DE2521899A1 - NEW DIAMINES, THE PROCESS FOR THEIR MANUFACTURING AND THE MEANS CONTAINING THEM - Google Patents

Description

PROF. DR. DR. J. REITSTÖTTER 7C71

DR.-ING. WOLFRAM BUNTE £. <SL · \

DR. WERNER KINZEBACH

D-8OOO MUNICH AO. BAUERSTRASSE 22 · FERNRUF (O89) 37 SS 83 ■ TELEX S21S2O8 ISAR POSTAL ADDRESS: D-8OOO MUNICH 43. POST BOX

Munich, May 16, 1975 M / 16098

L · OREAL 14, rue Royale, F-75008 Paris, France

New diamines, processes for their production and compositions containing them

The present invention "relates to new diamines, a process for their production and agents containing them.

The invention relates in particular to the diamines of the formula I.

CH, CH,

I ³ !

N A N (I)

ι I

RR

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and their addition salts with acids, where the substituents R and A have the following meanings: R stands for an aliphatic radical which has 3 to 20 carbon atoms, a cyclohexyl radical or a benzyl radical; A stands for A. or A ₂ , where A. is a meta- or para-xylylidene radical of the formula

and A _{2 represents} a radical of the formula

- (CH ₂ ) _y -CH- (CH ₂ ) _x -CH- (CH ₂ ) ₁ .-

means, where x, y and t mean integers starting from
0 to 11 can vary and are such that
the sum (x + y + t) greater than or equal to 1 and less than
18 is and where R. and R _{2 represent} a hydrogen atom or
are an aliphatic radical having fewer than 18 carbon atoms; with the exception of the diamines of the formula I with the following parameters:

a) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 4 or 8; and R = benzyl;

b) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 1; and R = cyclohexyl;

c) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 4; R stands for the 1,5,9-trimethyl-decyl radical or the 1,5,9,13-tetramethyltetradecyl radical;

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d) A = A ₂ , R ₁ = R ₂ = ethyl; y = t = o; x = 6; and R stands for the 2-ethylbutyl radical;

e) A = A ₁ and R = benzyl, cyclohexyl or isopropyl.

If R in general formula I is an aliphatic radical, it is in particular an alkyl radical having 3 to 20 carbon atoms and preferably 3 to 12 carbon atoms; if the substituents R ₁ or R _{2 represent} an aliphatic radical, it is in particular an alkyl radical having 1 to 17 carbon atoms and in particular 1 to 4 carbon atoms; the sum (x + y + t) is preferably greater than or equal to 1 and less than or equal to 10.

Among the diamines of the formula I defined above, there may be mentioned in particular those in which: R represents a cyclohexyl radical, beneyl radical or an alkyl radical having 3 to 16 carbon atoms, such as a propyl radical, butyl radical, hexyl radical, octyl radical, deeyl radical, dodecyl radical, hexadecyl radical; A is A-, namely a meta- or para-xylylidene radical; A denotes A ₂ , R ₁ and R _{2 represent} a hydrogen atom or, in other words, A denotes a polymethylene radical which has 3 to 12 carbon atoms and which in particular has 3, 5, 6, 8, 10 or 12 carbon atoms; or in which at least one of the substituents R ₁ and R _{2 is} an alkyl radical having 1 to 17 carbon atoms and in particular a methyl or ethyl radical and in this case the substituent R is preferably a linear alkyl radical with in particular the meanings given above; x, y and t are in particular 0, 1, 2, 3 or 4. If A stands for a meta- or para-xylylidene radical, R preferably denotes an alkyl radical having 4 to 12 carbon atoms or an n-propyl radical.

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The addition salts of the diamines of the formula I are in particular those which have the various meanings of the above correspond to specified substituents; they correspond to formula II

H-

CH,

CH

H (II)

wherein A and R have the meanings given above and X ^ stands for an anion derived from a mineral acid or an organic acid.

In general formula II, Xw stands in particular for a halogen anion (especially bromine or chlorine), or an anion that is different from other mineral acids, such as phosphoric acid or sulfuric acid and the like, or for an anion that is derived from an organic sulfonic acid or Carboxylic acid, especially an alkanoic acid having 2 to 12 carbon atoms (for example acetic acid), a Phenylalkanoic acid (for example phenylacetic acid), from benzoic acid, from lactic acid, from citric acid or from Paratoluenesulfonic acid.

The invention relates in particular to the diamines of the formula I and their addition salts, which are described below in the Examples 1 to 30 are described.

The diamines of the formula I are prepared according to one of the methods described below.

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METHOD 1

A primary 1min of the formula R-NHp is allowed to react with a dihalide of the formula Hal-A-Hal, where R and A have the meanings given above and Hal represents a halogen atom and preferably a bromine atom or iodine atom. One works between about 50 and 150 ⁰ C and uses an excess of primary amine, generally 2 to 5 mol of primary amine per mol of dihalide. After treating the reaction mixture with a basic solution, for example a solution of sodium hydroxide solution or potassium hydroxide solution, the disecondary diamine of the formula R-NH-A-NH-R is obtained.

The latter is now subjected to a methylation reaction, for example by the action of formaldehyde in the presence of formic acid, according to the method of ESCHWEILER-OLARKE. The latter is carried out with an excess of formaldehyde, namely 2.2 to 10 moles, and preferably 2.5 to 5 moles, of formaldehyde per 1 mole of diamine. The formic acid is also used in excess, namely from 2.5 to 10 moles and preferably from 5 to 8 moles per mole of diamine. The reaction takes place at a temperature between 40 and 100 C, preferably between 80 and 100 ⁰ C. The ditertiary diamine formed can be isolated by distillation.

METHOD 2

A primary amine R-NHp is left with an arylsulfonyl halide Ar-SOp-Hal react, where Ar is an aryl group, for example represents a phenyl or tolyl group and Hal represents a halogen atom, for example a chlorine atom. Man receives a sulfonamide of the formula Ar-SOp-NHR, which is subjected to a methylation reaction by first being a Alkali metal derivative, for example by the action of a

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Alkali metal alcoholates, such as sodium ethylate, and then this derivative is treated, for example, the sodium derivative with dimethyl sulfate. You get the Compound of formula

Ar - SO ₉ - N

by acid hydrolysis, for example with an aqueous solution of sulfuric acid, to the secondary amine of the formula

leads. This latter derivative is then allowed to react with a dihalide of the formula Hal-A-Hal (Hal and A have the same meanings as before) in the presence of a tertiary amine, such as N-ethyl-diisopropylamine, with at least two moles of secondary amine and tertiary amine used for 1 mole of dihalide. The reaction is preferably carried out without a solvent and at a temperature between 50 and 130 ⁰ C. At the end of the reaction, the mixture is taken up with water to dissolve the amine salts and extraction is carried out with a suitable solvent such as ethyl acetate. The extracts are then washed with an aqueous alkali solution (sodium hydroxide solution or potassium hydroxide solution), then with water. The organic phase is then dried, then the di-tertiary amine is isolated either by distillation or by concentration under reduced pressure.

METHOD 3

The mixture is allowed a primary amine R-NH ₂ with an arylsulfonyl halide, as indicated in Method 2, react. The received

"" ■ O ""

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Sulfonamide of the formula Ar-SO ₂ -NHR are employed with a dihalide of formula Hal-A-Hal in order at a temperature between about 80 and 140 ⁰ C. The disulfonamide of the formula formed

Ar-SO ₂ -NAN-SO ₂ -Ar RR

can be subjected directly to acid hydrolysis without isolation. This acidic hydrolysis can be carried out, for example, in an aqueous 85% sulfuric acid solution at a temperature between approximately 120 ^° C. and 145 ° C. for a time between 7 and 20 hours. The disecondary diamine of the formula is obtained

RR II

N - A - "KT

I I

H H

that a methylation reaction, for example by reaction with formaldehyde in the presence of formic acid, in accordance with the method of ESCHWEILER-CLARKE, subjected.

The addition salts of the diamines of the formula I are prepared according to customary methods by adding to the diamines of the Formula I adds acids of the formula X-H, where X has the meanings given above.

The diamines of the formula I are new industrial products, in particular as intermediates for the production of Polymers that contain quaternized ammonium groups are useful based on the repeating units of the general formula III

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•1

CH,

CH,

(in)

", in which A, R and X have the meanings given above and B, which can be the same as A or different from A, has the same definition as the A group.

To prepare the polymers of the formula III, a di-tertiary diamine of the formula is subjected

N-

CH,

■ N

and a dihalide of the formula

B-

• X

wherein A, B, R and X have the meanings given above, a polycondensation reaction.

For example, the polycondensation reaction is carried out in a solvent or a mixture of solvents, which promote the quaternization reactions, such as water, dimethylformamide, acetonitrile, lower alcohols, in particular the lower alkanols, such as methanol and the like, by.

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The reaction temperature may be between 10 and 150 ⁰ C and preferably vary between 20 and 100 ⁰ C.

The reaction time depends on the type of solvent, the initial reactants, and the desired degree of polymerization away.

In general, the starting reactants are allowed to react in equimolecular amounts, but it is also possible. borrowed either the diamine or the dihalide in light To use excess, this excess being less than 20 mol-Ji.

It is possible to regulate the mean length of the chains by adding one at the beginning or during the reaction small amount (1 to 15 mol $, based on one of the reactants) a monofunctional reactant, such as a tertiary amine or a monohalide.

The polymers of the formula III have important cosmetic properties when they are incorporated into cosmetic agents applied to the hair or skin.

When used alone or with other active substances during treatment such as shampooing, dyeing, Water waves etc. are applied to the hair, they significantly improve the properties of the hair.

For example, they promote the treatment and make it easier to straighten the wetted hair. Even with high concentration do not give the wetted hair a sticky grip.

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In contrast to common cationic agents, they "weigh down." not dry hair and facilitate voluminous hairstyles. They give dry hair bounce and a glow Appearance.

They are effective in reducing the deficiency of hair that has become fragile through treatments, permanent waving or dyeing to eliminate. It is well known that hair that has become sensitive is often dry, dull and rough and difficult to straighten and hairdressing.

The polymers of the formula III are in the cosmetic agents for hair according to the invention either as an additive or as the main active ingredient in water wave lotions, treatment lotions, Creams or gels for hairstyles, or as an additive for shampoos, water waving products, permanent waving products, Colorants, restructuring lotions, anti-dandruff treatment lotions or hair lacquers are useful.

The polymers of Formula III also have important cosmetic properties when applied to the skin will.

In particular, they promote the hydration of the skin and thus prevent it from drying out. In addition, lend they give the skin a considerable delicacy. They are in cosmetic agents for the skin, such as creams, gels or lotions.

The polymers of formula III have other interesting properties, especially germicidal properties and whole especially bactericidal and fungicidal properties. They also have surfactant and film-forming properties. Their germicidal, surfactant or film-forming properties make them useful, especially as preservatives

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agent, "for example in adhesives and glues or in Toiletries, or as an additive in leather treatment agents or in cellulose derivatives, especially in paper.

The addition salts of the diamines of the formula I, i.e. the compounds of formula II, are new industrial products that have interesting germicidal properties and in particular have antibacterial and antifungal properties, such as those used in chemotherapy in the field of combating bacteria and the harmful fungi are useful.

The compounds of the formula II act in particular on the following bacteria: Staphylococcus aureus, Bacillus subtilis, Sarcina lutea, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Proteus vulgaris, Corynebacterium acnes.

The compounds of formula II have a remarkable antifungal property against numerous fungi and Yeasts and especially against Aspergillus niger, Penicillum notatum, Candida, Pityrosporum ovale, Saccharomyces cerevisiae.

The present invention also relates to the use of the compounds of formula II as antibacterial and antifungal Medicinal products in human and veterinary therapy for the treatment of skin infections, of the phaners and the mucous membranes.

The compounds of the formula II can be used, for example, in the treatment of skin mycoses, hair mycoses and mycotic intertrigos or mycotic anal or vulvar dermatitis used will.

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The invention relates to pharmaceutical agents that contain at least contain a pharmaceutical as defined above. These funds are produced according to the usual methods.

These pharmaceutical agents can be used in particular by topical application to the skin, the phanera or the mucous membranes, administered.

For this purpose, they can be in the form of solutions, emulsions, suspensions, mouthwashes, creams, lotions, or pommades Aerosol preparations are available.

In the pharmaceutical compositions the concentration varies to addition salts of the 3? Ormel II generally between 0.2 and 10 wt .- #, and preferably between 0.4 and 5 I °>

The compounds of the formula II can also be used in the field of cosmetology. You can for example in combination with a suitable binder in the composition of cosmetic or hygienic preparations such as soaps, shampoos, hair lotions (in particular anti-dandruff lotions) or deodorizing Preparations, enter.

These cosmetic or hygienic preparations can be in the form of solutions, emulsions, creams, Pens or aerosols.

In these cosmetic or hygienic preparations, the concentration of the formula II varies generally between 0.05 and 10 wt .- #, and preferably between 0.1 and 5 $ of addition salts ·

In the cosmetic or hygienic agents for hair according to the invention, the compounds of the formula II have ins-

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• ΊΟ ·

special bactericidal and fungicidal effect; this effect can be particularly effective in anti-dandruff medication come, but also in all hair products of the color-supporting type, water wave lotions, various hair lotions, Shampoos and the like.

In the cosmetic or hygienic agents according to the invention for the skin, the compounds of the formula II in particular a bactericidal and fungicidal effect; this effect can especially be used in deodorants, in the form of sprays, sticks, emulsions, soaps and the like, for example, come into play.

The cosmetic means based on the "compounds of the Formula II include in particular:

(a) hair lotions and in particular hair treatment lotions, which are characterized in that they contain at least one compound of the formula II in aqueous, alcoholic or aqueous-alcoholic solution (where the alcohol is in particular ethanol).

The content of the compound of the formula II can be between 0.2 and 10 wt .- ^ and preferably between 0.4 and 5 wt .- # vary.

To treat the hair with a lotion of this type, this lotion is applied to the hair and left on for a period of time that can be up to 30 minutes, rinses and dries if necessary.

(b) Shampoos which are characterized in that they contain at least one compound of the formula II and one cationic or non-ionic detergent.

The cationic detergents are in particular quaternized ammonium compounds with a long chain,

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Esters of fatty acids and amino alcohols or amino polyethers.

The nonionic detergents are, in particular, esters of polyols and sugars, condensation products from ethylene oxide with a fatty substance, with alkylphenols with long chains, with mercaptans or with alcohols long chain or long chain amides and the polyhydroxylated polyethers of fatty alcohol.

These agents in the form of shampoos can also contain various adjuvants, such as Perfumes, dyes, preservatives, thickeners, foam stabilizers, softeners or one or more cosmetic resins.

In these shampoos, the concentration of detergent is generally between 5 and 50 wt. -Fi and the concentration of compounds of the formula II varies between 0.2 and 10 and preferably between 0.4 and io

5 <fo.

(c) Deodorizing preparations, which are characterized in that they contain at least one compound of formula II in a concentration that varies between 0.05 and 5 and io, preferably between 0.1 and 3 wt .- $, and a suitable cosmetic binder for use on the skin.

These deodorant preparations can be in the form of powders, which can be prepared by incorporating a compound of the formula II and optionally a perfume in a powder usually used as a cosmetic binder were obtained in the form of liquid preparations made by dissolving a compound of formula II in an aqueous or aqueous-alcoholic binder, in the form of creams or emulsions,

-H-

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• Αζ ·

which starting from a commonly used for cosmetic Creams or emulsions used based on which one the selected amount of the compound of formula II, previously was dissolved in an aqueous medium, added, are obtained in the form of aerosol preparations which a compound of the formula II dissolved in an alcoholic, aqueous or aqueous-alcoholic medium contains, the solution being mixed with a liquid or pressurized gaseous propellant gas placed in a hermetic, valved container, contained or in the form of Soaps or cleaning sticks.

The cosmetic agents according to the invention generally contain at least one adjuvant commonly used in cosmetic agents.

The adjuvants usually present in these cosmetic agents are, for example, perfumes, dyes, Emulsifiers, thickeners and the like.

The invention also relates to the use of the above-defined addition salts of the compounds of formula II as antibacterial and antifungal agents.

The invention relates in particular to the use of the salts of the formula II in pharmacy or cosmetology, the is characterized in that pharmaceutical, hygienic or cosmetic agents are produced which contain at least one Contain salt of formula II.

The invention also relates to a method for combating bacteria, fungi or parsitary yeasts of the skin, the phanera or the mucous membranes, which is characterized in that one

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at least one salt of the formula II is applied to the parts of the body parts under consideration in an amount which sufficient to obtain the desired bactericidal and / or fungicidal effect. This method can in particular be used by the salts of formula II by means of pharmaceutical, hygienic or cosmetic agents, such as described above.

The following examples explain the invention without, however, restricting it.

Example 1 (IETHOD 1) !!, N'-Dibutyl-I ^ N'-dimethyl-1,6-diaminohexane

(a) 61 g of 1,6-dibromohexane are slowly added to 91 g of n-butylamine, which has previously been brought to a temperature of 75 ° C., with stirring. The temperature of the reaction mixture increases gradually at ⁰ to 95 C. In the end of the addition the hydrobromide formed and the temperature rises crystallized at 110 ⁰ C. It is cooled to 60 ⁰ C, and sequentially outputs 250 cnr water and a concentrated aqueous sodium hydroxide solution 50 cnr solution.

The mixture is stirred for a further 1/2 hour and the precipitate is then separated off by filtration and drying under reduced pressure of N, N'-dibutyl-1,6-diaminohexane in the form of a hydrate away.

(b) 37 g of the latter product is added under stirring and maintaining the temperature below +5 ⁰ C to a mixture of 108 g of pure formic acid, and 11g water. 117 g of an aqueous 30% formaldehyde solution are then added in the course of 10 minutes. The temperature

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is now slowly raised to 100 ^° C. and the mixture is stirred at this temperature until the evolution of carbon dioxide has ended. The reaction mixture is now concentrated under reduced pressure and the residue is made alkaline by adding about 150 cm of an aqueous concentrated NaOH solution. It is extracted three times with 200 cnr isopropyl ether. The united or-

• 7.

ganischen phases are washed three times with 100 cnr water, dried and concentrated. The residue is distilled in vacuo and 72 g of NjN are obtained

N, N'-dimethyl-1,6-diaminohexane, which is below 0.1 mm of mercury distilled at 98 to 99 ° C.

Example 2 (METHOD 2) N _> N'-Dimeth.yl-N, N ^t -dioctyl-1,3-diaminopropane

(a) N-methyloctylamine.

523 g of the benzenesulfonamide of octylamine are dissolved in

3
1500 cm of anhydrous xylene. Then 835 cm of an ethanolic solution of 2.4N sodium ethylate are added with stirring and the ethanol is then removed by distillation. While stirring the reaction mixture at 100 to 110 ⁰ C, are added in the course of 1 hour. 385 cnr ⁵ is methyl sulfate to and heated 4 hrs. Under reflux. After cooling, the mineral salts are removed by filtration.

1500 cm of an aqueous concentrated NaOH solution is added to the piltrate, decanted and the xylene phase is washed four times with 1000 cnr water and then concentrated. The residue obtained is added to a mixture of 1400 g of concentrated sulfuric acid and 560 g of crushed ice and the whole is ^{kept at 160 °} C. for 16 hours with stirring. After cooling, the reaction mixture is on

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3 kg of crushed ice poured and cooked through. Addition of 3500 cnr of an aqueous concentrated NaOH solution made alkaline. It is extracted three times with 2000 ml of ethyl acetate, the organic phases are washed with water, dried and concentrated under reduced pressure. The residue is distilled and the ^{fraction which distills at 45 to 50 °} C. under 0.2 mm of mercury is removed.

(b) N, N ^I -dimethyl-N, N ^t -dioctyl-1,3-diaminopropane.

69 g of 1,3-dibromopropane are added to a mixture of 107 g of N-methyloctylamine and 87.5 g of N-ethyldiisopropylamine while maintaining the temperature at 100 to 105.degree. Subsequently, the mixture is stirred 7 h. At 120 ⁰ C, cooled, and 5CO cnr water and 200 cnr to ether. The aqueous phase is decanted and the ether phase is treated with 50 cur of an aqueous concentrated NaOH solution, decanted and washed three times with 100 ml of water. After drying, the ether is evaporated and then the starting N-methyloctylamine, which has not reacted. The residue obtained consists of two phases which are separated.

The upper clear phase is purified by distillation; ^{the Ν, Ν 1-} dimethyl-N, N'-dioctyl-1,3-diaminopropane, which distills at 150 to 153 ° C. under 0.5 mm of mercury, is obtained.

Example 3 (METHOD 3) NjN'-Didecyl-NjN'-dimethyl-1,5-diaminopentane

(a) N, N'-Didecyl-1,5-diaminopentane.

297 g of the benzenesulfonamide of decylamine are subjected to the action of sodium ethylate in a manner analogous to that in

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Example 2 "described to form the corresponding sodium derivative. · FEN After removal of the ethanol by Eindamp- are added with stirring at a temperature in the vicinity of 120 ⁰ C 162 g of 1,5-DiJοdpentan. Is maintained for 4 hrs., reflux of XyIöls and then cooled and added with stirring 500 cnr water to dissolve the formed mineral salts. the organic phase is then decanted, dried and concentrated under reduced pressure. the residue obtained is heated for 14 hrs. at 13O ⁰ C in Presence of 300 cnr 85% sulfuric acid After cooling, the reaction mixture is poured onto 1.5 kg of crushed ice and the pH is adjusted to 10 by adding an aqueous 30% strength NaOH solution. The precipitate formed is separated off by filtration and washed with water and dried, giving the N, N'-didecyl-1,5-diaminopentane.

b) N, N'-Didecyl-N, N'-dimethyl-1,5-diaminopentane.

By methylating the product obtained in a) according to an analogous described in Preparation No. 1 Method, one obtains the N, N'-didecyl-N, N'-dimethyl-1,5-diaminopentane with a boiling point of 193 to 195 ° C (0.4 mm Hg).

The ditertiary diamines listed in Table I below are prepared in an analogous manner:

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method TABLE I. (CH ₂ J ₁₀ (CH ₂ Jg R. example No. A. (CH ₂ J ₃ -CH ₀ -CH- (CH ₀ J _C -CH-CH _O -
² I ²⁵ I ² No. 2 (CH ₂ J ₆ -CH ₀ -CH-CH ₀ -
² I ^{2 C} 12 ^H 25 1 (CH ₂ J ₁₀ - 20 - C ₄ H ₉ VJl 2 (CH ₂ J ₁₀ 509849/1029 ^C 8 ^H 17 6th 2 (CH ₂ J ₆ ^C 8 ^H 17 7th 1 (CH ₂ J ₆ C ₄ H ₉ 8th 2 (CH ₂ J ₆ ^C 16 ^H 33 9 1 (CH ₂ J ₃ Cyclohexyl 10 1 (CH ₂ J ₆ Isobutyl 11 2 p-xylylidene C ₁₂ H ₂₅ 12th 2 m-xylylides C ₁₂ H ₂₅ 13th 1 (CH ₂ J ₁₂ ^C 4 ^H 9 14th 1 (CH ₂ J ₆ C ₄ H ₉ 15th 1 (CH ₂ J ₆ C ₄ H ₉ 16 1 (CH ₂ J ₃ C ₃ H ₇ 17th 1 -CH ₀ -CH ₀ -CH-
I. Isopropyl 18th 1 CH ₃ Benzyl 19th 1 Hexyl 20th 1 Isobutyl 21 2 ^C 8 ^H 17 22nd 2 23

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Examples of the preparation of salts of the formula II

These salts are prepared according to the method described below general procedure:

0.1 mole of the ditertiary diamine of the formula I is allowed with an aqueous-ethanolic solution of the desired acid the following composition react:

1 mole of organic acid or mineral acid, 34 ml of water,
120 ml ethanol,

for 15 min. with stirring between 30 and 50 ^° C. The reaction solution is evaporated in the heat under a pressure of 15 mercury and then the remaining part is removed by azeotropic distillation in the presence of 1.5 1 of ethyl acetate (5 x 0.3 Ltr.) Again.

The residue is taken up with 120 ml of methanol, which has previously been ^{cooled to approximately 5 °} C., and then suctioned off and washed three times with 120 ml of ether. The salt is dried under reduced pressure at 60 ^° C. and a yield in the order of magnitude of 70 to 95 $ is obtained.

Following the general procedure described above, those listed in Table II below are ditertiary Diamines of the formula II produced.

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rs? co

ro ro

Example no.

24 25 26

27 28

29 30

(CH ₂ ) ₆

(CH ₂ J ₆ (CH ₀ )

(CH ₂ J

TABLE II
Salts of the formula II

^C 8 ^H 17 Br ^C 8 ^H 17 Br ^C 8 ^H 17 Br ^C 12 ^H 25 Br ^C 12 ^H 25 Br C ₁₁ H ₉ Br C ^ H_ Br

yield
% Melting point
in ° c 97.5 260 91 226 92.5 153 69 > 260 74.5 240 98.5 209 69.5 263

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example

Carrier for cream colorant (oxidation coloring)

Cetostearyl alcohol 20 g

Oleic acid diethanolamide 4 g

Cetyl stearyl sodium sulfate 3 g

Compound according to Example 30 5 g

Ammonia of 22 ° Be 10 ml

Dyes ;

Egg diamino anisole sulfate 0.048 g

Resorcinol 0.420 g

m-aminophenol base 0.150 g

Nitro-p-phenylenediamine 0.085 g

p-tolylenediamine 0.004 g

Trilon B * 1 g

Sodium bisulfite d = 1.32 1,200 g

Water as much as necessary per 100 g

Mix 30 g of this formulation with 45 g hydrogen peroxide of 20 volumes and get a smooth, consistent, ZU3 Use a suitable cream that adheres well to the hair.

After a waiting time of 30 minutes, you rinse and dry.

With 100 # white hair you get a blonde coloration. That Sizing dampened and dry hair is easy. The hair shines, the handle is pleasant and supple

* Trilon B: ethylenediaminetetraacetic acid

* · * The titer of the hydrogen peroxide solution is here as usual Expressed in volumes, the volume being understood as the amount of oxygen in liters that is produced by decomposition one liter of the hydrogen peroxide solution is released.

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Example 2

Carrier for cream colorant (oxidation coloration)

Cetostearyl alcohol 20 g

Oleic acid diethanolamide 4 g

Cetyl stearyl sodium sulfate 3 g

Compound according to Example 28 5 g

Ammonia of 22 ° Be 10 ml

Dyes ;

m-diamino anisole sulfate 0.048 g

Resorcinol 0.420 g

m-aminophenol base 0.150 g

Nitro-p-phenylenediamine 0.085 g

p-tolylenediamine 0.004 g

Trilon B 1 g

Sodium bisulfite d = 1.32 1,200 g

Water as much as necessary per 100 g

Mix 30 g of this formulation with 45 g of 20 volumes of hydrogen peroxide and obtain a smooth, consistent zirconia Use a suitable cream that adheres well to the hair.

After a waiting time of 30 minutes, you rinse and dry.

With 100 % white hair you get a blonde color. Sizing wet and dry hair is easy. The appearance of the hair is bright, the handle is comfortable and pliable.

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Example 3

Water wave lotion for hair that has become sensitive

An alcoholic solution is made with the following ingredients:

Polyvinylpyrrolidone 1 g

Compound according to Example 26 1 g

Ethyl alcohol, as much as required in ..... 100 ml.

You apply this mixture to your hair, wave it with water and dry it.

The hair is hardened and made plastic. They shine and have volume. The handle is silky and the finishing is simple.

Example 4 Water wave lotion for hair that has become sensitive

Prepare an alcoholic solution with the following ingredients:

Polyvinylpyrrolidone 1 g

Compound according to Example 27 o 1 g

Ethyl alcohol, as much as required in ..... 100 ml.

The product is applied to the hair, waved in water and dried.

The hair has hardened and become plastic.

They are luminous and have volume. The handle is silky and finishing is easy.

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Example 5

Structuring lotion (use without rinsing)

Mix the following ingredients before use:

0.3 g of N, N'-di- (h; hydroxymethyl) -ethylthiourea with 25 ml a solution that consists of the following components:

Compound according to Example 24 · 0.4 g

Phosphoric acid as much as necessary for pH 2.7

Water as much as required per 100 ml.

The mixture is brought to the washed before the water curl and dried hair.

The hair is easy to trim, the handle is silky.

Make the water wave and dry.

The hair is bright, bouncy, it has body (volume), the handle is silky, the finishing is easy.

example

Treatment lotion (application with rinsing)

Apply 30 ml of the following to moistened and clean hair Solution to:

Compound according to Example 29 5g

Monoethanolamine as much as required for pH 7.5

Water as much as required per 100 ml.

You wait 5 minutes and rinse.

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The hair is soft to the touch and easy to trim. The water wave is carried out and dries. The dry hair is easy to straighten. They are bright, bouncy, and have bodies.

example

Structuring lotion (use with rinse) Before use:

2 g of N, N'-di (hydroxymethyl) ethyl thiourea with 25 ml a solution that contains the following ingredients:

Compound according to Example 25 4 g

Hydrochloric acid as much as required for pH 2.5 Water as much as required per 100 ml.

The mixture is applied to washed and dried hair.

You wait 10 minutes and then rinse. The hair straightening is easy, the hair has a soft (silky) Handle on.

You make the water ripple and dry under the hood.

The dry hair is easy to straighten, it is bright, bouncy and has body (volume).

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Example 8 Deodorant lotion for an atomizer

Compound according to Example 25 3.0 g

Propylene glycol 5.0 g

Polyoxyethylenated sorbitol monooleate

(with 20 moles of ethylene oxide) 1.0 g

Perfume 0.5 g

Alcohol from 96 # 50 ml

Water, as much as required per 100 ml,

Example 9

Soothing and deodorizing body emulsion

Compound according to Example 28 0.2 g

Oxyethylene cetostearyl alcohol

(with 15 moles of ethylene oxide) 3.0 g

Cetyl alcohol 0.5 g

Allantoin 0.3 g

Perfume 0.5 g

Alcohol from 96 # 40 ml

Water, as much as required per 100 ml,

Example 10

Alcoholic spray deodorant

Compound according to Example 26 0.2 g

Perfume 0.5 g

Absolute alcohol 29.3 g

Preon 11 42.0 g

Freon 12 28.0 g

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Example 11

Aqueous-alcoholic spray deodorant

Compound according to Example 27 0.1 g

Polyoxyethylene lanolin

(with 16 moles of ethylene oxide) 0.2 g

Perfume 0.5 g

Alcohol of 96 # 25.0 g

Water 34.2 g

Preon 12 40.0 g

Example 12

Polyglycidolated 1,2-diol with C ₁₁ to C ₁₄

(with 3 to 4 molecules of glycidol) 14 g

Compound according to Example 24 1.2 g

Lactic acid, as much as necessary for pH 3

Water as much as required per 100 ml

This shampoo has a clean appearance. When applied to hair, it gives a rich foam and makes it easy to finish the wetted hair. After drying, the hair is bouncy, light and shiny.

Example 13

Lauryl polyethoxylated with 12 moles of ethylene oxide

alcohol 8 g

Polyglycidolated 1,2-diol with G ₁₁ to C ₁ . -

(with 3 to 4 molecules of glycidol)] ^Ί . ^Ί .Τ η g

Compound according to Example 29 2 g

Triethanolamine, as much as necessary for pH 5

Water as much as required per 100 ml

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This clear-looking shampoo "has a very good one Foaming power, facilitates the finishing of "wetted" Hair and gives the hair suppleness. After drying, the hair is strong, shiny, soft and relatively little electric.

Example 14

Lauryl polyethoxylated with 12 moles of ethylene oxide

alcohol 15g

Copra diethanolamide 3 g

Trimethylcetylammonium bromide 3 g

Compound according to Example 29 2g

Triethanolamine, as much as necessary for pH 4

Water as much as required per 100 ml

This clear-looking shampoo has a very good foaming power. The wet sizing is good, the hair are soft and pliable. After drying, the hair is light, full, shiny and not very electric.

Example 15

Polyglycidolated 1,2-diol with C ₁₁ to C _1A

(with 3 to 4 molecules of glycidol) Il Il 10 g

Compound according to Example 28 1 g

Triethanolamine, as much as necessary for pH 6

Water as much as required per 100 ml

This shampoo has a clean appearance. It gives a rich foam, makes finishing easier and leads to dry ones Hair in good condition; they're bright, light, and easy to comb.

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Investigation of the germicidal properties of the salts of the formula II

The germicidal properties of the salts of formula II were determined according to the techniques described below:

1. Stitch technique (technique des cupules)

A nutrient medium (gelose nutritive), which is inoculated with the microorganisms to be examined, is placed in a Petri dish. To After this nutrient medium has cooled down, three equidistantly placed with the aid of a punching device with a diameter of 10 mm located holes. 0.1 ml of the solution of the compound to be tested is added to each hole.

Incubate the dishes in the heating furnace in the case of bacteria at 37 ° C and in the case of the fungi at 22 ⁰ C. After incubation, one measures the diameter, expressed in mm, of the zones of inhibition that have formed around the stitches around.

2. Brewing technique

1 ml of a mother solution of the compound to be investigated is introduced into tubes with nutrient broth in such a way that the final dilution corresponds to the dilution to be investigated. 0.1 ml of a germ suspension is used. Is incubated in a heating cabinet in the case of bacteria at 37 ⁰ C and in the case of the fungi at 22 ⁰ C. After incubation pricking back into liquid and solid nutrient media, incubated for these new tubes and evaluated after incubating the size of the culture as follows:

: no culture available

: according to the degree of culture (weak, medium or considerable).

The results are compiled in the table below.

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Names of the germs

TABEL

Gram + Brühentechnik results

Connection according to example 21 25 26 27 28

Mushroom yeast

Staphylococcus aureus Gr + Bacillus Subtilis Gr + Sarcina Lutea Gr + cn
ο Escherichia coli Gr- co
00 Klebsiella pneumoniae Gr- • Ρ-
CO Pseuaomonas aeruginosa Gr- ^ j Proteus Vulgaris Gr- O ~ * Saccharomyces Cerevisiae Yeast ro
co Candida yeast Aspergillus niger mushroom Penicillium notatum Mushroom + Pityrosporum ovale yeast Corynebacterium Acnes Gr +

IT = total inhibition

/ Through- \ ^

knife - * ■

Stitch technique results \ in mm j ^ "

link 25th according to example 28 30th VD
OD 21 32 26th 27 15th 21 30th 11.5 23 11 11.5 25th 12th 36 28 16 11.5 21.5 36 33 23 13.5 11 23 38 31 23 11 11.5 22.5 31 17.5 26.5 15.5 0 17.5 25th 28 0 0 17.5 23.5 35 21 21.5 18.5 0 16.5 20.5 20th 21 0 0 16.5 22nd 23 21.5 0 0 11 * 18.5 27 20th 0 0 19th 23.5 0 27 0 0 12th 0 IT 13th 0 15th 29 IT 12th ii ro
cn
ro OO
CD
CD

Claims (17)

PATENT CLAIMS as well as their addition salts with acids, where the substituents R and A have the following meanings: R stands for an aliphatic radical with 3 to 20 carbon atoms, a cyclohexyl radical or a benzyl radical; A stands for A. or A ₂ , where A _{1 is} a meta- or para-xylylidene radical and A _{2 is} a radical of the formula - (CH ₂ ) _y -CH- (CH ₂ ) _X -CH- (CH ₂ ) _t - R ₁ R ₂ represents where x, y and t are integers which can vary from 0 to 11 and which are such that their sum (x + y + t) is greater than or equal to 1 and less than 18, and where R ₁ and R ₂ denotes a hydrogen atom or an aliphatic radical having fewer than 18 carbon atoms, with the exception of the diamines of the formula I, in which: a) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 4 or 8; R = benzyl; - 32 509849/1029 M / 16098 b) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 1; R = cyclohexyl; c) A = A ₂ , R ₁ = R ₂ = H; (x + y + t) = 4; R represents the 1,5,9-trimethyldecyl radical or the 1,5,9,13-tetramethyl-tetradecyl radical; d) A = A ₂ , R ₁ = R ₂ = ethyl; y = t = O; x = 6; and R stands for the 2-ethyltyl radical; e) A = A ₁ and R = benzyl, cyclohexyl or isopropyl; mean. 2. diamines according to claim 1, characterized in that R represents an alkyl radical having 3 to 12 carbon atoms. 3. Diamines according to Claims 1 or 2, characterized in that R ₁ and R _{2 represent} a hydrogen atom or an alkyl radical having 1 to 17 carbon atoms and the sum (x + y + t) is greater than or equal to 1 and less than or equal to 10. 4. diamines according to any one of claims 1 to 3, characterized in that R ₁ and R _{2 represent} a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms. 5. diamines according to claim 2, characterized in that at least one of the substituents R ₁ or R _{2 is} an alkyl radical and R is a linear alkyl radical. 6. diamines according to claim 2, characterized in that A stands for an ortho- or para-xylylidene radical and R denotes an alkyl radical having 4 to 12 carbon atoms or an n-propyl radical. - 33 509849/1029 M / 16098 * 3s * 7. addition salts of diamines according to any one of claims 1 to 6, characterized in that they are of the general Formula II CH, CH, H N © A N © H (II) I I R R correspond, wherein A and R have the meanings given above and XW stands for an anion which is derived from a mineral acid or an organic acid. 8. addition salts according to claim 7, characterized in that X ^ is a halide anion, an anion which is derived from phosphoric acid or sulfuric acid or an anion which is derived from an organic Acid derived represents. 9. addition salts according to one of claims 7 or 8 as a particular antibacterial and antifungal medicament . 10. Pharmaceutical agents, characterized in that they contain at least one medicament according to claim 9 in one Concentration varying between 0.2 and 10 wt .- ^, contain. 11. Pharmaceutical agents according to claim 10, characterized in that they contain said medicament in a concentration which is between 0.4 and 5 Gev. ^r .-% varies. - 34 - 50 9849/1029 M / 16098 * w 12. Hygienic or cosmetic agents, characterized in that they contain at least one addition salt according to one of claims 7 or 8 in a concentration which varies between 0.05 and 10 » . 13. Composition according to claim 12, characterized in that it contains at least one addition salt of the formula II in aqueous, alcoholic or aqueous-alcoholic solution in a concentration between 0.2 and Wt .- #, in particular between 0.4 and 5 wt .- 5ε, varies, and make up hair lotions. 14. Composition according to claim 12, characterized in that it contains at least one addition salt of the formula II in one Concentration which varies between 0.2 and 10 wt .- #, in particular between 0.4 and 5 wt .- ^, and at least contain a cationic or non-ionic detergent and form shampoos. 15. Means according to claim 12, characterized in that they contain at least one addition salt of the formula II in a concentration between 0.05 and 5 # »in particular between 0.1 and 3% by weight, varies, and a suitable one cosmetic carriers for application to the skin and form deodorant preparations. 16. A process for the preparation of the diamines according to any one of claims 1 to 6, and their acid addition salts, thereby characterized that one: (A) a primary amine of the formula R-NH ₂ with a dihalide of the formula Hal-A-Hal, in which R and A have the meanings given above and Hai represents a halogen atom, the reaction mixture is treated with a basic solution to obtain the disecondary - 35 5 09849/1029 M / 16098 3 Obtaining diamine of the formula H-NH-A-NH-R and subjecting the latter to a methylation reaction; or (b) a primary amine R-NH ₂ with an arylsulfonyl halide of the formula Ar-SO ₂ -HaI, in which Ar represents an aryl group and Hai represents a halogen atom, to give a sulfonamide of the formula Ar-SO ₂ -NHR, which is subjected to a methylation reaction, whereby an alkali metal derivative is first formed by the action of an alkali metal alcoholate and this alkali derivative is treated with dimethyl sulfate, the compound of the formula being treated .R Ar-SO ₂ -N OH ₃ obtained, which is subjected to acid hydrolysis, the secondary amine of the formula H-H obtained and the latter with a dihalide of the formula Hal-A-Hal in the presence of a tertiary amine implements; or (c) a primary amine R-NHp reacts with an arylsulfonyl halide, the resulting sulfonamide of the formula Ar-SO ₂ -NHR reacts with a dihalide of the formula Hal-A-Hal, the disulfonamide formed of the formula Ar-SO ₉ -NAN-SO ₉ -Ar RR - 36 - 509849/1029 M / 16098 £ 3 subjected to acid hydrolysis, the disecondary diamine of the formula R R I I U A N I I H H obtained, which is subjected to a methylation reaction. 17. The method according to claim 16, characterized in that the diamine of the formula I obtained is used to form the corresponding addition salt subjected to the action of an acid. - 37 509849/1029