Patent GB-409728-A (GB)
Title: Process for the manufacture of new amino azo compounds
IPC: C09B43/11
Filed: 1932-11-04
Abstract: Aminoazo compounds which have a combative effect against protozoa and bacteria and contain at least one benzene ring combined with an azo grouping and possess in the benzene ring one amino group substituted by one basic residue, no other such basic residue being present in the molecule, are made according to known methods.  The basic residue is always an aminoalkyl group which p  may be substituted.  The following methods are given: (1) aromatic, heterocyclic or aromatic-heterocyclic diazo compounds are coupled with amines of the benzene series substituted in the amino group by a basic residue; (2) diazo compounds of aminobenzene derivatives substituted in one amino group by a basic residue are coupled with aromatic, heterocyclic or aromatic-heterocyclic compounds; (3) aromatic, heterocyclic or aromatic-heterocyclic nitroso compounds are condensed with diaminobenzenes containing a primary reactive amino group and also one amino group substituted by a basic residue; (4) aromatic, heterocyclic or aromatic-heterocyclic amines are condensed with C-nitroso compounds of aminobenzenes substituted in the amino group by a basic residue; (5) a basic residue is introduced into the primary or secondary amino group of aminoazobenzene compounds by the action of esters of aminoalcohols; (6) aminoazobenzene compounds in which the amino group in the benzene nucleus is substituted by a residue containing a replaceable group are treated in such a manner that the replaceable group is displaced by ammonia or a primary or secondary amine.  In all the above reactions free amino groups may be suitably protected, e.g. by acyl groups.  In examples, the following compounds are described: (1) 4-chloraniline --> N - (a  - diethylamino - d  - pentyl) - aniline; the corresponding 4-bromo, 4-iodo, 4-methoxy and 4-(5<1>-methylbenzthiazolyl-2<1>) compounds and 4-(a -diethylamino-d -pentylamino) -benzeneazo-4<1>-(1<1>-phenyl-2<1> : 3<1>-dimethylpyrazolone) are also described; (2) 3- or 2-chloraniline --> N-(a -diethylamino-d -pentyl)-aniline ; aniline --> 2- or 3-chlor-N-(a -diethylamino-d -pentylaniline; (3) 2 : 4<1>-dichloro-4-(a -diethylamino-d -pentylamino)-azobenzene and the corresponding 2-methyl-4<1>-chlor, 2-chlor-4<1>-ethyl, 2-methoxy-4<1>-chlor, 2-chlor-4<1>-methoxy, 2-chlor-4<1>-methylmercapto, 2-ethoxy-4<1>-chlor, 2-chlor-4<1>-n-butyloxy, 2-hexyloxy-4<1>-iodo, 2-iodo-4<1>-hexyloxy, 2-chlor-4<1>-isooctyloxy, 2-chlor-4<1>-dodecyloxy, 2-hydroxy-4<1>-iodo, 2-methyl-4<1>-iodo, 2 : 2<1>-dichlor-4<1>-methyl, 2 : 2<1>-dimethyl-4<1>-chlor, 3<1> : 5<1>-dimethyl, 3<1> : 5<1>-dichlor, 3<1> : 5<1>-diiodo, 2 : 4<1>-diiodo and 2 : 3<1> : 5<1>-triiodo compounds; (4) 4-chloraniline --> N-ethyl-N-(g -diethylamino - b  - hydroxy - a  - propyl) - aniline (cf. Specification 275,622), or 3-chlor-N-(g -diethylamino - b  - hydroxy - a  - propyl) - aniline or a  - diallylamino - g  - butylaminobenzene or a  - dibutylamino-g -butylaminobenzene; (5) 4-chloraniline --> N-(b -aminoethyl)-aniline, 4<1>-chloro-4-(g -methylamino-b -hydroxy-a -propylethylamino) - azobenzene, 4<1> - chloro - 4 - (g -piperidyl - b  - hydroxy - a  - propylethylamino) - azobenzene, 4<1> - chloro - 4 - (b  - guanidinethyl - methylamino) - azobenzene, 3<1> : 5<1> - dichlor - 4 - (g  - amino - b  - hydroxy - a  - propylamino) -azobenzene, 3<1> : 5<1>-dichlor-4-(g -amino-b -hydroxy-a -propyl-ethylamino) -azobenzene, 4<1>-chlor-4-(b -(acetamide)-aminoethylmethylamino) -azobenzene, 3<1> : 4<1> : 5<1> - trichlor - 4 - (g  - amino - b  - hydroxy-a -propylethylamino)-azobenzene, 4<1>-methoxy - 4 - (g  - amino - b  - hydroxy - a  - propyl-ethylamino)-azobenzene, 2-methyl-4<1>-iodo-4-(g -amino-b -hydroxy-a -propylethylamino) -azobenzene, 2-methyl-4<1>-decyloxy-4-(g -amino-b -hydroxy-a -propylethylamino)-azobenzene, 2-methyl-4<1>-sulphamido-4-(g -amino-b -hydroxy-a  -propylethylamino)-azobenzene, 4<1>-arsenious oxide-4-(g -amino-b -oxy-a -propylmethylamino)-azobenzene and 3<1> : 5<1>-diiodo-4-(g -amino-b -hydroxy-a -propylethylamino) -azobenzene; (6) p-toluidine is condensed with 4-nitroso-1-(N-methyldiethylaminoethylamino)-benzene (cf. Specification 274,058) or 4-nitrosotoluene is condensed with 4-amino-1-(N-methyldiethylaminoethylamino)-benzene to yield 4<1>-methyl-4-(diethylaminoethylmethylamino)-azobenzene; 3-amino-1-diethylaminoethylamino-benzene is condensed with 4-chloro-1-nitrosobenzene; (7) azobenzene-4-sulphamic acid or 4-aminoazobenzene is condensed with diethylaminoethyl chloride; (8) p-chloraniline --> acetylaminoethyl-methylaminobenzene is saponified to form 4<1>-chloro-4-(b -aminoethylmethylamino)-azobenzene; (9) p-chloraniline --> 3 : 4-dimethoxy-(g -diethylamino-b -hydroxy-a -propylamino)-benzene; (10) 4-amino-(b -diethylaminoethylmethylamino) - benzene --> resor - cinol.  The Specification as open to inspection under Sect. 91 comprises also the condensation of nitroso compounds with poly-aminobenzenes containing a primary reactive amino group and also one amino group substituted by the basic residue.  This subject-matter does not appear in the Specification as accepted. N-(a -diethylamino-d -pentyl)-aniline is made by melting aniline with the hydrochloride of a -diethylamino-d -chlorpentane.  2- or 3-Chlor-N-(a -diethylamino-d -pentyl)-aniline is similarly made from 2- or 3-chlor aniline.  3-Chlor-N-(g -diethylamino-b -oxy-a -propyl)-aniline is made by heating 3-chloraniline with diethylamino-epihydrin in xylene.  a -Diallylamino-g -butylaniline is made from a -diallylamino-g -chlorbutane and aniline.  a -Diallylamino-g -chlorbutane is obtained by condensing diallylamine with acetone and formaldehyde, reducing the a -diallylamino-g -butanone with sodium amalgam and acetic acid and treating the a -diallylamino-g -butanol with thionylchloride.  a  - Dibutylamino - g - butylaniline is prepared similarly from a  - dibutylamino - g  - butanone (from acetone, formaldehyde and dibutylamine) by reducing to the g -butanol and converting this into the corresponding g -chlor compound.  g  - Methylamino - b  - hydroxy - a  - propylethyl - aminobenzene is made by acting on monoethylaniline with epichlorhydrin and then with methylamine (see Specification 275,622). g  - Piperidyl - b  - hydroxy - a  - propylethylaniline is made by treating monoethylaniline with epichlorhydrin and then with piperidine.  b -Guanidinethyl-methylaniline is made from b -aminoethylmethylaniline and cyanamide.  g -Amino-b -hydroxy-a -propylaniline is made by acting on aniline with epichlorhydrin and then with ammonia (cf. Specification 275,622).  g -Amino-b -hydroxy-a -propylethylaniline is similarly made from monoethylaniline, epichlorhydrin and ammonia.  b  - (Acetamide) - aminoethylmethylaniline is made from b -aminoethylmethylaniline and chloracetamide.  4-Decyloxy-1-aniline used for making 2-methyl-4<1>-decyloxy-4-(g -amino-b -hydroxy-a -propylethylamino)-azobenzene is prepared by condensing potassium 4-nitrophenolate with decyl bromide and reducing.  Azobenzene - 4 - sulphamic acid is made from 4-aminoazobenzene, chlorsulphonic acid and pyridine.  3 : 4-Dimethoxy-(g -diethylamino-b -hydroxy-a -propylamino)-benzene is made from 4-amino-veratrol and diethylaminoepihydrin.  A sample has been furnished under Sect. 2 (5) of the hydrochloride of 3<1> : 5<1>-dichloro-4-(g -amino - b  - hydroxy - a  - propylethylamino) - azo benzene prepared by heating the azo compound 3 : 5 - dichloroaniline --> ethylphenylamino - epihydrin with ammonia.