toxic or irritant and of being perfectly harmless to the skin.

They distribute themselves uniformly in conventional cosmetic supports which are suitable for forming a continuous film, and in particular in fatty supports, and can thus be applied on the skin to 10 constitute an effective protective film.

The subject of the present invention is therefore the compounds of formula above.

In this formula, R, and R can denote, for example, a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or 1,1,3,3-tetramethylbutyl radical or a methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy or octyloxy residue.

R

4 Rs, R 6

R

7

R

8 and R 9 can denote alkyl radicals chosen from the radicals listed above for R, and R; when R 4 and R, or R 6 and R 7 form a ring with the carbon atom to which they are attached, this preferably contains 6 carbon atoms.

Among the preferred compounds of general formula there may be mentioned 3',5'-di-tert-butyl-4'-hydroxy-4benzylidenetetrahydro-2,2,5,5-tetramethylfuran-3-one, 7 C' 2 0 2 2 0 0 C C C 3' ,5 '-di-tert-butyl-2 -hydrrncy-4benzylidenetetrahydro-2, 2,5 ,5-tetramethylfuran-3-one, 3 5 -di-tert-butyl-4 I -hydroxy-4benzylidenetetrahydro-2 5-tetraethylfuran-3-one, 3' ,5 1-di-tert-butyl-4 I-hydroxy-4benzylidenetetrahydro-2 ,2,5,5 -bis (pentaamethylene) furan-3-one, 3' ,5 '-dimethyl-4 -hydroxy-4-benzyiidenetetrahydro- 2,2,5 ,5-tetramethylfuran-3-one, .0 3' ,5 '-dixnethoxy-4 '-hydroxy-4-benzylidenetetrahydro- 2,2,5, 5-tetraiethyfuran-3-one, 3 '-tert-butyl-2 '-hydroxy-5 '-methoxy-4benzylidenetetrahydro-2 5-tetrarnethyifuran-3-one, 3 '-tert--butyi-2 /-hydroxy-5 I'-meth~yi-4benzylidenetetrahydro-2, 2,5, 5-tetranmethylfuran-3-one, 3' ,5 '-di-tert-butyl-4 '-hyciroxy-4benzylidenetetrahydro-2, 5-dimethyl-2, butylfuran-3-one, 3' ,5 '-di-tert-butyl-4 I -hydroxy-4- '0 benzylidenetetrahydro-2, 5-diethyl-2, 3-one,* 3' -diisopropyl-4' -hydroxy-4-benzylidenetetrahydro- 2,2,5, 5-tetramethylfuran-3-one, 3' ,5 '-di-tert-butyi-4 '-hydroxy-4-benzylidene-2 ,2 tetramethylazacyclopentan-3-one, 31,5 1 -di-tert-butyl-4 I'-hydroxy-2-benzylidene-3 ,3,5,5tetramethyicyclopentan-1 -one, 040 04 OC C C 4'~

COO

C 00 GC C C C C I, ~C S S 31,41,51 -trihyd~roxy-4-benzylidenetetrahydro-2 ,2,5 tetramethylfuran-3-one, 3 '-tert--butyl-4 '-hycdroxy-4--benzylidenetetrahydzo- 2,2,5, 5-tetramethylfuran-3-one.

The compounds of formula are obtained by condensation of an aromatic aldehyde of formula:

R

X

R

4 R7 In the compounds of formula (II) and (III), R,

R~,R~,R

3

R

4

R

5 Rr 7 and X have the meanings indicated above. Condensation takes place with an aldehyde, the OH~ function of which is either free or protected by a trialkylsilyl alkyl) radical or by a benzyl radical.

9 SIn the case in which an aldehyde, the OH function of which is protected by a trialkylsilyl radical, is used, the condensation reaction is followed by a reaction to detach the trialkylsilyloxy radical in order to liberate the OH function. This reaction takes place, for example, in acetonitrile in the presence of tetrabutylammonium fluoride.

In the case in which an aldehyde, the OH i function of which is protected by a benzyl radical, is '10 used, the condensation reaction is followed by a i reaction for the reducing detachment of the benzyloxy l radical, by hydrogen transfer, for example by means of i formic acid or of cyclohexene as hydrogen donors, in the presence of a catalyst such as palladium-oncharcoal in a solvent, the reaction temperature being between 0°C and the boiling point of the reaction mixture.

The aldehydes of formula (II) are prepared a ccording to known methods.

The cyclanones of formula (III) can be prepared as described by C. Sandris and G. Ourisson in Bull.

Soc. Chim. Fr (1956) page 958 or by Ik. Korobitsyna in Zhur. Obschei. Khim. vol 25 page 734-738 and vol 27 page 1792-95.

The condensation of the aldehyde (II) with a cyclanone (III) can be carried out according to one of the two following processes: i iihaRI

B

d

I

i 10 1st Process: Condensation is carried out in the presence of an alkali metal alcoholate such as sodium methylate or potassium tert-butylate, in a solvent such as toluene or 1,2-dimethoxyethane, at a temperature of between -78'C and the boiling point of the solvent. The condensation can also be carried out in the presence of an inorganic base such as an alkali metal amide or hydride, in a solvent such as 1,2-dimethoxyethane, or 10 an alkali metal hydroxide in an alcohol, at a temperature between ambient temperature and the boiling point of the reaction mixture.

2nd Process: Condensation of the aldehyde (II) with a cyclanone (III) is carried out in the presence of a borane of formula (IV) which follows: -R11-R (IV) B 0 RI

(IV)

0' 0 aa o a 00 aa a a a a in which R 10 represents a C 1

-C

6 alkyl residue and R 1 1 represents a CI-C 4 alkyl residue. This compound is obtained according to the operating method described by L.H. Toporcer et al., J. Am. Chem. Soc. 87, 1236 (1965). It is not necessary to isolate and purify it in order to carry out the condensation of the aldehyde -I 11 I(II) with the cyclanone (III).

The condensation reaction is carried out at a temperature of about 150'C, without a solvent.

|i A subject of the present invention is therefore Ii 5 also the preparation process for the new compounds of formula Another subject of the invention is a cosmetic composition containing, in a cosmetically acceptable support containing at least one fatty phase, an effective quantity of at least one benzylidenecyclanone derivative of formula above.

The cosmetic composition of the invention can "be used as a composition to protect the human epidermis or hair or as a sunscreen composition.

A subject of the present invention is also a process for protecting the skin and natural hair or 00i 0 hair sensitized to solar radiation, consisting in Sooo applying on the skin or the hair an effective quantity of at least one compound of formula contained in a cosmetically acceptable support containing at least one 0 o 0o 0 fatty phase.

"Sensitized hair" is understood to mean hair which has undergone a permanent-waving, colouring or bleaching treatment.

A subject of the invention is also a coloured or colourless cosmetic composition which is stabilized to light and/or to oxidation, containing an effective -12quantity of at least one benzylidenecyclanone derivative of formula above.

When it is used as a composition intended to protect the human epidermis from ultraviolet rays, the cosmetic composition according to the invention can be presented in the most diverse forms normally used for thiL type of composition. It can, in particular, be presented in the form of oily or oily-alcoholic lotions, of emulsions such as a cream or a milk, of oily-alcoholic, alcoholic or water-alcoholic gels or of solid sticks, or can be packed in an aerosol.

It can contain the cosmetic additives which are normally used in this type of composition such as thickeners, emollients, humectants, surfactants, preservatives, anti-foams, fragrances, oils, waxes, 44 lanolin, propellants, colourants and/rr pigments having .the function of colouring the composition itself or the skin, or any other ingredient which is normally used in cosmetics.

The compound of formula is present in proportions by weight of between 0.1 and 2 with respect to the total weight of the cosmetic composition which protects the human epidermis.

An oil, a wax and in a general manner any glyceride, a lower mono-alcohol or a lower polyol or their mixtures can be used as a solubilization solvent.

The most particularly preferred mono-alcohols or I- 13 13 polyols are ethanol, isopropanol, propylene glycol, glycerol and sorbitol.

One embodiment of the invention is an emulsion in the form of a protective milk or cream containing, in addition to the compound of formula fatty 1 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.

0 0 10 Another embodiment is constituted by oily lotions based on natural or synthetic oils and waxes, lanolin and fatty acid esters, in particular fatty acid triglycerides, or by oily-alcoholic lotions based on a lower alcohol such as ethanol or a glycol such as propylene glycol and/or a polyol such as glycerol, and on oils, waxes and fatty acid esters such as fatty acid triglycerides.

The cosmetic composition of the invention can also be an alcoholic gel containing one or more lower alcohols or polyols such as ethanol, propylene glycol or glycerol and a thickener such as silica. The oily-alcoholic gels contain, in addition, a natural or synthetic oil or wax.

The solid sticks are constituted by natural or synthetic waxes and oils, fatty alcohols, fatty acid esters, lanolin and other glycerides.

14 The present invention also concerns cosmetic sunscreen compositions containing at least one compound of formula and capable of containing other UV-B and/or UV-A filters.

'4 In this case, the quantity of filter of formula is hbtween 0.2 and 15 by weight, the total quantity of the filters present in the sunscreen composition, that is to say the compound of formula (I) and optionally the other filters, being between 0.5 and 15 by weight with respect to the total weight of the 0 sunscreen composition.

In the case of a composition packaged in an 0 aerosol, the conventional propellants such as alkanes, fluoroalkanes and chlorofluoroalkanes are used.

When the cosmetic composition according to the invention is intended to protect natural or sensitized 0oo hair from UV rays, this composition can be presented in o 0° the form of a shampoo, a lotion, a rinsable gel or emulsion, to be applied before or after shampooing, o0 before or after colouring or bleaching or before or after permanent-waving, a styling or treatment lot ,in or gel, a lotion or gel for blowdrying or setting, hair lacquer, permanent-waving or colouring or bleaching composition for the hair. This composition can contain, in addition to the compound of the invention, various additives used in this type of composition, such as surfactants, thickeners, polymers, emollients, i i 15 *0 0 0 tI 0 5 454 004*) 004i S 004Ci 0040 0 0 00 0 O 00C 0 0 0 0 ;C 0 00 (40 0 preservatives, foam-stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, degreasers, colourings and/or pigments having the function of colouring the composition itself or the hair, or any other ingredient which is normally used in the haircare field.

It contains 0.25 to 2 by weight of compound of formula The present invention also concerns to cosmetic compositions containing at least one compound of formula as an agent for protection against ultraviolet rays and as an anti-oxidant, constituted by haircare compositions such as hair lacquers, optionally treating or disentangling setting lotions, shampoos, colouring shampoos and tinctorial compositions for hair, by make-up products such as nail varnish, skintreatment creams and oils, foundations, lipsticks, skincare compositions such as bath oils or creams, as well as any other cosmetic composition which may pose, because of its constituents, problems of stability to light and/or to oxidation during storage.

Such compositions contain 0.1 to 2 by weight of compound of formula The invention also concerns a process for protecting cosmetic compositions against ultraviolet rays and oxidation, consisting in incorporating an effective quantity of at least one compound of formula a 0 c -I 1' 16in these compositions.

Another subject of the invention is the use of the compounds of formula as anti-oxidants.

Another subject of the invention is the use of the compounds of formula as wide-band solar filters absorbing in the wavelength range between 280 and 380 nm.

A subject of the invention is also the application of the compounds of formula as cosmetic products.

As has been indicated above, the Applicant has, in addition, discovered during its research that the compounds of formula have a beneficial pharmacological activity in the field of the treatment of inflammations and allergies of the skin, and could also be used in the prevention of certain cancers.

o a 0 0 A subject of the invention is therefore the compound of formula in respect of its use as a medicament.

A subject of the invention is also a pharmaceutical composition containing an effective quantity of at least one compound of formula as active ingredient, in a non-toxic support or excipient.

The pharmaceutical composition according to the invention can be administered orally or topically.

Orally, the pharmaceutical composition can be presented in the form of tablets, capsules, dragees, 17 }I syrups, suspensions, solutions, emulsions and the like.

Topically, the pharmaceutical composition according to the invention is presented in the form of a salve, a cream, an ointment, a solution, a lotion, a gel, a spray, a suspension or the like.

This medicinal composition can contain inert or pharmacodynamically active additives, and in oo particular: hydrating agents, antibiotics, steroidal or j eo non-steroidal anti-inflammatory agents, carotenoids and i ,t 10 anti-psoriasis agents.

improvers, preservatives, stabilizers, humidity regulators, pH regulators, osmotic pressure modifiers, II emulsifiers, local anaesthetics, buffers and the like.

15 It can also be packaged in delayed or gradual l. release forms which are known per se.

The compound of formula according to the invention is present in the pharmaceutical compositions i; in proportions of between 0.01 and 80 by weight with Sb 20 respect to the total weight of the composition, and IS preferably between 0.1 and 20 by weight.

-In the therapeutic application, the treatment is determined by the doctor and can vary according to the age, the weight and the response of the patient as well as the gravity of the symptoms.

When the compounds of formula are administered orally, the dosage is generally between 1 4 1 j n 10 0u 4 0 I-4 044'"1 4 44 44~l 4 4 44 4

I:

i- 18 0.1 and 50 mg/kg/day, and preferably between 0.2 and mg/kg/day. The length of treatment is variable according to the gravity of the symptoms, and can range between 1 and 25 weeks, in a continuous or discontinuous manner.

The topical compositions preferably contain from 0.25 to 4 by weight of compound of formula Any conventional non-toxic supports or excipients can be used as support or excipient for the pharmaceutical composition of the invention.

The following examples are intended to illustrate the invention without, however, being limiting.

PREPARATION EXAMPLES EXAMPLE 1 Preparation of 3',5'-di-tert-butyl-4'-hydroxy-4benzylidenetetrahydro-2,2,5,5-tetramethylfuran-3-one of formula:

_,OH

i -L -19- 8.2 g (0.08 mol) of pivalic acid is added to 100 cm 3 of a 1 M solution of triethylborane in hexane at 0°C. After stirring for 15 minutes, the mixture is left to return to aiient temperature and then 5.4 g (0.038 mol) of tetrahydro-2,2,5,5-tetramethylfuran-3one and 8.9 g (0.038 mol) of 3,5-di-tert-butyl-4hydroxybenzaldehyde are added.

So The hexane is distilled off and the mixture So heated to 150C for 3 hours. The volatile products are distilled off under reduced pressure (2000 Pa, then 13 Pa).

The oily residue is recrystallized from an ethanol-water mixture; 5.5 g of the expected product I are then obtained in the form of pale-yellow crystals 15 having the following characteristics: i melting point: 146°C elemental analysis: C 23 H11 34 0 3 C H 0 calc. 77.05 9.56 13.39 i 20 found 76.65 9.56 13.78 UV spectrum (dichloromethane) Am 335 nm Se 18170 Ii Ui K 1 15 20 EXAMPLE 2 Preparation of 3',5'-di-tert-butyl-2'-hydroxy-4benzylidenetetrahydro-2,2,5,5-tetramethylfuran-3-one of formula:

^J

1 g of potassium tert-butylate is added to a solution of 1.3 g of tetrahydro-2,2,5,5tetramethylfuran-3-one in 50 cm 3 of 1,2-dimethoxyethane.

The mixture is heated under reflux for 15 minutes and then cooled to ambient temperature. 2 g of butyl-2-hydroxybenzaldehyde are added. After stirring for 24 hours at ambient temperature, the reaction mixture is diluted with water. It is extracted with ethyl acetate. The organic phase is dried over sodium sulphate and the solvent is distilled off under reduced pressure. The residue is chromatographed on silica gel using a mixture of heptane and ethyl acetate containing 96 of heptane as eluent. The product obtained has the following characteristics: melting point: 166°C elemental analysis: C 23

H

34 0 3 c- -e 21 C H 0 calc. 77.05 9.56 13.39 found 76.95 9.56 13.55 UV spectrum (CH 2 C1 2 305 nm E 5890 SA 350 nm 0 a *2 3430 EXAMPLE 3 Preparation of 3',5'-di-tert-butyl-4'-hydroxy-4benzvlidenetetrahvdro-2,2,5,5-tetraethylfuran-3-one of formula: 0 00 Et 0O 0 EtJ Et.

This compound is obtained using the operating me-thod described in Example 1, in which the tetrahydro- 2,2,5,5-tetramethylfuran-3 -one is replaced with tetrahydro-2,2,5,5-tetraethylfuran-3-one. The product obtained has the following characteristics: melting point: 1240C elemental analysis: C,7H,203 -22- C% H 0 caic. 78.21 10.21 11.58 found 78.29 10.18 11.81 U IV spectrum (CH 2 Cl 2 338 nm E 22800 EXAMPLE 4 Preparation of 3',5'-di-tert-butyl-4'-hvdroxy-4benzvlidenetetrahvdro-2 .2 .5,5-bis (pentamethylene' furan- 3-one of formula: 0- This compound is obtained following the operating method described in Example 1, in which the tetrahydro-2 5-tetramethylfuran-3-one is replaced with tetrahydro-2 5-bis (pentamethylene) furan-3-one.

The product obtained has the following characteristics: melting point: 162-164 0

C

elemental analysiste C,H4 2 0 3 -23- C% H 0 iicaic. 79.41 9.65 10.94 f ud79.16 9.62 11.21 U tV spectrumn (CH 2

C

2 .338rn 320 0 24 EXAMPLE Preparation of 3',5'-dimethyl-4' -hydroxy-4benzvlidenetetrahydro-2,2,5,5-tetramethylfuran-3-one of formula: 0 08 3 5.4 g (0.1 mol) of sodium methylate are added to a solution of 7.1 g (0.05 mol) of tetrahydro- 2,25,5,-tetramethylfuran-3-one in 30 cm 3 of 1,2dimethoxyethane. The mixture is cooled to about 5 0 C then 3.8 g (0.025 mol) of 3,5-dimethyl-4-hydroxybenzaldehyde in solution in 20 cm 3 of 1,2-dimethoxyethane are added with stirring. The reaction mixture is stirred for .4 minutes at ambient temperature, then heated under reflux for 30 minutes. After one night at ambient temperature the product is precipitated by the addition of dilute hydrochloric acid. It is filtered off, washed with water and dried. After purification by washing with dichloromethane, 1.6 g of the expected product is obtained in the form of pale yellow crystals having the following characteristics: melting point: 154-158 0

C

elemental analysis: C 17

H

2 zO 3 C H% 0 calc. 74.42 8.08 17.49 f ound 74.23 8.10 17.53 -UV spectrum (CH 2 Cl 2 .A 330 nm 2 20500 EXAMPLE 6 Preparation of 3' ,5 '-diinethoxy-4 '-hydroxvy-4benzvlidenetetrahvdro-2, 2, 5, 5 -tetraiethl furan- 3-one of formula: OC H 1 3

OCHJ

0 K A This compound is obtained according to the operating method described in Example 2, in which the 3 ,5-di-tert-butyl-2-hydroxybenzaldehiyde is replaced by A. 4-tert-butyldim~thylsilyloxy-3, The tert-butyldimethylsilyl protective group is removed by treatment with a solution of tetrabutylaimonium.

fluoride in acetonitrile for 10 minutes at ambient temperature. After diluting the reaction mixture with water, extracting with isopropyl ether and -26recrystallizing from a heptarie/acetone mixture, the expected product having the following characteristics is obtained: melting point: 148'C elemental analysis: C 17

H

22 0 C 0% caic. 66.65 7.24 26.11 CCfound 66.56 7.24 26.32 -UV spectrum (CH 2 C1 2 :363 rn 16300 EXAMPLE 7 Preparation of 3' .5 -di-tert-butyl-4 '-hydroxy-4benzylidenetetrahvdro-2 ,5-dimethyl-2 furan-3-one of formula: 0 OH This compound is obtained according to the operating method described in Example 1, in which the tetrahydro-2, 2, 5, 5-tetramethyl furan-3 -one is replaced by tetrahydro-2 ,5-dimethyl-2, 5-di-tert-butylfuran-3- 27 one. The product obtained has the following characteristics:.

melting point: 18000 1.1 elemental analysis: C 2 s!H 4 6 0 3 C 0% caic. 78.68 10.47 10.84 vifound 78.71 10.57 10.75 UV spectrum (CH 2 0 1 2 max 338 nm 15700 I EXAMPLE 8 Preparationof3 5dierbuy4'hdoybenzylidenete~tahydro-2.5-diethYl-2.5-dimethylfuran-3one of formula 1 E ti 1 This compound is obtained according to the operating method described in Example 1, In which the tetrahydro-2,2,5,5-tetramethylfuran-3-one is replaced by tetraihyd ,o2,5-diethyl-2,5-dimethylfurafl-3-one. The product obtained has the 3 6 following characteristics:

F,

I'

Ii

A

F

4 j 5 '2 o 0 '2 Q 10 2* 0.,

F

'20 I '2 28 melting point: 11202C elemental analysis: C, 5 H,.0 3 caic. 77.68 f ound 77.79 9.91 9.88 0 12.42 12 .52 UV spectrum (CH.C1 2 Am~ 338 rn =22300 EXAMPLE 9 Pre-paration of 3 -diiso-propvl-4 '-hvdroxv-4benzylidenetetrahvdro-2 .2 5, 5-tetramethylf uran-3 -one of f ormula: 0/ 0 YO This compound is obtained according to the operating method described in Example 5, in which the 3,5-dimethyl-4-hydroxybenzaldehyde is replaced by diisopropyl-4-hydroxybenzaldehyde. The product obtained has the following characteristics: melting point: 142 0

C

0 29 elemental analysis: C 21

H

3 0 0 3 C H calc. 76.33 9.15 found 76.57 9.23 UV spectrum (CHzCl 2 0~ 2~ 63rim E -22400 0 14.52 14.68 EXAMPLE ,Preparation of 3' 5 '-di-tert-butvl-4 '-hydroxv-4benzvlidene-2 ,2,5 .5-tetramethylazacyclopentan-3-one of formula: 04 4 0 04 4 0 This compound is obtained according to the operating method described in Example 1, in which the tetrahydro-2, 2,5, 5-tetramethylfuran-3-one is replaced by 2,2,5,5-tetramethylazacyclopentan-3-one. The product obtained has the following characteristics: melting point: 146'C elemental analysis: C 23

H

35 0 2 K C% H% N% 0% calc. 77.27 9.87 3.92 8.95 Kfound 77.36 9.82 3.85 9.08 UV spectrum (CH 2 C1 2 .Xgm,x 334 nm s =21400 EXAMPLE 11 Preparation of 5 '-di-tert-butyl-4'-hydroxy-2-a- 1 0 benzylidene-3.3.5.5-tetramethvlcyclopentan-1 -one of fomua

CH

1 2 This compound is obtained according to the operating method described in 1 Example 1, in which ;the tetrahydro-2,2,5,5-tetramethylfuran-3-one is replaced by 13,3,5,5-tetramethylcyclopentan-1 -one. The product obtained has the following j ~K 0 25 characteristics: j I 04 melting point: 16600 elemental analysis: C 24

H

36 0 2 31 S% H% 0% caic. 80.85 10.18 8.97 found 80.92 10.21 9.09 UV spectrum (CH 2 C1 2 330 nm 19500 0 4 S.4 4 I44 4- *4 4 EXAMPLE 12 Preparation of ,5 '-trihvdroxv-4benzvlidenetetrahydro-2,2,55-tetramethylfuran-3-one of formula: 4 4 4i 4 4 44 4 4 a) Preparation of 3',4',5'-tribenzvloxv-4benzvlidenetetrahvdro-2. 25. 5-tetramethvlfuran-3one 14.2 g (0.1 mol) of tetrahydzo-2,2,5,5tetramethylfuran-3-one and 5.4 g (0.1 mol) of sodium methylate in 30 cm 3 of 1,2-dimethoxyethane are heated under reflux for 15 minutes. A solution of 39.8 g '1 xCusw reD 32 (0.094 mol) of 3,4,5-tribenzyloxybenzaldehyde in 100 cm 3 of 1,2-dimethoxyethane is added hot.

The mixture is left at ambient temperature for minutes and then poured into an aqueous solution of sodium chloride acidified with hydrochloric acid. The mixture is extracted with dichloromethane. The solvent is distilled off under reduced pressure and the residue I is recrystallized from a minimum of heptane.

The expected product is obtained in the form of white crystals with a 65 yield.

b) Preparation of 3',4',5'-trihydroxy-4benzylidenetetrahydro-2,2,5,5-tetramethylfuran-3one 11 g (0.02 mol) of 3',4',5'-tribenzyloxy-4- 15 benzylidenetetrahydro-2,2,5,5-tetramethylfuran-3-one obtained above and 5 g of palladium-on-charcoal containing 50 water (5 by weight of palladium with respect to the charcoal) in a mixture of 100 ml of ethanol and 30 ml of formic acid are stirred under argon for 2 hours 30 minutes at ambient temperature, ii i then 1 hour in a boiling water bath. The mixture is left to cool and then diluted with 20 cm 3 of water. It is filtered on Celite. The Celite cake is washed with dichloromethane and then with water. The organic phase is washed with water and then evaporated to dryness.

The residue is recrystallized from diisopropyl ether.

LI -33- The expected product is obtained in the f orm of yellow crystals with a 45 yield. The product obtained has the following characteristics: -melting point: 156'C -elementary analysis: C 15

H

1 ,0 5 1,H 2 0 C C% H 0 h.calc. 60.81 6.75 32.43 f found 60.77 6.95 32.05 ~~UV spectrum (CH 2 Cl 2 10343 r e11780 EXAMPLE 13 Preparation of 3'-tert-butyl-4'-hydroxv-4benzylidenetetrahvdro- 2, 2, 5, 5-tetramethyl furan-3 -one of f ormula a) Preparation of 4 '-benzvloxv-' -tertbutylbenzvlidenetetrahvdro-2 ,2,.55tetramethvlfuran- 3-one This compound is obtained according to the operating method described in Example 12 in which the 3,4,5-tribenzyloxybenzaldehyde is replaced by 4- -34benzyloxy-3-tert-butylbenzaldehyde.

b) Preparation of 3'-tert-butyl-4'-hydroxv-4benzvlidenetetrahvdro-2,2 .5,.5-tetramethvlfuran-3one This compound is obtained according to the operating method described in Example 12 in which Ithe 3' ,51-rbnyoy4bnyieeerhdo 2,.2,5,5-tetramethylfuran-3-one is replaced by 4'- 00 benzyloxy-3 '-tert-butyl-4-benzylidenetetrahydro- 2,2,5,5-tetramethylfuran-3-one. The product obtained has the following characteristics: melting point: 140 0

C

elemental analysis: C 19

H

2 ,0 3 C H 0 calc. 75.46 8.67 15.87 found 75.48 8.67 15.72 It UV spectrum (CH 2 C1 2 =337 rim Ii 4 19400 COMPOSITION EXAMPLES Example A Skin-protecting gel Compound of Example 1 0.12 g Polyacrylic acid crosslinked by a polyfunctional agent, sold under the brand name S"Carbopol 934" (Goodrich) 0.80 g Se- Glycerol 12.00 g S- Ethanol 15.00 g Preservative 0.20 g Fragrance 0.20 g Triethanolamine qs pH 5.3 Demineralized water qs 100 g The filter is dissolved in the ethanolglycerol mixture; the water, the preservative and the oo fragrance are added. The Carbopol 934 is dispersed in this aqueous phase in a homogeneous manner and the pH is adjusted to 5.3 with triethanolamine.

a o Example B 20 Example'A is reproduced, using the compound of Example 11 in place of the compound of Example 1, in the same proportions.

M

36 Example C Sunscreen oil The following ingredients are mixed, optionally heating to 40-45 0 C in order to homogenize the mixture: Compound of Example 2 0.60 g Benzoate of C 12

-C

15 fatty alcohols, sold under the brand name "Finsolv TN" (Finetex) 30.00 g S- Refined stabilized sunflower oil 20.00 g Fragrance 1.00 g Cyclic dimethylpolysiloxane, sold under the brand name "Volatile Silicone 7207" (Union Carbide) qs 100 g Example D W/0 sunscreen milk i 15 Compound of Example 3 0.25 g Benzylidenecamphor 2.00 g V Mixture of fatty acid esters, polyglycerols ated esters and silicone surfactants, sold i 4 11 under the brand name "Abil WS08" (Goldschmidt) 5.00 g S 20 White vaseline 2.00 g Beeswax 2.50 g Benzoate of C 12

-C

15 fatty alcohols, sold under the brand name "Finsolv TN" (Finetex) 19.00 g Glycerol 5.00 g Sodium chloride 2.00 g Fragrance 0.40 g 37 Preservative 0.20 g Demineralized water qs 100 g l This W/O emulsion is prepared firstly by i dissolving the filters in the glycerides and the i i i 5 emulsifier and heating this fatty phase to about 70-80 0 C, and secondly by heating the aqueous phase, I constituted by the water, the sodium chloride and the glycerol, to the same temperature. The aqueous phase is S' added to the fatty phase with brisk stirring, then the mixture is left to cool with moderate stirring and at about 40°C the fragrance and the preservative are added.

Example E Example D is reproduced, using the compound of Example 13 in place of the compound of Example 3, in the same proportions.

Example F O/W sunscreen milk j This O/W emulsion is prepared by firstly dissolving the filters in the glycerides at about 70-80 0 C, and secondly by heating the aqueous phase, constituted by the water, the propylene glycol and the emulsifier, to about 70-80°C. The fatty phase is added t:o the aqueous phase with brisk stirring, the mixture is left to cool with moderate stirring and at about fragrance and preservative are added.

-38 Compound of Example 4 1.50 g 2-Ethylhexyl-p-methoxycinnamate, sold under the brand name "Parsol. MCXI' 3.50 g 11 2-Hydroxy--4--methoxybenzophenone, sold under the brand name "Uvinul M 40"1 1.00 g -Cetyl alcohol 1.00 g 1 Oleocetyl alcohol containing 30 moles of ED, sold under the brand name "Mergital 0C30" 4 I(Henkel) 5.00 g 10 Stearyl alcohol 4.00g Synthetic oil of formula: 2.00 g CLSHiJC00CH -CH0H-CH 9 -CH H-C H 9 15 31 220 2 a 0~ 90: 10 mixture of ketostearyl 2 -ethyl hexano ate and isopropyl myristate, sold under the brand 0name "Ceramoll" (Cr~ations Aromatiques) 2.00 g -Vaseline oil 8.00 g -Propylene glycol 4.00 g -Preservative 0.20 g -Fragrance 0.40 g -Deiineralized water qs 100 g 39 Example G Sunscreen stick The various compounds are melted at about 70-75 C so as to obtain a liquid phase in which the filter is dissolved. This solution is poured into moulds and left to cool.

Compound of Example 5 1.00 g o o Ceresin wax 20.00 g S- Beeswax 7.00 g Oleyl alcohol 12.00 g Hydrogenated lanolin, sold under the brand I name "Hydrolan H" (Onyx Chemical) 8.00 g Lanolin oil, sold under the brand name "Argonol 60" (Westbrook Lanolin) 8.00 g S 15 Carnauba wax 1.00 g Benzoate of C 12

-C

1 s fatty alcohols, sold Sunder the brand name "Finsolv TN" (Finetex) 17.00 g Octamethylcyclotetrasiloxane, sold under the brand name "Abil K4" (Goldschmidt) 3.00 g S 20 Vaseline oil qs 100 g Example H Example G is reproduced, using 0.5 g of the compound of Example 9 in place of 1 g of the compound of Example *k Example I 01W sunscreen cream This emulsion is prepared in the same way as in Example D, excep that the trimethylanmoniia-4-[(2-oxo- 3-bornylidene)methyljphenyl methylsulphate is dissolved in tChe aqueous phase comprising the water, the sorbitol, the sodium lactate and the emulsifier: Compound of Example 6 0.50 g Trimethylarmmonium-4-[ (2-oxo-3-bornylidene) methyllphenyl methylsuiphate 4.00 g Sodium lactate 1.00 g Mixture of cetylstearyl alcohol and cetyl.stearyl alcohol ethoxylated with 33 moles of ethylene oxide, sold under the brand name "Sinnowax AO" (Henkel) 7.50 g -Mixture of xon-autoemulsifiable glycce.col mono- and distearate 2.10 g Cetyl alcohol 1.00 g Myristyl alcohol, sold under the brand name 0 020 "Sipol C1411 (Henkel) 0.60 g 70 sorbitol 3.00 g Isopropyl palmitate 10.00 g Vaseline oil 7.00 g Preservative 0.20 g Fragrance 0.60 g Deminerali; -i water qs 100 g 41 Example J Sunscreen cream The following ingredients are mixed, optionally heating them to 40-45°C to homogenize them: Compound of Example 10 0.20 g Benzoate of C1 2 -Cs fatty alcohols, sold under the brand name "Finsolv TN" (Finetex) 30.00 g Sunflower oil 20.00 g Fragrance 1.00 g 10 Cyclic dimethylpolysiloxane, sold under the brand name "Volatile Silicone 7207" (Union Carbide) qs 100 g Demonstration of the anti-oxidant properties of the compounds of the invention by the Rancimat test 000 S 15 A vitamin F (a natural product consisting of fatty acids having several double bonds, such as o' I linoleic acid and linolenic acid) composition containing 2.27 millimoles of anti-oxidant compound is heated in a. bath controlled at 100°C while bubbling air ooBo 20 through it at 30 ml/min.

The current of gas is led into a second receptacle containing water. The conductivity of this aqueous medium, which increases with the appearance of the secondary oxidation products resulting from the degradation of the hydroperoxides and aldehydes formed by oxidation, is monitored.

42 The measured induction time corresponds to the latency time observed before the exponential increase of conductivity. The higher the induction time, the greater is the anti-oxidant acitivity of the compound used.

For the compound of Example 3 this time is 138 min, for the compound of Example 5 the time is 62 min, and, lastly, for the compound of Example 8 it Soo is 96 min.

1 0 As a control, for the vitamin F compositiofn containing no anti-oxidant, the induction time is min.

0 0 o

C,

C, C, 0C u 0 f i i

Claims

1. Benzylidenecyclanone derivative, characterized in that it corresponds to the formula: R R 6 i i I X 7 R 0 R 0 in which: RI and R, which may be identical or different, 0 o represent a hydrogen atom, a hydroxyl radical, a Ci-Cg linear or branched alkyl residue or a Ci-C 8 linear or branched alkoxy residue, with the reservation that at Sleast one of the radicals R, and R is other than a a hydrogen atom, R 2 and R 3 which may be identical or different, represent a hydrogen atom or a hydroxyl radical, it being understood that one at least of the radicals R 2 00 0 and R 3 represents a hydroxyl radical, R 4 R 5 R s and R 7 which may be identical or different, represent a Cl-Ci, linear or branched alkyl residue, an aralkyl residue such as benzyl which may be unsubstituted or substituted by a C 1 -C 4 alkyl or CI-C 4 alkoxy residue, an aryl residue such as phenyl which is unsubstituted or substituted by a C,-C 4 alkyl residue; the substituents R 4 and Rs and/or the substituents Rg I 4 1 o o0 1 n O 0 44 and R 7 can form, with the carbon atom of the ring to which they are attached, a saturated ring containing from 5 to 12 carbon atoms which is unsubstituted or substituted by one or more linear or branched alkyl residues, X represents a CHt-- radical in which n 1 or 2, or a radical in which R. represents a hydrogen atom, a linear or branched alkyl residue, an aralkyl residue such as benzyl which is unsubstituted or substituted by a CI-C 4 alkyl or C.-C 4 alkoxy residue, a hydroxyl radical, a residue in which P. represents a Cj-C 8 linear or branched alkyl residue, or alternatively X represents an oxygen atom or a sulphur atom.

2. Compound according to Claim 1, characterized in that it is chosen from 3',51-di-tert-butyl-.4'- hydroxy-4-benzylidenetetrahydro-2,2,5,5- tetramethylfuran-3-one, 3',5'-di-tert-butyl-2'- hydroxy-4-benzylidenetetrahydro-2 tetramethylfuran-3-one, 3',5'-di-tert-butyl-4'- hydroxy-4-benzylidenetetrahydro-2 ,2,5,5- tetraethylfuran-3-one, 3',5'-di-tert-butyl-4'-hydroxy-

4-benzylidenetetrahydro-2 furan-3-one, 3',5'-dimethyl-4' -hydroxy-4- benzylidenetetrahydro-2 ,2,5,5-tetramethylfuran-3-one, 3',5'-dimethoxy-4 '-hydxoxy-4-benzylidenetetrahydro- 2,2,5, 5-tetramethylfuran-3-one, 3' -tert-butyl-2' i 3 i 3 i i o CC 00 0) c0"", '-methoxy-4-benzylidenetetrahydro-2, 2,5,5- tetramethylfuran-3-one, 3 '-tert-butyl-2 '-hydroxy-5 methyl-4-benzylidenetetrahydro-2, 2,5,5- tetramethylfuran-3-one, -di-tert-butyl-4 hydroxy-4-benzylidenetetrahydro-2, 5-dimethyl-2, tert-butylfuran--3-one, -di-tert-butyl-4 '-hydroxy- 4-benzylidenetetrahydro-2, 5-diethyl-2 3-one, 5' -diisopropyl-4 '-hydroxy-4- benzylidenetetrahydro-2 ,2 ,5,5-tetramethylfuran-3-one, 3'1,5 -di-tert-butyl-4'-hydroxy-4-benzylidene-2,2,5,5- tetramethylazacyclopentan-3-one, 3' 4' -hydroxy-2-benzylidene-3, 3,5,5- tetramethylcyclopentan-1-one, 31,41,5w -trihydroxy-4- V benzylidenetetrahydro-2, 2,5, 5-tetramethylfuran-3-one and 3'-tert-butyl-4'-hydroxy-4-benzylidenetetrahydro- 2,2,5, 5-tetramethylfu: .an-3-one. 3. Process for the preparation of the compound V of formula according to Claim 1 or 2, characterized in that it consists in condensing an aromatic aldehyde of formula: R R 1

46- in which R, R 1 R 2 and R 3 have the meanings indicated in Claim 1, with a cyclanone of formula: R R-- 1 4 in which R 4 Rs, R 6 R 7 and X have the meanings indicated in Claim 1. ii 4. Process according to Claim 3, characterized in that the aromatic aldehyde of formula (II) carries a a OH function protected by a tri(C,-C 6 alkyl)silyl or benzyl radical and in that condensation is followed by Sa detaching the trialkylsilyloxy or benzyloxy radical in order to liberate the OH function. Process according to Claim 3 or 4, characterized in that the condensation of the aldehyde of formula (II) with the cyclanone (III) is carried out in the presence of an alkali metal alcoholate, in a solvent, at a temperature of between 73 0 C and the boiling point of the solvent. 6. Process according to Claim 3 or 4, characterized in that the condensation of the aldehyde of formula (II) with the cyclanone (III) is carried out 47 in the presence of an inorganic base, in a solvent, at a temperature between ambient temperature and the boiling point of the reaction mixture. 7. Process according to Claim 3 or 4, characterized in that the condensation of the aldehyde of formula (II) with the cyclanone (III) is carried out in the presence of a borane of formula: R 00 o o 1 o B 0 C R S0 (IV) C(b 11 in which R 1 0 represents a C 1 alkyl residue and R n 1 00.. represents a Cl-C 4 alkyl residue, at a temperature of about 150"C, without a solvent. 8. Cosmetic composition, characterized in that it contains an effective quantity of at least one S' compound of formula according to Claim 1 or 2, in a i cosmetically acceptable support containing at least one i fatty phase. 9. Cosmetic composition according to Claim 8, characterized in that it contains as compound at least one of the compounds chosen from: butyl-4'-hydroxy-4-benzylidenetetrahydro-2,2,5,5- tetramethylfuran-3-one, 3',5'-di-tert-butyl-2'- ft LI it 48 hydroxy-4-benzylidenetetrahydro-2, 2, 5,5 tetramethyl furan-3 -one, -di-tert-buty.-4 hydroxy-4-benzylidenetetrahydro-2, 2,5,5- tetraethylfuran-3-one, 31,5 '-di-tert-butyl- .'-hycdroxy- 4-benzylidenetetrahyd-ro-2, 2,5,5 -bis (pent amethyJ e ne) furan-3-one, 31'5 '-dimethyl-4 '-hydroxy-4- benzylidenetetrahydro-2, 2, 5, 5-tatramethylf uran-3 -one, 5' -dimethoxy-4 I -hydroxy-4-benzylidenetetrahydro- 2,2,5, 5-tetra-methylfuran-3-one, 3' -tert--butyl-2 '-methoxy-4-benzylidenetetrahydro-2, 2,5,5- tetramethylfuran-3-one, 3' -tert-butyl-2' -hydroxy-5' methyl-4-benzylidenetetrahydro-2, 2,5,5- tetramethylf uran- 3-one, 3',5 '-di--tert-butyl-4 hydroxy-4-benzylidenetetrahydro-2, 5-diinethyl-2, tert-butylf uran- 3-one, 3',5 '-di-tert-butyl-4 '-hydroxy- 4-benzylidenetetrahydro-2, 5-diethyl-2, 3-one, 3' -diisopropyl-4' -hydroxy-4- benzylidenetetrahydro- 2, 2, 5, 5 -tetramethyl furan- 3-one, 3 5 '-di--tert-butyl-4 '-hydroxy-4-benzylidene-2 ,2,5,5- tetramethylazacyclopentan-3 -one, 3' -di-tert-butyl- 4' -hydroxy-2-benzylidene-3, 3,5,5- tetramethylcyc lopentan- I-one, 3 4 5' -trihydroxy-4- 'benzylidenetetrahyciro- 2, 2, 5, 5-tetramethyl furan-3 -one and 3' -tert-butyl-4' -hydroxy-4-benzylidenetetrahydro- 2,2,5, 5-tetraniethylfuran-3-one. Cosmetic composition according to Claim 8 or 9, characterized in that it is presented in the form n j go g K -e II~- of an oily or oily-alcoholic lotion, an emulsion, an oily-alcoholic, alcoholic or water- alcoholic gel, a solid stick or an aerosol. 11. Cosmetic composition according to claim 10, characterized in that it contains in addition cosmetic additives chosen from thickeners, emollients, humectants, surfactants, preservatives, anti-foams, fragrances, oils, waxes, lanolin, lower monoalcohols and lower polyols, propellants, colourings and pigments. 12. Cosmetic composition according to claim 10 or 11, characterized in that it constitutes a composition which protects the human epidermis and contains 0.1 to 2% by weight of compound of formula 13. Cosmetic composition according to claim 10 or 11, presented in the form of a sunscreen composition, characterized in that. it contains 0.2 to 15% by weight of compound of formula 14. Sunscreen cosmetic composition according to claim 13, characterized in that it contains in addition a further ingredient selected from the group UV-B and UV-A filters. Cosmetic composition according to claim 8 or 9, intended to be applied on the hair, characterized in that it is presented in the form of a shampoo, a lotion, a rinsable gel or emulsion, a styling or treatment lotion or gel, a lotion or gel for blow- drying or setting, hair lacquer, permanent-waving or bleaching or colouring composition, and contains 0.25 to 2% by weight of compound of formula 16. Cosmetic composition according to claim 8 or 9, characterized in that it consists of a haircare composition, a make-up product or a composition for the care or treatment of the skin, containing 0.1 to 2% by weight of compound of formula 17. Process for protecting the skin and natural or sensitized hair from ultraviolet radiation, characterized in that it consists in applying on the skin or the hair an effective quantity of a cosmetic composition containing at least one benzylidenecycla- none derivative of formula according to claim 1 or 2. 18. Process for protecting a cosmetic composition against ultraviolet rays and oxidation, characterized in that it consists in incorporating an effective quantity of at least one compound of formula in this composition. 1 9. Use of at least one compound of formula according to claim 1 or 2 as an anti-oxidant. Use of at least one compound of formula according to claim 1 or 2 as a cosmetic product. S 21. Use of at least one compound of formula according to claim 1 or 2 as a wide-band sunscreen absorbing in the wavelength raige between 280 and 380 nm. 22. Compound of formula according to claim 1 or 2 in respect of its use as a medicament. 23. Compound of formula according to claim 1 or 2 in respect of its use in the treatment of inflammations and allergies of the skin. i S24. Compound of formula according to claim 1 or 2 in respect of its use in Sthe prevention of certain cancers. Pharmaceutical composition, characterized in that it contains an effective quantity of at least one compound of formula according to claim 1 or 2, in a non-toxic support or excipient. 26. Pharmaceutical composition intended to be administered topically, presented in the form of a cream, a salve, an ointment, a solution, a gel, a lotion, a spray or a suspension, characterized in that it contains at least one compound of formula (I) according to claim 1 or 2, together with a pharmaceutically acceptable carrier. 27. Pharmaceutical composition intended to be administered orally in the form of tablets, capsules, dragees, syrups, suspensions, solutions or emulsions, characterized in that it contains at least one compound of formula according to claim 1 or 2, A together with a pharmaceutically acceptable carrier. 'I *1 I 51 28. Pharmaceutical composition according to claim 26, characterized in that it contains the active compound of formula in proportions of between 0.25 and 4% by weight with respect to the total weight of the composition. 29. Pharmaceutical composition a,.cording to claim 27, characterized in that the active compound of formula is administered at doses of between 0.1 and mg/kg/day. Use of a compound of formula according to claim 1 or 2 when used in the preparation of a medicament intended for the treatment of inflammations and allergies of the skin. 31. Use of a compound of formula according to claim 1 or 2 when used in the preparation of a medicament intended for the preventive treatment of certain cancers. DATED this 20th day of August 1992. 0l SI 6 6 0 G o S U a o 6 D ao e L'OREAL WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA <J 0 ri 0 0 0 0 6