CH638549A5 - AZO CONNECTIONS. - Google Patents

Description

The invention relates to azo compounds of formula 65

wherein

R, C, 3-alkyl or phenyl optionally substituted by chlorine, bromine, methyl and / or C, 2-alkoxy,

R2 is hydrogen, chlorine, bromine, Q 2-alkyl or Q 2-alkoxy,

R3 is hydrogen, methyl or acylamino, R4 is optionally substituted by chlorine, bromine, methyl or phenyl, C3_.6-alkenyl or C3 6-alkynyl and

R5 hydrogen, C3 6-alkynyl, optionally substituted by chlorine, bromine, methyl or phenyl C3 6-alkenyl, optionally by chlorine, bromine, hydroxyl, cyano, rhodan, C, 3-alkoxy, formyloxy, Q 3-alkylcarbonyloxy, C, 3-alkoxy-carbonyl, Cj_3-alkoxy-carbonyloxy, chloro- or bromo-C, 3-alkylcarbonyloxy, benzoyloxy, phenyl, phenoxy, phenyl-Cj

2-alkoxy, C, _3-alkyl- or di- (C, 3-alkyl) -aminocarbonyl or -carbonyloxy, phenylamino-carbonyl or -carbonyloxy substituted C] 3-alkyl, C5_7-cycloalkyl, bearing 1,2 or 3 methyl groups Cyclohexyl or phenyl, which can carry chlorine, bromine, methyl or Q 2-alkoxy as substituents.

In each case independently of the other substituents in formula II are preferably R, C12-alkyl or phenyl, in particular methyl; R2 is hydrogen, methyl, chlorine or Ci_2-alkoxy, especially hydrogen or CI 2-alkoxy; R3 is hydrogen, methyl, C ^ alkylcarbonylamino, benzoylamino, C12 alkoxycarbonylamino, hydroxy, chlorine, bromine, C ^ alkoxy, phenyl, phenoxy or benzyloxycarbonylamino, C1_2-alkoxy-C1 .2-alkoxy-carbonylamino or C12-alkylsulfonylamino, in particular C, .2-alkyl-carbonylamino; R4 C3 4-alkynyl or optionally chlorine, bromine or methyl as substituent-bearing CM alkenyl, in particular allyl,

3-chloroallyl or 2-methylallyl and R5 are hydrogen, C34-alkynyl, optionally chlorine, bromine or methyl carrying C3 4-alkenyl or optionally by chlorine, bromine, hydroxyl, cyano, Q 2-alkylcarbonyloxy, CX2- CI 3-alkyl substituted by alkoxycarbonyl, Q 2-alkoxy-carbonyloxy, C12-alkoxy, phenyl or phenylaminocarbonyloxy, in particular allyl, 3-chloroallyl, 2-methylallyl, cyano-

3rd

638 549

ethyl, Ci -, - alkyl-carbonyloxyethyl or benzyl, especially ß-cyanoethyl.

The process for the preparation of the new compounds is characterized in that a diazotized amine of the formula III

with an amine of formula IV

H-K-A (IV)

13.9 parts of 5-amino-4-cyano-3-methyl-isothiazole are slowly added at 0-5 °, parts of concentrated sulfuric acid), 85 parts of glacial acetic acid and 15 parts of propionic acid. The mixture obtained is mixed at 0-5 ° with a mixture of 85 parts of 5 glacial acetic acid and 15 parts of propionic acid and then stirred at 0-5 ° for 3 hours.

A solution of 27.8 parts of 1-acetylamino-3- (N-2'-cyanoethyl) - (N-3'-chloroallyl) aminobenzene in 85 parts of glacial acetic acid and 15 parts of propionic acid is added dropwise and the mixture is stirred resulting coupling mixture for 3 hours at 0-5 °. The reaction mixture is then poured into a mixture of 600 parts of ice and 300 parts of water with stirring, the resulting dye precipitating. It is filtered off, washed free of acid and salt with water and dried. The dye of the formula thus obtained

15

couples.

The compounds of the formulas III and IV are known or can be easily prepared analogously to known processes. 20th

The processing of the new compounds of formula I into coloring preparations takes place in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the preparations which may have been dried in vacuo or by atomization, after adding more or less water, dyeing, padding or printing can be carried out in a so-called long or short liquor. The dyes are excellently absorbed from aqueous suspensions on textile material made from fully synthetic or semi-synthetic, hydrophobic, high-molecular organic substances. They are particularly suitable for dyeing or printing textile material made from linear, aromatic polyesters, as well as from cellulose 2 1/2 acetate, cellulose triacetate and synthetic polyamides. 35

You dye or print according to known, e.g.

the method described in French Patent No. 1,445,371.

The dyeings obtained have good general fastness properties; the lightfastness, the thermofi

40

xier, sublimation and pleating fastness.

In the following examples, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius.

45

example 1

To a mixture of 107 parts of nitrosylsulfuric acid (prepared by dissolving 7 parts of sodium nitrite in 100

H3C 1 If ™ CJ.CH

N \ s ^ -N = N- / O) -n / ^ 2 4

NHCOCH VV ^ CH2CH = CHC1 3

dyes synthetic fibers in red tones with excellent fastness properties.

Application example

7 parts of the dyestuff prepared according to Example 1 are ground with 4 parts of dinaphthylmethane disulfonic acid sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill for 48 hours to a fine powder.

1 part of the dye preparation thus obtained is pasted with a little water and the suspension obtained is added through a sieve to a dye bath containing 3 parts of sodium lauryl sulfate in 4000 parts of water. The fleet ratio is 1:40. 100 parts of cleaned polyester fiber material are then added to the bath at 40-50 °, 20 parts of a chlorinated benzene emulsified in water are added, the bath is slowly warmed to 100 ° and dyeing at 95-100 ° for 1-2 hours. The red colored fibers are washed, soaped, washed again and dried. The level dyeing has excellent fastness properties.

The following table shows further dyes of the formula I and the shade of their colorations on polyester fiber material.

table

E.g.

Nuance on poly

No.

ri r 2

r3

r4

r5

ester fiber material

1

-ch3

H

-NHCOCH3

-ch2ch = chci

-c2h4cn red

2nd

-c2h5

h do.

do.

do.

do.

3rd

ch3

H

-nhcoc2h5

do.

do.

do.

4th

-c6H5

H

-NHCOCH3

do.

do.

do.

5

do.

H

do.

-ch2ch = ch2

do.

do.

6

do.

h do.

-ch2c (ch3) = ch2

do.

do.

7

ch.,

H

do.

-ch2ch = ch2

do.

do.

8th

do.

h do.

-ch2c (ch3) = ch2

do.

do.

9

do.

H

do.

-ch2ch = chci

-ch-> ch = chc1

do.

10th

do.

h do.

ch2ch = ch,

-ch2ch = ch2

do.

11

do.

h do.

-ch2ce = CH

-c2h4cn do.

12

do.

h do.

-ch2ch = chci c2h4oconhc6h5

do.

13

do.

h do.

do.

-c2h4ococh3

do.

14

do.

h do.

do.

-coh4ocooCH3

do.

638 549

4th

(Continuation) table

Example No.

R,

R-.

Ri

R *

R <

Nuance on polyester fiber material

15

do.

h do.

do.

-c2h4oco2c2h5

do.

16

do.

h do.

do.

-c2h4co2c2h5

do.

17th

do.

h do.

do.

-c2h4c02ch3

do.

18th

do.

h do.

do.

-ch2c6h5

do.

19th

do.

H

-nhco2ch3

do.

-c2h4cn do.

20th

do.

H

-nhco2c2h5

do.

do.

do.

21st

do.

H

-NHCOQHJ

-ch2ch = chc1

-c2h4cn do.

22

do.

H

-ch3

do.

do.

do.

23

do.

h do.

do.

do.

Scarlet fever

24th

do.

h do.

-ch2ch = ch2

-ch2ch = ch2

red

25th

do.

h h

do.

do.

do.

26

do.

h h

-ch2ch = chc1

-ch2ch = chc1

do.

27th

do.

h h

do.

-c2h5

do.

28

do.

H

-ch3

do.

do.

do.

29

do.

H

-nhcoch3

do.

do.

violet

30th

do.

H

-nhco2c2h4och3

do.

-c2h4cn red

31

do.

H

-nhso2ch3

do.

do.

do.

32

do.

H

-nhcoc2h4ci do.

do.

do.

33

do.

H

-nhcoch3

do.

-c2h4scn do.

34

do.

h do.

-ch2ch = ch2

-c, h4oconhc6h5

do.

35

do.

h do.

-ch2 = ch

-c2h4co2c2h5

do.

36

do.

oc2h5

do.

do.

-c2h4cn purple

37

do.

do.

do.

-ch2ch = chc1

do.

do.

C.

Claims (3)

638 549 R, N- PATENT CLAIMS 1. The azo compounds of formula I CN N = N-K-A R " CN N = N - K - A (l). (I), where what Rj optionally substituted alkyl or phenyl, K represents the residue of a 1,4-phenylene radical which may carry further substituents and A is a secondary or tertiary amino group which contains at least one unsaturated aliphatic radical, the molecule bearing only those substituents which are customary in the chemistry of disperse dyes. 2. Azo compounds according to claim 1, formula II 15 / R4 (II), 20th R (optionally substituted alkyl or phenyl, K is the residue of a 1,4-phenylene radical which may carry further substituents A is a secondary or tertiary amino group which contains at least one unsaturated aliphatic radical, the molecule bearing only those substituents which are customary in the chemistry of disperse dyes. The unsaturated aliphatic radicals mentioned are to be understood as meaning alkenyl or alkynyl radicals which may carry substituents. The new compounds are excellent disperse dyes and are suitable as such for dyeing, pad dyeing or printing on fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances. Preferred azo compounds of the present invention correspond to formula II 30th 35 where 25 Ri C, 3-alkyl or phenyl optionally substituted by chlorine, bromine, methyl and / or C] _2-alkoxy, R2 is hydrogen, chlorine, bromine, C1-2-alkyl or Ci 2-alkoxy, R3 is hydrogen, methyl or acylamino, R4 C3 frAlkenyl or C3_6-alkynyl optionally substituted by chlorine, bromine, methyl or phenyl and R5 is hydrogen, C3 6-alkynyl, optionally by chlorine. Bromine, methyl or phenyl substituted C3_6-alkenyl, optionally by chlorine, bromine, hydroxyl, cyan, rhodan, Q 3-alkoxy, formyloxy, C1_3-alkylcarbonyloxy, Ci_3-alkoxy-carbonyl, C, _3-alkoxy-carbonyloxy, chloro- or Bromo-C 1-4 alkylcarbonyloxy, benzoyloxy, phenyl, phenoxy, phenyl-C, "2-alkoxy, Q 3-alkyl- or di- (Ci_3-alkyl) -amino-carbonyl or -carbonyloxy, phenylamino-carbonyl or -carbonyloxy 40 substituted C13-alkyl, C5 7-cycloalkyl, 1,2 or 3 methyl groups-bearing cyclohexyl or phenyl, which can carry chlorine, bromine, methyl or C12-alkoxy as substituents. 3. A process for the preparation of azo compounds of the formula I, characterized in that a diazotized amine of the formula III Egg || N> CN • N = N * 3 (II), 45 R_ CN • NH, (HI) with an amine of formula IV H-K-A couples. 50 55 (IV) 60