GB1597791A

GB1597791A - Azo dyes

Info

Publication number: GB1597791A
Application number: GB16421/78A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1977-04-27
Filing date: 1978-04-26
Publication date: 1981-09-09
Also published as: DE2718636A1; FR2388859B3; JPS53134829A; FR2388859A1; IT1096175B; IT7822206A0

Description

(54) AZO DYES (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to azo dyes.According to the invention there are provided azo dyes of the general formula I

where D is the radical of a diazo component, R is hydrogen or a substituted or unsubstituted aliphatic, cycloaliphatic, araliphatic or aromatic radical, which may for example be an

R1 is hydrogen, methyl, ethyl, methoxy or ethoxy, R2 is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, alkanoylamino of 1 to 4 carbon atoms, benzoylamino or alkoxycarbonylamino, where alkoxy is of 1 to 4 carbon atoms, A1 and A2 independently of one another are alkylene of 2 to 4 carbon atoms.

which may be interrupted by oxygen, X is a direct bond or -0-and Y is substituted or unsubstituted phenyl or naphthyl.

The radicals D of the diazo component are in the main derived from the benzene, azobenzene or heterocyclic series, for example the thiophen, thiazole, thiadiazole, benzthiazole, benzisothiazole, thienoisothiazole, triazole, pyrazole or indazole series. Specific examples are: aniline, o-, m- and p-cyanoaniline, o-, mmethylsulfonylaniline, o-, m- and p-nitroaniline, o-, m- and p-cyanoaniline, o-, mand p-chloroaniline, o-, m- and p-bromoaniline, o-, m- and p-trifluoromethyl aniline, 3 ,4-dichloroaniline, 2,5-dichloroaniline, 3 5-dichloroaniline, 2,4,5-tri- chloroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4-dicyanoaniline, 2,5 dicyanoaniline, 2-cyano-4-chloroaniline, 2-cyano-4-chloro-6-bromoaniline, 2,4dicyano-6-chloroaniline, 2-chloro-4-cyanoaniline, 2-trifluoromethyl-4-chloroaniline, 2-nitro-4-chloroaniline, 2-nitro-4-methylaniline, 2-methyl-4-nitroaniline, 2methoxy-4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-tri- fluoromethyl-4-nitroaniline. 2-trifluoromethyl-4-nitro-6-bromoaniline, 2-trifluoro methyl-4-nitro-6-cyanoaniline, 2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-4-nitro-6-bromoaniline, 2,6-dichloro4-cyanoaniline, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline, 2,4-dinitro-6-cyanoaniline, 2,6-dicyano-4-nitroaniline, 2-methylsulfonyl-4chloroaniline, 2-chloro-4-methylsulfonylaniline, 2-methylsulfonyl-4-nitroaniline, 2 nitro-4-ethylsulfonylanilin e, 2,4-dinitro-6-methylsulfonylaniline, 2-cyano-4-methylsulfonylaniline, 2-phenylsulfonylaniline, 2,6-dichloro-4-methylsulfonylaniline, 2,6dibromo-4-methylsulfonylaniline, methyl, ethyl, propyl, butyl, benzyl, phenyl, ss- methoxyethyl, p-ethoxyethyl and p-hydroxyethyl o-, m- and p-aminobenzoate, methyl and methoxyethyl 4-nitroanthranilate, 3- and 4-aminophthalic acid, dimethyl and diethyl 5-aminoisophthalate and aminoterephthalate, 3- and 4-aminobenzoic acid amide, methylamide, n-butylamide and methoxypropylamide, 2-, 3and 4-aminobenzoic acid dimethylamide, diethylamide, pyrrolidide, morpholide and N-methyl-N-ss-hydroxyethylamide, 5-aminoisophthalic acid diamide and dimethoxypropylamide, aminoterephthalic acid bis-diethylamide, 3- and 4-aminophthalic acid imide, p-hydroxyethylimide and phenylimide, 3-amino-6-nitrophthalic acid ss-hydroxyethylimide, 2-, 3- and 4-aminobenzenesulfonic acid dimethylamide, morpholide and N-methylanilide, I-amino-2-chlorobenzene-4- sulfonic acid dimethylamide, I-amino-2,5- and -2,6-dichlorobenzeneA-sulfonic acid dimethylamide, 2'-, 3'- and 4'-aminophenyl methylsulfonate, 2'-, 3'- and 4'aminophenyl benzenesulfonate, N-acetyl-p-phenylenediamine, 2-aminobenzophenone, l-aminoanthraquinone. I-amino-4-chloroanthraquinone, 1-amino-2- ethoxynaphthalene, 4-amino-naphthalic acid butylamide, 6-amino-5,7-dicyanoindan, 4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 3',2-dimethyl-4aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 4-amino-2-nitroazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-hydroxy-4-aminoazobenzene, 4' chloro-4-aminoazobenzene, 2-methyl-5-methoxy-4'-nitro-4-aminoazobenzene, 2,5 dimethoxy-4'-nitro-4-aminoazobenzene, 2,5-dimethoxy-2',6'-dichloro-4'-nitro-4aminoazobenzene, 2,5-dimethoxy-2'-chloro-4'-nitro-4-aminoazobenzene, 3-chloro4-aminoazobenzene, 4'-nitrophenylazo-4-aminonaphthalene, 2,3'-dichloroaminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 4-aminoazobenzene-4'-sulfonic acid dimethylamide, 2'- and 3'-chloro-4-aminoazobenzene, benzene-azo-4-aminonaphthalene, 3-amino-2, 1 -benzisothiazole, 3-amino-5-chloro-2, 1 -benzisothiazole, 3-amino-5-bromo-2,1 -benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole, 3amino-5-nitro-7-chloro-2, I-benzisothiazole, 3-amino-5-nitro-7-bromo-2, 1 -benzisothiazole, 3-amino-5,7-dichloro-benzisothiazole, 3-amino-5,7-dibromo-benziso- thiazole, 4-amino-7-nitro- 1 ,2-benzisothiazole, 4-amino-5-chloro-7-nitro- 1,2benz- isothiazole. 4-amino-5-bromo-7-nitro- 1 ,2-benzisothiazole, 4-amino-5-cyano-7 nitro ,2-benzisothiazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-4methyl-5-nitrothiazole, 2-amino-4-phenyl-5-nitrothiazole, 2-amino-5-phenyl-l, 3 ,4- thiadiazole, 2-amino-5-ethylmercapto-1,3,4-thiadiazole, 3-phenyl-5 -amino-l ,2,4- thiadiazole, 3-p-carbomethoxyethyImercapto-5-amino- 1,2,4-thiadiazole, 3-methyl mercapto-5-amino- 1 ,2,4-thiadiazole, 3-aminopyrazole, 3-amino-4-cyanopyrazole, 2 phenyl-3-amino-4-cyanopyrazole, 3-amino-5-(methyl, ethyl, phenyl or benzyl)pyrazole, 3-amino-l,2,4-triazole, 3-amino-5-(methyl, ethyl, phenyl or benzyl)-1,2,4triazole, 3-amino-I -phenyl-pyrazole, 3-aminopyridine, 3-aminoquinoline, 2-aminobenzthiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-(methoxy, ethoxy or butoxy)-benzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-thiocyanato-benzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-5,6-dichlorobenzthiazole, 2-amino6,7-dichlorobenzthiazole, 2-amino-4- and -6-methylsulfonylbenzthiazole, 2-amino3-nitro-5-methylsulfonylthiophen, 2-amino-3 ,5-bis-(methylsulfonyl)-thiophen, 2amino-3,5-dinitrothiophen, 2-amino-3-cyano-5-nitrothiophen, 2-amino-5-nitrothiophen, 5-amino-3-methyl-isothiazole and 3-amino-5-nitro-[2,3c]-thieno-iso- thiazole.

Examples of radicals R (other than

are alkyl of 1 to 5 carbon atoms, which is unsubstituted or substituted by chlorine, bromine, hydroxyl, cyano, alkoxy of 1 to 4 carbon atoms, phenoxy, alkanoyloxy of I to 8 carbon atoms, benzoyloxy or alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms), alkenyl of 3 to 5 carbon atoms, cyclohexyl, phenylalkyl (where alkyl is of I to 4 carbon atoms), phenyl, methoxyphenyl and ethoxyphenyl.

Specific examples are: methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, isopentyl, allyl, butenyl, cyclohexyl, phenyl, methoxyphenyl, ethoxyphenyl; benzyl, phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 2-phenoxyethyl, chloroethyl, bromoethyl, cyanoethyl, hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2-hydroxy-3chloropropyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3methoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-benzoyloxyethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, n-valeryloxyethyl, i-valeryloxyethyl, caproyloxyethyl, caprylyloxyethyl, benzoyloxyethyl, methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, butoxycarbonylethyl, methoxyethoxycarbonylethyl, isopropoxycarbonylethyl and isobutyryloxycarbonylethyl.

Specific examples of radicals R2, in addition to those already mentioned, are formylamino, acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino and butoxycarbonylamino.

Examples of radicals Al and A2 are -CH2CH2-, -CH2 C,H2CH3, -CH2,CHC2H5 and -C2H40C2H4-.

The radicals Y may be substituted, for example, by methyl, ethyl, methoxy, ethoxy, chlorine or bromine.

The dyes of the formula I can be manufactured by reacting a diazonium compound of an amine of the formula II D-NH2 II with a coupling component of the formula III

D, R, Rt, R2, A1, A2, X and Y having the above meanings. The diazotization and coupling exhibit no peculiar features compared to conventional processes.

The compounds of the formula III may be obtained from compounds of the formula

by reaction with compounds of the formula

The reaction is advantageously carried out in an aprotic solvent in the presence of a base, eg. pyridine.

Dyes of particular importance are those of the formula Ia

where R3 is alkyl of 1 to 4 carbon atoms, p-hydroxyethyl, ,B-hydroxypropyl, ,B- cyanoethyl, ,B-alkoxyethyl or,B-alkoxypropyl (where alkoxy is of I to 4 carbon atoms), phenoxyethyl, phenoxypropyl, p-alkanoyloxyethyl or P-alkanoyloxypropyl (where alkanoyloxy is of 2 to 4 carbon atoms), A-alkoxycarbonylethyl or p-alkoxy- carbonylpropyl (where alkoxy is of 1 to 4 carbon atoms), cyclohexyl, allyl, benzyl, phenylethyl or phenyl, R4 is hydrogen, methyl or methoxy, R5 is hydrogen, methyl, methoxy, chlorine, acetylamino or propionylamino, A3 is-CH2CH2-, -CH2 ÇHCH3 or-CH2 ÇHC2H5, A4 is -CH2CH2-, -CH2 CHCH3 or -C2H4 C2H4-, X is a direct bond or -0-and D has the above meaning Preferably, X is --OO-.

The radicals D are preferably derived from the benzene, thiophen, thiazole, thiadiazole, benzthiazole, benzisothiazole or azobenzene series.

Examples of preferred diazo components are those of the formula

where T' is hydrogen, chlorine, bromine, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl or alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms), T2 is nitro, cyano, hydrogen, chlorine, bromine, methylsulfonyl, ethylsulfonyl, phenylsulfonyl or phenylazo and T3 is hydrogen, chlorine, bromine, nitro or cyano, as well as 2-amino-5-nitrothiophen, 2-amino-3,5-dinitrothiophen, 2-amino-3-cyano-5-nitrothiophen, 2amino-3-nitro-5-methylsulfonylthiophen, 3-amino-5-chloro-2,1-benzisothiazole, 3amino-5-bromo-2,1-benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole, 3-amino5-nitro-7-chloro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-benzisothiazole, 4amino-7-nitro-1,2-benzisothiazole, 4-amino-5-chloro-7-nitro-1,2-benzisothiazole, 4amino-5-bromo-7-nitro-1,2-benzisothiazole, 4-amino-5-cyano-7-nitro-1,2-benzisothiazole, 2-amino-5-nitrothiazole, 2-amino-5-ethylmercapto-1,3,4-thiadiazole, 3phenyl-5-amino-1,2,4-thiadiazole, 3-ss-carbomethoxyethylmercapto-5-amino-1,2,4thiadiazole, 3-methylmercapto-5-amino- 1 2,4-thiadiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-thiocyanatobenzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-5,6-dichlorobenzthiazole, 2-amino-6,7-dichlorobenzthiazole or 2-amino-6-methylsulfonylbenzthiazole.

The dyes of formula I may be used for dyeing synthetic and cellulosic fibers, eg. cellulose acetate, nylons and especially polyesters. Dyeings having good fastness to light, to wet treatments and to thermofixation are obtained.

Some of the dyes are also suitable for the process described in British Patent 1,249,896.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1.

8.1 parts of 2-cyano-4-nitroaniline are dissolved in 50 parts of concentrated sulfuric acid and are diazotized with 16 parts of 45 NO strength nitrosylsulfuric acid at 0--5"C. After 5 hours, the excess nitrite is destroyed with urea and the solution is filtered. The diazo solution obtained is added dropwise at 05 C, to a solution of 16.5 parts of N-ethyl-N-(fi-phenoxyethoxycarbonyloxyethyl)-aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. The pH is brought to 2 by adding sodium acetate.After completion of coupling, the dye which has precipiated is filtered off, washed neutral and dried under reduced pressure at 60 C. 21 parts of the dye of the formula

are obtained; on polyester fibers the dye gives intense violet dyeings which are very fast.

EXAMPLE 2 7.2 parts of 2-amino-5-nitrothiazole are introduced into 20 parts of 96 per cent strength sulfuric acid at 10--150C, 100 parts of a mixture of glacial acetic acid and propionic acid (17:3) are added slowly at the same temperature, and diazotization is then carried out with 15 parts of 45% strength nitrosylsulfuric acid at 0--5"C. After 4 hours, the diazo solution obtained is added dropwise, at 0--50C, to a solution of 17.2 parts of N-ethyl-N-(ss-phenoxyethoxycarbonyloxyethyl)-m-toluidine in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. The pH is brought to 1.3 by adding sodium acetate.After completion of coupling, the dye which has precipitated is filtered off, washed neutral with water and dried under reduced pressure at 80 C. 15.5 parts of the dye of the formula

are obtained; on polyesters, the dye gives intense blue dyeings which are very fast.

EXAMPLE 3 9.8 parts of 3-amino-5-nitro-2,1-benzisothiazole are introduced into 50 parts of 85% strength sulfuric acid at 10--150C. 16 parts of 45% strength nitrosylsulfuric acid are added dropwise to this solution at 0-50C. The resulting diazo solution is stirred for a further 3 hours at 0--5"C and is then run into a solution of 16.5 parts of N-ethyl-N-(fi-phenoxyethoxycarbonyloxyethyl)-aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. The pH is brought to 1.5 by adding sodium acetate.After completion of coupling, the dye which has precipitated is filtered off, washed neutral with water and dried under reduced pressure at 50"C. 20.4 parts of the dye of the formula

EXAMPLE 4 10.4 parts of 2,6-dichloro-4-nitroaniline are dissolved in 50 parts of 85% strength sulfuric acid and are diazotized with 16 parts of 45% strength nitrosylsulfuric acid at 0--5"C. After 5 hours, the diazo solution obtained is run, at 05 C, into a solution of 16.5 parts of N-ethyl-N-(p-phenoxyethoxycarbonyloxyethyl)- aniline in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. The pH is brought to 1.0 by adding sodium acetate. After completion of coupling, the dye which has precipitated is filtered off, washed neutral with water and dried under reduced pressure at 700C. 21 parts of the dye of the formula

are obtained; on polyester fibers, the dye gives intense brown dyeings which are very fast.

EXAMPLE 5.

5.5 parts of 4-amino-5-cyano-7-nitro-l,2-benzisothiazole are introduced into a mixture of 50 parts of 85% strengh sulfuric acid and 15 parts by volume of a 17:3 mixture of glacial acetic acid and propionic acid, at 10 C. 9 parts of 45% strength nitrosylsulfuric acid are added dropwise at 0--50C and the mixture is then stirred for 4 hours at the same temperature. The excess nitrite is destroyed by adding urea and the diazo solution thus obtained is added dropwise, at 0--5"C, to a solution of 8.6 parts of N-ethyl-N-(fi-phenoxyethoxycarbonyloxyethyl)-m-toluidine in 15 parts of concentrated hydrochloric acid, 125 parts of water and 125 parts of ice. The pH is then brought to 1.3 by adding sodium acetate.After completion of coupling, the dye which has precipitated is filtered off, washed neutral and dried under reduced pressure at 600C. 10.2 parts of the dye of the formula

are obtained; on polyesters, the dye gives intense blue dyeing which are exceptionally fast.

EXAMPLE 6 12 parts of 2-bromo-4-nitro-6-cyanoaniline are dissolved in 80 parts of 85% strength sulfuric acid and are diazotized with 17 parts of 45% strength nitrosylsulfuric acid at 0--50C. After 5 hours, the excess nitrite is destroyed with urea and the mixture is filtered. The diazo solution thus obtained is added dropwise, at 0--50C, to a solution of 17.2 parts of N-ethyl-N-(p- phenoxyethoxycarbonyloxyethyl)-m-toluidine in 30 parts of concentrated hydrochloric acid, 250 parts of water and 250 parts of ice. The pH is brought to 1.5 by adding sodium acetate.After completion of coupling, the dye which has precipitated is filtered off, washed neutral and dried under reduced pressure at 50"C. 24.5 parts of the dye of the formula

are obtained; on polyester fibers, the dye gives intense violet dyeings which are very fast.

EXAMPLE 7 14.9 parts of the dye from Example 6, 5 parts of pyridine, 60 parts of dimethylformamide and 4.5 parts of copper-(I) cyanide are heated for 3 hours at 90--100"C. The solution, when cold, is poured into 500 parts of water, the mixture is filtered and the residue is introduced into a solution of 10 parts of iron-(III) chloride in 150 parts of 10% strength hydrochloric acid. After stirring overnight, the dye is filtered off, washed neutral and dried under reduced pressure at 500 C. 9.5 parts of the dye of the formula

are obtained; on polyester, the dye gives intense blue dyeings which are very fast.

Using the methods described above, the dyes identified in the Table below by specifying their substituents are obtained; on polyester fibers, they give dyeings of the stated hue. In the column headed by X in the Table the symbol "-" denotes a direct bond.

Ex- 2 am le D R R1 K2 A1 A X T Hue 0000W e > i s = r :1: h h Q Nll2 O2H5 H H O2H4 02H4002H4 0 oran cooc n o O 09 cu tl n m N UCU oA + c r t UCY m t Cl ea F 12 o2N N H H 'S N N red Yp g W W E: 13 OH3 m er m w w ;I N 0=D f4 V o N t N N a N 4 av ; E ax o ~ N m

s 4) &commat; ea : t o a :n o > o > e ç m ON K O2X'm(2 s o o o 02H4 02H4 o vriedodiietsh t CY 4cu c ~ ~ :cu w\ 17 N H H = F?cu u 602Cx3 NP; &num; O2H H H CH201H0H3 N W : Ol K O}(3O2972 &num; b H 14 IU W W N S e N N ew A; v v o e v A o o o S S v

0 g i :i h h r s s (4 P am 1 Cl 20 O2NNH2 CH2-OH-CR2 H + Cl X I1 02H5 H H N N O o trown 22 'S C2H4CC2H H CR3 N t N N 5 O ~ . cu r t r t r o 25 O2NmI2 t P; R W u R o u 26 II OH2 m tq X W X X I UE v ? t 0v q N tN Cd tu N p; O O O O O a S X E. N N X N e N

Ex dJ &commat; i n > am le D H s s s Br 27 O2NNR2 C 215 H H 0214 04 C brown FC o O O O O O Ol 28 zit 4 O o o 29 C2H H H .. 021400214 ~ 'S r 'S 0H2-CR-012 N CR3 'S t 2H4 O I Br > O2N1H2 0214000013 N H 0214 W M X B nre R w m S 32 'S 0215 N 013 'S 'S N W e xF 0 00 UE D st s F WN t8N %l N 14 O O O CZ O O % b R h h W ~~ O O O E N N N F

e w r Ex- o s K1 s t am le Br 33 O2NNH2 02H4004H9 H H 02H4 02H4 - violet ON Cl K I o o o O o o ON 35 'S 02H5 H OH3 'S N N 'S N J s s s g s s 0 No2 0 r i C2R4OC1OO2R40 002H5 N t t t t 4 U Ir\ ~ O O 50 t UIo "o Pi % tzt N 1 t: 3 < 0 0 &commat; o E W ' t s N N N h s t S oN N 0 & N a o o o Sj É > O as

ple D H RI H2 A1 A X Y Hue Cl o2NNl(2 O2R4ON 002R5 NHCCR3 02R4 O2R4 - navy blue NO2 0 0 41 C2R4CO&num;OO2H4 OCR 'S I' 'S - U 'S 3 a H : P s r Z X X | O O N MN J r 42 < 02H40O-OH3 CO 2R5 a ~ g N 'S 43 02N N2 02H5 H OR3 'S 'S 0 'S blue ~ > Ic\ P1K\ 44 II 0 4H9 X fi m t ON N ON NH tit N 2-2 oU p W gq g37 Q oN m N ti wJ N % N A; O O O O O O ~ N N N i O X E > R O c8Z 0t0 oZ A N O I J O ~ N v I gt E s

Ex- K K1 K2 A1 A2 X Y Hue am 1 ON o o ::C n = t t P t 46 | H O g C2H4 C2H4 O blue NO2 kip o ON O ~ ~ N t g t t 4 O ~ Ut 24 C 0=0 m 25 W 1SNR2 H K H 'S 02H4002H4 N 'S v m0 P: m o X eu Pt UE tUN V O O O O O eu Z; W 0N 0N n O O 1 X fiD F ) o 5

Ex lo a) GD a H H a t 2 Do ::1 g g H .n > Q t t t ? A2 x Hue n o o l 2H4 o red 2 CH3OC-O2H4S N rV4 cu t 25 t t + t 55 H 02R40H H m t t g N 56 O 02H5 H H M 'S N 'S bluish m % m wj (3 s r N N 1 O N tZ O ~ N Wfi = < O = ZR Pz x O O m5 r1 . N m t UO 80 tj E uo

D H H1 H2 A1 A2 x Hue am le o S t o Q t ~ 58 'S o I o o 'S red t+ Xe O t ~ 60 'S 02H5 H OK3 s 'S g N 'S o ON 61 oNNR2 'S K H 'S 'I 0 'S violet N s O O X X 4 . S t C: CV FW 0n 0 0 4 o o S

Ex ep se 4 3 s e k~ 9 62 O | O o o C2H4 0214 O blue CY plt CV t t 1 t + ~ ~ t g W s t r Lrjy O t OR2HCR3 'S O 'S 66 OR t W - 3 24 violet 67 '1 0215 X t UY t o ti N N S: I N tIt O O O O O N N N N N N A O O O 1. Q N > w > X g w w o W w

X &commat; i 2 D ~ 0 68 O2N%\3)NH2 O2H4OC11OO2K4 11 00113 02114 02114 - blue I I 0 0 0 69 0 2N '' NH2 C2H K 0113 'S 'S - 'S N 4 Ocu'U 70 02'QA%&num; ;?k 'S H H 'S CR20111 - N 'S NR2 0113 71 '1 0211400113 H 0113 'S 02114 1. '1 o td 00 oo 72 C2H4ON H NRp0H3 W O t N ~ ~ ~ eQ 73 .. 02114011 H NHChO2HS 'S 'S N N Q N 01 :N s t N N O O e: > O O N N FX= Oto N N N A O o o X É aa > > N tN

Ex- H K1 i2 A1 A2 X Hue am lb 0 i p h z t4 o o o o o o d PR r t ZU % s s t s oN g 2 76 'S C2R4OCH3 H H 'S 'S 0 'S I Br OCU I o cul bIC w o 3: t ca II w X 0214 o C6 red 79 II 'S 'S 'S 'S 'S -0- N red pott ? Ps t t N $ D t t ht E g JD t

Ex S &commat; ::s O ample o h D ,n 80 H5C6-NN-NH2 02 H H C2H4 02H4 S vC Cl X C6-NN -NE ' H , | o r red Cl CC 82 O2N--NN--M O2H40C6 H C2H4 02H4 - 06H5 blue tt V V X S X N V S3 02s$\2 C2 H C2H4 02H4 - 06H5 violet s '1 C2 H H 02H4 02H4 e C6H5 violet ". o'U Z" ZU 85 Br C2 ~ I . 2 X S ~ fE t mN X n > Xo 0N 0N 0N rsl O ~ N tt tn {t &commat;

Claims

WHAT WE CLAIM IS:

1. An azo dye of the general formula

where D is the radical of a diazo component, R is hydrogen or a substituted or unsubstituted aliphatic, cycloaliphatic, araliphatic or aromatic radical, R1 is hydrogen, methyl, ethyl, methoxy or ethoxy, R2 is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, alkanoylamino of I to 4 carbon atoms, benzoylamino or alkoxycarbonylamino, where alkoxy is of 1 to 4 carbon atoms, A1 and A2 independently of one another are alkylene of 2 to 4 carbon atoms, which may be interrupted by oxygen, X is a direct bond or -0- and Y is substituted or unsubstituted phenyl or naphthyl.

2. A compound as claimed in claim 1 in which R is an

radical where A', A2, X and Y have the meanings given in claim 1.

3. A compound as claimed in claim I or 2 of the formula

in which D is phenyl substituted by chlorine, bromine, cyano, nitro, C1 to C4 alkoxycarbonyl, methylsulfonyl, ethylsulfonyl, phenylazo, chlorophenylazo, nitrophenylazo, chloronitrophenylazo, methyl, methoxy or trifluoromethyl: 5-nitrothiazolyl; thiadiazolyl substituted by C1 to C4 alkylmercapto, A-(C1 to C4 alkoxycarbonyl)ethylmercapto or phenyl; benzthiazolyl substituted by chlorine, nitro, cyano, methylsulfonyl or ethylsulfonyl; benzisothiazolyl substituted by chlorine, bromine, nitro or cyano: or thienyl substituted by methyl, cyano, nitro, methylsulfonyl or C, to C4 alkoxycarbonyl; R is C1 to C4 alkyl;C2 or C3 alkyl substituted by chloro, hydroxy, C, to C4 alkoxy, phenoxy, cyano, C1 to C4 alkanoyloxy or C1 to C4 alkoxycarbonyl; allyl: cyclohexyl, benzyl; phenylethyl; phenyl; or

R2 is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, C1 to C4 alkanoylamino, benzoylamino or C, to C4 alkoxycarbonylamino, A1 and A2 are independently of one another C2 to C4 alkylene or -CH2CH20CH2CH2-, X is a direct bond or -0-and Y is phenyl; phenyl substituted by methyl, chlorine, methoxy or ethoxy: or naphthyl.

4. A compound as claimed in claim 3 in which D is phenyl substituted by chlorine, bromine, cyano, nitro, phenylazo, chlorophenylazo, chloronitrophenylazo, methyl or methoxy; 5-nitrothiazolyl; thiadiazolyl substituted by C1 to C4 alkylmercapto, ss-(C, to C4 alkoxycarbonyl)-ethyl-mercapto or phenyl; or benzisothiazolyl substituted by chlorine, bromine, nitro or cyano.

5. A compound as claimed in claim 3 or 4 in which R is C1 to C4 alkyl, ss- hydroxyethyl, ss-cyanoethyl, ss-C1 to C4 alkoxyethyl, phenoxyethyl or allyl.

6. A compound as claimed in claim 3, 4 or 5 in which R2 is hydrogen, chlorine, methyl, acetylamino or propionylamino.

7. A compound as claimed in any of claims 3 to 6 in which

A2 is -CH2Cll2- or -CH2ClI20CH2CH2-.

8. A compound as claimed in any of claims 3 to 7 in which Y is phenyl.

9. A compound as claimed in claim 3 of the formula

in which R is C1 to C4 alkyl, ss-cyanoethyl or ss-C1 to C4 alkoxyethyl, R2 is hydrogen, chlorine or methyl, A1 is -ClI2CH2- and X is a direct bond or -0-, and D has the meaning given in claim 3 or 4.

10. A dye as claimed in claim I and identified in any one of the foregoing specific Examples.

11. A process for the manufacture of an azo dye as claimed in claim 1 wherein a diazonium compound of an amine of the formula II D-NH2 II is reacted with a coupling component of the formula III

D, R, R1, R2, A1, A2, X and Y having the meanings given in claim 1.

12. A process as claimed in claim 10 carried out substantially as described in any one of the foregoing specific Examples.

13. A dye as claimed in claim 1 and whenever obtained by a process as claimed in claim 11 or 12.

14. A dye formulation for dyeing synthetic fibers wherein the dye constituent is a dye as claimed in any of claims 1 to 10 or 13.

15. A synthetic fiber dyed by a dye as claimed in any one of claims 1 to 10 or 13.

16. A polyester fiber dyed by a dye as claimed in any one of claims 1 to 10 or 13.