GB2160521A - Anionic surfactants with two fatty chains - Google Patents

Abstract

Anionic surfactants of the general formula (I): <IMAGE> in which one of Y1 and Y2 is H and the other is <IMAGE> R1 and R2 are C8-22 hydrocarbons (R1 + R2 is C18-32> X is O, S, sulphoxide or carbonyloxy u and v are each 0 or 1 (U is 0 when X is O, S or sulphoxide> p is 0-10 A is OH or a group containing carboxyl groups Z is H or CH2A1, where A1 may have the same meaning as A n is 0-10, the average number of anionic groups per molecule being 0.7-10, are useful in cosmetic and pharmaceutical compositions since these surfactants do not show such damage to the ocular mucosa as previously known surfactants.

Description

SPECIFICATION Anionic surfactants with two fatty chains and compositions containing them The present invention relates to new anionic surfactants and their use in compositions suitable for cosmetic or pharmaceutical use.

Many anionic surfactants are known in the prior art. These generally show damaging activity towards the ocular mucosa, and for this reason it is sought to replace them or to reduce their damaging activity by combining them with other compounds.

The main characteristic of the su rfactants of the present invention is that they contain, as regards the lipophilic portion, two hydrocarbon fatty chains, and as regards the hydrophilic portion, one or more carboxyl groups.

These products are soluble and are most frequently dipersible in water in the form of alkali metal salts, ammonium salts or amine salts. They can however be completely solubilised in the presence of other water-sol uble surfactants and/or solvents, and lead to clear compositions.

We have discovered that these anionic surfactants surprisingly show properties which make it possible to reduce the damaging activity, especially in the Draize test, of the compounds with which they are combined, and especially surfactants. This property is especially surprising in view of the known damaging activity of classical anionic surfactants towards the ocular mucosa.

Moreover, the presence of hydrocarbon chains which differ to a greater or lesser extent in their length and nature endow the molecules with a substantial lipophilic character, with relatively low melting points.

In addition to the properties mentioned above, the surfactants of the present invention have the advantage, when they are introduced in formulae for hair treatment, of providing, even at low concentrations, softness and sheen and making it easierto disentangle the hair.

The invention hence provides new anionic surfactants.

The invention relates to compositions containing these surfactants, and their use in cosmetics and pharmacy. Other subjects will become clear on reading the description and examples which follow.

The present invention provides an anionic surfactant of general formula (I):

in which one of Y1 andY2 is hydrogen and the other is a group formula (ill): R2OCH247 (II) R1 and R2 which may be the same or different are each aliphatic or alkylaryl hydrocarbon of 8 to 22 carbon atoms, the number of carbon atoms for R1 + R2 being greater than or equal to 18 and less than or equal to 32, X is oxygen, sulphur, sulphoxide or carbonyloxy, u and v, which may be identical or different, are each 0 or 1, u being 0 and X is oxygen, sulphur or sulphoxide, p is from Oto 10, Ais OH and/or

mis 1 or2, W is alkylene of 1 to 3 carbon atoms or -CH2O-CH2- M is hydrogen, alkali metal or alkaline earth metal, or a group of formula:

F3, R4 and Rg which may be the same or different are each hydrogen, alkyl of 1 to 3 C atoms or hydroxyalkyl or 2 or 3 C atoms, z is hydrogen or a group -CH2A1, in which A1, which may be identical to or different from A, has the same significance as A, n is from 0 to 10, the average number of anionic groups per molecule being from 0.7 to 10.

Preferably M is Na, Koran Mg equivalent, and the average number of anionic groups per molecule is from 0.8 to 5.

The surfactants which are especially preferred are those for which R1 and R2 are each linear or branched alkyl or alkylphenyl of to 18 carbon atoms, their sum being equal to or greater than 18 and less than or equal to 32, X is oxygen, sulphur, sulphoxide or carbonyloxy, p is from Oto 10 u and v are each 0 or 1, Ais

W is alkylene group of 1 to 3 carbon atoms or -CH2-O-CH2, M is hydrogen, sodium, potassium, magnesium or the group:

in which R3, R4 and F5 are each hydroxyalkyl, Z is hydrogen or -CH2A1, in which A1 is, in particular, S(CmH2m)-COOM in which m is 1 or 2; n is O to 10, the average number of anionic groups per molecule being from 0.7 to 10.

The surfactants are prepared by a process which contains several basic stages.

The process, which constitutes another subject of the invention, consists essentially in reacting an alcohol having two fatty chains, corresponding to the formula:

in which: F1, Y1, Y2, p, u and X are as defined above, with - either a cyclic anhydride of a diacid, - or, after tosylation or mesylation, with a mercaptoalkanoic acid such as mercaptoacetic or mercaptopropionic acid, - or, after formation of the sodium derivative, with chloracetic acid, these reactions optionally being preceded by a polyaddition of 1 to 10 moles of ethylene oxide or 1 to 10 moles of epihalohydrin when n is other than 0, the polyaddition with the epihalohydrin being, where appropriate, followed by hydrolysis of the halogenated derivatives when A1 denotes OH, or by a reaction in alkaline medium with a mercaptoalkanoic acid when A1 denotes -S(CmH2m)COOH.

The process can be carried out more especially under the following conditions, according to the nature of the final surfactant of general formula (I) which it is desired to prepare.

The intermediate compounds of formula (III) are converted to anionic compounds of formula (I) in which n equals 0 by the following procedures: (1) by reaction with a cyclic anhydride of a diacid of formula:

in which W is as defined above, optionally in the presence of a solvent such as an aliphatic or aromatic hydrocarbon, a chlorohydrocarbon solvent or an ether solvent, at a temperature of from 0 to 1 20"C, to obtain surfactants of formula (I) in which A is::

The alkali metal salts or alkaline earth salts, ammonium salts or amine salts are obtained by the processes of conventional salification, (2) by reaction of the tosylates or mesylates of the compounds (III) in basic medium with a mercaptoalkanoic acid, chosen preferably from mercaptoacetic or mercaptopropionic acid, or the corresponding methyl or ethyl ester, leading to surfactants of formula (I) in which: Ais -S-(C,H,,)-COOH in which m is as defined above. As above, salification can be performed in order to obtain the compounds in which: A denotes the group -S-(CmH2m)-COOM.

By oxidation with hydrogen peroxide, there are obtained the surfactants in which: A denotes

(3) by reaction of chloracetic acid or its methyl or ethyl esters with the sodium-containing compounds corresponding to the compounds offormula (III), optionally in the presence of a solvent such as aliphatic or aromatic hydrocarbons at a temperature between 50 and 140"C, in which case there are obtained surfactants of formula (I) in which: A denotes the group -O-CH2COOH, which, as mentioned above can be salified.

In the case where n is other than 0, ethylene oxide or an epihalohydrin is added to the intermediate compounds of formula (III).

(1) For the preparation of surfactants of formula (I) in which n is other than 0 and Z denotes hydrogen, from 1 to 10 molecules of ethylene oxide are added per molecule of intermediate compound of formula (III), to obtain the compounds of formula (IIIA):

The compounds (IIIA) are converted to surfactants of formula (I) either by the action of a cyclic anhydride or a diacid, or bytosylation or mesylation followed by reaction with a mercaptoalkanoic acid, or, after formation of the sodium derivative, by reaction with chloracetic acid as described above.

(2) In the case where surfactants of formula (I) are prepared in which n is other than 0 and Z denotes a group -CH2A" from 1 to 10 molecules of epihalohydrin, preferably epichlorohydrin, are added per molecule of intermediate of formula (III), to form the compounds of formula (IlIB)::

These halogenated derivatives can react directly in alkaline medium with a mercaptoalkanoic acid of formula HS-(CmH2m)COOH, or its methyl or ethyl ester, to lead to surfactants of formula (I) in which A1 denotes the group -S(CmH2m)COOH and A denotes OH, this surfactant optionally being able to be salified andfor oxidised, (3) the halogenated derivatives of formula (IIIB) can be hydrolysed to obtain the corresponding polyhydroxylated compounds, and these compounds can be reacted either with a cyclic anhydride of a diacid or, aftertosylation or mesylation, with a mercaptoalkanoic acid or, after formation of the sodium derivative, with chloracetic acid, as described above.

The cyclic anhydrides of diacids which can be more especially used are chosen from malonic, succinic, methylsuccinic, glutaric or diglycolic anhydride.

The intermediate compounds of formula (III) are prepared by processes known per se, described in particular in our French Patents Nos. 2,222,351 and 2,281,916.

These compounds can be prepared, in particular, as regards the lipophilic portion, by reaction of a compound or a mixture of compounds containing active hydrogen, corresponding to the formula (IV)

with an alkylene oxide, an alkyl or alkyl glycidyl ether or an alkylaryl glycidyl ether, our a mixture of these compounds, of formula (V)::

in which R1, R2, v, u, and p have the same significances as in the general formula (I), X denoting oxygen, sulphur or

This reaction is carried out either with acid catalyst in the presence of catalysts such as BF3, Snub, SbCI5, ZnCl2, TiCI4 and H2SO4, at a temperature of from 40 to 110 C, or with basic catalysis in the presence, for example, of sodium methylate or ethylate or potassium methylate or ethylate, at a temperature of from 100 to 1 600C.

Under these conditions, the main product of the reaction orthe main products formed can be represented by the general formula (III,):

but it is also possible to obtain, in lesser proportions, the isomers of formula (1112):

The compounds can contain small proportions of polyaddition products originating from the reaction of another molecule of epoxide of formula (V) with a product of formula (Illi) or (1112).

These various products can be partially or completely separated, or can be left with the main product, their presence not adversely affecting the properties.

Among the compounds containing active hydrogen, there may be mentioned, by way of example, fatty alcohols, optionally oxyethylenated, alkylphenols, optionally oxyethylenated, alkyl mercaptans, the corresponding alkylphenyl polyoxyethyl mercaptans, fatty acids, (polyoxyethyloxy)methylcarboxylic acids and alkylarly(polyoxyethyloxy)-methylcarboxylic acids, these compounds containing 8 to 22 carbon atoms in the alkyl or alkylaryl portion.

Among the epoxide compounds of formula (V), alkylene oxides, alkyl or alkenyl glycidyl ethers containing 8 to 22 carbon atoms in the R2 portion, and alkylaryl glycidyl ethers, and more especially alkylphenyl glycidyl ethers containing 8 to 22 carbon atoms in the R2 portion, can be used.

The surfactants take the form of viscous liquid products, pastes or solids, depending on the nature and length of the hydrocarbon radicals R1 and R2, according to the value ofv and according to whether they are isolated in the acid form or in the form of alkali metal, alkaline earth or amine salts.

The surfactants are especially suitable for use in cosmetic or pharmaceutical compositions.

They can be used, in particular, for reducing the damaging activity of surfactants and for improving the cosmetic properties of hair-care compositions, such as disentangling, softness and sheen.

These compounds can also be used as solubilising agents, as emulsifiers, as lipid constituents for preparing vesicles and the like.

They are typically used at concentrations of from 0.05 to 30% by weight relative to the total weight of the compositions, and especially in proportions of from 0.25 to 10% by weight.

In these compositions, they can be combined with anionic, surfactants other than those of formula (I), cationic, zwitterionic, non ionic surfactants of mixtures thereof, or anionic, cationic, nonionic or amphoteric natural or synthetic cosmetic polymers.

The compositions can furthermore contain thickeners, solvents, electrolytes, foam synergists, foam stabilisers, oils, waxes, superfatting agents, natural substances, protein derivatives, anti-seborrhoeic agents, anti-dandruff agents, sunscreens, oxidising agents, reducing agents, sequestering agents, colourings pigments, pearlescence agents, opacifiers, antiseptics, preservatives, alkalising or acidifying agents, and perfumes, as well as any other active substance which can have an action in respect of the treatment, care or protection of the skin or hair, and any adjuvants customarily used in cosmetic compositions.

The acids and bases are generally used in amounts suitable for adjusting the pH of the compositions to be from 5 to 10.

The pharmaceutical compositions may contain, in addition to the surfactants of the invention, active substances intended for the treatment of the human or animal body and pharmaceutically acceptable excipients.

For hair care, compositions containing the surfactants can be shampoos, hair conditioning compositions or dyeing compositions.

The shampoos can contain, in addition to the anionic surfactants according to the invention, one or more anionic, cationic, amphoteric or nonionic surfactants, or mixtures thereof, as well as other cosmetic adjuvants customarily used in this type of composition.

The dyeing compositions are based on precursors of so-called oxidation dyes or so-called direct dyes, or mixtures thereof.

The compositions containing the surfactants can also be used, according to the nature of the compositions, as hair-rinse lotions, cleansing milks for the body, moisturising creams, lipstick, makeupremoving lotions for the eyes, eye shadow, setting lotions, and laquers, as well as for other cosmetics applications.

These compositions can be aqueous, hydroalcoholic or oily, and can take the form of solutions, lotions, emulsions, pastes, gels, powders or aerosols.

The examples which follow are intended to illustrate the invention without being in any way limitative in nature.

Example 1 Preparation of the compound of formula (I) in which: R1 denotes C15H31 Ya or Y2 denotes

X denotes

A denotes -OCO-CH2-CH2-COOM M denotes H or N(CH2CH20H)3 n, p and u being equal to zero.

The intermediate compound of formula (III) is prepared from 254 g of hexadecanoic acid (1 mole) and 182 g (0.98 mole) of 2-ethylhexyl glycidyl ether by the process described in Example 5 of French Patent 2,222,351.

To 220 g (0.5 mole) of the compound thus obtained dissolved in 270 g of pyridine distilled over caustic potash, 50 g (0.5 mole) of succinic anhydride are added. The mixture is heated to 80"C for 2 h.

500 ml of cold water are then added. An organic phase is thus obtained which is washed 3 times with water to which 5% of hydrochloric acid (d = 1.19) has been added, and then a final time with pure water.

The product thus obtained is dissolved in isopropanol and dried over an hydrous sodium sulphate. After filtration and removal of the solvent,226 9 of an almost colourless oil are obtained.

204 g of this crude oil are purified by molecular distillation at 220"C and at 10-3 mm of mercury.

The product obtained is a pale yellow oil.

Acid value: 1.47 meq/g Saponification number 4.85 meqlg The triethanolamine salt yields a stable viscous dispersion in water.

Example 2 Preparation of the compound of formula (I) in which: R, denotes C15H31 Y1 orY2 denotes C,2H25-O-CH2- X denotes

A denotes -OCO-CH2-CH2-COOM M denotes H or -N(CH2-CH20H)3 n, p and u being equal to zero.

To 44.8 g (0.09 mole) of intermediate compound (III), prepared by a process similar to that of Example 1 from hexadecanoic acid and dodecyl glycidyl ether both solubilised in 50 g of pyridine distilled over caustic potash, 9.9 g (equivalent to 0.099 mole) of succinic anhydride are added, and the mixture is then heated to 80"C for 2 hours.

150 ml of cold water are then added to the mixture. The supernatant organic phase is washed twice with 100 ml of water at 40"C containing 10% of hydrochloric acid (d = 1.19). A final wash is then performed with 100 ml of pure water, and the mixture is then dehydrated by heating under reduced pressure.

52.6 g of product, which is solid when cold, are thus obtained, and this is recrystallised in 100 ml of heptane.

The final product is a white powder (39 g), the melting point of which is 45"C.

Acid value: 1.62 meq/g Saponification number: 5.0 meq/g In the form of triethanolamine salt at a concentration of 5% in water, it yields a stable, viscous dispersion.

Example 3 Preparation of the compound of formula (I) in which: R1 denotes C16H33 Y1 or Y2 denotes

X denotes -0 A denotes -OCO-CH2-CH2-COOM M denotes H, NH2-CH2-CHOH-CH3 or 1 Mg equivalent n, p and u being equal to zero.

To 119.8 g (0.28 mole) of the intermediate compound (Ill), prepared from hexadecanol and 2-ethylhexyl glycidyl ether by the process described in Example 2 of French Patent 2,222,351, 160 g of pyridine and then 30.8 g (equivalent to 0.31 mole) of succinic anhydride are added. The mixture is brought to 80"C for 2 h 30 min.

After the mixture is cooled, 300 ml of cold water are added and the supernatant phase is washed twice with 300 ml of water at 40"C containing 10% of HCI (d = 1.19) and then once with 300 ml of pure water. The mixture is then dehydrated by means of an hydros sodium sulphate, and the product thus obtained is purified by molecular distillation (removal of the light members by distillation at 175"C under a vacuum of 10-3 mm Hg, followed by distillation of the product at 205C under the same vacuum). 82.5 g of an almost colourless oil are thus obtained.

Acid value: 1.92 meq/g Saponification number: 3.71 meq/g.

Preparation of the monoisopropanolamine salt By mixing 26.5 g (0.05 mole) of acid of formula (I) with 3.8 g (0.05 mole) of monoisopropanolamine, a viscous liquid is obtained which is of low solubility in water.

Preparation ofthe magnesium salt 10.4 g (0.02 mole) of acid of formula (I) are dissolved in 20 ml of isopropanol and 5 g of water. 0.64 g (0.022 equivalent) of finely ground magnesium hydroxide are added with stirring at800C.

The insoluble particles are separated and the mixture is evaporated under reduced pressure.

the magnesium salt thus obtained takes the form of a viscous liquid.

Example 4 Preparation of the compound of formula (l) in which: R1 denotes C10H21 Y1 or Y2 denotes

X denotes -O A denotes -OCO-CH2-CH2-COOH n, p and u being equal to zero.

To 86 g (0.25 mole) of intermediate compound (III), obtained from 1-decanol and 2-ethylhexyl glycidyl ether by the same process as that described in Example 2 of French Patent 2,222,351, 110 g of pyridine distilled over caustic potash are added, followed by 25 g (equivalent to 0.25 mole) of succinic anhydride. The mixture thus obtained is heated to 800C for 2 hours.

250 ml of cold water are then added; the organic phase is washed twice with 250 ml of water containing 10 ml of hydrochloric acid (d = 1.19) at 40"C, followed by a final wash with pure water.

The organic phase is then dried over sodium sulphate after filtration, and the oil obtained is purified by molecular distillation at 1600C at 10-3 mm Hg.

A colourless oily liquid is thus obtained.

By thin layer chromatography on a silica plate with dichloromethane/propanol (95:5) as eluent, a single spot is detected having Rf = 0.38.

Acid value: 2.25 meq/g Saponification number: 4.25 meq/g.

Example 5 Preparation of the compound of formula (I) in which: R1 denotes C8H17 Y1 orY2 denotes C1cH21 X denotes -O A denotes -OCO-CH2-CH2-COOH n, p and u being equal to zero.

To 94.2 g (0.3 mole) of intermediate compound (III) (b.p. 153 C/10-3 mm Hg) prepared from n-octanol and 1,2-epoxydodecane by a process similar to that described in French Patent No. 2,465,780, 120 g of pyridine distilled over caustic potash and 30 g (0.3 mole) of succinic anhydride are added.

The mixture is heated to 80"C for 2 hours.

250 ml of cold water are added. The organic phase is washed twice with 250 ml of water at 40"C to which 10 ml of concentrated HCI (d = 1.19) have been added, and then once again with pure water.

The product is then dried over anhydrous sodium sulphate after filtration, and 114 g of a pale yellow oil are obtained.

this oil is purified by molecular distillation.

Volatile compounds are removed at 145 C at 10-3 mm Hg, andthe product is then distilled at 175"C.

By thin layer chromatography with a dichloromethane/panol (95:5) mixture as eluent, a single spot is obtained (Rf = 0.5).

Acid value: 2.60 meq/g.

Example 6 Preparation of the mixture of compounds of general formula (I) in which: F1 denotes C8H17 Y, or Y2 denotes C16H33 Xdenotes -O- A denotes -OH Z denotes -CH2-S-CH2-COONa p equals u equals 0 n equals 2.

To 79.6 g (0.2 mole) of intermediate compound (III) b.p. 193-205"C/0.08 mm Hg; m.p. 48-490C) prepared by a process similar to that described in French Patent No. 2,465,780,0.23 ml of SnC14 is added, followed at 60-65"C, in the course of 40 minutes, by 37 g (0.4 mole) of epichlorohydrin.

The product is then washed at 90"C with 25% strength Na2CO3 solution.

115 g of product thus obtained (396 meq of chlorine) are then added at 80"C to the mixture of 37.7 g of thioglycolic acid (396 meq) and 81.3 g of caustic soda solution (816 meq) under an atmosphere of nitrogen.

The reacting mass is heated to 100 Cfor2 hours.

To convert the medium to the liquid state, 30 ml of water and 60 ml of methyl cellosolve are then added, and the mixture is then heated to 1 OO"C for a further 2 hours.

The reacting mass is taken up with 350 ml of water and 38 ml of concentrated hydrochloric acid.

After addition of 60 ml of isopropanol, separation of the organic phase takes place at 60"C.

After decantation, the organic phase is washed again with 200 ml of water in the presence of 20 ml of isopropanol.

The product is taken up again with 120 ml of water and 32 g of 40% strength caustic soda.

After removal of the isopropanol under reduced pressure, 288 g of white paste is obtained, containing approximately 34% of active materials.

Base number: 1 meq/g.

On dilution, a turbid solution is obtained.

Example 7 Preparation of the compound of general formula (I) in which: R1 denotes C15H31 Y1 orY2 denotes C14H29 Xdenotes -COO A denotes -OOC-CH2-CH2-COOH n, p and u being equal to zero.

The intermediate compound of formula (III) is prepared from palmitic acid and 1,2-epoxyhexadecane by the process described in Example 12 of French Patent No.2,281,916.

To 148.8 g (0.3 mole) of this compound, 30 g (0.3 mole) of succinic anhydride are added followed by 180 g of pyridine distilled over caustic potash.

The mixture thus obtained is heated to 80"C for 2 hours, and 300 ml of water are then added at 50"C; the compound which salts out is washed 3 times with 300 ml of hot water containing 10 ml of concentrated hydrochloric acid, and then a final time with pure hot water.

The product is dissolved in ispropanol and dried over anhydrous sodium sulphate. After filtration and removal of the isopropanol, 141 g of a white product, which is solid when cold, are obtained.

50 g of this crude product are purified by preparative HPLC on a silica column, eluting with a dichloromethane/isopropanol (96:4) mixture.

A 33-g fraction of a white solid are thus obtained.

Acid value: 1.5 meq/g Saponification number: 4.4 meq/g.

Example 8 Preparation of the compound of general formula (I) in which R1 denotes C10H21 Y1 or Y2 denotes C14H29 Xdenotes -O A denotes

n, p and u being equal to zero.

The intermediate compound of formula (III) is prepared from decanol and 1,2-epoxyhexadecane.

To 30 g (0.075 mole) of this compound dissolved in 80 g of pyridine dried over caustic potash, 12.8 g of distilled citraconic anhydride (0.112 mole) are added at 25"C. The reaction medium is maintained for 48 hours at room temperature, and then poured dropwise with stirring into a solution of 49 g of sulphuric acid (d = 1.83) in 300 ml of iced water. The product is then extracted with 100 ml of hexane and the organic phase is dried over an hydros sodium sulphate.

The solution obtained is decolourised with activated charcoal and concentrated.

32.8 g of a yellow product, which is liquid when hot and waxy when cold, are thus obtained.

The product thus obtained is purified bysolubilisation in acetone.

Afterfiltration of the insoluble material and evaporation, 16.3 g of a clear clear viscous liquid, which crystallises very slowly, are obtained.

Acid value: 2.4 meq/g Saponification number: 4.2 meq/g Example 9 Preparation of the compound of general formula (I) in which: R1 denotes C10H21 Y1 or Y2 denotes C14H29 X denotes -0 A denotes -OCO-CH2-O-CH2-COOH n, p and u being equal to zero.

To 39.8 g (0.1 mole) of intermediate product of formula (ill) dissolved in 100 g of pyridine previously dried over caustic potash, 17.4 g (0.15 mole) of diglycolic anhydride are added.

The homogeneous mixture is maintained at 30"C for 24 hours, and the temperature is then brought to 70"C for 1 hour.

After being cooled, the solution is poured with stirring into a solution of 62 g of sulphuric acid (d = 1.84) in 250 ml of water, cooled to 10 C.

2. liquid phases are thus obtained, and these are separated.

The organic phase is dissolved in hexane and washed at 40"C with 100 ml of water; 60 ml of 10% strength NaCI are added to obtain better decantation, and the product is then dried over an hydros sodium sulphate.

After evaporation, 49 g of an almost colourless viscous liquid are obtained, and this crystallises after a few hours.

Acid value: 1.6 meq/g Saponification number: 3.3 meq/g.

After neutralisation with an excess of triethanolamine, the product yields a stable dispersion in water.

Example 10 Preparation of the compound of general formula (I) in which: R1 denoes C12H25 Y1 or Y2 denotes

X denotes -S A denotes -OCO-CH2-CH2-COOM M denotes H or -N-(CH2-CH2OH)3 n, p and u being equal to zero,.

The intermediate compound of formula (III) is prepared by reaction of 106.3 g (0.5 mole) of lauryl mercaptan with 93 g (0.5 mole) of 2-ethylhexyl glycidyl ether in the presence of sodium methylate as catalyst.

To 97 g (0.25 mole) of this compound dissolved in 125 g of pyriddine dried over caustic potash, 32 g (0.32 mole) of succinic anhydride are added and the mixture is heated to 600C for 3 hours.

200 ml of water are then added.

The product which salts out is dissolved in dichloromethane, washed twice with 200 ml of water to which hydrochloric acid has been added, and then once with pure water.

After dehydration over an hydros sodium sulphate and removal of the solvent, a yellow oil is obtained.

Acid value: 1.4 meq/g the product thus obtained is purified by molecular distillation.

After evaporation of the volatile compounds, an amber coloured liquid product is obtained, which has an acid value of 1.67 meqlg and is soluble in water in the presence of triethanolamine.

Example 11 Preparation of the compound of general formula (I) in which: R1 denotes C12H25 Y1 orY2 denotes

X denotes

A denotes -OCO-CH2-CH2-COOM M denotes H or N(CH2CH2OH)3 n, p and u being equal to zero.

5 g of compound prepared according to Example 10 are dissolved in 5 g of acetone. 0.95 ml of "130 volumes" hydrogen peroxide is then added at between 25 and 35"C.

The yellow coloured acetone solution is left for 24 hours at room temperature.

The solvent is then removed under reduced pressure.

A pale yellow viscous liquid is thus obtained, which is soluble in water in the presence of triethanolamine.

Example 12 Preparation of the compound of general formula (I) in which: R1 denotes C16H33 Y1 or Y2 denotes

X denotes -O A denotes -OCO-CH2-CH2-COOM M denotes H or N(CH2-CH20H)3 Z denotes H p equals u equals 0 n equals 10 The intermediate compound of formula (III) is prepared by reaction of 2-ethylhexyl glycidyl ether with octadecanol according to the procedure described for Example 2 of Patent 2,222,351.

To 34.2 g (0.08 mole) of compound thus obtained, 10.5 g (0.24 mole) of ethylene oxide are added in the presence of BF3, at 80"C; 1.4 g of a solution of sodium methylate in methanol, equivalent to 8.4 meq, and 28 g of ethylene oxide (0.63 mole) are then added at a temperature of 45"C. The product is then washed and dehydrated; it takes the form of a yellow oil, the number of oxyethylene units determined by NMR being 10.

To 8.7 g (0.01 mole) of polyoxyethyienated derivatives thus obtained, dissolved in 10 g of pyridine, 1 g (0.01 mole) of succinic anhydride is added.

The mixture is heated to 60"C for 3 hours.

15 ml of dichloromethane are then added and the mixture is washed twice with 20 ml of water to which hydrochloric acid has been added, and then with 20 ml of pure water.

The organic phase thus obtained is dehydrated over anhydrous sodium sulphate and, after filtration, the solvent is then removed by evaporation.

8.2 g of a yellow liquid, which is soluble in water after neutralisation with triethanolamine, are thus obtained.

Acid value: 1.15 meq/g.

Example 13 Preparation of the compound of formula (I) in which: R1 equals octylphenyl Y1 orY2 denotes CH3-(CH2)9 X denotes

A denotes O-CO-CH2-CH2-COOH p equals 4 u equals 1 n equals 0 I. Preparation of the intermediate compound of formula 111 To 97.1 g (200 meq of acid) of octylphenyl (polyoxyethyloxy)methylcarboxylic acid (4 oxyethyl units) sold under the name AKYPO OP 40, 1.1 g of a methanolic solution of sodium methylate containing 5.7 meq/g is added. The mixture is heated for 10 minutes at 1400C under vacuum to evaporate the methanol, and 200 meq (36.9 g) of 1,2-epoxydodecane are then gradually added at normal pressure in the course of 15 minutes.

Heating is continued for 9 hours at 120-130"C, and it is checked that the condensation is complete by carrying out an assay of epoxide, the value of which is zero.

The product is then washed with 200 ml of water at 60"C in the presence of 150 ml of chloroform, and then with twice 200 ml of water at 60"C.

The chloroform phase is dried over calcium chloride and then evaporated under vacuum.

II. Preparation of the compound of formula (I) 16 g (0.029 mole) of product obtained in the 1st stage are dissolved in 42.7 ml of anhydrous pyridine.

To this solution, 4.35 g (0.043 mole) of succinic anhydride are added, and the mixture is heated to 80"C for 2 hours.

The mixture is then poured gradually into 120 ml of 6 N hydrochloric acid solution, maintaining the temperature between 15 and 20"C. After decantation, the organic phase is first washed with 50 ml of water in the presence of 30 ml of methylene chloride, and then washed twice with 50 ml of an aqueous solution of 5% strength hydrochloric acid, and finally with twice 50 ml of water. The solution is dried over calcium chloride an then evaporated under vacuum.

A viscous liquid product is obtained.

Acid value: 1:1 meq/g Saponification number: 336 meq/g.

Example 14 Preparation of a compound of general formula (I) in which: R1 denotesC10H21 Y1 orY2 denotes C14H29 Xdenotes: -O- A denotes:

n, p and u being equal to zero.

The intermediate compound of formula (III) is prepared from decanol and 1,2-epoxyhexadecane.

To 30 g of this compound (75 meq) solubilised in 120 ml of anhydrous pyridine, 43 g of p-toluenesulphonyl chloride dissolved in 150 ml of the same solvent are added, and the mixture is left stirred at room temperature for 3 hours.

The reacting mass is taken up with 200 g of water and 200 g of ethyl acetate.

The organic phase is dried over magnesium sulphate and the solvent is removed by heating under reduced pressure.

The residue is solubilised in 50 g of dimethylformamide. 54 g of ethyl thioglycolate (450 meq) are added, followed by 79 g of sodium methylate in methanolic solution (450 meq).

The mixture is then heated for 12 hours at 50-60"C.

The product obtained is taken up with dioxane and 40% strength aqueous NaOH solution, and the reacting mass is heated to 90'Cfor 1 hour.

The mixture is acidified with concentrated hydrochloric acid solution.

The solvents are then removed by heating under reduced pressure.

The residue takes the form of a thick brown oil.

10 g (20 meq) of compound thus obtained are solubilised in 80 ml of isopropanol and 1.8 ml of "130 volumes" (39%) hydrogen peroxide are then added dropwise at 35"C.

The medium is stirred for 2 hours at 35-40"C. After the mixture has been left standing overnight at room temperature, it is washed with water and dried under reduced pressure.

A product is thus obtained which takes the form of a thick oil which is dispersible in water in the presence of triethanolamine.

Examples of Applications The following compositions were prepared with the compounds described in the examples above: Example A Face care cream - Compound of Example 2 (in the form of sodium salt) 4.8 g - cholesterol 3.2 g - glycerin 5.0 g - sunflower oil 17.0 g - high molecular weight carboyvinyl polymer sold under the name "Carbopol 941" by Goodrich Chemical 0.4 g - butylated hydroxytoluene 0.075 g - butylated hydroxyanisole 0.075 g - preservative 0.2 g - triethanolamine 0.4 g - perfume 0.2 g -demineralisedwaterq.s. 100 g Example 8 Dermatological fluid - Compounds of Example 6 (in the form of sodium salts) 2.5 9 - cholesterol 0.5g - hydrocortisone 0.1 g - preservative 0.2g - demineralised water q.s. 100 g Example C Makeup-removing lotion for the eyes - compounds of Example 3 in the form oftriethanolamine salts 1.0 g - alkylimidazoline of formula:

R equals coconut derivatives sold under the name "Miranol C2M" by Miranol 3.0 g - hexylene glycol 1.0 g - allantoin 0.05 g - preservative 0.3 g -phosphate buffer pH 7.2 q.s. 100 g Example D The following composition is prepared: - compound of Example 5 1.5 g A.M.

(A.M.: active material) - Surfactant of formula: R-CHOH-CH20(CH2CHOHCH20)nM R: mixtureofC9-C12alkyl radicals n: denotes an average statistical value of approximately 3.5 10 g A.M.

- water q.s. 100g The pH 7, adjusted with hydrochloric acid.

This composition is used as a shampoo for washing the hair.

Example E The following composition is prepared: - compound of Example 4 0.8 g A.M.

- nonionic surfactant based on poly glycerolated lauric alcohol (4.2 moles) of formula:

8.5 g A.M - water q.s. 100g pH equals 7.6, adjusted with sodium hydroxide.

This composition is used as a shampoo for washing the hair.

Example F The following composition is prepared: - compounds of Example 6 0.2 g A.M.

- quaternised cellulose sold under the name "JR 400" by General Aniline 0.5 g A.M.

- cycloimidazoline derivative of coconut oil, sold in solution containing 40% A.M. underthe name "Miranol C2M" by Miranol 1.0gA.M.

- hydroxyethylcellulose sold under the name "Natrosol HHR" by HERCULES 0.5 g A.M.

-water q.s. 100 g pH equals 8, adjusted with hydrochloric acid.

This composition is applied after a shampoo. After a few minutes' exposure, it is rinsed with water.

Example G The following composition is prepared: -terpolymer of vinyl acetate, crotonic acid and polyethylene glycol, sold underthe name "Résine TV 242" or "Aristo-flex A" by HOECHST 1.0 g A.M.

- compounds of Example 3 0.2 g A.M.

pH adjusted to 5 with lactic acid - ethanol q.s. 50" alcoholic strength, perfume, colouring, preservative, water q.s. 100g The composition, which takes the form of a lotion, is applied to the air, which is dried without preliminary rinsing.

Example H The following composition is prepared: - copolymer of vinylpyrrolidone and dimethylaminoethylmethacrylate quater nised with dimethyl sulphate, sold at a concentration of 50% of active material in ethanol under the name "Gafquat 734" by GAF 0.8gA.M.

- compound of Example 4 0.1 g A.M.

pH adjusted to 8 with 2-amino-2-methyl 1-propanol, perfume, colouring, preservative - water, q.s. 100g The compound takes the form of a lotion. It is applied to the hair, which is dried without preliminary rinsing.

Claims (23)

1. An anionic surfactant of general formula (I):

in which one of Y1 andY2 is hydrogen and the other is a group of formula (ill): R2 + OCH2 5 R1 and F2 which may be the same or different are each aliphatic or alkylaryl hydrocarbon of 8 to 22 carbon atoms, the number of carbon atoms for R1 + R2 being greater than or equal to 18 and less than or equal to 32, Xis oxygen, sulphur sulphoxide or carbonyloxy, u and v, which may be identical or different, are each 0 or 1, u being 0 when Xis oxygen, sulphur or sulphoxide, p is from 0 to 10, A is OH and/or

-S-(C,H2,)-COOM

or -O-CH2-COOM mis1 or2, W is alkylene of 1 to 3 carbon atoms or -CH2-O-CH2 M is hydrogen, alkali metal or alkaline earth metal, or a group of formula:

R3, R4 and F5 which may be the same or different are each hydrogen, alkyl or 1 to 3 C atoms or hydroxyalkyl of 2 or 3 C atoms, Z is hydrogen or a group -CH2A1, in which A1, which may be identical to or different from A, has the same significance as A, n is from 0 to 10, the average number of anionic groups per molecule being from 0.7 to 10.

2. A surfactant according to Claim 1, in which the average number of anionic groups per molecule is from 0.8 to 5.

3. A surfactant according to Claim 1 or 2, in which each R1 and R2 is a linear or branched alkyl, or alkylphenyl of from 8 to 18 carbon atoms, R1 and R2 having a total number of carbon atoms from 18 to 32.

4. A surfactant according to any one of the preceding claims, in which n is 0 and A is a group of formula:

in which W is alkylene of from 1 to 3 carbon atoms or -CH2-O-CH2-.

5. A surfactant according to Claim 1,2 or 3 in which n is other than 0 and Z is -CH2A1, in which A1 is a group of formula -S-(C,H1,)-COOM, or

and A is OH.

6. A surfactant as claimed in any one of claims 1 to 5 substantially as described in any one of Examples 1 to 14.

7. A process for preparing a surfactant as defined in any one of Claims 1 to 6, which comprises reacting a compound of formula (III):

in which R, p, u, X, Y1 and Y2 are as defined in claim 1, - with a cyclic anhydride of a diacid, - with a mecaptoalkanoic acid after prior tosylation or mesylation, or - with chloracetic acid, after prior formation of the sodium derivative of the compound of formula (III), each of these reactions optionally being preceded, by a polyaddition of ethylene oxide or an epihalohydrin, to give a surfactant in which n is other than 0, the polyaddition of epihalohydrin being followed, where appropriate, by hydrolysis to give a surfactant in which A1 is OH, or by a reaction in alkali medium with a mercaptoalkanoic acid, to give a surfactant in which A1 is -S(CmH2m)-COOH.

8. A process according to Claim 7, which comprises reacting a compound of formula (III) with a cyclic anhydride of a diacid corresponding to the formula:

in which W is as defined in Claim 1, optionally in the presence of a solvent which is an aliphatic or aromatic hydrocarbon, chlorohydrocarbon or ether solvent, at a temperature of from 0 to 1 200C to produce a surfactant of formula (I) in which n isO and A is O-CO-W-COOH.

9. A process according to Claim 7, which comprises tosylating or mesylating a compound of formula (III), and reacting the resulting compound in basic medium with mercaptoacetic or mercaptopropionic acid, or the corresponding ethyl of methyl ester, to give a surfactant in which A is -S-(C,H,,-COOH.

10. A process according to Claim 9, which comprises oxidixing the resulting surfactant with hydrogen peroxide to prepare a surfactant of formula (I) in which A is:

11. A process according to Claim 7, which comprises forming the sodium derivative of the compound of formula (III), and reacting the resulting product with chloracetic acid, or its methyl or ethyl ester, optionally in the presence of a solvent which is an aliphatic or aromatic hydrocarbon, at a temperature of from 50 to 140"C, to give a surfactant of formula (I) in which A is O-CH2-COOH.

12. A process according to Claim 7, which comprises carrying out the polyaddition of 1 to 10 molecules of ethylene oxide per molecule of intermediate compound of formula (III), to obtain a product of formula (lIlA):

in which F1, p, u, X, Y1 and Y2 are as defined in claim 1 and n is from 1 to 10, and reacting the resulting product with a cyclic anhydride of a diacid or, after tosylation or mesylation, a mercaptoalkanoic acid or, after forming the sodium derivative, with a chloracetic acid to give a surfactant of formula (I) in which n is other than 0 and Z is hydrogen.

13. A process according to claim 7, which comprises carrying out the polyaddition of 1 to 10 molecules of epihalohydrin per molecule of intermediate compound of formula (III), to form a product of formula (IIIB):

in which F1, p, u, X, Y1 and Y2 are as defined in claim 1 and n is from 1 to 10, producing the corresponding halogenated derivative, and reacting this with a mercaptoalkanoic acid of formula HS-(CmH2m)COOH in alkaline medium to give a surfactant of formula (I) in which A1 is -S-(CmH2m)COOH and A is OH.

14. A process according to Claim 13, which comprises hydrolysing the halogenated derivative of formula (IlIB) to give the corresponding poiyhyroxylated derivative, and reacting this with a cyclic derivative of a diacid, or after tosylation or mesylation reacting with mercaptoacetic or mercaptopropionic acid, or after forming the sodium derivative reacting with chloracetic acid.

15. A process according to any one of Claims 7 to 14, which comprises salifying the resulting compounds to form the corresponding alkali metal, alkaline earth metal, ammonium or amine salt.

16. A process according to any one of Claims 7 to 15 substantially as described in any of Examples 1 to 14.

17. A surfactant as claimed in any one of Claims 1 to 6 when produced by the process of any one of Claims 7 to 16.

18. A composition suitable for cosmetic or pharmaceutical use which comprises at least one compound as claimed in any one of Claims 1 to 6 or 17.

19. A composition according to Claim 18, which also contains an anionic, cationic, nonionic or zwitterionic surfactant.

20. A composition according to Claim 18 or 19, which comprises one or more cosmetically acceptable ingredient which is an alkalising or acidifying agent, thickener, solvent, electrolyte, foam synergist, foam stabiliser, oil, wax, superfatting agent, natural substance, protein derivative, anti-seborrhoeic agent, anti-dandruff agent, sunscreen, oxidising agent, reducing agent, sequestering agent, colouring, pigment, pearlescence agent, opacifier, antiseptic, preservative or perfume, as well as any other active substance useful in the treatment, care or protection of the skin or hair.

21. A composition according to any one of Claims 18 to 20 which contains 0.05 to 30% by weight of a surfactant of formula (I).

22. A composition as claimed in any one of claims 18 to 21 substantially as described in any one of the Application ExamplesAto H.

23. A process for cosmetic treatment of the hair or skin, which comprises applying to the hair or skin at least one surfactant as defined in any one of Claims 1 to 6 or 17.