LU86937A1 - NOVEL UNSATURATED UV-ABSORBING CHROMOPHORE COMPOUNDS, THEIR PREPARATION AND THEIR USE FOR THE PRODUCTION OF ANTI-SOLAR POLYMERS - Google Patents

Description

L-3177

* 0 0 '1 0ΚΛΝΙ>' υ1 "-’HÉDE LL'XEMBOLRG

Br \ et N Minister of July 3 .198.7 of the Economy and the Middle Classes _ ttfÎixl Intellectual Property Service

Title issued ..........- -.......- | Luxembourg is.y? Patent Application ............_............................... ......_........................................... .......__.............................._........... ut ^ I. Request

Société Anonyme known as: L’OREAL / 14 ...... rue Royale / F-75008 paris, (2) represented by Mr. Jean Waxweiler, 55 rue des Bruyères, Howald, acting as agent

- ................ ..... ........ ........... ......... ....... ............ .....-......................... ... - ............... .............................. ( 3d

deposited on July 3, one thousand nine hundred and eighty-seven .......... ........ {4) at 15/0 0 hours, at the Ministry of the Economy and the Middle Classes , in Luxembourg: 1. this request for obtaining a patent for an invention concerning:

New ..... compounds ..... unsaturated ..... chromophore ..... UV absorber. ... (5) their preparation ..... and their ....... use ...... for the realization of .............

anti-solar polymers ........................................... .................................................. ............... ^ 2. description in language ............... fr ançaise - - .. of the invention in triplicate : 3. ............ / .................................. ........ drawing boards, in triplicate; 4. the receipt of the taxes paid to the Luxembourg Registration Office, on the .............. 03.07.19 87 ..............; 5. the delegation of power, dated ........... i *. ET.: K§ ...................... ..................................... on .......... 02.07. 1987 ...........

6. the successor document (authorization): declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): (6)

Claudine LAPOIRIERE, 3 ...... rue de 1 Viser, ...... Fr9.4170 Le Perreux .....

ClauobMAHIEU, 90Avenue de Villiers, F-75017 Paris

Christos PAPANTONIOU, 17 rue des Basserons, F-95160 Montmorency claims) nt) for the above-mentioned patent application the priority of one (s) application (s) of (7) ............ ....... — ................ f .....-.............-_____________________________________________________________________ filed in (8) _______ j .............................. ...... ..... ..... ............................................

on (9) / ____________________________________________________________________________________________________________________________________________________________________________-........................................... .............. -................................... .............

under N ° (10) ........ J .................................. .................................................. .................................................. ............ .................................

on behalf of (11) ..... / ............... .................. ..... ......................... ......................... .................................................. .........................

elect) home for him and her. if appointed, for its representative, in Luxembourg ......................................... ...................

55 ....... rue des Bruyères, Howald ------------------------------------- -.....................__........................... .......... .................................... (12) requests (nt) the granting of a patent for the invention for the subject described and represented in the abovementioned appendices, with postponement of this grant to / d __________________ 18 ...... ...... ... ............. .......... months. (13)

The (| ggg§ax / agent: \ ........... _ ................ (14)

Vi Π. Deposit Minutes

The above application for a patent for invention has been filed with the Ministry of the Economy and the Middle Classes, Intellectual Property Service in Luxembourg, on: 03.07.1987 ^ **** ^ s'v VA Pr. Minister of the Economy and the Middle Classes, at 3 p.m. / * ^ \ jjnd.

I ï - I The head of the intellectual property department, v / a asikt »r Ot? 1 / y *. -s f ------- \ J1 _ / ____ S_______ f / r C. RELATIVE EXPLANATIONS Alj /; r '"* Misi'VeiieL Request- of the certificate d vy. to the patent application orimiPè! \ c> ....... / of ........... ,, - {2) mscnrt the name first name, proîes ^ mz.

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1, ♦ L -3177 \.

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DESCRIPTIVE MEMORY FILED IN SUPPORT OF A PATENT INVENTION APPLICATION IN THE GRAND DUCHY OF LUXEMBOURG

Société Anonyme known as: L'OREAL 14, rue Royale F-75008 Paris

New unsaturated compounds with UV absorbing chromophore. their preparation and their use for the production of anti-solar polymers * - "r * f -1- i

The present invention relates to new unsaturated compounds with a chromophore that absorbs ultraviolet radiation (UV).

These new unsaturated compounds are easily polymerizable and can therefore be used in the preparation of polymers having anti-sun properties, these being particularly suitable for the production of cosmetic compositions intended to protect the skin against the harmful effects of the sun.

It is known in fact that ultraviolet radiation having a wavelength between 280 and 350nm approximately are capable of OJ causing inflammation or erythema of the skin when the human body is subjected to solar radiation without special protection.

We also know that ultraviolet radiation with a wavelength of 315 to 400nm are essentially responsible for tanning.

j5 However, there are sensitive skins which do not tolerate exposure to UV radiation whatever the wavelength. As a result, a complete series of so-called "filter" compounds is required to meet the demand for protection of the human body depending on the nature of the skin.

2Q In this regard, various substances have already been proposed such as, for example, benzylidene-3 dl camphor as well as anti-sun polymers.

In French patents ne73.23254 and 76.23174, it has been recommended in particular to use sunscreen polymers obtained by covalent attachment of an organic compound known for its properties of absorption of ultraviolet radiation on a polymer.

It has also been proposed to use sunscreen polymers obtained by polymerization of monomers with a UV absorbing chromophore.

The use of anti-solar polymers compared to 2q organic compounds absorbing ultraviolet radiation has the advantage of reducing or even eliminating any penetration into the body by crossing the epidermis.

Until now, it has not been possible to develop anti-sun polymers with high specific absorbance (as) since the monomers with U.V absorbing chromophore used have a high molar mass.

It is indeed appropriate that the anti-sun cosmetic compositions can provide good protection without, however, that they contain a high concentration of anti-sun polymers.

BSB / BC / BR.75981 i * »-2-

In fact, too high a concentration of sunscreen polymers is capable of imparting undesirable cosmetic effects to the compositions.

The present invention makes it possible to remedy the drawbacks mentioned above in so far as it is proposed as "filter monomers" of new unsaturated compounds with UV absorbing chromophore having a low molar mass.

The subject of the present invention is therefore new unsaturated compounds with a UV absorbing chromophore having the following formula: 10 Rj R2 CH - C - (Z) - C - CH - CH - // \\ _- r 2 'R nay = (3 R, R,] 5 in which: ·> α n is 0 or 1 when n = 0, R represents a hydrogen atom when n = 1, R represents a hydrogen atom or a methyl radical Z represents a divalent radical taken from the group consisting of: (i) - C - NH - 20 0 (ii) - C - NH - CH0 - l \ 2 0 (iii) - C - NH - CH - \ l 1 0 ch3 25 (iv) - C - NH - CH - 1 \ l 0? H2 ^ CH \ CH3 CH3 30 (v) - C - NH - CH- ni 0 ch2 C6H5 35 f «3 and (vi) - C - NH - C - CH „- U 1 2 o ch3

Rj, R2, R3, R ^ and R ^, identical or different, represent a hydrogen atom, a linear or branched alkyl radical BSB / BC / BR.75981 i (.

-3- having from 1 to 8 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, a dialkylamino or dialkylaminoalkyl radical of formula:

- <cVm - K

5 ^ * 6 in which m is 1 to 3 and represents a methyl or ethyl radical, said radicals being optionally quaternized using a quaternizing agent taken from the group consisting of methyl chloride, dodecyl bromide, dimethyl sulfate and chloroacetic acid.

Among the particularly preferred compounds of formula (I) mention may be made in particular of those having the following meanings: R n 2 R1 R2 R3 R4 R5

HO - H H H HH

fH3

H 1 -C-NH-C -CH - H H H HH

Il I 2 o ch3 20 ÇH3

H 1 -C-NH-C -CH, - H H CH, HH

He I 2 3 0 ch3

CH

H 1 -C-NH-C -CH - H 0CH3 0C4H9 H H

Il I 2 25 0 CH3

/ ^ 3 H

H 1 -C-NH-C -CH, - H H -N H

Ü 2 f3

H 1 -C-NH-C -CH - H H. “N —- CH3 H H

30 II V 2 \ „„ O CH3 x ch3 S0aÔCH3 CH, I 3

H 1 -C-NH-C -CH, - H H OCH, H H

Il I 2 3 0 CH, 35 3

The present invention also relates to the process for the preparation of the compounds of formula (I), the latter being carried out according to the 40 conditions of the Claisen-Schmidt reaction by condensation of an aromatic aldehyde such as benzaldehyde or one of its substituted derivatives (_1) RRR / RP / RB 7ÇQR1 a ”.

-4- with a ketone derivative (2) in an alkaline medium, preferably in the presence of soda in hydroethanolic solution.

This reaction can be represented by the following reaction scheme: R2 R.

\ _ / NaOH

// \? (EtOH) r (/ VS— C = 0 + CH = C - (Z) -C - CH. ->

3 2 1 BS 3 -V

10 ® CH2 "f- (Z) n 'fl' C" 'CH— \ \ -R3 (I) 15 RO \ - / / “Λ

Among the aromatic aldehydes of formula (1), mention may in particular be made of benzaldehyde, 4-methylbenzaldehyde, 3-methoxy-4-butoxy-benzaldehyde, 4-dimethylamino benzaldehyde, 4-butoxy-benzaldehyde, 3-dimethoxy, 4 benzaldehyde, 4-ethoxy benzaldehyde, 2-methoxy-4-diethylamino benzaldehyde, ditertiobutyl-3,5-4-ethoxy-benzaldehyde and 4-methoxy-benzaldehyde.

Among the ketone derivatives of formula (2), mention may in particular be made of methylvinylketone, N- £ 2-methyl-oxo-4j 2-pentylacrylamide (or diacetone acrylamide), N- j ^ oxo-2 ^ j propyl- 1 acrylamide, N- £ methyl-1 oxo-Jj butyl-2 acrylamide, N- | ^ methyl-5 oxo-Tj hexyl-3 acrylamide, N-Qphenyl-1 oxo-3] butyl-2 acrylamide.

The present invention also relates to sunscreen polymers obtained by polymerization of the filter monomers of formula (I).

These polymers are characterized by the fact that they consist of units of the following formula: BSB / BC / BR.75981 * 1 -5- R - Γ i - CH2- c - 5 L <Z> „- * R , \ _ / h - CH * CH - (/ y- Rj

H

10 R5 R4 in which: n, R, Z, and have the same meanings as those given above.

It goes without saying that the polymers according to the invention can consist of other units resulting from formula (I) as well as units resulting from polymerizable monomers such as for example: (a) acrylic or methacrylic acid (b ) acrylic or methacrylic esters of formula: 20 CH2 “f - C00R7

R

in which: R represents a hydrogen atom or the methyl radical, and R ^ represents an alkyl radical having from 1 to 18 carbon atoms, ^ (c) the unsaturated amides or esters of formula: / Rß CH = Ç - CO (X) - (CHJ - N 2 | 2 mv R XR, 6 in which: R represents a hydrogen atom or the methyl radical, X is -NH- or -0-m is 2 or 3 and Rg is a radical methyl or ethyl, and (d) the acrylamides or methacrylamides of formula: 35 / R8

CH „= C - CON

2 1 \ R \ R8 in which: R and Rg represent a hydrogen atom or the methyl radical.

(e) UV-absorbing acrylamides or methacrylamides of general formula: 40 * i.

-6-

CH_ = C-CO-NH-Y

2 I

R

where R represents a hydrogen atom or the methyl radical and Y represents an aromatic group conferring on the monomer an absorption of the ultraviolet in the zone of wavelengths which can range from 280 to 400 nm.

Among the monomers of this type, mention may in particular be made of those described in French patents 73,23254 (2,237,912) and 76.23174 (2,359,857).

The polymerization reaction can be carried out according to conventional methods, that is to say by mass, in solution, in suspension or in emulsion using a polymerization initiator. Preferably the polymerization reaction is carried out in solution or in suspension.

The polymerization initiators are generally conventional radical polymerization initiators. Among the various initiators which can be used, mention may in particular be made of peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, benzoyl hydroperoxide, hydrogen peroxide, initiators such as azobisisobutyronitrile, redox initiation systems such as sodium persulfate or sodium bisulfite 2q or else the redox system consisting of the hydrogen peroxide-ascorbic acid pair. The concentration of the initiator is generally between 0.2 and 35% and preferably between 0.5 and 20% by weight relative to the total weight of the monomer.

The molecular weight of the polymer can be adjusted by all known methods, for example by polymerization in dilute solution, by polymerization in the presence of large quantities of initiators or by the introduction of chain regulating agents.

The molar mass of the polymers is generally between 1,000 and 50,000 and preferably between 2,000 and 20,000.

2Q The present invention also relates to cosmetic compositions for protection against ultraviolet radiation containing as active ingredients at least one sunscreen polymer as defined above.

These compositions can be in the form of aqueous or hydroalcoholic solutions, oily solutions or emulsions or also in the form of sticks. They can also be incorporated in combination with a propellant and constitute compositions in the form of aerosols.

The cosmetic compositions according to the invention may also contain various adjuvants usually present in anti-sun cosmetic compositions, namely moisturizers, emollients or BSB / BC / BR.75981 4 -7- thickeners, surfactants, agents of conservation, perfumes or pigments.

The concentration of sunscreen polymers in the compositions according to the invention is generally between 0.2 and 20% by weight relative to 2 of the total weight of the composition.

Absorbance is defined by the term "specific absorbance" (ag) defined by French standard T.01030 (January 1972) linked to Ksp by the relation:

Ksp 10 - = 1000 a s

According to the present application, the absorbance is expressed by means of the specific absorbance.

We will now give by way of illustration and without any jç. limiting character several examples of unsaturated compounds with UV absorbing chromophore as well as several examples of sunscreen polymers. EXAMPLE 1

Preparation of 2-methyl-2-oxo-4 (4-methylphenyl) -6 hexene-5 yl-2 ~ | acrylamide.

20, f * 3 (Compound of formula (I) in which n = l, Z = -C-NH-C-CH -, 8 L3 R = RX = R2 = R4 = R5 = H and R3 = -CHg).

30 g of sodium hydroxide 2 d are introduced into a 1 liter flask. dissolved in 100g of water and 50g of ethanol, the whole being kept at a temperature below 10 ° C. 42.2 g (0.25 mol) of acrylamide diacetone are then introduced, with stirring, at the same temperature. After dissolution of the acrylamide diacetone, a solution of 30.6 g (0.25 mol) of 4-methylbenzaldehyde (purity about 98%) is introduced in solution in 3q 100g of ethanol. The reaction mixture is kept under stirring for 3 hours at the same temperature, then the mixture is allowed to return to 20 ° C. and stirring continues for 1 hour. The expected product insoluble in the reaction medium precipitates.

After filtration, wash thoroughly with water until the washings are neutral and dry under reduced pressure. 61 g of the expected compound are obtained. Melting point = 96 ° C.

Thin layer chromatography (C.C.M.): on Kieselgel Merck 60 F 254, eluent: cyclohexane / ethyl acetate: 1/1, developer: iodine and U.V., a single spot at R ^ = 0.50.

ucn / RP / nw 7ςθΑ1 -8-

Elementary analysis: C H N 0 calculated: 75.3 7.75 5.15 11.8 found: 75.5 7.6 5.20 11.7

UV spectrum: | \ max = 305nm a = 92 (at 1 mg / 100 ml 5 in CHC1_).

3 1

NMR spectrum of H: in agreement with the expected structure.

EXAMPLE 2

Preparation of N- ^ methyl-2 oxo-4 phenyl-6 hexene-5 yl-2 ~ j acrylamide.

CH „\ 3 (Compound of formula (I) in which n = l, Z ^ C-NH-C-CH ^ -, io ä ch3 and R = R ^ = R2 = R ^ = R ^ - R ^ = H ) ·

According to the same procedure as that described in Example 1, 42.2 g of diacetone acrylamide are reacted with 25 g of distilled benzaldehyde, previously dissolved in 50 g of ethanol in the presence of 30 g of NaOH in solution in 100 g of water. The temperature is maintained at 10 ° C for 1 hour and then allowed to rise to 20 ° C for 2 hours.

The reaction mixture is then poured into 500 g of ice water and the supernatant phase is extracted 3 times with 50 ml of chloroform and then washed with water until neutral.

After removal of the chloroform on a rotary evaporator, 64 g of a yellow oil are obtained.

C.C.M. under the conditions of Example 1: R ^ = 0.60 Elementary analysis: C H N 0

Calculated: 74.7 7.39 5.45 12.45 25 Found: 74.1 7.0 5.0 14.0

U.V spectrum,: max = 293nm ag = 78 (at lmg / lOOml in chci3).

EXAMPLE 3

Preparation of 2-methyl-2-oxo-4 (3-methoxy-4-butoxyphenyl) -6 hexene-5 yl-0 acrylamide.

CH-I 3 (Compound of formula (I) in which n = l, Z = -C-NH-C- CH ^ -, 0 ch3 R = Rx = R4 = R5 = H, R2 = -0CH3 and Rß = - 0C4Hg).

According to the same procedure as that described in Example 1, 42.2 g of diacetone acrylamide are reacted with 52 g of 3-methoxy-4-butoxy-benzaldehyde previously dissolved in 100 g of ethanol, in the presence of 30 g of NaOH in solution in 100g of ice water and 50g of ethanol.

The temperature is maintained at 10 ° C for 1 hour and then allowed to rise to 20 ° C for 4 hours. The reaction mixture is neutralized BSB / BC / BR.75981 -9- with 4N hydrochloric acid, maintaining the temperature at 20 ° C. and then 200 ml of water are added thereto. It is extracted with dichloroethane (3x150ml), then washed with water until neutral.

The 1,2-dichloroethane is removed on a rotary evaporator and then the yellow oily residue is taken up in 100 ml of diethyl ether and precipitated with 400 ml of petroleum ether. After a further precipitation, 62 g of the expected compound are obtained: Melting point 77-78 ° C.

C.C.M under the conditions of Example 1: = 0.40

Elementary analysis: C H N 0 10 Calculated: 70.2 8.1 3.9 17.8

Found: 70.15 8.1 3.85 18.0

UV spectrum: A max = 340nm a = 57 (at lmg / 100ml in the s CHC1).

D 1

NMR spectrum at H: in agreement with the expected structure.

15 EXAMPLE 4 1st step. Preparation of N-methyl-2 oxo-4 (4-dimethylamino) 6-phenylhexene-5 yl-2 acrylamide.

CtL 1 3 (Compound of formula (I) in which: n = l, Z = -C - NH - C - CH „- ll 1 ^ 20 O CH3 E = R, = R, = K, = R.-H and R, - -N / CH3).

1 2 4 5 3 "-CHj To a solution of 120g of sodium hydroxide in 400g of water is introduced at 10 ° C, 169g of diacetone acrylamide in solution in 200g of ethanol, 300g of ethanol and 149g of N, N -dimethylamino-4-benzaldehyde. The reaction medium is stirred for 1 h at a temperature below 10 ° C., then allowed to rise to ambient temperature for 4 h, still with stirring. A yellow precipitate is formed. Poured into a solution hydrochloric acid (about 300 g of 33% HCl solution), ensuring that the medium remains well alkaline, filtered and washed with water to obtain 200 g of crude product, which is recrystallized from a mixture of 700 ml of methanol and 450 ml of water to obtain 173 g of product which is used as it is in the next step.

2nd step. Preparation of N-j methyl sulfate ~ 2-methyl-oxo-4 35 (4-trimethylammonio phenyl) -6 hexene-5 yl-2] acrylamide.

CH-I 3 (Compound of formula (I) in which: n = 1, Z = -C-NH-C-CH ^ - o ch3 ô l 3 q 40 R = R. = R = R. = R = H and R. a -N CH „SO. CH.) 1245 3 | 3 4 3 CH3 BSB / BC / BR.75981 -10- To a solution of 153g (0.51mole) of the compound prepared in the 1st step in 850g of acetonitrile maintained at 60 ° C is added dropwise 71g (0, 56 mol) of dimethyl sulfate. After the end of the addition, the reaction mixture is brought to reflux for two hours. After the end of the reaction, the reaction mixture is concentrated and the oily residue is dispersed in 3 liters of methylene chloride. The precipitate obtained is collected after spinning on sintered glass and then recrystallized from 400ml of acetonitrile. After filtration and cooling the expected product crystallizes. It is filtered and then washed twice with methylene chloride and dried. 138 g of methyl sulfate are obtained (yield: 64%).

Melting point: 100 ° C.

Thin layer chromatography: on silica gel, solvent: water, eluent cyclohexane / ethyl acetate: 1/1, developer: iodine and UV. Main product Rf = 0, starting product (~ 1%) Rf = 0.35.

15 Elementary analysis: C H N 0 S

Calculated: 56.34 7.28 6.57 22.53 7.51

Found: 56.28 7.35 6.57 22.31 7.42

UV spectrum: (\ max = 285nm a = 49 (at lmg / 100ml in water).

S

EXAMPLE 5 Preparation of N- ^ ethyl-2 oxo-4 (4-methoxyphenyl) -6 hexene-5 and 1-2 ^] acrylamide.

CH0 1 3 (Compound of formula (I) in which: n = l Z = -C - NH - Ç - CH ^ -, l0 ch3 25 R = Rx = R2 = R4 = R5 = H and R3 = -0CH3).

200 g of water, 100 g of ethanol and 60 g of sodium hydroxide pellets are introduced into a reactor while maintaining the temperature at 10 ° C. After dissolution, 84.5 g (0.5 mol) of acrylamide diacetone are added in portions. A solution of 68 g (0.5 mol) of anisaldehyde in 3 × 100 g of ethanol is then added dropwise. The reaction mixture is kept for 2 hours at 10 ° C. and then at room temperature for 2 hours. After the end of the reaction, the white precipitate formed is filtered and then washed with water until neutral. After drying, 132 g of product are obtained which is recrystallized from a mixture of 260 g of ethanol and 900 g of hexane.

After filtration and drying, 108 g of expected pure product are obtained (yield: 75%).

Melting point: 107 ° C.

Thin layer chromatography: on silica gel, solvent: chloroform, eluent: cyclohexane / ethyl acetate: 1/1, developer: iodine and 40 U.V, a single spot at Rf: 0.50.

BSB / BC / BR.75981 r “-11-

UV spectrum: \ max = 325nm a = 98 (at lmg / 100ml in

S

CHC13).

EXAMPLE 6

Preparation of the homopolymer of the monomer described in Example 2.

5 50 g of the compound obtained in Example 2, 100 g of isopropanol, 2.5 g of dodecanethiol and a solution of 10 g of ascorbic acid in 50 g of water are introduced into a 500 cc reactor. The mixture is brought to 80 ° C. and then a 40 g solution of water and 37.5 g of 30% hydrogen peroxide solution is introduced therein at a constant flow rate in 40 minutes. The polymerization is continued for 6 hours. After cooling, the polymer deposited at the bottom of the reactor is collected, then dissolved in 15 g of dichloromethane and washed with water. After separation of the organic layers, 350 g of isopropyl ether are added thereto and the dichloromethane is removed at 70 ° C. under ordinary pressure. The precipitated polymer is collected and dried. 18 g of expected homopolymer are obtained.

C.C.M. : on Kieselgel Merck 60 F 254, solvent CHCl ^ eluting ethyl acetate / cyclohexane = 2/1.

Polymer R ^ = 0; absence of residual monomer.

U.V. spectrum: (\ max = 295nm ag = 43 (at 1 mg / 100 ml in 20 CHC13).

EXAMPLE 7

Preparation of the homopolymer of the monomer prepared according to Example 1.

According to the same procedure as that described in Example 6, 25g of pure homopolymer is obtained from 50g of the compound obtained in Example 1.

C.C.M,: on Kieselgel Merck 60 F 254, solvent: CHCl ^, eluent: ethyl ether / ethyl acetate = 2/1.

Polymer Rf = 0; absence of residual monomer

U.V. spectrum: Amax = 305nm a = 48 (lmg / lOOml in the

S

30 CHC13).

EXAMPLE 8

Preparation of the homopolymer of the monomer prepared according to Example 3.

50g of the compound obtained according to Example 3, 100g of isopropanol and 7.5g of 30% hydrogen peroxide solution are introduced into a 500 cc reactor. The mixture is heated to 80 ° C. and then a solution of 5g of ascorbic acid in 100g of water is introduced into it at a constant flow rate for 3 hours. The polymerization is continued for 7 hours and then allowed to cool. The polymer collected is dissolved in 150 g of dichloromethane and then 350 g of isopropyl ether are added thereto. The dichloromethane is removed 40 to 70 ° C under ordinary pressure and the precipitated polymer is collected and dried. 31 g of pure homopolymer are thus obtained.

BSR / Rr / RR_7SQfi1 »m -12- C.C.M. : on Kieselgel Merck 60 F 254, solvent CHCl ^ eluting cyclohexane / ethyl acetate 1/1,

Polymer: R ^ = 0; absence of residual monomer.

UV spectrum: max = 340nm a = 33 (at lmg / lOOml in

S

5 CHC13).

EXAMPLE 9

Preparation of the homopolymer of the monomer prepared according to the 2nd step of Example 4.

10g of monomer prepared according to the second step of Example 4, 40g of water and then a solution of 4g of ascorbic acid in 20g of water are introduced into a 250ml reactor fitted with a dropping funnel. The mixture is heated with stirring to 90 ° C. then 15 g of a 30% solution of hydrogen peroxide diluted with 6 g of water are regularly introduced over 1 hour. After the end of the addition, the reaction is continued for 4 hours.

The crude reaction mixture is concentrated until a syrupy solution is obtained, then this is dispersed in 500 ml of ethanol.

The polymer is collected by filtration and then dried. 10 g of expected homopolymer are thus obtained.

C.C.M: on silica RP2 impregnated with 0.5% Na lauryl sulfate in 20 methanol-water * 80/20, solvent: water, eluent 0.5% Na lauryl sulfate, methanol / water = 80/20, developer: iodine.

Polymer R ^ = 0 starting monomer (££ 1%) R ^ = 0.55.

UV spectrum: <\ max = 285nm a = 16.5 (at lmg / 100ml in

S

H20).

25 EXAMPLE 10

Preparation of the homopolymer of the monomer prepared according to Example 5.

90g of monomer prepared according to Example 5 and 180g of isopropanol are introduced into a 1 liter reactor fitted with a dropping funnel. After heating the mixture to 80 ° C., a solution of 18 g of ascorbic acid in 90 g of water is introduced and then regularly in 1 hour 67.5 g of a 30% solution of hydrogen peroxide diluted with 27 g of water. . After the end of the addition, the reaction is continued for 4 hours.

The crude reaction mixture is concentrated, diluted with 150 ml of acetone and then precipitated in 5 liters of diethyl ether with vigorous stirring. The precipitate obtained is again dissolved in 150 ml of acetone and precipitated in 5 liters of diethyl ether. The purified polymer is then dried and 66g of pure product is obtained (yield: 73%).

C.C.M: on silica gel, solvent: chloroform, eluent: ethyl acetate 40 / cyclohexane® 1/1 developer: iodine.

Polymer R ^ = 0 starting monomer R ^ = 0.5.

BSB / BC / BR.75981

U.V spectrum: f \ max 325nm a = 45 (at lmg / 100ml in the

S

CHC13).

FORMULATION EXAMPLES

5 EXAMPLE I

An anti-sun cream is prepared having the following formulation: - Homopolymer obtained according to Example 6 ...... 5g - Magnesium stearate ................... ... 4g - Octyl dodecanol ............................ 10g 10 - Hydrogenated lanolin sold under the name HYDROLAN-H by the

ONYX Company ............................... 1g - Clear Lanolin ............. ............... 4g ^ - Beeswax ............................ 6g - Sorbitan sesquioleate ................... 4.5g - Glycerol monostearate ............. Ig - Oleic alcohol .. ........................... 5g - Palmitic ester of 2-ethylhexyl 20 glyceryl ether ......... .................... 2g - Vaseline oil ......................... .20g - Preservative ............................... 0.2g - Demineralized water qs ........ ........... 100g

In this example, the homopolymer of example 6 can be replaced by one of the homopolymers of examples 7 and 8, or by 2.5 g of

The homopolymer of Example 4 and 2.5 g of the homopolymer of Example 6. EXAMPLE II

A thickened oil is prepared having the following formulation: - Homopolymer obtained according to Example 6 ...... Ig 30 - Paramethoxy cinnamate of 2-ethylhexyl ..... 2g - Myristic alcohol with 3 moles of oxide of propylene sold under the name WITCONOL-APM by the company WITCO .......... 5g - 2-ethylhexyl palmitate ................. 10g 35 - Ditertiobutyl paracresol ................... 0.05g - Silica sold under the name AEROSIL-R 972 by the company DEGUSSA ..... 6g - Perfume ..................................... 0.5g - Isostearyl benzoate qs ... ........... 100g 40 In this example the homopolymer of example 6 can be replaced by one of the homopolymers of examples 7 and 8. One can also use, BSB / BC / BR. Weight by weight in this example, a mixture of the homopolymer of example 8 and the homopolymer of example 6 or of example 7.

BSB / BC / BR.75981

Claims (11)

1. Unsaturated compounds with UV absorbing chromophore, characterized in that they correspond to the following formula: y / · CH - C - <Z) - C - CH - CH - (/ YS R (I) 2. aby = T in which: '' Rc R. n is 0 or 1 3 H 10 when n = O, R represents a hydrogen atom when n = 1, R represents a hydrogen atom or a methyl radical and Z represents a divalent radical taken from the group consisting of: (i) - C - NH - 15 0 (ii) - C - NH - CH2 - O (iii) - C - NH - CH - U 1 o ch3 20 (iv) - C - NH - CH- II I °, CH2 / CH \ CH3 CH3 25 (v) - C - NH - CH- II io çh2 C6H5 30 fH3 and (vi) - C - NH - C - CH - Il | 2 o ch3 Rj, R ^, r3, R ^, R ^, identical or different, represent a hydrogen atom, a linear or branched alkyl radical having from 1 to 8 carbon atoms, an alkoxy radical having from 1 to 4 atoms of carbon, a dialkylamino or dialkylaminoalkyl radical of formula: - <CVm - <^ R6 40 in which m is 1 to 3 and R ^ represents a methyl radical e or ethyl, said radicals being optionally quaternized. BSB / BC / BR.75981 »v * -16- 2. Compounds according to Claim 1, characterized in that when at least one radical R ^,, R ^ »^ 4 and / ° u represents a dialkylamino or dialkylaminoalkyl radical, the latter is quaternized using a quaternizing agent taken from the group consisting of methyl chloride, dodecyl bromide, dimethyl sulfate or chloroacetic acid. 3. Compounds according to claim 1 or 2, characterized in that they are: - N- ^ methyl-2-oxo-4 (4-methylphenyl) -6 hexene-5 yl-ÎQ 10 acrylamide, - N - | 2-ethyl-4-oxo-6-phenyl-5-yl-2-yl-2] acrylamide, - N-2-methyl-oxo-4 (3-methoxy-butoxy-4-phenyl) -6 hexene-5-yl-2 ^ acrylamide, - 2-methyl-2-oxo-4 (4-dimethylamino) 6-phenylhexene-5] 5 yl-2 ^ acrylamide, - 2-methyl-2-methyl oxo-4 (4-trimethylammonio phenyl) hexene- 5 yl-T] acrylamide, - N-jjiiethyl-2 oxo-4 (4-methoxyphenyl) -6 hexene-5 yl-F] acrylamide. 4. Process for the preparation of the compounds of formula (I), characterized in that it consists in carrying out, under the conditions of the Claisen-Schmidt reaction, the condensation of an aromatic aldehyde of formula: _A 0.î_A-s 25 ° - / 1 in which: R4 R ^ to R ,. have the same meanings as in claim 1 with a ketone derivative of formula: CH2 - Ç - (Z) n - C - CH3 R 0 in which: R, Z and n have the same meanings as in claim 1, said condensation being carried out in an alkaline medium. 5. Method according to claim 4, characterized in that the aromatic aldehyde is benzaldehyde, 4-methyl benzaldehyde, 3-methoxy-4-butoxy-benzaldehyde, 4-dimethylamino benzaldehyde, 4-butoxy-benzaldehyde, dimethoxy -3.4 benzaldehyde, 4-ethoxybenzaldehyde, 2-methoxy-4-diethylamino benzaldehyde and ditertiobutyl-40 3,5 ethoxy-4 benzaldehyde and 4-methoxy benzaldehyde. BSB / BC / BR.75981 ¥ -17- ”* * 'Ψ 6. Method according to claim 4, characterized in that the ketone derivative is methylvinyl ketone, N- pmethyl-2 oxo-4 ~ j pentyl-2 acrylamide (or diacetone acrylamide), N- (oxo-2-) propyl-1 acrylamide, N- (methyl-l oxo-3) butyl-2 acrylamide, N- (methyl-5 oxo-2) hexyl-3 acrylamide or N- (phenyl-l oxo-3) butyl- 2 acrylamide. 7. Anti-solar polymers, characterized in that they consist of units having the following formula: R - Γ I - ch2- c - ^ RRLJ ", J \ / ·, C - CH CH —U ' v— R1 'H r5 R4 in which: n, R, Z, R ^, R ^, R ^, and R ^ have the same meanings as in claim 1. 8. Polymers according to claim 7, characterized in that they also comprise other units deriving from the polymerization of at least one monomer taken from the group consisting of: (a) acrylic or methacrylic acid, (b ) acrylic or methacrylic esters of formula: 25 ch2 = jî - COOR? R in which: R represents a hydrogen atom or the methyl radical, and R ^ represents an alkyl radical having from 1 to 18 carbon atoms, (c) the unsaturated amides or esters of formula: CH „= C - CO (X) - (CHJ - N 2 l 2 m R \ R6 in which: 35. represents a hydrogen atom or the methyl radical, X is -NH- or -O m is 2 or 3 and Rg is a methyl radical or ethyl, (d) the acrylamides or methacrylamides of formula: BSB / BC / BR.75981%>; - / R8 CH2 - C - CON ^ t \ r8 in which: ^ R and Rg represent a hydrogen atom or the methyl radical (e) UV absorbing acrymaids or methacrylamides of formula CH = C - CO - NH - Y 2 IR where R represents a "hydrogen atom or the methyl radical and Y is a jq aromatic group conferring on the monomer UV absorption in the wavelength range between 280 and 400nm. 9. Polymers according to claim 7 or 8, characterized in that they have a molar mass of between 1,000 and 50,000 and preferably between 2,000 and 20,000. 10. Cosmetic composition for protection against ultraviolet radiation, characterized in that it contains as active substance at least one sunscreen polymer as defined according to one of claims 7 to 9. 11. Composition according to claim 10, characterized by the 2Q fact that it contains from 0.2 to 20% by weight of at least one sunscreen polymer. 25 BSB / BC / BR.75981