GB2028856A

GB2028856A - Diazothiazole cationic dyes, a process for their manufacture and their use for colouring synthetic polymeric materials

Info

Publication number: GB2028856A
Application number: GB7925869A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1978-08-24
Filing date: 1979-07-25
Publication date: 1980-03-12

Abstract

These dyes which are water soluble and devoid of carboxylic acid and sulphonic acid have the formula: <IMAGE> in which R is an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group, R<1> is hydrogen or an optionally substituted alkyl, aryl or aralkyl group or forms a 5 or 6 membered ring with the nitrogen atom and the ring A, the ring A is optionally substituted or has a ring fused thereon, Z is an optionally substituted alkylene group of 2 or more carbon atoms or an optionally substituted arylene group, K<(+)> is a group containing a quaternary nitrogen atom and X<-> is an anion. The dyes give valuable bright violet to reddish-blue shades of excellent fastness properties to washing, perspiration, steam pleating and light and are especially useful for dyeing polyacrylonitrile material.

Description

SPECIFICATION Diazothiazole cationic dyes, a process for their manufacture and their use for colouring synthetic polymeric materials This invention relates to new water-soluble azo dyestuffs, to their manufacture and to the use of such dyestuffs for the colouration of synthetic polymeric materials in the form of ribbons, tapes, fibres, films, threads and textile materials generally. The dyestuffs are particularly valuable for the colouration of polymers and copolymers of acrylonitrile and dicyanoethylene and also acid-modified polyesters and polyamides.

Thus according to the present invention there are provided azo dyestuffs devoid of carboxylic acid and suiphonic acid groups and of the formula:

wherein R is an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group, R1 is hydrogen or an optionally substituted alkyl, aryl or aralkyl group or can form a 5 or 6 membered ring with the nitrogen atom and the ring A, the ring A can optionally be substituted or can have a ring fused thereon, Z is an optionally substituted alkylene group of 2 or more carbon atoms or an optionally substituted arylene group, K3 is a group containing a quaternary nitrogen atom and Xo is an anion.

R may be any optionally substitued alkyl, alkenyl, cycloalkyl, especially cyclohexyl, or aralkyl, especially phenylalkyl, group. Suitable substituents include halogen, especially chlorine, lower alkoxy, hydroxy, hydroxy lower alkoxy, carbamoyl, lower alkoxycarbonyl acyloxy, aryloxy, especially phenyloxy, hydroxyaryíoxy, especially hydroxyphenyloxy, cycloalkoxy, especially cyciohexyloxy and cyano.

Examples of R include lower alkyl and alkenyl, optionally carrying substituents as aforementioned, such as methyl, ethyl, propyl, butyl, allyl, 2-hydroxyethyl and 1 -chloro-2-hydroxypropyl, benzyl, 4'methylbenzyl, 2-ca rba moylethyl, 2-ca rba moyl-2-methylethyi, 2-ch loroethyl, 2-bromoethyl, 2acetoxyethyl, cyclohexyl, phenylethyl, methoxyethyl and methoxycarbonylethyl.

Preferably R is methyl, ethyl or benzyl, especially methyl, R1 may be hydrogen or an optionally substituted alkyl, especially lower alkyl, cycloalkyl, aryl, especially phenyl, or aralkyl, especially phenylalkyl, group or can form a 5- or 6-membered ring with the nitrogen atom and the ring A. Suitable substituents which may be present include those aforementioned in respect of R.

Thus, examples of R' include hydrogen, methyl, ethyl, propyl, butyl, phenyl, hydroxy lower alkyl such as 2-hydroxyethyl and 2-or 3-hydroxypropyl, lower alkoxy lower alkyl such as 2-(methoxy or ethoxy)ethyi and 3-methoxypropyl, cyano lower alkyl such as 2-cyanoethyl, aryl lower alkyl such as benzyl and /3-phenylethyl, acyloxy lower alkyl such as 2-acetoxyethyl, lower alkoxycarbonyl lower alkyl such as 2-methoxycarbonylethyl, hydroxy lower alkoxy-lower alkyl such as 2-(2'-hydroxyethoxy)ethyl, lower a Ikoxy-lower alkoxycarbonyl-lower a Ikyl such as 2-(2'-methoxyethoxyca rbonyl)ethyl, 2carbamoylethyl, cycloalkyl such as cyclohexyl, hydroxyaryloxy lower alkyl such as hydroxyphenoxyethyl, cycloalkoxy-lower alkyl such as cyclohexyloxyethyl and aryl such as phenyl.

Where the terms lower alkyl, lower alkenyl and lower alkoxy are used in this specification they mean respectively alkyl, alkenyl and alkoxy having from 1 to 4 carbon atoms.

R1 may also form a 5-or 6-membered ring with the nitrogen atom and the ring A i.e. of the type

Examples of coupling components of such a type include indole, indoline and tetrahydroquinoline and their substituted derivatives.

The ring A may optionally be substituted for example by lower alkyl, lower alkoxy, aryloxy, trifluoromethyi, sulphamoyl, substituted suíphamoyl, such as alkylsulphamoyl, lower alkoxycarbonyl, acylamino and ureido groups.

Specific examples of substituents which may be present in A include methyl, ethyl, methoxy, ethoxy, chloro, bromo, trifluoromethyl, sulphamoyl, dimethylsulphamoyl, diethylsulphamoyl, methoxycarbonyl, ethoxycarbonyl, phenoxy, acetylamino, formamido, propionylamino and ureido.

The ring A may have a ring fused thereon, for example a benzene ring to give a coupling component of the type

Z is an optionally substituted alkylene group of 2 or more carbon atoms, usually 2 to 4 carbon atoms, or an optionally substituted arylene group. Hydroxy is a preferred substituent in an alkylene group.

Xzqples of Z include

and Thenylene.

Ke is a group containing a quaternary nitrogen atom.

Examples of K include cyclammonium groups and trialkylammonium groups attached either directly to Z or attached to Z through slinking group such as an oxyalkylene group, for example -OCH2CH2-. The alkyl groups in the trialkylammonium may be substituted, for example by hydroxy or phenyl groups.

Cyclammonium groups are heterocyclic groups containing a quaternised nitrogen atom in the ring, the ring is preferably but not necessarily attached to the remainder of the molecule through the quaternised nitrogen atom.

Examples of cyclammonium groups include pyridinium, a-picolinium, /3-picolinium, y-picolinium, quinolinium, iso-quinolinium, N-methyl-piperidinium and N-methylmorpholinium.

Examples of trialkylammonium groups include the groups of the formula

wherein R2, R3 and R4 are for example methyl, ethyl, propyl, P-hydroxyethyl and benzyl, particularly methyl.

As anions represented by X- there may be mentioned for example inorganic anions such as chloride, bromide, iodide, tetrachlorozincate. bisulphate or sulphate or organic anions such as acetate, propionate, methosulphate, methyl sulphonate, and p-tolylsulphonate. In those cases where the anion is polyvalent the water-soluble dyestuffs will contain a corresponding molar proportion of the cationic part of the dyestuff.

Replacement of one anion by another anion in the dyestuff may be carried out by metathesis.

A preferred class of dyestuffs of the present invention is that of the formula

wherein R5 is a lower alkyl group preferably methyl, R1 slower alkyl optionally substituted by hydroxy or cyano, Z is alkylene optionally substituted by hydroxy, Ko is trialkylammonium, or optionally lower alkyl substituted pyridinium and may be linked to Z through an oxyalkylene group, and X is as hereinbefore defined.

As a further feature of the present invention there is provided a process for the manufacture of the dyestuff of the present invention which comprises quaternising a compound of the formula

wherein A, R', Z, Ko and Xs are as hereinbefore defined.

As examples of quaternising agents there may be mentioned alkyl halides such as methyl, ethyl, propyl and butyl chlorides and the corresponding bromides, alkenyl halides such as alkyl chloride or bromide, alkyl halides such as benzyl chloride or bromide, dialkyl sulphates such as dimethyl sulphate, diethyl sulphate, dipropyl sulphate and dibutyl sulphate, alkyl esters of aryl sulphonates such as methyl and ethyl p-toluene sulphonate and other lower alkyl esters of strong mineral acids or organic sulphonates. Other quaternising agents may themselves carry substituents, for example chloropropionitrile, bromopropionamide and bromohydrin.

The reaction between the quaternising agent and dyestuff of formula (oil) may be carried out neat without addition of other solvents, or again may be carried out in an inert organic solvent such as benzene, toluene, xylene, chlorobenzene, nitrobenzene, acetone, carbontetrachloride, tetrachloroethane, perchloroethylene, chloroform, dimethylformamide, acetonitrile, acetic acid, formic acid or 2ethoxyethanol. The quaternisation may also be effected in aqueous phase optionally in the presence of an organic solvent. The quaternising agent may be used in considerable excess, for example up to 6 moles for each mole of dyestuff. Suitable temperatures are from 200 to 1 500C and particularly 20--900C. The inclusion of an acid-binding agent is often beneficial.Such agents include magnesium oxide, sodium and potassium carbonate, sodium and potassium bicarbonate, magnesium and calcium carbonate, potassium acetate or mixtures of such agents.

Quaternisation of dyestuffs of formula (II) may also be carried out by reacting with, for example, acrylamide in an organic or mineral acid such as acetic, formic or hydrochloric acid or mixtures of these at between 500 and 1 000C.

Quaternisation may also be carried out by reacting a dyestuff of formula (oil) with ethylene oxide dr its derivatives of formula:

wherein R6 and R7 represent hydrogen or an optionally-substituted lower alkyl group.

This reaction is carried out in a solvent in the presence of a mineral or organic acid which provides the anion X, at temperatures of 100 to 1000C and preferably 40--900C. Suitable acids include sulphuric, hydrochloric, hydrobromic, phosphoric, benzenesulphonic, toluenesulphonic, formic, acetic or propionic. Such acids may also serve as solvent or may be used in admixture with each other or with other organic solvents such as dimethylformamide, acetonitrile, dioxan, tetrahydrofuran, chlorobenzene, toluene, xylene, nitrobenzene, acetone or methylethylketone.

When the reaction is effected in hydrophobic organic solvents the alkylated dyestuff is normally insoluble and may be isolated by filtration. If desired, the alkylated dyestuff may be isolated from aqueous solution by precipitation in the form of a salt such as tetrachlorozincate obtained by adding zinc chloride to the aqueous solution.

As a result of the quaternisation the dystuff may be obtained, for example, in the form of the chloride, bromide or methosulphate according to the alkylating agent used. If the dyestuff is required as the salt of a different anion, then one anion may be replaced by another by known methods of metathesis.

Compounds of formula (II) which can be used as starting materials in the above process can be made by diazotising 2-aminothiazole and coupling the diazo component with a coupling component of the formula

wherein R, A, Z, K&commat; and Xe are as hereinbefore defined.

Coupling components which may be used in the above reaction include 2-(N-phenyl-N-ethylamino)ethylpyridinium chloride, 2-(N-phenyi-N-methylamino)ethylpyridinium chloride, 2AN-phenyl-N-ethylamino)ethyi-,z-picolinium chloride, 2(N-phenyl-N-ethylamino)ethyl-(y-dimethylamino)pyddinium ch íoride, 2-(N-phenyl-N-ethylamino)ethylisoth iou ronium chloride, 2-(N-phenyl-N-methylam ino)ethyltrimethylam mon ium chloride, 2-(N-phenyl-N-propylamino)ethyltrimethylphosphonium chloride, 2-(N-3'-methylphenyl-N-ethyl)ethylpyridinium chloride, 2-(N-3'-acetylaminophenyl-N-ethyl)ethylpyridinium chloride, 3-(N-phenyl-N -ethylamino)-2-hydroxypropylpyridinium chloride, 3-(N-phenyl- N-ethylamino)-2-hydroxypropyl-y-picoliniu m chloride, methyl-[4-83-(N-phenyl-N-ethylamino)ethyl]pyridinium chloride, i.e.

2-(N,N-diphenylamino)ethyl pyridinium chloride 4-(N-iJhenyla mino)phenyl trimethyl ammonium chloride 4-(N-phenyl-N-methylamino)phenyl trimethyl ammonium chloride 3-(4-[N-methyl-N-phenylaminojphenoxy)-2-hydroxypropyl pyridinium chloride.

In an alternative process which is a further feature of this invention the dyestuff of the invention may be made by (a) reacting a compound (II) of formula

wherein A, R' and Z are as hereinbefore define, X is a direct link or a linking group and Y is halogen, sulphato our a sulphato ester group, with a tertiary amine such as pyridine ortrimethylamine followed by reaction with a quaternising agent as in the process previously described; or (b) reacting a compound (II) as above defined with a secondary amine and then reacting the product with two or more moles of a quatemising agent.

The dyestuffs of the present invention may be used to colour polymeric synthetic materials by application from an aqueous bath. The present dyestuffs gave valuable bright shades of high tinctorial strength.

In particular the dyestuffs of the invention are valuable for dyeing polyacrylonitrile materials and may be applied to polyacrylonitrile materials from acid, neutral or slightly alkaline dyebaths, (i.e. pH from 3-8) at temperatures between 40-1 200C and preferably between 80-1 200C or by printing techniques using thickened print pastes. Bright violet to reddish-blue dyeings of excellent fastness properties to washing, perspiration, steam pleating and light are obtained.

The dyestuffs of the present invention may be used for the colouration of polymeric textile materials, particularly polymers and copolymers of acrylonitrile, by the wet transfer printing process. In this process a support, such as paper, is printed with an ink containing a dyestuff, the printed support is placed in contact with a textile material and the whole then subjected to heat pressure under humid or wet conditions and the dyestuff transferred to the textile material.

The dyestuffs of the present invention contain two water soiubilising groups and yet surprisingly have Compatability Values of 3 to 3.5. As related dyestuffs having only one water solubilising group tend to have high Compatability Values of 5 or 5+ it is most surprising that the presence of a further solubilising group should lower this to a value of 3 to 3.5 which signifies a much more commercially acceptable rate of dyeing.

Compatability Values can be assessed by the method described in the Joumal of the Society of Dyers and Colourists, Volume 87, No.2, page 60 (1971). They are assessed on a scale of 1 to 5 and dyers engaged in the dyeing of poiyacrylonitrile materials show a strong preference for dyestuffs having a Compatability Value (C.V.) of 2.5 to 3.5 or about 3. Dyestuffs of this C.V. are compatible in dyeing properties with the large majority of mainstream commercial dyes used in the dyeing of polyacrylonitrile and the dyeing rates of mixtures of dyestuffs with C.V. about 3 is such that the dyeing can be more easily controlled and the shade determined and adjusted during dyeing if this should be necessary.

The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight unless otherwise stated. Where parts by volume are given, the relation of weight to volume is the relation of gram to millilitre.

EXAMPLE 1 (a) Mono cationic dyebase 1.00 parts of 2-aminothiazole is added cautiously to 5.5 parts of sulphuric acid (S.G. 1.84) at less than 250C. The mixture is then cooled to 0 and 10 parts of ice added. 5.0 parts of 2N sodium nitrite is then added dropwise at OOC over 4 hour and the mixture stirred for a further 1 hour. Sulphamic acid is then added to remove excess nitrous acid.

The diazo mixture is then added to 4.72 parts of a 48.1% solution of 2-(N-ethyl-Nphenylaminoethyl)pyridinium chloride and 50 parts of water over 20 minutes at OOC. The mixture is then stirred for 2 hours at 0 and 10 parts of sodium acetate is finally added when the colour changes from blue to red. The product is salted out, by adding 4 parts of 50% zinc chloride solution and salt to 10%, and finally filtered off and dried. The constitution of the product is as follows:

(b) Bis cationic dyes The product from (aj above is stirred at 700C with 0.5 parts of light magnesium oxide and 30 parts of glacial acetic acid and 2 parts of dimethyl sulphate added over 5 minutes. The mixture is then stirred at 700 for 2 hours then a further 2 parts of dimethyl sulphate and 0.5 parts of magnesium oxide added. After a further 2 hours at 700C the mixture is drowned onto water and screened. The liquors are treated with 1.15 parts of 50% zinc chloride solutions and salt is then added to 20%. The resultant mixture is stirred overnight and the product which has the structure (I) is filtered off then dried in a steam oven.

It imparts a bright bluish-violet shade to acrylic fibres which has excellent light fastness and wet fastness properties.

Further bluish-violet dyestuffs can be obtained by similar methods and are described in the following table.

The first column shows the substituent R2 in the benzene ring of the coupling component, the second column shows the substituent R1, the third column the alkylene substituent and the final column the quaternary containing group KO.

CH, ,tN = N4wN\ 2 S f=/ Alkylene - 3 R

xample R1 K+ R- alkglene / CH, CH 3 3 CR3 C2H5 CHaCRa NCR3 4 H C2H.5 42CE.CH2 - < OH Further, bluish-violet to blue dyestuffs can be obtained by methods simiiar to that of Example 1 and are described in the following table.

The first column shows the substituent R2 in the benzene ring attached to the azo group, the second column the substituent R1, the third column the bridging group Z, and the final column the quaternary containing group Ke.

Example ~ K8) 5 H CH3 ~ss3 -CH2CE2-t 6 CR CH, 0mCR3 M CR3 7 | H -CR2CR20H 2CX =zw aSz5

Example R2 R1 z Na. Z 18 9 H H -C2E5 2 -CH,.C . . l 10 H 3 CR3 .CH2- -CH2.CR2 e r4 11 OCR3 H < - -CH2CH2$2) .~. . ~ . 12 Cl C2H3 -CR21 2 OH

Claims

1. An azo dyestuff devoid of carboxylic acid and sulphonic acid groups and of the formula:

in which R is an optionally substituted-alkyl, alkenyl, cycloalkyl or aralkyl group, R1 is hydrogen or an optionally substituted alkyl, aryl or aralkyl group or forms a 5 or 6 membered ring with the nitrogen atom and the ring A, the ring A is optionally substituted or has a ring fused thereon, Z is an optionally substituted alkylene group of 2 or more carbon atoms or an optionally substituted arylene group, Ko is a group containing a quaternary nitrogen atom and Xo is an anion.

2. A dyestuff as claimed in claim 1 in which the substituents optionally carried by R and R' are selected from the group comprising halogen, lower alkoxy, hydroxy, hydroxyloweralkoxy, carbamoyl, lower alkoxycarba m oyi, acyloxy, a ryloxy, hyd roxyaryloxy, cycloa lkoxy and cyano.

3. A dyestuff as claimed in claim 1 in which R1 forms an indole, indoline or tetrahydroquinoline ring with the nitrogen atom and the ring A.

4. A dyestuff as claimed in any one of the preceding claims in which the substituents optionally carried by ring A are selected from the group comprising lower alkyl, lower alkoxy, aryloxy, trifluoromethyl, sulphamoyl, lower alkyl sulphamoyl, lower alkoxycarbonyl, acylamino and ureido.

5. A dyestuff as claimed in any one of the preceding claims in which the ring A has a benzene ring fused thereon.

6. A dyestuff as claimed in any one of the preceding claims in which the Z is a lower alkylene group containing from 2 to 4 carbon atoms, branched or unbranched, optionally carrying a hydroxy substituent, or a phenylene group.

7. A dyestuff as claimed in any one of the preceding claims in which Ko is a cyclammonium or trialkylammonium group attached either directly to Z or through an oxyalkylene group.

8. A dyestuff of the formula:

wherein R5 is a lower alkyl group, R1 Is lower alkyl optionally substituted by hydroxy or cyano. Z is alkylene optionally substituted by hydroxy, Kçs is trialkylammonium, or optionally lower alkyl substituted pyridinium and may be linked to Z directly or through an oxyalkylene group, and X is as hereinbefore defined.

9. A dyestuff as herein described with reference to any one of Examples 1 to 12.

10. A process for the manufacture of the dyestuff claimed in claim 1 which comprises quaternising a compound of the formula:

wherein A, R, Z, Ke and Xe are as hereinbefore defined.

11. A process for the manufacture of the dyestuff claimed in claim 1 which comprises either (a) reacting a compound (II) of formula:

wherein A, R' and Z are as hereinbefore defined, X is a direct link or a linking group and Y is halogen, sulphato or a sulphato ester group, with a tertiary amine such as pyridine ortrimethylamine followed by reaction with a quatemising agent, or (b) reacting the compound (II) with a secondary amine and then reacting the product so obtained with two or more moles of a quaternising agent.

12. A process substantially as hereinbefore described with reference to any one of Examples 1 to 12.

13. A dyestuff obtained from a process claimed in any one of claims 10 to 12.

14. Polymeric synthetic materials whenever coloured by a dyestuff as claimed in any one of claims 1 to 9.