CH626391A5 - Process for preparing concentrated solutions of basic dyes - Google Patents

Description

626391

2nd

PATENT CLAIMS 1. Process for the preparation of stable, concentrated solutions of basic dyes of the formula

R,

'-> rsN

r'V

r c-n = n-a a;

r3-so3

means in which

R <for hydrogen, optionally substituted by hydroxy or phenyl Ci-Gt-alkyl, for Ci-Gt-alkoxy, Ci-Ct-alkoxycarbonyl, Ci-Ct-alkylcarbonylamino, optionally 5 by Ci-Ct-alkyl, Ci-Ct-alkoxy or chlorine-substituted phenoxy or phenoxysulfonyl,

R9 represents hydrogen, Ci-Ct-alkyl, nitro or optionally substituted by Ci-Gt-alkyl, Ci-Ct-alkyl or chlorine and phenyl

Rio represents hydrogen, Ci-Ci-alkylcarbonyl, Ci-Gi-alkylsulfonyl, benzoyl, carboxyl, Ci-Gt-aikyloxycarbonyl or amino-carbonyl,

A 'a rest of the formulas

10th

wherein R is an alkyl radical, R 1 and R 2 independently of one another are hydrogen, a nonionic substituent or a carboxyl group or both together are a fused, optionally substituted benzene ring, A is the rest of a coupling component and R 3 is an aryl radical or R-O-, characterized in that color bases of the formula

R,

or

1 3

20 Rg

R.

* 11 r

12

•> N

C-n = n-a

CS)

with esters of sulfuric acid or arylsulfonic acids of the formula

R3-SO3R

(III)

in organic solvents which are completely or partially miscible with water and which, under the quaternization conditions, do not react with the esters or react more slowly than the bases.

2. The method according to claim 1, characterized in that color bases of the formula

X

\

C-N-N-A '

N '

with esters of the formula

R3-SO3R

to dyes of the formula

Ï

C-N = N-A1

N

1

r implements what

R3-S ° 3

CS)

means in which

R5 for hydrogen, optionally substituted by hydroxy, Ci-Gt-alkoxy, chlorine, cyano, Ci-Gt-alkoxycarbonyl, Ci-Gt-alkylcarbo-25 nyloxy, mono- or di-Ci-Gt-alkylamino or C1-C4-alkyl or for phenyl or benzyl optionally substituted by Ci-Gt-alkyl, Ci-Gt-alkoxy or chlorine,

R & for hydrogen, optionally substituted by hydroxy, C1-C4-alkoxy, chlorine, cyano, Ci-Ct-alkoxycarbonyl, Ci-Gt-alkylcarbo-30 nyloxy or for optionally by chlorine, Ci-O-alkyl or Ci-Ct-alkoxy substituted benzyl,

R7 for hydrogen and

Rs represent hydrogen, Ci-Ct-alkyl, Ci-Ct-alkoxy, chlorine, bromine, 35 Ci-Ct-alkylcarbonylamino or nitro and

Re together with Rs or with R7 and N can form a 5- or 6-membered ring, and

Rn for Ci-Ct-alkyl or phenyl optionally substituted by Ci-Ct-alkyl, Ci-Gt-alkoxy or chlorine,

40 R12 for hydrogen, optionally substituted by hydroxy, chlorine, cyano, Ci-Gt-alkoxy, Ci-Ct-alkylcarbonyloxy, aminocarbonyl or amino and Ci-Ct-alkyl and

R13 represents hydrogen, halogen, Ci-Ct-alkyl, Ci-CU-alkoxy or Ci-Ct-alkylcarbonylamino, and wherein R and R3 have the meaning given in claim 1.

3. The method according to claim 1 and 2, characterized in that color bases of the formula

50

R,

with esters of the formula

8th

55

I.

i '>

n

R3-SO3R

to dyes of the formula

1

r

60

a remainder of the formulas n xx:

c-

or

X * c "

^ n

65

I.

r l10

r8. r.

r3-so3

U)

3rd

626391

wherein the symbols which have the meaning given in claims 1 and 2 are implemented.

4. The method according to claim 1, characterized in that color bases of the formula

R

V * nî

n10

with esters of the formula to dyes of the formula

R3-SO3R

ren amino group coupled aromatic amine means, converted with suitable alkylating or aralkylating agents to color salts.

Any aromatic amino compounds coupling in the p-position to a primary, secondary or tertiary amino group can be used as azo components, which may be further substituted, but may not contain any groups dissociating in acidic water. Aromatic, primary, secondary or tertiary amino compound 10 fertilizers come into consideration, which can belong to the isocyclic or the heterocyclic series.

DT-AS 1 057 706 describes a process for the preparation of basic dyes, in which an azo dye-15 substance of the general formula free of acid-dissociating, salt-forming groups is described

; x> -

XCr

13

1

20th

Rß-SO ^ 25

30th

wherein the symbols have the meaning given in claims 1 and 2.

5. The method according to claim 1, characterized in

that the reaction is carried out in the presence of a tertiary amine which is substituted by space-filling radicals, preferably 35 triisopropanolamine.

6. The method according to claim 1, characterized in that

that a dialkyl sulfate is used as the ester.

7. The method according to claim 6, characterized in that

that 1 to 4 moles of dialkyl sulfate are used per mole of color base. 40

8. The method according to claim 7, characterized in that

that after the reaction, the excess dialkyl sulfate is destroyed by adding a substance which reacts with dialkyl sulfate.

9. The method according to claim 8, characterized in that 45 adding ethylene glycol or water,

10. The method according to claim 1, characterized in

that butylene glycol (1,4) or ethylene cyanohydrin is used as the solvent.

11. Dyeing preparation, prepared by the process according to claim 50, which is suitable for dyeing polyacrylonitrile, acid-modified polyesters and polyamides.

DT-AS 1 050 940 describes a process for the preparation of basic dyes, in which an azo dye of the general formula free from acid-dissociating, water-solubilizing groups is described

R1_0-S ^> M = N ~ R2

where Ri is a non-ionic substituent and R2 is the remainder of one in the p-position to a primary, secondary or tertiary

cn = nc where A is an alkylene radical which is connected to the S atom and the N atom at two adjacent carbon atoms linked by a double bond and which may be further substituted, and wherein the unsaturated C atom connected to the azo group is the Forms part of any azo component, reacted at a higher temperature with suitable alkylating agents. The unsaturated carbon atom attached to the azo group can form part of an aliphatic, cycloaliphatic, isocyanic-aromatic or heterocyclic-aromatic group.

The esters of strong mineral acids or organic sulfonic acids of preferably lower alcohols, which may optionally also be further substituted, are used as alkylating agents.

The reaction is carried out in an inert organic solution, the color salts separating out.

Suitable inert organic solvents are, for example, benzene hydrocarbons, halogen and nitrobenzenes, higher-boiling aliphatic and alicyclic hydrocarbons and stable halogen alkanes such as carbon tetrachloride and tetrachlorethylene.

The reaction can also be carried out in aqueous or alcoholic solution in special cases, for example when ethyl bromide is used as the alkylating agent. The color salts are then isolated by salting out their aqueous solutions.

More recently, dyes in liquid formations have been used to an increasing extent in the dyeing industry, since these do not have the disadvantage of dusting and also offer the possibility of continuous dosing. The dyes, the production of which have been described in German Auslegeschrift 1,050,940 and 1,057,706 and in a large number of subsequent patents, have so far been dissolved in an organic solvent, optionally with the addition of water and / or an organic acid, after isolation and marketed as a liquid formulation.

It has now been found that stable, concentrated solutions of these dyes can be prepared without isolation of the dyes after the alkylation. The invention relates to the preparation of stable, concentrated solutions of basic dyes of the formula

60

65

r

\

l c-n = n-a

(I)

r3-so3

626391

wherein R is an alkyl radical, R 1 and R 2 independently of one another are hydrogen, a nonionic substituent or a carboxyl group or both together are a fused, optionally substituted benzene ring, A is the radical of a coupling component and R 3 is an aryl radical or R-O-, by quaternization of color bases of the formula

'1 \

Tl C-N = N-A

U N

(II)

with esters of sulfuric acid or arylsulfonic acids of the formula

R3-SO3R

(III)

15

in those organic solvents which are wholly or partly miscible with water and which, under the quaternization conditions, do not react with the esters or react more slowly than the color base (II). 20th

R preferably represents a C 1 -C 4 -alkyl radical, in particular a methyl radical.

Nonionic substituents R 1 and R 2 are, for example, Ci-Ct-alkyl, Ci-Gt-alkoxy, Ci-Ct-alkylsulfonyl, benzyl, phenyl-ethyl, benzyloxy, halogen, especially chlorine and bromine, car- 25 boxy, Ci-Ct-alkoxycarbonyl , Benzyloxycarbonyl, optionally substituted by one or two Ci-G alkyl radicals and / or by a phenyl or benzyl radical, aminocarbonyl or amino, acetylamino, benzoylamino, methylsulfonylamino, phenylsulfonylamino, phenyl, acetyl, benzoyl, acetoxy, 30 benzoyloxy, phenoxy, Naphthoxy or nitro. If the substituents R 1 and R 2 together form a benzene ring, this can also be substituted by the radicals mentioned, for example once or twice.

R3 is in particular a Ci-Ct alkoxy radical or a phenyl, tolyl or chlorophenyl radical, preferably methoxy.

The coupling component H-A can belong to the aliphatic, isocyclic-aromatic and heterocyclic-aromatic series. In the latter case, the azo bridge can be connected to both an isocyclic and a heterocyclic ring. The coupling component is derived, for example, from acetoacetic acid-N-phenylamide, benzene, naphthalene, indole, dihydroindole, tetrahydroquinoline, pyrrole or pyrazolone. 45

Suitable diazo and coupling components for the preparation of the color bases used as starting material are described in the following publications:

German design documents 1 271 858,

1 163 775.1 088 631.1 105 540.1 127 015.1 204 764.1 218 094, so 1619 328.1 050 940.1 056 757.1 057 706 and 1 058 171;

German Offenlegungsschriften 2 001 705.2 028 457,

2 037 040.1 806 582.1 619 415 and 1 937 885:

French Patents 1,256,899.1,217,248.1,224,183 and 146,4267; 55

U.S. Patents 3,480,612,3,078,137 and 2,889,315;

Belgian Patent 579,965;

British Patents 1,220,852.1,186,753 and 1,200,340.

Suitable solvents include:

1. Aliphatic carboxylic acid esters; preferred are esters which are derived from formic acid or from optionally substituted mono- or dihydric, saturated or unsaturated carboxylic acids with 1 to 4 carbon atoms in the alkyl or alkylene radical and from mono-, di- or trihydric alkyl alcohols with 1 to 4 carbon atoms Derive atoms. The acids can be substituted, for example, by cyano groups or the alkyl or alkylene radical can be interrupted by a carbonyl group; examples are:

Methyl and ethyl esters of orthoformic acid, acetic acid, propionic acid, acetoacetic acid and cyanoacetic acid, dimethyl and diethyl esters of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid and acetone dicarboxylic acid, ethylene glycol diacetate, glycerol diacetate. The di- and trihydric alcohols can be etherified with 1 or 2 Ci-Gt-alkyl groups, e.g. B. Ci-Ci-alkyl ethylene glycol acetate. The acids can also be esterified with polyglycols or their ethers; preferred polyglycols are di-, tri- or tetraethylene glycol, which are optionally etherified by a Ci-Ct-alkyl group, e.g. B. methyl diethylene glycol acetate and diethylene glycol diacetate;

2. alkyl ethers of polyhydric alcohols or polyglycols; Ci-Gt-alkyl ethers of di- and trivalent C2-C4-alkyl alcohols or of di-, tri- or tetra-ethylene glycols are preferred. Examples are ethylene glycol dimethyl and diethyl ether, di and triethylene glycol dimethyl and diethyl ether and glycerol 1,3-diethyl ether;

3. Polyglycols such as diethylene glycol, triethylene glycol and tetraethylene glycol;

4. co, Co'-dihydroxyalkanes with 4 to 6 carbon atoms such as butylene-glycol (1,4) or hexylene-glycol (1,6);

5. lactones, cyclic esters of carbonic acid and cyclic ethers; e.g. B. aliphatic derivatives such as y-butyrolactone, ethylene and propylene carbonate and tetrahydrofuran;

6. nitriles; e.g. B. alkyl nitriles such as acetonitrile, propionitrile, butyronitrile, methoxy and ethoxyacetic acid nitrile, ß-hydroxy, ß-methoxy, ß-ethoxy, ß-hydroxy-ethoxy, ß-ethoxy-ethoxy, ß-propoxy and ß -Butoxy-propionitrile;

7. alkyl ketones; e.g. B. Ci-Ct-alkyl mono- or diketones such as acetone, methyl ethyl ketone and acetylacetone;

8. Dialkylformamides; e.g. B. dimethyl and diethylformamide;

9.5- and 6-membered lactams; N-methylpyrrolidone;

10.5-membered sulfones; e.g. B. Sulfolan and Sulfolen.

Preferred solvents are methyl cyanoacetate and acetic acetic acid, methyl ester and ethyl ester, methyl oxalate, malone and succinic acid methyl ester and ethyl ester, methyl glycol acetate, diethylene glycol mono- and dimethyl ether, ethylene and propylene carbonate, butylene glycol ) l, 4), ethylene cyanohydrin, methoxypropionitrile or diethylene glycol.

Of these solvents, butylene glycol (1,4) and ethylene cyanohydrin are particularly suitable.

In order to achieve complete conversion, the alkylation is preferably carried out in the presence of an acid-binding agent, for example MgO, NaHC03 or a tertiary amine which is substituted by bulky radicals. Suitable amines are listed in large numbers in British Patent 1,232,714. Among the amines mentioned, the triisopropanolamine is particularly noteworthy. The tertiary amines used as alkaline agents are added in an amount of 5 to 50 mol%, based on the color base (II) to be quaternized.

The alkylation can be carried out in such a way that the solution or slurry of the color base (II) in the solvent is mixed with the dialkyl sulfate at room temperature or at up to 100 ° C. and then heated or kept at this temperature. The reaction temperature is preferably 20 to 100 ° C, the reaction time 0.5 to 12 hours.

The alkylating agent is used in particular in an amount of 1 to 4 moles per mole of color base.

As a rule, it is necessary for the ready-to-use dye solutions according to the invention to be free from dialkyl sulfates. Excess dialkyl sulfate must therefore be destroyed after the alkylation has ended. This is achieved by heating the reaction solution after adding a substance which reacts with dialkyl sulfate. Examples include glycerol and preferably ethylene glycol and what

62639t ser. One heats z. B. 1 hour at 80 to 100 ° C.

If the alkylation is carried out in a solvent which reacts more slowly with the dialkyl sulfate than the dye base, the excess dialkyl sulfate can also be destroyed by further heating the reaction solution after the alkylation, for example for 1 to 6 hours at 80 to 100 ° C.

In this way, the finished dye solutions with a dye content of the formula I of, for example, 15 to 55%, preferably 20 to 35%, are obtained directly.

There is no wastewater pollution from table salt, since the dye of formula (I) is no longer isolated by salting out.

Surprisingly, it was found that solvents, which have only a low solubility in water, give solutions due to the solubilizing effect of the dye, which can be mixed with water in any ratio.

A preferred group of dyes, the concentrated solution of which can advantageously be prepared by the new process, corresponds to the general formula

10th

X1

\

c-n = n-a '

n i

r

(iv)

VS03

wherein

I.

, c-

n t

r

35

a rest of the formulas

"XX

n

S

* c-

or

40

i / "

^ N

k10

means in which

R4 for hydrogen, optionally substituted by hydroxy or phenyl Ci-C4-alkyl, for Ci-C4-alkoxy, C1-C4-alkoxycarbonyl, Ci-C4-alkylcarbonylamino, optionally by Ci-CU-alkyl, Ci-C4-alkoxy or chlorine substituted Phe- 50 noxy or phenoxysulfonyl,

Rs is hydrogen, Ci-Gt-alkyl, nitro or phenyl optionally substituted by Ci-Ct-alkyl, Ci-Ct-alkoxy or chlorine and

Rio represents hydrogen, Ci-Ct-alkylcarbonyl, Ci-Ct-alkylsulfonyl, benzoyl, carboxyl, Ci-Ct-alkyloxycarbonyl or amino-carbonyl,

A 'a rest of the formulas

R5 represents hydrogen, optionally substituted by hydroxy, Ci-Ct-alkoxy, chlorine, cyano, Ci-Ct-alkoxycarbonyl, Ci-Gt-alkylcarbonyloxy, mono- or di-Ci-Ct-alkylamino or for Ci-Gt-alkyl phenyl or benzyl optionally substituted by Ci-Gt-alkyl, Ci-Gt-alkoxy or chlorine,

Ré for hydrogen; alkyl optionally substituted by hydroxy, C1-C4-alkoxy, chlorine, cyano, Ci-Ct-alkoxycarbonyl, Ci-Gt-alkylcarbonyl-oxy or optionally substituted by chlorine, Ci-Gt-alkyl or Ci-Gt-alkoxy Benzyl, R7 for hydrogen and

Rs represent hydrogen, Ci-Ct-alkyl, Ci-Gt-alkoxy, chlorine, bromine, Ci-Gt-alkylcarbonylamino or nitro and Re together with Rs or with R7 and N can form a 5- or 6-membered ring, and

R11 is Ci-Ct-alkyl or phenyl optionally substituted by Ci-C4-alkyl, Ci-Gt-alkoxy or chlorine,

R12 for hydrogen, optionally substituted by hydroxy, chlorine, cyan, Ci-Gt-alkoxy, Ci-C4-alkylcarbonyloxy, aminocarbonyl or amino Ci-Gt-alkyl and

R13 represents hydrogen, halogen, Ci-Ct-alkyl, Ci-Gt-alkoxy or Ci-Ct-alkylcarbonylamino and in which R and R3 have the meaning given in formula (I).

The alkyl groups can be substituted, for example, by one or two of the radicals described and the phenyl groups by one to three of these radicals.

Rs can be shared with Rs and N e.g. B. form a morpholine or piperidine ring, and with R7, N and the fused benzene ring a dihydroindole or tetrahydroquinoline ring.

Among the dyes of the formula (IV), the dyes of the formulas (V) and (VI) are preferred

/ R5

R3 ~ S03 (v)

: x> -

"n'î

1.

+

R3-s ° 3-

(vi)

in which the substituents have the meaning given in formula (IV).

Other groups to be emphasized, whose concentrated solutions can be advantageously prepared using the new process, correspond to the general formulas

or r,

r 60 F R '

ijy13 [

R 1 'Iv

11 Ri 2 15 - C1b: 8

(vii)

ch3-o-so ~

means in which in which

626391

R '* for methoxy or ethoxy,

R'5 for methyl, ethyl, propyl, butyl, benzyl, hydroxyethyl or hydroxypropyl,

R 's represent R' s and also phenyl and R 's are hydrogen, methyl, methoxy, chlorine, bromine and nitro, and

I •

12

10th

(viii)

ch3-0s03 15

in which 20th

R '9 represents hydrogen, methyl or phenyl,

R '10 for hydrogen, phenyl, methyl, nitro, cyano, acetyl, benzoyl, carboxyl or carboxylic acid ethyl ester and

R '12 represent methyl, ethyl, cyanoethyl or aminopropyl. After the alkylation has taken place, further solvents and diluents can be added to the dye solutions, for example organic acids, such as formic acid, acetic acid, methoxyacetic acid, ethoxyacetic acid, propionic acid, methoxypropionic acid, ethoxypropionic acid, lactic acid, diglycolic acid or polyvalent alcohols and their esters and 30 ethers.

In addition, emulsifiers can also be added, such as polyethylene oxide adducts with long-chain alcohols, such as stearyl or oleyl alcohol or with phenols, such as nonylphenol or dodecylphenol. 35

Treatment of the dye solutions with activated carbon, diatomaceous earth or aluminum oxide is possible as a cleaning operation.

The dye solutions are particularly suitable for dyeing polyacrylonitrile and acid-modified polyesters and polyamides.

The dye solutions are characterized by very good storage stability, even at low temperatures.

Example 1 45

20 parts by weight of the azobase, which is obtained by coupling dia-doped 2-amino-6-methoxybenzthiazole to dimethylaniline, are heated to 45 ° C. with stirring, 50 parts by weight of ethylene cyanohydrin and one part by weight of magnesium oxide. 16 parts by weight of 50 dimethyl sulfate are added dropwise at this temperature and the reaction mixture is stirred at 45 ° C. for 3 hours. A dark blue solution forms. After this time, the color base used as the starting material can no longer be detected in the thin-layer chromatogram.

The solution is diluted with 50 parts by weight and 10 parts by weight and 55 parts of glacial acetic acid and the solution is left to stir for a further hour at 45 ° C. to destroy excess dimethyl sulfate. Then let them cool to room temperature and vacuum them off. There is practically no residue on the filter. This gives 144 g of a dye solution which dyes textile materials 60 made of polyacrylonitrile in a clear blue with excellent fastness properties.

Example 2

33 parts by weight of the color base, which are obtained in a known manner by coupling 65 diazotized 2-amino-6-methoxybenzothiazole to ethyloxethyl-aniline, are mixed with 50 parts by weight of butylene glycol (1,4) and one part by weight. Part of magnesium oxide stirred and heated to 30 ° C. Then 27.5 parts by weight of dimethyl sulfate are added dropwise in the course of 10 minutes and the mixture is subsequently stirred at 30 ° C. for 2 hours. Then another 0.5 part by weight of magnesium oxide and 5 parts by weight of dimethyl sulfate are added to the reaction mixture and the solution is stirred for a further 1 hour at 30 ° C. The starting material can then no longer be detected in the thin-layer chromatogram. 50 parts by weight of water are now added and the solution is left to stir at 26 to 28 ° C. for 30 minutes. 50 parts by weight of water and 40 parts by weight of ethylene glycol are then added and the solution is cooled to room temperature with stirring. You suck it off. There is practically no residue on the filter. This gives 257 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a clear blue with excellent fastness properties.

Example 3

35 parts by weight of the color base, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole on ethylhydroxypropylaniline, with 50 parts by weight of butylene glycol (1, 4) and 6 parts by weight of sodium bicarbonate Heated to 30 ° C. 27.5 parts by weight of dimethyl sulfate are added dropwise at this temperature in the course of 10 minutes. After stirring for 2 hours at 30 ° C., a further 2.5 parts by weight of sodium bicarbonate and 5 parts by weight of dimethyl sulfate are added, and the reaction mixture is stirred at 30 ° C. for a further 2 hours. After this time, no starting material can be detected in the thin-layer chromatogram. The dark blue dye solution is now diluted with 50 parts by weight of water and the mixture can be stirred at 27 ° C. for a further 30 minutes. Then 77 parts by weight of water and 13 parts by weight of glacial acetic acid are added to the solution. After cooling to room temperature, they are suctioned off. There is practically no residue on the filter. This gives 266 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a clear blue with excellent fastness properties.

Example 4

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to diethylaniline, are heated to 45 ° C. with stirring, 60 parts by weight of ethylene cyanohydrin and one part by weight of magnesium oxide. 16 parts by weight of dimethyl sulfate are added dropwise at this temperature and the reaction mixture is stirred at 45 ° C. for 3 hours. After this time, no starting material can be detected in the thin-layer chromatogram. The solution is diluted with 30 parts by weight of water, 10 parts by weight of glacial acetic acid and 10 parts by weight of ethylene glycol and the solution is stirred for a further hour at 45 ° C. to destroy excess dimethyl sulfate. After cooling to room temperature, the dark blue solution is filtered and 144 parts by weight of a dye solution are obtained, which dye textile materials made of polyacrylonitrile in a clear blue with excellent fastness properties. In the above example, if the 10 parts by weight of ethylene glycol are replaced by 10 parts by weight of 3-chloropropane, dye solutions with similar properties are obtained.

Example 5

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to dimethylaniline, are stirred with 50 parts by weight of propylene carbonate and 16 parts by weight of dimethyl sulfate are added dropwise. The reaction mixture is heated to 100 ° C. and left to stir at this temperature for 6 hours. Then it is diluted with 50 parts by weight of ethylene cyanohydrin and allowed to cool to room temperature. The dark blue dye solution is filtered. There is practically no residue on the filter. 150 parts by weight of a dye solution are obtained, the textile material

7

626391

made of polyacrylonitrile in a clear blue color with excellent fastness properties.

If the solvent used instead of propylene carbonate is an equal amount of acetonitrile, methyl cyanoacetate, methoxypropionitrile or diethyl oxalate, 5 dye solutions with similarly good properties are obtained.

Example 6

20 parts by weight of the azobase, which is obtained by coupling dia-10-quoted 2-amino-6-methoxybenzthiazole on diethylaniline, are mixed with 70 parts by weight of ethylene cyanohydrin and 22 parts by weight of methyl p-toluenesulfonate at 100 ° for 3 hours C warmed. After cooling, the solution is filtered. It stains polyacrylonitrile materials in a clear blue. 15

Example 7

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole onto N-ethyl-N-ox-ethylaniline, are mixed with 70 parts by weight of ethylene cyanogen-2o and one part by weight. Part of magnesium oxide heated to 45 ° C. 14 parts by weight of dimethyl sulfate are added dropwise at this temperature and the reaction mixture is stirred at 45 ° C. for 2 hours. Then another 20 parts by weight of the azobase and another part by weight of magnesium oxide are added to the reaction mixture to 25 and stirring is continued for a quarter of an hour. Then another 14 parts by weight of dimethyl sulfate are added dropwise and the mixture is heated at 45 ° C. for a further 2 hours. Starting material is no longer detectable in the thin-layer chromatogram. The dark blue dye solution is diluted with 110 parts by weight of water 30 and 40 parts by weight of ethylene glycol and stirred at 45 ° C. for 1 hour to destroy the excess dimethyl sulfate. After cooling to room temperature, the mixture is filtered and 278 parts by weight of a dye solution are obtained, which dye textile materials made of polyacrylonitrite in a clear blue with excellent fastness properties.

If, in both methylation stages, 4.2 parts by weight of sodium bicarbonate or 2.7 parts by weight of sodium carbonate are used instead of one part by weight of magnesium oxide, dye solutions with similarly good properties are obtained. 40

Example 8

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to N-ethyl-N-ox-ethylaniline, are heated to 80 ° C. with 70 parts by weight of methylglycol acetate and 20 parts by weight of dimethyl sulfate were added dropwise. The reaction mixture is allowed to stir at this temperature for 2 hours. After this time, no starting material can be detected in the thin-layer chromatogram. Then the solution is diluted with 30 parts by weight of ethylene glycol and 50 filtered. This gives 135 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a clear blue with excellent fastness properties.

If, instead of methylglycol acetate, methoxypropionitrile, diethyl malonate or methyl cyanoacetate is used as the solvent and the procedure is otherwise the same, valuable dye solutions are also obtained.

Example 9

20 parts by weight of the azobase which are obtained by coupling dia-60-quoted 2-amino-6-methoxybenzthiazole onto N-ethyl-N-ox-ethylaniline are heated to 80 ° C. with 70 parts by weight of oxalic acid diethyl and at 15 parts by weight of dimethyl sulfate are added dropwise to this temperature. The reaction mixture is allowed to stir at this temperature for 3 1/2 hours, 65 parts by weight of dimethyl sulfate are again added to 65 and stirring is continued at 80 ° C. for a further 1 2 hours. Thereafter, no starting material can be detected in the thin-layer chromatogram. The solution is now mixed with 30 parts by weight of oxypropionitrile, cooled to room temperature and filtered. This gives 135 parts by weight of a dye solution which dyes polyacrylonitrile in real blue tones.

If, in the above example, diethylene glycol dimethyl ether, propionitrile, 3-methoxypropionitrile, dimethylformamide, acetonitrile, propylene carbonate, diethyl malonate or ethyl acetoacetate are used instead of oxalic acid diethyl ester and the procedure is otherwise the same, valuable dye solutions are also obtained.

Example 10

33 parts by weight of the azobase obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to N-ethyl-N-oxy-ethylaniline are stirred with 50 parts by weight of diethylene glycol monomethyl ether and 6 parts by weight of sodium bicarbonate . At 25 ° C., 27.5 parts by weight of dimethyl sulfate are added dropwise in 15 minutes and the reaction mixture is stirred at room temperature overnight. The next morning 100 parts by weight of water are added and the mixture is stirred at 25 ° C. for 30 minutes. Then 40 parts by weight of diethylene glycol monomethyl ether are added and the solution is filtered. This gives 257 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a clear blue. If the same amount of diethylene glycol is used in place of the diethylene glycol monomethyl ether and the procedure is otherwise the same, a valuable dye solution is also obtained.

Example 11

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to N-ethyl-N-hydroxypropylaniline, are stirred with 70 parts by weight of ethylene cyanohydrin and one part by weight of magnesium oxide and to 45 ° C warmed. 14 parts by weight of dimethyl sulfate are added dropwise at this temperature and the reaction mixture is stirred at 45 ° C. for 2 hours. Then another 20 parts by weight of the azobase and one part by weight of magnesium oxide are added. After stirring for a quarter of an hour, 14 parts by weight of dimethyl sulfate are added dropwise, the reaction mixture is stirred for a further 2 hours at 45 ° C. and then cooled to room temperature. After this time, starting material is no longer detectable by thin layer chromatography. The dark blue solution is diluted with 130 parts by weight of water and 20 parts by weight of ethylene glycol and heated to 45 ° C. for a further hour to completely destroy excess dimethyl sulfate. Then the solution is filtered. This gives 275 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a clear blue with excellent fastness properties.

If 4.2 parts by weight of sodium bicarbonate or 2.7 parts by weight of sodium carbonate are used as the acid-binding agent in the two methylation stages instead of one part by weight of magnesium oxide and the procedure is otherwise the same, valuable dye solutions are also obtained.

Example 12

35 parts by weight of the azobase, which is obtained by coupling diazotized 2-amino-6-methoxybenzthiazole to N-ethyl-N-hydroxypropylaniline, are mixed with 50 parts by weight of diethylene glycol and one part by weight of magnesium oxide at 30 ° C. warmed up. 27.5 parts by weight of dimethyl sulfate are added dropwise within 15 minutes and the reaction mixture is stirred at 30 ° C. for 2 hours. Then another 0.5 part by weight of magnesium oxide and 10 parts by weight of dimethyl sulfate are added and the mixture is stirred at 30 ° C. for a further 2 hours. After this time, starting material is no longer detectable by thin layer chromatography. 50 parts by weight of water are added to the dye solution, the mixture is subsequently stirred at 30 ° C. for 10 minutes and 45 parts by weight of butylene glycol and 46 parts by weight of water are then added. After filtration you get

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266 parts by weight of a dye solution that stains polyacrylonitrile materials in clear blue tones.

If you use diethylene glycol monomethyl ether instead of diethylene glycol as a solvent and otherwise discolor in the same way, you get a similar valuable dye solution.

Example 13

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-aminothiazole to 1-methyl-2-phenylindole, are heated to 80 ° C. with 40 parts by weight of ethylene cyanohydrin and 5 parts by weight of triisopropanolamine, and 15 parts by weight Dropped in parts of dimethyl sulfate. The reaction mixture is allowed to stir at this temperature for 3 hours. After this time, starting material is no longer detectable by thin layer chromatography. The solution is then diluted with 20 parts by weight of water and 5 parts by weight of glacial acetic acid, allowed to cool to room temperature and filtered. This gives 95 parts by weight of dye solution which dyes polyacrylonitrile textile materials in a yellowish red with excellent fastness properties.

Example 14

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-aminothiazole to 1-methyl-2-phenylindole, are heated to 100 ° C. with 20 parts by weight of ethylene cyanohydrin and 10 parts by weight of triisopropanolamine. 5 parts by weight of diethyl sulfate are added dropwise at this temperature and the reaction mixture is stirred at 100 ° C. for 2 hours. Then 15 parts by weight of dimethyl sulfate are added dropwise and the reaction mixture is stirred at 100 ° C. for a further 2 hours. After this time, no starting material can be detected in the thin-layer chromatogram. The reaction solution is mixed with 35 parts by weight of water and 5 parts by weight of glacial acetic acid and, after cooling to room temperature, filtered. This gives 105 parts by weight of a dye solution which dyes textile materials on polyacrylonitrile in a yellowish red with excellent fastness properties.

Example 15

20 parts by weight of the azobase, which is obtained by coupling diazotized 2-aminothiazole onto 1-ethyl-2-phenylindole, are heated to 100 ° C. with 70 parts by weight of ethylene cyanohydrin and 20 parts by weight of diethyl sulfate are added dropwise. The reaction mixture is allowed to stir at this temperature for 6 hours and then diluted with 10 parts by weight of ethylene glycol. For destruction

Excess diethyl sulfate is left to stir at 100 ° C. for a further hour, then the solution is cooled and filtered. This gives 115 parts by weight of a dye solution which stains polyacrylonitrile materials in a real yellowish red.

If the same amount of propylene carbonate or triacetin is used instead of the ethylene cyanohydrin, valuable dye solutions are also obtained.

Example 16

20 parts by weight of the azobase used in Example 15 are heated to 100 ° C. with 70 parts by weight of methoxypropionitrile and 26 parts by weight of ethyl p-toluenesulfonate are added. The reaction mixture is heated to 100 ° C. for 3 hours, then another 5 parts by weight of ethyl p-toluenesulfonate are added and the mixture is stirred at 110 ° C. for a further 2 hours. The reaction mixture is then diluted with 30 parts by weight of ethylene cyanohydrin, allowed to cool to room temperature and filtered. This gives 145 parts by weight of a dye solution which dyes polyacrylonitrile textile materials in a yellowish red with excellent fastness properties.

If instead of methoxypropionitrile propylene carbonate, triacetin or methyl glycol acetate is used as the solvent, valuable dye solutions are also obtained.

Example 17

20 parts by weight of the color base used in Example 15 are heated to 100 ° C. with 70 parts by weight of ethylene cyanohydrin and 23 parts by weight of methyl p-toluenesulfonate are introduced. The reaction mixture is allowed to stir at 100 ° C. for 2 hours. Thereafter, no starting material can be detected in the thin-layer chromatogram. The solution is then further diluted with 30 parts by weight of ethylene cyanohydrin, cooled to room temperature and filtered. This gives 140 parts by weight of a dye solution which stains polyacrylonitrile materials in a yellowish red.

If, instead of 70 parts by weight Äthylencyanhydrin the same Gewichtsmerige methoxypropionitrile, propylene carbonate, methyl glycol acetate, propionitrile, oxalic acid di-ethyl ester, methyl cyanoacetate, Bernsteinsäurediäthyl ester, ethyl acetoacetate or ethylene carbonate, and the procedure is otherwise in the same way, we obtain also valuable dye solutions. If the azo color bases listed in the table below are used as starting materials and one of the examples described above is used, valuable dye solutions are also obtained.

8th

5

10th

15

20th

25th

30th

35

40

45

9

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Diazo component

Coupling component

Color on polyacrylonitrile

2-amino-6-methoxybenz-

N-butyl-N-hydroxy-ethyl

Blue thiazole aniline

2-amino-6-ethoxybenz-

N-methyl-N-hydroxyethyl

Blue thiazole aniline

2-amino-6-methoxybenz-

N, N-dihydroxyethylaniline

Blue thiazole

2-amino-6-methoxybenz-

N-ethyl-N- ß-dimethylamino-

Blue thiazole

ethylaniline

2-amino-6-ethoxybenz-

N-methyl-N-cyanoethylaniline reddish thiazole

blue

2-amino-6-methoxybenz-

Bis (2,3-dihydroxypropyl) -

Blue aniline thiazoi

2-amino-6-ethoxybenz-

Ethyl phenyl benzylamine

Blue thiazole

2-amino-6-acetylamino

3 (N-ethyl-N-hydroxyethyl) -

Blue benzothiazole aminotoluene

2-amino-6-methoxybenz-

N-ethyl-3-tolylbenzylamine

Blue thiazole

2-amino-6-methyloxybenz-

Phenyldibenzylamine

Blue thiazole

2-amino-6-methoxybenz-

3-tolyl-dibenzylamine

Blue thiazole

2-amino-6-ethoxybenz-

3-diethylamino-l-ethoxy-

Blue thiazole benzene

2-amino-6-ethoxybenz-

N, N-diethyl-3-chloroaniline

Blue thiazole

2-aminothiazole

N, N-diethyl-3-chloroaniline reddish blue

2-amino-6-methoxybenz-

1,2-Dimethylindole bluish thiazole

red

2-amino-thiazole

1-ethyl-2-methylindole yellowish red

2-aminothiazole

1,2-Dimethylindole yellowish red

2-aminothiazole

1-cyanoethyl-2-phenylindole yellowish red

2-aminothiazole

1-Butyl-2-phenylindole yellowish red

6-methoxy-2-aminobenzothiazole l-methyl-2-phenylindole bluish

Bordo

G