Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1,457, 532, GB 1,536, 429, FR-A 1,531, 147, US 3,776, 898, JP 55161857, GB 2,104, 088, EP 0 685 531 A1 and WO 95/20014.

The inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.

The present invention claims dyestuffs of the formula I wherein D is a group of the formula (Ila)

wherein T', T2 and T3 are, independently, hydrogen, halogen or nitro; T4 is hydrogen, halogen, cyano or nitro; wherein at least one of T', T2, T3 and T4 is not hydrogen; or a group of the formula (lib)

wherein T5 is hydrogen or halogen ; and T6 is hydrogen-S02CH3,-SCN or nitro; wherein at least one of T5 and T6 is not hydrogen; or a group of the formula (IIc) or a group of the formula (IId) wherein T7 is nitro,-CHO or a group of the formula wherein T10 is -H, halogen, nitro and cyano; T8 is hydrogen or halogen ; and T9 is nitro, cyano, -COCH3 or -COOT10, wherein T10 is (C1-C4)-alkyl; or a group of the formula (lie) R'is hydrogen, (C1-C4)-alkyl or-NCOR6, where R6 is (C1-C4)-alkyl or phenyl ; R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; R3 is hydrogen or methyl ; R4 is hydrogen or methyl ;

R5 is hydrogen, methyl or phenyl ; R'is hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2 ; s is 0 or 1 ; with the proviso that in the case R', R3, R4, R5 and R7 are hydrogen and n = 0 D is a group of the formula (IIc), (IId), (IIe) or (Ila) wherein T'is not nitro if T2, T3 and T4 are hydrogen, if T2 and T3 are hydrogen and T4 is chlorine or cyano and if T2 and T4 are hydrogen and T3 is chlorine ; and with the further proviso that is unsubstituted (C1-C6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n = 0.

Alkyl groups standing for R', R6 or T10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R, which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R2are preferably substituted by hydroxyl, (C1-C4)-alkoxy or halogen.

Halogen standing for T', T2, T3, T4, T5 or T3 are preferably chlorine or bromine.

Preferred examples for D derive from the following amines: 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2- nitroaniline, 2-bromo-4-nitroaniline, 2, 6-dichloro-4-nitroaniline, 2,6-dibromo-4- nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano- 4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-chloro-4-nitroaniline, 2, 4-dinitroaniline, 2-chloro-4, 6-dinitroaniline, 2-bromo-4, 6-dinitroaniline, 2,6- dicyano-4-nitroaniline, 2-cyano-4, 6-dinitroaniline, 2-amino-5-nitrothiazole, 2- amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 2- amino-3-acetyl-5-nitrothiophene, 2-amino-3-cyano-5-nitrothiophene, 2-amino-3-

cyano-4-chloro-5-formylthiophene, 7-amino-5-nitrobenzoisothiazole, 2-amino-6- nitrobenzothiazole, 2-amino-6-methylsulphonylbenzothiazole ; 2-amino-6- thiocyanatobenzothiazole, 2-amino-5, 6-dichlorobenzothiazole and 2-amino-6,7- dichlorobenzothiazole (mixture).

Preferred disperse dyestuffs according to the present invention are of the general formula (la) wherein D is a group of the formulae (Ila), (Ilb), (llc), (Ild) or (IIe) ; R1 is (C1-C4)-alkyl ; R2 is unsubstituted (C1-C6)-alkyl, benzyl or phenylethyl ; and n is 0, 1 or 2.

In especially preferred dyestuffs of formula (la) R'is methyl, R2 is ethyl and n is 0.

Other preferred disperse dyestuffs according to the present invention are of the general formula (lb) wherein T3 is bromo or chloro ; and R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; In especially preferred dyestuffs of formula (lb) R2 is ethyl, benzyl or phenethyl. Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ic)

wherein D is a group of the formulae (Ila), (Ilb), (Ilc), (lid) or (Ile) ; R'is hydrogen, (C1-C4)-alkyl or -NCOR6, where R6 is (C1-C4)-alkyl or phenyl ; R2 is unsubstituted (C1-C6)-alkyl, substituted (C,-C6)-alkyl, benzyl or phenylethyl ; and R3 is hydrogen and R4 is methyl or R3 is methyl and R 4is hydrogen.

Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id) wherein D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe) ; R'is hydrogen, (C1-C4)-alkyl or -NCOR6, where R6 is (C1-C4)-alkyl or phenyl ; R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; and R5 is methyl or phenyl ; Still other preferred disperse dyestuffs according to the present invention are of the general formula (le)

wherein D is group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe) ; R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; R6 is (C1-C4)-alkyl or phenyl ; R'is chloro, methoxy or ethoxy ; and n is 0, 1 or 2.

Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)

wherein R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; R8 is nitro ; and n is 0, 1 or 2 ; Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)

wherein D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe); R1 is hydrogen, (C1-C4)-alkyl or -NCOR6, where R6 is (C1-C4)-alkyl or phenyl; R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl ; and R3 is hydrogen or methyl.

The compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazbtisation of an amine of the formula III D-NH2 (111) wherein D is defined as given above, and coupling onto a compound of the formula IV wherein R', R2, R3, R4, R5 and R7 are defined as given above.

Typically the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methyinitrite at a temperature from-10°C to 10°C. Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.

After coupling the compound of the formula (I) may be recovered from the reaction mixture by any convenient means such as filtration.

The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in literature or known to the skilled person.

The compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours I-e which have excellent wet fastness properties.

Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 110°C, by the exhaust process or by the HT process in a dyeing autoclave at 110 to 140°C,

and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 180 to 230°C The fibre goods mentioned can as well be printed in a manner known pers e by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated, if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230°C to fix the dyestuff.

The dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.

The fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended ina liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible.

The particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m.

The dispersing agents used can be nonionic or anionic. Nononic dispersing agents are, for example, reaction products of alkylen oxides, such as, for example, ethylene oxide or propylene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersing agnets are, for example, lignin- sulphonates, alkyl-or alkylarylsulphonates or alkylaryl polyglycol ethersulphates.

For most methods of use, the dyestuff formulations thus obtained should be ,.

@>rable. The dyestuff and dispersing agent content is therefore limited in these cases. In general, the dispersions are brought to a dyestuff content of up to 50 per cent by weight and a dispersing agent content of up to 25 per cent by weight. For economic reasons, the dyestuff contents usually do not fall below 15 per cent by weight.

The dispersions can also comprise other auxiliaries, for example those which act

as oxidizing agents or fungicidal agents. Such agents are well known in the art.

The dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.

For certain fields of use, powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.

A preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.

Example 1 4- (4-nitrophenylazo)-3-methyl-N-ethyl-N- (2-cyanomethoxy- carbonylethyl) aniline 4-nitroaniline (4.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts). Nitrosyl sulphuric acid 40% (11. 4parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution obtained was added gradually to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl)-m-toluidine (7.3parts), methanol (50parts), water (200parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- <BR> <BR> <BR> <BR> (4-nitrophenylazo)-3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline<BR> <BR> <BR> <BR> <BR> <BR> (6.5parts) % max = 486nm (acetone)<BR> d When applied to polyester materials from aqueous dispersion, red shades, h excellent wet and light fastness properties were seen.

The following examples of dyes of formula (laa) : were prepared by the procedure of Example (see Table 1) Table 1 Example T¹¹ T¹² T¹³ T14 R8 #max (nm) 2 -H -H -NO2 -H -C2H5 479 3 -H -NO2 -H -H -C2H5 468 4 -NO2 -H -Cl -H -C2H5 508 5 -Cl -H -NO2 -H -C2H5 501 6-N02-H-Br-H-C2H5 507 7 -NO2 -H -Cl -Cl -C2H5 450 8 -NO2 -H -Br -Br -C2H5 449 9 -NO2 -H -Cl -Br -C2H5 449 10 -NO2 -Cl -H -Cl -C2H5 518 11-N02-H-CN-H-C2H5 534 12-N02-H-CN-Br-C2H5 544 13 -NO2 -H -CN -Cl -C2H5 545 14-N02-H-N02-H-C2H5 535 15 -NO2 -H -Br -NO2 -C2H5 542 16 -NO2 -H -Cl -NO2 -C2H5 544 17 -NO2 -H -CN -CN -C2H5 582 18-N02-H-CN-N02-C2H5 590 19 -NO2 -H -H -H -C4H9 490

Example T¹¹ T¹² T¹³3 T14 R8 #max (nm) 20 -NO2 -H -Cl -H -C4H9 513 21 -NO2 -H -Cl -Cl -C4H9 453 22 -NO2 -H -Cl -Br -C4H9 453 23-N02-H-Br-Br-C4H9 452 24-N02-H-CN-H-C4Hg 539 25 -NO2 -H -NO2 -H -C4H9 540 26 -NO2 -H -CN -Br -C4H9 549 27 -NO2 -H -CN -Cl -C4H9 548 28 -NO2 -H -Br -NO2 -C4H9 548 29 -NO2 -H -Cl -NO2 -C4H9 549 30-H-H-N02-H-C4H9 483 31 -NO2 -H -CN -CN -C4H9 586 32-N02-H-H-H-CH2 [C6H5] 479 33 -NO2 -H -NO2 -H -CH2[C6H5] 530 34 -H -H -NO2 -H -CH2[C6H5] 470 35-H-N02-H-H-CH2 [C6H5] 460 36 -NO2 -H -Cl -H -CH2[C6H5] 498 37 -NO2 -H -Cl -Cl -CH2[C6H5] 446 38-N02-H-Br-Br-CH2 [C6H5] 445 39-N02-H-Br-Cl-CH2 [C6H5] 444 40 -NO2 -H -CN -H -CH2[C6H5] 528 41 -NO2 -H -CN -Br -CH2[C6H5] 539 42 -NO2 -H -CN -Cl -CH2[C6H5] 539 43 -NO2 -H -Br -NO2 -CH2[C6H5] 538 44 -NO2 -H -Cl -NO2 -CH2[C6H5] 537

Example T¹¹ T¹² T¹³ T14 R8 #max (nm) 45 -NO2 -H -CN -NO2 -CH2[C6H5] 580 46 -NO2 -H -CN -CN -CH2[C6H5] 577 47 -NO2 -H -H -H -C3H7 487 48 -NO2 -H -Cl -H -C3H7 509 49 -NO2 -H -Cl -Cl -C3H7 452 50 -NO2 -H -Cl -Br -C3H7 451 51 -NO2 -H -Br -Br -C3H7 452 52-N02-H-CN-H-C3H7 536 53-N02-H-N02-H-C3H7 537 54-N02-H-CN-Br-C3H7 546 55 -NO2 -H -CN -Cl -C3H7 548 56 -NO2 -H -Br -NO2 -C3H7 544 57 -NO2 -H -Cl -NO2 -C3H7 545 58 -H -H -NO2 -H -C3H7 480 59 -NO2 -H -CN -CN -C3H7 584 60 -NO2 -H -Cl -H -CH3 504 61 -NO2 -H -CN -H -CH3 529 62 -NO2 -H -Cl -CN -CH3 543 63-N02-H-Br-CN-CH3 542 64 -NO2 -H -Br -NO2 -CH3 539 Example 65 4- (2, 6-dichloro-4-nitrophenylazo)-N-ethyl-N- (2-cyanomethoxy- carbonylethyl) aniline

2, 6-dichloro-4-nitroaniline (6.2parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (11. 4parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2 (cyanomethoxycarbonylethyl)-aniline (8.3parts), methanol (50parts), water (300parts) and sulphamic acid (1 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4- (2, 6-dichloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline (9.5parts) #max = 432nm (acetone) When applied to polyester materials from aqueous dispersion, yellow brown shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (Iba) were prepared by the procedure of Example 65 (see Table 2) Table 2 R9 #max Example T15 T16 (nm) 66-CI-CI-C3H7 433 67-Cl-Cl-C4H9 434 R9 #max Example T15 T16 (nm) 68-C [C6H5] 420 69-Cl-CI-CH3 425 70 -Cl -Br -C2H5 430 71 -Cl -Br -C3H7 431 72-Cl-Br-C4Hg 433 73-Cl-Br-CH2 [C6H5] 420 74-Cl-Br-CH3 424 75 -Br -Br -C2H5 430 76-Br-Br-C3H7 432 77-Br-Br-C4H9 431 78 -Br -Br -CH2[C6H5] 421 79-Br-Br-CH3 424

Example 80 <BR> <BR> 4- (6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline 2-amino-6-nitrobenzothiazole (3.9parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7. 6parts) was added below 5°C and the mixture was stirred for 1 hour.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9parts), methanol (25parts), water (200parts) and sulphamic acid (0. 5parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield,

4- (6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanometh oxyca rbonyl ethyl) aniline (2.4parts) #max = 545nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (lab) : were prepared by the procedure of Example 80 (see Table 3) Table 3 Example T17 T18 R10 R¹¹ #max nm 81-S02CH3-H-CH3-CH3 527 82-N02-H-CH3-CH3 543 83-N02-H-CH3-C3H7 545 84 -NO2 -H -CH3 -C4H9 548 85 -NO2 -H -CH3 -CH2[C6H5] 538 86 -Cl -Cl -CH3 -C2H5 526 87 -Cl -Cl -CH3 -CH3 522 88 -Cl -Cl -CH3 -C3H7 528 89 -Cl -Cl -CH3 -C4H9 530 90 -Cl -Cl -CH3 -CH2[C6H5] 521 91-S02CH3-H-CH3-C3H7 531 92 -SO2CH3 -H -CH3 -C4H9 533 93 -SO2CH3 -H -CH3 -CH[C6H5] 525 94-SCN-H-CH3-C2H5 534 95-SCN-H-CH3-CH3 530 -SCN-H-CH3-C3H7 535

Example T17 T18 R10 R11 #max nm 97 -SCN -H -CH3 -C4H9 537 98-SCN-H-CH3-CH2 [C6H5] 529 99 -NO2 -H -H -C4H9 535 100-N02-H-H-CH2 [C6H5] 525 101-SCN-H-H-C4H9 523 102 -SCN -H -H -CH2[C6H5] 516 103 -Cl -Cl -H -C4H9 519 104 -Cl -Cl -H -CH2[C6H5] 509 105-SO2CH3-H-H-C4H9 521 106 -SO2CH3 -H -H -CH2[C6H5] 512

Example 107 <BR> <BR> <BR> 4- 3, 5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N- (2-cyanomethoxycarbonylethyl) aniline

2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts). Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 mins.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonyethyl)-m-toluidine (4. Oparts), acetone (50parts), water (300parts) and sulphamic acid (O. 5parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4- (3, 5- d (2-cyanomethoxycarbonyl- ethyl) aniline (3. Oparts) #max = 640nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (Iac) :

were prepared by the procedure of Example 107 (see Table 4) Table 4 Example T19 T20 T²¹ T¹² R¹³ #max (nm) 108-NO2-NO2-H-H-C2H5 620 109-N02-N02-H-H-C4H9 625 110 -NO2 -NO2 -H -H -C3H7 622 111 -NO2 -NO2 -H -H -CH2[C6H5] 611 112 -NO2 -NO2 -H -CH3 -C4H9 645 113 -NO2 -NO2 -H -CH3 -C3H7 640 114 -NO2 -NO2 -H -CH3 -CH2[C6H5] 632 115-COOC2H5-NO2-H-CH3-C2H5 595 116-COOC2H5-N02-H-H-C4H9 583 117-COCH3-N02-H-CH3-C2H5 599 118 -COCH3 -NO2 -H -CH3 -C4H9 603 119-COCH3-N02-H 120-CN-N02-H-CH3-C2H5 604 121-CN-N02-H-CH3-CH2 [C6H5] 595 122 -CN -CHO -Cl -CH3 -C2H5 585 Example T19 T20 T²¹ R¹² R¹³ #max (nm) 123-CN-CH0-Cl-CH3-C4Hg 591 124-CN-CHO-Cl-H-C4H9 579 125-COOC2H5-N02-H-H-CH2 [C6H5] 565 126 -COOC2H5 -NO2 -H -CH3 -C4H9 601

Example 127<BR> <BR> <BR> 4- (5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N- (2- cyanomethoxycarbonylethyl) aniline 7-amino-5-nitrobenzoisothiazole (2. 9parts) was added to a mixture of sulphuric acid 98% (15parts) and phosphoric acid (4parts) stirring at room temperature.

The mixture was heated to 55°C and was stirred at that temperature for 30mins. Nitrosyl sulphuric acid 40% (6. 1 parts) was added below 5°C and the mixture was stirred for 2hrs.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N- (2-cyanomethoxycarbonylethyl)-m-toluidine (4. 8parts), acetone (50parts), water (100parts) and sulphamic acid (0.5parts). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water and dried to yield, 4-(5- . ntrobenzisothiazol-yl-azo)-3-methyl-N-methyl-N-(2-cyanometho xycarbonylethyl) aniline (2. 4parts) Bmax = 601nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (lad)

were prepared by the procedure of Example 127 (see Table 5) Table 5 #max Example R14 R15 (nm) 128-H-C2H5 588 129-H-CH2 [C6H5] 578 130-H-C4Hg 589 131-CH3-C3H7 603 132 -CH3 -CH2[C6H5] 593 133-CH3-C4H9 608

Example 134 4- (5-nitrothiazol-yl-azo)-N-butyl-N- (2-cyanomethoxy- carbonylethyl) aniline

2-amino-5-nitrothiazole (2.9parts) was was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts). Nitrosyl sulphuric acid 40% (7. 0parts) was added below 5°C and the mixture was stirred for 30 mins.

The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2 (cyanomethoxycarbonylethyl)-aniline (5.2parts), acetone (50parts), water

(200parts) and sulphamic acid (0.5parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(5- nitrothiazol-yl-azo)-N-butyl-N- (2-cyanomethoxycarbonylethyl) aniline (2. 9parts) Amax = 571 nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (lae)

were prepared by the procedure of Example 134 (see Table 6) Table 6 Example R16 R17 #max (nm) 135 -H -CH2[C6H5] 557 136-CH3-C2H5 575 137-CH3-C4H9 582 138-CH3-CH2 [C6H5] 569

Example 139 ( 4-(2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2- cyanomethoxycarbonylethyl)-aniline

2-chloro-4-nitroaniline (3.5parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7. 0parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of 3 (N- ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3parts), methanol (40parts), water (200parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N- (2-cyanomethoxy- carbonylethyl)-aniline (4. 1parts) Smax = 525nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.

The following examples of dyes of formula (lea) :

were prepared by the procedure of Example139 (see Table 7) Table 7 max Example D'R'$ R'9 R2° (nm) Br 140 0 2N N-CH3-H-C2H5 550 I'' NO2 sr 141 \ND m/3-H-C2H5 5 5 3 N0z max Example D'R"R R (nm) Br 142 02N-0-N-CH3-H-C4H9 552 Nos Br 143 02 N-0-N-C2H5-H-C2H5 550 NO, Br 144 u"w N CH,-OCH3-C2H5 596 NO, Br 145 °aN \/N-CH3-OCH3-C4H9 603 NO, Br 146 02N9N < ~OCH3-H 600 NOS cl 147 o : N-C2Hs-OCH3-C2H5 X NOS ci 148 02N- (-N-CH3-H-C4H9 551 NOS Br 149 02N4N-CH3-H-C2H5 574 CN Ber ber'-' Br 150 a C, 11,-H-C2H5 550 NOS A, max Example D'R'8 R9 Rzo cl 151 02N4N-CH3-H-C4H3 5'5 Ber bu 628 152 02N4N ~CH3-OCH3 ~CzHs check check CN 153'-CHs-H-CHg 539 NO, 154 02N<N ~CH3-OCH3-C2H5 574 NOS Nos 155 02NCN-CH3-H-C2H5 634 NO2. _ NO, 156-CH3-OCH3-C2H5 660 OzN S N Example 157 4- (2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N- (4- cyanomethoxycarbonylbutyl)-anil ine

2-cyano-4-nitroaniline (3. 2parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (50parts). Nitrosyl sulphuric acid 40% (7.6parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N- (4-cyanomethoxycarbonylbutyl)-m-toluidine (6. 0parts), methanol (50parts), water (200parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-cyano-4-

nitrophenylazo)-3-methyl-N-ethyl-N- (4-cyanomethoxycarbonyl butyl)-aniline.

(5.3parts) 2,, max = 548nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (laf) were prepared by the procedure of Example157 (see Table 8) Table 8 max Example D"R2'Rz2 n (nm) 158 02N<N ~H-C2H5 4 491 159 O2N<N C-C2H5 3 486 Noya 160 CH3-C2H5 4 649 OZN S N Nos 161 CH3-C2H5 3 642 OaN S N Br 1, 62 02N N-CH H5 4 561 3-C2 ce Br 163 o2N N-CFi3-C2H5 3 556 CN max Example D"R R n (nm) Br 164 c N-CH3-C3H7 3 558 CN cl 165 \>-3-C2H5 4 535 ce CN 166 0 _-C2H5 4 548 con CN 167 02N4N ~CH3-C2H5 3 536 . CN 168 02N N-H-C2H5 4 529 z

Example 169 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1-cyanoe thoxy)<BR> <BR> carbonylethyl)-aniline

2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (4. 9parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1-cyanoethoxy)carbonylethyl)-m-toluidine (3.7parts), acetone (50parts), water (300parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-cyano-4- nitrophenylazo)-3-methyl-N-ethyl-N- (2- (1-cyanoethoxy) carbonylethyl)-aniline (3.5parts) #max = 534nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (Ida)

were prepared by the procedure of Example169 (see Table 9) Table 9 max Example Dl"R23 R24 R25/% max (nm) CN 170 02 N--d-N-CH3-C2H5 533 Z CN 171 02N<N-CH,-C2H5"zX= 544 Br cl 172 02N4N ~CH3-C2H5 < 507 z cl 173 02N<N ~CH3-C2H5 < 446 ci N 174 -N-CH3-C2H5 580 CN 175 02N4N H-C2H5 t/> 523 Z rnax Example D"'R23 R24 R2s Bmax (nm) - 176 02N SN-H-C2H5 < 494 2 CN 177 02N4N ~H-C2H5-CH3 522 Z 178 02 N-aN-H-C2H5-CH3 473 179 o, ~H ~C4Hg-CH3 480 ci 180 02N iN H-C2H5 % 494 ci 181 02N4N ~H-C2H5-CH3 439 c cl 182 U H-C4H9 H 441 ci 183 02N4N ~H-C2H5-CH3 521 N N 184/¢0NW H-C2Hs CH. 533 o N s N 185 02N/-H-C2H5-CH3 590 N N Cl 186 0 N \/N'CH3-C2H5-CH3 449 Cl , max Example D"'R23 R24 R25 (nm) (nm) Br 187 02N4N ~CH3-C2H5-CH3 544 CN N 188 0, N s 3-N-CH3-C2H5-CH3 581 s N 189 \>-N-CH3-c2Hg-CH3 544 on - 190 02N4N-CH3-C2H5-CH3 533 N 1 91 02N/+-CH3-C2H5-CH3 601 N N ci 192 02N4N ~CH3-C2H5-CH3 506 NO NO, 193/\-H-CzHS-CH3 640 OZN-S-N Example 194 4- (2-chloro-4-nitrophenylazo)-N-ethyl-N- (2-cyanomethoxy carbonylpropyl)-aniline

2-chloro-4-nitroaniline (parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (4. 9parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2- (cyanomethoxycarbonylpropyl)-aniline (parts), acetone (50parts), water (300parts) and sulphamic acid (1 part). After two hours the product was isolated

by filtration, washed with cold water and dried to yield, 4-(2-chloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-ani line (3.5parts) Smax = 534nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (Ica)

were prepared by the procedure of Example194 (see Table 10) Table 10 Smax Example D""R26 R27 R28 (nm) (nm) 195 o-N-H-H-CH, 521 2 196 02N N-H-H-CH3 473 ci - H-CH3 440 ci N02 198 02N4N-H-H-CH3 521 N 02N"SN-H-H-CH3 569 Cl _ 200 o2N N-CH3-H-CH3 505 max Example D""R26 R27 R2s ~ Bmax (nm) cl 201 02N<N ~CH3-H-CH3 448 ci Cl 202 02N4N-CH3-H-CH3 532 CN 203 02N4N-CH3-H-CH3 541 Br ___ 204 02N4sXN-CH3-H-CH3 579 205 a2N \/N-CH3-H-CH3 525 N N 206 o2N<sS-CH3-H-CH3 541 N 207 S-CH3-H-CH3 599 02N-- N N 208 S-H-H-CH3 588 N N CN 209 o2N4N C H,-CH3 H 535 Z CN 210 02N N-CH3-CH3-H 544 Br N 211 OZNN'CHs-CH3-H 594 N 212 SN-CH3-CH3-H 549 own Example 213 4-(4-nitrophenylazo)-N-ethyl-N-(2 » cyanoethoxy) carbonylpropyl)-aniline

4-nitroaniline (2. 0parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts). Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N- (2- (1-cyanoethoxy) carbonylpropyl)-aniline (4.7parts), acetone (50parts), water (200parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (4-nitrophenylazo)-N- ethyl-N-(2-(1-cyanoethoxy) carbonylpropyl)-aniline (2.9parts) Smax = 473nm (acetone) When applied to polyester materials from aqueous dispersion, scarlet shades with excellent wet and light fastness properties were seen.

The following examples of dyes of Formula (Ih) : were prepared by the procedure of Example 213 (see Table 11) Table 11 Bmax Example D""'R29 R30 R3' (nm) CN 214 o N N-H-CH3-CH3 519 max Example D""'R R'° R (nm) ci 215 02N S N-CH3-CH3-CH3 504 CON CN 216 02N4N ~C H3-C H3-C H3 5 0 CN 217 02N<N-CH3-CH3-CH3 537 Br N 218 02NX CH,-CH3 U 597 N N Br 219 02N<N-H-CH3-CH3 517 Nos ci 220 %, < H-CH3-C H. 428 cl ci 221 ozN N-H-CH3-CH3 428 Br ci 222 02N N-CH3-CH3-CH3 449 cl Br 223 2 N-CH3-CH3-CH3 539 nô :, NOS NOa 224 o N N-CH3-CH3-CH3 524 z Example 225 4- (2-cyano-4-nitrophenylazo)-N-ethyl-N- (1-cyanomethoxy carbonylethyl)-m- toluidine

2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (6.6parts) was added below 5°C and the mixture was stirred for 30 minutes.

The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N- (1-cyanomethoxycarbonylethyl)-m-toluidine (4. 1parts), methanol (40parts), water (200parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-cyano-4- nitrophenylazo)-N-ethyl-N-(1-cyanomethoxywarbonylethyl)-m-to luidine 13. 9parts) Smax = 510nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.