GB2068402A - Dyestuffs Comprising Two 5- Membered Heterocyclic Nuclei Fused to a Central Cyclohexadiene Nucleus - Google Patents

Abstract

Dyestuffs of the general formula: <IMAGE> wherein Z<1> and Z<2> are oxygen, sulphur or <IMAGE> in which Y<1> is an optionally substituted hydrocarbon radical or an acyl radical; R<3> and R<4> each represent a naphthyl radical or an optionally substituted phenyl radical; X<3> and X<4> each independently represent a hydrogen atom, chlorine, bromine, cyano, lower alkyl, lower alkoxy, optionally substituted aryl, optionally substituted carbamoyl, optionally substituted sulphamoyl, carboxylic acid or carboxylic acid ester group, provided that Z<1> and Z<2> may be the same or different when R<3> and R<4> are different, and Z<1> and Z<2> are different when R<3> and R<4> are the same.

Description

SPECIFICATION Dyestuffs Comprising Two 5-membered Heterocyclic Nuclei Fused to A Central Cyclohexadiene Nucleus This invention relates to dyestuffs comprising two 5-membered heterocyclic nuclei fused to a central cyclohexadiene nucleus.

United States Patent Specification No. 4115404 discloses dyestuffs of the general formula:

wherein each Z is oxygen or -NY in which Y is an optionally substituted hydrocarbon radical or an acyl radical; R1 and R2 each independently represent a naphthyl radical, an unsubstituted phenyl radical or a phenyl radical substituted by at least one of the following: nitro, halogen, lower alkyl, lower alkoxy, phenyl, lower alkoxyphenyl, phenoxy, cyano, carboxylic acid, carboxylic acid ester, optionally substituted carbamoyl, sulphuric acid, sulphonyl chloride, sulphonic acid ester, optionally substituted sulphamoyl, mercapto, lower alkylthio, phenyl thio, primary, secondary, tertiary or quaternary amino, acyl amino, phosphonic acid, phosphonic acid ester, lower alkylsulphonyl, phenylsulphonyl, aldehyde, azo, and acyloxy groups of the formula O.--CO.T in which T is an alkyl group containing at least two carbon atoms, a substituted phenyl group, a lower alkoxy group or a phenoxy group; and X' and X2 each independently represent a hydrogen atom, chlorine, bromine, cyano, lower alkyl, lower alkoxy, optionally substituted carbamoyl, carboxylic acid or carboxylic acid ester group.

According to the present invention there are provided dyestuffs of the general formula (I):

wherein Z1 and Z2 are oxygen, sulphur or -NY1 in which Y' is an optionally substituted hydrocarbon radical or an acyl radical; R3 and R4 each represent a naphthyl radical, an unsubstituted phenyl radical or a phenyl radical substituted by at least one of the following::- nitro, halogen, lower alkyl, lower alkoxy, phenyl, hydroxy, lower alkoxyphenyl, phenoxy, cyano, carboxylic acid, carboxylic acid ester, optionally substituted carbamoyl, sulphonic acid, sulphonyl chloride, sulphuric acid ester, optionally substituted sulphamoyl, mercapto, lower alkylthio, phenylthio, primary, secondary, tertiary or quaternary amino, acylamino, phosphonic acid, phosphonic acid ester, lower alkylsulphonyl, phenylsulphonyl, aldehyde, azo, and acyloxy groups of the formula O.CO.T' in which T1 is an alkyl group containing at least two carbon atoms, a substituted phenyl group, a lower alkoxy group or a phenoxy group;; X3 and X4 each independently represent a hydrogen atom, chlorine, bromine, cyano, lower alkyl, lower alkoxy, optionally substituted aryl, optionally substituted carbamoyl, optionally substituted sulphamoyl, carboxylic acid or carboxylic acid ester group, provided that Z' and Z2 may be the same or different when R3 and R4 are different, and Z1 and Z2 are different when R3 and R4 are the same.

Examples of the optionally substituted hydrocarbon radicals represented by Y1 are alkyl and preferably lower alkyl such as methyl, ethyl, n-propyl and isopropyl, substituted alkyl and preferably substituted lower alkyl such as P-hydroxyethyl, p-methoxyethyl and jB-ethoxyethyl, phenyl and substituted phenyl such as tolyl, chlorophenyl, nitrophenyl and lower alkoxyphenyl.

Examples of the acyl radicals represented by Y' are acetyl, propionyl, butyryl, isobutyryl, unsubstituted benzoyl and benzoyl substituted by halogen, nitro, lower alkyl, lower alkoxy or hydroxy.

Examples of acylamino groups which may be present as substituents on the phenyl radicals represented by R3 and R4 are acetylamino, propionylamino, benzoylamino, methanesulphonylamino, benzenesulphonylamino and toluenesulphonylamino.

Examples of substituted phenyl groups represented by R' are tolyl, chlorophenyl and lower alkoxyphenyl.

Examples of optionally substituted aryl groups represented by X3 and X4 are unsubstituted phenyl and phenyl substituted in ortho, meta orpara positions by halogen, lower alkyl, nitro, lower alkoxy, phenyl or carboxylic acid ester. Two or more such substituents, which may be the same of different, may be present.

The optionally substituted carbamoyl and sulphamoyl groups which may be present as substituents on the phenyl radicals represented by R3 and R4, and which are represented by X3 and X4, are preferably of the formula:

respectively wherein Lr and L2 are each independently hydrogen, lower alkyl or phenyl. The carboxylic acid ester groups which may be present as substituents on the phenyl radicals represented by R3 and R4, and which are represented by X3 and X4 are preferably of the formula: -COOL3 wherein L is an optionally substituted alkyl, in particular lower alkyl or monocyclic aryl, in particular phenyl, radical.

Throughout this specification the terms "lower alkyl" and "lower alkoxy" are used to denote alkyl and alkoxy groups respectively containing from 1 to 4 carbon atoms.

Dyestuffs of the present invention in which R3=R4 may be prepared by reaction of 1 mol proportion of a compound of formula (ill):

wherein X3, X4, Z1 and Z2 have the previously defined meanings, with at least 2 mol proportions of a compound of formula (III):

wherein B is hydrogen, lower alkyl or alkyl, A is hydroxyl, O-acyl or halogen, and R3 has the previously defined meaning, either as a melt or in a high-boiling inert solvent such as di- or tri-chlorobenzene.

Specific examples of compounds of formula (II) which may be used are 4-mercaptophenol, 4acetamidophenol, 4-N-methylaminophenol and 4-N4sopropylaminophenol.

Specific examples of compounds of formula (III) which may be used are mandelic acid (a- hydroxyphenylacetic acid), 2- and 4-chloromandelic acid, 4-methylmandelic acid and 4methoxymandelic acid.

A reaction temperature of 1 90-1 950C is generally satisfactory, although temperatures higher or lower than this may be used in particular circumstances.

The product initially obtained from the above reaction is the dihydro intermediate of formula (IV):

which may be isolated if desired, although it is more convenient to oxidise it in situ, for example, by heating it in nitrobenzene or by treating it with another oxidising agent such as hydrogen peroxide in acetic acid.

Dyestuffs of formula (I) in which R3 and R4 may be either the same or different may be prepared by the stepwise reaction scheme given below:

R45 I x z x3 1 4 1 R N x z z2 0 0 (viz) (I) in which A, B, R3, R4, X3, X4, Z1 and Z2 have the previously defined meanings.

In a variation of the above scheme dyestuffs of formula (I) in which R3 and R4 are different may be prepared in admixture with dyestuffs in which R3 and R4 are the same by reacting the compound of formula (II) with a mixture of the compound of formula (III) and the compound of formula (VI). In this generalised example it is assumed that X3=X4 and Z1=Z2. If this is not so then further isomers are possible but components where R3 and R4 are different will be present.

When Zr and Z2 are both oxygen, dyestuffs in which R3 and R4 are different may also be obtained by reaction of the quinone (VIII)

with a compound of the formula (IX):

in which B, R3, X3 and X4 have the previously defined meanings, 0 is hydrogen, hydroxyl or O-acyl and X5 and X6 are hydrogen, chlorine or bromine, provided that when Q is hydrogen, at least X3 and X4, or X5 and X6, must be chlorine or bromine, to give a compound of the formula (X)

which is then further reacted with a compound of formula (XI):

wherein B, Q and R4 have the previously defined meanings, to give a compound of the formula (XII):

which then cyclises with bond rearrangement to give a dyestuff of formula (I) in which Za and Z2 are both oxygen.

The dyestuffs in which R3 and R4 are different (regardless of whether Z' and Z2 are the same or different) have better build-up properties on aromatic polyester textile materials than the corresponding dyestuffs in which R3 and R4 are the same. Similarly the dyestuffs in which Zr and Z2 are different (regardless of whether R3 and R4 are theesame or different) have better build-up properties on aromatic polyester textile materials than the corresponding dyestuffs in which Z1 and Z2 are the same.

Having prepared dyestuffs by the method of synthesis described above, other substituents can be introduced by conventional methods, or substituents already present can be converted into other substituents in known manner. The following are illustrative of such reactions:- (a) sulphonic acid groups can be introduced by sulphonation methods, and sulphonyl chloride groups by reaction with chlorosulphonic acid.

(b) nitro groups can be introduced by nitration methods, (c) hydroxy groups can be converted into acyloxy groups by treatment with acylating agents, (d) nitro groups can be reduced to amino groups, (e) amino groups can be converted into acylamino groups by treatment with acylating agents, (f) tertiary amino groups can be converted into quaternary amino groups.

If desired, the structure of the dyestuff of the present invention can also be incorporated into other dyestuff systems. Thus, for example, dyestuffs containing both the said structure and an azo system can be prepared by coupling a diazotised amino on to a dyestuff of the present invention which contains a phenolic hydroxy group. Alternatively a dyestuff of the present invention which contains a diazotisable amino group can be diazotised and coupled on to a coupling component. Also a dyestuff of the present invention which additionally contains an azo group can be obtained by synthesis of the dyestuff directly from an intermediate which already contains an azo group.As a further example, dyestuffs containing both the structure of the present dyestuffs and a nitro dyestuff system can be obtained by, for example, condensing a dyestuff of the present invention containing an aminophenyl residue with a halogenonitrobenzene.

The dyestuffs of the invention are valuable for colouring natural and synthetic textile materials.

Thus the dyestuffs of the invention which are free from water-solubilising groups (i.e. sulphonic acid, carboxylic acid or quaternary ammonium groups) are valuable for colouring synthetic textile materials, for example cellulose acetate and cellulose triacetate textile materials, polyamide textile material such as polyhexamethyleneadipamide textile material, polyacrylonitrile textile materials, and preferably aromatic polyester textile materials such as polyethylene terephthalate textile materials. Such textile materials can be in the form of threads, yarn, or woven or knitted fabric. If desired, the said synthetic textile materials can be in the form of blends with other textile materials, for example blends of polyester textile materials with cellulose or woollen textile materials.

Such textile materials can conveniently be coloured with the water-insoluble dyestuffs, as hereinbefore defined, by immersing the textile material in a dyebath comprising an aqueous dispersion of one or more of the said dyestuffs, which dyebath preferably contains a non-ionic, cationic and/or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature.

In the case of secondary cellulose acetate textile materials it is preferred to carry out the dyeing process at a temperature between 600 and 850C; in the case of cellulose triacetate or polyamide textile materials it is preferred to carry out the dyeing process at 95 to 100 C; in the case of aromatic polyester textile materials the dyeing process can either be carried out at a temperature between 900 and 1 O00C, preferably in the presence of a carrier such as diphenyl or o-hydroxydiphenyl, or at a temperature above 100 C, preferably at a temperature.between 1 200 and 1400 C, under superatmospheric pressure.

Alternatively, the aqueous dispersion of the said dyestuff can be applied to the textile material by a pddding or printing process, followed by heating at temperatures up to 2300C depending on the textile material, 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 azo dyestuff.

At the conclusion of the colouring process it is preferred to give the coloured textile material a rinse in water or a brief soaping treatment before finally drying the coloured textile material. In the case of aromatic polyester textile materials it is also preferred to subject the coloured textile material to a treatment in an aqueous solution of an alkali, such as sodium carbonate or sodium hydroxide, before the soaping treatment in order to remove loosely attached dyestuff from the surface of the textile material.

The water-insoluble dyestuffs have excellent affinity and building-up properties on aromatic polyester textile materials, so enabling deep shades to be obtained. The resulting colorations have good to excellent fastness to light, to wet treatments, to perspiration, and in particular to dry heat treatments such as those carried out at high temperatures during pleating operations.

If desired, the water-insoluble dyestuffs of the invention can be applied to synthetic textile materials in conjunction with other disperse dyes, such as are described in, for example, British Specifications Nos. 806271, 83581 9, 840903, 847175, 852396, 852493, 859899, 865328, 872204,894012,908656,909843,910306,913856,919424,944513,944722,953887, 959816,960235, 961412, 976218, 993162 and 998858.

Those dyestuffs of the invention which are soluble in water by virtue of the presence of quaternary ammonium groups can be used as Basic Dyestuffs for the dyeing of polyacrylonitrile textile materials or of polyamide and polyester textile materials which contain acidic groups which confer affinity on such textile materials for Basic Dyestuffs. The said dyestuffs can be applied in conventional manner to these textile materials from acid, neutral or slightly alkaline dyebaths, the pH of which is preferably maintained in the range of 3 to 8, at temperatures between 400C and 1 200C, preferably between 800 and 1 2O0C, or by printing techniques using thickened print pastes containing the said dyestuffs.

Those dyestuffs of the invention which are soluble in water by virtue of the presence of acidic water-solubilising groups can be used for colouring natural or synthetic polyamide textile materials such as wool, silk or polyhexamethylene adipamide textile materials. Such dyestuffs can be applied in conventional manner to the said textile materials from aqueous dyebaths, the pH of which is preferably maintained in the range of 4 to 8.

Those dyestuffs of the invention which contain acidic water-solubilising groups can be used for colouring cellulose textile materials, the dyestuffs being applied by conventional methods to such textile materials.

Dyestuffs of the invention can also be applied to textile materials by transfer printing processes, including such processes carried out at reduced pressures or under moist or humid conditions.

Dyestuffs of the invention can also be used in mass colouration processes.

Insoluble dyestuffs of the present invention 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 invention is illustrated by the following Examples in which the parts and percentages are by weight.

Example 1 A mixture of 5.04 parts of 4-mercaptophenol and 14.72 parts of 4-methoxymandelic acid is stirred for 10 hours at 1 950C, 8 parts of nitrobenzene are added and the heating continued for a further 30 minutes. The mixture is cooled to 250C, 1 50 parts of ethanol are added and the mixture is stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with ethanol and dried.

Crystallisation from toluene gives 3,7-di(4-methoxyphenyl)-2,6-dioxo-2,6-dihydrothienoj'2:3- f]benzofuran. [Found: C, 69.5; H, 3.9; S, 7.5. C24H,605S requires C, 69.2; H, 3.85; S,7.7%]. Mass spectrum showed a terminal ion at m/e=416. The product dissolves in chloroform to give a red solution having :Lmax 523 nm, Emax 48,700. When dispersed in aqueous medium the product dyes aromatic polyester textile materials in strong bluish red shades having good fastness to light and to wet treatments. Any unfixed dyestuff on the surface of the textile material is removed by treatment in a 0.6% aqueous solution of sodium hydroxide at 800C.

Example 2 The procedure described in Example 1 is repeated except that in place of the 14.72 parts of 4methoxymandelic acid there are used 12.16 parts of mandelic acid, with a reaction time of 16 hours.

Crystallisation of the product from cellosolve gives 3,7-diphenyl-2,6-dioxo-2,6-dihydrothieno[2:3- f]benzofuran. [Found: C, 73.7; H, 3.43; 9.1. C22H12O3S requires C, 74.1; H, 3.37; S, 8.99%]. Mass spectrum shows a terminal ion at m/e=356 and a breakdown pattern consistent with this structure.

The product dissolves in chloroform to give a yellow solution with AmaX 470 nm, Emax 45,000. When applied to aromatic polyester textile materials from an aqueous dispersion the product gives strong yellow shades showing good fastness to light.

Example 3 The procedure described in Example 1 is repeated except that in place of the 14.72 parts of 4methoxymandelic acid there are used 13.28 parts of 4-methylmandelic acid, with a reaction time of 10 hours. Crystallisation of the product from cellosolve gives 3,7-di(4-methylphenyl)-2,6-dioxo-2,6 dihydrothieno[2:3-f]benzofuran. [Found: C, 74.7; H, 4.25; S, 8.5. C24H,603S requires C, 75; H, 4.17; S, 8.33%]. Mass spectrum shows a terminal ion at m/e=384 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give an orange solution having Amax 485 nm, Emax 35,000.The product gives orange shades with good build-up properties when applied to aromatic polyester textile materials from aqueous dispersions. The dyeings show good fastness properties to light and washing.

Example 4 A mixture of 6.04 parts of 4-acetamidophenol and 1 2.1 6 parts of mandelic acid is stirred for 10 hours at 1 900C, 8 parts of nitrobenzene are added and heating is continued for a further 30 minutes.

The mixture is cooled to 250C, 1 50 parts of ethanol are added and the mixture is stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with ethanol and dried. Crystallisation from cellosolve gives 3,7-diphenyl-2,6-dioxo-2,6-dihydro-5H-furo[2:3-flindole. [Found: C, 77.4; H, 3.8; N, 4.02. C22H,303N requires C, 77.88; H, 3.83; N, 4.13%]. Mass spectrum shows a terminal ion at m/e=339 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give a yellow solution having Amax=459 nm, Emax=39,000 A mixture of 4 parts of the above furoindole, 50 parts of acetic anhydride and 1 part of 98% w/v sulphuric acid is stirred and heated under reflux for 2 hours during which time the product gradually precipitates. After cooling the reaction mixture the product is filtered off, washed with alcohol and dried to give 5-acewl-3,7-diphenyl-2,6-d,ioxo-2,6-dihydrn-5H4urn[2:34]indole. [Found: C, 76.1; H, 4.2; N, 3.81. C24H,504N requires C, 75.6; H, 3.93; N, 3.67%j. Mass spectrum shows a terminal ion at m/e=381 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give a yellow solution having Ajax=465 nm, Emax=43 ,300. When applied to aromatic polyester textile materials from an aqueous dispersion the product gives strong yellow shades showing good fastness to light and to wet treatments.

Example 5 The procedure described in Example 4 is repeated except that in place of the 12.16 parts of mandelic acid there are used 14.72 parts of 4-methoxymandelic acid, with a reaction time of 5 hours.

Crystallisation of the product from cellosolve gives 3,7-di(4-methoxyphenyl)-2,6-dioxo-2,6-dihydro- 5H-furo[2:3-f]indole. Acetylation of this product with acetic anhydride and sulphuric acid gives 5 acetyl-3,7-die4-methoxyphenyl)-2,6-dioxo-2,6-dihydro-5H-furo[2:3-f]indole [Found: C, 70.5; H, 4.45; N, 3.19. C2eH1gOeN requires C, 70.75; H, 4.31; N, 3.17%]. Mass spectrum shows a terminal ion at m/e=441 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a red solution having may=518 nm.

Example 6 The procedure described in Example 4 is repeated except that in place of the 12.16 parts of mandelic acid there are used 13.28 parts of 4-methylmandelic acid, with a reaction time of 10 hours.

Crystallisation of this product from cellosolve gives 3,7-di(4methylphenyl-2,6-dioxo-2,6-dihydrn-5H- furo[2:3-f]indole. Acetylation of this product with acetic anhydride and sulphuric acid gives 5-acetyl 3,7-di-(4-methylphenyl)-2,6-dioxo-2,6-djhydro-5H-furo[2:3-flindole. [Found: C, 75.9; H, 4.70; N, 3.47.

C26H1904N requires C, 76.28; H, 4.64; N, 3.42%]. Mass spectrum shows a terminal ion at m/e=409 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give an orange solution hving Ajax=482 nm, Emax=43t000 When applied to aromatic polyester textile materials from aqueous dispersions the product gives strong orange shades showing good fastness properties to light and to wet treatments.

Example 7 A mixture of 4.92 parts of N-methylaminophenol and 12.16 parts of mandelic acid is stirred for 10 hours at 1 900C, 8 parts of nitrobenzene are added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 125 parts of methanol are added and the mixture is stirred at 250C for 2 hours. The precipitated solid is filtered off, washed with methanol and dried. Crystallisation from toluene gives 3,7-diphenyl-2,6-dioxo-5-methyl-2,6-dihydro-5H-furo-[2 :3-fjindole. [Found: C, 77.9; H, 4.31; N, 4.08. C23H,503N requires C, 78.19; H, 4.25; N, 3.97%]. Mass spectrum shows a terminal ion at m/e=353 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give a yellow solution having ,tmax4S8 nm, Emax 33,200. When applied to aromatic polyester textile materials from aqueous dispersions the product gives yellow shades with good buildup properties and good fastness to light and to wet treatments.

Example 8 The procedure described in Example 7 is repeated except that in place of the 12.1 6 parts of mandelic acid there are used 14.72 parts of 4-methoxymandelic acid, with a reaction time of 3 hours.

Crystallisation from toluene gives 3,7-di(4-methoxyphenyl)-2,6-dioxo-5-methyl-2,6-dihydro-5H- furo[2:34]indole. [Found: C, 72.7; H, 4.9; N, 3.31. C25H1gO8N requires C, 72.64; H, 4.6; N, 3.39%].

Mass spectrum shows a terminal ion at m/e=413 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a red solution having Amax 517 nm, Emax 37,400.

The product dyes aromatic polyester textile materials in bluish-red shades having good build-up properties and showing good fastness to light and to wet treatments.

Example 9 The procedure described in Example 7 is repeated except that in place of the 12.16 parts of mandelic acid there are used 13.28 parts of 4-methylmandelic acid, with a reaction time of 5 hours.

Crystallisation of the product from toluene gives 3,7-di(4-methylphenyl)-2,6-dioxo-5-methyl-2,6- dihydro-5H-furo[2:3-f]indole. [Found: C, 78.5; H, 5.1; N, 3.63. C25H1903N requires C, 78.74, H, 4.99; N, 3.67%]. The mass spectrum shows a terminal ion at m/e=381 and a breakdown pattern consistent with this structure. The product dissolved in chloroform to give an orange solution having may=475 nm, Emax=41 ,500. The product dyes aromatic polyester textile materials from aqueous dispersions in orange shades showing good build-up properties and having good fastness to light and to wet treatments.

Example 10 The procedure described in Example 8 is repeated except that in place of the 4.92 parts of 4-Nmethylaminophenol there are used 6.04 parts of 4-N-isopropylaminophenol, with a reaction time of 1+ hours. Crystallisation of the product from cellosolve gives 3,7-di(4-methoxyphenyl)-2,6-dioxo-5 isopropyl-2,6-dihydro-5H-furo[2 :3-f]indole. [Found: C, 73.5; H, 5.27; N, 3.09. C2,H2305N requires C, 73.47; H, 5.21; N, 3.17%]. The mass spectrum shows a terminal ion at m/e=441 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a red solution having Amax 507 no, Emax 41,800.The product gives bluish-red shades on polyester textile materials showing good build-up properties and having good fastness to light and to wet treatments.

Example 11 A mixture of 9.04 parts of 5-hydroxy-2-oxo-3-phenyl-2:3-dihydrobenzofuran and 6.64 parts of 4methylmandelic acid is stirred for 13 hours at 1 950C, 8 parts of nitrobenzene are then added and heating continued for a further 30 minutes. The mixture is cooled to 250C, 1 50 parts of methanol are added and the mixture stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with methanol and dried. Crystallisation from toluene gives 3-phenyl-7-(4-methylphenyl)-2,6-dioxo-2,6 dihydrobenzotl :2-b, 4:5-b']difuran. [Found: C 78.1; H, 3.9. C23H1404 requires C, 77.97; H,3.95%T. The mass spectrum shows a terminal ion at m/e=354 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to given an orange solution having AmaX 476 nm, Emax 50,300. When applied to aromatic polyester textile materials from aqueous dispersions the product gives orange shades with very good build-up and good fastness to light and to wet treatments.

Example 12 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 7.28 parts of 4-methoxymandelic acid, with a reaction time of 2 hours. Crystallisation of the product from toluene gives 3-phenyl-7-(4-methoxyphenyl)-2,6-dioxo-2,6dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C, 74.2; H, 3.82. C23H14Os requires C, 74.59; H, 3.78%].

The product dyes aromatic polyester textile materials from aqueous dispersions in attractive red shades with good build-up properties and showing good fastness to light and to wet treatments. The mass spectrum shows a terminal ion at m/e 370 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a red solution having ,tmax 498 nm, Emax 48,900.

Example 13 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 7.46 parts of 2-chioromandelic acid, with a reaction time of 4 hours. Crystallisation of the product from cellosolve gives 3-phenyl-7-(2-chlorophenyl)-2,6-dioxo-2,6dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C, 70.48; H, 3.03; Cl, 9.41. C22H1'O4CI requires C, 70.49; H, 2.94; Cl. 9.28%]. The mass spectrum shows a terminal ion at m/e=375 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a yellow solution having jwmax 447 nm, Emax 39,900.The product dyes aromatic polyester textile materials in yellow shades with good build-up properties and having good fastness to light and to wet treatments.

Example 14 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 7.46 parts of 4-chloromandelic acid, with a reaction time of 1 T hours. Crystallisation of the product from toluene gives 3-phenyl-7-(4-chlorophenyl)-2,6-dioxo-2,6- dihydrobenzo[l:2-b, 4:5-b']difuran. [Found: C, 70.4; H, 3.1; Cl, 9.1. C22H1'O4CI requires C, 70.48; H, 3.03; Cl, 9.41%]. The mass spectrum shows a terminal ion at m/e=375 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a yellow solution having Amax 471,may 40,000.The product dyes aromatic polyester textile materials in yellow shades with good build-up properties and having good fastness to light and to wet treatments.

Example 15 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 7.28 parts of 2-methoxymandelic acid, with a reaction time of 4 hours. Crystallisation of the product from toluene gives 3-phenyl-7-(2-methoxyphenyl)-2,6-dioxo-2,6dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C, 74.03; H, 3.67. C23H,406 requires C, 74.59; H, 3.78%].

The mass spectrum shows a terminal ion at m/e=370 and a breakdown pattern consistent with this structure. The product dyes aromatic polyester textile materials in orange shades with good build-up properties and having good fastness to light and to wet treatments.

Example 16 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 7.84 parts of 4-ethoxymandelic acid, with a reaction time of 2 hours. Crystallisation of the product from toluene gives 3-phenyl-7-(4-ethoxyphenyl)-2,6-dioxo-2,6dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 74.7; H 4.2. C24H,805 requires C 75.0; H 4.16%]. The mass spectrum shows a terminal ion at m/e=384 and a breakdown pattern consistent with this structure. The product dyes aromatic polyester textile materials in bright red shades with good build-up properties and having good fastness to light and to wet treatment.

Example 17 The procedure described in Example 11 is repeated except that in place of the 6.64 parts of 4methylmandelic acid there are used 8.4 parts of 4-n-propoxymandelic acid, with a reaction time of 2 hours. Crystallisation of the product from toluene gives 3-phenyl-7-(4-n-propoxyphenyl)-2,6-dioxo2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 75.3; H 4.7. C25H,805 requires C 75.4; H 4.5%]. The mass spectrum shows a terminal ion at m/e=398 and a breakdown pattern consistent with this structure. The product dyes aromatic polyester textile materials in bright red shades with good build-up properties and having good fastness to light and to wet treatments.

Example 18 A mixture of 9.6 parts of 5-hydroxy-2-oxo-3-(4-methylphenyl)-2 :3-dihydrobenzofuran and 8.4 parts of 4-isopropoxymandelic acid is stirred for 2 hours at 1 950C, 8 parts of nitrobenzene are then added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 1 50 parts of ethanol ere added and the mixture is stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with ethanol and dried. Crystallisation from toluene gives 3-(4-methylphenyl)-7-(4 isopropoxyphenyl)-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 75.6; H 4.8. C2eH2005 requires C 75.73: H 4.85%]. The mass spectrum shows a terminal ion at m/e=412 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give a bright red solution having a,,, 513 nm, Emax 48,500. When applied to aromatic polyester textile materials from aqueous dispersions the product gives bright red shades with excellent build up and good fastness to light and wet treatments.

Example 19 A mixture of 10.24 parts of 5-hydroxy-2-oxo-3-(4-methoxyphenyl)-2,3-dihydrobenzofuran and 7.28 parts of 2-methoxymandelic acid is stirred for 3 hours at 1 950C, 8 parts of nitrobenzene are then added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 150 parts of ethanol are added and the mixture is stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with ethanol and dried. Crystallisation from cellosolve gives 3-(4-methoxyphenyl)-7-(2 methoxyphenyl)-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 72.2; H 4.1. C24H,608 requires C 72.0; H 4.0%]. The mass spectrum shows a terminal ion at m/e=400 and a breakdown pattern consistent with this structure.The product dyes aromatic polyester textile material in scarlet shades with good build up properties and having good fastness to light and to wet treatments.

Example 20 A mixture of 9.6 parts of 5-hydroxy-7-methyl-2-oxo-3-phenyl-2,3-dihydrobenzofuran and 7.28 parts of 4-methoxymandelic acid is stirred for 2 hours at 1 950C, 8 parts of nitrobenzene are then added and the heating is continued for a further 30 minutes. The mixture is cooled to 250C, 150 parts of ethanol are added and the mixture is stirred for 2 hours at 250C. The precipitated solid is purified by chromatography and subsequent crystailisation from toluene gives 3-phenyl-7-(4-methoxyphenyl)-8methyl-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 74.5; H 4.1..C24H1eO5 requires C 75.0; H 4.16%]. The mass spectrum shows a terminal ion at m/e-384 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give an orange solution having Amax 474 nm. When applied to aromatic polyester textile materials from aqueous dispersions the product gives orange shades with excellent build-up and good fastness to light and wet treatments.

Example 21 The procedure described in Example 20 is repeated except that in place of the 9.6 parts of 5 hydroxy-7-methyl-2-oxo-3-phenyl-2,3-dihydrobenzofuran there are used 11.4 parts of 5-hydroxy-7 .methoxycarbonyl-2-oxo-3- phenyl-2,3-dihydrobenzofuran. Crystallisation of the product from toluene gives 3-phenyl-7-(4-methoxyphenyl )-8-methoxycarbonyl-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5- b']difuran. [Found: C 70.0; H 3.6. C25HO, requires C 70.1; H 3.73%]. The mass spectrum shows a terminal ion at m/e=428 and a breakdown pattern consistent with this structure. When applied to aromatic polyester textile materials from aqueous dispersions the product gives bright red shades with excellent build-up and good fastness properties to light and wet treatments.

Example 22 A mixture of 10.64 parts of 5-acetamido-2-oxo-3-phenyl-2,3-dihydroindole and 6.64 parts of 4methylmandelic acid is stirred for 2 hours at 1 900C, 8 parts of nitrobenzene are added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 150 parts of acetic anhydride and 2 parts of 98% w/v sulphuric acid are added and the resulting solution is stirred and heated under reflux for 2 hours. After cooling the reaction mixture, the product is filtered off, washed with ethanol and dried to give N,N'-diacetyl-3-(4-methylphenyl)-7-phenyl-2,6-dioxo-1 ,2,5,6-tetrahydrobenzo[1 :2-b, 4:5-b']dipyrrole. [Found: C 74.1; H 4.61; N 6.45. C2,H20N204 requires C 74.3; H 4.59; N 6.42%]. The mass spectrum shows a terminal ion at m/e=436 and a breakdown pattern consistent with this structure.When applied to aromatic polyester textile materials from an aqueous dispersion the product gives strong orange shades having good fastness to light and to wet treatments.

Example 23 The procedure described in Example 5 is repeated except that in place of the 6.04 parts of 4acetamidophenol there are used 8.8 parts of 4-acetamidb-2,6-dichlorophenol. Acetylation of this product with acetic anhydride and sulphuric acid gives 5-acetyl-8-chloro-3,7-di(4-methoxyphenyl) 2,6-dioxo-2,6-dihydro-5H-furo[2:3-flindole. [Found: C 65.2; H 3.69; N 3.01; Cl 7.52. C2 Hr8CINO6 requires C 65.61; H 3.78; N 2.95; Cl 7.47%]. The mass spectrum shows a terminal ion at m/e=475 and a breakdown pattern consistent with this structure. The product dissolves in chloroform to give a red solution having imax 526 nm.

Example 24 A mixture of 10.68 parts of 5-acetamido-2-oxo-3-phenyl-2,3-dihydrnbenzofuran and 7.28 parts.

of 4-methoxymandelic acid is stirred for 4 hours at 1 850C, 8 parts of nitrobenzene are added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 1 50 parts of acetic anhydride and 2 parts of 98% w/v sulphuric acid are added and the mixture is then stirred and heated under reflux for 2 hours. After cooling the reaction mixture the product is filtered off, washed with ethanol and dried to give 5-acetyl-7-(4-methoxyphenyl )-3-phenyl-2,6-dioxo-2,6-dihydro-5H-furo [2:3- f]indole. [Found: C 73.1; H 4.2; N 3.3. C26H"NO5 requires C 73.0; H 4.14; N 3.4%]. The mass spectrum shows a terminal ion at m/e=41 1 and a breakdown pattern consistent with this structure.The product dissolves in chloroform to give a bright red solution having Amax 492 nm.

Example 25 A mixture of 1 part of the dyestuff of Example 12 and 20 parts of 98% w/v sulphuric acid is stirred for 1 hour at 250C. The mixture is poured into a solution of sodium chloride at OOC and the precipitated solid is filtered off, washed with an aqueous solution of sodium chloride and dried.

Analysis shows that the product consists essentially of the disodium salt of 3-(4 methoxysulphophenyl)-7-(sulphophenyl)-2,6-dioXo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. The resulting product dyes wool and synthetic polyamide textile materials in red shades from an aqueous dyebath.

Example 26 A mixture of 9.04 parts of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran and 6.72 parts of 4-hydroxy-mandelic acid is stirred for 1.5 hours at 1 950C, 8 parts of nitrobenzene are then added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 100 parts of methanol are added and the mixture 1s stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with methanol and dried. Crystallisation from cellosolve gives 3-phenyl-7-(4-hydroxyphenyl)-2,6-dioxo-2,6dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 74.2; H 3.3. C22H,205 required C 74.16; H 3.37%].

The mass spectrum shows a terminal ion at m/e=356 and a breakdown pattern consistent with this structure. The product dissolves in acetone to give a red solution having imax 499 nm, Emax 39,500.

When applied to aromatic polyester textile materials from aqueous dispersions the product gives red shades with very good build-up and good fastness to light and to wet treatments.

Example 27 The procedure described in Example 26 is repeated except that in place of the 6.72 parts of 4hydroxymandelic acid there are used 7.28 parts of 4-hydroxy-3-methylmandelic acid with a reaction time of 2 hours. Crystallisation of the product from cellosoive gives 3-phenyl-7-(4-hydroxy-3 methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 74.4; H 3.5. C23Ht405 requires C 74.59; H 3.78%]. The mass spectrum shows a terminal ion at m/e=370 and a breakdown pattern consistent with this structure. The product dissolves in acetone to give a red solution having imax 504 nm, Emax 41,400.

Example 28 A mixture of 9.6 parts of 5-hydroxy-2-oxo-3-(4-methylphenyl)-2,3-dihydrobenzofuran and 8.1 parts of 3-chloro-4-hydroxymandelic acid is stirred for 2 hours at 1 850C, 8 parts of nitrobenzene are then added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 100 parts of methanol are added and the mixture is stirred for 2 hours at 250C. The precipitated solid is filtered off, washed with methanol and dried.Crystallisation from methanol gives 3-(3-chloro-4 hydroxyphenyl)-7-(4-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 68.1; H 3.2; Cl 8.8. C23H,3CIO5 requires C 68.23; H 3.21; Cl 8.78%]. The mass spectrum shows a terminal ion at m/e=404 and a breakdown pattern consistent with this structure.

When applied to aromatic polyester textile materials from aqueous dispersions the product gives bright red shades with very good build-up and good fastness to light and to wet treatments.

Example 29 A mixture of 4.92 parts of 4-N-methylaminophenol and 16.2 parts of 3-chloro-4-hydroxymandelic acid is stirred for 3 hours at 1 800 C, 8 parts of nitrobenzene are added and heating is continued for a further 30 minutes. The mixture is cooled to 250C, 100 parts of ethanol are added and the mixture is stirred at 250C for 2 hours. The precipitated solid is filtered off, washed with ethanol and dried.Crystallisation from cellosolve gives 3,7-di(3-chloro-4-hydroxyphenyl)-2,6-dioxo-5-methyl-2,6- dihydro-5H-furo[2:3-f]indole. [Found C 60.7; H 2.7; N 3.1; Cli 15.4. C23H,3Cl2NO5 requires C 60.8; H 2.86; N 3.08; Cl 1 5.64%]. The mass spectrum shows a terminal ion at m/e=454 and a breakdown pattern consistent with this structure. The product dissolves in acetone to give a bluish-red solution having Amax 498 nm. When applied to aromatic polyester textile materials from aqueous dispersions the product gives strong bluish-red shades showing good fastness to light and to wet treatments.

Example 30 A mixture of 7.4 parts of the dyestuff of Example 27, 4.2 parts of 5-naphthoyl chloride, 2.2 parts of triethylamine and 1 50 parts of dioxan is stirred at 1 000C for 1 hour. The precipitated product is filtered off at 1 O00C, washed separately with dioxan and water and then dried. Analysis shows the product to be 3-phenyl-7-(3-methyl-4-naphth-2-yl-carbonyloxyphenyl)-2,6-dioxo-2,6- dihydrobenzo[1 :2-b, 4:5-b']difuran. [Found: C 77.7; H 3.6. C34H20Os requires C 77.86; H 3.82%]. The mass spectrum shows a terminal ion at m/e=524 and a breakdown pattern consistent with this structure.The product has very low solubility in organic solvents and when incorporated in known manner into conventional ink or paint formulations orange shades are obtained with high fastness to light.

Example 31 The procedure described in Example 30 is repeated except that in place of the 7.4 parts of the dyestuff of Example 27, there are used 7.4 parts of 3- (4-hydroxyphenyl)-7-(4-methylphenyl)-2,6-' dioxo-2,6-dihydrobenzo[1 :2-b, 4:5-b']difuran. Analysis shows the product to be 3-(4-methylphenyl)-7 (4-naphth-2-ylcarbonyloxyphenyl)-2,6-dioxo-2,6-dihydrnbenzo[1 :2-b, 4:5-b']difuran. [Found: C 77.75; H 3.7. C34H20O6 requires C 77.86; H 3.82%]. The mass spectrum shows a terminal ion at m/e=524 and a breakdown pattern consistent with this structure.

The product has very low solubility in organic solvents and when incorporated in known manner into conventional ink or paint formulations red shades are obtained having high fastness to light.

Example 32 A mixture of 7.12 parts of the dyestuff of Example 1, 2.03 parts of terephthaloyl chloride, 2.2 parts of triethylamine and 200 parts of dimethylformamide is stirred for 1 hour at 11 00C. The precipitated product is filtered off at 1 1 OOC, washed separately with dimethylformamide and water and then dried.

Analysis shows the product to be 1 ,4-bis[4-(7-phenyl-2,6-dioxo-2,6-dihydrobenzo[1 :2-b, 4:5- b']difur-3-yl)phenoxycarbonyl]benzene. [Found: C 73.9; H 3.12. C52H26012 requires C 74.1; H 3.09%].

The product has low solubility in organic solvents and when incorporated in known manner into conventional ink or paint formulations orange shades are obtained having high fastness to light.

Claims (14)

Claims

1. Dyestuffs of the general formula (I):

wherein ZX and Z2 are oxygen, sulphur or -NY1 in which Y' is an optionally substituted hydrocarbon radical or an acyl radical; R3 and R4 each represent a naphthyl radical, an unsubstituted phenyl radical or a phenyl radical substituted by at least one of the following:: nitro, hagogen, lower alkyl, lower alkoxy, phenyl, hydroxy, lower alkoxyphenyl, phenoxy, cyano, carboxylic acid, carboxylic acid ester, optionally substituted carbamoyl, sulphonic acid, sulphonyl chloride, sulphonic acid ester, optionally substituted sulphamoyl, mercapto, lower alkylthio, phenylthio, primary, secondary, tertiary or quaternary amino, acylamino, phosphonic acid, phosphonic acid ester, lower alkylsulphonyl, phenylsulphonyi, aldehyde, azo, and acyloxy groups of the formula O.CO.T' in which T1 is an alkyl group containing at least two carbon-atoms, a substituted phenyl group, a lower alkoxy group or a phenoxy group;; X3 and X4 each independently represent a hydrogen atom, chlorine, bromine, cyano, lower alkyl, lower alkoxy, optionally substituted aryl, optionally substituted carbamoyl, optionally substituted sulphamoyl, carboxylic acid or carboxylic acid ester group, provided that Z1 and Z2 may be the same or different when R3 and R4 are different, and Z1 and Z2 are different when R3 and R4 are the same.

2. Dyestuffs as claimed in claim 1 wherein the optionally substituted hydrocarbon radicals represented by Y1 are optionally substituted lower alkyl radicals or optionally substituted phenyl radicals.

3. Dyestuffs as claimed in claim 1 or claim 2 wherein the optionally substituted carbamoyl and sulphamoyl groups which may be present as substituents on the phenyl radicals represented by Ra and R4, and which are represented by X3 and X4, are of the formula:

respectively, in which L1 and E2 are each independently hydrogen, lower alkyl or phenyl.

4. Dyestuffs as claimed in any one of claims 1 to 3 wherein the carboxylic acid ester groups which may be present as substituents on the phenyl radicals represented by R3 and R4, and which are represented by X3 and X4, are of the formulaCOOL3 wherein L3 is an optionally substituted lower alkyl or phenyl radical.

5. Dyestuffs substantially as hereinbefore described in any one of the foregoing Examples.

6. A process for the preparation of the dyestuffs claimed in claim 1 which comprises reacting 1 mol proportion of a compound of formula (ill):

wherein X3, X4, Z1 and Z2 have the meanings defined in claim 1, with at least 2 mol proportions of a compound of formula (III):

wherein B is hydrogen, lower alkyl or aryl, A is hydroxyl, O-acyl or halogen, and R3 has the meaning defined in claim 1, either as a melt or in a high-boiling inert solvent, to give the intermediate of formula (lav):

which is subsequently oxidised to give the dyestuff of formula (I).

7. A process for the preparation of the dyestuffs claimed in claim 1 which comprises reacting substantially equimolar proportions of the compound of formula (ill):

wherein X3, X4, Z1 and Z2 have the meanings defined in claim 1, and the compound of formula (Ill):

wherein A and B have the meanings defined in claim 6 and R3 has the meaning defined in claim 1, to give the intermediate of formula (V):

which is subsequently reacted with 1 mol proportion of the compound of formula (Vl):

wherein A and B have the meanings defined in claim 6 and R4 has the meaning defined in claim 1, to give the intermediate of formula (VII):

which is subsequently oxidised to give the dyestuff of formula (I).

8. A process for the preparation of the dyestuffs claimed in claim 1 wherein Z1 and Z2 are both oxygen which comprises reacting a quinone of formula (VIII):

with a compound of'the formula (IX):

in which R3, X3 and X4 have the meanings defined in claim 1, B has the meaning defined in claim 6, X5 and X6 are hydrogen, chlorine or bromine, and Q is hydrogen, hydroxyl or O-acyl, provided that when Q is hydrogen, at least X3 and X4, or X5 and X6 must be chlorine or bromine, to give a compound of formula (X):

which is then further reacted with a compound of formula (Xl):

wherein B and 0 have the meanings defined above and R4 has the meaning defined in claim 1, to give a compound of the formula (XII)::

which then cyclises with bond rearrangement to give a dyestuff of formula (I).

9. A process as claimed in claim 6 substantially as hereinbefore described in any one of the foregoing Examples 1 to 10, 23, 29 and 32.

1 0. A process as claimed in claim 7 substantially as hereinbefore described in any one of the foregoing Examples 11 to 22, 24 to 28, 30 and 31.

11. Dyestuffs whenever obtained by a process as claimed in any one of claims 6 to 10.

1 2. A process for colouring synthetic textile materials which comprises applying to the synthetic textile material by a dyeing, padding, or printing process an aqueous dispersion of a dyestuff as claimed in claim 1.

13. A process as claimed in claim 12 wherein the synthetic textile material is an aromatic polyester textile material.

14. Synthetic textile materials whenever coloured by means of a process as claimed in claim 12 or claim 13.