DE3035899A1 - (BETA) - (BENZYLAMINOTHIOCARBONYLMERCAPTO) - (ALPHA), (ALPHA) -DIPHENYLPROPIONIC ACID AND COSMETIC AGENT CONTAINING (OMEGA) - (AMINOTHIOCARBONYLMERCAPTO) ALKANIC ACIDS - Google Patents

Description

WELLA Darmstadt, September 23rd, 1989 Corporation

β- (Benzylaminothiocarbony! mercapto) = <χ ₃ cx diphenylpropionic acid and cosmetic agents contain end ω - (Amino thiocarbony! mercapto ■) alkanoic acids

The invention relates to the compound ß- (Benzylamino thiocarbony! Mercapto) - (X _s (Y-dipheny! Propionic acid and cosmetic agents containing at least one CJ- (aminothiocarbonylmercapto) alkanoic acid and / or its salts »

Numerous substances have already been recommended as active ingredients for combating dandruff. These include compounds that increase blood flow such as nicot in acid ester, panthenol _s icloidal sulfur, hydroxyquinoline _s phenols., Quaternary ammonium compounds, selenium sulfide ₃ pyridinthione and numerous other compounds.

Of the compounds mentioned, the l-hydroxy-2-pyridinthione and its salts, zinc sais in particular, is particularly effective against dandruff. Due to the limited solubility of zinc pyridinthione in common cosmetic solvents such as water and alcohols however, it can only be incorporated into clear cosmetic products with difficulty will.

The compounds previously proposed as active ingredients for the treatment of dandruff can in terms of their effectiveness against dandruff, in toxicological and derma ™ From a ecological point of view or - as in the case of zinc pyridinthione - because of its poor solubility in cosmetic solvents do not fully satisfy the requirements set.

There was therefore the task ©, cosmetic agents with a content of an active ingredient To combat dandruff to create those mentioned above Better meet requirements »

It has now been found that cosmetic compositions comprising conventional cosmetic carriers and additives _s characterized by a content of at least one CO - (! Aminothiocarbony mercapto) alkanoic acid and / or its salt of the general formula

»Γ Ί

R-NH-C-S- Cl., - COOA (I)

in the

R one of the radicals H ₉ alkyl _s Hydro3syalkyl _s Carboxyalky1, Halogeraalkyl _a Cyanoalkyl _s Alkoxyalkyl, Cycloalkyl, Alkenyl ₉ 35

Alkynyl, arylalkyl ₉ ary! Alkyl substituted in the aryl part, aryl _s alkyl, halogen, nitro =, alkoxy = », aryloxy, cyano-substituted aryl, thiazolyl, benzthiazolyl, thienyl, FuryI ₃ pyrazolyl, imidazolyl, pyridazolyl, thiadiazolyl, Pyrimidiny1, triazinyl or RR means N group, wherein R and R are each independently H, alkyl, cycloalkyl, Ary! alkyl, alkenyl, aryl, _s = alkyl, halogen, nitro, alkoxy, aryloxy = s =, aryl Cyanosub3tituiertes mean or

1 ?
but R and R together with the nitrogen atom to which they are attached are part of a heterocyclic ring and in this ring the segment - (CHg) _n -X- (CH ₂ ) - with X = CH ₂ , O ₉ S ₅ NR ⁵ (R's alkyl, arylalkyl, aryl) _s w. ~ 0 to 3 and p = 1 to 3, represent _s with the proviso that m is only 0 when X = CHp,

Y means H ₅₁ alkyl, hydroxyalkyl, carboxyalkyl haloalkyl, alkoxy = alkyl, cycloalkyl _s arylalkyl, arylalkyl substituted in the aryl part ₉ aryl, alkyl-j, halogen = _s alkoxy, aryloxy "• oä © r-substituted aryl has _s

A H, an organishep Katian © der

means inorganic cation and 35

η represents an integer from 1 to IO,

to combat dandruff the provided ones Meet requirements to a large extent. 5

In particular, these agents have excellent effectiveness against dandruff on, and when using the GJ (aminothiocarbonyl mercapto) alkanoic acids mentioned here and / or their salts - in contrast to zinc pyridinthione - clear cosmetic hair and scalp treatment agents without any problems produce.

Another advantage is that the aforementioned contained in the means Compounds have a significantly lower toxicity compared to zinc pyridinthione, for example for the compound ß-CNjN-dimethylhydrazinothioearbonylmercapto) propionic acid is about the pactor smaller.

Examples of suitable ₃ compounds according to the formula (I) contained in the agents according to the invention are

Methylaminothioearbonylmereapt © acetic acid ,,

N, N-Dimethylhydrazinothioearbonylmer ^> eapt0-acetic acid,

ß-CBenzylaminothioearbonylmsreapto) = Ot _s OC = dipheny! propionic acid and
35

- 8 =

ß-CNjN-dimethylhydrazinothioearbonylmercapto) propionic acid.

The salts of the abovementioned compounds according to the formula (I) are especially those Alkali or ammonium salts into consideration.

The compounds of the formula (I) described here are partly known and partly known they can be used just like the well-known

1 2)

bonds are prepared according to the organic synthesis methods described ^{in the literature s} '.

A primary amine is used for their representation, a hydrazine, an N-monosubstituted hydrazine, a Ν, Ν-disubstituted hydrazine or the salts these compounds in a suitable polar solvent, for example ether, ethanol or pyridine, with carbon disulfide and one Base, preferably sodium hydroxide solution or potassium hydroxide solution, converted to the dithiocarbamate (II) (see Equation 1),

R - NH ₂ + CS ₂ - »R-NH-CS cation (1) (II)

1) PC Brown et al, J. Or-g. Chem. '2M ^ IO56 (1959)

2) W. Hanefeld ₉ Arch. Pharra. 507, 476 35

ft * *

The dithiocarbamate (II) then reacts with an ω-chlorine-substituted carboxylic acid (III) to the salt of GJ ~ (arainothioearbonylmercapto) alkanoic acid (IV) (see equation 2),

R-NH-C-S

(ID

S II R-NH-C-S

Cation + Cl - CY,

- COOH

(III)

cation

(IV)

(R, Y and η have the meanings already given above.)

(2)

ß- (aminothiocarbonyl mercapto) = alkanoic acids (VI) can also be obtained by reacting the dithiocarbamate s (II) with a β = Laeton (V) (see equation 3) »

S R-NH-C-S - cation

(II)

R-NH-C-S

- H ₁ ■

.CY ₂ - CI ₂

ο — c - ο

(V)

COO cation

(3)

(VI)

The free Cd (aminothioearboay! Mercapto) - -alkanoic acid is obtained by first removing the solvent from the resulting saline (IV) and the residue is then treated with aqueous hydrochloric acid "

As a synthesis example of the presentation of the new compound is .beta. below (Benzylaminothiocarbony! Mercapto) -efjef-diphenylpropionic also welnhe subject of this application is given _s "

6.4 g (0.06 mole) of benzylamine dissolved in 50 ml of dry diethyl _s are at about - 10 C was added with 2.3 g (Q, '03 mol) of carbon disulfide and the precipitated quantitatively Benzy ammoniumbenzyldithiocarbamat filtered off!. The reaction product, 8.7 g '(0 _s 03 mol) ₈ is with 6.7 g (0.03 mol) οζ , eC-Diphenylprepiolaeton in 50 g pyridine for one hour at about 0 ° C and then for one hour at Stirred at room temperature. The solution is concentrated in vacuo at 60 ° C. and the viscous residue is shaken out several times with a mixture of 10% aqueous hydrochloric acid and methylene chloride. After drying with WapSO ^ and concentration of the methylene chloride phase obtained, partly crystalline, partly. ', _S zähe.JIasse is .with Toluol'versetzt, wherein the viscous components are dissolved on stirring and the remaining colorless crystals having a melting point of 159 - 163 ° C can be extracted.

9! -f

- ii -

Yield: 10.62 g (corresponding to 87 % of theory)

Analysis: N calculated - 3.44 %

(C ₂₅ H ₂₁ NO ₂ S ₂ ) N found = 3.31 %

S calculated = 15.73 %

S found = 15.62 %

Absorption 3335 cm (NH)

in the infrared range: 2520 - 3000 cm " ¹ (COOH)

1690 cm " ¹ (C = O)

The compounds mentioned as a constituent of the cosmetic agents described here according to the formula (I) have for the agents according to the invention are · = the concentrations show excellent effectiveness against dandruff. You can also they because of their good solubility in the solvents customary for cosmetic preparations like water and water-alcohol mixtures in most cosmetic preparation forms Find use.

The above compounds according to formula (I) are in any suitable _s for hair and scalp treatment cosmetic preparations, such as insoles in forward @ ₃ Rinses _s styling gels, hair oils Frisiereremes ,, _s hair pomades, hair treatments, Wassenkellotionen. Powders, sprays, but preferably in shampoos and hair lotions, use.

These are preparations that, depending on their intended use, remain on the hair and scalp for a shorter or longer period of time *. Due to their content of the compounds of the formula (I) described, a dandruff treatment is effected at the same time. It is also possible, however, preparations herzust © _s cases mainly or exclusively aimed at fighting dandruff serve =

The concentration of the compounds according to formula (I) is in the preparations which remain on the hair and scalp, such as in hair tonics and insertion means, about 0.1 to 5.0 weight "JS ₉ is preferably 0.5 to 2 , 0% by weight . Preparations which are rinsed off shortly after their application, such as shampoos and rinses contain ω - (Aminothioearbony mercapto!) - alkanoic acids and / or salts thereof in an amount of about 1.0 to 10.0 percent, "% _s preferably 1.0 to 3.0 GeWo %. The compounds mentioned can be present in these preparations either alone or as a mixture with one another.

The composition of these cosmetic preparations represents a mixture of the compounds according to the formula (I) with the constituents customary for such preparations, such as carriers and Additives.

- 13 -

The cosmetic carrier can be a carrier that is customary for topical use, such as an ointment base, a powder or, above all, a liquid carrier such as water, alcohols or aqueous-alcoholic mixtures. Alcohols suitable for this purpose are, for example, ethanol, n-propanol, i-propanol and also polyhydric alcohols such as glycerol and propylene glycol.
10

Liquid carriers such as water and alcohols are particularly preferred because When they are used, they usually result in clear solutions and these carriers are particularly intense come into contact with the scalp.

Preferred preparations are hair lotions and shampoos against dandruff, the latter being one anionic, cationic, nonionic or amphoteric detergent as usual detergent Part included.

Conventional additives in cosmetic preparations, for example, cosmetic resins, emulsifiers, thickeners such as higher fatty alcohols, starch, cellulose derivatives, paraffin oil coming _s also care substances, such as lanolin derivatives, cholesterol and pantothenic acid, and also dyes, perfume oils, solid fillers, propellants and other concerned.

The examples below are intended to = the blessing explain the status of the invention in more detail «·

example 1

10

15th

20th

25th

2.0 S. 30.0 G 4.0 S. 0.2 S. ο, ι G 63.7 S. 100.0 G example 2

1.5 g

40.0 G 0.2 G 0.1 G 58.2 G 100.0 G

- 14 ■ -

Beis piele Shampoo

Methylaminothioearbony! Mercaptoacetic acid Sodium lauryl alcohol diglycol- © ether sulfate _s 28% aqueous solution Sodium chloride Parfüra oil Coloring material Water

Hair lotion

NjN-diethylhydrazinothiocarbonyl mercaptoacetic acid Isopropanol perfume oil dye water

30 Example 3 1.0 g

3.0 g 35

ß ™ (N, N-Diiaethylhyürazinothiocarbonylmercapto) -propionic acid copolymer from 60 % vinylpyrrolidone and 40 % vinyl acetate, in powder form

- 15 -

40.0 G Ethanol, 94 0.2 G Perfume oil 0.1 G dye 55.7 G water

100.0 g

Example 4 Hairdressing Gel 10

1.5 G ß-CNjN-diraethylhydrazinothiocarbonyl- mercapto) propionic acid 29.4 G Oleylcetyl alcohol, ethoxylated with 7-8 moles of ethylene oxide, 80 sig (Eumulgin M 8 from Henkel) 17.5 G Paraffin oil 0.2 G Perfume oil 0.1 G dye 51.3 G water

100.0 g

25 All percentages given in the present application represent percentages by weight »

Claims (5)

Claims in the R one of the radicals H, alkyl, hydroxyalkyl, carboxyalkyl, haloalkyl, cyanoalkyl, Alkoxyalkyl, cycloalkyl, alkenyl, Alkynyl, arylalkyl, substituted arylalkyl in the aryl moiety, aryl, alkyl, halo, nitro, alkoxy, aryloxy, cyano-substituted aryl _s thiazolyl _a benzothiazolyl, thienyl, furyl, pyrazolyl, imidazolyl, Pyridasolyl, thiadiazolyl, pyrimidinyl, thiazinyl or a® R ¹ R ² N group, where R ¹ and R independently of one another are each H, alkyl, cycloalkyl, arylalkyl, alkenyl, aryl, alkyl, halogen, nitro, alkoxy, aryloxy = ₉ cyano » substituted aryl or R and R together with the Nitrogen atom to which they are bound are ₉ part of a netroeyelic ring and in this ring the segment - (CHg) -X- (CH ₂ ) - with X = CH ₂ , O ₈ S, MR '(R' s Alkyl, Arylalkyl ₉ Aryl), a = 0 to 3 and P = I to 3p represent mater of the requirement j, that m mar then means 0 _s ti®wa X ^s GH «i Y means H ₅ alkyl _B hydroxyalkyl, carboxyalkyls haloalkyl _s alkoxyalkyl, cycloalkyl _s arylalkyl ", arylalkyl substituted in the aryl part, aryl, alkyl- _s halogen = ,, nitro =., Alkoxy-, aryloxy = or cyano-substituted aryl has _s A means H, an organic cation or inorganic cation and η represents an integer from 1 to 10 », to combat head dandruff * 2. Means according to claim I _3, characterized in that the compound of the formula (I) is selected from Methylaminothioearbonylsasreaptoacetic acid, Ν, Ν-dimethylhydrazinothioearbonylmercaptoacetic acid, β- (Benzylinothioearbony! mercapto) - of, OT-dipheny! propionic acid and ß-CN ^ -Dimethylhydrasinothioearbonylmereapt ©) -propionic acid. 3. Composition according to claim 1 and 2 ₉ j characterized in that the compounds of formula (I) in an amount of about 0.1 to 10.0 wt.%, Preferably y O ₅ 5-3 0 ₉ wt.% ₃ are. ^1- component agent according to Claims 1 to 3 _3, characterized in that it is a shampoo © that is a hair tonic. 5. ß-C-benzylaminothiocarbony! Mercapto) - of » ΰ (· dipheny! Propionic acid