Polycyclic dyes

Abstract: Polycyclic dyes of the formula: wherein: X¹ and X² are both H; Z¹ and Z² are both O; R¹ and R² each independently is H, alkyl, alkenyl, cycloalkyl, aralkyl or aryl; and Ring B carries a methyl group adjacent to NR¹R²; and Ring A is unsubstituted or substituted in the 4-position by an alkyl or alkoxy group and of the formula: wherein: X¹ and X² each independently is H, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH or carboxylic acid ester; Z¹ and Z² each independently is -O-, -S- or -NY- in which Y is H, an optionally-substituted hydrocarbon group or an acyl group; R¹ and R² each independently is H or an optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl group; or R¹ and R² together with the N atom to which they are attached, form a heterocycle; R⁴ and R⁵ each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group; or R¹ and R⁴ together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; or R² and R⁵ together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; R⁶ is H, halogen, an optionally substituted alkyl or alkoxy group or a group NR¹R² in which each of R¹ and R² independently is as hereinbefore defined; R⁷ and R⁸ each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group; or R¹ and R⁷ together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Ring A; or R² and R⁸ together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Ring A; and where R⁶ is NR¹R², this may be the same as or different from the NR¹R² group present in Ring B. The present polycyclic dyes may be used for the coloration of polyester textile material in shades from green through to reddish-blue.

Description: This specification describes an invention relating to certain polycyclic dyes. EP-A-0252406 discloses a range of polycyclic dyes prepared by a process in which an α-keto acid or derivative is reacted with a benzofuranone. A specific example is 3-phenyl-7-(4-N,N-dimethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b; 4:5-b']-difuran. EP-A-0033583 discloses a range of 3,7-diphenyl-2,6-dioxo-2,6-dihydrobenzo[1:2-b; 4:5-b']-difuran dyes, processes for their preparation and their use in the coloration of synthetic textile materials. At least one of the phenyl groups is substituted such that the dyes are asymmetrical. An optional substituent is a primary, secondary or tertiary amino group. FR-A-2343785 discloses a range symmetrical 3,7-diphenyl-2,6-dioxo-2,6-dihydrobenzo[1:2-b; 4:5-b']-difuran dyes and their use in the coloration of synthetic textile materials. An example of a 3,7-di[N,N-diethylaminophenyl] compound is given. Our copending EP-A-0363034 discloses a process for the preparation of a polycyclic dye of the Formula I: by reacting a phenyltartronic acid of Formula II: wherein: W is -NR 1 R 2 or -OR 3 ; R 3 is H or an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group; R 1 and R 2 each independently is H, or an optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl group; or R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclic ring; or R 1 or R 2 together with the nitrogen atom and the adjacent carbon atom of Ring B form a heterocyclic ring; and Ring B is unsubstituted, apart from the group W, or is substituted by one or two further groups; with either (a) a compound of the Formula III: wherein: Z 1 and Z 2 each independently is -O-, -S- or -NY- in which Y is H, an optionally-substituted hydrocarbon group or an acyl group; X 1 and X 2 each independently is H, halogen, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH or carboxylic acid ester; & Ring A is unsubstituted or is substituted by from one to three groups; or (b) a compound of the Formula IV: wherein: Z 1 , Z 2 , X 1 and X 2 are as hereinbefore defined; and oxidation of the intermediate compound to dehydrogenate the peripheral heterocyclic rings. The optionally substituted hydrocarbon group represented by Y is preferably C 1-8 -alkyl, and more preferably C 1-4 -alkyl, or monocyclic aryl, more preferably phenyl. The acyl group represented by Y is preferably C 1-4 -alkyl- or monocyclic-aryl-carbonyl or -sulphonyl which may be substituted by one or more groups selected from hydroxy, halogen, nitro, C 1-4 -alkyl and C 1-4 -alkoxy. Examples of the optionally substituted hydrocarbon groups represented by Y are alkyl and preferably C 1-4 -alkyl, such as methyl, ethyl, n -propyl and iso-propyl; substituted alkyl, preferably substituted C 1-4 -alkyl, such as β-hydroxyethyl, β-methoxyethyl and β-ethoxyethyl; phenyl and substituted phenyl such as tolyl, chlorophenyl, nitrophenyl and C 1-4 -alkoxyphenyl. Examples of the acyl groups represented by Y are acetyl, propionyl, n -butyryl, iso-butyryl, benzoyl and nitrobenzoyl, chlorobenzoyl, methylbenzoyl, methoxybenzoyl and hydroxybenzoyl. The aryl group represented by X 1 or X 2 is preferably monohomocyclic aryl, that is phenyl and substituted phenyl. The C 1-4 -alkyl and alkoxy groups represented by X 1 or X 2 may also be substituted and suitable substituents for these and the aryl group are hydroxy, halogen, nitro, C 1-4 -alkyl and C 1-4 -alkoxy. The halogen represented by X 1 or X 2 is preferably chlorine or bromine. The carbamoyl and sulphamoyl groups represented by X 1 or X 2 are preferably of the formula -CONL 1 L 2 or -SO 2 NL 1 L 2 wherein L 1 and L 2 are each independently hydrogen, C 1-4 -alkyl or monocyclic aryl, preferably phenyl. The carboxylic acid ester groups represented by X 1 and X 2 are preferably of the formula -COOL 3 wherein L 3 is optionally substituted alkyl, especially C 1-4 -alkyl, or monocyclic aryl, especially phenyl, in which the substituents are as defined above. When any of R 1 to R 3 is alkyl or alkenyl it preferably contains up to 20, more preferably up to 10 carbon atoms and especially up to 4, carbon atoms, with a preferred minimum of 3 carbon atoms for alkenyl groups); when cycloalkyl it is preferably C 4-8 -cycloalkyl, such as cyclohexyl; and when aryl or aralkyl, the aryl is preferably monohomocyclic aryl, i.e. phenyl, and the aralkyl is preferably phenyl-C 1-4 -alkylene, such as benzyl and phenylethyl. Where the groups represented by R 1 to R 3 are substituted, examples of preferred substituents are alkyl, alkoxy, nitro, halogen, alkoxyalkoxy, cyclohexyl, phenyl, diphenyl, hydroxy, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyloxy, alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, cyano and amino in which each alkyl is preferably C 1-4 -alkyl. Where the groups represented by R 1 and R 2 , together with the nitrogen atom to which they are attached, form a heterocyclic group this is preferably alicyclic, such as piperidino or morpholino. Where a group represented by R 1 or R 2 together with the nitrogen atom to which it is attached and an adjacent carbon atom of Ring B or Ring A form a heterocyclic group fused to Ring B or Ring A respectively, this is preferably a 6-membered heteroaliphatic ring, i.e. R 1 or R 2 is trimethylene, and the combined fused rings preferably form a tetrahydroquinolyl group. It is preferred that the compound of Formula I is "unsymmetrical" by virtue of differences in the definitions of Z 1 and Z 2 , X 1 and X 2 and/or Ring A and Ring B, because lack of symmetry generally gives rise to an improvement in dyeing performance, especially in build-up on the fibre. However, it is generally preferred that Z 1 and Z 2 are identical and X 1 and X 2 are identical and that the lack of symmetry arises from differences in Rings A and B. Where Ring A and Ring B are different, the difference preferably lies in the nature and/or the number of substituents carried by each ring. The difference lies preferably in the identity of the groups R 1 to R 3 but may lie in the identity and/or the number of the substituents carried by the rings. Examples of further substituents for Ring B, in addition to the group W, are alkyl; alkenyl; alkoxy; alkoxyalkoxy; alkoxycarbonyalkoxy; alkoxyalkoxycarbonylalkoxy; alkylcarbonyloxyalkoxy; cyanoalkoxy, hydroxyalkoxy; halogen, especially chlorine or bromine; hydroxy; alkylthio; arylthio; aryloxy; alkylcarbonyl and alkylsulphonyl; and especially such groups in which the alkyl or alkenyl contains up to 4 carbon atoms and the aryl is phenyl. Examples of substituents for Ring A, in addition to those listed above for Ring B, are NR 1 R 2 , OR 3 and NHacyl, especially NHCOC 1-4 -alkyl and -NHSC 3 C 1-4 -alkyl. It is preferred that X 1 and X 2 are both hydrogen and also preferred that Z 1 and Z 2 are both oxygen. When both these pairs of groups are identical, the preferred asymmetry in the compound of Formula I is provided by differences in Rings A and B. By this is meant that there is either a different number or different pattern of substituents on each ring. The present process may be performed by heating the reactants in a melt but preferably in an acidic medium, preferably an organic acid, and especially an alkanecarboxylic acid such as acetic acid, propionic acid or butyric acid. It is preferred to perform the process in which W is OR 3 in the presence of a strong acid catalyst, especially H 2 SO 4 . However, where W is NR 1 R 2 such a catalyst is not generally required and is believed to have an adverse effect on the process. The process is preferably performed at a temperature from 50°C to 100°C, especially 70°C to 100°C, where a solvent is present, conveniently under reflux. Reaction is preferably continued until all the starting materials are consumed which can take up to 25 hours. Further reactions of the dyes in which any or all of R 1 , R 2 and R 3 are H with alkylating, arylating or acylating agents permits the preparation of a wide range of substituted hydroxy and amino (secondary and tertiary amino) groups. The final oxidation step may be effected by any convenient oxidising agent for dehydrogenating a carbon-carbon single bond, such as a persulphate or hydrogen peroxide. The compound of Formula III, in which Ring A also carries a group NR 1 R 2 , may be prepared by the reaction of an amino-mandelic acid (in which the amino group is protected, if necessary, by acylation) with a hydroquinone in accordance with the procedures described in GB-A-2 068 402. EP-A-0 363 034 also discloses a process for the preparation of a compound according to Formula III in which Ring A carries a group NR 1 R 2 in the 4-position which comprises reacting a mandelic acid of the Formula V: wherein A has the same meaning as in Formula I with a compound of the Formula VI: wherein X 1 and X 2 have the same meanings as in Formula I. It is preferred that, in Formula VI, X 1 and X 2 are both hydrogen. This reaction is conveniently performed in an acidic medium in the presence of a strong acid catalyst as described above for the preparation of the compound of Formula I but at a lower temperature in the range 40°C to 80°C especially from 49°C to 75°C. The present process is especially suitable for the preparation of compounds of Formula I in which: (a) Ring B carries a group, NR 1 R 2 , and both rings, optionally, carry one or more other substituents; or (b) Rings A and B both carry a group, NR 1 R 2 , which may be the same or different, and, optionally, one or more other substituents. According to the present invention, there is provided a compound of Formula I in which W is, specifically, NR 1 R 2 , Ring B carries a substituent, as defined below, adjacent to NR 1 R 2 and Ring A is unsubstituted or substituted in the 4-position in the manner defined below. Such compounds give blue shades when applied to synthetic fibres, especially polyesters, by disperse dyeing processes, and build up well to give navy shades. According to the present invention there is provided a compound of the formula: wherein: X 1 and X 2 each independently is H, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH or carboxylic acid ester; Z 1 and Z 2 each independently is -O-, -S- or -NY- in which Y is H, an optionally-substituted hydrocarbon group or an acyl group; one of R 1 and R 2 is H or an optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl group; and the other of R 1 and R 2 is H; R 4 and R 5 each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group, provided that at least one of R 4 and R 5 is other than hydrogen; or R 1 and R 4 together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; or R 2 and R 5 together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; R 6 is H, halogen or an optionally substituted alkyl or alkoxy group or a group NR 9 R 10 in which each of R 9 and R 10 is H or an optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl group; or R 9 and R 10 together with the N atom to which they are attached form a heterocvcle. R 7 and R 8 each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group provided that when R 7 or R 8 is other than H, one of R 9 and R 10 is H: or R 7 and R 9 together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Rina A; or R 8 and R 10 together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Ring A; and where R 6 is NR 9 R 10 this may be the same as or different from the NR 1 R 2 group present in Ring B. In the compounds of the formula (VIII), one of R 1 and R 2 , in the group NR 1 R 2 substituted on Ring B or, when R 6 is NR 9 R 10 , each of R 9 and R 10 in the group NR 9 R 10 substituted on Ring A, may be H, C 1-6 -alkyl, C 3-4 -alkenyl, cyclohexyl or C 1-4 -alkyl substituted by a group selected from C 1-4 -alkyl, C 1-4 -alkoxy, C 1-4 -alkoxy-C 1-4 -alkoxy, nitro, cyano, halogen, cyclohexyl, phenyl, diphenyl, hydroxy, C 1-4 -alkylcarbonyl, amino C 1-4 -alkoxycarbonyl, C 1-4 -alkoxy-C 1-4 -alkoxycarbonyl, C 1-4 -alkoxycarbonyloxy or R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidino or morpholino group. In such a range of compounds R 4 may be C 1-4 -alkyl, C 3-4 -alkenyl, C 1-10 -alkoxy or halogen. It is preferred that the compound of Formula VII is "unsymmetrical" by virtue of differences in the definitions of Z 1 and Z 2 , X 1 and X 2 and/or the number and pattern of substituents on Ring A and Ring B, because lack of symmetry generally gives rise to an improvement in dyeing performance, especially in build-up on the fibre. It is preferred that X 1 and X 2 are the same and preferably H. It is also preferred that Z 1 and Z 2 are the same and preferably oxygen. Where X 1 and X 2 are identical and Z 1 and Z 2 are identical it is preferred that the lack of symmetry arises from a difference in the number or pattern of substituents on Ring A and Ring B. Preferences for the groups represented by X 1 , X 2 , Z 1 and Z 2 are the same as for the same groups in Formula I. In Ring A it is preferred that R 6 is independently selected from H, halogen, C 1-10 -alkyl (which may be a C 1-6 -alkyl), C 3-10 -alkenyl (which may be a C 3-4 -alkenyl), C 1-10 -alkoxy and NR 9 R 10 in which each of R 9 and R 10 is independently H; C 1-6 -alkyl, more especially C 1-4 -alkyl; or C 1-4 -alkyl substituted by a group selected from alkoxy, alkoxyalkoxy, hydroxy, cyano, halogen especially chlorine or bromine, phenyl, alkoxycarbonyl, alkoxyalkoxycarbonyl and alkylcarbonyloxy in which all the alkyl groups preferably contain up to 4 carbon atoms. In one subgroup of such compounds, R 6 is H, C 1-6 -alkyl, C 3-4 -alkyl, C 1-10 -alkoxy or halogen and R 4 (in Ring B) is C 1-4 -alkyl or C 1-4 -alkoxy. Alternatively either R 9 and R 7 or R 10 and R 8 , together with the N atom to which R 9 and R 10 is attached and two carbon atoms in Ring A, may form a piperidine ring fused to Ring A or R 9 and R 10 , together with the N atom to which they are attached, may form a pendant mono or bicyclic heterocyclic group, especially piperidine or mopholino, attached to Ring A through the N atom. Where R 6 is not NR 9 R 10 , it is preferred that each of R 7 and R 8 is H. In Ring B it is preferred that one of R 1 and R 2 independently is H; C 1-4 -alkyl, more especially C 1-4 alkyl; or C 1-4 -alkyl which is optionally substituted by a group selected from alkoxy, alkoxyalkoxy, hydroxy, cyano, halogen especially chlorine or bromine, phenyl, alkoxycarbonyl, alkoxycarbonyloxy, alkoxyalkoxycarbonyl and alkylcarbonyloxy in which all the alkyl groups preferably contain up to 4 carbon atoms; or that either R 1 and R 4 or R 2 and R 5 , together with the N atom to which R 1 or R 2 is attached and two carbon atoms in Ring B, form a piperidine ring fused to Ring B. At least one of R 4 and R 5 is other than hydrogen and, especially, an alkyl or alkoxy group as hereinafter more specifically defined. The alkyl group represented by R 4 , R 5 , R 6 , R 7 or R 8 is preferably C 1-4 -alkyl, especially methyl or ethyl. The alkenyl group represented by R 4 , R 5 , R 6 , R 7 or R 8 is preferably C 3-4 -alkenyl, especially allyl. The alkoxy group represented by R 4 , R 5 , R 6 , R 7 or R 8 is preferably an unsubstituted C 1-10 -alkoxy or a C 1-4 -alkoxy group which is substituted by a group selected from alkoxy, hydroxy, alkylcarbonyloxy, alkoxyalkoxycarbonyl, alkoxycarbonyl, halogen and cyano, in which all the alkyl groups preferably contain up to 4 carbon atoms. The halogen represented by R 4 , R 5 , R 6 , R 7 or R 8 is preferably chlorine or bromine. In one preferred sub-class of the compounds of Formula VII, X 1 , X 2 and R 1 are H; Z 1 and Z 2 are oxygen; R 2 is H or C 1-4 -alkyl; R 4 is C 1-4 -alkyl or C 1-10 -alkoxy, more especially C 1-4 -alkoxy; R 5 , R 7 and R 8 each independently is H, C 1-4 -alkyl or C 1-10 -alkoxy, more especially C 1-4 -alkoxy; and R 6 is NH 2 . The dyes of this preferred sub-class of Formula VII, generally give reddish-blue to turquoise shades on polyester textile materials with excellent fastness properties, especially heat and wet fastness. Within this sub-class are dyes wherein X 1 , X 2 , R 1 , R 7 and R 8 are H. Specific examples of such dyes are: R 1 R 2 R 4 R 5 R 6 R 7 R 8 H H CH3 H NH 2 H H H H OCH 3 H NH 2 H H H H Cl H NH 2 H H H H C 2 H 5 H NH 2 H H H H CH 3 CH 3 NH 2 H H In another preferred sub-class of the compound of Formula VII, X 1 , X 2 , R 1 , R 5 , R 7 and R 8 are H; Z 1 and Z 2 are oxygen; R 2 is C 1-4 -alkyl; R 4 is C 1-4 -alkyl or C 1-10 -alkoxy, more especially C 1-4 -alkoxy; and R 6 is H, C 1-4 -alkyl or C 1-4 -alkoxy. The dyes of this preferred sub-class of Formula VII build up strongly on polyester textile materials to give strong navy shades with excellent fastness properties, especially heat and wet fastness. Specific examples of such dyes are: R 1 R 2 R 4 R 5 R 6 R 7 R 8 H H CH 3 H H H H H H CH 3 H CH 3 H H H H C 2 H 5 H OC 3 H 7 H H H H n-C 3 H 7 H C 3 H 7 H H H H OCH 3 H H H H H H OC 2 H 5 H OC 3 H 7 H H H H O-n-C 3 H 7 H OC 3 H 7 H H H C 2 H 5 CH 3 H H H H Examples of other dyes according to Formula VII are: R 1 R 2 R 4 R 5 R 6 R 7 R 8 X 1 H C 2 H 5 CH 3 H NH 2 H H H H i-C 3 H 7 CH 3 H NH 2 H H H H H C 2 H 5 H NH 2 CH 3 H H H -CH 2 CH 2 CH 2 - H NH 2 H H H H H CH 3 CH 3 NH 2 CH 3 H H H C 2 H 4 OH CH 3 H NH 2 H H H H s-C 4 H 9 CH 3 H NH(s-C 4 H 9 ) H H H In Table 3 and subsequent tables s-C 4 H 9 is The invention is further illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated. Example 1 A mixture of 2.84g of 5-hydroxy-2-oxo-3- (4-acetylaminophenyl)-2,3-dihydrobenzofuran, 4.8g of 4-amino-3-methyl-phenyltartronic acid (as the dipotassium salt) and 50ml of glacial acetic acid was stirred under reflux for 18 hours. At the end of this period 2.5g of ammonium persulphate was added and heating continued for a further 1 hour. After cooling to ambient the precipitated solid was filtered, washed acid-free with water, then methanol, and dried. A mixture of 3.6g of this product in 110ml of 70% sulphuric acid was heated at 95°C for 7 hours. After cooling, this mixture was drowned into 1 litre of water and the crude product, 3-(4-aminophenyl)-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']-difuran, isolated by filtration. This was then extracted into pyridine, screened and the solvent removed under vacuum. The product dissolved in pyridine to give a blue solution with an absorption maximum at 657nm. When applied to polyester material from an aqueous dispersion it gave a bright mid-blue shade with excellent heat and wet fastness properties and it also built up well. The 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran used in this Example was prepared by stirring 21g of 4-acetylaminomandelic acid and llg of hydroquinone in 95ml of glacial acetic acid and 5ml 100% sulphuric acid at 55°C for 21 hours, cooling to ambient and drowning into 1 litre of water. The precipitate was isolated by filtration, washed acid-free with water and dried. Example 2 The procedure of Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there were used 4.7g of 3-methyl-4-N-ethylaminophenyltartronic acid to give 3-(4-aminophenyl)-7-(3-methyl-4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo [1:2-b,4:5-b']difuran. This dissolved in pyridine to give a greenish-blue solution having an absorption maximum at 672nm. When applied to a polyester textile material from an aqueous dispersion it gave a greenish blue shade having good fastness to wet treatments and it built up well. Example 3 The procedure of Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there were used 4.6g of 4-amino-3-methoxyphenyltartronic acid to give 3-(4-amino-phenyl)-7-(4-amino-3-methoxyphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2b,4:5-b']difuran. When applied to a polyester textile material from an aqueous dispersion it gave a greenish-blue shade with high heat fastness and very good perspiration and wash fastness. Example 4 The procedure described in Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there were used 5.0g of 4-amino-3-chlorophenyltartronic acid to give 3-(4-aminophenyl)-7-(4-amino-3-chlorophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a blue solution having an absorption maximum at 645nm. When applied to a polyester textile material from an aqueous dispersion it gave a reddish blue shade with good fastness to wet treatments. Example 5 The procedure of Example 1 was repeated except that the 2 .84g of 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo-furan was replaced by 2.26g of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydro-benzofuran to give 3-phenyl-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo [1:2-b, 4:5-b']difuran. This dissolved in pyridine to give a blue solution having an absorption maximum at 620nm. When applied to polyester from an aqueous dispersion it built up well to give a navy blue shades with good fastness to heat and wash treatments. Example 6 The procedure of Example 1 was repeated except that the 2.84g of 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo-furan was replaced by 3.0g of 5-hydroxy-2-oxo-3-(3-methyl-4-acetylaminophenyl)-2,3-dihydrobenzofuran and the 4.8g of 4-amino-3-methylphenyltartronic acid by 4.8g of 4-morpholino-phenyltartronic acid. The product, 3-(3-methyl-4-aminophenyl)-7-(4-morpholinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']-difuran, dissolves in pyridine to give a blue solution having an absorption maximum at 655nm. When applied to polyester from an aqueous dispersion it gives bright blue shades with good heat fastness and wash treatments. The 5-hydroxy-2-oxo-3(3-methyl-4-acetylaminophenyl)-2,3-hydrobenzofuran used in this Example was prepared by stirring 14g of 3-methyl-4-acetylaminomandelic acid with 6.9g of hydroquinone in 95ml of acetic acid and 5ml of 100% sulphuric acid at 80°C for 12 hours, cooling to ambient temperature and drowning into 1 litre of water. The precipitate was isolated by filtration, washed acid-free with water and dried. Example 7 The procedure of Example 6 was repeated except that in place of the 4.8g of 4-morpholinophenyltartronic acid there was used 4.0g of 4-amino-3-ethylphenyltartronic acid. The product, 3-(3-methyl-4-aminophenyl)-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having an absorption maximum at 660nm. When applied to polyester from aqueous dispersions it gives bright blue shades with good fastness to heat and wash treatments. Example 8 The procedure of Example 1 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 3.9g of 4-N-isopropylamino-3-methylphenyltartronic acid. The product, 3-(4-aminophenyl)-7-(4-isopropylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having an absorption maximum at 655nm. When applied to polyester from aqueous dispersions it gives bright blue shades with good wet fastness and good heat fastness. Example 9 1.0g of the product obtained as in Example 1 was dissolved in a mixture of 25ml of methylethylketone and 10ml of acetic acid. 1.0g of sodium borohydride was added portionwise, the temperature rising to 50°C. After stirring for 1 hour a further 1.0g of sodium borohydride was added, the temperature again rising to 50°C. After 15 minutes the reaction was complete as judged by TLC. The reaction mixture was poured into 250ml water and the precipitated product, 3-(4-sec-butylaminophenyl)-7-(4-sec-butylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, isolated by filtration, washing with water and drying. It dissolves in pyridine to give a greenish-blue solution having an absorption maximum at 695nm. When applied to polyester materials from aqueous dispersions it gives greenish-blue shades with good heat and wet fastness. Example 10 The procedure of Example 1 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 5.0g of 4-β-hydroxyethyl-3-methylphenyltartronic acid to give 3-(4-aminophenyl)-7-(4-8-hydroxyethylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo(1:2-b, 4:5-b']difuran. This dissolved in pyridine to give a blue solution having an absorption maximum at 670nm. When applied to polyester materials from aqueous dispersions it gave blue shades with good heat and wet fastness. Example 11 The procedure of Example 1 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.6g of 4-amino-3,5-dimethylphenyltartronic acid to give 3-(4-aminophenyl)-7-(4-amino-3,5-dimethylphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. It dissolves in pyridine to give a blue solution having an absorption maximum at 662nm. When applied to polyester materials it gave blue shades with good heat and wet fastness. Example 12 The procedure of Example 1 was repeated except that the 2.84g of 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran was replaced by 2.84g of 5-hydroxy-2-oxo-3(4-n-propoxyphenyl)-2,3-dihydrobenzofuran to give 3-(4-n-propoxyphenyl)-7-(4-amino-3-methyl phenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. It dissolves in pyridine to give a reddish-blue solution having an absorption maximum at 620nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 13 The procedure of Example 9 was repeated except that the 3.0g of 5-hydroxy-2-oxo-3(3-methyl-4-acetylaminophenyl)-2,3-dihydrobenzofuran was replaced by 2.84g of 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran to give 3-(4-aminophenyl)-7-(4-morpholinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']-difuran. This dissolves in ethylacetate to give a blue solution having an absorption maximum at 618nm. When applied to polyester materials it gives reddish-blue shades with good heat and wet fastness. Example 14 The procedure of Example 1 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.8g of 4-amino-3-ethylphenyltartronic acid. The product, 3-(4-amino-phenyl)-7-(4-amino-3-ethylphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue shade having an absorption maximum at 657nm. When a 50/50 mixture of this product and that of Example 1 was applied to polyester materials from aqueous dispersions it gave bright blue shades with good build up and good heat and wet fastness. Example 15 The procedure of Example 1 was repeated except that the 2.84g of 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo-furan was replaced by 3.0g of 5-hydroxy-2-oxo-3-(4-acetylamino-3-methylphenyl)-2,3-dihydrobenzofuran. The product, 3,7-di-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having an absorption maximum at 660nm. When applied to polyester textile materials it gives bright blue shades with good heat fastness and good fastness to wash treatments. Example 16 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.4g of 4-amino-3,5-dimethylphenyltartronic acid to give 3-phenyl-7-(4-amino-3,5-dimethylphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 580nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 17 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.6g of 4-amino-3-ethylphenyltartronic acid to give 3-phenyl-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 568nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 18 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.7g of 4-amino-3-n-propylphenyltartronic acid to give 3-phenyl-7-(3-n-propyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 568nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 19 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 4.5g of 4-amino-3-methoxyphenyltartronic acid to give 3-phenyl-7-(3-methoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 600nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 20 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 5.3g of 4-amino-3-ethoxyphenyltartronic acid to give 3-phenyl-7-(3-ethoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 600nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 21 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 5.5g of 4-amino-3-n-propoxyphenyltartronic acid to give 3-phenyl-7-(3-n-propoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 605nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. Example 22 The procedure of Example 5 was repeated except that the 4.8g of 4-amino-3-methylphenyltartronic acid was replaced by 5.0g of 3-methyl-4-N-ethylaminophenyltartronic acid to give 3-phenyl-7-(3-methyl-4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blue shade having an absorption maximum at 620nm. When applied to polyester materials it builds up to give navy blue shades with good heat and wet fastness. The dyes identified in Tables 4 and 5 were prepared by the method of Example 1 using equivalent amounts of the substituted mandelic acid in place of the 4-acetylaminomandelic acid and of the substituted phenyl tartronic acid in place of 4-amino-3-methylphenyltartronic acid. In the case of the substituted mandelic acids in which R 1 and R 2 are H or R 6 is NH 2 , the amino group was protected with an acetyl group which was subsequently removed by acid hydrolysis as described in Example 1. In Table 4 the dyes correspond to Formula VII in which X 1 , X 2 , R 5 and R 8 are all H and Z 1 and Z 2 are both 0. In Table 4 and the subsequent tables: -[CH] = cyclohexyl Ph = phenyl -EtCOOMe = -C 2 H 4 CO 2 CH 3 -EtCOOEt = -C 2 H 4 CO 2 C 2 H 5 -EtOCOMe = -C 2 H 4 OCOCH 3 -OEtOEt = -OC 2 H 5 OC 2 H 5 -OEtOCOMe = -OC 2 H 5 OCOCH 3 In Table 5 the dye corresponds to Formula VII in which X 1 , X 2 , R 5 , R 7 and R 8 are all H and Z 1 and Z 2 are both O. Ex R 6 R 1 R 2 R 4 λmax/Shade 38 -CH 3 -H -H -CH 3 Raddish-blue Further dyes in accordance with Formula VII which can be made by the same process as the dyes in Tables 4 and 5 are shown in Tables 6, 7 and 8. In the dyes shown in Table 6 X 1 , X 2 , R 5 , R 7 and R 8 are all H and Z 1 and Z 2 are both O. Ex R 6 R 4 R 1 R 2 39 -H -Cl -H -H 40 -H -C 4 H 9 -H -H 41 -H -CH 3 -H -C 2 H 4 OH 42 -H -CH 3 -H -C 2 H 4 CN 43 -H -CH 3 -H -C 2 H 4 Cl 44 -H -C 2 H 5 -H -EtOCOMe 45 -H -C 2 H 5 -H -EtCOOMe 46 -H -CH 3 -H -C 2 H 4 OCH 3 47 -H -CH 3 -H -C 3 H 6 -Ph 48 -H -OC 4 H 9 -H -H 49 -H -OEtOEt -H -H 50 -H -OEtOCOMe -H -H 51 -H -OC 2 H 4 CN -H -H 52 -H -OCH 3 -H -C 2 H 4 CN 53 -H -OCH 3 -H -EtOCOMe 54 -H -Br -H -C 2 H 4 OCH 3 55 -CH 3 -CH 3 -H -H 56 -C 2 H 5 -CH 3 -H -C 2 H 3 57 -Cl -CH 3 -H -C 3 H 7 58 -H -CH 3 -H -C 6 H 13 In the dyes shown in Table 7 X 1 , X 2 , R 5 and R 8 are all H and Z 1 and Z 2 are both O. Ex R 6 R 7 R 4 R 1 R 2 59 -NH 2 -Cl -CH 3 -H -C 2 H 5 60 -NH 2 -C 2 H 5 -CH 3 -H -C 2 H 4 CN 61 -N(C 2 H 5 ) 2 -H -CH 3 -H -EtOCOMe 62 -NHC 2 H 4 OH -CH 3 -CH 3 -H -C 2 H 4 CN 63 -NH 2 -H -CH 3 -H -Ph In the dyes shown in Table 8 X 1 and X 2 are both H and Z 1 and Z 2 are both O. Ex R 7 R 6 R 8 R 4 R 5 R 1 R 2 64 -H -NH 2 -H -CH 3 -C 2 H 5 -H -H 65 -Cl -NH 2 -Cl -H -H -C 2 H 5 -H 66 -H -H -H -C 2 H 5 -H -H -H

Claims: A compound of Formula VII: wherein: X 1 and X 2 each independently is H, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH or carboxylic acid ester; Z 1 and Z 2 each independently is -O-, -S- or -NY- in which Y is H, an optionally-substituted hydrocarbon group or an acyl group; one of R 1 and R 2 is H or an optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl group; the other of R 1 and R 2 is H; R 4 and R 5 each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group, provided that at least one of R 4 and R 5 is other than hydrogen; or R 1 and R 4 together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; or R 2 and R 5 together with the N atom and the two carbon atoms in Ring B to which they are attached form a heterocycle fused to Ring B; R 6 is H, halogen, a C 3-10 -alkenyl group, an optionally substituted alkyl or alkoxy group or a group NR 9 R 10 in which each of R 9 and R 10 independently is H or an optionally substituted alkyl, alkenyl, cycloalkyl, aryl or aralkyl groups; or R 9 and R 10 together with the N atom to which they are attached form a heterocycle; R 7 and R 8 each independently is H, halogen or an optionally substituted alkyl, alkenyl or alkoxy group, provided that when R 7 or R 8 is other than H, one of R 9 and R 10 is H ; or R 7 and R 9 together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Ring A; or R 8 and R 10 together with the N atom and the two carbon atoms in Ring A to which they are attached form a heterocycle fused to Ring A; and where R 6 is NR 9 R 10 , this may be the same as or different from the NR 1 R 2 group present in Ring B. A compound according to claim 1, wherein X 1 and X 2 are both hydrogen. A compound according to claim 1 or claim 2, wherein Z 1 and Z 2 are both oxygen. A compound according to any preceding claim, wherein R 1 is H, C 1-6 -alkyl, C 3-4 -alkenyl, cyclohexyl or C 1-4 -alkyl substituted by a group selected from C 1-4 -alkyl, C 1-4 -alkoxy, C 1-4 -alkoxy-C 1-4 -alkoxy, nitro, cyano, halogen, cyclohexyl, phenyl, diphenyl, hydroxy, C 1-4 -alkycarbonyl, amino C 1-4 -alkoxycarbonyl, C 1-4 -alkoxy-C 1-4 -alkoxycarbonyl or C 1-4 -alkoxycarbonyloxy. A compound according to claim 4, wherein R 4 is C 1-4 -alkyl, C 3-4 -alkenyl, C 1-10 -alkoxy or halogen. A compound according to any preceding claim, wherein R 6 is NR 9 R 10 in which R 9 and R 10 each independently is H, C 1-6 -alkyl, C 3-4 -alkenyl, cyclohexyl or C 1-4 -alkyl substituted by a group selected from C 1-4 -alkyl, C 1-4 -alkoxy, C 1-4 -alkoxy-C 1-4 -alkoxy, nitro, cyano, halogen, cyclohexyl, phenyl, diphenyl, hydroxy, C 1-4 -alkycarbonyl, amino C 1-4 alkoxycarbonyl, C 1-4 ,-alkoxy-C 1-4 -alkoxycarbonyl, C 1-4 -alkoxycarbonyloxy or R 9 and R 10 together with the nitrogen atom to which they are attached form a piperidino or morpholino group. A compound according to any one of claims 1 to 5, wherein R 6 is H, C 1-10 -alkyl, C 3-10 -alkenyl, C 1-10 -alkoxy or halogen. A compound according to claim 7, wherein R 6 is H, C 1-6 -alkyl, C 3-4 -alkenyl, C 1-10 -alkoxy or halogen and R 4 is C 1-4 -alkyl or C 1-4 -alkoxy. A compound of the formula: wherein X 1 , X 2 , R 1 , R 7 and R 8 are H, Z 1 and Z 2 are oxygen, R 2 is H or C 1-4 -alkyl, R 4 is C 1-4 -alkyl or C 1-4 -alkoxy, R 5 is H, C 1-4 -alkyl or C 1-4 -alkoxy and R 6 is NH 2 . A compound of the formula: wherein X 1 , X 2 , R 1 , R 5 , R 7 and R 8 are H, Z 1 and Z 2 are oxygen, R 2 is C 1-4 -alkyl, R 4 is C 1-4 -alkyl or C 1-4 -alkoxy and R 6 is H, C 1-4 -alkyl or C 1-4 -alkoxy. A compound: 3-(4-aminophenyl)-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, 3-(4-aminophenyl)-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran. 3-phenyl-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, 3-phenyl-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:S-b']-difuran, 3-phenyl-7-(3-methoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, 3-phenyl-7-(3-ethoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, 3-phenyl-7-(3-n-propoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, 3-phenyl-7-(3-n-propyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']-difuran, 3-phenyl-7-(3-methyl-4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']-difuran, or 3-(4-n-propoxyphenyl)-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']-difuran.

Inventors: KENYON RONALD WYNFORD, NEWTON DAVID FRANCIS, THORP DEREK, KENYON, RONALD WYNFORD, NEWTON, DAVID FRANCIS, THORP, DEREK
Applicants: BASF AG, BASF AKTIENGESELLSCHAFT
Application year: 1989
Main classification: C09B57
IPC codes: C09B57