DE2924229A1 - COSMETIC PREPARATIONS FOR THE TREATMENT OF OIL HAIR AND OIL SKIN, SUITABLE ACTIVE SUBSTANCE COMPOUNDS AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAHl

PATENT LAWYERS
P.O. Box 8602 45 8000 Munich 86 2924229

June 15, 1979

Attorney's file: 30 166

L ¹ OREM.

Cosmetic preparations for the treatment of oily hair and skin, therefor suitable drug compounds and processes for their preparation.

Series 214

ι C * 9> 13272 Tektrammo; BmkkonUn: Hypo-Bank MUnchen 44101228 »

S »SJ'J BERGSTATFPATENT Manchen (BLZ 70O2O0I1) Swifi Code: HYPO DE MM

»*" * TELEX: Bay «Vweinsbank MUnchen 45J100 (BLZ 70020270)

^{n 3310} 0S24JiO BERG d Postichi?: * Manchen 653 43-808 (BLZ TCO10080)

909851/0904

- r-

DESCRIPTION

The invention relates to cosmetic preparations for combating oily hair and oily skin or of fat levels of the hair and skin.

It has already been suggested for the treatment of oily hair and skin using ß-aminoethanethiol to use derived thioethers with a primary amino group.

Of these compounds, in particular, the use of 2-S-benzylthio-ethylamine hydrochloride was used suggested.

It has now surprisingly been shown that the effectiveness of certain already known compounds amplified and at the same time their toxicity can be reduced, if one by the primary amino group at least one alkyl group substituted in the ß-position with respect to the nitrogen atom has a hydroxyl group.

The excellent effectiveness of the invention Connections were in no way expected as the 214 series

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substituted by non-hydroxylated alkyl groups Compounds have no effect, as will be made clear below.

The invention therefore relates to a cosmetic preparation for combating greasy and greasy hair Skin, which is characterized in that it is in combination with a suitable carrier material at least an effective compound of the general formula I below

R ₁ -S-CH ₉ -CH ₉ -N-CH ₉ -CH-Ro (I)

I ₁ Δ ti / i _t O

(O) _n OH

contains, in the
15 η O, 1 or 2,

R _{2 is} a hydrogen atom or a group of the following formulas -CH ₂ -CH ₂ OH, -CH ₂ -CH-CH ₃ or

OW

-CH ₂ -CH-CH ₂ OH

OH

R _{3 is} a hydrogen atom or a group of the following formulas -CH ₃ or -CH ₃ OH, and

R _{1 is} a group of the following formulas:

(i) -CH ₃ , 25th (ii)
(iii) -CH ₉ -CH ³ CH ₉ ,
-CH ₂ -CH ₂ OH, (iv) - (CH ₉ ) -CH-COOH,
λ m, Series 214 NH-R ₄

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(ν)

(vi)

«5

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where m is 1 or 2 and R.

a water material or a group of.

Formula -CORc is where R, - is a

saturated or unsaturated alkyl group

with 1 to 8 carbon atoms,

-CH ₂ -COR ₆ ,

wherein Rg is a group of the formula -OH or

of the formula -N '

represents

where r ¹ and r ", which can be identical or different, represent hydrogen atoms or alkyl groups with 1 to 5 carbon atoms or together represent a divalent radical of the following formula - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ ~ or the formula - (CH ₃ J ₅ represent,

-CH

and

(vii)

mean.

Series 214

in'der R _{7 is} either a group of the formula -NH ₂ or a group of the formula -COOH,

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The compounds according to the invention can be in the form of the free base or in the form of an addition salt with an inorganic or organic acid or as mixtures of these two forms will.

Suitable acids for the formation of these addition salts are: hydrochloric acid, Hydrobromic acid, tartaric acid, malic acid, nico

10 tinsic acid, salicylic acid, N-oxonicotinic acid,

Palmitic acid, gentisic acid, pyrrοlidoncarboxylic acid, Ascorbic acid, p-chlorophenoxyisobutyric acid, Retinoic acid, 0 (-hydroxyxsobutyric acid, oC- and ß-hydroxybutyric acid, 5-amino-3-thia-hexanedi-

15 acid. Pyruvic acid, glycolic acid, citric acid, Aspartic acid, glutamic acid, oxo-glutaric acid, camphor sulfonic acid, thiodiglycolic acid and the uronic acids.

Of the active compounds that can be used in the preparations according to the invention, the following are particularly preferred:

Connections No.

1. N- (2-methylthio-ethyl) -ß-hydroxyethylamine

2. N- (2-methylsulfinyl-ethyl) -β-hydroxyethylamine

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

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- sr -

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-dihydroxypropyl) -amine

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

7a.N- (2-allylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-

tartrate

10 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-dihydroxypropyl) -amine 9 '-.N- (2-allylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-

glutaraat

10. N- (2-ß-hydroxyethylthioethyl) bis (2-hydroxypropyl) amine

11. N- (2-ß-Hydroxyethylsulfinyl-ethyl) -bis (2-hydroxypropyl ) -amine

12. 3- (2-ß-Hydroxyethylamino-ethylthio) -alanine

13. 3- / 2- (2-Hydroxy-propylamino) -ethylthio_7-alanine

14. 3- / 2- (bis (2-hydroxy-propyl) -amino-ethylthiqj-alanine

15. 3- / 2-bis (2,3-c.ihydroxy-propyl) -amino-ethylthio-7-alanine

25 16. 2-Acetamido-3- / 2- (2-hydroxy-ethylamino) -äthylthio / -

propionic acid
17. 2-Acetamido-3- / 2-bis (2-hydroxy-propyl) -amino-

ethylthiq7-propionic acid
Series 214

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-St-

18. 2-Acetamido-3- / 2-bis (2,3-dihydroxypropyl) -amino-

ethylthio_ / - propionic acid
1 9. 2-Amino-4- / 2- (2-hydroxy-ethylamino) -äthylthiqT "-

butyric acid 5 20. 2-Amino-4- / 2-bis (2,3

21. 2-Amino-4- / £ 2- (2-hydroxypropyl) -amino-ethylthio.7-butyric acid

22. 2-Amino-4 - ^ - bis (2-hydroxypropyl) -amino-ethylthio / butyric acid

23. 2- (2-Hydroxy-ethyiamino) -ethylthio-acetic acid

24. 2- / BXS (2-hydroxypropyl) amino / ethylthioacetic acid

25. N-Z ^ -Morpholinocarbonylmethylthio-ethylZ-bis (2-hydroxyethyl) amine

26. N-Z ^ -Morpholinocarbonylmethylthio-ethylj-bis (2-hydroxypropyl) amine

2 6a. N - ^ - Morpholinocarbony lmethyl thio-ethyl_7-bis (2-hydroxypropyl) amine hydrochloride . 26b.N - /? - Morpholinocarbonylmethylthio-ethyl7-bis (2-

hydroxy propyl ammonium pyruvate 26c.N- / 2 ^ MorpholinocarbonyImethylthio-ethyl7-bis (2-

hydroxy-propyl) -ammonium-p-chlorophenoxyisobutyrate 2 6d. Di - / ^ - (2-mor phol inocarbony lmethyl thio-ethyl) -bis (2-hydroxy-propyl) -ammoniumy-malate 26e.Di- / Ti- (2-morpholinocarbonylmethylthio-ethyl) -bis

(2-hydroxy-propyl) -ammonium-7-tartrate

Series 214

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27. N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylamine 27a.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl-

ammonium gentisate

27b.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylammonium-p-chlorophenoxyisobutyrate 27c.Di- / N- (2-o-aminophenylthio-ethyl) -ß-hydroxy-

ethylammonium 7-malate
27d.Di- / N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl-

ammonium7 "tartrate

27e.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylammonium) malate

28. N- (2-o-aminophenylthioethyl) bis (2-hydroxyethyl) amine

29. N- (2-o-aminophenylthio-ethyl) -bis (2, 3-dihydroxy-15 propyl) -amine

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

31. 2- (2-ß-Hydroxyethylamino-ethylthio) -benzoic acid

32. 2- (2-ß-Hydroxyethylamino-ethylsulfinyl) -benzo-20 acid

33. 2- / 2-bis (2-hydroxypropyl) -amino-ethylthiojbenzoic acid

34. 2- / 2-BiS (2-hydroxypropyl) -amino-ethylsulfinyl-7-benzoic acid

²⁵ 35. 2- / 2-bis (2,3-dihydroxypropyl) -amino-ethylthio7-

benzoic acid

36. 2- / 2-BXS (2,3-dihydroxy-propyl) -aitiino-ethylsulfinyl-7-benzoic acid

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ono / oon ^ L ¹ OREAL

37. N- (2-Benzylthio-ethyl) -ß-hydroxyethylamine 37a.N ~ (2-Benzylthio-ethyl) -ß-hydroxyethylamine ~ hydrochloride

38. N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine 38a.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine-

hydrochloride
3 8b.N- (2-benzylthioethyl) bis (2-hydroxyethyl) ammonium pyruvate

38c.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-p-chlorophenoxyisobatyrate 38d.N ~ (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -

ammonium pyrrolidone carboxylate 38e.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-ma1at
⁵ 38f .N- {2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -

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

38h.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-2-oxo-glutarate

39. N- (2-Benzylthio-ethyl) -bis (2,3-dihydroxypropyl) amine

40. N- (2-Benzylthioethyl) bis (2-hydroxypropyl) amine

40a.N- (2-Benzylthio-ethyl) -bis (2-hydroxypropyl) amine hydrochloride

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

Seroe 214

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40c.N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) -

ammonium inalate
4Od.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -ammoniumo (-hydroxyl so butyr at
4Oe.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -

ammonium pyruvate
4Of.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) -ammonium-2-oxo-glutarate

40g.N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-ascorbate

40h N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) -

ammonium 3-hydroxy butyrate
4Oi.N- (2-Benzylthio-ethyl) -bis (2-hydroxypropyl) -ammonium-c ampho sulfonate
5 4Oj.N- (2-Benzylthio-ethyl) -bis (2-hydroxypropyl) -

ammonium S-amino-S-thia-hexanedioate
40k.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-nicotinate

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

41. N- (2-Benzylsulfinyl-ethyl) -bis (2-hydroxypropyl} -am in

42. N- (2-Benz} lthio-ethyl) -N- (2-hydroxy-ethyl) -2-hydroxypropylamine

42a.N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2- hydroxy-propylamine hydrochloride

4.3. N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2,3-dihydroxypropylamine

Series 214

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- ie -

The meanings of R ₁ , R ₂ / R ₃ ^u ^ d η of the compounds given above are in the following

Table I compiled:

Table I.

Connection: R: R: R,: η

No. ' "*

1 : -CH ₃ : H : H : 0 2 : -CH ₃ : H H : 1 3 : -CH ₃ : -CH ₂ CH ₂ OH : H : 1 4th : -CH ₂ : -CH ₂ CH ₂ OH H : 2 5 : -CH ₃ -CH ₉ CH-CH-
OH ^J : -CH ₃ I. 6th : -CH ₃ : -CH -CH-CH OH
. OH : -CH ₂ OH: 1 7th .: -CH ₂ -CH = CH ₂ : -CH ₉ -CH-CH
OH : -CH ₃ : 0 8th : -CH ₂ -CH = CH ₂ : -CH -9H-CH-
OH ^Δ : -CH ₃ : 1 9 : -CH ₂ -CH = CH ₂ : -CH ₂ -CH-CH ₂ OH .: -CH ₂ OH: 0 10
1 1 : -CH ₂ -CH ₂ OH:
: -CH ₂ -CH ₂ OH: ² OH ³
-CH ₉ -CH-CH-
OH ^J : -CH ₃ :
: -CH ₃ 0
1 12th : -CH ₂ -CH-COOH: H H
• ti 0 13th : -CH ₂ -9H -COOH: CH -9H-CH
^Z OH ^J : H : 0 14th : -CH ₂ -CH -COOH: -CH-CH-CH
OH ^J : -CH ₃ : 0 15th : -CH ₉ -CH -COOH:
NH ₂ -CH ₉ -9H-CH OH
OH : -CH ₂ OH: 0 16 : -CH ₉ ~ 9H -COOH:
NHCOCH ₃ H : H : 0 17th : -CH ₉ -CH -COtDH:
NHCOCH ₃ -CH ₀ -CH-CH ₃ : -CH ₃ : 0 1 p • _f! H -ΠΙ -Γ.ΟΟΙΙ: _ CH -CH-CiLOH: -CH-OH: 0

NHCOCH ₃ OH series 214

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To be continued in Table I.

Connection no.

R. R,

^R 3

19 :-( CH ₂ ) ₂ -CH-CO aH: H

20th

T- (CH ₉ ) ,, - CH-COOH: -CH ₉ -CH-CH ₉ OH: -CH ₉ OH NH "OH

21 :-( CH) -9H-COOH: H

NH.

NH 23: -CH ₂ -COOH

24: -CH ₂ -COOH

25: -CH ₂ CON 9
OH

: -CH ₀ CH-CH-

Ό: -CH ₂ -CH ₂ OH

- ^CH

22 :-( CH ₂ ) ₂ -CH-C00H: -CH ₂ -CH-CH ₃ : -CH ₃

-CH. H

26: -CH ₂ CON

27: -CH ₀ CH-CH ₀ : -CH

' ² OH ³ '

H: H

28

29: -CH ₀ CH-CH ₉ OH: -CH_0H OH

30:

COOH

: -CH.

32:

33 34 35

Series 214

: -CH

-CH ₉ CH-CH: -CH:

"OH - ^J

CH CH-CH OH: -CH ₉ OH: OH ^l

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Table I continued
Link . _R : R ₀ : R,: n

36: (f \ : -CH CH-CH ₉ OH: -CH_0H

\ - / OH ^{λ ί} COOH

37: -CH ₀ -CH ₁ . : H: H

Z DJ

38: -CIl ₀ -C, !! ,,: -CH "CH_0H: H:

39: -CH ₀ -C, H,: -CH ₀ CH-CH ₀ OH: -CH ₀ OH: ^{2 6 5 2} OH ^{2 2}

₀ OH: -CH ₀

^{2 2} ;

40: -CH ₀ -CH. : -CH ₀ -CH-CH. : -CH,

2 6 5 ² Sh 3 3

41: -CH ₀ -CH ₁ . : -CH ₀ -CH-CH,: -CH,

Z ο 3 Z x "i 5

42: -CH ₀ -C _n H ₁ . - CH ₀ -CH ₀ OH: -CH, Zod ZZ 3

43: -CH ₂ -C ₆ H ₅ : -CH ₂ -CH ₂ OH: -

The cosmetic preparations according to the invention contain at least one active or active compound of the above general formula I or a salt of this compound in suspension or in solution in water, in an alcohol (such as ethanol or isopropyl alcohol), in a watery-alcoholic. Solution, in an oil, in an emulsion or in a gel.

Series 214

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If the active compound is acidic or basic in character, it can be in situ in the Preparation can be completely or partially neutralized, for example with an inorganic or organic base or with an inorganic or organic acid, the latter in particular is chosen from the acids mentioned above for the formation of the salts of the compounds of the general Formula I are given.

The concentration of the active compound in the preparation is generally between 0.1 and 20% and preferably between 1 and 10%.

The capillary preparations according to the invention can the active compounds of the general formula I either alone or in the form of mixtures with one another or in the form of mixtures, with other compounds that are already used to combat the hair is known to be greasy and unsightly.

The capillary preparations according to the invention can furthermore ingredients such as penetration-enhancing agents or fragrances that are usually present used in cosmetics.

Series 214

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The cosmetic preparations according to the invention can also be used in the form of a dry shampoo Powder form or aerosol form which does not contain a surfactant and which dry hair is applied. There is a time to wait when using this procedure after application and then brushes out the hair.

The preparations according to the invention can also be in the form of varnishes or well lotions, which at least one active compound in a suitable cosmetic carrier material in combination with contain at least one common cosmetic resin.

Suitable cosmetic resins are in particular polyvinylpyrrolidone; Copolymers of polyvinyl pyrrolidone and vinyl acetate; Copolymers of vinyl acetate and a unsaturated carboxylic acid such as crotonic acid; Copolymers obtained by polymerizing vinyl acetate, crotonic acid and an acrylic acid ester or methacrylic acid ester; Copolymers obtained by copolymerization obtained from vinyl acetate and an alkyl vinyl ether; and copolymers obtained by copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long chain carboxylic acid or an allyl ester or a methallyl ester of a long chain carbon series 214

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acid receives; Etc.

The cosmetic resins present in the preparations in the form of varnishes or waving lotions can also be colored polymers, i.e. polymers that have dye molecules in their macromolecular chain contain, which give the hair a special color or tint.

These preparations can also contain direct dyes that color or tint the hair cause. They can also contain the ingredients that are customary for cosmetic preparations fix the hair in a certain condition, such as penetrants, cationic compounds, Quaternary ammonium salts, vitamins, proteins, more or less strongly hydrolyzed peptides, starch derivatives or cellulose derivatives, surfactants, dyes, fragrances, etc.

The cosmetic carrier materials and binders suitable for the production of such preparations and / or auxiliaries, can be classic mixtures that are used for the production of varnishes and white lotions or used for hairdressing preparations will.

Series 214

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So these cosmetic preparations in the form of a well lotion can contain the effective compound and that Resin in alcoholic or aqueous alcohol Solution included.

The alcoholic or aqueous-alcoholic solution of the active compound can also be mixed with a suitable one Amount of a propellant liquefied under pressure mixed and contained in an aerosol container and form a preparation called hair lacquer or hairspray.

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

The cosmetic preparations according to the invention

may also be in the form of treatment shampoos that are liquid, clear, opaque, or have a pearlescent appearance or are in the form of a cream or gel and which are suitable

25 net, the fat and unaesthetic in an effective way Combat appearance of hair.

Series 214

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These preparations in the form of shampoos are essentially characterized in that they are a Mixture of at least one anionic, cationic, non-ionic or amphoteric detergent with contain at least one active compound of the general formula I.

The following can be mentioned in particular as anionic detergents: alkyl sulfates, alkyl ether sulfates, alkyl polyether sulfates, Alkyl sulfonates (where the alkyl groups have 8 to 18 carbon atoms), sulfated Monoglycerides, sulfonated monoglycerides, sulfated Alkanolamides, sulfonated alkanolamides, soaps of fatty acids, monosulfosuccinates of fatty alcohols, Condensation products from fatty acids and isethionic acid, condensation products from fatty acids and methyl taurine, Condensation products from fatty acids and sarcosine and condensation products from fatty acids and a protein hydrolyzate.

As cationic detergents one can in particular long-chain quaternary ammonium compounds, esters from Name fatty acids and amino alcohols and polyether amines.

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Examples of nonionic detergents suitable according to the invention are, in particular, esters of Polyols and sugars, condensation products from ethylene oxide and fatty acids, fatty alcohols, long-chain Alkylphenols, long-chain mercaptans and long-chain amides, polyethers of polyhydroxylated Fatty alcohols.

Examples of amphoteric detergents are asparagine derivatives, Condensation products from monochloroacetic acid and imidazolines, alkylaminopropionates, Betaine derivatives and amine oxides.

The shampoo preparations generally contain 0.1 to 15% and preferably 1 to 10% of the effective Link. In general, they contain, for example, 4 to 20% by weight and preferably 5 to 10% by weight of the detergent dissolved in an aqueous medium.

The above-defined shampoos can also contain customary cosmetic ingredients such as fragrances and Dyes. You can also use thickening agents such as fatty acid alkanolamides,

25 cationic polymers, such as quaternized vinyl pyrrolidone copolymers, cationic cellulose polymers etc., cellulose derivatives such as carboxymethyl-

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cellulose or hydroxymethyl cellulose, esters of long-chain polyols, natural gums, etc., so that they are in the form of a cream or gel.
5

These shampoos can still be in the form of powders that are either applied to wet hair or dissolved in a certain volume of water before washing the hair.

These shampoo preparations can also contain dyes which are used to color the hair.

In general, you will get a satisfactory result if you wash your hair once a week, which makes it possible to reduce the greasy appearance of the hair and in certain cases even to prevent it, while at the same time normal care of the hair is ensured.

20th

It has also been shown that the active compounds defined above in combination with a suitable cosmetic carrier material, binding agent and / or auxiliary material can be applied to the skin

25 and improve their appearance.

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Such preparations that are applied to the skin are generally in the form of creams, milk preparations, gels, skin treatment compositions or pens or aerosol pre-foam. These preparations can also be in the form of aqueous or watery-alcoholic lotions are present. she generally contain the active compounds defined above in an amount of 0.1 to 15% and preferably in an amount of 1 to 5%.

These preparations can also contain any of the usual ingredients, such as fat, Preservatives, fragrances, dyes, waxes etc. They can also contain colored pigments, that color the epidermis and mask skin imperfections.

The invention also relates to the new compounds of the general formula Ϊ below

? 2

R ₁ -S-CH ₀ -CH ₀ -N-CH ₀ -CH-R-, (I) 1.22 2.3

(O) _n OH

in the

η 0, 1 or 2,

R2 is a hydrogen atom or a group of the following formulas: -CH ₂ -CH ₂ OH, -CH ₂ -CH-CH ₃ or

-CH ₂ -CH-CH ₂ OH, ^OH

OH

Series 214

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R _{3 is} a hydrogen atom or a group of the following formulas: -CH ₃ or -CH ₃ OH and RJ is a group of the following formulas:

(ij -CH ₃ ,

⁵ (ü) -CH ₂ -CH = CH ₂ , (iii) -CH ₂ -CH ₂ OH, '

(iv) - (CH ₂ J _1n -CH-COOH,

NH-R ₄

in which m 1 or 2 and R _{4 represent} a hydrogen atom or a group of the formula -COR ₅ , in which Rg represents a saturated or unsaturated alkyl group having 1 to 8 carbon atoms, (v) -CH ₂ COR ₆ ,

wherein R _{g is} a group of the formula

-OH or the formula -N,

^ r "

in which r ¹ and r ", which can be identical or different. Hydrogen atoms or alkyl groups with 1 to 5 carbon atoms or together one two

valent group of the following formeins - (CH ₂ J ₂ -O- (CH ₂ J ₂ - or - (CH ₂ J ₅ -,

(Vi)

woboi in this case the group R ₂ only

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represents a hydrogen atom when the group R _{3 represents} a hydrogen atom, and

(vii)

5 wherein R ^ is a group of the formula -NH ₂ or

represents a group of the formula -COOH, where in the latter case the groups R ^ and R ₃ are different for one and the same compound of hydrogen atoms,

mean, as well as the salts of these compounds, which one with .den above inorganic or organic Acids received.

The new compounds of the invention of the above

general formula are those on pages 4 to 9 above

listed, with the exception of connections 31 and 32,

The invention also relates to a process for the preparation of the inventions of the above general formula I.

These compounds are generally obtained by reacting an oxirane with a compound of the following general formula II according to the following reaction scheme:

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1.22 2 .2y 3

⁽⁰⁾ η (II) V

R ₁ -S-CH ₂ -CH ₂ -N-CH ₂ -CH-R ₃

OH

Xl

The oxirane used can be ethylene oxide (R ₃ = H), propylene oxide (R ₃ = -CH ₃ ) or glycidol (R ₃ = -CH ₂ OH).

The addition reaction can take the most varied of forms Solvents, but is preferably carried out in a polar solvent, as in water or an alcohol, which solvents individually or in the form of mixtures

T5 can be used.

When the group R ^ has an acid group, will this is preferably neutralized beforehand with the aid of an alkali metal hydroxide.

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

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It can also be ended by keeping the participants in the reaction for several days Let stand room temperature. The reaction product is generally obtained by concentrating the resulting mixture isolated under reduced pressure after any neutralization with the aid of an acid.

The compound obtained can, if appropriate, be purified by being passed over silica gel or an ion exchange resin (if the reaction mixture contains inorganic salts) leads, or by making them washes or finally recrystallized using a suitable solvent.

The compounds of the general formula I in which the group R2 is a group of the following general

formula

-CH ₂ -CH-R ₃

OH

you can start directly from the connections of the general formula II, in which R ^ is hydrogen atom represents, produce by adding two equivalents of the oxirane.

Although the compounds of the general formula I ^ ^{5 are} preferably prepared using the procedure given above, it is still possible to prepare them by using a hydroxyalkyl halogen id rait S6rie214 9098S1 / 0904

a compound of the general formula II according to the following reaction scheme:

R ₁ -S-CH ₉ -CH ₀ -NH-R ₉ + X-CH ₉ -CH-Ro

1.22 2 j 2.3

(O) j OH (ID

? 2

R ₁ -S-CH ₂ -CH ₂ -N-CH ₂ -CH-R ₃ + XH

O OH

wherein X represents a chlorine atom or a bromine atom. 10

The compounds according to the invention in which the group R ₂ denotes a hydrogen atom and η has the value 0 can also be prepared by reacting a thiol of the general formula R ^ SH with an N-hydroxyalkylaziridine according to the reaction scheme below:

• R ₁ -SH + CH ₂ -CH ₂ ^ R ₁ -S-CH ₂ -CH ₂ -NH-CH ₂ -CH-R ₃

\ / OH

CH ₉
t 2

CH-OH

R ₃ .

The reaction conditions are analogous to those in.

the reaction of an oxirane with a thioether

be turned.

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If the thiol of the general formula R - SH a Has carboxylic acid group, this can optionally before the reaction with the substituted Aziridine can be neutralized.

The general procedure for the preparation of the active compounds in the form of the salt is, at normal temperature in an equimolecular solution of the inorganic or organic acid corresponding to the desired salt to enter a solution of the active compound to be converted into the salt.

The solvents used, which can be the same or different, are generally listed under the alcohols and the chlorinated hydrocarbons selected.

The mixture is stirred for about 1 hour and the like then concentrated under reduced pressure. The evaporation residue is then washed with ether and finally dried over phosphorus pentoxide at 50 ° C. in vacuo.

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If a diacid is used as the organic acid, is it possible using the same. Procedure either the monosalt or the To prepare disalt, which is accomplished by adding either one mole of the amine or two moles of the Amine used per mole of acid.

Effect of the compounds according to the invention.

Determinations were made to clarify the specific properties of the compounds according to the invention the lipid content of the skin after repeated application of these compounds and in comparison to the application a placebo solution and compounds that have a structure similar to the compounds of general Formula I own carried out. It is known that the greasy appearance of the skin or hair is related to the lipid content of the epidermis.

In order to give these comparative studies a good statistical significance, the studies carried out on a genetically stable and controlled model, which was previously carried out by a specific Food has been adjusted to a characteristic (seborrheic) Pett state, for which purpose the method of Aubin et Coil. (Parf.CosnuSav.France (Vol. 1 (1971) No. 8) was applied. Series 214

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The substances tested were used for 12 consecutive Days applied to the skin at a concentration of 80 mmol / 1. The lipid content the epidermis was then compared to that of the same age control individuals who were in the same frequency with the same number of applications only one control solution (water) were treated.

The comparative test was applied to the following compounds:

links

A. C ₆ H ₅ -CH ₂ -S-CH ₂ -CH ₂ -NH ₂ , HCl 15

B. C ₆ H ₅ -CH ₂ -S-CH ₂ -CH ₂ -NH-CH ₃ , HCl

CH ₃

C. CgH ₅ -CH ₂ -S-CH ₂ -CH ₂ -N, HCl

CH ₃

D. CgH ₅ -CH ₂ -S-CH ₂ -CH ₂ -N

, HCl

E. CgH ₅ -CH ₂ -S-CH ₂ -CH ₂ -N ^^ / , HCl

F. CgH ₅ -CH ₂ -S-CH ₂ -CH ₂ -N NH, 2HCl

CH ₂ -CH ₂ OH

G. (No .: 38a) C ₆ H ₅ -CH ₂ -S-CH ₂ -CH ₂ -N, HCl

,. ^ , CH ₀ -CH ₀ OH

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H. (No .: 37a) C ₆ H ₅ -CH ₂ -S-CH ₂ -Ch ₂ -NH-CH ₂ -CH ₂ OH, HCl

CH ₀ -CHOH-CH,

/ ^{2 3} I. (No .: 40a) C ₆ H ₅ -CH ₂ -S-CH ₂ -CH ₂ -N, HCl

CH ₂ -CHOH-CH ₃

The determination of the oxide content of the skin gave the following results in μg / cm ^{2 of} the skin (mean values):

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¹⁶ untreated treated seborrheic individuals ίο seborrheic

CD CO O

Individuals A BCDEP GH I

2098 1710 1972 2622 2706 2496 2979 1469 1490 1637

co Δ% -18.5% -6% + 25% + 29% + 19% + 42% -30% -29% -22%

CD CO CO

cn,

L ¹ OREAL

From these results it can be seen that the substitution of the primary amine with a methyl group (Compound B), which practically completely prevents the activity observed with Compound A. The double Substitution through which the compound A is converted into a tertiary amine manifests itself in the representative compounds C, D, E and F by a considerable increase in the lipid content of the Skin in terms of content observed in the seborrheic individuals not having any of the applied Substances have been treated. This increase in lipid content ranges from +19 to + 42%. in the In contrast, the compounds according to the invention (G, H and I) surprisingly lead to contrary set results which are even better than those of the most active comparison substances (compound A).

The following examples serve to further illustrate the invention and deal with both Preparation of the active compounds of the invention and various examples of cosmetic preparations based on these compounds.

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Manufacturing examples
example 1

2 (2-ß-Hydroxyäthylartiino-äthylthio) -benzoic acid (Compound 31)

A solution of 6.16 g of thiosalicylic acid is stirred in 60 ml of methanol under nitrogen at room temperature. A solution of 3.48 g is then added dropwise N- (2-hydroxyethyl) aziridine in 40 ml of methanol.

The precipitate formed is filtered off and

sucks, whereupon the filtrate is concentrated. The residue obtained is then with the precipitate in ethanol crystallizes and 9 g of a white product are obtained which melts at 235.degree.

15th Analysis: C. 1 ^H 15 ^NO 3 ^S 6th H
, 26 N
5.80 S.
13.28% about »: C.
54.75 6th , 20 5.68 13.05% found: 54.58 20th Example 2

N- (2-methylthio-ethyl) -ß-hydroxyethylamine (compound 1)

A mixture of 25.8 g of N- (2-hydroxyethyl) aziridine is heated and 21 g of sodium methylthiolate in

Boiling ethanol under a nitrogen atmosphere

Reflux. When the reaction has ended, series 214 is neutralized

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the mixture with an equivalent amount of 5N hydrochloric acid and concentrated under reduced pressure a. The residue is extracted with chloroform and, after the solvent has been driven off, distilled. 28 g of a colorless oil which boils at 145 ° C./26 mmHg are obtained.

Amine index: calc .: 7.40 meq / g found: 7.40 meq / g.

10 Example 3

N- (2-methylsulfinylrathyl) -ß-hydroxyethylamine (Connection 2)

An equivalent amount of hydrogen peroxide is added dropwise to a solution of 13.5 g of the compound 1 obtained according to Example 2 in methanol, the temperature being kept below 30 ^° C. After the reaction has ended, the solution is concentrated under reduced pressure and the residue is purified by filtration through silica gel. 8 g of a colorless oil, which is the hemihydrate of compound 2, are obtained.
Analysis: C ₅ H ₁₃ NO ₃ S, 1/2 H ₃ O

21st ber .: 4th 37 C.
, 4O δ H
, 78 8th N
, 75 20th S.
, OO 25th found: 37 , 22 δ , 48 8th , 80 20th , 25 series

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Sis

Examples 4 and 5

3-N- / 2-ß-hydroxyethylamino-ethylthio7-alanine (Compound 12)

An aqueous-alcoholic solution of 8.7 g of N- (2-hydroxyethyl) aziridine is added dropwise under a nitrogen atmosphere to a solution of 12.1 g of cysteine in 200 ml of 50% strength aqueous ethanol. The temperature of the reaction mixture is kept at 25 ° C. for 4 hours and then left to stand at room temperature for 24 hours. The mixture is filtered and the filtrate is concentrated under reduced pressure. The residue taken up with ethanol gives a crystalline solid which is filtered off and suctioned off. 17 g of compound 12, which ^{melts at 178 °} C., are obtained.
Analysis: C ^ H ₁₆ N ₂ O ₃ S

CHN S

calc .: 40.36 7.74 13.45 15.59%

found: 40.34 7.69 13.40 15.41%

Compound 16 is prepared under the same conditions by replacing cysteine with N-acetylcysteine. The compound is obtained in the form of a colorless one Oil that corresponds to hemihydrate.

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Analysis: C ₉ H ₁₈ N ₃ O ₄ S, 1/2

6th 41 C. 7th H N 1 2 S. ber .: 41 , 68 7th , 38 10.80 1 2 .36% found ϊ , 66 , 25 10.84 .43% example

2- (2-Hydroxy-ethylamino) -äthylthioessigsüure (Compound 23)

An equimolar mixture of ethyl thioglycolate is heated and N- (2-hydroxy-ethyl) aziridine in methanol for 2 hours under nitrogen Reflux. The reaction mixture is then concentrated under reduced pressure and the mixture is stirred Residue in a 2N aqueous potassium hydroxide solution containing a little ethanol. Brings it 24 hours later the pH is adjusted to 4 by adding hydrochloric acid. The reaction is concentrated reduced pressure and dissolve the residue in boiling ethanol. Those formed by cooling Crystals are filtered off and dried (yield = 50%). F = 110 ° C.

Analysis: CgH ₃ NO ₃ S

CHN S calc .: 40.21 7.31 7.82 17.89%

found: 40.07 7.07. 7.64 17.86% Series 214

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Example 7

N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylamine (Compound 27)

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

Analysis: ( ^: io ^H 1 6 ^N 2 ° > P 7th H
, 59 1 3 N
, 19th 15th S.
, 1O ber .: 56 C.
, 57 7th , 81 1 3 , 02 14th , 96 found: 56 , 39

Examples 8 to 11

2-N-Benzylt.hio-ethyl-bis {2-hydroxy-ethyl) -amxn (Compound 38)

Into a reaction flask and a gas inlet tube is provided with a "sea salt brine cooler, with a heated to 50 ⁰ C solution of 50 g of 2-benzylthio-ethylamine in 150 ml of absolute alcohol. After the solution with a nitrogen

25 has cleaned electricity, you run a slow one

Stream ethylene oxide until absorption in solution stops. Then you pass nitrogen again :? one and

Series 214 909851/0904

-η-

Finally, the solution is concentrated under reduced pressure and the oily residue is dried over phosphorus pentoxide. 54 g of an oil are obtained, the analysis and NMR spectrum of which correspond to the expected product.

Analysis: ^C 1 3H ₂₁ N o ₂ s H
, 29 5 N
, 49 S.
12.56 ber .: 61 C.
, 14 8th , 34 5 , 64 12.40 found: 60 , 93 8th

Compounds 3, 4 and 25, which are in the form of colorless, hygroscopic oils. The details of these connections are summarized in the table below.

set:

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O CU Od cn

example link
No. yield
% Analysis: calculated%
found % C. H N S. 9
10
11 3
4th
25th 60
70
99 43.07
43.17
39.79
39.60
47.81
47.98 8.77
8.75
8.11
8.28
8.36
8.26 7.17
7.20
6.63
6.53
9.29
9.26 16.42
16.36
15.18
15.04
10.64
10.90

L ¹ CREAL

Example 12

N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -amine (Compound 40)

To a solution of 16.7 g of 2-benzylthio-äthylarain in 96% ethanol, which have been cooled to 0 ⁰ C, is added dropwise with stirring 3 equivalents of propylene oxide. The reaction mixture is heated to 30 ^° C. for 6 hours and then concentrated under reduced pressure, whereupon the remaining oil is dried in a desiccator charged with phosphorus pentoxide. 28 g of a pale yellow oil are obtained.

Analysis: C ₁₅ H ₂₅ NO ₂ S

CHN S

15 cal .: 63.56 8.89 4.94 11.31%

found 5 63.76 8.74 5.08 11.55% Examples 13 to 24

N- (2-methylsulfynyl-ethyl) -bis (2-hydroxy-propyl) -amine (Compound 5)

To an aqueous solution of 10.7 g of 2-methylsulfinylethylamine three equivalents are added dropwise at a temperature of less than 10.degree. C. with stirring Propylene oxide. The temperature is left at room temperature rise and then let stand for 30 hours (whereby the course of the reaction is thin-layered

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«2

followed chromatographically). Then it is concentrated in a rotary evaporator and what remains is dried oil in vacuum in desiccator over phosphorus pentoxide. In this way, 21.5 g of a colorless oil are obtained.

Analysis: CqH ₀₁ NOoS

C H NS

calc .: 48.40 9.48 6.27 14.36%

found: -48.48 9.30 6.12 14.23% 10

The compounds listed in Table II below are prepared in the same way:

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ta

L ¹ OREAI.

Table II

Case: Connection: Ausspiel _M o .. booty

ber.
Analysis: found

14th

15.: 8 16
17th

IS
19th
20th
21
22nd

10 11 17 24 26 30 33

23:34

(Dihydrate)

24:41

(Halbhvdrafc)

99

:

(D

;

50

:

:

98

82

70

98

99 (2)

(2)

(3)

(3)

(2)

56.61 56.42

52.98 52.70

50.60 50.22

47.40 47.10

48.43 48.41

47.79 47.63

52.47 52.56

59.12 59.04

54.35 54.22

49.29 49.53

58.41 58.77

13th
13th , 73
, 50 12th
12th / 71 13th
13th ta ta
to Ln
ο ο 12th
12th in ο
from tn
ta 'ta 9,
9, 94
78 12th
12th , 76
, 50 10
10 , 00
, 13 11
11 , 27
, 29 9,
9, 67
74

10.39 9.87

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(1) Purified by passing over silica gel

(2) One equivalent of sodium hydroxide is added at the beginning of the reaction and after the end of the reaction one equivalent of hydrochloric acid. The reaction mixture is carried out via an acidic ion exchange resin filtered.

(3) Reaction solvent: methanol.

Example 25

N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2-hydroxy-propylamine (Compound 42)

A mixture of 3.3 g of the compound 37 in 30 ml of ethanol, which is mixed with 1 g of propylene oxide in 15 ml of water has been added, stand for 24 hours. It is then concentrated under reduced pressure and dried the remaining viscous liquid in the desiccator. 3.8 g of compound 42 are obtained.

Amine index: calc .: 3.72 meq / g found: 3.72 meq / g

Example 26

N- (2-Benzylthio-ethyl) -bis (2,3-dihydroxy-pfopyl) amine (Compound 39)

A mixture of 13 g of 2-benzylthioethylamine and 14.5 g of excess glycidol is heated in

200 ml of toluene for 3 hours to reflux.

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fob

The product formed separates out in the form of an oil on cooling. You separate the oil from the Toluene phase and washes it with benzene. In this way, 24.5 g of compound 39 are obtained in the form of the monohydrate.

Amine index: calc .: 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-methyl-sulfinylethylamine is heated and 19.5 g of glycidol in 50 ml of ethanol during 8 hours to reflux. Then you narrow

the reaction mixture is concentrated under reduced pressure and the oily residue obtained is thoroughly purified Transfer over silica gel. 32 g of compound 6 are obtained in this way.

20 Analysis: CqH ₀₁ NO ₁ -S

CHN S

calc .: 42.33 8.29 5.49 12.56%

found: 42.11 8.54 5.46 12.37%

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

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W.

Receives hemihydrate.

Analysis: C ₁₄ H ₃₃ NO ₃ S, 1/2 H ₃ O

29 57 C. 8th H 5 4th N S S ber .: 56 , 06 8th ,1 3 4th , 75 10.89 found: , 98 ,1 , 63 10.57 example

N- (2-o-aminophenylthio-ethyl) -bis (2, 3-dihydroxy-

propyl) amine (compound 29)
10

A solution of 16.8 g of 2-o-aminophenylthioethylamine and 14.8 g of glycidol in 96% ethanol is left
stand for 6 days at room temperature. The reaction mixture is then concentrated under reduced pressure
. _ and washes the oily residue with toluene,

whereupon the material is dried in a desiccator in the presence of phosphorus pentoxide. You get in
this way 29 g of compound 29.

Α ** ³ * «» ^C 14 ^H 24 ^N 2 ° 4 ^S

CHN S

calc .: 53.14 7.64 8.85 10.13%

found: 52.88 7.61 8.76 9.94%

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Example 30

2-Acetamido-3-j / 2-bis (2,3-dihydroxy-propyl) -aminoethylthio_ / -propionic acid (Compound 18)

A solution of 20.6 g of 2-acetamido-3— is heated

ß-aminoethylthio-propionic acid, 4 g of sodium hydroxide and 14.8 g of glycidol in 50% aqueous ethanol for 7 hours at a temperature of 40 ^° C. Then 1 equivalent of hydrochloric acid is added and purified by transferring it over an ion exchange resin (H),

After evaporation of the solvent under reduced pressure, 19g of a viscous liquid which crystallized in the form of the monohydrate, melting at 90 ⁰ C is obtained.

Analysis: C ₁ , H -, ^ NO ₇ S, H ₀ O

C HN S calc .: 41.92 7.58 7.52 8.61%

found: 41.84 7.57 7.62 8.87% Example 31

■

2- / 2-B1S (2,3-dihydroxy-propyl) -amino-ethylsulfynyl / -

benzoic acid (compound 36)

One prepares the connection in the same way as that Compound 18 (example 30) starting from glycidol and 2-ß-aminoethyl-sulfinyl-benzoic acid »

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Production of 2-ß-aminoethylsulfinyl-benzoic acid

A solution of 8.6 g of ethyleneimine in 200 ml of ethanol is added slowly under a nitrogen atmosphere at 35 ° C. to an ethanolic solution of 30.8 g of thio salicylic acid. The 2-ß-aminoethylthiobenzoic acid formed precipitates to the extent that it is formed. It is filtered off with suction and crystallized from a water / acetonitrile mixture. This gives 37 g of crystals, melting at 120 ⁰ C (monohydrate), WO

when an anhydrous product is formed, which

begins to decompose at 200 ° C.

21.5 g of this product are dissolved in acetic acid and 10 ml of hydrogen peroxide (110 vol.) ^{Are then added dropwise at 0 ° C.} The mixture is left to stand at room temperature for 5 days and then concentrated under reduced pressure and the residue is crystallized from water. 19.5 g of 2-ß-aminoethylsulfynylbenzoic acid, which melts at 240 ° C., are obtained. 20th

Analysis: C ₉ H ₁₁ NO ₃ S

C HN S

calc .: 50.68 5.19 6.56 15.03%

found: 50.58 5.35 6.75 15.07%

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

Analysis: C ₁₅ H ₃₃ NO ₇ S, 1/2 H ₃ O

CHN calc .: 48.63 6.52 3.78%

found: 48.60 6.89 3.71%

Examples of the preparation of the salts. 10 Example 32

N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine hydrochloride (Compound 38a)

45 ml of a 4N hydrochloric acid solution are added

in ethanol to an ethanolic solution of 38 g 15

of compound 38. After 2 hours at room temperature, the resulting solution is concentrated and crystallized the residue from 1,2-dichloroethane. After drying, 33 g of the compound are obtained, which at 77.degree

melts.
20th

Analysis: C Series 214 Ί3 ^Η 2 C
, 50 NO ₃ S H
, 60 4th N
, 80 10 S.
, 99 ber .: 53 / 33 7th , 5S. 4th , 57 10 , 82 found: 53 7th

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LOR3AL

Examples 33 and 34

N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -amine hydrochloride {Compound 40a)

30 ml of a 4N hydrochloric acid solution 5 are added

in ethanol to 30 g of the compound 40, which is in

Has dissolved chloroform. The mixture is left to stand at room temperature for 2 hours and then 80 ml of ether are added, whereupon the compound 40a crystallizes. After filtering and drying, 30 g of crystals are obtained 10

Melting 95 ° C.

Analysis: C ₁ ςΗ ,,, - Cl

ber .: 56 ? 32 8th , 19th 4th ? 38 found: 56 , 32 7th , 96 4th , 41

1O? O2% 10.08%

Proceeding from the compound 42, the hydrochloride 42a, which ^{melts at 88 °} C., is obtained in the same way

Analysis: ( ^: 14 ^H 24 ^C1 NO ₂ S. 4th N
, 58 10 S.
, 48 % ber .: 54 C.
, 97 7th H
, 91 4th , 52 1O , 52 % found : 54 , 72 7th , 95

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Examples 35 and 36

N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-gentisate (Connection 4Ob)

To a methanolic solution containing 4.6 g of gentisin contains acid, 8.5 g of the compound dissolved in methanol: are added 40 and the mixture is stirred for 1 hour at room temperature. Then you narrow the received Solution under reduced pressure, filter the residue and wash with ether. After the

Dry 12.9 g of white crystals that are at 59 ° C

melt.
Analysis: C ₂₂ H., ..NOgS

calc .: 60 ^ 38 7? 14 3? 2O 7? 32% found: 60.38 7.16 3.41 7.34%

Compound 27b is obtained in the same way starting from compound 27 and p-chlorophenoxyisobutyric acid. The compound is obtained in the form of white-20 borrowed crystals that melt at 58 ° C.

Analysis: ^C 2O ^H 27 N ₂ O ₄ S N S. C. H 6.56 7.51 ber .: 56.26 6.37

found: 56.03 6.49 6.51 7.70 series 214

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Examples 37 to 59

Following the procedure of Examples 32 to 36, the salts of the compounds 7, 26, 27, 38 and 40, which are summarized in Table III below (the salts are oily or semi-solid and strongly hygroscopic).

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Table III

L'OREAL

at
game ^: Connect
application no. 'Sunmen form
• Analysis: be
ge r. %
f.% N: 8th,
8th, S. 37 : 7a : C ₁₅ H ₂₉ NO ₈ S: C. : H 3.65:
3.38: 7,
6, 36
13th 38 : 7b : C ₂₁ H ₃₄ Cl NO ₅ S: 46.98:
46.75: 7,
7, 62:
67: 3.12:
2.93: 8th
8th, 15th
98 39 : 26a : C ₁₄ H ₂₉ ClN ₂ O ₄ S:
• 56.29:
56.00: 7,
7, 64:
46: 7.85
7.73: 5
6th
8th
8th 98
90 40
41 : 2 6c
: 26d : C ₂₄ H ₃₉ C1 N ₂ O ₇ S:
, H ₂ O
^{: C} 32 ^H 62 ^N 4 ° 13 ^S 2 ^: 47.11:
46.94: 8th,
8th, 19:
31: 5.06:
4.84:
7.22:
.7.12: 7th
8th
8th
8th 79
, 08
, 27
, 32 42
43 : 26e
: 27a ^{: C} 32 ^H 62 ^N 4 ° 13 ^S 2 ^:
, 2 H ₂ O
^{: C} 17 ^H 22 ^N 2 ° 5 ^S: 52.11:
51.97:
49.59:
49.38: 7,
7,
8th,
8th, 47:
46:
06:
36: 6.77
6.81:
7.64
7.72 . 1
: 1 , 75
, 05
, 75
.58- 44 : 27c ^{: C} 24 ^H 38 ^N 4 ° 7 ^S 2 ^: 46.47 j
46.25:
55.72
55.53 8th,
8th,
6,
6, 04:
09:
05:
16: . 10.02
: 10.27 : 9
: 9 1.47
1.33 45 : 27d ^{: C} 14 ^H 22 ^N 2 ° 6 ^S: 51, 59
51, 57 6,
: 6, 85
98 : 8.08
: 8.01 : 1
: 1 , 25
, 22 46 : 27e ^{: C} 24 ^H 38 ^N 4 ° 14 ^S 2 ^: 48.54
48.25 : 6,
: 6, 40
68 : 9.94
: 10.26 : 9
: 9 1.16
1.37 47 : 38b : C ₁₆ H ₂₅ NO ₅ S: 50.15
50.31 : 6,
: 6 _: 66
, 65 : 4.07
: 4.17 : 6
: 6 , 33
.50 48 : 38c : C ₂₃ H ₃₀ ClNO ₅ S: 55.95
55.85 : 7
: 7 , 33
, 30 : 2.98
: 2.96 , 82
, 92 58.77
58.74 : 6
: 7 , 86
, 06

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- 52 -

Table III continued

^Example: connection game dunq no

Molecular formula

Analvse:

here. % found %

38d : C ₁₈ H ₂₈ N ₂ O ₅ S C. N S. 49: , H ₂ O : 53.71 : 6.96 38e : C ₁₇ H ₂₇ NO ₇ S 53.88 . 6.96 50: 38f : C ₂₀ H ₂₇ NO ₆ S : 52.42
52.25 3.59
: 3.76 : 8.23
. 8.17 51: 38g : C ₁₉ H ₃₁ NO ₉ S : 58.66
: 58.86 : 3.42:
: 3.57 ■ 7.83
: 7.85 52: 38h
40c : C ₁₈ H ₂₇ NO ₇ S
, H ₂ O
: C ₁₉ H ₃₁ NO ₇ S : 50.76
50.96 : 3.11
: 3.03 : 7.13
ι 7.33 53:
54: 4Od : C ₁₉ H ₃₃ NO ₅ S : 51.53
51, 68
: 54.65
54.75 • 3.34:
. 3.58.
• 3.35
: 3,4Q: . 7.64
. 7.92
: 7.67
. 7.70 55: 4Oe : C ₁₈ H ₂₉ NO ₅ S : 58.88
58.75 .3.61
. 3.77 ' : 8.27
. 8.12 56: : 58.19
: 58, .10. ■ 3.77;
3.82 ■ 8.63
■ 8.93 : H : : 7.51 : 7.50 6.98
. 6.90 : 6.64
: 6.71 : 6.95
: 7.20 . 6.96:
6.82
7.48
: 7.51 8.58
8.59 7.86
7.61

4Of : C 2O ^H 31 ^NO 7 S. : 53.67: 7th * , 43 : 3.12: 7th • , 16 , H ₂ O 53.54: 7th Λ
• , 30 : 3.12: 7th • , 33 40g : C 21 ^H 33 ^K0 8
, H ₂ O S. : 52.81 • 7.38 : 2.93 •
* 6.71 19 ^H 33 ^N0 5 52.60 • 7.36 ι 3.29 •
• 6.73 40h : C S. : 58.88 8.58 : 3.61 8.27 : 58.75 8.24 : 3.48 8.38

Series 214

909851/0904

L'OREAL

Examples of preparations Example A

Cream for the treatment of oily skin
Compound 38c 1.5 g

Benzalkonium chloride 0.3 g

Glycol stearate 1g

Cetyl alcohol 4 g

Polyoxyethylene stearate based on 6 g of 20 moles of ethylene oxide
10

Isopropyl palmitate 10 g

Calophyllum oil 1 g

Preservative (p-hydroxy- '0.3 g benzoate)

Fragrances in the required quantity
De-mineralized, sterile water, ad 100 g

Applying this cream daily allows a remarkable improvement in the oily appearance of the skin. One achieves a similar effect _ when the connection 38c by the compounds 4OD r 4of or replacing 40 g.

Series 214

909851/0304

L ¹ OREAL

Example B.

Capillary lotion for oily hair

Compound 40 0.8 g

Calcium pantothenate 0.5 g

Fragrance 0.1 g

40% aqueous ethyl alcohol to 100 ml

Example C

Skin stick

Alkanoyloxyethyl sulfonate 80 g

Lantrol (liquid lanolin fraction 12 g (Malmstrom))

Purcellin oil (branched fatty acid- 2 g ester (Dragoco))

Bis-I-T- (2-oxypyridyl-thio) - 0.05 g

aluminum camphosulfonate

Titanium dioxide 2 g

Fragrance 2.5 g

Compound 30 3g

example

One can connect 30 through connection 27a

or replace 27b.

Series 214

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L ¹ OREAL

Example D

Lotion for the daily care of oily hair

Pyridoxine camphosulfonate 0.3 g

Fragrance 0.1 g

Dye 0.1 g

Compound 26b 0.4 g

50% ethyl alcohol to 100 ml

One can connect 26b through the connections

26d or replace g in a concentration -from 0.7 26e.

Example E.

Milk preparation for the treatment of oily skin

Compound 31 1.4g

crosslinked polyacrylic acid
(in trade under the name
"Carbopol 934" available) 0.375 g

Isopropyl ester of lanolin fatty acid 1 g

with 5 to 20 moles of ethylene oxide
^ O oxyethylated lanolin 2.5 g

oxyethylated cetostearyl alcohol 3 g

Myristic monoethanolamide 2 g triethanolamine ad pH = »8

methyl p-hydroxybenzoate 0.1 g

Propyl p-hydroxybenzoate 0.1 g

Water ad 100 g series 214

909851/0904

-.56 -

L ¹ OREAL

The compound 31 can be replaced by the compound 32 in this preparation.

Example F
Shampoo powder

Sodium Lauryl Sulphate 40 g

Condensation product from coconut fatty acids and sodium isocyanate ("Hostapon K.A" from Hoechst) 3 9 g

Connection 12 10g

Perfume 1 g

Example G

Fluid hair gel to be used daily

Vinyl pyrrolidone / vinyl acetate

Copolymer (70/30) 2 g

Lanolin oxyethylated with 5 to 20 moles of ethylene oxide

Polyethylene glycol 300
Connection 7

methyl p-hydroxybenzoate propyl p-hydroxybenzoate tert-butylhydroxytoluene
tert-butyl hydroxyanisole
Fragrance
Water ad

Series 214

909851/0904

1 G 5 G 0.5 G 0.1 G 0.1 G 0.1 G 0.2 G 0.1 G 100 ml

L ¹ OREAL

Example H

Capillary lotion for the treatment of oily hair. The lotion should be used after shampooing before wave laying applied to damp hair. 5

Vinyl acetate / vinyl pyrrolidone copolymer (30/70)

Connection 30
Fragrance

25% ethanol ad

Example I.

1.5 G 1 G 0.1 G 100 ml.

Milk preparation for oily skin

Compound 33 2.6 g

crosslinked polyacrylic acid
(Carbopol 934) 0.375 g

Isopropyl ester of lanolin fat - 1 g acids

Lanolin oxyethylated with 5 to 20 moles of ethylene oxide

oxyethylated cetostearyl alcohol coconut oil monoethanolamide
Triethinolamine ad pH = 8
methyl p-hydroxybenzoate propyl p-hydroxybenzoate water

Series 214

909851/0904

2, 5 G 1 3 G 2 G 0, 1 G 0, 1 G ad 1OO ml

L ¹ OREAL

BO

Example J

Clear shampoo liquid

(with 12 moles of ethylene oxide) poly-

ethoxylated lauric alcohol 13 g

Coconut fat diethanolamide 4 g

quaternized vinyl pyrrolidone copolymer (Gafquat 755, sold from GAF) 0.4 g

Connection 38f 3g

Fragrance 0.2 g

Water to 100 ml

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

Example K

- ■

Shampoo cream

Sodium Lauryl Sulphate 12 g

box-shaped condensate product
from coconut fatty acids and methyl taurine
(Hostapon CT from Hoechst) 40 g

Lauric acid monoethanol amxd 2 g Glycerin monostearate 4 g Connection 39 2 g Fragrance 0.2 g Lactic acid ad pH = 6.5 water ad 100 g

Series 214

909851/0904

L ¹ OREAL

Example L

Mother-of-pearl shampooing liquid oxyethylated with 2.2 moles of ethylene oxide

Sodium lauryl sulfate ad 9 G Sodium monolauryl sulfosuccinate 1 G Polyethylene glycol distearate 2 G Lauric acid dxethanolamide 2 G Connection 5 4th G Fragrance 0.3 G water 100 G

The connection 5 can through the connections 6
or 24 to be replaced.

Example M ■

Cream for oily hair

polyoxyethylated stearate (Myrj 4 9) 3 g

Glycerine monostearate 4 g

Cetyl alcohol 7 g

Petroleum jelly. 8g

Isopropyl myristate 5 g

Compound 38d 12 g

methyl p-hydroxybenzoate 0.3 g

1% solution of crosslinked polyacrylic acid (Carbopol 941 der

Goodrich) 40 g

Triethanolamine ad pH 6.5

Series 214

Water ad 100 g

909851/0904

L ¹ OREAL

This cream is applied to the after shampooing Applied to the scalp. You massage in gently, leave it on for about 15 minutes and then rinse.

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

Example N ¹⁰ Lotion for Oily Hair

Compound 38 0.6 g

50% pyrrolidone carboxylic acid 3 g

water-soluble neo-purcellin
(branched esters of polyethoxylated fatty acids (with
4 moles of ethylene oxide)) 0.5 g

Fragrance in the required amount of preservative 0.2 g

Water ad 100 g

One can get the connection 38 through the connections or replace 40.

Example 0

Lacquer for oily hair

By mixing the ingredients listed below one prepares a paint according to the invention;

Series 214

909851/0904

L ¹ OREAL

Poly (vinyl pyrrolidone / vinyl acetate) -

Resin ("E 335" from General Anilin) 1Q g

Compound 37a O, 5 g

Methyl cellosolve 2 g

Absolute alcohol. ad 1ÖO g

Example P

Treatment lotion for the skin

Compound 40 1.8g

Nicotinic acid 0.8 g

Benzalkonium Chloride O, 2 g

Ethyl alcohol 13 ml

Polyethylene glycol .- 10g

Fragrance in the required amount

soluble dyes in the required 15 borrowed crowd

Demineralized, sterile water to 1OO g Example Q

Cream for oily skin

20 polyethoxylated sorbitan monostearate

(Tween 60) 1g

self-emulsifiable glyceryl monostearate 6 g Stearyl alcohol 1.5 g

Stearic acid. 2 g

Vaseline oil 15 g

Sweet almond oil 2 g

series

909851/0904

Triethanolamine 5 Example R L'OREAL at
- it - Connection 16 Lotion for oily skin 2924229 Fragrance Compound 3 9 0.1 g water trans-sulfolanediol
10
3,6-dioxa-octanol 1 g Ethanol 0.4 g 5- ainino-3-thia-hexanedioic acid ad 100 g water 15th
Example p 0.4 g 0.4 g
1st floor 9 g - 0.3 g ad 100 g

Cream for oily skin

Sipol wax 5 g

Glyceryi monostearate. 2 g

hydrogenated polyisobutylene 3 g

Vaseline oil 3 g

Cetyl alcohol 1. g

Purcellin oil 3.5 g

Preservative 0.3 g

Compound 13 1.4g

Salicylic acid 0.9 g

Water ad 100 ml series 214

909851/0904

L ¹ OREAL

Example T

Mask for oily skin

Compound 30 2g

5-amino-3-thia-hexanedioic acid 1/2 g

^ Gelatin 1g "

Tragantguirani 1 g

Bentonite 4 g

Kaolin 26 g

Titanium dioxide 2 g

Camphor 0.04 g of dye in the required amount
Fragrance in the required amount

demineralized, sterile water ad 100 g

¹⁵ Example U Liquid shampoo

Prepare a liquid shampoo (which you can use for 5 minutes before the final rinsing process) by mixing the following ingredients:

(with 4 moles of glycerine) polyglycerated
Lauric alcohol 15g

quaternized vinylpyrrolidone copolymer (Gafquat 755 from
GAF) O ₇ 4 g

Compound 12 3.6 g

polyethoxylated alkylamine (Ethomeen

18/15 from Rhone Progil) 0.8 g

Series 214 909851/0904

L ¹ OREAL

Lactic acid ad pH = 6

Fragrance in the required amount

Water to 100 ml

Example V

Mask for the treatment of oily skin

Lanolin oxyethylated with 5 to 20 moles of ethylene oxide

Cetyl alcohol

10 self-emulsifiable ethylene glycol. stearate

Vaseline Codex

kaolin

Titanium dioxide

Preservatives 15

link

Glutamic acid

Water ad

Example W

5 G 2 G 7th G 5 G 10 G 8th G 0.3 G 1/4 G 0.8 G 1OO G

Face lotion

A lotion for treating the skin is prepared by mixing the ingredients listed below bold appearance of the face:

Series 214

909851/0904

L ¹ OREAL

Compound 27a Ig

Propylene glycol 2 g

Sodium ethylenediamine tetraacetate 0.1 g

Ethyl alcohol 16 g

methyl p-hydroxybenzoate 0.1 g

Propyl p-hydroxybenzoate 0.1 g fragrance in the required amount
Dye in the required amount

Water ad 100 g

'

The connection 27a can be replaced by the connection 40b ¹ .

Example X

Cream for oily skin

Cetyl alcohol ^{5 g}

Isopropyl palmitate 6g

Vaseline oil 6g

polyethoxylated sorbitan

monostearate (Tween 60) 4.5 g

Glyceryl monostearate 2g

Preservative 0.3 g

Compound 25 1.6 g

Aspartic acid 0.8 g demineralized, sterile water to 100 g -

Series 214

909851/0904

L'OREAL

The connection 25 can be replaced by the connections 40, 26 or 38.

Example Y.

Lotion for oily skin

Compound 19 0.8 g

Diisobutyl-creosoxyäthoxyäthyldimethylbenzylammonium-chloride (Hyamine 10X)

Salicylic acid

Polyethylene glycol tert-dodecylthioether

Hydroxyethyl-carboxymethyl-2-alkyl ixnidazolinium (Miranol C2M)

Fragrance in the required amount of demineralized, sterile water ad 100 g.

0, 3 G 0, 2 G 0, 1 G 10 G

The connection 19 can be replaced by the connection 31.

Series 214

909851/0904

Claims (43)

DR. BERG DIPL.-ING. STAPF DIPL-ING. SCHWABE DR. DR. SANDMAIR PATENTANWÄLTE PO Box 860245 · 8000 Munich Attorney's file: 30 166 -1- PATENT CLAIMS 1./Cosmetic preparation for the treatment of oily hair and oily skin, characterized that they contain at least one active compound in a suitable cosmetic carrier material of the general formula I. -S-CH ₂ -CH ₂ -N-CH ₂ -CH-R ₃ (I) (O) OH contains, in which η 0, 1 or 2, R _{2 is} a hydrogen atom or a group of the following formulas -CH ₂ -CH ₂ OH, -CH ₂ -CH-CH ₃ or -CH ₂ -CH-CH ₂ OH, ^0H OH R _{3 is} a hydrogen atom or a group of the following formulas —CH ₃ or —CH ₂ OH, and R- is a group of the following formulas (i) -CH.
(ii) series f (089) 9S8272 988273 9SS274 933310 3 ' -CH ₂ -CH = CH ₂ , OH, (iv) - (CH ₀ ) -CH-COOH NH-R, Telegrams: BERGSTAPF PATENT Munich TELEX: Bank accounts: Hypo-Bank Munich 4410122850 (BLZ 70020011) Swift Code: HYPO DE MM Bajer VereinsbanJc Mttnchen 453ICO (BLZ 70020270) 0524560 BERG d 009851/0904 ^Potascheik München 65343-808 (BU 70010030) L ¹ OREAL where m is 1 or 2 and. R. is a hydrogen atom or a group of the formula -CORc, where Rc is a saturated or unsaturated alkyl group with 1 to 8 carbon atoms, (v) -CH ₂ -COR ₆ , wherein Rg is a group of the formula -OH or of the formula -N , \ _r ii where r ¹ and r ", which can be identical or different, represent hydrogen atoms or alkyl groups with 1 to S carbon atoms or together represent a divalent radical of the following formula - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ - or of the formula - (CH ₂ ) ₅ ~ represent, and (vi) -CH ₂ -V _ (vii) either represents a group of the formula -NH ₂ or a group of the formula -COOH, hedge. Series 214 909851/0904 L'OREAL 2. Preparation according to claim 1 / characterized in that that the effective compound with an inorganic or organic acid partially or is completely converted into a salt. 3. Preparation according to one of claims 1 and 2, characterized in that the inorganic or organic acid is selected from the group consisting of hydrochloric acid and hydrogen bromide acid, tartaric acid, malic acid, nicotinic acid, salicylic acid, N-oxonicotinic acid, palmitic acid, Gentisic acid, pyrrolidonecarboxylic acid, ascorbic acid, p-chlorophenoxyisobutyric acid, retinoic acid, o (-Hydroxyi sobutt er acid, oC- and ß-hydroxybutyric acid, S-Amino-S-thia-hexanedioic acid, pyruvic acid, Glycolic acid, citric acid, aspartic acid, glutamic acid, Oxo-glutaric acid, camphor sulfonic acid, thiodiglycolic acid and uronic acids. 4. Preparation according to one of claims 1 to 3, characterized in that it contains as an effective compound a compound selected from the following group: Connections No. 1.N- (2-methylthio-ethyl) -ß-hydroxyethylamine 2. N- (2-methylsulfinyl-ethyl) -ß-hydroxyethylamine 3.N- (2-methylsulfinyl-ethyl) -bis (2-hydroxy ^ ethyl) - am. '. n series 214 909851/0904 4. "N- (2-methylsulfonylethyl) bis (2-hydroxyethyl) amine 5. N- (2-methylsulfinyl-ethyl) -bis (2-hydroxy-propyl) -amine 6. N- (2-methylsulfinyl-ethyl) -bis (2,3-dihydroxypropyl) -amine 7. N- (2-Allylthio-ethyl) -bis (2-hydroxy-propyl) -amine 7a.N- (2-allylthio-ethyl) -bis (2-hydroxypropyl) -ammoniuiti- tartrate
7b.N- (2-allylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium- p-chlorophenoxy isobutyrate 8. N- (2-Allylsulfinyl-ethyl) -bis (2-hydroxypropyl) -amine 9. N- (2-Allylthio-ethyl) -bis (2,3-dihydroxypropyl) -amine 9'.N- (2-allylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium- β ·. glutamate 10. N- (2-ß-hydroxyethylthioethyl) bis (2-hydroxypropyl) amine 11. N- (2-ß-Hydroxyäthylsulfinyl-ethyl) -bis. (2-hydroxypropyl ) -amine 12. 3- (2-ß-Hydroxyethylamino-ethylthio) -alanine 13. 3- / 2- (2-Hydroxy-propylamino) -ethylthiq_7-alanine 14. 3- / 2- (bis (2-hydroxy-propyl) -amino-ethylthioj'-alanine 15. 3- / 2-Bis (2,3-dihydroxy-propyl) -amino-ethylthio_7-alanine 16. 2-Acetamido-3- / 2- (2-hydroxy-ethylamino) -ethylthiojpropionic acid 17. 2-Acetamido-3- / 2-bis (2-hydroxypropyl) aminoethyl thio_7-propionic acid Series 214 9098B1 / 090A L ¹ OREAL 18. 2-Acetamido-3- / 2-bis (2,3-dihydroxy-propy: 2) 9 «2n4ii & 2 ethylthio / propionic acid 19. 2-Amino-4- / 2- (2-hydroxy-ethylamino) -äthylthiq / -butyric acid 20. 2-Amino-4- / 2-bis (2,3-dihydroxy-propyl) -aminoethylthiq7-butyric acid 21. 2-Amino-4 - / 2- (2-hydroxypropyl) -amino-ethylthiqybutyric acid 22. 2-Amino-4 - / ^ - bis (2-hydroxypropyl) -amino-ethylthigT— butyric acid 23. 2- (2-Hydroxy-ethylamino) -ethylthio-acetic acid 24. 2- / bis (2-hydroxypropyl) amino / ethylthioacetic acid 25. N-Z ^ -Morpholinocarbonylmethylthio-ethyl-bis (2-hydroxy-ethyl) -amine . '- - 26. N- / 2-morpholinocarbonylmethylthio-ethyl7-bis (2- hydroxy-propyl) amine 26a.N-ZS-Morpholinocarbonylmethylthio-ethylZ-bis (2- hydroxy-propyl) amine hydrochloride 26b.N- / 2-morpholinocarbonylmethylthio-ethyl7-bis (2- hydroxy-propyl) ammonium pyruvate 26c. N-Z ^ -Morpholinocarbonylmethylthio-athyiy-bis (2- hydroxy-propyl) -ammonium-p-chlorophenoxyisobutyrate 26d.Di- / N- (2-morpholinocarbonylmethylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-7-malate 26e.Di- / N- (2-morpholinocarbonylmethylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium j-tartrate Series 214 909851/0904 L ¹ OREAL 27. N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylamine 27a.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl- ammonium gentisate 27b.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyäthy1- ammonium p-chlorophenoxyisobutyrate 27c.di / N- (2-o-aminophenylthio-ethyl) -ß-hydroxy- ä t hy 1 ainmon ium7-ma 1 at
27d.Di- / N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl- airunonium7 ~ tartrate 27e.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylammonium) malate 28. N- (2-o-aminophenylthio-ethyl) -bis (2-hydroxyethyl) -amine 29. N- (2-o-aminophenylthio-ethyl) -bis (2, 3-dihydroxypropyl) -amine 30. N- (2-o-aminophenylthio-ethyl) -bis (2-hydroxypropyl) amine 31. 2- (2-ß-Hydroxyethylamino-ethylthio) -benzoic acid 32. 2- (2-ß-Hydroxyethylamino-ethylsulfinyl) -benzoic acid 33. 2- / 2-bis (2-hydroxypropyl) -amino-ethylthiq7-benzoic acid 34. 2- / 2-BXS (2-hydroxypropyl) -amino-ethylsulfinyl-7-benzoic acid 35. 2- / 2-BiS (2,3-dihydroxypropyl) -amino-ethylthioybenzoic acid 36. 2- / 2-bis (2 _f 3-dihydroxy-propyl) -amino-ethylsulfinyl-7-benzoic acid Series 214 909851/0904 L ¹ OREAL 37. N- (2-Benzylthio-ethyl) -ß-hydroxyethylamine.
37a.N- (2-benzylthio-ethyl) -ß-hydroxyethylamine- hydrochloride 38. N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine 38a.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine- hydrochloride
38b.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium pyruvate
38c.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - airanonium p-chlorophenoxy isobutyrate
38d.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium pyrrolidone carboxylate
38e.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium malate
38f.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium gentisate
38g.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium glucuronate
38h.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-2-oxo-glutarate 39. N- (2-Benzylthio-ethyl) -bis (2,3-dihydroxypropyl) -amine 40. N- (2-Benzylthioethyl) bis (2-hydroxypropyl) amine 40a.N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - amine hydrochloride
40b.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) -ammonium-gentisate Seroe 214 909851/0904 L ¹ OREAL 4OcN- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - ainmon ium-mal at
4Od.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - ammonium o (hydroxyl isobutyrate
4Oe.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium pyruvate
4Of.N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium-2-oxo-glutarate
40g N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium ascorbate
40h N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium 3-hydroxy butyrate
4Oi.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - ainmon ium-c ampho su 1 f ona t
4Oj.N- (2-Benzylthio-ethyl) -bis (2-hydroxypropyl) - ammonium S-amino-S-thia-hexanedioate
40k.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - ammonium 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-hydroxy-ethyl) -2-hydroxy-propylamine 42a.N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2-hydroxy-propylamine hydrochloride 43. N- (2-Benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2,3-dihydroxypropylamine Series 214 909851/0904 L'OREAL 5. Preparation according to one of claims 1 to 4, characterized in that they the active compound in a concentration between 0.1 and 20%, preferably between 1 and 10%, based on the total weight of the preparation. 6. Preparation 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 an aqueous-alcoholic solution, in an oil, in an emulsion or contains in a gel and is a capillary preparation for the treatment of the scalp. 7. Preparation according to one of the preceding claims, characterized in that it the active compound in alcoholic or aqueous-alcoholic solution in combination with a customary one Contains cosmetic resin. 8. Preparation according to claim 7, characterized in that the usual resin is selected from the group consisting of polyvinylpyrrolidone; Copolymers of polyvinyl pyrrolidone and vinyl acetate; Copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid; Copolymers made by Polymerization of vinyl acetate, crotonic acid and Series 214 909851/0904 L ¹ OREAL an acrylic acid ester or methacrylic acid ester have been formed; Copolymers obtained by copolymerizing vinyl acetate, crotonic acid and a Vinyl alkyl ethers have been formed; and copolymers obtained by copolymerization of vinyl acetate, crotonic acid and a vinyl ester of a long chain carboxylic acid or an allyl ester or a methallyl ester a long chain carboxylic acid have been formed; includes. 9. Preparation according to one of claims 7 and 8, characterized in that they contains a propellant liquefied under pressure and is in the form of an aerosol spray paint 10. Preparation according to one of claims 7 and .8, characterized in that they contain 0.1 to 10%, preferably 1 to 3%, of the effective Compound and 0.1 to 10% of the resin in alcoholic or aqueous-alcoholic solution. 11. Preparation according to one of claims 1 to 5, characterized in that it the active compound in a concentration between 0.1 and 15%, preferably between 1 and 10%, in a mixture with at least one anionic, cationic, non-ionic or amphoteric detergent contains and in the form of a treatment shampoo pre-series 214 909851/0904 L ¹ OREM. lies. 12. Preparation according to claim 11, characterized in that that the concentration of the anionic, cationic, non-ionic or amphoteric detergent is between 4 and 20%, preferably between 5 and 10%, based on the total weight of the preparation. 13. Preparation according to one of claims 1 to 5 for Improving the appearance of the skin, thereby characterized in that they contain the active compound in a concentration between 0.1 and Contains 15% and preferably between 1 and 5% in a suitable cosmetic carrier material. 14. Preparation according to claim 13, characterized in that that they are in the form of an aqueous or aqueous-alcoholic lotion, a cream, a milk, a gel, a skin treatment material or pen or aerosol foam. 15. Preparation according to one of the preceding claims, characterized in that it additionally contains any of the usual ingredients used in cosmetic preparations - like fragrances, dyes, the penetration Series 214 909851/0904 L ¹ OREAL improving auxiliaries, surface-active agents, thickeners, emulsifiers, preservatives, cationic compounds, quaternary ammonium salts, vitamins, proteins, peptides, more or less may be highly hydrolyzed, and contain derivatives of starch or cellulose. 16. Compounds of the general formula I JN ..] DV ^ Xl ₉ V. ¹ I ^ (O) ₉ OH (D in the η 0.1 or 2, R _{9 is} a hydrogen atom or a group of the following formulas: -CH ₂ -CH ₃ OH, -CH ₂ -CH-CH ₃ or OH -CH ₉ -CH-CH ₉ OH, Oh
R _{3 represents} a hydrogen atom or a group of the following Formulas: -CHo or -CH ₂ OH, and R _{1 is} a group of the following formulas: (i) (ii) (iii) (iv) Series 214 -CH ₃ , -CHo "" CH ²³ CHo / -CH ₂ -CH ₂ OH, - (CH ₉ ) -CH-COOH, IU. ι NH-R ₄ in which m represents 1 or 2 and R _{4 represents} a hydrogen atom or a group of the formula -COR5, in which R ^ represents a saturated or unsaturated alkyl group with 1 909851/0904 L ¹ OREAL (ν) (vi) (vii) -13- up to 8 carbon atoms, -GH ₂ CORg, where Rg is a group of the formula V -OH or the formula -N ' stands. in which r 'and r ", which can be identical or different, contain hydrogen atoms or alkyl groups with 1 to 5 carbon atoms or together a divalent group of the following formulas: - (CH ₂ ) ₂ ~ 0- (CH ₂ ) ₂ ' or J ₅ - represent, -CH in which case the group R _{2 is} only a hydrogen atom when the group Rj is a hydrogen atom, and ^R 7
wherein R ^ is a group of the formula -NH ₂ or represents a group of the formula -COOH, where in the latter case the groups R ₂ and R ₃ are different for one and the same compound of hydrogen atoms, mean. Series 214 909351/0904 17. Compounds according to claim 16, characterized in that they are in the form of salts with an inorganic or organic acid. 18. Compounds according to claim 17, characterized in that that the inorganic or organic acids used to form the salts are selected from the group consisting of hydrogen chloride acid, hydrobromic acid, tartaric acid, malic acid, nicotinic acid, salicylic acid / N-oxonicotinic acid, Palmitic acid, ascorbic acid, p-chlorophenoxyisobutyric acid, Retinoic acid, Ct -hydroxyisobutyric acid, c <- and ß-hydroxybutyric acid, 5-amino-3-thia-hexanedioic acid, Pyruvic acid, glycolic acid, citric acid, aspartic acid, glutamic acid, oxo-glutaric acid, camphor sulfonic acid, thiodiglycolic acid and uronic acids. 19. Process for the preparation of the compounds according to
one of claims 16 to 18, characterized
marked that one is an oxirane of the general formula CH ₉ -CH-R-, in which R _{3 represents} a hydrogen atom or a group of the following formulas: -CH ₃ or -CH ₂ OH, in a polar solvent medium with a compound series 214 909851/0904 L ¹ OREAL the general formula R ₁ -S-CH ₀ -CH ₀ -NH-R ₀ I, Ζ Ζ ί converts, in which R ₁ , R ₂ and η have the meanings given in claim. 20. The method according to claim 19, characterized in that the reaction is carried out at a temperature from O ⁰ C to the boiling point of the solvent. 21. Process for the preparation of the compounds according to one of claims 16 to 18, characterized in that a hydroxyalkyl halide is used the general formula X-CH ₂ -CH-R ₃ OH in which X stands for a chlorine atom or a bromine atom and R-, a hydrogen atom or a group of the formulas -CH ^ or -CH ₂ OH, with a compound of the general formula I ₁ -S-CH ₂ -CH ₂ -NH-R ₂ (O) _n converts, in which R ₁ , R ₂ and η have the meanings given in claim. Series 214 909851/0904 _-] _b _ L ¹ OREAL 22. A method for the preparation of the compounds according to any one of claims 16 to 18, in which R2 is a Hydrogen atom and η 0 mean thereby characterized in that a thiol of the general formula R ₁ SH in which R _{1 has} the meanings given in claim 16, in a polar solvent medium with an N-hydroxyalkylaziridine of the general formula CH ₂ - CH ₂ CH ₂ CH-OH ^R 3 converts, in the R-, a hydrogen atom or a group of the following formulas -CH, or -CH ₀ OH. 23. Compounds according to claims 16 to 18, namely: 1. N- (2-methylthio-ethyl) -ß-hydroxyethylamine. 2. N- (2-methyl sulfynyl-ethyl) -ß-hydroxyethylamine. 3. N- (2-methyl sulfynyl-ethyl) -bis (2-hydroxy-ethyl) -amine. Series 214 909851/0904 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-dihydroxypropyl) -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-chlorophenoxy isobutyrate 8. N- (2-Allylsulfinyl-ethyl) -bis (2-hydroxypropyl) -amine 9. N- (2-Allylthio-ethyl) -bis (2,3-dihydroxypropyl) -amine 9 '.N- (2-allyithio-ethyl) -bis (2-hydroxy-ethyl) -ammonium- glutamate 10. N- (2-ß-hydroxyethylthioethyl) bis (2-hydroxypropyl) amine 11. N- (2-ß-Hydroxyethylsulfynyl-ethyl) -bis {2-hydroxypropyl ) -amine 12. 3- (2-ß-Hydroxyethylamino-ethylthio) -alanine 13. 3- / 2- (2-Hydroxy-propylamino) -ethylthiq7-alanine 14th 3- / 2- (bis (2-hydroxy-propyl) -amino-ethylthiq7-alanine 15. 3- / 2-Bis (2,3-dihydroxy-propyl) -amino-ethylthiq7 ~ alanin
1 6. 2-Acetamido-3- / 2- (2-hydroxy-ethylamino} -ethylthio7 ~ propionic acid 17. 2-acetamido-3- / 2-bis (2-hydroxy-propyl) -amino- äthylthiq7-propionic acid series 214 909851/09 OA L ¹ OREAL - J α - 18. 2-acetamido-3- / 2-bis (2,3-dihydroxy-yropyl) -dmino- ^; ethylthio / propionic acid 19. 2-Amino-4- / 2- (2-hydroxy-ethylamino) -äthylthiq / -butyric acid 20. 2-Amino-4- / 2-bis (2,3-dihydroxypropyl) -aminoethylthio7-butyric acid 21. 2-Amino-4- / 2- (2-hydroxypropyl) -amino-ethylthio.7-butyric acid 22. 2-Amino-4- / 2-bis (2-hydroxypropyl) -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-ethyl7 ~ to C2-hydroxy-ethyl) amine 26. N-Z ^ -Morpholinocarbonylraethylthio-ethylZ-bis (2-hydroxypropyl) amine 26a.N-Z2-morpholinocarbonylmethylthio-ethyl7-bis (2- hydroxy-propyl) amine hydrochloride
26b.N - /? - Morpholinocarbonylmethylthio-'ethyl7-bis (2- hydroxy propyl ammonium pyruvate
26c.NZ ^ -Morpholinocarbonylmethylthio-athyiy-bis (2- hydroxy-propyl) -ammonium-p-chlorophenoxyisobutyrate 26d.Di- / N- (2-morpholinocarbonylmethylthio-ethyl) -bis (2-hydroxy-propyl) -ammonium-Z-malate 26e.Di- / N- (2-morpholinocarbonylmethylthio-ethyl} -bis (2-hydroxy-propyl) -ammonium-tartrate Series 214 909851/0904 2324229 ^L ' ^0REÄL 27. N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethylamine 27a.N- (2-o-aminophenylthio-ethyl} -ß-hydroxyethylammonium gentisate 27b.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl- ammonium p-chlorophenoxyisobutyrate 27c.di / N- (2-o-aminophenylthio-ethyl) -ß-hydroxy- äthylammonium7-malat 27d.Di- / N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl- ammoniuin7 "tar entered 27e.N- (2-o-aminophenylthio-ethyl) -ß-hydroxyethyl- ammonium) malate 28. N- (2-o-aminophenylthioethyl) bis (2-hydroxyethyl) amine 29. N- (2-o-aminophenylthioethyl) bis (2,3-dihydroxypropyl) amine 30. N- (2-o-aminophenylthio-ethyl) -bis (2-hydroxypropyl} amine 33. 2- / 2-bis (2-hydroxy-propyl) -araino-ethylthio7-benzoic acid 34. 2- / 2-bis 2-hydroxy-propyl) -amino-ethylsulfinyl, 7-benzoic acid 35. 2- £ 2-bis (2,3-dihydroxypropyl) -amino-ethylthiQ_7-benzoic acid 36. 2- / 2-bis (2,3-dihydroxy-propyl) -amino- ethyTsulfonylbenzoic acid Series 214 909851 / 090A 37. N- (2-Benzylthio-ethyl) -ß-hydrc:; yäthyla; uin 37a.N- (2-benzylthio-ethyl) -ß-hydroxyethylamine hydrochloride 38. N- (2-Benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine 38a.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -amine- hydrochloride
38b.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - airanonium pyruvate
38c.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium p-chlorophenoxy isobutyrate 38d.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium pyrrolidone carboxylate 38e.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium malate
38f.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium gentisate
38g.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) - ammonium glucuronate
38h.N- (2-benzylthio-ethyl) -bis (2-hydroxy-ethyl) -ammonium-2-oxo-glutarate 39. N- (2-Benzylthio-ethyl) -bis (2,3-dihydroxy-propyL) -amine 40. N- (2-Benzylthioethyl) bis (2-hydroxypropyl) amine 4Oa.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - amine hydrochloride
40b.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl} -ammonium-gentisate Seroe 214 909851/0904 L ¹ OREAL -21-4OcN- (2-benzylthio-ethyl) bis (2-hydroxypropyl) - ammonium nalat
4Od.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) - ammonium o (-hydroxyisobutyrate
4Oe.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium pyruvate
4Of.N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium-2-oxQ-glutarate
40g N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium ascorbate
40h N- (2-benzylthio-ethyl) -bis (2-hydroxy-propyl) - ammonium 3-hydroxy butyrate
4Oi.N- (2-Benzylthio-ethyl) -bis (2-hydroxy-propyl} - ammonium camphosulfonate
4Oj.N- (2-Benzylthio-ethyl) -bis (2-hydroxypropyl) - ammonium S-amino-S-thia-hexanedioate 40k.N- (2-benzylthio-ethyl) -bis (2-hydroxypropyl) -. ammonium nicotinate
401. N- (2-Benzylthioethyl) bis (2-hydroxypropyl) ammonium salicylate 41. N- (2-Benzylsulfinyl-ethyl) -bis (2-hydroxypropyl) -ami n 42. N- (2-Benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2-hydroxy-propylamine 42a.N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2-hydroxy-propylamine hydrochloride 43. N- (2-benzylthio-ethyl) -N- (2-hydroxy-ethyl) -2,3-dihydroxypropylanine Series 214 909851/0904