DE1770782C3 - Process for the production of basic dyes - Google Patents

Description

C = CH-N = N-A

in which R, R ₁ and A have the meaning given, on the azo nitrogen connected to the radical A with quaternizing agents in the presence of alkaline agents, characterized in that the alkaline agent used is 5-50 mol%, based on the color base to be quaternized, tertiary amines added to the nitrogen atom by two radicals of the formula

K ₄

R ₃

R ₅

R ₃

R ₄ -C- (CH ₂ L

N-CH ₂ -CH-CH ₂
OH

where R is the remainder of an indoline ring, R _{1 is} an alkyl, cycloalkyl, aralkyJ or aryl radical, R _{2 is} an alkyl, cycloalkyl or aralkyl radical, A is an aromatic radical and X is an anion, by quaternizing color bases general formula

25th

where η is an integer from 1 to 5, carry, and where a radical

R ₄ -C- (CH ₂ L-

and the third substituent on nitrogen also common form a piperidine, morpholine or piperazine ring with the nitrogen atom (s) be able.

2. The method according to claim 1, characterized in that the tertiary amine is triisopropanolamine clogs.

3 ° A process for the preparation of basic dyes of the general formula (I) is known from French patent specification 12 14 896

35

40

C = CH-N = N-A

X ^e

45

where m = 0 or 1, where in the case of m = 1 R _{3 is} an alkyl radical, R _{4 is} an alkyl radical or a hydroxyl group and R _{5 is} hydrogen or an alkyl radical, where in the case of m = 0 R ₃ and R ₄ stand for alkyl radicals and R ₅ stands for hydrogen, and where R ₃ and R _{4 can} also be components of a cyclopentyl or cyclohexyl ring system, when R _{5 stands} for hydrogen, are substituted and as the third substituent on nitrogen is a QQ-alkyl radical, a / f-Hydroxypropyl radical or a radical of the formulas in which R is the remaining component of a 5- or 6-membered heterocyclic ring, R _{1 is} an alkyl, cycloalkyl, aralkyl or aryl radical, R _{2 is} an alkyl, cycloalkyl or aralkyl radical, A is aromatic or heterocyclic radical and X is an acid radical.

This process is characterized in that color bases of the general formula (II)

55

C = CH-N = N-A

R ₄ -C- (CH ₂ L-

R ₅

-N- (CH ₂ L-CH ₂

in which R, R ₁ and A have the meaning given in formula (I), mii reacting agents with quaternization of the azo nitrogen linked to the radical A.

The color bases mentioned are produced by using diazotized amines of the general form! (IV)

, Methylene bases of the general formula, 111) in the ring, R ₁ an alkyl, cycloalkyl, aralkyl · or .Ir way couples and the resulting aryl radical, R _{2 is} an alkyl, cycloalkyl · or _& A "iKjj" / J l ^ i n ^{P P} For el _m (V) with aqueous Alka residue a is an aromatic radical f ** * ™ ™? ^

kmnter way clutching

ι. Apt general formula (V) with aqueous alkali

_{n transferred} into the color bases (11):

Aryl radical, R ₂

rest, A an aromatic residue f? de \ itet, by quaternizing color bases of the 5 my formula

, R

= CH-N = N-A (Ha)

C = CH-N = N-A

(V)

χο

-HX (Il)

20th

in the formulas (HI), (IV) and (V) R, R ₁ , A «Λ X have the meaning given in formula (1). ^A large number of suitable heterocycles of the formula (III) as well as certain substances on which the diazonium salts IV are based are described in the French ntPnKchrift 12 14 896.

%? e Qua ernierung the color bases (II) proceeds • JS, incomplete and with poor yields, ^J l _n is Sbafen and alkylating agents, η Sscher employing purity. If you work the

i .noTpemic of the quaternization in the. technically ^S "ESSShef manner is the aqueous phase in ^g? r ReaSn in such the unreacted a5 of FarSbasen II to the color salts (V) per-St offe The contaminated with the dye salts (V) Färb (D have, compared to the pure dyes ^F erhebHche disadvantages;. they result ζ example on duller from polyacrylonitrile dyeings r to light and sublimation değer A dye salts (V) to the wasserunlösworin R, R ₁ and A have the meaning given, connected to the to the radical A Azo nitrogen with quaternizing agents in the presence of alkaline agents proceeds almost completely and with very good yields if the alkaline agent used is 5-50 mol%, based on the color base to be quaternized, of tertiary amines which are represented by two radicals of the formula on the nitrogen atom

R ₄ -C- (CH ₂ L-

R ₅

(VI)

where m = 0 or 1, where in the case of in = 1 R ₃ door is an alkyl radical, R _{4 is} an alkyl radical or a hydroxyl group and R _{5 is} hydrogen or an alkyl radical, where in the case of in = 0 R ₃ and R _4th are alkyl radicals and R _{5 is} hydrogen, and where R ₃ and R _{4 can} also be components of a cyclopentyl or cyclohexyl system, if R _{5 is} hydrogen, they are substituted and a C ₁ -C _{4 as the third substituent on nitrogen} -AIkylrest, an O-Hydroxypropylrest or a residue of the formulas

Wissasi5

which also at temperatures of 60 C and R ₄ -C- (CH ₂ L

-N- (CH ₂ ) "- CH ₂ - (VII)

shear dyes of the general formula

R,

C = CH-N = N-A

-

R ₄ -C- (CH ₂ L

-N-CH ₂ -CH-CH ₂ -

OH

(VIII)

(Ia)

where η denotes an integer from 1 to 5, and where a radical (VI) and the third substituent on 65 nitrogen can also form a piperidine, morphour. = or pipei azin ring together with the nitrogen atom (s),
wherein R is the remaining component of an indoline Suitable tertiary amines of the type mentioned, which are used in

the quaternization of the color bases (IIa) are used are, for example, the following amines or their mixtures:

N-methyl or N-ethyl or N-n-propyl or N-n-butyl-N.N-diisopropylamine,

N-methyl- or N-ethyl- or N-n-propyl- or N-n-butyl-N, N-diisobutylamine, N-methyl or N-ethyl or N-n-propyl or

N-n-Butyl-N-isopropyl-N isobutylamine, '°

N-Methyl- or N-Ethy! - or N-n-Propyl- or N-n-Butyl-N, N-bis- (2-methyl-butyl) -amine, N-methyl or N-ethyl or N-n-propyl or N-n-butyl-N, N-bis (2,2-dimethylpropyI) amine, N-methyl- or N-ethyl- or N-n-propyl- or N-n-butyl-N.N-dicyclopentylamine, N-methyl- or ΐ ^ -AthyI- or N-n-propyl- or N-butyl-tyN-dicyclohexylamine, Ν, Ν, Ν-triisopropanolamine,

N-2-hydroxy per pyl-N.N-diisobutylamine, N-2-hydroxypropylN-isopropyl-N-isobutylamine,

N-2-hydroxypropyl-N, N-bis- (2-methyl-butyl) -amine,

N-2-hydroxypropyl-N, N-bis- (2,2-dimethyl-2 ;,

propyl) amine,

N ^ -hydroxypropyl-HN-dicyclopentylainin, N ^ -hydroxypropyl-KN-dicyclohexylamine, N-isopropyl-N, N-bis- (2-hydroxypropyl) -amine, N-isobutyl-N, N-bis- (2-hydroxypropyl) -amine, Ν, Ν-tetraisopropyl- and N, N'-tetraisobutylethylenediamine,

N.N'-Diisopropyl-N ^ '- diisobutyl-ethylenediamine,

N, N'-tetra- (2-methyl-butyl) -ethylenediamine, N, N'-tetra- (2,2-dimethylpropyl) -ethylenediamine, N.N'-tetra-cyclopentyl-ethylenediamine, N.N'-tetra-cyclohexyl-ethylenediamine, Ν, Ν'-tetraisopropyl- and N, N'-tetraisobutylpropylenediamine, N.N'-diisopropyll-N.N'-diisobutyl-propylenediamine,

N, N'-tetra- (2-methyl-butyl) -propylenediamine, N, N'-tetra- (2,2-dimethylpropyl) -propylenediamine, N ^ '- Tetra-cyclopentyl-propylenediamine, N.N'-Tetra-cyclohexyl-propylenediamine, Ν, Ν'-tetraisopropyl- and N, N'-tetraisobutylbutylenediamine,

HN'-diisopropyl-N.N'-diisobutyl-butylenediamine,

N, N'-tetra- (2-methyl-butyl) -butylenediamine, N, N'-tetra- (2,2-dimethylpropyl) -butylenediamine, N.N'-tetra-cyclopentyl-butylenediamine, KN'-tetra-cyclohexyl-butylenediamine, Ν, Ν'-tetraisopropyl- and N, N'-tetraisobutylpentienediamine,

KN'-Diisopropyli-HN'-diiso-butyl-pentylenediamine,

N, N'-tetra- (2-methyl-butyl) -pentylenediamine, N, N'-tetra- (2,2-dimethylpropyl) -pentylenediamine, Ν, Ν'-Tetra-cyclopentyl-pentylenediamine, Ν, Ν'-Tetra-cyclohexyl-pentylenediamine, Ν, Ν'-tetraisopropyl- and N, N'-tetraisobutylhexylenediamine, Ν, Ν'-diisopropyl-N.N'-diisobutylhexylenediamine, N, N'-tetra- (2-methyl-butyl) -hexylenediamine, N, N'-tetra- (2,2-dimethylpropyl) -hexylenediamine, N.N'-Tetia-cyclopentyl-hexylenediamine,

N ^ '- Tetra-cyclohexyl'iexylenediamine,

1,3-bis (diisopropylamino) -2-hydroxy-propane,

I, 3-bis (diisobutylamino) -2-hydroxy-propane,

1,3-bis- [di- (2-methylbutyl) -amino] -2-hydro.xy-

propane,

1,3-bis (dineopentylamino) -2-hydroxy-propane,

!, S-bis-idicyclopentylaminoJ ^ -hydroxy-propane,

!, S-Bis-idicyclohexyiaminoj ^ -hydroxy-propane,

1,3-Bis- [di- (2-hydroxypropyl) -amino] -2-hydroxypropane.

The following heterocyclic !: Amines are used:

1-isopropyl-, 1-isobutyl- and 1-neopene! Vl-2-methyl-piperidine,

4-isopropyl, 4-isobutyl and 4-neopentyl

2,6-dimethyl-morphoJin,

4- (2-hydroxypropyl) -2,6-dimethyl-morpholine,

1,4-bis (2-hydroxypropyl) -2,5-dimethyl-piperazine,

1,4-bis (isopropyl) -, 1,4-bis (isobutyl) - and

1,4-bis- (neopentyl) -2,5-dimethyl-piperazine, 1,3-bis- [2-methyl-piperidino- (l)] - 2-hydroxy-

propane,
1,3-bis [2,6-dimethyl-morpholino- (4)] - 2-hydroxy-propane,

1,3-bis- [4-isopropyl-2,5-dimethyl-piperazino (1)] - 2-hydroxy-propane,

1,3-bis [4-isobutyl-2,5-dimethyl-piperazino- (l)] -2-hydroxy-propane,

1,3-bis [4-neopentyl-2,5-dimethyl-piperazino- (l)] -2-hydroxy-propane,

1,3-Bis- [4- (2-hydroxypropyl) -2,5-dimethylpiperazino- (l)] -2-hydroxypropane.

The following amines or mixtures thereof are preferred for the quaternization according to the invention Color bases (IIa) suitable:

N-methyl- or N-ethyl- or N-n-propyl-N, N-diisopropylamine,

N-n-propyl- or N-n-butyl-N, N-diisobutylamine,

N-methyl- or N-ethyl-N ^ -dicyclohexylamine Ν, Ν, Ν-triisopropanolamine,

N, N-diisobutyl-N- (2-hydroxypropyl) -amine, N-isobutyl- or N-isopropyl-N ^ -bis- (2-hydroxypropyl) -amine,

Ν, Ν'-Tetraisopropyl-ethylene-diamine, 1,3-bis-fdiisopropylamino) -2-hydroxypropane, 1,3-bis [di- (2-hydroxypropyl) amino] -2-hydroxypropane,

1 -isopropyl-2-methyl-piperidine, 4-isopropyl-2,6-dimethyl-morpholine, 4- (2-hydroxypropyl) -2,6-dimethyl-morpholine, 1,4-bis- (2-hydroxypropyl) -2,5-dimethylpiperazine I, 3-bis- [2,6-dimethyl-morpholino- (4)] - 2-hydroxypropane,

1,3-bis- [4-isopropyl-2,5-dimethyl-piperazino- (1)] -2-hydroxy-propane.

Among the amines mentioned, triisopropanolamine is to be emphasized, since it is the most soluble ability of the color bases (II a) and especially the quaternary Dyes (Ia) in the alkylating medium considerably

increased so that the amount of the solvent decreased can graze.

The tertiary amines used as alkaline agents are used in an amount of 5-50, preferably 15-25 mole percent, based on the quater- S Nating color base (Ha), added.

In the German Auslegeschrift 11 32 135 is described been that tertiary amines of the type to be used according to the invention due to their acid-binding properties Effect as an aid to the alkylation ι ο of primary to tertiary amines and dehydrohalogenation reactions can be applied. In contrast to this, quaternization reactions take place such as those of the type according to the invention, with addition of the alkylating agent to the one to be quaternized Connection and thus by nature not with splitting off of protons. It is therefore surprising that the degree of conversion and the yield of the quaternization of the color bases (lla) to the dyes (I a) is increased in the presence of the tertiary amines mentioned above. On the contrary, it was to be expected that the high basicity of the amines to be used according to the invention compared to that already mentioned above Decomposition of the dyes (la) would lead to their carbinol bases. The high basicity of these amines is characterized in that the in hydrous glycol monomethyl ether compared to perchloric acid pK value determined potentiometrically with a glass electrode calibrated in aqueous media (cf. S. Hü η i g and M. Ki e s s e 1, J. Prakt. Chemie [4], 5, 224 [1958]) is above 5.5.

German Patent 12 05 638 describes the preparation of dyes of the general formula (IX) known

ν / ¹ _ν / = CH - _R. R ₃ \ /
C. N I " N / A ^/ \ I. N = N-A T ί C = R ₆ ϊ R ₄

X "(IX)

wherein A is the radical of an aromatic amine of the benzene or naphthalene series, X is an anion, R ₁ and R _{2 are} identical or different or interconnected short-chain alkyl radicals, R ₃ and R _{4 are} hydrogen atoms or nonionic substituents and R ₅ and R _{6 are} alkyl radicals by one color bases of the general tautomeric formula (X)

- N = N-A

CH = N-N-A

wherein A, R ₁ , R ₂ , R ₃ and R _{4 have} the meaning given under (IX), treated in the presence of acid-binding agents with alkylating agents. Sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, magnesium oxide, zinc oxide or calcium carbonate are listed as acid-binding agents, magnesium oxide being particularly emphasized in the exemplary embodiments.

In the process of German patent specification 12 05 638, two alkyl groups are gradually stirred into the dye molecule (IX). First, the alkylation of a secondary amine nitrogen to a tertiary amine nitrogen takes place. Experience has shown that the equivalent of acid released during this process requires the acid-binding agent only at this stage. The quaternization reaction that follows in a second stage proceeds with addition of an alkyl group to the compound to be quaternized, with no protons being released, so that for this second process step, according to the teaching of German patent specification 12 05 638, basically no acid-binding agent The fact that acid-binding agents are also present in the second stage, ie in the quaternizing reaction, is based solely on the fact that the acid-binding agent required in the first reaction stage was not removed and the reaction was completed in a single process step It cannot therefore be inferred from German patent specification 12 05 638 that the quaternization of the color bases (Ha) in the presence of acid-binding agents is of technical advantage. In fact, this would not be the case in this broad scope. It is therefore extremely surprising that the quaternization of the color bases (II a) the addition of very special alkaline agents, namely tertiary amines, which are space-filling substituted on the nitrogen atom, leads to particularly advantageous results.

The quaternization according to the invention enables the dyes (I a) to be obtained in greater purity al: so far this has been done through additional cleaning and separating operations according to the well-known quaternization method was achievable.

The known preparation of indolinyl dyes of the formula (Ia) by quaternizing the dye bases (II a) have hitherto been carried out without the addition of amines ii organic solvents, in particular in toluene Quaternicrungcn of this type are except in the above-mentioned FR-PS 12 14 896 in GB-PI 9 15 139. As in the following two Tables is shown by the presence of a tertiary amine according to the invention in the de Patent documents known reaction of the alkylation: degree of the dyes in an unforeseen way ei increases. The dyes obtained are also distinguished by clearer hues and better colors micrcchtheil off.

709 M2 /

9 Source material 17 70 782 \ 10 DMSO ₄ base No. mission Solution
medium (g / mole-aqu.) (g / mole eq H,( (g / mole-aqu.) (B) V 63, og / 1.00 - a - ^ \ V-OCH ₃ 153.5 g / 1.00 toluene
1000g 85.0 / 1.35 - b 153.5 g / 1.00 toluene
1000 g 85.0 / 1.35 DIPEA
12.8 / 0.20 C. 153.5 g / 1.00 toluene
1000 g 85.0 / 1.35 - d 153.5 g / 1.00 CHCI ₃
1850 g 85.0 / 1.35 DIPEA
12.8 / 0.20 e 153.5 g / 1.00 CHCl ₃
185Og 85.0 / 1.35 TRIPA
19.0 / 0.20 r H ₃ < 153.5 g / 1.00 CHCl,
185Og V 85.0 / 1.35 - G 145.5 g / 1.00 toluene
1000 g 85.0 / 1.35 DIPEA
12.8 / 0.20 H 145.5 g / 1.00 toluene
1000g : CH ₃ If V = CH-N = N
A _n /
I. CH ₃ the same the same the same the same the same Z CH ₃ if> = CH —N = N
A _n /
ι CH ₃ the same

H ₃ C CH ₃

V CH-N = N-AVn- Ν ^ (Λ 190.5 g / 1.00 toluene ^{J v} - ^/ ^ ^ = ^ 1520 g

CH ₃

the same

DIPEA = diisopropylethylamine. TRIPA = triisopropanolamine. DMSO ₄ = dimethyl sulfate.

continuation

No. Work-up yield, Cichnlt an Method g (anhydrous) Λ / obase

(DC)

190.5 g / 1.00 toluene
G

85.0 / 1.35 -

85.0 / 1.35 TRIPA 19.0 / 0.20

Yield in% Flirb. evaluation

versus comparison (nuance)

spectroscopic

Conditions of Use Temperature Time

201.3 g 8th% 205.0 g 5% 227.5 g 0.3 "/!

174 g

10%

Compare - 100%
105%
105 ",,

102 ",.

golden yellow
little greener

dll. greener
something clearer

little redder
somewhat süinv.ifer

80 85 C
80 85 C
80 85 "C

55 W) C IO h

Preparation
method 11th Content of
Azo base
(DC) 17 70782 12th Color Manufacturing
(Nuance) Reaction conditions
Temperature time 10 h T 2 5% little greener
a little duller 55-60 ° C 10 h continuation 2 Yield,
g (anhydrous) <0.1% Yield in%
against comparison
spectroscopic dtl. greener
little clearer 55-60 ° C 4h No. 1 175.2 g 3% 102% yellow 80-85 C. 4h e 1 178.5 g 1% 103% little greener
little clearer 80-85 ° C 10 h f 1 210 g 2% Compare = 100% orange 75-80 ° C 10 h G 1 224 g <0.5% 98% little greener 75-80 ° C H 254.0 g Compare = 100% i 285.0 g 100% j

TLC = thin layer chromatogram.

Processing method :

'= Suction from the solvent (as methosulphate); dry.

2 = remove the solvent by steam distillation, sow the aqueous dye solution with sodium chloride; Dye (as Chloride) vacuum and dry.

A particularly preferred embodiment of the present invention consists in the dye bases (Ha) in water-immiscible organic, aprotic solvents such as benzene, toluene, xylene and their halogenated derivatives, in particular chlorobenzene, as well as anisole and chloroform in the presence of 5-50, preferably 15-25 mole percent (based on the color base) triisopropanolamine with an excess of dimethyl sulfate at 50-90 ⁰ C, preferably 60-85 ⁰ C implement. The excess of dimethyl sulfate is such that the reaction mixture reacts acidic when water is added. The quaternary dye is isolated in a known manner,

z. B. by steam distillation and cooling the aqueous solution, optionally with addition Inorganic salts that reduce the solubility.

In the following examples, the relationship between parts by weight and parts by volume is the same as that between kilograms and liters.

example 1

To a mixture of 155 parts by volume of hydrochloric acid and 250 parts by volume of 19.5 Be water are added at 58 ° C 61.7 parts by weight of p-anisidine are diazotized and the suspension of the hydrochloride in 0-3 ^D C with a solution of 35.1 parts by weight of sodium nitrite in 100 parts by volume of water. The excess nitrite is destroyed with urea or aminosulfonic acid and 86.7 parts by weight of 1,3,3-trimethyl-2-methylenemdolenine are added to the diazo solution at 5 ° C. Coupling is carried out by adding 400 parts by volume of an aqueous solution containing 200 g of sodium acetate per liter. The coupling product is converted into the dye base by adding 440 parts by volume of 2.5N sodium hydroxide solution. It is heated for some time at 6O ⁰ C, is then filtered off, the electrolytes are washed out with water and the product is dried at 70 ⁰ C under vacuum to constant weight. There are 155 parts by weight of the anhydrous color base of the formula

H, C

-N-- N

receive. 120 parts by weight of this paint bottle were dissolved in 1000 parts by volume of anhydrous chloroform and mixed with 10 parts by weight of N-ethyl-NN-diisopropylamine. At 50-55 ° C are added 50 parts by volume of pure dimethyl sulfate to and maintaining the mixture for a further 10 hours at 55-6O ⁰ C. Then the solvent is distilled imit water vapor, fills with water to 1000 parts by volume, and the dyestuff is salted with 85 parts by weight Sodium chloride aius. The suspension is allowed to 20 ° C to cool and filtered off the precipitated dye, washed with 10% sodium chloride solution, which is provided with a little hydrochloric acid to pH 1 to remove the mother liquor and dried the product at 6O ⁰ C in vacuo. There are 160 parts by weight of the dye of the formula

ilO

C-CU-N = N

OCHj

receive. The dye stains materials from Pol

fts acrylonitrile golden yellow. In the thin layer chroinutogrum

are only traces of the unmcthylicrtcii exit

materials detectable.

In this example, instead of chlorine

forms equal amounts of benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene or anisole, the Dye obtained in approximately the same yield.

If you proceed as described in the previous example, but instead of there as a diazo component p-anisidine used and the 1,3,3-trimethyl-2-methylene-indolenine used as a coupling component if equivalent amounts of the components mentioned in the table below are used, dyeing corresponding to the above formula is obtained fabrics that dye materials made of polyacrylonitrile in the specified shades:

Coupling product is converted into the color base without intermediate isolation with dilute sodium hydroxide solution. The color base is washed neutral with hot water and dried at 60 ° C. in vacuo. Man receives 144 parts by weight of the anhydrous color base

Diazo component coupling component

1-amino

4-methyl-

benzene

1-amino

4-chlorobenzene

I-amino

2-methoxy

benzene

4-aminodi-

phenyl ether

4-aminoazo-

benzene

2-amino

naphthalene

Aminobenzene

1-amino

4-methoxy

benzene

1-amino

4-methylbenzene

1-amino

4-methoxy

benzene

1,3,3-trimethyl-2-methylene indolenine
the same

the same

1,3,3-trimethyl-2-methylene indolenine
the same

the same

1,3,3-triimethyl

5-methoxy-

2-methylene

indolcnin

the same

1,3,3-trimethyl

5-chloro-2-me-

ethylene indolenine

1,3,3-trimethyl

5-nitro-2-me-

ethylene indolenine

Hue of the quaternary dye on polyacrylonitrile

yellow

reddish yellow greenish yellow

golden yellow

orange

golden yellow

reddish yellow

yellowish orange

yellow

orange

CH ₃

120 parts by weight of this color base are dissolved in 175 parts by volume of anhydrous chlorobenzene with heating. 16.0 parts by weight of anhydrous triisopropanolamine are added and the mixture is heated to 80-85 ° C. At this temperature, 52.8 parts by volume of dimethyl sulfate are allowed to flow in with cooling and the mixture is kept at 80-85 ° C. for a further 10 hours. The excess is then hydrolyzed Dimethyl sulfate with water, the chlorobenzene is distilled off with steam, made up to 1000 parts by volume with water and the dye is salted out with 85 parts by weight of sodium chloride.The suspension is left at 20 ° C., the dye is filtered off with suction and washed with 10% sodium chloride solution removal of the mother liquor and dried the product at 6O ⁰ C in vacuo. There are 156 parts by weight of the quaternary dye of the formula

CH ₃

CH ₃

Example 2

53.7 parts by weight of p-toluidine are diazotized in dilute hydrochloric acid in the usual way and in acetate-buffered medium coupled to 86.7 parts by weight of 1,3,3-trimethyl-2-methylcnindoline. The receive.

Only traces of the unmethylated starting material can be detected in the thin-layer chromatogram.
If one proceeds as described in the preceding example, but instead of the p-toluidine used there as the diazo component and the 1, SS-trimethyl ^ -methylcnindolenine used as the coupling component, equivalent amounts of the components mentioned in the table below are obtained, dyes corresponding to the above formula are obtained who color materials made of polyacrylonitrile in the specified shades.

Pin / okoniponcnle

Coupling component hue of the whirling Dye on polyacrylonitrile

-Amino-3,4-dimethylbenzene / ol

-AmincM-chlorbcn / nl

-Amino-2-methoxyben / ol

the same.

lolstichiggclb reddish yellow greenish yellow

I. 15th continuation 17 70 782 16 Coupling component Hue of the Quaternary
ParKclfifTt ΐΐιιΓ Diazo component ΓαΓΡαιυίΒΑ ttUl
Polyacrylonitrile 1,3,3-trimethyl-2-methylene-indolenine yellow 1-amino ^ -methoxy- ^ methylbenzene the same yellow 1-amino ^ -methoxy-S-methylbenzene the same reddish yellow 1 -Amino ^ -methoxy - ^ - chlorobenzene the same greenish yellow 1-amino ^ -methoxy-S-chlorobenzene the same golden yellow 1-amino-4-methoxy benzene the same golden yellow 1-amino-S-chloro- ^ methoxybenzene the same golden yellow 1-amino-2,4-dimethoxybenzene the same reddish yellow 1-amino-2,5-dimethoxybenzene the same golden yellow 4-aminodiphenyl ether the same greenish yellow 2-aminodiphenyl ether the same yellowish orange 4-aminoazobenzene the same orange l-amino-4-acetylaminobenzene the same red-brown 4-amino-2-ethoxy-diphenylamine the same greenish yellow l-aminobenzene- ^ carboxylic acid ethyl ester the same golden yellow 2-aminonaphthalene 1,3,3-trimethyl-5-nitro-2-methylene
ITl HoIfMIl Π yellowish orange 1-amino-4-methylbenzene 1J .1U- KJ 1 ^ l 1 i 11
the same orange 1-amino-4-methoxy benzene 1,3-trimethyl-5-chloro-2-methylene yellow 1-amino-4-methylbenzene indolenine l, 3,3-trimethyl-7-chloro-2-methylene
inrfoipnin yellowish orange 1-amino-4-methoxybenzene lllVlv IwI 1111
1,3,3-trimethyl-2-methylene-indolenine- orange 1-amino-4-methoxybenzene 5-carboxylic acid methyl ester the same reddish orange 2 ', 3-dimethyl-4-aminoazobenzene l-ethyl-3,3-dimethylbenzo- (6,7) - reddish orange 1-amino-4-methoxybenzene 2-methylene-indolenine l-dimethylamino ^ -methyl-S-phenyl- reddish yellow 1-amino-4-methylbenzene 2-methylene-indolenine 1,3,5-tetramethyl-2-methylene indolenine yellow Aminobenzene the same golden yellow 1-amino-4-methoxybenzene the same golden yellow l-amino-4-ethoxybenzene the same yellowish orange 1-amino-3-chloro-4-methoxybenzene 1,3-trimethyl-5-methoxy-2-methylene reddish yellow Aminobenzene indolenine the same yellowish orange 1-amino-4-methoxybenzene the same yellowish orange 1-amino-2,4-dimethoxybenzene the same orange 4-aminoazobenzene

Example 3

120 parts by weight in the usual way from p-chloroaniline and 1,3,3-trimethyl-2-methylene-indoline prepared anhydrous color base of the formula

are dissolved in 500 parts by volume of anhydrous chlorobenzene and mixed with 12.4 parts by weight of 1,3-bis [di- (2-hy-

droxy-propyl) -amino-2-hydroxypropane added. At 70 "C., 47.5 parts by volume of dimethyl sulfate are added and The mixture holds 8 hours at 70 "C. Then distilled if the chlorobenzene is removed with steam, the aqueous dye solution is made up to 2000 parts by volume and the dye falls by cooling the solvent

H ₃ C

Solution to 0 "C. The dye is filtered off with a 2% sodium chloride solution at 0" C to Washed removal of the mother liquor and dried at 60 ° C. in vacuo. It becomes 170 parts by weight of the dye of the formula

C-CH-N =

receive.

The dye is obtained in the same yield if, instead of 1,3-bis [di- (2-hydroxypropyl) -amino] -2-hydroxypropane uses equivalent amounts of the following tertiary amines:

N-methyl-, N-ethyl-, N-n-propyl- and N-n-butyl-N, N-diisoprc pylamine, N-methyl-, N-ethyl-, N-n-propyl- and n-butyldiisobutylamine,

Methyl and ethyl dicyclohexylamine, Triisopropanolamine,

Diisobutyl (2-hydroxypropyl) amine, isobutyl and isopropyl bis (2-hydroxypropyl) amine,

Ν, Ν'-Tetraisopropyl-ethylene-diamine, 1,3-bis (diisopropylamino) -2-hydroxypropane, 1,3-bis [di- (2-hydroxypropyl) amino] -2-hydroxypropane,

N-methyl-, N-ethyl-, N-n-propyl- or N-n-butyl-N-isopropyl-N-isobutylamine, N-methyl-, N-ethyl-, N-n-propyl- or N-n-butyI-N, N-bis - (: i-methyl-butyl) amine, N-methyl-, N-ethyl, N-n-propyl- or N-n-butyl-N, N-bis-C !, 2-dimethylpropyl) amine, N-methyl-, N-ethyl-, N-n-propyl- or N-n-butyl-RN-dicydopentylamine, Ν, η-propyl- or N-n-butyl-N.N-dicyclohexylamine.

N-2-hydroxypropyl-N-isopropyl-N-isobuiylamine,

35

40

45

N-2-hydroxypropyl-bis-N, N- (2-methyl-butyl) -amine,

N-2-hydroxypropyl-bis-N, N- (2,2-dimethyI-propyl) -amine,

N-2-hydroxypropyl-N, N-dicyclopentylamine, N-2-hydroxypropyl-N, N-dicyclohexylamine, HN-diisopropyl-N.N'-diisobuiylethylenediamine, N, N, N ', N'-tetra- (2-methylbutyl) -ethylenediamine, N, N, N', N'-tetra- (12-dimethylpropyl) -ethylene-

diamine,

N ^^ '. N'-Tetracyclopentylethylenediamine, Ν, Ν, Ν ', Ν'-tetracyclohexylethylenediamine, Ν, Ν, Ν', Ν'-tetraisopropyl and Ν, Ν, Ν'.Ν'-tetra-

55

60 CH ₃ OSO ₃

isobutylpropyiendiamine,
N ^ '- Diisopropyl-RN'-diisobutylpropyiendiamine,
N, N, N ', N'-Tetra- (2-methylbutyl) -propylenediamine,
N, N, N ', N'-tetra- (2,2-dimethylpropyl) -propylene-

diamine, Ν, Ν, Ν ', Ν'-tetracyclopentyl- and -cyclohexylpropylenediamine,

Ν, Ν, Ν ', Ν'-tetraisopropyl and Ν, Ν, Ν', Ν'-tetraisobutyl-butylenediamine,

N, N, N ', N'-Tetra- (2,2-dimethylpropyI) -pentyIen-

diamine, Ν, Ν, Ν ', Ν'-tetraisopropyl- and Ν, Ν, Ν', Ν'-tetraisobutylhexylene diamine,

Ν, Ν, Ν ', Ν'-Tetracyclopentyl- and -cyclohexylhexylenediamine,

1,3-bis (diiso-butylamino) -2-hydroxypropane, 1,3-bis-di- (2-methylbutylamino) -2-hydroxy-

propane, 1,3-bis (dicyclopentylamino) -2-hydroxypropane, l ^ -Bis-idicyclohexylaminoJ-I-hydroxypropane, 1-isopropyl-2-methyl-piperidine,

1-isobutyl- or l-neopentyl-2-methylpiperidine, 4-isopropyl-2,6-dimethylmorpholine, 4-isobutyl- or 4-neopentyl-2,6-dimethylmorpholine,

4- (2-hydroxypropyl) -2,6-dimethyl-morpholine, 1,4-bis- (2-hydroxypropyl) -2,5-dimethylpiperazine, 1,3-bis _: [2,6-dimethyl-morpholino- ( 4)] - 2-hydroxypropane,

1,3-bis [4-isopropyl-2,5-dimethyl-piper-

azino- (1 j] -2-hydroxypropane,

1,4-bis-isopropyl-, 1,4-bis-isobutyl- or 1,4-bisneopentyl-2,5-dimethylpiperazine, 1,3-bis- (2-methyl-piperidino-1) -2-hydroxy-

propane, 1,3-bis- (4-isobutyl-2,5-dimethylpiperazino-1) -2-hydroxypropane,

1,3-bis- (4-neopentyl-2,5-dimethylpiperazino-1) -2-hydroxypropane and

1,3-bis (4- (2-hydroxypropyl) -2,5-dimethylpiperazino-1 ) -2-hydroxypropane.

Claims (1)

Patent claims: 1. Process for the preparation of basic dyes of the general formula R ₂ = CH-N = N-A X ⁽