JPS6210224B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to new cosmetic compositions for treating hair and skin in a fatty state and to new compounds with such activity. It has already been proposed to use functional thioethers of primary amines derived from β-aminoethanethiol to treat fatty conditions of hair and skin. Among these compounds, the use of 2-S-benzylthio-ethylamine chlorohydrate has been proposed. The inventors have now discovered, quite unexpectedly, that some of these known compounds have a primary amine function substituted by at least one alkyl group with a hydroxy function in the β-position of the nitrogen atom. It has been found that in some cases its activity can be enhanced and moreover its toxicity can be reduced. The superior activity of the compounds of the invention was completely unexpected since compounds substituted with non-hydroxylated alkyl groups lacked activity as shown below. The present invention provides a cosmetic composition for treating fatty hair and skin, which composition has as an active ingredient the following formula: [In the formula, n is 0, 1 or 2; _R2 is a hydrogen atom or _-CH2 - _CH2OH ,

[Formula] and

Represents a group selected from [Formula]; R ₃ represents a hydrogen atom, -CH ₃ or -CH ₂ OH; R ₁ represents (i) -CH ₃ , (ii) -CH ₂ CH=CH ₂ , ( iii) _{−CH2
-CH2OH} ,

[Formula] (where m is 1 or 2, R ₄ is a hydrogen atom or -
( _{v ) -CH2-}
COR ₆ (However, R ₆ is -OH group or

[Formula] represents a group, and r' and r'' may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or r' and r'' together represent a group of the formula -
( _CH2 ) ₂ -O-( _CH2 ) _2- or forming a divalent group of the formula -( _CH2 ) _5- ),

[Formula] and

[Formula] (where R ₇ represents a _-NH2 group or a -COOH group)]
It contains at least one compound represented by the following in combination with a suitable carrier. The active compounds according to the invention can be used in the form of the free base, in the form of salts with inorganic or organic acids or also as mixtures of these two forms. Among acids, especially hydrochloric acid, hydrobromic acid, tartaric acid,
Malic acid, nicotinic acid, salicylic acid, N-oxonicotinic acid, palmitic acid, gentisic acid, pyrrolidonecarboxylic acid, ascorbic acid, parachlorophenoxyisobutyric acid, retinoic acid, α-hydroxyisobutyric acid, α- and β-hydroxybutyric acid , 5
-amino-3-thia-hexanedioic acid, pyruvic acid, glycolic acid, citric acid, aspartic acid,
Mention may be made of glutamic acid, oxoglutaric acid, camphorsulfonic acid, thiodiglycolic acid and uronic acid. Among the active compounds which can be used in the compositions according to the invention, mention may be made in particular of the following: Compound number 1.N-(2-methylthioethyl)β-
Hydroxyethylamine, 2.N-(2-methylsulfinyl-ethyl)β-hydroxyethylamine, 3.N-(2-methylsulfinyl-ethyl)bis(2-hydroxy-ethyl)amine, tertiary
4.N-(2-methyl-sulfonylethyl)bis(2-hydroxy-ethyl)amine, 5.N-(2
-Methylsulfinyl-ethyl)bis(2-hydroxy-propyl)amine, 6.N-(2-methylsulfinylethyl)bis(2,3-dihydroxypropyl)amine, 7.N-(2-hydroxypropyl)amine, -allylthioethyl)bis(2-hydroxy-propyl)amine, 7a. N-(2-allylthioethyl)bis(2-hydroxy-propyl)ammonium tartrate, 7b also p-chlorophenoxyiso Butyrate, No. 8.N-(2-allylsulfinylethyl)bis(2-hydroxy-propyl)
Amine, 9th N-(2-allylthio-ethyl)bis(2,3-dihydroxypropyl)amine, 9th
9′.N-(2-allylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-glutamate, 10.N-(2-β-hydroxyethylthio-
ethyl)bis(2-hydroxy-propyl)amine, 11.N-(2-β-hydroxyethyl-sulfinyl-ethyl)bis(2-hydroxy-propyl)amine, 12.3(2-β-hydroxyethylamino- Ethylthio)alanine, No. 13.3-[2
-(2-hydroxy-propylamino)ethylthio]alanine, No. 14.3-[2-bis(2-hydroxypropyl)amino-ethylthio]alanine,
Chapter 15.3 - [2-bis-(2,3-dihydroxy-propyl)amino-ethylthio]alanine, Chapter 16.2
-acetamido-3-[2-(2-hydroxy-ethylamino)ethylthio]propionic acid, No. 17.2
-acetamido-3-[2-bis(2-hydroxy-propyl)amino-ethylthio]propionic acid, 18.2-acetamido-3-[2-bis(2,3-dihydroxy-propyl)amino-ethylthio]propionic acid, No. 19.2-Amino-4-
[2-(2-hydroxy-ethylamino)-ethylthio]butyric acid, 20.2-amino-4-[2-bis(2,3-dihydroxy-propyl)amino-ethylthio]butyric acid, 21.2-amino-4-[ 2-(2
-hydroxy-propyl)amino-ethylthio]
Butyric acid, 22.2-amino-4-[2-bis(2-hydroxy-propyl)amino-ethylthio]butyric acid, 23.2-(2-hydroxy-ethylamino)-
Ethylthioacetic acid, No. 24.2-[Bis(2-hydroxy-propyl)amino]ethylthioacetic acid, No. 25.
N-[2-morpholinocarbonylmethylthio-ethyl]bis-(2-hydroxy-ethyl)amine, 26.N-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxypropyl)
Amine, No. 26a.N-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxy-propyl)amine-chlorohydrate, No. 26b.N
-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxy-propyl)ammonium-pyruvate, No. 26c. Also p-chlorophenoxy-isobutyrate, No. 26d. Di[N-(2-
Morpholinocarbonylmethylthio-ethyl)bis(2-hydroxy-propyl)ammonium]malate, No. 26e. Also tartrate, No. 27.N-
(2-o-aminophenylthio-ethyl) β-hydroxyethylamine, No. 27a. N-(2-o-aminophenylthio-ethyl)-β-hydroxyethyl-ammonium-gentisate, No. 27b. Also p- Chlorphenoxyisobutyrate, Chapter 27c.
Di[N-(2-o-aminophenylthio-ethyl)β-hydroxyethyl-ammonium]malate, No. 27d. Also tartrate, No. 27e.N-(2
-o-aminophenylthio-ethyl) β-hydroxyethyl-ammonium malate, No. 28.N
(2-o-aminophenylthio-ethyl)bis(2-hydroxy-ethyl)amine, No. 29.N-
(2-o-aminophenylthio-ethyl)bis(2,3-dihydroxy-propyl)amine,
30.N-(2-o-aminophenylthio-ethyl)
Bis(2-hydroxy-propyl)amine,
31.2-(2-β-hydroxyethylamino-ethylthio)benzoic acid, 32.2-(2-β-hydroxyethylamino-ethylsulfinyl)benzoic acid, 33.2-[2-bis(2-hydroxy-propyl)] Amino-ethylthio]benzoic acid, No. 34.2-
[2-bis(2-hydroxypropyl)aminoethylsulfinyl]benzoic acid, No. 35.2-[2-bis(2,3-dihydroxy-propyl)amino-
Ethylthio]benzoic acid, No. 36.2-[2-bis(2,3-dihydroxy-propyl)amino-ethylsulfinyl]benzoic acid, No. 37.N-(2-benzylthio-ethyl)-β-hydroxyethylamine, No. 37a. Also chlorhydrate, No. 38.N
-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)amine, No. 38a. Also chlorhydrate, No. 38b. N-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-pyruvate, No. 38c. Also p-chlorophenoxyisobutyrate, No. 38d. Also pyrrolidone carboxylate, No. 38e. Also malate, No.
38f. Also gentisate, No. 38g. Also glucuronate, No. 38h. Also 2-oxoglutarate,
No. 39.N-(2-benzylthio-ethyl)bis(2,3-dihydroxy-propyl)amine, no.
40.N-(2-benzylthio-ethyl)bis(2-
Hydroxy-propyl)amine, No. 40a. Also chlorhydrate, No. 40b. N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)
Ammonium-gentisate, No. 40c. Also malate, No. 40d. Also alpha-hydroxyisobutyrate, No. 40e. Also pyruvate, No. 40f. Also 2-
Oxoglutarate, 40th g. Also ascorbate, 40th h. Also 3-hydroxy-butyrate,
No. 40i. Also camphor sulfonate, No. 40j. Same as 5.
-Amino-3-thiahexanedioate, Section 40k.
Also nicotinate, No. 40. Also salicylate, No. 41. N-(2-benzylsulfinyl-ethyl)bis(2-hydroxypropyl)amine,
No. 42. (2-benzylthio-ethyl) N-(2-hydroxy-ethyl) 2-hydroxypropylamine, No. 42a. Also chlorhydrate, No. 43. N-
(2-benzylthio-ethyl)N-(2-hydroxy-ethyl)2,3-dihydroxy propylamine. The above compounds are summarized in Table 1 below by the groups R ₁ , R ₂ , R ₃ and n.

【table】

【table】

【table】

[Table] The cosmetic composition according to the invention may contain at least one active compound of the above formula () or a salt thereof in water, alcohol (such as ethanol or isopropanol), aqueous alcoholic solution, suspension in oil, solution, milk, etc. It may be contained as a suspension or gel. If the active compound is acidic or basic, it can be partially or totally neutralized in situ in the composition by inorganic or organic bases or acids, respectively, after which it can be neutralized in particular by salts of compounds of formula (). For forming purposes, one can choose from among the acids mentioned above. The concentration of active compounds according to the invention is generally between 0.2 and 20%, preferably between 1 and 10%. The hair compositions according to the invention may contain active compounds of formula () alone or in combination or in admixture with other compounds known for use in the treatment of fatty hair. The hair composition according to the invention may also contain ingredients such as penetrating agents or fragrances commonly used in cosmetics. The cosmetic composition according to the invention can also be in the form of a dry shampoo as a powder or an aerosol for application to dry hair without surfactants. To use, simply brush your hair after a few moments of application. They may also be in the form of lacquers or settlers containing at least one active compound in combination with at least one customary cosmetic resin in a suitable cosmetic carrier. Among the cosmetic resins that can be used, in particular polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of unsaturated carboxylic acids such as crotonic acid and vinyl acetate, copolymers of vinyl acetate, crotonic acid, and acrylic or methacrylic esters. Copolymers produced by copolymerization of vinyl acetate and alkyl vinyl ether, copolymers produced by copolymerization of vinyl acetate, crotonic acid, and long-chain organic acid vinyl ester or long-chain organic acid allyl or methallyl ester. The cosmetic resins contained in these compositions in the form of lacquers or setting lotions are also colored polymers, i.e. polymers containing in their polymeric chains coloring molecules capable of imparting color or a special tone to the hair. It can also be constructed from These compositions can also include direct dyes to color or tone the hair.
In addition, there are products that fix hair in a specific state, such as penetrants, cationic compounds, quaternary ammonium salts, vitamins, proteins, peptides, their hydrolysis products, starch or cellulose derivatives, surfactants, coloring agents, and fragrances. It may also contain conventional ingredients of cosmetic compositions. Cosmetic carriers that can be used to make compositions of this type can be constituted by conventional mixtures used for making lacquers, setting lotions or hair-conditioning compositions. These cosmetic compositions can therefore be constituted by an alcoholic or hydroalcoholic solution of the active compound and a setting resin. An alcoholic or hydroalcoholic solution of the active compound can also be mixed with a suitable amount of pressurized liquefied propellant gas and placed in an aerosol container to form a hair lacquer. In these types of compositions in the form of setlots or lacquers, the concentration of active compound is generally from 0.1 to 10%, preferably from 1 to 3%, while the concentration of resin is preferably from 0.1 to 10% (by weight). %). The cosmetic composition according to the invention can also effectively combat the unaesthetic appearance of fatty, transparent hair. It may also be in the form of a shampoo treatment in the form of an opaque or pearlescent liquid or in the form of a cream or gel. These compositions in the form of shampoos essentially contain at least one anionic, cationic, nonionic or amphoteric detergent and at least one formula ()
It is characterized in that it contains a mixture of active compounds. Among anionic detergents, especially alkyl sulfates,
Alkyl ether sulfate, alkyl polyether sulfate, alkyl sulfonate (alkyl group has 8 to 18 carbon atoms), sulfated monoglyceride, sulfonated monoglyceride, sulfated alkanolamide, sulfonated alkanolamide, fatty acid soap, fatty alcohol monosulfosuccinate,
Examples include condensation products of fatty acids and isethionic acid, condensation products of fatty acids and methyltaurine, condensation products of fatty acids and sarcosine, and condensation products of fatty acids and protein hydrolysates. Among cationic detergents, mention may be made in particular of long-chain quaternary ammonium salts, esters of fatty acids and amino alcohols, and amine polyethers. Among non-ionic detergents, in particular esters of polyols and sugars, condensation products of ethylene oxide and fatty acids, fatty alcohols, long-chain alkylphenols, long-chain mercaptans or long-chain amides, polyethers of polyhydroxy fatty alcohols. Examples of amphoteric detergents include asparagine derivatives, monochloroacetic acid-imidazoline condensation products,
Detergents such as alkylamino propionates, betaine derivatives or amino acid compounds can be mentioned. Compositions in the form of such shampoos generally contain from 0.1 to 15% of active compound, preferably from 1 to 10%, and of detergent in aqueous solution, for example from 4 to 15% by weight.
It contains 20%, preferably 5 to 10%. Shampoos as defined above may contain other conventional cosmetic ingredients such as perfumes and colorants. In addition, thickeners such as fatty acid alkanolamides, cationic polymers such as quaternized vinyl pyrrolidone polymers, cationic cellulose polymers, cellulose derivatives such as carboxymethyl- or hydroxymethyl-cellulose,
It can also be made into a cream or gel form by incorporating long chain polyol esters and natural rubber. Finally, these shampoos can also be in powder form to be applied to damp hair and also to be dissolved in an amount of water before washing the hair. Such compositions in the form of shampoos can also contain dyes for hair dyeing. Satisfactory results are generally obtained with weekly shampooing, which reduces and in some cases eliminates the fatty appearance of the hair, and also ensures normal maintenance of the hair. The inventor has also recognized that the active compounds as defined above can be applied to the skin in combination with suitable cosmetic carriers to improve its appearance. Compositions of this type which can be applied to the skin are preferably in the form of creams, emulsions, gels, dermatological pastes or aerosol foams. These compositions can also be in the form of aqueous or hydroalcoholic lotions. They generally contain from 0.1 to 15%, preferably from 1 to 5%, of the active compounds defined above. These compositions may further contain any conventional ingredients such as fatty substances, preservatives, fragrances, colorants, waxes and the like. It may also contain colored pigments that can color the epithelium and cover skin imperfections. The present invention also provides novel compounds of the general formula: [In the formula, n is 0, 1 or 2; _R2 is a hydrogen atom or _-CH2 - _CH2OH ,

[Formula] and

Represents a group selected from [Formula]; R ₁ is (i) -CH ₃ , (ii) -CH ₂ CH=CH ₂ , (iii) -CH ₂ -
_CH2OH ,

[Formula] (where m is 1 or 2, R ₄ represents a hydrogen atom or a -COR ₅ group, and R ₅ represents a saturated or unsaturated alkyl group having 1 to 8 carbon atoms) (v) -CH ₂ −COR ₆
(However, R ₆ is -OH group or

[Formula] represents a group, and r' and r'' may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or r' and r'' together represent the formula -(CH ₂ ) ₂ -O
−(CH ₂ ) ₂ − or forming a divalent group of the formula −(CH ₂ ) ₅ −)

[Formula] (in this case, R ₂ represents a hydrogen atom only when R ₃ is a hydrogen atom) and

[Formula] (However, R ₇ represents a group of -NH ₂ or -COOH, and in the latter case, R ₂ and
(at least one of R ₃ is not a hydrogen atom) and salts thereof. The present invention also provides a method for preparing the compound of formula () above. These compounds are generally given the formula () to oxirane
Prepared by reacting the compound: The oxirane used is ethylene oxide (R ₃ =
H), propylene oxide (R ₃ =-CH ₃ ) or glycidol (R ₃ =-CH ₂ OH). The above addition reaction can be carried out in a wide variety of solvents, but preferably polar solvents such as water or alcohol are used alone or in combination. If R ₁ has an acid function, it is preferably neutralized beforehand with an alkali hydroxide. The addition reaction is carried out at temperatures between 0° and the boiling point of the solvent, depending on the oxirane used. The reaction can also be completed by leaving the reactants at room temperature for several days. The reaction products are generally separated by concentrating the mixture under reduced pressure, optionally after neutralization with acid. The compounds obtained can optionally be purified by passing through silica gel or, if the reaction mixture contains inorganic salts, through an ion exchange resin or by washing or crystallization using a suitable solvent. R ₂ is

A compound of formula () corresponding to [Formula] can be obtained directly from a compound of formula () in which R ₂ is a hydrogen atom by adding twice the equivalent amount of oxirane. The compound of formula () is preferentially obtained by the above method, but it can also be obtained by reacting the compound of formula () with a hydroxyalkyl halide according to the reaction formula below. Compounds of the invention with R ₂ =H, n=0 can also be prepared by addition of a thiol R ₁ SH to N-hydroxyaziridine according to the following reaction scheme: The reaction conditions are similar to those for the reaction between oxirane and thioether. If the thiol R ₁ SH has a carboxylic acid function, it can optionally be neutralized prior to reaction with the substituted aziridine. A general method for obtaining active compounds in salt form consists in adding, at room temperature, a solution of the active compound to be salted to an equimolar solution of the inorganic or organic acid in question. Each solvent may be the same or different and is generally selected from alcohols or chlorinated hydrocarbons. The mixture is stirred for about 1 hour and then concentrated under reduced pressure. Wash the evaporation residue with ether,
Can be dried with phosphoric anhydride at 50°C. If dibasic acids are used as organic acids, the monosalts or di-salts are obtained in the same way, depending on whether 1 or 2 mol of amine is used per mol of acid. Activity of the compounds according to the invention In order to clarify the properties of the compounds according to the invention:
The proportion of epidermal lipids was determined, followed by repeated applications of these compounds, and for comparison a placebo solution as well as a compound of similar structure to the compound of formula ().
Indeed, it is known that the fatty appearance of the skin or hair is related to the proportion of lipids present in the epidermis. To ensure good statistical significance for these comparative measurements, the experiments were carried out using Parf, Cosm, Sav,
Aubin and Coll. France, 1971, Vol. 1, No. 8.
A stable and controlled model was preconditioned with a special diet to produce a characteristic fatty state (seborrheic) according to the method described by [1]. The tested substances were applied to the skin at a concentration of 80 mmol/day for 12 consecutive days. Epidermal lipids were compared with those of strictly age-matched control individuals who received the same number and frequency of applications of the control solution (water). Comparative experiments were conducted on the following compounds: Compound Epidermal lipid measurements, expressed in μg/ ^cm2 of skin, yielded the following results (average values):

[Table] These results show that when the primary amine is replaced with a methyl group (compound B), the activity observed with compound A is almost completely abolished. The double substitution converting Compound A to a tertiary amine results in representative compounds C, D, E, and F as a significant increase in epidermal lipid proportions compared to the proportions seen in seborrheic individuals not treated with the test substance. appear. This increase in lipids ranges from +19% to +42%. Conversely, and quite unexpectedly, the compounds of the invention (compounds G, H and I) showed exactly the opposite, lower results than even the most active reference compound (compound A). Next, the present invention will be further explained by examples. Example 1 Compound No. 31 2-(2-β-Hydroxyethylamino-ethylthio)benzoic acid A solution of 6.16 g of thiosalicylic acid dissolved in 60 ml of methanol is stirred at room temperature in a nitrogen atmosphere. N-(2-
A solution of 3.48 g of hydroxy-ethyl)aziridine in 40 ml of methanol is added dropwise. The resulting precipitate is separated and dried, and the liquid is concentrated. The resulting residue was crystallized with ethanol along with the precipitate, and the melting point was
9 g of white product at 235° C. are obtained. Analysis: C ₁₁ H ₁₅ NO ₃ S Calculated value: %
C 54.75 H 6.26 N 5.80 S 13.28 Actual value:%
54.58 6.20 5.68 13.05 Example 2 Compound 1 N-(2-methylthio-ethyl)β-hydroxyethylamine N-(2-hydroxy-ethyl)aziridine (25.8 g) and sodium methanethiolate (21 g) were dissolved in nitrogen atmosphere. Boil the mixture with the one dissolved in ethanol. Upon completion of the reaction, the mixture is neutralized with an equivalent amount of 5N hydrochloric acid and then concentrated under reduced pressure.
The residue is extracted with chloroform, the solvent is removed and then distilled. 28 g of a colorless oil with a boiling point of 145° C. at 26 mm Hg are obtained. Amine index: Calculated value 7.40 meg/g Actual value 7.40 meg/g Example 3 Compound 2 N-(2-methylsulfinyl-ethyl)β-hydroxyethylamine 13.5 g of Compound 1 obtained in Example 2 Add an equivalent amount of hydrogen peroxide dropwise to the solution dissolved in methanol, keeping the temperature below 30℃. After the reaction is completed, it is concentrated under reduced pressure and the residue is purified by filtration through silica gel. 8 g of colorless oil are obtained, which is the second hemihydrate of the compound. Analysis: C ₅ H ₁₃ NO ₂ S・1/2H ₂ O Calculated value%
C 37.40 H 8.78 N 8.75 S 20.00 Actual value%
37.22 8.48 8.80 20.25 Examples 4 and 5 Compound No. 12 3-N-[2-β-hydroxyethylamino-ethylthio]alanine An aqueous alcoholic solution of N-(2-hydroxy-ethyl)aziridine (8.7 g) was heated under nitrogen atmosphere. 50% at
Add dropwise to a solution of cysteine (12.1 g) in 200 ml of ethanol water. The temperature of the reaction mixture is kept at 45° for 4 hours and then left at room temperature for 24 hours. The mixture is filtered and the liquid is concentrated under reduced pressure. When the residue is taken up in ethanol, a crystalline solid aromatic acid precipitates as it forms. It is separated and crystallized from a mixture of water and acetonitrile. Crystals (-
37 g of hydrate was obtained, which began to decompose at 200° with the formation of anhydride. 21.5 g of this product are dissolved in acetic acid and then 10 ml of hydrogen peroxide (110 volumes) are added dropwise at 0°C. After the mixture is left at room temperature for 5 days, it is concentrated under reduced pressure and the residue is crystallized from water. 2- with a melting point of 240°
19.5 g of β-aminoethylsulfinylbenzoic acid are obtained. Analysis: C ₉ H ₁₁ NN ₃ S Calculated value %:
C 50.68 H 5.19 N 6.56 S 15.03 Actual value%:
50.58 5.35 6.75 15.07 Compound No. 36 is obtained in the form of a yellow oil corresponding to the hemihydrate. Analysis: C ₁₅ H ₂₃ NO ₇ S1/2H ₂ O Calculated %: C 48.63 H 6.52 N 3.78 Found %: 48.60 6.89 3.71 The mixture is concentrated under reduced pressure and the residue is dissolved in boiling ethanol. Separate and dry the crystals formed after cooling (yield 50%). Melting point 110℃ Analysis: C ₆ H ₁₃ NO ₃ S Calculated value C 40.21 H 7.31 N 7.82 S 17.89 Actual value
40.07 7.07 7.64 17.86 Example 7 Compound 27 N-(2-0-aminophenylthio-ethyl)-β
-Hydroxyethylamine N-(2-hydroxy-ethyl)-aziridine
5 g of 0-aminothio-phenol dissolved in methanol is slowly added to 3.48 g of methanol solution. After standing at room temperature for 72 hours, the reaction mixture is concentrated, the residue is dissolved in benzene and filtered through silica gel. 8 g of pale yellow oil are obtained. Analysis: C ₁₀ H ₁₆ N ₂ OS Calculated value: %
C 56.57 H 7.59 N 13.19 S 15.10 Actual value:%
56.39 7.81 13.02 14.96 Example 8-11 Compound No. 38 N-2benzylthio-ethyl-bis(2-hydroxyethyl)amine A solution of 50 g of 2-benzylthio-ethylamine dissolved in 150 ml of absolute alcohol was brought to a temperature of 50°C and cooled with salt water. into a reactor equipped with a container and a diffuser. After the solution is purged with a stream of nitrogen, a slow stream of ethylene oxide is passed through until absorption by the solution is complete. After passing nitrogen through again, the solution is concentrated under reduced pressure and the oily residue is dried over phosphoric anhydride. 74g of oil was obtained and its analysis and NMR
The spectrum corresponds to the desired product. Analysis: C ₁₃ H ₂₁ NO ₂ S Calculated value: %
C 61.14 H 8.29 N 5.49 S 12.56 Actual value:%
60.93 8.34 5.64 12.40 Under the same conditions compounds 3, 4 and 25 are obtained in the form of hygroscopic colorless oils:

[Table] Example 12 Compound No. 40 N-(2-benzylthio-ethyl)-bis(2-hydroxypropyl)amine 16.7 g of 2-benzylthio-ethylamine was heated at 96°C.
A solution of 20% in ethanol is cooled to 0°C, and 3 times the equivalent amount of propylene oxide is added dropwise with stirring. The reaction mixture is kept at 30 DEG C. for 6 hours and then concentrated under reduced pressure and the resulting oily residue is dried in an oven containing phosphoric anhydride. 28 g of pale yellow oil are obtained. Analysis: C ₁₅ H ₂₅ NO ₂ S Calculated value C 63.56 H 8.89 N 4.94 S 11.31 Actual value
63.76 8.74 5.08 11.55 Example 13-24 Compound No. 5 N-(2-methylsulfinyl ethyl)bis(2-hydroxypropyl)amine Three times the equivalent amount of propylene oxide was added with stirring at a temperature below 10°. Add dropwise to an aqueous solution of 2-methylsulfinyl ethylamine (10.7 g). Return to room temperature and leave for 30 hours (progress of reaction is followed by thin layer chromatography). It is then concentrated in a rotary evaporator (the oily residue is dried in vacuo over phosphoric anhydride in a desiccator, thus leaving 21.5 g of a colorless oil).
is obtained. Analysis: C ₉ H ₂₁ NO ₃ S calculated value %
C 48.40 H 9.48 N 6.27 S 14.36 Actual value%
48.48 9.30 6.12 14.23 Similarly, the compounds summarized in the table below are prepared:

【table】

[Table] Example 25 Compound No. 42 N-(2-benzylthio-ethyl)-N-(2-hydroxy-ethyl)2-hydroxypropylamine A solution of 3.3 g of Compound No. 37 in ethanol (30 ml) was added with propylene oxide. Add 1 g dissolved in water (15 ml) and leave the mixture for 24 hours. Concentrate under reduced pressure and dry the residual viscous liquid in an oven. 3.8 g of compound No. 42 is obtained. Amine index: Calculated value: 3.72meg/g Actual value: 3.72meg/g Example 26 Compound No. 39 N-(2-benzylthio-ethyl)-bis(2.3
-dihydroxypropyl)amine 2-benzylthio ethylamine (13g), excess glycidol (14.5g), toluene (200g)
ml) and boil the mixture for 3 hours. After cooling, the product becomes an oil which is separated from the toluene phase and washed with benzene. 24.5 g of compound No. 39 are thus obtained in the form of a hydrate. Amine index: Calculated value 3.02meg/g Actual value 3.02meg/g Examples 27 and 28 Compound 6 N-(2-methylsulfinyl-ethyl)bis(2,3-dihydroxy-propyl)amine 2-methylsulfinyl A solution of 14 g of nyl-ethylamine and 19.5 g of glycidyl dissolved in 50 ml of ethanol is boiled for 8 hours. The reaction mixture is concentrated under reduced pressure and the oily residue obtained is purified by passing through silica gel. 32 g of compound No. 6 are obtained. Analysis: C ₉ H ₂₁ NO ₅ S Calculated value %
C 42.33 H 8.29 N 5.49 S 12.56 Actual value%
42.11 8.54 5.46 12.37 Compound No. 43 is similarly prepared and obtained in the hemihydrate form with a yield of 60%. Analysis: C ₁₄ H ₂₃ NO ₃ S1/2H ₂ O Calculated value %
C 57.06 H 8.15 N 4.75 S 10.89 Actual value%
56.98 8.13 4.63 10.57 Example 29 Compound No. 29 N-(2-0-aminophenylthio-ethyl)bis(2,3-dihydroxy-propyl)amine 2-0-aminophenylthio-ethylamine
A solution of 16.8 g and 14.8 g of glycidol dissolved in ethanol at 96°C is left at room temperature for 6 days. The reaction mixture is concentrated under reduced pressure and the oily residue is washed with toluene and then dried in the presence of phosphoric anhydride in an oven. Compound No. 29.29 g is thus obtained. Analysis: C ₁₄ H ₂₄ N ₂ O ₄ S Calculated value %:
C 53.14 H 7.64 N 8.85 S 10.13 Actual value%:
52.88 7.61 8.76 9.94 Example 30 Compound No. 18 2-acetamido-3-[2-bis(2,3-dihydroxy-propyl)amino-ethylthio]propionic acid 2-acetamido-3-β-aminoethylthio-propionic acid 20.6 g A solution of 4 g of sodium hydroxide and 14.8 g of glycidol in 50% ethanol water is heated to a temperature of 40° C. for 7 hours. Add an equivalent amount of hydrochloric acid and purify by passing through an ion exchange resin (H ⁺ ). After evaporating the solvent under reduced pressure, a viscous liquid19
g is obtained, which crystallizes in the form of a -hydrate with a melting point of 90°C. Analysis: C ₁₃ H ₂₆ N ₂ O ₇ S・H ₂ O Calculated value %:
C 41.92 H 7.58 N 7.52 S 8.61 Actual value%:
41.84 7.57 7.62 8.87 Example 31 Compound No. 36 2-[2-bis(2,3-dihydroxy-propyl)amino-ethylsulfinyl]benzoic acid This compound was prepared similarly to Compound No. 18 (Example No. 30). Prepared from glycidol and 2-β-aminosulfinylbenzoic acid. Preparation of 2-β-aminoethylsulfinylbenzoic acid A solution of 8.6 g of ethyleneimine dissolved in 200 ml of ethanol was gradually added to an ethanol solution of thiosalicylic acid (30.8 g) at 35° C. in a nitrogen atmosphere.
The resulting 2-β-amino-ethylthio-benzene is separated and dried. 17 g of compound No. 13 are obtained. Melting point 178℃ Analysis: C ₇ H ₁₆ N ₂ O ₃ S Calculated value %
C 40.36 H 7.74 N 13.45 S 15.59 Actual value%
40.34 7.69 13.40 15.41 Compound No. 16 is obtained under the same conditions but using N-acetylcysteine instead of cysteine. Obtained as a colorless oil corresponding to the hemihydrate salt. Analysis: C ₉ H ₁₈ N ₂ O ₄ S1/2H ₂ O Calculated value%
C 41.68 H 7.38 N 10.80 S 12.36 Actual value%
41.66 7.25 10.84 12.43 Example 6 Compound 23 2-(2-Hydroxy-ethylamino)-ethylthioacetic acid A methanol solution of an equimolar mixture of ethyl thioglycolate and N-(2-hydroxy-ethyl)aziridine was prepared in a nitrogen atmosphere. Boil for 2 hours. The reaction mixture is concentrated under reduced pressure and the residue is stirred in a 2N aqueous potassium hydroxide solution containing a small amount of ethanol. After 24 hours, add HCl to return the pH to 4. Example 32 Compound No. 38a N-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)amine chlorohydrate A 4N ethanol solution (45 ml) of hydrochloric acid was added to Compound No. 38a.
Add to the ethanol solution of 38 (38 g). 2 at room temperature
After standing for a period of time, the obtained solution was concentrated and the residue was reduced to 1.2
-Crystallize with dichloroethane. After drying, 33 g of a compound with a melting point of 77° are obtained. Analysis: C ₁₅ H ₂₂ ClNO ₂ S Calculated value %:
C 53.50 H 7.60 N 4.80 S 10.99 53.33 7.58 4.57 10.82 Examples 33 and 34 Compound 40a N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)amine chlorohydrate 30 ml of a 4N ethanol solution of hydrochloric acid was added to Compound No. 40 30
Add to the chloroform solution of g. After leaving it at room temperature for 2 hours, add 80 ml of ether. Compound No. 40a crystallizes. After separation and drying, 30 g of crystals with a melting point of 95° are obtained. Analysis: C ₁₅ H ₂₆ ClNO ₂ S Calculated value %:
C 56.32 H 8.19 N 4.38 S 10.02 Actual value%:
56.32 7.96 4.41 10.08 Compound no. 42 to compound no.
42a was obtained with a melting point of 88°C. Analysis: C ₁₄ H ₂₄ ClNO ₂ S Calculated value %:
C 5497 H 791 N 458 S 1048 Actual value%:
5472 795 452 1052 Examples 35 and 36 Compound No. 40b N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium gentisate A methanol solution of 4.6 g of gentisic acid is added to a methanol solution of Compound No. 40 8.5 g. , the mixture is stirred at room temperature for 1 hour. The resulting solution is concentrated under reduced pressure and the residue is separated and washed with ether. After drying, 12.9 g of white crystals with a melting point of 59° C. are obtained. Analysis: C ₂₂ H ₃₁ NO ₆ S Calculated value %:
C 60.38 H 7.14 N 3.20 S 7.32 Actual value%:
60.38 7.16 3.41 7.34 Compound No. 27b was similarly prepared from Compound No. 27 and p-chlorophenoxyisobutyric acid, and was in the form of whitish crystals with a melting point of 58°C. Analysis: C ₂₀ H ₂₇ ClN ₂ O ₄ S Calculated value %:
C 56.26 H 6.37 N 6.56 S 7.51 Actual value%:
56.03 6.49 6.51 7.70 Examples 37 to 59 Compounds No. 7, No. 26, No. 27, No. 38 and No. 40, summarized in the table below, were prepared according to the same procedure as described in Examples No. 32 to No. 36. (These salts are highly hygroscopic and oily or semi-solid).

【table】

[Table] Composition Examples Example A Cream compound for oily skin No. 38C 1.5 g Benzalkonium chloride 0.3 g Glycol stearate 1 g Cetyl alcohol 4 g Polyoxyethylene stearate with 20 moles of ethylene oxide 6 g Isopropyl paramitate 10 g Carofilm Oil 1g Preservative (parahydroxybenzoate) 0.3g Fragrance Add required amount of sterile demineralized water 100g This cream can be applied daily to significantly improve the oily appearance of the skin. Compound No. 38C Compound No.
The same effect can be obtained by replacing it with 40d, 40f, or 40g. Example B Hair styling lotion compound No. 40 for oily hair 0.8 g Calcium pantothenate 0.5 g Fragrance 0.1 g Add 40% alcohol water to 100 ml Example C Skin paste Alkanoyl oxyethane sulfonate 80 g Lantrol (from MALMSTROM): Lanolin Liquid fraction 12g Purcellin oil (from DRAGOCO): Fatty acid branched ester 2g BisN-(2-oxypyridyl thio)aluminum camphor sulfonate 0.05g Titanium dioxide 2g Fragrance 2.5g Compound No. 30 3g Compound No. 30 is Compound No. 30 27a or 27b can be substituted. Example D Lotion for daily oily hair care Pyridoxine Camphor Sulfonate 0.3g Fragrance 0.1g Colorant 0.1g Compound No. 26b 0.4g Add 50% alcoholic water to 100ml Compound No. 26b is compound No. 26d at a concentration of 0.7g or No.
Can be replaced with 26e. Example E Emulsion Compound No. 31 for Oily Skin 1.4 g Reticulated polyacrylic acid commercially available under the trade name “CARBOPOL 934” 0.375 g Lanolin fatty acid/isopropyl ester 1 g Lanolin oxyethylated with 5-20 moles of ethylene oxide 2.5 g Oxyethylated Cetyl stearyl alcohol
3g Myristate monoethanolamide 2g Triethanolamine Amount required to make PH8 Methyl parahydroxybenzoate 0.1g Propyl parahydroxybenzoate 0.1g Add water to 100g Compound No. 31 is compound No. 32 in this composition.
It can be replaced with Example F Powdered sodium laurel sulfate 40 g Copra fatty acid/sodium isocyanate condensation product commercially available from HOECHST under the name "HOSTAPONK.A" 39 g Compound No. 12 10 g Fragrance 1 g Example G Fluid gel vinyl for hair conditioning for daily use Pyrrolidone/vinyl acetate (70/30) copolymer 2g Lanolin oxyethylated with 5-20 moles of ethylene oxide 1g Polyethylene glycol 300 5g Compound No. 7 0.5g Methyl parahydroxybenzoate 0.1g Propyl parahydroxybenzoate 0.1g t-butyl Hydroxytoluene 0.1g t-Butylhydroxyanisole 0.2g Fragrance 0.1g Add water to 100ml Example H Hair conditioning lotion for oily hair A lotion for use on damp hair after washing and prior to setting. Vinyl acetate/vinylpyrrolidone copolymer (30/
70) 1.5g Compound No. 30 1g Fragrance 0.1g 25% ethanol 100ml Example I Emulsion Compound No. 33 for oily skin 2.6g Reticular polyacrylic acid known under the trademark CARBOPOL 934 0.375g Lanolin fatty acid/isopropyl ester 1g Ethylene oxide 5 -20 mol oxyethylated lanolin 2.5 g oxyethylated cetyl stearyl alcohol 3 g copra fatty acid monoethanolamide 2 g Required amount to make triethanolamine PH 8 Methyl parahydroxybenzoate 0.1 g Propyl parahydroxybenzoate 0.1 g Add water to 100 ml Example J Clear liquid shampoo (12 moles of ethylene oxide) polyethoxylated lauryl alcohol 13 g Copra fatty acid diethanolamide 4 g Quaternized vinylpyrrolidone copolymer commercially available from GAF under the name GAFQUAT 755
0.4g Compound No. 38f 3g Flavor 0.2g Add water to 100ml In this example, Compound No. 38f can be replaced by the same amount of Compound No. 40c. Example K Cream Cyan sodium laurel sulfate 12 g Pastacopra fatty acid/methyltaurine condensation product commercially available from HOECHST under the name "HOSTAPON CT" 40 g Lauric acid monoethanolamide 2 g Glycerol monostearate 4 g Compound No. 39 2 g Flavor 0.2 g Lactic acid 100g with the required amount of water to give a pH of 6.5 Example L Pearlescent liquid shampoo Sodium lauryl sulfate oxyethylated with 2.2 moles of ethylene oxide 9g Sodium monolauryl sulfosuccinate 1g Polyethylene glycol distearate 2g Lauric acid diethanolamide 2g Compound No. 5 4g Flavor 0.3g Add water to 100g Compound No. 5 can be replaced with Compound No. 6 or No. 24. Example M Cream for oily hair Polyoxyethylenized stearate (Myrj49) 3 g Glycerol monostearate 4 g Cetyl alcohol 7 g Vaseline oil 8 g Isopropyl myristate 5 g Compound No. 38d 12 g Methyl parahydroxybenzoate 0.3 g Product name from GOODRICH Carbopol 941" commercially available 1% reticulated polyacrylic acid solution 40g Triethanolamine Add the required amount of water to pH 6.5 to 100g This cream is applied to the scalp after washing the hair. Lightly pine surge and leave for about 15 minutes, then rinse. In this example, the active compound is preferably an equal amount of the compound.
40h can be substituted. Example N Lotion compound for oily skin No. 38 0.6g 50% pyrrolidone carboxylic acid 3g Water-soluble neopurcerin: fatty acid branched ester polyethoxylated with 4 moles of ethylene oxide 0.5g Fragrance Required amount Preservative 0.2g Add water to 100g Compound No. 38 can be replaced with Compound No. 39 or Compound No. 40. Example O Lacquer for Oily Hair A lacquer is prepared according to the invention by mixing the following ingredients: Poly(vinylpyrrolidone-vinyl acetate) commercially available from GENERAL ANILIN under the trade name "E 335"
Resin 10g Compound No. 37a 0.5g Methyl cellosolve 2g Absolute alcohol 100g Example P Skin treatment lotion Compound No. 40 1.8g Nicotinic acid 0.8g Benzalkonium chloride 0.2g Ethyl alcohol 13ml Polyethylene glycol 10g Fragrance Required amount Soluble coloring Add the required amount of sterile demineralized water to 100g Example Q Cream for oily skin Polyoxyethylated sorbitan monostearate (Tween60) 1g Self-emulsifying glyceryl monostearate 6g Stearyl alcohol 1.5g Stearic acid 2g Vaseline oil 15g Tonsil oil 2g Triethanolamine 0.1g Compound No. 16 1g Fragrance 0.4g Add water to 100g Example R Lotion for oily skin Compound No. 39 0.4g Trans-sulfolanediol 0.4g 3,6-dioxa Octanol 10g Ethanol 9g 5-amino- 3-thia hexanedioic acid 0.3g Add water to 100g Example S Cream for oily skin Cipol wax 5g Glyceryl monostearate 2g Hydrogenated polyisobutylene 3g Vaseline oil 3g Cetyl alcohol 1g Purcellin oil 3.5g Preservative 0.3g Compound No. 13 1.4g Salicylic acid 0.9g Add water to 100ml Example T Mask for oily skin Compound No. 30 2g 5-amino-3-thia hexanedioic acid 1.2g Gelatin 1g Tragacanth 1g Bentonite 4g Kaolin 26g Titanium dioxide 2g Camphor Brain 0.04 g Colorant Add the required amount of sterile demineralized water to 100g Example U Liquid shampoo Prepare a liquid shampoo by mixing the following (apply and leave for 5 minutes before rinsing): (with 4 moles of glycerol) ) Polyglycerolized lauryl alcohol 15 g Quaternized vinyl pyrrolidone copolymer available from GAF under the name Gafquat 755 0.4 g Compound 12 3.6 g Polyglycerolized lauryl alcohol available from Rhone Progil under the name “Ethomeen 18/15” Ethoxylated alkylamines
0.8g Lactic acid Amount required to reach pH 6 Fragrance Required amount Water 100ml Example V Treatment mask for oily skin Lanolin oxyethylated with 5-20 moles of ethylene oxide 5g Cetyl alcohol 2g Self-emulsifying ethylene glycol stearate 7g Pharmacopoeia Vaseline 5g Kaolin 10g Titanium oxide 8g Preservative 0.3g Compound No. 40 1.4g Glutamic acid 0.8g Add water 100g Example W Facial lotion Mix the following ingredients to treat oily conditions on the face. Prepare the lotion: Compound No. 27a 1g Propylene glycol 2g Sodium ethylenediaminetetraacetate 0.1g Ethanol 16g Methyl parahydroxybenzoate 0.1g Propyl parahydroxybenzoate 0.1g Flavor Required amount Coloring agent Add required amount of water 100g Compound No. 27a can be replaced with compound No. 40b. Example Add sterile demineralized water to 100 g Compound No. 25 can be replaced with Compound No. 40, No. 26, or No. 38. Example Y Lotion compound for oily skin No. 19 0.8 g Hyamine 10X: Diisobutyl cresoxyethoxyethyldimethylbenzylammonium chloride 0.3 g Salicylic acid 0.2 g Polyethylene glycol-tert-dodecyl thioether 0.1 g Miranol C2M: Hydroxyethyl carboxymethyl 2-Alkylimidazolinium 10g Fragrance Add required amount of water 100g Compound No. 19 can be replaced with Compound No. 31.

Claims (1)

[Claims] 1. General formula: [In the formula, n is 0, 1 or 2; R ₂ represents a hydrogen atom or a group selected from -CH ₂ -CH ₂ OH, [Formula] and [Formula]; R ₃ represents a hydrogen atom, - Represents _CH3 or _-CH2OH ; _R1 is (i) _-CH3 , (ii) _-CH2CH = _CH2 , (iii) _-CH2
-CH ₂ OH, [Formula] (where m is 1 or 2, R ₄ is a hydrogen atom or -
( _{v ) -CH2-}
COR ₆ (However, R ₆ represents an -OH group or a [Formula] group, and r' and r'' may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or r' and r″ together with the expression −
(CH ₂ ) ₂ -O-(CH ₂ ) ₂ - or a divalent group of the formula -(CH ₂ ) ₅ -), [Formula] and [Formula] (where R ₇ is -NH ₂ group or - Represents a group selected from (represents a COOH group)]
A cosmetic composition for treating fatty skin and hair, which contains the compound represented by the formula as an active ingredient. 2. A composition according to claim 1, in which the active compound is present in partially or fully chlorinated form with an organic or inorganic acid. 3 The inorganic or organic acid is hydrochloric acid, hydrobromic acid, tartaric acid, malic acid, nicotinic acid, salicylic acid, N-oxonicotinic acid, palmitic acid, gentisic acid,
Pyrrolidone carboxylic acid, ascorbic acid, parachlorophenoxyisobutyric acid, retinoic acid, α-hydroxy-isobutyric acid, α- and β-hydroxybutyric acid, 5-amino-3-thia-hexanedioic acid, pyruvic acid, glycolic acid, 3. A composition according to claim 1 or 2, which is selected from citric acid, aspartic acid, glutamic acid, oxoglutaric acid, camphor sulfonic acid, thiodiglycolic acid and uronic acid. 4 The active compound is compound number 1.N-(2-methylthio-ethyl)β-hydroxyethylamine,
2.N-(2-methylsulfinyl-ethyl)-β
-Hydroxyethylamine, 3.N-(2-methylsulfinyl-ethyl)bis(2-hydroxy-ethyl)amine, 4.N-(2-methylsulfonyl-ethyl)bis(2-hydroxy-ethyl)
Amine, 5.N-(2-methylsulfinyl-ethyl)bis(2-hydroxy-propyl)amine, 6.N-(2-methylsulfinyl-ethyl)bis(2,3-dihydroxy- Propyl)amine, 7.N-(2-allylthio-ethyl)bis(2-hydroxy-propyl)amine, 7a.N-
(2-allylthio-ethyl)bis(2-hydroxy-propyl)ammonium tartrate,
7b.N-(2-allylthio-ethyl)bis(2-hydroxy-propyl)ammonium-p-chloro-phenoxyisobutyrate, No. 8.N(2-allylsulfinyl-ethyl)bis(2- hydroxy-propyl)amine, 9'N-(2-allylthio-ethyl)bis(2,3-dihydroxy-propyl)-amine, 9'N-(2-allylthio-ethyl)bis(2-hydroxy-ethyl) ) Ammonium glutamate, No. 10.N-(2-β-hydroxyethylthio-ethyl)bis(2-hydroxy-
11.N-(2-β-hydroxyethyl-sulfinyl-ethyl)bis(2-hydroxy-propyl)amine, 12.3-(2-β-
-hydroxyethylamino-ethylthio)-alanine, No. 13.3-[2-(2-hydroxypropylamino)-ethylthio]-alanine, No. 14.3-[2
-bis(2-hydroxypropyl)-amino-
Ethylthio]alanine, 15.3-[2-bis(2,3-dihydroxy-propyl)amino-ethylthio]alanine, 16.2-acetamido-3
-[2(2-hydroxy-ethylamino)ethylthio]propionic acid, 17.2-acetamide-3
-[2-bis(2-hydroxy-propyl)amino-ethylthio]propionic acid, 18.2-acetamido-3-[2-bis(2,3-dihydroxy-propyl)amino-ethylthio]propionic acid, 19.2-amino -4-[2(2-hydroxy-ethylamino)-ethylthio]butyric acid, No. 20.2-
Amino-4[2-bis(2,3-dihydroxy-
Propyl)-amino-ethylthio]butyric acid, Chapter 21.2
-Amino-4-[2-(2-hydroxy-propyl)amino-ethylthio]butyric acid, 22.2-amino-4[2-bis(2-hydroxy-propyl)amino-ethylthio]butyric acid, 23.2-(2- Hydroxy-ethylamino)-ethylthio-acetic acid,
24.2-[bis(2-hydroxy-propyl)amino]ethylthioacetic acid, 25.N-[2-morpholinocarbonylmethylthio-ethyl]bis-(2-hydroxy-ethyl)amine, 26.N-[2-morpholino] Carbonylmethylthio-ethyl]-bis(2-hydroxypropyl)amine, No. 26a.N
-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxypropyl)amine.
Chlorhydrate, No. 26b.N-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxy-propyl)ammonium-pyruvate, No. 26c.N-[2-morpholinocarbonylmethylthio-ethyl]bis(2-hydroxypropyl) ) Ammonium p-chlorophenoxyisobutyrate, Section 26d. Di[N-(2-morpholinocarbonylmethylthio-ethyl)bis(2-hydroxypropyl)ammonium]malate, Section 26e.
Di[N-(2-morpholinocarbonylmethylthio-ethyl)bis(2-hydroxy-propyl)ammonium] tartrate, No. 27.N-(2-o-
Aminophenylthio-ethyl)-β-hydroxyethylamine, No. 27a.N-(2-o-aminophenylthio-ethyl)-β-hydroxyethyl ammonium gentisate, No. 27b.N-(2-o
-aminophenylthio-ethyl) β-hydroxyethylammonium-p-chlorophenoxyisobutyrate, 27c. di[N-(2-o-aminophenylthio-ethyl)β-hydroxyethylammonium] malate , 27th d. Di[N-(2-o-
Aminophenylthio-ethyl) β-hydroxyethyl ammonium tartrate, No. 27e.N-
(2-o-aminophenylthio-ethyl)-β-hydroxyethylammonium] malate, No. 28.
N-(2-o-aminophenylthio-ethyl)bis(2-hydroxy-ethyl)amine, No. 29.N
-(2-o-aminophenylthio-ethyl)bis(2,3-dihydroxypropyl)amine,
30.N-(2-o-aminophenylthio-ethyl)
Bis(2-hydroxypropyl)amine,
31.2-(2-β-hydroxyethylamino-ethylthio)benzoic acid, 32.2-(2-β-hydroxyethylamino-ethylsulfinyl)benzoic acid, 33.2-[2-bis(2-hydroxypropyl)] Amino-ethylthio]benzoic acid, No. 34.2-
[2-bis(2-hydroxypropyl)amino-
Ethylsulfinyl]benzoic acid, No. 35.2-[2-
Bis-(2,3-dihydroxy-propyl)amino-ethylthio]benzoic acid, No. 36.2-[2-bis(2,3-dihydroxy-propyl)amino-ethylsulfinyl]benzoic acid, No. 37.N-( 2-benzylthio-ethyl)-β-hydroxyethylamine, No. 37a.N-(2-benzylthio-ethyl)
β-Hydroxyethylamine-chlorohydrate, No. 38.N-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)amine, No. 38a.N-
(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)amine-chlorohydrate,
38b.N-(2-benzylthio-ethyl)bis(2
-hydroxy-ethyl)ammonium-pyruvate, No. 38c.N-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-p
-Chlorphenoxyisobutyrate, No. 38d.N-
(2-Benzylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-pyrrolidonecarboxylate, No. 38e.N-(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-malate, No. 38f.N- (2-benzylthio-
Ethyl)bis(2-hydroxy-ethyl)ammonium-gentisate, No. 38g.N-(2-benzyl-thio-ethyl)bis(2-hydroxy-ethyl)ammonium glucuronate, No. 38h.N-
(2-benzylthio-ethyl)bis(2-hydroxy-ethyl)ammonium-2-oxoglutarate, No. 39.N-(2-benzylthio-ethyl)
Bis(2,3-dihydroxy-propyl)amine, No. 40.N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)amine, No. 40a.N
-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)amine chlorhydrate, No. 40b.N-(2-benzylthio-ethyl)-bis(2-hydroxy-propyl)ammonium.
Gentisate, No. 40c.N-(2-benzylthio-
Ethyl)bis(2-hydroxy-propyl)ammonium-malate, No. 40d.N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium α-hydroxyisobutyrate, No. 40e.N-(2- Benzylthio-ethyl)-bis(2-hydroxy-propyl)ammonium-
Pyruvate, No. 40f.N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium-2-oxo-glutarate, No. 40g.N-
(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium-ascorbate, No. 40h.N-(2-benzylthio-ethyl)bis(2-hydroxypropyl)ammonium-3
-Hydroxy-butyrate, No. 40i. N-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium-camphor sulfonate, No. 40j.
N-(2-Benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium-5-amino-3-thia-hexanedioate, No. 40k.N-
(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium-nicotinate,
No. 40 lN-(2-benzylthio-ethyl)bis(2-hydroxy-propyl)ammonium salicylate, No. 41.N-(2-benzylsulfinyl-ethyl)bis(2-hydroxy-propyl)
Amine, No. 42.N-(2-benzylthio-ethyl)
N-(2-hydroxy-ethyl)2-hydroxypropylamine, No. 42a.N-(2-benzylthio-ethyl)N-(2-hydroxy-ethyl)-2-
Hydroxy-propylamine-chlorohydrate, No. 43.N-(2-benzylthio-ethyl)N-
A composition according to any one of claims 1 to 3, which is selected from (2-hydroxy-ethyl)-2,3-dihydroxy-propylamine. 5 The active compound is 0.1 to 0.1% based on the total weight of the composition.
A composition according to any one of claims 1 to 4 containing at a concentration of 20%, preferably 1 to 10%. 6. Patent claims for use in hair treatment for the nourishment of the scalp containing active compounds in the form of suspensions, solutions, emulsions or gels in water, alcohol, hydroalcoholic solutions, oils, etc. The composition according to any one of Ranges 1 to 5. 7. Compositions according to any of claims 1 to 6, which contain the active compounds as alcoholic or hydroalcoholic solutions in combination with customary cosmetic resins. 8 Commonly used resins include polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone and vinyl acetate, a copolymer of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid, a copolymer of vinyl acetate, crotonic acid, and acrylic acid.
or a copolymer obtained by copolymerization with methacrylic ester, a copolymer obtained by copolymerization of vinyl acetate, crotonic acid, and alkyl vinyl ether, a copolymer obtained by copolymerization of vinyl acetate, crotonic acid, and a long-chain organic acid, vinyl ester, or long-chain organic The composition according to claim 7, which is selected from copolymers obtained by copolymerization with acid/allyl or methacrylic esters. 9. A composition according to claim 7 or 8, which is in the form of an aerosol lacquer containing a pressurized liquefied gas propellant. 10. A composition according to claim 7 or 8, containing from 0.1 to 10% of active compound, preferably from 1 to 3%, and from 0.1 to 10% of resin in alcoholic or hydroalcoholic solution. 11 0.1 to 15% of active compound, preferably 1
Claims 1 to 5 are in the form of a shampoo treatment containing at least one of anionic, cationic, nonionic, or amphoteric detergents at a concentration of 10% to 10%. Composition of. 12. A composition according to claim 11, wherein the concentration of anionic, cationic, nonionic or amphoteric detergent is between 4 and 20%, preferably between 5 and 10%, based on the total weight of the composition. 13. Claim 1 for improving the appearance of the skin containing active compounds in a suitable cosmetic carrier in a concentration of 0.1 to 15%, preferably 1 to 5%.
The composition according to any one of items 5 to 6. 14. The composition of claim 13 in the form of an aqueous or aqueous-alcoholic lotion, cream, emulsion, gel, paste or aerosol foam. 15 Cosmetics such as fragrances, colorants, penetrants, surfactants, thickeners, emulsifiers, preservatives, cationic compounds, quaternary ammonium salts, vitamins, proteins, peptides, their hydrolysis products, and starch or cellulose derivatives. 15. A composition according to any one of claims 1 to 14, containing ingredients conventionally used in food compositions. 16 The following general formula: [In the formula, n is 0, 1 or 2; R ₂ represents a hydrogen atom or a group selected from -CH ₂ -CH ₂ OH, [Formula] and [Formula]; R ₃ represents a hydrogen atom, - Represents _CH3 or _-CH2OH ; _R1 is (i) _-CH3 , (ii) _-CH2CH = _CH2 , (iii) _-CH2
-CH ₂ OH, [Formula] (where m is 1 or 2, R ₄ is a hydrogen atom or -
( _{v ) -CH2-}
COR ₆ (However, R ₆ represents an -OH group or a [Formula] group, and r' and r'' may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or r' and r″ together with the expression −
(CH ₂ ) ₂ -O-(CH ₂ ) ₂ - or a divalent group of the formula -(CH ₂ ) ₅ -), [formula] (when R ₁ represents this group, R ₂ is R ₃ represents _{a hydrogen} atom _{only when} represents a group selected from (which is not a hydrogen atom)]. 17. The compound according to claim 16, which is in the form of a salt obtained using an inorganic or organic acid. 18 Inorganic or organic acids include hydrochloric acid, hydrobromic acid, tartaric acid, malic acid, nicotinic acid, salicylic acid, N-
Oxonicotinic acid, palmitic acid, ascorbic acid, p-chlorophenoxyisobutyric acid, retinoic acid, α-hydroxyisobutyric acid, α- and β-hydroxybutyric acid, 5-amino-3-thia-hexanedioic acid, pyruvic acid 18. The compound according to claim 17, which is selected from the group consisting of , glycolic acid, citric acid, aspartic acid, glutamic acid, oxo-glutaric acid, camphor sulfonic acid, thiodiglycolic acid and uronic acid.