Process for the preparation of azo dyestuffs having an aniline-type coupler by aminolysis of the appropriate ether group-containing compounds

Abstract

An azo dyestuff of the formula ##STR1## wherein D=a diazo component,R.sub.1 and R.sub.2 =alkyl or aralkyl,R.sub.3 =H, R or OR.sub.1 andR.sub.4 =a hydrocarbon radical or acyl,which are prepared in a simple manner by aminolysis with ammonia or an amine of the formula ##STR2## of an azo compound of the formula ##STR3## these dyestuffs dye polyester fibres in blue-green to green shades with good fastness to light.

Description

The invention relates to a process for the preparation of non-ionic azo dyestuffs of the formula ##STR4## wherein D represents the radical of a diazo component which conains at least one non-ionic electron-withdrawing substituent,

R.sub.1 and R.sub.2 independently of one another denote hydrogen or an optionally substituted alkyl or aralkyl radical, or--together--denote an alkylene group, R.sub.3 denotes hydrogen, OR.sub.1 or R.sub.1 and R.sub.4 denotes hydrogen or an alkyl, aralkyl, aryl, hetaryl or acyl radical.

The compounds of the formula I are known in most cases and are useful disperse dyestuffs.

Suitable diazo components D are both aromatic and heteroaromatic radicals, in particular those of the benzene, naphthalene, thiophene, thiazole, thiazole, thiadaizole, benzothiazole, benzisothiazole and pyrazole series.

Suitable electron-withdrawing substituents are CF.sub.3, alkylsulphonyl, arylazo, acyl, CN and, above all, NO.sub.2.

Suitable acyl radicals are radicals of the formulae --COR.sub.1, --COOR.sub.1, --CONH.sub.2, --CONHR.sub.1, --CONR.sub.1 R.sub.2, --COH and --COR.sub.3, R.sub.3 denoting aryl or hetaryl.

Suitable alkyl radicals R.sub.1 /R.sub.2 are, for example, those with 1-6 C atoms which are optionally substituted by OH or C.sub.1 -C.sub.4 -alkoxy.

Suitable aryl radicals R.sub.1 -R.sub.3 and X, inter alia, are phenyl radicals, which can be substituted by CF.sub.3, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy.

Suitable aralkyl radicals are phenyl-C.sub.1 -C.sub.3 -alkyl radicals, which can be substituted in the phenyl radical as described above.

Suitable alkylene groups R.sub.1 +R.sub.2 are --(CH.sub.2).sub.n (n=4-5).

Suitable halogen atoms are F and, above all, Br and Cl.

The compounds I are usually obtained by a process in which amines of the formula D--NH.sub.2 are diazotized and the diazotization products are coupled with anilines of the formula ##STR5##

This process has the diasvantage, however, that the coupling components of the formula shown are frequently relatively difficult to obtain and/or the coupling itself does not proceed quantitatively, which results in low yields and an insufficient purity of the process products.

It has now been found that the compounds of the formula I are obtained in a more simple manner and in some cases in a better quality and yield by a process in which azo compounds of the formula ##STR6## wherein D, R.sub.3 and R.sub.4 have the abovementioned meaning and

R represents R.sub.1, are reacted with ammonia or amines of the formula ##STR7##

It must be regarded as decidedly surprising that this reaction proceeds so smoothly, since such exchange reactions usually only lead to satisfactory results if the --OR substituent in the para-position is very highly activated by nitro groups in the ortho-position (compare German Pat. No. A-2,528,866) or a quaternary diazo component D (compare German Pat. Nos. A-1,137,815 and 2,908,135), and is not--as in the present case--singly or doubly deactivated by the substituent --NHR.sub.4 and, where appropriate, with R.sub.3 .noteq.H.

It was also not to be excluded from the beginning that cleavage of the azo bridge takes place during aminolysis of the OR group (compare Chem. Abstr. 82, 124 931s (1975) and 89, 129 453s (1982)).

The process according to the invention can be carried out in water or organic solvents or in aqueous-organic media. The process is advantageously carried out with a stoichiometric excess of the amines III, which then at the same time assume the role of solvent. The aminolysis is in general carried out at 50.degree.-150.degree. C., preferably 80.degree.-120.degree. C., that is to say under relatively mild conditions.

The course of the reaction and the end of the reaction can easily be monitored or determined by thin layer chromatography.

Preferred azo compounds II which are to be employed are:

(1) Compounds of the formula ##STR8## wherein R.sub.4 denotes hydrogen or an alkyl, aralkyl, aryl, hetaryl or acyl radical,

R'.sub.1 denotes C.sub.1 -C.sub.4 -alkyl, R'.sub.2 denotes C.sub.1 -C.sub.4 -alkyl, Y.sub.1 denotes F, Cl, Br, I, CN or NO.sub.2 and Y.sub.2 denotes Y.sub.1 or CF.sub.3, SO.sub.2 R'.sub.1, CO.sub.2 R.sub.1, COR'.sub.1 or OR.sub.1,

(2) and those of the formula ##STR9## wherein D' denotes the radical of a heterocyclic diazo component of the type mentioned above, in particular those of the formulae ##STR10## wherein T.sub.1 =NO.sub.2, CN or COOR.sub.1,

T.sub.2 =H or CH.sub.3, T.sub.3 =NO.sub.2, CN, COOR.sub.1, COR.sub.1, COR.sub.3, SO.sub.2 R.sub.1, SO.sub.2 R.sub.3 or phenylazo, T.sub.2 +T.sub.3 =--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 -- or --CH.sub.2 CH.sub.2 CH.sub.2 --, T.sub.4 =H, CH.sub.3 or phenyl, T.sub.5 =NO.sub.2, COOR.sub.1, CN or phenylazo, T.sub.6 =Br, NO.sub.2 or CN, T.sub.7 =H, R.sub.1, R.sub.3 or SO.sub.2 R.sub.1 /R.sub.3, T.sub.8 =Cl, Br, CN, phenyl or SR.sub.1, T.sub.9 =Cl, Br, CF.sub.3, SO.sub.2 R.sub.1 /R.sub.3 or SR.sub.1, T.sub.10 =R.sub.1, R.sub.3, Cl, Br or COOR.sub.1, T.sub.11 =H or R.sub.1, T.sub.12 =NO.sub.2, CN, Cl, Br, COOR.sub.1 and T.sub.13 =H, CN or R.sub.1, and wherein R.sub.1 /R.sub.3 /R.sub.4 have the abovementioned meaning, it being possible for the rings labelled A and the phenylazo radical to be substituted by R.sub.1, Cl, Br, NO.sub.2, CN, COOR.sub.1, SCN or SO.sub.2 R.sub.1.

The compounds of the formulae II, IV and V are known only in an individual case (compare German Patent Specification Nos. 643,058 and 744,215 and U.S. Pat. No. 2,870,137), but are in all cases readily accessible by methods which are known per se.

Compounds of the stated formulae from the benzisothiazole series are especially preferred.

Examples which may be mentioned of compounds of the formula III are: methylamine, ethylamine, chloroethylamine, hydroxyethylamine, butylamine, hexylamine, isopropylamine, 3-methyl-butanamine, allylamine, stearylamine, diethylamine, dipropylamine, dibutylamine, 2-ethyl-hexylamine, ditridecylamine, N-ethylisoprylamine, N-methylisobutylamine, N-methylstearylamine, 2-ethoxyethylamine, diallylamine, di-2-methoxyethylamine, 3-ethylaminopropionitrile, N-ethyl-butylamine, 3-methoxypropylamine, 3-ethoxy-propylamine, 3-butoxypropylamine, 3-(2-ethoxyhexoxy)-propylamine, diethanolamine, isopropanolamine, diisopropanolamine, 2-(2-amino-ethoxy)ethanol, 2-propylaminoethanol, 2-butylaminoethanol, cyclopropane-amine, cyclohexane-amine, N-ethyl-cyclohexane-amine, benzylamine, 2-phenylethylamine, 2-methoxyphenylethylamine, 4-methoxyphenylethylamine, 3,4-dimethoxyphenylethylamine, 4-hydroxyphenylethylamine, 2-diethylaminoethylamine, 3-dimethylaminopropylamine, N-methyl-1,3-propanediamine, diethylenetriamine, aniline, 4-methoxyaniline, 3-chloroaniline, 4-dimethylamino-aniline, 3,4-dimethoxyaniline, p-toluidine, 3-amino-acetanilide, 1-aminonaphthalene, pyrrolidine, piperidine, piperazine, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, 4-methylpiperidine, morpholine, 2-aminomethyl-furan, hexamethyleneimine, imidazole, butyl 3-butylamino-propionate, dimethyl 2-butylamino-ethanephosphate, 3-butylaminopropionitrile, 2-methylaminoethanesulphonic acid, 3-aminopropionic acid and 3-amino-tetramethylene sulphone.

Possible solvents for the aminolysis are: water, amines employed in excess and alcohols, such as methanol, ethanol, propanol, isopropanol, n- or iso-butanol, glycol, glycol ethers, such as 2-methoxy-ethanol, 2-ethoxyethanol, 2-isopropoxy-ethanol, 2-butoxyethanol, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and propylene glycol monoethyl ether, dioxane, esters, such as methyl glycol acetate and propylene glycol monomethyl ether-acetate, amides, such as formamide, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone and tetramethylurea, nitriles, such as acetonitrile, 2-hydroxy-propionitrile and 2-methoxy-propionitrile, sulphones, such as dimethyl sulphone and tetramethylene sulphone, dimethylsulphoxide and (het)aromatic compounds, such as toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, pyridine, picoline or quinoline.

The solvents can also be employed as a mixture with one another.

In the examples which follow, "parts" denote parts by weight.

Dyestuffs of the formula ##STR11## wherein Z.sub.1 =C.sub.1 -C.sub.4 -alkyl,

Z.sub.2 =C.sub.1 -C.sub.4 -alkyl, Z.sub.3 =H, Z.sub.4, ##STR12## --SO.sub.2 --Z.sub.4 or ##STR13## and Z.sub.4 =C.sub.1 -C.sub.4 -alkyl, are new and therefore the invention likewise relates to them.

They dye polyester fibres in blue-green to green shades with good fastness to light.

Particularly preferred dyestuffs are those of the formula (IV) wherein:

Z.sub.1 =C.sub.1 -C.sub.2 -alkyl Z.sub.2 =CH.sub.3, C.sub.2 H.sub.5 or n--C.sub.4 H.sub.9 and Z.sub.3 =COCH.sub.3, and mixtures of these dyestuffs which differ in respect of the definition of Z.sub.2.

EXAMPLE 1

5.5 parts of the dyestuff of the formula ##STR14## (prepared according to German Reichspatent No. 744,215) are heated at 100.degree. C. in a mixture of 50 parts of dimethylformamide and 10 parts of pyridine with 5 parts of 2-methoxyethylamine for 75 minutes. After the mixture has cooled to 80.degree. C., 50 parts of methanol are added and the dyestuff formed, of the formula ##STR15## is filtered off, after cooling; yield: 5 parts. It dyes polyethylene terephthalate fibres in red-violet; shades and is characterized by a .lambda..sub.max value of 560 nm at a molar extinction .epsilon..sub..lambda.max of 40,800 [l/mol-cm], measured in dimethylformamide.

EXAMPLE 2

5.5 parts of the dyestuff of the formula ##STR16## (prepared by coupling diazotized 2-amino-5-nitro-benzonitrile to 3,4-dimethoxy-butyric acid anilide) are heated at 100.degree. C. in 50 parts of N-methylpyrrolidone with the addition of 3 parts of p-anisidine for 20 hours, with stirring. After addition of 50 parts of methanol, 6 parts of the dyestuff of the formula ##STR17## are isolated, after cooling. It dyes polyester fibres in reddish-tinged blue shades which are fast to light and sublimation. .lambda..sub.max : 600 nm; .epsilon..sub..lambda.max 45,415 (dimethylformamide).

EXAMPLE 3

6.8 parts of the dyestuff of the formula ##STR18## (prepared from diazotized 2-bromo-4,6-dinitro-aniline and 3,4-dimethoxy-acetanilide) are heated at 100.degree. C. in 50 parts of dimethylacetamide with 5 parts of ethyl-3,6,9-trioxadecylamine for 3 hours. After cooling, the dyestuff formed is precipitated with 100 parts of water. It probably has the following structure ##STR19## and dyes polyester in navy blue shades; .lambda..sub.max : 608 nm, .epsilon..sub..lambda.max : 34,420 (dimethylformamide).

EXAMPLE 4

67 parts of the dyestuff of the formula ##STR20## (prepared from diazotized 2,6-bromo-4-dinitro-aniline and N-[3,4-dimethoxyphenyl]-butanesulphonic acid amide) are warmed at 100.degree. C. in 80 parts of dimethylformamide with 14 parts of zinc cyanide, 2 parts of copper(I) cyanide and 30 parts of 4-ethoxy-aniline. After cooling and addition of 200 parts of methanol, 52 parts of the reaction product of the formula ##STR21## are isolated. The dyestuff dyes polyester fibres in greenish-tinged blue shades with good fastness to light and sublimation.

.lambda..sub.max 592 nm; .epsilon..sub..lambda.max : 66,900 (dimethylformamide).

The dyestuffs of the formula ##STR22## according to the following Table 1 are obtained in an analogous manner starting from corresponding azo compounds of the formula II (wherein R=CH.sub.3 or CH(CH.sub.3).sub.2):

TABLE 1 Example .lambda.max (nm) No. X.sub.1 X.sub.2 X.sub.3 X.sub.4 X.sub.5 R.sub.3 R.sub.1 R.sub.2 R.sub.4 Solvent Temp. (.degree.C.) in DMF 5 Cl H NO.sub.2 H H CH(CH.sub.3).sub.2 CH.sub.2CH.sub.2 CH.sub.2 CH.sub.2 COCH.sub.3 DMF/Pyridine 25 588 6 Cl H NO.sub.2 H H CH(CH.sub.3). sub.2 H (CH.sub.2).sub.3OCH.sub.3 COCH.sub.3 DMF/Pyridine 80 564 7 Cl H NO.sub.2 H H CH(CH.sub.3).sub.2 H C.sub.4 H.sub.9 COCH.sub.3 DMF/Pyridine 100 568 8 Br H NO.sub.2 H H OCH.sub.3 H C .sub.6 H.sub.11 COCH.sub.3 DMF/Pyridine 100 565 9 NO.sub.2 H NO.sub.2 H H OCH.sub.3 CH.sub.2CH.sub.2CH.sub.2CH.sub.2 COC.sub.2 H.sub.5 DMF 80 607 10 NO.sub.2 H NO.sub.2 H H OCH.sub.3 CH.sub.3 CH.sub.2C.sub.6 H.sub.5 COC.sub.2 H.sub.4OCH.sub.3 DMF 80 574 11 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2CH.sub.3 NMethylpyrrolidine 25 598 12 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.2 H.sub.5 C.sub.4 H.sub.9 SO.sub.2C.sub.4 H.sub.9 NMethylpyrrolidine 25 600 13 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2 C.sub.6 H.sub.5 NMethylpyrrolidine 25 582 14 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 ( CH.sub.2).sub.6 COC.sub.3 H.sub.7 NMethylpyrrolidine 25 618 15 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 CH.sub.3 C.sub.18 H.sub.37 COCH.sub.3 Dimethylacetamide 80 610 16 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.4 H.sub.9 C.sub.2 H.sub.4 P(OCH.sub.3).sub.2 COCH.sub.3 DMF/Pyridine 100 17 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.4 H.sub.9 C.sub.2 H.sub.4 COOC(CH.sub.3).sub.3 COCH.sub.3 DMF/Pyridine 100 18 NO.sub.2 H NO.sub.2 H Br OCH.sub.3 C.sub.4 H.sub.17 C.sub.8 H.sub.17 COC.sub.3 H.sub.7 DMF/Pyridine 80 618 19 CN H NO.sub.2 H H OCH.sub.3 H (CH.sub.2).sub.3 OC.sub.3 H.sub.7 COC.sub.2 H.sub.4 OC.sub.2 H.sub.5 DMF 80 590 20 CN H NO.sub.2 H H OCH.sub.3 (CH.sub.2).sub.6 COC.sub.2 H.sub.4 OC.sub.2 H.sub.5 DMF 80 602 21 CN H NO.sub.2 H Br OCH.sub.3 H C.sub.4 H.sub.9 COC.sub.2 H.sub.4 OCH.sub.3 DMF 25 628 22 CN H NO.sub.2 H Br OCH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 COC.sub.2 H.sub.4 OCH.sub.3 DMF 60 628 23 CN H NO.sub.2 H Br OCH.sub.3 H ##STR23## COC.sub.2 H.sub.4 OCH.sub.3 DMF 25 610 24 CN H NO.sub.2 H Br OCH.sub.3 H C.sub.2 H.sub.4 OCH.sub.3 COC.sub.2 H.sub.4 OCH.sub.3 DMF 60 618 25 CN H NO.sub.2 H Br OCH.sub.3 H ##STR24## COCH.sub.3 DMF/Pyridine 140 629 26 CN H NO.sub.2 H Br OCH.sub.3 (CH.sub.2).sub.6 COCH.sub.3 DMF/Pyridine 25 643 27 Br H NO.sub.2 H NO.sub.2 H CH.sub.3 C.sub.2 H.sub.5 COCH.sub.3 DMF/Pyridine 25 563 28 CN H NO.sub.2 H NO.sub.2 H C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3 H.sub.7 DMF/Pyridine 25 604 29 CN H NO.sub.2 H NO.sub.2 OCH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 COCH.sub.3 DMF/Pyridine 25 642 30 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4N(CH.sub.3).sub.2 (p) SO.sub.2C.sub.4 H.sub.9 DMF 40 616 31 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4NHCOCH.sub.3 (m) SO.sub.2C.sub.4 H.sub.9 DMF 60 584 32 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4Cl(p) SO.sub.2C.sub.4 H.sub.9 DMF 85 586 33 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.4CH.sub.3 (o) SO.sub.2C.sub.4 H.sub.9 DMF 85 576 34 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.10 H.sub.7 (.alpha.) SO.sub.2C.sub.4 H.sub.9 DMF 80 584 35 CN H NO.sub.2 H CN OCH.sub.3 H C.sub.6 H.sub.5 SO.sub.2C.sub.4 H.sub.9 DMF 60 584 36 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 SO.sub.2 CH.sub.3 DMF 45 636 37 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2 C.sub.6 H.sub.5 DMF 25 640 38 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2 H.sub.5 C.sub.4 H.sub.9 COC.sub.6 H.sub.4CH.sub.3(m) DMF 50 646 39 CN H NO.sub.2 H CN OCH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 COOC.sub.2 H.sub.5 NMethylpyrrolidone 25 640 40 CN H NO.sub.2 H CN OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3 H.sub.7 NMethylpyrrolidone 80 640

EXAMPLE 41 ##STR25## (prepared from diazotized 3-amino-5-nitro-benzisothiazole (2.1) N-(3,4-dimethoxyphenyl)-propionic acid amide) are heated at 80.degree. C. in 100 ml of dimethylformamide with 10 parts of N-ethyl-propylamine for 2 hours, with stirring. After addition of 200 ml of methanol and cooling, 10 parts of the dyestuff of the formula ##STR26## are isolated. It dyes polyester materials in bluish-tinged green shades with good fastness to light; .lambda..sub.max : 665 nm (dimethylformamide).

The dyestuffs of the formula ##STR27## listed in Table 2 were obtained from the dyestuffs ##STR28##

TABLE 2 Example Temp. in .lambda..sub.max (DMF) No. D R.sub.3 R.sub.1 R.sub.2 R.sub.4 Solvent (.degree.C.) in nm 42 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 COCH.sub.3 NMethylpyrrolidone 50 668 43 ##STR29## OCH.sub.3 CH.sub.3 C.sub.2 H.sub.4 OH COCH.sub.3 NMethylpyrrolidone 80 662 44 ##STR30## OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.7 COC.sub.3 H.sub.7 NMethylpyrrolidone 80 669 45 ##STR31## OCH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 COC.sub.3 H.sub.7 NMethylpyrrolidone 80 672 46 ##STR32## OCH.sub.3 CH.sub.3 C.sub.18 H.sub.37 COCH.sub.3 Dimethylformamide 80 666 47 ##STR33## OCH.sub.3 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH COCH.sub.3 Dimethylformamide 100 668 48 ##STR34## OCH.sub.3 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COCH.sub.3 Dimethylformamide 90 628 49 ##STR35## OCH.sub.3 (CH.sub.2).sub.4 OC.sub.2 H.sub.4 COCH.sub.3 Dimethylformamide 25 680 50 ##STR36## OCH.sub.3 H (CH.sub.2).sub.3N(CH.sub.3).sub.2 COCH.sub.3 Dimethylformami de 80 656 51 ##STR37## OCH.sub.3 H C.sub.2 H.sub.4 OCH.sub.3 COC.sub.2 H.sub.5 Dimethylformamide 70 649 52 ##STR38## OCH.sub.3 H C.sub.4 H.sub.9 COC.sub.2 H.sub.5 Dimethylsulphoxide 80 654 53 ##STR39## OCH.sub. 3 H (C.sub.2 H.sub.4 O).sub.4 CH.sub.3 COCH.sub.3 Dimethylformamide 80 652 54 ##STR40## OCH.sub.3 H C(CH.sub.3).sub.3 COCH.sub.3 Dimethylformamide 90 646 55 ##STR41## OCH.sub.3 H ##STR42## COCH.sub.3 Dimethylformamide 80 646 56 ##STR43## OCH.sub.3 H (CH.sub.2).sub.3OC.sub.4 H.sub.9 COCH.sub.3 Water 80 654 57 ##STR44## OCH.sub.3 H (CH.sub.2).sub.3OCH.sub.3 COCH.sub.3 Dimethylformamide 60 652 58 ##STR45## OCH.sub.3 H (CH.sub.2).sub.3OC.sub.2 H.sub.5 COCH.sub.3 Dimethylformamide 60 657 59 ##STR46## OCH.sub.3 H (CH.sub.2).sub.3OCH(CH.sub.3).sub.2 COCH.sub.3 Water 80 654 60 ##STR47## OCH(CH.sub.3).sub.2 H (CH.sub.2).sub.3 COOH COC.sub.2 H.sub.5 DMF 80 650 (i) 61 ##STR48## OCH(CH.sub.3).sub.2 H C.sub.2 H.sub.4SO.sub.3 H COC.sub.2 H.sub.5 NMethylpyrrolidone 80 668 62 ##STR49## OCH.sub.3 CH.sub.3 C.sub.2 H.sub.4SO.sub.3 H CONH.sub.2 DMF 80 63 ##STR50## OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.3 H.sub.7 SO.sub.2 C.sub.4 H.sub.9 Tetramethylenesulphone 80 764 (i) 64 ##STR51## OCH.sub.3 CH.sub.2CH.sub.2 CH.sub.2CH.sub.2 SO.sub.2 C.sub.6 H.sub.5 Tetramethylsulphone 60 758 65 ##STR52## OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 SO.sub.2 C.sub.4 H.sub.9 DMF 80 764 66 ##STR53## OCH(CH.sub.3).sub.2 (CH.sub.2).sub.4 COCH.sub.3 DMF 25 688 67 ##STR54## OCH(CH.sub.3).sub.2 CH.sub.3 C.sub.1 8H.sub.37 COCH.sub.3 Dimethylformamide 90 668 68 ##STR55## OCH(CH.sub.3).sub.2 H C.sub.16 H.sub.33 COC.sub.3 H.sub.7 Dimethylformamide 80 661 69 ##STR56## OCH(CH.sub.3).sub.2 H ##STR57## COC.sub.3 H.sub.7 Dimethylformamide 80 660 70 ##STR58## OCH.sub.3 H C.sub.6 H.sub.5 COCH.sub.3 Dimethylformamide 100 662 71 ##STR59## OCH.sub.3 H C.sub.6 H.sub.4OCH.sub.3 (p) COCH.sub.3 Dimethylformamide 110 674 72 ##STR60## OCH.sub.3 H C.sub.6 H.sub.3 (OCH.sub.3).sub.2 (3,4) COCH.sub.3 Dimethylformamide 110 680 73 ##STR61## OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COC.sub.2 H.sub.5 Dimethylformamide 50 74 ##STR62## OCH.sub.3 C2H.sub.5 C.sub.2 H.sub.5 SO.sub.2 C.sub.4 H.sub.9 Dimethylformamide 80 75 ##STR63## OCH.sub.3 C2H.sub.5 C.sub.2 H.sub.5 CONH.sub.2 Dimethylformamide 80 671 76 ##STR64## OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COC.sub.4 H.sub.9 NMethylpyrrolidone 80 625 (i) 77 ##STR65## OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COCH.sub.3 NMethylpyrrolidone 30 78 ##STR66## OCH.sub.3 C2H.sub.5 C.sub.3 H.sub.7 COCH.sub.3 Dimethylformamide 80 608 nm (i)

EXAMPLE 79

258.9 parts of the dyestuff of the formula ##STR67## (prepared according to German Reichspatent No. 744,215) are heated at 100.degree. C. in a solution of 22.9 parts of 3-methoxypropylamine, 26.5 parts of 3-ethoxypropylamine and 33.7 parts of n-butoxypropylamine in 600 parts of dimethylformamide for 75 minutes. After cooling to 80.degree. C., 50 parts of methanol are added and the dyestuff formed, of the formula ##STR68## is filtered off, after cooling. Yield: 215.3 parts.

The dyestuff is distinguished by a good affinity for polyethylene terephthalate fibres, which are dyed in a green colour shade.

Claims

1. A process for the preparation of a non-ionic azo dyestuff of the formula ##STR69## wherein D represents the radical of a diazo component which contains at least one non-ionic electron-withdrawing substituent selected from the group consisting of CF.sub.3, alkylsulphonyl, arylazo, acyl, CN and, NO.sub.2,

R.sub.1 and R.sub.2 independently of one another denote hydrogen, unsubstituted alkyl or alkyl substituted by HO or C.sub.1 -C.sub.4 -alkoxy, unsubstituted aralkyl or aralkyl substituted in the aryl portion by OF.sub.3, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, or R.sub.1 and R.sub.2 taken together denote a C.sub.4 -C.sub.5 -alkylene group,

R.sub.3 denotes hydrogen, OR.sub.1 or R.sub.1 and

R.sub.4 denotes hydrogen, alkyl, aralkyl, aryl, or acyl,

wherein an azo compound of the formula ##STR70## in which R represents R.sub.1 is reacted with ammonia or an amine of the formula ##STR71## wherein said reaction is carried out in water, an organic solvent or in aqueous-organic media at a temperature of from 50.degree.-150.degree. C.

2. A process according to claim 1, wherein a compound of the formula ##STR72## wherein R.sub.4 denotes hydrogen, alkyl, aralkyl, aryl, hetaryl or acyl,

R'.sub.1 denotes C.sub.1 -C.sub.4 -alkyl,

R'.sub.2 denotes C.sub.1 -C.sub.4 -alkyl,

Y.sub.1 denotes F, Cl, Br, I, CN, NO.sub.2 or OR'.sub.1 and

Y.sub.2 denotes Y.sub.1 or CF.sub.3, SO.sub.2 R'.sub.1, CO.sub.2 R.sub.1 or COR'.sub.1, is reacted with ammonia or the amine.

3. A process according to claim 1, wherein a compound of the formula ##STR73## wherein D' denotes a hetaryl of the formula ##STR74## wherein T.sub.1 =NO.sub.2, CN or COOR.sub.1,

T.sub.2 =H or CH.sub.3,

T.sub.3 =NO.sub.2, CN, COOR.sub.1, COR.sub.1, COR.sub.3, SO.sub.2 R.sub.1, SO.sub.2 R.sub.3 or phenylazo,

T.sub.2 +T.sub.3 =--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 -- or --CH.sub.2 CH.sub.2 CH.sub.2 --,

T.sub.4 =H, CH.sub.3 or phenyl,

T.sub.5 =NO.sub.2, COOR.sub.1, CN or phenylazo,

T.sub.6 =Br, NO.sub.2 or CN,

T.sub.7 =H, R.sub.1, R.sub.3 or SO.sub.2 R.sub.1 /R.sub.3,

T.sub.8 =Cl, Br, CN, phenyl or SR.sub.1,

T.sub.9 =Cl, Br, CF.sub.3, SO.sub.2 R.sub.1 /R.sub.3 or SR.sub.1,

T.sub.10 =R.sub.1, R.sub.3, Cl, Br or COOR.sub.1,

T.sub.11 =H or R.sub.1,

T.sub.12 =NO.sub.2, CN, Cl, Br, COOR.sub.1 and

T.sub.13 =H, CN or R.sub.1,

the rings labelled A and the phenyl-azo are unsubstituted or substituted by R.sub.1, Cl, Br, NO.sub.2, CN, COOR.sub.1, SCN or SO.sub.2 R.sub.1, is reacted with ammonia or the amine.

4. A process according to claim 1, wherein the reaction is carried out at 50.degree.-150.degree. C.

5. A dyestuffs of the formula ##STR75## wherein Z.sub.1 =C.sub.1 -C.sub.4 -alkyl,

Z.sub.2 =C.sub.1 -C.sub.4 -alkyl,

Z.sub.3 =H, Z.sub.4, --SO.sub.2 --Z.sub.4 or ##STR76## and Z.sub.4 =C.sub.1 -C.sub.4 -alkyl.

6. Dyestuff according to claim 5, wherein

Z.sub.1 =C.sub.1 -C.sub.2 -alkyl, and

Z.sub.2 =CH.sub.3, C.sub.2 H.sub.5 or n-C.sub.4 H.sub.9.