CH629177A5 - Process for the preparation of new diamine salts - Google Patents

Description

The subject of the present invention is the process for the preparation of the new diamine salts of general formula II defined in claim 1.

In general formula II, when R represents an aliphatic radical, it is in particular an alkyl radical having from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms; when the substituent R! or R2 is an aliphatic radical, it is in particular an alkyl radical having from 1 to 17 carbon atoms, and 65 in particular from 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 formula II defined above, mention will be made more particularly of those for which: R is a cyclohexyl radical,

R

i ° i

I

H

3

629177

benzyl or an alkyl radical having 3 to 16 carbon atoms, such as a propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl radical; A represents A ,, that is to say a meta- or paraxylylidene radical; A represents A2, Ri and R2 representing a hydrogen atom, in other words A is a polymethylene radical having from 3 to 12 carbon atoms, and having in particular 3,5,6,8,10 or 12 carbon atoms; or at least one of the substituents R 1 and R 2 represents an alkyl radical having from 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 having in particular the values indicated above; x, y and t are in particular equal to 0, 1,2,3 or 4. When A represents a meta- or paraxylylidene radical, R is preferably an alkyl radical having 4 to 12 carbon atoms, or an n-propyl radical .

In general formula II, X © represents in particular a halide anion (in particular bromide or chloride), or an anion derived from other mineral acids such as phosphoric acid or sulfuric acid, etc., or also a derivative anion of an organic sulfonic or carboxylic acid, in particular an alkanoic acid having from 2 to 12 carbon atoms (for example acetic acid) a phenylalkanoic acid (for example phenylacetic acid), benzoic acid, l lactic acid, citric acid or paratoluene sulfonic acid.

The diamine salts of formula II are prepared according to one of the methods described below.

Method 1:

A primary amine of formula R — NH 2 is reacted with a dihalide of formula Hai-A — Hai, R and A being defined as above and Hai being a halogen atom and preferably a bromine or iodine atom. The operation is carried out between approximately 50 and 150 ° C., using an excess of primary amine, generally 2 to 5 mol of primary amine per mole of dihalide. After treating the reaction mixture with a basic solution, for example a sodium hydroxide or potassium hydroxide solution, the disecondary diamine of formula R-NH-A-NH-R is obtained.

The latter is then subjected to a methylation reaction, for example by the action of formic aldehyde in the presence of formic acid according to the Eschweiler-Clarke method. The latter is implemented with an excess of formaldehyde, at a rate of 2.2-10 mol and preferably 2.5-5 mol of formaldehyde per 1 mol of diamine. Formic acid is also used in excess, at a rate of 2.5 to 10 mol and preferably 5 to 8 mol per mole of diamine. The reaction is carried out at a temperature between 40 and 100 ° C, preferably between 80 and 100 ° C. The ditertiary diamine formed can be isolated by distillation.

Method 2:

A primary amine R — NH2 is reacted with an arylsulfonyl halide Ar — SO2 — Hai, Ar being an aryl group, for example a phenyl or tolyl group, and Hai being a halogen atom, for example a chlorine atom . A sulfonamide of formula Ar — SO 2 —NHR is obtained which is subjected to a methylation reaction, by first forming an alkali metal derivative, for example by the action of an alkali metal alcoholate such as the ethylate. sodium, then treating this derivative, for example the sodium derivative, with dimethyl sulfate. The compound of formula is obtained:

IV

Ar-S02-N ^

CH3

which, by acid hydrolysis, for example using an aqueous solution of sulfuric acid, leads to the secondary amine of formula:

^ CH3

H_N \ R

The latter is then reacted with a dihalide of formula Hai-A-Hai (Hai and A being defined as above) in the presence of a tertiary amine such as N-ethyl diisopropylamine, using at least 2 mol of amine secondary and tertiary amine per 1 mol of dihalide. The reaction is preferably carried out without solvent and at a temperature between 50 and 130 ° C. At the end of the reaction, the mixture is taken up in water to dissolve the amine salts, and extraction is carried out with an appropriate solvent, such as, for example, ethyl acetate. The extracts are then washed with an alkaline aqueous solution (soda or potash), then with water. The organic phase is then dried, then the ditertiary diamine is isolated either by distillation or by concentration under reduced pressure.

Method 3:

A primary amine R — NH2 is reacted with an arylsulfonyl halide, as indicated in method 2. The sulphonamide obtained, of formula Ar — SO2 — NHR, is reacted with a dihalide of formula Hai — A — Hai. temperature between 80 and 140 ° C approximately. The disulfonamide formed, of formula:

Ar - SO, - N - A - N - SO, - Ar "I I

R R

can be directly subjected, without being isolated, to acid hydrolysis. This acid hydrolysis can, for example, be carried out in an 85% aqueous solution of sulfuric acid, at a temperature between approximately 120 and 145 ° C., for a time between 7 and 20 h. We obtain the secondary diamine of formula:

R R

I I

NOPE

I I

H H

which is subjected to a methylation reaction, for example by reaction with formaldehyde in the presence of formic acid, according to the Eschweiler-Clarke method.

The addition salts of the diamines are prepared according to the usual methods, by addition to the diamines obtained of the acids of formula X — H, X being defined as above.

The addition salts of formula II prepared by the process according to the invention are new industrial products which have interesting germicidal properties and in particular antibacterial and antifungal properties which make them usable in chemotherapy in the field of the fight against pathogenic bacteria and fungi.

The compounds of formula II prepared by the process according to the invention act in particular on the following bacteria: Staphylo-coccus aureus, Bacillus subtilis, Sorcina lutea, Escherichia coli, Klebsiella pneumoniae, Pseudomomas aeruginosa, Proteus vulgaris, Corynebacterium acnes.

The compounds of formula II prepared by the process according to the invention have a remarkable antifungal activity vis-à-vis many fungi and yeasts, and in particular Aspergillus niger, Penicillum notatum, Candida, Pityrosporum ovale, Saccharomyces cerevisiae.

The compounds of formula II prepared by the process according to the invention can be used, for example, in the treatment of skin mycoses, hair mycoses, mycotic intertrigos or mycotic, anal or vulvar dermatitis.

The compounds of formula II can also find their use in cosmetology. They can for example, in combination with an appropriate excipient, enter into the composition of cosmetic or hygienic preparations such as soaps, shampoos, hair lotions (in particular anti-dandruff lotions) or deodorant preparations.

The invention therefore also relates to a hygienic or cosmetic composition which contains, as active compound,

5

10

15

20

25

30

35

40

45

50

55

60

65

629177

4

minus a diamine salt of formula II, this being prepared by any process.

These cosmetic or hygienic preparations can be presented in particular in the form of solutions, emulsions, creams,

sticks or aerosols.

In these cosmetic or hygienic preparations, the concentration of addition salts of formula II generally varies between 0.05 and 10% by weight, and preferably between 0.1 and 5%.

In the cosmetic or hygienic compositions for hair according to the invention, the compounds of formula II have in particular a bactericidal and fungicidal effect; this effect can be taken advantage of in particular in anti-dandruff compositions, but also in all the hair compositions of the dye media type, styling lotions, various hair lotions, shampoos, etc.

In the cosmetic or hygienic compositions for the skin according to the invention, the compounds of formula II have in particular a bactericidal and fungicidal effect; this effect can be used in particular in deodorant compositions presented, for example, in the form of sprays, sticks, emulsions, soaps, etc.

Cosmetic compositions based on compounds of formula II include in particular:

a) Hair lotions and in particular treating hair lotions, characterized in that they contain at least one compound of formula II in aqueous, alcoholic or hydroalcoholic solution (the alcohol being in particular ethanol).

The content of compound of formula II can vary between 0.2 and 10% by weight, and preferably between 0.4 and 5%.

To treat the hair using such a lotion, the said lotion is applied to the hair, it is left to act for a time which can reach 30 min, it is optionally rinsed and dried.

b) Shampoos, characterized in that they contain at least one compound of formula II and a cationic or nonionic detergent.

The cationic detergents are in particular long chain quaternized ammoniums, fatty acid esters of amino alcohols, or polyether amines.

Non-ionic detergents are in particular esters of polyols and sugars, the condensation products of ethylene oxide on fatty substances, on long-chain alkylphenols, on mercaptans or long-chain alcohols or on amides long chains, and polyhydric fatty alcohols polyhydroxylated.

These compositions in the form of shampoos can also contain various adjuvants such as, for example, perfumes, dyes, preservatives, thickening agents, foam stabilizing agents, softening agents, or even one or more cosmetic resins.

In these shampoos, the concentration of detergent is generally between 5 and 50% by weight and the concentration of compounds of formula II varies between 0.2 and 10% and preferably between 0.4 and 5%.

c) Deodorant preparations, characterized in that they contain at least one compound of formula II at a concentration varying between 0.05 and 5% and preferably between 0.1 and 3% by weight, and an appropriate cosmetic excipient for application to the skin.

These deodorant preparations can be presented in the form of powders, obtained by incorporating a compound of formula II, and optionally a perfume, into a powder usually used as a cosmetic excipient; in the form of liquid preparations obtained by dissolving a compound of formula II in an aqueous or aqueous-alcoholic excipient; in the form of creams or emulsions obtained from a base usually used for cosmetic creams or emulsions, to which is added the chosen quantity of compound of formula II previously dissolved in an aqueous medium; in the form of aerosol preparations containing a compound of formula II dissolved in an alcoholic, aqueous or hydroalcoholic medium, the solution being placed, in mixture with a liquid or gaseous propellant under pressure, in an airtight container fitted with a valve, or also in the form of soaps or cleaning bars.

The cosmetic compositions according to the invention generally comprise at least one adjuvant usually used in cosmetic compositions.

The adjuvants generally present in these cosmetic compositions are, for example, perfumes, dyes, emulsifying agents, thickening agents, etc.

The following examples 1 to 30 illustrate the process according to the invention.

Example 1 (method 1):

N, N'-dibutyl N, N'-dimethyldiamino-1,6 hexane a) 61 g of 1,6-dibromo hexane are slowly added with stirring to 91 g of n-butylamine previously brought to a temperature of 75 ° C. . The temperature of the reaction mixture gradually rises to 95 ° C. At the end of the introduction, the hydrobromide formed crystallizes and the temperature increases up to 110 ° C. Cooled to 60 ° C and successively introduced 250 cm3 of water and 50 cm3 of concentrated aqueous sodium hydroxide solution.

Stirring is continued for Vi h, then the precipitate of N, N'-dibutyldiamino-1,6 hexane is separated by hydrate in the form of filtration and drying under reduced pressure.

b) 37 g of the latter product are added, with stirring and keeping the temperature below + 5 ° C, to a mixture of 108 g of pure formic acid and 11 g of water. Then 117 g of a 30% aqueous formaldehyde solution are introduced over 10 min. The temperature is then slowly brought to 100 ° C. and the mixture is stirred at this temperature until the release of carbon dioxide. The reaction mixture is then concentrated under reduced pressure and the residue made alkaline by the addition of approximately 150 cm3 of concentrated aqueous sodium hydroxide solution. Extraction is carried out three times with 200 cm 3 of isopropyl ether. The combined organic phases are washed three times with 100 cm3 of water, dried and concentrated. The residue is distilled under vacuum and 72 g of N, N'-dibutyl N, N'-dimethyldiamino-1,6 hexane are collected, distilling at 98-99 ° C under 0.1 mm of mercury.

Example 2 (method 2):

N, N'-dimethyl N, N'-dioctyldiamino-1,3 propane a) N-methyloctylamine.

523 g of benzenesulfonamide of octylamine are dissolved in 1500 cm 3 of anhydrous xylene. Then introduced, with stirring, 835 cm 3 of an ethanolic solution of sodium ethylate 2.4N, then the ethanol is removed by distillation. While keeping the reaction mixture stirred at 100-110 ° C, 385 cm3 of methyl sulfate are introduced over 1 hour and the mixture is heated at reflux for 4 hours. After cooling, the mineral salts are filtered off. 1500 cm3 of concentrated aqueous sodium hydroxide solution are added to the filtrate, decanted and the xylene phase is washed 4 times with 1000 cm3 of water, 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 brought, with stirring, to 160 ° C for 16 h. After cooling, the reaction mixture is poured onto 3 kg of crushed ice, and made alkaline by the addition of 3500 cm 3 of concentrated aqueous sodium hydroxide solution. Extraction is carried out three times with 2000 cm 3 of ethyl acetate, the organic phases are washed with water, dried and concentrated under reduced pressure. The residue is distilled and the distilling fraction is collected at 45-50 ° C under 0.2 mm of mercury.

b) N, N'-dimethyl N, N '-dioctyldiamino-1,3 propane.

69 g of 1,3-dibromo-propane are added to a mixture of 107 g of N-methyloctylamine and 87.5 g of N-ethyldiisopropylamine while maintaining the temperature at 100-105 ° C. The mixture is then stirred for 7 h at 120 ° C, cool and add 500 cm3 of water and 200 cm3 of ether. The aqueous phase is decanted and the ethereal phase is treated with 50 cm3 of concentrated aqueous sodium hydroxide solution, decanted and washed three times with 100 cm3 of water. After drying, the ether is evaporated and then the unreacted starting N-methyloctylamine. The residue obtained has two phases which are separated.

5

10

15

20

25

30

35

.40

45

50

55

60

65

5

629177

The clear upper phase is purified by distillation; N, N'-dimethyl N, N'-dioctyldiamino-1,3 propane is collected distilling off at 150-153 "C under 0.5 mm of mercury.

Example 3 (method 3):

N, N'-didecyl N, N'-dimethyldiamino-1,5 peritane a) N, N'-didècyldiamino-1,5 pentane.

297 g of benzenesulfonamide of decylamine are subjected to the action of sodium ethylate, in a manner similar to that described in Example 2, to form the corresponding sodium derivative. After having eliminated the ethanol by evaporation, 162 g of diiodo-1,5 pentane are introduced with stirring, at a temperature close to 120 ° C. Xylene is refluxed for 4 h, then cooled and added with stirring 500 cm 3 of water to dissolve the mineral salts formed. The organic phase is then decanted, dried and concentrated under reduced pressure. The residue obtained is heated for 14 h at 130 ° C in the presence of 300 cm3 of 85% sulfuric acid. After cooling, the reaction mixture is poured onto 1.5 kg of crushed ice and brought to pH 10 by addition of a 30% aqueous sodium hydroxide solution. The precipitate formed is separated by filtration, washed with water and dried. N, N'-didecyldiamino-1,5 pentane is obtained.

b) N, N'-didecyl N, N'-dimethyldiamino-1,5pentane.

By methylation of the product obtained in a), according to a method analogous to that described in preparation No. 1, N, N'-didecyl N, N'-dimethyldiamino-1,5 pentane is obtained. Bp = 193-195 ° C (0.4 mm Hg).

Similarly, the ditertiary diamines indicated in Table I were prepared.

Table I

Example no

Method #

to r

4

2

(ch2) 10

cl2h25

5

1

(ch2) 3

c4h9

6

2

(ch2) 6

CsH17

7

2

(ch2) 10

c8h17

8

1

(ch2) 10

c4h9

9

2

(ch2) 6

ci <sh33

10

1

(ch2) 6

cyclohexyl

11

1

(ch2) fi isobutyle

12

2

(ch2) 3

cl2h25

13

2

(ch2) 6

ci2h25

14

1

p-xylylidene c4h9

15

1

m-xylylidene c4h9

16

1

(ch2) 12

c4h9

17

1

(ch2) 8

c3h7

18

1

(ch2) 6

isopropyl

19

1

(ch2) 3

benzyl

20

1

-ch2 - ch2 - ch-1

hexyl

ch3

21

1

(ch2) 8

isobutyle

22

2

-ch2 - ch - (ch2) 5 - ch - ch2-

c8h17

c4h9 c4h9

23

2

-ch2 - ch - ch2-1

c4h9

Ci2h25

Examples of preparation of the salts of formula II:

These salts are prepared according to the general process below:

0.1 mol of ditertiary diamine of formula I is reacted with a hydroethanolic solution of the desired acid, of the following composition:

1 mol of organic or mineral acid 55

34 ml of water 120 ml of ethanol for 15 min, with stirring between 30 and 50 ° C. The reaction solution is evaporated while hot, under a pressure of 15 mm of mercury, then the residual part is taken up by azeotropic distillation in the presence of 1.51 of ethyl acetate (5 times 0.3 ml).

The residue is taken up with 120 ml of methanol, previously cooled to 5 ° C., then filtered and washed three times with 120 ml of ether. The salt is dried under reduced pressure at 60 ° C and a yield of about 70 to 95% is obtained. 65

According to the general procedure described above, the salts of ditertiary diamines of formula II, indicated in Table II, were especially prepared.

Table II Salts of formula II

Example no.

at

R

x

Yield (%)

Melting point (° c)

24

(ch2) 3

c8hi7

Br

97.5

260

25

(ch2) 6

c8h17

Br

94

226

26

(ch2) 10

c8hi7

Br

92.5

153

27

(ch2) 3

c12h25

Br

69

> 260

28

(ch2) 6

c12h25

Br

74.5

240

29

(ch2) 3

c4h9

Br

98.5

209

30

(ch2) 5

CioH2I

Br

69.5

263

Examples I to XV below illustrate the cosmetic or hygienic composition according to the invention.

629177

6

Example I:

Cream dye carrier (oxidation coloring)

- Cetylstearyl alcohol 20 g

- Oleic diethanolamide 4 g

- Sodium cetylstearyl sulfate 3 g

- Compound of Example 30 5 g

- Ammonia at 22 ° B 10 ml

Dyes:

- M-diaminoanisol sulfate 0.048 g

- Resorcin 0.420 g

- m-Aminophenolbase 0.150 g

- Nitro-p-phenylenediamine 0.085 g

- p-Toluylenediamine 0.004 g

- * Trilon B 1 g

- Sodium bisulphite d = 1.32 1.200 g

- Eauq.s.p. 100g

30 g of this formula are mixed with 45 g of hydrogen peroxide at 20 volumes, a smooth, consistent cream which is pleasant to apply and which adheres well to the hair is obtained.

After a 30-minute break, rinse and dry.

On 100% white hair, a blonde shade is obtained. Detangling wet and dry hair is easy. Shiny appearance of the hair, pleasant and silky touch.

* Trilon B: ethylenediaminetetraacetic acid.

Example II:

Cream dye carrier (oxidation coloring)

- Cetylstearyl alcohol 20 g

- Oleic diethanolamide 4 g

- Sodium cetylstearyl sulfate 3 g

- Compound of Example 28 5 g

- Ammonia at 22 ° B 10 ml

Dyes:

- M-diaminoanisol sulfate 0.048 g

- Resorcin 0.420 g

- m-Aminophenolbase 0.150 g

- Nitro p-phenylenediamine 0.085 g

- p-Toluylenediamine 0.004 g

- Trilon B 1 g

- Sodium bisulphite d = 1.32 1.200 g

- Eauq.s.p. 100g

30 g of this formula are mixed with 45 g of hydrogen peroxide at 20 volumes; a smooth, consistent cream, pleasant to apply and which adheres well to the hair, is obtained.

After a 30-minute break, rinse and dry.

On 100% white hair, a blonde shade is obtained. Detangling wet and dry hair is easy. Shiny appearance of the hair, pleasant and silky touch.

Example III:

Styling lotion for sensitized hair

An alcoholic solution is prepared with:

- Polyvinylpyrrolidone 1 g

- Compound of example 26 1 g

- Ethyl alcohol q.s. 100 ml Apply to the hair. We do the styling. We dry. The hair is hardened and plasticized. They are shiny and have volume; the touch is silky and the disentangling is easy.

Example IV:

Styling lotion for sensitized hair

An alcoholic solution is prepared with:

- Polyvinylpyrrolidone 1 g

- Compound of Example 27 1 g

- Ethyl alcohol q.s. 100 ml

Apply on the hair. We do the styling. We dry. The hair is hardened and plasticized.

They are shiny and have volume; the touch is silky and the disentangling easy.

Example V:

Structuring lotion (application without rinsing)

0.3 g of N, N'-di (hydroxymethyl) ethylenethourea is mixed before use with 25 ml of a solution containing:

- Compound of example 24 0.4 g

- Phosphoric acid q.s. pH = 2.7

- Eauq.s.p. 100 ml The mixture is applied to washed and towel-dried hair before styling.

Hair is disentangled easily, the touch is silky.

We do the styling and dry.

The hair is shiny, nervous, they have body (volume), the touch is silky, the disentangling easy.

Example VI:

Treatment lotion (application with rinsing)

30 ml of the following solution are applied to wet and clean hair:

- Compound of example 29 5 g

- Monoethanolamine q.s. pH 7.5

- Eauq.s.p. 100 ml

Leave to stand for 5 min and rinse.

Hair has a soft feel and is easily detangled. We do the styling and dry. Dry hair is easily disentangled. They are bright, nervous and have body.

Example VII:

Structuring lotion (application with rinsing)

The following are mixed before use: 2 g of N, N'-di (hydroxy-methyl) ethylenethiourea with 25 ml of a solution containing:

- Compound of Example 25 4 g

- Hydrochloric acid q.s. pH2.5

- Eauq.s.p. 100 ml The mixture is applied to washed and towel-dried hair.

Leave to stand for 10 min and rinse.

Detangling is easy, the hair has a soft (silky) feel. We do the styling and dry under helmet.

Dry hair is easily disentangled, it is shiny, nervous and has body (volume).

Example VIII:

Deodorant lotion for spray

- Compound of Example 25 3.0 g

- Propylene glycol 5.0 g

- Polyoxyethylenated sorbitan monooleate

(at 20 mol of ethylene oxide) 1.0 g

- Perfume 0.5 g

- 96% alcohol 50 ml

- Eauq.s.p. 100 ml

Example IX:

Softening and deodorizing body emulsion

- Compound of Example 28 0.2 g

- Oxyethylenated cetylstearyl alcohol

(at 15 mol of ethylene oxide) 3.0 g

- Cetyl alcohol 0.5 g

- Allantoin 0.3 g

- Perfume 0.5 g

- 96% alcohol 40 ml

- Eauq.s.p. 100 ml

5

10

15

20

25

30

35

40

45

50

55

60

65

Example X:

Alcoholic deodorant spray

- Compound of Example 26 0.2 g

- Perfume 0.5 g

- Absolute alcohol 29.3 g

- Freon 11 42.0 g

- Freon 12 28.0 g

Example XI:

Hydro-alcoholic deodorant spray

- Compound of Example 27 0.1g

- Polyoxyethylenated lanolin

(at 16 mol of ethylene oxide) 0.2 g

- Perfume 0.5 g

- 96% alcohol 25.0 g

- Water 34.2 g

- Freon 12 40.0 g

Example XII:

- Diol 1-2 in Cn-C14 polyglycidolated

(3-4 molecules of glycidol) 14

- Compound of Example 24 1.2

- Lactic acid q.s.p. pH = 3

- Eauq.s.p. 100

This shampoo has a clear appearance. Applied to the hair, it gives abundant foam and promotes detangling wet hair. After drying, the hair is nervous, light and shiny.

Example XIII:

- Polyethoxylated lauryl alcohol

(to 12 mol of ethylene oxide)

8

- Diol 1-2 in Ci i-C14 polyglycidolated

(3-4 molecules of glycidol)

7

- Composed of example 29

2

- Triethanolamine q.s.p.

pH = 5

- Eauq.s.p.

100

This shampoo, of clear aspect, has a very good foaming power.

health, promotes the disentangling of wet hair and gives flexibility to the hair. After drying, the hair is nervous, shiny, soft and relatively not very electric.

Example XIV:

- Polyethoxylated lauryl alcohol

(to 12 mol of ethylene oxide) 15

- Coconut diethanolamide 3

- Trimethylketylammonium bromide 3

629177

- Compound of example 29 2

- Triethanolamine q.s.p. pH = 4

- Water q.s.p. 100 This shampoo, of clear aspect, has a very good foaming power. Good wet detangling, soft and supple hair. After drying, the hair is light, swelling, shiny and not very electric.

Example XV:

- Diol 1-2 in Q rC14 polyglycidolated

(3-4 glycidol molecules) 10

- Compound of example 28 1

- Triethanolamine q.s.p. pH = 6

- Eauq.s.p. 100

This shampoo has a clear appearance. It gives an abundant lather, promotes detangling and leaves dry hair in good condition, shiny, light and easy to comb.

Study of the germicidal properties of salts of formula II prepared by the process according to the invention.

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

1. Cup technique:

Nutrient agar seeded with the microorganisms to be studied is poured into petri dishes. After this agar has cooled, three equidistant holes are made using a 10 mm diameter cookie cutter. 0.1 mol of the test compound solution is placed in each hole.

The dishes are incubated in an oven at 37 ° C for bacteria and at 22 ° C for fungi. After incubation, the diameter, expressed in millimeters, of the zones of inhibition which have formed around the wells is measured.

2. Broth technique:

In tubes of nutritive broth, 1 ml of a mother solution of compound to be studied is incorporated such that the final dilution corresponds to the dilution to be tested. 0.1 ml of a germ suspension is incorporated.

It is incubated at 37 ° C for bacteria and at 22 ° C for fungi. After incubation, it is subcultured on liquid and solid nutritive media, these new tubes are incubated and, after incubation, the importance of the culture is appreciated:

-: absence of culture

+ + 1 depending on the degree of culture (low, medium or high)

+ + + d

The results are summarized in the following table:

7

5

10

15

20

25

30

35

40

45

(Table on next page)

629177

8

Board

Names of sprouts

Gram + or - Yeast Mushroom

Broth technique Results

Cup technique Results (diameter in mm)

Composed of the example

Composed of the example

Staphylococcus aureus

Gr +

24

25

26

27

28

30

24

25

26

27

28

30

-

-

-

-

-

30

32

23 '

14

15

21

Bacillus subtilis

Gr +

-

-

+

+

■

-

42

41.5

28

16

14.5

25

Sorcina lutea

Gr +

-

-

-

-

-

36

36

23

13.5

14.5

21.5

Escherichia coli

Gr-

-

-

-

-

-

38

33

23

14

14

23

Klebsiella pneumoniae

Gr -

-

-

-

-

-

-

34

34

26.5

15.5

14.5

22.5

Pseudomonas aeruginosa

Gr -

-

-

-

-

-

-

25

17.5

0

0

0

17.5

Proteus vulgaris

Gr -

-

-

-

-

+

-

35

28

24.5

18.5

17.5

23.5

Saccharomyces cerevisiae

Yeast

-

-

-

-

-

-

20.5

21

21

0

0

16.5

Candida

Yeast

-

-

-

-

-

-

22

20

21.5

0

0

16.5

Aspergillus niger

Mushroom

-

-

-

+ +

+

-

18.5

23

20

0

0

14

Penicillium notatum

Mushroom

+

-

-

+

-

-

23.5

27

27

0

0

19

Pityrosporum ovale

Yeast

0

0

13

0

0

12

Corynebacterium acnes

Gr +

IT

IT

42

14

15

29

IT = Total inhibition.

r

Claims (15)

629177 2 1. Process for the preparation of diamine salts as new compounds of formula II: X © CH3 CH3 X © I 1 H N © A N © H (II) I I R R in which R represents an aliphatic radical having from 3 to 20 carbon atoms, a cyclohexyl radical or a benzyl radical; A represents a meta- or paraxylylidene radical or a radical of formula: - (CH2) y - ÇH - (CH2) X - ÇH - (CH2) t— Ri R2 in which x, y and t are whole numbers which can vary from 0 to 11 and such that the sum (x + y + t) is greater than or equal to 1 and less than 18, and Rt and R2 represent a hydrogen atom or an aliphatic radical having less than 18 carbon atoms, and X represents an anion of a mineral or organic acid, characterized in that an amine of formula is reacted: R-NH-Z Z being a hydrogen atom or the group - SO 2 Ar, Ar being an aryl group, with a dihalide of formula Hai-A-Hai and with a methylating agent, by subjecting the intermediate product to a hydrolysis reaction acid in the case where Z represents the group - SO 2 Ar, then, if necessary, the product obtained is transformed into the desired addition salt. 2. Method according to claim 1, characterized in that the reaction is carried out first with the dihalide, then the reaction with the methylating agent. 3. Method according to claim 1, characterized in that the reaction is carried out first with the methylating agent, then with the dihalide. 4. Method according to claim 2, characterized in that a primary amine of formula R — NH2 is reacted with the dihalide of formula Hai — A — Hai, treats the reaction mixture with a basic solution to obtain the secondary diamine of formula R — NH — A — NH — R and subjects the latter to a methylation reaction. 5. Method according to claim 3, characterized in that the primary amine R — NH2 is reacted with an arylsulfonyl halide of formula Ar — SO2 — Hai, to obtain a Sulfonamide of formula Ar — SO2 — NHR which is subjected to a methylation reaction, first forming an alkali metal derivative by the action of an alkali metal alcoholate, then treating this alkaline derivative with dimethyl sulfate to obtain the compound of formula : R Ar - S02 - N ^ which is subjected to acid hydrolysis, ^ ch3 ^ H3 to form a secondary amine of formula H - N i \ R then reacts the latter with the dihalide of formula Hai-A-Hai in the presence of a tertiary amine. 6. Method according to claim 2, characterized in that a primary amine R — NH2 is reacted with an arylsulfonyl halide, reacts the sulfonamide obtained of formula Ar — SO2 — NHR with the dihalide of formula Hai — A — Hai, subjects the disulfonamide formed of formula: Ar - S02 - N - A - N - S02 - Ar I I R R to acid hydrolysis to obtain a disecondary diamine of formula: R I A N I H which is subjected to a methylation reaction. 7. Method according to one of claims 1 to 6, characterized by the 15 means that R is an alkyl radical having from 3 to 12 carbon atoms. 8. Method according to one of claims 1 to 7, characterized in that R! and R2 represent a hydrogen atom or an alkyl radical having from 1 to 17 carbon atoms and the sum (x + y +1) is greater than or equal to 1 and less than or equal to 10. 9. Method according to one of claims 1 to 8, characterized in that R 1 and R 2 represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms. 10. Method according to claim 8, characterized in that at least one of the substituents R! where R2 is an alkyl radical, and R 25, then represents a linear alkyl radical. 11. Method according to claim 8, characterized in that A is an ortho- or paraxylylidene radical, and that R is an alkyl radical having from 4 to 12 carbon atoms, or an n-propyl radical. 12. Method according to one of claims 1 to 11, characterized by The fact that X © represents a halide anion, an anion derived from phosphoric or sulfuric acid or an anion derived from an organic acid. 13. Hygienic or cosmetic composition, characterized in that it contains as active compound at least one salt of 35 diamine of formula II above, at a concentration of between 0.05 and 10% by weight. 14. Composition according to claim 13, characterized in that it contains as active compound at least one addition salt of formula II in aqueous, alcoholic or hydro-alcoholic solution, 40 a concentration varying between 0.2 and 10% by weight, preferably between 0.4 and 5% by weight, and constitutes a hair lotion. 15. Composition according to Claim 13, characterized in that it contains as active compound at least one addition salt of formula II, at a concentration-varying between 0.2 and 10% by weight, of 45 preferably between 0.4 and 5% by weight, and at least one cationic or nonionic detergent, and constitutes a shampoo. 16. Composition according to Claim 13, characterized in that it contains as active compound at least one addition salt of formula II at a concentration varying between 0.05 and 5%, 50 preferably between 0.1 and 3% by weight, and a cosmetic excipient suitable for application to the skin, and constitutes a deodorant preparation.