FR2482128A1 - Nonionic surfactant mixt. for cosmetic and pharmaceutical compsns. - more easily dispersible with better emulsifying property - Google Patents

Abstract

The cpds. have the formula, (I). RO-(C2H3(OZ)-)R1 (I) in which R is a 4-20C aliphatic radical; R1 is alkyl, alkoxymethyl or alkenyloxymethyl in which the alkyl/alkenyl radicals are 4-20C; Z is a radical of formula (-(C2H30)(CH2A)-)H in which n is 2-20, and A is OH1-S(O)u-CH2CH2OH or -S(O)u CH2CH (OH)CH2OH in which u is 0-1, the total C atoms in R and R1 is 12-38 also the cpds. above in which the OH groups have been reacted with ethylene oxide or glycidal. The cpds. are used in cosmetics and pharmaceutical compsns. The cpds. are more soluble/dispersible in water and have better emulsifying properties.

Description

 The present invention relates to novel nonionic surfactants, process for their preparation and compositions containing them.

 A major concern in recent years, laboratories preparing compositions for the care and treatment of skin and hair, is to find surfactants used as commodities, as carriers of active products, as excipients or additives, which are perfectly well tolerated by man.

 The applicant has, for its part already proposed a number of surfactants, including nonionic surfactants, already showing progress over existing products.

 It has described in particular in its French patent application No. 2,401,187, the preparation of new surface-active block oligomers, consisting of a succession of lipophilic units and a succession of hydrophilic units which already constituted a significant progress by These compounds also have satisfactory surface and solubility properties for the intended applications.

 The Applicant has found, however, that, for the development of different formulas, the properties obtained with this type of compounds were sometimes markedly inadequate and more precisely with regard to the behavior in water or in the environment. alcoholic.

 Behavior in water, solubility or ease of dispersion in this medium or the formation of lyotropic mesomorphic phases more homogeneous and more favorable to the preparation of oil-in-water or water-in-oil emulsions, or lipid membranes capable of carrying substances; active.

 In particular, for certain cosmetic or pharmaceutical compositions, it is often very advantageous to be able to reduce the level of alcoholic compounds of the formula by increasing the solubility in water of the compounds.

 The Applicant has now discovered new surfactant compounds having precisely from these points of view improved properties compared with the products described above.

 The compounds according to the invention are indeed more easily dispersible in water or more completely soluble, and generally have better emulsifying properties.

 They also make it much easier to form lipid membranes suitable for the transport of active molecules. For products that are soluble in hydroalcoholic solutions, the alcohol content can be substantially lowered by using the compounds according to the invention.

 The compounds according to the invention comprise a lipophilic part consisting of two fatty chains, connected to a hydrophilic part comprising ether and hydroxyl groups and optionally thioether and / or sulfoxide. The Applicant has found that by separating and purifying the lipophilic portion constituted by the two fatty chains, products having improved properties such as those indicated above and in particular with regard to purity and solubility, without loss, are obtained. at the level of the surface activity or at the level of the biological properties with respect to compounds of the same type, the lipophilic portion of which comprises fatty chains in variable numbers, these numbers being statistically distributed around an average value of between 2 and 10 .

 The subject of the present invention is therefore new polyhydroxylated polyether surfactants with two hydrocarbon chains. Another subject of the invention consists of the process for the preparation of these compounds. The invention also relates to cosmetic or pharmaceutical compositions for the care and treatment of the body or the hair containing such surface-active compounds.

 Other objects of the invention will become apparent in the light of the description and examples which follow.

dans laquelle R désigne un radical aliphatique linéaire ou ramifié, saturé ou insaturé comportant 4 à 20 atomes de carbone Rl désigne (1) un radical alcoyle de préférence linéaire,
(2) un radical alcoxyméthyle linéaire ou ramifié
(3) un radical alcényloxyméthyle, les parties alcoyle ou alcényle de ces radicaux comportent de 4 à 20 atomes de carbone
Z désigne un enchaînement polyéther répondant à la formule

dans laquelle n désigne une valeur statistique moyenne de 2 à 20 et A désigne
a) le groupement OH, b) le groupement

dans lequel u désigne 0 ou 1 c) le groupement

dans lequel u désigne 0 -ou 1.The surfactant compounds according to the invention are essentially characterized by the fact that they correspond to formula I,

in which R denotes a linear or branched, saturated or unsaturated aliphatic radical containing 4 to 20 carbon atoms R1 denotes (1) a preferably linear alkyl radical,
(2) a linear or branched alkoxymethyl radical
(3) an alkenyloxymethyl radical, the alkyl or alkenyl parts of these radicals contain from 4 to 20 carbon atoms
Z denotes a polyether chain corresponding to the formula

where n denotes a mean statistical value of 2 to 20 and A designates
a) the OH group, b) the group

in which u is 0 or 1 c) the grouping

wherein u is 0 or 1.

The radicals R 1 and R must in total have a carbon number of between 12 and 38 and preferably between 12 and 32,
R preferably denotes a linear or branched hydrocarbon radical and in particular chosen from butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, ethyl-2-hexyl, hexyl-2-decyl etc. groups.

dans laquelle R et R1 ont les mêmes significations que celles indiqués ci-dessi en faisant réagir un alcool de formule ROH dans laquelle R à la même significa que celle indiquée ci-dessus avec un composé de formule,

dans laquelle le groupement R1 a la même signification que celle indiquée ci-dessus. Cette réaction -est réalisée én présence d'un c-atalyseur acide au sens de Lewis tels que le trifluorure de bore, le chlorure stannique ou la pentachlorure d'antimoine, dans les proportions de 0,2 à 5% en poids par rapport à la masse réactionnelle et à une température comprise entre 20 et 120 C et de préférence entre 50 et 100 C. Elle peut également être réalisée en présence d'un mtalyseur alcalin tel que le sodium ou le potassium, le méthylate, éthylate ou tertiobutylate de sodium ou de potassium, dans des proportions de 0,2 à 15% par rapport à la masse réactionnelle et de préfé renc de 0,5 à 10%, à une température comprise entre 100 et 180 C et de préférence entre 100 et 150 C.R 1 preferably denotes a radical chosen from the groups hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, the alkoxymethyl radicals derived from the preceding groups, or the radicals ethyl-2 hexyloxymethyl, hexyl -2 decyloxymethyl or octyl-2-dodecyloxymethyl ,
The compounds of formula I are pre-paid by a three-step process. The compounds of formula II are first prepared in a first step.

in which R and R 1 have the same meanings as indicated above by reacting an alcohol of formula ROH in which R is the same as that indicated above with a compound of formula,

in which the group R1 has the same meaning as that indicated above. This reaction is carried out in the presence of a Lewis acid c-amine analyzer such as boron trifluoride, stannic chloride or antimony pentachloride, in proportions of 0.2 to 5% by weight relative to the reaction mass and at a temperature between 20 and 120 C and preferably between 50 and 100 C. It can also be carried out in the presence of an alkali metal catalyst such as sodium or potassium, sodium methoxide, ethylate or tert.-butylate or potassium, in proportions of 0.2 to 15% relative to the reaction mass and preferably from 0.5 to 10%, at a temperature between 100 and 180 C and preferably between 100 and 150 C.

 Stoichiometric proportions of ROH alcohol and epoxy compound are used, or preferably in the presence of an excess of one of the two reagents. When the alcohol is used in excess, the unreacted alcohol is distilled off. In the opposite case where the epoxide is in excess, it reacts completely giving alcohol compounds to several lipophilic chains.

 It may be possible to use an aliphatic or aromatic hydrocarbon as a solvent although generally this is not necessary. In all cases, the compounds of formula (II) are purified by conventional distillation under reduced pressure-od by molecular distillation.

Depending on the opening direction of the epoxy group, two structures are obtained. possible for the compounds of formula (II)

dans laquelle R et R1 ont les significations indiquées ci-dessus et Y désigne un enchaînement polyéther de formule

dans laquelle B désigne un atome d'halogène ou un groupement tertio-butoxy, n ayant la même signification. que ci-dessus, sont obtenus en procédant à une polyaddition d'épihalohydrine ou de tertiobutyl glycidyléther avec un alcool gras à deux chaînes lipophiles de formule II, ces composés i ; intermédiaires étant transformés suivant des procédés connus en eux-mêmes pour obtenir les composés de formule (I).In the second step the compounds of formula (Iv)

in which R and R 1 have the meanings indicated above and Y denotes a polyether sequence of formula

wherein B denotes a halogen atom or a tert-butoxy group, n having the same meaning. above, are obtained by carrying out a polyaddition of epihalohydrin or tert-butyl glycidyl ether with a lipophilic two fatty-chain fatty alcohol of formula II, these compounds i; intermediates being transformed by methods known per se to obtain the compounds of formula (I).

 More particularly, the compounds of formula (IV) are prepared by reacting alcohols with two lipophilic chains of formula (II) with h molecules of epichlorohydrin, epibromohydrin or tert-butyl glycidyl ether in the presence of an acidic catalyst and optionally of a solvent. . The acidic catalysts are preferably chosen from Lewis acids, such as boron trifluoride, stannous chloride or antimony pentachloride, in proportions of 0.2 to 5% by weight relative to the mass-reaction. and at a temperature of between 20 and 120 ° C. and preferably between 50 and 100 ° C.

 The solvents, when they are used, are chosen more particularly from aromatic hydrocarbons such as benzene, toluene or xylene or aliphatic hydrocarbons such as hexane or heptane. Preferably, the preparation of the compounds of formula ( IV) takes place in the absence of solvent.

 It is possible, in the context of the use of tert-butyl glycidyl ether, to carry out the polyaddition in the presence of an alkaline catalyst such as, for example, sodium or potassium methylate, ethylate or tetiobutylate at a temperature of 120 to 180 ° C.

 The n molecules of epihalohydrin or tert-butyl glycidyl ether give rise to the formation of mixtures of compounds having a number of halogenated units or lower tert-butoxy, equal to or greater than the value n, the latter representing a statistical average number.

et par les formules développées :-

During this reaction, depending on the opening direction of the epoxide group, two structures can be obtained for the halogenated unit, both represented by the overall formula

and by the developed formulas: -

 Although the proportion of units having the structure (V) is most likely, there may be some amount of VI structure motifs.

 According to the third step, the preparation of the compounds of formula I apart from compounds of formula (IV) is carried out when A denotes the group 011; (1) either by heating the halogenated compounds in the presence of sodium or potassium acetate in a solvent of the glycol or glycol ether type, such as, for example, ethylene, propylene or butylene glycol, diethylene or dipropylene glycol , or the butyl ether of diethylene glycol at a temperature of 180 ° C. to 190 ° C. for 3 to 6 hours, then after filtration of the inorganic salts and removal of the solvents under reduced pressure, by saponification in the presence of sodium hydroxide or concentrated potassium hydroxide or by alcohol in metha nol or absolute methanol in the presence of sodium or potassium methylate or ethoxide, (2) by heating the polytertiobutoxy derivatives in the presence of strong acid such as sulpho carboxylic acids, sulfuric acid or para-toluenesulphonic acid with 80-llo0C.

 The compounds of the invention in which the group A designates (b) or (c) are obtained by reacting thioethanol or thioglycerol with the polyhalogenated compounds in the presence of sodium hydroxide or potassium hydroxide, solvents such as methanol, isopropanol, propanol, butanol, ethylene, propylene or butylene glycol, monomethyl ethyl or butyl ether of ethylene glycol and optionally su. The polyhydroxy polythioether compounds can then be oxidized with hydrogen peroxide at a temperature of 25 to 50 ° C in the presence of optionally acetic or lactic acid.

It follows from the two types of structure (V) and (VI) the two formulas developed for the units of formula (I)

 The simultaneous presence of two types of structure is in no way detrimental to the properties of the products according to the invention.

 The compounds of formula (I) according to the invention are generally in the form of oil, paste or wax. These compounds will be, according to the number of carbon atoms of R and R1 and according to the number of average units n, rather lipophilic, dispersible in water or completely soluble. Thus, the lower the number of carbon atoms and the higher the number, the more hydrophilic the products will be.

 The hydrophilicity and solubility in water of the compounds according to the invention can be increased by eliminating by niolecular distillation the most lipophilic terms, either by reacting. ethylene oxide or glycidol with the hydroxyl groups, this reaction can be carried out under the usual conditions in the presence of acid or alkali catalysts and optionally solvents.

 The compounds according to the invention can be used alone or as a mixture, in aqueous or aqueous-alcoholic solution or dispersion, in the form of a water-in-oil or oil-in-water emulsion, in the form of wax or in aerosol, in the proportions from 0.05 to 80% and preferably from 0.5 to 50% relative to the total weight of the composition.

 By hydroalcoholic solution is meant solutions of water and a lower alcohol which may be methanol, a glycol or a glycol ether.

 The compounds according to the invention may in particular be introduced as a base surfactant or as an additive in cosmetic or pharmaceutical compositions which may be in the form of aqueous or aqueous-alcohol solution or dispersion, cream, milk or compact of sticks or packaged under aerosol form.

 They can be used as a cleansing agent for the skin or for the hair as wetting, emulsifying, dispersing, solubilizing, superfatting, emollient, as a mild and inert excipient or as lipids capable of carrying active substances.

 By way of example of cosmetic compositions, mention may in particular be made of shampoos, rinses, set-up lotions, products for blow-drying, compositions of perms or dyes, foundations, make-up removing lotions for eyes, make-up milks, body milks, makeup bases, sunscreen compositions, antiperspirant or deodorant creams, etc.

 In the case where the compounds according to the invention are used in the preparation of lipid vesicles, they may or may not be combined in order to modify the permeability of these vesicles to alcohols or long-chain diols, to sterols such as cholesterol or sitosterol and possibly although often not required for positively or negatively charged substances, such as, for example, sodium diketyl phosphate or diethyl diodecyl ammonium chloride or bromide.

The fact that lipid vesicles can be made entirely nonionic represents a great originality of the compounds of the invention.

Cosmetic or pharmaceutical compositions containing one or more products according to the invention may further contain other constituents such as cationic or amphoteric anionic surfactants, well known in the state of the art, animal, mineral or vegetable oils. , anionic, cationic nonionic or amphoteric resins commonly used in cosmetics, sunscreens, thickeners, opacifiers, preservatives, perfumes, dyes, lower alcoholic solvents, pH-modifying agents, inorganic salts, active substances that may have an action in the treatment, care or protection of the skin or hair
The following examples are intended to illustrate the invention, without being limiting in nature.

(exemple 2 du tableau 1)
A 558g de dodécanol-l (3 moles) vendu sous le nom d'Alfol 12, on ajoute 17g de liqueur méthanolique de méthylate de sodium à 6 meq/g. Le méthanol est eliminé par chauffage à 120 C sous pression réduite. On ajoute ensuite en 1h30 à 150 C, sous atmosphère d'azote, 242g de dodécyl glycidyl éther mole)
Après 4 heures de chauffage le taux de réaction, déterminé par dosage des groupements époxyde restants, est pratiquement quantitatif. La masse réactionnelle est lavée avec 3 fois 800 ml d'eau à 90 C. On ajoute 170 ml dispropanol pour faciliter la décantation. La phase organique est ensuite chauffée sous pression réduite.Après élimination du dodécanol en excès, le composé alcool à deux chaînes lipophiles est distillé par distillation moléculaire à 160 C sous une pression de 10- mm de mercure.EXAMPLES OF COMPOUND PREPARATION
Preparation of the compound of Example 2A
a) Preparation of the compound represented by the formula

(example 2 of table 1)
To 558 g of dodecanol-1 (3 moles) sold under the name of Alfol 12, 17 g of methanolic sodium methoxide liquor are added at a concentration of 6 meq / g. The methanol is removed by heating at 120 ° C. under reduced pressure. 242 g of dodecyl glycidyl ether mole are then added over 1 hour 30 min at 150 ° C. under a nitrogen atmosphere.
After 4 hours of heating, the reaction rate, determined by assaying the remaining epoxide groups, is practically quantitative. The reaction mass is washed with 3 times 800 ml of water at 90 ° C. 170 ml dispropanol is added to facilitate the decantation. The organic phase is then heated under reduced pressure. After removal of the excess dodecanol, the lipophilic two-chain alcohol compound is distilled by molecular distillation at 160 ° C. under a pressure of 10 mm of mercury.

 It is in the form of a white wax of melting point 40-410 C.

- -b) Preparation of the decomnosed mixture corresponding to the formula

R denotes C12H25- -
R1 denotes C12H25-O-CH2n denotes a statistical value equal to 5.

107 g of the compound prepared above (0.25 mol) are added 0.7 g of
BF3 then, dropwise, at 70 ° C. in 2 hours, 115.5 g of epichlorohydrin (1.25 moles).

 The heating is maintained for another hour after the addition. The polyhalogenated derivative is then washed 3 times with 250 ml of boiling water and then dehydrated.

 The product obtained is then taken up with 90 g of dipropylene glycol and 106 g of potassium acetate (1.07 mol) and heated at 185 ° C. under a nitrogen atmosphere for 6 hours. After filtration of the potassium chloride and distillation of the solvent, the product is saponified in the presence of an excess of 40% sodium hydroxide and washed 3 times with 200 ml of boiling water in the presence of primary butanol to facilitate the separation of the organic phase. After distillation of the solvents under reduced pressure, a product is obtained which is in the form of a brown oil soluble in petroleum jelly (H.V.) and dispersible in water.

The cloud point measured at a concentration of 5% active ingredient in 25% butyl diglycol (RDG) in water is 82 ° C.

Preparation of the compound of Example 5A

To 48.4 g (0.1 mol) of the molten intermediate compound obtained according to the method described in Table 1, 0.54 ml of SnCl 4 was added. The mixture is heated to 100 ° C. and then 57.5 g of epichlorohydrin (0.6 mol) are added dropwise.

It was maintained at 100 C for another 1:30 after the end of the addition. The reaction is then almost complete.

To lolg of polychlorinated product thus obtained (580meq in chlorine) is added 100g of cellosolve and 63g of thioglycerol (0.58mol). The reaction mass is heated to 1000 ° C. and then 58 g of 40% sodium hydroxide (0.58 mol) are added dropwise.

After heating for 3 hours at 100.degree.-1050.degree. C. 230 g of n-butanol-1 are added and the reaction mass is washed twice with approximately 500 ml of boiling water.

The organic phase is then heated under reduced pressure to remove the solvents.

This gives an amber paste, dispersible in water. Cloud point measured at 5% active ingredients in B.D.G. at 25% in water is greater than 100 C.

Preparation of the compound of Example 5B

At 50 g (171meq in thioeeher group) of product described according to the example
N05A dissolved in 50 ml of methanol is added dropwise, 12.2 ml of hydrogen peroxide to 158.6 volumes.

The temperature is maintained between 30 and 45 rpm for 1 h 30 after the end of the addition.

After 24 hours at room temperature, 200 mg of SU3Na2 are added to destroy unreacted oxygenated water, and the methanol and water are distilled off under reduced pressure.

The product thus obtained is a translucent paste, soluble in water.
Preparation of the compound of Example 6A

34.5 g (0.15m) of intermediate compound prepared according to the method described for Example 2 are added 3ml of a solution of sodium methylate in methanol at 6meq / g (18meq).

The methanol is distilled under reduced pressure and then the temperature is raised to 1550C. 78 g (0.6 mol) of tert-butylglycidyl ether are then added dropwise. After the end of the addition, it is still left for 3/4 hours at 160 ° C. and then the product obtained is washed 3 times with its weight of water in the presence of dilute HCl. It is heated by heating under reduced pressure. 1 g of sulfoacetic acid is then added and the mixture is heated at 100 ° C. for 2 hours. There is a gas evolution of isobutylene.

The product obtained is dissolved in 70 g of butanol-1 and then washed twice with 150 ml of boiling water.

After dehydration, heating under reduced pressure gives a brown liquid, soluble in water.

The aqueous solution obtained with 5% of active ingredients is clear and viscous.

The cloud point measured at 0.5% in demineralized water is 70 ° C.

 The compounds indicated in the following tables, the characteristics of which are shown in Tables 1 to 4, are prepared in the same way as in the preparation examples indicated above.

Tables 1 and 2 relate to the preparation of compounds of formula II. In these paintings are nature,
the weight and the molar amount of the alcohol and the compound of formula III used, the nature of the catalyst and its amount, the reaction temperature and the characteristics of the product corresponding to the general formula II thus obtained.

Table 3 relates to the preparation of the compounds corresponding to formula I by passing through the compound of formula
IV. This table defines the nature, weight and molar amount of the compound
II and the epoxide used, the average value n of the number of halogenated or tert-butoxy units, the nature of the catalyst, the amount used and the reaction temperature, the hydrolysis catalyst in the case of tert-butoxy groups, the solvent and the type of treatment (alcoholysis or saponification for polyhalogenated derivatives.

 Table 4 groups the physical properties of the compounds of formula (I) obtained according to one of the processes described in the examples for the preparation of compounds 2A, 5A or 6A.

In these tables, the abbreviations and signs have the following meanings
MeONa denotes sodium methoxide in methanolic solution at 6meq / g: iso C8H17 denotes an ethyl-2-hexyl group; iso C16H33 denotes a 2-hexyl decyl group; epi refers to epichlorohydrin;
S is soluble;
I denotes insoluble;
D denotes dispersible;
L denotes ladle.

* 5% cloud point in 25% butyl diglycol in water, ** 0.5% cloud point in water,
S * denotes soluble after removal of volatile compounds by molecular distillation, BDG denotes butyldiglycol,
DEG refers to diethylene glycol
DPG refers to dipropylene glycol
Pe indicates the boiling point
Pf indicates the melting point.

TABLE 1 - Compound II

Ex <SEP> ROH <SEP>#<SEP> (III) <SEP> Catalyst <SEP>#<SEP> in <SEP> C <SEP> Characteristics
<tb><SEP> Weight <SEP> Weight <SEP> Pe <SEP> in <SEP> C <SEP> Pf <SEP> meq / g
<tb><SEP> R <SEP> Weight <SEP> Mole <SEP> R1 <SEP> (g) <SEP> Mole <SEP> Nature <SEP> (g) <SEP> / Pmm <SEP> Hg <SEP > in <SEP> C <SEP> IOH
<tb><SEP> ()
<tb> 1 <SEP> C8H17 <SEP> 271 <SEP> 2.1 <SEP> C16H33-O-CH2- <SEP> 238.5 <SEP> 0.8 <SEP> MeONa <SEP> 13.5 <SEP> 150 <SEP> 160 / 10- <SEP> 35 <SEP> 2,3
<tb> 2 <SEP> C12H25 <SEP> 558 <SEP> 3 <SEP> C12H25-O-CH2- <SEP> 242 <SEP> 1 <SEP> MeONa <SEP> 17 <SEP> 150 <SEP> 165 / 10- <SEP> 41 <SEP> 2.4
<tb> 3 <SEP> C16H33 <SEQ> 485 <SEP> 2 <SEP> N / A <SEP> C8H17-O-CH2 <SEP> 186 <SEP> 1 <SEP> MeONa <SEP> 4.8 <SEP> 150 <SEP> 160-185 / 5.10- <SEP> 13 <SEP> 2,2
<tb> 4 <SEP> iso <SEP> C16H33 <SEP> 435.5 <SEP> 1.8 <SEP>"<SEP> 111.5 <SEP> 0.6 <SEP> MeONa <SEP> 10.2 <SEP> 150 <SEP> 165 / 5.10- <SEP><-10
<tb> 5 <SEP> C16H33 <SEP> 726 <SEP> 3 <SEP> C12H25-O-CH2 <SEP> 242 <SEP> 1 <SEP> MeONA <SEP> 17 <SEQ> 140 <SEQ> 210/10 - <SEP> 41
<tb> TABLE 2 - COMPOUNDS II

Ex <SEP> ROH <SEP>#<SEP> (III) <SEP> Catalyst <SEP>#<SEP> in <SEP> C <SEP> Characteristics
<tb><SEP> Pe <SEP> in <SEP> C <SEP> Pf <SEP> meq / g
<tb><SEP> R <SEP> Weight <SEP> Mole <SEP> R1 <SEP> Weight <SEP> (g) <SEP> Mole <SEP> Nature <SEP> Weight <SEP> (g) <SEP> / Pmm <SEP> Hg <SEP> in <SEP> C <SEP> IOH
<SEQUENCE NOTICE>
<tb><SEP> 7 <SEP> C10H21 <SEP> 474 <SEP> 3 <SEP> C10H21 <SEP> 184 <SEP> 1 <SEP> t. <SEP> Bu <SEP> k <SEP> 10 <SEP > 150 <SEP> 165 / 5.10- <SEP> 46
<tb><SEP> 8 <SEP> C8H17 <SEP> 390 <SEP> 3 <SEP> C16H33 <SEP> 268 <SEP> 1 <SEP> MeONa <SEP> 8.5 <SEP> 150 <SEP> 193- 205 / 8.10- <SEP> 49
<tb><SEP> 9 <SEP> iso <SEP> C8H17 <SEP> 390 <SEP> 3 <SEP> C16H33 <SEP> 268 <SEP> 1 <SEP> MeONa <SEP> 8.5 <SEQ> 145 <SEP> 190 / 5.10- <SEP> 24 <SEP> 2.4
<tb> 10 <SEP> C10H21 <SEP> 711 <SEP> 4.5 <SEP> C14H29 <SEP> 360 <SEP> 1.5 <SEP> MeONa <SEP> 12.8 <SE> 140 <SEP> 190 /5.10- <SEP> 50 <SEP> 2.4
<tb> 11 <SEP> C12H25 <SEP> 558 <SEP> 3 <SEP> C12H25 <SEP> 212 <SEP> 1 <SEP> MeONa <SEP> 8.5 <SEQ> 145 <SEP> 190-205 / 10 - <SEP> 59 <SEP> 2.5
<tb> 12 <SEP> C12H25 <SEP> 279 <SEP> 1.5 <SEP> C16H33 <SEP> 135 <SEP> 0.5 <SEP> MeONa <SEP> 4.5 <SEP> 145 <SEP> 210 -215 / 10- <SEP> 58
<tb> 13 <SEP> C14H29 <SEP> 642 <SEP> 3 <SEP> C14H29 <SEP> 240 <SEP> 1 <SEP> MeONa <SEP> 8.5 <SEQ> 145 <SEQ> 245 / 3.10- <SEP> 69 <SEP> 2
<tb> 14 <SEP> iso <SEP> C16H33 <SEP> 363 <SEP> 1.5 <SEP> C12H25 <SEP> 106 <SEP> 0.5 <SEP> MeONa <SEP> 8.5 <SEP> 150 <SEP> 200 / 10-
<tb> 15 <SEP> C18H37 <SEP> 648 <SEP> 2.4 <SEP> C10H21 <SEP> 147 <SEP> 0.8 <SEP> MeONa <SEP> 8.5 <SEP> 150 <SEP> 2 2
<tb> 16 <SEP> C16H33 <SEP> 435.5 <SEP> 1.8 <SEP> C16H33 <SEP> 162 <SEP> 0.6 <SEP> MeONa <SEP> 5 <SEP> 145 <SEP> 250 / 10-
<tb> 17 <SEP> iso <SEP> C16H33 <SEP> 290 <SEP> 1.2 <SEP> C16H33 <SEP> 107 <SEP> 0.4 <SEP> MeONa <SEP> 12 <SEP> 145 <SEP > 250 / 10-
<tb> TABLE 3 - Compounds I

EX <SEP> COMPOUND <SEP> II <SEP> EPOXYDE <SEP>#<SEP> CATALYST <SEP># C <SEP> HYDROLYSIS
<tb><SEP> alcoholysis
<tb><SEP> Ex <SEP> Q <SEP> moles <SEP> Name <SEP> Q <SEP> moles <SEP> Nature <SEP> Q <SEP> catalyst <SEP> solvent <SEP> saponification
<tb><SEP> (g) <SEP> (g) <SEP> (g)
<tb> 1A <SEP> 1 <SEP> 107 <SEP> 0.25 <SEP> TBGE <SEP> 260 <SEP> 2 <SEP> 8 <SEP> MeONa <SEP> 4 <SEP> 150 <SEP> acid
<tb><SEP> sulfopal- <SEP> - <SEP>
<SEP> mitic
<tb><SEP> 1.5%
<tb> 2A <SEP> 2 <SEP> 107 <SEP> 0.25 <SEP> Epi <SEP> 115.5 <SEP> 1.25 <SEP> 5 <SEP> BF3 <SEP> 0.7 <SEP > 70 <SEP> - <SEP> BDG <SEP> saponif.
<Tb>

3A <SEP> 3 <SEP> 95.5 <SEP> 0.2 <SEP> Epi <SEP> 55.5 <SEP> 0.6 <SEP> 3 <SEP> BF3 <SEP> 0.4 <SEP> 75 <SEP> - <SEP> DPG <SEP> alcoholysis
<tb> 3B <SEP> 3 <SEP> 30.8 <SEP> 0.07 <SEP> Epi <SEP> 32.5 <SEP> 0.35 <SEP> 5 <SEP> BF3 <SEP> 0.15 <SEP> 75 <SEP> - <SEP>"<SEP>"
<tb> 3C <SEP> 3 <SEP> 110 <SEP> 0.25 <SEP> Epi <SEP> 185 <SEP> 2 <SEP> 8 <SEP> BF3 <SEP> 1.2 <SEP> 75 <SEP > - <SEP>"<SEP>"
<tb> 3D <SEP> 3 <SEP> 110 <SEP> 0.25 <SEP> Epi <SEP> 185 <SEP> 2 <SEP> 8 <SEP> BF3 <SEP> 1.2 <SEP> 75 <SEP > - <SEP> - <SEP>"<SEP>
<SEP> glycidol <SEP> 74 <SEP> 1 <SEP> 4 <SEP> MeONa <SEP> 0.2 <SEP> 150
<tb> 4A <SEP> 4 <SEP> 34.2 <SEP> 0.08 <SEP> TBGE <SEP> 31.2 <SEP> 0.24 <SEP> 3 <SEP> t-BuOK <SEP> 6 <SEP> 150 <SEP> acid <SEP> sul- <SEP> - <SEP>
<SEP> fopalmitic
<tb><SEP> 2.5%
<tb> 5A <SEP> 5 <SEP> 48.4 <SEP> 0.1 <SEP> Epi <SEP> 57.5 <SEP> 0.6 <SEP> 6 <SEP> SnCl4 <SEP> 0.54 <SEP> 100 <SEP> - <SEP> - <SEP> 5B <SEP> 5 <SEP>"<SEP>"<SEP>"<SEP>"<SEP>"<SEP>"<SEP>"<SEP>"<SEP>"<SEP> - <SEP> MeOH <SEP> Oxidation
<tb> 6A <SEP> 6 <SEP> 34.5 <SEP> 0.15 <SEP> TBGE <SEP> 78 <SEP> 0.6 <SEP> 4 <SEP> MeONa <SEP> 3 <SEP> 155 <SEP> acid <SEP> sulfo
<tb><SEP> acetic acid <SEP> - <SEP>
<SEP> 1g
<tb> TABLE 3 compounds I (continued)

EX <SEP> COMPOUND <SEP> II <SEP> EPOXYDE <SEP>#<SEP> CATALYST <SEP># C <SEP> HYDROLYSIS
<tb><SEP> alcoholysis
<tb><SEP> EX <SEP> Q <SEP> moles <SEP> name <SEP> Q <SEP> moles <SEP> nature <SEP> Q <SEP> catalyst <SEP> solvent
<tb><SEP> (g) <SEP> (g) <SEP> (g) <SEP> saponification
<tb><SEP> 7A <SEP> 7 <SEP> 102.5 <SEP> 0.3 <SEP> Epi <SEP> 111 <SEP> 1,2 <SEP> 4 <SEP> BF3 <SEP> 0, 6 <SEP> 75 <SEP> - <SEP> DPG <SEP> Alcoholysis
<tb><SEP> 8A <SEP> 8 <SEP> 99.5 <SEP> 0.25 <SEP> Epi <SEP> 115.5 <SEP> 1.25 <SEP> 5 <SEP> BF3 <SEP> 0.6 <SEP> 70 <SEP> - <SEP>"<SEP>"
<tb><SEP> 8B <SEP> 8 <SEP> 67.5 <SEP> 0.17 <SEP> Epi <SEP> 157.3 <SEP> 1.7 <SEP> 10 <SEP> BF3 <SEP> 1.3 <SEP> 70 <SEP> - <SEP>"<SEP>"
<tb><SEP> 9A <SEP> 9 <SEP> 21.3 <SEP> 0.05 <SEP> Epi <SEP> 23.8 <SEP> 0.15 <SEP> 3 <SEP> BF3 <SEP> 0.1 <SEP> 75 <SEP> - <SEP> DEG <SEP>"
<tb><SEP> 9B <SEP> 9 <SEP> 17 <SEP> 0.04 <SEP> Epi <SEP> 18.5 <SEP> 0.2 <SEP> 5 <SEP> BF3 <SEP> 0, 1 <SEP> 75 <SEP> - <SEP> DPG <SEP>"
<tb><SEP> 9C <SEP> 9 <SEP> 42.5 <SEP> 0.1 <SEP> Epi <SEP> 74 <SEP> 0.8 <SEP> 8 <SEP> BF3 <SEP> 0, 5 <SEP> 75 <SEP> - <SEP> DPG <SEP>"
<tb><SEP> 9D <SEP> 9 <SEP> 42.5 <SEP> 0.1 <SEP> Epi <SEP> 74 <SEP> 0.8 <SEP> 8 <SEP> BF3 <SEP> 0, 5 <SEP> 75 <SEP> - <SEP>"<SEP>"
<tb><SEP> glycidol <SEP> 51.8 <SEP> 0.7 <SEP> 7 <SEP> MeONa <SEP> 0.3 <SEP> 150 <SEP> - <SEP> - <SEP> 10A <SEP> 10 <SEP> 159 <SEP> 0.4 <SEP> Epi <SEP> 74 <SEP> 0.8 <SEP> 2 <SEP> BF3 <SEP> 0.6 <SEP> 55 <SEP> - <SEP> DEG <SEP> saponif.
<Tb>

10B <SEP> 10 <SEP> 119.5 <SEP> 0.3 <SEP> Epi <SEP> 111 <SEP> 1.2 <SEP> 4 <SEP> BF3 <SEP> 0.6 <SEP> 55 <SEP> - <SEP> DEG <SEP>"
<tb> 10C <SEP> 10 <SEP> 79 <SEP> 0.2 <SEP> Epi <SEP> 92.5 <SEP> 1 <SEP> 5 <SEP> BF3 <SEP> 0.5 <SEP> 75 <SEP> - <SEP> DPG <SEP> alcoholysis
<tb> 10D <SEP> 10 <SEP> 99.5 <SEP> 0.25 <SEP> Epi <SEP> 162 <SEP> 1.75 <SEP> 7 <SEP> BF3 <SEP> 1 <SEP> 55 <SEP> - <SEP> DPG <SEP> saponif.
<Tb>

10E <SEP> 10 <SEP> 59.2 <SEP> 0.15 <SEP> Epi <SEP> 111 <SEP> 1.2 <SEP> 8 <SEP> BF3 <SEP> 0.7 <SEP> 75 <SEP> - <SEP>"<SEP> alcoholysis
<tb> 10F <SEP> 10 <SEP> 99.5 <SEP> 0.25 <SEP> Epi <SEP> 208 <SEP> 2.25 <SEP> 9 <SEP> BF3 <SEP> 1.2 <SEP > 55 <SEP> - <SEP> DPG <SEP> saponif.
<Tb>

10G <SEP> 10 <SEP> 79.5 <SEP> 0.2 <SEP> Epi <SEP> 185 <SEP> 2 <SEP> 10 <SEP> SnCl4 <SEP> 2.5 <SEP> 100 <SEP> - <SEP>"<SEP>"
<tb> 10H <SEP> 10 <SEP> 119.5 <SEP> 0.3 <SEP> Epi <SEP> 333 <SEP> 3.6 <SEP> 12 <SEP> BF3 <SEP> 1.8 <SEP > 55 <SEP> - <SEP> DPG <SEP> alcoholysis
<tb> TABLE 3 - Compounds I (continued)

EX <SEP> COMPOUND <SEP> II <SEP> EPOXYDE <SEP>#<SEP> CATALYST <SEP># C <SEP> HYDROLYSIS
<tb><SEP> alcoholysis
<tb><SEP> EX <SEP> Q (g) <SEP> Moles <SEP> Name <SEP> Q (g) <SEP> Moles <SEP> nature <SEP> Q (g) <SEP> Catalyst <SEP > solvent
<tb><SEP> saponification
<tb> 11A <SEP> 11 <SEP> 119.5 <SEP> 0.3 <SEP> Epi <SEP> 138.7 <SEP> 1.5 <SEP> 5 <SEP> BF3 <SEP> 0.8 <SEP> 70 <SEP> - <SEP> DPG <SEP> alcoholysis
<tb> 12A <SEP> 12 <SEP> 90.8 <SEP> 0.2 <SEP> Epi <SEP> 111 <SEP> 1.2 <SEP> 6 <SEP> BF3 <SEP> 0.6 <SEP > 70 <SEP> - <SEP>"<SEP>"
<tb> 13A <SEP> 13 <SEP> 45.5 <SEP> 0.1 <SEP> Epi <SEP> 55.5 <SEP> 0.6 <SEP> 6 <SEP> BF3 <SEP> 0.4 <SEP> 75 <SEP> - <SEP> DPG <SEP>"
<tb> 14A <SEP> 14 <SEP> 25 <SEP> 0.055 <SEP> Epi <SEP> 30.6 <SEP> 0.33 <SEP> 6 <SEP> BF3 <SEP> 0.2 <SEP> 75 <SEP> - <SEP>"<SEP>"
<tb> 15A <SEP> 15 <SEP> 59 <SEP> 0.13 <SEP> Epi <SEP> 72.2 <SEP> 0.78 <SEP> 6 <SEP> BF3 <SEP> 0.4 <SEP > 55 <SEP> - <SEP>"<SEP> saponif.
<Tb>

16A <SEP> 16 <SEP> 76.5 <SEP> 0.15 <SEP> TBGE <SEP> 78 <SEP> 0.6 <SEP> 7 <SEP> MeONa <SEP> 2.4 <SEP> 150 <SEP> aci. <SEP> sulf. <SEP> - <SEP>
<SEP> palmitic
<tb><SEP> 2.5%
<tb> 17A <SEP> 17 <SEP> 49.5 <SEP> 0.1 <SEP> Epi <SEP> 62.5 <SEP> 0.7 <SEP> 7 <SEP> BF3 <SEP> 0.5 <SEP> 60 <SEP> - <SEP> DPG <SEP> alcoholysis
<Tb>
TABLE IV

<tb> EX <SEP><SEP> PHYSICAL <SEP> PROPERTIES <SEP> COMPOUNDS <SEP> I
<tb> SOLUBILITIES
<tb> ASPECT <SEP> Pt <SEP> of <SEP> Trouble <SEP> Oil <SEP> of <SEP> Vaseline <SEP> WATER
<tb><SEP> 1A <SEP> Paste <SEP> brown <SEP> dark <SEP>><SEP> 100 <SEP> * <SEP> D
<tb><SEP> 2A <SEP> Oil <SEP> brown <SEP> 82 * <SEP> S <SEP> D
<tb><SEP> 3A <SEP> Oil <SEP> Yellow <SEP> 67 * <SEP> S <SEP> I
<tb><SEP> 3B <SEP> Oil <SEP> Brown <SEP> 88 * <SEP> L
<tb><SEP> 3C <SEP> -PA <SEP> brown <SEP> clear <SEP>><SEP> 100 * <SEP> little <SE> S <SEP> D
<tb><SEP> 3D <SEP> Paste <SEP> brown <SEP> clear <SEP>><SEP> 100 ** <SEP> I <SEP> S
<tb><SEP> 4A <SEP> Oil <SEP> black <SEP> 61 * <SEP> I <SEP>
<tb> 5A <SEP> Paste <SEP> soft <SEP> amber <SEP>><SEP> 100 * <SEP> D
<tb><SEP> 5B <SEP> Paste <SEP> yellow <SEP> clear <SEP> S
<tb><SEP> 6A <SEP> Oil <SEP> Brown <SEP> 70 ** <SEP> I <SEP> S
<tb><SEP> 7A <SEP> Oil <SEP> brown <SEP> 80 * <SEP> S <SEP> I
<tb><SEP> 8A <SEP> Paste <SEP> brown <SEP> clear <SEP> 86 * <SEP> little <SEP> S <SEP> D <SEP>
<tb><SEP> 8B <SEP> Paste <SEP> brown <SEP>><SEP> 100 ** <SEP> I <SEP> S
<tb><SEP> 9A <SEP> Oil <SEP> Brown <SEP> clear <SEP> 72 * <SEP> S <SEP> I
<tb><SEP> 9B <SEP> Oil <SEP> Brown <SEP> clear <SEP> 87 * <SEP> S <SEP> D
<tb><SEP> 9C <SEP> Paste <SEP> yellow <SEP>><SEP> 100 * <SEP> little <SE> S <SEP> D
<tb><SEP> 9D <SEP> Paste <SEP> amber <SEP>> 100 ** <SEP> I <SEP> S
<tb><SEP> 10A <SEP> Oil <SEP> Brown <SEP> clear <SEP> (I *) <SEP> S <SEP> I
<tb><SEP> 10B <SEP> Amber <SEP> Oil <SEP> 74 * <SEP> S <SEP> D
<tb><SEP> lOC <SEP> Paste <SEP> brown <SEP> 87 * <SEP> S <SEP> D
<tb><SEP> 10D <SEP> Paste <SEP> brown <SEP> 93 * <SEP> S <SEP> D
<tb><SEP> 10E <SEP> Paste <SEP> brown <SEP>> 100 * <SEP> D
<tb><SEP> 10f <SEP> Paste <SEP> brown <SEP> clear <SEP>> 100 * <SEP> few <SE> S <SEP> D
<tb><SEP> 100 <SEP> Paste <SEP> brown <SEP>> 100 * <SEP> I <SEP> D
<tb><SEP> 10H <SEP> Paste <SEP> brown <SEP>> 100 * <SEP> I <SEP> S
<tb><SEP> llA <SEP> Paste <SEP> brown <SEP> D
<tb><SEP> 12A <SEP> Paste <SEP> brown <SEP># 100 * <SEP><SEP> S <SEP> D
<tb><SEP> 13A <SEP> Paste <SEP> brown <SEP> clear <SEP> 94 * <SEP> S <SEP> D
<Tb>
TABLE IV (Continued)

<tb> EX <SEP><SEP> PHYSICAL PROPERTIES
<tb><SEP> SOLUBILITIES
<tb> ASPECT <SEP> Pt <SEP> from <SEP> Troubel <SEP> OIL <SEP> FROM <SEP> VASELINE <SEP> WATER
<tb><SEP> 14A <SEP> Paste <SEP> brown <SEP> 91 * <SEP> S <SEP> D
<tb><SEP> 15A <SEP> Paste <SEP> brown <SEP> 93 * <SEP> S <SEP> D
<tb><SEP> 16A <SEP> Wax <SEP> brown <SEP>> 100 * <SEP> I
<tb><SEP> 17A <SEP> Paste <SEP> brown <SEP> clear <SEP> 90 * <SEP> few <SE> S <SEP> D
<Tb>
The following examples are intended to illustrate the use of the compounds according to the invention in cosmetic formulations.
COMPOSITION 1
Makeup Base O / W Formula Oil. 22 g
C15H31COO CH2 - CHOH - CH2 - O - CH2 - CH - C4H9
C2H
Compound of Example 3C of Formula * 7 g

Perfume and preservative .......................... QS
Sterile demineralized water ......................... qs 100g
COMPOSITION 2
Night cream E / H
Isopropyl myristate ......................... 40 g
Compound of Example 9B of Formula ......................... 10 g

parfum et conservateur ........................QS
Eau déminéralisée stérile ........................qsp 100G
COMPOSITION 4
Crème de soin H/E
Huile d'amande douce ........................40 g
Composé de l'exemple 10d de formule .......................;10 g

Fragrance and preservative
Sterile demineralized water .......................... qs 100 g
COMPOSITION 3
Body milk H / E
Vaseline Oil Codex v ..................... 30 g
Compound of Example 8A of Formula O 7 g

perfume and preservative ........................ QS
Sterile demineralized water ........................ qs 100G
COMPOSITION 4
H / E skincare cream
Sweet almond oil ........................ 40 g
Compound of example 10d of formula .......................; 10 g

Perfume and preservative ....................... QS
Sterile demineralized water ....................... qs 100 g
COMPOSITION 5
Cleansing lotion for the eyes
Compound of Example 8B of Formula ........................ 4 4 g

Hexylene glycol 1 g
Allantoin ....................... 0.05 g
Potassium dihydrogen phosphate ....................... 0,1 g
Dipotassium hydrogen phosphate 3H2O ....................... 0.4 g
Sodium ethyl mercurithiosalycilate QS
Sterile demineralized water qs lOOg
Perfume ........................ QS
COMPOSITION 6
Humectant composition
2 g of compound of Example IOC are mixed with 5 g of a 3% aqueous solution of glycerol.

After homogenization for 30 minutes using an ultra-disperser, a dispersion of spherules is obtained.

COMPOSITION 7
Sunscreen composition
4.8 g of 13A compounds and 3.2 g of cholesterol are intimately mixed at the temperature of 90 ° C.

20 g are then added. of a 4% aqueous solution of para-aminobenzoyl polyoxyethylenated with 25 moles of ethylene oxide.

The mixture is allowed to return to room temperature with stirring, and then another 72 g of 4% aqueous para-aminobenzoic acid solution is added to 25 moles of ethylene oxide.

After homogenization for 30 minutes using an ultra-disperser; we obtain small esserules whose average size is close to one micron.

Claims (11)

 1. Mixture of nonionic surfactant compounds, characterized in that they correspond to the formula

 in which R denotes a linear or branched, saturated or unsaturated aliphatic radical containing 4 to 20 carbon atoms R1 denotes (1) an alkyl radical which is preferably linear,  (2) a linear or branched alkoxymethyl radical,  (3) an alkenyloxymethyl radical, the alkyl or alkenyl parts of these radicals contain from 4 to 20 carbon atoms Z denotes a polyether sequence corresponding to the formula

 in which a mean statistical value of 2 to 20 is indicated and A designates

 in which u is 0 or 1

 in which u is 0 or 1, the radicals R and R1 having in total between 12 and 38 carbon atoms and the derivatives of the above compounds resulting from the reaction of ethylene oxide or glycidol with the OH groups.  2. Mixture of compounds according to claim 1, characterized in that the radicals R are chosen from butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 2-ethylhexyl, 2-hexyl decyl and the radicals R 1 are chosen from hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl groups, the alkoxymethyl radicals derived from these groups or from the 2-dllyl-hexyloxyethyl, 2-hexyl decyloxy-methyl and 2-octyl dodecyloxymethyl groups.  3. Composition for use in cosmetics or pharmacy characterized in that it contains at least one compound as defined in claims let2 as surfactant.  4. Composition according to claim 3, characterized in that it additionally contains one or more adjuvants used in cosmetics and / or pharmaceuticals selected by the nonionic surfactants, anionic cationic or amphoteric3 mineral oils , animal or vegetable, anionic, cationic, nonionic or amphoteric resins, sunscreens, thickeners, enhancers, preservatives, perfumes, dyes, alcoholic solvents, fold modifiers, mineral salts, active substances having an action in the treatment, care or protection of the skin and hair.  5. Composition according to claim 3 being in the form of dispersion of lipid vesicles, whose wall consists of at least one compound as defined in claims 1 and 2, capable of carrying active substances in pharmacy or cosmetics.  6. Composition according to claim 5, characterized in that the compounds of formula I are associated with alcohols or long chain diols, sterols and optionally positively or negatively charged substances.  7. Process for the preparation of the compounds of formula (I) according to claim 1, characterized in that 1) the addition of n moles of epihalide or TBGE per mole is carried out.

 where R and R 1 have the meanings indicated in claim 1 to form a compound of formula (IV)

 where Y denotes a polyether chain of formula

 B is halogen, in the presence of sodium hydroxide or potassium hydroxide and a solvent; polyhydroxylated polythioether compounds being optionally oxidized with hydrogen peroxide in the presence of lactic acid or acetic acid.  or thioglycerol with the intermediate compound IV in which  where B is halogen or tert-butoxy, n, R and R1 have the meanings given in claim 1, and thioethanol is reacted  8. Preparation process according to claim 7, characterized in that it proceeds in a first step to the reaction of an alcohol of formula ROH with a compound with terminal epoxide group of formula

 wherein R and R 1 have the meanings indicated above in the presence of an acidic or basic catalyst to prepare the compound of formula II.  9. Preparation process according to claims 7 or 8, characterized in that to increase the hydrophilicity of the compounds of formula (I) of claim 1, a polyaddition of ethylene oxide or glycidol to a compound is carried out. of formula I in the presence of an acidic or basic catalyst and optionally solvents.  10. Process according to claim 7, characterized in that in the first step the epihalohydrin or TBGE is added to the alcohol of formula (II) in the presence of a Lewis acid catalyst, at a temperature compressed between and 120 C in the presence of solvent.  11. The method of claim 7, characterized in that in the first step is added the TBGE alcohol of formula (II) in the presence of an alkaline catalyst at a temperature between 120 and 180 C.