DE1569721C - Process for the production of basic dyes - Google Patents

Description

or their functional derivatives, in which R is an alkyl, cycloalkyl, aralkyl or aryl radical and R _{1 is} hydrogen or a nitrile group, with compounds of the general formulas

R, - CH = C

20th

R, - CH, - C

30th

where R _{2 is} hydrogen or a nitrile group, R _{3 is} an alkyl, cycloalkyl, aralkyl or aryl radical, A is the remaining component of an unsaturated heterocyclic 5- or 6-ring, to which further rings can be fused, and X ~ is an anion , wherein at least one of the radicals R ₁ and R _{2 represents} a nitrile group, with the formation of dyes of the general formula

R-N-C = C-CH = C-C

X "

45

in which R, R ₁ , R ₂ , R ₃ and A have the meaning given above and in which the aromatic rings and the radicals R, R ₃ and A can contain nonionic substituents, optionally in the presence of customary dehydrating agents such as acids or acid anhydrides or chlorides, condensed.
2. Modification of the process for making RN = C-CH ₂ R ₁

with compounds of the formula

O = CH - C = C

in which R, R ₁ , R ₂ , R ₃ , A and X have the meaning given in claim 1 and in which the aromatic rings and the radicals R, R ₃ and A can contain nonionic substituents, or condensed with functional derivatives of the aldehyde compounds.

3. Process for the preparation of basic dyes, characterized in that one Dyes of the formula

, A-

R-N-C = C-CH = C-C

wherein R, R ₁ , R ₂ and A have the meaning given in claim 1 and the aromatic rings and the radicals R and A can have nonionic substituents, treated with quaternizing agents.

4. The method according to any one of claims 1, 2 or 3, characterized in that such Starting products used in which A takes the rest

wherein the benzene nucleus can contain nonionic substituents, and R ₃ denotes a lower alkyl radical.

of basic dyes according to claim 1, 60 my formula characterized in that compounds of the formulas

It has been found that dyes of the general

RNC = CH-R ₁

R-N-C = C-CH = C-C

X ©

(I)

can be produced in a manner known per se by condensing or quaternizing. In the formula (I) means

R is an alkyl, cycloalkyl, aralkyl or aryl radical,

R ₁ and R _{2 are} hydrogen or the nitrile group, where at least one of the radicals R ₁ and R _{2 is} a nitrile group,
R _{3 is} an alkyl, cycloalkyl, aralkyl or aryl radical,

A the remaining members of an unsaturated heterocyclic 5- or 6-ring, to the other Rings can be condensed, and

X is an anion.

The aromatic rings and the radicals R, R ₃ and / or A can contain nonionic substituents.

The dyes (I) are obtained when compounds of the general formula

R-N-C = C-CHO

(H)

R ₂ - CH = C

in the presence of conventional agents promoting such condensation or with their salts of the formula

CH, - C

■ 3 _

X "

(III a)

with compounds of the formula

or their functional derivatives with compounds of the general formula

(III)

40

45

(V)

IO

or their functional derivatives condensed. In the formulas II, III, IHa, IV, IVa and V, R, R ₁ , R ₂ , R ₃ and A have the meaning given above, the radicals X stand for anions, and the aromatic rings as well as R, R ₃ and A can contain non-ionic substituents.

According to another method of preparation, the new dyes can be built up by one Color base of the general formula

R-N-C = C-CH = C

treated with quaternizing agents. The starting dyes VI used for this purpose can, for. B. manufactured by combining a compound (II) with a compound of the formula

R, -CH, -C

(VII)

condensed and the color salt obtained is converted into the color base (VI) in the usual way. In Formulas VI and VII, R, R ₁ , R ₂ and A are as above

condensed, or when one compounds of the formula given meaning, and the aromatic rings

50 R and A can contain nonionic substituents. Suitable quaternizing agents in this process are, for. B. dimethyl sulfate, diethyl sulfate, toluenesulfonic acid ester, methyl iodide, benzyl chloride, 2-chloro diethyl ether and monochloroacetone ...
(IV) 55 Suitable compounds of the formula (IV) are listed below in a list. The position of the core substituents Y, Y ₁ , Y ₂ is represented by the following formula.

NC = CH-R ₁

in the presence of customary acids or their salts of the formula

60

RN = C-CH ₂ R ₁

RNC = CH-R ₁

X ^e (IVa)

R. hydrogen Y Y, methyl Cyan hydrogen hydrogen methyl hydrogen hydrogen hydrogen methyl hydrogen bromine hydrogen methyl hydrogen hydrogen hydrogen methyl hydrogen hydrogen hydrogen ethyl hydrogen hydrogen hydrogen ethyl hydrogen bromine hydrogen ethyl hydrogen bromine bromine ethyl Cyan chlorine chlorine ethyl Cyan hydrogen hydrogen ethyl . hydrogen hydrogen hydrogen n-butyl Cyan hydrogen hydrogen isV-amyl Cyan hydrogen hydrogen Cyclohexyl hydrogen hydrogen hydrogen Benzyl hydrogen hydrogen hydrogen Phenyl hydrogen hydrogen hydrogen 4-ethoxyphenyl hydrogen hydrogen

Y,

hydrogen

hydrogen

hydrogen

Dimethylamino

Methoxy

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

They are in the form of their salts of formula (IVa) according to the process of Belgian patent 645 accessible. From these compounds one obtains by introducing the aldehyde group in the usual way Procedure, e.g. B. according to V i 1 s m e i e r, suitable compounds of the formula (II).

Suitable compounds of the formula (III) or (III a) are for example:

1,3,3-trimethyl-2-methylene-dihydro- (2,3) -indole, 1,3-trimethyl-2-cyanomethylene-dihydro- (2,3) -

indole,
l _t 3,3-trimethyl-2-cyanomethylene-5-methoxy-

dihydro- (2,3) -indole,!, S ^ -trimethyl ^ -cyanmethylene-S-ethoxy-

dihydro- (2,3) -indole, l ^ S-trimethyl ^ -cyanmethylene-S-chlorodihydro- (2,3) -indole,

dihydro- (2,3) -indole, ihl

yy

dihydro- (2,3) -indole,!, S ^ -trimethyl ^ -cyanmethylene-S-isopropyl-

dihydro- (2,3) -indole,!, S ^ -trimetliyW-cyanomethylene-S-carboxy-

methyl-dihydro- (2,3) -indole,! ^, S-trimethyl ^ -cyanmethylene-S-acetamino-

dihydro- (2,3) -indole, hl

sulfonylamino-dihydro- (2,3) -indole, Sihlhlh

yy

dihydro- (2,3) -indole,!, S ^ -trimethyl ^ -cyanmethylene-V-methoxy-

dihydro- (2,3) -indole,! ^ Srihl

dihydro- (2,3) -indole,! ^, S-trimethyl ^ -cyanmethylene-S-methoxy-

7-chloro-dihydro- (2,3) -indole, l-ethyl-3,3-dimethyl-2-cyanomethylene

dihydro- (2,3) -indole, l-benzyl-3,3-dimethyl-2-cyanmethylene-5-methoxy-dihydro- (2,3) -indole, 2,3-dimethyl-benzthiazolium-methosulfate,
2-cyanomethyl-3-methyl-benzthiazolium-

chloride, bromide, iodide and methosulphate,
2-cyanomethyl-3-ethyl-benzthiazolium-

p-toluenesulfonate,
1,3-dimethyl-2-cyanmethyl-benzimidazolium-

chloride,

l-Isobutyl ^ -cyanmethyl-S-ethyl-benzimidazolium ethyl sulfate,

l-phenyl ^ -cyanmethyl-S-ethyl-benzimide-

azolium iodide,
1,3,6-trimethyl-4-methylene-dihydro- (3,4) -

pyrimidone- (2),
1,4-dimethyl-2-methylene-dihydro- (1,2) -

quinoxalone (3),

1,2- and 1,4-dimethyl pyridinium methosulfate,
1,2- and 1,4-dimethyl quinolinium methosulfate

and
1 -Methyl-4-cyanomethyl-quinolinium-metho-

sulfate.

These compounds can also be used in the usual way, for. B. after V i 1 smeier, an aldehyde group in the CH or CH ₂ group of the compounds of

. Introduce formulas III and III a, products of formula V being obtained.

Suitable compounds of the general formula (VII) are, for example, 2,3,3-trimethyl-indolenine, 2-cyanomethyl-benzimidazole, 1-methyl-2-cyanomethyl - benzimidazole, 1 - phenyl - 2 - methyl - benzimidazole, 2-cyanmethyl-benzoxazole, 2-cyanmethyl-benzothiazole, 2 - cyanomethyl-perimidine and 1 - phenyl-2-cyanomethyl-triazole- (1,3,4).

The condensation of the various starting components for the illustration of the novel dyes (I) are prepared by treating the components with dehydrating agents at temperatures between 25 and 150 ° C, preferably between 50 and 12O ⁰ C.

It is advantageous to use an inert liquid and / or an excess of the condensing agent as Use solvents or thinners. Suitable condensing agents are, for. B. inorganic

Niche and organic acids such as hydrochloric acid, phosphoric acid, polyphosphoric acid, formic acid, acetic acid. Propionic acid, chloroacetic acid, acid anhydrides such as acetic anhydride, acid chlorides such as phosphorus oxychloride, Phosphorus trichloride. Thionyl and suI furyichloride and phosgene, as well as mixtures of such Medium.

Suitable solvents or diluents are, for. B. ethylene chloride, chloroform, carbon tetrachloride, Acetylene tetrachloride, benzene, chlorobenzene and dichlorobenzene, nitrobenzene and dioxane, among others.

The dyes obtainable according to the invention are new. They are suitable for dyeing and printing synthetic, semi-synthetic and natural fiber materials, such as polymers and copolymers of acrylonitrile and asym. dicyanethylene, of cellulose esters, silk and stained cotton. They can also be used for production of · writing fluids and ballpoint pen pastes serve and are used to dye paper, coconut or jute and in rubber printing.

The new dyes are very extensive and are characterized by very good drawability high compensatory capacity. They do not stain the wool content of mixed fibers or fabrics. Colorations and prints on materials which are wholly or predominantly composed of polymers and / or copolymers consist of acrylonitrile and / or asymmetrical dicyanethylene, are characterized by exceptional brilliance and excellent fastness properties, especially due to very good light, wet, decatur, Rubbing and subjecting fastnesses.

In comparison with the cationic dye known from Example 7 of Soviet patent specification 122,229 the formula

CH

CH, -N = C-CH = *

he

40

have the next comparable dyes of the formulas available according to the process

45

CH ₃
CH ₃ -NCC-CH = C

CN

CH,

CH ₃ -NC = C-CH = CJ

CN

he

The parts mentioned in the examples are parts by weight. The type of anion is for the dyeing The behavior of the dyes is not decisive.

¹ B eis ρ ie 1 1 5.6 parts of the compound

H ₅ C ₂ -NC = CH-CHO

he

clearly superior lightfastness of the dyeings on polyacrylonitrile.

and 5.0 parts of 1,3,3-trimethyl-2-cyanomethylene-dihydro- (2,3) -indole are heated to 50 ° C. with 50 to 100 parts of chloroform while stirring. The mixture 5 to 10 parts of phosphorus oxychloride are added dropwise, followed by a further 20 to 30 minutes kept simmering. The chloroform is then, advantageously under slightly reduced pressure, distilled off and the remaining dye from 500 parts of water at about 90 ° C recrystallized. The dye of the formula is obtained in a very good yield

CH,

CH,

H ₅ CN = C-CH = CH-C = ¹

CN

which dyes polyacrylonitrile fibers blue with very good fastness properties.

The aldehyde used was prepared as described in Example 1 of Belgian patent 647 036.

If the equivalent is used instead of the aldehyde Amount of the enamine salt of the formula

C ₂ H ₅ -N = C-CH = CH-N

CH,

CH ₃

egg ©

this gives the same dye. The enamine salt is produced in analogy to that in the example 2 of Belgian patent 647 036 described preparation of the corresponding iodide.

This is also the case using formylmethylaniline instead of dimethylformamide available enamine salt of the formula

C ₂ H ₅ -N = C-CH = CH-N- ^ A

CH,

usable.

209 583/293

i 569

and 22.6 parts 1,3,3-trimethyl-2-cyanomethylene-dihydro- (2,3) -indole-eo-aldehyde are heated with 75 parts of glacial acetic acid and 25 to 35 parts of acetic anhydride with stirring at 95 to 105 ° C for 2 to 3 hours. After cooling, the dye solution obtained is diluted with 1000 to 2000 parts of water. The dye of Example 1 separates out on addition of common salt.

The starting product was according to the information in Example 2 of Belgian patent specification 645 980 manufactured.

B e i s ρ i e 1 3

5.6 parts of the aldehyde used in Example 1 and 5.7 parts of 1,3,3-trimethyl-2-cyanomethylene-5-methoxy-dihydro- (2,3) -indole are with 75 to 100 parts of ethylene chloride and 7 to 10 parts of phosphorus oxychloride Heated to 70 to 80 ° C. for 1 hour while stirring. Thereafter, the excess phosphorus oxychloride destroyed by adding water and the ethylene chloride is distilled off with steam. The dyestuff of the formula is separated from the remaining aqueous solution when it cools

CH ₃

C ₂ H ₅ -N = C-CH = CH-C = X _n

CN

OCH,

Cl "

10

The aldehyde used was according to the information in Example 1 of Belgian patent 647 036 manufactured.

Example 2
23.2 parts of the compound

C ₂ H ₅ in -C C1I3

he is used instead of the abovementioned aldehyde, the analogously accessible compound of the formula

C, H _S —N ~ C = CH -

(Melting point 160 to 163 ° C), one obtains
same procedure the dye of the formula

CH ₃
C ₂ H ₅ -N = C-CH = CH-C

CN

OCH,

CH,

40 which dyes polyacrylonitrile materials with excellent fastness properties in a brilliant greenish blue.

Example 4

42 parts 1,3,3-trimethyl-2-methylene-5-aminodihydro- (2,3) -indole are stirred with 150 parts of glacial acetic acid and 90 to 100 parts of acetic anhydride Heated to 70 to 80 ° C for 1 hour. The mixture is then added with 52 parts of the compound

C ₂ H ₅ -NC = C-CHO

CN

45 added and held for 3 hours at 100 to 105 ° C,

partially off. The excretion is added by adding. After cooling down to about 45 ° C one adds

completed by saturated saline solution. The 2500 parts of H ₂ O and 200 parts of saturated sodium chloride

dye obtained in this way dyes fibers and fabrics from solution or the corresponding amount of solid cooking

Polyacrylonitrile with excellent fastness properties is added to fluorescent salt and sucks off the precipitated dye.

tend blue. He is according to the formula

C ₂ H ₅ -NC = C-CH = CH-

NHCOCH ₃

he

composed and dyes polyacrylonitrile fibers and fabrics deep blue.
The aldehyde used was prepared as follows: 100 parts of 6% strength aqueous cyanogen chloride solution are underlaid with 200 parts of chloroform. First you give 12 parts of the compound

N ^ = ³ C CH ₁

ci ^e

, then the solution of 8.5 parts of sodium hydrogen carbonate is added dropwise with stirring at room temperature in 100 parts of water and leave the mixture for a few hours or overnight at room temperature stir. The separated chloroform layer leaves behind on evaporation with an almost quantitative yield the compound of formula

C ₂ H ₅ -NC = CH-CN

which is obtained in sufficient purity for further processing. After recrystallization from methylcyclohexane, the melting point is 127 ^° C.

6.6 parts of the chloroform residue are dissolved in 20 parts of dimethylformamide with heating. 6 parts of phosphorus oxychloride are added dropwise to the solution at 50 to 60 ° C. with thorough stirring, and the mixture is kept them for another 2 hours at this temperature. When discharging the reaction mixture to 100 to 200 parts Water gives an orange-colored solution from which the addition of about 20 parts is concentrated Caustic soda the aldehyde of the formula

20th

N-C = C-CHO

C ₂ H ₅ -NC = C-CH = CH- ¹ ^
CN

cr

composed and colors polyacrylonitrile real blue-green.

If you use the equivalent amount of l-methyl-4-n-propyl- or l-methyl-4-phenyl-2-methylene-dihydro- (1,2) -

quinoxalone- (3), very similar dyes are obtained with the same procedure. The quinoxalone derivatives were manufactured according to the specifications of the Belgian patent specification 606 907.

B e i s ρ i e 1 6

24.8 parts of the aldehyde used in Example 4 and 14 parts of 1,3,6-trimethyl-4-methylene-dihydro- (3,4) -pyrimidone- (2) are with 90 parts of glacial acetic acid and 20 parts of acetic anhydride for 3 to 4 hours Heated from 100 to 105 ° C. The cooled dye solution is converted into about 1000 parts of 5 to 10% saline solution poured, taking the dye of the formula

CH,

35 CA-N = C-C = CH-CH = CC = O

HC

N-CH,

CH,

fails. It is suitable for dyeing and printing acetate silk in blue tones.

Example 7

55 parts of the compound of formula
H ₅ C ₂ -NC = CH-CN

excreted in pure form. The melting point is 176 to 180 ° C

B e i s ρ i e 1 5

24.8 parts of the aldehyde used in Example 4 and 19 parts of 1,4-dimethyl-2-methylene-dihydro- (1,2) -quinoxalone- (3) are treated with 200 to 300 parts of carbon tetrachloride and 20 parts of phosphorus oxychloride for 2 hours heated to boiling. The precipitated dye is recrystallized from dilute acetic acid. It is according to the formula which was prepared by the method described in Example 4, and 51 parts of 1,3,3-trimethyl-2-methylene- dihydro- (2,3) -indole-ω- aldehyde are 1000 to 2000 Parts of chloroform and 65 to 75 parts of phosphorus oxychloride are heated to boiling for 2 hours with stirring. After the chloroform has been distilled off, the residue is recrystallized from water at about 90.degree. The dye of the formula is obtained

55

60 CH,

CH;

H ₅ C ₂ -NC = C-CH = CH- ^ _n

CN

CH,

which dyes polyacrylonitrile fibers blue with very good fastness properties.

If the equivalent amount of 5-methyl, 5-methoxy, 5-ethoxy, 5-chloro, 5-bromine, 5-carbomethoxy, 7-chloro, 7-ethyl is used in place of the above-mentioned aldehyde - or 7-methoxy-1,3,3-trimethyl-2-methylene-dihydro- (2,3) -indole-cu-aldehyde _J , dyes with similar coloristic properties are obtained with the same procedure.

i 569 72

Example 8

8.6 parts of 1-methyl-2-cyanomethylbenzimidazole and 11.1 parts of the aldehyde used in Example 1 are stirred with 100 parts of ethylene chloride. On addition of 17 parts of phosphorus oxychloride the increases. Temperature quickly to about 60 ⁰ C; one erwä'rmtweiter to boiling, holding the mixture for 2 to 3 STUN ^=: the reflux and distilled ethylene chloride then from. The residue, which is only sparingly soluble in alcohol, is boiled with 200 parts of alcohol and then stirred with excess 20% sodium carbonate solution for a few hours at room temperature. The product thus obtained consists essentially of the compound of the formula

C ₂ H ₅ -NC = CH-CH = CC

CN

CH

C ₂ H ₅ -NC = CH-CH = CC

CN

CH,

CH ₃ SO |>

15th

and melts at 200 to 204 ° C.

5 parts of this crude product are dissolved in about 500 parts of toluene and 2 parts of acid-free Dimethyl sulfate heated to boiling for 1 to 2 hours. The dye of the formula

25th

30th

35

is eliminated. He dyes polyacrylonitrile fibers and - Violet fabric with very good fastness properties.

Is used instead of 1-methyl-2-cyanomethyl-benzimidazole the equivalent amount in each case

1-ethyl-, 1-n-propyl-, 1-iso-butyl- or 1-phenyl-2-cyanomethyl-benzimidazole, in this way, with the same procedure, dyes with similar coloristic properties are obtained Properties.

"" "'■' Dyeing instructions

\. In an aqueous dye bath, which per liter

0.75 g -30% acetic acid,
0.40 g of sodium acetate and
0.20 g of the dye of the formula

CH,

CH ₃
H ₅ C ₂ -NC = CH-CH = CJ

CN

OCH ₃

Cl ^e

CH ₃

the amount of polyacrylonitrile fibers corresponding to the 1:40 liquor ratio is brought at 40 to 50 ° C a, heats the bath to the boil in about 30 minutes while agitating the fiber material and keep it simmering for 30 minutes to 1 hour. After the fiber has been rinsed and dried, one is obtained very clear, blue coloration with excellent fastness properties.

A polyacrylonitrile fabric is printed with a paste of the following composition:

30 parts of the dye prepared according to Example 1,

50 parts of thiodiethylene glycol,

30 parts of cyclohexanol,

30 parts of 30% acetic acid,
500 parts of crystal rubber,

30 parts of aqueous zinc nitrate solution (d - 1.5) and 330 parts of water.

After drying, the pressure is dampened for 30 minutes and then rinsed. You get one very real, blue print.

Claims (1)

Patent claims: 1. A process for the preparation of basic dyes, characterized in that 's that compounds of the general formula R-N-C = C-CHO IO