GB2116195A - Disperse Dyestuffs - Google Patents

Abstract

Disperse dyestuffs of the formula: <IMAGE> where A = the radical of a diazotisable amine ANH2, R is H or optionally substituted hydrocarbyl, R<1> and R<2> are H, optionally substituted hydrocarbyl or acyl, Y is H, NHR<3>, SR<4>, OR<5>, halogen or optionally substituted hydrocarbyl where R<3>, R<4>, R<5> are each H or optionally substituted hydrocarbyl. Dyestuffs are valuable for colouring polyester fibres.

Description

SPECIFICATION Disperse dyestuffs This invention relates to disperse dyestuffs, in particular azopyrimidinyl disperse dyes.

Colouring matters in the form of azo compounds derived from pyrimidine coupling components are well known and many have been proposed for the colouration of polyester fibres. Azo pyrimidine compounds have also been investigated for biological activity.

We have now found a novel class of pyrimidine dyestuffs of value in colouring hydrophobic fibres especially polyester fibres.

Thus according to the present invention there is provided disperse dyestuffs of the formula:

where A = the radical of a diazotisable amine ANH2, R is H or optionally substituted hydrocarbyl, R' and R2 are H, optionally substituted hydrocarbyl or acyl, Y is H, NHR3, SR4, OR5, halogen or optionally substituted hydrocarbyl where R3, R4, R5 are each H or optionally substituted hydrocarbyl providing that one or both of R' and R2 are acyl.

ANH2 may be any of the carbocyclic or heterocyclic amines conventionally used in disperse azo dyestuff manufacture. Numerous examples of such amines which are free from water solubilising substituents are known from the patent and other literature.

It is preferred that A is an optionally substituted phenyl radical free from water solubilising substituents especially one of the formula:

where m is O or 1 when m is 0 one of R6 may occupy the 4 position, n and p are each independently 0, 1, 2 or 3, each of the n substituents Re are independently selected from halogen, NO2, CN, CF3, C 1-4 alkyl, C14 alkoxy, C14 acyl, C14 acylamino, C 1-4 alkoxycarbonyl, C14 alkylsulphonyl, N2N.SO2, C14 alkylaminosulphonyl, di(C,~4 alkyl)aminosulphonyl and aryloxysulphonyl, and each of the p substituents R, are independently selected from the atoms and groups given for R6.

The preferred aryloxysulphonyl groups are phenoxysulphonyl in which the phenyl radical is optionally substituted by 1-3 substituents selected from halogen, C14 alkyl or C14 alkoxy.

As examples of the amines ANH2 which may provided the radical A there may be mentioned aniline, 4-nitroaniline, 4-cyanoaniline, 4-methoxyaniline, 4-(methylthio)aniline, 4 (methylsulphonyl)aniline, 4-(methoxycarbonyl)aniline, 4-(ethoxycarbonyl)aniline, 4aminoacetophenone, 4-aminoazobenzene, 4-aminobenzenesulphonamide, 4-aminobenzenesulphon-N methyiamide, 4-aminobenzenesulphon-N,N-dimethylamide, 4-thiocyanatoaniline, 4-bromoaniline, 4chloroaniline, 4-phenoxysulphonylaniline, 4-(4'-methylphenoxy)sulphonylaniline, 4-(4' chlorophenoxy)sulphonyianiline, 4-(4'-methoxyphenoxy)sulphonylaniline, 4-[(betaethoxy)ethoxycarbonyl]aniline, methyl 4-aminobenzenesulphonate, 4-aminobenz-N,Ndiisopropylamide, 2,4-dinitroaniline, 2-chloro-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methoxy-4nitroaniline, 4-chloro-2-methoxyaniline, 3,4-dichloroaniline, 3,4-dicyanoaniline, 2,4-dichloroaniline, 2,4-dicyanoaniline, 2,6-dichloro-4-nitroaniline, 2-bromo-6-chloro-4-nitroaniline, 4-chloro-2nitroaniline, 4-chloro-3-nitroaniline, 4-(ethoxycarbonyl)-2-nitroaniline, 2-chloro-4ethylsulphonylaniline, 2-methylaminosulphonyl-4-nitroaniline, 4-ethylaminosulphonyl-2-nitroaniline, 2 (isopropoxycarbonyl)-4-nitroaniline, 4-nitro-2-trifluoromethyl aniline, 2-ethoxycarbonyl4-nitroaniline, 3,4-bis(methoxvcarbonyl)aniline, 3-chloro-6-methyl-4-nitroaniline, 2-hvdroxy4-nitroaniline, 2-nitroaniline, 2-chloroaniline, 2-bromoaniline, 2-methoxycarbonylaniline, 2-ethoxycarbonylaniline, 2-cyanoaniline, 2-methoxy-5-methylaniline, 2-cyano-3-methoxyaniline, 2,6ethoxycarbonylaniline, 2-cyanoaniline, 2-methoxy-5-methylaniline, 2-cyano-3-methoxyaniline, 2,6dicyanoaniline, 2-amino-6-methoxybenzamide, 2-acetoxyaniline, 2-methyl-6-nitroaniline, 2-(nbutoxycarbonyl)aniline, 2,3-bis(ethoxycarbonyl)aniline, 2-cyano-4-methylaniline, 2-amino-6ethoxybenzamide, 2-amino-4,4'-dimethylazobenzene, 2-aminophenol, 4-amino-3-nitrodiphenyl, 5chloro-2-ethoxyaniline, 5-chloro-2-methoxyaniline, 3-nitroaniline, 2,4-dimethyl-5-nitroaniline, 3chloro-2-methylaniline, 5-ethoxy-2-methylaniline, 3,5-dimethoxyaniline, 3,5-dinitroaniline, 3-methoxy5-nitroaniline, 3-ethoxy-5-nitroaniline, 3,5-dichloroaniline, 4-methyl-3-nitroaniline, 3-aminobenzenesulphonamide, 3-nitro-5-trifluoromethylaniline, 2,5-difluoroaniline, 3,5-bis(methoxycarbonyl)aniline, 3,5bis(aminosulphonyl)aniline, 2-bromo-5-nitroaniline, 5-bromo-2-methylaniline, 3-trifluoromethylaniline, 3-amino-4-chloroacetophenone, 3-amino-4-chlorobenzenesulphon amide, 2-chloro-5-cyanoaniline, 2chloro-5-ethoxycarbonylaniline, 2-chloro-4-methyl-5-nitroaniline, 2,5-dichloro-4-methylaniline, 2,5dichloroaniline, 4-chloro-3-methylaniline, 4-chloro-2-methylaniline, 2-aminothiazole, 2-amino-3,5dinitrothiophene, 2-am ino-3-ethoxycarbonyl-5-nitrothiophene, 2,4-dicyanothiophene, 2-amino-6-thiocyanatobenzthiazole and 2-amino-6-methoxybenzthiazole.

The groups R, R', R2, R3, R4, R5 and Y when optionally substituted hydrocarbyl may include various optionally substituted aryl, araikyl, alkenyl and alkyl groups. Preferred groups are phenyl, benzyl and phenyl ethyl in all of which the ring may carry 0 to 2 substituents each selected from halogen, NO2, C 1-4 alkyl especially CH3 and C14 alkoxy especially OCH3; together with the especially preferred groups which are C14 alkyl groups substituted by O or 2 atoms or groups each selected from halogen, especially Cl or Br, CN, OH, C14 alkoxy or C14 alkoxycarbonyl.

Preferred dyes include those in which one or more of R, R', R2 and R3 are H.

Specific examples of optionally substituted alkyl groups are methyl, ethyl n-propyl, isopropyl, nbutyl, beta-chloroethyl, beta-bromoethyl, gam ma-chloro-beta-hydroxypropyl, beta-cyanoethyl, betahydroxyethyl, beta-methoxyethyl, beta-ethoxyethyl, methoxycarbonylmethyl and (beta-methoxycarbonyl)ethyl.

Preferred halogen for the group Y are Br or especially Cl, The acyl groups which may be represented by R' and R2 may have the structure derived from any organic acid by removal of OH. Such groups may be from carboxylic, sulphonic or sulphinic acid or from acids which do not normally exist in the free form e.g. R1 or R2 may be an alkoxycarbonyl group or a carbamoyl group.

Preferred acyl groups are of the formula:

where n is 1 or 2 and each X is independently H, halogen, NO2, OH, C 1-4 alkyl or C14 alkoxy.

Specific examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, benzoyl, 3nitrobenzoyl, 4-chlorbenzoyl, 4-bromobenzoyl, 2-chlorobenzoyl, 2-, 3- or 4-methylbenzoyl, 2- and 4methoxybenzoyl, 4-hydroxybenzoyl, 2,5- and 3,5-dimethylbenzoyl, 4-isopropylbenzoyl, methane sulphonyl, ethane sulphonyl, p-toluene sulphonyl, benzene sulphonyl, methane sulphinyl, ethane sulphinyl, p-toluene sulphinyl, methane sulphenyl, benzene sulphenyl, methoxy carbonyl, ethoxy carbonyl, propoxy carbonyl, phenoxy carbonyl, amino carbonyl, diethylamine carbonyl, methylamino carbonyl.

Preferred dyes of formula (1) are those having one or more of the following features: (1) A as defined by formula (2) above.

(2) Acyl groups as defined by formula (4) or especially formula (3) above.

(3) R and R' are each H or C14 alkyl groups with 0--2 substituents as defined above.

(4) R2 is acyl.

(5) Y is H, CI, Br, C14 alkoxy, C14 alkylthio, benzylthio, NH2 or C14 alkylamino the alkyl group having 0--2 substituents as defined above.

The invention also provides a process for the manufacture of dyestuffs of the formula (1) which comprises coupling the diazonium salt from an amine of formula ANH2 with a pyrimidine coupling component of the formula:

where A, Y, R, R' and R2 have the meanings given above.

The diazonium salt from the amine ANH2 may be obtained by diazotisation of amine ANY2.

The diazotisation and coupling may be carried out by known methods for these reactions. For example, the diazotisation may be carried out by adding sodium nitrite to a solution or dispersion of the amine ANH2 in hydrochloric acid or aqueous sulphuric acid, or to a solution of the amine in concentrated sulphuric acid, or a mixture of concentrated sulphuric acid with an organic acid such as acetic acid and/or propionic acid, or by stirring the amine with nitrosylsulphuric acid, followed by addition of the resulting solution or dispersion of the diazonium compound to a solution of the coupling component in water or in a mixture of water and a water-miscible organic liquid, if necessary adjusting the pH of the mixture to facilitate the coupling reaction, and finally isolating the resulting dyestuff by conventional methods.

Usually diazotisations are carried out at temperatures below room temperature e.g. 0-1 00C and coupling at around room temperature e.g. 1030 C.

Examples of amines ANH2 are given above.

As examples of the pyrimidine coupling component of formula (5) there may be mentioned 4acetylamino-2-N,N-diethylamino pyrimidine; 4-propionyiamino-2-N,N-diethylamino pyrimidine; 4benzene sulphonylamino-2-N,N-diethylamino pyrimidine; 4-acetylamino-2-N,N-diethylamino-6 chloropyrimidine; 4-acetylamino-2-N,N-diethylamino-6-n-butylamino pyrimidine; 4-acetylamino-2- N,N-diethylamino-6-(3-methoxypropylamino)pyrimidine; 4-butyrylamino-2-N,N-diethylamino-6-(2- hydroxyethylamino)pyrimidine; 4-acetylamino-2-N,N-diethylamino-6-methyl pyrimidine; 2,4di(acetylamino)-6-chloro pyrimidine; 4-acetylamino-2-N,N-diethylamino-6-(2-acetoxyethylamino) pyrimidine.

These pyrimidine coupling components can be obtained by various methods which involve one or more known steps.

For example, 2-amino-4,6-dihydroxypyrimidine and various N-substituted analogues may be prepared from diethyl maionate and the appropriate guanidine. This may then be halogenated in the 4,6-positions with say POCI3 or POBr3. One of the halogens can then be replaced by reaction with ammonia or primary amine and the other is left for Y = halogen or for the other values of Y is replaced by reaction with suitable reagent e.g. ammonia primary amines, water, alcohols, a metal hydrosulphide or thiols. Finally the acyl amino groups are formed by a conventional acylation e.g. reaction with carboxylic acid anhydride or halide, sulphonic or sulphinic acid halide, chloroformate ester or an isocyanate. It will be appreciated that the extent and position of acylation will be determined by the conditions used and the reactivity of the various amino groups present.Compounds having an unacylated amino group of reactive character can be difficult to prepare and may need to be obtained by reversal of the order of some of the above stages.

Pyrimidines with 4-hydrocarbyl substituents may be obtained by replacing the diethyl malonate by an acyl acetic ester e.g. ethylacetoacetate.

Alternatively 2,4,6-trihalopyrimidines, obtained from barbituric acid, may be reacted with ammonia, amines, thiols, etc. but care is necessary to ensure that when a secondary amine is used to introduce a tertiary nitrogen to the 2-position, any unwanted isomeric 4-compound which is usually produced at the same time, is removed.

The invention also provides a second process for the manufacutre of dyestuffs of formula (1) which comprises reacting a dyestuff of the formula (1) wherein A, R, R', R2 and Y have the meanings given above with the proviso that one or both of R1 and R2 are H, with an acylating agent.

This reaction is carried out under conventional condition appropriate to the acylating agent.

As examples of acylating agents there may be mentioned carboxylic acid anhydrides e.g. acetic anhydride and propionic anhydride which are normally heated with the amino dyestuff at said 50 to 1 200C, acid halides e.g. acetyl chloride, propionyl chloride, butyryl chioride, benzoyl chloride, p-toluene sulphonyl chloride, p-nitrobenzoyl chloride, p-nitrobenzene sulphonyl chloride and benzene sulphinyl chloride, which are usually reacted at -10 to 500C often in the presence of material to neutralise the liberated acid.

Other acylating agents include chloroformate ester e.g. ethylchloroformate and isocyanates e.g.

phenyl isocyanate and p-nitrophenyl isocyanate which are usually reacted at about ambient temperatures in a medium free from water or other active hydrogen compounds.

Additionally acylation may be achieved in some instances by use of the free acid e.g. formic acid or by heating with esters e.g. ethyl acetate, propionate or butyrate usually under conditions where the liberated alcohol is displaced.

The dyestuffs of formula (1) in which one or. both R1 and R2 are H for use in the second process of the invention may be obtained by coupling the diazonium salt from ANH2 with a pyrimidine coupling component of formula (5) where A, R, R', R2 and Y have the meanings given above with the proviso that one or both of R' and R2 are H.

As examples of such dyestuffs there may be mentioned 4-amino-2-N,N-diethylamino-5-(4nitrophenylazo)pyrimidine; 4-amino-2-N,N-dimethylamino-5-(2,4-dinitrnphenylazo)-6- chloropyri midine; 4-amino-2-N,N-diethylamino-5-(2-chloro-4-nitrophenylazo-6-n-butylamino pyrimidine; 2,4-diamino-5-(2-cyano-4-nitrophenylazo)-6-chloro pyrimidine; 2-amino-4-n-butylamino5-(4-nitrophenylazo)-6-methyl pyrimidine; 4-amino-2-N,N-dimethylamino-5-(2-chloro-4,6- dinitrophenylazo)-6-ethylthio pyrimidine.

It will be appreciated that the second process will not always be applicable to the manufacture of every dyestuff e.g. it is usually difficult to acylate one amino group and leave another equally or more active amino group unreacted.

The invention further provides a process for the colouration of hydrophobic fibres which comprises applying a dyestuff of formula (1) as defined above and heating to fix the dyestuff on the fibre.

The term "hydrophobic fibres means those fibres not having a substantial affinity for water and which are normally coloured by disperse dyestuffs. Typical of such fibres are synthetic polyamides such as nylon 6 and 66, cellulose acetates with various degrees of acetylation up to triacetate and aromatic polyesters particularly poly)ethylene terephthalate).

The dyestuff may be applied to the hydrophobic fibres in the form of an aqueous dispersion which may be prepared by conventional methods, for example, by milling the dyestuff with water and a suitable dispersing agent such as the sodium salt of a naphthalene-2-sulphonic acid/formaldehyde condensate.

The dyestuff may be applied to the hydrophobic fibres in a loose form or when converted into yarns, threads or woven or knitted textile materials. The various hydrophobic fibres may be present as blends with other types of fibres e.g. aromatic polyester and cellulose fibres such as cotton.

The above-defined colouration process may conveniently be carried out by immersing the fibres in whatever form in an aqueous dyebath containing one or more of the said dyestuffs, which dyebath preferably contains a non-ionic, cationic or anionic surface-active agent, or a cationic or anionic surfaceactive agent together with a non-ionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature. The dyeing process can either be carried out at a temperature between 90 and 1 O00C, preferably in the presence of a carrier such as biphenyl or o-hydroxybiphenyl, or at a temperature above 1 000C, preferably at a temperature between 1200 and 1 400C, under superatmospheric pressure.

Alternatively, the aqueous dispersion of the dyestuff can be applied to the fibres in fabricated textile materials by a padding or printing process, followed by heating at temperatures up to 2300 C, or by steaming of the textile material. In such processes it is preferred to incorporate a thickening agent, such as gum tragacanth, gum arabic or sodium alginate, into the aqueous dispersion of the said dyestuff.

At the conclusion of the colouring process it is preferred to give the coloured fibres a "reduction clear" treatment in a warm, dilute aqueous alkaline solution of sodium hydrosulphite in order to remove any unfixed azo dyestuff from the surface of the fibres. In the case of those dyestuff which are soluble in aqueous alkali or which contain at least one group which is converted into a water-solubilising group by the action of aqueous alkali, the treatment with sodium hydrosulphite may be omitted, a simple treatment with warm dilute aqueous alkali free from reducing agent being sufficient to remove unfixed dyestuff.

The dyestuffs may also be applied to textile materials by known methods of transfer colour printing such as sublimation transfer printing, optionally under reduced pressure, and wet transfer printing.

The dyestuffs also find application for the melt colouration of polymers such as aromatic polyesters, and can also be used as pigments for the colouration of inks and paints, such dyestuffs being incorporated in known manner into conventional ink or paint formulations.

The dyestuffs of the present invention and fibres coloured with them are characterised by high strength, good build-up to deep shades and good light fastness and good stability to heat which is often much superior to closely related dyes.

The invention is illustrated by the following Examples.

EXAMPLE 1 4-Nitroaniline (1.38 parts) suspended in 2N hydrochloric acid (10 parts) and water (30 parts) at 0--50C was diazotised by the addition of 5N aqueous sodium nitrite solution (1.2 parts).

4-Acetyla mino-2-N,N-diethylamino-6-chloro pyrimidine (2.43 parts) was dissolved in acetic acid (15 parts) and the solution added to water (40 parts) stirring at O-50C. The solution of diazotised amine was added to the pyrimidine suspension at O-50C and the pH of the mixture was adjusted to 4 by the addition of sodium acetate crystals. The mixture was stirred at O-50C for 24 hours, the product is collected, washed with water and crystallised from ethoxyethanol.

The dyestuff had Amax 438 nm, max = 32,200. When applied to aromatic polyester textile material from an aqueous dispersion a bright golden yellow shade was obtained having excellent fastness to washing, light and changes in pH.

EXAMPLE 2 A mixture of 2-N,N-diethylamino-4-amino-6-n-butylamino-5-(2-bromo-6-cyano-4- nitrophenylazo)pyrimidine (0.5 parts), acetic acid glacial (10 parts) and acetic anhydride (10 parts) was stirred under reflux for 10 minutes. The mixture was cooled to room temperature, the precipitated product was filtered off, washed with water and dried. Crystallisation from acetic acid yields 2-N,Ndiethylamino-4-acetylamino-6-n-butylamino-5-(2-bromo-6-cyano-4-nitrophenylazo)pyrimidine lmax 526 nm, Emax = 60,000.

EXAMPLES 3-10 The following dyestuffs were obtained by diazotizing in a known manner the amine given in the second column of the table and coupling the resulting diazonium compound with the coupling component given in the third column of the table, using essentially the method described in Example 1.

Most of the dyestuffs can also be prepared by the method described in Example 2 i.e. acylation of azoamino pyrimidines.

The shade obtained when each dyestuff is applied to aromatic polyester textile material is given in the fourth column and the Amax and Emax values of each dyestuff are listed int he final column.

Example Amine Coupling Component Shade #max (# max) 3 4-nitroaniline 4-acetylamino-2-N,N-diethylamino-6- Golden yellow 430 (32,000) methylpyrimidine 4 2-chloro-4-nitroaniline " Orange 456 (37,000) 5 2-cyano-4-nitroaniline " Orange 462 (37,500) 6 4-nitroaniline 4-acetylamino-2-N,N-dimethylamino- Yellow 420 (31,000) pyrimidine 7 " 2,4-di(acetylamino)-6-ethylthio- Golden yellow 438 (27,100) pyrimidine 8 " 2-acetylamino-4-chloro-6-methylamino- Yellow 427 (30,400) pyrimidine 9 2-chloro-4-nitroaniline 4-acetylamino-2-N,N-diethylamino-6- Orange 450 (36,000) chloropyrimidine 10 2-chloro-4,6-dinitroaniline 4-acetylamino-2-N,N-diethylamino-6-n- Red 522 (55,000) butylaminopyrimidine 11 4-nitroaniline 4-chloro-2-N,N-dimethylamino-6-N-acetyl, Yellow 429 (45,000) N-methylaminopyrimidine

Claims (1)

1. CLAIM

   Disperse dyestuffs of the formula:

   where A = the radical of a diazotisable amine ANH2, R is H or optionally substituted hydrocarbyl, R' and R2 are H, optionally substituted hydrocarbyl or acyl, Y is H, NHR3, SR4, OR5, halogen or optionally substituted hydrocarbyl where R3, R4, R5 are each H or optionally substituted hydrocarbyl.