DE1444644C - Process for the production of water-insoluble monoazo dyes ^ their use for inks and printing as well as water-insoluble monoazo dyes - Google Patents

Description

Subject of the present invention 1-.1 the Production of sulfonic acid and carbon:> free from acid groups water-insoluble monoazo dyes of the formula

R-N = N- - (Uli

NHCOClI, - R ₁

wherein R is an optionally substituted phenyl radical. Y hydrogen. Alkyl or alkoxy. R, OH or CN. R, hydrogen, alkyl, acyloxyalkyl or carb- tlkoxyalkyl and R _{3 is} hydrogen or alkyl, including the preparation of the dyes of the general formula obtained according to German patents 1,232,292 and 1,260,654

CH ₂ CHXOOK ₁

R · --N = N-- ';'

■ ^; ν

(IV)

NHCOCH ₁ -R,

(Il

- NH ₂

wherein R is an optionally substituted phenyl radical means with an arylamine of the general I ormel

R.

NHCOCH ₂ R ₁

wherein Y, R ₁ , R ₁ and R _{3 have} the abovementioned meaning , couples in the p-position to the amino group.

The starting component is coupled in the usual way, preferably in an acidic solution or suspension. AU diazo components prove to be particularly advantageous which contain at least one cyano group. Suitable diazo components include 4-nitro-2-chloroaniline. 4-nitro-2 - cyananiline, 2,4 - dicyananiline, 3 - chloro - 4 - cyananiline. 2 · cyano - 5 · chloroaniline. 3,4 - dicyananiline. 2.5 · dicyananiline, 2,6-dichloro-4-nitroaniline, 2-chloro-4-cyananiline, 4-aminophenylmethylsulfone, 4-aminotcetophenone, 2 - amino - 5 - nitrotoluene. 2 - amino-5-nitranieol. 3-nitro-4-aminotulol, 2.5-dichloro-4-nitroaniline, 3-chloro-4-aminobenzo-trifluoride. 2-i van-4.5.6-trtchlorajiilin, 2-cyano-6-bromo-4-nitrani- Hn. 2,4-dicyano-6-chloroaniline. Methyl 2-amino-5-nitrobenzoate, methyl 4-aminobenzoate.

As a coupling component, for. B. the amines of the following constitution are used:

- N (C ₂ H,),
NHCOCH ₂ OH

wherein R 'represents the residue of a 2,4-dinitro-6-halogenobenzene- 1 or a 1-cyano ^ nitro-o-halogenobenzene-1. R ₄ is alkyl and R, the above mentioned Be significance and X is hydrogen or door alkoxy, sov / ie their use Ziirn dyeing and printing hydrophobic fiber materials, in particular fiber materials of aromatic polyesters such as Polyäthylenglykolterephthalaten.

The dyes of the formula (III) according to the invention are obtained when the diazo bond of an amine of the formula

40 NHCOCH ₂ OIl
OCH.,

-NHC ₂ H ₄ COOCH.,

NHCOCIKOH

C ₂ H ₅
-NC ₂ H ₄ OCOCH,

NHCOCH ₂ CN

OCH.,

- N

C ₃ H,

C ₂ H ₄ COOCH.,
NHCOCH ₂ OH

The invention also relates to * asscrunlö> Liche monoazo dyes of the general formula

RN N

(purple)

NHCOCH,

R,

wherein R is optionally substituted by CN. NO ₂ . Cl. Br. CH ₃ . CF.,. OCHj, SO ₂ CH ₃ . COCHj and or COOCH, denotes substituted phenyl radical and Y denotes hydrogen or methoxy. R, for OH or (N. R ₂ for hydrogen, alkyl with 1 to 3 carbon atoms, acetoxyethyi or methoxycarbonylethyl and Rj for hydrogen or alkyl with 1 to 3 carbon atoms, with the exception of those prepared according to German patents 1,232,292 and 1,260,654 Dyes of the general formula IV given above.

Azo dyes consisting of any benzene diazo component and a 3-acylaminoaniline coupling component are generally known (see, for example, German patent I 108 355, USA patents 2 155 755 and 2 261 175 and German Auslegeschrift I 069 313) .

Compared to the closest comparable known dyes of the German Auslegeschrift I 069 313 show the dyes of the formula I according to the invention better frberic properties.

For example, the I-ormel dye, which is available at an increased price, stands out

_._ C ₄ H,

O ₁ N -; . ~ -N = -N— '- ■ N

^ CH ₁ CH ₁ OCOCH.,

CN I

NHCOCH ₂ OH

compared to the dye of the form described in Example 50 of the German Auslegeschrift cited above

O ₂ N- ·· "> -N = N- f VN

I ' ^{i =} "^ CH ₁ CH ₁ OCOCHj

cn!

NHCOCH.,
through better fastness to sublimation on polyethylene terephthalate fabrics.

example 1

14.3 parts by weight of 2,4-dicyanobenzene are poured onto about 3000 parts by weight of ice in 3 hours.

400 parts by weight of concentrated sulfuric acid at 25.

Dissolved 0 to 15 C and removed with 170 parts by volume of nitro acid and the solution was filtered. This solution

sylsulfuric acid (42 g of nitrite in 100 ml of H ₂ SO ₄ ) is then added to a solution of 27 parts by weight

good stirring and cooling and diazotized after about the amino compound of the formula

, ζ C, H,

\ _V ^N

P "'V ₂ H ₁ COOCH ₃

NHCOCH ₂ OH

combined, partially new with dilute caustic soda, additives finely distributed, in clear red tralisicrt and coupling with sodium acetate to give shades of good washfastness and lightfastness.
found led. The dye is filtered and the corresponding washings can be made in the same way. In the dry state, it forms a black powder, the starting components the following color red powder, which dissolves in organic solvents, substances that dissolve the fabric from aromatic polywic acetone or alcohol with a red color. Acetate esters, such as polyethylene terephthalates. or polyamide silk and polyamide fabric dyes it. color by suitable colors in the specified shades:

Bluish red

Cl --N = N - '' ',; - N ζ ». O ₂ N - ' '/ " NHCOCH ₂ Cl N --- N ■ X '
VN ₂ H ₄ COOCH, NC / ^c JH ₄ CO (KH, ^X C
OH

Red H ₄ CO (KH,

NHC (XH ₂ OH

O ₂ N - <ζ ~ \ - N = N-- ^Y '' ■ / - N (C ₃ H ₇ I ₂ blue

CN NHC (XHjOFI

CH ₃ OOC- / VN = NV V-NHC ₂ H ₄ COOCH ₃ Orunge

NHCOCH ₂ OH

I 444

(Jl.

(ι, Ν

N N

NIK () (H, (N

Cl

HlaiMicliiui > i

("ι, Ν

CN

NNN (C ₁ HI,

NIICOCH.ι ill UIa Li

I .it hliMi ikf I .1!

.ml Sup. ι po | \ .iMiii

NC

Cl
Cl

N - N NiC.II. ι,

NIICOCH. OH RoI

NN ■ NIC ₁ II-N

CN NIICOCH, Oil

NC - ', - N - N N (C. IL I,

CN NHCOCiI, Oil

R.H

Claims (3)

Patent claims: I. Process / to manufacture water-insoluble! Monoazo dyes. d a d u r c h ge k e η π / e i c hncl. that one is the dia / overbonding of an amine of the formula Nile, where K is an optionally substituted phenyl radical means with an arylamine dei general formula K. N- NIK OCIi, R, where Y is hydrogen. Alkyl or alkoxy. R ₁ for OH or CN. R ₂ for water ice lollipop. Alkyl. Are Acjloxyalkyl iriei (arboalkoxyalk \ I and R, fiii hydrogen odci Alk> I, / coupled in a p-in Stelhmg amino group while the Aiispingskomponcntcn selects home, son Sullonsiiure- to \ (aibonsäuregriippen, wherein the lleislelhmg (lei ιΐίκ-Ιι the German l'alenlschiilun I ? i ?.? ') 2 and I 2i) () iiS4 eihallenen l'aibslofle dii alli'i my ormel R'N CILCH-COOR ₄ mn NHCOCH, R, worm R 'represents the residue of a 2.-M) inilic.-.'-- halogenben / ol-1 or a Z-Cyan - ^ - nilio-d-lialogenlien- / ol-l. R _{4 represents} alkyl and U has the meaning given above! and X fiii W'asseist () ff or alkoxy is excluded. 2. Water-insoluble monoa / olai bstolle of general formula RN R ₁ NIIC (X w οι in R a possibly dme h (N. NO ,. (I. Hi 'II, - Cl.,. O (Ii _1. S () _; CH ,. COCH, lmdodei ((' () (H, substiluieiten l'hcns reads means and> Nil Waseisloll odei Metlioxy. R ₁ Im Oll odci (\ R, fiii Wasseislofl. Alkyl with I Ins 1 Kolilenstojl sli'iiieii. Nei'liiw.illnl οι!. · ι M ₁ ilmuri'lm nyläthyl and R, stand for hydrogen or alkyl with 1 to 3 carbon atoms, except the dyes prepared according to the German patents 1,232,292 and 1,260,654 of the present Claim I given general formula III. 3. Use of dyes according to claim I for dyeing and printing hydrophobic fiber materials.