DE2452321A1 - BASIC COLORS - Google Patents

Description

BASF

Our reference: OZ 30 959 Bg / ah 67OO Ludwigshafen, November 4, 1974

Basic dyes

The invention relates to dyes of the formula I.

CH ο Χ-Ν - (/ 3- ^ν ^ "2'ηΛ * / A ^θ I,

ε5

E ¹

in the

η the numbers 1 or 2,

R optionally substituted alkyl or aralkyl,

2
R is hydrogen or optionally substituted alkyl or aralkyl,

R- ^ hydrogen, chlorine, bromine, methyl or methoxy, R hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or cyano,

R- ⁵ hydrogen, chlorine, methyl or methoxy,

4 ^
R and R ^ together form a fused-on benzene ring, X is a nitrogen atom or the methine group, Y is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, benzyl,

Methoxycarbonyl or ethoxycarbonyl and Α ^θ mean an anion.

1 2
In addition to hydrogen, radicals R and R are, for example, methyl, ethyl, benzyl, ß-hydroxyethyl or -propyl, ß-cyanoethyl or ß-hydroxy-7-chloropropyl.

To prepare the dyes of the formula I where X = CH, compounds of the formula II can be used

H, C CH ₅

CH-CHO II

ti

524/74 -2-

609819/1183

(KZ, 30 959

with compounds of the formula III

condense and optionally quaternize the reaction products with R = H and a diazo compound of amines can be used for X-N of the formula III with compounds of the formula IV

in which R is hydrogen or a radical R, couple and the reaction

Quaternize 5 ion products if necessary; n, R ~ to R and Y have the meanings given *

The reactions are known in principle and take place among comparable ones Conditions analogous. Details can be found in the examples.

Dyes of the formula Ia are of particular industrial importance

^H 3 ° ^0H 3

I a,

in the

7th
R 'methyl, ethyl, benzyl, ß-hydroxyethyl ^ ß-hydroxypropyl or ß-hydroxy-y-chloropropyl,

O.Z. 30 959 R hydrogen or a radical R ^ and 2452321

R are hydrogen, chlorine, methyl or cyano and n, X, Y and Α ^{θ have} the meanings given.

7 Q

Particularly preferred for R is methyl, for R ^ hydrogen and for Y hydrogen.

The new dyes are greenish yellow to orange and produce on anionically modified fibers, such as acrylonitrile polymers, Polyesters and polyamides have partly brilliant dyeings with very good fastness properties, especially light and decal fastness. the The color strength of the new dyes is high.

In the following examples, parts and percentages are based on weight.

example 1

coupling

19.9 parts of p-aminophenol benzyl ether are dissolved in 250 parts of water Suspended and 28.8 parts of 30 percent hydrochloric acid, then 50 parts of ice and 30 parts of a 23 percent within 30 minutes aqueous sodium nitrite solution at 0 to 5 ° C added. The reaction solution is stirred for 2 hours at 0 to 5 ° C, then excess nitrite is removed with sulfamic acid. the filtered diazonium salt solution is then in 30 minutes at 0 to 5 ° C to a solution of 17.4 parts of 1,313-trimethyl-2-methyleneindoline in 100 parts of water and 25.2 parts of 30 percent hydrochloric acid, then the pH is about 25 parts

acetate
Sodium / adjusted to 4 to 4.5. The coupling mixture is stirred for a further 12 hours, the temperature slowly rising to 20.degree. The precipitated coupling product is filtered off with suction, washed out with 600 parts of water and dried at 60.degree. Yield: 38 parts of coupling product.

-4-

609819/1183

O. Z. 30,959

38 parts of the coupling product are dissolved in 250 parts of chloroform and heated to reflux, then 4 parts Magnesium oxide and gradually 19 parts of dimethyl sulfate were added. The mixture is stirred at the same temperature for 10 hours, then the chloroform is distilled off with the simultaneous dropwise addition of 200 parts of 3 percent hydrochloric acid. After removing the Chloroform becomes 1500 parts of water and after heating to 95.degree 2 parts of activated charcoal are added and the mixture is then filtered. The dye is saturated by adding 400 parts of a Sodium chloride solution precipitated, filtered off with suction after the mixture has cooled, with 300 parts of a 3 percent sodium nitrite solution washed and dried at 60C. 39.4 parts of the dye of the formula are obtained in this way

Cl

CH-NH Jf

Example 2

21.2 parts of p-aminophenolphenyl ethyl ether are suspended in 250 parts of water and 28.8 parts of 30 percent strength hydrochloric acid, then 50 parts of ice and 30 parts of a 23 percent strength aqueous sodium nitrite solution are added over the course of one hour. The reaction solution is stirred for two hours at 0 to 5 ° C, then the excess nitrite is removed with sulfamic acid and the diazonium salt solution is filtered. In the course of 30 minutes at 0 to 5 ° C., the diazonium solution is then added to a solution of 17 * 4 parts of 1,3-trimethyl-2-methyleneindoline in 100 parts of water and 25 * 2 parts of 30 percent hydrochloric acid. The pH is adjusted _{to 4 to 4 a} 5 with approximately 25 parts of sodium acetate. After 12 hours of stirring, the temperature slowly rises to 20 ⁰ C, pH adjustment is sucked to 6 with sodium hydroxide solution, the precipitated product after the coupling, ■ washing overall with 700 parts of water and dried at 6O ⁰ C.
Yield: 38.5 parts of _β

S0981S / 11Ü

O.Z. 50 959

-S.

The 38 »5 parts of the coupling product are dissolved in 250 parts of chloroform dissolved, mixed with 4 parts of magnesium oxide and heated to boiling under reflux, after which 20 parts of dimethyl sulfate are added dropwise. The mixture is stirred at reflux temperature for 10 hours, the chloroform is then distilled off with the simultaneous dropwise addition of 250 parts of 5% hydrochloric acid. After removing 1200 parts of water of the chloroform are added, the mixture is heated to 95 ° C., and 2 parts of activated charcoal are added and filtered. After cooling to room temperature, the precipitated dye is suctioned off and 500 parts of a 5 percent Washed out NaCl solution. After drying at 60 ° C., one obtains 59.7 parts of the dye of the formula

^E 5 ° J ^H 3 OH ₃

OCH ₂ CH ₂ -Aj

Cl

The dyes listed in the following table are also obtained analogously:

-6-

609819/1186

Line 30 959

example

Dye hue

H ₂ C CH

/> - CH = N-N-AVy. OCH

Cl

golden yellow

S CH CH = NN- ^ VY. OCH ₂ - ^^ - Cl

₂ - ^

Cl

golden yellow

H, .C. CH ₂ _ "3 CH ₂

¹ I 0 ~ CH = NN- ^

Cl

yellow

CH

CH = N-K- ^ V- OCH

-U ^

CH,

Cl

golden yellow

Cl

HC CH ₃ ^

\ [ / V CH = NN -P \ - OCH ₉ ^ Ν _Λ ^{Χ = /}

CH,

Cl

golden yellow

OH, II /) - CH = N-N ^

CH

OCH ₉

Cl

golden yellow

-7-

609819/1186

example

dye

o.Z. 30 959

hue

HC CH

/> - CH = N-N - (/ V) -OCH - (/ \)

CH, Cl orange

10

OCh

-fö

C ₂ H ₅ Cl

CH ₂

ι 3,

. OCH

CH, -Py

Cl

golden yellow

yellow

12th

H ₂ C CH,

CH = N-N _ ^ j \ _ OCH

- ^

CH, Cl ^ö golden yellow

H.C

Cl ^Θ golden yellow

CH

? CH, Cl ^Ό golden yellow

-8th-

609819/1186

OZ 30 959

example

dye

hue

H, C CH

CH = N-N-A VN

OCH

₂ - // J

Cl

golden yellow

16

H ₃ COOC

CH = N-N

Cl

golden yellow

Example 17

31 parts of the coupling product from Example 2 are dissolved in 120 parts of glacial acetic acid. Ethylene oxide is gassed into this solution at 60 ° C. until complete conversion is determined by means of thin-layer chromatography (approx. 11 hours). The glacial acetic acid is partly distilled off under reduced pressure, the residue taken up in 500 parts of water, heated to 80 to 9O ⁰ C and concentrated with 300 parts sodium chloride solution, the dye is precipitated and then filtered with suction. After drying at 60 ° C., J> 6 parts of the dye of the formula are obtained

CJ ₂ H ₄ OH CH = NN _ // VS

.OCH ₂ CH ₂

Cl

-9-

60981 9/1186

Example l8

-ί

z. 30 959

2.5 parts of formic acid are added at room temperature to a solution of 10 parts of 1,3,5-trimethyl-2-methylenindoline-iJ-aldehyde, 11.7 parts of 4-aminophenol-4'-chlorobenzyl ether and 35 parts of isobutanol. The reaction solution is stirred for 30 minutes at room temperature, then 5 parts of conc. Sulfuric acid was added dropwise. After cooling to 5 to 10 ^° C., the dye is filtered off with suction, washed with 30 parts of cold isobutanol and dried ^{at 50 ° C.} This gives 24.1 parts of the dye of the formula

CH-CH-H - // \ yOC

HSO

Example 19

9.2 parts of formic acid are added to a solution of 40.2 parts of 1,3,3-trimethyl-2-methyleneindoline-6-aldehyde, 38.8 parts of p-aminophenol benzyl ether and 120 parts of methanol. After half an hour of stirring at room temperature, 24.2 parts of a 80prozentigen phosphoric acid are added dropwise at 20 to 30 ⁰ C and after cooling to 5 to 10 ⁰ C the precipitated dyestuff is filtered off. The residue is washed out with 100 parts of cold methanol and then dried at 50 to 60.degree.

94.7 parts of the dye of the formula are obtained in this way

H_C CH
5

fh CH = CH-N -V NV OC

^H 2 ^P0 4

Instead of 9.2 parts of formic acid, you can also use 12 parts of glacial acetic acid use.

-10-

609819/1186

O.ζ. 30 959

The dyes in the following table are obtained analogously:

example

dye

hue

20th

H ₂ C CH,

"CH,

\ V OCH ₂ - ^

greenish yellow

21

H ₂ C CH,

HSO,

greenish yellow

609819/1186

-11-

O.z. 30 959

example

Dye hue

22nd

H, C CH 'Ν'

CH = CH-N

OCH

₂ - ^ J greenish yellow

^J H CH = CH-N - ^ / \ V OCH,

CH,

₂ -Q H ₂ PO ₄ -

greenish yellow

24

H CH = CH-N - //

Cl

CE,

HSO.

greenish yellow

• 1 /> - CH = CH-N - // \

H ₂ PO ₄ -

greenish yellow

₁ II / V CH = CH-N

CH

HSO,

greenish yellow

28

H, C CH

^J HZ) -CH = CH-N - ^ / XV OCH _n - (/ \ N ^H 2 ^P0 4 ^eBlb

H _x C CH _x 5 vx ^

CH = CH-N- ^ S

ιθ

CH ₃

greenish yellow

-12-

609819/1186

ο.Ζ. 30 959

reliable

greenish yellow

H, C CH

H _n PO

greenish yellow

GH = CH-N

greenish yellow

Example 33

25 g of an acid-modified polyacrylonitrile fiber is added at 70 ⁰ C to a solution of 0.75 S 30prozentiger acetic acid, 0.38 g of sodium acetate and 0.125 g of dye of Example 1 in 1 1 water. The bath is ^{heated to 100 °} C. within 30 minutes and kept at this temperature for 30 to 60 minutes. After rinsing and drying, a golden yellow dyeing with very good fastness properties is obtained.

If the dye of Example 19 * is used, the fibers are dyed greenish yellow with very good fastness properties

-13-

Claims (3)

Claims 1. Basic dyes of the general formula in the η the numbers 1 or 2, R optionally substituted alkyl or aralkyl, ρ
R is hydrogen or optionally substituted alkyl or aralkyl, Ir is hydrogen, chlorine, bromine, methyl or methoxy, R is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or cyano, r5 hydrogen, chlorine, methyl or methoxy, 4 B
R and ~ Br together form a fused benzene ring, X a nitrogen atom or the methine group, Y hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, benzyl, Methoxycarbonyl or ethoxycarbonyl and Α ^θ mean an anion. 2. Dyestuffs according to Claim 1 of the formula Ia H ₅ C CH ₃ in the R 'methyl, ethyl, benzyl, ß-hydroxyethyl, ß-hydroxypropyl or ß-hydroxy-7-chloro-propyl,
Br is hydrogen or a radical R ^ and r "are hydrogen, chlorine, methyl or cyano and n, X, Y and Α ^{θ have} the meanings given. 3. A process for the preparation of dyes according to claim with X = CH, characterized in that compounds of the Formula II -14- 609819 / 118S oZ. 30 959 with compounds of the formula III _Ώ 3 condensed and the reaction products with R = H optionally quaternized _o A process for the preparation of dyestuffs according to claim 1 · Rait X = N ₅ wherein _B comprises reacting a diazo compound of an amine of the formula III with compounds of formula IV Kn GH. in which R is hydrogen or a radical R, couples and the reaction products optionally quaternized _o 5ο dye preparations for dyeing anionically modified fibers ^ containing, in addition to the usual ingredients, dyes according to claim l _o BASF Aktiengesellschaft I /