Disperse azo dyes, a process for the preparation thereof and the use thereof

Abstract

The present invention relates to azo dyes of formula ##STR00001##
wherein R.sub.1 denotes C.sub.1-C.sub.12 alkyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkoxy groups, hydroxyl groups, amino groups, cyano groups or halogen atoms and which may be interrupted one or more times by the radical O, S, NR.sub.4, COO or OOC; R.sub.4 is hydrogen or C.sub.1-C.sub.12 alkyl; either R.sub.2 is cyano and R.sub.3 is halogen or R.sub.2 is halogen and R.sub.3 is cyano; and Ar represents a carbocyclic or heterocyclic aromatic radical, to the process for the preparation thereof, to mixtures containing said dyes and to the use thereof in dyeing or printing semi-synthetic and especially synthetic hydrophobic fiber materials, more especially textile materials.

Claims

1. An azo dye of formula ##STR00059## wherein R.sub.1 denotes ethyl, propyl or i-propyl; either R.sub.2 is cyano and R.sub.3 is halogen or R.sub.2 is halogen and R.sub.3 is cyano; and Ar is a radical of the formula ##STR00060## ##STR00061## wherein R.sub.5 denotes hydrogen, chloro, methyl, methoxy, 2-hydroxyethyl or COOR.sub.19, wherein R.sub.19 has one of the meanings given for R.sub.1 above; R.sub.6 is NHCOR.sub.20 wherein R.sub.20 denotes a C.sub.1-C.sub.12 alkyl which is unsubstituted or substituted by one or more C.sub.1 -C.sub.12 alkoxy groups, C.sub.1 -C.sub.12 alkylcarbonyl groups, C.sub.7 -C.sub.25 arylcarbonyl groups, hydroxyl groups, amino groups, cyano groups or halogen atoms and which may be interrupted one or more times by the radical O, Sor NR.sub.4; R.sub.7 is ethyl and R.sub.8 is methyl, ethyl, n-propyl, n-butyl, allyl, benzyl, 4-nitrobenzyl, 4-methoxybenzyl, 3-methoxybenzyl, 2-cyanoethyl, 2-methoxyethyl, 2-phenylethyl, 2-hydroxy-3 -phenoxypropyl, or 2-hydroxy-3 -i-propoxyethyl; X denotes ethylene, trimethylene or oxyethylene; R.sub.9 is vinyl, allyl, benzyl or has one of the meanings given for R.sub.1 above; R.sub.10 is hydroxy or phenylamino; R.sub.11 is hydrogen, COOR.sub.21 or C.sub.6-C.sub.24 aryl that is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkyl groups, C.sub.1-C.sub.12 alkoxy groups, hydroxyl groups, amino groups, cyano groups or halogen atoms wherein R.sub.21 has one of the meanings given for R.sub.1 above; R.sub.12 is hydrogen or SO.sub.2NHR.sub.22, wherein R.sub.22 has one of the meanings given for R.sub.1 above; R.sub.13 is hydrogen or hydroxy; R.sub.14 denotes C.sub.1-C.sub.12 alkyl or trifluoromethyl: R.sub.15 is cyano or CONH.sub.2; R.sub.16 has one of the meanings given for R.sub.1 above; R.sub.23 and R.sub.24 are each independently of the other hydrogen, vinyl, allyl or C.sub.1-C.sub.6 alkyl which is unsubstituted or substituted by cyano, carboxy, hydroxy, C.sub.1-C.sub.6 alkoxy-, C.sub.2-C.sub.8 alkoxyalkoxy- or C.sub.6-C.sub.24 aryl; and R.sub.18 is hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy or C.sub.6-C.sub.24 aryl that is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkyl groups, C.sub.1-C.sub.12 alkoxy groups, hydroxyl groups, amino groups, cyano groups or halogen atoms with the proviso that R.sub.8 in the claimed formula (2a) is chosen from 2-methoxyethyl and 2-methoxycarbonylethyl group.

2. The azo dye of formula (1) according to claim 1, wherein R.sub.1 denotes ethyl.

3. The azo dye of formula (1) according to claim 1, wherein R.sub.2 is cyano and R.sub.3 is bromo.

4. The azo dye of formula (1) according to claim 1, wherein Ar is a radical of the formula (2a) wherein R.sub.5 is hydrogen, methyl or methoxy.

5. A dichromatic or trichromatic dye mixture comprising at least one azo dye of formula (1) according to claim 1 and at least one further disperse dye.

6. A process for dyeing or printing semi-synthetic hydrophobic fibre material comprising applying a dye of formula (1) according to claim 1 to the semi-synthetic hydrophobic fibre material.

7. A semi-synthetic hydrophobic fibre material dyed or printed by the process according to claim 6.

8. A process for dyeing or printing synthetic hydrophobic fibre material comprising applying a dye of formula (1) according to claim 1 to the synthetic hydrophobic fibre material.

9. A synthetic hydrophobic fibre material dyed or printed by the process according to claim 8.

Description

I. PREPARATION EXAMPLES

I.1 Dyestuff of Formula (101)

(1) ##STR00012##

(2) 8.48 g (0.015 mol) of the dye of formula (101a)

(3) ##STR00013##
which was prepared as described in U.S. Pat. No. 3,980,634 are dissolved under stirring at RT (room temperature) in 120 ml of pyridine. 0.147 g (0.003 mol) finely powdered NaCN and 1.343 g (0.003 mol) finely powdered CuCN are given to 100 ml pyridine and suspended under vigorous stirring. The suspension so obtained is within 4 h slowly dropped to the solution of the dye of formula (201) at RT. The reaction mixture is stirred over night and then diluted with 150 ml pyridine. The blue precipitate is filtered off and washed with water; after drying 2 g of crude product is obtained.

(4) According to HPLC analysis, the raw product essentially consists of a mixture of three different dyestuffs namely about 30% of educt (201), 50% of the dyestuff of formula (101) and 20% of the dicyano compound of formula (202) which are separated by conventional chromatographic methods.

(5) ##STR00014## m.p. (melting point)=156-158 C. .sub.max=472 nm (.sub.max=wavelength of the absorption maximum) Elemental Analysis:

(6) TABLE-US-00001 in theory found C 46.70% 46.65% H 4.10% 4.15% N 12.39% 12.30% Br 28.27% 28.05%

(7) ##STR00015## m.p.=204-208 C. .sub.max=586 nm

(8) TABLE-US-00002 in theory found C 54.02% 53.87% H 4.53% 4.80% N 15.63% 19.12% Br 18.44% 16.90% Elemental Analysis: .sup.1H-NMR (DMSO-d.sub.6, 250 MHz): =9.39 (s, broad, NH), 8.17 (s, broad, 1H), 8.06 (d, broad, J=2.0, 1H), 8.03 (s, 1H), 6.53 (d, broad, J=4.0, 1H), 3.79 (q, J=3.0, 2H), 3.57 (q, J=3.0, 4H), 2.22 (s, 3H), 1.23-1.35 (m, 9H).

(9) ##STR00016## m.p.=128-131 C. .sub.max=608 nm Elemental Analysis:

(10) TABLE-US-00003 in theory found C 63.00% 62.80% H 5.07% 5.20% N 21.44% 22.60% Br 0.00% 0.10%

(11) The dyes of formulae (102)-(457) listed in the following Tables 1 and 2 can be prepared in analogy to the method described above.

(12) TABLE-US-00004 TABLE 1 Dyestuffs of formula (1a) (1a) Dye R.sub.1 R.sub.5 R.sub.6 R.sub.7 R.sub.8 .sub.max/nm 102 ethyl H acetylamino ethyl methyl 582 103 ethyl H acetylamino ethyl n-propyl 588 104 ethyl H acetylamino ethyl benzyl 574 105 ethyl H acetylamino ethyl n-butyl 590 106 ethyl H acetylamino 2-methoxyethyl 2-methoxyethyl 579 107 ethyl H acetylamino ethyl 2-methoxyethyl 583 108 ethyl H acetylamino ethyl 2-cyanoethyl 568 109 ethyl H acetylamino 2-methoxyethyl benzyl 568 110 ethyl H methyl ethyl benzyl 542 111 ethyl OCH.sub.3 acetylamino ethyl 2-cyanoethyl 601 112 ethyl H acetylamino ethyl 2-phenylethyl 583 113 ethyl H acetylamino n-propyl n-propyl 587 114 ethyl H propionylamino ethyl benzyl 575 115 ethyl H H ethyl 2-cyanoethyl 511 116 ethyl H acetylamino 2-cyanoethyl benzyl 549 117 ethyl OCH.sub.3 acetylamino 2-cyanoethyl benzyl 589 118 ethyl H H 2-cyanoethyl 2-cyanoethyl 482 119 ethyl OCH.sub.3 acetylamino 2-acetoxyethyl benzyl 601 120 ethyl H H 2-cyanoethyl benzyl 495 121 ethyl H acetylamino methoxycarbonylethyl 1-methoxycarbonylmethyl 531 122 ethyl OCH.sub.3 acetylamino methoxycarbonylethyl 1-methoxycarbonylmethyl 577 123 ethyl OCH.sub.3 acetylamino 2-methoxyethyl 2-methoxyethyl 601 124 ethyl H acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 531 125 ethyl OCH.sub.3 acetylamino methoxycarbonylmethyl benzyl 595 126 Ethyl H acetylamino ethyl ethoxycarbonylmethyl 563 127 Ethyl H acetylamino ethyl 2-methoxycarbonylethyl 577 128 Ethyl H acetylamino ethyl 2-acetoxyethyl 575 129 Ethyl H acetylamino ethyl 2-hydroxy-3-phenoxypropyl 582 130 Ethyl H acetylamino allyl allyl 571 131 Ethyl H acetylamino ethyl 2-ethoxycarbonylethyl 577 132 Ethyl H acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 584 133 Ethyl H methyl 2-methoxyethyl 2-methoxyethyl 545 134 Ethyl H methyl ethyl 2-methoxyethyl 555 135 Ethyl H H 2-methoxyethyl 2-methoxyethyl 525 136 Ethyl H trifluoromethyl 2-methoxyethyl 2-methoxyethyl 487 137 Ethyl H chloro 2-methoxyethyl 2-methoxyethyl 513 138 Ethyl Cl acetylamino H 1-methoxycarbonylethyl 527 139 Ethyl Cl acetylamino H 1-phenylethyl 541 140 Ethyl H H ethyl 1-methoxycarbonylethyl 505 141 Ethyl H H ethyl 2-methoxycarbonylethyl 527 142 Ethyl H H ethyl methoxycarbonylmethyl 505 143 Ethyl H acetylamino 2-methoxycarbonylethyl 2-ethoxycarbonylethyl 531 144 Ethyl CH.sub.3 acetylamino ethyl 1-methoxycarbonylethyl 535 145 ethyl H methyl 2-methoxyethyl 2-methoxycarbonylethyl 538 146 ethyl H methyl ethyl 1-methoxycarbonylethyl 526 147 ethyl OCH.sub.3 acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 604 148 ethyl H methyl ethyl 1-ethoxycarbonylethyl 528 149 ethyl H H ethyl 1-ethoxycarbonylethyl 512 150 ethyl H methoxycarbonyl 2-methoxyethyl 2-methoxyethyl 518 151 ethyl OCH.sub.3 acetylamino 2-acetoxyethyl 2-acetoxyethyl 600 152 ethyl OCH.sub.3 acetylamino benzyl 1-methoxycarbonylethyl 586 153 ethyl OCH.sub.3 acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 576 154 ethyl H acetylamino ethyl 1-methoxycarbonylethyl 564 155 ethyl H acetylamino ethyl 1-ethoxycarbonylethyl 566 156 ethyl H cyano 2-methoxyethyl 2-methoxyethyl 504 157 ethyl H acetylamino H 1-methoxycarbonylethyl 546 158 ethyl H methyl ethyl 2-methoxycarbonylethyl 546 159 ethyl OCH.sub.3 acetylamino H 1-methoxycarbonylethyl 592 160 ethyl H methyl 2-cyanoethyl 2-methoxycarbonylethyl 512 161 ethyl H H 2-cyanoethyl 2-methoxycarbonylethyl 496 162 ethyl H acetylamino 2-cyanoethyl 2-methoxycarbonylethyl 550 163 ethyl H acetylamino benzyl 2-methoxycarbonylethyl 564 164 ethyl H acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 562 165 ethyl H acetylamino ethyl 4-nitrobenzyl 566 166 ethyl OCH.sub.3 acetylamino ethyl 4-nitrobenzyl 612 167 ethyl H acetylamino n-butyl n-butyl 588 168 ethyl H acetylamino ethyl 4-methoxybenzyl 578 169 ethyl H acetylamino ethyl 3-methoxybenzyl 579 170 ethyl CH.sub.3 acetylamino ethyl benzyl 556 171 ethyl H acetylamino n-butyl benzyl 579 172 ethyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-phenoxypropyl 568 173 ethyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 568 174 ethyl H acetylamino ethyl n-butyl 586 175 ethyl CH.sub.3 acetylamino ethyl 2-phenylethyl 572 176 ethyl OCH.sub.3 acetylamino allyl allyl 618 177 ethyl H acetylamino ethyl 3-phenoxypropyl 584 178 ethyl H acetylamino ethyl n-propyl 586 179 ethyl H acetylamino ethyl 4-acetoxybutyl 586 180 methyl H acetylamino ethyl ethyl 585 181 methyl H acetylamino ethyl methyl 582 182 methyl H acetylamino ethyl n-propyl 580 183 methyl H acetylamino ethyl benzyl 574 184 methyl H acetylamino ethyl n-butyl 590 185 methyl H acetylamino 2-methoxyethyl 2-methoxyethyl 579 186 methyl H acetylamino ethyl 2-methoxyethyl 583 187 methyl H acetylamino ethyl 2-cyanoethyl 568 188 methyl H acetylamino 2-methoxyethyl benzyl 568 189 methyl H methyl ethyl benzyl 544 190 methyl OCH.sub.3 acetylamino ethyl 2-cyanoethyl 601 191 methyl H acetylamino ethyl 2-phenylethyl 583 192 methyl H acetylamino n-propyl n-propyl 587 193 methyl H propionylamino ethyl benzyl 575 194 methyl H H ethyl 2-cyanoethyl 511 195 methyl H acetylamino 2-cyanoethyl benzyl 549 196 methyl OCH.sub.3 acetylamino 2-cyanoethyl benzyl 583 197 methyl H H 2-cyanoethyl 2-cyanoethyl 482 198 methyl OCH.sub.3 acetylamino 2-acetoxyethyl benzyl 601 199 methyl H H 2-cyanoethyl benzyl 495 200 methyl H acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 531 201 methyl OCH.sub.3 acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 577 202 methyl OCH.sub.3 acetylamino 2-methoxyethyl 2-methoxyethyl 601 203 methyl H acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 531 204 methyl OCH.sub.3 acetylamino methoxycarbonylmethyl benzyl 595 205 methyl H acetylamino ethyl ethoxycarbonylmethyl 563 206 methyl H acetylamino ethyl 2-methoxycarbonylethyl 577 207 methyl H acetylamino ethyl 2-acetoxyethyl 575 208 methyl H acetylamino ethyl 2-hydroxy-3-phenoxypropyl 562 209 methyl H acetylamino allyl allyl 571 210 methyl H acetylamino ethyl 2-ethoxycarbonylethyl 577 211 methyl H acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 584 212 methyl H methyl 2-methoxyethyl 2-methoxyethyl 545 213 methyl H methyl ethyl 2-methoxyethyl 555 214 methyl H H 2-methoxyethyl 2-methoxyethyl 525 215 methyl H trifluoromethyl 2-methoxyethyl 2-methoxyethyl 487 216 methyl H chloro 2-methoxyethyl 2-methoxyethyl 513 217 methyl Cl acetylamino H 1-methoxycarbonylethyl 527 218 methyl Cl acetylamino H 1-phenylethyl 541 219 methyl H H ethyl 1-methoxycarbonylethyl 506 220 methyl H H ethyl 2-methoxycarbonylethyl 527 221 methyl H H ethyl methoxycarbonylmethyl 505 222 methyl H acetylamino 2-methoxycarbonylethyl 2-ethoxycarbonylethyl 530 223 methyl CH.sub.3 acetylamino ethyl 1-methoxycarbonylethyl 535 224 methyl H methyl 2-methoxyethyl 2-methoxycarbonylethyl 537 225 methyl H methyl ethyl 1-methoxycarbonylethyl 526 226 methyl OCH.sub.3 acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 602 227 methyl H methyl ethyl 1-ethoxycarbonylethyl 528 228 methyl H H ethyl 1-ethoxycarbonylethyl 512 229 methyl H methoxycarbonyl 2-methoxyethyl 2-methoxyethyl 518 230 methyl OCH.sub.3 acetylamino 2-acetoxyethyl 2-acetoxyethyl 599 231 methyl OCH.sub.3 acetylamino benzyl 1-methoxycarbonylethyl 586 232 methyl OCH.sub.3 acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 576 233 methyl H acetylamino ethyl 1-methoxycarbonylethyl 564 234 methyl H acetylamino ethyl 1-ethoxycarbonylethyl 564 235 methyl H cyano 2-methoxyethyl 2-methoxyethyl 503 236 methyl H acetylamino H 1-methoxycarbonylethyl 545 237 methyl H methyl ethyl 2-methoxycarbonylethyl 545 238 methyl OCH.sub.3 acetylamino H 1-methoxycarbonylethyl 592 239 methyl H methyl 2-cyanoethyl 2-methoxycarbonylethyl 512 240 methyl H H 2-cyanoethyl 2-methoxycarbonylethyl 495 241 methyl H acetylamino 2-cyanoethyl 2-methoxycarbonylethyl 550 242 methyl H acetylamino benzyl 2-methoxycarbonylethyl 562 243 methyl H acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 563 244 methyl H acetylamino ethyl 4-nitrobenzyl 566 245 methyl H acetylamino n-butyl n-butyl 588 246 methyl H acetylamino ethyl 4-methoxybenzyl 578 247 methyl H acetylamino ethyl 3-methoxybenzyl 579 248 methyl CH.sub.3 acetylamino ethyl benzyl 556 249 methyl H acetylamino n-butyl benzyl 583 250 methyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-phenoxypropyl 568 251 methyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 584 252 methyl H acetylamino ethyl n-butyl 585 253 methyl CH.sub.3 acetylamino ethyl 2-phenylethyl 572 254 methyl OCH.sub.3 acetylamino allyl allyl 620 255 methyl H acetylamino ethyl 3-phenoxypropyl 584 256 methyl H acetylamino ethyl n-propyl 585 257 methyl H acetylamino ethyl 4-acetoxybutyl 586 258 n-propyl H acetylamino ethyl ethyl 587 259 n-propyl H acetylamino ethyl methyl 584 260 n-propyl H acetylamino ethyl n-propyl 588 261 n-propyl H acetylamino ethyl benzyl 575 262 n-propyl H acetylamino ethyl n-butyl 591 263 n-propyl H acetylamino 2-methoxyethyl 2-methoxyethyl 575 264 n-propyl H acetylamino ethyl 2-methoxyethyl 581 265 n-propyl H acetylamino ethyl 2-cyanoethyl 570 266 n-propyl H acetylamino 2-methoxyethyl benzyl 543 267 n-propyl H methyl ethyl benzyl 602 268 n-propyl OCH.sub.3 acetylamino ethyl 2-cyanoethyl 583 269 n-propyl H acetylamino ethyl 2-phenylethyl 587 270 n-propyl H acetylamino n-propyl n-propyl 589 271 n-propyl H propionylamino ethyl benzyl 576 272 n-propyl H H ethyl 2-cyanoethyl 513 273 n-propyl H acetylamino 2-cyanoethyl benzyl 549 274 n-propyl OCH.sub.3 acetylamino 2-cyanoethyl benzyl 591 275 n-propyl H H 2-cyanoethyl 2-cyanoethyl 483 276 n-propyl OCH.sub.3 acetylamino 2-acetoxyethyl benzyl 603 277 n-propyl H H 2-cyanoethyl benzyl 496 278 n-propyl H acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 531 279 n-propyl OCH.sub.3 acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 577 280 n-propyl OCH.sub.3 acetylamino 2-methoxyethyl 2-methoxyethyl 600 281 n-propyl H acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 532 282 n-propyl OCH.sub.3 acetylamino methoxycarbonylmethyl benzyl 595 283 n-propyl H acetylamino ethyl ethoxycarbonylmethyl 565 284 n-propyl H acetylamino ethyl 2-methoxycarbonylethyl 578 285 n-propyl H acetylamino ethyl 2-acetoxyethyl 576 286 n-propyl H acetylamino ethyl 2-hydroxy-3-phenoxypropyl 584 287 n-propyl H acetylamino allyl allyl 572 288 n-propyl H acetylamino ethyl 2-ethoxycarbonylethyl 577 289 n-propyl H acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 585 290 n-propyl H methyl 2-methoxyethyl 2-methoxyethyl 547 291 n-propyl H methyl ethyl 2-methoxyethyl 556 292 n-propyl H H 2-methoxyethyl 2-methoxyethyl 526 293 n-propyl H trifluoromethyl 2-methoxyethyl 2-methoxyethyl 487 294 n-propyl H chloro 2-methoxyethyl 2-methoxyethyl 515 295 n-propyl Cl acetylamino H 1-methoxycarbonylethyl 542 296 n-propyl Cl acetylamino H 1-phenylethyl 505 297 n-propyl H H ethyl 1-methoxycarbonylethyl 527 298 n-propyl H H ethyl 2-methoxycarbonylethyl 507 299 n-propyl H H ethyl methoxycarbonylmethyl 533 300 n-propyl H acetylamino 2-methoxycarbonylethyl 2-ethoxycarbonylethyl 535 301 n-propyl CH.sub.3 acetylamino ethyl 1-methoxycarbonylethyl 538 302 n-propyl H methyl 2-methoxyethyl 2-methoxycarbonylethyl 538 303 n-propyl H methyl ethyl 1-methoxycarbonylethyl 522 304 n-propyl OCH.sub.3 acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 605 305 n-propyl H methyl ethyl 1-ethoxycarbonylethyl 529 306 n-propyl H H ethyl 1-ethoxycarbonylethyl 512 307 n-propyl H methoxycarbonyl 2-methoxyethyl 2-methoxyethyl 519 308 n-propyl OCH.sub.3 acetylamino 2-acetoxyethyl 2-acetoxyethyl 600 309 n-propyl OCH.sub.3 acetylamino benzyl 1-methoxycarbonylethyl 587 310 n-propyl OCH.sub.3 acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 576 311 n-propyl H acetylamino ethyl 1-methoxycarbonylethyl 565 312 n-propyl H acetylamino ethyl 1-ethoxycarbonylethyl 566 313 n-propyl H cyano 2-methoxyethyl 2-methoxyethyl 507 314 n-propyl H acetylamino H 1-methoxycarbonylethyl 547 315 n-propyl H methyl ethyl 2-methoxycarbonylethyl 546 316 n-propyl OCH.sub.3 acetylamino H 1-methoxycarbonylethyl 594 317 n-propyl H methyl 2-cyanoethyl 2-methoxycarbonylethyl 512 318 n-propyl H H 2-cyanoethyl 2-methoxycarbonylethyl 497 319 n-propyl H acetylamino 2-cyanoethyl 2-methoxycarbonylethyl 553 320 n-propyl H acetylamino benzyl 2-methoxycarbonylethyl 565 321 n-propyl H acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 565 322 n-propyl H acetylamino ethyl 4-nitrobenzyl 568 323 n-propyl H acetylamino n-butyl n-butyl 578 324 n-propyl H acetylamino ethyl 4-methoxybenzyl 580 325 n-propyl H acetylamino ethyl 3-methoxybenzyl 580 326 n-propyl CH.sub.3 acetylamino ethyl benzyl 557 327 n-propyl H acetylamino n-butyl benzyl 580 328 n-propyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-phenoxypropyl 570 329 n-propyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 570 330 n-propyl H acetylamino ethyl n-butyl 587 331 n-propyl CH.sub.3 acetylamino ethyl 2-phenylethyl 572 332 n-propyl OCH.sub.3 acetylamino allyl allyl 617 333 n-propyl H acetylamino ethyl 3-phenoxypropyl 588 334 n-propyl H acetylamino ethyl n-propyl 586 335 n-propyl H acetylamino ethyl 4-acetoxybutyl 586 336 n-butyl H acetylamino ethyl ethyl 588 337 n-butyl H acetylamino ethyl methyl 584 338 n-butyl H acetylamino ethyl n-propyl 590 339 n-butyl H acetylamino ethyl benzyl 578 340 n-butyl H acetylamino ethyl n-butyl 592 341 n-butyl H acetylamino 2-methoxyethyl 2-methoxyethyl 582 342 n-butyl H acetylamino ethyl 2-methoxyethyl 585 343 n-butyl H acetylamino ethyl 2-cyanoethyl 571 344 n-butyl H acetylamino 2-methoxyethyl benzyl 572 345 n-butyl H methyl ethyl benzyl 546 346 n-butyl OCH.sub.3 acetylamino ethyl 2-cyanoethyl 603 347 n-butyl H acetylamino ethyl 2-phenylethyl 585 348 n-butyl H acetylamino n-propyl n-propyl 587 349 n-butyl H propionylamino ethyl benzyl 576 350 n-butyl H H ethyl 2-cyanoethyl 513 351 n-butyl H acetylamino 2-cyanoethyl benzyl 553 352 n-butyl OCH.sub.3 acetylamino 2-cyanoethyl benzyl 592 353 n-butyl H H 2-cyanoethyl 2-cyanoethyl 486 354 n-butyl OCH.sub.3 acetylamino 2-acetoxyethyl benzyl 603 355 n-butyl H H 2-cyanoethyl benzyl 498 356 n-butyl H acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 533 357 n-butyl OCH.sub.3 acetylamino 1-methoxycarbonylethyl methoxycarbonylmethyl 577 358 n-butyl OCH.sub.3 acetylamino 2-methoxyethyl 2-methoxyethyl 604 359 n-butyl H acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 532 360 n-butyl OCH.sub.3 acetylamino methoxycarbonylmethyl benzyl 597 361 n-butyl H acetylamino ethyl ethoxycarbonylmethyl 565 362 n-butyl H acetylamino ethyl 2-methoxycarbonylethyl 579 363 n-butyl H acetylamino ethyl 2-acetoxyethyl 576 364 n-butyl H acetylamino ethyl 2-hydroxy-3-phenoxypropyl 583 365 n-butyl H acetylamino allyl allyl 573 366 n-butyl H acetylamino ethyl 2-ethoxycarbonylethyl 579 367 n-butyl H acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 585 368 n-butyl H methyl 2-methoxyethyl 2-methoxyethyl 547 369 n-butyl H methyl ethyl 2-methoxyethyl 556 370 n-butyl H H 2-methoxyethyl 2-methoxyethyl 524 371 n-butyl H trifluoromethyl 2-methoxyethyl 2-methoxyethyl 490 372 n-butyl H chloro 2-methoxyethyl 2-methoxyethyl 515 373 n-butyl Cl acetylamino H 1-methoxycarbonylethyl 529 374 n-butyl Cl acetylamino H 1-phenylethyl 543 375 n-butyl H H ethyl 1-methoxycarbonylethyl 507 376 n-butyl H H ethyl 2-methoxycarbonylethyl 530 377 n-butyl H H ethyl methoxycarbonylmethyl 506 378 n-butyl H acetylamino 2-methoxycarbonylethyl 2-ethoxycarbonylethyl 532 379 n-butyl CH.sub.3 acetylamino ethyl 1-methoxycarbonylethyl 537 380 n-butyl H methyl 2-methoxyethyl 2-methoxycarbonylethyl 540 381 n-butyl H methyl ethyl 1-methoxycarbonylethyl 529 382 n-butyl OCH.sub.3 acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 607 383 n-butyl H methyl ethyl 1-ethoxycarbonylethyl 530 384 n-butyl H H ethyl 1-ethoxycarbonylethyl 515 385 n-butyl H methoxycarbonyl 2-methoxyethyl 2-methoxyethyl 520 386 n-butyl OCH.sub.3 acetylamino 2-acetoxyethyl 2-acetoxyethyl 602 387 n-butyl OCH.sub.3 acetylamino benzyl 1-methoxycarbonylethyl 588 388 n-butyl OCH.sub.3 acetylamino methoxycarbonylmethyl methoxycarbonylmethyl 576 389 n-butyl H acetylamino ethyl 1-methoxycarbonylethyl 567 390 n-butyl H acetylamino ethyl 1-ethoxycarbonylethyl 568 391 n-butyl H cyano 2-methoxyethyl 2-methoxyethyl 507 392 n-butyl H acetylamino H 1-methoxycarbonylethyl 549 393 n-butyl H methyl ethyl 2-methoxycarbonylethyl 547 394 n-butyl OCH.sub.3 acetylamino H 1-methoxycarbonylethyl 594 395 n-butyl H methyl 2-cyanoethyl 2-methoxycarbonylethyl 515 396 n-butyl H H 2-cyanoethyl 2-methoxycarbonylethyl 499 397 n-butyl H acetylamino 2-cyanoethyl 2-methoxycarbonylethyl 555 398 n-butyl H acetylamino benzyl 2-methoxycarbonylethyl 566 399 n-butyl H acetylamino 2-methoxycarbonylethyl 2-methoxycarbonylethyl 565 400 n-butyl H acetylamino ethyl 4-nitrobenzyl 568 401 n-butyl H acetylamino n-butyl n-butyl 590 402 n-butyl H acetylamino ethyl 4-methoxybenzyl 580 403 n-butyl H acetylamino ethyl 3-methoxybenzyl 580 404 n-butyl CH.sub.3 acetylamino ethyl benzyl 557 405 n-butyl H acetylamino n-butyl benzyl 581 406 n-butyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-phenoxypropyl 572 407 n-butyl CH.sub.3 acetylamino ethyl 2-hydroxy-3-isopropoxypropyl 570 408 n-butyl H acetylamino ethyl n-butyl 588 409 n-butyl CH.sub.3 acetylamino ethyl 2-phenylethyl 575 410 n-butyl OCH.sub.3 acetylamino allyl allyl 615 411 n-butyl H acetylamino ethyl 3-phenoxypropyl 586 412 n-butyl H acetylamino ethyl n-propyl 588 413 n-butyl H acetylamino ethyl 4-acetoxybutyl 587

(13) TABLE-US-00005 TABLE 2 Dye .sub.max/nm 417 585 418 480 419 0 580 420 602 421 610 422 620 423 605 424 607 425 597 426 604 427 602 428 409 429 0 410 430 411 431 411 432 412 433 413 434 411 435 411 436 428 437 435 438 435 439 0 446 440 590 441 594 442 598 443 593 444 587 445 570 446 572 447 555 448 556 449 0 532 450 533 451 552 452 552 453 594 454 580 455 554 456 528 457 586

II. APPLICATION EXAMPLES

II.1: Dyeing of Polyester

(14) 1 part by weight of the dye of formula (101) prepared in Example I.1 is milled together with four parts of a commercially available dispersing agent and 15 parts of water. Using that formulation, a 1% dyeing (based on the dye and the substrate) is produced on woven polyester by high temperature exhaust process at 135 C.

(15) Test results: the light fastness of the dyeing is excellent as well as the results in the AATCC 61 and ISO 105 tests. The build up properties of the dye are very good.

II.2: Dyeing of Polyester

(16) Example II.1 is repeated by using the dyes of formulae (102)-(186) instead of the dye of formula (101). The build up properties of the dyes are very good and the dyeings exhibit good light fastness and very good results in the AATCC 61 and ISO 105 tests.