DE2927205A1 - ORGANIC COMPOUNDS, THEIR PRODUCTION AND USE - Google Patents

Description

2327205

- 4 - Case 150-4200 / A

Organic compounds, their production and use,

The invention relates to basic azo compounds free of sulfonic acid groups the formula

R "-CN _; . _/ - (A

R-C N * '

4 t

^R 2 ^R 6
where R and R each independently represent an unsubstituted (1-

J, 4L

4C) -alkyl radical,

R and R, independently of one another, each: partly hydrogen or an unsubstituted tuierten (1-4C) -Alk} 'l residue,

R ₁ . Hydrogen, an unsubstituted (1-4C) -alkyl radical or a (2-4C) -alkyl radical substituted by OH or -0- (l-4C) -alkyl,

R halogen and

A mean an anion.
Advantageous compounds correspond to the formula

II,

wherein R ₁ and R independently of one another are each methyl or ethyl,

Ia I. a

R V7asse?: Substance, methyl, ethyl, 2-hydroxyethyl, 2-IIydiOxypropyl or

-C H-O-CIL and 3 6 3

R ,. Mean chlorine odexfluor. 6a

Particularly advantageous compounds correspond to the formula

© R. H • NH-R ₁ . , la / H-C- I. ^, C-N = N- <pV H-C- ■ W'S \
Ha R ₄ .
6a

CH ₃ H

HC lL / (Α ^Θ

J © WOhH-E III,

nc ir j— ^{1 D}

CH

₃ 6a
wherein R is hydrogen or methyl.

90988W07S5

Case 150-4200 / A

The process for the preparation of compounds of the formula I is characterized in that that you can get a compound of the formula

V ^c - ^N v / - (©

^V 4,

^E 2 \

where X is halogen,

with a compound of the formula H "N-R V implements,

this conversion can take place in a generally known manner.

Another process for the preparation of compounds of the formula I is characterized in that in a compound of the formula

VI,

where Y is -CO- or -SO- and Q is a (1-4C) -alkyl radical,

with a dissociable acid H-A, or with a Base.worin A in a Anion A convertible radical means, according to known methods, the radical -Y-Q splits off. -

In the above formulas, R ₁ and R are increasingly important

R and R, or for CH;,; '

la ■ * a. j

R and R, for hydrogen;

R ,. for R_, or for R,.,;

5 5a 5b

R. for R,.

6 6a

R and R in the meaning of an alkyl radical mainly represent methyl or EthyI, especially for methyl;

R in the meaning of an alkyl radical, mainly represents methyl or EthyI, especially for methyl;

Rj. In the meaning of a substituted alkyl radical mainly represents 2-hydroxyethyl, 2-hydroxypropyl or -C ₀ H ^ -O-CH ₀ ;

3 6

909884/0755

- 6 - Case 150-420Ό / Α

R in the meaning of halogen mainly represents chlorine or fluorine especially for chlorine;

As the anion A, those customary in basic dye chemistry come into question, mainly non-chromophoric anions are suitable. Under anion A are both to understand organic and inorganic ions, such as halide, such as chloride or bromide, also sulfate, bisulfate, methyl sulfate, aminosulfate, Oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, Methanesulfonate or benzoate ions or complex anions, such as that of zinc chloride double salts, also the anions of the following acid: boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid or addition products of orthoboric acid with polyalcohols or cis-polyols.

In the compounds of formula 1, the anion A can be replaced by other anions exchange according to known methods, e.g. with the help of an ion exchanger or by reaction with salts or acids, if necessary in several stages, e.g. via the hydroxide or via the bicarbonate or according to the German Offenlegungsschrift 2,001,748 or 2,001,816.

The compounds of the formulas IY, V and VI are known and can be prepared by known methods. The cleavage of the YQ--group in the compounds of formula VI, is mainly in aqueous solution and in the presence of a strong mineral acid, for example hydrochloric acid or in a mixture of an organic acid, eg acetic acid and a mineral acid at temperatures of 50-100 ⁰ C advantageously between 60 and 80 ⁰ C. The reaction of a compound of the formula IV with a compound of the formula V can be carried out by known methods.

The compounds of formula I can be used well with; other basic dyes, especially combine with a low cation weight when dyeing.

The new compounds can be converted into coloring preparations. The processing stable solid or liquid coloring preparations can be made in a generally known manner, such as by grinding mixing or granulation Spray drying. Stable liquid preparations are made by dissolving the Dyes in suitable solvents or solvent mixtures, if necessary after

909884/0756

■ -7'-. "" ■ Gases 150-4200 / A

previous anion exchange and, if necessary, with the addition of auxiliaries such as e.g. solubilizers or antioxidants. Such preparations can e.g. according to the information in French patents 1,581,900 and 1,572,030 or in accordance with the German Offenlegungsschriften 2.001.748 and 2.001. 816 received xrerden.

The new compounds are dyes and are used for dyeing, padding or printing flakes, fibers, threads, tapes, woven or knitted fabrics made from polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, -ircidazole, -alcohol, acrylic and methacrylic acid esters ^ and -amides, as. Dicyanäthylen, or flakes, fibers, threads, tapes, woven and knitted fabrics from acidic modified aromatic. Polyesters and acid-modified polyamides. Acid modified aromatic polyesters, such as, for example, polyethylene glycol therephthalates containing sulfonic acid groups, are described in Belgian patent specification No. 549,179 and American patent specification 2,893,816. Acid modified polyamides are described, for example, in American patents 3,039,990 and 3,454,351. The new dyes are also used to dye fiber blends and the blended fabrics made from them, such as polyacrylonitrile / wool blends. The new compounds are also suitable for dyeing leather and paper and plastics.

The new connections are also suitable for continuous dyeing of wet cables (Gel staining process), a liquid staining preparation being particularly suitable is. The continuous dyeing of cash register cable is e.g. in the magazine "Textilveredlung" JO, 63 (1975).

As is customary with canonical dyes, textile material can advantageously be dyed from neutral or acidic, aqueous liquor in liquor ratios of 1: 3 to 1:80 and at temperatures from 60 ^° C. to 100 ^° C. or under pressure at over 100 ^° C. The dyeing can be carried out with the addition of the usual auxiliaries, such as, for example, bodecyldimethylbenzylamraonium chloride as a retarder or, for example, stearyl alcohol with 50 mol of ethylene oxide as a nonionic auxiliary or E.B.-BenzylojryjJ: opionitrile as a coloring accelerator.

Those dyes that are used in organic solvents, such as ζ, .Β. Chlorinated carbon? are only readily soluble, are also suitable for coloring from these solutions;? - Mittel, -wi α e.g. described in the German Ofienleg.ingsschrift 2,437,549

^isu 9.9884 / 07.8

·· 8 - Case 150-42Q0 / A

When used for printing the specified polymers, the printing inks Usual auxiliaries such as wetting agents and thickeners added.

The dyes or the dyeings and prints are generally distinguished Brilliance, high color strength, good drawability and a high level of fastness, which means that the dyes or the dyeings and prints in usually due to good light fastness, pH stability, combinability, migration ability, Pre-cooking stability, ironing fastness, heat resistance, wool reserve, steam fastness, washing fastness, perspiration fastness, pleating fastness, decatation fastness, Fastness to dry cleaning, fastness to over-dyeing, resistance to hydrolysis, as well as good solubilities, a high saturation limit and a low one Characterize electrolyte sensitivity.

The compounds of the formula I are particularly suitable for the uniform dyeing of polyacrylonitrile materials with different drawing speeds, in particular of slow, normal or fast drawing polyacrylonitrile material. When dyeing such material, the compounds of formula I have good migration capacity; they can advantageously be colored without a retarder; if they are colored with a retarder, it is advantageous that the retarder also has the ability to migrate. Such retarders are known. Slow, normal or fast drawing polyacrylonitrile material is known, for example, from German Offenlegungsschrift 25 ^f 48'009.

In the following examples, parts mean parts by weight and percentages Weight percent. The temperatures are given in degrees Celsius.

B e is ρ ie 1 1

37 parts of 2-chloro-4-aetylamino-ani] in 350 parts of water, 10Q parts Acetic acid and 50 parts of 30Z hydrochloric acid at 0-5 ° with 60 parts of sodium nitrite solution, 4n, diazotized. After destroying the excess nitrous acid 1.5 parts of aminosulfonic acid are added dropwise to the clear diazonium salt solution a 0-5 ° cold solution consisting of 13.6 parts of imidazole in 100 parts of water. During the coupling, the pH is increased by continuous addition held at 9-10 by 30% sodium hydroxide solution. The temperature will kept below 5 ° by adding ice. The suspension is stirred for a further 2 hours and the precipitated dye is filtered off.

90988A / 07ES

- 9 - Case 150-4200 / A

The filter cake is washed with 500 parts of water and at 50 ° in vacuo dried. 27.5 parts of the dried and ground dye of the formula

NHCOCH ₃

Cl

are suspended in 250 parts of water with the addition of 2.5 parts of sodium carbonate and the suspension is heated to 40 °. Then 63 parts of dimethyl sulfate at once added at 40 °. After 3 hours of stirring at 35-40 ° and a pH range of 7.5-8.5, this is done by adding 30% sodium hydroxide solution is observed, a thin-layer chroniatographic control shows no Starting product more. After adding 130 parts approx. 26% -igei- brine and 20 Parts of zinc chloride, the dye suspension is stirred until cold; cooled and washed with 15% sodium chloride solution.

The moist press cake is then stirred in 400 parts of 6% hydrochloric acid and heated to 75 ° for 2 hours. Then-the solution with 30% sodium hydroxide solution brought to pH 6, the resulting The suspension is filtered off at 40-50 °, with 100 parts of 10% sodium chloride solution washed and dried at 50-60 ° in vacuo. A dye of the formula is obtained

Cl

the polyacrylonitrile or anionically modified polyester fibers in real orange or scarlet red tones and good migration capacity on polyacrylonitrile having.

Example 2

48 parts of the dye of the formula

obtained by coupling diazotized! 2,4-dichloroaniline based on imidazole known method, are stirred in 500 parts of dioxane at 40 ° and 84 parts Magnesia added. Q09884 / Q756

- 10 - Case 150-4200 / A

HQ parts of dimethyl sulfate are added dropwise within j hours and the mixture is subsequently stirred in this temperature range for 1-2 hours. It is then diluted with 600 parts of water ^at 40 ° and the yellow solution is admixed with 15 parts of activated charcoal. After clarifying filtration, concentration to half the volume under reduced pressure, the resulting solution is again clarified by filtration over a little filterard (Hyflo) and mixed with 14 parts of zinc chloride and 280 parts of approx. 26% sodium chloride solution. The yellow suspension is stirred for a further 2 hours, the precipitated dye is filtered off, the residue is washed with a little cold 10% sodium chloride solution and dried at 50 ° in vacuo. 41.5 parts

of the dried dye of the formula with a titer of approx. 90% CH ₃

ZnCl, " ²

are in a solution consisting of 500 parts of water at 50 °. 40 parts of ethanolamine and 1.5 parts of glacial acetic acid are added and the solution is stirred at 60 ° for 2 hours. Allow to cool to room temperature. After clarifying filtration, the scarlet filtrate is blunted with hydrochloric acid to a pH of 5-5.5. 100 parts of sodium chloride are then added and, after stirring for hours, the dyestuff which has precipitated out is filtered off. The red dye can be further purified by dissolving it in 10% acetic acid, shaking it out with toluene or trichlorethylene and reprecipitating it as a chloride salt. After drying the moist presscake in vacuo at 50 °, the dye of the formula CH,

Cl

3 dyes the polyacrylonitrile or anionically modified polyester fibers in real orange or scarlet red tones.

90988A / 0755

- 11 - Case 150-4200 / A

Dyeing instructions A

PolyacrylnltriIfasern at 60 ⁰ C in a liquor ratio L; incorporated 80 in an aqueous bath containing, per liter of 0.125 g of glacial acetic acid, 0.375 g of sodium acetate and 0.15 g of the dye described in Example 1 (or the corresponding amount of a solid or liquid preparation of this dye ) contains. The mixture is heated to the boil within 20 to 30 minutes and the bath is kept at this temperature for 90 minutes. After rinsing, an orange dyeing with good fastness properties is obtained.

Dyeing instruction B

Acid-modified polyester fibers are ^{introduced into an aqueous bath at 20 °} C. in a liquor ratio of 1:40, which contains 3 g of sodium sulfate, 2 g of ammonium sulfate and 2.5 g of a carrier based on a nonionic dyeing aid per liter and adjusted to pH with formic acid Value of 5.5 has been set. The mixture is heated to 60 ^° C. and 0.15 g of the dye described in Example 1 or the corresponding amount of a solid or liquid preparation of this dye is added and the mixture is heated to the boil in about 30 minutes. The bath is kept at this temperature for 60 minutes. It is then rinsed and dried. An orange dyeing with good fastness properties is obtained.

Dyeing instruction C

Acid-modified polyester fibers are ^{introduced into an aqueous bath at 20 °} C. in a liquor ratio of 1:30, which contains 6 g of sodium sulfate, 2 g of ammonium sulfate and 0.15 g of the dye described in Example 1 or the corresponding amount of a solid or liquid preparation thereof per liter Contains dye. A pH of 5.5 is set with formic acid. ^{It is heated to 120 °} C. in the course of 45 minutes in a closed vessel and this temperature is maintained for 60 minutes with shaking. After rinsing and drying, an orange dyeing with good fastness properties is obtained.

Dyeing instruction D

Proceed in the same way as in dyeing instruction C, but heat the closed vessel to 110 ^° C.

909884/0755

2327205

Case 150-4200 / A

FM rb ά ν ο rs ch rift E

Acid-modified polyamide fibers are placed at 20 ⁰ C in a liquor ratio of 1:80 in an aqueous bath containing, per liter, 3.6 g potassium hydrogen phosphate 0.7 g üinatriumhydrogenphosphat Ig of an aid such as a zB.-Unisetzungsprodukt a phenol nit excess Aer.hylenoxid and 0 , 15 g of the dye described in Example 1 (or the corresponding amount of a solid or liquid preparation of this dye) contains. The mixture is heated to the boil in about 30 minutes and the bath is kept at this temperature for 60 minutes. After rinsing and drying, an orange dyeing with good fastness properties is obtained.

The structure of further dyes is given in Table I below. They can be prepared according to the information in Examples 1 and 2 and correspond to the formula

® \ CK = N- (O

N-:

-H
• R.

worm R _lj r « _unc j ρ di _{e ln f} ] _en columns have given meanings. as

Θ.

Anion A are those listed in the description.

E.g. ^R l ^R 2 909884 / Λ ^R 5 3 -CH ₃ -CH ₃ F. H 4th do. do. F. -CH ₃ 5 do. do. F. ^ C ₂ H ₅ 6th do. do. F. -C ₂ H ₄ -OH 7th do. do. F. -C ₃ H ₆ OH 8th do. do. F. -C ₃ H ₆ OCH ₃ 9. do. do. F. ~ ^C 4 ^H 9 10 do. do. Cl -CH ₃ 11 do. do. Cl ~ ^C 2 ^H 5 12th do. do. Cl -CH-CHOH-CH 13th do. do. Cl -C ₃ H ₆ GCH ₃ 14th do. do. Cl ~ ^C 4 ^H 9 1755

E.g, Λ ^R 2 15th -CH, -CH ₃ 16 -C ₂ H ₅ -C ₂ H ₅ 17th -CH ₃ -CH ₃ 18th do. do.

13 -

Case 150-Λ200 / Α

The dyes of Examples 3 and 16 dye polyacrylonitrile in orange tones, those of Examples 4-15, 17 and Ϊ & in scarlet tones.

3700 / ZG / SG

909884 / 07B5

Claims (3)

SANDOZ-PATENT-GMBH Case 150-4200 / A Lörrach Organic compounds, their production and use, patent claims 1. Basic azo compounds free of sulfonic acid groups of the formula I © \ cN = N / 0 / NH-R I, R-C N ^) - ' R ₂ ^R 6 wherein R and R each independently represent an unsubstituted (1-4C) -alkyl radical,
and R, independent
unsubstituted (1-4C) -alkyl radical,
Hydrogen, an unsubstituted
(2-4C) -alkyl radical substituted by OH or -0- (1-4C) -alkyl, R and R, independently of one another, are each hydrogen or one unsuccessful
R is hydrogen, an unsubstituted (1-4C) -alkyl radical or a R, halogen and A mean an anion. 2. Azo compounds according to claim 1 corresponding to the formula ? la H _θ H-C -— N ^ y— (A- - J Φ. ^ CNN- (OV-NH-R ₅ II, HC W > - ^y ID R. 6a
2a wherein R and R independently of one another are each methyl or ethyl, X. ei A SL R. hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl or "-CH.-0-CH ₀ and JOj R, chlorine or fluorine mean.
3. Azo compounds according to claim 1 corresponding to the formula TT fi ^^^ ₁ ^ j Γ1 V7 - ^HC "~ * · \ I 90988A / 075 $ where R "is hydrogen or methyl. r> b 2327205 ^Case 3 5Q-4200 / A 4. A process for the preparation of azo compounds of the formula I according to claim 1, characterized in that a compound of the formula Α ^θ where X is halogen, with a compound of the formula HN-R V implements. 5. A process for the preparation of azo compounds of the formula I according to claim 1, characterized in that in a compound of the formula wherein Y -CO- or -SO - and Q is a (1-4C) -alkyl radical, with a dissociable acid H-A, or with a base in which A is an in an anion A convertible radical means, the Rast -Y-Q cleaves by known methods. 6. Process for dyeing, padding and printing fibers, threads or from them manufactured textiles, which consist of homo- or copolymers of acrylonitrile ^ or asymmetrical dicyanoethylene, or contain such, or those of synthetic polyamides which are modified by acidic groups, consist or contain such, or those of synthetic Polyesters which are modified by acidic groups, exist or contain such, characterized in that for this purpose sulfonic acid group-free basic azo dyes of the formula I according to claim 1 are used. 7. A method for dyeing or printing plastics and leather, characterized in that that for this purpose basic dyes of the formula I which are free from sulfonic acid groups are used. 909884/0758 - X- Case 15Q-A200 / A 8. A method for dyeing or printing paper, characterized in that • For this purpose, basic azo dyes of the formula I which are free from sulfonic acid groups are used according to Claim 1 used. 9. Die.gemäss claim 6 dyed, padded or printed textiles. IQ. The materials dyed or printed according to claims 7 and 8. 9098 8 4/0765