DE1218091B - Process for the production of water-insoluble or poorly water-soluble azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C09b

German class: 22a-l

1 218 091
F38639IVc / 22a
December 22nd, 1962
June 2, 1966

The present invention relates to a process for the preparation of sulfonic acid and carboxylic acid groups-free Azo dyes of the general formula

A-N = N-B-N

(CH ₂ ^ -OCD-CORi

Here, A denotes the radical of a carbocyclic or heterocyclic diazo component, B stands for an aromatic residue in which the azo and the

/ R

- N _v group

\ CHa) "

are in the p-position to one another, D denotes an aromatic-carbocyclic radical, R denotes hydrogen or an alkyl or acyl radical, Ri denotes an aliphatic radical and η denotes the number 2 or 3; the radicals A, B, D, R and Ri do not contain any sulfonic acid or carboxylic acid groups, but can otherwise have any nonionic substituents such as hydroxyl, alkoxy, halogen, cyano, acylamino, alkyl, nitro, trifluoroalkyl -, sulfofluoride, carboxylic acid ester, sulfone and sulfonamide groups.

The new azo dyes are prepared by adding a carbocyclic or heterocyclic diazo component with an azo component of the general formula

B-N

(CH ₂ ) _re - O - C - D - CORi

wherein B, D, R, Ri and η have the meaning given above, in the p-position to

Process for the production of water-insoluble or sparingly water-soluble azo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Hermann Wunderlich, Cologne-Mülheim

holding dyes that are sparingly soluble to insoluble in water are isolated in the customary manner.

Suitable diazo components are, for. E.g .: 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 4-chloro-3-nitroaniline, 2-cyano-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2 , 4-dinitro-6-chloroaniline, 2,4-dinitro - 6 - bromaniline, 2 - bromo - 4 - nitro - 6 - cyananiline, 4 - methylsulfonaniline, 2 - bromo -A- ethylsulfonaniline,

2 - bromine - 4 - ethyl sulfone - 6 - nitroaniline, 2 - methoxy

4 - nitroaniline, 4 - cyananiline, 3,4 - dicyananiline, 2-cyano-5-chloroaniline, 4-chloroaniline, 2,4-dichloroaniline, 4-amino-benzoic acid methyl ester, 5-amino-

3 - methylthiadiazole -1,2,4, 5 - amino - 3 -phenyl - thiadiazole-1,2,4, S-amino ^ -benzylmercapto-thiadiazole-1,2,4, 5 - amino - 3 - ethylsulfon - thiadiazole - 1,2,4,

5 - nitro - 2 - aminothiazole, 2 - amino - 6 - methylsulfonbenzothiazole-1,3.

The azo components to be used according to the method are, for. B. by reacting /? - Hydroxyäthylanilinderivaten with aromatic dicarboxylic acid esters, such as terephthalic acid and phthalic acid dimethyl ester, available. Suitable azo components are, for example

/ C ₂ H ₅

- N

(CH ₂ ) *

-Group

COCH ₃

couples and thereby chooses the starting components so that the final dye does not contain sulfonic acid and contains carboxylic acid groups.

The starting components are preferably acidic, aqueous or organic or organic-aqueous Medium coupled and the

609 577/394

/ C ₂ H ₄ - CN
CH ₂ CH ₂ -OCO

CH ₃
CH ₂ CH

CH ₃

/ CH ₃

OCH ₃

/ C ₂ H ₅

CH ₂ CH ₂ -OC

NHCOCH ₃

According to a modified procedure, the new azo dyes can also _{be COCH 3 io by reacting.} Azo dyes of the general formula

A-N = N-B-Nf

\ CH ₂ ) _re - OH

in which A, B, R and η have the meaning given, with the aliphatic diesters of aromatic dicarboxylic acids of the general formula

HO-C-D ^ COH

/ C ₂ H ₅

^ CH ₂ CH ₂ - O - C - /

OCH ₃

OCH ₃

where D has the above meaning, produce (transesterification).

The new dyes are ideal for dyeing and printing synthetic materials Fibers, in particular synthetic polyamide fibers, terephthalic acid polyglycol ester fibers and of Cellulose ester fibers including triacetyl cellulose, or woven and knitted fabrics made therefrom. Since the dyes are insoluble or only sparingly soluble in water, dyeing is expedient in the presence dispersing compounds carried out. To speed up the dyeing you can swelling agents are added to the dyebath; optionally can also at higher temperatures be stained in closed apparatus.

Compared to the disperse dye known from Example 1 of Belgian Patent 618,249 shows the dye of the formula obtainable according to the process

NC

N = N

/ C ₂ H ₅

CH2CH2OOC

COOCH ₃

CN

superior wet fastness properties of the dyeings on synthetic superpolyamide fabrics.

The parts given in the following examples are parts by weight.

example 1

2.7 parts of 5-amino-3-phenyl-thiadiazole-l, 2,4 are dissolved in 30 parts of 90% sulfuric acid and 4.6 parts of nitrosylsulfuric acid are added at 0 to 5 ° C. After the approach was still 5 hours this temperature was stirred, a solution of 4.75 parts of the transesterification product of N-ethyl-N-ß-hydroxyethylaniline with dimethyl terephthalate, which is the formula

/ C ₂ H ₅

CH ₂ CH ₂ OC

C-OCH ₃

owns, added in 20 ml of glacial acetic acid. The reaction mixture is then left for about 30 minutes stirred, then poured onto 100 parts of ice and blunted with saturated sodium acetate solution. Of the failed dye has the constitution

C ₆ H ₅

/ C ₂ H ₅ CHb-OC- /

If the dye is applied to polyamide fibers with the addition of dispersants according to customary methods when dyed, a clear, bluish red with very good fastness properties is obtained.

The azo component used as a starting compound was prepared in the following manner: In 165 parts of N-ethyl-N-ß-hydroxyäthylanilin, which was diluted with 100 parts of xylene, 1 part of sodium at 100 dissolved to 110 ⁰ C for about, and then at 130 ⁰ C 200 g of dimethyl terephthalate were added all at once. The methanol released is distilled off via a fractionation attachment. 30 parts of methanol are isolated. The reaction mixture is then heated to 200 ° C bath temperature at 0.1 mm. The residue that remains contains 250 parts of the specified coupling component. Yield: 76.5%.

Analysis:

Found ... saponification number 330,

C 69.64%, H 6.48%;
calculated ... saponification number 343, C 69.75%, H 6.42%.

For coupling with this azo component, use the ones listed in the following table Diazo components, valuable dyes are obtained, the polyester fibers in the specified Color shades.

Diazo component Hue of the Fär
exercises of receiving
ten dye
on terephthalic
acid ester fibers 2-cyano-5-chloroaniline orange 4-nitroaniline orange 2-chloro-4-nitroaniline Red 2-cyano-4-nitroaniline ruby 2-bromo-4-methylsulfonaniline .... orange 2,6-dichloro-4-nitroaniline orange 3-chloro-4-cyananiline orange 5-Amino-3-phenyl-thiazole-1,4 ... Red

Example 2

A diazo solution prepared by customary methods from 2.7 parts of 2-chloro-4-nitroaniline is combined with 5.15 parts of the transesterification product from N-butyl-N - ^ - hydroxyethylaniline and dimethyl phthalate in glacial acetic acid, 7 parts of a monoazo dye of the following constitution are obtained :

O ₂ N

The dye dyes polyester fibers from an aqueous dispersion in a red that is washable and sublimation-fast.

If the diazo components in the following table are used instead of the 2-chloro-4-nitroaniline, this also gives valuable azo dyes, the polyester fibers in the specified color shades to dye.

50

55

60

Claims (2)

Patent claims: 1. Process for the production of water-insoluble or sparingly water-soluble azo color Hue of the Fär exercises of receiving Diazo component ten dye on terephthalic acid ester fibers 2-cyano ~ 5-chloroaniline orange 4-nitroaniline orange 2-cyano-4-nitroaniline ruby 2-bromo-4-methylsulfonaniline .... orange 4-cyananiline yellow 3-chloro-4-cyananiline orange 5-Amino-3-phenyl-thiazole-1,4 ... Red 5-Amino-3-phenyl-thiadiazole-1,2,4 Red OCH ₃ substances, characterized in that one is a carbocyclic or heterocyclic Diazo component with an azo component of the general formula β — ν: ^ R ^s (CH ₂ ) _re - O - C - D - CORi
0 0 where B is an aromatic radical, D is an aromatic-carbocyclic radical, R is hydrogen or an alkyl or acyl radical, Ri is an aliphatic radical and η is the number 2 or 3, in the p-position to - N R.
(CHa) ₁₁ -Group couples and thereby selects the starting components in such a way that the final dye does not contain sulfonic acid and has carboxylic acid groups. 2. Process for the production of azo color substances of the type obtainable according to claim 1 • as a modification of the method according to claim 1, characterized in that an azo color substance of the general formula A-N = N-B-N - OH in which A is the radical of a carbocyclic or heterocyclic diazo component and B, R and η have the meaning given in claim 1, with an aliphatic diester ίο of an aromatic carboxylic acid of the formula HO-C-D-COH Il Il ⁰⁰ where D is the specified in claim 1 has meaning, with the formation of a dye of the general formula A-N = N-B-N ^X (CH ₂ ) »- O - C - D - CORi O O in which A, B, D, R, Ri and η have the meaning given above, is reacted and the starting components are selected in such a way that the final dye has no sulfonic acid or carboxylic acid groups. _____ Considered publications:
Belgian patent specification No. 618 249. When the application was announced, two coloring tables with explanations were laid out.