AU697458B2 - Ethylenically unsaturated alkoxybenzotriazoles and their use in the preparati on of new sunscreen agents - Google Patents

Description

DI -1 b

IB

21

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s):

L'OREAL

Invention Title: ETHYLENICALLY UNSATURATED ALKOXYBENZOTRIAZOLES AND THEIR USE IN THE PREPARATION OF NEW SUNSCREEN AGENTS s .4 )q *4 Ir~ 4 4 a S Sp*cS

'I

II vo V *4 The following statement is a full description of this invention, including the best method of performing it known to me/us: 1: i I i t- u, t 1 14

I

E

i: cc rr r r cc isr cc n 1A ETHYLENICALLY UNSATURATED ALKOXYBENZOTRIAZOLES AND THEIR USE IN THE PREPARATION OF NEW SUNSCREEN AGENTS (This application has been divided from AU-31700/95 (682624)) The present invention relates to new ethylenically unsaturated alkoxybenzotriazoles and their use in the synthesis of particular short-chain, linear or cyclic diorganosiloxane or triorganosilane type compounds having at least one alkoxybenzotriazole function.' Australian patent 31700/95 (682624) describes new short-chain, linear or cyclic diaorganosiloxane and triorganosiloxane type compounds having at least one akoxybenzotriazole function, which compounds are usable as organic sunscreen agents in cosmetic compositions intended for protecting the skin and hair against ultraviolet 20 radiation. These compounds display many advantages over benzotriazole type screening substances of the prior art.

In particular these compounds have improved solubility in common organic solvents including in fats and oils, improved cosmetic properties and superior UV absorbing power.

In particular, the invention of AU-31700/95 (682624) relates to compounds formed by combining one or more particular benzotriazole derivatives with a particular linear or cyclic silicone chain or a particular silane.

The compounds of the invention of AU-31700/95(682624) are characterized in that they correspond to one of the following formulae to r L H:\Prianka\Keep\eci\akoxybenzotriazo e .adiv.1orea1.doe 7/10/97 15 2 R R R

R

_I

I

0 Si-- B R R A

R

r s SR R I I -Si-o i-o

RI

t U A-Si(R') 3 *444 4.

A 1*SS in which formulae to R, which may be identical or different, are chosen from Cz-Cjo alkyl, phenyl and 3,3,3-trifluoro-propyl radicals, at least 80% in numerical terms of the radicals R being methyl, B, which may be identical or different, are 30 chosen from the above radicals R and the radical A defined below, which may be identical or different, are chosen from Cz-Ca alkyl radicals and phenyl radicals, r is an integer between 0 and 50 inclusive, and s is an integer between 0 and 20 inclusive, on H \Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal.doc 7/10/97

V

W7 -I 3 condition that, if s is zero, then at least one of the two symbols B denotes A, u is an integer between 1 and 6 inclusive, and t is an integer between 0 and 10 inclusive, on the understanding that t+u is equal to or greater than 3, and the symbol A denotes a univalent radical linked directly to a silicon atom, and which corresponds to the following formula N OH

I

(X)m-(CH 2 )p-CH-CH2-

Z

5t~4*4

S

in which formula Y, which may be identical or different, are chosen from CI-C 8 alkyl radicals, halogens and Ci-C 4 alkoxy radicals, on the understanding that, in the latter case, two adjacent radicals Y on the same aromatic ring can form together an alkylidenedioxy group in which the alkylidene group contains from 1 to 2 carbon atoms, X represents 0 or NH, Z represents hydrogen or a Ci-C 4 alkyl radical, n is an integer between 0 and 3 inclusive, HI\Priyanka\Keep\speci\alkoxybenzotriazoles.dIv.lorf1al.doc 7/10/97

T

17 I J ed4~e~a__L I it r d b i i Lr 4 m is 0 or 1, on the understanding that, when m is zero, or when m is equal to 1 and X represents NH, then necessarily n cannot be zero and (ii) at least one of the radicals Y is an alkoxy radical, p represents an integer between 1 and inclusive.

It has been found that new ethylenically unsaturated benzatriazole derivatives can be produced and that these derivatives are suitable for use in the synthesis of the new compounds of formula or The present invention therefore provides ethylenically unsaturated derivatives corresponding to the formula: N OH .00 1 (Y) (4a) (X)m,(CH 2

)P-C,=CH

2 z in which Y, X, Z, n, m and p have the meaning given above for the formula The monoethylenically unsaturated organic benzotriazole derivatives of formula (4a) above constitute new products which are useful per se. Furthermore the derivatives also form an integral part of the compounds described in AU-31700/95 (682624) which find use as sunscreen agents in the UV-A and/or UV-B range, especially in cosmetic compositions intended for photoprotection of the skin or hair.

H:\Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal.doc 7/10/97

'T

In the above formulae to A hence represents the group derived from benzotriazole which, after attachment to the starting short silicone chain or to the starting silane, endows the compounds of the linear diorganosiloxane type (formula or cyclic diorganosiloxane type (formula or of the triorganoslane type (formula with absorbing properties with respect to ultraviolet in a wavelength region which can range from 280 to 400 nm. As mentioned before, and as is apparent from the definition of the formula given above, this group necessarily possesses at least one alkoxy function attached to at least one of the two aromatic rings of the benzotriazole, it being possible for this alkoxy function to be supplied either by a substituent Y or by the chain link which provides the coupling of the benzotriazole to the silicone chain or to the silane. One of the great advantages of the compounds of formula or is Sthat, depending on the position occupied by this/these alkoxy group(s) on the screening unit A, it is possible to obtain screening agents which are either purely UV-A or, on the contrary, purely UV-B, with extinction coefficients in all cases well above those obtained with the silicone screening agents of the prior art.

SAs is apparent from the formula given above, the coupling of the chain link to the benzotriazole unit, which hence provides for connection k of the said benzotriazole unit to the silicon atom of the silicone chain or of the silane, can, take place in all the available positions afforded by the two aromatic rings of the benzotriazole: H:\Priyanka\Keep\speci\alkoxybenzotria;oles.dv.loreal.doc 7/10/97 19 6 il~l

OH

6' 45 N 4 4b'e 4 a -S S *5

*WS

I)

4 J* S Preferably, this coupling takes place at position 3,4,5 (aromatic ring bearing the hydroxyl function) or 4' (benzene ring adjoining the triazole ring), and still more preferably at position 3,4 or Likewise, the coupling of the substituent unit Y can take place in all the other available positions within the benzotriazole. However, this coupling preferably takes place at position 3,4,4',5 and/or 6.

In the above formulae to the alkyl radicals can be linear or branched and chosen, in particular, from methyl, ethyl, n-propyl, isopropyl, nbutylp isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n- 25 hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals. Preferred alkyl radicals R, R' and B according to the invention are methyl, ethyl, propyl, n-butyl, noctyl and 2-ethylhexyl radicals. Still more preferably, the radicals R, R' and B are all methyl radicals.

Among the compounds of formulae to above, it is preferable to employ those corresponding to the formula or to the formula that is to say shortchain, linear or cyclic diorganosiloxanes.

Among relevant linear or cyclic diorganosiloxanes statistical or well-defined block-containing derivatives H:\Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal.doc 7/10/97 Fi 20 a~A~ C L-~J

A

-7displaying at least one, and still more preferably all, of the following features are preferred more especially: R is alkyl and is still more preferably methyl, B is alkyl and still more preferably methyl (this applies to the linear compounds of formula r is between 0 and 3 inclusive; s is between 0 and 3 inclusive (this applies to the linear compounds of formula t+u is between 3 and 5 (this applies to the cyclic compounds of formula n is not zero and is preferably equal to 1 or 2, and Y is then chosen from methyl, tert-butyl and

C

1

-C

4 alkoxy, but preferably from C 1

-C

4 alkoxy, and is still 20 more preferably methoxy, t.

o s g~0 .4.4

A,

t* *4A4 S. *r '7

II

L

Z is hydrogen or methyl, X represents O (m 0) p is equal to 1, on the understanding that, in all cases, at-least one alkoxy function is coupled directly to the benzotriazole derivative.

To prepare the silicone screening agents of formulae and it is possible to proceed in a traditional manner, employing a hydrosilylation reaction (namely =Si -H CH 2 C- E-Si-CH 2

-CH-)

starting from the corresponding silicone in.which, for example, all the radicals A are hydrogen atoms. This Hi\Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal doc 7/10/97 i; i;i i:i I-8-B 8 starting silicone is designated hereinafter SiH-containing derivative; the SiH groups may be present in the silicone chain and/or at the ends of the silicone chain. These SiHcontaining derivatives are well-known products in the silicone industry, and are generally available on the market. They are, for example, described in American Patents US-A-3,220,972, US-A-3,697,473 and US-A-4,340,709.

This SiH-containing derivative mayhence be represented either by the following formula (la):

R

I

B' (1a) 6 0 S ft te* ft in which R, r and s have the meaning given above for the formula and the radicals which may be identical or different, are chosen from the radicals R and a hydrogen atom, or by the following formula (2a): si-_ o R (2a) *3 C i' i i j« T H:\Priyanka\Keep\speci\alkoxybenzotriazole.div.loreal.doc 7/10/97 (la) or a traditional hydrosilylation reaction, carried out in the presence of a catalytically effective amount of a platinum-based catalyst, may be perfsr_-ed on an organic benzotriazole derivative of formula (4a).

Processes suitable for the preparation of the products of formula (4a) above are described, in particula., in Patents US-4,316,033 and US-4,328,346.

In addition, the details of the working conditions to be followed for conducting the hydrosilylation reaction between the compounds of formula (la) or (2a) above with the compound of formula (4a) above are given in Patent Application EP-0,392,883 cited above, the teaching of which is, in this respect, completely included in the present description by way of reference.

As regards the preparation of the screening agents of the triorganosilane type of formula given earlier, it is possible to proceed as described above, still by a hydrosilylation reaction, between a starting S. silane of fermula 3 Si-H (formula (3a))i in which R' Shas the same meaning as for the compound of formula and an organic benzotriazole derivative of formula (4a) q defined hereinbefore.

Relative to the silicone screening agents of the prior art as are described in Patent Application EP-0,392,883 the silicone screening agents according formed using compounds of formula 4(a) display one or several 1 35 essential structural differences which are the source of their exceptional properties: the silicone chains onto which the benzotriazole unit is grafted are, in the first H:\Priyanka\Keep\speci\alkoxybenzotriazoles.div.1oreal.doc 7/10/97 I

I

ii I,

I

ii 'IvN/t/) 1 -1 Psk~i~~4~ ITi rr'C iL ~a4? P~ i i- I 10 i place, much shorter; next, the unit derived from benzotriazole always bears at least one alkoxy function.

As mentioned earlier, the compounds of formulae to alove display excellent intrinsic screening power with respect to ultraviolet radiation (UV-A or UV-B, depending on the structure of the product). By mixing products of different structure, that is to sy, more specifically, by mixing products according to the invention displaying purely UV-A activity with products according to the invention displaying purely UV-B activity, it is thus possible to have at one's dispos&.l a composition which will display overall an exceptional screening activity over the entire range of harmful UV (UV-A UV-B), which constitutes a considerable advantage.

As described in AU-31700/95 (682624) the compounds of formulae to are also useful for their cosmetic properties. In particular they are useful in cosmetic preparations for use as protective compositions for the human epidermis or hair against ultraviolet rays, as an antisun composition or as a make-up product.

This composition may take the form, in particular, of a lotion, th-ckened lotion, gel, cream, milk, powder or solid stick, and be packaged, where appropriate, as an aerosol and take the form of a mousse or spray.

It can contain the cosmetic adjuvants customarily used in the field, such as fats, organic solvents, Eilicones, thickeners, emollients, additional sunscreen agents, foam inhibitors, hydrating agents, perfumes, preservatives, surfactants, fillers, squestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellents, alkalinizing or acidifying agent, colorants, pigments or nanopigments, especially H!\Priyanka\Keep\speci\alkoxybenzotriazoles.div.lorealdoc 7/10/97 f i i' q c *q.

~O 1 11 those designed to provide for an additional photoL >tective effect by physically blocking the ultraviolet radiation, or any other ingredient customarily used in cosmetics, especially for the manufacture of antisun compositions.

Among organic solvents, lower polyols and alcohols, such as ethanol, isopropanol, propylene glycol, glycerol and sorbitol, may be mentioned.

The fats can consist of an oil or wax or mixtures thereof, fatty acids, fatty acid esters, fatty alcohols, petroleum jelly, paraffin, lanolin, hydrogenated lanolin and acetylated lanolin. The oils may be chosen from animal, vegetable, mineral or synthetic oils, and in particular hydrogenated palm oil, hydrogenated castor oil, liquid petrolatum, paraffin oil, Pu-'cellin oil, volatile or non-volatile silicone oils and isoparaffins.

When the cosmetic composition according to the invention is intended more especially for protecting the human epidermis against UV rays or as an antisun composition, it can take the form of a suspension or dispersion in solvents or fats, or alternatively the form of an emulsion (in particular of the O/W or W/O type, but preferably O/W) such as a cream or milk, or of a vesicular dispersion, or the form of an ointment, gel-, so.id stick or aerosol mousse. The emulsions can contain, in addition, anionic, nonionic, cationic or amphoteric surfactants.

When the composition according to the invention is used for protecting the hair, it can take the form of a shampoo, lotion, gel or composition to be rinsed, to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening, styling or treatment lotion or gel, blowdrying or setting lotion or gel, hair lacquer or composition for permanent-waving or straightening, dyeing H:\Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal.doc 7/10/97 t: V 12 or bleaching the hair.

When the cosmetic composition according to the invention is used as a make-up product for the eyelashes, eyebrows, skin or hair, such as a cream for treating the epidermis, make-up foundation, lipstick, eyeshadow, blusher, eyeliner, mascara or colouring gel, it can be in solid or pasty, anhydrous or aqueous form, such as oil-inwater or water-in-oil emulsions, suspensions or alternatively gels.

The subject of the invention is also a process for protecting the skin and hair against ultraviolet radiation, especially solar radiation, which consists in applying to the skin or hair an effective amount of the cosmetic composition defined above, or a benzotriazole derivative of formula as are defined above.

The examples which follow illustrate the 20 invention without, however, limiting its scope.

EXAMPLE 1 This example illustrates the preparation of a compound according to the invention of formula:

SCH

3 CH3 CH 3 I 30 i I CH Si- O i-O- si- CH3 SI I SA CH 3

CH

3 i :\riyanka\Keep\speci\alkoxybenzRriazoles.div. oreal.doc /10/97 i"i; S13 in which A represents: 0-CH 2

-H-CH

2 CH3 (this product corresponds to a compound of formula for which R B CH 3 r 0; s 1; Y OCH- 3 at position 4'; n 1; m 1 and X 0; p 1; Z CH 3 a) First stage: preparation of 4-(4-methoxy-2nitrophenylazo) benzene-1,3-diol SA solution of diazonium salt, obtained beforehand by diazotrization of 67.2 g (equivalent to 0.4 mol) of 4methoxy-2-nitroaniline contained in 150 ml of concentrated SHC1 with a sodium nitrite solution containing 28 g (equivalent to 0.4 mol) in 100 ml of water at 0-5C, is added at a temperature of between 5 and 10 0 C and over one hour into a reactor containing 44 g (equivalent to 0.4 mol) hours. The red precipitate is filtered off and then rinsed copiously with water. 86 g (yield: 74%) of the desired product are thereby obtained.

b) Second stage: preparation of 2-(4-methoxy-2nitrophenylazo)-5-(2-methylallyloxy) phenol 81 g (equivalent to 0.28 mol) of the product obtained above, 220 ml of DMF and 42.6 g (equivalent to 0.308 mol) of potassium carbonate are introduced into a round-bottomed flask equipped with appropriate attachments.

SH:\Priyanka\Keep\speci\alkoxybenzotrlholes.div orealdo 7/10/97 4{rudbtoe ls qipdwt pporaeatcmns 3~ j k 14 The mixture is brought to 80-90 0 C, and 28 g (equivalent to 0.308 mol) of methallyl chloride are then introduced into it dropwise over 30 minutes. The mixture is then left stirring at 90 0 C for 4 h 30 min. The reaction mixture is then poured into 200 g of ice-cold water and the precipitate obtained is filtered off. This precipitate is then taken up in dichloromethane, dried over sodium sulphate, concentrated and passed through a bed of silica After evaporation of the solvent and drying, 47 g of a red powder (yield: 49%) consisting of the desired product are obtained.

c) Third Stage: preparation of 2-(5-methoxy-2benzotriazolyl)-5-(2-methylallyloxy)phenyl 32.54 g (equivalent to 0.134 mol) of the product obtained above and 400 ml of ethanol are placed in a roundbottomed flask. 48.4 g (equivalent to 0.269 mol) of glucose dissolved in 400 ml of 2N sodium hydroxide are added portionwise to it over half an hour, and the mixture is left stirring overnight. 44.4 g of powdered cinc are then added and the mixture is left stirring for 3 hours.

The mixture is then filtered and the residue is washed with dichloromethane. The filtrate is extracted with 25 dichloromethane. The organic liquors are combined, washed with water and dried. After concentration and drying, 36.6 g of a grey-brown-coloured powder are obtained. It is recrystallized in ethanol, thereby to obtain 41.8 g (yield: of the desired product of formula:

I

I..

t

S

CH3O

O-CH

2

-C=CH

2 ~1 Li_ H\Priyanka\Keep\specj\alkoxybenootriazoles.div.loea .doc 7/10/97 f'* b' 'II C 15 d) product Fourth stage: preparation of the desired final A reactor equipped with all appropriate attachments is charged with 21.8 g of the product obtained above and 35 ml of toluene. The mixture is brought to 80 0

C

under nitrogen. The catalyst (complex containing 3-3.5% by weight of Pt in cyclovinylmethyl-siloxane from Hils Petrarch PC085: 1001) is added, and 16.5 g of heptamethyltrisiloxane are then added dropwise over minutes. The heterogeneous mixture is brought to reflux for 8 hours under nitrogen. The reaction medium is concentrated and chromatography is then performed on silica under pressure (eluent: heptane with a gradient of CH 2 C1 2 25 g of a solid are then recovered, which is recrystallized in methanol to obtain finally 23.5 g (yield: 63%) of the desired final product.

The UV absorption characteristics (measured in ethanol) of this product are as follows:

I-

I

a a

S.

ax: 349 nm Emax: 27,200

I~

j Hence this product may be used very effectively as a sunscreen agent which is active in the UV-A.

EXAMPLE 2 Following the same procedure as the one given in Example 1 (the only difference being that, in stage 1, 4methoxy-2-nitroaniline has been replaced here by 2nitroaniline), 8.5 g (yield: 67%) were prepared of another compound according to the invention and corresponding to the following formula: Hi\Priyanka\Keep\speci\alkoxybenzotriazoles.div.loreal.doc 7/10/97 ii ii i' i.: i i i i f ii 16

CH

3

CH

3

CH

3 I I I CHY- Si- 0 1 I I O 1

R

I I I>i Ai in which A in this instance represents: *t

A

N OH

O-CH

2 -CH-CH2- Hence this product differs from the one of Example 1 above only in the absence of the OCH 3 substituent on the benzotriazole unit.

The UV absorption characteristics (measured in ethanol) of this product are as follows: 9.

9 5~ It 342 nm 8~m: 24,500 Hence this product may be used very effectively as a sunscreen agent which is active in UV-A.

It will be noted that the intermediate product obtained at the end of stage No. 3 in the sequence of the process was of the formula: 1 I11.F -TCllltlltl i 11 1 H:\Priyanka\Keep\speci\alkoxybenzotriazolesdiv. loreal.doc 7110/97 TrI ni i.

;j 17

N

N.

O-C

H2

-C=CH

2

CH

3 \l: 2r

V;

EXAMPLE 3 4,.i [i in ii i r* r iiir asrr ,rr r* .Oo pp Following the same procedure as the one given in Example 1 (the only difference being that, in stage 1, resorcinol was replaced here by 4-methyl-2- (2methylallyloxy)phenol), 2g were prepared (yield: 54%) of another compound according to the invention and 20 corresponding to the following formula:

CH

3

CH

3

CH

3 I I C

CH

3 Si- 0 i 3 I I in which A in this instance represents: I 1, i; Ilr~' H:\priyanka\Keep\speci\alkoxybenzotrizoles.div. loreal.doc 7/10/97 ~b i: 18 N-f OH CH 2

CH

3 2 A The UV absorption characteristics (measured in of this product are as follows: ethanol) max: 303 nm Xm: 348 nm max: 10,900 Emax: 22,200 S9* j i l s 0

S

1S*44 1*4*44 rr I i

I~*

Hence this product may be used very effectively as a sunscreen agent which is moderately active in the UV-B and strongly active in the UV-A.

It will be noted that the intermediate product obtained at the end of stage No. 3 in the sequence of the process was of the formula: C3N OH N CH2-C=CH 2 CH3 EXAMPLE 4 Following the same procedure as the one given in Example 1 (the only differences being that, on the one H:\Priyanka\Keep\speci\alkoxybenzotrlaioles.div.loreal .doc 7/10/97 !1 H:\Priyanka\Keep\speci\kxyenotbezotledv.loe.doc 7/10/97 19 hand, in stage 1, 4-methoxy-2-nitroalilile and resorcinol were replaced here by 2-nitroanilile and eugenol, respectively, and that, on the other hand, stage No. 2 was eliminated), 13g (yield: 67%) were prepared of another compound according to the invention and corresponding to the following formula: .0 CH 3

CH

3

CH

3 CM Si 0 Cx- CHJ- si 0

CH

3 L in which A in this instance represents:

A

NA

N

N

4 ~4 4 4 *4444 4 4 4.

4. "f3

CH

2

CH

2

CH

2 The UJV absorption characteristics (measured in of this product are as follows: ethanol) 3 10 nm E.:17,-800 Hence this product may be3 used very effectively litkPriyanka\reep\speci\alkoxybenzotriazoles.div. loreal.doc 7/10/97

V

K'

20 as a sunscreen agent whichis active in the UV-B.

It will be noted that the intermediate product obtained before carrying out the last step in the sequence of the process was of the formula: OH OH

NCH

CH

2

CH=CR

2 EXAMPLE A specific formulation of an antisun cosmetic composition according to the invention, namely an antisun cream, is illustrated here.

N.

N,

N,

*9 9 9 .4 0* 4 9 4 9. .4 U S *49* 4449 49 .4 5 9 9 5*5959 *4 5 9.55 9 Compound of Example 1 7 Mixture of cetyl/stearyl alcohol and oxyethylenated cetyl/stearyl alcohol containing 33 mol of EO- ("SINNOVAX AO" from HENKEL) Non-self-emulsifying mixture of glycerol mono and distearates Cetyl alcohol Benzoate Of C 1 2

-C

15 alcohols ("FINSOLV TN" from WITCO) Polydimethylsiloxane Glycerol Perfume, preservative qs Water qs Bg 7g 2g 1. 1. 17.5g bOog H:\Priyanka\Keep\speci\alkoxybenzotriazoles.div~loreal doc 7/10/97 C i i r d

I'

ii This cream is prepared according to the traditional techniques for preparing emulsions, by dissolving the screening agent in the fatty phase containing the emulsifiers, heating this fatty phase to about 70-80 0 C and adding the water, heated to the same temperature, with brisk stirring. The stirring is maiitained for 10 to 15 minutes, the mixture is then allowed to cool with moderate stirring and, at about 40 0

C,

perfume and preservative are finally added.

'I

kF *a

V

*9.99 *99** 99 9 fil

I

E1 H\priyanka\Keep\speci\alkoxybenzotrazole .div.loreal.doc 7/10/97

Claims (12)

1. New ethylenically unsaturated benzotriazole derivatives corresponding to the formula: N OH N Y (4a) (X)m-(CH 2 )p-C=CH2 in which formula (4a): S* Y, which may be identical or different, are S" 20 chosen from Ci-Ce alkyl radicals, halogens and C1-C4 alkoxy radicals, on the understanding that, in the latter case, two adjacent radicals Y on the same aromatic ring can form together an alkylidenedioxy group in which the alkylidene group contains from 1 to 2 carbon atoms, X represents 0 or NH, S- Z represents hydrogen or a C 1 -C 4 alkyl radical, n is an integer between 0 and 3 inclusive, m is 0 or 1, on the understanding that, when m S..is zero, or when m is equal to 1 and X represents NH, then necessarily n cannot be zero and (ii) at least one of the radicals Y is an alkoxy radical, p represents an integer between 1 and inclusive.

2. New derivatives according to claim 1, characterized in that n is not zero and is preferably equal C;I- H:XPriyanka\Keep\speci\alkoxybenzotriaooes.div.oreal .doc 7/10/P7 -23 to 1 or 2, and Y is chosen from methyl, tert-butyl and C1-C 4 alkoxy.

3. New derivatives according to claim 2, characterized in that Y is methyl or methoxy.

4. New derivatives according to claim 3, characterized in that Y is methoxy.

5. New derivatives according to any one of claims 1 to 4, characterized in that Z is hydrogen or methyl.

6. New derivatives according to any one of claims 1 to 5, characterized in that m is not zero and in that X represents 0.

7. New derivatives according to any one of claims 1 to 6, characterized in that p is equal to 1. 4* 9 4 4o 20 8. New derivatives according to any one of claims 1 to 7, characterized in that the coupling of the chain link (X)m (Ch,)p-C(Z)=CH 2 to the benzotriazole unit take place at position 3, 4, 4' or 5 of the latter.

9. New derivatives according to claim 8, characterized in that the said coupling takes place at a position 3, 4 or i t New derivates according to any one of claims 1 to t 9, characterized in that the coupling of the substituent Y to the benzotriazole unit takes place at position(s) 3, 4, 5 and/or 6 of the latter.

11. A process of preparing silicone screening agentr of formulae or as hereinabove.described comprising the step of carrying out a hydrosilation reaction between a derivative of formulae (la) or (2a) as hereinabove i Hi\Prlyanka\Keep\speLi\alkoxybenzotriazoles.div.loreal,doc 7/10/97 24 described with an organic benzotriazole derivative of claim 1 in the presence of a catalytically effective amount of platinum-based catalyst.

12. A process of preparing triorganosilance screening agents of formula as hereinabove described comprising the step of carrying out a hydrozilation reaction between a silane of formula 3 Si-H (formula in which R' has the same meaning as for the compound of formula and an organic benzotriazole derivative of claim 1.

13. A cosmetic preparation suitable for protecting the skin and hair against ultraviolet radiation comprising a benzotriazole derivative of claim 1.

14. A process for protecting the skin and hair against ultraviolet radiation comprising applying an effective amount of a benzotriazole derivative of claim 1 or a cosmetic preparation comprising a benzotriazole 20 derivative of claim 1. A process of preparing silicone screening agents of formulae or substantially as herein oo described- with. reference to the examplps. S" Dated this 5TH day of November 1997 L'OREAL By their Patent Attorneys a GRIFFITH HACK Fellows Institute of Patent Attorneys of Australia Hs\PriyankA\Keep\speci\alkoxybenzotriazoles.div.lorea .doc 7/10/97 I* ABSTRACT New ethylenically unsaturated benzotriazole derivatives corresponding to the formula: 1 0 4 a S(X)m-(CH)p C =CH2 in which formula (4a): Y, which may be identical or different, are 20 chosen from C 1 -C 8 alkyl radicals, halogens and CI-C 4 alkoxy .4 radicals, on the understanding that, in the latter case, two adjacent radicals Y on the same aromatic ring can form together an alkylidenedioxy group in which the alkylidene group contains from 1 to 2 carbon atoms, X represents O or NH, Z represents hydrogen or a Ci-C4.alkyl radical, n is an integer between 0 and 3 inclusive, m is 0 or 1, on the understanding that, when m '6 is zero, or when m is equal to 1 and X represents NH, then necessarily n cannot be zero and (ii) at least one of the radicals Y is an alkoxy radical, v p represents an integer between 1 and inclusive. I H\Prrtyanka\Keep\speci\alkoxybenzotriazolesdiv.loreal.doc S/11/97