CH639556A5 - COSMETIC COMPOSITIONS FOR THE TREATMENT OF THE FATTY CONDITION OF THE HAIR AND THE SKIN, COMPOUNDS AND THEIR PREPARATION METHOD. - Google Patents

Description

The present invention relates to new cosmetic compositions for combating the fatty state of the hair and of the skin.

It has already been proposed to use, for the purpose of combating the fatty state of the hair and of the skin, thioethers derived from ß-amino-ethanethiol in which the amine function was primary.

Among these compounds, the use of S-benzylthio-2 ethylamine hydrochloride has been particularly suggested.

It has been found, quite surprisingly, that the activity of certain of the previously known compounds could be enhanced and that, moreover, their toxicity could be reduced when the primary amine function was substituted by at least one alkyl radical carrying a hydroxy function in ß of the nitrogen atom.

The excellent activity of the compounds according to the invention was completely unpredictable, given that the compounds substituted by non-hydroxylated alkyl radicals were devoid of any activity, as will be shown below.

The subject of the present invention is a cosmetic composition for combating the fatty state of the hair and the skin, this composition containing, in combination in a suitable vehicle, at least one active compound corresponding to the following formula:

r2

I

R! - S - CH2 - CH2 - N - CH2 - CH - R3 (I)

I I

(0) n OH

in which:

n is 0, 1 or 2,

R2 represents either a hydrogen atom or a radical taken from the group consisting of:

-CH2 - CH2OH, -CH2 - CH - CH3

I

OH

and -CH2 - CH - CH2OH,

I

OH

R3 represents either a hydrogen atom or a radical taken from the group consisting of - CH3 and - CH2OH, and Ri represents a radical taken from the group consisting of:

i) -CH3,

ii) ~ CH2 - CH = CH2,

5

to

15

20

25

30

35

40

45

50

55

60

65

639,556

6

iii) -CH2 - CH2OH,

iv) - (CH2) m - CH - COOH,

NH - R4

m being 1 or 2 and R4 representing a hydrogen atom or the radical —COR 5, R5 being an alkyl radical, saturated or unsaturated, having from 1 to 8 carbon atoms,

v) - CH2 - COR6, R6 representing a radical —OH or

-Nv r 'and r ", identical or different, representing a hydrogen atom or an alkyl radical having from 1 to 5 carbon atoms or r' and r" together forming a divalent radical of formula - (CH2) 2 - O - (CH2) 2 -, or of formula - (CH2) 5 -,

vi) -CH JS "

Vil

R7 representing either the - NH2 radical or the --COOH radical.

The active compounds according to the invention can be used either in the form of a free base, or in the form of an addition salt with a mineral or organic acid or else as a mixture of these two forms.

Among the acids, mention may in particular be made of: 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, a-hydroxyisobutyric acid, a and ß-hydroxybutyric acid, amino acid 5 thia-3 hexanedioic acid, pyruvic acid, glycolic acid, citric acid, aspartic acid, glutamic acid, oxoglutaric acid, camphosulfonic acid, thiodiglycolic acid and uroni- acids ques.

Among the active compounds which can be used in the compositions according to the invention, the following may be mentioned in particular:

1. N- (2-methylthioethyl) P-hydroxyethylamine

2. N- (2-methylsulfinylethyl) P-hydroxyethylamine

3. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxyethyl) amine

4. N- (2-methylsulfonylethyl) -bis- (2-hydroxyethyl) amine

5. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine

6. N- (2-methylsulfinyl ethyl) -bis- (2,3-dihydroxy propyl) amine

7. N- (2-allylthio-ethyl) -bis- (2-hydroxypropyl) amine

7a. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) ammoniumtartrate 7b. N- (2-allylthio-ethyl-bis- (2-hydroxypropyl) ammonium-p-chlorophenoxyisobutyrate

8. N- (2-allylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine

9. N- (2-allylthio ethyl) -bis- (2,3-dihydroxy propyl) amine

9 '. N- (2-allylthio ethyl) -bis- (2-hydroxyethyl) ammoniumglutamate

10. N- (P-hydroxyethylthio-2 ethyl) -bis- (2-hydroxypropyl) amine

11. N- (P-hydroxyethylsulfinyl-2 ethyl) -bis- (2-hydroxypropylamine)

12. N- (P-hydroxyethylamino-2 ethylthio) -3 alanine

13. [(2-hydroxypropylamino) -2 ethylthio] -3 alanine

14. [bis- (2-hydroxypropyl) 2-aminoethylthio] -3 alanine

15. [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -3 alanine

16. Acetamido-2 acid [(2-hydroxyethylamino) -2 ethylthio] -3

propionic

17. Acetamido-2 acid [bis- (2-hydroxypropyl) amino-2 ethylthio] -3

propionic

18. Acetamido-2 acid [bis- (2,3-dihydroxy propyl) 2-amino ethyl-

thio] -3 propionic

19. 2-Amino acid [(2-hydroxyethylamino) -2 ethylthio] -4

butyric

20. 2-Amino acid [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -4

butyric

21. 2-amino acid [(2-hydroxypropyl) 2-aminoethylthio] -4

butyric

22. 2-Amino acid [bis- (2-hydroxypropyl) 2-aminoethylthio] -4

butyric

23. (2-Hydroxyamino) -2 ethylthioacetic acid

24. [bis- (2-hydroxypropyl) amino] -2 ethylthioacetic acid

25. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (2-hydroxy

ethyl) amine

26. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2

propyl) amine

26a. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2

propyl) amino hydrochloride 26b. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2

propyl) ammoniumpyruvate 26c. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2

propyl) ammonium-p-chlorophenoxyisobutyrate 26d. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (hydroxy-2

propyl) ammonium] malate 26e. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (2-hydroxypropyl) ammonium] tartrate

27. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylamine

27a. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium-gentisate

27b. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium-

p-chlorophenoxyisobutyrate 27c. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -malate

27d. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -tartrate

27th. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium) -malate

28. N- (o-aminophenylthio-2 ethyl) -bis- (2-hydroxyethyl) amine

29. N- (2-o-aminophenylthio) -bis- (2,3-dihydroxy propyl amine

30. N- (2-o-aminophenylthio) -bis- (2-hydroxypropyl) amine

31. Benzoic acid (2-hydroxyethylamino-2 ethylthio) -2

32. Benzoic (2-hydroxyethylamino-2-ethylsulfinyl) -2 acid

33. [bis- (2-hydroxypropyl) amino-2 ethylthio] -2 benzoic acid

34. [bis- (2-hydroxypropyl) amino-2-ethylsulfinyl] -2 acid

benzoic

35. Acid [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -2

benzoic

36. [bis- (2,3-dihydroxypropyl) amino-2-ethylsulfinylj-2 acid

benzoic

37. N- (2-benzylthioethyl) p-hydroxyethylamine

37a. N- (2-benzylthioethyl) P-hydroxyethylaminechlorohydrate

38. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) amine

38a. N- (2-benzylthioethyl) -bis- (2-hydroxyethyl) amino hydrochloride 38b. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-pyruvate

38c. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-

p-chlorophenoxyisobutyrate 38d. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-

pyrrolidonecarboxylate 38e. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-malate

38f. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium gentisate

38g. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-glucuronate

38h. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) 2-ammoniumoxo glutarate

39. N- (2-benzylthioethyl) -bis- (2,3-dihydroxy propyl) amine

40. N- (b.enzylthio-2 ethyl) -bis- (2-hydroxypropyl) amine

5

10

15

20

25

30

35

40

45

50

55

60

65

639,556

40a. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) aminechlor-hydrate

40b. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium gentisate

40c. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-malate

40d. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-a-hydroxyisobutyrate

40th. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium-pyruvate

40i. N- (benzyIthio-2 ethyl) -bis- (2-hydroxypropyl) ammonium-camphosulfonate

40d. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-amino-5-thia-3 hexanedioate 5 40k. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium-nicotinate

401. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-salicylate

41. N- (benzylsulfinyI-2 ethyl) -bis- (2-hydroxypropyl) amine

40f. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) 2-ammoniumoxo 42. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2-hydroxypropyl-

glutarate amine

40g. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium- 42a. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2-hydroxypropyl-

amino ascorbate hydrochloride

40h. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- 15 43. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2,3-dihydroxy

3-hydroxypropylamine butyrate

The meanings of the radicals R „, R2, R3 and n of the compounds listed above are collated in Table I.

Table I

Compounds No ri r2

r3 '

not

1

-ch3

h h

0

2

-ch3

h h

1

3

-ch3

-ch2ch2oh h

1

4

-ch2

-ch2ch2oh h

2

5

-ch3

-ch2ch - ch3

1

-ch3

1

Oh

6

-ch3

-ch2 - ch - ch2oh

1

-ch2oh

1

Oh

7

-ch2 - ch = ch2

-ch2 - ch - ch3

1

-ch3

0

Oh

8

-ch2 - ch = ch2

-ch2 - ch - ch3

1

-ch3

1

Oh

9

1

0 35

1

s

II

n 35

-ch2 - ch - ch2oh

-ch2oh

0

Oh

10

-ch2 - ch2oh

-ch2 - ch - ch3

1

-ch3o

0

Oh

11

-ch2-ch2oh

-ch2 - ch - ch3

1

-ch3

1

Oh

12

-ch2 - ch - cooh

1

h h

0

I

nh2

13

-ch2 - ch - cooh

1

h

-ch3

0

1

nh2

14

-ch2 - ch - cooh

1

-ch2 - ch - ch3

1

-ch3

0

l nh2

Oh

15

-ch2 - ch - cooh |

-ch2 - ch - ch2oh

1

-ch2oh

0

nh2

Oh

16

-ch2 - ch - cooh

1

h h

0

I

nhcoch3

17

-ch2 - ch - cooh

1

-ch2 - ch - ch3

1

-ch3

0

1

nhcoch3

Oh

639,556

8

Table I (continued)

Compounds No ri rz r3

not

18

ch2 - ch - cooh

1

-ch2 - ch - ch2oh

1

-ch2oh

0

I

NHCOCH3

1

Oh

19

- (ch2) 2 - ch - cooh

1

h h

0

nh2

20

- (ch2) 2 - ch - cooh

1

-ch2 - ch - ch2oh

I

-ch2oh

0

nh2

Oh

21

- (ch2) 2 - ch - cooh

1

h

-ch3

0

1

nh2

22

- (ch2) 2 - ch - cooh

1

-ch2 - ch - ch3

I

-ch3

0

nh2

Oh

23

-ch2 - cooh h

h

0

24

-ch2 - cooh

-ch2ch - ch3 I

-ch3

0

Oh

25

-ch2con ^ 0

-ch2 - ch2oh h

0

26

-ch2con ^

—F ~ \

-ch2ch - ch3

1

-ch3

0

Oh

TI

h h

0

n2w

28

"

-ch2 - ch2oh h

0

29

"

-ch2ch — ch2oh

1

-ch2oh

0

Oh

30

"

-ch2 - ch - ch3

1

-ch3

0

—I

Oh

31

h h

0

cooh

32

"

h h

1

33

"

-ch2ch - ch3

I

-ch3

0

Oh

34

"

-ch2ch - ch3

1

-ch3

1

Oh

35

"

-ch2ch - ch2oh

I

-ch2oh

0

r ~ \

Oh

36

—0

-ch2ch - ch2oh

I

-ch2oh

1

cooh oh

37

—Ch2 - c8h5

h h

0

38

—Ch2 - c6h5

-ch2ch2oh h

0

39

—Ch2 - c6h5

-ch2ch - ch2oh

1

-ch2oh

0

Oh

40

-ch2 - c6h5

-ch2 - ch - ch3

1

-ch3

0

Oh

9

Table I (continued)

639,556

Compounds No ri r2

r3

not

41

—Ch2 - c6h5

-ch2 - ch - ch3

1

-ch3

1

Oh

42

—Ch2 - C6h5

-ch2 - ch2oh

-ch3

0

43

-ch2 - c6hs

-ch2 - ch2oh

-ch2oh

0

The cosmetic compositions according to the invention contain at least one active compound according to formula (I) above, or one of its salts, in suspension or in solution in water, in an alcohol (such as ethanol or isopropanol), in a hydroalcoholic solution, in an oil, in an emulsion or in a gel.

When the active compound has an acidic or basic character, it can be neutralized in situ in the composition, either completely or partially, respectively by a mineral or organic base, or by a mineral or organic acid, the latter being especially able to be chosen from the acids mentioned above for obtaining the salts of the compounds of formula (I).

The concentration of active compound according to the invention is generally between 0.1 and 20% and preferably between 1 and 10%. 25

The hair compositions according to the invention may contain the active compounds of formula (I) either alone, or as a mixture between them, or even as a mixture with other compounds already known for combating the greasy and unsightly appearance of the hair.

30

The hair compositions according to the invention can also contain ingredients such as penetration agents or perfumes which are generally used in cosmetics.

The cosmetic compositions according to the invention can also take the form of dry shampoo in the form of powder or 3J of aerosol, not containing a surface-active agent, and intended for the application to dry hair. In the implementation process, it is allowed to pause for a certain time after the application, then we simply brush the hair.

They can also take the form of lacquers or styling lotions 40 containing at least one active compound in combination, in an appropriate cosmetic vehicle, with at least one traditional cosmetic resin.

Among the cosmetic resins which can be used, mention may in particular be made of: polyvinylpyrrolidone; polyvinyl-45 copolymers

pyrrolidone and vinyl acetate; copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid; copolymers resulting from the polymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester; the copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether, and the copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long carbon chain acid or an allyl or methallyl ester of a long carbon chain acid, etc.

The cosmetic resins contained in these compositions in the form of lacquers or styling lotions can also consist of colored polymers, that is to say polymers containing in their macromolecular chain dye molecules which make it possible to confer to the hair a particular color or shade. 60

These compositions can also contain direct dyes intended to cause coloring or shading of the hair. They may also contain traditional ingredients with cosmetic compositions intended for fixing the hair in a particular state such as penetration agents, 65 cationic compounds, quaternary ammonium salts, vitamins, proteins, more or less hydrolyzed peptides, derivatives of starch or cellulose, surfactants, colorants, perfumes, etc.

The cosmetic vehicles which can be used for the production of such types of compositions may consist of conventional mixtures used for the production of lacquers and styling lotions or even styling compositions.

This is how these cosmetic compositions can be constituted by an alcoholic or hydroalcoholic solution of the active compound and of the resin to constitute a styling lotion.

The alcoholic or hydroalcoholic solution of the active compound can also be mixed with a suitable quantity of propellant liquefied under pressure and packaged in an aerosol container and constitute what is commonly called a hair spray.

In these types of composition in the form of styling lotions or lacquers, the concentration of active compound is generally between 0.1 and 10%, but preferably between 1 and 3%, while the resin concentration is preferably between 0.1 and 10% by weight.

The cosmetic compositions according to the invention may also take the form of treating shampoos having the liquid, limpid, opaque or pearly appearance, or else the appearance of cream or gel, and making it possible to effectively combat the fatty and unsightly appearance. of the hair.

These compositions in the form of shampoos are essentially characterized by the fact that they contain, as a mixture, at least one anionic, cationic, nonionic or amphoteric detergent with at least one active compound of formula (I).

Among the anionic detergents, mention may in particular be made of: alkyl sulfates, alkyl ether sulfates, alkyl polyethersulfates, alkyl sulfonates (alkyl groups having 8 to 18 carbon atoms), sulfated monoglycerides, sulfonated monoglycerides, sulfonated alkanolamides, alkanolamides, alkanolamides sulfonates, fatty acid soaps, monosulfosuccinates of fatty alcohols, condensation products of fatty acids with isethionic acid, condensation products of fatty acids with methyltaurine, condensation products of fatty acids with sarcosine, the condensation products of fatty acids with a protein hydrolyzate. Among the cationic detergents, mention may be made in particular of: long chain quaternary ammoniums, esters of fatty acids and amino alcohols, polyether amines.

Among the nonionic detergents, mention may be made in particular of: polyol and sugar esters, condensation products of ethylene oxide with fatty acids, with fatty alcohols, with long chain alkylphenols, with long-chain mercaptans, on long-chain amides, polyethers of polyhydroxylated fatty alcohols or amphoteric detergents such as asparagine derivatives, condensation products of monochloroacetic acid on imidazolines, alkyllaminopropionates , betaine derivatives or amine oxides.

These compositions in the form of shampoos generally contain from 0.1 to 15%, but preferably from 1 to 10% of active compound. They also contain for example from 4 to 20%, but preferably from 5 to 10% by weight of detergents in solution in an aqueous medium.

The shampoos as defined above can also contain the usual cosmetic ingredients such as perfumes and dyes. They can also contain thickeners such as alkanolamides of fatty acids, cationic polymers such as

639,556

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quaternized vinylpyrrolidone copolymers, cationic cellulosic polymers, etc., cellulose derivatives such as carboxy-methyl- or hydroxymethylcellulose, long-chain polyol esters, natural gums, etc., so as to be present in form of cream or gel. s

These shampoos can finally be in the form of powders intended either to be applied to wet hair, or to be dissolved in a certain volume of water before washing the hair.

These compositions in the form of shampoos can also comprise dyes intended for dyeing the hair.

In general, a satisfactory result is obtained by running a weekly shampoo, which makes it possible to reduce and, in certain cases, to remove the greasy appearance of the hair, while also ensuring normal maintenance. of the hair. 15

The licensee also noted that the active compounds as defined above could, in combination with an appropriate cosmetic vehicle, be applied to the skin to improve its appearance.

Such compositions which can be applied to the skin are preferably in the form of creams, milks, gels, dermatological breads or aerosol foams. These compositions can also be in the form of aqueous or hydroalcoholic lotions. They generally contain from 0.1 to 15% of active compounds as defined above, and preferably from 1 to 5%. 25

These compositions can also contain any traditional ingredient such as fatty substances, preservatives, perfumes, dyes, waxes. They can also contain colored pigments which make it possible to tint the epidermis and to mask the defects of the skin. 30

A subject of the present invention is also, as new compounds, the compounds corresponding to the following general formula:

R2

together forming a divalent radical of formula - (CH2) 2 - O - (CH2) 2-, or of formula ~ (CH2) 5-,

R, - S - CH2 - CH2 - N - CH2 - CH - R,

(I)

(0) „

OH

vi)

-omT)

in this case, R2 only represents a hydrogen atom when R3 represents a hydrogen atom, and

R7 representing either the —NH2 radical or the —COOH radical, in the latter case R2 and R3 in the same compound being different from a hydrogen atom, and the salts of said compounds obtained using a mineral acid or organic such as those listed above.

The new compounds according to the above formula are those given above, with the exception of compounds 31 and 32.

The present invention also relates to the process for the preparation of the compounds of formula (I) above.

These compounds are generally prepared by the action of an oxirane on a compound of formula (II):

Rj - S - CH2 - CH2 - NH - R2

I

(0) n (II)

R.

CH2 - CH - R3

V

45

in which:

n is 0.1 or 2,

R2 represents either a hydrogen atom or a radical taken from the group consisting of

-CH2 - CH2OH, -CH2 - CH - CH3

I

OH

and -CH2 - CH - CH2OH,

I

OH

R3 represents either a hydrogen atom or a radical taken from the group consisting of -CH3 and -CH2OH, and

Ri represents a radical taken from the group consisting of:

i) -CH3,

ii) -CH2 - CH = CH2,

iii) -CH, - CH2OH, 55

iv) - (CH2) m - CH - COOH,

I

NH - R4

m being 1 or 2 and R4 representing a hydrogen atom or the radical —COR5, Rs being an alkyl radical, saturated or unsaturated, having from 1 to 8 carbon atoms,

v) —CH2 - COR6, R6 representing a radical —OH or

-NOT

r 'and r ", identical or different, representing a hydrogen atom or an alkyl radical having from 1 to 5 carbon atoms or r' and r"

Ri - S - CH2 - CH2 - N - CH2 - CH - R3

I I

(0) n OH

The oxirane used can be ethylene oxide (R3 = H), propylene oxide (R3 = - CH3) or glycidol (R3 = - CH2OH).

The addition reaction can be carried out in a wide variety of solvents, but it is preferably carried out in a polar solvent medium such as water or alcohols, used alone or as a mixture.

When the radical Rj has an acid function, this is preferably neutralized beforehand with an alkali hydroxide.

The addition reaction can be carried out between 0 ° C. and the boiling point of the solvent depending on the oxirane used.

It can also be completed by leaving the reagents for several days at ordinary temperature. The reaction product is generally isolated by concentration of the mixture under reduced pressure after optional neutralization with an acid.

The compound obtained can optionally be purified by passing over silica gel or an ion exchange resin (when the reaction mixture contains mineral salts) or by washing or else by crystallization using an appropriate solvent.

The compounds of formula (I), in which the radical R2 is identical to the radical

-CH2 - CH - R3 I

OH

can be obtained directly from a compound of formula (II) in which R2 = H by addition of two equivalents of oxi-ranne.

Although the compounds of formula (I) are preferably obtained according to the process described above, it is also possible to obtain them by reaction of a hydroxyalkyl halide on a compound of formula (II), according to the reaction scheme following:

R, - S - CH2 - CH2 - NH - R2 + X - CH2 - CH - R3

(0) n

(II)

OH

11

639,556

R: - S - CH2 - CH2

i

(We

R2 i i

N - CH2

CH - r3 + XH

OH X = Cl or Br

The compounds according to the invention in which the radical r2 = h and n = 0 can also be prepared by adding a thiol ri - sh to an N-hydroxyalkylaziridine, according to the following reaction scheme:

r, - sh + ch2 - ch2 _>

\ /

NOT

i

CH2 15

i ch - oh i

r.3

-> rj - s - ch2 - ch2 - nh - ch2 - ch - r3 20

i oh

The reaction conditions are analogous to those relating to the action of an oxirane on a thioether.

When the thiol Rj - SH comprises a carboxy-Iic acid function, this can be optionally neutralized prior to the reaction with the substituted aziridine.

To obtain the active compounds in the form of a salt, the general method consists in adding at ordinary temperature a solution of the active compound which it is desired to salify in an equimole-circular solution of the mineral or organic acid corresponding to the desired salt.

30

The respective solvents, identical or different, are generally chosen from alcohols or chlorinated hydrocarbons.

The mixture is stirred for approximately 1 h, then it is concentrated under reduced pressure. The evaporation residue is then washed with ether, then dried at 50 ° C. under vacuum over phosphoric anhydride.

When diacids are used as organic acid, it is possible to obtain, according to the same operating procedure, either monosalt or disel, depending on whether 1 mol of amine or 2 mol of amine per mole is used respectively. acid.

Activity of the compounds according to the invention

To demonstrate the specific properties of the compounds according to the invention, epidermal lipid levels were determined, following the iterative application of these compounds, and compared to the application of a placebo solution, as well than that of compounds having structures similar to the compounds of formula (I). We know that the oily appearance of the skin or hair is linked to the level of lipids present in the epidermis.

In order to ensure these statistical determinations a good statistical significance, the studies were carried out on a genetically stable and controlled model, conditioned beforehand by a specific diet to establish a fatty (seborrheic) state characterized, according to the method described by Aubin and coll., in “Parf. Cosm. Sav. France ”, 1971, vol. 1, No. 8.

The test substances were applied to the skin, at a concentration of 80 mmol / l, for 12 consecutive d. The level of epidermal lipids was compared with that of control individuals, of strictly equal age, who received the same number of applications of a control solution (water) with the same frequency.

The comparative study focused on the following compounds:

Compound:

A. c6h5 -

b. c6h5 -

ch2 -

ch2 -

S - ch2 -S - ch2 -

ch2 -ch2 -

vs. c6h5 -

ch2 -

S - ch2 -

ch2-

D. c6h5 -

ch2 -

S - ch2 -

ch2 -

e. c6h5 -

ch2 -

S - ch2 -

ch2 -

F. c6hs -

ch2 -

S - ch2 -

ch2 -

G. (No 38a)

qh, -

■ ch2 - S -

- ch2 -

> ch3: \ ch3

, HCl

| , HCl y, HCl

NH, 2HC1

^ CH2 - CH2OH

"CH2 - CH2OH

HCl

H. (No 37a) C6H5 - CH2 - S - CH2 - CH2 - NH - CH2 - CH2OH, HCl

CH2 - CHOH - CH3

I. (N »40a) C6H5 - CH2 - S - CH2 - CH2 - N ^, HCl

CH2 - CHOH - CH3

The epidermal lipid measurements gave the following results, expressed in micrograms per square centimeter of skin (average values):

Untreated seborrheic individuals

Seborrheic individuals treated by:

AT

b

VS

D

e f

G

H

I

2098

1710

1972

2622

2706

2496

2979

1469

1490

1637

AT%

-18.5%

-6%

+ 25%

+ 29%

+ 19%

+ 42%

-30%

-29%

-22%

639,556

12

It appears from these results that the substitution of the primary amine with a methyl radical (compound B) almost entirely cancels the activity observed with compound A. The double substitution, by which the compound A is transformed into tertiary amine, is reflected , in representative compounds C, D, E and F, by a considerable increase in the level of epidermal lipids compared to the level observed in seborrheic individuals who have not received any substance in application. This increase in lipids ranges from + 19% to + 42%. On the other hand, and in a completely unpredictable manner, the compounds according to the invention (compounds G, H and I) give completely opposite results and even lower than the most active reference compound (compound A).

In order to better understand the invention, we will now give by way of example, and without any limiting character, several examples of preparation of the active compounds according to the invention, as well as various examples of cosmetic compositions based on these. .

Examples of preparation.

Example I:

Benzoic acid (2-hydroxyethylamino-2-ethylthio) -2:

compound 31

A solution of 6.16 g of thiosalicylic acid in 60 ml of methanol is stirred at room temperature under a nitrogen atmosphere. A solution of 3.48 g of N- (2-hydroxyethyl) aziridine in 40 ml of methanol is added dropwise. The precipitate formed is filtered and drained and the filtrate is concentrated. The residue obtained is then crystallized with the precipitate from ethanol and 9 g of a white product, melting at 235 ° C., are obtained.

Analysis for CnH ^ NOjS:

Calculated: C 54.75 H 6.26 N 5.80 S 13.28%

Found: C 54.58 H 6.20 N 5.68 S 13.05%

Example 2:

N- (2-methylthioethyl) ß-hydroxyethylamine: compound 1

A mixture of N- (2-hydroxyethyl) aziridine (25.8 g) and sodium methanethiolate (21 g) in ethanol is brought to the boil under a nitrogen atmosphere. At the end of the reaction, the mixture is neutralized with an equivalent of 5N hydrochloric acid, then concentrated under reduced pressure. The residue is extracted with chloroform, then distilled after removal of the solvent. 28 g of a colorless oil boiling at 145 ° C. under 26 mm Hg are collected.

Amine index: Calculated: 7.40 mEq / g Found: 7.40 mEq / g

Example 3:

N- (methylsulfinyl) -2 ethyl) p-hydroxyethylamine: compound 2

An equivalent of hydrogen peroxide is added dropwise to 13.5 g of compound 1 (obtained according to Example 2) in solution in methanol, the temperature being maintained below 30 ° C. When the reaction is complete, the solvent is concentrated under reduced pressure and the residue is purified by filtration on silica gel. 8 g of a colorless oil are obtained, which is a hemihydrate of compound 2.

Analysis for C5H, 3N02S, Vi H20:

Calculated: C 37.40 H 8.78 N 8.75 S 20.00%

Found: C 37.22 H 8.48 N 8.80 S 20.25%

Examples 4 and 5:

N- (p-hydroxyethylamino-2 ethylthio) -3 alanine: compound 12

A hydroalcoholic solution of N- (2-hydroxyethyl) aziridine (8.7 g) is added dropwise to a solution of cysteine (12.1 g) in 200 ml of 50% aqueous ethanol, under an atmosphere of nitrogen. The temperature of the reaction mixture is maintained at 45 ° C. for 4 h, then it is left to stand for 24 h at room temperature. The mixture is filtered and the filtrate is concentrated under reduced pressure. The residue taken up in ethanol gives a crystallized solid which is filtered and drained. 17 g of compound 12 are obtained, melting at 178 C.

Analysis for C7H16N203S:

5 Calculated: C 40.36 H 7.74 N 13.45 S 15.59%

Found: C 40.34 H 7.69 N 13.40 S 15.41%

Compound 16 is prepared under the same conditions, replacing cysteine with N-acetylcysteine. It is obtained in the form of a colorless oil corresponding to a hemihydrate.

Analysis for C9H18N204S, 'A H20:

Calculated: C 41.68 H 7.38 N 10.80 S 12.36%

Found: C 41.66 H 7.25 N 10.84 S 12.43%

15 Example 6:

(2-hydroxyethylamino) -2 ethylthioacetic acid: compound 23

An equimolecular mixture of ethyl thioglycolate and N- (2-hydroxy-2-ethyl) aziridine in methanol is brought to boiling for 2 h under a nitrogen atmosphere. The reaction mixture is concentrated under reduced pressure and the residue is stirred in a 2N aqueous potassium hydroxide solution containing a little ethanol. 24 h after, the pH is brought back to 4 by addition of HCl. The reaction mixture is concentrated under reduced pressure and the residue dissolved in boiling ethanol. The crystals formed by cooling are filtered and dried (yield = 50%).

Melting point: 110 ° C.

Analysis for C6HI3N03S:

Calculated: C 40.21 H 7.31 N 7.82 S 17.89% 30 Found: C 40.07 H 7.07 N 7.64 S 17.86%

Example 7:

N- (o-aminophenylthio-2 ethyl) P-hydroxyethylamine: compound 27

A methanolic solution of 3.48 g of N- (2-hydroxyethyl) -aziridine is gradually added to 5 g of o-aminothiophenol dissolved in methanol. After 72 h at room temperature, the reaction mixture is concentrated and the residue, dissolved in benzene, is filtered through silica gel. 8 g of a pale yellow oil are obtained.

Analysis for C10Hi6N2OS:

Calculated: C 56.57 H 7.59 N 13.19 S 15.10%

Found: C 56.39 H 7.81 N 13.02 S 14.96%

45 Examples 8 to 11:

N- (2-benzylthioethyl) -bis- (2-hydroxyethyl) amine: compound 38

A solution of 50 g of 2-benzylthioethylamine in 150 ml of absolute alcohol, brought to the temperature of 50 ° C., is placed in a reactor equipped with a brine refrigerant and a diffuser. After having purged the solution with a stream of nitrogen, a slow stream of ethylene oxide is passed until the end of absorption by the solution. Nitrogen is bubbled again, then the solution is concentrated under reduced pressure and the oily residue is dried over phosphoric anhydride. 74 g of an oil are obtained, the analysis and NMR spectrum of which correspond to the expected product.

Analysis for CI3H21N02S:

Calculated: C 61.14 H 8.29 N 5.49 S 12.56% m Found: C 60.93 H 8.34 N 5.64 S 12.40%

The compounds 3, 4 and 25 obtained in the form of colorless hygroscopic oils are prepared under the same conditions.

(Table at the top of the next page)

Example 12:

65

N- (ben: ylthio-2 ethyl) -bis- (hydroxy-2propyl) amine: compound 40

To a solution of 16.7 g of 2-benzylthioethylamine in ethanol at 96 C cooled to 0 C, added dropwise with stirring

13

639,556

Example

Compound No.

Yield (%)

Analysis: Calculated (%) Found (%)

VS

H

NOT

S

9

3

60

43.07

8.77

7.17

16.42

43.17

8.75

7.20

16.36

10

4

70

39.79

8.11

6.63

15.18

39.60

8.28

6.53

15.04

11

25

99

47.81

8.36

9.29

10.64

(hemihydrate)

47.98

8.26

9.26

10.90

3 Eq of propylene oxide. The reaction mixture is brought to 30 ° C for 6 h, then it is concentrated under reduced pressure and the residual oil obtained is dried in a desiccator containing phosphoric anhydride.

28 g of a pale yellow oil are collected. 20

Analysis for ClsH25N02S:

Calculated: C 63.56 H 8.89 N4.94 S 11.31%

Found: C 63.76 H 8.74 N5.08 S 11.55%

Examples 13-24: 25

N- (2-methylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine:

compound 5

3 Eq of propylene oxide are added dropwise at a temperature below 10 ° C. and with stirring to an aqueous solution of 2-methylsulfinylethylamine (10.7 g). The mixture is allowed to return to ambient temperature and is left to stand for 30 h (the progress of the reaction is followed by thin layer chromatography). Then concentrated on a rotary evaporator and the residual oil is dried in a desiccator under vacuum and on phosphoric anhydride. 21.5 g of a colorless oil are thus obtained.

Analysis for Ct, H21N03S:

Calculated: C 48.40 H 9.48 N 6.27 S 14.36%

Found: C 48.48 H 9.30 N6.12 S 14.23%

The compounds collected in Table II are prepared in the same way:

Table II

Example

Compound No

Yield (%)

Analysis: Calculated (%) Found (%)

VS

H

NOT

S

14

7

99

56.61

9.93

6.00

13.73

56.42

9.84

5.94

13.50

15

8

671

52.98

9.29

5.61

12.85

52.70

9.06

5.44

12.71

16

10

98

50.60

9.76

5.90

13.50

50.22

9.99

5.59

13.20

17

11

99

47.40

9.15

5.52

12.65

47.10

9.35

5.74

12.50

18

17

402

48.43

8.13

8.69

9.94

48.41

8.45

8.65

9.78

19

24

502

47.79

8.42

5.57

12.76

47.63

8.26

5.39

12.50

20

26

903

52.47

8.80

8.74

10.00

52.56

8.66

8.87

10.13

21

30

983

59.12

8.50

9.84

11.27

59.04

8.29

9.94

11.29

22

33

982

54.35

7.60

4.22

9.67

(monohydrate)

54.22

7.60

4.52

9.74

23

34

822

49.29

7.44

3.83

(dihydrate)

49.53

7.82

3.67

24

41

701

58.41

8.49

4.54

10.39

(hemihydrate)

58.77

8.42

4.34

9.87

1 Purified by passage over silica gel.

2 1 Eq of sodium hydroxide is added at the start and 1 Eq of hydrochloric acid after the end of the reaction. The reaction mixture is filtered through an acid exchange resin.

3 Reaction solvent: methanol.

639,556

14

Example 25:

N- (2-benzylthioethyl) N- (2-hydroxyethyl) 2-hydroxypropylamine: compound 42

A mixture of 3.3 g of compound 37 in ethanol (30 ml) is added for 24 h, added with 1 g of propylene oxide in water (15 ml). It is concentrated under reduced pressure and the residual viscous liquid is dried in a desiccator. 3.8 g of compound 42 are obtained.

Amine number: Calculated: 3.72 mEq / g Found: 3.72 mEq / g

Example 26:

N- (2-benzylthio ethyl) -bis- (2,3-dihydroxypropine) amine:

compound 39

A mixture of 2-benzylthio-ethylamine (13 g) and excess glycidol (14.5 g) in toluene (200 ml) is brought to the boil for 3 h; the product formed settles on cooling in the form of an oil. This is separated from the toluene phase and washed with benzene. 24.5 g of compound 39 are thus obtained in the form of a monohydrate.

Amine number: Calculated: 3.02 mEq / g Found: 3.02 mEq / g

Examples 27 and 28:

N- (2-methylsulfinyl-ethyl) -bis- (2,3-dihydroxy propyl) amine: compound 6

A solution of 14 g of 2-methylsulfinylethylamine and 19.5 g of glycidol in 50 ml of ethanol is brought to the boil for 8 h. The reaction mixture is concentrated under reduced pressure and the oily residue obtained is purified by passage over silica gel. 32 g of compound 6 are collected.

Analysis for C9H21NOsS:

Calculated: C 42.33 H 8.29 N5.49 S 12.56%

Found: C 42.11 H 8.54 N5.46 S 12.37%

Compound 43 is prepared in the same way, which is obtained with a yield of 60% in the form of hemihydrate.

Analysis for C14H23N03S, lA H20:

Calculated: C 57.06 H 8.15 N 4.75 S 10.89%

Found: C 56.98 H 8.13 N 4.63 S 10.57%

Example 29:

N- (o-aminophenylthio-2 ethyl) -bis- (2,3-dihydroxy) amine: compound 29

A solution of 16.8 g of 2-o-aminophenylthioethylamine and 14.8 g of glycidol in ethanol at 96 ° is left for 6 d at room temperature. The reaction mixture is concentrated under reduced pressure and the oily residue is washed with toluene, then dried in a desiccator in the presence of phosphoric anhydride. 29 g of compound 29 are thus obtained.

Analysis for C14H24N204S:

Calculated: C 53.14 H 7.64 N 8.85 S 10.13%

Found: C 52.88 H 7.61 N 8.76 S 9.94%

Example 30:

Acetamido-2 acid [bis- (2,3-dihydroxy propyl) 2-amino-ethyl-thio] -3 propionic: compound 18

A solution of 20.6 g of 2-acetamido-3-aminoethylthio-3-propionic acid, 4 g of sodium hydroxide and 14.8 g of glycidol in 50% aqueous ethanol is heated for 7 h at a temperature of 40 ° C. 1 Eq of hydrochloric acid is added and purified by passage over an ion exchange resin (H +). After concentration of the solvent under reduced pressure, 19 g of a viscous liquid are obtained which crystallizes in the form of a monohydrate melting at 90 ° C.

Analysis for C13H26N207S, H20:

Calculated: C 41.92 H 7.58 N 7.52 S 8.61%

Found: C 41.84 H 7.57 N 7.62 S 8.87%

Example 31:

Benzoic [bis- (2,3-dihydroxypropyl) amino-2-ethylsulfinyl] -2 acid: compound 36

This compound is prepared in the same way as compound 18 (Example 30) from glycidol and 2-aminoethylsulfinyl-2 benzoic acid.

Preparation of P ~ 2-aminoethylsulfinyl benzoic acid

A solution of 8.6 g of ethylene imine in 200 ml of ethanol is slowly added at 35 ° C. under a nitrogen atmosphere to an ethanolic solution of thiosalicylic acid (30.8 g). The p-aminoethyl-2-thio-benzoic acid formed precipitates progressively. It is drained and crystallized from a mixture of water and acetonitrile. 37 g of crystals are obtained, melting at 120 ° C. (monohydrate), with the formation of the anhydrous product which decomposes from 200 ° C.

21.5 g of this product are dissolved in acetic acid, then 10 ml of 110% hydrogen peroxide are added dropwise at 0 ° C. The mixture is left for 5 d at room temperature, then it is concentrated under reduced pressure and the residue crystallizes in water. 19.5 g of 2-aminoethylsulfinyl-benzoic acid are collected, which melts at 240 ° C.

Analysis for CgHnNOjS:

Calculated: C 50.68 H 5.19 N6.56 S 15.03%

Found: C 50.58 H 5.35 N6.75 S 15.07%

Compound 36 is obtained in the form of a yellow oil corresponding to a hemihydrate.

Analysis for C15H23N07S, Vi H20:

Calculated: C 48.63 H 6.52 N 3.78%

Found: C 48.60 H 6.89 N 3.71%

Examples of salt preparation.

Example 32:

N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) amino hydrochloride: compound 38a

A solution (45 ml) of 4N hydrochloric acid in ethanol is added to an ethanolic solution of compound 38 (38 g). After 2 h at ordinary temperature, the solution obtained is concentrated and the residue is crystallized from 1,2-dichloroethane. After drying, 33 g of compound melting at 77 ° C. are collected.

Analysis for C13H22C1N02S:

Calculated: C 53.50 H 7.60 N 4.80 S 10.99%

Found: C 53.33 H 7.58 N4.57 S 10.82%

Examples 33 and 34:

N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) amino hydrochloride: compound 40a

30 ml of a 4N solution of hydrochloric acid in ethanol are added to 30 g of compound 40, dissolved in chloroform. It is left to stand for 2 h at ordinary temperature, then 80 ml of ether are added: compound 40a crystallizes. After filtration and drying, 30 g of crystals melting at 95 ° C. are collected.

Analysis for Ci5H26C1N02S:

Calculated: C 56.32 H 8.19 N 4.38 S 10.02%

Found: C 56.32 H 7.96 N4.41 S 10.08%

According to the same procedure, hydrochloride 42a is obtained from compound 42, which melts at 88 ° C.

Analysis for C14H24C1N02S:

Calculated: C 54.97 H 7.91 N4.58 S 10.48%

Found: C 54.72 H 7.95 N4.52 S 10.52%

5

10

15

20

25

30

35

40

45

50

55

60

65

15

639,556

Examples 35 and 36:

N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium gentisate: compound 40b

A methanolic solution containing 4.6 g of gentisic acid is added to 8.5 g of compound 40 dissolved in methanol and the mixture is stirred for 1 h at ordinary temperature. The solution obtained is concentrated under reduced pressure and the residue is filtered and washed with ether. 12.9 g of white crystals, melting at 59 ° C., are obtained after drying.

Analysis for C22H31N06S:

Calculated: C 60.38 H 7.14 N3.20 S 7.32%

Found: C 60.38 H 7.16 N 3.41 S 7.34%

Compound 27b is prepared in the same way, starting from compound 27 and p-chlorophenoxyisobutyric acid: it is in the form of whitish crystals melting at 58 ° C.

Analysis for C20H27C1N204S:

5 Calculated: C 56.26 H 6.37 N6.56 S 7.51%

Found: C 56.03 H 6.49 N 6.51 S 7.70%

Examples 37 to 59:

According to the same procedure as that described in Examples 32 to 36, the salts of compounds 7, 26, 27, 38 and 40 were also prepared, which are collated in Table III (the salts are oily or semi-solid and strongly hygroscopic).

Table III

Example

Compound #

Brute formula

Analysis: Calculated (%) Found (%)

VS

h n

s

37

7a c15h29no8s

46.98

7.62

3.65

8.36

46.75

7.67

3.38

8.13

38

7b c21h34cino5s

56.29

7.64

3.12

7.15

56.00

7.46

2.93

6.98

39

26a c14h29cin2o4s

47.11

8.19

7.85

8.98

46.94

8.31

7.73

8.90

40

26c c24h39cin2o7s, h2o

52.11

7.47

5.06

5.79

51.97

7.46

4.84

6.08

41

26d c32Hs2N4oi3S2

49.59

8.06

7.22

8.27

49.38

8.36

7.12

8.32

42

26th

C32H62N4oi4S2, 2H20

46.47

8.04

6.77

7.75

46.25

8.09

6.81

8.05

43

27a c17h22n2o5s

55.72

6.05

7.64

8.75

55.53

6.16

7.72

8.58

44

27c c24H38n407S2

51.59

6.85

10.02

11.47

51.57

6.98

10.27

11.33

45

27th c14h22n2o6s

48.54

6.40

8.08

9.25

48.25

6.68

8.01

9.22

46

27d c24h38n4o8s2

50.15

6.66

9.94

11.16

50.31

6.65

10.26

11.37

47

38b c16h25no5s

55.95

7.33

4.07

9.33

55.85

7.30

4.17

9.50

48

38c c23h32cino5s

58.77

6.86

2.98

6.82

58.74

7.06

2.96

6.92

49

38d c18h28n2o5s, h2o

53.71

7.51

6.96

53.88

7.50

6.96

50

38th c17h27no7s

52.42

6.98

3.59

8.23

52.25

6.90

3.76

8.17

51

38f c20h27no6s

58.66

6.64

3.42

7.83

58.86

6.71

3.57

7.85

52

38g ci9h3ino9s

50.76

6.95

3.11

7.13

50.96

7.20

3.03

7.33

53

38h c18h27no7s, h2o

51.53

6.96

3.34

7.64

51.68

6.82

3.58

7.92

54

40c ci9h3ino7s

54.65

7.48

3.35

7.67

54.75

7.51

3.40

7.70

55

40d c19h33no5s

58.88

8.58

3.61

8.27

58.75

8.59

3.77

8.12

56

40th

C18H29NOsS

58.19

7.86

3.77

8.63

58.10

7.61

3.82

8.93

57

40f c20h31no7s, h2o

53.67

7.43

3.12

7.16

53.54

7.30

3.12

7.33

639,556

16

Table III (continued)

Example

Compose #

Brute formula

Analysis: Calculated (%) Found (%)

VS

h n

s

58

40g c21h33no8s, h2o

52.81

7.38

2.93

6.71

52.60

7.36

3.29

6.73

59

40h c19h33no5s

58.88

8.58

3.61

8.27

58.75

8.24

3.48

8.38

Examples of compositions.

Triethanolamine q.s.p. pH 8

Example A - Cream for oily skin.

15

Methyl parahydroxybenzoate

0.1g

Compound 38c

1.5g

Propyl parahydroxybenzoate

0.1g

Benzalkonium chloride

0.3 g

Water q.s.p.

100g

Glycol stearate

1 g

Compound 31 can be replaced by Compound 32 in this

Cetyl alcohol

4g

composition.

20 mol polyoxyethylene stearate

20

ethylene oxide

6g

Example F— Powder shampoo.

Isopropyl palmitate

10g

Sodium lauryl sulfate

40 g

Calophyllum oil

1 g

Fatty acid condensation product

Preservative (parahydroxybenzoates)

0.3 g

25

copra on sodium isocyanate,

Perfume q.s.

marketed under the name of

Sterile demineralized water q.s.p.

100g

Hostapon K.A. by Hoechst

39g

Daily application of this cream improves

Compound 12

10 g definitely the oily appearance of the skin. A comparable effect can be

Perfume

1 g obtained by replacing compound 38c with compounds 40d, 40f

30

or 40g.

Example G - Styling Gelfluide, for Application

daily.

Example B - Hair lotion for oily hair.

Vinylpyrrolidone / acetate copolymer

Compound 40

0.8 g

vinyl (70/30)

2g

Calcium pantothenate

0.5 g

35

Oxyethylenated lanolin using

Perfume

0.1g

5 to 20 mol of ethylene oxide

1 g

40% aqueous ethyl alcohol q.s.p.

100 ml

Polyethylene glycol 300

5g

Example C - Dermatological bread.

Compound 7

Methyl parahydroxybenzoate

0.5 g 0.1g

Alkanoyloxyethanesulfonate

80g

40

Propyl parahydroxybenzoate

0.1g

Lantrol: liquid fraction of lanolin (Malmstrom)

12 g t-Butylhydroxytoluene

0.1g

Purcellin oil: branched esters

t-Butylhydroxyanisole

0.2 g fatty acids (Dragoco)

2g

Perfume

0.1g

Bis-N- (oxypyridyl-2) camphosulfonate

Water q.s.p.

100 ml thio) aluminum

0.05 g

Titanium dioxide

2g

45

Example H— Hair lotion for oily hair.

Perfume

2.5g

Lotion to use after shampooing, on wet hair, before

Compound 30

3g

styling.

Compound 30 can be replaced by compounds 27a or 27b.

Vinyl acetate / vinyl copolymer

Example D - Lotion for daily use for the care of oily hair.

50

pyrrolidone (30/70) Compound 30 Perfume

1.5 g 1 g 0.1 g

Pyridoxine camphosulfonate

0.3 g

Perfume

0.1g

Ethanol 25% q.s.p.

100 ml

Dye

0.1g

Compound 26b

0.4 g

55

Example I— Milk for oily skin.

50% ethyl alcohol q.s.p.

100 ml

Compound 33

2.6g

Compound 26b can be replaced by compounds 26d or 26e

Known cross-linked polyacrylic acid

at the concentration of 0.7 g.

under the brand name Carbopol 934 Isopropyl ester of fatty acids

0.375 g

Example E - Milk for oily skin.

60

lanolin

1 g

Compound 31

1.4 g

Oxyethylenated lanolin using

Crosslinked polyacrylic acid marketed

5 to 20 mol of ethylene oxide

2.5 g under the brand Carbopol 934

0.375 g

Oxyethylenated cetylstearyl alcohol

3g

Isopropyl ester of lanolin fatty acids

1 g

Coconut monoethanolamide

2g

Oxyethylenated lanolin using 5 to 20 mol

65

Triethanolamine q.s.p. pH 8

ethylene oxide

2.5g

Methyl parahydroxybenzoate

0.1g

Oxyethylenated cetylstearyl alcohol

3g

Propyl parahydroxybenzoate

0.1g

Myristic monoethanolamide

2g

Water q.s.p.

100 ml

17

639,556

Example J— Clear liquid shampoo.

Polyethoxylated lauryl alcohol (12 mol ethylene oxide)

Coconut diethanolamide Quaternized vinylpyrrolidone copolymer marketed under the name of Gafquat 755 by GAF Compound 38f Parfum Eau q.s.p.

In this example, compound 38f can be replaced with the same amount of compound 40c.

13 g 4g

0.4 g 3g

0.2 g 100 ml

Example K— Cream shampoo.

Sodium lauryl sulfate 12 g

Condensation product of copra fatty acids on methyltaurine, paste marketed under the name Hostapon C.T. by the company Hoechst 40 g

Lauro monoethanolamide 2 g

Glycerol monostearate 4 g

Compound 39 2 g

Perfume 0.2 g

Lactic acid q.s.p. pH 6.5

Water q.s.p. 100g

Example L - Pearly liquid shampoo.

Oxyethylenated sodium lauryl sulfate

2.2 mol of ethylene oxide 9 g

Sodium monolaurylsulfosuccinate 1 g

Polyethylene glycol distearate 2 g

Diethanolamide lauric 2 g

Compound 5 4 g

Perfume 0.3 g

Water q.s.p. 100g

Compound 5 can be replaced by compounds 6 or 24. Example M - Cream for oily hair.

Polyoxyethylenated stearate (Myrj 49)

3g

Glycerol monostearate

4g

Cetyl alcohol

7g

Vaseline oil

8g

Isopropyl myristate

5 g

Compound 38d

12 g

Methyl parahydroxybenzoate

0.3 g

1% polyacrylic acid solution

crosslinked sold under the trade name Carbopol 941 by the company Goodrich 40 g

Triethanolamine q.s.p. pH 6.5

Water q.s.p. 100g

This cream is applied to the scalp after shampooing. Massage lightly, leave to stand for about 15 minutes, then rinse.

In this example, the active compound can be advantageously replaced by the same amount of the compound 40h.

Example N - Lotion for oily skin.

Compound 38

50% pyrrolidonecarboxylic acid

Water-soluble neo-purcellin: branched esters of polyethoxylated fatty acids (4 mol of ethylene oxide) 0.5 g

Perfume q.s.

Conservative

Water q.s.p.

Compound 38 can be replaced by compounds 39 or 40.

Example O - Lacquer for oily hair.

A lacquer is prepared according to the invention by mixing the following ingredients:

Poly (vinylpyrrolidone / vinyl acetate) resin sold under the trade name E 335 by the company *

General Anilin 10 g

Compound 37a 0.5 g

Methylcellosolve 2 g

Absolute alcohol q.s.p. 100g

Example P - Treatment lotion for the skin.

Compound 40 15 Nicotinic acid

Benzalkonium chloride Ethyl alcohol Polyethylene glycol Perfume q.s.

20 Soluble dyes q.s.

Sterile demineralized water q.s.p.

Example Q - Cream for oily skin. Polyoxyethylenated sorbitan monostearate 25 (Tween 60)

Self-glyceryl monostearate

emulsifiable Stearyl alcohol Stearic acid 30 Vaseline oil

Sweet almond oil Triethanolamine Compound 16 Perfume 35 Water q.s.p.

Example R - Lotion for oily skin.

Compound 39 T ranssulfolanediol 40 Dioxy-3,6 octanol Ethanol

5-amino-3-thia-hexanedioic acid Water q.s.p.

45 Example S - Cream for oily skin.

Sipol wax

Glyceryl monostearate Polyisobutylene hydrogenated Vaseline oil 50 Cetyl alcohol Purcellin oil Preservative Compound 13 Salicylic acid 55 Water q.s.p.

Example T - Mask for oily skin.

1.8 g 0.8 g 0.2 g 13 ml 10 g

100g

1 g

6g 1.5g 2g 15g 2g 0.1g lg 0.4g 100g

0.4 g 0.4 g 10 g

9g 0.3g 100g

5g 2g 3g 3g 1 g 3.5 g 0.3 g 1.4 g 0.9 g 100 ml

Compound 30

2g

5-amino-3-thia-hexanedioic acid

1.2 g g

60 Gelatin lg g

Tragacanth gum lg

Bentonite

4g

Kaolin

26 g g

Titanium dioxide

2g

65 Camphor

0.04 g g

Colorant q.s.

g

Perfume q.s.

Sterile demineralized water q.s.p.

100g

639,556

18

Example U— Liquid shampoo.

A liquid shampoo is prepared (leave on for 5 minutes before final rinsing) by mixing:

Lauryl alcohol polyglycerolated (4 mol glycerol)

Quaternized vinylpyrrolidone copolymer sold under the name Gafquat 755 by GAF Compound 12

Polyethoxylated alkylamine marketed under the name Ethomeen 18/15 by Rhône Progil Lactic acid q.s.p. pH 6 Perfume q.s.

Water q.s.p.

15g

0.4 g 3.6 g

0.8 g

100 ml

Example V - Treatment mask for oily skin.

Oxyethylenated lanolin using 5 to 20 mol of ethylene oxide 5 g

Cetyl alcohol 2 g

Self-emulsifying ethylene glycol stearate 7 g

Vaseline Codex 5 g

Kaolin 10 g

Titanium oxide 8 g

Preservative 0.3 g

Compound 40 1.4 g

Glutamic acid 0.8 g

Water q.s.p. 100g

Example W— Face lotion.

A lotion intended to combat the oily appearance of the face is prepared by mixing the following ingredients:

Compound 27a 1 g

Propylene glycol 2 g

20

25

30

Sodium ethylenediaminotetracetate 0.1 g

Ethyl alcohol 16 g

Methyl parahydroxybenzoate 0.1 g

Propyl parahydroxybenzoate 0.1 g Perfume q.s.

Colorant q.s.

Water q.s.p. 100 g Compound 27a can be replaced by compound 40b.

Example X— Cream for oily skin.

Cetyl alcohol 5 g

Isopropyl palmitate 6 g

Vaseline oil. 6 g Polyoxyethylene sorbitan monostearate

(Tween 60) 4.5 g

Glyceryl monostearate 2 g

Preservative 0.3 g

Compound 25 1.6 g

Aspartic acid 0.8 g

Sterile demineralized water q.s.p. 100g

Compound 25 can be replaced by compounds 40, 26 or 38.

Example Y— Lotion for oily skin.

Compound 19

Hyamine 10 X: diisobutylcresoxy chloride-

ethoxyethyldimethylbenzylammonium Salicylic acid

Polyethylene glycol tertiododecylthioether Miranol C2M (hydroxyethylcarboxymethyl-

2-alkylimidazolinium)

Perfume q.s.

Sterile demineralized water q.s.p.

Compound 19 can be replaced by compound 31.

0.8 g

0.3 0.2 g 0.1g

10g

100g

R

Claims (23)

639,556 1. N- (2-methylthioethyl) p-hydroxyethylamine 1. N- (2-methylthioethyl) P-hydroxyethylamine 1. Cosmetic composition for combating the fatty state of the hair and of the skin, characterized in that it contains, in combination, in an appropriate cosmetic vehicle, at least one active compound corresponding to the following general formula: R2 I r, - s - ch2 - ch2 - n - ch2 - ch - r3 (i) I I (0) n oh in which: n is 0.1 or 2, R2 represents either a hydrogen atom or a radical taken from the group consisting of -CH2 - CH2OH, -CH2 - CH - CH3 I oh and -CH2 - CH - CH2OH, I Oh R3 represents either a hydrogen atom, or a radical taken from the group consisting of - CH3 and - CH2OH, and R! represents a radical taken from the group consisting of: i) -CH3, ii) -CH, - CH = CH2, iii) -CH2 - CH2OH, iv) - (CH2) m - CH - COOH, I nh - r4 m being 1 or 2 and R4 representing a hydrogen atom or the radical —CORs, Rs being an alkyl radical, saturated or unsaturated, having from 1 to 8 carbon atoms, v) - CH2 - COR6, R6 representing a radical —OH or -NC r 'and r ", identical or different, representing a hydrogen atom or an alkyl radical having from 1 to 5 carbon atoms or r' and r" together forming a divalent radical of formula - (CH,) 2 - O - (CH2) 2-, or of formula - (CH2) 5-, vi) -CH2 vii) R7 representing either the - NH2 radical or the --COOH radical. 2. N- (2-methylsulfinylethyl) p-hydroxyethylamine 2. N- (2-methylsulfinylethyl) p-hydroxyethylamine 2. Composition according to claim 1, characterized in that the active compound is in partially or totally salified form using a mineral or organic acid. 2 claims 3. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxyethyl) amine 3 639,556 30. N- (o-aminophenylthio-2 ethyl) -bis- (2-hydroxypropyl) amine 31. Benzoic acid (2-hydroxyethylamino-2 ethylthio) -2 32. Benzoic (2-hydroxyethylamino-2-ethylsulfinyl) -2 acid 33. Benzoic [bis- (2-hydroxypropyl) amino-2-ethylthio] -2 acid 34. [bis- (2-hydroxypropyl) amino-2-ethylsulfinyl] -2 acid benzoic 35. Acid [bis- (2,3-dihydroxypropyI) 2-aminoethylthio] -2 benzoic 36. Acid [bis- (2,3-dihydroxy propyl) 2-amino-ethylsulfinyl] -2 benzoic 37. N- (benzyIthio-2 ethyl) P-hydroxyethylamine 37a. N- (2-benzylthioethyl) P-hydroxyethylaminechlorohydrate 38. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) amine 38a. N- (2-benzylthioethyl) -bis- (2-hydroxyethyl) amino hydrochloride 38b. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-pyruvate 38c. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium- p-chlorophenoxyisobutyrate 38d. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium- pyrrolidonecarboxylate 38e. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-malate 38f. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium gentisate 38g. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-glucuronate 38h. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) 2-ammoniumoxo glutarate 39. N- (benzyIthio-2 ethyl) -bis- (2,3-dihydroxy propyl) amine 40. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) amine 40a. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) aminechlor-hydrate 40b. N- (benzyIthio-2 ethyl) -bis- (2-hydroxypropyl) ammonium gentisate 40c. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-malate 40d. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium- a-hydroxyisobutyrate 40e. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium-pyruvafe 40f. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) 2-ammoniumoxo glutarate 40g. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-ascorbate 40h. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- 3-hydroxy butyrate 40i. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- camphosulfonate 40d. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- amino-5 thia-3 hexanedioate 40k. N- (2-benzylthio ethyl) -bis- (2-hydroxypropytyammonium-nicotinate 401. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-salicylate 41. N- (2-benzylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine 42. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2-hydroxy propylamine 42a. N- (2-benzylthioethyl) N- (2-hydroxyethyl) 2-hydroxypropylaminechlorohydrate 43. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2,3-dihydroxy propylamine 3. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxyethyl) amine 3. Composition according to claim 2, characterized in that the mineral or organic acid is taken from the group consisting of: hydrochloric acid, hydrobromic acid, tartaric acid, malic acid, acid nicotinic, salicylic acid, N-oxonicotinic acid, palmitic acid, gentisic acid, pyrrolidonecarboxylic acid, ascorbic acid, parachlorophenoxyisobutyric acid, retinoic acid, acid a -hydroxyisobutyri-que, a- and ß-hydroxybutyric acid, 5-amino-3-thia-hexane-dioic acid, pyruvic acid, glycolic acid, citric acid, aspartic acid, glutamic acid, oxoglutaric acid, camphosulfonic acid, thiodiglycolic acid and uronic acids. 4. N- (2-methylsulfonylethyl) -bis- (2-hydroxyethyl) amine 4 R3 represents either a hydrogen atom or a radical taken from the group consisting of - CH3 and - CH2OH, and R represents a radical taken from the group consisting of: i) -CH3, ii) -CH2 - CH = CH2, iii) -CH2 - CH2OH, iv) - (CH2) m - CH - COOH, NH - R4 m being 1 or 2 and R4 representing a hydrogen atom or the radical - CORs, Rs being an alkyl radical, saturated or unsaturated, having from 1 to 8 carbon atoms, v) - CH2 - COR6, R6 representing a radical —OH or r 'and r ", identical or different, representing a hydrogen atom or an alkyl radical having from 1 to 5 carbon atoms or r' and r" form together a divalent radical of formula - (CH2) 2 - O - (CH2) 2-, or of formula - (CH2) 5—, vi) -CH2- (3 in this case, R2 only represents a hydrogen atom when R3 represents a hydrogen atom, and vii) - R7 representing either the radical —NG2 or the radical —COOH, in the latter case R2 and R3 in the same compound being different from a hydrogen atom. 4. N- (2-methylsulfonylethyl) -bis- (2-hydroxyethyl) amine 4. Composition according to one of claims 1 to 3, characterized in that the active compound is taken from the group consisting of the following compounds: 5 639,556 38g. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-glucuronate 38h. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) 2-ammoniumoxo glutarate 39. N- (2-benzylthioethyl) -bis- (2,3-dihydroxy propyl) amine 40. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) amine 40a. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) aminechlor-hydrate 40b. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium gentisate 40c. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-malate 40d. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- a-hydroxyisobutyrate 40e. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium-pyruvate 40f. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) 2-ammoniumoxo glutarate 40g. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-ascorbate 40h. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- 3-hydroxy butyrate 40i. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- camphosulfonate 40d. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium- amino-5 thia-3 hexanedioate 40k. N- (2-benzylthio ethyl) -bis- (2-hydroxypropyl) ammonium-nicotinate 401. N- (2-benzylthioethyl) -bis- (2-hydroxypropyl) ammonium-salicylate 41. N- (benzylsuI-2-ethyl) -bis- (2-hydroxypropyl) amine 42. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2-hydroxy propylamine 42a. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2-hydroxypropylaminechlorohydrate 43. N- (2-benzylthio ethyl) N- (2-hydroxyethyl) 2,3-dihydroxy propylamine 5 5. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine 5 5. Composition according to one of claims 1 to 4, characterized in that it contains the active compound at a concentration of between 0.1 and 20% and preferably between 1 and 10% relative to the total weight of the composition. 5 5. N- (2-methylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine 6. N- (2-methylsulfinyl ethyl) -bis- (2,3-dihydroxy propyl) amine 6. Composition according to one of the preceding claims, characterized in that it contains the active compound, in suspension or in solution in water, in an alcohol, in a hydroalcoholic solution, in an oil, an emulsion or in a gel and constitutes a hair composition for the maintenance of the scalp. 6. N- (2-methylsulfinyl ethyl) -bis- (2,3-dihydrqxy propyl) amine 7. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) amine 7a. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) ammoniumtartrate 7b. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) ammonium-p-chlorophenoxyisobutyrate 7. Composition according to one of the preceding claims, characterized in that it contains the active compound in alcoholic or hydroalcoholic solution in combination with a traditional cosmetic resin. 7. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) amine 7a. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) ammonium tartrate 7b. N- (2-allylthio ethyl) -bis- (2-hydroxypropyl) ammonium-p-chloro-phenoxyisobutyrate 8. N- (2-allylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine 8. Composition according to claim 7, characterized in that the traditional resin is taken from the group consisting of: polyvinylpyrrolidone, copolymers of polyvinylpyrrolidone and vinyl acetate; copolymers of vinyl acetate and an unsaturated carboxylic acid such as ero tonic acid; copolymers resulting from the polymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester; the copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an alkyl vinyl ether, and the copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long carbon chain acid or an allyl or methallyl ester of a long carbon chain acid. 8. N- (2-allylsulfinyl ethyl) -bis- (2-hydroxypropyl) amine 9 '. N- (2-allylthio ethyl) -bis- (2-hydroxyethyl) ammoniumglutamate 9. N- (2-allylthio ethyl) -bis- (2,3-dihydroxy propyl) amine 9. Composition according to one of claims 7 or 8, characterized in that it contains a propellant gas liquefied under pressure and constitutes an aerosol lacquer. 9 '. N- (2-allylthio ethyl) -bis- (2-hydroxyethyl) ammoniumglutamate 9. N- (2-allylthio ethyl) -bis- (2,3-dihydroxy propyl) amine 10 10. N- (P-hydroxyethylthio-2 ethyl) -bis- (2-hydroxypropyl) amine 10 10. Composition according to one of claims 7 or 8, characterized in that it contains in alcoholic or hydroalcoholic solution from 0.1 to 10%, but preferably from 1 to 3% of the active compound and from 0.1 10% resin. 10 10. N- (P-hydroxyethylthio-2 ethyl) -bis- (2-hydroxypropyl) amine 11. N- (P-hydroxyethylsulfinyl-2 ethyl) -bis- (2-hydroxypropyl amine 11. Composition according to one of claims 1 to 5, characterized in that it contains the active compound at a concentration of between 0.1 and 15%, but preferably between 1 and 10%, in mixture with at least an anionic, cationic, nonionic or amphoteric detergent and constitutes a treating shampoo. 11. N- (P-hydroxyethylsulfinyl-2 ethyl) -bis- (2-hydroxypropyl) - amine 12. N- (P-hydroxyethylamino-2 ethylthio) -3 alanine 12. Composition according to Claim 11, characterized in that the concentration of anionic, cationic, nonionic or amphoteric detergent is between 4 and 20%, but preferably between 5 and 10%, relative to the total weight of the composition . 12. N- (P-hydroxyethylamino-2 ethylthio) -3 alanine 13. [(2-hydroxypropylamino) -2 ethylthio] -3 alanine 13. Composition according to one of claims 1 to 5, for improving the appearance of the skin, characterized in that it contains the active compound, at a concentration between 0.1 and 15% and preferably between 1 and 5%, in an appropriate cosmetic vehicle. 13. [(2-hydroxypropylamino) -2 ethylthio] -3 alanine 14. [bis- (2-hydroxypropyl) 2-aminoethylthio] -3 alanine 14. Composition according to claim 13, characterized in that it is in the form of an aqueous or hydroalcoholic lotion of a cream, a milk, a gel, a dermatological bread or aerosol foam. 14. [bis- (2-hydroxypropyl) 2-aminoethylthio] -3 alanine 15 15. [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -3 alanine 15 15. Composition according to one of the preceding claims, characterized in that it also contains any traditional ingredient used in cosmetic compositions such as perfumes, dyes, penetration agents, surfactants, thickeners, emulsifiers, preservatives, cationic compounds, quaternary ammonium salts, vitamins, proteins, more or less hydrolyzed peptides and derivatives of starch or cellulose. 15 15. [bis- (2,3-dihydroxypropyl) 2-aminoethylthio] -3 alanine 16. Acetamido-2 acid [(2-hydroxyethylamino) -2 ethylthio] -3 propionic 16. Compounds characterized by the fact that they correspond to the following general formula: r2 I R, - S - CH2 - CH2 - N - CH2 - CH - R3 (la) I I (0) n oh in which: - n is 0.1 or 2, R2 represents either a hydrogen atom or a radical taken from the group consisting of ~ CH2 - CH2OH, -CH2 - CH - CH3 I OH and _CH2 - CH - CH2OH, I OH 16. Acetamido-2 acid [(2-hydroxyethylamino) -2 ethylthio] -3 propionic 17. Acetamido-2 acid [bis- (hydroxy-2 propyl) amino-2 ethylthio] -3 propionic 17. Compounds according to claim 16, characterized in that they are in the form of salts obtained using a mineral or organic acid. 17. Acetamido-2 acid [bis- (hydroxy-2 propyl) amino-2 ethylthio] -3 propionic 18. Acetamido-2 acid [bis- (2,3-dihydroxy propyl) 2-amino ethyl- thio] -3 propionic 18. Compounds according to claim 17, characterized in that the mineral or organic acid is taken from the group consisting of: hydrochloric acid, hydrobromic acid, tartaric acid, malic acid, acid nicotinic, salicylic acid, N-oxonicotinic acid, palmitic acid, ascorbic acid, para-chlorophenoxyisobutyric acid, retinoic acid, a-hydroxyisobutyric acid, a- acid and ß-hydroxybutyric acid, 5-amino-3-thia-hexanedioic acid, pyruvic acid, glycolic acid, citric acid, aspartic acid, glutamic acid, oxoglutaric acid, camphosulfonic acid , thiodiglycolic acid and uronic acids. 18. Acetamido-2 acid [bis- (2,3-dihydroxy propyl) 2-amino ethyl- thioj-3 propionic 19. 2-Amino acid [(2-hydroxyethylamino) -2 ethylthio] -4 butyric 19. Compounds according to claim 16 which are the following: 19. 2-Amino acid [(2-hydroxyethylamino) -2 ethylthio] -4 butyric 20. Process for preparing the compounds according to one of claims 16 to 19, characterized in that it consists in reacting in an polar solvent medium, an oxirane of formula: CH2 - CH - R3 in which R3 represents either a hydrogen atom or a radical taken from the group consisting of - CH3 and - CH2OH, on a compound of formula: Rt - S - CH2 - CH2 - NH - R2 I (0) „ in which: Ri, R2 and n have the same meanings as in claim 16. 20 25 30 35 40 45 50 55 60 65 20. 2-Amino acid [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -4 butyric 20 25 30 35 40 45 50 55 60 65 639,556 20 25 30 35 40 45 50 55 60 65 20. 2-amino acid [bis- (2,3-dihydroxy propyl) 2-amino ethyl- thio] -4 butyric 21. The method of claim 20, characterized in that the reaction is carried out at a temperature of 0 ° C to the boiling temperature of the solvent. 21. 2-amino acid [(2-hydroxypropyl) 2-aminoethylthio] -4 butyric 21. 2-amino acid [(2-hydroxypropyl) 2-aminoethylthio] -4 butyric 22. Process for preparing the compounds according to one of claims 16 to 19, characterized in that it consists in reacting a hydroxyalkyl halide of formula: X - CH2 - CH - R3 I OH in which X represents a chlorine or bromine atom and R3 represents either a hydrogen atom or a radical taken from the group consisting of - CH3 and - CH2OH, on a compound of formula: R, - S - CH2 - CH2 - NH - R2 I (0) „ in which R ,, R2 and n have the same meanings as in claim 16. 22. Amino-2 [bis- (hydroxy-2 propyl) amino-2 éthyIthioJ-4 acid butyric 23. Acid (2-hydroxyethylamino) -2 ethylthioacetic 24. [bis- (2-hydroxypropyl) amino] -2 ethylthioacetic acid 25. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (2-hydroxy ethyl) amine 26. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) amine 26a. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) amino hydrochloride 26b. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) ammoniumpyruvate 26c. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) ammonium-p-chlorophenoxyisobutyrate 26d. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (hydroxy-2 propyl) ammonium] malate 26e. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (2-hydroxypropyl) ammonium] tartrate 27. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylamine 27a. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium-gentisate 27b. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium- p-chlorophenoxyisobutyrate 27c. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -malate 27d. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -tartrate 27th. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium) -malate 28. N- (o-aminophenylthio-2 ethyl) -bis- (2-hydroxyethyl) amine 29. N- (2-o-aminophenylthio) -bis- (2,3-dihydroxy propyl amine 30. N- (o-aminophenylthio-2 ethyl) -bis- (2-hydroxypropyl) amine 33. [bis- (2-hydroxypropyl) amino-2 ethylthio] -2 benzoic acid 34. [bis- (2-hydroxypropyl) amino-2-ethylsulfinyl acid] -2 benzoic 35. Acid [bis- (2,3-dihydroxy propyl) 2-aminoethylthio] -2 benzoic 36. Acid [bis- (2,3-dihydroxy propy]) 2-aminoethylsulfinyl] -2 benzoic 37. N- (2-benzylthioethyl) P-hydroxyethylamine 37a. N- (2-benzylthioethyl) P-hydroxyethylaminechlorohydrate 38. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) amine 38a. ' N- (2-benzylthioethyl) -bis- (2-hydroxyethyl) amino hydrochloride 38b. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-pyruvate 38c. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium- p-chlorophenoxyisobutyrate 38d. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium- pyrrolidonecarboxylate 38e. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium-malate 38f. N- (2-benzylthio ethyl) -bis- (2-hydroxyethyl) ammonium gentisate 22. 2-Amino acid [bis- (2-hydroxypropyl) 2-aminoethylthio] -4 butyric 23. Acid (2-hydroxyethylamino) -2 ethylthioacetic 24. [bis- (2-hydroxypropyl) amino] -2 ethylthioacetic acid 25. N- [2-morpholinocarbonylmethylthio] -bis- (2-hydroxy ethyl) amine 26. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) amine 26a. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) amino hydrochloride 26b. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) ammoniumpyruvate 26c. N- [morpholinocarbonylmethylthio-2 ethyl] -bis- (hydroxy-2 propyl) ammonium-p-chlorophenoxyisobutyrate 26d. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (hydroxy-2 propyl) ammonium] malate 26e. di- [N- (morpholinocarbonylmethylthio-2 ethyl) -bis- (2-hydroxypropyl) ammonium] tartrate 27. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylamine 27a. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium-gentisate 27b. N- (o-aminophenylthio-2 ethyl) P-hydroxyethylammonium- p-chlorophenoxyisobutyrate 27c. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -malate 27d. di- [N- (o-aminophenylthio-2 ethyl) p-hydroxyethylammonium] -tartrate 27th. N- (2-o-aminophenylthio) p-hydroxyethylammonium) -malate 28. N- (o-aminophenylthio-2 ethyl) -bis- (2-hydroxyethyl) amine 29. N- (2-o-aminophenylthio) -bis- (2,3-dihydroxy propyl) - amine 23. Method for preparing the compounds according to one of claims 16 to 19, in which R2 = H, and n = 0, characterized in that it consists in reacting in a polar solvent medium a thiol of formula R, SH in which R, has the same meanings as in claim 16, on an N-hydroxyalkylaziridine of formula: CH2 - CH2 \ / NOT I CH2 I CH - OH I r3 in which R3 represents either a hydrogen atom or a radical taken from the group consisting of —CH3 and —CH2OH.