CH621812A5 - Process for the preparation of novel azo dyestuffs - Google Patents

Description

The present invention relates to a process for the preparation of new azo dyes of the formula

R

25 o2N- <^ -N = N-T y-N

NHAc "

30th

(II) 35

wherein

X has the meaning given above, diazotized and on anilines of the formula 40

(III)

NHAc where

50

Rj to R3 and Ac have the meaning given above, couples.

2. The method according to claim 1, characterized in that

that azo dyes of the formula I are prepared, in which

X is NO2, CN, Cl, Br or Q — C2 alkylsulfonyl, 55

Ac for formyl, Cj-Q-alkylcarbonyl; C1-C2 alkoxycarbonyl, Ci-C ^ alkylsulfonyl or benzoyl;

Rj for hydrogen, C1-C4-alkyl, C1-C4-alkoxy, phenoxy or Cl,

R2 for hydrogen, Ci-C6-alkyl; C2-C4-hydroxyalkyl, ß- 60 hydroxy-y-chloropropyl, C2-C4-chloroalkyl, cyanoethyl, Q-C2-alkylcarbonyloxy-C2-C4-alkyl, phenyl-Ci-C3-alkyl, Q-CV alkoxycarbonyl-C2- C4-alkyl or C1-C2-alkoxycarbonyloxy-C2-C4-alkyl and

R3 represents R2 or cyclohexyl or phenyl. 65

3. The method according to claim 1 for the preparation of azo dyes of the formula I in which X = CN, characterized in that azo dyes of the formula in which

X represents N02, CN, halogen or alkylsulfonyl,

Ac for acyl,

Rx represents hydrogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted cycloalkyl, aryloxy, aralkoxy, halogen, CN or alkoxycarbonyl,

R2 for hydrogen, optionally substituted alkyl and

R3 represents optionally substituted aralkyl, aryl or cycloalkyl or alkyl, hydroxyalkyl, halgoenalkyl, hydroxyhaloalkyl, cyanoalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, carboxyalkyl, carbamoylalkyl or carbamoyloxyalkyl.

The substituents of the hydrocarbon radicals mentioned above are common substituents in azochemistry.

The expression “acyl” should be understood in the broadest sense, that is, as the residue of an organic acid; suitable acyl radicals are: formyl, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, cycloalkylcarbonyl, aralkylcarbonyl, alkylsulfonyl, arylsulfonyl and optionally substituted carbonoyl and sulfonoyl radicals, e.g. -S02NR2R3, S02 (R2) 2, CONR2R3 and CON (R2) 2. Alkylcarbonyl radicals are preferred.

The alkyl or alkoxy radicals mentioned above in any context are preferably to be understood as those having 1-6 C atoms, which are preferably once by OH, CN, halogen, QQ-alkoxy, Q-Cs-alkylcarbonyloxy, Cj-C6-alkoxycarbonyl, CONH2, COOH, OCONH2 are substituted.

Cycloalkyl is preferably understood to mean cyclohexyl, which may be replaced by OH, CN, halogen, CONH2, COOH, alkoxy, Cj-Cg-alkylcarbonyloxy; Q-Cg-Alkoxycarbonyl is substituted.

Aryl is preferably taken to mean phenyl which is optionally substituted once by halogen, CN, alkoxy, C 1 -C 6 -alkylcarbonyloxy, Q-Cg-alkoxycarbonyl. Halogen, which is to be understood as preferably Cl or Br, can also occur 2 or 3 times. "Bulky" remains, such as tert-butyl are preferably in positions where they are

3rd

621 812

do not cause steric hindrance, e.g. in the p-position of a phenyl radical.

Among the new dyes, preference is given to those which correspond to the formula I in which

X is N02, CN, Cl, Br or Cj-Q-alkylsulfonyl, 5

Ac for formyl, Cj-C4 alkylcarbonyl; Q-Q-alkoxycarbonyl, Q-C2-alkylsulfonyl or benzoyl;

R] for hydrogen, Q-C4-alkyl, C1-C4-alkoxy, phenoxy or Cl,

R2 for hydrogen, Cj-Q-alkyl; C2-C4-hydroxyalkyl, β-10 hydroxy-y-chloropropyl, C2-C4-chloroalkyl, cyanoethyl, QQ-alkylcarbonyloxy-C2-C4-alkyl, phenyl-Cj-Q-alkyl, Cj-C2 ~ alkoxycarbonyl-C2-C4 -alkyl or C1-C2-alkoxycarbonyloxy-C2-C4-alkyl

R3 represents R2 or cyclohexyl or phenyl. 15

Among these, preferred dyes are those in which X is CN and preferably NOz.

Dyes of the formula I in which X is CN or — preferably — NO 2, are particularly preferred,

Ac for C1-C2-alkylcarbonyl, Q-Cj-alkoxycarbonyl or 20 C] -C2-alkylsulfonyl,

Rx for hydrogen, methyl, methoxy, ethoxy or chlorine, R2 for hydrogen, Ci-C4-alkyl, hydroxyethyl, ß-hydroxy-y-chloropropyl, cyanoethyl, C1-C2-alkoxycarbonyl-oxyethyl, benzyl or phenylethyl and 25

R3 is Q-Çj-alkyl, hydroxyethyl or Q-Q-alkoxy-carbonyloxyethyl.

The new dyes of the formula I are prepared according to the invention by using a-naphthylamines of the formula

30th

-NH,

II

35

wherein

X has the meaning given, diazotized and on anilines 4o of the formula

III

NHAc where 50

Rj-R3 and Ac have the meaning given, couples. The dyes of the formula I in which X = CN are preferably prepared by azo dyes of the formula

55

IV

Y represents halogen, preferably Br, and in which Ac and Rj-R3 have the meaning given, reacted with a metal cyanide.

This exchange reaction is known per se (see, for example, German Offenlegungsschrift 1 544 563 = British Patent 1 125 683 and takes place by means of metal cyanides, preferably CuCN or CuCN-forming compounds in polar aprotic solvents at temperatures of 60-120 ° C. dyes Formula I, in which X stands for alkylsulfonyl, could furthermore be obtained by exchanging the substituent Y for -S02CH3 or S02C2H5 in azo dyes of the formula IV, in which y stands for halogen or NO2.

This exchange reaction is also known in principle (cf. German Offenlegungsschrift 1 809 921, British Patent 1 255 367) and is preferably carried out with alkylsulfinic salts in organic solvents, such as e.g. Dimethylformamide, optionally with the addition of water and Cu (I) compounds at temperatures between 50 and 100 ° C.

The dyes IV used as starting materials are easily accessible in a known manner by diazotizing corresponding a-naphthylamines and combining them with corresponding coupling components.

The following aromatic amines may be mentioned as diazo components II:

2,4-dinitronaphthylamine-l, 2-chloro-4-nitronaphthylamine, 2-bromo-4-nitro-naphthylamine-1,2-cyano-4-nitro-naphthylamine-1,2-methylsulfonyl-4-nitronaphthylamine-l, 2- Ethylsulfonyl-4-nitronaphthylamine-1.

Suitable coupling components III are e.g. the following substituted anilines:

3-acetylamino-NN-diethylaniline, 3-acetylamino-NN-di-ethylaniline, 3-acetylamino-NN-dipropylaniline, 3-acetylamino-N-ethyl-N-propylaniline, 3-acetylamino-NN-dibutyl- aniline, 3-acetylamino-N- (ß-cyanoethyl) -N-ethyl-aniline, 3-acetylamino-N- (ß-cyanoethyl) -N- (ß-hydroxyethyl) aniline, 3-ace-tylamino- N-ethyl-N- (ß-hydroxy-ethyl-aniline, 3-acetylamino-NN-di- (ß-hydroxyethyl) aniline, 3-acetylamino-N-ethyl-N- (ß-carbomethoxyethyl) aniline, 3 -Acetylamino-NN-di- (ß-carbo-ethoxy-ethyl) -aniline, 3-benzoylamino-N-ethyl-N- (ß-ethoxy-ethyl) -aniline, 3-acetylamino-6-methoxy-NN-diethyl- aniline, 3- (methoxy-carbonyl-amino) -6-ethoxy-N-ethyl-N- (ß-cyano-ethyl) -aniline, 3-acetylamino-6-methoxy-NN-di (ß-acetoxy-ethyl) aniline, 3-acetylamino-N-ethyl-N- (ß-carboxyethyl) -ani-iine, 3-formylamino-N-ethyl-N- [ß- (ß'-carboxy-propionyloxy) ethyl] aniline, 3-ß-carboxypropionylamino) -NN-diethylaniline.

The new dyes are very strong in color and are suitable for dyeing fiber materials made from linear aromatic polyesters, such as polyethylene terephthalates and cellulose esters, such as cellulose triacetate, by the customary carrier process, but especially by the HT process. This gives violet to blue colorations with good fastness properties, in particular sublimation, wet and rub fastness. A particularly good drawing power can be achieved here by mixing the dyes of the formula I. The mixtures can be produced not only from the finished dyes, but also by coupling a diazo component onto a mixture of the coupling components.

example 1

Preparation of the dye of the formula

X X = 50% N (C2H5) 2 50% N (C3H7) 2

65

HNCOCH-

67.6 g of 2,4-dinitronaphthylamine-1 and 60 ml of nitrosylsulfuric acid (42%) are added in succession with stirring

621 812

4th

35-40 ° C slowly in 175 ml 93 percent. Sulfuric acid entered. The mixture is stirred for a further 2 hours at 35-40 ° C. To a solution or suspension of 10 g of urea, 46.6 g of 3-dipropylaminoacetanilide and 38.0 g of 3-diethylaminoacetanilide in 11 water, by adding 300 g Ice has been cooled to 5 ° C, the sulfuric acid diazotization is allowed to flow in slowly while cooling further ice. Here, by simultaneously adding 700 ml of 40%. Sodium hydroxide solution maintained a pH of 1.5-1.7. The mixture is allowed to warm to room temperature, suction filtered and washed with water. A dark powder is obtained which dyes polyester navy blue with good fastness to sublimation and rubbing.

10th

fer (I) cyanide was heated to 70 ° C for 30 minutes. After cooling to room temperature, it was precipitated with water, then suction filtered and washed with methanol. For decoupling, the dye was stirred overnight in a solution of 4.7 g of anhydrous iron (III) chloride in 20 ml of conc. Hydrochloric acid and 80 ml of water, then suctioned off and washed with water. The dye obtained dyes polyester dark blue.

Similar good results can be achieved if an appropriate amount of Zn (CN) 2 is used instead of CuCN in the presence of catalytic amounts of a Cu-I compound (CuCN, CuBr and the like).

Example 2 Preparation of the dye of the formula y

y -N = N- ^ y -N ^

/ C2H5

HNCOCH.

C2H5

15

20th

8 ml of nitrosylsulfuric acid (42%) was added dropwise at 0-5 ° C. to a suspension of 11.6 g of 2-bromo-4-nitro-naphthyl-amine-1 in 30 ml of propionic acid and 120 ml of glacial acetic acid. Stir for 5 hours at this temperature. The diazotization obtained was slowly at 0-5 ° C a solution of 12 g of diethylamino-acetanilide and 2 g of amidosulfonic acid in 300 ml of ice water and 2 ml of conc. Added sulfuric acid. It was dulled to pH = 3 with sodium acetate, the mixture was stirred for another hour and then the red-violet bromine dye was suctioned off.

14 g of 3-acetylamino-4- [2-bromo-4-nitro-naphthalene-1] azo-N.N-di-ethylaniline were suspended in 50 ml of dimethylformamide and 4 drops of pyridine. After adding 2.86 g of copper

30th

35

Example 3 Preparation of the dye of the formula

SO_CH-

9 g of 3-acetylamino-4- [2,4-dinitronaphthalene-1] -azo-N.N-diethyl-anüin were dissolved in 200 ml of dimethylformamide and 1 ml of pyridine. After adding 22.5 g of sodium methyl sulfinate and 2 g of copper (I) bromide, the mixture was heated to 50 ° C. for 30 minutes. After cooling to room temperature, it was precipitated with water, suction filtered and washed with methanol. The dye obtained dyes polyester violet.

The dyes listed in the table below can be obtained by similar processes.

Example No.

dye

Nuance blue

(CH2CH20C02CH3) 2

blue blue

Example No.

dye

nuance

N (CH2CH2OH)

NHCOCH.

blue

NO,

OCH.

o2n

2 y

- // NN-n = N- ^

n (c2 h5) 2

blue

\\ ff

NHCOCH.

NO,

02n

. «/ Ì.

-N (CH2CH2OCOCH3) 2

NHCOCH.

blue

10th

fHC02C2H5 CH2CH2OH

blue

11

NO,

CH.

.-T \

O2n-f v-N = N- / ~ ^ -N ^ 2

v /

NHCOCH3 C2H5

blue

12

CH, -CH-CH,

Z, | £.

OH Cl blue

13

CN

och

o2n

/ ~ N = N- ^ / ~ N ^ \ /) NHCOCH

H

0

blue

621 812

Example No.

dye

nuance

14

no,

o2n-

c4h9 "n

-n

CAE0 ~ n hncoch 4 9

blue

15

NHCOCH 3 ^ H2-CH2-C02H

blue

16

n = n-

// / C2H5

—TCt-v x \ -m ^ ^ D

n blue nhcoch.

ch "ch" -ococh_ch "c0 ^ h

/ z z / z.

17th

no nhcoch = ch- co2 ^

blue

C.

Claims (3)

621812 2nd PATENT CLAIMS 1. Process for the preparation of new azo dyes of the formula R. R, 0 «N ~ v \> - N = N - // M-N ' 5 2 X ~ / "X - / - NHAc (IV) // (I) NHAc where X represents N02, CN, halogen or alkylsulfonyl, Ac for acyl, Rj represents hydrogen, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted cycloalkyl, aryloxy, aralkoxy, halogen, CN or alkoxycarbonyl, R2 for hydrogen, optionally substituted alkyl and R3 represents optionally substituted aralkyl, aryl or cycloalkyl or alkyl, hydroxyalkyl, haloalkyl, hydroxyhaloalkyl, cyanoalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylalkyl, carboxyalkyl, carbamoylalkyl or carbamoyloxyalkyl, characterized in that a-naphthylamines of the formula io wherein Y stands for halogen and Ac and R! to R3 have the meaning given in claim 1, with a metal cyanide. 4. The method according to claim 3, characterized in that Y is bromine.