CH617955A5 - Process for preparing azo dyes - Google Patents

Description

617 955

PATENT CLAIMS 1. Process for the preparation of azo dyes of the formula

° 2NW

\ = y \

C0H ..ON x "2 q

N

CgH ^ CN

C ^ OCONHC ^ -n

®2 ^ ~ \ / "N = N-y * y-N 6. The method of claim 1 for the preparation of the dye

^ jF ^ XA-0-C0-NHZ {I) fixed formula

Y

in which mean:

A C2 to C4 alkylene,

X is hydrogen, chlorine or bromine,

Y is hydrogen or methyl and Z is C4 to C6 alkyl or C4 to C6 chloroalkyl,

characterized in that a diazotized amine of the formula

,, v C0Hi, CN

° 2n "^ 3" n = n "^^" nn

VC9H1, OCONHC4Hg-n

Cl

2 (1 The invention relates to the preparation of azo dyes of the formula

° 2N "^ - ^ ~ NH2

X

to a coupling component of the formula

(II)

^ C? HUCN - \ ^ A-OCONHZ

X Y

(I)

30th

/ c2ehcu

35

(III)

A-O-Q

wherein

A C2 to C4 alkylene,

X is hydrogen, chlorine or bromine Y is hydrogen or methyl and Z is C4 to C6 alkyl or C4 to C6 chloroalkyl. Preferred dyes are those of the formula I in which A = -C2H4- and X and Y = H.

The new azo dyes of the formula I are obtained by amines of the formula y "

o ^ h

(ii)

wherein

X has the meaning given above,

diazotized and with coupling components of the formula

50

CK

/ C2h4cn

55 /

A-O-Q

(m)

where Q is hydrogen or -C-NHZ, couples and,

II

O

if in formula III Q is hydrogen, the product obtained with a compound of the formula

O = C = N-Z or

Hal-C-NH-Z,

II

O

where shark means chlorine or bromine.

2. Process for the preparation of azo dyes of formula I, characterized in that a diazotized amine *

of the formula II couples to a coupling component of the formula III, in which Q for phenoxycarbonyl reacts the product obtained with an amine of the formula Z-NH2. 60 in which

3. The method according to claim 1 for the preparation of color Y and A have the abovementioned meaning and substances of the formula I in which A is -C2H4- and X andY is H Q for hydrogen, phenoxycarbonyl or -C-NH-Z. where II

4. The method according to claim 2 for the preparation of dye-Z has the meaning given above, O substances of the formula I in which A couples for -C2H4- and X and Y for H 65 and, in the event that Q denotes hydrogen, that are . Coupling product then with compounds of the formula

5. The method according to claim 1 for the preparation of the dye of the formula 0 = C = N-Z (IV)

617 955

or the formula

V-C-NH-Z II

O

(v)

wherein

V means chlorine or bromine,

and in the event that Q is phenoxycarbonyl, the coupling product with amines of the formula

Z-NH2

(VI)

^^ - NHCgH ^ CN y with compounds of the formula Cl-A-OCONHZ

(vii)

(VIII)

example 1

13.8 g of 4-nitraniline are dissolved in dilute hydrochloric acid at 0 to 5 ° C., then an aqueous solution of 7 g of NaNOz is added dropwise at 0 ° C. The mixture is stirred at 0 to 5 ° C. for an hour, excess nitrite is destroyed with a little amidosulfonic acid and a solution of 28.8 g of base of the formula is added dropwise to the diazonium salt solution thus obtained with stirring

/ c2h4cn. The coupling takes place smoothly in acidic, optionally buffered medium.

Suitable compounds of the formula IV are n-butyl isocyanate, n-pentyl isocyanate and n-hexyl isocyanate.

Suitable compounds of the formula V are n-pentylcarbamic acid chloride and n-hexylcarbamic acid chloride.

Suitable compounds of the formula VI are n-butylamine, n-pentylamine and n-hexylamine.

Finally, compounds of the formula III, where Q is CO-NH-Z, can be obtained by using anilines of the formula

CK

c2hijoconhclthg in dilute hydrochloric acid, neutralized with sodium hydroxide solution until the reaction is weakly acidic, sucks off the precipitated dye, washes neutral with water and dries the dye thus obtained.

211 Using suitable dispersants, finely divided, the dye dyes polyester fibers in clear orange tones with good fastness to sublimation when using the usual dyeing processes.

25 Example 2

35 g of the dye of the formula

02N <^ N-NÌX

C2H4GN

c2h4oh implemented in a manner known per se. The compounds of formula VII are known. Compounds of the formula VIII are also known or can be obtained by reacting Cl-A-OH with corresponding carbamic acid halides or isocyanates 4 (1.

The reaction of the coupling products, in which Q = H, with compounds IV is also carried out according to methods known per se in an inert solvent, if appropriate in the presence of acid-binding agents (cf. e.g. DP 45 1 810 063 = GB 1 241 705).

Suitable diazo components of the formula II are, for example: 4-nitroaniline, 2-chloro-4-nitroaniline and 2-bromo-4-nitroaniline.

The coupling components of the formula III with Q = H 50 are also known, for example:

N-ß-cyanoethyl-N-oxyethyl-aniline, N-ß-cyanoethyl-N-oxy-ethyl-m-toluidine, N-ß-cyanoethyl-N-oxybutylaniline, N-ß-cyanoethyl-N-oxybutyl- m-toluidine.

The dyes of the formula I obtained according to the invention are particularly suitable for dyeing synthetic hydrophobic fiber materials such as those made from aromatic polyesters, cellulose esters and superpolyamides by the dyeing processes customary for the respective fiber types.

The dyeings obtained are distinguished by clarity and 60 good general fastnesses, and the polyester dyeings are distinguished, for example, by good sublimation fastness.

55

are heated to about 50 to 100 ° C. in 100 g of chlorobenzene with stirring. 10 g of butyl isocyanate are added and stirring is continued for a further 1 / hour at this temperature. After cooling, a dye which is identical to the product obtained according to Example 1 crystallizes out.

If analogous starting materials are used and one of the processes described above is used, the valuable dyes listed in the following table are obtained which dye polyester fibers in the specified shades:

table

Dyes of the general formula I

No.

X

Y

Z

A

Color h

H

-c2h4-

n-C6H13

orange

Cl h

-c2h4-

ii-c4h9

reddish orange

Cl ch3

-c2h4-

II-c4h9

yellowish red cl

H

-c2h4-

II-c5h9

reddish orange

Br ch3

-c2h4-

II-c4h9

yellowish red h

ch3

-c2h4-

n-C4H9

orange h

H

-c2h4-

n-C6H12Cl orange

H

H

-c4h8

11-c4h9

orange

65