CA1040193A - Azo dyestuffs - Google Patents

Abstract

Abstract of the Disclosure A water-insoluble azo dyestuff of the formula wherein D is the residue of a benxene, napthalene, anthraquinone or heterocyclic diazo component which is free of ionic groups;
X is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, furyl, thienyl, thiazoyl, pyridyl, benzothiazolyl, inidazolyl, benzimidazolyl, pyrrolyl or hydrogen;
Y is cyanno, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, -COOR1, -COR2, , -8O2R2, or hydrogen with the proviso that only one of X and Y is simultaneously hydrogen;

Z1 is , , -NH-OR10 or and Z2 is -O-(CnH2nO)m-R12 or -S-(CH2H2nO)m-R12 wherein R1 and R2 are alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, piperazino, furyl, thienyl, pyridyl, thiazoyl, benzothiazoyl, imidazoyl, benzimidazoyl or pyrrolyl;
R3 and R4 taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety or phenyl or substituted phenyl and R3 and R4, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen;
R5 and R6, taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cyclo-alkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety and R5 and R6, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen;

R7 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substituted phenyl, R8 and R9 are alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substituted phenyl;
R10, taken separately, is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety or phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety;
R11, taken separately, is alkyl substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety;
R10 and R11, taken together, are alkylene having 2 to 5 carbon atoms;
R12 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl or substituted phenyl;
n is 2, 3 or 4;
m is 0, 1 or 2;
there being up to two substituents for each of said substituted alkyl and substituted alkenyl, each said substituent being selected from the group consisting of cyano, hydroxy, acetoxy, alkoxy having 1 to 2 carbon atoms, phenoxy, alkylamino-carboxyloxy having 2 to 3 carbon atoms, phenylaminocarboxyloxy, monoalkylamino and dialkylamino having 1 to 2 carbon atoms in each alkyl moiety, wherein Z is alkylene containing 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen and wherein R13 is alkyl having 1 to 2 carbon atoms and R14 is acetyl or benzoyl:
there being up to two substituents for each of said substituted cycloalkyl, substituted phenalkyl and substituted phenyl, each of said substituents being selected from the group consisting of bromine, chlorine, cyano, alkyl having 1 to 3 carbon atoms and alkoxy having 1 to 2 carbon atoms and the total number of carbon atoms in X, Y, Z and Z2 being not more than 24;
process of producing said dyestuffs and use of said dyestuffs for dyeing and printing hydrophobic materials.

Description

AZO DYESTUFFS

A water~insoluble azo dyestuf~ of the formula D-N_N ¦ Y
Il ~J
Zl~ ~ ~ Z;, wherein D is the residue of a benzene, naphthalene, anthraquinone or heterocyclic diazo component which is free of ionic groups;
X is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moie~y, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, furyl, thienyl, thiazolyl, pyridyl, benzothiazolyl, imidazolyl~ benzimidazolyl, pyrrolyl or hydrogen;
Y is cyano, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloal.~cyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, -COORl, -COR2, -CO-N 3, -S02R2, -S02-N~

or hydrogen with the proviso that only one of X and Y is simultaneously hydrogen;

LV~3 ~"
Zl is -N~ , ~N-N-~8, -NH-OR1o or -N lO `d Z is -O-(C H~nO)m -R12 or -S-(CH2H2n m 12 wherein Rl and R2 are alkyl or substi*uted alkyl having 1 to 12 carbon atoms in the alkyl moiety~ alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkyenyl moiety, cyclaalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, piperazino, furyl, thienyl, pyridyl, thiazoyl, benzothiazoyl, imidazoyl, benzimidazoyl or pyrrolyl;
R3 and R4 taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety or phenyl or substituted phenyl and R3 and R4, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene in-terrupted by oxygen, sulfur or nitrogen;
R5 and R6, taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cyclo-alkyl having 3 to 8 carbon atoms in the cycloalkyl maiety,phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety and R5 and R6, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen;

R7 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substituted phenyl, R8 and Rg are alky~ or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substi-tuted phenyl;
Rlo, taken separately, is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety or phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety;
Rll, taken separately, is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety;
Rlo and Rll, taken together, are alkylene having 2 to 5 carbon atoms;
R~2 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl or substituted phenyl;
n is 2, 3 or 4;
m is 0, 1 or 2;
there being up to two substituents for each of said substituted alkyl and substituted alkenyl, each said substituent being selected from the group consisting of cyano, hydroxy7 acetoxy, alkoxy having 1 to 2 carbon atoms, phenoxy, alkylamino carboxyloxy having 2 to 3 carbon atoms, phenylaminocarbonyloxy, monoalkylamino and dialkylamino having 1 to 2 carbon atoms in each alkyl moiety, -N ~Z wherein Z is alkylene containing 2 to S carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen and -N~ 13 wherein R13 is alkyl having 1 to 2 carbon 9)3 atoms and R14 is acetyl or ~en~oyl;
there being up to two subs~ituents for each of said substituted cycloalkyl, substituted phenalkyl and substituted phenyl, each of said substi~uents being selected from the group consisting of bromine, chlorine, cyano, alkyl having 1 to 3 carbon atoms and alkoxy having 1 to 2 carbon atoms and the total n~nber of carbon atoms in X, Y, Zland Z2 being not more than 24;
process of producing said dyestuffs and use o said dyestuffs for dyeing and printing hydrophobic ma~erials.

.
. . .

Water-insoluble azo dyestufIs o* *h~ formula D-N=N ~
Zl Z2 wherein D is the residue o~ a benzene, naphthalene~
anthraquinone or heterocyclic diazo component which is :eree o~ ionic groups;
~ is alkyl or substituted alkyl having ~ to 1~
carbon atom~ in the alkyl mo~ety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atom~ in the alkyl moiety, phenyl, substituted phenyl, ~uryl, thienyl, thiazolyl, pyridyl, benzothiazolyl, imidazolyl, benzimidazolyl, pyrrolyl or hydrogen;
Y is cyano, alkyl or substituted alkyl hav~ng 1 to 1~ carbon atoms in the alkyl moiety, alkenyl or ~ub~tltuted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or subRtituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl havin~ 1 to 2 carbon atoms in the alkyl moiety, phenyl substituted phenyl, -COORl, -COR2, -C0-N ~ 3, -S02R2, -S0~-N 3 or hydrogen with the proviso that only one o~ X and Y is simultaneously hydrogen;

~4~
~ is ~N 5 9 7~ -N 8, -NH-OR~o or -N ~ 10 and Z2 is ~o-(CnH2nO)m~R~2 ~ -S-( ~J2~n)m 12 wherein R1 and R2 are alkyl or substituted alkyl having 1 to 12 carbon ~toms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms în the alkenyl moiety, cycloalkyl or substituted cycloalkyl ha~ing 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or ~ubstituted phenalkyl:.
having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, piperazino, iuryl, thienyl, pyridyl, thiazoyl, benzothiazoyl, imidazoyl, ben2imidazoyl or pyrrolyl;
~ 3 and ~, taken separately, are hydrogen, alkyl vr substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety or phenyl or substituted phenyl and ~3 and R4, taken together, are alkylene hav~ng 2 to 5 carbon atom~ or said alkylene interruptad by 2C oxygen, sul~ur or nitrogen;
R5 and R6, taken separately, are hydrogen, alkyl or subst~tuted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having z to ~ carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phen~lkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety and R5 and R6, tal~en together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted by oxygen, suliur or nitrogen;

' R7 ls hydrogen, alkyl or substituted alkyl hav~ng 1 to 12 carbon atoms in the alkyl moiety, phenyl or su~stituted phenyl;
R~ and R9 are alkyl or sub~tituted alkyl having ~ to 12 carbon atoms in the alkyl moiety9 phenyl or substituted phenyl;
Rlo, taken separately, is hydrog n, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety or phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety;
R11, taken separatsly, is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety;
Rlo and R11, taken together, are alkylene having 2 to 5 carbon atoms;
R12 is hydrogen, alkyl or substit~ted alkyl having 1 to ~2 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in thc alkyl molety, phenyl or substituted phenyl n is 2, 3 or 4;
m is 0, 1 or 2;
thereibeing up to two substituents ~or each of said substituted alkyl and substituted alkenyl, each sald substituent being selected ~rom the group consisting o~ cyano, hydroxy, acetoxy, alkoxy having 1 to 2 carbon atoms, phenoxy, alkylamino-carboxyloxy having 2 to 3 carbon atoms, phenylaminocarbonyloxy, monoalkylamino and dialkylamino having 1 to 2 carbon atoms in each alkyl moiety, -N Z wherein Z is alkylene containing 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sul~ur or nitrogen and -N~ 13 wherein R13 ~s alkyl having 1 to 2 carbon lLO~ g3 atoms and Rl4 is acetyl or benzoyl;
there b~ing up ~o two substituents for each of said substituted cycloalkyl, substituted phenalkyl and substitu~ed ~ phenyl, each of said substituents being selected from the group S consisting of bromine, chlorine, cyano, alkyl having l to 3 carbon atoms and alkoxy having l to 2 carbon atoms and the total number of carbon atoms in X, Y, Z and Z2 bei.ng not more than 24.
: The dyestuffs of this in~ention are obtained by diazotizing an amine which is free of ionic groups and of the formula:
- D - NH~ (II) and then coupling the resulting product with an aminopyridine of the ~ormula: .

. ' , ~ .
~y 11 ,1 (III~ ..
N~æ2 ....
lS wherein D, X, Y, Zl and Z2 are as a~oresaid.
When forming dispersion dyestuffs, it may be advantageous to couple a diazotized amine of formula II
~ith a mixture of two or more aminopyridines of formula III.
Typical substituents for the radical D of the diazo 20 component include, for example: halogen, preferably chlorine;
cyano; nitro; trifluorome~hyl; alkyl, preferably having l to 6 carbon atoms; alkoxy, preferably having l to 6 carbon a~oms; acyl, preferably having l to 6 carbon atoms; acyloxy, preferably having

2 to 7 carbon acoms; benzoyl; phenoxycarbonyl; alkoxycarbonyl, , ,, ~

8V . .

~4¢;~ 3 preferably having 2 to 7 carbon atoms, optionally N-mono or N,N-disubstituted carboxylic or sulfonic acid amides, wherein pr~ferably alkyl having 1 to 4 carbon atoms and phenyl are - considered as substituents; alkylsulforlyl, preferably.having .5 1 to 4 carbon atoms; al~ylsulfonylal~yl, preferably having 2 to 8 carhon atoms; alkenylsulfonyl, preferably having 3 to 6 carbon atoms; alkoxysulfonyl, preferably having 1 to 6 carbon atoms;
phenoxysulfonyl; ~-substituted and N,N-disubstituted aminosulfoliyloxy, preferably alkyl having 1 to 6 carbon atoms are substituents and optionally substituted phenyl azo.
The amines of formula II include, for example:
aniline, 2-, 3- and 4-aminotoluene, 2-,3- and 4-aminobenzyl dimethylamine, 4-aminophenethyl-~ -dimethylamine, 4-aminobenzyl-N-piperidine, 3-aminotrifluoromethylbenzene, 3- and 4-amino-1, 2-dimethylbenzene, 4-amino-n-butylbenzene, 4-amino-n-hexylbenzene, 2-, 4- and S-amino-1,3-dimethylbenzene, 4-amino-1,3,5-tri-methylbenzene, 2-, 3- and 4-aminoanisole, 2-, 3- and 4-arnino-phenetole, 2-, 3- and 4-ami.no-n-butoxybenzene, 2-amino~
dimethoxybenzene, 2-amino-1,4-diethoxybenzene, 2-amino-1, 4-diisopropoxybenzene, 2-, 3- and 4-chloroaniline, 2-, 3- and 4-bromoaniline, 2,3-, 2,4-, 2,5- or 3,4-dichloroaniline, 2,5-dibromoaniline, 2-, 3- and 4-aminodimethylamino benzene, 2-, 3-and`4-aminodiethylamino benzene, 2,4,5-, 2,4,6-, 3,4,5- and 3,4, 6-trichloroanili.ne, 3-, 4-, 5- and 6-chloro-2-aminotoluene, ~-chloro-3-arninotoluene, 2-chloro-4-arninotoluene, 5-chloro-2-aminotrifluoromethylbenzene, ~,5- and 4,6-dichloro-2-aminotoluer.e, ' .

_ g _ ,~

~ .

~0~ 3 2,5- and 4,6-dichloro-3-aminotoluene~ 2,5- and 3,5-dichloro-4-aminotoluene, 4,5,6-trichloro-2-aminotoluene, 4-chloro-2-amino-1,

3-dimethylbenzene, 2-, 3- and 4-aminobenzyl methylsulfone,

4-aminophenylpropyl methylsulfor,e, 6-chloro-3-aminoanisole, 2-chloro-4-aminoanisole, 2-chloro-~-amino-n-hexoxybenzene, 3-chloro 4-aminoanisole, 2-, 3- and 4-nitroaniline, 2-nitro-4-aminotoluene, 3-nitro-4-aminotoluene, 4-nitro-2-aminotoluene, 2-ethyl-4-nitroaniline, 5-nitro-2-aminotoluene, 5-ni-tro-4-amino-1, 3-dimethyl~enzene, 6-nitro-4-aminoanisole, 3-nitro-4-aminoanisole, 3-nitro-4-amino-n-butoxybenzene, 5-nitro-2-aminophenetole, 2-ni~ro-4-aminophenetole, 3-nitro-4-aminophenetole, 5-ni~ro-2-amino-1,4-dimethoxybenzene, 5-nitro-2-amino-1,4-diethoxybenzene, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline, ~,6-dichloro-2-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2,4-dinitroaniline, 6-chloro-2,4-`~. dinitroaniline, 6-bromo-2,4-dinltroaniline, 2,4,6-trinitroan.iline, 2-, 3- and 4-aminobenzonitrile, 1-amino-2-cyano-5-chlorobenzene, 2-cyano-4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 4-cyano-3-nitroaniline, 1-amino-2,4-dicyanobenzene, l-amino-2,6-dicyano-4-nitrobenzene,l-amino-2-chloro-4-methyLsulfonylbenzene, 2-methylsulfonyl-4-nitroaniline, 2-iso-butylsulfonyl-4-nitroaniline., 4-methylsul~onyl-2-nitroaniline, 4-allylsul~onyl-2-nitroaniline, 4-phenylsulfonyl-2-nitroaniline, 2-, 3- and 4-aminobenzaldehyde, 2-, 3- and 4-aminodiphenylether, 2-amino-4-chloro- and 4,4'-dichlorodipherylether, 2-, 3- and 4-amino ~ -dimethylamino acetophenone, 2-,3an~-a~lir3O-~ ~diethyl-amino acet.o~henone, 2 , 3- and 4-~llinoacetophenone, 4-amin~--n-butyrophenone, 4-amlno-n-caprophellone, 2-amino-5-nitroace~ophe~n~ne, ' 2-,3- and 4 amino-benzo~henone, 2-, 3- ancl 4-amin~-4~-methyl benzopnerlone, 2-, 3- and 4-amino-4'-isopropyl benzophenone, 2-, 3- and 4-amino-4i-n bu-tyl benzophenone~ 2-~ 3- and 4-amino-2', 4~-dimethyl benzophenone, 2-, 3- and 4-amino-4'-methoxy benzophenone, 4-amino-5-nitrobenzophenone 5 2-, 3- and 4-aminobenzoic a~id methyl ester and 2-, 3- and 4 aminobenzoic acid ethyl ester, 2-, 3- and 4-aminobenzoic acid n-butyl ester, 2-, 3- and 4-aminobenzoic acid n-decylester, 1-aminobenzene-3,5-dicarboxylic acid dimethyl ester, 1-aminobenzene-3,5-di-ln carboxylic acid diethyl ester, 2-~ 3- and 4-aminobenzoic acid `
phenyl ester, 2-3 3- and 4-aminobenzoic acid 4'-tertiary butyl phenyl ester, 2-, 3- and 4-aminobenzoic acid 4'-isohexyl phenyl ester, 2-, 3- and 4-aminobenzoic acid cyclohexyl es-ter, 2-~ 3-and 4-aminobenzoic acid benzyl ester, 2-, 3- and 4-aminobenzoic acid 6-methoxyethyl ester, 2-, 3- and 4-aminobenzoic acid ~-ethoxyethyl ester, 2-, 3- and 4-aminobenzoic acid ~ -butoxyethyl ester, 2-, 3- and 4-aminobenzoic acid methyldiglycol ester, 2-, 3- and 4-aminobenzoic acid ethyldiglycol ester, 2-~ 3- and 4-aminobenzoic acid methyl-trialycol ester, 2-, 3-.and 4-aminobenzoic acid ethyltriglycol ester, 2-, 3- ~nd 4-amino-benzoic acid -hydroxyethyl ester, 2-, 3- and 4-aminobenzoic acid ~-acetoxyethyl ester, 2-, 3- and 4-aminobenzoic a~id ~-(~-hydroxyethoxy)-ethyl ester, 2-, 3- and 4-aminobenzoic acid ~-hydroxyproply ester, 2-, 3- and 4-aminobenzoic acid ~
hydroxypropyl ester, 2-, 3- and 4-aminobenzoic acid ~-hydroxy-butyl ester, 2-, 3- and 4-aminobenzoic acid~-hydroxyhexyl ester, 2-, 3- and 4-aminobenzoic acid 4-nitroanthranilic acid methyl ester, 4-nitroanthranilic acid isobutyl ester, 4-nitro-anthranilic acid methyldiglycol ester, 4-nitroanthranilic acid ~-methoxyethyl ester, 4-nitroanthranilic acid B-butoxyethyl ester, 4-nitroanthranilic acid methyldi~lycol ester, 2-, 3- and 4-am~nobenzoc .
acid amide, 2-, 3- and ~-aminobenzoic acid monome~hyl amide, 2~, 3- and 4-c~ninobenzoic acid dimethyl amide, 2-, 3- and -4-aminobenzoic acid ethyleneimide,2-, 3- and ~-aminobenzoic acid iso-propylamide, 2-, 3- and 4-aminobenzoic acid ~iethyl amide, 2-, 3- and 4-aminobenzoic acid di-n-butylamide, 2-, 3- and 4-aminobenzoic acid morpholicle, 2-, 3- and 4-amino~nzoic acid anilide, 2-, 3- and 4-amillobenzoic acid N-rnethyl~nilide, 2-, 3-and ~-aminobenzoic acid-N,N-dimethylhydrazide, ~-, 3- and 4-aminobenzoic acid-( ~-dimethylaminopropylamide), 2-, 3- and 4-aminophenylbenzoic acid ester, 2-, 3- and 4-amino~henyl-4'-tertiary butylbenzoic acid ester, 2-, 3- ~nd 4-~ inopllenyl-2', 4 ~.t 6'-trimethylbenzoic acid ester, 2-, 3- and 4-c~l~inophenylmethyl sulfonic acid est~r, 2-, 3- and 4-aminophenylethyl sulfonic acid ester, 2-, 3- and 4-aminophenyl-~ -ethyl chloride sulfonic acid ester, 2-, 3- and 4-arminophenylbutyl sulfonic acid ester, 2-, 3-and 4-aMinophenyl-n-hexyl sulfonic acid ester, 2-, 3- and 4-aminophenyl phenylsulfonic acid ester, 2-, 3- and 4-arninophenyl- -(4'-methylphenyl)-sulfonic aci~ ester, 2-, 3- and ~-aminophenyl-~4'-n-butylphenyl)-sulfonic acid ester, 2-, 3- and 4-aminophenyl-(4'-methoxyphenyl)-sulfonic acid ester, 2-, 3- and 4-aminobenzene . sulfonic acid phenyl ester, 2-, 3- and 4-aminoben~ene sulfonic acid 4'-n-butylphenyl ester, 2-,. 3- and 4-aminophenyl-~-ethoxyethy~
sulfamic acid ester, 2-, 3- and ~-aminophenyl dimethyl sulfamic acid ester, 2-, 3- and 4-aminophcnylethyl sulfam.ic acid ester, 2-, 3- and 4-aminophenyldi~thyl sulfamic acid es~r, 2-, 3-and 4-aminophenyl di-n-~utyl sulfamic acid estcr, 2-, 3- and 4-aminophenylcyclolle~yl sul~amic acid est~r, 4-aminopheIIylmetllyl-sulfone, ~-aminodiphenylsulfone, 2-, 3- and ~I-arni.nobenzene sulfonic acid amide, 2-, 3- and q-arninobenzene ~ul~onic acid monomethylamide, 2-, 3- and ~-aminobenz~ne sulfonic acid di- ,~:~-metll~amide, 2-, 3- and 4--aminobenzene sul.fonic acid ethyleneimid~, 2-, 3- and ~-aminoberlzene sulfonic acid diet~lylamide, 2-, 3- and 4-aminobenzene sulfonic acid cli-n-butylamide, 2-, 3- and 4-aminobenzene sulfonic acid morpho].ide, 2-~ 3- and ~-aminobenzene sulfonic acid cyclohexylamide, 2-, 3- and ~-aminobenzene sulfonic

5 acid anilide, 2-, 3- and 4-aminobenzen~ sulfonic acid N-methyl-anilide, l-methyl-2-aminobenzene-4-sulfonic acid amide, 1-methyl-2-aminobenzene-4-sulfonic acid n-hexylamide, 1-methoxy-2-aminoben-zene-4-sul~onic acid amide, 1-methoxy-2-aminobenzene-4-sulfonic acid dimethylamide, l-methoxy-2-aminobenzene-4-sulforlic acid di-10 n-butylamide, 1-methoxy-2--aminobenzene-4-sulfonic acid N-m~thylanilide, l--chloro-2-aminobenzene-4 sul~onic acid dimethyl-amide, l~chloxo-3-aminobenzene-5-sulfonic acid ~-ethoxyethylamide, l-chloro-2-aminobenzene-~-sulfonic acid amlde, 1-chloro-4-aminobenzerle-2-sulfonic aci~ dirnethylarnide, 4-aminobenzene phenyl 15 urethane, 2-, 3- and 4-aminoacetanilide~ 2-,. 3- and 4-amino-phenoxy acetanilide., 2-, 3- and 4-amino-N-methyl aoetanilide, l~aminoanthraquinone, l-amino-~-and-~5-benzoylaminoanthraquinone, l-amino-4-chloranthraquinone, l-aminonap}lthaline, 1-amj.no-5-ethoxynaphthalene, 8-chloro-1-aminonaphthalene, 2-aminonaphthalene, 20 2-aminonaph~halene-6-sulfonic acid dimethylamide, 4-aminoazobenzene, ~amino-4'-hydroxyazobenzene, 2',3-dimethyl-4-aminoazobenæene, ~,5-dimethyl~~-aminoazobenzell~, 2-methyl-5-methoxy-4-aminoazo- ,-benæene, ~'-nitro 2,5-dimethoxy-4-aminoazobenzene, 4'-pitro-2-methyl-5-methoxy-4-aminoa~obenzene, 1-phenylazo~4-aminonaphthal~ne, 25 2-amino-5-ni~rothiazole, 2-amino-4-methyl-5-nitrothiazole, ?-amino-

6-nitrobenzothiazole, 2-amino-5-phenyl-1,3,4-thladiazole, 3-phenyl-5-amino-1,2,4-thiadiazole, 4-aminobenzo-1,?,3-triazole, 2-amino-1,3,5-thiadiazole-~-methylt'nio ~th~.r, 3-amino-5-nitro-2,1-benzisothi.azole, 3~~mino-5-nitro-7~chloro-2,1-benæisothiazole, 30 3-ar,lino-7~nitro-2,1-benzisothiazole, 4-am.ino~7--ni.tro-1,2-benziso-th~.azole, 4-arnino-1,2-bQnzisothi~zol~ and 3-amino-S-nitro-1,2-bellzisothiazole.

- ~ .
~ l .
'' ~0~ 3 : Suitable coupling components of formula III may contain hydrocJen in the X position or, for ex~mple, methyl, ethyl, n-propyl, isopropyl, vinyl, C'methylvinyl, n-butyl, isobutyl, ~ secondary butyl, n-amyl, isoamyl, n-hexyl, n-dodecyl, 2-di-methylaminoethyl, 2 diethylaminoethyl, 2-morpholinoethyl, 2-piperidinoethyl, 2-pyrrolidinoethyl, N-methyl-N'-piperazinoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-acetoxye-thyl~ 2-phenoxyacetoxyethyl, N-ethyl carbamoyl oxyethylIN-phenyl carbamoyl oxyethyl, 2-phenoxyethyl, 3-methoxypropyl, cyclohexyl, benzyl, 3~methylbenzyl, phenyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-chlorophenyl, 4-; chlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,5-dimethyl-4-chlorophenyl, ~ , S~ 2 ~ , .

-~2C ~ ~ ~ ~ d ~ C-The coupling components of formula III may contain hydrogen in th-e Y position or ~or example, cyano, methyl, ethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-acetoxymethyl, 2-benzoyloxyethyl, 2-m~thoxyet~ly~, 2-phenoxyethyl, 2~monomothyla]llinoethyl, 2-mono-methylanlino~thyl or 2-dimethylam:inoethyl or 2-diethylaminoethyl, 2-morpllolinoethyl, 2-E~iperidinoet}lyl, 2-pyrrolidirlc~ethyl, n-propyl, isopropyl, vinyl, X-methylvinyl, n-butyl, isobutyl and secondary butyl, n--amyl, isoamyl, n-hexyl, isooctyl, n-dodecy~, ~ ' ~34~
cyclohexyl~ benzyl, phenyl~ methoxycarbonyl~ ethoxycarbonyl~
n-propyloxyoarbonyl~ isopropyloxycarbonyl, n--butoxycarbonyl, isobutoxycarbonyl, secondary butyloxycarbonyl, n-amyloxycarbonyl, isoa~yloxycarbonyl, n-hexyloxycarbonyl, acetyl, acryloyl, propionyl, capronyl, capryl, hexahydrobenzoyl, ?henacetyl, benzoyl, 4-methyl-benzoyl, 2,4-dimethylbenzoyl, 4-methoxy benzoyl, 4-chlorobenzoyl~
aminocarbonyl, monomethylaminocarbonyl, dimethylaminocarbonyl, e~hleneiminocarbonyl, monoethylaminocarbonyl, mono-iso-propylaminocarbonyl, diethylaminocarbonyl, mono-hydroxyethylamino-carbonyl, mono- -methoxypropylaminocarbonyl, morpholinocarbonyl, piperidinocarbonyl, cyclohexylaminocarbonyl, benzylaminocarbonyl, anilinocarbonyl, 4-methyl-anilinocarbonyl, N-methyl-anilinocarbonyl, methylsulfonyl, e~thylsulfonyl, n-propylsulfonyl, iso-propylsulfonyl, n-butylsulfonyl, iso-butylsulfonyl, secondary butylsulfonyl, n-amysul:Fonyl, isoamylsulfony~
n-hexylsulfonyl, benzylsulfonyl, phenylsulfonyl, 4-methylphenyl-sulfonyl, 2,4-dimethylphenylsulfonyl, 4-me-thoxyphenylsulEonyl, 4-chlorophenylsulfonyl, aminosulfonyl, monomethylAminoslllfonyl, dimethylaminosulfonyl, ethyleneiminosulfonyl, monoethylamino-sulfonyl, mono-iso-propylaminosulfonyl, die-thyLaminosulfonyl, mono-hdroxyethylaminosulfonyl, mono- -methoxypropylaminosulfonyl, morpholinosulfonyl, piperidinosulfonyl, cyclohexylaminosulfonyl, benzylaminosulfonyl, anilinosulfonyl, 4-methylanilinosulfonyl, N-methylanilinosulfonyl, .

.,.~ !

!~ 1L93 .oc ~~3 oc~3 --oc ~ o~ ~N
OC ~, . -. ~ C-CO~ C-CO~, -H2C ~ 3 , ' . -~2C-H2C ~ - and -~2C-~2C ~
~ , , .
, The coupling COMpOnentS of formula I~I, may contain Zl radicals, for example, of ~he following primary or secondary :~ amines, diamines or hydroxylamines:

Primary amines Ammonia, methylalnine, ethylami.ne, 2-hydroxyethylamine, 2-metho~:y-ethylamine, 3-phenoxyethylamine, 3-cyanoethylamine, n-propylamine ~K,~ 10 isopropylamine, 3-hydroxyl~ropylamne.(l), 3-methoxypropylamine(l), 3-isopropoxypropylamine(l), 3-cyanopropylamine(l), allylamine, l-methallylamine, 2-methallylamine, n-hutyl~nin~, isobutylamine, .sec.-butylamine, tert,-butylamine, 2-amino-2-methylpropaIlol-(l), crotylamine, 3-aminopentane, n-amylamine, isoamylamine, n-lS hexylamine, isohexylamine, dodecylamine, cyclohexylamine, ben~yl-:amine, 2-phenylethylamine, aniline, 4-methylaniline, ~-methoxy-!~t~. aniline, 2,'L-dimethylaniline, l-aminonaphthalene, 2-amino-naphthalene, '' ~; ' ,` ~ ' . ' .

- 16.-: .

~ 93 E-l2NI~2C ~

CH2l~lll2 H2MEI2CH2C~ H2NH2CH2 and ~ ~I2N~2 Secondary Amines Dimethylamine, d.iethylamine, N (2-cyanoethyl)-N-(2-hydroxye-thyl) amine, N-di (2-hydroxyethyl)aminc, N-di-(2-cy~noethyl)amine, N-methyl-N-(2-hydro~yethyl)amine,N-isopropyl-N-~2-hydroxyethyl) amine~ N-n-butyl-N-(2-hydroxyethyl)amine, N-cyclohexyl-N-(2-hydroxyethyl)amine, M-benzyl-N-(2-hydroxyethyl)amine,di-n-propylamine diisopropy].amine, di-n-butylamine, diisobutylamine, di-n-amylamine, di-n-hexylamine, I`~ e~hyl-n-hexylamine~ morpholine, pyrrolidine, p;peridine, M-methylpiperazine, M-methylcyclohexylamine, N-ethylcyclohexylamine, N-methylbenzylamine, i~i-methyl-3-methyl-benzylamine, N-methylaniline, N-ethylaniline, N-2-hydroxyethyl-aniline, N-benzylaniline, N-methyl-2-chloroaniline and N-e-thyl-2-chloroan.iline.
Diamines N-methyl-N',N~-dimethylhydrazine, N,N-dimethyl}lydrazine, M,N-diethyl-hydrazine, N-methyl-M-phenylhydrazine, N-aminopyrrolidine, N-aminopiperidine, N-aminopiperazine, N-aminomorpholine, N,N-dimethylethylene diamine, N,N-diethyl ethylene diamine, N,N-dimethyl propylene diamine(l,3), N,N-diethyl propylene diamine(l,3), 2-morpholinoe-thylamine, 2-piperidinoethylamine or 2-pyrrolidino-ethylamine and N-methyl-N'-3-amino-n-propylpiperazine of the formula 2 2 2 2 ~ CH -CH ~ ~ 2 . ~ . .

Hydroxylamines ~' ' CEI ~C~2CI 3 ~CE~2CH20H
~N-OH~N ~ 3 ~N~ HN ~

. . 3 0~2c~3 , 0-C~12 ~ , C~2C~3 ~N~ C~2C~20~I ~2 O--CH2 ,OC~3 , C~2C~3 , OCH

' c2 '' ' ~;
H21 C~ ~ C~12C~O~ CH 3 , 0/ ~;'' HN ~ - CH3 :
, ;, ' / , ' .

C~CH3 C~2-CE~2-O~iI C~
~N ~ CH3 ~N ~ and HN ~ 2 , 0-~12-C~2-C~3 ~3 .. .... .. . . . . . ..... . . .. . . .. . . ..
;. In ~ormula III o~ t~e coupling componen~, Z~ may be, for example, a radical o~ one o~ the ~ollowing alcohols, phenols or naphtho~;
Methanol, ethanol, 2-cyanoethanol-(1), ethylene glycol mono-methylether, ethylena glycol monoethylether, ethylene glycol mono-isopropylethe~ ethylene glycol mono~n-butylether, ethylene ; glycol monophenylether, ethylene glycol monoxylellylether, diethylene glycol monomethylether, diethylene glyco;l monoethylether, ethylene glycol mono-n-butyle~her, triethylene glycol m~nomethylether triethylene glycol monoethylether, triethylene glycol mono-n-butylether, n-propanol, isopropanol, propylene glycol monomethylether propylene glycol mon~ethy].e~her, dipropylene glycol monoethylcther, ' :

propene-~1)-ol-~3j~ 2-methylpropene (1~-ol-(3) t n-butanol, sec.-butanol , i~ohutanol , tert . -butanol , 3-methoxybutanol~ (1), 4-methoxybutanol-(l), butene~ ol-~2), n-pentanol, isopentanol, n-hex~nol, isoheptenol, sec.-octanol, isooctanol, n-decanol, n-dodecanol, cyclohexanol, 4~methylcyclohexanol, 4-methoxycyclo-hexanol, phenylmethyl alcohol, (4-chlorophenyl~-methyl alcohol, phenylethyl alcohol, (4-cyanophenyl)-ethyl alcohol, phenol, 2-methylphenol, 3-methylphenol, 2,3-dimethylphenol, 2, 4-dimethylphenol, 2,5-dimethylphenol, 2, 6-dimethylphenol, 10 3,4-dimethylphenol, 3,5-dimethylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-3-methylphenol~ 2-methoxy-4-methylphenol, 2-methoxy-5-methylphenol, 2-methoxy-6-methylphenol, 3-methoxy-5-methylphenol, 3-methoxy-6-methylphenol, 4-methoxy-5-methylphenol, 4-methoxy-6-methylphenol, 2 t 3-dimethoxy-15 phenol, 2,4-dimethoxyphenol, 3,5-dimethoxyphenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2,3-dichlorophenol, 2-4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichloroph~nol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,3-20 dibromophenol, 2,4-dibromophenol, 2,5-dibromophenol, 2,6-dibromo-phenol, 3,4-dibxomophenol, 2,5-dibromophenol, 2-methyl-3-chloro-phenol, 2-methyl-4-chlorophenol, 2-methyl-5-chlorophenol, 2-methyl-6-chlorophenol, 2-methyl~3-bromophenol, 2-methyl-4-bromophenol, 2-methyl-5-bromophenol, 2-methyl-6-bromophenol, 3-25 methyl-2-chlorophenol, 3-methyl-4-chlorophenol, 3-methyl-6-chlorophenol, 3-methyl-2-bromophenol, 3-mathyl-4-bromophenol, 3-methyl-6-bromophenol, 4-methyl-5-chloro-phenol, 4-methyl-6-chlorophenol, 4-methyl-S-bromophenol, 4-methyl-6-bromophenol, 4-chloropyrocatechol-1-methylether, 5-chloropyro-30 catechol-l-methylether, 4-bromopyrocatechol-1-methylether, S-bromopyrocatechol-l-methylether, 4-chlororesorcinol-1-methylether, 4-chlororesorcinol-3-methylether, 4-bromoresorcinol-1 methylethex t 4 bromoresorcinol-3-methylether, 5-chlororesorcinol-1-mPthylether, 2-chlorohydroquinone-1-methyl~ther, 2-chlorohydroquinone-2-5 methylether, l-naphthol, 2-naphthol, 2-methyl-1-naphthol, 3-methyl-l-naphthol, 4-m~thyl-1-naphthol, 7-methyl-1-naphthol, 3,6-dimethyl-1-naphthol, 3,7-dimethyl~l-naphthol, ~,6-dimethyl-1-naphthol, 4,7-dimethyl-l-naphthol, 6,7-dimethyl-1-naphthol, 4-methoxy-l-naphthol, 5-methoxy-1-naphthol, 6-methoxy-1-naphthol, 10 7-methoxy-1-naphthol, 8-methoxy-1-naphthol, 2-chloro--1-naphthol, 3-chloro-1-naphthol, 4-chloro-1-naphthol, 5-chloro-l~naphthol,

7-chloro-1-naphthol, 8-chloro-1-naphthol, 2,3-dichloro-1-naphthol, 2,4-dichloro-1-naphthol, 5,7-dichloro-1-naphthol, 5,8-dichloro-1-naphthol, 2-chloro-4-bromo-1-naphthol,-2-bromo-1-naphthol, 3-15 bromo-l-naphthol, 4-bromo-1-naphthol, 5-bromo-1-naphthol, 6-bromo-1-naphthol, 7-bromo-1-naphthol, 8-bromo-1-naphthol, 2-ethyl-4-bromo-l-naphthol, 2,4-dibromo-1-naphthol, 1-methyl-2-naphthol, 6-methyl-2-naphthol, 1,4-dimethyl-2-naphthol, 3,6-di-methyl-2-naphthol, 3,7-dimethyl-2-naphthol, 6,7-dimethyl-2-20 naphthol, 1-chloro-2-naphthol, 3-chloro-2-naphthol, 4-chloro-2-naphthol, 5-chloro-2-naphthol, 6-chloro-2-naphthol, 7-chloro-2-naphthol, 8-chlor~-2-naphthol, 1,3-dichloro-2-naphthol, 1,4-dichloro-2-naphthol, 1-bromo-2-naphthol, 3-bromo-2-~aphthol, 4-bromo-2-naphthol, 5-bromo-2-naphthol, 6-bromo-2-naphthol, 25 7-bromo-2-naphthol, 8-bromo-2-naphthol, 1-methyl-6-bromo-2-naphthol, l-ethyl-6-bromo-2-naphthol, 1,6-dibromo-2-naphthol, 3,6-dibromo-2-naphthol, 3,7-dibromo-2-naphthol or 4,6-dibromo-2-naphthol.

. ~

~0~ 3 , Furthermore, Z2 may be the radical of one of the thioalco~ols, thiophenols or thionaphthols corresponding to the above alcohols, phenols and naphthols~
Starting materials for the preparation of the 5 coupling components of ~ormula III are 2,6-dihydroxypyrldines o~
the formula ..~ . ..

. .
X IV
110~

wherein X and Y are as defined above. These may be prepared in a known manner in accordance with the methad described by 10 Guareschi, Berl~chte der Deutschen_Chemischen Gesellschaft [Reports of the German Chem~cal Society], Abstracts 29 (1897), pp. 65~-656, by the condensation of appropriately substituted acetic acid ; amides with appropiately substituted ~ -ketocarboxylic ac.id estels They may also be prepared in accordance with other various 15 processes such as described, for example, in the monograph "~Ietexocyclic Compounds Pyridine and its Derivatives Part 3" by ~lingsbe~g. This mono~raph appeared within the series "The Chemistry of Heterocyclic Components," edited by Arnold ~eissberger and published by Interscience Publishers. The 2,6-20 dihydroxypyridine derivativès of formula IV are converted inaccordance with Bobbitt and Scola, Journ. Org. Chem. 25, 560, by means of phosphoroxychloride or analoyously by means of phospho~oxybromide at temperatures of up to 200C', optionaliy in an lnert diluent, into the corresponding 2,6-dichloro- or - 25 2,6-dlbromopyridines of ~he formula 0~"~

nl - 21 ~

. . .
: . ... ..

wherein X and Y are as defined above and Hal is chlorine or bromine, preferably chlori~e.
For the preparation o coupling components o~ formula ~- III, a compound of formula V i5 reacted first with a compound of - 5 formula VI in accordance with the react.~on equation: !

X X

+~71 V YI VII

;, The foregoing reaçtlon is carried out with equimolar ratios o~ V and VI at temperatures of 20 - 100C in a suitable incx1: 50~ nt~ ~lcE~ra~ al: d te"~ rdL-Ir~ of ILOIII ~U to 50-C.
lO Pre~erably alcohols with a chain length of l to 4 carbon atoms are employed as the inert solvent. In the event the physical properties allow it, an excess of one o the reactants may serve as the solvent.
The exchange of the chlorine or bromine atom in the 6 15 position of the oregoing reaction is assured by analysis of the NMR absQrptions of the products obtained, The compounds of formula VII are then further reacted in accordance with the following reaction equation to obtain the couplin~ component of formula III: -~: X X
i Z1 ~ n1 +Q~2 _Q~ ~ 22 VII VIII III

In formula VIII, Q is an alkali metal, preferably sodium or potassium. The reactants are rea~ted at temperatures of ~0-150C~ preferably at 60-100C, in a suitable inert sol~ent, for example, an aromatic hydrocarb~n such as benzene, tolue~e or xylene, or also, where appxopriate, in an excess of the reactant HOR12 or ~SR12 as solvent.

The novel dyestuffs are especially suitable for the dyeing and prin~ing of products made of hydrophobic materials such as, for 0xample, polyolefins, polyvinyl compounds, polyamide, polyacrylonitrile, cellulose-2 1/2-a~etate, cellulose triacetate and especially polyester materials such as polyethylene glycol terephthalate. They yield thereon, following the customary dyeing and printing processes, deep yellow to violet dyeings and prints having very good fastness properties, particularly lS fastness to light, dry heat pleating fastness and dry heat fixing fastness.
The dyeing of the above stated materials with the dye~tu~fs of this invention may take place with an aqueous ~uspension, in the presence of conventional carriers, between about ~0 80 - 100C, in the absence of such carriers between about 110 -1400C, as well as in accordance with the so-called thermofixing process at about 180-230C. The printing of the stated materials may be carried out in such a manner that the goods printed with the novel dyestuffs are steamed in the presence of a conventional carrier at temperatures of between about 80 - 110C or, in the absence of a carrier, at about 110 - 140C or are treated also in accordance with the so-called thermofixing process at about 180 - 230C.
The dyestuffs of this invention are also soitable or the dyeing of the above-men~ioned hydrophobic materials u~ing organic solvents and for d~eing in bulk.

of particular technical interest are dyestuffs ~f the formula : X
D-N-N ~ ~ (I) ~1 Z2 wherein D is phenyl or phenyl substituted with 1 to 3 substituents selected from the group consisting of cyano, nitro, chlorine and bromine, X is methyl, Y is cyano or ca~bamoyl, .
~ Zl iS H3C~-H2C-H2C-HN- or H3Co-H2C_H2c_ H2c_HN_ - æ2 is alkoxy having 1 to 12 carbon atoms, pre~erably 4 to 8 , carbon atoms, or -O-(Cn~l2nO)m-R12 wherein R12 is hydrogen, : methyl or ethyl, n is 2 or 3 and m is 1 or 2.

. ' .
;
i ' ' .~~ ' - ' ~, 'l' ~, , ; ' ' ~ .

~he following examI?les illustrate the present invention.

Example 1 (a) There are diazotized 13.8 parts by weight 4-nitroaniline in 150 parts by weight glacial acetic acid with 34.2 parts be weight nitrosylsulfuric acid (41.3%) under external Cooling a~ 15C. The clear diazo solution is then allowed to run in~o a suspension of 22.8 parts be weight 2-methoxy-3-cyano-4-methyl 6~(2'-hydroxyethylamino~-pyridine having the ormula ~C ~ CN

Ho-H2C-H2C-HN~ ~N l OCH3 and 66.0 parts be weight anhydrous sodium acetate in 240 parts 10 by weight ethyl alcohol. The reaction temperature is maintained during the coupling at 0 to 5C by extexnal cooling. The xesultant dyestuff is recovered upon the compl~tion of the coupling, washed with ethyl alcohol, then with water, and dried.
It is an orange powder which di~solves as a red dye in concentrat-15 ed sulfuric acid.
(b) The 2-methoxy-3-cyano-4-methyl-6-(2'-hydroxy-ethylamino)-pyridine, needed as the coupling constituent, may be prepared by agitating a solution o~ 93.0 parts by weight 2,6-dichloro-3-cyano-4-methylpyridien and 66.0 parts by weight 20 2-hydroxyethylamine in 200 parts by weight ethyl alcohol for 24 hour3 at 15C. By mixing the reaction solution with water, the re~ultant2-chloro-3-cyano-4-methyl-6-(2'-hydroxyethylamino)-- :
pyridine is then precipitated, subsequently recovered, washed with water and dried.

Analysis: CgHloClN3O Calculated: 16.6% Cl 19.9 % N
Found: 16.5% Cl 19.5 % N

There are introduced into a sodium methylate solution, prepared from 10.1 parts by weight metallic sodium and 200 parts by weight methanol, 42.2 parts by weight 2-chloro-3-cyano-4-methyl-6-(2'-hydroxyethylamino)-pyridine. Subsequently, the reaction solution is heated to boiling for 18 hours. Then the methyl alcohol is distilled off, the residue mixed with water, and the resultant 2-methoxy-3-cyano-4-methyl-6-(2'-hydroxy-ethylamino)-pyridine is recovered and washed with water. It may be purified by vacuum distillation.
Analysis: C10~13N32 Calculated: 20.3% N 0.0 % Cl Found: 20.4% N 0.0 % Cl (c) One part by weight of the finely dispersed dyestuff obtained in accordance with l(a) and having the formula O2N ~ ~ OCH

is stirred into 2000 parts by weight. This is standardized with acetic acid to a pH of 5-6 and mixed with 4.0 parts by weight ammonium sulfate and 2.0 parts by weight of a commercial dispersing agent which is a naphthalene sulfonic acid condensate with formaldehyde.
There are introduced into the dye bath obtained above 100 parts by weight of a polyethylene glycol terephthalate polyester fabric and said fabric is dyed 1 1/2 hours at 130C.
After subsequent washing, reductive post-treatment with a 0.2%
alkaline sodium dithionite solution for 15 minutes at 70 - 80C, ~;

washing, and drying, there is obtained a deep yellowish-orange dyeing with very good color properties, particularly very good fastness to light, dry heat pleating fastness and dry heat fixing fastness.

Example 2 (a) There are diazotized 16.3 parts by weight 2-cyano-4-nitroaniline aS described in Example l(a) and the product is coupled with 35.5 parts by weight 3-cyano-4-methyl-6-(3'-methoxy-propylamino)-pyridine-2- ~ -(~ '-methoxy)-ethoxy~-ethylether having the formula ~H3 CN

H3CO-E~2C-H2C-H2C--HN - (CH2-CH2-) 2-CH3 and isolated. The resultant dyestuff represents a red powder, which dissolves as an orange dye in concentrated sulfuric acid.

(b) The 3-cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine-2- ~ - ~ '-methoxy)-ethoxy -ethylether, needed as the coupling constituent, may be prepared by dissolving 93 parts by weight 2,6-dichloro-3-cyano-4-methyl-pyridine and 100 parts by weight 3-methoxypropylaminè in 400 parts by weight ethyl alcohol.
After 24-hours stirring at room temperature, the crystallized 2-chloro-3-cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine is then recovered, washed with 200 parts by weight ethyl alcohol, then with 1000 parts by weight water, and dried.
Analysis: C11H14ClN3O Calculated: 14.7% Cl 17.6 % N

Found: 14.4% Cl 17.7 % N
at 50 There are dissolved/in 400 parts by weight diethylene glycol monomethyl ether 10.1 parts by weight metallic sodium.

~ ter addi~g 95.6 parts ~y weight 2-chloro-3~cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine, the reaction solution is then heated ~or 18 hours at 100C. The excess diethylelle glycol monomethyl ether is then distilled under vacuum, the residue stirred with 500 parts by weight water, the resultant 3-cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine-2-~ '-methoxy) -ethoxy]~ethylether recovered, washed with water and dried.
Calculated: 13~/o N 0.0 % Cl ~ound: 13.0% N a. o % cl (c) There are incorporated in finely divided form 30.0 parts by weight of the dyestu~f obtained in accordance with Example 2(a), of the formula ~N CH~

O~N - ~ N~N - ~ CN
~3CO-H2c-H2c-H2~ Nl O-(C~12-C~I2-0)2-CI~3 into a printing paste which contains aS~o parts by weight carob bean flour, 6.0 parts by weight of the soclium salt o~ 3-nitro-ben2ene sulfonic acid and 3.0 parts by weight citric acid per 1~00 paxts by welght. Upon printing ~ith this ~aste, drying and fixing in the thermoixing frame for ~5 seconds at 215C, washing and finishing, as described in paragraph 2 of Example l(c), there is obtained, on a polyester fabric, a deep reddish-~ orange print having very good color/properties, particularly very -I good fastness to light, dry heat l~le~ting fastness and dry heat i fixing fastness. The dyestuf yields a r~ddish-orange print of . I . .

; .
~ ~ .
.
.__ _ .. .

stic ~7~ very good co~7prop~rties in the printing of tri~cetate fabric if the dyestu~ is used in the form of ~he above p~inting paste and the printed fabric, upon drying 10 minutes at 105 atmospheres gauge, is steamed, washed, soaped, washed a~ain, and dried.
Exam~le 3 ~a) There are diazotized 2~.2 parts by wei~ht 2-cyclno-4-nitro-6-bromoaniline as described in ExaMple lta~, the product is coupled with 25,9 parts by weight 2-mcthoxy-3-cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine of the formula C~13 7I3CO-~2C-~2C-H2C-HN 1N1OCH3 and the resultant dyestuff is isolatea. It is a red powder, which dissolves as an orange dye in concentrated sulfuric acid, ; (b) The 2-methoxy-3-c~ano-4-methyl-6-(3'-methoxy-propylamino)-pyridine, needed as the couplin~ constituent, may be 1~ prepared by introducin~ into a soclium metllyl~te solution prepared from 25.3 parts by weight metallic soclium and 1000 parts by weight .
methanol, 215.1 parts by weight 2-chloro-3-cyano-4-methyl-6-(3' -methoxypropylamino)-pyridine prepared in accordance with Exampl~
~2 (b) o Subsequently, the reaction solution is hea~ed to boiling for 18 hours. Then the excess methyl alcohol is distilled off, the residue stirred with 1000 parts by weight water and the resultant 2-methoxy-3-cyano-~-methyl-6-(3'-methoxypropylamino)-pyridine isolated. It may be purifiecl by vaccuum distillatlon.
Analysis: C12H17N30 Calculated: 17.9~/o N 26.4% -OCH3 Found: 18.1% N 2~.2% -OCH3 .

' ,~L
~, (c) A fabric of polyethyl~ne glycol terephthalate is padded on the pad at 30C with a liquor which contains 30 parts by weight of the finely dispersed dyestuff obtained in accordance with Example 3(a) and of the formula CN CH

Br ~ 3 1.0 parts by weight polyacrylamide having a K-value of 120, 0.5 parts by weight of a polyglycol ether of oleyl alcohol and 968.5 parts by weight water. After the drying, fixing takes place for 60 seconds at 215C in the thermofixing frame. After subsequent washing and finishing as described in paragraph 2 of Example l(c), there is obtained a red dyeing of very good fastness properties, particularly very tood fastness to light.
Example 4 One hundred parts by weight of a polyester material are handled for 30 minutes at 121C in 1500 parts by weight ethylene tetrachloride, in which are dissolved 2.0 parts by weight of the dyestuff described in Example 2(a). Washing proceeds with warm and cold ethylene tetrachloride, and a strong reddish-orange dyeing is obtained having very good color properties.
Equally reddish-orange dyeings having very good coloristic - properties are obtained if the polyester material of the above example is replaced by 100 parts by weight triacetate or 2-1/2-acetate material and is dyed for 45 minutes at 110C or 45 minutes at 80C.

. , .

~4~3~
Example 5 (a) There are diazotized 24.9 parts by weight 3-aminophenyl phenylsulfonic acid ester of the formula ~ S02-0 ~-- NH2 as described in Example l(a) and the product is coupled with 32.2 parts by weight 3-cyano-4-methyl-6-(3'-methoxypropylamino) -pyridine-2-n-butylthioether having the formula CN

H3CO-H2C-H2C-H2C--HI~ S-CH2-CH2-CH2-CH3 and the resulting dyestuff is isolated. It is an orange powder which dissolves as a red dye in concentrated sulfuric acid.
(b) The 3-cyano-4-methyl-6-(3'-methoxypropylamino)-pyridine-2-n-butylthioether needed as the coupling constituent may be prepared in accordance with the data of Example 2(b) using 400 parts by weight n-butylmercaptan in place of the di-ethylene glycol monomethyl ether.
Analysis: C15H23N3S Calculated: 14~3%N 10.9 % S
Found: 14.6%N 10.6 ~ S
(c) Thirty parts by weight of the finely dispersed dyestuff described in Example 5(a) yield, under the printing procedure of Example 2 (c), an orange print of very good color properties, particularly very good light and thermofixing fastness.

In the following tabulationr further novel dyestuffs of the ~ormula:

Z N Z

are described. These yield, on polyester rnaterials, deep yellow ! to violet dyeings or prints with equally very good coloristic propertie~.

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;-~ IL93 ho. B X Y Zl 2 N~2 --CH3 -CN --N~2 4 9(1l) Cl 2 ~N02 -CH3 -CN -NH-CH3 C6~13(iso) ~N
C 3 _r~ -N~-C2H5 -0-C2H5 --N2 -CH3 -C N -NH-C EI2-C E12-C N -~-C 3H7 ( i so ) N~
~Cl -CH3 -CN -NH-CH2-CH20H -CH2-CH=CE~2 Br 6 ~-N2 CH3 -CN -NH-CH2-CH2-OcH3 --(C2~4 )2 3 ICN
7 ~3No2 -CH3 -CN -NH-CH2-CH2-0CH3 -S-C2H5 ;

~-02S e3

8 ~~ -C~3 -CN -NH-cH2-c~2-ocH3 ~~C4~9 Sn)

9 ~ d ~ -CH3 -CN -NH-cH2-cH2-o~E3 --C~3 Cl ~3 -CH3 -CN -NH-C3H7( ) ~~~ 6H13(II) Br : .
.

No. D X Y Zl Z~

11 ~CO CH3 CH3 -CN -NH-C3R7(iso) --C6 H13(n~

NO

12 ~Br -c~3 -CN -NH-CH2-CH=cH2 -O-C 4E~g ( i so ) CN
13 ~ -CH3 -CN ~N~ 41~9(n) C4EI9(sek.

CN

14 ~N2 -CH3 -CN -NH-CH2-C-CEI2 -O- ~C H2 ~2 ) 2 2 Cl ~Cl -CH3 -CN -N~-C4H9~iso) ~~~!6~13(n~

Cl Cl 16 ~ -CH3 -CN -NH-C4Hg(tert~ ~ ~~C10~21~n) 17 -b CCH3 -CH3 -CN -NH-C5Hll~iso) ~~C12H25(n) 2 -~H3 -CN -NH~C6H13(n~ -0-~::4H9(tert.

19 ~ C3 -CN -Nll-C6il13(190) -o-C336(11) 3 20 ~3 -C~3 -CN ~NH~Cla~25(n) -0-CH3 No. D X Y Z:L Z2 l 2 21 ~3 -c~3 -CN -NH{~> -O~CH2-C~2-CN

22 ~C~3 -C~3 -CN -NH-CH2~ -O-C 4~9 ( n ) 23 ~ 4 9(n) 3 CN -NE-CBa-CBa~~O~c4B9~n) 24 ~ -CH3 -CN -NH~ -O-CH3 ~-Br -c~3 -CN -NN-CB2-C ~ CB -O-Call5 26 ~N02 -CH3 -CN -NH-CH2~N -O-C2HS

~, 27 ~N02 -CH3 -CN -NH-CB - CH2 28 ~N02 -CH3 -CN -NH-CH2~ -0-C2H5 29 ~3CH3-CH3 -CO-NH~ -N H O -o-CH3 ~N02 CH3 -CO-NEI2 -N~3 -0-CEI3 No. I) X t~' 21 ~2 31 ~3 ", CH3 -N N N-CE~3-0-CH3 32 ~3C3EI2-N 2 -CH3-CN -N ~N-C2~5-0-C~I3 CH
0-0 2S-N~ 3 : E3 ~ -C~I3-C N -N~7 -0-CH3 ~ ~ -C1~3-CN -NEI-~ ,C~3--~2H5 35 ~O~Cl -CH3 -CN -N - N -O-C2H5 3ff ~30~Cl -CH3-CN -NH-N~ 2-C)-C2H5 : 0~
37 ~ -CH3-CN -NH_N~ 2~5-0-C2H5 . ~

38 ~N2 CH3 CN -NH N H o -O-C3H7(iSo) 39 ~l CN3 -CN -NN-CN2-CN2-N~ -O-C4Ng - 36 _ :. ~ - ''' ` '.

~L~4~:~L93 N3 . D X Y ~Z 3 Z~

~S2 CE~3 -CH3 -CN-NH-cH2-cEI2-cE~2-N 3 ~~C41~9 41 ~3Co-CH3 -CH3 -CNNH CH CH CE~ N~ C2 5 o Cl 42 ~N2 3 :2 C~2 ~3[2-N~ o -O-CH3 Cl 43 ~N--CH3 ~3 -CN-N~I-cH2-cH2-cE~ ~ -0-CH3 ~N
~ 2 -CH3 CN -N~-O~I -O-C2H5 ~Co-ocloa2l-C113 -CN -N ~ 3 -0-C 4H9 1 n 46 ~3Co-oc2H5CH3 CN-N--CH2 CH2-~ C21~5 47 ~ -C~13 -CN -N~ 2~ 0 C4H9(n~

CO~OC4H9 48 ~ 3 `0-C1~2-C1~3 0 C4ij9 -- 37 _ ':

104~3 N~. D X Y 1 2 2-CH ~CNEl2C ~H
3 -N ~CH2 0 C4H9(n) ~` H2 ~ 2 -CH3 -CN ~o/ 2 ~~C4~9~n) 51 4~ 24 9(n)CH3 -CN-NH-CH2-CE~2~ 0-C1~

52 ~ c~3 -CN -NH~ -O-CE[3 53 ~0-CH3 -CH3 -CN -NH~Cl -O-C2~I5 ~ C4H9 ~ n ) -C H3 -CN -NEI~c~3 -O-C 2H5 55 ~ -CH -CN -NH~30-CH3 -0-C2H5 56 43 CH3 -CN -NH~c~3 -0-C2EI5 M o . D ~ ; 1 Z ?

CN

4~ 2 -CH3 C ~ 0-C2H5 5~ ~CEI2-~ -c~3 -CN -NH-CH2~3 -0-CEI3 59 ~C0 CH2-N~ 3 -~3 -CN -N~-C~{ -CH ~N 0 C~

~ -c~3 -CN -NH~ -S-CH3 Cl 61 ~N02 -C~3 -CN -NH-C4~9 ( ) 4H9 ~n CN
G2 ~N2 -C113 -C0-N~2 -N~l-C~2-C~3-0~ S C4119(iso) 63 ~N0~ CH3 CN -NEI-CH2-CEI2-c~2-~cH3 -S C12~25(n) CN
64 ~N02 H3 CN ~CH -0-C2H5 CN
~3No2 H3 CN C2~5 -0-C2H5 CN
66 -~-N2 C~3 CN - C2H5 0 C4H9(n) - 39 _ ~`
"' ' -, -- . . .

No. D X YZl Z2 67 ~N02 -C~3 ~CH2-CH2-OH -o-CH3 Cl 68 ~N2 -CH3 -CNN ~ H2 CH2 CN 4 9(n) CN
69 ~N02 -CH3 -CNC 2-CH2-C O C

Cl 70~3No2 -CH3 ~ CH3 -0-C2H5 71~3No2 -C}~3 CH2~ -0-CH3 72~CH3 -CH3 , C6E~13(n~ -0-CH3 ,., ~
73 ~Cl -CH3 -CN-NH-~ -0~ C2H5 Cl 75 ~ -CH3 -CN-~ N~ -O-C2H5 Cl u~ t T

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Claims (25)

WHAT IS CLAIMED IS:

1. A water-soluble azo dyestuff of the formula wherein D is the residue of a benzene, naphthalene, anthraquinone or heterocyclic diazo component which is free of ionic groups;
X is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, furyl, thienyl, thiazolyl, pyridyl, benzothiazolyl, imidazolyl, benzimidazolyl, pyrrolyl or hydrogen;
Y is cyano, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, -COOR1, -COR2, , -SO2R2, or hydrogen with the proviso that only one of X and Y is simultaneously hydrogen;

Z1 is , , -NH-OR10 or and Z2 is -O-(CnH2nO)m-R12 or -S-(CH2H2nO)m-R12 wherein R1 and R2 are alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl. moiety, phenalkyl or substituted phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl, substituted phenyl, piperazino, furyl, thienyl, pyridyl, thiazoyl, benzothiazoyl, imidazoyl, benzimidazoyl or pyrrolyl;
R3 and R4, taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety or phenyl or substituted phenyl and R3 and R4, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted-by oxygen, sulfur or nitrogen;
R5 and R6, taken separately, are hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl, or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety and R5 and R6, taken together, are alkylene having 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen;

R7 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substituted phenyl;
R8 and R9 are alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, phenyl or substituted phenyl;
R10, taken separately, is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety or phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety;
R11, taken separately, is alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety;
R10 and R11, taken together, are alkylene having 2 to 5 carbon atoms;
R12 is hydrogen, alkyl or substituted alkyl having 1 to 12 carbon atoms in the alkyl moiety, alkenyl or substituted alkenyl having 2 to 12 carbon atoms in the alkenyl moiety, cycloalkyl or substituted cycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety, phenalkyl or substituted phenalkyl having 1 to 2 carbon atoms in the alkyl moiety, phenyl or substi-tuted phenyl;
n is 2, 3 or 4;
m is 0, 1 or 2;
there being up to two substituents for each of said substituted alkyl and substituted alkenyl, each said substituent being selected from the group consisting of cyano, hydroxy, acetoxy, alkoxy having 1 to 2 carbon atoms, phenoxy, alkylamino-carboxyloxy having 2 to 3 carbon atoms, phenylaminocarbonyloxy, monoalkylamino and dialkylamino having 1 to 2 carbon atoms in each alkyl moiety, wherein Z is alkylene containing 2 to 5 carbon atoms or said alkylene interrupted by oxygen, sulfur or nitrogen and wherein R13 is alkyl having 1 to 2 carbon atoms and R14 is acetyl or benzoyl;
there being up to two substituents for each of said substituted cycloalkyl, substituted phenalkyl and substituted phenyl, each of said substituents being selected from the group consisting of bromine, chlorine, cyano, alkyl having 1 to 3 carbon atoms and alkoxy having 1 to 2 carbon atoms and the total number of carbon atoms in X, Y, Z1 and Z2 being not more than 24.

2. A water-insoluble azo dyestuff of claim 1 wherein X is methyl.

3. A water-insoluble azo dyestuff of claim 1 wherein Y is cyano or carbamoyl.

4. A water-insoluble azo dyestuff of claim 1 wherein Z1 is 2-methoxyethylamino or 3-methoxypropylamino.

5. A water-insoluble azo dyestuff of claim 1 wherein Z2 is alkoxy having 1 to 12 carbon atoms.

6. A water-insoluble azo dyestuff of claim 1 wherein Z2 is -O-(CnH2nO)m-R12 wherein R12 is hydrogen, methyl or ethyl, n is 2 or 3 and m is 1 or 2.

7. A water-insoluble azo dyestuff of claim 1 wherein X is methyl, Y is cyano or carbamoyl, Z1 is H3CO-H2C-H2C-HN-or H3CO-H2C-H2C-H2C-HN- and Z2 is alkoxy having 1 to 12 carbon atoms or -O-(CnH2nO)m-R12 wherein R12 is hydrogen, methyl or ethyl, n is 2 or 3 and m is 1 or 2.

8. A method for dyeing or printing hydrophobic materials which comprises applying a dyestuff of claim 1.

9. A water-insoluble azo dyestuff according to claim 1 wherein D is phenyl which may be substituted in the 2-position by Cl, Br, CN, NO2, OCH3 or -SO2CH3, in the 4-position by NO2 and in the 6-position by Cl or CN.

10. A water-insoluble azo dyestuff according to claim 1 wherein D is phenyl which may be substituted in the 3-position by phenylsulfonyloxy or in the 2- and 5-position by Cl.

11. A water-insoluble azo dyestuff according to claim 1 wherein D is 2,1-benzisothiazolyl-(3) or 5-nitro-(2,1)-benzisothiazolyl-(3).

12. A water-insoluble azo dyestuff according to claim 1 wherein D is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is alkyl, having 1 to 12 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms or methoxyalkyl having 2 or 3 carbon atoms in the alkyl moiety, Z2 represents -O-(CnH2nO)m-R12 wherein m is 0, n is 2 and R12 is alkyl having 1 to 12 carbon atoms or phenyl.

13. A water-insoluble azo dyestuff according to claim 1 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is alkyl, having 1 to 12 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms or methoxyalkyl having 2 or 3 carbon atoms in the alkyl moiety, Z2 represents -O-(CnH2nO)m-R12 wherein m is 1 or 2, n is 2 and R12 is methyl or phenyl.

14. A water-insoluble azo dyestuff according to claim 1 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is hydroxyethyl or methoxypropyl, Z2 represents -O-(CnH2n-O)m-R12 wherein m is 0, n is 2 and R12 is alkyl having 1 to 10 carbon atoms or phenyl or Z2 is -(CH2CH2O)2-CH3.

15. A water-insoluble azo dyestuff according to claim 1 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is hydroxyethyl or methoxypropyl, Z2 represents methoxy, ethoxy, butoxy, decyloxy, phenoxy or -(CH2-CH2-O)2-OH3.

16. A water-insoluble azo dyestuff according to claim 1 wherein X is methyl, Y is cyano, and Z1 is -NH-R5 wherein R5 is hydroxyethyl when Z2 is methoxy or R5 is methoxypropyl when Z2 is methoxy, butoxy, decyloxy or -O(CH2CH2O)2-CH3.

17. A water-insoluble azo dyestuff according to claims 9, 10 or 11 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is alkyl, having 1 to 12 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms or methoxyalkyl having 2 or 3 carbon atoms in the alkyl moiety, Z2 represents -O-(CnH2nO)m-R12 wherein m is 0, n is 2 and R12 is alkyl having 1 to 12 carbon atoms or phenyl.

18. A water-insoluble azo dyestuff according to claims 9, 10 or 11 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is alkyl, having 1 to 12 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms or methoxyalkyl having 2 or 3 carbon atoms in the alkyl moiety, Z2 represents -O-(CnH2nO)m-R12 wherein m is 1 or 2, n is 2 and R12 is methyl or phenyl.

19. A water-insoluble azo dyestuff according to claims 9, 10 or 11 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is hydroxyethyl or methoxypropyl, Z2 represents -O-(CnH2n-O)m-R12 wherein m is 0, n is 2 and R12 is alkyl having 1 to 10 carbon atoms or phenyl or Z2 is -(CH2CH2O)2-CH3.

20. A water-insoluble azo dyestuff according to claims 9, 10 or 11 wherein X is methyl, Y is cyano, Z1 represents -NH-R5 wherein R5 is hydroxyethyl or methoxypropyl, Z2 represents methoxy, ethoxy, butoxy, decyloxy, phenoxy or -(CH2-CH2-O)2-CH3.

21. A water-insoluble azo dyestuff according to claims 9, 10 or 11 wherein X is methyl, Y is cyano, and Z1 is -NH-R5 wherein R5 is hydroxyethyl when Z2 is methoxy or R5 is methoxypropyl when Z2 is methoxy, butoxy, decyloxy or -O(CH2CH2O)2-CH3.

22. A water-insoluble azo dyestuff according to claim 1 wherein D is phenyl which may be substituted in the 2-position by Cl, Br, CN, NO2, OCH3 or -SO2CH3, in the 4-position by NO2 and in the 6-position by Cl or CN or D is phenyl which may be substituted in the 3-position by phenylsulfonyloxy or in the 2- and 5-position by Cl or D is 2,1-benzisothiazolyl-(3) or 5-nitro-(2,1)-benzisothiazolyl-(3), X is methyl, Y is cyano, and Z1 is -NH-R5 wherein R5 is hydroxyethyl when Z2 is methoxy or R5 is methoxypropyl when Z2 is methoxy, butoxy, decyloxy or -O(CH2CH2O)2-CH3.

23. A water-insoluble azo dyestuff according to claim 1 of the formula

24. A water-insoluble azo dyestuff according to claim 1 of the formula

25. A water-insoluble azo dyestuff according to claim 1 of the formula