CA1095898A - Preparation of azo dyestuffs - Google Patents

Abstract

Ref. 3056 PREPARATION OF AZO DYES

Abstract of the Disclosure Azo dyes are very simply made in high purity and very good yield by coupling a diazonium compound with a coupling compound in a mixture essentially of water with a simple alkanol having four to six carbons and soluble in water to the extent of not over about 15%
by weight at 15°C. This procedure is particularly effective with compounds that are ordinarily difficult to couple.

Description

109~898 The present invention relates to a process for the manufacture of azo dyestuffs by coupling a diazonium com-pound with a coupling component, in which the diazonium compound, which, if appropriate, is produced in situ, is coupled, at temperatures between 0 and 80C in the presence of an acid, with the coupling component in a solvent or dispersing medium consisting of a mixture of 90 to 15% by weight of an aliphatic alcohol having a chain length of 4 to 6 C atoms ; and a solubility in water of not more than 15% by weight at 15C, and 10 to 85% by weight of water.
Azo dyestuffs are manufactured in the conventional way by a two-stage process. This process consists in manufacturing a solution or suspension in aqueous mineral acid of a diazonium salt of a primary aromatic or hetero-cyclic amino compound and coupling the latter in a second vessel with a solution or suspension in aqueous mineral acid, or alkali, of a coupling component.
Furthermore, processes have been disclosed which make it possible also to manufacture azo dyestuffs by a one-stage process.
Thus, in accordance with German Patent DAS 2,139,311, a diazo component is treated in an acid, liquid medium with a ~k l`~g5898 coupling component, for example from the series of the dialkyl-anilines. In this process the acid used is preferably hydro-chloric acid or acetic acid, the diazotisation agent is preferably sodium nitrite and the diluent is preferably water and/or a water-soluble organic solvent, for example isopropanol.
German Patent DAS 1,927,453 describes a process in which azo pigments are obtained by diazotisation and coupling in organic ; solvents which contain not more than 10% of water, from diazonium compounds and coupling components which are free from sulphonic acid groups. Examples of organic solvents according to the invention are benzene, toluene, chloro-benzene, o-dichlorobenzene, chloroform and tetrachloroethane and also glacial acetic acid and methanol. In order to form the pigment, the reaction mixture must be stirred for up to 65 hours ~Example 7).
German Patent DOS 2,058,299 describes the manufacture of azo dyestuffs which are free from sulphonic acid groups by diazotisation of a diazotisable amine by means of an ester of nitrous acid in the presence of an organic acid and coupling with a coupling component in an anhydrous, organic solvent which is insoluble in water, preferably aliphatic and aromatic halogenated hydrocarbons, while German Patent DOS

2,509,560 claims in addition the use of water-miscible (hydro-philic)solvents, for example aliphatic alcohols, such as methanol> ethanol and isopropanol. In order to form the dye-stuff, the reaction mixture must be stirred for up to 22 hours : `
:, ~f 1~9S898 (Examples 80 - 82).
Impure azo dyestuffs are obtained by the processes hitherto known in many cases and especially when the solubility relationships of the diazo compounds or of the coupling components in the reaction media are used are unfavourable. A decrease in yield is also generally associated with the occurrence of impurities in the azo dyestuffs. Furthermore, the coupling ; reaction takes place very slowly in some of the known processes, so that reaction times which are uneconomically long are required.
It has now been found, surprisingly, that the disadvantages inherent in the processes hitherto known can be avoided if, in the manufacture of azo dyestuffs, the diazonium compound which, if appropriate, is produced in situ, is coupled, at temperatures between 0 and 80C in the presence of an acid, with the coupling component in a solvent or dispersing medium consisting of a mixture of 90 to 15% by weight of an aliphatic alcohol having a chain length of 4 to 6 C atoms and a solubility in water of not more than 15% by weight at 15C, and 10 to 85% by weight of water.
Thus, this invention provides for a process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound of the diazo-tized amine of the general formula I or II
Xl X5 ~ - N = N ~ ~ - NH2 x3 X6 X8 (I) (II) wherein Xl and X2 each denote hydrogen, halogen, alkyl or alkoxy each having from 1 to 4 C atoms, nitro, cyano, trifluoromethyl or alkoxycarbonyl, alkylcarbonyl, carbonamide, N-monoalkyl-carbonamide, N, N-dialkyl-carbonamide, alkylsulphonyl, sulphonamide, N-monoalkyl-sulphonamide or N, N-dialkyl-sulphonamide each having from 1 to 8 C atoms, or phenoxy, phenalkoxy, phenylsulphonyl or benzoyl each being optionally substituted by halogen or ; by alkyl or alkoxy having from l to 4 C atoms, and X3 denotes hydrogen or ~ halogen, , .>.
~' f 1~9~8 X4 and X5 denote hydrogen or halogen~ alkyl or alkoxy having from 1 to 4 C
atoms, nitro, cyano, tri1uoromethyl or alkoxycarbonyl, alkylcarbonyl or alkylsulphonyl having from 1 to 8 C atoms, X6 denotes hydrogen or halogen and X7 and X8 are identical or different and each denote hydrogen or ; halogen or alkyl or alkoxy group having from 1 to 4 C atoms, and X8 also denotes an acylamino group containing from 1 to 8 C atoms with a coupling component of the general formula III

~ N ~1ll) X

; wherein X7 and X8 have the same meaning as defined above, and Xg and X10 each denote alkyl having from 1 to 4 C atoms and optionally substituted by halogen hydroxyl, cyano, or acyloxy or alkoxy having from 1 to 4 C atoms, alkoxycarbonyl or alkoxycarbonloxy each having from 1 to 4 C atoms in the alkyl radicals, or phenoxycarbonyl, phenoxycarbonloxy, cyclohexyl, phenyl or phenoxy each of which is optionally substituted by halogen or by alkyl or alkoxy group having from 1 to 4 C atoms, or Xg and X10 together with the adjacent nitrogen represent a heterocyclic ring wherein a hetero-atom is joined to said nitrogen by alkylene radicals, or of the general formula IV

(IV) t Xll wherein Xll represents hydrogen or has the same meaning as Xg or X10, as defined hereinbefore in formula III, at a temperature of from 0 to 80C and in the presence of an acid, in a solvent or dispersing medium comprising a mixture of from 90 to 15% by weight of an aliphatic alcohol having a chain length of from 4 to 6 C atoms and a solubility in water of not more than 15%
by weight at 15C, and 10 to 85% by weight of water.
In carrying out the process according to the invention it is prefer--3a-.....
Ai ~

109589~

able to use a solvent or dispersing medium consisting of 50 to 25% by weight of an aliphatic alcohol having a chain length of 4 to 6 C atoms and a solubility in water of not more than 15% by weight at 15C, and 50 to 75% by weight of water.
Examples of aliphatic alcohols which have a chain length of 4 to 6 C atoms and which are contained in the -3b-~1~95898 solvents or dispersing media to be employed according to the invention, as components of the mixture, are n-butanol, iso-butanol, n-amyl alcohol, diethyl carbinol, isobutyl carbinol, n-hexanol and iso-hexanol.
n-Butanol and iso-butanol are preferred.
The advantages of the process according to the invention are conditioned by ~he sum of the physico-chemical properties of the two-phase system to be employed according to the invention as the solvent or dispersing medium.
In this connection a particular significance attaches to the solubility in water of the aliphatic alcohols to be employed.
The solubilities in water of the preferred alkanols, n-butanol and iso-butanol, are 6.8 and 7.4% by weight, respectively, at 15C.
Conversely, the solubility of water in n-butanol is 27.3% by weight and in isobutanol is 16.~/o by weight at this ; temperature.
The process according to the invention can be ~arried out in a single stage if the dia~onium compound is produced in situ, that is to say in the reaction mixture itself, from a diazotisable aromatic amine and a diazotisa-tion agent.
~v In this process a diazotisation agent is introduced into a mixture of a diazotisable aromatic amine, a coupling component, a mineral acid and the solvent or dispersing medium. If necessary, the temperature of the reaction mixture can be kept between 0 and +60C, preferably 0 and +5C, by external cooling.

lvss~g~

This process can be carried out with amines which can be diazotised easily, that is to say amines which contain not more than one group of a positive character in the mole-cule, and with coupling components which couple easily or are readily soluble in organic solvents.
The diazotisation agents used are the salts of nitrous acid, particularly the alkali metal salts, such as, for example, sodium nitrite, and also substances which evolve nitrous acid, such as nitrosylsulphuric acid and the esters of nitrous acid, especially of primary, monohydric, aliphatic alcohols having 1 to 6 carbon atoms, for example the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, n-pentyl, isopentyl or n-hexyl esters.
~ he process according to the invention can also be carried out in a quasi-single stage, by introducing a stabilised diazonium compound which has been isolated and, if appropriate, dried, of a diazotisable aromatic amine into a mixture of a coupling component and the solvent or dis-persing medium.
In this case it is not necessary to add a mineral acid and a diazotisation agent to the reaction medium.
The process according to the invention can be carried out in two stages by introducing a solution of a diazonium compound in an aqueous or concentrated inorganic or organic acid into a mixture of a coupling component and the solvent or dispersing medium.
In this process the solution of the diazonium com-pound which is to be introduced is manufactured in a reaction 109~8 stage prior to the coupling, by diazotising a diazotisable aromatic amine in an aqueous or concentrated inorganic or organic acid with one of the diazotisation agents mentioned.
In this case also, the reaction temperature can be kept between 0 and 80C, preferably 0 and 50C, by external cooling.
It is appropriate to select this process when using diazotisable amines which contain more than one group of positive character in the molecule or with coupling components which couple with difficulty, Suitable acids for use according to the invention are, in principle, all adequately strong inorganic and organic acids which are known for the diazotisation of amines and coupling in an acid medium.
Hydrochloric acid, hydrobromic acid, sulphuric acid or the various phosphoric acids are mentioned as examples of 'r suitable inorganic acids. Formic acid, acetic acid, chloroacetic acid and propionic acid are examples of acids from the series of organic acids which can be used.
In order to accelerate the coupling and to take up the quantities of acid which are additionally liberated during the coupling, it can be advisable to buffer the reac-tion mixture. Buffer substances which are in themselves known are added to the reaction mixture fsr this purpose;
known buffer substances are, inter alia, the alkali metal salts of fairly weak acids, such as, for example, sodium acetate.
Particularly when carrying out the process according 1~958g8 to the invention in a quasi-single stage by adding a diazo-component which has been isolated and, if appropriate, stabilised, it is very advisable to buffer the acid liberated.
It is possible to employ, for the process according to the invention, the optionally stabilised diazo compound of a diazotisable aromatic amine of the general formula I

çr ~

wherein Xl and X2 denote hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 to 4 C atoms, nitro, cyano or trifluoromethyl groups, alkoxycarbonyl, alkylcarbonyl, carbonamide, N-monoalkyl-carbonamide, N,N-dialkyl-carbonamide, alkylsulphonyl, sulphonamide, N-monoalkyl-sulphonamide or N,N-dialkyl-sulphonamide groups containing 1 to 8 C atoms, or phenoxy, phenalkoxy, phenylsulphonyl or benzoyl groups which are optionally substituted by halogen atoms or by alkyl or alkoxy groups containing 1 - 4 C atoms, and X~ denotes a hydrogen or halogen atom and also of aminoazo compounds of the general formula II

X5 ~ N ~ 2 II

wherein X4 and X5 denote hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 to 4 C atoms, nitro, cyano or trifluoromethyl groups or ~lkoxycarbonyl, alkylcarbonyl or 109SI~9~

alkylsulphonyl groups containing 1 - 8 C atoms, X6 denotes a hydrogen or halogen atom, X7 and X~ are identical or different and denote a hydrogen or halogen atom or an alkyl or alkoxy group containing 1 to 4 C atoms, and X8 also denotes an acylamino group containing 1 - 8 C atoms.
The following amines may be mentioned as examples:
aniline,2-,3- or4-chloroaniline, 2,4- or2,5- dichloroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2-, 3- or 4-methylaniline, 4-n.-butylaniline, 2-methyl-3-, -4-, -5- or -6-chloroaniline, 2-, 3- or 4-methoxyaniline, 2- or 4-phenoxyaniline, 2,5-dimethoxyaniline, 2,5-diethoxyaniline, 2,5-dimethoxy-4-chloroaniline, 2-methoxy-5-chloroaniline, 2-ethoxy-5-chloroaniline, 2-phenoxy-5-chloroaniline, 2-, 3-or 4-nitroaniline, 2-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 2,4-dinitroaniline, 2,4-dinitro-6-chloro-aniline, 2,4-dinitro-6-bromoaniline, 2,5-dichloro-4-nitro-aniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitro-aniline, 2-chloro- or 2-bromo-4-nitroaniline, 2-methoxy-4-nitroaniline, 4-methoxy-2-nitroaniline, 2-ethoxy-4-nitro-aniline, 4-ethoxy-2-nitroaniline, 2-, 3- or 4-cyanoaniline, 2,4-dicyanoaniline, 2-methyl-4-cyanoaniline, 2-cyano-4-nitroaniline, 2,6-dichloro-4-cyanoaniline, 5-chloro-4-cyano-2-nitroaniline, 2,4-dinitro-6-cyano-aniline, 3-trifluoro-methylaniline, 3,5-bis-(trifluoromethyl)-aniline, 2-tri-fluoromethyl-4-chloro-aniline, 2-trifluoromethyl-5-chloro-aniline, 2-, 3- or 4-amino-benzoic acid ethyl ester, 2-, 3-or 4-amino-benzoic acid n.-butyl ester, 2-, 3- or 4-amino-benzoic acid 2'-ethyl-n.-hexyl ester, 2-amino-3- or -4-~0~3g8 chloro-benzoic acid methyl ester, 2-amino-3,5-dichloro-benzoic acid methyl ester, 4-amino-3-bromo-benzoic acid methyl ester, 3-amino-4-chloro-benzoic acid methyl ester, 2-, 3- or 4-amino-benzoic acid amide, 2-, 3- or 4-amino-benzoic acid monomethylamide, 2-, 3- or 4-amino-benzoic acid dimethylamide, 2-, 3- or 4-amino-benzoic acid isopropylamide, 2-, 3- or 4-amino-benzoic~acid diethylamide, 2-, 3- or 4-amino-benzoic acid di-n.-butylamide, 2-, 3- or 4-amino-benzoic acid 2'-ethyl-n.-hexylamide, 2-, 3- or 4-amino-benzenesulphonic acid amide, 2-, 3- or 4-amino-benzene-sulphonic acid monomethylamide, 2-, 3- or 4-amino-benzene-sulphonic acid dimethylamide, 2-, 3- or 4-amino-benzene-sulphonic acid diethylamide, 2-, 3- or 4-amino-benzene-sulphonic acid di-n.-butylarnide, 2-, 3- or 4-amino-benzene-sulphonic acid 2'-ethyl-n -hexylamide, 1-methyl-2-amino-benzene-4-sulphonic acid amide, 1-methyl-2-amino-benzene-4-sulphonic acid n.-hexylamide, l-methoxy-2-amino-benzene-4-sulphonic acid amide, l-methoxy-2-amino-benzene-4-sulphonic acid dimethylamide, l-rnethoxy-2-amino-benzene-4-sulphonic acid di-n.-butylamide, l-chloro-2-amino-benzene-4-sulphonic acid dimethylamide, 1-chloro-3-amino-benzene-4-sulphonic acid amide, l-chloro-4-amino-benzene-2-sulphonic acid dimethylamide, l-nitro-4-amino-benzene-3-sulphonic acid di-n.-butylamide, 2-, 3- or 4-aminoacetophenone, 2-, 3- or 4-aminobenzophenone, 4-amino-4'-chlorobenzophenone, 4-amino-2',4'-dichlorobenzophenone, 2-amino-4'-bromobenzophenone, 2-amino-2',~'-dimethylbenzophenone, 4-amino-2'-methylbenzo-r~ n(,r,e, 1~ 1(1ir~ -eI,ilyl~erlz~ erl-,rl~, ~-alllirll,-4'-rrl~t~loxy-l~gS89B

benzophenone, 3-amino-3',4'-dimethoxybenzophenone, 4-amino-4'-methoxybenzophenone, 3-amino-4'-methoxybenzophenone, 4-amino-4'-n.-butylbenzophenone, 4-amino-4'-isopropylbenzo-phenone, 2-amino-4'-fluorobenzophenone, 2-a~ino-5-bromo-benzophenone, 4-amino-3-chlorobenzophenone, 2-amino-4,5-dichlorobenzophenone, 4-amino-3,5-dibromobenzophenone, 4-amino-2-methylbenzophenone, ,2-amino-5-methylbenzophenone, 2-amino-4,5-dimethylbenzophenone, 3-amino-2,4-dimethylbenzo-phenone, 2-amino-4,5-dimethoxybenzophenone, 2-amino-4-methoxybenzophenone, 2-methylsulphonyl-aniline, 3-methyl-sulphonyl-aniline, 4-methylsulphonyl-aniline, 4-chloro-2-methylsulphonyl-aniline, 2-chloro-4-methylsulphonyl-aniline, 2-phenylsulphonyl-aniline, 3-phenylsulphonyl-aniline, 4-phenylsulphonyl-aniline, 2-chloro-4-phenylsulphonyl-aniline, 4-chloro-2-(4'-chlorophenylsulphonyl)-aniline, 4-(4'-bromo-phenylsulphonyl)-aniline, 3-chlo~o-4-(phenylsulphonyl)-aniline, 5-chloro-2-(phenylsulphonyl)-aniline, 4-chloro-3-(phenylsulphonyl)-aniline, 4-chloro-2-(phenylsulphonyl)-aniline, 2-bromo-4-(phenylsulphonyl)-aniline, 4-(2',4'-dichlorophenylsulphonyl)-aniline, 4-(4'-methylsulphonyl)-aniline, 4-(4'-isopropylphenylsulphonyl)-aniline, 4-(4'-fluorophenylsulphonyl)-aniline, 4-(3'-chloro-4'-methoxy-phenylsulphonyl)-aniline, ~-(2',4'-dimethoxyphenylsulphonyl)-aniline, 4-(3',5'-dimethoxyphenylsulphonyl)-aniline, 4-(4'-methoxyphenylsulphonyl)-aniline, 4-(4'-ethoxyphenylsulphonyl)-aniline, 2-(4'-methoxyphenylsulphonyl)-aniline, 4-(4'-n.-butylphenylsulphonyl)-aniline, 4-(4'-n.-butoxyphenylsulphonyl)-aniline, 4-(2',4'-dimethylphenylsulphonyl)-aniline~4-amino-` 10~5898 diphenyl ether, 4-amino-3-nitro-diphenyl ether, 4-amino-3-nitro-4'-chloro-diphenyl ether, 4-amino-3-nitro-4'-methyl-diphenyl ether, 4-amino-3-nitro-4'-n.-butoxy-diphenyl ether, 4-amino-diphenylmethane, 4-amino-3-nitro-diphenylmethane, 4-amino-azobenzene, 4-amino-4'-nitroazobenzene,l4-amino-2,2'-dimethyl-azobenzene, 4-amino-4'-isobutyl-azobenzene, 4-amino~4'-n.-butoxy-azobenz,ene, 4-amino-3-methoxy-6-methyl-2'-cyano-4'-nitro-azobenzene, 4-amino-3-methoxy-6-methyl-2',4'-dinitro-azobenzene, 4-amino-3,6-dimethyl-2'-cyano-4'-nitro-azobenzene, 4-amino-3,6-dimethyl-2',4'-dinitro-azo-benzene, 4-amino-3,6-dimethoxy-4'-nitro-azobenzene, 4-amino-

3,6-dimethoxy-2'-chloro-4'-nitro-azobenzene, 4-amino-3,6-dimethoxy-2',6'-dichloro-4'-nitro-azobenzene, 4-amino-3-ethoxy-4'-nitro-azobenzene, 4-amino-3-sec.-butoxy-2'-chloro-

4'-nitro-azobenzene, 4-amino-6-isopropyl-4'-nitro-azobenzene, 4-amino-4'-trifluoromethyl-azobenzene, 4-amino-4'-ethoxy-carbonyl-azobenzene, 4-amino-3,6-dimethoxy-4'-(2"-ethyl-n.-hexoxycarbonyl)-azobenzene, 4-amino-~,6-dimethyl-4'-methyl-carbonyl-azobenzene, 4-amino-3,6-dimethyl-4'-methylsulphonyl-azobenzene, 4-amino-3-methoxy-6-methyl-4'-(2"-ethyl-n.-hexyl-~ulphonyl)-azobenzene, 4-amino-2-chloro-4'-nitro-azobenzene, 4-amino-2-methyl-2'-chloro-4'-nitro-azobenzene, 4-amino-6-acetylamino-2'-cyano-4'-nltro-azobenzene, 4-amino-6-(2"-ethyl-n.-hexanamid~-2'-cyano-4'-nitro-azobenzene, 4-amino-3-methoxy-6-acetylamino-2'-cyano-4'-nitro-azobenzene, 4-amino-3-ethoxy-6-n.-butyrylamino-2',4'-dinltro-azobenzene, 4-amino-3-n.-butoxy-6-acetylamino-2'-chloro-4'-nitro-azobenzene, 2-amino-4-methoxy-5-methyl-2'-chloro-4'-nitro-azobenzene, 2-1~5 ' amino-4-methoxy-5-methyl-2'-methylsulphonyl-4'-nitro-azo-benzene, 4-amino-3-chloro-3'-nitro-azobenzene, 4-amino-3-chloro-4'-nitro-azobenzene, 4-amino-3-methyl-6-methoxy-2'-nitro-4'-methyl-azobenzene and 4-amino-3,6-dimethoxy-3'-nitro-azobenzene.
: Coupling components which can be used in this pro-cess are both tertiary, aromatic amines of the general formula N ~ Xg ~ `X10 III

wherein X7 and X8 have the meaning indicated in the preceding text and X9 and X10 denote alkyl radicals which contain 1 to 4 C atoms and which can optionally be substituted by halogen atoms, hydroxyl or cyano groups, acyloxy or alkoxy groups containing 1 to 4 C atoms, alkoxycarbonyl or alkoxycarbonyl-oxy groups having 1 to 4 C atoms in the alkyl radicals, or phenoxycarbonyl, phenoxycarbonyloxy, cyclohexyl, phenyl or phenoxy groups which are optionally substituted by halogen atoms or by alkyl or alkoxy groups containing 1 to 4 C atoms, and the alkyl radicals Xg and X10 can also be linkedtof~m a ring by a hetero-atom, and heterocyclic coupling components containing a hetero-N-atom of the general ~ormula I I~

.~

10~'~8 wherein Xll has the meaning of hydrogen or of Xg or X10.
The following coupling components may be listed as examples: N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-3-methyl-aniline, N,N-diethyl-2-methyl-aniline, N,N-di-(n.-propyl)-2-methoxy-aniline, N-methyl-N-(~-cyano-ethyl)-aniline, N-ethyl-N-(~-cyanoethyl)-aniline, N,N-bis-(~-cyanoethyl)-aniline, N,N-dimethyl-2-chloro-aniline, N,N-diethyl-3-chloro-aniline, N-methyl-N-(~-cyano-n.-propyl)-3-methoxy-aniline, N-cyanoethyl-N-(~-acetoxyethyl)-aniline, N,N-bis-(~-acetoxyethyl)-aniline, N,N-bis-(r-n.-butyryloxy-n.-propyl)-2-methyl-aniline, N-ethyl-N-(~-cyanoethyl)-3-methyl-anlline, N-(~-cyanoethyl)-N-(~-hydroxyethyl)-aniline, N,N-bis-(~-hydroxyethyl)-aniline, N,N-bis-(~-hydroxyethyl)-3-methyl-aniline, N,N-dimethyl-3-chloro-aniline, N-ethyl-N-benzyl-2-methoxy-5-acetylamino-aniline, N-~-phenethyl-N-~-cyanoethyl-aniline, N-methyl-N-~-phenethyl-3-methyl-aniline, N,N-dibenzyl-2-methoxy-5-acetylamino-aniline, N,N-diethyl-3-acetylamino-aniline, N,N-diethyl-3-(-ethyl-n.-hexanamino)-aniline, N-benzyl-N-~-cyanoethyl-3-acetylamino-aniline, N,N-bis-~-acetoxyethyl-3-acetylamino-aniline, N,N-bis-~-n.-butyryloxyethyl-3-propionylamino-aniline, 2-methoxy-5-acetyl-amino-N,N-diethylaniline, N,N-dimethyl-2-methoxy-5-methyl-aniline, N,N-bis-(~-hydroxyethyl)-2-methoxy-5-chloro-aniline, N,N-dimethyl-2,5-dimethoxy-aniline, N-methyl-N-(~-~-dihydroxy-n.-propyl)-2-chloro-5-methyl-aniline, N-phenyl-morpholine, N-(2'-methoxy-phenyl)-morpholine, N-(2'-methyl-phenyl)-morpholine, N,N-diethyl-2~methoxy-5-methyl-aniline, N,N-diethyl-3-methoxy-aniline, N,N-dimethyl-3-methyl-aniline, N-1~9~

ethyl-N-(~-ethoxy-carbonyl-ethyl)-aniline, N-(~-cyanoethyl~-N-(~-n.-butoxy-carbonyl-n.-propyl)-aniline, ~-açetylamino-N-methyl-N-(~-ethoxy-carbonyl-ethyl)-aniline, N-ethyl-N-(~-ethoxy-carbonyloxy-ethyl)-aniline, N-~-chloroethyl-N-(~-ethoxy-carbonyloxy-ethyl)-aniline, N-ethyl-N-(~-phenoxy-carbonyl-ethyl)-aniline, N-ethyl-N-(~-phenoxy-carbonyl-n.-propyl)-aniline, N-(~-hydrqxyethyl)-N-(~-4-methyl-phenoxy-carbonyl-ethyl)-aniline, N-methyl-N-(~-phenoxy-carbonyloxy-ethyl)-aniline, N-methyl-N-~-cyclohexyl-ethyl-aniline, N-~-cyanoethyl-N-(4-methoxy-benzyl)-aniline, N-~-cyanoethyl-N-(4-chloro-~-phenethyl)-aniline, N-ethyl-N_(4-n.-butyl-~-phenethyl)-aniline, N-~-cyanoethyl-N-(~-4-methyl-phenoxy-ethyl)-aniline, carbazole, N-methyl-carbazole, N-ethyl-carbazole, N-sec.-butyl-carbazole, N-n.-butyl-carbazole, N-~-hydroxy-ethyl-carbazole, N-~-cyanoethyl-carbazole, N-~-acetoxy-ethyl-carbazole, N-~-n.-butyryloxy-n.-propyl-carbazole, N-~-phenethyl-carbazole, N-(~-4'-methyl-phenethyl)-carbazole, N-(~-4'-methoxy-phenethyl)-carbazole, N-(4'-phenoxy-carbonyl-phenyl)-carbazole, N-(~-ethoxy-carbonyl-ethyl)-carbazole, N-(~-n.-butoxy-carbonyl-n.-propyl)-carbazole, N-(~-ethoxy-carbonyloxy-ethyl)-carbazole and N-(~phenoxy-carbonyl-ethyl)-carbazole.
The azo dyestuff which is produced by the process according to the invention in a good yield and state of purity can either be separated out by driving off, by means of steam, the aliphatic alcohol used as the solvent or can be isolated by immediate filtration and, if approprlate, subsequent washing with the aliphatic alcohol used. The 1~958~8 -solvent employed can also be regenerated from the filtrate by distillation, optionally with steam.
The aliphatic alcohols recovered by both processes of working up can be employed again in a further batch if consideration is glven to their water content.
The process according to the invention for the manu-facture of azo dyestuffs is particularly advantageously suitable for the manufacture of amino-disazo dyestuffs which are only produced in a very impure form when coupling of the diazotised amino-azo compound with a coupling component in dilute, aqueous, mineral acid solution, wi*h optional buffering by means of sodium acetate. This is furthermore the case when using coupling components which are very sparingly soluble in acids, such as, for example, N-~-phen-ethyl-N-~-cyanoethyl-aniline, which is coupled industrially in 50% strength sulphuric acid, which is no longer tolerable for reasons of environmental protection, and with coupling components which couple with difficulty, such as, for example, carbazole.
The process claimed also makes it possible to manu-facture azo dyestuffs industrially in a simple marmer and in a high yield and state of purity from these diazo components and coupling components.
Example 1:
A suspension of 43.0 parts by weight of 2-chloro-4-nitroaniline in 475.0 parts by weight of water and 86.5 parts by weight of crude hydrochloric acid (D = 1.153) is diazotised, at 0 to +5C with external cooling, ~9s8~

using a solution oi' 19.3 parts by weight o~ sodium nitrite in 62.5 parts by weight o~ water. The i'iltered diazo solution is then run into a suspension oi' 43.8 parts by weight o~ carbazole in 400.0 parts by weight oi n-butanol at 40~C. There is a negative diazo reaction after approximately 8 hours. The mixture is stirred overnight at 40 C. The dyestu~f which has precipitated is ~iltered ofi and is well rinsed on the ~ilter, i'irst with 160.0 parts by weight o~ n-butanol at room temperature and then with water and is dried. It is an orange powder which dissolves in concentrated sulphuric acid to give a red-violet colour which changes to red on standing. 72.0 parts by weight of the dyestu~ of the ~ormula 2N ~ N ~ N ~

are obtained. This has a purity o~ 99.4 %, determined by comparison of physical measurements against a crystallised sample.
I~ the n-butanol is removed irom the coupling batch by steam distillation and i~ the dyestui'i which has preclpi-tated is subsequently ~iltered o~f, rin~ed with hot water and dried, 82.6 parts by welght o~ dyestuff having a degree of purlty oi 86.0g are obtained.
Dyestuf~s were also prepared using the materials listed in Table 1 by the process described in the preceding text.

j 1095898 Table 1 No. Dlazo comPonent Coupl~nR comPo-nent Solvent Br 1. 02N ~ NH2 ~ n-butanol H

2 ~ 2 3. Cl ~ NH2 l1 1l Cl i~obutanol Br

5. 02N ~ NH2 ~ ~

C4H9(n) Cl

6. 02N ~ N1~2 ~

7- ~2N ~ NH2 ~ n-butanol 1o9s898 No. Diazo component Couplin~ component Solvent

8 H C~-NH2 ~3 n-butanol CH2-cH2-o-co-cH3 '

9 2 1~-NH2 ~ "

CH2-CH2-0-CO C3H7(n) ~3CO

10 . 02N~_ N~12 C~,

11. ~5C20 ~ )-NH2 ~ 3 "

CH2_CH2~oCH3

12. NC~)-NH2 ~;~

CH2-C~2-CO-Oc2H5 ~13~

13 NC~)-NH2 ~3 109589~3 ' No. Diazo comPonent Cou~lln~ comnonent Solvent . Cl

14. NC ~ -NH2 ~ n-butarlol Cll2-c~32-o-co-oc2H5 Cl

15.02~-N~2 0~3 ~' C{~3 .

16.~I3C-02S~ NH2 ~} C O S

17.~N~I2 CH2-C~2-C~l3 ' 3 8 . 2N~N~2 ~J3 .. ., . , CH2-cH-c~3 OH .
' ' . ' '' ' ' ' .

Example 2 16.3 parts by weight oi 2-cyano-4-nitroaniline are introduced at 0 to +5 C into a solution oi nitrosylsulphuric acid which has been prepared by warming 7.7 parts by weight oi sodium nitrite in 140.0 parts by weight o~ 66Bé sulphuric . - 19 -.

ll~9S898 acid at 70C ~or one hour, and diazotisation is carried out at this temperature by stirring i'or a further two hours.
This diazo solution is then run, at 0 to ~5 C, into a suspen-sion oi 25.1 parts by weight oi N-~-phenethyl-N-~-cyano-ethyl-anillne, 200.0 parts by weight of lsobutanol and 500.0 parts by weight oi water. There is a negatlve diazo reactlon withln one hour.
The isobutanol is driven oi'f irom the coupling batch by steam dlstillation and the dyestui?~ which has precipitated ls i'iltered o~$, rinsed with water and dried. It ls a red powder which dlssolves ln concentrated sulphuric acid to give a yellowlsh-tinged brown colour. 39.5 parts by weight oi dyestu~ oi the rormula NC
02N ~ N - N ~ N 2 2 ~

are obtained. This has a purlty o~ 94.5X, det~mined by 8 comparlson oi' physlcal measurements agalnst a crystallised sample.

Dyestu~rs were also prepared using the materials llsted in Tabl~ 2 by the process described ln the preceding text.

.

. Table 2 No. Dlazo componentCoupling component Solvent ,, . A~

1. 02N ~ N~2 ~ N ~ 2 CH2 ~ isobutanol CH2-CH2_CN

2~ .
2N ~ ~ NH2 1~ n Br . ~C 02S ., 3. 02N ~ N~2 Cl . ' 4 02N~- NH2 C~ ' 5 2~NH2 n Br ~ .
H3C -O~S
6. 02N- ~ 2 . n Br NC

7. 2 ~ NH2 ~ , CH2 ~ n-butanol . CH2-CH2-CN

,~ , .

1~95898 i.
No Dlazo component Couplin~ component Solvent a. 02N ~ -Nl~2 ~ ~ C2l2-CI~3 n-butanol 9. 02N ~ -NH2 ~ Cll2 CH2 CN

10. 02N~-NH2 ~ ~ CH2 Cl NH-CO-CH3 '` 11 . 02N ~ - N112 ~3 N ,C 113 O N
~ -Nll2 ~ ,CH2-CH2-0-CO-C3~7(n) iso-12. 02N ~ ~ CH2-cH2-o-co-c3H7(~) butanol Cl NH-co-c~2-cH2-cil3 .
NC -13. ~2N ~ NH2 ~ ~ C~-CII2-OH n-butanol Br ~C
14. ~2N ~ N~2 ~ ~ C~l2 CH~ carbinol ?i;

11~95898 No. Diazo component Couplin~ com~onent Solvent NC

15.02N ~ -NH2~ N ~ 2 CH2 CN isobutyl `CH2-CH2-CN carbinol NC

16.02N ~ NH2 ~ ~CH2 CH2 n-butanol ` CEI2-CH2-CN

Ex_m~le 3:
34.2 parts by weight oi 42~ strength nitrosyl-sulphuric acid are run, at +15C, into a suspension oi' 16.3 parts by weight o~ 2-cyano-4-nitroaniline in 100.0 parts by weight oi glacial acetic acid. Aiter stirring ior a ~urther hour, the diazo solution ls run into a suspension oi 26.2 parts by weight oi N-~-phenethyl-N-~-cyanoethyl-aniline, 160.0 parts by weigbt oi isobutyl alcohol and 50.0 parts by weight o~ water. There is a negative diazo reaction within one hour. The dyestu~f which has precipitated is ~iltered o~f, rinsed ~irst with 80.0 parts by weight o~ iso-butanol at room temperature and then with water, and dried.
38.7 parts by weight o~ dyestu~ corresponding to the ~ormula o~ Example 2 are o~tained. The dyestui~ has a purity o~
99.8g, determined by a comparison o~ physical measurements against a crystallised sample.
Dyestui~s were also prepared us$ng the materlals listed in Table 3 by the process described in the preceding text.

Table 3 No. Diazo com~onent COUD1 in~ com~on-nt Solvent 1. ~ ~ n-butanol Cl H

Cl 2. 02N ~ NH2 n Br Br 3. 02N ~ NH2 Br 4. 02N ~ NH2 "
~, ; 02N

5.02N ~ -NH2 Cl NC

6.02N ~ N~2 " n H3C-O~

7. 02N ~ -N~2 "

No. Diazo com~onent Cou~lin~ com~onent Solvent 8.02N ~ NH2 ~ N ~ n-butanol NC
9 02N~NH2 11 " .
:

10.02N ~ NH2 ~ lsobutanol , NCI
,~ 11.02N ~ NH2 n "

;, 02N
12.02N ~ NH2 ~ CH2 CH3 n-pentanol Br NH-CO-CH3 13.02N ~ NH2 ~ CH2 CH3 n-hexanol Cl NH-CO-CH3 14. 02N ~ NH2 ~ N ~ H2 C~3 Cl , CH2 CH2 CH2 CH3 C2~5 `- lO9S898 No. Diazo component Coupling component Solvent :

02N ~ OC~I3 ~ fi-~ ,CH -CH -O-CO-CH
15~ O N~ NH \~-N 2 2 3 n-butanol . 2 ~ 2 ~ `CH2-CH2-O-CO-CH
Cl NH CO-CH3 C2~5 ~ ~ CH -CH -O-CO-CH
16. O~N~ NH2 ~ ~ 2 2 3 C~ NH-co-cH3 02N C~H3 ~\ /, ~ , CH -C~ -O-CO-CH
17. 02N~/ ~ N~2 ( \~N 2 2 3 ~, \=~/ ~/ ~CH2-cH2-cN
Br NH-CO-CH3 3 ' ' .
2~ OCH
~ ~ 3 CI~ -CH -o-co-ocH

18.02N~ ~ ~H2 (/ \~ ~'~ 2 2 3 \=~ ' ~/ CH2-CH2-0-CO-OC~3 Br NH-CO-CH3 ~2C -02S
lg. 02N ~ N~2 ~ N ~ CH2 CH3 lsobutanol \~1/ 1 ` CH2-C~3 - B~ NH-CO-CH3 ~r ~O, 02N ~ NH~ ~ N 2 3 Br ~U-CO-C~3 ~l . CH3 21. 02N ~ ~2 ~ ~ ~ CH2-CH2-CH2~0-co-c3H7(n) 1 ~=/ `CH2-CH2-CH2~~C~C3H7(n~
Cl , ~, _ 1~95898 No. Diazo comPonent Coulin~ com~onent Solvent 22. (n) gC4 HCI H2C HN 02S ~ NH2~ / CH3 n-hexanol 23. N-OC ~ N~2 ~ ~ C32~C~2-O~
H3C ~CH2-CH2-OH
Cl n-butanol 5C2~ N OC OCH
24 5 2 ~ ~ N~C 2 CH3 "

CH3 ~CH3 25. ~ -NH2 ~ CH2 CH3 OCH3 oc~3 26. ~ -NH2 2 3 3 ~ N_ 27. 3N-02S ~ N~2 ~ ~c~3 28. ~ NH2 ~ CH2-CH2-OH
~CH2-C H2-OH

1~95898 . No. Diazo comnonent COUD1 in~ Com~onent Solvent 29. ~ ,C,- ~ NH2 ~ N~ 2 3n-butanol 30. H3C ~ -&- ~ -NH2 ~ ,CH2-CH2-OH
O ~ ~ CH2-CH2-OH carbinol 31. H C ~ C_ ~ NH ~ ~ ~H2-CH3isobutanol 3 ~ 2 ~ CH2 CH3 (n) 9C4 ~ C- ~ NH2 ~ N~C 2 C

33- H3CO ~ Oc~ ~ NH2 ~ C2H5 34. Cl ~ -C ~ -NH2 ~ N~ CH2 CH2 OH
o CH2-CH2-OH

Cl OCH
35. ~ -C ~ NH ~ ~ CH2-CH3 n 2 ~ 2 C 3 36. ~ C ~ CH3 ~ N~ 2 3 o \~=/ ~CH2-CH3 ~ 9S898 No. Diazo comPonent Couplin~ com~onent Solvent 3,C ~H2 37. ~ -C ~ CH3 ~ ,CH2-cH2-oH
o \1=/ CH2-CH2-OH
NH-co-cH3 ,. NH2 38. ~ -C ~ OCH ~ ~CH2-CH3 n-butanol " 3 ~ `CH2-CH3 39. ~ C- ~ ~ N ~ 2 ciI2 CO C 3 "
o \=1/ CH2-CH2-0-CO-CH3 40.~ -02S ~ -NH2 ~ N ~ 2 3 "

NH-co-cH3 Cl 41.~ 02S ~ NH ~ N~ CH2 CH3 "
2 ~ C 2 CH3 oc~3 42. H3C ~ 02S ~ NH2 ~ N ~ 2 3 "
\~==/ --CH2-CH3 (n)H9C4~ ~ -02S g -NH ~ C 2 C 3 oc~3 1~5898 . -No. Dlazo comDonent Couplin~ comDonent Solvent 44, H CO ~ O S ~ NH ~ N ,CH2 3 n-butanol 3 \==/ 2 \==/ 2 ~ C 2 CH3 , .

~ 45- ~ -O2S ~ Cl ~ ~C~2-cH3 :'~ \~/ ~ CH2-CH3 NH-co-cH3 ,. NH2 46.~ -02S ~ CH3 ~ N~ CH2 CH3 "

47.~ O ~ NH ~ ~ ~ CH2-CH3 48.~ ~ NH2 CH2 CH3 lsobutanol 49'~ ~ NH2 ~ N~ CH2 CH3 n-pentanol 50. H3C- ~ O ~ -NH2~ ~CH2-cH2-oH
`~H2 CH2-OH

1~395898 No. Diazo comPonent Couplin~ comDonent Solvent (n) 9 4 ~ 0 ~ 2 ~ `CH2-CN2-OH n-hexanol 52. ~ 2C ~ N 2 ~ ~CH2-CH3 D-butanol 1=' 2-CH3 NH-co-cH3 Exam~le 4:
70.0 parts by weight o~ crude hydrochloric acid (D
1.153) are run, at 0 to ~5C and in the course oi one hour, into a mixture o~ 320.0 parts by weight oi isobutanol, 100.0 parts by welght oi' water, 55.0 parts by weight oi N-~-phen-ethyl-N-~cyanoethyl-aniline, 43.4 parts by welght of 2-bromo-4-nltroanillne and 15.4 parts by weight o~ sodium nitrtte. There ls a negative diazo reaction wlthin one hour. The mixture is subsequently stlrred overnight at a temperature which rlses to room temperature. The dye-stu~i which has precipitated is iiltered o~i, rlnsed on the iilter first with 160.0 parts by weight oi isobutanol at room temperature and then with water, and dried. It is a red powder which dissolves in concentrated sulphurlc acid to give a bluish-tlnged red colour. 90.8 parts by weight of dye-stuif o~ the ~ormula Br ~ /CH -CH
02N~ N ~ N ~ 2 2 \==
\==/\==/ ` CH2-CH -CN

are obtained. This has a purity oi 92.0~, determined by ,s a comparison of physical measurements against a crystal-~; lised sample. The resulting dyestu~i is obtained in a ; similar yield and in a similar purity ii the isobutanol is driven oi~ irom the coupling batch by steam distillation beiore the dyestuii is iiltered oif.
The dyestuiis listed in Table 4 were prepared b~ the process described ~n the preceding text.

Table 4 No.Diazo comPonent Couplina com~onent Solvent Cl 0 N ~ NH ~ N' 2 CH2 ~ n-butanol 2 2 ~CH2-CH2-CN

2.02N ~ NH2 ~ N' 2 2 ~ "
~CH2-CH2-CN

Z ~ 2 ~ ~CH2-CH2-CN 3 "

Br 4.02N- ~ \~ NH ~ ,CH2 ~
2 ' CH2-CH2-CN

2 ~ ,CH3 n-hexanol 1t~95898 .

:'' No.Diazo componentCou~lin~ component Solvent . Cl 6.~ NH2 ~ N~ 2 3 n-hexanol Cl 7.(n3HgC4-0 ~ NH2 ~ ~ C2H5 isohexanol ~CH2-cH2-cN isobutyl 8.H3C ~ NH2 ~ N carbinol ~==/ \==/ ~ CH2-CH2 CN

9. H CO ~ NH2 ~ N ~C 2 CH3 3 ` CH2-CH2-CN

10. ~ O- ~ NH ~ ,CH3 n-butanol 11. ~ -NH2 ~ ,CH2-cH2-oH
\1=/ CH2-CH2-OH

12. ~ N 2 ~ ,CH2-cH2-cN "
\~/ CH2-CH2-~)H
Cl 2N oc~3N}~2 ~3 ~ CH2-CH2-CN

~ l~9S898 No. Diazo component Couplin~ comPonent Solvent ( n ) HgC 4-7C -H2C -HN oc 14 C2H5 ~ _NH ~-N~ 2 2 CO CH3 \=/ 2 ~=~ 2 C112-0-CO_cH3n~butano 15. 3 ~ 2 ~ ,CH2~3 16.H5C20-OC~-NH2 <~NJ~O "

7'(n)~9C40 GC~NH2 ~-N H O

18.(n)HgC4~HIC ~I2C ~3-NH2 ~ 3-N H O

19.H2N-o2S4~-NH2 ~3 CH3 ( n ) HgC 4 -HN-O~; CH3

20. ~-NH2 ~, CH3 3C oC~3NH2 CH2-CH
3 i sobutanol No . Diazo component Coul in~ comPonent Solvent Cl CH3 22 . H C -O S~NH2~3 ~ CH2-cH2-o-co C 3 isobutanol 3 2~CH2-CH2-0-CO-CH3 23. ~3NH2~N 2 2 C2H5 "

24. Cl{~NHa~3 `CH2-CH3 25. Cl~)-NN2~ CH2-C 2-~

02N~ , CH2-cH2~-cl "

2~CH2 -C H2 -C N

27. ~NH2 e3 ~CH2-CH2~C4H9(n) "

F3 ~ ~N ~ CH2~30CH3 ~3 2 C H2 -C H2 -C N
F3C Cl H5C20-0C-e~NH2 ~;3 H3 lV95898 No. Diazo component Couplin~ com~onent Solvent 5C20 qC OCH3 30- ~ NH2 ~CH2-CH2-CH3 isobutanol Cl ` CH2-C~2-CH3 (n) 9 4 ~ NH2 H2 CH3 Example 5 417.7 parts by welght oi the zinc chloride double salt oi diazotised 4-amino-3,6-dimethoxy-4'-nitro-azo-benzene oi' the ~ormula ~. ~0 _ +
02N ~ -N ~ N ~ N ~ N Cl ~ . 1/2 ZnCl2 are lntroduced, in the cour~e Or hali an hour and at O to +5C, into a suspension oi 4000.0 parts by weight o~
water, 1,600.0 parts by weight o~ n-butanol, 179.0 parts by weight o~ N,N-dlethyl-anillne and 328.0 parts by weight o~
sodium acetate. There is a negatlve diazo reaction a~ter 3 hours. The mixture is subsequently stirred overnight at a temperature which ri~es to room temperature. The coupling batch is then warmed at 90 for one hour. The resulting dyestuif is ~iltered, rinsed iirst with 1,600.0 parts by weight oi n-butanol at 90C and then with water, and l~9S898 dried. It is a black powder which dissolves in concen-trated sulphuric acid to give a blue colour. 442.0 g of dyestui~ o~ the ~ormula 02N ~ N ~ N ~ ~ ~C2H5 ,, .
s are obtained. This has a purity oi 95.6~, determined by a comparison o~ physical measurements against a crystallised , sample.
Dyestui~s were also prepared using the materials listed in Table 5 by the process described in the preceding text, using zinc chloride double satls o~ the diazotised amino-azo s compounds.

Table 5 No. Amino-azo comPound Cou~lin~ com~onent Solvent 1. 02N ~ N ~ N ~ NH2 ~ N/ 2 3n butanol ~ ~CH2-CH3 2. 02N ~ -N ~ N ~ -NH2~ -N /CH2 CH3 "

NC H C
3. 02N ~ -N ~ N ~ NH2~ N / 2 CH3 "

4. 02N ~ N = N ~ NH2 CH2 CH3 . .

No. Aminoazo compound CouDlin~ com~onent Solvent Cl C4H9(sec) ~5~ 02N ~ N ~ N ~ NH2 ~ 2 H3 n-butanol : NÇ
6- 02N ~ N ~ N ~ NH2 ~ CH2-CEI3 NH-co-cH3 7. 02N ~ N ~ N ~ NH2 CH2 C13 NC
~- 02N ~ N ~ N ~ NH2~ N ~C 2 3 "
NH-CO-cE~~c4H0(n) NC
9. 02N ~ N - N- ~ -NH2~ N ~CH2 CH3 "
NH-~O-CI~3 Cl O-C4Hg(n) 2N ~ -N ~ N ~ -NH2~ N~ H2 CH3 "

ll. O N ~ -N ~ N ~ NH2~ N' 2 CH3 "
2 ~ C 2 C 3 1~95898 . .
No.Amino-azo compound Coupling com~onent Solvent .

~5 ` OC~3 12. 2~ ~ N - N ~ N~2 ~ -N 2 3 n-butanol ; ~C H3C l~3 13. 02N ~ N - N ~ -N~2 ~~CH2-CI{3 C~2 ~H3 C
N~ ~3C 3 1~, 02N ~ -N - ~' ~ -N~2 ~ -N ~ 2 ~3C

1 2 :

15- -2~ ~N ~ ~ OCH ~ ~CH2-CH3 3 `CH2-C~I3 C-02S N~2 16 . 02N~N - N~ ~ ~ CH2-CH3 \~1/ CH2-C~3 ' $~ C
Q2 N Cl 17. Cl~2 Cl~3 Cl 1~. 02N ~ -N ~ N ~ -N~~ ~ ~C 2.CH3 "
. 2 C~2 CH3 , .

1~;ii9S89~
"
No.Amino-azo compoundCoupling comPonent Solvent ' ;, 02N H3CI
19.H3C ~ N 8 N ~ N 2~ N~ H2 CH3 n-butanol ~=/ CH2-CH3 ; OCH3 02N O~CH3 20. ~ -N - N ~ NH2 ~ N ~ H2 CH3 "

21. 02N ~ N - N ~ NH2 ~ N~ H2 C

22- 02N ~ N - N ~ NH2 ~ ~CH2-CH2-OH

23. 02N ~ N - N ~ NH2 ~ ~ CH2-CH2-CN
~ ~ CH2-CH2-OH

24. 02N ~ N N ~ NH2 ~ CH2-CH2-OH
~ CH2-CH2-OH

fl H3CO

25. 02N ~ N ~ N ~ NH2 ~ N -CH2 CH3 4o ` 1t~958~38 No. Amino-azo compound Coupling component Solvent

26 02N ~ N = N ~ 2 ~ N n-butanol ,. OCH3 NH-CO-CH3

27 02N ~ N = N ~ NH2 2 3 Cl OCH3

28 0 N ~ N ~ ~ / 2 3 Cl OCH3 NH-CO-CH3

29 02N ~ N = N ~ ~ / H3 02N ~ N = N ~ NH2~ / ~H3 Example 6 The dyestuff of Example 5 can also be prepared in the following way: 13.8 parts by weight of 4-nitro-aniline in 300.0 parts by weight of water and 34.6 parts by weight of crude hydrochloric acid (D = 1.1153) are diazotised at a to +5C with a solution of 7.1 parts by weight of sodium nitrite in 50.0 parts by weight of water. After destroying excess sodium nitrite with a 25% strength solution of sulphamic acid, the filtered diazo solution is run, at O to +5C, with external cooling, into a solution of 15.8 parts by weight of aminohydroquinone dimethyl ether in 625.0 parts by weight of water and 11.5 parts by weight of crude hydrochloric acid (D = 1.153). The coupling is complete after one hour. After stirring for a further three hours, 80.0 parts by weight of 33 Bé sodium hydroxide 2Q solution are stirred into ~95898 the coupling batch in order to remove by-products ~ormed.
The mixture is subsequently stirred o~ernlght at a tempera-ture whlch rises to room temperature. The resulting amino-azo dyestui~ oi' the ~ormula 02N~N~N~NH2 is then ~iltered o~$, rinsed wlth water and dried.
A solution oi 5.3 parts by weight of sodium nltrite in 50.0 parts by weight oi' water is run, at 18 to 20& and in the course oi one hour, into a suspension o~ lS.0 parts by weight oi the amino-azo dyestuii of the above iormula in 850.0 parts by welght oi water and 17.3 parts by welght o~
crude hydrochloric acid (D - 1.153). The diazotlsation batch is stirred ior a i'urther 1 1/2 hours at room temperature and ls then warmed at 50 C ior one hour. The illtered diazo solutlon is then run, at 0 to +5C, into a solution oi 320.D parts by welght oi n-butanol and 11.2 parts by welght o~ N,N-diethylaniline in the presence of 16.4 parts by weight oi sodium acetate. There is a negative dlazo reaction wlthin one hour. The coupling batch is now warmed at 90 C
~or one hour. The dyestu~i which has preclpitated is filtered oi~, rinsed ~irst with 80.0 parts by welght o~ n-butanol at 90C snd then with water, and dried. Thin layer chromstography (migratlng agent : benzene) shows it to be identical with the dyestu~ o~ Example 5.
The dyestufis were prepared also using the materialslisted in Table 6 by the process described in the preceding text.
Table 6 No. Amlnoazo comDound Cou~lin~ component _olvent N - N ~ NH2 ~ -N~ H2 CH3 isobutanol , .

2. ~ N - N ~~ ~CH2-cH2-oH
~ CH2-CHa-OH
' 3. ~ -N - N ~ NH2~ ,CH2-cH2-cN

.~ CH2-CH2-OH

4 ~ N - N ~ NH~ N ~CH2 CH3 "

5- 02N- ~ -N ~ N ~ N 2 ~ N~ CH2 CH3 n-butanol 02N ~ N - N ~ NH2 ~ N ~ 2 CH3 "

H3C ~H3 7. ~ -N - N ~ NH2 ~ `CH2-CH3 ` 1095898 No. Aminoazo com~ound Couvlln~ com~onent Solvent ;'' 8. (iSo)Hllc5 ~ -N-N ~ N 2 ~ N ' 2 3 n-butanol NH-CO_CH3 9- (n)H9C4 0 ~ N-N ~ -N~2 ~ N ~C32 CH3 ~, NH-CO_CH3 10. 02N ~ N-N ~ NH2 ~ N ~ 2 3 1Yobutanol ', OC2H5 11. 02N ~ N~N ~ NH2 ~ N ,CH2 CH3 ~, 12- H5C2-C ~ ~ 2 ~CH2-CH2-OH
` CH2-CH2-OH
n-butanol 13. H3C-OC ~ N~N ~ NH2 ~ ,cH2-cH2-oH
CH3 isobutanol 14. H3C-OC ~ N-N ~ -NH2 ~ ,CH2-cH2-oH
~CH2-CH2-0~1 CH3 isobutanol la. H3C-02S ~ N-N ~ NH2 ~ N~ CH2 CH3 CH3 n-butanol No. Aminoazo comPound Couplin~ component Solvent 16- H3C-02S~N - N~NH2 ~3 ` CH2-CH2-CN

CH

17 . H3C-02S-~-N ~ N~NH2 Ç3 CH2 CH3 CH3 NH-CO-C~I3 18. 02N~N - N~NH2 ~ N~ 2 CH3 isobutanol Cl CH
19, 02N~N - N~NIi2 ~3 N~ CH2 Cli3 "

Cl CH3 20 . 02N-~N ~ N~3-NH2 Ç~ 2 3

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound of the diazotized amine of the general formula I or II

(I) (II) wherein X1 and X2 each denote hydrogen, halogen, alkyl or alkoxy each having from 1 to 4 C atoms, nitro, cyano, tri-fluoromethyl or alkoxycarbonyl, alkylcarbonyl, carbonamide, N-monoalkyl-carbonamide, N, N-dialkyl-carbonamide, alkyl-sulphonyl, sulphonamide, N-monoalkyl-sulphonamide or N, N-dialkyl-sulphonamide each having from 1 to 8 C atoms, or phenoxy, phenalkoxy, phenylsulphonyl or benzoyl each being optionally substituted by halogen or by alkyl or alkoxy having from 1 to 4 C atoms, and X3 denotes hydrogen or halogen, X4 and X5 denote hydrogen or halogen, alkyl or alkoxy having from 1 to 4 C atoms, nitro, cyano, trifluoromethyl or alkoxycarbonyl, alkylcarbonyl or alkylsulphonyl having from 1 to 8 C atoms, X6 denotes hydrogen or halogen and X7 and X8 are identical or different and each denote hydrogen or halogen or alkyl or alkoxy group having from 1 to 4 G atoms, and X8 also denotes an acylamino group containing from 1 to 8 C atoms with a coupling component of the general formula III

(III) wherein X7 and X8 have the same meaning as defined above, and X9 and X10 each denote alkyl having from 1 to 4 C atoms and optionally substituted by halogen hydroxyl, cyano, or acyloxy or alkoxy having from 1 to 4 C atoms, alkoxycarbonyl or alkoxycarbonyloxy each having from 1 to 4 C atoms in the alkyl radicals, or phenoxycarbonyl, phenoxycarbonyloxy, cyclohexyl, phenyl or phenoxy each of which is optionally substituted by halogen or by alkyl or alkoxy group having from 1 to 4 C atoms, or X9 and X10 together with the adjacent nitrogen represent a heterocyclic ring wherein a hetero-atom is joined to said nitrogen by alkylene radicals, or of the general formula IV

(IV) wherein X11 represents hydrogen or has the same meaning as X9 or X10, as defined hereinbefore in formula III, at a temperature of from 0 to 80°C and in the presence of an acid, in a solvent or dispersing medium comprising a mixture of from 90 to 15% by weight of an aliphatic alcohol having a chain length of from 4 to 6 C atoms and a solubility in water of not more than 15% by weight at 15°C, and 10 to 85% by weight of water.

2. A process as claimed in claim 1, wherein the solvent or dispersing medium comprises a mixture of from 50 to 25% by weight of the aliphatic alcohol and from 50 to 75% by weight of water.

3. A process as claimed in claim 1, or claim 2, wherein the aliphatic alcohol is n-butanol or isobutanol.

4. A process as claimed in claim 1, which includes the preliminary step of forming said diazonium compound in situ.

5. A process as claimed in claim 4, wherein a diazotisation agent is introduced into a mixture of a diazotisable aromatic amine, the coupling component, a mineral acid and the solvent or dispersing medium.

6. A process as claimed in claim 5, wherein sodium nitrite or potassium nitrite, nitrosylsulphuric acid or an ester of nitrous acid with an alkanol having from 1 to 6 C atoms is employed as the diazotisation agent.

7. A process as claimed in claim 1, wherein the diazonium compound is used in the form of a stabilized diazonium compound.

8. A process as claimed in any of claims 4 and 7, wherein the reaction is carried out at a temperature of from 0 to 60°C.

9. A process as claimed in any of claims 4, 5 and 7, wherein the reaction is carried out at a temperature of from 0 to 5°C.

10. A process as claimed in claim 1, wherein the diazonium compound is used in the form of a solution, in an aqueous or concentrated inorganic or organic acid which is introduced into a mixture of the coupling component and the solvent or dispersing medium.

11. A process as claimed in claim 10, wherein the reaction is carried out at a temperature of from 0 to 50°C.

12. A process as claimed in claim 1, wherein the acid is hydrochloric acid, hydrobromic acid, sulphuric acid or phosphoric acid.

13. A process as claimed in claim 1, wherein the acid is formic acid, acetic acid, chloroacetic acid or propionic acid.

14. A process as claimed in claim 1, wherein the acid is buffered during the coupling.

15. A process as claimed in claim 1, wherein the diazonium compound is the optionally stabilized diazo compound of a diazo-tisable aromatic amine of the general formula I

wherein X1 and X2 each denote hydrogen, halogen, alkyl or alkoxy each having from 1 to 4 C atoms, nitro, cyano, trifluoromethyl or alkoxycarbonyl, alkylcarbonyl, carbonamide, N-monoalkyl-carbonamide, N, N-dialkyl-carbonamide, alkylsulphonyl, sulphonamide, N-monoalkyl-sulphonamide or N, N-dialkyl-sulphonamide each having from 1 to 8 C atoms, or phenoxy, phenalkoxy, phenylsulphonyl or benzoyl each being optionally substituted by halogen or by alkyl or alkoxy having from 1 to 4 C atoms, and X3 denotes hydrogen or halogen, or of an aminoazo compound of the general formula II

= wherein X4 and X5 each denote hydrogen or halogen, alkyl or alkoxy having from 1 to 4 C atoms, nitro, cyano, trifluoromethyl or alkoxycarbonyl, alkylcarbonyl or alkylsulphonyl having from 1 to 8 C atoms, X6 denotes hydrogen or halogen and X7 and X8 have the same meaning as defined hereinabove in formula III of claim 1, is employed.