CA1113480A - Benzylidenecamphors, production and cosmetic compositions thereof - Google Patents

Abstract

Compounds of general formula II: II in which Y denotes H or SO3H and the corresponding salts with organic or mineral bases; Z 'denotes the groups -CH2I, -CH2R, -CH'R', -CHO, -COOR "with R = -NR1R2, -? R1R2R3, -OR4, -OCOR5, -SR6, -CN, -COOR", - SSO2Na, R1 and R2 = H, C1-18 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as morpholine, piperidine, pyrrolidine, piperazine, N-methyl-piperazine, Nphenylpiperazine; R3 = C1-4 lower alkyl, hydroxyalkyl, or sulfonatopropyl; R4 = H, alkyl, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkylaminoalkyl; R5 = alkyl, alkenyl, aryl, aromatic or non-aromatic heterocycle containing 5 to 6 members; R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3; R '= -OR'4 or -SR'6 in which R'4 and R'6 can respectively have the same values as R4 and R6, except the hydrogen, polyoxyethylene, hydroxyalkyl, 3-alanyl and aryl values; R "= hydrogen or alkyl; it being understood that, when R = NR1R2 the compound may be in the form of an addition salt with a mineral or organic acid; when R = R1R2R3, with R1 and R2 different from H, l the ionic balance (2) of the molecule is ensured either by R3 when it has the sulfonatopropyl value, or by an anion X-, X which can take the values SO4 alkyl, SO3 aryl, SO3 alkyl or halogen. They are new compounds, useful in particular as protective filters in cosmetic compositions with a view to protecting the human epidermis against actinic radiation Compositions containing compounds of formula II Process for the preparation of these compounds.

Description

- - \

The present invention relates to novel compounds constituted by p-monobromomethyl- and p-dibromomethyl-; ~
benzylidene camphors, as well as their process of preparation and their use in the cosmetic field. The invention relates to also no derivatives prepared from brominated compounds mentioned above, and their use in the doma: cosmetic ine.
The compounds of the invention have remarkable properties.
specific absorption of actinic radiation, one very wide range of solubilities, and they can be used in particular ment for the preparation of cosmetic compositions intended to preserve the human epidermis.
We know that light radiation between 280 and 400 nanometers (nm) allow the browning of the epi-human dermis, but that the area between 280 and 320 nm pro-there is erythema and skin burns, the severity of which is increasing quickly with the duration of the exposure. So a good agent pro-floor covering must have a high absorbency in the area of 280 at about 320 nm, but it must let the radiation pass as widely as possible in the area above 320 nm, to offer the best conditions for a tan without erythema. he must also have good photo-stability properties chemical, thermal, chemical, in particular in contact with the eur, as well as good solubility in various solvents or ingredients constituting the vehicle for cosmetic compositions.
We already know the French patent n 73.34140, relative has benzylidene camphor derivatives carrying an ammonium radical quaternary on the benzene nucleus in para position relative to the bornylidene radical. We also know the French patent n 74 05427 relating to benzylidene camphor derivatives, sulfo-born on the methyl radical in ~ of the carbonyl radical or on the benzene nucleus.
Although the compounds of the aforementioned French patents - 1 - ~
... ..

~ $ ~
~, have good anti-actinic properties, and are used i in cosmetic compositions for browning the skin human skin, they nevertheless constitute families comprising a relatively small number of compounds. I1 results that they are not fully satisfied, particularly with regard to concerns the preparation of a wide range: L of formulations in which they are not always suitable in particular for reasons solubility or compatibility sounds, with solvents and ingredients usually used in cosmetics.
The object of the invention is in particular to remedy the incon-aforementioned products, and to obtain a large family of compounds which;
while retaining for each of the compounds good properties as a sun filter present, with the various solvents and ingredients dients used in cosmetic compositions for the bron-zage without erythema of the human epidermis, a very lective as well as a wide range of solubilities and good compatibility, especially when the composition includes several phases. ~;
The invention first relates to the brominated derivatives of , 20 para-methylbenzylidene camphor with the formula: `

Y-CH

~ ~ ' F H
`~

IZ
in which Y denotes H or the SO3H radical and its salts with the organic or mineral bases, and Z denotes the radicals -CH2Br or -CH BrBr.
Among the compounds of formula I, mention may be made of the

- 2 -posed from table 1 below in which the number of each com- ~;
posed is the same as that of his example of preparation.
TABL, WATER 1 N of -compound Description of the compound 1 (4-bromomethyl benzylidene) -3 camphor 2 (4-dibromomethyl benzylidene) -3 camphor 52 acid (4-bromomethyl benzylidene) -3 campho-10 sul-; ~ -Mention may also be made of the salts of acid n 52 ci-.
above, formed with mineral or organic bases.
`The compounds of formula I are new compounds which are useful either as synthesis intermediates for pre-.
adorn the compounds of formula II below, either as filters protectors in cosmetic compositions for protection of the human epidermis against actinic radiation.
- The invention also relates to the compounds of formula general II:

CH ~.

~. '' II -in which Y denotes H or SO3H and the corresponding salts a-with organic or mineral bases;
Z 'denotes the groups -CH2I, -CH2R, -CHR'R', -CHO, -COOR "a-1 2 ~ ~ RlR2R3, -OR4, -OCOR5, -SR6, -CN -COOR "-SSO
N / A;
Rl and R2 = H, C1_8 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as mo ~ pholine, ~ / 7 ~

- 3 -piperidine, pyrrolidine, piperazine, N-methyl-piperazine, N-phenylpiperazine;
R3 = lower C1-4 alkyl, hydroxyalkyl, or sulfonatopro- ~;
pyle;
R4 = H, alkyl, polyoxyethylene, substituted or unsubstituted aryl, menthy-le, dialkylaminoalkyle R5 = alkyl, alkenyl, aryl, aromatic heterocycle or not holding 5 to 6 links ~
R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3 R '= -OR'4 or -SR'6 in which R'4 and R'6 may have respected: ~
the same values as R4 and R6, except the hy-drogen, polyoxyethylene, hydroxy-alkyl, alanyl-3 and aryl; .
R "= hydrogen or alkyl:.:
it being understood that, when R = NRlR2 the compound may be under the form of an addition salt with a mineral or organic acid:
when R = ~ RlR2R3, with Rl and R2 different from H, the equilibrium ionic content of the molecule is ensured either by R3 when it has the sulfonatopropyl value, either by an anion X, X which can take dre the values SO4 alkyl, SO3 aryl, SO3 alkyl or halogen.
The compounds of formula II are new compounds, useful in particular as protective filters in the compositions cosmetics to protect the human epidermis against actinic diations.
Among the compounds of the invention there may be mentioned in particular the compounds of table 2 below, in which the number mero of each compound is the same as that of its example of ~ `
preparation.

30 N of the compound Description of the compound 3. (4-dimethylaminomethyl benzylidene) -3 camphor

4. (4-diethylaminomethyl benzylidene) -3 camphor ~ 3 ~
,.:

5. 4-diethylamino methyl benzyl hydrochloride dene) -3 camphor:.

6. ~ oxo - 2 bornylidene-3) methyl7 camphosulfonate , -4 benzyl diethylammonium

7. ~ bis (2-hydroxyethyl) amino methyl-4-benzylide.
- ne ~ -3 camphor 7. bis ~ bis (2-hydroxyethyl) amino hydrochloride ~
4-thyl benzylidene ~ -3 camphor; ~
. 8. (4-diisopropylaminomethyl benzylidene) -3 camphor

8. bis hydrochloride (4-diisopropylaminomethyl benzyl- -, ~
idene) -3 camphor

9 (4-dibutylaminomethyl benzylidene ~ -3 camphor ~: ~
9 bis. 4-dibutylaminomethyl benzyl hydrochloride dene) -3 camphor ~:
~ bis- (octadecyl) amino-methyl-4 be ~ zylidene ~ -3 camphor ~:
11 (4-piperidino-methyl benzylidene) -3 camphor 12 (4-morpholinomethyl benzylidene) -3 camphor 13 acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyl-aminQ ~ -4 benzoic 14 (2-oxo-3-bornylidene-methyl) -4 benzyl diethyl -: ~
methyl ammonium, p-toluene sulfonate.
(2-oxo-3-bornylidene methyl) -4 benzyl diethyl methyl ammonium, methane sulfonate 16 N- ~ (2-oxo-3-bornylidene-methyl) -4 benzyl7N-methyl morpholinium, methane sulfonate . 17 N- ~ oxo-2 bornylidene-3 methyl) -4 benzyl7N-: methyl morpholinium, methyl sulfate 18 N- ~ (2-oxo-3-bornylidene-methyl) -4 benzyl ~ N-methyl morpholinium iodide 19 N- ~ (2-oxo-3-bornylidene-methyl) -4 benzy ~ N-methyl piperidinium, p-toluene sulfonate ~ 3 ~
~ .:

N- ~ oxo-2 bornylidene-3 methyl) -4 benzy ~ N-methyl piperidinium, methane sulfonate 21 (2-oxo-3-bornylidene-methyl) -4 benzyl triethyl-ammonium, bromide 22 (2-oxo-3-bornylidene-methyl) -4 benzyl tris-~ (2-hydroxyethyl) ammoniwn, bromide 23 (2-oxo-3-bornylidene methyl) -4 benzyl dimethyl dodecyl ammonium, bromide 24 (2-oxo-3-bornylidene-methyl) -4 benzyldimethyl :: ~
tetradecyl ammonium, bromide (4-hydroxymethyl benzylidene) -3 camphor i:
26 (4-methoxymethyl benzylidene) -3 camphor 27 (4-butoxymethyl benzylidene) -3 camphor 28 (4-dodecyloxymethyl benzylidene) -3 camphor 29 (4-tetradecyloxymethyl benzylidene) -3 camphor, ~
; -, ~
(4-hexadecyloxymethyl benzylidene) -3 camphor 31 (4-phenoxymethyl benzylidene) -3 camphor ;:;:., 32 (~ -naphthoxymethyl-4 benzylidene) -3 camphor: ~
33 (p-benzoylphenoxymethyl-4 benzylidene) -3 camphor: ~
34 ~ (2-oxo-3-bornylidene methyl) -4 benzyloxy ~ -2 methyl benzoate: `;
acid ~ 2-oxo-3-bornylidene-methyl) -4 benzyloxy ~
2 benzoic 36 (2-oxo-3-bornylidene-3 methyl) tetradecanoate -4 benzyl ~ -37 (2-oxo-3-bornylidene-3 methyl) hexadecanoate -4 ~, benzyl 38 (2-oxo-3-methyl-3-benylate) benzoate -4 benzyl 39 (4-mercaptomethyl benzylidene) -3 camphor (4-methylthiomethyl benzylidene) -3 camphor 41 (4-methylsulfinylmethyl benzylidene) -3 camphor :
42 acid ~ oxo-2 bornylidene-3 methyl) -4 benzyl- ~
thio ~ -2 acetic; ~.
43 acid ~ oxo-2 bornylidene-3 methyl) -4 benzyl-succinic thioJ-2 44 ~ (2-oxo-3-bornylidene met-hyl) -4 benzylthio ~ -3 .;
alanine?
~ -diethylaminoethylthiomethyl-4 hydrobromide. ~ - ~
benzylidene) -3 camphor:;
46 ~ (2-benzothiazolyl thiomethyl) -4 benzylidene ~ -3:
camphor.
47 4-cyanomethyl-3-benzylidene camphor :
48 acid (2-oxo-3-bornylidene-methyl) -4 phenylaceous- ~: ~
tick 49 (2-oxo-3-bornylidene-methyl) -4 benzoic acid.
dimethoxymethyl-4 benzylidene-3 camphor. ~
51 (4-formyl benzylidene) -3 camphor. :
acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyl-thiQ7-2 benzoic 56 2,5-dihydroxy benzoate (oxo 2 bornylidene-3 methyl) -4 benzyl 57 di (t-butyl) 3,5 4-hydroxy (2-oxo-borzoate) nylidene-3 methyl) -4 benzyl 58 Benzyl (2-oxo-3-bornylidene-methyl) -4 oleate 59 ~ (2-Ethyl hexyloxymethyl) -4 benzylidene7-3 cam- ~:
phre (4-octyloxymethyl benzylidene) -3 camphor 61 (4-hexyloxymethyl benzylidene) -3 camphor 62 (4-Menthyloxymethyl benzylidene) -3 camphor 63 ~ di (t-butyl) -2.6 methyl-4 phenoxymethyl) -4 benzylidene ~ -3 camphor '~
64 ~ (dimethylaminoethyloxymethyl) -4 benzylidene ~ -3 camphor acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyl-;
thio ~ -3 propionic.
66 (2-oxo-3-bornylidene methyl) -4 benzyl trimethyl-ammonium methyl sulfate.
67 N- ~ oxo-2 bornylidene-3 methyl) -4 benzyl ~ N-(2-hydroxyethyl) morpholinium chloride 68 N- (2-hydroxyethyl) N- ~ ¦-oxo-2 bornylidene-3 methyl) -4 benzyl ~ dimethylammonium bromide 69 ~ oxo-2 bornylidene-3 methyl) -4 benzyl dimethyl- ~;
ammonio ~ -3 propane-sulfonate !
(4-oleyloxymethyl benzylidene) -3 camphor ~
.,:
71 (4-iodomethyl benzylidene) -3 camphor 72 (~ -hydroxyethyloxymethyl-4 benzylidene) -3 camphor 73 Acid (2-oxo-3-bornylidene-methyl) -4 benzyldi-thiodiacetic 1 74 Acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyldi-: thio ~ -3.3 'dipropionic Acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyldi-: thio ~ 'disuccinique .-76 ~ (2,5-hydroxy-dioxa-2,5 heptyl) -4 benzylidene ~ -3 ~ -, camphor 77 Bis-N, N '~ (2-oxo-3-bornylidene-methyl) -4 benzy piperazine 78 N-methyl N- ~ (2-oxo-3-bornylidene-methyl) -4 benzy ~ 7piperazinium bromide 79 N-methyl NlNl-bis- ~ (2-oxo-3-bornylidene-methyl) -4 benzyl ~ piperazinium bromide N, N 'bis (2-hydroxyethyl) N, N'-bis ~ (2-oxo bornyli- ~:
dene-3 methyl) -4 benzyl ~ piperazinium dibromide 81 N, N'-bis (2-hydroxypropyl) N, N'-bis ~ 2-oxo bornyl-;
idene-3 methyl) -4 benzylJpiperazinium dibromide 82 N, N'-bis (2-hydroxy-ethyl) N- ~ (2-oxo bornylidene-3 methyl) -4 benzy ~ piperazinium bromide The compounds of Table 2 can optionally be pre ~
smell in the form of addition salts with a mineral acid or - ~
organic. ~.
All the compounds of formulas I and II have a maximum absorption in the area between 290 and 305 nm of the ultraviolet spectrum. They have the property of absorbing the ma-part of the so-called erythematogenic solar radiation, which.
are between 285 and 320 nm, and in particular the most harmful diations. Their molar absorbance coefficient re (am) calculated according to the French standard nT 01-030 for the maximum:
absorption mum is very high, since it is on average higher than laughing or equal to 25,000, which corresponds to an absorbent power.
exceptional.
While the coefficient (am) of the compounds of art an-tieur is at most of the order of 24,500, the coe ~ ficient ~ am) compounds of the invention can reach up to 45,000 as indicated in Table 3 below:. -. _. ~:
~ the compound of the wavelength:
20 table 1 or 2 in (nm) absorbance (am), 1,299 28,650 : 11 296 28.300 `
13 299 38.100 33,295 45,000 41 298 28 ~ 800: ~:
46 301 39.600 49 301 32.700 51,305 30,000 ._._. , A 290 21,000 . 284 24,500 In this table the compounds of the invention are indicated by their corresponding number in table 1 or 2 and the posed from the prior art are respectively benzylidene cam-phre is A, and the methyl sulfate of ~ 2-oxo-3-bornylidene) thyl ~ -4 phenyltrimethylammonium or B, having respectively formulas: `

[~ CH / 13 ~ H / ~ 1 ~ _ CH3, 50 ~ CH3 AB
Excellent radiation absorption properties erythematogens, i.e. radiation between 285 and 320 nm, are highlighted for the compounds of the invention tion in table 4 below indicating the percentage of ra-transmitted diations according to their wavelength. These shifts their were determined by interposing on the route of the ra-incident diation a thickness of 10 mm from a solution containing 2 mg of the compound to be examined in 100 ml of ethanol, and calculating the ratio expressed as a percentage between the flow transmitted and the incident flux, for different wavelengths between 260 and 360 nm.

Length Percentage of flow transmitted by report wave due to incident flux for the following compounds.
inci- flow tooth in nm AB nl nll n13 n33 n46 n49 260 29 26 51 ~ 9 25 22 25 35 290 2 8 3 3 1.5 1 2 1 300 3 18 2 2 1 1 1 0.5 TABLE ~ (continued):

Length Percentage of the flow transmitted compared to wave due to incident flux for the following compounds. :
inci- flow.
tooth in nm _ ~ nl nll n13 n33 n46n49 320 55 94 15 21 9 33 124 `:

340 90 100 91 91 74 89 8672: ~

It is generally observed that the protection conferred rée by the compounds of the invention covers more selectively that with compounds A and B, the range of wavelengths called erythematogenic, and that their absorbency is greater than that of these compounds A and B.
The very wide range of solubilities offered by compounds of the invention in the usual cosmetic vehicles, is highlighted in Table 5 below, in which the solubility of certain compounds is indicated in grams in 100 ~;
ml of solvent.

:

SOLVENT #

compound I _ _ water ethanol paraffin oil 0.6 0 6 190 210 .0 28 0 100 0.; ~

.
,. ;.
;,, TABLE 5 (continued) ~.
_ ,, ~
~ from S 0 LVANT

compound water ethanol paraffin oil 42 0 150 ~, So some compounds have higher solubility 100% in water, ethanol or paraffin oil, a: When others are insoluble in the aforementioned solvents, and that dlau-very finally are only soluble in one of the aforementioned solvents and insoluble in the other two.
Another subject of the invention is the process for preparing tion of the mono- and di-brominated compounds of formula I. Indeed, the plaintiff discovered that it was possible to obtain the posed above by selective bromination of the compounds of formula I ':

Y-CH2 i '.
~ ~ 0,:, H

CH3 I ' in which Y has the above values, and this with an excel ~

slow yield without bromine fixation on the radical methyl located in ~ of the carbonyl radical of camphor, nor on the benzylidene double bond, nor on non carbon atoms substituted for the aromatic nucleus.
Bromination can be carried out either with bromine or with N-bromo-succinimide, in an inert solvent, when cold or hot and under exposure to radiation in the ~ soul of ionic lengths from 200 to 800 nm, possibly in the presence a neutralizing agent.
When operating cold, i.e. at temperature ambient, the reaction time is 3 to 4 hours and when that is operated hot, preferably at reflux, the duration of the action is 30 to 60 minutes. We use as inert solvents, preferably chlorinated hydrocarbons such as tetrachloride carbon, or ether, acetic acid, benzene or carbon sulfide, and as an optional neutralizing agent-

10 alkali or alkaline earth carbonate. ``
To obtain the monobromo compound of formula I in the-which Z denotes -CH2Br, the reactants are used in an amount rigorously stoichiometric, the yield being practically quantitative. At the end of the reaction, it is filtered off any mineral salts formed, the solvents are removed, the residual mixture is concentrated and obtained by cooling a raw product which is recrystallized with a yield 85 to 90% in a solvent such as isopropanol. Compounds mono- and di-bromines of formula I thus obtained can be con-served easily and without alteration, without taking any special precautions.
When performing bromination with bromine, we in-produces it in solution in a progressive inert solvent-while stirring in the solution of the compound of formula I
in the same inert solvent. When bromination takes place a-with N-bromo-succinimide the two reagents can be introduced entirely in the inert solvent at the start of the operation, and the reaction is carried out with stirring, preferably hot.
It is possible to first obtain the mono-brominated compound ~, of formula I in which Z = CH2Br and to prepare subsequently the dibromo compound of formula I in which Z = CB r2 from of the mono-brominated compound, using both bromine and N-:

bromosuccinimide.
When it is desired to obtain a compound of formula I in which Y denotes SO3H, the reaction is carried out in the absence of the neutralizing agent, or else the reaction is terminated by an acid dification.
From the mono- and di-brominated compounds of formula I, the derivatives of formula II can be prepared.
The compounds of formula are generally prepared.
II monosubstituted on the methyl radical of the benzene nucleus that is to say in which Z 'has the value -CH2R, by doing rea ~ -gir a compound of formula I on a nucleophilic compound carrying the radical R having the meaning already mentioned, and according to the diagram:

Y- ~ CH2 y_ H2 [~ H ~ ~ H

H2Br + R ~ H2R + Br in which Y and R have the above values.
The amino compounds of formula II are prepared in lacquer ~
the radical R has the value -NRlR2, the radicals Rl and R2 having the above values, by reacting a compound of formula in which Z = -CH2Br, on an excess of ammonia or of the amine corresponding of formula HNRlR2, in an inert solvent, of pre-refers to a chlorinated solvent, an aromatic solvent, an alcohol or core a dipolar aprotic solvent such as dimethylformamide, possibly in the presence of a neutralizing agent such as alkaline or alkaline earth carbonate. Among the amines that can be used, we can cite the following: dimethylamine, di ~

ethylamine, diisopropylamine, dibutylamine, distearylamine, di-thanolamine, morpholine, piperidine, pyrrolidine, piperazine, N-methyl-piperazine, N-phenylpiperazine, without this list being limiting.
This process is illustrated in particular by examples n 3, 4, 7, 8, 9 to 13 and 77. `
The quaternary compounds of formula II are prepared by reacting a compound of formula I in which Z = -CH2Br -by heating with a tertiary amine of formula NRlR2R3 in - which the RlR2R3 radicals each have the aforementioned values except the hydrogen value. The reaction is carried out in the absence solvents or in the presence of a solvent such as those already lied ~;

: .-born above.
This process is illustrated in examples n 21 to 24 and 78.
The compounds of formula II are prepared in which has the value -OR4; -SR6; and -OCOR5 by reacting on a compound sé monobromé de ~ ormule I respectively, either an alcohol or a phenol of formula HOR4, either a thiol of formula HSR6, or a 20 acid of formula HO-COR5, the radicals R4, R5 and R6 having the ~ `
aforementioned values. In general, the reaction is carried out.
in the presence of a mineral base, a hydroxide or carbonate alkaline or alkaline earth, alkaline alcoholate, hydride sodium, an alkali metal, or an organic base such than triethylamine.
We can mention in the above process:
- the following alcohols and phenols: methanol, butanol, dodecanol, tetradecanol, hexadecanol, phenol, naphthol, hydroxybenzophenone, methyl salicylate (2-hydroxy methyl benzoate), 2-ethyl hexanol, oleic alcohol, octanol, hexanol, dimethylaminoethanol, ethylene glycol, diethylene glycol, di t-butyl p-cresol, menthol;

- the following thiols: methanethiol, thioglycolic acid, aci-mercapto-succinic, cysteine, diethylaminoethanethiol, mercap-to-2 benzothiazole, mercapto-2 benzoic acid, mercapto-3 acid propionic, ~ -aminoethanethiol, - the following acids: tetradecanoic, hexadecanoic acids, benzoic, gentisique, di-t-butyl-3,5 hydroxy-4 benzo ~ que, oléi-than.
When R4 has the hydrogen value, the radical R then has the value -OH, and an i generator is used as reagent;
ons OH which can be a carbonate or a hydroxide as illustrated in Example 25.
Likewise when R6 has the hydrogen value, one can use read as reagent, either an alkaline sulfhydrate, or thiou-then carrying out an alkaline hydrolysis according to the techniques usual nics for the preparation of thiols. ``
This process is illustrated in particular by the examples n `
39; 25; 36; 37, 38; 40; 42, 43; 44; 45; 46; 55; 26, 27; 28; 29;
30; 31; 32; 33; 34; 56; 57; 60; and those in Table 11. We prepare re the compounds of formula II in which Z 'has the value -CHR'R', the radical R 'having the value -OR'4 and the radical R'4 having the aforementioned values, according to the diagram:

[i ~ H [+ ~ H

CHBr2 + 2R '~ CHR'R' + 2Br r in which Y, and R 'have the aforementioned values, by reaction of a compound of formula I in which Z = CHBr2 and an alcohol of HOR'4 formula. The reaction is carried out in the presence of a base, as in the process for preparing the compounds of Formula II
monosubstituted comprising the radicals R4 and R6. -:

.:. . . . . ~.

~ 3 ~

Mention may be made in the above process of the use of tion of methanol as illustrated by Example 50.
The aldehydes corresponding to the formula ge-neral II in which Z 'has the value -CHC) according to the scheme ~

CH ~ OR 4 ~ HOH ~ CHO ~ 2 HOR ' in which Y and R'4 have the above values, by performing hydrolysis in an acidic aqueous medium of an acetal of general formula rale II in which R 'has the value -OR'4, as illustrated by Example 51.
We can also obtain the same aldehyde by oxidizing direct tion of the monobrominated derivative of formula I.
Compounds in which Z 'has the value -CHR'R' and R ' at the value SR'6 are preferably prepared from alde-. ; ~
corresponding hyde in which Z '= CHO and a thiol R'6SH (2 é-:
molar equivalents) in acid catalysis according to known methods mercaptal preparation, such preparation is illustrated by example 73.
The acids of general formula II are prepared according to the diagram: ~:

.. ,,. . . :, ..... .

3 ~ W ~

Y - CH2 y_ ('2 [~ C ~ I ~ CH

CHO ~ O ~ ~ COOH
in which Y has the aforementioned values, by oxidation of an aldehy-of general formula II in which Z 'has the value -CHO, com-illustrated by example 49.
The esters of general formula II are obtained in the-which Z 'has the value -COOR ", by esterification of the acid to using an alcohol of formula ~ IOR "in which R" has the values mentioned above.
The acids of formula II are also prepared in the-which Z 'has the value -CH2-COOH by oxidation of the corresponding nitriles-layers of formula II themselves prepared by reaction of a laid of formula I with a cyanide; and we get the esters correspondents by esterification using a formula alcohol HOR ".
The preparation of the compounds for which Z 'denotes `~
-CH2I or -CH2S2O3Na is carried out from the corresponding compound ~, '20 of formula I on which is reacted respectively an io ~ ure : alkaline or sodium thiosulfate for example in hydro medium alcoholic or in dimethylformarnide at a temperature of 50 at 100C. ;
Finally, we can also prepare the compounds quater- ::
. naries of general formula II by quaternization of the compounds of general formula II in which Z 'has the value -CH2-NRlR2 and in which Rl and R2 do not have the hydrogen value. From quaternizing agents which can be advantageously used i sés we can mention: dimethyl and cliethyl sulfates - 18 -:

,; "

that, alkyl halides or sulfonates, halides hydroxyalkyl, propane sultone, as illustrated in particular in examples 14 to 20 and 66 to 69.
The invention finally relates to a cosmetic composition that containing one or more compounds of formula I or II, sta-light radiation, and ensuring a pro-effective detection of the human epidermis against radiation in the range of erythematogenic wavelengths from 280 to 320 nm, but allowing selectively the radiation having a 10 - wavelength greater than 320 nm to obtain excellent ~
tanning conditions without erythema. -The composition of the invention can be presented under the form of a solution, lotion, emulsion such as do cream, gel, milk, or oil, and generally, con in all the usual forms of cosmetic compositions;
anti-actinics. It may also contain adjuvants cosmetics such as thickening agents, softeners, greases, emollients, wetting agents, surfactants, as well as preservatives, anti-foaming agents, perfumes or any other compatible ingredient usually used in cos-metic. The composition may also contain one or more a-propellants such as Freons *, light hydro-carbides, carbon dioxide or nitrous oxide, and be presented under the shape of a "spray" or aerosol can.
The composition of the invention contains 0.5 to 10% and preferably 1.5 to 6% by weight of one or more compounds of formula I or II. Among the solvents used, there may be mentioned:
water, mono- or poly-alcohols containing 1 to 4 carbon atoms bone, as well as their mixtures, or hydro-al-coolic. The alcohols preferably used are ethanol, isopropyl alcohol, propylene glycol, glycerol, sor-bitol, oleic alcohol and hydro-alcoholic mixtures are * trademark preferably mixtures of water-ethyl alcohol.
The composition of the invention can be as well colored than colored with usual dyes and / or pigments-ment used in anti-sun compositions, in particular a ~
with iron oxides in proportions of about 0.01 to 0.2%
by weight relative to the total weight of the composition, as in the case of examples B4 B5 and B6.
The great flexibility of formulation offered by the use of the compounds of formulas I and II appears all the same particularly in compositions-comprising different phases-annuities such as "water in oil" or "oil in water ". Indeed as the few examples show as in table 5, it is possible in particular to incorporate both in the composition, a water soluble compound and an oil soluble compound, such that one and the other of the phases contains an effective filter to stop unwanted actinic radiation, by choosing from compounds with the desired solubility, those with the best compatibility with solvents and other ingredients ents contained in the composition. This great flexibility of formulation is made possible thanks to the vast family of com-layered of the invention which while having the same properties particularly selective filters with regard to actinic radiation, between the erythematogenic zone and the zone non-erythematogenic browning (wavelength greater than 320 nm), also offer a wide range in terms of do their solubility and compatibility with solvents and usual cosmetic ingredients.
Among the examples of compositions comprising a filter in each of the two phases we can mention in particular the compositions of Examples A7, B1 and B6.
The composition of the invention may also contain ~ 3 ~ D

,,, other agents known for their protective action against solar radiation, such as agents absorbing part of the radiation, such as the above-mentioned compounds A and B, as illustrated by examples A1 and A6.
The composition of the invention may also contain agents promoting hydration of the skin or slowing down ~ -its dehydration, such as pyrrolidone acid salts car-boxylic, hydroxy acid salts, amino acids or ~ 'u-as shown in example B8, and this in a quantity 0.3 to 3 / O.
When the composition contains amino compounds of the invention, it is advantageous to obtain the characteristics solubility, compatibility, or even the conditions most favorable safety conditions, use them under the form of a preparation, carried out before or at the time of the use, and resulting from their total neutralization or by- ~ -tial with a mineral or organic acid. The composition conti ~
ent then either the corresponding ammonium salt of the amino compound, or the mixture of the aforementioned ammonium salt and the amino compound.
Such a composition is illustrated by examples A1, A4, A5, ~;

A6, Bl and B7.
Similarly, the composition may contain either compounds acids of the invention, either salts of these acids, or alternatively mixtures resulting from their partial neutralization by a base mineral or organic, carried out before or at the time of use, always to obtain advantageous conditions solubility or compatibility, or even better tolerance rancid skin.
When the composition contains compounds of the invention tion comprising two filtering structures, in particular in the case of compounds n 13, 33, 34, 35 and 46, protection is obtained particularly effective, as illustrated in the examples.

.
;, .

The various types of composition of the invention are illustrated as follows:
the milks by examples A1 to A7, the creams by examples B1 to B8;
the lotions with examples C1 to C5;
sprays by examples Dl to D4, foams by examples El E2;
sun oils by examples F1 F2.
Among the cosmetic adjuvants used in positions of the invention in an amount of 1 to 40% by weight relative to the weight of the composition, lanoli-ne, fatty acid triglycerides, glycerin, polyethylenes neglycols, ethoxylated lanolins, palmitate and myristate isopropyl, castor oil, cetylstearyl alcohol, glycerol monostearate, cetyl alcohol, bu stearate tyle, organic and mineral waxes.
The following nonlimiting examples in which the percentages are understood unless otherwise stated by weight, and the temperatures in degrees centigrade, allow better understanding the object of the invention.
EXAMPLES OF PREPARATION EXAMPLE 1 - Pre ~ aration of compound N 1 from table 1: (bromome ,.
4-thyl benzylidene) -3 camphor.
1st method: a mixture containing 127 g is heated to reflux (0.5 mol.) P-tolylidene camphor, 60 g sodium carbonate anhydrous and 600 ml of carbon tetrachloride. After homogeni-complete heating is stopped, then a solution is added 27.5 ml. (0.5 ml) of bromine in 100 ml of tetrachloride of carbon, while exposing the reaction mixture to the action a 150 watt white light lamp. We adjust the speed introduction of bromine to maintain a gentle reflux.
At the end of the reaction, the mineral salts are filtered off.
rals formed and the solution is concentrated to dryness. We recrystallize the residual solid in isopropanol and l ~ 144 g are obtained pale yellow needles melting at 125C.
Analysis: Calculated% C 64.86 H 6.30 Br 24.02 C18H21Br Found% 64.90 6.42 24.05; ~
2nd method: A mixture containing 12.7 g ~ is heated to reflux -~ 50 millimoles) of camphor p-tolylidene and 8.9 g (S0 m. Moles) of N-bromo succinimide in 100 ml of whole carbon tetrachloride by exposing it to the action of a white light lamp of 150 watts. After filtration of the suspension thus obtained and concen ~
10 ~ filtration of the filtrate, collecting 16.5 g of compound n 1.
EXAMPLE 2 Preparation of Compound No. 2 in Table 1: (dibromo-4-methylbenzylidene) -3 camphor.
1st method: One heats with stirring until boiling solution containing 203 g (0.8 mole) of p-tolylidene camphor in 1200 ml of carbon tetrachloride with 195 g of carbonate anhydrous potassium. 87.5 ml (1.6;
moles) of bromine dissolved in 200 ml of carbon tetrachloride, by exposing everything to the action of a 150 watt light lamp re white. The speed of introduction of the bromine and the 20 heating so that the mixture is kept boiling tion. After the end of the introduction, heating is continued under illumination for about 30 minutes, then filter it;
everything and the filtrate is concentrated to dryness. We recrystallize the resi-of the solid thus obtained in 600 ml of isopropanol. We collect 278 g of compound 2 in the form of dark pale yellow needles at 96C.
Analysis: Calculated% C 52.43 H 4.85 Br 38.83 C18H20 2 Found% 52.42 4.99 38.86 2nd method: Heat at reflux for 1 hour and under illu-mination by white light of a 150 watt lamp, 50 m.moles of N-bromo-succinimide and 50 m. moles of (bromo-methyl-4 benzylidene) -3 camphor in 100 ml of carbon tetrachloride.

The succinimide formed gradually collects on the surface , ~,. ,::
"~ ''. '~'.,,:
. -. .:

and it is separated by filtration. The filtrate is concentrated to dryness and thus collecting 20.5 g of compound n 2.
3rd method: We react 50 m. moles of p-tolylidene camphor and 100 m. moles of N-bromo-succinimide, under the operating conditions racks and solvent indicated in the second method but by heating at reflux for about 2 hours.
EXAMPLE 11 Preparation of Compound No. 11 in Table 2: (piperi-4-dinomethyl benzylidene) -3 camphor t ~ ~ 0, `, ' ~ ~ CH

~ 83 g of compound n are added to the spatula in portions ; 1, in 100 ml of a solution containing 64 g of piperidine in ethanol. The mixture is stirred for 24 hours at room temperature.
rature room, then we ~ ilter the whole, we concentrate the filtrate, the residue is dissolved in sulfuric ether and filtered.
The ethereal solution is concentrated to dryness to obtain 75 g of a residual solid which is recrystallized from a mixture of ether petroleum and isopropanol. We obtain pale yellow crystals melting at 96C.
Analysis C23H31N -Calculated% C 81.90 H 9.20 N 4.15 Found% 81.80 9.00 4.05 EXAMPLE 10 Preparation of Compound No. 10 in Table 2: ~ Bis-(octadecyl) 4-aminomethyl benzylidene ~ -3 camphor:
It is stirred in a boiling water bath for 8 hours one mixture containing] 66.5 g of compound 1 and 521 g of distearyl 3 ~

amine. After cooling, the whole is taken up with e-ther of petroleum, it is filtered, and the filtrate is concentrated to dryness.
290 g of a yellow product melting at 37C are thus collected.
Analysis C54H95NO -Calculated% C 84.04 ~ I 12.46 N 1.63; ; ~
Found% 84.11 12.12 1.92 EXAMPLE 4 Preparation of Compound No. 4 in Table 2: (diethyl-;
. , 4-aminomethyl benzylidene) -3 camphor: -It is heated to 60C with stirring for 30 minutes u-10 do solution containing 33 g of compound n 1 and 22 g of dléthylami-ne in 100 ml of carbon tetrachloride. We separate the preci-filtered by filtration and the filtrate is concentrated to dryness. We get `
ent 31 g of a chromatographically pure yellow oil. ~
Analysis C22H31NO ~ ;;
Calculated% C 81.18 H 9.60 N 4.91 Found% 81.02 9.43 4.77 Compounds 3, 7, 8, 9, 12, 13, 77 of Table 2 by reaction of an amine on (4-bromomethyl benzyli-;
dene) -3 camphor according to a procedure similar to that of 1 '-20 example 4, but using diethylamine as ami; ~
our co-correspondents for each compound, as indicated in the table 6 below. This table also mentions the solvent u-used, the temperature and the duration of the reaction as well as the melting point of the compound obtained or its appearance, and its index of amine calculated and found expressed in milli-equivalent per gram.

_ ..:.
~ omitted Amine used Solvent Temp- Duration Point Index of a-reacting with used stripped of mine meq / g n the compound nl of reac- reac-tion tionsion _ CC ClaéCU ~ vé

3 dimethylamine methanol 20 120 h 65 3.37 3.41 7 diethanolamine thanol 80 5 h oil 2.80 2.83 ,:,,. ::,:.

TABLE 6 (continued) Compound Amine used Solvent Temperate Duration = Amine index¦
reacting with used rature of meq / g n the compound nl of re-react- _ action tlon sion CC Calculated Found ~;

8 diisopropyl ethanol 80 6h 89 2.83 2.85 9 dibutylamine ethanol 80 2h oil 2.63 2.72 12 ethanol morpholine 80 5h 89 2.95 2.98 13 p-aminoben- metha 65 6h 207 2.57 2.55 zoate nol 77 piper ethanol 80 lh 204 2.39 2.39 ~; ~

Preparation of the salts formed with a mineral acid or orqaniq ~
from amino compounds of formula II.
Generally, the acid is introduced into a solution of the amino compound of formula II at ordinary temperature `~ -or by heating slightly. The mixture is concentrated to dryness and crystallizes the residue in a suitable solvent. As an example-, ~:
ples table 7 below indicates the preparation conditions compounds 5, 6, 7a, 8a and 9a in Table 1 from corresponding amino compounds, mentioning each time the acid and solvent used. This table also indicates for each compound obtained, the crystallization solvent, the point of fusion and elementary analysis as a percentage of C, ~ I and ~ cal-assfucked and found.

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PREPARATION OF THE QUATERNIZED COMPOUNDS OF FORMULA II.
; EXAMPLE 14 Preparation of Compound No. 14 in Table 2:
-p-toluene sulfonate of (2-oxo-3-bornylidene-methyl) -4 benzyl di-ethylmethylammonium.
The mixture is refluxed in toluene for 4 h 30 min, 65 g;
of compound n4 of table 2 and 41 g of p-toluene sulfonate of methane thyle. After cooling, the precipitate formed is drained and crystallizes it out from methyl methyl ketone. 86 g are thus obtained.
of product in the form of whitish flakes melting at 155C ~;
Analysis - C80H41N4S -Calculated% C 70.41 H 8.08 N 2.74 S 6.27 Found% 70.31 7.96 2.92 6.41 A procedure analogous to that of Example 14 allows puts to prepare compounds n 15 to 24, 66 to 69 and 78 of the table 2, as shown in Table 8 below. This table mentions-ne for each compound prepared, the compound of formula II or a-starting mine, the quaternization agent which can be a compound se monobromé of formula I such as those appearing in the table 1, the solvent used, and the duration of the reaction ~ The table also indicates for each compound obtained the melting point as well as the elementary analysis in percentage of C, H and N cal- ~ `
assfucked and found.

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EXAMPLE 25 Preparation of Compound No. 25 in Table 2: (hydroxy-4-methylbenzylidene) -3 camphor.
33 g of compound n 1 are added all at once in an ethanolic solution containing 6.2 g of potassium hydroxide, and it is heated fe all at the boil. The mixture is maintained for one hour at reflux and then evaporated to dryness. We take the residue with benzene, and after filtration the extract is concentrated to dryness benzene. A pale yellow solid is thus obtained, which after crystallization from petroleum ether, gives yellow crystals not pale melting at 35C.
Analysis - C18H222 Calculated% C 80.00 H 8.15 Found% 80.18 8.31 EXAMPLE 27 Preparation of Compound No. 27 in Table 2: (butoxy-4 benzylidene) -3 camphor.
19.5 g of sodium butylate are prepared, leaving to act 4.6 g of sodium in 50 ml of butanol. At the end of the reaction tion, 66.6 g of compound nl and 100 ml of toluene are added. We heat the mixture for 8 hours in a boiling water bath, then it is filtered and the filtrate is concentrated to dryness. So we collect if 64 g of a pale yellow oil, which can be distilled to give ner an oily product having a boiling point of 210C under 0.5 mm Hg.
Analysis - C22H30O2 Calculated% C 80.98 H 9.20 Found% 80.66 9.07 Compounds n 26, 28 and 30 are prepared according to a method analogous to that of Example 27, except that we replace butanol respectively by methanol (example 26 ~, dodé-canol (example 28) and hexadecanol (example 30), and that in example 26 methanol is used as solvent instead of to-luene. The following compounds are obtained respectively:

. ,,., -,.

Compound # 26: Boiling point at 175C at 0.25mm Hg.
Analysis - ClgH24O
Calculated% C 80.28 H 8.45 Find% 80.29 8.46 Compound # 28: pale yellow non-distillable oil ~
~ analysis ~ C30H462 Calculated% C 82.19 H 10.50 Found% 82.05 10.27 -;
Compound No. 30: pale yellow solid melting at 40C.
. .
Analysis - C34H542 Calculated% C 82.59 H 10.93 Found% 82.33 10.75 EXAMPLE 29 Preparation of Compound No. 29 in Table 2: (tetra-4-decyloxymethyl benzylidene) -3 camphor.
75 g of myristic alcohol are introduced into a solution containing 18.9 ~ / O of sodium methylate in methanol. After ~
having evaporated to dryness the mixture obtained, the residue is taken up by ~ ~ `
~, benzene and 116.5 g of compound N 1 are added.
~ mixture at reflux for 8 hours, then filtered, evaporated Dry the filtrate and the oily residue obtained is distilled. We re-thus collects 111 g of an oil (Eb = 250C under 0.2 mm Hg) which solidifies quickly giving a solid beige melting at 35C.
Analysis ~ C32H502 Calculated% C 82.40 H 10.73 Found% 82.22 10.70 `
EXAMPLE 31 - separation of compound n 31 from Table 2: (phenoxy-4-methylbenzylidene) -3 camphor.
11.6 g of sodium phenate are prepared by reaction of the ~ ~
corresponding amounts of phenol and soda in alcoholic solution - -olique, followed by dry evaporation. We submit the phenate re-picked with stirring for 10 hours at reflux with 33.3 g of compound n 1 in 100 ml of methyl ethyl ketone. After filtering ",.,..,. ~: ~"'~
'. ': ~,'! ':. . .. i,,. l ~

tion of the reaction medium, the filtrate is evaporated to dryness. We ob-holds 26 g of a white product melting at 139C.
Analysis - C24H2602 Calculated% C 83.24 H 7.51 Found% 83.27 7.62 EXAMPLE 34 Preparation of Compound No. 34 in Table 2: ~ oxo-2 bornylidene-3 methyl) -4 benzyloxy ~ -2 methyl benzoate.
o "
L-- ~
where fH

CH3OOC ~
A solution is heated for 4 hours at the boil methanolic containing 7.6 g (50 m mol.) of methyl salicylate, 2 g of sodium hydroxide, and 16.5 g (50 m mol.) Of compound n 1. We concentrate dry the reaction mixture and extract the residue with hot benzene. The benzene solution is concentrated and crystal-read the residue in methanol. 14 g of cris-white rates melting at 120C.
Analysis - C26H2804 Calculated% C 77.23 H 6.93 Found% 77.07 7.06 Preparing in a manner analogous to that of Example 34 compounds n 32, 33, 36, 37, 38 of Table 2. For this purpose, always use compound # 1 but replace salicylate methyl respectively by ~ -naphthol (example 32), hydroxy-4 benzophenone (example 33), myristic acid (example 36), :., ..:. ... .

~ L3 ~
': `
palmitic acid (example 37) or benzoi'que acid (example 38).
Table 9 below indicates for each example, the hydroxylated compound or the acid reacting with compound nl, the ; duration of the reaction, the number of the compound obtained, are point of fusion, and the corresponding elementary analysis in percentage of C and H calculated and found.

Compound Hydroxy compound- Duration Point Elemental analysis the reacted acid or n sliding with CH reaction compound nl tion C
Calc.% Tr.% Calc.% Tr.%

32 ~ -naphthol 6h 120 84.85 84.62 7.07 7.38 33 hydroxy-4 ben- 5h 122 82.67 82.53 6.67 6.61 zophenone 36 myristic acid 2h 29 80.00 79.7410.00 9.98 37 palmitic acid 6h 30 80.31 80.5810.24 10.27 38 benzoic acid 8h 63 80.21 ~ 30.286.95 6.99 EXAMPLE 35 Preparation of Compound 35 in Table 2: Acid ~ (2-oxo-3-bornylidene-methyl) -4 benzyl oxy ~ -2 benzoic.
Compound 34 is heated at reflux for 3 hours.
in an alcoholic potassium solution ~ The acid is precipitated by acidification and a white product is obtained which melts at 128C.
Analysis - C25H2604 Calculated% C 76.92 H 6.67 Found% 77.01 6.96 Preparation of thioethers:

EXAMPLE 39 Preparation of Compound No. 39 in Table 2: (mercap-4-tomethyl benzylidene) -3 camphor.
The mixture is heated under reflux for 1 hour in isopropanol, 7.6 g ~ 0.10 mol.) Of thiourea, and 33 g (0.10 mol.) Of compound nl.

. ~,; , .. ~.:, ~ 3 ~ 6 ~
'.

The precipitate formed is filtered off and collected in this way.
if 35 g of isothiouronium salt melting at 264C.
Analysis - C10H25BrN2 S -; Calculated% C 55.74 H 6.16 S 7.83 Found% 55.74 6.37 7.83 25 g of isothiouronium salt are hydrolyzed by prolonged heating with an excess of sodium hydroxide in a hydroethanolic medium. AT-after neutralization by an acid, the precipitated product is drained and it is crystallized from methyl isobutyl ketone. We obtain white crystals melting at 87C.
Analysis - C18H22OS; ~
Calculated% C 75.48 H 7.74 S 11.19 Found% 75.49 7.61 11.10 Preparing in a manner analogous to that of the example 39 the thioethers of formula II, by heating at low temperature derived from compound n 1 and the corresponding thiol compound in pre sence of a basic agent. This agent can be deleted if the thiol product itself has a basic function, for example-ple a tertiary amine function. The separation of the product is then perform according to the usual techniques.
The conditions for the preparation of compounds 40, 42 to 46 and 55 of Table 2 are shown in Table 10 below.
This table mentions for each compound prepared, the thiol compound used in place of the thiourea of Example 39, the base and the solvent used, the temperature and the duration of the reaction, as well as the number of the compound obtained, are fu-sion and its elementary analysis as a percentage of C, H and S cal-assfucked and found.

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EXAMPLE 47 - Preparation of Compound No. 47 in Table 2: (cyano ~
4-methylbenzylidene) -3 camphor.
7 g of compound n 1 of table 1 are added to a solution.
methanol containing 2.5 g of potassium cyanide and heat everything at reflux for 30 minutes ~ Concentrate at dry the mixture obtained, the residue is taken up in water, dried filters the insoluble fraction and crystallizes it in ethanol to obtain whitish crystals melting at 127C.

Analysis - ClgH21NO
Calculated% C 81.68 H 7.58 N 5.01 Found / O 81.41 7.36 5.22 -EXAMPLE 48 Preparation of Compound No. 48 in Table 2: Acid (2-oxo-3-bornylidene-methyl) -4 phenylacetic.
0.050 mol of the compound is heated under prolonged reflux # 47 in Table 2 with an excess of a mixture of acetic acids and hydrochloric acid and after filtration and washing white crystals melting at 134C.
Acid number (meq / g) y C 1 gH 2 2 3 Calculated: 3.36 "
Found: 3.33 EXAMPLE 5b - Preparation of Compound No. 50 in Table 2: (dim-4-thoxymethyl benzylidene) -3 camphor.
One mole of com is heated for two hours at reflux.
posed n 2 of table 1 in a methanolic solution containing 2 moles of sodium methylate. The mixture is concentrated to dryness, extract the residue with benzene, filter the extract, then the filtrate is evaporated to dryness. A yellow powder is thus obtained blade melting at 98C.
Analysis - C20H26O3 Calculated% C 76.43 H 8.28 Found% 76.26 8.47 EXAMPLE 51 Preparation of Compound No. 51 in Table 2: (forrnyl-4 benzylidene) -3 camphor.
By complete hydrolysis of compound 50 in Table 2 in a water-dioxane mixture in the presence of hydrochloric acid after obtaining the concentration of the solvent, the separation of a pale yellow product melting at 116C.

AnalySe - C18H202 Calculated% C 80.60 H 7.46 Found% 80.64 7.56 `~
The same compound 51 can also be prepared by complete oxidation of compound n 1 using dimethyl sulfoxy-of in the presence of potassium carbonate.
EXAMPLE 49 Preparation of Compound No. 49 in Table 2: Acid (2-oxo-3-bornylidene-methyl) 4 benzoic.
The oxidation of compound No. 51 in Table 2 is carried out.
with potassium permanganate in a water-acetone mixture. AT-after filtration and washing of the precipitate in the same water mixture - -acetone, a white product is obtained by acidification of the filtrate melting at 240C.
Analysis - C18H20O3 Calculated% C 76.06 H 7.04 Found% 76.17 7.06 EXAMPLE 56 Preparation of Compound No. 56 in Table 2: Dihydro-xy-2,5 (2-oxo-bornylidene-3-methyl) -4 benzoate benzoate.
Compound 56 is prepared according to Example 31, starting from gentisic acid- it is a white powder melting at 220C.
AnalySe - C25H265 Calculated% C 73.89 H 6.40 Found% 73.82 6.57 30 EXAMPLE 57 - Preparation of co ~ sé n 57 du_tableau 2 ~ di (t-butyl) 3,5-4-hydroxy (2-oxo-3-bornylidene-methyl) benzoate -4 benzyl.

- -,,,:;

Compound 57 is prepared according to Example 31, from di (t-butyl) -3.5-hydroxy-4-benzoic acid, replacing erasing methyl ethyl ketone with dimethyl ~ ormamide. He pre-smells in the form of a pale yellow solid ~ waving at 132C.
ANALYSIS ~ C33H424 Calculated% C 78.88 H 8.37 Found% 79.13 8.42 EXAMPLE 60 Preparation of Compound No. 60 in Table 2: (Octyloxy-4-methylbenzylidene) -3 camphor.
A suspension of 2.1 g (50 millimoles) of hydride sodium (in oil) is added little by little, while stirring 6.5 g (50 millimoles) of octanol-1 in 100 ml of toluene. When-that the evolution of hydrogen is finished, we add in portions 16.6 g (50 millimoles) of p-bromomethyl benzylidene-3 camphor, ~ -then the mixture is brought to reflux for 3 hours. After addi-tion of water, the toluene phase is decanted, dried and concentrated this one dry. The residual syrup is distilled under pressure scaled down. 8.8 g of yellow liquid boiling are thus collected.
240C under 0.1 mm Hg.
Analysis - C26H38O2 Calculated% C 81.67 H 9.95 Found% 81.52 10.15 The compounds of the following table 11:

~ omitted Alcohol used Duration Point ~ usion Elemental analysis reac- or Eb. VS
n tion Calc / O Tr.% "slc.% Tr ~ O

._. _. ___ _._:
62 Menthol 4 h Oil 82.35 82.16 9.80 9.88 59 Ethyl-2 hexa- Oil 81.67 81.98 9.95 9.95 ... . . .

~ 3 ~
TABLE 11 (continued) ~
-Compound Alcohol used Duration Melting point Elementary analysis reac- or Eb. VS _ n tion CH

__ _ _ Calc.% Tr.% Calc.% Tr. ~

70 Oleic alcohol 8h Oil 83.08 83.16 10.77 11.19 64 Dimethylamino 3h Hydrochloride 69.91 69.70 8.53 8.66 ethanol F = 152 72 Ethylene glycol 5h Eb = 195 76.45 76.48 8.28 8.14 F 54C - ~

76 Diethylene gly- 6h Oil 73.7473.77 8.38 8, ~
,,:
EX ~ MPLE 63 - Preparation of compound n 63 of Table 2: ~ (di (t-butyl) -2.6 methyl-4 ph ~ noxymethyl) -4 benzylideneJ-3 camphor.
Compound 63 is prepared according to Example 29, starting from di-tertio-butyl p-cresol, replacing benzene with di-me ~ hylformamide. A whitish powder is obtained which melts at 135C.

Analysis - C33H4402 Calculated% C 83.90 H 9.32 Found% 83.94 9.52 EXAMPLE 71 Preparation of Compound No. 71 in Table 2: tIodome-4-thyl benzylidene) -3 camphor.
A mixture of 66.6 g of compound 1 and 40 g of iodide sodium in acetone (500 ml) is heated under reflux for three hours. The reaction product is precipitated by addition of water, filtered, and wrung. 70 g of a dark yellow solid are obtained.
at 108C.
Analysis - C18H21IO .- ~

Calculated% C 56.84 H 5.53I 33.42 Found% 56.58 5.6033.18 3 ~

EXAMPLE 73 Preparation of Compound 73 in Table 2: Acid (2-oxo-3-bornylidene-methyl) -4 benzyldithiodiacetic.
A solution of 26.8 g of compound 51 and 16.4 g of acid thioglycolic in dichloroethane is heated to the boil for 3 hours, in the presence of concentrated sulfuric acid. Then concentrated to dryness. The residue is extracted with ether; the phase é-is washed with water, then concentrated to dryness. We thus obtain if 38 g of a whitish solid, melting at 116C.
Calculated acid number 4.61 meq / g Found 4.64 meq / g ~
EXAMPLE 79 Preparation of Compound 79 in Table 2: N-methyl N, N'-bisf oxo-2 bornylidene-3 methyl) -4 benzyl ~ piperazinium bro-; ripe.
33 g of compound 1 and 5 g of N-methylpiperazine are stirred for 1 h at room temperature in toluene (200 ml) in the presence of sodium carbonate (6 g). The insoluble matter is filtered;
rewashed with a mixture of water and toluene, then wrung out. We re-picks, after drying, 23 g of a white solid melting around 200C
with decomposition.
20 Dosages: Tertiary amine index Ionized chromium -Calculated%: 1.46 meq / g 1.46 meq / g Found% ~ 1.48 meq / g 1.47 meq / g COMPOSITION EXAMPLES
::
In general, the compounds of formula I or II; ~
can be incorporated directly into a composition intended to protect the human epidermis against solar radiation.
However when they are in the form of an acid, that is to say that at least one of the radicals Y, and Z 'denotes a acid radical, they can be easily neutralized at the preferred pH

30 using a mineral or organic base, chosen as a function of its particular cosmetic properties and of the solubility r desired. Similarly, the basic amino compounds according to the invention can be neutralized to the preferred pH with a mineral acid or I ~.

3L3 ~

organic.
A. Compositions of sunscreen milks::
Example A1 - Preparing the medium protective sunscreen milk do as shown below:
oxyethylenated cetylstearyl alcohol containing 25 moles of oxide 5 ethylene EO, ie "to 25 EO"
cetyl alcohol 1 2-octyldodecanol 15 vaseline oil Codex 5 10 alfalfa unsaponifiables 0.2 benzylidene camphor 1 - :.
compound n 6 2.5.
methyl parahydroxybenzoate qs perfume 0 5 water qs 100 Exernple A2 ~ The following sunscreen milk is prepared:
Sipol wax 5 Vaseline oil 6 Isopropyl myristate 3 -:
20 Silicone oil cetyl alcohol glycerin 20 preservative o, 3; ~
fragrance 0.3:, compound n ~ 22 3 water qs 100:
EXAMPLE A3 The nonionic sunscreen protective milk is prepared.
as following: ~.
Sipol wax 5 30 Vaseline oil 6 Isopropyl myristate 3 dimethylpolysiloxane cetyl alcohol 1.

3 ~
Preservative 0.3 glycerin 20 Compound # 14 2.5 `
perfume 0, water qs 100 `
Example A4 - The following sunscreen milk is prepared:
Sipol 5 wax vaseline oil 6 isopropyl myristate 3 10 dimethylpolysiloxane 1 `~
cetyl alcohol preservative 0.3 glycerin 20 compound # 7 3 perfume 0.5 malic acid 1,2 water qs 100 Example A5 - The following protective milk is prepared: -The same composition is prepared as in Example A, except that compound # 6 and benzylidene camphor are replaced by:
Compound No. 42 0.5 Magnesium salt of compound 42 2.9 Example A6 ~ The following sunscreen milk is prepared:
oxyethylenated cetylstearyl alcohol containing 25 moles of oxide ethylene EO, ie "to 25 EO" 5 cetyl alcohol 2-octyldodecanol 15 vaseline oil Codex 5 alfalfa unsaponifiables 0.2 30 benzylidene camphor compound n 42 neutralized to pH 6 with potash aqueous 5 N 3 ~

'.:

~ $: ~ 3 ~

methyl parahydroxybenzoate qs perfume 0.5 water qs. 100 Example A7 - The sunscreen protective milk is prepared following non-ionic:
Sipol 5 wax vaseline oil 6 isopropyl myristate 3 `
dimethylpolysiloxane 1 10 cetyl alcohol preservative 0.3 glycerin 20 ~ -compound # 6 2.5;
compound # 9 2 perfume 0 5 water qs 100; ~
B. Compositions of sunscreen creams:
:., Example Bl - The following strong anti-sun cream is prepared protection:
20 polyoxyethylene hydrogenated palm oil "at 25 EO" 5 cetylstearyl alcohol "at 15 EO" 5 ~; ~
lanolin 3 lanolin alcohols sunflower oil 5 vaseline oil 10 compound n 26 2.5 compound n 8 Bis 4 propylene glycol 5 conservatives qs 30 fragrance 0.5 water qsu 100 , ~.,.

Example B2 ~ The following anti-sun cream is prepared:
cetylstearyl alcohol 2 glycerol monostearate 4;
cetyl alcohol 4 vaseline oil 5 butyl stearate 5 propylene glycol 7 0.125 silicone oil 0.5% polyox 3.5 10 preservative 0.3 perfume 0.4 compound # 14 4 water qs 100 Example B3 - The non-sunscreen protective cream is prepared next pic:
Sipol 7 wax glycerol monostearate 2 vaseline oil 15 silicone oil 1.5 20 cetyl alcohol 1.5 preservative 0.3 -glycerin 10 ~
Compound # 27 5 r ~ perfume 0 5 : water qs 100 ~:
Example B4 - Anioni sun protection cream is prepared as following:
self-emulsifying glycerol monostearate 6, . polyoxyethylene sorbitan monostearate "at 60 EO" 2 30 stearic acid 2 cetyl alcohol 1,2 lanolin 4 .,:::,: ,,.

~ L3 ~

vaseline oil 30 preservative 0.3 triethanolamine 0.1 - ~
compound # 37 3:
iron oxides 0.2 perfume 0 5 water qs 100 Example B5 - The following anti-sun cream is prepared: -; cetylstearyl alcohol 2 10 glycerol monostearate 4 cetyl alcohol. 4 ~ ~;
vaseline oil 5 butyl stearate 5 propylene glycol 7 0.125 silicone oil: ~
0.5% polyox 3.5 preservative 0.3 perfume 0 4 compound n 49 1 '' 20 iron oxides 0.01. :
0.4S potash water qs 100 ~, Example B6 ~ The following anionic protective cream is prepared: ~:
self-emulsifying glycerol monostearate 6 - polyoxyethylenated sorbitan monostearate "at 60 EO" 2 stearic acid 2 cetyl alcohol 1,2 lanolin 4 vaseline oil 30 30 preservative 0.3 triethanolamine 0.1 compound # 29 2 . ,; . ,::

~ 3 ~
compound # 7 3 iron oxides 0.1 perfume 0.6 water qs 100 `
Example B7 - The following anti-sun cream, neutrali- - is prepared partially seated:
cetylstearyl alcohol 2 glycerol monostearate 4:
cetyl alcohol 4 10 petrolatum oil 5 -butyl stearate 5 propylene glycol 7 0.125 silicone oil 0.5% polyox 3.5 ~:
preservative 0.3 `
perfume 0.4 compound n 52 0.75 triethanolamine salt of compound no 52 3 .. -Example B8 ~ The following moisturizing anti-sun cream is prepared: '~; ~
20 Sipol 7 wax glycerol monostearate 2 ~:
vaseline oil 15 silicone oil 1.5 cetyl alcohol 1.5 preservative 0.3 glycerin 10 compound 27 5 sodium pyrrolidone carboxylate 2:
perfume o, 5 30 water qs 100 We obtain a good analogous result by replacing in the above sunscreen, pyrrolidone carboxylate sodium with sodium glycolate in an amount of 1 g. or in adding 1 g of sodium glycolate to the composition of example ple B2.
C. Examples of sunscreen lotions:
Example Cl - The following anti-sol lotion is prepared:
lanolin 2.5 butylhydroxyanisole 0.025: ~
butylhydroxytoluene 0.025 0.0125 ~ octyl gallate:
C8 - C12 fatty acid triglycerides 40 perfume 1.25 compound # 28 4 alcohol 96 qs `100 ~;
Example C2 - The following sunscreen lotion is prepared:
: glycerin 5.
polyethylene glycol 400 0.5:, 'ethoxylated lanolin 1 ~:
; soluble scent 2:
compound n 16 2 20 a 96 96 alcohol water qs 100 Example C3 - The hydro-alcoholic sunscreen lotion is prepared next:
compound n 14 3:
glycerin 5 polyethylene glycol 400 0.5 96 50 alcohol soluble scent 2 water qs 100 Example C4 - The oleo-alcoholic anti-sun lotion is prepared next: :
compound n 8 bis 3 - 4 ~ 3 -fatty acid triglycerides C8-C12 40 96 56.5 ethanol perfume 0 5 Example C5 - The following sunscreen lotion is prepared: -compound # 19 10 glycerin 5 96 50 alcohol polyethylene glycol 400 0.5 oxyethylenated lanolin 1 -10 soluble scent 2 water qs 100 D. Examples of sunscreen sPraY:
Example Dl - The following sunscreen spray is prepared::
absolute alcohol 30 isopropyl myristate 20 castor oil 2 lanolin 5 perfume compound n 17 2:
20 freon 12 40., ~
Example D2 ~ The oleo-alcoholic anti-sun spray is prepared next:.: ~
compound # 27 3 absolute alcohol 30 `.
isopropyl myristate 24 castor oil 2 perfume 1 ~:
Freon 12 * 40 Example D3 - The following sunscreen spray is prepared:
30 absolute alcohol 35 methylene chloride 20 * trademark . 3 .f ~ ~ ~
compound 1 1 2.5 isopropyl myristate 20 castor oil 2 lanolin 5 perfume carbon dioxide qs up to a pressure of 8 bars.
Example D4 - The following sunscreen spray is prepared:
absolute alcohol 30 methylene chloride 15 10 compound n 1 1 benzylidene camphor 1.5 isopropyl myristate 20 castor oil 2 perfume nitrous oxide qs up to a pressure of 8 bars.
E. Examples of aerosol foams: -Example E1 - The following liquid mixture is first prepared:
Sipol wax 3.5 vaseline oil 6 20 isopropyl myristate 3; ~
preservative 0.3 glycerin 10 perfume 0 3 compound # 15 2.5 water qs ~ p. 100 Then prepare the aerosol spray can which always contains in percentage by weight:
liquid mixture above 87 -Freon F 12 * 13 Example E2 ~ The following liquid mixture is prepared for foam aerosol:
* trademark ~ L $ ~
. '' cetylstearyl and oleocetyl alcohols at 25 EO
(melar, age 50:50) 3 ~ 5 vaseline oil 6 isopropyl myristate 3 preservative 0.3 glycerin 10 . ::
perfume 0.3 dial ~ n 37 2.5 ~
water qs 100 `
The aerosol foam bomb is prepared containing:
liquid mixture above 85 nitrous oxide 15 F. Examples of sun oils:
Example F1 - The following sun oil is prepared: ~:
compound # 29 10 ethanol 10 :: ~ f perfume 0.6 ~.
castor oil qs 100 ~. Example F2 ~ The following solar oil is prepared:
;, 20 compound n 36 2 `0.6 scent ethanol 15 propylene glycol 10 isopropyl palmitate qs 100 Generally speaking, obtaining good ana-logues when replacing:
in compositions A1 to A7, the compound or compounds of the invention, by at least one of the compounds n 6, 7, 9, 14, 22, 42, 8 bis, 27 and 37;
in compositions B1 to B8 the compound or compounds of the invention, with at least one of the compounds n 8 bis, 26, 27, 29, 37, 49 and 52; ~ -in compositions C1 to C5, the compound or compounds of the invention, by at least one of the compounds n 8 bis, 14, 16, 19 and 28, in the compositions Dl to D4 the compound or compounds of the inventi.on,; ~
by at least one of the compounds n 1, 17 and 27., The same applies to the compositions ElE2 and FlF2 The following compounds can be incorporated into compositions indicated below:
Compound 72 in compositions C1 to C5; ~:
Compounds 70, 62 and 60 in compositions Cl to C5 and FlF2, Compound 64 in composition A
Compound 64 in the form of the hydrochloride in the compositions Al, A31 B2;
Compound 57 in compositions C2C3 ~
This request is a division of request No.
298.909 filed March 14, 1978.

Claims (19)

The embodiments of the invention, about which an exclusive right of property or privilege is claimed, are defined as follows: - 1. Compounds having the general formula:
(II) in which Y denotes H or SO3H and the corresponding salts with organic or mineral bases, Z 'denotes the groups -CH2I -CH2R, -CHR'R', -CHO, -COOR "a-with R = -NR1R2, -? R1R2R3, -OR4, -OCOR5, -SR6, -CN -COOR ", -SSO3-Na, R1 and R2 = H, C1-18 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as morpho-line, piperidine, pyrrolidine, piperazine, N-methyl-piperazine, N-phenylpiperazine; R3 = C1-4 lower alkyl, hydroxyalkyl, or sulfonatopropyl; R4 = H, alkyl, polyoxyethylene, aryl sub-stitued or not, menthyl, dialkylaminoalkyl; R5 = alkyl, alkeny-the, aryl, aromatic heterocycle or not containing 5 to 6 links;
R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3; R '= -OR'4 or -SR'6 in which R'4 and R'6 can a-see respectively the same values as R4 and R6, except the hydrogen, polyoxyethylene, hydroxyalkyl, alanyl-3 and a- values ryle; R "= hydrogen or alkyl; it being understood; that when R =
-NR1R2, the compound may be in the form of an addition salt a-with a mineral or organic acid; when R = NR1R2R3, with R1 and R2 different from H, the ionic balance of the molecule is ensured either by R3 when the latter has the sulfonatopropyl value, either by an anion X-, X possibly taking the SO4 alkyl values, SO3 aryl, SO3 alkyl or halogen. 2. Cosmetic composition for protection against actinic rays, characterized in that it comprises in a solvent medium at least one compound of general formula:

(II) in which Y denotes H or SO3H and the corresponding salts with organic or mineral bases, Z 'denotes groups -CH2I-CH2R, -CHR'R ', -CHO, -COOR "with R = -NR1R2, -? R1R2R3, -OR4, -OCOR5, -SR6, -CN, -COOR ", -SSO3Na, R1 and R2 = H, C1-18 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as morpholine, piperidine, pyrrolidine, pipé
razine, N-methyl-piperazine, N-phenylpiperazine, R3 = alkyl-C1-4 lower, hydroxyalkyl, or sulfonatopropyl; R4 = H, al-kyle, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkyl-aminoalkyl; R5 = alkyl, alkenyl, aryl, aromatic heterocycle or not containing 5 to 6 links; R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3; R '= -OR'4 or -SR'6 in which R'4 and R'6 can have the same respectively values as R4 and R6, except hydrogen, polyoxyethyl-lene, hydroxyalkyl, alanyl-3 and aryl; R "= hydrogen or alkyl, Being heard that; when R = -NR1R2 the compound may be under the form of an addition salt with a mineral or organic acid; when-that R =? R1R2R3, with R1 and R2 different from H, the ion equilibrium that of the molecule is ensured either by R3 when the latter has the sulfonatopropyl value, either by an anion X-, X which can take the values -SO4 alkyl, -SO3 aryl, -SO3 alkyl or halogen a) and at least one adjuvant chosen from thickeners, softeners, superfats, emolients, wetters lants, surfactants, preservatives, agents anti-foam, perfumes, dyes and / or pigments, moisturizers; or b) in the presence of one or more cosmetic adjuvants chosen from lanolin, fatty acid triglycerides, glycerin, polyethylene glycols, ethoxylated lanolines, isopropyl myristate and palmitate, castor oil, cetylstearic alcohol, glycerol monostearate, alcohol cetyl, butyl stearate, organic and mid-waxes in an amount of 1 to 40% by weight. 3. Cosmetic composition for protection against actinic rays, characterized by the fact that it comprises minus a compound of general formula:
(II) in which Y denotes H or SO3H and the corresponding salts with organic or mineral bases, Z 'denotes groups -CH2I-CH2R, -CHR'R ', -CHO, -COOR "with R = -NR1R2, -? R1R2R3, OR4, -OCOR5, -SR6, -CN, -COOR ", -SSO3Na, R1 and R2 = H, C1-18 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as morpholine, piperidine, pyrrolidine, pipé
razine, N-methyl-piperazine, N-phenylpiperazine, R3 = alkyl-C1-4 lower, hydroxyalkyl, or sulfonatopropyl; R4 = H, al-kyle, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkyl-aminoalkyl; R5 = alkyl, alkenyl, aryl, aromatic heterocycle or not containing 5 to 6 links; R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3; R '= -OR'4 or -SR'6 in which R'4 and R'6 can have the same respectively values as R4 and R6, except hydrogen, polyoxyethyl-lene, hydroxyalkyl, alanyl-3 and aryl; R "= hydrogen or alkyl;
Being heard that; when R = -NR1R2 the compound may be under the form of an addition salt with a mineral or organic acid; when-that R =? R1R2R3, with R1 and R2 different from H, the ion equilibrium that of the molecule is ensured either by R3 when the latter has the sulfonatopropyl value, either by an anion X-, X which can take the values -SO4 alkyl, -SO3 aryl, -SO3 alkyl or halogen, in a vehicle chosen from thickeners, softeners, health, super fats, emolients, wetting agents, surfactants, preservatives, anti foam, perfumes, dyes and / or pigments, agents moisturizers. 4. Cosmetic composition for protection against actinic rays, characterized in that it comprises at least one compound of general formula:

(II) in which Y denotes H or SO3H and the corresponding salts with organic or mineral bases, Z 'denotes groups -CH2I-CH2R, -CHR'R ', -CHO, -COOR "with R = -NR1R2, -? R1R2R3, -OR4, -OCOR5, -SR6, -CN, -COOR ", -SSO3Na, R1 and R2 = H, C1-18 alkyl, hydroxyalkyl or else they form together with the nitrogen atom a heterocycle such as morpholine, piperidine, pyrrolidine, pipé
razine, N-methyl-piperazine, N-phenylpiperazine, R3 = alkyl-C1-4 lower, hydroxyalkyl, or sulfonatopropyl; R4 = H, al-kyle, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkyl-aminoalkyl; R5 = alkyl, alkenyl, aryl, aromatic heterocycle or not containing 5 to 6 links; R6 = H, alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3; R '= -OR'4 or -SR'6 in which R'4 and R'6 can have the same respectively values as R4 and R6, except hydrogen, polyoxyethyl-lene, hydroxyalkyl, alanyl-3 and aryl; R "= hydrogen or alkyl;
Being heard that; when R = -NR1R2 the compound may be under the form of an addition salt with a mineral or organic acid; when-that R =? R1R2R3, with R1 and R2 different from H, the ion equilibrium that of the molecule is ensured either by R3 when the latter has the sulfonatopropyl value, either by an anion X-, X which can take the values -SO4 alkyl, -SO3 aryl, -SO3 alkyl or halogen, in the presence of one or more cosmetic adjuvants chosen from lanolin, fatty acid triglycerides, glycerin, polyethylene glycols, ethoxylated lanolines, myris-tate and isopropyl palmitate, castor oil, alcohol cetylstearic, glycerol monostearate, cetyl alcohol-that, butyl stearate, organic and mineral waxes, in an amount of 1 to 40% by weight. 5. Cosmetic composition according to claim 2, ca-characterized by the fact that it comprises at least one compound of formula II in an amount of 0.5 to 10% by weight in a vehicle which is a solution, an emulsion, a gel, a dispersant sion, suspension or foam. 6. Cosmetic composition according to claim 2, ca-characterized by the fact that it comprises at least one compound of formula II in an amount of 1.5 to 6% by weight in the form of a solution, an emulsion, a gel, a dispersion, suspension or foam. 7. Cosmetic composition according to claim 2, ca-characterized by the fact that it contains as solvent or as suspending agent, water, alcohol, a mixture of alcohols or a hydro-alcoholic mixture. 8. Composition according to claim 7, characterized by the fact that the solvent or suspending agent is water. 9. Composition according to claim 7, characterized by the fact that the alcohol used is ethanol, the alcohol iso-propyl, propylene glycol, glycerol, sorbitol, or oleic alcohol. 10. Composition according to claim 7, characterized by the fact that the solvent is ethyl alcohol or a mixture of ethyl alcohol. 11. Composition according to claim 5, characterized by the fact that it contains compound II in a solution oil in alcohol. 12. Composition according to claim 5, characterized by the fact that it contains compound II in an emulsion oil in water or water in oil. 13. Composition according to claim 12, characterized by the fact that it contains at least one compound of formula general II with high oil solubility, and at least one compound of general formula II with high solubility in water. 14. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains at least one compound of formula II which is an acid, and at least one compound of formula II which is a mineral or organic salt of the above-mentioned acid. 15. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains at least one compound of formula II in which Z 'denotes the radical -NR1R2 partial-slightly or totally neutralized by a mineral or organic acid fuck. 16. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains a moisturizing agent of the skin in an amount of 0.3 to 3% by weight relative to the weight of the composition. 17. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains iron oxides in an amount of 0.01 to 0.2% by weight relative to the weight of the composition. 18. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains a propellant and that it is packaged in the form of an aerosol can. 19. Composition according to one of claims 2 to 4, ca-characterized by the fact that it contains a propellant and that it is conditioned in the form of an aerosol can, the-said propellant being chosen from the group consisting of a FREON, carbon dioxide, nitrous oxide, and a hydro-light carbide.