CA1134865A - Diamines, their preparation and uses - Google Patents

Abstract

Diamines of general formula: <IMG> (I), as well as their addition salts with acids, the substituents R and A having the following definitions: R represents an aliphatic radical having from 3 to 20 carbon atoms, a cyclohexyl radical or a benzyl radical; A represents A1 or A2, A1 being a meta- or para-xylylidene radical and A2 being a radical of formula <IMG> 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 R1 and R2 represent a hydrogen atom or an aliphatic radical having less than 18 carbon atoms, with the exception of the diamines of formula I for which: a) A = A2, R1 = R2 = H; (x + y + t) = 4 or 8; R = benzyl b) A = A2, R1 = R2 = H; (x + y + t) = 1; R-cyclohexyl c) A = A2, R1 = R2 = H; (x + y + t) = 4; R represents the trimethyl-1,5,9 decyl radical or the tetramethyl-1,5,9,13 tetradecyl radical; d) A = A2, R1 = R2 = ethyl; y = t = 0; x - 6; and R represents the 2-ethyl butyl radical; e) A = A1 and R = benzyl, cyclohexyl or isopropyl. The diamines of formula (I) are industrial products which can be used in particular as intermediate products in the preparation of polymers having quaternized ammonium groups and having advantageous cosmetic properties for hair or the skin. The addition salts of the diamines of formula (I) have interesting germicidal properties and in particular antibacterial and antifungal properties.

Description

~ L ~ l3 ~ 65 lia pxése ~ ie illY ~ ntio ~ concQ ~ de ~ ouv ~ di ~ es their preparation and application.
ention has more specifically the di ~ es from ~ ormule I:
CH ~; ICH3 A - ~. (I) RR
ai: ~ i that their ~ addition salts has ~ e ¢ leæ acids ~ le ~ substita ~ ts R and A a ~ ra ~ t the following ~ i ~ itions ~ tes: R: r ~ epxésen ~ e a radical aliphatic having 3 ~ 20 atoms of caxbo: ~ e7 ull radical oyclo-he2 ~ rle or a benzyl radical; A repx ~ e ~ te A ~ or A ~ Al eta ~ t un radica: L meta or paxa-æylylidèn ~ de ~ ormule , / CH2 -CH2 ~) ct ~ 2 eta; llt u ~ radical of the formula t 2) yi (CH ~) x ~ IH - (CH2) t- in which x ~ y and t R, ~ 2 soxr ~ whole numbers which can go; riex from 0 ~ 11 and such that the sum (x ~ y ~ t) is ~ upéxieure ou ég ~ e` ~ 1 et ir ~ érieure ~
18 ~ and R1 and R2 represent ~ tent an atom of ~ hgdrog ~ e or U31 radical aliphatic ayaIlt minus dc 18 c ~ bone atom; ~ xception of ~ diamines of ~ ormule I for which ~:
a) A = A29 ~ 2 ~ H; (x ~ g ~ t) - 4 or 8; e ~ R _ be ~ z ~ le;
b) A_ A ~ R1 ~ R2 - H; (x ~ y ~ t) - 17 and ~ cyclohe-: s ~ ri ~; `, C) ~ g Rl 3 F ~ 2 - H; ~) = 4; R ~ pr ~ e ~
the tximeth radical ~ 5.9 ~ a ~ icyle or the tetramethyl radical ~
59 9j13 tetradecylo;
id) ~ - A2 ~ 3 ~ th; rls; y - t ~ o; : ~: = 6; and R r ~ éserlte the 2-ethyl-butyl radical: e;
e) A = A1 ~ t R = bexlzyle ~ cyclohs: ~ yle or i ~ opropyl ~.

~ 1 -~ 3 ~ 6 ~

l ~ s ~ general formula I ~ when: R rep ~ ése: ~ te u ~ ra ~
dical ~: Liphatiqueg il ~ no ~ amm0n ~ diu ~ xad; Lca; L al} s; yle aga ~ t of ~ ~ 20 to ~ omes of ca: rbo.e ~ of pre ~ renCe of 3 ~ 12 atvmes of carbon; when the substitution ~ t Rl or R2 is an aliphati radical ~
that it is in particular dlun radical allcyle aya ~ t of 1 ~ 17 ato ~
of car ~ one ~ and in pa ~ ticu: Link ae 1 ~ 4 to ~ ome ~ 3 carbon; the sum (~ t) is pre ~ er ~: ~ this greater than or equal ~ 1 and ~: greater than or equal to ~ ~ 07 - Among the diamines of ~ ormule I deI ~ ies ci des ~ us 9 O ~ l 10 will more particularly cite those for which: R is u: ~ ra-dical cycl ~ he ~ rle5 ~ be ~ yle ou U ~ l alkyl radical a ~ t de 3 ~ 16 atomas de carbo ~ e9 such as ~ u ~ radioal propyl, butyl ~ hex ~ le, oc-tyle, d ~ c ~ le, dod ~ cyle, hexadéc; ~ le ~ A repr ~ ente ~ 19 c ~ est ~ dire u ~ ~ meta adical ~ u pa ~ a-xylylid ~ r ~ e9 A repr ~ se ~ te A2 ~ R1 and ~ 2 xep ~ ése ~ nt an atom of ~ hya: rog ~ e9 au ~ reme ~ says A es ~ un radica ~
polymethyle ~ ea ~ ant of 3 ~ 12 carbon atoms9 and ayan ~ ~ otam-~ meIlt 3 ~ 5 ~ 678 ~ 0 or 12 atoms of caxbone; or l ~ u ~ at mo ~ s of subs ~ itua ~ s R, l and ~ represellte u: ~ radical al ~ s; yle a; ya; nt d ~
~ ~ ~ 7 ~ tomes of ca ~ bone ~ and in p ~ particular U: ll radieal methyl or 20 ét ~ le ~ e ~ da ~ this case the subst ~ killing R is pre ~ erence a ra-~ dical linear s.lkyle a ~ rant ~ especially the ~ ralet7rs indicated3 preee-demment; x, y and t are ~ o ~ equal equal ~ 07 1 ~ 2 ~ 3 or 40 ~ orsg ~ e A represents a meta or para-xylylid radical ~ ne ~ R is pre ~ eren-this an alkyl radical having ~ ant of 4 ~ 12 atom ~ of carbon ~ or a ra-dica; l n-propyleO
- ~ es s ~ l ~ dfadditio ~ diamirles de ~ ormule I sor ~ notam . ment those who correæpo ~ tooth to dif ~ er6nte ~ ~ raleurs de ~ sub ~ ti ~ uants indicated above ~ sus; they respond ~ t ~ la ~ ormule II

36 ~
~) f ~ 3 RR
da ~ s which A and R have the v ~ leure i: ~ diquee precedem ~ en-t ~ et ~) represents an anion of ~ riv ~ d ~ u ~ mineral or organic acid.
Da ~ la ~ ormule g ~ érale II, X ~) r ~ pr ~ e ~ ta ~ otamme ~ t u ~ a ~ ion halé ~ ure (in particular ~ bromide or chlor ~ Lre), or a aniorl derivative ~ other mineral ~ c such ~ ue phosphoriqu acid ~ or . a ~ ide sul ~ urique ~ etcO5 or ~ ax ~ o ~ dexivated agun aoi ~ e organic ~ onique, or carb ~ rlique9 including u ~ aoide alcanoi that ayan ~ from 2 to 12 atom ~ of carbo ~ e (for example the acid aeéti- ~
que) an acid ph ~ urla; Lca ~ oique (pa ~ r eæeDIple aeide phenyl-acéti-that) ~ bexLzoic acid ~ lactic acid "citric acid" or ~
cidé paratoluè ~ esul ~ onique.
~ ti ~ re ~ tio ~ aims equalDns: ~ tu ~ process ds pr ~ p ~ atio ~ des , diami ~ e ~ de ~ ormule I challenge ~ ie oi above ~ l qu2 their salts d ~ a ~ ditiQ ~ e ~ diamilles of ~ ormul ~ I ~ or ~ prepa ~ ée ~ ~ lo ~ l ~ une methods described ~ ci ~ essous ~
- We had a primary reaction of fo ~ ul ~ R ~
~ with a dihaloge ~ ure de Io ~ mule Eal - A ~ R and A ~ ta ~ lt dé ~ inis c ~ me previous ~ t and Hal eta: ~ t UXI atom d ~ halogè ~ ee ~ de pré ~ é
xe ~ this Ull atom of bromine or of iodine ~ We operate e: between 50 and 150C e: n v ~ ron9 e ~ used a s ~ cc ~ s d1amine prima ~ ire ~ generslement 2 ~ 5 moles of primary amine per mole of dihalideO After very tightly of m ~ la ~ s reaction ~ el a ~ ec a solutio ~ ba ~ ique9 pa ~ example u ~ e ~ olutio ~ soda or pota ~ se, orl gets the secondary diamine - de ~ oxqn ~ ls R ~ A - NH R.
This der ~ i ~ re e ~ t alor ~ ~ oumi ~ e ~ a r ~ actiorL de méthy ~
lation ~ for example by the action of aldehyde ~ ormic in presence ~
dtacide formic se.Lon the method d7ESC ~ ER ~ a ~ ARKE ~ Ce ~ e der-~ 5 ni ~ re is implemented ~ a ~ ec eæc ~ s aldehyle ~ o ~ ique ~ ~
raiso ~ of 2.2 10 moles, and da pre ~ erence 295 ~ 5 moles dl ~ laa-hy ~ .e ~ ormic for one mole of diamIne ~ ~ 'acid ~ ormi ~ ue est éga ~
leme ~ t utili ~ é e ~ exc ~ s, ~ reason of 2.5 a ~ 0 moles, e ~ of prefec-ren ~ e 5 ~ 8 moles ~ per mole of di ~ mi ~ e. ~ a reactio ~ a ~ te ~ done tempera ~ uxe between 40 and 100C9de pre ~ erence e ~ tre 80 and 100C. ~ a diami ~ e ditertiary formed can ~ be isolated by dis-tillation.
Method: 2 - We react to a friend ~ primary ~ ~ H2 with u ~ halo ~
gé ~ ure d'ar ~ l-sulfonyl ~ x ~ ~ 2 ~ Hal, ~ r éta ~ tu ~ grouping aryle ~ for example a gr ~ upeme ~ t phën ~ le or tolyle, and ~ al being u ~ dlhalogè atom ~ e, for example u ~ chlorine atom. 0 ~ gets a sulfo ~ de de ~ ormule AX - S0 ~ ~ HR que 11O ~ s ~ umet ~ une reactio ~ of methylatio ~ en ~ orma ~ td ~ first a drift of metal alkaline p ~ re ~ example by actio ~ d ~ an alkali metal alooolate as the ~ thylate of ~ od.iuma then e ~ t ~ aitant ee deriv ~ 9 for example ~
ple le d ~ ri ~ é sod ~ by le ~ ul ~ a ~ e de dimét ~ yle ~ 0 ~ obtis ~ le composed of ~ o ~ mule Ar ~ S02 ~ N <qui9 by acid hydololysis ~ 9 aH3 for example using an aqueous solution of sulphonic acid?
¢ o ~ duit ~ mi ~ e ~ eco ~ dixe de ~ ormule CH3 -.

, 0 ~ ~ then react the latter with R
a dihalo ~ nure of ~ ormule Hal - A - Hal (Eal and A ~ t ~ nt de ~ inis as previously) e ~ presents ~ this dtu ~ e friend ~ e tertiary comm ~ the N- ~ thyl di ~ isopropylamine7 using at least two moles dla;
secondary mirle and tertiary friend for one mole of dihalogen re ~, ~ ar ~ action ~ te ~ feotée of prefer ~ n ~ e ~ olvant and ~ tem-p ~ ratur ~ compr ~ ae ~ tre 50 ~ t 130C ~ E ~ de r ~ actio ~ 9 le méla 30 g ~ is taken up by the ~ powr to ~ oudre the ~ dlami salts ~ 0s ~ and o ~
~ extracted by u ~ solvent approprle co ~ e by e ~ example 11 acetate t ~ urleO 0 ~ la ~ e then the extracts to ~ ec Ime solut.ion agueus ~ alca ~

~ 6 ~
li ~ e (soda or potash), then ~ water. ~ a pha ~ e organic e ~ t then dried ~ then o ~ isolates the di ~ mine ~ i tertiary either by di ~ -till.atlon ~ either by concentxation sou ~ pressure reduced ~ reduced ~
- 0 ~ ~ a react a primaix amine R ~ with a halo-g ~ ur ~ d ~ aryl-sul ~ on ~ l2f co ~ tells me da ~ la m ~ -thode 20 0 ~ ~ ait r ~ act the ~ ulfonamide obtained ~ foxmule Ar-S02- ~ HR ~ Yec a diha-.
logenure of formula ~ al - A - Hal, ~ u ~ e temperature comp ~ ise en ~ re 80 and 140 ~ C e ~ i ~ o ~ ~ a disul ~ on ~ de form ~ e ~ de ~ ormule Ar.- SO2 ~ A; ~ - S02; Ar ~ RR
can be directly ~ t subject ~ sa ~ s ~ be isolated 9 ~ 11 hydrolysis sourO This hydrol ~ aoide can atre for example e ~ made dan ~
a solu ~ io ~ aqueous ~ 85% of sul ~ uric acid9 ~ ~ temperature com- ~
- taken at 120C and 145C e ~ vIro ~ pe ~ during u ~ time between 7 and 20 heureaO We get ~ t the c1i ~ mi ~ e di-seco ~ dair ~ de ~ ormule RR
7 ~ A - ~
H
~ ue.l'on submit ~ u ~ e methylation9 reaction by e ~ example by ~ actio ~ ave ~ le ~ orm ~ ldehyde in prese ~ ce d ~ acid ~ ormique9 selo ~
la mé ~ hode dl ~ SCHE ~ EIIER-CIAE ~ Eo ~ es salts d ~ additio ~ de ~ diamin3 ~ de ~ o ~ mule I so ~ t prepa-res according to the ~ usual methods ~ by additio ~ to the diamlnes of formu-the acid I ~ of formula X ~ H ~ X was ~ t challenge ~ i as above ~ -m ~ nt.
~ es diami ~ es de ~ ormule I are industrial products ~ triels ~ new ~ which so ~ t usable note ~ me ~ t as intermedia products-res dan ~ the preparatio ~ of polym ~ res having groupeme ~ ts am ~
~ onium quater ~ isés9 ~ mo base ~ recursive from ~ ormul ~ general ~
III

3 ~; 3 ~ 5 fx ~ X ~ 1 ~ 3 ~ - ~ 11 B (III) L
-da ~ s which A9 R and X are challenge ~ is co ~ me precedelmnent "and: B, mistletoe can be equal to ~ A or di ~ érex ~ t from ~ A ~ po ~ sbde the same d8 ~
tion that A, To prepare polymers of formula III, O: Cl s ~ umet 10 ~ er ~ a ~ tion of poly ¢ o ~ urLe density diam ~ e ditertia ~ ra da ~ or-mule ~ 3f - YEAR
R. R
and a d ~ halOg ~ nure of ~ ormule X ~ BX ~ in which A ~: B, R ek ~ ont ïes sig ~ i ~ icatio ~ s ment ~ on ~ lées pré ~ édemme ~ tO
0 ~ e ~ Ie ¢ tue9 p ~ r example ~ the polyco reaction ~ der ~ sa-tio ~ dan ~ a solva ~ t or daIls a mela ~ ge of solvaxlts iavorisa ~ t les r ~ actio ~ s of guaterni ~ atio: ~ 9 such as gue eau9 la d ~ né ~ yl ~ ormamide ~
liacéto ~ itrile ~ alcohols i ~ laughing ~ ^ xLo ~ ammex: ~ t alkanols i ~ o Ierieur ~ like meth ~ ol, etc ~
I, at reaction temperature: ~ can v ~ ier erltre 10 and 150 ~
and preferably e ~ ltre 20 and 100C ~
~ e reaction time depends on the nature of the solvent ~ fles r ~ acti ~ s of depaxt and d ~ of ~ re of poly ~ erisation desired, O ~ has g ~ generally react the ~ reacti ~ s of d ~ pa: rt e ~
~ uan ~ equimolécul itites ~ ircs3 but ii is possible to use either the diamine be the dihalide e ~ légex exc ~ s ~ ce e ~ c ~ s ~ tant lower ~ 20 ~ e ~ moles, It is possible to adjust ~ r lo ~ eu: r mo ~ enne des cha ~
nes e ~ aaouta ~ t at the beginning or in the course of xaction a ~ low guan ti-t0 (1 ~ 15 mol% per xappoxt ~ l ~ u ~ de ~ reacti ~ d ~ u ~

-~ ~ 3 ~ ~ 5 reacti ~ mono functional such as a tertiary amine or mono halide ~
~ es polym ~ res of formula III have properties interesting cosmetics when they are introduced into cosmetic compositions applied to the hair or to the skin.
This is how when applied to the cheYe-lure either alone or with other active substances ~ ~ oc-casion of ~ n treatment such as shampoos, dyeing, setting folds, etc. they significantly improve the qualities of the hair For example, they ~ favor treatment and facilitate the shifting of wet hair. ~ 8th at high concentration, they do not give wet hair a gooey touch ~
~ Unlike conventional cationic agents9 they do not ~
do not say dry hair, and ~ therefore acilitate hairstyles bulky. They give dry hair qualities of nervousness and a shiny appearance.
They effectively help to eliminate faults hair sensitized by treatments such as bleaching, perms, or dyes. We know that sensitized hair are often dry ~ 9 te ~ nes and rough, and difficult ~ dismantle and ~ coi ~ er, ~ es polymers of formula III can be used in cosmetic compositions for hair according to the invention, namely title of additive, ie ~ title of active ingredient ~ main in styling lotions, treating lotions, creams or coi ~ fants gels, or even as an additive in compositions of shampoos, styling, perms, tinctures, restructuring lotions, treating lotions antiseborrheic, or hairsprays ~, ~ es polymares de ~ ormule III also have interesting cosmetic properties when applied 3 ~ 5 on the skin.
In particular ~ they promote hydration of the skin and therefore avoid its ~ chement ~ They conf ~ rent or re ~ skin appreciable softness to the touch ~ They can be used ~ in cosmetic compositions for the skin such as cr ~ mes, gels or lotions.
~ polymers ~ res of ormule III poss ~ other teeth ~ properties interesting is notably germicidal properties, in particular bactericides and ~ ongicidesO They also have properties surfactants and ~ ilmogens ~ ~ their properties ~ germicidal ~ ten-sio-active or ~ ilmog ~ nes make them usable in particular as preservatives, for example in glues or pro-toilet duits or additive cost in milking products leather or cellulose derivatives7, in particular paper ~
~ es addition salts of diamines of formula I9 c9est- ~
say the compounds of ~ ormule II7 are industrial products new ones with interesting germicidal properties and in particular de8 properties an ~ ibactériennes and anti ~ ongi that ~ which make them usable in chemotherapy dan ~ le do ~
mainline in the fight against pathogenic bacteria and fungi genesO
~ es compounds of ~ ormule II act in particular on following bacteria ~ Staphylococcus aureus ~ ~ acillus subtilis, Sarcina lutea, Escherichia coli; Klebsiella pneumoniae, Pseu-domomas aeruginosa, Proteus vulgaris, Corynebacterium acnesO
~ es compounds of formula II have antifongicj.de activity remarkable ~ is- ~ -vis many mushrooms and yeasts, and especially Aspergillus niger, P ~ nicillum notatum ~ Candlda, Pi-tyros-oval porum, SaccharoTnyces cerevisiae.
A ~ elm of realization of] .a present invention relates therefore the application in hwnaine and veterinary therapy of ~ ~ 3 ~

compounds of ~ ormule I ~ as antibacterial drugs and antifungalsf in particular in the treatment of in ~ e ~ tions of the skin, appendages ~ and mucous membranes.
~ es compounds of formula II can ~ be used by example in the treatment of cutaneous mycoses, pilar mycoses, fungal intertrigos or dermatitis ~ ~ ycosiques, anales ou vul ~
vaires.
~ the invention extends to ~ pharmaceutical compositions ren-~ ermant at least one drug such as die ~ ini above ~ These compositions are prepared according to the usual methods ~
These pharmaceutical compositions can be administered very particularly by topical application to the skin, the skin appendages or the mucous membranes.
To this effect, they can be presented in the form of solutions, emulsions, suspension ~ sions, mouthwashes, creams ~ lotions, ointments or aerosol preparations.
In these pharmaceutical compositions, the concentration in addition salts of ~ ormule II generally varies between 0.2 and 10% by weight, and preferably between 0.4 and 5%.
~ es compounds of formulas II can also be found their job in cosmetology ~ They can for example, in pairing with an appropriate excipient, enter the composition cosmetic or hygienic preparations such as soaps9 shampoos, hair lotions (especially anti-dandruff lotions rings) or deodorant preparations.
These cosmetic or cosmetic preparations can be presented especially in ~ form of solutions, emulsions ~ cr ~ mes ~ 7 `sticks, or aerosols.
In these cosmetic or hygienic preparations, the addition salt concentration of formula II generally varies between 0.05 and 10 ~ o by weight, and pre ~ erence between 0.1 and 5% ~
In cosmetic or hygienic compositions for ~ 3 ~

hair according to the invention ~ the components ~ és d0 formula II have no-ta ~ ment a bactericidal effect and ~ ongicide; this ~ fet can ~ be put ~ pro ~ it especially in anti-dandruff compositions, but also in all hair compositions of the type dye carriers ~ styling lotions ~ capillary lo-tions res various9 shampoos, etc ~
In cosmetic or hygienic compositions for the skin according to the inventiont the compounds of ~ ormule II are notam-ment a bactericidal effect and ~ ongicide9 this e ~ and can ~ be put ~ profit in particular in deodorant compositions tees, for example under ~ elm of sprays ~ sticks, emulsions, sa ~ ons, and co ~ es cosmetic compositions based on compounds of-mule II include in particular:
a) hair lotions and in particular lotions treating capillaries, characterized in that they ren ~ erment at least one compound of formula II in aqueous alcoholic solution9 or hydroalcoholic (alcohol being in particular ethanol) ~
The compound content of ~ ormule II can ~ range from 0.2 and 10% by weight, and preferably between 0.4 and 5%.
To treat hair ~ using such a lotion, apply the said lotion to the hair, leave to act for a time of up to 30 minutes9 you may rinse, and we dry.
b) shampoos ~ characterized by the fact that they ~ erment at least one compound d0 formula II and a detergent catio-nique or non-ionic O
~ es cationic detergents are in particular ammoniums long chain quaternized, fatty acid and amino esters alcohols, or polyether amines ~ non-ionic detergents are in particular the esters of polyols and sugars, the condensation products of the oxide ~ 3 ~
d ~ ethyl ~ ne ~ ur fatty substances, on alkylphenols ~ long ~
chains, on mercap ~ years or alcoo1g ~ lsngues chains ~ or ~ ur amides ~ long chains ~ nes, and polyethers of al ~ ool polyhydroxylated fats.
These compositions in ~ form of shampoos can also also contain various adjuvants such as, for example, perfumes, dyes, preservatives, thickening agents, foam stabilizers, 9 softeners, or one or more cosmetic resins ~
In these shampoos ~ the detergent concentration is generally between 5 and 50% by weight and the concentration in ~ omposed of formula II varies between 0.2 and 10 ~ and preferably between 0.4 and 5%.
c) deodorant preparations, characterized by ~ may they ren ~ erment at least one compound of formula II ~ a concentration varying between 0905 and 5 ~ and preferably between 0.1 and 3% in poida, and a cosmetic excipient suitable for application to the skin.
These odorless preparations can be presented 20 in ~ powder form, obtained by incorporating a compound of ~ ormule II and optionally one per ~ um, ~ a powder ha-usually used as a cosmetic excipient; under ~ elm of liquid preparations obtained by dissolving a compound of formula II in an aqueous or hydroalcoholic excipient, under form of cream or emulsion obtained ~ from a base ha--usually used for cosmetic creams or emulsions ~
to which we add the chosen quantity of compound of ~ ormule II previously d.ls ~ ous in an aqueous medium; in the form of aerosol preparations containing a compound of formula II dissolved 30 in an alcoholic, aqueous or hydro-alcoholic medium, the solu tion being placed, mixed with a liquid or gas propellant under pressure, in an airtight container fitted with a valve;

3 ~; r ~

or 80US in the form of soaps or cleaning bars ~
~ The cosmetic compositions according to the invention include-usually have at least one commonly used adjuvant in cosmetic compositions.
~ es adjuvants generally present in these compositions cosmetics are for example perfumes9 dyes, emulsifying agents, thickening agents, etc.
~ The invention also relates to the application as agents an-tibacterial and antifungal addition salts for ~ ule II
as defined above ~
Another embodiment of the invention relates to the use in pharmacy or cosmetology of the salts of ~ ormule II; characterized by the fact that compositions are made pharmaceutical, hygienic or cosmetic containing at least a salt of formula II.
~ The invention also relates to a method of combating bacteria, fungi or yeast parasite ~ of the skin9 of pha-ners or mucous membranes, characterized in that one applies on the body parts considered9 at least one salt of formula II en ~ uantité suf ~ isante to obtain the ~ e ~ and bactericide and /
or desired fungicide. This process can be implemented in particular by applying the salts of ~ ormule II using the compositions pharmaceutical, hygienic ~ 3 or cosmetic described above ~ es following examples illustrate the invention san ~ tou-you limit it.
EXEMP ~ E ~ - (method 1) ~ N ~ dibutyl N, N'-dimethyl diamino-1,6 hex ~ ne a) Gn adds slowly and with stirring 61 g of dibromo-1l6 hexane ~ 91 ~ of n-butylamine previously supplied ~ a tempe ~
75C deletion. ~ at the temperature of the reaction mixture s ~ é ~ ve pro ~ e ~ ively up to ~ 95C. At the end of the introduction, the bro ~ hydra-te formed crystallizes and the temperature rises up to ~ 110C.
: ' ~; 3 ~ 5 Cool to ~ 60C and int; roduct successively 2 ~ 0 cm of water and 50 cm3 of aqueous solution ~ l concentrated sodium hydroxide.
We continue 1 ~ agitati ~) n pendan t 1/2 hour then ~ spares by ~ iltration and drying under reduced pressure, the precipitate of N ~ N ~ -dibutyl di amino-1,6 hex ~ e ~ under ~ hydrate elm.
b) 37 g of the latter product are added, with stirring and maintaining the lower temperature ~ ~ 5C ~ ~ u ~ mixture 108 g of formal acid pu; r and 11 g of waterO Then we introduce delivers in 10 minutes 117 gd ~ an aqueous solution ~ 30 ~ of ~ or-maldehyde. ~ at temperature is then brought slowly ~ 100C
and stirred ~ this temperature ~ until ~ in ~ of gas evolution carbonic. ~ e reaction mixture is then concentrated ~ oU8 reduced pressure and the residue made alkaline by addition of about 150 cm3 of concentrated aqueous sodium hydroxide solution.
~ kings ~ ois by 200 cm3 of isopropyl ether. ~ es orga phases ~
ni ~ ues combined are washed three times with 100 cm3 of water, dried et.concentréesO The residue e ~ t vacuum distilled and collected 72 g of N, ~ '-dibutyl N, N'-dimethyl diamino-1,6 hexane ~ distilling ~ 98 99C under 0.1 mm of mercury.
EXEMP ~ E 2 - (method 2) N? N'-dimethyl_ ~, NI-dioctyl diamino-1? 3 propane a) ~ -methyl octylamine.
Dissolve 523 g of benæene ~ u ~ octylamine onamide in 1500 cm3 of anhydrous xylene. Then, with stirring, 835 cm3 of an ethanolic eth ~ late solution of ~ odium 2.4 ~
then the ethanol is removed by distillatio ~. ~ out now the reaction mixture stirred at 100 110 a, introduced over 1 hour 385 cm3 of methyl sulphate and chau ~ fe ~ re ~ lux for 4 hours-res. After re ~ stiffening ~ the salts are removed by ~ iltration `minerals ~ 1500 cm3 of aqueous solution are added to the filtrate soda concentrate, decant and wash ~ fo ~ s xylenic phase with 1000 cm3 of water, then concentrate. ~ the residue obtained is added -13 ~

a mixture of 1400 gd ~ sul: euric acid concentrated ~ and 560 g of peeled ice and the whole is worn, with stirring, 160GC during after 16 hours after cooling, the reaction mixture is poured over 3 kg of crushed ice, and made alkaline by addition 3500 cm3 of concentrated aqueous sodium hydroxide solution. We extract three ~ three per 2000 cm3 of ethyl acetate, wash the pha ~ es or-~ aniques ~ water ~ dry and concentrated under reduced pressure. ~ e residue e ~ t distilled and we collect the reaction dlstillant to 45-50C under 092 mm of mercury.
b) N, N ~ -dimethyl ~, N ~ -dioctyl diamino-1,3 propane.
69 g of dibromo-1 ~ 3 propane are added.
107 g of N ~ m ~ thyl octylamine and 87.5 g of N-ethyl dii ~ opro-pylamine maintaining the temperature ~ re ~ 100C-105 ~ Co We stir then pendan ~ 7 hours at 120C9 cools and adds 500 cm3 of water and 200 cm3 of ether. ~ the aqueous phase is decanted and the ethereal phase is treated with 50 cm3 of aqueous solution con centered on soda, decanted and washed three times per 100 cm3 of water.
After drying ~ the ether is evaporated then the N-methyl octylamine unreacted starting material O ~ e residue obtained has two pha $ es that we separate ~
- the limpid upper phase is puri ~ ed by distilla-tion; collecting the N7 ~ -dimeth ~ 1 N, NI-dioctyl diamino-1,3 propane distilling at 150-153C ~ OU8 0 ~ 5 mm of mercury.
EXEMP ~ E 3 - (method 3 ~
N, N ~ - idea ~ l N, Nt-dimethyl diamino ~ l, 5 pentane a) N, N'-didecyl diamino-1,5 pentaneO
On ~ oumet 297 g of benzene sulfonamide of decylamine ~ the action of sodium thylate ~ analogously ~ that described in ex0mple 2, to ~ form the d ~ corresponding soda rivé ~
After having eliminated ethanol by evaporation, we introduce stirring, at temperature ~ 120 ° C., 162 g of diiodo-1.5 penta ~ le, We maintain for 4 hours at re ~ lux of xyl ~ not pui ~

~ 14 ~ 8 ~ 5 cools and adds with stirring 500 cm3 of water to dissolve the mineral salts formed. ~ the organic phase is then decanted ~ e, dried and concentrated under reduced pressure. ~ e residue obtained is heated for 14 hours ~ 130C in the presence of 300 cm3 sulfuric acid ~ 85% ~ After cooling, pour the reaction mixture ~ ur 1 ~ 5 kg of crushed and dull ice ~ pH 10 by adding ~ 30% aqueous sodium hydroxide solution. ~ e preci-formed pity is separated by ~ iltration, the ~ é ~ water and dry O Cr obtains N, N'-didecyl diamino-175 pentane.
b) N, N'-d ~ dec ~ l N, N '~ dimethyl diamino-1,5 pentane.
By methylation of the product obtained in a), according to a method analogous to that described in preparation n 1, we obtain N, N ~ -didecyl N9N ~ -dimethyl diamino-1,5 pentane, ~ b _ 19 ~ -195C (Q ~ 4 mm Hg).
Analogous way, we prepared the ditertiary diamines indicated in the following table I:

TAB: C.EAU: 1 Example Method _ Poi nt No No AR by Ebullitio OC / mmHg _ 4 ** 2 - (CH2) 10 C12H25 1 (CH2) 3 C4Hg 65-66 / 0.1 6 2 (CH2) 6 C8H17 167 169 / 0.15 7 2 (CH2) 10 C8H17 185-187 / 0.1 8 1 (CH2) 10 C4Hg 135-137 / 0.1 9 ** 2 (CH2) 6 C16H33 1 (CH2) 6 cyclohexyl 170-172 / 0.25 11 1 (CH2) 6 isobutyl 86-87 / 0.25 12 * 2 (CH2) 3 C12H25 200-205 / 0.3 13 * 2 (CH2) 6 C12H25 235-242 / 0.2 14 1 p-xylylidene C4Hg 110-112 / 0.25 1 m-xylylidene C4Hg 133-134 / 0.3 16 1 ~ CH2) 12 C4Hg 136-137 / 0.1 17 1 (CH2) 6 C3H7 94-95 / 0.25 18 1 (CH2) 6 isopropyl 94-95 / 1 1 9 1 (CH2) 3 benzyl 163-165 / 0.6 1 -CH2-CH2-CH- hexyl 124-126 / 1 21 1 CH2) 8 isobutyl 100-102 / 0.15 22 ** 2 CH2 IH (CH2) 5 1 CH2 C8H17 23 ** 2 ICH2 ~ CH - CH2 - C4Hg *: characterized in the form of hydrobromide (see examples 27 and 28) **: Product studied by potentiometric dosage of functions amine (perchloric acid) only: pu: reté ~ 96 ~ 16 -~ 8 ~ 5 Examples of ~ .reparation of the salts of ~ ormule II.
These salts are prepared ~ .eJ, the general process below:
We react 0.1 mole of diamine ~ itertiary formula (I) with a solu ~ hydroethanolic ion of desired acid, of following composition:
1 mole of organic or mineral acid 34 ml of water 120 ml of ethanol, for 15 minutes ~ with stirring between 30 and 50C. We evaporate ~ hot ~ under a pressure of 15 mm of mercury, the solution reaction, then resumes the residual part by distillation azeotropic in the presence of 1.5 l of ethyl acetate (5 times 0.3 ml).
The residue is taken up with 120 ml of methanol, before-ment re ~ roidi towards 5C, then we spin and wash 3 ~ ois with 120 ml of ether. We dry the salt under reduced pressure ~ 60C and obtain a yield of the order of 70 ~ 95%.
According to the general procedure described above, we have in particular prepared the salts of ditertiary diamines of ~ ormule IIt indicated in the following table (Table II) o i ~.
'1 ; s 'rABI ~ WATER II
Salts of formula II
. _ _ - ~ n 24 (CH2) 3 C8H1 7: E ~ r 9 7 ~ 5 ~ 6 0

2 5 (CH2) 6 C8H17: 1 ~ 94% 226 26 (CH2) 10 C8H17: E ~ r 92 ~ 5% 153 27 (CH2) 3 C12H ~ 5: Br 69%> 260 28 (CH2) 6 C12H2 5 ~ 3r 74 ~ 5% 240 29 (CH2) 3 C4Hg Br 98.5% 209 lC112 ~ ClOH71 ~ _ ____ 263 ~ ~ 3 ~ 5 EXAMPLE MI
.. .. _. _ DYE-CREAM PORT (oxidation coloration) - Cetyl stearyl alcohol. ~ 0 .. ~ ............... 20 g - Oleic ethanolamide.O ....... OO. ~ 4 g - Cetyl stearyl sul ~ sodium ate -... O ~ ... OO- 3 g - Compound of example 30 .. 0 .... 0 ..................... 5 g - Ammonia at 22 Be .......... ~ ........... ... O 10 ml COLORAN ~ S:
- M-diamino anisol sulphate ...................... 0.048 g ~ Resorcin .................... ~ ........ ~ ..... O .... O 9 420 g - m-amino phenol base .......... ~ ........ O .......... 09 150 g - Nitro-p-phenylene diamine .... 7 ~ 0 ~ 085 g - p-toluylene diamine ~ .... O .............. ~ ... --- O 0 ~ 004 g - Trilon s * Ø. ..O ...... ~ .............. ... ~ .... ~ 1 g - Sodium bisulphite d = 1.32. ................. ~ 1,200 g - Water q. ~ P. ~ ... .... ~ .. ~ .............. ..... ~. 100g 0 ~ mix 30 g of this ~ ormule with 45 g of water oxygenated ~ 20 volumes, a cr ~ me read ~ e, consistent, pleasant ~ the application and which adheres well to che ~ them.
After a 30-minute break, rinse and dry.

On 100% white hair you get a blonde shade.
Detangling wet and dry hair is easy. Aspect shiny hair, pleasant and silky touch.
* Trilon B (trademark): ethylene diamine tetraacetic acid.
EXAMPLE N ~ II
DYE SUPPORT CREAM (dyeing dye) - Cetyl stearyl alcohol- .. - ~ OO 20 g ~ Oleic diethanolamide .. ~ .......................... 4 g - Cetyl ~ tearyl Bul ~ a-te de ~ odium .. ~ ...... ..... 3 g - Composed of Example 28 ................. ~ .......... 5 g - Ammonia ~ 22 ~ é ..... ....., ..................... 10 ml d - 1 9 ~ .J

`: ~
36 ~ 5 COI.ORAN'rS:
Sul ~ ate of m-diamino anisol ~ .......... 0.048 g - Resorcinol. ~ ... 7 ~ O ~ O ~ 420 g - m-amino phenol base.O0 ..... ~ .., .. ~ .. ..O., ...... 0.150 g - nitro p ~ phenylene diamine ..... ... ... ~ .......... 0.085 g - p-toluylene diamineO ... O .. ~ .................... OqO04 g - Trilon B (brand name) ...................... 1 g - sodium sisulfite d = 1,320 .. ~, .., ....... 1,200 g - Water q. sp .. ~ ~ OO 1 ~ D ~ ~ ~ O ~ O - 100 g We mix ~ 0 g of this ~ ormule with 45 g of hydrogen peroxide ~ 20 volumes, ~ n obtains a smooth, consistent, pleasant cream on application and which adheres well to hair.
After a 30 minute break 9, rinse and dry.
On 100% white hair, a blonde shade is obtained.
~ e dismounting of wet and dry hair is easy. Aspect shiny hair, pleasant and silky touch.
EXEMPI.EN III
I. POSITIONING OPTION FOR SENSITIVE HAIR
We prepare - ~ no alcoholic solution with:
- Poly ~ inyl pyrrolidone ..... r ~ ... .O ~ ... ~. lg - Composed of 19example 26. ~ ...................... lg - Ethyl alcohol qs. ~ ....... 0.O ~ .., ......... lOO ml We apply on the hairO we do the styling We dry The che ~ them are hardened ~ and plasti ~ iésO They are shiny and have volume; the touch is silky and the disassembly is ~ sharp.
E ~ EMPI.E ~ IV
~ OTIO ~ DE MI ~ SE EN P ~ IS FOR CH VEUX SENSIBI ~ ISES
An alcoholic solution is prepared with:
- Polyvinyl pyrrolidone ~ -. ~ -.- .-- O ~ -. lg - Composed of example 27 ~ o ~ o ~
- Ethyl alcohol qs .............................. ... O ...... lOO ml - 20 ~

..

~ ~ l3 ~

Apply on the hair. We have the styling.
We dry.
The hair is hardened and plasticized.
They are shiny and have volume; the touch is silky and dem ~ la ~ e easy.
EXEMP ~ IN ~ V
STRUCTURING LOTION (Application without rinsing ~
Before mixing:
0.3 g of N, N '~ di- (hydroxymethyl) ethylene-thiourea with 25 ml of a solution containing:
- Compound of example 24 ~ o ~ 0 ~ 4 g - Phosphoric acid q ~ s .. O .. ~ OO ........ pH = 2.7 - Water q ~ s ~ p ~ O ~ O ~ e ~ O ~ lOO ml The mixture is applied to hair washed and towel-dried before to proceed with the styling ~ es hair is dem ~ slow ~ acilely, the touch is silky.
We have styling and l90n dry Hair is shiny, nervous, they have body (volume), the touch is silky, the removal easy 20 EXEMP ~ E ~ VI
~ r1o ~ r ~ A ~ (Application with rinsing) Apply to wet and clean hair 30 ml of the following solution:
- Composed of example 29 ~ o ~ o ~ 5 g - Monoethanolamine qs ... ~ ..... ~ ... ~ .O. ~ Ph 7.5 - Water qs ~ o ~ o ~ oo ~ o ~ O ml Leave to stand for 5 minutes and rinse.
~ es haYeux have a soft touch and dem ~ slow easily.
We do the styling and we dry. ~ dry hair is loose slow easily. They are bright, nervous and have body.

~ ..3 ~ 5 EXEMPI.EN VII
_ UCTURAMTE (Application with rinse ~ age) Before mixing:
2 g of N, NI-di- (hydroxymethyl) ethylene-thiourea with 25 ml of solution containing:
- Compound of example 25 Ø ........ ~. ~ O ~, ............. .4 g - Hydrochloric acid q.sO ~ o ~ o ~ ph 2 ~ 5 ~ Water qspr 0 ...... OOOO .... O ........ ...... ~ ............. 100 ml Apply the mixture to washed and towel-dried hair Leave to stand for 10 minutes and rinse.
~ untangling is easy9 hair has a soft feel (silky).
We have the styling and we dry under helmet ~ dry hair is easily unraveled, it is shiny lants, nervous and have body (volume).
EXEMP ~ IN VIII
I, O ~ I ON I) ESODORI SANTE POUR VAPORI SA "'EUR
- Composed of example 25 ...., ...... ~ ....... ~ Ø ..... ~. 3 ~ 0 g - Propyl ~ ne glycol ØO ...... ~ .O. ~ .......... ..... .. O.,. 5.0 g ~ Polyoxy-thylenated sorbitan monooleate (~ 20 moles of ethylene oxide) Ø0 .. 0 ..... ~ ....... 1.0 g - Perfume ........ OOO ... OO .... O ~ ..................... 0.5 g - Alcohol ~ 96% ........ 0 ..... O .......... O .. ~ ....... 50 ml - Water q. ~ Op. , 0.O.OO .... O ....... O ~ OO .. ~ ....... O. 100 ml EXEMP ~ IN IX
~: MULSION_CORPORELI.E SOFTENING and AIR FRESHENING
- Compound of example 28 .......... ~ .................. 0 ~ 2 g Cetyl-s-tearyl alcohol o ~ ethylenated.
(~ 15 moles of ethyl ethylene oxide) ................... ....... ~ ........... 390 g - Cetyl alcohol .............. ~ ..... .... ~ .............. 0.5 g

3 - Allantoine ~ -. -. - .- .. - ~ - .. --.-.--- ~ -........... 093 g By ~ um. ~ ..., ......,. ~., ...................... Ø ... ~ ... ........... 0 ~ 5 g 6 ~

- Alcohol ~ 96% .. ... ~ ....................... 40 ml - ~ at q-S9p ~ o ~ oo ~ 0 EXEMP ~ EN ~ X
DES0D0RISAN SPRAY ~ ALC00LIQUE
- Compound of example 26 ~ o ~ 0 ~ 2 g Fragrant ~ ........ ... ~ O .......... n ~ 0 ~ 5 g Absolute alcohol. ~ 0. ~ ........, ..... .., 0Ø ..... 29.3 g - ~ éon 11 (trademark) ...., ........... 42 ~ 0 g - ~ area 12 tmarc ~ commercial eu) ......... 2890 g E ~ CEMPI.EN XI
SPR ~ Y DESODORI SANT HYDROAI COOLIQUE
- Compound of example 27 ~ o ~ o ~ 0 7 1 g - ~ polyoxyethylenated anoline (at 16 moles of ethyl oxide ~ ne) ........ 0 ~ 2 g - Perfumed ~. ~ ......... .. i ... ~ ..... ~ .. ~ .O ~ 0, ~ g - 96% alcohol OY ~ 25.0 g - Water ~ a ~ o ~ 3472 g - Freon 12 ~ O ~ - 40.0 g EXAMPLE N XII
- Diol 1-2 in C11-a14 polyglycidolated (~ 3-4 molecules of glycidol) ...... O .......... Q ~ 14 - Compound of example 24 ~ ---- '- - --- - 1 t 2 - Lactic acid qOs.p. ~ o ~ oo ~ pH = 3 - Water qs. ~ ..............., ............... .... 100 This shampoo has a clear appearance ~ Applied ~ for hair, it gives an abundant foam, and promotes the removal wet hairO After drying, the hair is nervous, light and shiny.
EXEMP ~ IN XIII
30 - Lauric alcohol poly ~ thoxyl ~ ~
12 moles of ethylene oxide. .. 8 - Diol 1-2 in Cl1-C14 polyglycidolated ~ ~ 3 ~ t3 (~ 3-4 ~ glycidol molecules) .. 0 .... ~ Ø .................. 7 Compo ~ é of excmple 29 ~ ....... ...... ............ "O 2 - ~ riéthanolamine qsp ....... ~ O .... Ø ............ pH - 5 - I ~ at qs .. DO ~ ~ - ~ ~ ~ ~ O ~ ~ ~ ~ O ~ ~ ~ ~ D ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 100 This limpid-looking shampoo ~ has very good power foaming ~ ~ aVorise the removal of wet hair7 e ~ don ~ e flexibility to che ~ them. After ~ 3 drying ~ the hair is ner ~ them, bright, soft and relatively not very electric.
~ XEMP ~ IN XIY
,,. ,,, .. _ ~ _ - Polyethoxylated lauryl alcohol ~ 12 moles of ethylene oxideOO.O ... O .. ~ O ~ ... ~ .. ~ ... ~ .. ~ .O. 15 - Coconut diethanolamide ........... ............. 0 ..... ..... 3 - ~ rom ~ re of trimethylcétyl ammonium ...... ~. ~ ............ ...... 3 - Composed of ~ e ~ example 29 ~ o ~ o ~ o ~ o ~ 2 - ~ riéthanolamine q.sOp. .. 0, ....... ~ ...... 4 ~ ~ pH ~ 4 - E ~ u qsp .............. ~, ............... ~ .O ........... . o ~ 100 ~ e crystal clear shampoo9 ~ very good power foaming. Pon dem ~ wet lage ~ soft hair ~ and flexible. After drying, the hair is light ~ swelling ~ shiny and little electric.
EXAMPLE N XV
- ~ iol 1-2 in Cll -C14 polyglycidolé
(~ 3-4 glycidol molecules) ,. ~ ......, 4 ~, ... 10 ~ Composed of example 28 ~ O ~ o ~ D ~ o ~ a ~
- ~ riéthanolamine qvs.pO. ~ 0 ~ Ø9 ~ r ... ~ D ~ pH = 6 - ~ at qOsp, ~ OD ~ O ~ O ~ ~ O ~ 9 ~ ~ O 100 This shampoo has a clear appearance. It gives a foam abundant ~ promotes the removal ~ lage and leaves dry hair in good condition, shiny, light and ~ acile to coi ~ iron.
E '~ UDE OF GER ~ ICIDES PROPERTIES OF ~ S SE ~ S OF ~ ORMU ~ E II
The germicidal properties of the salts were determined.
formula II according to the technique ~ described ~ below ~ or ~.

3 ~; 5 c = = = ~. . _ We pour in a Petri dish of the nu-tritive elose teach mencées by microorganisms ~ study. After cooling of this agar, ~ e ~ makes three equidistant holes ~ 17aide dlun takes ~ 10 mm diameter piecesD We place dan ~ each hole 091 ml of the compound solution ~ study.
We incubate the boxes ~ your ~ incubator ~ 37C for bacteria and at 22C for the mushrooms D ~ pr ~ s incubation7 we measure the diameter ~ e9 expressed in mm, ~ inhibition ones that have formed-mées around the cups.
2: - TE ~ HNI ~ UE D ~ S BCUI ~ LONS
In tubes of nutritious broth ~ 1 ml is incorporated of a stock solution of compound ~ study such as dilution ~ inale corresponds ~ the dilution to be tested ~ 071 ml is incorporated dlune suspension of germs ~ I
We incubate ~ l9étuve ~ 37C for b ~ ctéries and 22C
for mushrooms ~ Ap ~ s incubation9 we transplant on half nitriti ~ s places liquid and solid9 we incubate ces.nouveaux tubes and after incubation we appreciate the importance of the culture:
. - ~: absence of culture ~ depending on the degree of cultivation ~ (low, medium, or high) t ~) ~ The results are summarized in the following table:

t ~ t , '' t ~ ``. '' r ~) ~

~ 13 ~ B ~ 5 r ~

. O
_ ~ ~ 1 ~ ~ ~ ~ ~ 1 ~ ~ 1 ~ ~ rl ~ ~
. _ __ ~ 1 ~ ~ 1 ul u ~ ~ ~
o ~ n ~ r ~ r ~~ r oI ~ oo ooou ~
, ~ ~ ~ ~ ~ ~ ~ 1 _ _ __ hu ~ ~ n Ln a) la ~ ~ ~ ~ r ~ gr ~ ~ r In O 0 ~ OOOOO ~ r . ~ ~ ~~ 1 ~ ~ 1 ~ J ~ ~ ~
: ~. ~ ~ _ _ _ _ _ _ _ ~ ~ ~ a) ~ r) In ~
., 1 ~ a ~ D ~ 00 ~ ~~ DO ~ ~~ 1 O l` ~ ~
~: ~ q O ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ r ..
_ __ E ~ ~ O u ~ u ~
~ u ~~ ~ i ~ ~ ~ r 1 ~ o ~, 1 or ~ r ~ o rq ~ ItY ~ ~ r ~ ~ ~ ~ 1 ~ `3 ~ I ~ I ~ 1` 1 H
_ ~ __ n _ ~
~ o ~ ~ oo ~ r ~ u ~ O ~ 00 ~
OE ~
_ ~ _ ~ ~) ~) _ ~ 1 t ~ _ ~ 1 ~ 1 NH
. ~
. oa) ~ ll .1 lll 1 llll, '~ 1 ~ _ __ _ l .-OX 1 ~ 1 l + llll + .1 l +
,: .4 ~ Q '_ __ _ _. __ _ a) ~ ~ ~ `l + ll ~ llll., ~
'~ ~ ~ _ ~ _ _ _ _ _ a) ~ q ~ l + lllllllll ~ Oq ~ _ _ ___ _ _ not a) ~ _ _ _ E ~ ~ llllllllll _ + _ ~ 1 ~ ~ h ~, ~ h ~ t), l ~ t ~ ~ t ~ t ~ C ~ ~ q -1, - ~ ~ ~ 1 ~ 3 _ _ - ~ d __ _ _ a ~

~. ., 1 ~ ~ ~ ~
u ~ ~ ~: ~, ~ ~ a ~ c) oO) ~, qot: l ~ h ~ ~, ~, ~ ~ ~ ~ q ~ ~ d s ~, ~ ~ ~ h, ~ t ~ ~) ~ ~ 3 a) ~ q -, 1 C) a) h ~ 1 OO ~ O
C ~: ~ ~) ~ do ~: ~ C ~ u ~ ~ æ r,., U ~ ~ ~ ~ ~ ~ ~ ~
u ~ O ~ ~) ~ d u7 1_l ~> u ~ 1 ~ ~ O rl C ~ O u ~ ~ rl ~ d ~ d ~ ~ O ~ :) ~ h. ~) R
O Ul H ~ ~ 1 op ~ o dl ~ 1 rl O ~ d u ~ rl ~ ~ d rl (U ~ u ~ h ut ~ d rl ~ 1 U ~ ~ 1 ~ ~ ~ 1 ~: Sl ~ O: 1 ~ d-rl ~ to rl O a) H
o ~ ~ -1 ~ 1 a) u ~ rd a) ~ ~ ~ 1 ~ O ~ 'J 1:
ZP ~ rl U ~ R ~ ~ U a) ~ 1 a) rl ~ 1 ~ 11 1 ~ l O h O (1) OOO 5-1 1 ~ 1 1: ~) ~ 1 .IJ ~ d 0 u ~ 1-l 0 ~ 5-1 ~ d C) ~ du ~ O ~ O El u ~ p: l _ _. K ~ _ U ~ O ~.) _._ _ p ~ _ H
. ___ _ ._._ ___.__, _

Claims (27)

The embodiments of the invention about which a exclusive right of ownership or pririlège is claimed, are defined as follows: 1. Process for the preparation of diamines of general formula the:
(I), as well as their addition salts with acids, substituents R and A having the following definitions; R represents a radical aliphatic having from 3 to 20 carbon atoms, a cyclo radical hexyl or a benzyl radical; A represents A1 or A2, A 1 being a meta- or para-xykykidene radical at to 2 being a radical of formula in which x, y and t are integers that 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 R1 and R2 represent a hydrogen atom-ne or an aliphatic radical having less than 18 carbon atoms, with the exception of the diamines of formula I for which:
a) A = A2, R1 = R2 = H; (x + y + t) = 4 or 8; R = benzyl b) A = A2, R1 = R2 = H; (x + y + t) = 1; R = cycohexyl c) A = A2, R1 = R2 = H; (x + y + t) = 4; R represents the 1,5,9-trimethyl radical decyl or the 1,5,9-tetramethyl radical, 13 tetradecyl;
d) A = A2, R1 = R2 = ethyl; y = t = 0; x = 6; and R represents feels the 2-ethyl butyl radical;
e) A = A1 and R = benzyl; cyclohexyl or ispropyl, characterized by the fact that:
(a) a primary amine of formula is reacted R- NH2 with a dihalide of formula Hal - A - Hal, H and A
being defined as above and Hal being a halogen atom, treat the reaction mixture with a basic solution to obtain hold the secondary diamine of formula R - NH - A - NH - R and subjects the latter to a methylation reaction,?
(b) reacts a primary amine R - NH2 with a halo-arylsulfonyl genide of formula Ar - SO2 - Hal, Ar being a aryl group and Hal being a halogen atom, to obtain a sulfonamide of formula Ar- SO2 - NHR which is subjected to a methylation reaction, first forming a metal derivative alkaline by the action of an alkali metal alcoholate then in treating this alkaline derivative with dimethyl sulfate to obtain the compound of formula which is subjected to acid hydrolysis, to form the secondary amine of formula then reacts the latter with a dihalide of formula Hal - A - Hal in the presence of a tertiary amine, or (c) reacts a primary amine R - NH2 with a halo arylsulfonyl genide, reacts the sulfonamide obtained from mule Ar - SO2 - NHR with a dihalide of formula Hal - A - Hal, subject disulfonamide of formula to acid hydrolysis to obtain the disecondary diamine of formu-the which is subjected to a methylation reaction, and d) if necessary, submit the diamine of formula I obtained the action of a mineral or organic acid to form the salt corresponding addition. 2. Method according to claim 1, characterized by the causes a primary amine of formula R - NH2 to react with a dihalide of formula Hal - A - Hal, R and A being defined as before and Hal being a halogen atom, processes the reaction mixture with basic solution to obtain the diameter of formula R - NH - A - NH - R and subjects it to a methylation reaction. 3. Method according to claim 2, characterized by the fact that the reaction between the primary amine and the dihalide is performed at a temperature between 50 and 150 ° C. 4. Method according to claim 3, characterized by the causes the primary amine to be used in an excess of about 2 to 5 moles per mole of dihalide. 5. Method according to claim 2, characterized by the fact that the methylation reaction is carried out by the action of formic aldehyde in the presence of formic acid. 6. Method according to claim 5, characterized by the fact that the methylation reaction is carried out at a temperature between 40 and 100 ° C. 7. Method according to claim 6, characterized by the fact that the formaldehyde is used in an excess of about 2.2 to 10 moles per mole of secondary diamine. 8. Method according to claim 7, characterized in that formic acid is used in an excess of about 2.5 to 10 moles per mole of disecondary diamine. 9. Method according to claim 1, characterized by the fact that a primary amine R - NH2 is reacted with an arylsulfonyl halide of formula Ar - SO2 - Hal, Ar being an aryl group and Hal being a halogen atom, to obtain a sulfonamide of formula Ar - SO2 - NHR that we submit to a methylation reaction, first forming an alkali metal derivative by the action of an alcoholate alkali metal and then treating this alkaline derivative with sul-dimethyl fate to obtain the compound of formula which is subjected to acid hydrolysis, to form the secondary amine of formula then reacts the latter with a dihalide of formula Hal - A - Hal in the presence of a tertiary amine. 10. Method according to claim 9, characterized by the fact that the reaction between the secondary amine and the dihalide in the presence of a tertiary amine is performed solvent-free and at a temperature between 50 and 130 ° C. 11. Method according to claim 10, characterized by the fact that at least two moles of secondary amine and a-tertiary mine are used for one mole of dihalide. 12. Method according to claims 9, 10 or 11, characterized by the fact that the tertiary amine is N-ethyl di-isopropylamine. 13. Method according to claim 1, characterized by the fact that a primary amine R - NH2 is reacted with an aryl sulfonyl halide, reacts sulfona-mide obtained of formula Ar - SO2 - NHR with a dihalide of formula Hal - A - Hal, subjects the disulfonamide formed of formula to acid hydrolysis to obtain the secondary diamine of formula which is subjected to a methylation reaction. 14. Method according to claim 13, characterized by the fact that the reaction between sulfonamide and dihalo-genure is carried out at a temperature between 80 and 140 ° C. 15. Method according to claim 13, characterized by the fact that acid hydrolysis is carried out within a 85% aqueous solution of sulfuric acid, at a temperature between approximately 120 and 145 ° C and for a time between 7 and 20 hours. 16. Method according to claim 13, characterized by the fact that the methylation reaction is carried out by the action of formaldehyde in the presence of formic acid. 17. Method according to claim 1, characterized in that an amine is used as the starting material primary R-NH2 in which R is an alkyl radical having from 3 to 12 carbon atoms. 18. Method according to claim 1, characterized in that a dihalide is used as the starting material of formula Hal - A - Hal in which A is a radical of formula:

in which R1 and R2 represent a hydrogen atom or an alkyl radical having from 1 to 17 carbon atoms and the sum (x + y + t) is greater than or equal to 1 and less greater than or equal to 10. 19. method according to claim 1, characterized in that a dihalide is used as the starting material of formula Hal - A - Hal in which A is a radical of formula:

in which R1, and R2 represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms and n, y and t are defined as in claim 1. 20. Method according to claim 1, characterized in that an amine is used as the starting material primary R - NH2 in which R is a linear alkyl radical, and in that we use, as another starting product, a dihalide of formula Hal - A - Hal in which A is a radical of formula:

in which R1, R2, x, y and t are defined as in the claim 1, except that at least one of substituents R1 or R2 is an alkyl radical. 21. Method according to claim 1, characterized in that we use as starting materials, an amine primary R - NH2 in which R is an alkyl radical having from 4 to 12 carbon atoms or an n-propyl radical and a dihalide of formula Hal - A - Hal in which A is a ortho-or para-xylylidene radical. 22. The diamines of general formula I

(I), as well as their addition salts with acids, substances killing R and A having the following definitions: R represents an aliphatic radical having from 3 to 20 carbon atoms, a cyclohexyl radical or a benzyl radical; A represents A
or A2, A1 being a meta- or para-xylylidene radical and A2 being a radical of formula in which x, y and t are whole numbers that can vary from 0 to it and such that the sum (x + y + t) is greater than greater than or equal to and less than 18, and R1 and R2 represent a hydrogen atom or an aliphatic radical having less 18 carbon atoms, with the exception of diamines of the formula I for which:
a) A = A2, R1 = R2 = H; (x + y + t) = 4 or 8; R = benzyl b) A = A2, R1 = R2 = R1; (x + y + t) = 1; R = cyclohexyl c) A = A2, R1 = R2 = R1; (x + y + t) = 4; R represents the trimethyl-1,5,9 decyl radical or the tetramethyl- radical 1,5,9,13 tetradecyl;
d) A = A2, R1 = R2 = ethyl; y = t = 0; x = 6; and R
represents the 2-ethyl butyl radical;

e) A = A1 and R = benzyl, cyclohexyl or isopropyl, each time they are obtained by the process of claim 1 or its obvious chemical equivalents. 23. The diamines according to claim 22, in which R is the alkyl radical having 3 to 12 atoms carbon, each time obtained by the process of claim 17 or its obvious chemical equivalents. 24. The diamines according to claim 22, in which R1 and R2 represent a hydrogen atom or a alkyl radical having from 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, each time they are obtained by the process of claim 18 or its obvious chemical equivalents. 25. Diamines according to claim 22, in which R1 and R2 represent a hydrogen atom or a alkyl radical having from 1 to 4 carbon atoms, each time that they are obtained by the process of claim 19 or its obvious chemical equivalents. 26. Diamines according to claim 22, in which the at least one of the substituents 1 or R2 is a radical alkyl, and R represents a linear alkyl radical, at each once obtained by the process of claim 20 or its obvious chemical equivalents. 27. Diamines according to claim 22, in which A is an ortho- or para-xylydidene radical, and R
is an alkyl radical having 4 to 12 carbon atoms, or an n-propyl radical, each time they are obtained by the method of claim 21 or its equivalents manifest chemicals.