FR2565846A1 - ANIONIC SURFACTANT ANIONIC COMPOUNDS WITH TWO FATTY CHANNELS AND COSMETIC AND PHARMACEUTICAL COMPOSITIONS CONTAINING SAME - Google Patents

Abstract

THESE COMPOUNDS HAVE THE FORMULA: (CF DRAWING IN BOPI) OR Y AND Y DESIGNATE ONE HYDROGEN AND THE OTHER (CF DESIGN IN BOPI) R AND R DESIGNATE ALIPHATIC OR ALKYLARYL RADICALS IN C8-22, RR BEING IN C18- 32, X IS OXYGEN, SULFUR, SULFOXIDE OR CARBONYLOXY, U AND V IS 0 OR 1; WHERE X MEANS HYDROGEN, SULFUR OR SULFOXIDE U 0; P DESIGNATES A NUMBER FROM 0 TO 10, A DESIGNATES OH ETOU-O-C-W-C-OM; -S- (CH) -COOM; -S- (CH) -COOM OR -O-CH-COOM; M DESIGNATES 1 OR 2; W DESIGNATED C1-3 OR -CH-O-CH ALCOYLENE, M DESIGNED HYDROGEN, AN ALKALINE OR ALKALINO-EARTH METAL OR NRRR, R, R AND R DESIGNED HYDROGEN, C1-3 ALKYL OR HYDROXYALCOYL C2-3, Z DESIGNED HYDROGEN OR -CHA, AA THE MEANINGS INDICATED FOR A, N REFER TO A NUMBER FROM 0 TO 10. ANIONIC SURFACTANT COMPOUNDS ARE SUITABLE FOR USE IN COSMETIC OR PHARMACEUTICAL COMPOSITIONS.

Description

The subject of the present invention is new compounds or mixtures

  new anionic surfactant compounds and their use in

  compositions for cosmetic or pharmaceutical use.

  Many anionic surfactant compounds are known in the state of the art. These compounds generally have an aggressiveness vis-à-vis the ocular mucous membranes and are therefore sought to replace or

  reduce their aggressiveness by associating them with other compounds.

  The compounds in accordance with the invention have, as an essential characteristic, two lipophilic fatty chains with respect to the lipophilic part and, with regard to the hydrophilic part, one or more

  several carboxylic group (s).

  These products are soluble and most often dispersible in water in the form of alkali metal salts of ammonium or amine salts. They

  may nevertheless be completely solubilized in the presence of other surfactants.

  hyrosoluble active agents and / or solvents and lead to clear compositions

  of. The Applicant has discovered that these anionic compounds surprisingly exhibit properties that make it possible to reduce the aggressiveness, in particular in the Draize test, of the compounds with which they are associated, and in particular the surfactants. This property is particularly surprising

  when we know the aggressiveness vis-à-vis the ocular mucous membranes of

classical anionic actives.

  Furthermore, the presence of hydrocarbon chains of a more or less different length and nature gives the molecule a lipophilic character.

  important with relatively low melting points.

  In addition to the properties mentioned above, the compounds according to the invention are of interest, when they are introduced into the hair treatment formulas, even at low concentrations, to provide

  softness and shine and facilitate disentangling.

  The subject of the invention is therefore new anionic surfactant compounds

assets.

  Another subject of the invention is constituted by compositions containing

  these compounds and their use in cosmetics and pharmaceuticals.

  Other objects will appear on reading the description and

examples that follow.

  The compounds in accordance with the invention may be represented by the following general formula (I): R 1 OCHr CH 2 OCR 2

1 CE

p. u

Y1 - CH

Y2 C -CH-- CHH2 -A

  In which Y1 or Y2 denotes a monovalent radical, one of them being a hydrogen atom and the other a radical of formula:

R2 OCH2

  R1 and R2 denote aliphatic or alkylarylic hyrocarbon radicals having 8 to 22 carbon atoms, the number of R1 + R2 atoms being greater than or equal to 18 and less than or equal to 32, X denotes an oxygen atom, ( -O-), a sulfur atom, (-S-), a sulfoxide group, (-S = O) or a carbonyloxy group (- C - O -) Il u and v identical or different represent the value O or 1 where u is O when X is oxygen, sulfur, or sulphoxide, p is A where A is OH and / or -OCWC-OM Il 11 OO S- (CmH2m) COM - S - (CmH2m) COOM

0

  or -O-CH 2 -COOM m denotes 1 or 2, W denotes an alkylene group having 1 to 3 carbon atoms or the group -CH 2 -O-CH 2 -, M denotes a hydrogen atom, an alkali metal or alkaline metal; earthy

  that more particularly Na, K, an equivalent Mg or a group

Formula 1t3

N R4

  R5 in which R3, R4 and R5 independently of one another denote an atom

  hydrogen, an alkyl group having 1 to 3 carbon atoms or a group

  hydroxylalkyl having 2 or 3 carbon atoms, Z denotes a hydrogen atom or a group --CH2A1 in which A1 has the same meanings as A, A and A1 may be identical or different, n denotes an integer or decimal number between O and 10, the average number of anionic groups per molecule being between

  0.7 and 10 and preferably between 0.8 and 5.

  The compounds which are particularly preferred according to the invention are those for which the radicals R 1 and R 2 denote, independently of one another, linear or branched alkyl or alkylphenyl radicals having 8 to 18 carbon atoms, their sum being equal to or greater than 18 and less than or equal to 32, X denotes an oxygen atom, a sulfur atom, a sulphoxide group, a carbonyloxy group, p denotes any number from 0 to 10 u and v the value O or 1, A denoting a radical OH or OCWC-OM, It is OOW denoting an alkylene group having from 1 to 3 carbon atoms or the group -CH2-O-CH2, M denoting hydrogen, sodium, potassium, magnesium or the grouping: / R3

N - R4

  R5 in which R3, R4, R5 denote a hydroxyalkyl group, Z denoting either a hydrogen atom or a group -CH2A1, where A1 denotes in particular the group S (CH2) -COOM m denoting 1 or 2; n having a value of 0 or 10, the average number of anionic groups per

  molecule being between 0, 7 and 10.

  The compounds according to the invention are prepared according to a process

  comprising several elementary steps.

  The process, which constitutes another object of the invention, consists essentially of

  the reaction of an alcohol with two fatty chains corresponding to the formula: ## STR2 ##

Y - CH

Y2 - CHOH

  in which: R1i Y1i Y2, p, u and X have the meanings indicated above, with - either a cyclic anhydride of diacid, - or after tosylation or mesylation, with a mercapto-alkanoic acid such as mercapto-acetic acid or mercapto -propionic, or, after sodation, with chloroacetic acid, these reactions possibly being preceded by a polyaddition of 1 to 10 moles of ethylene oxide or of 1 to 10 moles of epihalohydrin when n is not 0, the polyaddition with the epihalohydrin being, if appropriate, followed by a hydrolysis of the halogenated derivatives when A1 denotes OH, or of an alkaline reaction with a mercapto alkanoic acid when A1

denotes -S (CmH2m) C00H.

  The process according to the invention can be carried out more particularly

  under the following conditions depending on the nature of the final compound of

  formula (I) that we want to prepare.

  The intermediate compounds of formula (III) are converted into

  Anionic compounds of formula (I) wherein n is 0, according to the following procedures: (1) by reaction with a diacid cyclic anhydride of the formula:

O O

  w W / W having the meaning mentioned above in the possible presence of a

  solvent such as an aliphatic or aromatic hydrocarbon, a hydro-

  chlorocarbon or an ethereal solvent at a temperature between 0 and C, to obtain the compounds of formula (I) in which A designates:

0 - C -W - COOH

0

  The salts of alkali or alkaline earth metals, ammonium or amines are obtained according to the conventional salification processes, (2) by reaction of the tosylates or mesylates of the compounds (III) in a basic medium with a mercapto alkanoic acid, chosen from preferably from mercapto-acetic or mercapto-propionic acid, or the corresponding methyl or ethyl ester resulting in the compounds of formula (I) in which: A signifies -S- (C 2 H 2) -COOH in which ma the meaning indicated ci -above. As before, salification can be carried out in order to obtain the compounds in which:

  A denotes the group -S- (CmH2m) -cOOM.

  By oxidation with hydrogen peroxide are obtained the compounds in which: A denotes -S- (C 2 H 2) COCM, ilm 2m o (3) by reaction of chloroacetic acid or its methyl or ethyl esters with the corresponding soda compounds to compounds of formula

  (III) optionally in the presence of a solvent such as aliphatic hydrocarbons.

  or in the case of the compounds of formula (I) in which:

salified.

  In the case where n is different from O, we add ethylene oxide

  or an epihalohydrin intermediate compounds of formula (III).

  (1) For the preparation of compounds of formula (I) in which n is

  different from 0 and Z denotes hydrogen, it is added per molecule of

  intermediate of formula (III) of 1 to 10 molecules of ethylene oxide to obtain the compounds of formula (IIIA) R1 0 CH-CH2p [C 2 R ff 2jp - {-. CH2j- X

Y1-CH (III A)

1

  The compounds (III A) are converted into compounds of formula (I) either by the action of a cyclic anhydride of a diacid, or by tosylation or mesylation followed by a reaction with a mercaptoalkanoic acid, or, after sodation, by reaction with chloroacetic acid as described above. (2) In the case where the compounds of formula (I) are prepared in which n is different from 0 and Z represents a group -CH 2 Al, we add by

  molecule of intermediate compound of formula (III) of 1 to 10 epoxide molecule

  halohydrin, preferably epichlorohydrin, to form the compounds of formula (III B):

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R 1OCHrCH O CH X

Y1-CH (III B)

  These halogenated derivatives can react directly in an alkaline medium with

  a mercaptoalkanoic acid of formula HS- (CmH2m) COOH, or its methyl ester;

  or ethyl to give the compound of formula (I) wherein A1 denotes the group -S (CmH2m) COOH and A denotes OH, this compound may optionally be salified and / or oxidized, (3) The halogenated derivatives of formula (III B) to obtain the corresponding polyhydroxy compounds, these compounds being capable of being reacted either with a cyclic anhydride of a diacid, or after tosylation or mesylation with a mercaptoalkanoic acid or, after sodation,

  with chloroacetic acice as indicated above.

  The cyclic anhydrides of diacid more particularly usable

  according to the invention are selected from malonic anhydride,

  nicotine, methylsuccinic, glutaric or diglycolic

  The intermediate compounds of formula (III) are prepared according to the processes known per se, described in particular in French patents

  Nos. 2,222,351 and 2,281,916 to the applicant.

  These compounds can be prepared in particular with regard to the lipophilic part by reacting a compound or a mixture of active hydrogen compounds corresponding to formula (IV):

R OCH-C2 CH2 XH (IV)

  with an alkylene oxide, an alkyl or alkenylglycidylether or an alkylaryl-

  glycidyl ether or a mixture of these compounds of formula (V):

R OCH 'CH-CH (V)

2 2 CH-CH2 (y) v O

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  in which R 1, R 2, v, u, and p have the same meanings as in the general formula (I), X denoting oxygen, sulfur or -CO This reaction is carried out either by acid catalysis in the presence of catalysts such as BF3, SnCl4, SbCl5, ZnCl2, TiCl4 and H2SO4, at a temperature between 40 and 110 C, or in basic catalysis in the presence of

  example of sodium or potassium methoxide or ethoxide at a temperature of

between 100 and 160 ° C.

  Under these conditions, the main product of the reaction or the main products formed can be represented by the general formula (III1):

R1 OCH-CH 2 -OCH2- X

could

CH2 (III1)

R2 C CHOR

v

  but it is also possible to obtain in lower proportions the isomers of

mule (III2):

R1 OCH2 CH2 OCH2 - X

could

R2 OCH CH (III2)

2 2

v CH2OH

  The compounds may contain small amounts of

  addition from the reaction of another epoxide molecule of formula

  (V) with a product of formula (III1) or (I112).

9 2565846

  These different products can be separated partially or totally or left with the main product, their presence not being detrimental

properties.

  Among the active hydrogen compounds that can be used in the spirit of

  example, fatty alcohols or alkylamines may be mentioned as examples.

  optionally oxyethylated phenols, alkyl mercaptans, alkylphenyl

  corresponding polyoxyethylmercaptans, fatty acids, polybasic acids,

  oxyethyloxy methylcarboxylic acids alkylaryl polyoxyethyloxy methyl carboxylic acids, these compounds having in the alkyl or alkylaryl part,

8 to 22 carbon atoms.

  Among the epoxide compounds of formula (V), the alkyls can be used

  ethylene oxide, alkyl or alkenylglycidyl ether having 8 to 22 carbon atoms

  carbon in the R2 part, alkylarylglycidylethers and more particularly

  Alkylphenylglycidyl ethers containing 8 to 22 carbon atoms are

in the R2 part.

  The compounds in accordance with the invention are in the form of viscous liquid products, pastes or solids, depending on the nature and the length of the hydrocarbon radicals R 1 and R 2 according to the value of v and according to whether they are isolated in the form of acid or in the form of alkaline salts,

alkaline earth or amines.

  According to another aspect of the invention, the compounds thus defined and

  prepared are particularly suitable for use in

  cosmetic or pharmaceutical positions.

  They can in particular be used to reduce the aggressiveness of surfactants and to improve cosmetic properties such as

  detangling, softness, shine of hair compositions.

  These compounds can also be used as solubilizers;

  emulsifiers, as lipid constituents for the preparation of vesicles

  them, etc. They can be used at concentrations between 0.05 and

  % by weight relative to the total weight of the compositions and in particular.

  in the proportions between 0.25 and 10% by weight.

  In these compositions, they may be combined with surfactants

  anionic active agents, different from those of formula (I), cationic, zwitterionic

  or non-ionic compounds or mixtures thereof with natural cosmetic polymers

  or synthetic anionic, cationic, nonionic or amphoteric.

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  The compositions may further contain thickeners, solvents, electrolytes, foam synergists, foam stabilizers, oils, waxes, superfatting agents, natural substances, protein derivatives, antiseborrhoeic agents, anti-dandruff agents, , oxidants, reducers, sequestering agents, dyes, pigments, pearlescent agents, opacifiers, antiseptics, preservatives, alkalizing or acidifying agents, perfumes as well as

  any other active substance that may have an action at the level of

  care or protection of the skin or hair and all adjuvants

  usually used in cosmetic compositions.

  Acids and bases are used in amounts appropriate for

  adjust the pH of the compositions between 5 and 10.

  In addition to the surfactants of the invention, the pharmaceutical compositions contain the active substances intended for the treatment of the human body or

  animal and pharmaceutically acceptable excipients.

  For hair care compositions containing the compounds according to the invention can be shampoos, conditioning compositions

  hair or dye compositions.

  The shampoos may contain, in addition to the anionic surfactants according to the invention, one or more anionic cationic surfactants,

  amphoteric, nonionic or mixtures thereof, as well as other cosmetic adjuvants.

  ticks usually used in this type of composition.

  The dyeing compositions are based on dye precursors

  so-called oxidation or so-called direct dyes or their mixtures.

  The compositions according to the invention can also be used

  depending on the nature of the components such as lotions for rinsing hair, body fluid milks, moisturizing creams, lipsticks, eye lotions, eye shadow, lotions for

  folds, lacquers, as well as for other cosmetic applications, these composi-

  containing at least the anionic surfactants conforming to

The invention.

  These compositions may be aqueous, hydroalcoholic or oily and may be in the form of solutions, lotions, emulsions, pastes,

gels, powders, aerosols.

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  The examples which follow are intended to illustrate the invention without

  both have a limiting character.

EXAMPLE 1

  Preparation of the compound of formula (I) in which R1 denotes C15H31

  Y1 or Y stands for C4H9 - CH - CH20 - CH -

C2H5

X is - C -0 -

  I! o A denotes - OCO - CH 2 - CH 2 - COOM M denotes H or

N (CH 2 CH 2 OH) 3

n, p and u being zero.

  The intermediate compound of formula (III) is prepared from 254 g of hexadecanolic acid (1 mole) and 182 g (0.98 mole) of glycidyl ethyl-2 hexyl ether according to the method described in Example 5 French patent

2,222,351.

  To 220 g (0.5 mol) of the compound thus obtained dissolved in 270 g of

  pyridine distilled on potassium hydroxide, 50 g (0.5 mole) of succinic anhydride

  Picnic. The mixture is heated for 2 hours at 800C.

  500 ml of cold water are then added. This gives an organic phase

  that it is washed 3 times with 5% hydrochloric acid

  drique (d = 1,19) then one last time with pure water.

  The product thus obtained is dissolved in isopropanol and dried over anhydrous sodium sulphate. After filtration and removal of the solvent,

  226 g of an almost colorless oil are obtained.

  204 g of this crude oil are purified by molecular distillation at

220 C under 1073 mm of mercury.

  The product obtained is a pale yellow oil.

  Acid number: 1.47 meq / g Saponification number: 4.85 meq / g The triethanolamine salt gives a viscous dispersion in water

stable.

12 2565846

EXAMPLE 2

  Preparation of the compound of formula (I) in which: R1 denotes C15H31

Y or Y denotes C12H25 -O-CH2 -

1 2 ge12 252

X is - C - O -

  O A is OCO - CH 2 - CH 2 - COOM M is H or --N (CH 2 --CH 2 OH) 3

n, p and u being zero.

  44.8 g (0.09 mol) of intermediate compound (III) prepared according to a process analogous to that of Example (I), starting from hexadecanololic acid and dodecylglycidyl ether solubilized in 50 g of pyridine distilled on potassium hydroxide 9.9 g (ie 0.099 mole) of succinic anhydride are added and then

heated at 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% hydrochloric acid (d = 1.19). Then one last wash with 100 ml of water

  pure and then dehydrated by heating under reduced pressure.

  In this way 52.6 g of cold solid product is obtained, which is recrystallized.

read in 100 ml of heptane.

  The final product is a white powder (39 g), whose melting point

is 45 C.

  Acid number: 1.62 meq / g Saponification number: 5.0 meq / g As triethanolamine salt in the concentration of 5% in

  water, it gives a viscous and stable dispersion.

EXAMPLE 3

  Preparation of the compound of formula (I) in which: R1 denotes C16H33

  Y or Y denotes C4H CH- CH - CH - - CH2 -

i 2 4 9 2 2

C2H5

X is - O -

  A denotes - OCO - CH 2 - CH - COOM M denotes H,

13 2565846

NH2-CH2-CHOH-CH3

or 1 equivalent Mg

n, p and u being zero.

  To 119.8 g (0.28 mol) of intermediate compound (III) prepared from hexadecanol and 2-ethylhexyl glycidyl ether, according to the process described in Example 2 of French Patent 2,222,351, 160 g of pyridine and then 8 g (ie 0.31 mole) of succinic anhydride are added. The mixture is brought to 80 ° C

during 2 hours 30 minutes.

  After cooling, 300 ml of cold water are added and the supernatant phase

  geant is washed twice with 300 ml of water at 40 C containing 10% HCl (d = 1, 19) and then once with 300 ml of pure water. It is then dehydrated by means of

  anhydrous sodium sulphate and the product thus obtained is purified by distillation.

  molecular solution (elimination of the light terms by distillation at 175 ° C. under a vacuum of 10-3 mmHg and then distillation of the product at 205 ° C. under the same

  empty). 82.5 g of a virtually colorless oil are thus obtained.

Acid number: 1.92 meq / g

  Saponification index: 3.71 meq / g.

  Preparation of the salt of monoisopropanolamine By mixing 26.5 g (0.05 mol) of acid of formula (I) with 3.8 g (0.05 mol) of monoisopropanolamine, a viscous liquid is obtained slightly

soluble in water.

Preparation of magnesium salt

  4 g (0.02 mol) of acid of formula (I) are dissolved in 20 ml of iso-

  propanol and 5g of water. 0.64 g (0.022 equivalents) of finely hydrated magnesia

  milled are added with stirring at 80 C.

  The insoluble particles are separated and evaporated under reduced pressure.

  The magnesium salt thus obtained is in the form of a viscous liquid.

EXAMPLE 4

  Preparation of the compound of formula (I) in which: R1 denotes CloH21

Y or Y denotes C4H9-CH-CH2-O-CH2-

1 2 e4 9 2 2 C2H5

* X denotes -O-

A denotes -OCO-CH2-CH2-COOH

n, p and u being zero.

14 2565846

  86 g (0.25 mole) of intermediate compound (III) obtained from decanol-1 and 2-ethylhexyl glycidyl ether, according to the same process as that described in Example 2 of French Patent 2,222,351 , we add 110 g of

  pyridine distilled on caustic potash, then 25 g (0.25 mole) of anhy-

  succinic dride. The mixture thus obtained is heated at 80 ° C. 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.,

  then a last wash with pure water.

  The organic phase is then dried over sodium sulfate after filtration.

  The resulting oil is purified by molecular distillation at 160.degree.

under 10-3 mmHg.

  A colorless oily liquid is thus obtained.

  By thin layer chromatography, on a silica plate with an eluent

  dichloromethane / propanol: 95/5, a single task is detected Rf. = 0.38.

Acid number: 2.25 meq / g

  Saponification number: 4.25 meq / g.

EXAMPLE 5

  Preparation of the compound of formula (I) wherein R1 is C8H17 Yi or Y2 is CloH21

X is -O-

A denotes -OCO-CH2-CH2-COOH

n, p and u being zero.

  To 94.2 g (0.3 mole) of intermediate compound (III) (PE 153 C / 10 -3 mmHg)

  prepared from n-octanol and epoxydodecane-1,2, in an analogous

  to that described in French Patent No. 2,465,780, 120 g of

  pyridine distilled on potassium hydroxide and 30 g (0.3 mole) of succinic anhydride.

It is heated for 2 hours at 80 ° C.

  250 liters of cold water are added. The organic phase is washed twice with 250 ml of water at 40 ° C., followed by addition of 10 ml of concentrated HCl (d = 1.19), and then

again with pure water.

  It is then dried over anhydrous sodium sulphate after filtration and

  114 g of a light yellow oil.

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  This oil is purified by molecular distillation.

  The volatile compounds are eliminated at 145 ° C. under 10-3 mmHg and then

product is distilled at 175 C.

  By thin layer chromatography, eluting with the mixture of

  chloromethane / propanol (95/5), a single task is obtained (Rf = 0.5).

Acid number: 2.60 meq / g.

EXAMPLE 6

  Preparation of the mixture of compounds of general formula (I) in

  which: R1 is C8H17 Y1 or Y2 is C16H33

X is -O-

  A is -OH Z is -CH2-S-CH2-COONa p = u = O n = 2. A 79.6 g (0.2 mole) of intermediate compound (III) (Pe / O, 0.8 mmHg: 193-205 ° C., mp: 48-490 ° C.) prepared according to a process analogous to that described in French Patent No. 2,465 780, 0.23 ml of SnCl.sub.4 and then at 60.degree.-65.degree.

  40 minutes, 37 g (0.4 mole) of epichlorohydrin.

  The product is then washed at 90 ° C. with a 25% solution of Na 2 CO 3.

  g of product thus obtained (396 meq of chlorine) are then added to OC in the mixture of 37.7 g of thioglycolic acid (396 meq) and 81.3 g of sodium hydroxide solution (816 meq) under a nitrogen atmosphere. . The reaction mass

  is heated for 2 hours at 100 C.

  To fluidify the medium, 30 ml of water and 60 ml of

  thylcellosolve and then heated for another 2 hours at 100 C.

  The reaction mass is taken up with 350 ml of water and 38 ml of acid

concentrated hydrochloric acid.

  After addition of 60 ml of isopropanol, at 60 ° C.

the organic phase.

  After decantation, it is washed again with 200 ml of water in the presence of 20

ml of isopropanol.

  It is then resumed with 120 ml of water and 32 g of 40% sodium hydroxide.

162565846

  After removal of the isopropanol under reduced pressure,

  288 g of white paste with about 34% of active ingredients.

Basicity index: 1 meq / g.

  By dilution, a cloudy solution is obtained.

EXAMPLE 7

  Preparation of the compound of general formula (I) in which: R1 denotes C 15 H 31 1 or Y 2 denotes C 14 H 29

X denotes -COO-

A denotes -OOC-CH2-CH2-COOH

n, p and u being zero.

  The intermediate compound of formula (III) is prepared from palmitic acid and epoxy-1,2 hexadecane by the method described in the example

12 of French Patent No. 2 281 916.

  To 148.8 g (0.3 mole) of this compound is added 30 g (0.3 mole) of anhydride.

  succinique then 180g of pyridine distilled on potash.

  The mixture thus obtained is heated at 80 ° C. for 2 hours and then 300 ml of water are added at 50 ° C .; the releasing compound is washed 3 times with 300 ml of hot water containing 10 ml of concentrated hydrochloric acid and then

  last time with pure hot water.

  The product is dissolved in isopropanol and dried over sodium.

  anhydrous sodium fate. After filtration and removal of isopropanol,

  gets 141 g of a cold solid white product.

  g of this crude product are purified by preparative column HPLC

  of silica and elution with a dichloromethane / isopropanol mixture: 96/4.

  A fraction of 33 g of a white solid is thus obtained.

Acid number: 1.5 meq / g

Sapo index: 4.4 meq / g.

EXAMPLE 8 Preparation of the compound of general formula (I) in which: R1 represents

CloH21 Y1 or Y2 denotes C14H29

X is -0-

A denotes -OCO-CH-CH 2 -COOH i 2

CH3

n, p and u being zero.

17 2565846

  The intermediate compound of formula (III) is prepared from

nol and epoxy-l, 2 hexadecane.

  To 30 g (0.075 mol) of this compound dissolved in 80 g of pyridine dried over potassium hydroxide is added 12.8 g of distilled citraconic anhydride (0.12 mol) at 25 C. It is maintained for 48 hours at room temperature then the reaction medium is poured dropwise with stirring into a solution of 49 g of sulfuric acid (d = 1.83) in 300 ml of ice water. It is then extracted with 100 ml of hexane and the organic phase is dried over sodium sulfate.

anhydrous soda.

  The solution obtained is discolored on activated charcoal and concentrated.

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

  The product thus obtained is purified by solubilization in acetone.

  After filtration of the insoluble matter and evaporation, 16.3 g of

  clear viscous liquid that crystallizes very slowly.

Acid number: 2.4 meq / g

Sapo index: 4.2 meq / g.

EXAMPLE 9

  Preparation of the compound of general formula (I) wherein R1 is CloH21 Y1 or Y2 is C14H29

X is -O-

A denotes -OCO-CH 2 -O-CH 2 -COOH

n, p and u being zero.

  To 39.8 g (0.1 mole) of intermediate product of formula (III) dissolved in 100 g of pyridine previously dried over potassium is added

  17.4 g (0.15 mol) of diglycolic anhydride.

  The homogeneous mixture is kept at 30 ° C. for 24 hours and then the temperature

  The temperature is raised to 70 ° C. for 1 hour.

  The solution, after cooling, is cast under stirring in a solution of 62 g of sulfuric acid (d = 1.84) in 250 ml of water cooled with C.

  This gives two liquid phases that are separated.

  The organic phase is dissolved in hexane and washed at 40 ° C. with 100 ml of water; 60 ml of 10% NaCl is added to obtain a better

  settling and then dried over anhydrous sodium sulphate.

18 0D4

  After evaporation, 49 g of a viscous, slightly colored liquid are obtained which

  crystallizes after a few hours.

Acid number: 1.6 meq / g

  Saponification number: 3.3 meq / g.

  The product, after neutralization with an excess of triethanolamine, gives

in water a stable dispersion.

EXAMPLE 10

  Preparation of the compound of general formula (I) in which: R1 denotes C12H25

  Y1 or Y2 is C4 H-CH-CH2-O-CH2-

1 2 4 9 1 2 2

C2H5

X denotes -S-

  A is -OCO-CH2-CH2-COOM M is H or -N- (CH2-CH20H) 3

n, p and u being 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 methoxide as a catalyst.

  To 97 g (0.25 mole) of this compound, dissolved in 125 g of dried pyridine qir potassium, is added 32 g (0.32 mole) of succinic anhydride and

heat for 3 hours at 60 C.

200 ml of water are then added.

  The liberated product is dissolved in dichloromethane, washed twice with 200 ml of water containing hydrochloric acid, and then once with

pure water.

  After dehydration on anhydrous sodium sulphate and elimination of

  solvent, a yellow oil is obtained.

Acid number: 1.4 meq / g

  The product thus obtained is purified by molecular distillation.

  After evaporation of the volatile compounds, a liquid product is obtained

  of amber color, acid value 1.67 meq / q and water-soluble in pre-

triethanolamine.

192565846

EXAMPLE 11

  Preparation of the compound of general formula (I) in which: R1 denotes C12H25

  Y1 or Y2 is C4H9-CH-CH2-O-CH2-

1 2 ig 4 9, C2 C2 C2H5

X denotes -S-

  O A denotes -OCO-CH 2 -CH 2 -COOM M denotes H or N (CH 2 CH 2 OH) 3

0 n, p and u being zero.

  g of the compound prepared according to Example 10 are dissolved in 5 g of acetone. Then 0.95 ml of hydrogen peroxide at 130 volumes is added between 25 and C. The yellow acetone solution is left for 24 hours.

at room temperature.

  The solvent is then removed under reduced pressure.

  A viscous liquid of light yellow color, 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 is C4H9-CH-CH2-O-CH2-

C2H5

X is -0-

  A denotes -OCO-CH 2 -CH 2 -COOM M denotes H or N (CH 2 -CH 2 OH) 3 denotes H pu = O n- The intermediate compound of formula (III) is prepared by reaction of 2-ethylhexyl glycidyl ether on octadecanol according to the procedure

  described for example 2 of the patent 2,222,351.

  To 34.2 g (0.08 mol) of the compound thus obtained, 10.5 g (0.24 mol) of ethylene oxide in the presence of BF 3 are added at 80 ° C .; 1.4 g of a methylate solution in methanol, ie 8.4 meq and 28 g of oxide, are then added.

^^^

  ethylene (0.63 moles) at 45 ° C. The product is then washed and dehydrated; it is in the form of a yellow oil, the number of

  Ethylenoxy units determined by NMR is 10.

  8.7 g (0.01 mol) of polyoxyethylated derivatives thus obtained, in

  In 10 g of pyridine, 1 g (0.01 mole) of succinic anhydride is added.

  The mixture is heated for 3 hours at 60 ° C.

  15 ml of dichloromethane are then added and the mixture is washed twice with 20 ml

  water added with hydrochloric acid, then with 20 ml of pure water.

  The organic phase thus obtained is dehydrated on sodium sulphate

  anhydrous and after filtration, the solvent is removed by evaporation.

  This gives 8.2 g of a yellow liquid soluble in water after

  neutralization with triethanolamine.

Acid number: 1.15 meq / g.

EXAMPLE 13

  Preparation of the compound of formula (I) wherein: R1 - octyl phenyl

Y1 or Y2 denotes CH3- (CH2) 9-

X denotes -C-O-

  A denotes O-CO CH 2 -CH 2 -COOH p 4 u-1 u = 1 n-1 I. Preparation of the intermediate compound of formula III A 97.1 g (20C meq in acid) "octylphenyl polyoxlethyloxymethyl carboxy" (4 oxyethyl units) sold under the name AKYPO OP 40, 1.1 g of a methanolic solution of sodium methoxide at 5.7 meq / g are added and the mixture is heated for 10 minutes at 140 ° C. under vacuum to evaporate. methanol, then, at normal pressure, 200 meq (36.9 g) of 1,2-dodecane epoxide are gradually added in over 15 minutes, the heating is continued for 9 hours at 120 ° C. and one verifies that the condensation is terminated by an epoxy dosage of which

the index is zero.

  The product is then washed with 200 ml of water at 60 ° C. in the presence of 150 ml.

  chloroform, then twice with 200 ml of water at 60 ° C.

  The chloroform phase is dried over calcium chloride then

evaporated under vacuum.

  II. Preparation of the compound of formula (I) 16 g (0.029 mol) of product obtained in the first step are dissolved in 42.7 ml of anhydrous pyridine. To this solution is added 4.35 g (0.043 mol) of anhydride

  succinique and the mixture is heated for 2 hours at 80 ° C.

  The mixture is then gradually poured into 120 ml of a 6N 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 water. ml of methylene chloride, then washed twice with 50 ml of a 5% aqueous solution of hydrochloric acid, and finally with 2 times 50 ml of water. The solution is dried on

  calcium chloride and then evaporated under vacuum.

  A viscous liquid product is obtained.

Acid number: 1.1 meq / g

  Saponification number: 3.36 meq / g.

EXAMPLE 14

  Preparation of a compound of general formula (I) in which R1 denotes C10H21 Y1 or Y2 denotes C14H29

X is: -O-

A designates: - CH 2 - COOH

n, p, u being zero.

  The intermediate compound of formula (III) is prepared from

  decanol and epoxy-1,2 hexadecane.

  To 30 g of this compound (75 meq) solubilized in 120 ml of pyridine

  43 g of p-toluenesulphonyl chloride are added

  under 150 ml of the same solvent, and the mixture is left stirring at

  room temperature for 3 hours.

  The reaction mass is taken up with 200 g of water and 200 g

of ethyl acetate.

  The organic phase is dried over magnesium sulfate and the

  The solvent is removed by heating under reduced pressure.

22 2Z565846

  The residue is solubilized in 50 g of dimethylformamide. We

  54 g of ethyl thioglycolate (450 meq) and then 79 g of methy-

  sodium sulfate in methanolic solution (450 meq).

  Then heated for 12 hours at 50-60 C.

  The product obtained is then taken up with dioxane and NaOH in 40% aqueous solution and the reaction mass is heated.

for 1 hour at 90 C.

  It is acidified with a concentrated solution of hydrochloric acid.

  The solvents are then removed by heating under pressure

scaled down.

  The residue is in the form of a thick oil of

brown color.

  g (20 meq) of the compound thus obtained are solubilized in ml of isopropanol and then added to 35 C, dropwise,

  1.8 ml of hydrogen peroxide at 130 volumes (39%).

  The medium is stirred for 2 hours at 35-40 C. After a night of rest at room temperature, it is washed with water and dried under

reduced pressure.

  This produces a product which is in the form of a

  thick oil, dispersible in water in the presence of triethanolamine.

EXAMPLES OF APPLICATIONS

  The following compositions were prepared with the compounds described in the preceding examples:

EXAMPLE A

  Face care cream - Compound of Example 2 (as sodium salt) 4.8 g - Cholesterol 3.2 g - Glycerin 5.0 g - Sunflower oil 17.0 g

  - High molecular weight carboxyvinyl polymer

  sold under the name "Carbopol 941" by Goodrich Chemical Company 0.4 g

23 2565846

  - Butylhydroxy toluene 0.075 g - Butylhydroxyanisole 0.075 g Preservative 0.2 g - Triethanolamine 0.4 g - Fragrance 0.2 g - Demineralized water q.s. 100 g

EXAMPLE B

  Dermatological fluid - Compounds of Example 6 (in the form of sodium salts) 2.5 - Cholesterol 0.5 g - Hydrocortisone 0.1 g - Preservative 0.2 g - Demineralized water q.s. 100 g

EXAMPLE C

  Cleansing Lotion for the Eyes - Compounds of Example 3 in the Form of Triethanolamine Salts 1.0 g - Alkyl Imidazoline of Formula: ## STR5 ## COOH - Na R - Coprah Derivatives under the name "Miranol C2M" by the company Miranol 3.0 g - Hexylne glycol 1.0 g PAantoinoine 0.05 g - Preservative 0.3 g - Phosphate buffer pH 7.2 qsq 100 g

EXAMPLE D

  The following composition is prepared:

  - Compound of Example 5 1.5 g M.A.

(M.A .: active ingredient)

24 2565846

  - Surfactant of formula: R - CHOH - CH 2 0 (CH 2 CHOH CH 2 O n MR: mixture of C 9 -C 12 alkyl radicals n: represents an average statistical value of approximately 3.5 10 g MA - Water, qs 100 g

  The pH is adjusted with hydrochloric acid.

  This composition is used as a shampoo for washing

hair.

EXAMPLE E

* The following composition is prepared:

  - Compound of Example 4 0.8 g M.A.

  - Nonionic surfactant based on polyglycerol lauryl alcohol (4.2 moles) of formula:

C12H25OO CH2-CH1 OH

4.2

CH2 OH 8.5 g M.A.

- Water, q.s. 100 g

  pH = 7.6 adjusted with sodium hydroxide.

  This composition is used as a shampoo for washing

hair.

EXAMPLE F

  The following composition is prepared:

  Compounds of Example 6 0.2 g M.A.

  Quaternized cellulose sold under the name "JR 400" 1 by the

  Societe Generale Aniline 0.5 g M.A.

  Cycloimidazolinic derivative of coconut oil sold in 40% M.A. solution under the name "Miranol C2M" by the Company

Miranol 1.0 g M.A.

  - Hydroxyethylcellulose sold under the name

  "Natrosol HHR" by the company HERCULES 0.5 g M.A.

  - Water, q.s. 100 g pH = 8 adjusted with hydrochloric acid This composition is applied after shampooing. After

  a few minutes of laying it is rinsed with water.

EXAMPLE G

  The following composition is prepared:

  Terpolymer of vinyl acetate of crotonic acid and polyethylene glycol sold under the name Resine TV 242

  or "Aristo-flex A" by the company HOECHST 1.0 g M.A.

  Compounds of Example 3 0.2 g M.A.

  pH adjusted to 5 with lactic acid - Ethanol q. s.p. 50 alcoholic pafum, dye, preservative, water q.s. 100 g The composition in the form of a lotion is applied

  on hair that is dried without preliminary rinsing.

EXAMPLE H

  The following composition is prepared:

  copolymer of vinylpyrrolidone and dimethyl

  aminoethyl methacrylate quaternized by dimethyl sulphate and sold at a concentration of 50% of active ingredient in ethanol under the name

  "Gafquat 734" by GAF Company 0.8 g M.A.

  - Compound of Example 4 0.1 g M.A.

  pH adjusted to 8 by 2-amino 2-methyl 1-propanol perfume, dye, preservative - Water, q.s. 100 g The composition is in the form of a lotion. She is

  applied to hair that is dried without preliminary rinsing.

26 2565846

Claims (18)

  Anionic surfactant compound, characterized in that it meets the formula R H2-CH2 OCH X 1 2 2 2 Y - CH 1 * 1   In which Y1 or Y2 denotes a monovalent radical, one of them denoting a hydrogen atom and the other a radical: ## STR2 ## R2 OCR2   R 2 and R 2 denoting aliphatic or alkylaryl hydrocarbon radicals containing from 8 to 22 carbon atoms, the number of carbon atoms for R 1 + R 2 being greater than or equal to 18 and less than or equal to 32,   X denotes an oxygen atom, sulfur atom, a sulphoxide or carbon   nyloxy, u and v identical or different designating the value O or 1, u being equal to O when X denotes an oxygen atom, a sulfur atom or a sulphoxide group, p denotes an integer or decimal number from 0 to 10 inclusive; , A denotes an OH group and / or a group -O-C-W-C-OM He has O0 0   - S - (CmH2m) - CO0CM - S - (C H 2m) - COCM Ad m 2m or -O - CH 2 --COOOM m denotes 1 or 2, W denotes an alkylene group having 1 to 3 carbon atoms or grouping -CH2-O-CH2-   M denotes a hydrogen, alkali or alkaline earth metal atom or a group of formula: 272565846 R3 N R   R 4 R 5 R 3, R 4 and R 5 denoting independently of each other a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroalkyl group having 2 to 3 carbon atoms, Z denotes an atom of hydrogen or a group - CH2A1 A1 identical to or different from A and having the same meanings as A, n denotes an integer or decimal number from 0 to 10, the average number of anionic groups per molecule being between 0.7 and 10.   2. Compound according to claim 1, characterized in that the average number of anionic groups per molecule is between 0.8 and 5. 3. Compound according to claim 1 or 2, characterized in that R and R2 are chosen from alkyl groups, linear or branched alkylphenyl or having 8 to 18 carbon atoms, R1 and R2 having a number   total of carbon atoms between 18 and 32.   4. A compound according to any one of the preceding claims, which is   characterized in that n is 0 and A is a radical of the formula: -O-C-W-C-OM   wherein W denotes an alkylene group having 1 to 3 carbon atoms or the group -CH2-O-CH2-.   5. Compound according to claim 1, characterized in that n is different from O and that Z denotes a group -CH2A1 in which A1 denotes 2 1 the groups of formula: - S- (CmH2m) COQ, - S - (CmH2m ) COOM, 0 A having the meaning OH.   6. Process for preparing the compound as defined in any one   conque of claims 1 to 5, characterized by the fact that a compound of formula (III) 28 2565846 R 1 OCHf-CH 2 OeH 2 1 X P u (III) Y - CH I Y2 - CHOH   with a cyclic anhydride of diacid, with a mercapto alkanodic acid after tosylation and preliminary mesylation, or with chloroacetic acid after prior sodation of the compound of formula (III), these reactions possibly being preceded when n is different from O,   by a polyaddition of ethylene oxide or an epihalohydrin, the polyaddition   epihalohydrin is followed, where appropriate, by hydrolysis when   A1 denotes OH, or a reaction in alkaline medium, with a mercapto acid   alkanoic when A denotes -S (C H2m) -COOH.   6. Process according to claim 5, characterized in that a compound of formula (I) is prepared in which n is equal to O and A = O-COW-COOH by reaction of the compound of formula (III) with a cyclic anhydride of diacid corresponding to the formula: O O C-O-C XC - 0 CX W   wherein W has the meaning indicated in claim 1 in which   whether or not a solvent selected from aliphatic or aromatic hydrocarbons, hydrochlorocarbon solvents or ether solvents is   temperature between 0 and 1200C.   7. Process according to claim 5, characterized in that the compound of formula (III) is tosylated or mesylated and then reacted with   resulting compound in basic medium with mercapto-acetic acid or mercapto-acetic acid   propionic acid or their corresponding ethyl or methyl esters for   prepare the compounds in which A is -S- (CmH2m) -COOH. 29 2565846   8. Process according to Claim 7, characterized in that the resulting compound is oxidized with hydrogen peroxide to prepare a compound of formula (I) in which A denotes the group: -S- (CmH2m) -COOH O   9. A method according to claim 5, characterized in that it proceeds to the sodation of the compound of formula (III) and that the resulting compounds are reacted with chloroacetic acid or its methyl or ethyl esters in the presence optionally an aromatic solvent chosen from aliphatic or aromatic hydrocarbons at a temperature of between 50 and 140 ° C. in order to obtain the compounds of formula (1) in which A represents O-CH2-COOH.   10. Process according to claim 5, characterized in that a compound of formula (I) is prepared in which n denotes a different number of O and Z denotes a hydrogen atom by proceeding with the polyaddition of 1 to 10 ethylene oxide per molecule of intermediate compound of formula (III) to obtain a compound of formula (IIIA) R1 OCH2 CH '[f OCH tX Y-CH   The resulting compounds, either by the action of a cyclic anhydride of a diacid, or after tosylation or mesylation with the action of a   mercapto-alkanoic acid, either after sodation with the action of acetic.   11. Process according to Claim 5, characterized in that the polyaddition of 1 to 10 epihalohydrin molecules per molecule of intermediate compound of formula (III) is carried out to form the compounds of formula (IIIB): Ri -ft-H C2I1 - OCH2jw X Y1-CH (IIIE) Y2-CH OCH2-CH OH L CH2Cl - 2565846   and that the corresponding halogenated derivatives are reacted with a mercaptoalkanoic acid of formula HS- (CmH2m) COOH in an alkaline medium to yield m 2m to the compounds of formula (I) in which A1 denotes the grouping -S- (CmH2m) COOH and A denotes OH.   12. Process according to Claim 11, characterized in that the halogenated derivatives of formula (IIIB) are hydrolysed to give the corresponding polyhydroxy derivatives and then the reaction is carried out with the reaction with a cyclic anhydride of a diacid. either tosylation or mesylation   followed by the reaction with mercaptoacetic or mercapto-propionic acid   or sodation followed by reaction with chloroacetic acid.   13. A method according to any one of claims 6 to 12,   characterized by salification of the resulting compounds to form the alkali, alkaline earth metal, ammonium or corresponding amines.   14. Cosmetic or pharmaceutical composition characterized in that it contains at least one compound as defined in any one of the Claims 1 to 5.   15. Composition according to claim 14, characterized by the fact   it additionally contains an anionic, cationic, nonionic surfactant ionic or zwitterionic.   16. Composition according to claim 14 or 15, characterized in that it contains cosmetically acceptable ingredients chosen   alkalinizing or acidifying agents, thickeners, soil sol-   electrolytes, foam synergists, foam stabilizers, oils, waxes, superfatting agents, natural substances, protein derivatives, antiseborrhoeic agents, antidandruff agents, solar fibers, oxidants, reducers, sequestering agents , dyes, pigments, pearlescent agents, opacifiers, antiseptics, preservatives, alkalizing or acidifying agents, perfumes as well as   any other active substance which may have an action in the treatment of   care or protection of the skin or hair.   17. Composition according to any one of claims 14 to 16,   characterized in that it contains the compound of formula (I) in   proportions of 0.05 to 30% by weight. 31 6 J QE2565846   18. A process for the cosmetic treatment of hair or skin,   characterized by applying at least one compound as defined   in any one of claims 1 to 5.