GB2032447A

GB2032447A - Improvements in or relating to organic compounds

Info

Publication number: GB2032447A
Application number: GB7924048A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1978-07-13
Filing date: 1979-07-10
Publication date: 1980-05-08
Also published as: DE2927205A1; FR2430963B1; GB2032447B; FR2430963A1; BR7904449A; IT7949644A0; JPS5513792A

Abstract

Compounds of formula I <IMAGE> in which R1 and R2 are independently unsubstituted C1-4 alkyl, R3 and R4 are independently hydrogen or unsubstituted C1-4 alkyl, R5 is hydrogen, unsubstituted C1-4 alkyl or C2-4 alkyl mono-substituted by OH or C1-4 alkoxy, R6 is halogen and A<(-)> is an anion, are useful as basic azo dyestuffs having good fastness and migration properties.

Description

SPECIFICATION Improvements in or relating to organic compounds This invention relates to basic azo compounds free from sulphonic acid groups.

More particularly, the invention provides basic azo compounds of formula I

in which R1 and R2 are independently unsubstituted C1-4alkyl, R3 and R4 are independently hydrogen or unsubstituted C1~4alkyl, R5 is hydrogen, unsubstituted Alkyl or Alkyl mono-substituted by OH or C1~4alkoxy, R6 is halogen and A# is an anoin.

By 'halogen' is meant fluorine, chlorine or bromine.

R1 and R2 are preferably R1a and R2a, where R1a and R2a are independently methyl or ethyl, more preferably R1 and R2 are both methyl.

R3 and R4 are preferably both hydrogen.

Where R5 is unsubstituted alkyl it is preferably methyl or ethyl, more preferably methyl; where R5 is substituted alkyl it is preferably 2-hydroxyethyl, 2-hydroxypropyl or 3-methoxypropyl. R5 is preferably R5a where R5a is hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-methoxypropyl; more preferably R5b where R5b is hydrogen or methyl.

R6 is preferably R6a where R6a is fluorine or chlorine, more preferably chlorine.

Preferred compounds of formula I are those of formula la

in which R1a, R2a, R5ar R6a and A are as defined above.

More preferred compounds are those of formula Ib

in which R5b, R6a and As are as defined above.

The invention also provides a process for the preparation of compounds of formula I, characterised by either a) treating a compound of formula 11

in which R1~6 and As are as defined above, Y is -CO- or -SO2 and Q is C14 alkyl with an acid HA in which A is a group capable of forming the anion A3, or b) by reacting a compound of formula Ill

in which P1, R2, R3, R4 R6 and A3 are as defined above and Rx is an anionic leaving group, for example halogen (including iodine) or alkoxy, whith a compound of formula IV P5 NH2 IV in which R5 is as defined above.

The cleavage of the group -Y-O from compounds of formula 11 is suitably carried out in aqueous solution in the presence of a strong mineral acid; for example hydrochloric acid, or in a mixture of an organic acid, for example acetic acid, and a mineral acid at a temperature of from 50-1 000C, preferably from 60--809C. The reaction of compounds III and IV is conventional and may be carried out in known manner.

The compounds of formulae II, Ill IV are either known or may be prepared from known compounds by conventional methods.

The anion A9 in compounds of formula I may be a non-chromophoric organic or inorganic anion, for example chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphate, perchlorate, chlorozincate, tetrafluoroborate, lactate, succinate, tartrate, malate, methansulphonate or benzoate: or may be a complex anion for example of boric, citric, glycollic, diglycollic or adipic acids.

The anion AO may be exchanged for other anions for example with the aid of an ion-exchange resin or by reaction with salts or acids. Such reaction may take place in more than one step, for example through the hydroxide or bicarbonate, or according to French Patent 2,028,725 or 2,028,726.

The compounds of formula I are dyestuffs and are useful for the dyeing of cationically dyeable substrates such as leather, paper and plastics, and particularly for the dyeing or printing of textile substrates containing or consisting of fibres of homopolymers or copolymers of acrylonitrile or asymmetric dicyanoethylene, or of acid-modified polyamides or polyesters. Such polyamides and polyesters are described in Belgian Patent 706 104 and U.S. Patent 3,379,723 respectively.

The compounds may be worked up by conventional means into solid or liquid compositions, for example by granulation or by dissolving in a suitable solvent, optionally in the presence of additives such as stabilisers or solubilising agents such as urea. Such preparations may be obtained for example as described in French Patents 1,572,030 and 1,581,900 or German latent Publications 2,001,748 and 2,001,816.

Polymers may be dyed for example by the continuous gel-dyeing process, for which liquid compositions of the dyes are particularly suitable. Textile material may be dyed in neutral or acidic aqueous media at temperatures of from 60o1 000C at atmospheric pressure or at temperatures over 1000C under pressure. Alternatively, dyeing may be carried out in organic solvents, for example as described in German Patent Publication 2,437,549.

The dyestuffs exhibit good build-up power and give deep, brilliant dyeings having good fastnesses, for example fastness to light, ironing, heat, steam, washing, sweat, pleating, decatizing, dry cleaning and cross-dyeing. The dyestuffs reserve wool, and have notable pH-stability, combination properties, migration, stability to boiling, resistance to hydrolysis, good solubility, and high saturation limits and are scarcely affected by electrolytes.

The compounds of formula I are primarily useful for giving even dyeing of polyacrylonitrile materials of varying exhaust rates. In dyeing such materials, the compounds of formula I particularly those having cation molecular weights below 290, show good migration properties and can be dyed without the use of a retarder. If they are dyed in the presence of a retarder it is advantageous if the retarder also has good migration properties. Slow-, normal-, or fast-exhaust polyacrylonitrile materials are described for example in German Offenlegungsschrift 2,548,009.

The following Examples, in which parts and percentages are by weight, and temperatures are in degrees Centigrade, illustrate the invention.

EXAMPLE 1 37 Parts 2-chloro-4-acetylaminoaniline are added to 350 parts water, 100 parts acetic acid and 50 parts 30% hydrochloric acid and diazotised with 60 parts 4N sodium nitrite at O5 . After removal of excess nitrous acid with 1.5 parts aminosulphonic acid, the clear diazonium salt solution is dropped into a solution of 13.6 parts imidazole in 100 parts water at O5 . During coupling the pH is held at 9-10 by addition of 30% sodium hydroxide solution, and the temperature held below 50 by adding ice.

The suspension is stirred for 2 hours, filtered and the residue washed and dried at 500 in vacuo, to give a compound of formula:

This intermediate (27.5 parts) is suspended in 250 parts water containing 2.5 parts sodium carbonate, and the suspension warmed to 400. Then 63 parts dimethyl sulphate is added all at once, and the mixture stirred for 3 hours at 35--400, the pH I being kept at 7.5-8.5 by addition of 30% NaOH solution, until thin layer chromatography shows no remainaing starting material. After addition of 130 parts of 26% brine and 20 parts zinc chloride the dye suspension is stirred, cooled, filtered and washed with 15% brine.

The moist filter cake is finally stirred in 400 parts 6% HCI and heated to 750 for 2 hours. The solution is then brought to pH 6 by addition of 30% NaOH solution and the resulting suspension filtered at 40--500, washed with 100 parts 10% brine and dried in a vacuum oven at 50--600, to give the dyestuff of formula:

The product dyes polyacrylonitrile and anionic-modified polyester fibres at fast orange to scarletred tones, and show good migration properties on polyacrylonitrile.

EXAMPLE 2 In manner analogous to Example 1, 2,4-dichloroaniline is coupled to imidazol to give the compound of formula:

48 parts of which are stirred into 500 parts dioxane at 400 and treated with 84 parts magnesium oxide. Dimethyl sulphate (110 parts) is added dropwise over 1 hour, and the mixture is stirred for 1-2 hours, then diluted with 600 parts water at 400. The yellow solution is treated with 1 5 parts activated charcoal, clear filtered, evaporated to half of its volume under reduced pressure, clear filtered a second time and treated with 14 parts zinc chloride and 28Q parts 26% brine. The yellow suspension is stirred for 2 hours, and the precipitated dyestuff filtered off, washed with a little cold 10% brine and vacuum dried at 500.

The quaternised product (41.5 parts, 90% pure) is added to a solution of 40 parts ethanolamine and 1.5 parts glacial acetic acid in 500 parts water at 500, and the mixture stirred for 2 hours, then cooled to room temperature. After clear filtration, the scarlet-red filtrate is brought to pH 5-5.5 with HCI, then 100 parts NaCI are added and the precipitated dyestuff is filtered off after stirring for 4 hours. the red dye may be further purified by solution in 10% acetic acid, extraction with toluene or trichloroethylene, and reprecipitation as the chloride salt. The resulting dyestuff, of formula:

dyes polyacrylonitrile and acid-modified polyester fibres in fast orange to scarlet tones.

EXAMPLES 3-1 8 In manner analogous to Examples 1 and 2, and using corresponding starting materials, dyestuffs of formula I may be obtained in which R3 and R4 are hydrogen and RX, R2, R5 and R6 are as listed in the following Table.

The anion Ae may be any one of those listed above.

Ex. R1 R2 R6 R5 No. 3 -CH3 -CH3 F H 4 do. do. F -CH3 5 do. do. F -C2H5 do. do. F -C2H4-OH 7 do. do. F -C3H60H 8 do. do. F -C3H6oCH3 9 do. do. F -C4H9 10 do. do. C1 -CH3 11 do. do. C1 -C2H5 12 do. do. C1 -CH2-CHOH-CH3 13 do. do. C1 -C3H6oCH3 14 do. do. C1 -C4H9 15 -OH3 -CH3 C1 -C3H7 16 -C2H5 -C2H5 C1 H 17 -CH3 -CH3 C1 CH2 /CH3 CH CH3 18 do. do. F do.

The dyestuffs of Examples 3 and 16 dye polyacrylonitrile in orange tones, those of the remaining Examples in scarlet tones.

APPLICATION EXAMPLE A Polyacrylonitrile fibres are added to an aqueous dyebath at 600 containing 0.125 g/l glacial acetic acid, 0.375 g/l sodium acetate and 0.1 5 g/l of the dyestuff of Examples 1 (or a corresponding quantity of solid or liquid preparation of this dyestuff), the liquor-to-goods ratio being 80:1. The dyebath is brought to the boil over 20-30 min., and kept at the boil for 90 min. The substrate is rinsed and dried to give an orange dyeing with good fastness properties.

APPLICATION EXAMPLE B Acid-modified polyester fibres are added to an aqueous dyebath at 200, containing 3 g/l sodium sulphate, 2 g/l ammonium sulphate and 2.5 g/l of a nonionic carrier, the liquor-to-goods ratio being 40:1. The pH is regulated to 5.5 by addition of formic acid. The bath is heated to 600, and 0.15 g/l of the dyestuff of Example 1 (or a corresponding amount of a solid or liquid preparation thereof) is added. The bath is heated to boiling point over 30 minutes, and held at the boil for 60 min. After rinsing and drying, an orange dyeing with good fastness properties is obtained.

APPLICATION EXAMPLE C Acid-modified polyester fibres are added to an aqueous dyebath at 200C containing 6 g/l sodium sulphate, 2 g/l ammonium sulphate and 0.15 g of the dyestuff of Example 1 (or a corresponding amount of a solid or liquid preparation thereof). The liquor-to-goods ratio is 30:1. The pH is regulated to 5.5 with formic acid, and the bath is heated in a closed vessel to 1 10--1200 over 45 minutes, and held at that temperature, with shaking, for 60 minutes. After rinsing and drying, an orange dyeing with good fastness properties is obtained.

APPLICATION EXAMPLE D Acid-modified polyamine fibres are added to an aqueous dyebath at 200, containing 3.6 g/l potassium dihydrogen phosphate, 0.7 g/l disodium hydrogen phosphate, 1 g/l of an auxiliary consisting of the reaction product of a phenol with excess ethylene oxide, and 0.1 5 gIl of the dyestuff of Example 1 (or a corresponding amount of a solid or liquid preparation thereof). The liquor-to-goods ratio is 80:1.

The bath is heated to the boil over 30 minutes and kept at the boil for 60 minutes. After rinsing and drying an orange dyeing with good fastness properties is obtained.

The dyestuffs of the remaining Examples may be applied in the same way.

Claims

1. A compound of formula I

in which RX and R2 are independently unsubstituted C1~4alkyl, R3 and R4 are independently hydrogen or unsubstituted C1~4alkyl, R5 is hydrogen, unsubstituted C14alkyl or C24alkyl mono-substituted by OH or C14alkoxy, R6 is halogen and As is an anoin.

2. A compound as claimed in Claim 1 in which R, and R2 are independently methyl or ethyl.

3. A compound as claimed in Claim 2 in which R, and R2 are both methyl.

4. A compound as claimed in any one of the preceding claims in which R3 and R4 are both hydrogen.

5. A compound as claimed in any one of the preceding claims in which R5 is hydrogen, methyl, ethyl, 2-hydroxymethyl, 2-hydroxypropyl or 3 methoxypropyl.

6. A compound as claimed in Claim 5 in which R5 is hydrogen or methyl.

7. A compound as claimed in any one of the preceding claims in which R6 is fluorine or chlorine.

8. A compound as claimed in Claim 1 of formula la

in which Rra and R2a are independently methyl or ethyl, R5a is hydrogen, methyl, ethyl, 2-hydroxymethyl, 2-hydroxypropyl or 3-methoxypropyl, R6a is fluorine or chlorine, and At is an anion.

9. A compound as claimed in Claim 8 of formula Ib

in which R5b is hydrogen or methyl, R6a is as defined in Claim 8, and AO is an anion.

10. A compound as claimed in Claim 9 of formula Ib, stated in Claim 9, in which Rsb is hydrogen and R6b is chlorine.

11. A process for the preparation of a compound of formula I, stated in Claim 1, characterised by either a) treating a compound of formula II

in which R,~6 and AO are as defined in Claim 1, Y is-CO-or -SO2 and Q is C14 alkyl with an acid HA in which A is a group capable of forming the anion Ae, or (b) by reacting a compound of formula Ill

in which Ri, R2, R3, R4, R6 and As are as defined in Claim 1 and Rx is an anionic leaving group, with a compound of formula IV P5 NH2 IV in which R5 is as defined in Claim 1.

12. A compound of formula I, stated in Claim 1, whenever prepared by a process as claimed in Claim 11.

13. A compound of formula I, as described in any one of Examples 2-18.

14. A process for the dyeing or printing of basic dyeable substrates comprising application of a dyestuff as claimed in Claim 1.

1 5. Basic-dyeable substrates whenever dyed by the process of Claim 14.