United States Patent (19) (11) 4,421,739 Bouillon Et Al

Home , Cetyl alcohol

United States Patent (19) (11) 4,421,739 Bouillon et al. (45) Dec. 20, 1983 (54) BENZYLIDENE-CAMPHORS, PROCESSES (57) ABSTRACT FOR THEIR PREPARATION AND The invention provides compounds which are particu COSMETIC COMPOSITIONS CONTAINING larly valuable for use as the active ingredient in sun tan THEM lotions and creams and the like. These compounds have 75) Inventors: Claude Bouillon, Eaubonne; Charles the general formula: Vayssié, Aulnay-sous-Bois, both of France 73) Assignee: L'Oreal, Paris, France Y-CH, 21 Appl. No.: 886,560 2O

(22 Filed: Mar. 14, 1978 CH (30) Foreign Application Priority Data Mar. 15, 1977 (FR) France...... 77 07720 Sep. 9, 1977 FR) France ...... 77 27343 51 Int. Cl...... C07C 49/433; A61K 7/42; CO7C 49/627 52 U.S. C...... 424/47; 560/19; 564/282; 560/51; 560/254; 564/285; 562/427; in which Y denotes hydrogen or the radical SO3H or a 562/433; 564/428; 562/462; 544/399; 544/159; salt-thereof with an organic or inorganic base, and Z 544/158; 544/162; 544/163; 544/175; 544/171; denotes the radical -CH2Br or -CHBrBr or a radical 546/284; 568/659; 568/808; 568/632; 568/634; Z' which denotes the radical -CH2I, -CH2R, 260/398; 204/158 R; 424/59;568/327;568/42; -CHR'R'', -CHO or -COOR", in which R denotes 260/453 RY; 260/457; 260/508; 260/509; -NR1R2, -NR1R2R3, -OR4, -OCORs, -SR6, 260/510; 260/511; 260/465 D; 260/465 E; -CN, -COOR' or -SSO3Na, in which R1 and R2 260/465 F; 260/501.12; 260/501.15; 560/9 independently denote hydrogen, C-18 alkyl or hydroxy 58) Field of Search ...... 260/590 B, 453 RY, 457, alkyl, or R1 and R2, together with the nitrogen atom to 260/508, 509, 510,511, 465 D, 465 E, 465 F, which they are attached, denote a heterocyclic ring, R3 260/501.12, 501.15, 398; 424/59, 47,568/327, denotes C1-4 alkyl or hydroxyalkyl or sulphonatopro 568/42; 560/9, 19, 51,254; 562/427, 433, 462; pyl, R4 denotes hydrogen, alkyl, polyoxyethylene, aryl 564/282, 285, 428; 544/399, 159, 158, 162, 163, which is optionally substituted, menthyl or dialkylami 175,544/171; 540/284; 568/659,808, 532, 634; noalkyl, R5 denotes alkyl, alkenyl, aryl or a 5 or 6 mem 204/158 R bered heterocyclic ring which is optionally aromatic, 56) References Cited and R6 denotes hydrogen, alkyl, carboxyalkyl, aminoal U.S. PATENT DOCUMENTS kyl, hydroxyalkyl, aryl or 3-alanyl, R' denotes -OR'4 or -SR'6, in which R"4 and R'6 are as defined under R4 3,415,875 12/1968 Luethi et al...... 424/59 and R6, respectively, except for hydrogen, polyoxyeth 3,449,732 7/1973 Rody et al...... 424/59 ylene, hydroxyalkyl, 3-alanyl and aryl, and R' denotes 3,781,417 12/1973 Welters et al...... 424/59 hydrogen or alkyl, such that when R denotes 3,821,307 6/1974 Hoch ...... 260/590 B NR1R2R3, R1 and R2 are not hydrogen and either R3 FOREIGN PATENT DOCUMENTS denotes sulphonatopropyl, or the compound is in the form of a salt with an anion, which is SO4alkyl, SO3a 2407733 8/1974 Fed. Rep. of Germany ... 260/590 B ryl, SO3alkyl or halogen or an inorganic or organic acid 2282426 3/1976 France ...... 260/590 B addition salt thereof when R denotes -NR1R2. Primary Examiner-James H. Reamer Attorney, Agent, or Firm-Fleit, Jacobson, Cohn & Price 51 Claims, No Drawings 4,421,739 1. BENZYLIDENE-CAMPHORS, PROCESSES FOR THER PREPARATION AND COSMETC COMPOSITIONS CONTAINING THEM The present invention relates top-monobromometh yl- and p-dibromomethyl-benzylidene-camphors, as well as to the process for their preparation and to their use in the field of cosmetics. The invention also relates 10 to derivatives prepared from the abovementioned bro mine-containing compounds, and to their use in the field of cosmetics. Z The compounds of this invention have remarkable in which Y denotes H or the radical SO3H and its salts properties regarding absorption of actinic radiation of 15 with organic or inorganic bases, and Z denotes the certain wavelengths and a very wide solubility range, radical -CH2Br or -CHBrBr. and they can be used, in particular, in the preparation of Amongst the compounds of the formula I, there may cosmetic compositions intended for protecting the be mentioned the compounds of Table 1 below, in human epidermis. which table the number of each compound is the same It is known that light radiations of between 280 and as that of its preparation example. 400 nanometers (nm) make it possible to tan the human TABLE 1 epidermis, but that the zone between 280 and 320 mm No. of the causes erythema and skin burns, the seriousness of compound Name of the compound which increases rapidly with the exposure time. Thus, a 25 1. 3-(4-bronomethylbenzylidene)-camphor 2 3-(4-dibromomethylbenzylidene)-camphor good protective agent must have a high absorbing 52 3-(4-bromomethylbenzylidene)-camphor-10-sulphonic power in the zone from about 280 to 320 nm, but it must acid (C18H2BrO4S); melting point = 232 C. allow the radiation in the zone above 320 nm to pass as well as the salts of the above acid No. 52. through as much as possible, in order to offer the best 30 conditions for bronzing without erythema. In addition, The compounds of the formula I can be used either as it must possess good photochemical, heat and chemical synthesis intermediates for preparing the compounds of stability properties, especially in contact with perspira the formula II below, or as protective filters in cosmetic tion, and good solubility in the various solvents and composition for protecting the human epidermis against ingredients forming the vehicle of the cosmetic compo 35 actinic radiation. sition. The present invention thus also provides the com French Pat. No. 73/34,140 describes benzylidene pounds of the general formula II: camphor derivatives carrying a quaternary ammonium radical on the benzene nucleus in the para-position rela Y-CH2 II tive to the bornylidene radical. French Pat. No. 74/05,427 describes benzylidene-camphor derivatives 20 which are sulphonated on the methyl radical in the o-position to the carbonyl radical or on the benzene CH nucleus. 45 Although these compounds have good anti-actinic properties and can be used in cosmetic compositions for tanning the human epidermis, they are rather restricted in number. As a result, they do not give complete satis Z faction, especially as regards the preparation of a wide 50 range of formulations, in which they are not always in which Y denotes H or SO3H and the corresponding compatible, especially for reasons of solubility or of salts with organic or inorganic bases, and Zdenotes the groups -CH2, -CH2R, -CHR'R', -CHO or compatibility with the solvents and ingredients which -COOR", where R= -NRR2, -NR1R2R3, are usually employed in cosmetics. 55 -OR4, -OCOR5, -SR6, -CN, -COOR' or -S- This invention aims, in particular, to overcome the SO3Na, in which R1 and R2 = H, C1-18 alkyl or hydrox abovementioned disadvantages and to enable a vast yalkyl, or they form, together with the nitrogen atom, a family of compounds which, whilst each compound heterocyclic ring such as morpholine, piperidine, pyr possesses good sunlight-filter properties, exhibits, with rolidine, piperazine, N-methylpiperazine or N-phenyl the various solvents and ingredients used in cosmetic 60 piperazine, R3 = C1-4 lower alkyl, hydroxyalkyl or sul compositions for bronzing the human epidermis, very phonatopropyl, R4 = H, alkyl, polyoxyethylene, aryl which may or may not be substituted, menthyl or dial selective protection as well as a wide range of solubili kylaminoalkyl, R5= alkyl, alkenyl, aryl, or a heterocy ties and good compatibility, in particular when the com clic ring which may or may not be aromatic and con position comprises several phases. 65 tains 5 to 6 chain members, and Ré= H, alkyl, carboxy The present invention provides the bromine-contain alkyl, aminoalkyl, hydroxyalkyl, aryl or 3-alanyl, ing derivatives of para-methylbenzylidene-camphor R= -OR4 or -SR'6, in which R4 and R'6 can have which have the formula: respectively the same meanings as R4 and Ré, except for

4,421,739. 5 6 genic solar radiations, which are between 285 and 320 absorbing power is greater than that of these compouns nm, and particularly of absorbing the most harmful A and B. radiations. For the absorption maximum, their molari The very large range, of solubilities, offered by the absorption coefficient (am), calculated in acordance compounds of the invention, in the usual cosmetic vehi with French Standard Specification No. T. 01-030, is cles is shown by Table 5 below, in which the solubility very high, since it is greater than or equal to 25,000 on of certain compounds is indicated in grams per 100-ml average, which corresponds to an exceptional absorb of solvent. ing power. w . . Whereas the coefficient (an) of known compounds TABLE 5 has a maximum of the order of 24,500, the coefficient 10: No. of the Solvent (an) of the compounds of the invention can reach compound water ethanol paraffin oil 45,000, as indicated in Table 3 below: 4 0. 500 25 5 10 0.6 O TABLE 3. 6 190 210 O No. of the compound Wavelength Absorption coefficient 9 : . . . . . 0 100 300 . . . of Table or 2 in (nm) (an) 15. 16 50 100 . . 0...... i 1 299 28,650: 27 0 100 100. 11 296 28,300 28 0 100 . 0 13 299 38,100 42 0 150 o 33 295, 45,000 41 298 28,800 20 46 301 39,600 Thus, certain compounds have a solubility greater. 49 301 32,700 . . . than 100% in water, ethanol or paraffin, oil, whereas: 51 305 30,000 others are insoluble in the abovementioned solvents: A 290 2,000 and, lastly, others are only soluble in one of the above B 284 24,500 mentioned solvents and insoluble in the other two. . . . - ... 25 The invention also provides a process for the prepara. In this table, A is benzylidene-camphor, and 4-(2-oxo tion of the mono- and di-brominated compounds of the 3-bornylidenemethyl)-phenyl-trimethylammonium . formula I. We have discovered that, it is possible to methyl-sulphate B, which respectively have the formu obtain the abovementioned compounds by selectively: lae: - brominating the compounds of the formula I': 30 CH3 CH3 O O fH, . . . ; Y-CH2 I'.

doctric-richScH ScH CH3 sociv . . A B , , , 35 Sch The excellent properties of absorption of the ery thematogenic radiations, that is to say the radiations at between 285 and 320 nm, are shown for the compounds of the invention in Table 4 below, which indicates the 40, percentage of transmitted radiations as a function of their wavelength. These values were determined by. CH3 placing a 10 mm thickness of a solution, in 100 ml of ethanol, containing 2 mg of the compound to be exam in which Y has the abovementioned meanings, in excel ined, in the path of the incident radiation, and by calcu 45 lent yield with brominating the methyl radical situated lating the ratio, expressed as a percentage, of the trans in the a-position to the carbonyl radical of the camphor, mitted flux to the incident flux for various wavelengths or the double bond of the benzylidene, or the aromatic of between 260 and 360 nm. nucleus. "; TABLE 4 The bromination is suitably carried out either with 50 bromine, or with N-bromosuccinimide, in an inert sol Percentage of transmitted flux relative to the Wavelength of incident flux for the compounds below vent, in the cold or with heating, and with exposure to the incident O. O. O. O. O. IO. radiation in the wavelength range from 200 to 800 nm, flux in nm A. B 1 11 13 33 46 49. optionally in the presence of a neutralising agent. 260 29 26 51 49 25 22 25 35 When carried out in the cold, that is to say at ambient 270 10 12 23 20 8 10 10 15 55 temperature, the reaction generally takes 3 to 4 hours, 280 3 7 8 7 3 3 4 4 and when carried out under the action of heat, prefera 290 2 8 3 3 1.5 1 2 bly under reflux, the reaction generally takes 30 to 60 300 3 18 2 2 1 1. 0.5 310 11 58 4. 5 2. ' 5 3. minutes. Preferably chlorohydrocarbons such as carbon 320 55 94 15 21 9 33 2 4. tetrachloride, or ether, acetic acid, benzene or carbon 330 86 98 63 69 43 76 50 38 disulphide, are used as the inert solvents, and an alkali 340 90 100 - 91 . 91 74 89 86 72 metal or alkaline earth metal carbonate is used as the 350 92 100 95 96 86 93 95, 82 neutralising agent...... 360 92 100 95 98 91 98 98 86 In order to obtain the monobrominated compound of the formula I, in which Zdenotes -CH2Br, a rigor In general terms, it is found that the protection pro 65 ously stoichiometric amount of the reactants is used and vided by the compounds of the invention covers the the yield is virtually quantitative. At the end of the range of so-called erythematogenic wavelengths more reaction, the inorganic salts, which may have been selectively than do compounds. A and B, and that their formed can be filtered off, the solvents driven off, the 4,421,739 7 8 residual mixture concentrated and a crude product ob The quaternary compounds of the formula II can be tained on cooling, which can be recrystallised, from a solvent such as isopropanol, with a yield of 85 to 90%. prepared by reacting a compound of the formula I, in The mono- and di-brominated compounds of the for which Z= -CH2Br, with heat with a tertiary amine of mula I which are thus obtained can be stored easily the formula NRR2R3, in which the radicals RR2R3 without deterioration, without any special precautions each have the abovementioned meanings except hydro being taken. gen. The reaction can be carried out in the absence of When the bromination is carried out with bromine, a solution of the latter in an inert solvent is introduced solvents or in the presence of a solvent such as those gradually, and whilst stirring, into a solution of the O already mentioned above. compound of the formula I in the same inert solvent. This process is illustrated in Examples Nos. 21 to 24 When the bromination is carried out with N-bromosuc and 78. cinimide, all the reactants can be introduced into the inert solvent at the start of the operation, and the reac The compounds of the formula II, in which R repre tion is carried out whilst stirring, and preferably under 15 sents -OR4, -SR6 and -OCOR5, can be prepared by the action of heat, reacting either an alcohol or a phenol of the formula It is possible to first obtain the mono-brominated HOR4, or a thiol of the formula HSR6, or an acid of the compound of the formula I, in which Z=CH2Br, and to subsequently prepare the di-brominated compound of formula HO-COR5, respectively, with a mono the formula I, in which Z=CHBrBr from the mono 20 brominated compound of the formula I, the radicals R4, brominated compound, using either bromine or N R5 and Ré, having the abovementioned meanings. In bromosuccinimide. s general, the reaction is carried out in the presence of an When it is desired to obtain a compound of the for mula I in which Y denotes SO3H, the reaction should be inorganic base, an alkali metal or alkaline earth metal carried out in the absence of the neutralising agent, or 25 hydroxide or carbonate, an alkali metal alcoholate, so the reaction is completed with an acidification. dium hydride, an alkali metal, or also an organic base The derivatives of the formula II can be prepared such as triethylamine. from the mono- and di-brominated compounds of the In the above process, there may be mentioned: formula I. In general terms, the compounds of the formula II 30 The following alcohols and phenols: methanol, buta which are mono-substituted on the methyl radical of the nol, dodecanol, tetradecanol, hexadecanol, phenol, benzene nucleus, that is to say those in which Z'has the naphthol, hydroxybenzophenone, methyl salicylate, meaning -CH2R, can be prepared by reacting a com methyl 2-hydroxybenzoate, 2-ethylhexanol, oleyl alco pound of the formula I with a nucleophilic compound 35 hol, octanol, hexanol, dimethylaminoethanol, ethylene carrying the radical R in accordance with the equation: glycol, diethylene glycol, di-(t-butyl)-p-cresol and men thol; Y-CH2 Y-CH2 the following thiols: methanethiol, thioglycolic acid, mercaptosuccinic acid, cysteine, diethylaminoethane eO eO thiol, 2-mercaptobenzothiazole, 2-mercaptobenzoic

Sa. Sn acid, 3-mercaptopropionic acid and 6-aminoethane NoH NoH thiol; and 45 the following acids: tetradecanoic, hexadecanoic, benzoic, gentisic, 3,5-di-(t-butyl)-4-hydroxybenzoic and oleic acids. CHBr + R. --Ge. CH2R -- Br When R4 represents hydrogen, the radical R then 50 represents -OH, and a generator of OH ions, which in which Y and R have the abovementioned meanings. can be a carbonate or a hydroxide as illustrated in Ex The amino compounds of the formula II, in which the ample 25, is used as the reactant. radical R represents -NRR2, can be prepared by re acting a compound of the formula, in which Similarly, when Ré represents hydrogen, either an Z= -CH2Br, with an excess of ammonia or of the 55 alkali metal hydrosulphide or thiourea can be used as corresponding amine of the formula HNR1R2, in an the reactant, and an alkaline hydrolysis is then carried inert solvent, preferably a chlorine-containing solvent, out in accordance with the usual techniques for the an aromatic solvent, an alcohol, or also a dipolar aprotic preparation of thiols, solvent such as dimethylformamide, and optionally in This process is illustrated, in particular, by Examples the presence of a neutralising agent such as an alkali 60 metal or alkaline earth metal carbonate. Amongst the Nos. 39, 25, 36, 37, 38, 40, 42, 43, 44, 45, 46, 55, 26, 27, amines which can be used, the following may be men 28, 29, 30, 31, 32, 33, 34, 56, 57, and 60, and by those of tioned: dimethylamine, diethylamine, diisopropylamine, Table 1. dibutylamine, distearylamine, diethanolamine, morpho The compounds of the formula II, in which Z repre line, piperidine, pyrrolidine, piperazine, N-methylpiper 65 azine and N-phenylpiperazine. sents -CHR'R'', the radical R' represents -OR4 and This process is illustrated, in particular, by Examples the radical R4 having the abovementioned meanings, Nos. 3,4,7,8,9 to 13 and 77 below. can be prepared in accordance with the equation: 4,421,739 10 The acids of the general formula II can be prepared in Y-CH2 Y-CH2 accordance with the equation: 2 2 O 5 Y-CH2 Y-CH2 O O SaNCH ScH a 2 - SnNCH NCHN 10

CHBr2 + 2R'--Se CHR'R' + 2Br in which Y and R' have the abovementioned meanings, bHole COOH by reacting a compound of the formula I, in which 5 Z=CHBr2, with an alcohol of the formula HOR'4. The in which Y has the abovementioned meanings, by oxi reaction is suitably carried out in the presence of a base, dising an aldehyde of the general formula II, in which Z’ has the meaning -CHO, as illustrated by Example as in the process for the preparation of the monosubsti 49. tuted compounds of the formula II which contain the 20 The esters of the general formula II, in which Z' radicals R4 and Ró. represents -COOR", can be obtained by esterifying The use of methanol, as illustrated by Example 50, the acid by means of an alcohol of the formula HOR' in may be mentioned in the above process. which R" has the abovementioned meanings. The aldehydes corresponding to the general formula The acids of the formula II, in which Z' represents II, in which Z represents -CHO, can be prepared in 25 -CH2-COOH, can also be prepared by oxidising the accordance with the equation: corresponding nitriles of the formula II, which are themselves prepared by reacting a compound of the Y-CH2 formula I with a cyanide, and the corresponding esters 30 are obtained by esterifying by means of an alcohol of eO the formula HOR". The compounds in which Z'= -CH2I or CH2S2O3Na can be obtained from a NCH monobromo compound of formula I by reaction with respectively for example sodium iodide or with sodium 35 thiosulphate, for example in an aqueous alcoholic me dium or dimethylformamide, at 50 to 100 degrees C. Finally, the quaternary compounds of the general for OR'4 / mula II can also be prepared by quaternising the com CH + HOH-Ge. pounds of the general formula Ii, in which Z represents N -CH2-NR1,R2 and in which R1 and R2 do not represent OR'4 hydrogen. Amongst the quaternising agents which can advantageously be used, there may be mentioned: di Y-CH2 methyl and diethyl sulphates, alkyl halides or sulpho eO nates, hydroxyalkylhalides and propanesultone, as illus 45 trated, in particular, in Examples 14 to 20 and 66 to 69. Finally, the present invention provides a cosmetic NCH composition containing one or more compounds of the formula I or II together with a carrier or diluent, which compounds are stable to light radiation and which make 50 it possible to provide an effective protection of the human epidermis (skin) against radiation in the range of CHO + 2 HOR'4 erythematogenic wavelengths from 280 to 320 nm, but which selectively allow radiation having a wavelength in which Y and R4 have the abovementioned meanings, greater than 320 nm to pass through, thereby providing by hydrolysing, in an acid aqueous medium, an acetal of 55 excellent conditions for bronzing without erythema. the general formula II in which R" represents -OR4, as The composition of the invention can be in the form illustrated by Example 51. of, for example, a solution, a lotion, an emulsion such as Furthermore, the same aldehyde can be obtained by a cream, a gel or a milk, or an oil, and in general in all the direct oxidation of the monobrominated derivative the usual forms of anti-actinic cosmetic compositions. It 60 can also contain cosmetic adjuvants such as thickeners, of the formula I. softening agents, superfatting agents, emollients, wet The compounds in which Z represents -CHR'R'', ting agents and surface-active agents, as well as preser and R' represents SR'6, are preferably prepared from vatives, anti-foam agents, perfumes or any other com the corresponding aldehyde, in which Z'=CHO, and patible ingredient usually employed in cosmetics. The from a thiol R'6SH (2 molar equivalents) by acid cataly 65 composition can also contain one or more propellants, sis in accordance with the known methods for the prep such as Freons, volatile hydrocarbons, carbon dioxide aration of mercaptals; such a preparation is illustrated gas or nitrous oxide, and it can be in the form of a by Example 73. "spray' or an aerosol. 12 The composition of the invention generally contains with an inorganic or organic base, which neutralisation 0.5 to 10%, and preferably 1.5 to 6%, by weight of one can be carried out beforehand or at the time of use, or more compounds of the formula I or Ii. Among again in order to obtain advantageous conditions of suitable solvents used, there may be mentioned water, solubility or compatibility, and/or better skin tolerance. mono- or poly-alcohols containing 1 to 4 carbon atoms, When the composition contains compounds of the as well as mixtures thereof and, aqueous-alcoholic solu invention which contain two different filtering activi tions. The alcohols which are preferably used are etha ties, and especially in the case of compounds Nos. 13, nol, isopropyl alcohol, propylene glycol, glycerol, Sor 33, 34, 35 and 46, a particularly effective protection can bitol and oley alchol, and the aqueous-alcoholic mix be obtained. tures are preferably mixtures of water and ethyl alco 10. The various types of composition of the invention are hol. illustrated in the following manner: milks by Examples The composition of the invention can be either co A1 to A7, creams by Examples B1 to B8, lotions by lourless or coloured with colorants and/or pigments Examples C1 to C5, sprays by Examples D1 to D4, foams which are usually employed in anti-sunburn composi by Examples E1 and E2, and sun oils by Examples F1 tions, and especially with iron oxides, typically in an 15. and F2. amount from 0.01 to 0.2% by weight relative to the Amongst the cosmetic adjuvants included in the com total weight of the composition, as illustrated in Exam positions of the invention in an amount of, say, 1 to 40% ples B4, B5 and B6. by weight relative to the weight of the composition, The very great flexibility of formulation offered by there may be mentioned lanolin, fatty acid triglycerides, the use of the compounds of the formulae I and II is 20 glycerol, polyethylene glycols, oxyethyleneated lano particularly apparent in compositions comprising differ lins, isopropyl palmitate and myristate, castor oil, ce ent phases, such as "water-in-oil" or "oil-in-water” tyl/stearyl alcohol, glycerol monostearate, cetyl alco emulsions. In fact, as shown by Table 5, it is possible, in hol, butyl stearate and organic and inorganic waxes. particular, to incorporate both a water-soluble com : The Examples which follow, in which the percent pound and oil-soluble compound into the composition, 25 in such a way that each of the phases contains an effec ages are by weight unless otherwise stated, and in tive filter for stopping undesirable actinic radiation, by which the temperatures are in degrees Centigrade, fur choosing from amongst the compounds having the de ther illustrate the present invention. sired solubility those which possess the best compatibil PREPARATION EXAMPLES ity with the solvents and other ingredients contained in 30 the composition. This great flexibility of formulation is EXAMPLE 1: Preparation of compound No. 1 of Table made possible by means of the large number of the compounds of this invention, which, whilst exhibiting 3-(4-bromomethylbenzylidene)-camphor the same filtering properties, between the erythemato 1st method: genic zone and the non-erythematogenic tanning Zone 35 A mixture containing 127 g (0.5 mol) of p-tolylidene (wavelength greater than 320 nm), offer a wide range of camphor, 60 g of anhydrous sodium carbonate and 600 solubilities and compatibilities in relation to the usual ml of carbon tetrachloride is heated under reflux. After cosmetic solvents and ingredients. complete homogenisation, the heating is stopped and a Amongst the examples of compositions containing a solution of 27.5 ml (0.5 mol) of bromine in 100 ml of filter in each of the two phases, the compositions of 40 carbon tetrachloride is then added, whilst exposing the Examples A7, B1 and B6 may be especially mentioned. reaction mixture to the action of a 150 watt lamp giving The composition of the invention can also contain white light. The rate of introduction of the bromine is other agents which are known for their protective ac controlled so as to maintain a gentle reflux. At the end tion against solar radiation, such as agents which absorb of the reaction, the inorganic salts which have formed part of the radiation, like the abovementioned com 45. are filtered off and the solution is concentrated to dry pounds A and B, as illustrated by Examples A1 and A6. ness. The residual solid is recrystallised from isopropa The composition of the invention can also contain nol and 144 g of pale yellow needles, which melt at agents which favour the hydration of the skin or slow 125, are obtained. down its dehydration, such as pyrrolidonecarboxylic Analysis: C18H2BrO: Calculated 9%; C 64.86; H 6.30; acid salts, hydroxy-acid salts, amino-acids or urea, as 50 Br 24.02. Found %: C 64.90; H 6.42; Br 24.05. illustrated in Example B8, generally in an amount from 2nd method: 0.3 to 3% by weight. - A mixture containing 12.7 g (50 millimols) of p-tolyli When the composition contains amino compounds of dene-camphor and 8.9 g (50 mmols) of N-bromosuccini the invention, it is advantageous, in order to obtain the mide in 100 ml of carbon tetrachloride is heated under desired solubility and compatibility characteristics, or 55 to obtain the most favourable conditions of harmless reflux, whilst exposing it to the action of a 150 watt ness, to use them in the form of a preparation which is lamp giving white light. After filtration of the suspen prepared beforehand or at the time of use and which sion thus obtained and concentration of the filtrate, 16.5 results from their total or partial neutralisation with an g of compound No. 1 are collected. inorganic or organic acid. The composition then con 60 EXAMPLE 2: Preparation of compound No. 2 of Table tains either the corresponding ammonium salt of the 1. amino compound or a mixture of the abovementioned ammonium salt and the amino compound. Such a com 3-(4-dibromomethylbenzylidene)-camphor. position is illustrated by Examples A1, A4, A5, A6, B1 : 1st method: and B7. 65 A solution containing 203 g (0.8 mol) of p-tolylidene Similarly, the composition can contain either acid camphor in 1,200 ml of carbon tetrachloride is heated to compounds of the invention, or salts of these acids, or the boiling point with 195 g of anhydrous potassium also mixtures resulting from their partial neutralisation carbonate, whilst stirring. 87.5 ml (1.6 mols) of bromine 4,421,739 13 14 dissolved in 200 ml of carbon tetrachloride are intro tallised from a mixture of petroleum ether and isopropa duced gradually, whilst exposing the whole to the ac nol. Pale yellow crystals, which melt at 96, are ob tion of a 150 watt lamp giving white light. The rate of tained. introduction of the bromine and the heating are con ... Analysis: C23H31NO: Calculated 9%: C 81.90; H 9.20; trolled so that the mixture is kept at the boiling point. At N 4.15. Found %: C 81.80; H 9.00; N 4.05. the end of the introduction, the heating is continued under illumination for about 30 minutes, the whole is EXAMPLE 10: Preparation of compound No. 10 of then filtered and the filtrate is concentrated to dryness. Table 2 The solid residue thus obtained is recrystallised from 3-(4-bis-(octadecyl)-aminomethylbenzylidenel-cam 600 ml of isopropanol. 278 g of compound No. 2 are 10 phor collected in the form of pale yellow needles which melt at 96. A mixture containing 166.5g of compound No. 1 and Analysis: C18H20BR2O: Calculated %: C 52.43; H 521 g of distearylamine is stirred in a boiling water bath 4.85; Br 38.83. Found %: C 52.42; H 4.99; Br 38.86. for 8 hours. After cooling, the whole is taken up with 2nd method: 15 petroleum ether, the solution is filtered and the filtrate is 50 mmols of N-bromosuccinimide and 50 mmols of concentrated to dryness. 290 g of a yellow product, 3-(4-bromomethylbenzylidene)-camphor in 100 ml of which melts at 37, are thus collected. carbon tetrachloride are heated under reflux for 1 hour Analysis: C54H95NO: Calculated 9%: C 84.04; H under illumination by a 150 watt lamp giving white 12.46; N 1.63. Found %: C 84.11; H 12.12; N 1.92. light. The succinimide formed gradually comes to 20 EXAMPLE 4: Preparation ofcompound No. 4 of Table gether at the surface and it is filtered off. The filtrate is concentrated to dryness and 20.5g of compound No. 2 are thus collected. 3-(4-diethylaminomethylbenzylidene)-camphor . 3rd method: A solution containing 33 g of compound No. 1 and 22 50 mmols of p-tolylidene-camphor and 100 mmols of 25 g of diethylamine in 100 ml of carbon tetrachloride is N-bromosuccinimide are reacted under the operating heated at 60' for 30 minutes, whilst stirring. The precip conditions and solvent conditions indicated in the sec itate is filtered off and the filtrate is concentrated to ond method, but by heating under reflux for about 2 dryness. 31 g of a yellow oil, which is chromatographi hours. cally pure, are obtained. 30 Analysis: C22H31NO: Calculated 9%: C 81.18; H 9.60; EXAMPLE 11: Preparation of compound No. 11 of N 4.91. Found %: C 81.02; H 9.43; N 4.77. Table 2 The compounds Nos. 3, 7, 8, 9, 12, 13 and 77 of Table 3-(4-piperidinomethylbenzylidene)-camphor. 2 are prepared by reacting an amine with 3-(4- bromomethylbenzylidene)-camphor in accordance with 20 35 a method of operation which is analogous to that of Example 4, but using the corresponding amines for each

compound, in the place of diethylamine, as indicated in Table 6 below. This table additionally mentions the solvent used, the temperature and the reaction time, as well as the melting point of the compound obtained or its appearance, and its calculated and found amine num ber, expressed in milliequivalents per gram.

TABLE 6 Compound Amine used, reacting Amine number Reaction Reaction Melting milliequivalents/g No. with compound No. 1 Solvent used temperature time point Calculated Found 3 dimethylamine methanol 20 120 hours 65 3.37 3.41 7 diethanolamine ethanol 80 5 hours oil 2.80 2.83 8 diisopropylamine ethanol 80 6 hours 89 2.83 2.85 9 dibutylamine ethanol 80 2 hours oil 2.63 2.72 12 morpholine ethanol 80° 5 hours 89 2.95 2.98 13 piperazine p-amino- methanol 65° 6 hours 207 2.57 2.55 benzoate - 77 piperazine p-amino- ethanol 80 1 hour 204 2.39, 2.39 benzoate Preparation of the salts formed with an inorganic or organic acid from the amino compounds of the formula 60 I 83 g of compound No. 1 are added, in portions using The acid is generally introduced, at ordinary temper a spatula, to 100 ml of a solution containing 64 g of ature or with gentle heating, into a solution of the amino piperidine in ethanol. The mixture is stirred for 24 hours compound of the formula. II. The mixture is concen at ambient temperature, the whole is then filtered, the trated to dryness and the residue is crystallised from an filtrate is concentrated, the residue is dissolved in a 65 appropriate solvent. By way of examples, Table 7 below solution of sulphuric acid in ether and the resulting indicates the conditions of the preparation of the com solution is filtered. The ether solution is concentrated to pounds Nos. 5, 6, 7 bis, 8bis and 9 bis of Table 1 from dryness to obtain 75 g of a residual solid which is recrys the corresponding amino compounds, the acid and the 4,421,739 15 16 solvent used being mentioned in each case. For each methyl ethyl ketone. 86 g of product are thus obtained compound obtained, this table also indicates the crystal in the form of whitish platelets melt at 155°. lisation solvent, the melting point and the calculated Analysis: C30H4NO4S: and found percentage elementary analysis of C, H and Calculated 9%; C 70.41; H 8.08; N 2.74; S 6.27. N. 5 Found %: C 70.31; H 7.96; N 2.92; S 6.41. TABLE 7 Melting point Elementary analysis Starting (crystal- C H N Compound compound Solvent lisation Calcu- Calcu- . Calcu No. No. Acid used used solvent) lated Found lated Found lated Found 6 4. camphor- ethanol 170° 68.90 68,96 8.49 8.39 2.51 2.41 sulphonic (AcOEt) s 4. hydro- acetone 245 73.00 72.97 8.91 8.88 3.87 4.08 chloric (iProH) 7 bis 7 hydro- ethanol 230 67.09 67.22 8.13 8.9 3.56 3.57 chloric (iProH) 8bis 8 hydro- ether 205 73.91 74.13 9.30 9,12 3.59 3.34 chloric (iProH) 9 bis 9 hydro- Water 139 74.70 74.7O 9.64 9.47 3.35 3.42 chloric (MIBK) MIBK = methyl isobutyl ketone; AcOE = ethyl acetate iProH = isopropanol 25. A method of operation which is analogous to that of PREPARATION OF THE QUATERNISED Example 14 makes it possible to prepare compounds COMPOUNDS OF THE FORMULA II Nos. 15 to 24, 66 to 69 and 78 of Table 2, as indicated in EXAMPLE 14: Preparation of compound No.14 of Table 8 below. For each compound prepared, this table Table 2 mentions the compound of the formula II or the starting 4-(2-oxo-3-bornylidene-methyl)-benzyldiethylme 30 amine, the quaternisation agent which can be mono thylammonium p-toluenesulphonate brominated compound of the formula I, such as those included in Table 1, the solvent used and the reaction 65 g of compound No. 4 of Table 2 and 41 g of methyl time. For each compound obtained, the table also indi p-toluenesulphonate are heated under reflux in toluene cates the melting point, as well as the calculated and for 4 hours 30 minutes. After cooling, the precipitate found percentage elementary analysis of C, H and N. which has formed is drained and recrystallised from TABLE 8 Amine compound Elementary analysis Con- of the formula C --- N pound II or starting Quaternisa- Reaction Melting Calcu- Calcu- Calcu No. amine tion agent Solvent time point lated Found lated Found lated Found 15 Compound No. 4 CH3SO3CH3 (without 30 162 66.17 66.33 8.56 , 8.54 3.22 3.04. solvent) minutes 16 Compound No. 12 CH3SO3CH3 toluene 5 hours 192 64,14 64.30 7.80 7.72 3.12 3.04. 17 Compound No. 12 SO4(CH3)2 ethyl 3 hours 160 6.94 6.80 7.53 7.26 3.01 3.25 acetate 18 Compound No. 12 ICH3 ICH3 4 hours 200 57.38 57.24 6.65 6.85 2.91 2.73 19 Compound No. 11 CH3 toluene 10 hours 167 7.13 7.20 7.84 7.81 2.68 2.77 p-tolyl-SO3 20 Compound No. 11 CH3SO3CH3 toluene 5 hours 170 67.11 67.37 8.28 8.20 3.13 3.08 21 N(C2H5)3 Compound (without 5 230 63.7 63.56 8.40 8.8 3.10 2.70 No. 1 solvent) minutes 23 C12H25NCCH3)2 Compound toluene 4 hours 83 70.31 70.35 9.59 9.29 2.56 2.41 No. 1 24 C14H29N(CH3)2 Compound benzene 5 hours 100° .708 71.30 9.76 9,55 2.44 2.52 No. 1 66 Compound No. 3 SO4(CH3)2 ethyl 1 hour 1770 62.41 62.34 7.80 8.05 3.31 3.30 W acetate 67 Compound No. 12 CECH2CH2OH (without 8 hours 200 68.65 68.50 8.10 8.33 3.34 3.2 solvent) 68 Compound No. 3 BrCH2CH2OH methyl 3 hours 20 62.56 62.37 7.58 7.69 3.32 3.29 ethyi ketone 69 Compound No. 3 propane- toluene 5 hours 260 64.48 64.48 7.94 8.03 3.27 3.18 sultone (hemi hydrate) 78 N-methyl- Compound . toluene 3 hours 200 63.74 64.05 7.62 7.86 6.47 6.21 piperazine No. 1 22 N(C2H4OH)3 Compound (without oil 59.75 - 59.5 7.47 7.55 2.90 2.92 No. 1 solvent) 82 N,N'-bis- Compound toluene 2 hours 184 61.54 61.54 7.69 7.78 5.52 5.37. (hydroxy- No. 1 ethyl)- 4,421,739 17 18 TABLE 8-continued Amine compound Elementary analysis : Com- of the formula C H N pound II or starting Quaternisa- Reaction Melting Calcu- Calcu- Calcu No. annine tion agent Solvent time point lated Found lated Found lated Found piperazine

10 EXAMPLE 29: Preparation of compound No. 29 of Table 2 3-(4-tetradecyloxymethylbenzylidene)-camphor EXAMPLE 25: Preparation of compound No. 25 of 75g of myristyl alcohol are introduced into a solution Table 2 15 containing 18.9 g of sodium methylate in methanol. 3-(4-hydroxymethylbenzylidene)-camphor After the mixture obtained has been evaporated to dry 33 g of compound No. 1 are added all at once to an ness, the residue is taken up with benzene and 116.5g of ethanolic solution containing 6.2 g of potassium hydrox compound No. 1 are added. The mixture is heated ide, and the whole is heated to the boiling point. The under reflux for 8 hours, it is then filtered, the filtrate is mixture is kept under reflux for one hour and then evap 20 evaporated to dryness and the oily residue obtained is orated to dryness. The residue is taken up with benzene distilled. 111 g of an oil (boiling point=250” under a and, after filtration, the benzene extract is concentrated pressure of 0.2 mm Hg) are thus collected, which solidi to dryness. A pale yellow solid is thus obtained which, fies rapidly to give a beige solid which melts at 35°. after crystallisation from petroleum ether, gives pale 25 Analysis: C32H5OO2: yellow crystals which melt at 35. Calculated 2%: C 82.40; H 10.73. Analysis: C18H22O2: Found %: C 82.22; H 10.70. Calculated 9%: C 80.00; H 8.15. EXAMPLE 31: Preparation of compound No. 31 of Found %: C 80.18; H 8.31. Table 2 EXAMPLE 27: Preparation of compound No. 27 of 30 3-(4-phenoxymethylbenzylidene)-camphor Table 2 11.6 g of sodiumphenate are prepared by reacting the 3-(4-butoxybenzylidene)-camphor corresponding amounts of phenol and sodium hydrox 19.5 g of sodium butylate are prepared by allowing ide in an alcoholic solution, followed by evaporation to 4.6 g of sodium to react with 50 ml of butanol. At the 35 dryness. The phenate collected is stirred under reflux end of the reaction, 66.6 g of compound No. 1 and 100 for 10 hours with 33.3g of compound No. 1 in 100 ml of ml of toluene are added. The mixture is heated in a methyl ethyl ketone. After filtration of the reaction boiling water-bath for 8 hours, it is then filtered and the E. t St. Sport dryn 2. of a filtrate is concentrated to dryness. 64 g of a pale yellow W E. s ; me S a , are Obtained. oil are thus collected, which can be distilled to give an 40 nalysis: C2426O2: oily- product having a boiling point of 210 under a Calculated 9%: C 83.24;.. H 7.51. pressure of 0.5 mm Hg. Found %: C 83.27; H 7.62. Analysis: C22H3002: EXAMPLE 34: Preparation of compound No. 34 of Calculated 2%: C 80.98; H 9.20, Table 2 Found %: C 80.66; H 9.07. 45 methyl Compounds Nos. 26, 28 and 30 are prepared in accor- 2-4-(2-oxo-3-bornylidenemethyl)-benzyloxy-benzoate. dance with a method of operation which is analogous to that of Example 27, except that the butanol is replaced by methanol (Example 26), dodecanol (Example 28) and hexadecanol (Example 30) respectively, and that, in 50 CH3 Example 26, methanol is used as the solvent instead of O toluene. The following compounds are obtained respec tively: Sa Compound No. 26: melting point of 175 under a SCH pressure of 0.25 mm Hg. 55 Analysis: C18H24O2: Calculated 9%: C 80.28; H 8.45. Found %: C 80.29; H 8.46. Compound No. 28: pale yellow oil which cannot be distilled. 60 CH2 Analysis: C30H46O2: O Calculated 7%: C 82.19; H 10.50. Found 9%; C 82.05; H 10.27. Compound No. 30: pale yellow solid which melts at CH3OOC 40. 65 Analysis: C34H54O2: A methanolic solution containing 7.6 g (50 mmols) of Calculated 2: C 82.59; H 10.93. methyl salicylate, 2 g of sodium hydroxide and 16.5g Found %: C 82.33; H 10.75. (50 mmols) of compound No. 1 are heated at the boiling 4,421,739 19 20 point for 4 hours. The reaction mixture is concentrated to dryness and the residue is extracted with hot ben- . PREPARATION OF THE THIOETHERS zene. The benzene solution is concentrated and the EXAMPLE 39. Preparation of compound No. 39 of residue is crystallised from methanol. 14 g of white Table 2 crystals, which melt at 120, are thus obtained. 5 3-(4-mercaptomethylbenzylidene)-camphor. Analysis: C26H28O4: ; Calculated 7%: C 77.23; H 6.93. 7.6 g (0.10 mol) of thiourea and 33 g (0.10 mol) of Found %: C 77.07; H 7.06. ... compound No. 1 are heated under reflux in isopropanol Compounds Nos. 32, 33, 36, 37 and 38 of Table 2 are for 1 hour. The precipitate which has formed is filtered prepared in an analogous manner to that of Example 34. 10 off and 35 g of the isothiouronium salt, which melts at For this purpose, compound No. 1 is used in each case, 264, are thus collected. but the methyl salicylate is replaced by a-naphthol Analysis: C10H25BrN2OS: (Example 32), 4-hydroxybenzophenone (Example 33), Calculated 9%: C 55.74; H 6.16; S 7.83. myristic acid (Example 36), palmitic acid (Example 37) Found 9%: C 55.74; H 6.37; S 7.83. or benzoic acid (Example .38), respectively. . . . . 15 25 g of the isothiouronium salt are hydrolysed by For each example, Table 9 below indicates the hy prolonged heating with an excess of sodium hydroxide droxylic compound or acid which reacts with scom in an aqueousethanolic medium. After neutralisation pound No. 1, the reaction time, the number of the com with an acid, the product which has precipitated is pound obtained, its melting point and the corresponding drained and crystallised from methyl isobutyl ketone. calculated and found percentage elementary analysis of 20 White crystals, which melt at 87, are obtained. C and H. Analysis: C18H22OS: TABLE 9 Hydroxylic Elementary analysis compound C. : : H Com- or acid, reac- Calcu- . . . Calcu pound ting with Reaction Melting lated Found lated Found No. compound No. 1 time point % % % % 32 a-naphthol 6 hours 120° 84.85 84.62 7,07 7.38 33 4-hydroxy- 5 hours 122 82.67 82.53 6.67 6.61 benzophenone f : . . 36 myristic acid 2 hours 29° 80.00 79.74 10.00 9.98 37 palmitic acid 6 hours 30° 80.31 80.58 10.24 10.27 38 benzoic acid 8 hours 63 80.21 80.28 6.95: , 6.99

- Calculated 2: C 75.48; H 7.74; S 11.19. EXAMPLE 35: Preparation of compound No. 35 of Found %: C 75.49; H 7.61; S 11.10. Table 2 ' ' - : The thioethers of the formula II are prepared in an 2-[4-(2-oxo-3-bornylidenemethyl)-benzyloxy)-benzoic analogous manner to that of Example 39 by heating acid. compound No. 1 and the corresponding thiol com pound at a moderate temperature in the presence of a Compound 34 is heated under reflux in an alcoholic basic agent. This agent can be omitted if the thiol prod solution of potassium hydroxide for 3 hours. The acid is uct itself contains a basic function, for example a ter precipitated by acidification, and a white product, tiary amine function. The product is then separated off withsts.Ö obtained. 45 in accordance with the usual techniques. Calculated 2: C 7692. H 6.67 The conditions for the preparation of compounds Found %: C 77.01; H 6 96 r Nos. 40, 42 to 46 and 55 of Table 2 are indicated in • Wes a M. V. Table 10 below. For each compound prepared, this table mentions the 50 thiol compound used in the place of the thiourea of Example 39, the base and the solvent used, the reaction temperature and reaction time, as well as the number of the compound obtained, its melting point and its calcu lated and found percentage elementary analysis of C, H 55 and S. TABLE 10 Elementary analysis C H S Cat- Cal- Cal Com- Thiol compound Tem- Melt- C- C- C pound reacting pera- Reaction ing lated Found lated Found lated Found No. with compound No. 1 Base Solvent ture time point % % % % % % 40* CH3SH CH3ONa ethanol 40° 1 hour 44° 76.00 76.18 800 8.05 10.67 10.87 42 HO2C-CH2-SH NaOH (mixture: 60 1 hour 90 69.73 69.79 7.02 7.02 9.3 9.45 . . . water/ 30 methanol) minutes 4,421,739 21 22 TABLE 10-continued Elementary analysis S- - - S Cal- Cal- Cal Com- Thiol compound Tem- Melt- C- Cl- Ct pound reacting pera- Reaction ing lated Found lated Found lated Found No. with compound No. 1 Base Solvent ture time point % % % % % % 43 thiomalic acid N(C2H5)3 acetone 20' 45 hours 210 65.65 65.84 6.51 649, 7.97 8.10 Hoc-h-sh HO2C-CH2

44 cysteine KOH mixture: 60° 2 hours 190 67.53 67.36 7.29 7.27 8.58 8.64 (watera ethanol) 45 (C2H5)2N-CH2-CH2-SH (no methanol 65° 1 hour 169** 61.79 61.67 7.78 7.64 6.87 7,07 basic • -

agent) - - 46 2-mercapto- CO3Na2 ethanol 80 l hour 114 7.56 71.58 6.01 6.20 15.28, 15.23 benzothiazole . - : 55 thiosalicylic acid N(C2H5)3 acetone 20 2 hours 198 73.89 73.68 6.40 6.57 7.88 7.83. peroxide.Compound No. 41, which, after recrystallisation from ethanol, is in the form of a white solid which melts at 119, is obtained by oxidising compound No. 40 with hydrogen Analysis C19H24O2S Calculated 26 C 72.11 H 7.64 S 10.13 Found 2% 72.08 7.72 10.37 Melting point of the hydrobromide.

EXAMPLE 47: Preparation of compound No. 47 of Table 2 EXAMPLE 51: Preparation of compound No. 51 of 3-(4-cyanomethylbenzylidene)-camphor Table 2 ..' . 7 g of compound No. 1 of Table 1 are added to a 3-(4-formylbenzylidene)-camphor methanolic solution containing 2.5 g of potassium cya By completely hydrolysing compound No. 50 of nide, and the whole is heated under reflux for 30 min Table 2 in a mixture of water and dioxane in the pres utes. The mixture obtained is concentrated to dryness, 35 ence of hydrochloric acid, and after having concen the residue is taken up with water, and the insoluble trated the solvent, a pale yellow product, which melts fraction is filtered off and crystallised from ethanol to at 116, separates out. obtain whitish crystals which melt at 127. Analysis: C18H20O2: Analysis: C19H21NO: Calculated 2%: C-80.60; H 7.46. Calculated 9%: C 81.68; H 7.58; N 5.01. 40 Found %: C 80.64; H 7.56. Found %: C 81.41; H 7.36; N 5.22. The same compound No. 51 can also be prepared by EXAMPLE 48: Preparation of compound No. 48 of completely oxidising compound No. 1 using dimethyl Table 2 sulphoxide in the presence of potassium carbonate. 4-(2-oxo-3-bornylidenemethyl)-phenylacetic acid. 45 EXAMPLE 49: Preparation of compound No. 49 of 0.050 mol of compound No. 47 of Table 2 is heated Table 2 under prolonged reflux with an excess of a mixture of 4-(2-oxo-3-bornylidenemethyl)-benzoic acid. aceticacid and hydrochloric acid, and, after filtering Compound No. 51 of Table 2 is oxidised with potas and washing, white crystals are obtained which melt at 50 sium permanganate in a mixture of water and acetone. 134. After filtering off the precipitate and washing it with Analysis: C19H22O3: acid number (mil the same mixture of water and acetone, a white product, liequivalents/g): which melts at 240, is obtained by acidifying the fil Calculated 3.36; Found: 3.33. trate. ' ' s EXAMPLE 50: Preparation of compound No. 50 of 55 Analysis: C18H20O3: Table 2 Calculated 2%: C 76.06; H 7.04. 3-(4-dimethoxymethylbenzylidene)-camphor Found %: C 76.17; H 7.06. EXAMPLE 56: Preparation of compound No. 56 of 1 mol of compound No. 2 of Table 1 is heated under Table 2 - reflux for two hours in a methanolic solution containing 60 2 mols of sodium methylate. The mixture is concen 4-(2-oxo-3-bornylidenemethyl)-benzyl trated to dryness, the residue is extracted with benzene, 2,5-dihydroxybenzoate. the extract is filtered and the filtrate is then evaporated Compound 56 is prepared according to Example 31 to dryness. A pale yellow powder, which melts at 98, from gentisic acid; it is a white powder which melts at is thus obtained. 65 220. Analysis: C20H26O3: Analysis: C25H26Os: Calculated 9%: C 76.43; H 8.28. Calculated 76: C 73.89; H 6.40. Found %: C 76.26; H 8.47. Found %: C 73.82; H 6.57. 4,421,739 23 24 adding water, filtered off and drained. 70g of a yellow EXAMPLE 57: Preparation of compound No. 57 of solid, which melts at 108, are obtained. Table 2 Analysis: C18H211O: 4-(2-oxo-3-bornylidenemethyl)-benzyl Calculated 2%: C 56.84; H 5.53; I 33.42. 3,5-di-(t-butyl)-4-hydroxybenzoate 5 Found %: C 56.58; H 5.60; I 33.18. Compound 57 is prepared according to Example 31 EXAMPLE 73: Preparation of compound No. 73 of from 3,5-di-(t-butyl)-4-hydroxybenzoic acid, replacing Table 2 methyl ethyl ketone with dimethylformamide. It is in the form of a pale yellow solid which melts at 132. 4-(2-oxo-3-bornylidenemethyl)-benzyldithiodiacetic Analysis: C33H42O4: 10 acid Calculated 2%: C 78.88; H 8.37. A solution of 26.8 g of compound 51 and 16.4 g of Found %: C 79.13; H 8.42. thioglycolic acid is heated at the boiling point in dichlo roethane for 3 hours, in the presence of concentrated EXAMPLE 60: Preparation of compound No. 60 of sulphuric acid. The mixture is then concentrated to Table 2 15 dryness. The residue is extracted with ether; the ether 3-(4-octyloxymethylbenzylidene)-camphor phase is washed with water and then concentrated to A suspension of 2.1 g (50 millimols) of sodium hy dryness. 38g of a whitish solid, which melts at 116, are dride (in oil) is added in small amounts to 6.5 g (50 thus obtained. millimols) of octan-1-ol in 100 ml of toluene, whilst 20 Acid number: Calculated: 4.61 milliequivalents/g. stirring. When the evolution of hydrogen has ended, Found: 4.64 milliequivalents/g. 16.6 g (50 millimols) of 3-(p-bromomethylbenzylidene)- EXAMPLE 79: Preparation of compound No. 79 of camphor are added in portions, and the mixture is then Table 2 heated under reflux for 3 hours. After adding water, the N-methyl-N,N'-bis-(4-(2-oxo-3-bornylidenemethyl)- toluene phase is decanted, dried and concentrated to 25 benzyl-piperazinium bromide dryness. The residual syrup is distilled under reduced pressure. 8.8 g of a yellow liquid, which boils at 240 33 g of compound 1 and 5 g of N-methylpiperazine under a pressure of 0.1 mm Hg, are thus collected. are stirred in toluene (200 ml) at ordinary temperature Analysis: C26H38O2: for 1 hour, in the presence of sodium carbonate (6 g). Calculated 9%: C 81.67; H 9.95. 30 The insoluble material is filtered off, made into a slurry Found %: C 81.52; H 10.15. again with a mixture of water and toluene and then The compounds of the following Table 11 are pre drained. After drying, 23 g of a white solid, which melts pared under the same conditions: at about 200 with decomposition, are collected. TABLE 11 Elementary analysis C H Compound Reaction Melting or Calcu- Calcu No. Alcohol used time boiling point lated 9%. Found 2% lated 2 Found 9% 62 menthol 4 hours oil 82.35 82.6 9.80 9.88 59 2-ethylhexanol oil 81.67 81.98 9.95 9.95 70 oleyl alcohol 8 hours oil 83.08 83.6 10.77 11.9 64 dimethylaminoethanol 3 hours hydrochloride 69,91 69,70 8.53 8.66 melting point s 152 72 ethylene glycol 5 hours boiling point = 195 76.45 76.48 8.28 8.14 under a pressure of 0.3 mm Hg melting point 54 76 diethylene glycol 6 hours oil 73.74 73.77 8.38 8.25

EXAMPLE 63: Preparation of compound No. 63 of 50 Table 2 3-4-(2,6-di(t-butyl)-4-methylphenoxymethyl)-ben Determinations: zylidene-camphor Tertiary amine number Ionised bromine Calculated 26 1.46 milliequivalents/g 1.46 milliequivalents/g Compound 63 is prepared according to Example 29 Found 9% 1.48 milliequivalents/g 1.47 milliequivalents/g from di-(tertiary butyl)-p-cresol, replacing the benzene 55 by dimethylformamide. A whitish powder, which melts at 135, is obtained. COMPOSITION EXAMPLES Analysis: C33H44O2: In general terms, the compounds of the formula I or Calculated 9%: C 83.90; H 9.32. 60 II can be incorporated directly into a composition in Found %: C 83.94; H 9.52. tended for protecting the human epidermis against solar EXAMPLE 71: Preparation of compound No. 71 of radiation. However, when they are in the form of an Table 2 acid, that is to say that at least one of the radicals Y and Z' denotes an acid radical, they can be easily neutralised 3-(4-iodomethylbenzylidene)-camphor 65 to the preferred pH using an inorganic or organic base . A mixture of 66.6 g of compound 1 and 40 g of so which is chosen depending on the desired cosmetic dium iodide in acetone (500 ml) is heated under reflux properties and on the desired solubility. Likewise, the for three hours. The reaction product is precipitated by basic amino compounds according to the invention can 4,421,739 25 26 be neutralised to the preferred pH with an inorganic or The same composition as in Example A is prepared, organic acid. except that compound No. 6 and benzylidene-camphor A. COMPOSITIONS OF ANTI-SUNBURN MILKs are replaced by: Example A1 compound No. 42 0.5 The medium-protection anti-sunburn milk indicated magnesium salt of compound No. 42 2.9 below is prepared:

oxyethyleneated cetyl/stearyl alcohol containing 5 10 Example A6 25 mols of ethylene oxide E.O., that is to say "containing 25 EO" The following anti-sunburn milk is prepared: cetyl alcohol 2-octyldodecanol 15 Codex vaseline oil 5 oxyethyleneated cetyl/stearyl alcohol containing 5 unsaponifiable constituents of lucerne 0.2 15 25 mols of ethylene oxide E.O., that is to say benzylidene-camphor 1. "containing 25 EO" compound No. 6 2.5 cetyl alcohol 1 methyl para-hydroxybenzoate qs. 2-octylidodecanol 5 perfume Codex vaseline oil 5 0.5 unsaponifiable constituents of lucerne 0.2 water C.S.p. 100 benzylidene-camphor 20 compound No. 42 neutralised to pH 6 with 5 N aqueous 3 potassium hydroxide methyl para-hydroxybenzoate qs. Example A2 perfume 0.5 The following anti-sunburn milk is prepared: Water C.S.p. 100 25 Sipol wax vaseline oil Example A7 isopropyl myristate silicone oil The following non-ionic anti-sunburn protective milk cetyl alcohol is prepared: glycerol 30 preservative 0.3 perfume 0.3 Sipol wax 5 compound No. 22 3 vaseline oil 6 water qS.p. 00 isopropyl myristate 3 dimethylpolysiloxane 1 cetyl alcohol 35 preservative 0.3 Example A3 glycerol 20 compound No. 6 2.5 The following non-ionic anti-sunburn protective milk compound No. 9 2 is prepared: perfume 0.5 40 Water q.S.p. 100 Sipol wax 5 vaseline oil 6 isopropyl myristate 3 B. COMPOSITIONS OF ANTI-SUNBURN dimethylpolysiloxane l CREAMS: cetyl alcohol l preservative 0.3 45 Example B1 glycerol 20 compound No. 14 2.5 The following high-protection anti-sunburn cream is perfume 0.5 prepared: Water C.S.p. 100 50 poloxyethyleneated hydrogenated palm oil 5 "containing 15 EO" Example A4 cetyl/stearyl alcohol "containing 15 EO" 5 lanolin 3 The following anti-sunburn milk is prepared: lanolin alcohols 1 sunflower oil 5 55 vaseline oil 10 Sipol wax 5 compound No. 26 2.5 vaseline oil 6 compound No. 8bis 4 isopropyl myristate 3 propylene glycol 5 ... dimethylpolysiloxane preservatives qs. cetyl alcohol perfume O.S preservative 0.3 water q.s.p. 100 glycerol 20 compound No. 7 3 perfume 0.5 malic acid 1.2 Example B2 water C.S.p. 100 The following anti-sunburn cream is prepared: 65 Example A5 cetyl/stearyl alcohol The following protective milk is prepared: glycerol monostearate i 4,421,739 28 -continued -continued cetyl alcohol 4 polyoxyethyleneated sorbitan monostearate 2 vaseline oil 5 "containing 60 EO" butyl stearate 5 stearic acid 2 propylene glycol 7 5 cetyl alcohol 1.2 silicone oil 0.125 lanolin 4. 0.5% strength polyox 3.5 ' 'vaseline oil 30 preservative 0.3 preservative 0.3 perfume 0.4 triethanolamine 0. compound No. 14 4 compound No. 29 2 Water q.S.p...... 100 10. compound No. 7 3 iron oxides 0.1 perfume 0.6 Example B3 Water C.S.P. 100 The following non-ionic anti-sunburn protective 15 cream is prepared: Example B7 The following anit-sunburn cream, which is partially Sipol wax 7 , ; ''', neutralised, is prepared: glycerol monostearate ... 2 vaseline oil 5 silicone oil 1.5 cetyl alcohol 1.5. . . . . cetyl/stearyl alcohol 2 preservative 0.3 -'s glycerol monostearate 4. glycerol 10 cetyl alcohol 4 compound No. 27 5. vaseline oil. 5 perfume 0.5 "" butyl stearate 5 water C.S.p. 100 25. propylene glycol 7 silicone oil 0.125 0.5% strength polyox 3.5 , preservative 0.3 Example B4 perfume 0.4 compound No. 52 0.75 The following anionic anti-sunburn protective cream 30 triethanolamine salt of compound No. 52 3 is prepared: . . ------

self-emulsifying glycerol monostearate 6 Example B8 polyoxyethyleneated sorbitan monostearate 2 "containing 60 EO" 35 The following moisturising anti-sunburn cream is stearic acid 2 prepared: cetyl alcohol 1.2 lanolin ": " 4 vaseline oil ; 30 Sipol wax 7 preservative * 0.3 glycerol monostearate 2 triethanolamine , 0.1 40. vaseline oil 15 compound No. 37 3 ... silicone oil . . . 1.5 iron oxides 0.2 cetyl alcohol 1.5 perfume ... 0.5 preservative 0.3 water q.s.p. 100 glycerol 10 compound No. 27 5 45 sodium pyrrollidonecarboxylate 2 Example B5 perfume 0.5 Water C.S.p. 100 The following anti-sunburn cream is prepared: An analogous good result is obtained by replacing the cetyl/stearyl alcohol 2 50 sodium pyrrollidonecarboxylate, in the above anti-sun glycerol monostearate 4. cetyl alcohol 4. burn cream, with sodium glycolate in an amount of 1 g, vaseline oil 5 or by adding 1 g of sodium glycolate to the composition butyl stearate 5 of Example B2 propylene glycol 7 silicone oil 0.125 55 C. EXAMPLES OF ANTI-SUNBURN LOTIONS 0.5% strength polyox 3.5 preservative 0.3 Example C1 perfume 0.4 compound No. 49 The following anti-sunburn lotion is prepared: iron oxides 0.01 potassium hydroxide 0.45 60 Water C.S.p. 100 lanolin 2.5 butyl hydroxyanisole 0.025 butyl hydroxytoluene 0.025 octyl gallate 0.0125 Example B6 triglycerides of C8-C12 fatty acids 40 perfume 1.25 The following anionic protective cream is prepared: 65 compound No. 28 4 96' strength alcohol q.S.p. 100 self-emulsifying glycerol monostearate 6 4,421,739 29 30 Example C2 -continued

The following anti-sunburn lotion is prepared: castorisopropy oil myristate 242 perfume l 5 Freon 12 40 glycerol 5 polyethylene glycol 400 0.5 oxyethyleneated lanolin l soluble perfume 2 Example D3 5.ompound Earth No. Rico 16 502 10 The following anti-sunburnp spray is prepared: water q.s.p. 100 absolute alcohol 35 methylene chloride 20 Example C3 compound No. 1 2.5 The following aqueous-alcohlic anti-sunburn lotion is 15 Ep: myristate ag prepared: anolin 5 perfume carbon dioxide gas q.s.p. to a pressure of 8 bars. compound No. 14 3 glycerol 5 20 polyethylene glycol 400 0.5 96 strength alcohol 50 Example D4 solublewater perfumeq.s.p. 1002 The following anti-sunburni- spray ise prepared:w

25 absolute alcohol 30 Example C4 methylene chloride 15 The following oily-alcoholicw anti-sunburn lotion is Siphorcompound No. 1 1.51 prepared: isopropyl myristate 20 castor oil 2 30 perfume 1 compound No. 8bis 3 nitrous oxide q.s.p. to a pressure of 8 bars. triglycerides of C8-C12 fatty acids 40 96 strength ethanol 56.5 perfume 0.5 E. EXAMPLES OF AEROSOL FOAMS 35 Example E1 Example C5 The following liquid mixture is initially prepared: The following anti-sunburn lotion is prepared: Sipol wax 3.5 compound No. 19 10 40 vaseline o s glycerol s 1sopropy myristate 0.3 96 strength alcohol 50 Stive 1 o polyethylene glycol 400 0.5 E. 0.3 oxyethyleneated lanolin 1 e d No. 15 s soluble perfume 2 O t pound No. 100 water q.s.p. 100 45 water q.s.p. Thereafter, the aerosol foam container is made up; it D. EXAMPLES OF ANTI-SUNBURN SPRAYS contains, in each case, in percentage by weight: Example D1 50 The following anti-sunburn spray is prepared: above liquid mixture 87 Freon F 12 13

absolute alcohol 30 isopropyl myristate 20 Example E2 castor oil 2 55 a lanolin 5 The following liquid mixture for an aerosol foam is perfume 1 prepared: compound No. 17 2 Freon 12 40 60 cetyl/steary and oleyl/cetyl alcohols containing 3.5 25 E.O. (50:50 mixture) Example D2 vaseline oil 6 The following oily-alcoholico anti-sunburno spray is isopropylpreservative myristate 0.33 prepared: glycerol 10 65 perfume 0.3 compound No. 37 2.5 compound No. 27 3 Water q.s.p. 100 absolute alcohol 4,421,739 3. 32 The aerosol foam container is made up, it contains the in which Y denotes hydrogen or the radical SO3H or a following: - . . . . . - - - - - salt thereof with an organic or inorganic base, and Z denotes the radical -CH2Br or -CHBrBr or a radical Z' which denotes the radical -CH2, -CH2R, above liquid mixture 85 5 nitrous oxide 15 -CHR'R'', -CHO or -COOR', in which R denotes -NRR2, -N-R1R2R3, -OR4, -OCOR5, -SR6, -CN, -COOR or -SSO3NA, in which R1 and R2 independently F. EXAMPLES OF SUN OILS denote hydrogen, C1-18 alkyl or hydroxyalkyl, or R1 and R2, together with the nitrogen atom to which they are Example F1 10. attached, denote a heterocyclic ring, R3 denotes C1-4 The following sun oil is prepared: alkyl or hydroxyalkyl or sulphonatopropyl, R4 denotes hydrogen, alkyl, polyoxyethylene, aryl which is option ally substituted, menthyl or dialkylaminoalkyl, R5 de compound No. 29 O notes alkyl, alkenyl, aryl or a 5 or 6 membered hetero ethanol O 15 perfume 0.6 cyclic ring which is optionally aromatic, and Ré denotes castor oil C.S.p. 100 3 hydrogen, alkyl, carboxyalkyl, aminoalkyl, hydroxyal kyl, aryl or 3-alanyl, R'R' denotes -OR4 or -SR'6 in which R"4 and R'6 are as defined under R4 and Ré, re Example F2 20 spectively, except for hydrogen, polyoxyethylene, hy droxyalkyl, 3-alanyl and aryl, and R" denotes hydrogen The following sun oil is prepared: or alkyl, such that when R denotes NR1R2R3, R1 and R2 are not hydrogen and either R3 denotes sulphonato compound No. 36 2 propyl, or the compound is in the form of a salt with an perfume 0.6 anion, which is SO4alkyl, SO3aryl, SO3alkyl or halogen ethanol : 15. 25 or an inorganic or organic acid addition salt thereof propylene glycol : 10 when R denotes -NR1R2 isopropyl palmitate C.S.p. OO. : : 2. A compound according to claim 1 in which Z denotes -CH2Br or -CHBr3r. In general, analogous good results are obtained when: 3. A compound according to claim 1 in which Z in compositions A1 to A7, the compound or com- 30 denotes a radical Z'. pounds of the invention is or are replaced by at least one 4. The compound of claim 1, 3-(4-bromomethylben of compounds Nos. 6, 7, 9, 14, 22, 42, 8 bis, 27 and 37; zylidene)-camphor. in compositions B1 to B8, the compound O. CO 5. The compound of claim 1,3-(4-dibromomethylben pounds of the invention is or are replaced by at least one zylidene)-camphor. of compounds Nos. 8bis, 26, 27, 29, 37, 49 and 52; 35 6. The compound of claim 1, 3-(4-bromomethylben in compositions C1 to Cs, the compound or com zylidene)-camphor-10-sulphonic acid. pounds of the invention is or are replaced by at least one 7. Process for preparing a compound as defined in of compounds Nos. 8bis, 14, 16, 19 and 28; and . . . . in compositions D1 to D4, the compound or com claim 2 which comprises reacting a compound of the pounds of the invention is or are replaced by at least one 40 general formula: , of compounds Nos. 1, 17 and 27...... This is also the case as regards compositions E1, E2 Y-CH2 and F and F. ' x The following compounds can be incorporated into the compositions indicated below: ...... 45 Compound 72 into compositions C1 to C5. Compounds 70, 62 and 60 into compositions C1 to C5 and F and F2: - Compound 64 in composition A4; Compound 64 in the form of the hydrochloride, in 50 compositions A1, A3 and B2; and Compound 57 in compositions C2 and C3 CH3 We claim: i. A compound having the general formula: with bromine or with N-bromosuccinimide, in an inert 55 solvent, and in the presence of radiation of wavelength from 200 to 800 nanometres. Y-CH I 8. Process according to claim 7 which is carried out eO in the presence of a neutralishing agent. 9. Process according to claim 7 for preparing a mono 60 brominated compound by using the reactants in stoi SCH chiometric amounts. 10. Process according to claim 7 for preparing a di brominated compound by using the reactants in stoi chiometric amounts or with a slight excess of brominat 65 ing reagent relative to the compound of formula I'. 11. Process for preparing a compound as defined in Z claim 2, in which Zdenotes -CHBr2 which comprises brominating a compound as defined in claim 2 in which 4,421,739 33 34 Z denotes -CH2Br, the brominating agent being used from 0.3 to 3% by weight based on the weight of the in stoichiometric amounts or in a slight excess relative composition. to the monobrominated compound. 26. A composition according to claim 12 which con 12. A composition suitable for application to the skin tains iron oxide in an amount from 0.01 to 0.2% by which comprises at least one compound as claimed in weight based on the weight of the composition. any one of claims 1 to 6 and a compatible diluent or 27. A composition according to claim 12 which con carrier. tains a propellant and is packaged in the form of an 13. A composition according to claim 12, which con aerosol container. tains at least one compound of the formula I or II 0.5 to 28. A composition according to claim 27 in which the 10 propellant is a fluorinated hydrocarbon, carbon dioxide 10% by weight of the compound, the composition being gas, nitrous oxide or a volatile hydrocarbon. in the form of a solution, an emulsion, a gel, a disper 29. A method of bronzing the skin which comprises sion, a suspension or a foam. applying thereto a composition as defined in claim 12. 14. A composition according to claim 13, which con 30. The compound of claim 1, 3-(4-diethylamino tains 1.5 to 6% by weight of the compound. 15 methylbenzylidene)-camphor. 15. A composition according to claim 12 which con 31. The compound of claim 1,3-(4-diisopropylamino tains at least one cosmetic adjuvant which is lanolin, a methylbenzylidene)-camphor. fatty acid triglyceride, glycerol, a polyethylene glycol, 32. The compound of claim 1, 3-(4-methoxymethyl a oxyethyleneated lanolin, isopropyl myristate or palmi benzylidence)-camphor. tate, castor oil, cetyl/stearyl alcohol, glycerol monoste 20 33. The compound of claim 1,3-(4-butoxymethylben arate, cetyl alcohol, butyl stearate, and organic and Zylidene)-camphor. inorganic waxes, in an amount from 1 to 40% by 34. The compound of claim 1,3-(4-tetradecyloxyme weight. thylbenzylidene)-camphor. 16. A composition according to claim 12 which con 35. The compound of claim 1, 3-(4-p-benzoylphenox tains, as a solvent or suspending agent, water, an alco 25 ymethylbenzylidene)-camphor. hol, a mixture of alcohols or an aqueous-alcoholic mix 36. The compound of claim 1, 4-(2-oxo-3-bor ture. nylidenemethyl)-benzyl tetradecanoate. 37. The compound of claim 1, 4-(2-oxo-3-bor 17. A composition according to claim 16 in which the nylidenemethyl)-benzoic acid. solvent or suspending agent is water. 30 38. The compound of claim 1, 3-(4-dimethylaminoe 18. A composition according to claim 16 in which the thoxymethylbenzylidene)-camphor. alcohol is ethanol, isopropyl alcohol, propylene glycol, 39. The compound of claim 1, 3-4-(2-oxo-3-bor glycerol, sorbitol or oleyl alcohol. nylidenemethyl-benzylthiol-propionic acid. 19. A composition according to claim 16 in which the 40. The compound of claim 1, N-(2-hydroxyethyl)-N- solvent is ethyl alcohol or a mixture of water and ethyl 35 4-(2-oxo-3-bornylidenemethyl)-benzyl)-dimethylam alcohol. monium bromide. 20. A composition according to claim 12 which com 41. The compound of claim 1, 3-(4-oleyloxymethyl prises a solution of oil in alcohol. benzylidene)-camphor. 21. A composition according to claim 12 in the form 42. The compound of claim 1, N,N'-bis-(2-hydroxye of an oil-in-water or water-in-oil emulsion. 40 thyl)-N-4-(2-oxo-3-bornylidenemethyl)-benzyl 22. A composition according to claim 21 which con piperazinium bromide. tains at least one compound of formula (I) which is 43. The compound of claim 1, wherein Z is either highly soluble in oil, and at least one compound of -CH2Br or -CHBr2. formula (I) which is highly soluble in water. 44. The compound of claim 1, wherein Z is -CH2I. 23. A composition according to claim 12 which con 45 45. The compound of claim 1, wherein Ris-NR1R2. tains at least one compound of formula (I) which is an 46. The compound of claim 1, wherein Z' is -CH2 acid, and at least one compound of formula () which is NR1R2R3. an inorganic or organic salt of the above-mentioned 47. The compound of claim 1, wherein R is -OR4; acid. -SR6; or -OCOR5. 50 48. The compound of claim 1, wherein. Z' is 24. A composition according to claim 12 which con -CHR'R''. tains at least one compound of formula (I) in which Z' 49. The compound of claim 1, wherein Z is -CHO. denotes the radical -NR1R2, which is at least partially 50. The compound of claim 1, wherein Z is neutralised with an inorganic or organic acid. -COOR'. 25. A composition according to claim 12 which con 55 51. The compound of claim 1, wherein R is -CN. tains an agent for moisturising the skin, in an amount st k . . k.