MXPA97002312A - Phosphoric steres of dianhydro-1,4: 3,6-d-glucitol of alkyl or acil, procedure of preparation and uses of the mis - Google Patents

Abstract

The present invention relates to compounds of formula (I): the invention also relates to a process for the preparation of said compounds, which consists of: a) reacting dianhydro-1,4: 3,6-D- glucitol with a compound of the formula RCOOR'o RCH2Y, in the presence of a catalyst to form the compounds of the formula: in which Y represents a halogen or an alkyl or arylsulfonic radical, R'represents a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, R represents a saturated or unsaturated alkyl radical, linear or branched, containing 5 to 21 carbon atoms, X represents CO or CH 2, b) reacting the product of step a) with phosphorus oxychloride, a base and an anhydrous solvent, to form the compounds of formula (i) and / or (II), and optionally separate them, the compounds forming the subject matter of the invention can be used in the field of surfactants, in particular for the preparation of preparations cosmetic or for the pe

Description

PHOSPHORIC ESTERS OF DIANHIDRQ-1, 4: 3, 6-D-GLUCITOL OF ALKYL OR ACIL, PROCEDURE OF PREPARATION AND USES OF THE SAME FIELD OF THE INVENTION The invention relates to novel phosphoric esters of d? Anhydro-1, 4: 3,6-D-gluc? Tol (or isosorbide), to a process for their preparation and applications. More precisely, the invention relates to the phosphoric esters of alkyl or acyl isosorbide having surfactant properties, to a process for their preparation and their use, in particular to prepare cosmetic compositions or detergents.

BACKGROUND OF THE INVENTION It is known that grafts on the glucides, in particular, of alkyl or acyl substituents, leads to compounds which frequently have specific surfactant properties and which are also biodegradable. In particular, the carbohydrates of the dianhydro-l, 4: 3,6-D-glucol tol series have been the subject of many studies. From this source, it has been proposed to prepare the? D?? H h h dro dro dro dro,,,,,, 4: 3,6-D-glucolol, by selective chemical fication in position 2 or 5 for example Cekovic Z. and Tokiec Z., Synthesis, pp. 610-612 (1989); Le Lem G. and others, BuLl. Soc. Chim. Fr., No. 3, pp. 567-570 (1988); Pibenhaun 1). and others, Carbohyd. Res., 261, pp. 255-266 (1994) 3.

These compounds are used in particular as intermediates in the synthesis of vasodilators (home-2 and Mon? S-5). Mukesh D. and others. íBiotech. Lett. Vol. 15 No. 2, pp. 1243-1246 (1993)], describe a mixture of d-anhydr-1, 4:, 6-D-glucol tolone onooleates, obtained by Li tic acid esterification using an immobilized lipase. Zarif L. and others. CJ. Fluorine. Chein. Vol. 44, pp. 73-85 (1989)], propose to prepare monoesters of d? Anh? Dro-1, 4: 3,6-1) - petrofluoroalkyl glucitol, which can be used in the bio-medical field (blood substitutes). Jazmski W. and Ropusyns i S. l "CA 79: 146 767 h; CA 80: 61 387e; CO 80: 146 hl propose a mixture comprising the derivatives 2- (pyrophosphate of trisodium), α- (pórophospho + or of disodium) and 2-phosphate of 5-acιld anhydro-l, 4 : 3 6-D-gluc? tol, in which the acyl radical represents an oleyl, yl stea or lauryl radical. Lastly, SAHEKI and others. CaAOC, Vol. 63 No. 7, pp. 927-930 (1986)] propose 5-alkylalkyl-1-anhydro-1, 4: 3, 6-D-glucolol sulfates, in which the alkyl radical contains from 8 to 16 atoms of carbon. Said compounds can be used as surfactants. In the field of surfactants, there is a great need to study compounds whose resistance to hydrolysis and compatibility with the skin and mucous membranes are improved.

DESCRIPTION OF THE INVENTION Thus, the subject of the present invention are the novel phosphoric esters of the formula: or wherein R represents a saturated alkyl radical or . Unsaturated, linear or branched, containing from 5 to 21 carbon atoms. X represents CO or CH2, Zi and Z2, which are identical or different, represent a hydrogen atom, an alkali metal, a metal ? R; alkaline earth or a quaternary ammonium of formula: wherein Ri, 2, R3 and RA, which are identical or different, represent a hydrogen atom, an alkyl or hydroalkyl radical containing from L to 5 carbon atoms or a basic amino acid residue. The subject of the invention is also a process for the preparation of the aforementioned compounds of formula (I) or (II), which consists of: a) reacting dianh-dro-1, 4: 3,6-D- glucitol with a compound of formula RCOOR'o RCH2Y, in the presence of a catalyst to form the compounds of formulas: wherein: Y represents a halogen or an alkyl or aryl-ionic radical, R 'represents a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, R and X have the meaning indicated above, optionally separating said compounds in (III) and in (IV), and b) reacting the product of step a) with phosphorus oxychloride, a base and an anhydrous solvent. Another subject of the invention relates to the application of the aforementioned compounds of formulas (I) and (II) as surfactant agents. Another subject of the present invention relates again in particular to cosmetic compositions or detergents comprising the aforementioned compounds. The process for preparing the compounds according to the invention is described in detail in the following text. STEP A PREPARATION OF THE COMPOUNDS OF FORMULAS (III) AND IV) 1. Preparation of esters (X = CO) The ethers of formulas (III) and (IV) are obtained by reacting dianhydro-l, 4: 3,6-D -glucose with a fatty acid or a fatty acid ether of the formula RCOOR 'in the presence of a catalyst.

The fatty acid ester is chosen from fatty acids with a saturated or unsaturated chain, linear or branched, from 6 to 22 carbon atoms, preferably from 7 to 18 carbon atoms. The fatty acid ester is chosen from the esters of the aforementioned fatty acids in which the ester group comprises from 1 to 6, and preferably from 1 to 2 carbon atoms. The catalyst varies depending on the nature of the compound of formula RCOOR '. When a fatty acid is used, the catalyst consists of an acid. 0 way of illustration, there can be mentioned hydrochloric acid, sulfuric acid, alkylsulfunic acids, for example decyl sulfunic acid or lauplsulfunic acid; sulfonic acids, for example benzenesulfonic acid, paratoluenesulfonic acid or camphor sulphonic acid; alkylsulphonic acids, for example rnetanosulonic acid, decyl sulphonic acid, phonic lauplsul or sulphosuccinic acid; or an alkyl sulfosuccinate such as decyl or lauryl sulfosuccmate, perhalogenhydric acids, for example, perclopco acid, hypophosphorous acid or mixtures of these acids. and preferably use sulfuric acid, an alkylsulfupic acid, methanesulonic acid, succinic acid or an alkyl elastous phosucemate, hypophosphorous acid or mixtures of these acids. When a fatty acid ester is used, the catalyst is a base. By way of illustration of said base, mention may be made of metal alkoxides such as nitroxides or ethoxides of an alkali metal such as sodium or potassium, carbonates and bicarbonates, for example of an alkali metal such as sodium or potassium, compounds of formula Í ( 0H) X in which M is an alkaline metal or an alkaline earth metal and x is the valence of the metal; Basic aluminas, quaternary ammonium hydroxides of formula: in Ri, R2, R3 and R ", which are identical or different, represent an alkyl or alkylaryl radical containing from 1 to 18 carbon atoms, or mixtures of these bases. Conveniently, a phase-transfer catalyst chosen from known catalysts such as, for example, tetrabutylammonium halides (in particular bromide) or rhtiltyl ammonium halogenides (in particular chloride) may be added to the base mentioned above. The aforementioned catalyst is generally used in a proportion of 0.1 to 20%, and preferably 1 to 5% by weight with respect to dianhi dro-1,4: 3, 6-D-gluc? part 1da tol. The aforementioned esters can be prepared in the presence of a solvent, either of the fatty acid or of the acid ester. As an example, mention may be made of alkanes, oxide ethers such as tetrahydrofuran, dioxane or diethylene glycol dinityl ether, halogenated hydrocarbons such as dichloromethane, chloroform or dichloroethane, solvents of the amide type such as N-netilforrnarni, N, N-dimethylformarnide, N, N-dirnethylacetamide or N-methyl-2-? -rolidone, nitriles such as acetonitrile, eulfoxides such as dimethyl sulfoxide, aromatic solvent talee or toluene or xylene, and mixtures of these solvents. In the preparation of the esters according to the invention, from 0.1 to 20 molar equivalents and preferably from 0.5 to 10 equivalents, of dianhydro-l, 4: 3,6-D-glucolol; 0.5 x 10-3 to 2 molar equivalents of acid or basic catalyst, and preferably 1 x IQ-3 1 x LQ-i equivalent (acid catalyst) or 1 x 10-2 to 1 equivalent, (basic catalyst); and from 0 to 20 equivalents by weight, and preferably 0 to 10 equivalents of solvent, calculated on the basis of a weight equivalent of fatty acid or esters of said starting acid. The reaction is generally carried out at a temperature between 25 and 200 ° C, and preferably 70 to 180 ° C, during a period which may vary from 1 minute to 48 hours, and preferably 2 minutes to 24 hours, and to a pressure between 0.013 and 101.325 kPa .. Conveniently, in particular to decrease the time, the reaction is carried out under irradiation of rni cro as. After the reaction, the reaction medium is generally filtered so as to remove the catalyst. The filtrate thus obtained contains the esters of formulas III and IV; the compounds can optionally be separated, for example by chromatography on a silica column or by precipitation and / or recrystallization from a solvent chosen from the aforementioned solvents and solvents from the family of esters such as ethyl acetate, propyl or butyl. 2.- Preparation of the Ethers (X = CH2i The ethers of formulas III and IV are prepared by reacting d? Anh-dro-1, 4: 3,6-D-glucitol with? N composed of formula RCH2Y in the presence of a Catalyst The compound of formula RCH2Y, in which R and Y are as defined above, is preferably chosen from compounds containing a chlorine atom or a sulphonyl radical such as ethansylphonyl or para-tol-ens? The catalyst is chosen from the bases defined above, the alkali metals and the hydrides of these metals, preferably sodium, potassium, sodium hydride, or lithium hydride is conveniently used. selected phase transfer of the quaternary ammonium salts such as tetraalkylammonium halides or tetraarylalkyl onium, for example, tetrabutylammonium chloride or bromide, and ammonium acid sulfates, for example, inetiitpoctylammonium acid sulfate, benzyltrimet iiamomo or benciltpetila or io. This catalyst can also contain salts such as halides or perchlorates of an alkali metal, for example rubidium or cesium. The reaction can also be carried out in the presence of one of the aforementioned solvents, water and iscible or immiscible mixtures of these compounds. In the preparation of the ethers according to the invention, generally from 1 to 20 molar equivalents, and preferably from 1 to 5 equivalents of d? Anh? Dro-l, 4: 3,6-D-gl? Cyol, are used, of the 20 molar equivalents and preferably 1 to 5 equivalents of catalyst, and from 0 to 20 equivalents by weight, and preferably from 0 to 10 equivalents of solvent, calculated on the basis of? n weight equivalent of the compound < the formula RCH2Y. The reaction is generally carried out at a temperature of between 0 and 200 ° C, and preferably 25 to 160 ° C, during a period which may vary from 1 minute to 48 hours, and preferably 2 minutes to 24 hours. Conveniently, in particular to decrease the time, the reaction is carried out or irradiation of micronutrients. After the reaction, the ethers of formulas III and IV are recovered from the reaction medium. These ethers can optionally be separated, for example, by chromatography on a silica column.

STEP B: PREPARATION OF FORMULAS I AND II COMPOUNDS The reaction product of step a) is reacted with phosphorus oxychloride, a base and a solvent to hydro. The reaction product of step a) generally consists of the compound of formula III or IV in the form of either an ester (X = C0) or an ether (X = CH2). However, these compounds can be used in the form of a mixture of esters or ethers, or esters and ether. Phosphorus oxychloride is usually distilled beforehand. The base is selected from pyridine, N, N-dimethyl- or -diethylamine-4-pyridine and tertiary amines such as N-rneti.l- or N-e i1-orpholine. The anhydrous solvent is generally chosen from the solvents mentioned above. Preferably, chlorinated solvents such as chloroform, dichloromethane or dichloroethane and oxide ethers are used such as tetrahydro urane, dioxane, ethylene glycol -dirnet.-ethyl ether or diethylene glycol dirnet.-ethyl ether. To carry out step b) of the process according to the invention generally from 1 to 5 molar equivalents, and preferably from 1 to 2 equivalents, of phosphorus oxychloride, from 1 to 5 molar equivalents, and preferably from 1 to 5 5 equivalents of the base, and from 1 to 50 equivalents by weight, and preferably from 1 to 20 equivalents of the solvent, calculated on the basis of one equivalent in weight of the starting compound of formula III and / or IV. The reaction is carried out gene «> at a temperature of between -20 and + 60 ° C, and preferably -10 to + 40 ° C, during a period ranging from 1 hour to 7 days, and preferably from 1 hour to 48 hours. Conveniently, the reaction is carried out under an anhydrous inert atmosphere, for example by bubbling argon and nitrogen. After the reaction, the chloride corresponding to the bath used is removed from the reaction medium by filtration. The filtrate, to which a solvent is added as defined above, and preferably an alkane (for example hexane or heptane), is removed by evaporation. The evaporation residue to which 1 to 20 weight equivalents of ice water are added is maintained at a temperature of between 0 and 40 ° C, preferably 10 and 30 ° C, for 30 minutes to 5 hours, preferably 1 a 2 hours, with vigorous shaking. The compound I or II present in the aqueous phase thus obtained can be recovered in several ways, for example: - By means of concentration of said phase, in particular under vacuum and at a temperature in the region of 60 ° C. - By means of extracting said fae at least with an organic solvent especially for this purpose and concentration of the organic fae (s). -By basification of said phase and addition of at least one solvent that is capable of causing the aforementioned compound to be separated by precipitation, being possible then, for this compound, to be conveniently recovered by means of filtration, for example through a concretion funnel.

The compound of formula II can optionally be subjected to an additional purification step, for example by means of exclusion chromatography on a gel column such as cyano-econosil prepCN (90 fi; 15-35 μm; Alltech) or by means of ion exchange chromatography in a strong catonic ream such as Amberlite IR 120H +, or by means of recrystallization. The phosphorus esters of formula I and TI have surfactant properties, in particular properties of solubilization, emulsification, foaming, wetting and dispersion. Furthermore, the compounds according to the invention have the property of not being aggressive towards the skin and the mucous membranes, thereby making them particularly suitable for the preparation of compositions intended for hygiene, such as shampoos and cosmetics or hair compositions. , for example ointments, creams, beauty milks, etc. Because of their sputtering power and their ability to soften the skin, the compounds according to the invention can also be used in bath compositions (foam baths) or compositions for shower (shower gel) as well as in soaps in particular type syndet ("Detergent Synthetic "). The compounds according to the invention can also be used as unsightly agents for the treatment of textiles, wetting agents and detergents for special uses, wetting agents for the treatment of textiles and leather, and anti-seize agents in the fields such as petroleum research, metal treatment and suspension polymerization, the following examples will illustrate the invention.

For the examples, the following methods of analysis are used: The Rf is measured by means of thin layer chromatography on silica (film thickness: 200 μm, particle size: 5-10 μm). The migration solvent is a 50/50 (v / v) ethyl acetate / hexane mixture. The migration spots are detected by means of spraying with sulfuric acid at a concentration of 50 by volume in water and heating at 120 ° C for 2 minutes. Nuclear magnetic resonance (RtIN). - 1H: carried out at 250 MHz in the presence of CDCI3. The chemical shifts are expressed in ppm and the coupling constants (3) in Hz. -13C, performed at 75 MHz in the presence of CDCI3 (Examples 1-4, 7-8) or D2O (Example 5). The chemical shifts are expressed in ppm and the coupling constants (3) in Hz.

EXAMPLE 1 Preparation of the compounds of formulas (Ill-a) and (IV-a): X = CO and R = CnH23. 1.52 g (10.4 mmoles) of d? Anh? Dro-l, 4: 3, dD-gluc? Tol (Roquette Frères), 4.46 g (20.8 m.rnoles) of methyl dodecanoate (Fina Chemicals), 0.94 g are mixed together. (6.8 mmoles) of potassium carbonate, 0.1 g (0.31 mmoles) of tetrabrylammonium bromide and 2 ml of dimethylforrnarnide. The mixture obtained is subjected to a microwave irradiation of 20 watts for 15 minutes with stirring. After cooling, the obtained cake is solubilized in 20 ml of ethyl acetate and the solution is concentrated under vacuum in a rotary evaporator (60 ° C, 2.4 kPa and then 0.1 kPa). The solution thus concentrated is chromatographed on a column (0 = 2.5 cm, length = 15 cm) filled with silica (200-200 mesh, ASTN), eluted with heptane and then with a heptane / ethyl acetate mixture. 5 (v / v). Is successively 0.586 g of 2-0-dodecane? Ld? Anh? Dro-l, 4: 3.dD-gluc? Tol (IV-a) and 1.67 g of 5-0-dodecane? Ld? Anh? -l, 4: 3,6-D-glucolol (Tll-a), that is, yields equal to 17.1% and 48.9%, respectively i 'amenté, calculated on the basis of d? anh? dro-l, 4 : 3,6-D-glucolol starting.

EXAMPLE 2 Preparation of the compounds of formulas (Ill-a) and (IV-a): X = CO and R = C 11 H 23 A mixture comprising 150 g (748.8 rnmoles) of dodecanoic acid is heated (ref 15, 378-8) Aldrich), 547 g (3743 mmoles) of d? Anh? Dro-1, 4: 3, 6-D-gl? Citol (Roquette F rers), and 1.75 g of an equimolar mixture of methane sulphonic acid and hypophosphorous acid at 160 ° C for 8 hours under a nitrogen atmosphere. The reaction medium obtained (678 g) is dissolved in one liter of heptane and placed at 4 ° C for 24 hours. A precipitate is formed which is recovered by filtration and partially dissolved in ethyl acetate (4 x 200 rnl). The organic phases are combined, washed with water (2 x 100 ml), dried (magnesium sulfate), filtered (funnel No. 3) and concentrated in a rotary evaporator. The evaporation residue is recrystallized from pentane. The recrystallized compound (104 g) consists of 2-0-dodecane? Ld? Anhydr-l, 4: 3,6-D-gluc? Tol (IV-a), that is, a yield, calculated in starting dodecanoic acid, equal to 42%. The organic phase (heptane) is concentrated in a rotary evaporator and the residue obtained is precipitated from pentane. After filtration, the organic phase is washed with water, dried (magnesium sulfate), filtered and concentrated in a rotary evaporator. 53 g of 5-0-dodecanoyldianhydro-1,: 3,6-D-glucitol (111-a) are recovered, that is to say a calculated yield, in bae of the starting dodecanoic acid, equal to 21.6%. The characteristics of The compounds (Ill-a) and (IV-a) are presented below. Melting point • compound (IV-a): 78 ° C (pentane) • compound (Ill-a): oil Rf "on thin layer chromatography • compoteto (? V ~ a): 0.5 • compound (Ill-a) : 0.4 H NMR 13 C HVN EXAMPLE 3 Preparation of the compounds of formulas (Ill-b) and (IV-b): X = CH2 and R = CnH23. 10 g (68 mmol) of dianhydro-1, 4: 3,6 ~ D-gl? Citol (Roq? Ette Freres) are dissolved in a mixing mixture of 35 ml of dimethyl sulfoxide and 10 ml of deionized water. 5.8 g (89 mmol) of potassium hydroxide are added to the aforementioned solution and the mixture obtained is placed in an oil bath at 90 ° C. The mixture is stirred for 20 minutes and 13 g (52 mmoles) of bromododecane (B6, 551-1, Aldrich) are added dropwise. After 24 hours, the reaction mixture is filtered through 10 ml of silica (230-400 mesh, ASTM). The filtrate is concentrated in a rotary evaporator (60 ° C, 2.4 kPa and then 0.01 kPa), and the residue obtained, taken in 100 ml of a water / ethyl acetate 50/50 (v / v) mixture, is added. Stir at 400 rpm for 5 minutes. The organic phase is recovered, washed with water (2 x 20 ml), dried (magnesium sulfate) and concentrated on a rotary evaporator (50 ° C, 2.4 kPa). The obtained residue is adsorbed on 5 ml of silica (230-400 mesh, ASTM) and subjected to chromatography on a column (0 = 5.6 crn, - length = 25 c) filled with the aforementioned silica and provided with a detection system by means of differential refractometry. Elution using a gradient of heptane / ethyl acetate (100/0 to 50/50 (v / v), per minutes), allows the recovery of 0.95 g of 2-0-dodec? Ldianhydro-l, 4: 3,6-D-glucitol (IV-b) and 2.3 g of 5-0-dodec? Ldianhydro-l, 4 : 3,6-D-gluc? Tol (Ill-b), successively, that is, yields calculated on the basis of the starting point, equal to 6.1 and 14.0% respectively.

EXAMPLE 4 Preparation of compounds of formulas (Ill-b) and (IV-b): X = CH2 and R = CnH23 43.9 g (0.3 moles) of dianhydro-1,4: 3,6-D-glucitol are introduced (Roquette Fréres) in a round bottom flask of 250 rnl equipped with a mechanical agitator system, a condenser and a sheltered tube (CaCl2). The flask is heated to 90 ° C and 1 g (0.12 mole) of lithium hydride are added in portions. After 1 hour, 24.9 g (0.1 mole) of briododecane (20, 104-9, Aldpch) are added dropwise, the mixture is stirred for 3 hours at 140 ° C and cooled to 60 ° C. The mixture is transferred to a one liter round bottom flask and 100 ml of deionized water and 200 ml of ethyl acetate are carefully added. The mixture is stirred for 5 minutes and the organic phase is recovered, washed with water (2 x 50 ml), dried (magnesium sulfate) and concentrated on a rotary evaporator. 21.4 g of brown oil is obtained, which is subjected to column chromatography (< t > = 5.8 crn; length = 25 c), filled with silica (230-400 mesh, ASTN) provided with a detection system by means of differential refractivity. The column is eluted using a 50/50 ethyl acetate / hexane mixture (v / v) at a rate of 40 rnl / in. 3 g of 2-0-dodec? Ld? Anhydr-1, 4; 3,6 ~ D-glucol tol (IV-b), 5 g of 5-0-dodecyl-d-anhydro are recovered successively. -1,: 3,6-D-glucolol (ITI-b), and 1.6 g of a mixture of the two aforementioned compounds (IV-b and III ~ b); that is, the yields calculated based on the starting bromododecane are equal to 9.5, 16 and 5% respectively. The characteristics of the compounds (IV-b) and (III-b) are presented below. 71 Melting point - compound (IV-b): oil - compound (Ill-b): 55 ° C (pentane) Compound (IV-b): 0.60 (ethyl acetate / heptane) 0.45 (ethyl acetate / heptane) compound (Ill-b): 0.40 (ethyl acetate / heptane) 0.26 (ethyl acetate / heptane) 1H NMR EXAMPLE 5 Preparation of compound (Il-a): X = CO; R = CnH23 and Z? = Z2 = H 1 g (3.04 mmol) of 2-0-dodecane.ldianhydro-l, 4: 3,6-D-gl? Citol (comptato IV-a) of Example 1 are dissolved in 10 ml of distilled dichloromethane and anhydrous (washed with water, dried with CaCl 2 * distilled over P 2 O 5). The solution is placed at 0 ° C under an argon atmosphere and 0.385 g (3.34 mmolee) of deethylated N-ethylmorpholine are added, together with the dropwise addition of 0.469 g (3.05 mmoles) of distilled phosphorus oxychloride. . The obtained mixture becomes yellow. 9; This mixture, kept at 20 ° C with stirring for 4 hours, is concentrated in a rotary evaporator. The evaporation residue is suspended in 20 ml of heptane at 0 ° C, stirred for 10 minutes and filtered through a concreting funnel (porosity 3). The filtrate thus recovered, maintained at 0 ° C, is hydrolysed with 20 ml of an aqueous buffer solution (acetic acid / sodium acetate, pH = 4.75). After stirring for 1 hour at 20 ° C, the mixture is concentrated on a rotary evaporator (60 ° C, 2.4 kPa). The evaporation residue is purified by means of chromatography on a column of Cianoeconosil Prep-CN (Olltech, pore diameter: 90 fl, particle size: 15-35 μm), eluted using a gradient ethyl acetate / hexane ( 0/100 to 50/50 (v / v)) and a gradient ethyl acetate / ethanol (90/10 to 0/100 (v / v)). After concentration of the organic phases in a rotary evaporator, a yellowish pasty foam containing 0.281 mg of 2-O-dodecane-5-osphate is recovered. dro-l, 4: 3.6-D-glucol tol (Il-a), that is, a yield calculated on the basis of the starting compound (IV-a), equal to 22%. The characteristics of the compound (II-a) are presented below. 1H NMR '5-f osf ato of 2-0-dodecanoyldianhydro-l, 4: 3,6-D-glucitol (H-a) 10 O II O-P-OH: 8.30-8.00; my OH H2 5.20-5.15; m H4.5 4.90-4.70; m H3 4.55-4.45; m Hia, Ib, 6b: 4.15-3.85; m H6a 3.90-3.70; m CH2-2 '2.40-2.20; t CH2-3 '1.70-1.50; m CH 4'-ll ': 1.50-1.00; m CH3-12 '1.70-0.75; m ?! =; 31 P NMR: reference H3 PQ4 Phosphate peak at 0 ppm 31 P NMR: potassium salt CO: 184.57 Ci-Cß: 87.07; B1.54; 76.07; 75.05; 74.08; 69.99; (CH2) n -? '- H': 38.25; 31.94; 29.61; 29.39; 29.31; 26.55; 22.72; CH3-1? ': 14.03 EXAMPLE 6 Preparation of compound (I-a): X = CO; R = CnH23 and Z? = Z2 = H. A solution of 2.3 g (15 mol) of freshly distilled phosphorus oxychloride in 40 ml of anhydrous tether anhydrous (sodium / benzofon system), maintained at 0 ° C with stirring for 30 minutes, is added a solution containing 4.75 g (Idrnrnoles) of pin dina in 60 ml of tetrahydrofuran together with the addition in the form of drops of 3.29 g (10 mmoles) of 5-O-dodecane? ld? an? dro- 1 , 4: 3, 6-D-gluc? tol (compound Ill-a, in accordance with example 1) dissolved in 60 ml of tet rahí drofuran. After 1 hour at 0 ° C and 18 hours at 20 ° C, a precipitate of pipidium chloride is formed, which is removed by filtration through a concreting funnel (porosity 3). The obtained filtrate is stirred, to which 80 rnl of a water / crushed ice mixture (800 rpm, 1 hour) are added. After the addition of 100 ml of a chlorof or mo / methanol 2/3 (v / v) mixture, followed by separation of the phases after sedimentation has occurred, the whitish organic phase is recovered and treated with a solution of 50% by weight potassium hydroxide until the pH equals 9.5. The brown emulsion formed in this way is concentrated in a rotary evaporator in the presence of ethanol and then toluene. The evaporation residue, dissolved in water, is subjected to column chromatography filled with a strong cationic resin (Rmberlite IR 120 H +). After concentration under vacuum (40 ° C, 13. Pa) of the solution obtained from the column, 2 g of 5-0-dodecane-2-osphate are recovered? Ld? Anh? Dro-l, 4: 3.6 -D-gluc? Tol (Ta).

EXAMPLE 7 Preparation of the compound (I-b): X = CH2, = CnH23 and Z? = Z2 = H. The procedure is carried out under the conditions of example 5 in the presence of 5-0-dodec? Ld? Anh? Dro-l,: 3,6-D-glucitol (compound Tll-b according to example 4), Hydrolysis is carried out using 10 ml of water. They got better 0. 37 g (yield: 32%) of 2-phosphate of 5-0-dodec? Ld? Anh? Dro-l, 4: 3,6-D-gluc? Tol (I-b). The characteristics of the compound (I-b) are shown below. 1H and 13Q NMR lH "C H2: 4.84-4.76 C3: 86.37 H4: 4.76-4.71 C2: 80.92 H3: 4.71-4.65 C4: 80.28 Hlb: 4.20-4.10 C5: 80.00 H5, the, 6b: 4.07-3.90 Cl: 74.17 Hl'b: 3.70-3.60 Cl ': 71.17 H6a: 3.60-3.52 C6: 70.08 Hl'a: 3.48-3.37 C2'-C11 ': "31.94-29.67 29.53-29.38 26.01-22.69 C12': 14.11 EXAMPLE B Preparation of the compound (Il-b): X = CH2, R = Cn H23 and Z? = Z2 = H The procedure is carried out under the conditions of example 6 in the presence of 2-0-dodecyldianhydro-l,: 3,6-D-glucitol (compound IV-b) according to example 4. 1.52 g are recovered (yield: 40%) of 2-0-dodecyldianhydro-l, 4: 3,6-.D-glucitol 5-phosphate (Il-b) The characteristics of the compound Il-b ee are given below. lH 13C H4.5: 5.00-4.70; m C3: 85.7 H3: 4.50-4.40; di C2: 84.0 Hia, Ib, 6b, 2: 4.10-3.80; m C4: 81.1 H6a: 3.80, 3.60; m C5: 76.1 Hl'a, l 'b: 3.50-3.30; m Cl: 73.7 CH2-2 ': 1.70-1.55; m C6: 70.3 CH2-3 ', 11': 1.45-1.15 (14H) m CH2-1 ': 70.1 CH3-12 ': 0.95-0.80; m CH2-2 ', 11': 32.0-22.8 CH, -12 ': 14.2

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - The compounds of formula; or wherein R represents a saturated or unsaturated alkyl radical, linear or branched, containing from 5 to 21 carbon atoms; X represents CO or CH2; Zi and Z2, which are identical or different, represent a hydrogen atom, an alkali metal, an alkaline earth metal or a quaternary ammonium of the formula: wherein Ri, R2, 3 and ", which are identical or different, represent a hydrogen atom, an alkyl or hydroxyalkyl radical containing from 1 to 6 carbon atoms or a basic amino acid residue.

2. The compounds according to claim 1 in which R contains from 6 to 17 carbon atoms.

3. The process for the preparation of the compounds according to claim 1 or 2, characterized in that it consists of a) reacting dian idro-1,4: 3,6-D-giuc? Tol with a compound of the formula RCOOR or RCH2Y, in preference to a catalyst to form the compounds of formulas: wherein Y represents halogen or an alkyl or arylsulfone radical, R 'represents a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, R represents a saturated or saturated, linear or branched, containing from 5 to 21 carbon atoms, X represents CO or CH2; b) reacting the product of step a) with phosphorus oxychloride, a base and an anhydrous solvent, to form the compounds of formula (T) and / or (II), and optionally separating them.

4. The process for the preparation of the compounds according to claim 3, characterized in that the ratio of the number of molar equivalents of dianhydro-l, 4: 3,6 ~ D-glucitol to the number of molar equivalents of the compound of formula RCOOR 'is between 0.1 and 20.

5. The process for the preparation of the compounds according to claim 3, further characterized in that the ratio of the number of molar equivalents of dianhydro-l, 4: 3,6-D- glucol tol the number of molar equivalents of the compound of formula RCH2Y is between 1 and 20.

6. - The process for the preparation of the compounds according to one of claims 3 to 5, characterized in that the base is chosen from pi ri di na, N, N ~ dimethyl- or -d? Et? iamino-4-p? ridi na and tertiary amines. 7 - The process for the preparation of the compounds according to one of claims 3 to 6, further characterized in that the number of molar equivalents of phosphorus oxychloride at the number of molar equivalents of the product of step a) is between 1 and 5. The use of the compounds according to claim 1 or 2 for preparing compositions intended for hygiene. 9. The use of The compounds according to claim 8, characterized in that the compositions are chosen from shampoos and cosmetics or hair compositions. 10. The use of the compounds according to claim 9, further characterized in that the cosmetic compositions belong to the group consisting of ointments, creams, beauty milks, foaming baths, shower gels and synthetic detergent type soaps. 11. The use of the compounds according to claim 1, or 2 for the antistatic treatment of textiles. 12. The use of the compounds according to claim 1 or 2 for the treatment of metals. 13. The use of the compounds according to claim 1 or 2 in suspension polymerization reactions. SUMMARY OF THE INVENTION The invention relates to compound of formula: or The invention also relates to a process for the preparation of said cornpueetoe, which consists of: a) reacting d anhydr-1, 4: 3,6-I) -glucitol with a compound of formula RCOOR 'or RCH and, in the presence of a catalyst to form the compounds of formula: wherein Y represents a halogen or an alkyl or aryl sulphonic radical, R 'represents a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms, R represents a saturated or saturated, linear or branched, containing from 5 to 21 carbon atoms, X represents CO or CH2, - b) reacting the product of step a) with phosphorus oxychloride, a base and an anhydrous solvent, to form the compounds of formula (I) ) and / or (II), and optionally separate them; The compounds forming the material of the invention can be used in the field of surfactants, in particular for the preparation of cosmetic preparations or for hair. Efi / aed * lgm * l ss * avrn P97 / 249