High wet fast disperse dyes and mixtures thereof

Abstract

Dyes of formula (1) ##STR00001##
their production and their use are described.

Claims

1. A dye of formula (I) ##STR00028## wherein X is hydrogen and K is an aromatic or heteroaromatic coupling component with the proviso that K is not a naphthyl radical, and wherein the following dyes a) and b) are excluded: ##STR00029## wherein X is hydrogen, R.sup.1 is C.sub.1 alkoxy, R.sup.2 is acylamino, and R.sup.3 and R.sup.4 are C.sub.2H.sub.4CN.

2. The dye according to claim 1, wherein K is selected from the group consisting of N-heterocyclic fused ring system and a phenol radical, each of which may be unsubstituted or substituted.

3. The dye according to claim 2, wherein K is selected from the group consisting of aminobenzene, quinolone and a phenol-radical, each of which is optionally substituted.

4. The dye according to claim 1, wherein K is a radical of formula (2) ##STR00030## wherein independent from each other R.sup.1 is hydrogen, unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted or substituted C.sub.1-C.sub.4-alkoxy, chloro, bromo, benzyloxy or O(CH.sub.2).sub.n-A.sup.1-C.sub.1-C.sub.4-alkyl, R.sup.2 is hydrogen, hydroxyl, unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted C.sub.1-C.sub.4-alkoxy, chloro, bromo, acyloxy, acylamino or alkylsulfonylamino, wherein n is 1 to 4 and A is O, OCO, OCOO or COO and wherein at least one R.sup.1 or R.sup.2 is not hydrogen, and R.sup.3 and R.sup.4 is unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl, or R.sup.1 and R.sup.3 together form a 5- or 6-membered aliphatic, heteroaliphatic, aromatic or heteroaromatic ring, which 5- or 6-membered ring is unsubstituted or substituted and R.sup.3 and R.sup.4 are not both C.sub.2H.sub.4CN, and wherein the dye: ##STR00031## is excluded.

5. The dye according to claim 1 having formula (II) ##STR00032## wherein independent of each other X is hydrogen, R.sup.1 is hydrogen, hydroxyl, C.sub.1-C.sub.4-alkyl, bromo, chloro or C.sub.1-C.sub.4-alkoxy, R.sup.2 is hydrogen, hydroxyl, carboxy, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, halogen, acyloxy, acylamino or sulfonylamino, wherein at least one R.sup.1 or R.sup.2 is not hydrogen, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.4-alkyl, (CH.sub.2).sub.n-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.nOH, (CH.sub.2).sub.nO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO-phenyl, (CH.sub.2).sub.nO-benzyl, (CH.sub.2).sub.nO(CH.sub.2).sub.mOH, (CH.sub.2).sub.nO(CH.sub.2).sub.mO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.mO-phenyl, (CH.sub.2).sub.nO(CH.sub.2).sub.nO-benzyl, (CH.sub.2).sub.nCOOH, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nOCO-phenyl, (CH.sub.2).sub.nOCO-benzyl, COO(CH.sub.2).sub.n-2-furfuryl, COO(CH.sub.2).sub.n-2-dehydropyranyl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-dehydropyranyl, CHR.sup.2(CH.sub.2).sub.p(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.p phenyl, CHR.sup.2CH?CH.sub.2, CHR.sup.2(CH.sub.2).sub.pOH, CHR.sup.2(CH.sub.2).sub.pO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pO-phenyl, CHR.sup.2(CH.sub.2).sub.pO-benzyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mOH, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mOH, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-phenyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOOH, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.p(CHR.sup.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.mO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.nO-phenyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pOCO-phenyl, CHR.sup.2(CH.sub.2).sub.pOCO-benzyl, COOCHR.sup.2(CH.sub.2).sub.p-2-furfuryl, COOCHR.sup.2(CH.sub.2).sub.p-2-dehydropyranyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.n-2-furfuryl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.n-2-dehydropyranyl, whereby all benzyl and phenyl rings can be substituted by C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, halogen, nitro, cyano or COOR.sup.2, n is 1 to 4, m is 1 to 4 and p is 0 to 3.

6. The dye according to claim 5, having formula (II) wherein independent from each other X is hydrogen, R.sup.1 is hydrogen, methyl or methoxy, R.sup.2 is hydrogen, hydroxy, COOH, COOC.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy, chloro, bromo, NHCOC.sub.1-C.sub.2-alkyl, NHCO-aryl, NHCO-benzyl, NHSO.sub.2C.sub.1-C.sub.2-alkyl or NHSO.sub.2-aryl, and wherein at least one R.sup.1 or R.sup.2 is not hydrogen, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.2-alkyl, (CH.sub.2)-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.2O(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O-phenyl, (CH.sub.2).sub.2O-benzyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O(CH.sub.2).sub.nO-phenyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO-benzyl, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nOCO-phenyl, (CH.sub.2).sub.nOCO-benzyl, COO(CH.sub.2).sub.n-2-furfuryl, COO(CH.sub.2).sub.n-2-dehydropyranyl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.nO(CH.sub.2).sub.n-2-dehydropyranyl, CHR.sup.2CH?CH.sub.2, CHR.sup.2(CH.sub.2).sub.pO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pO-phenyl, CHR.sup.2(CH.sub.2).sub.pO-benzyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-phenyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-benzyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pOCO-phenyl or CHR.sup.2(CH.sub.2).sub.pOCO-benzyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.

7. The dye according to claim 5, having formula (II) wherein independent from each other X is hydrogen, R.sup.1 is hydrogen, methyl or methoxy, R.sup.2 is hydrogen, hydroxy, COOH, COO(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl, chloro, bromo, NHCO(C.sub.1-C.sub.2)-alkyl, NHSO.sub.2(C.sub.1-C.sub.2)-alkyl, and wherein at least one R.sup.1 or R.sup.2 is not hydrogen, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.2-alkyl, (CH.sub.2)-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.2O(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O-phenyl, (CH.sub.2).sub.2O-benzyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nOCO-phenyl, COO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2)O(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.pCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.2)-alkyl or CHR.sup.2(CH.sub.2).sub.pOCO-phenyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.

8. The dye according to claim 1, having formula (III) ##STR00033## wherein independent from each other X is hydrogen, R.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, bromo, chloro or C.sub.1-C.sub.4-alkoxy, R.sup.5 is hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.4-alkyl, (CH.sub.2).sub.n-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.nOH, (CH.sub.2).sub.nO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO-phenyl, (CH.sub.2).sub.nO-benzyl, (CH.sub.2).sub.nO(CH.sub.2).sub.mOH, (CH.sub.2).sub.nO(CH.sub.2).sub.mO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.mO-phenyl, (CH.sub.2).sub.nO(CH.sub.2).sub.mO-benzyl, (CH.sub.2).sub.nCOOH, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nOCO-phenyl, (CH.sub.2).sub.nOCO-benzyl, COO(CH.sub.2).sub.n-2-furfuryl, COO(CH.sub.2).sub.n-2-dehydropyranyl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-dehydropyranyl CHR.sup.2(CH.sub.2).sub.p(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.p-phenyl, CHR.sup.2CH?CH.sub.2, CHR.sup.2(CH.sub.2).sub.pOH, CHR.sup.2(CH.sub.2).sub.pO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pO-phenyl, CHR.sup.2(CH.sub.2).sub.pO-benzyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mOH, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mOH, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-phenyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOOH, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.p(CHR.sup.2).sub.mCO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.mO(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.mO-phenyl, (CH.sub.2).sub.nO(CH.sub.2).sub.p(CHR.sup.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.4)-alkyl, CHR.sup.2(CH.sub.2).sub.pOCO-phenyl, CHR.sup.2(CH.sub.2).sub.pOCO-benzyl, COO CHR.sup.2(CH.sub.2).sub.p-2-furfuryl, COOCHR.sup.2(CH.sub.2).sub.p-2-dehydropyranyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.n-2-furfuryl or CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.n-2-dehydropyranyl, whereby all benzyl and phenyl rings can be substituted by (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, nitro, or COOR.sup.2, n is 1 to 4, m is 1 to 4 and p is 0 to 3.

9. A process for the production of the dye of formula (I) and mixtures thereof ##STR00034## comprising: a) diazotizing ##STR00035## wherein X is defined as in claim 1 and b) coupling the diazonium salt obtained in step a) with compounds of formula (2) ##STR00036## wherein R.sup.1 is hydrogen, unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted or substituted C.sub.1-C.sub.4-alkoxy, chloro, bromo, benzyloxy or O(CH.sub.2).sub.n-A.sup.1-C.sub.1-C.sub.4-alkyl, R.sup.2 is hydrogen, hydroxyl, unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted C.sub.1-C.sub.4-alkoxy, chloro, bromo, acyloxy, acylamino or alkylsulfonylamino, wherein n is 1 to 4 and A.sup.1 is O, OCO, OCOO or COO and R.sup.3 and R.sup.4 is unsubstituted or substituted C.sub.1-C.sub.4-alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted benzyl or R.sup.1 and R.sup.3 together form a 5- or 6-membered aliphatic, heteroaliphatic, aromatic or heteroaromatic ring, which 5- or 6-membered ring is unsubstituted or substituted.

10. A chemical composition comprising one or more dye(s) according to claim 1.

11. A chemical composition consisting of two or more dyes according to claim 1.

12. An aqueous dispersion for dying comprising one or more dyes according to claim 1.

13. A process for dyeing or printing hydrophobic materials with the dye according to claim 1.

14. An ink for digital textile printing comprising the dye according to claim 1.

15. A process for dying fibers which comprises contacting the fibers with the dye according to claim 1, wherein the fibres are selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.

16. Fiber and blends comprising a fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers and comprising one or more dye(s) according to claim 1 either in chemically and/or physically bound form.

17. A dye of formula (III) ##STR00037## wherein independent from each other X is hydrogen, R.sup.1 is hydrogen, methyl or methoxy, R.sup.5 is methyl or ethyl, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.2-alkyl, (CH.sub.2)-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.2O(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O-phenyl, (CH.sub.2).sub.2O-benzyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO-phenyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO-benzyl, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCN, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-benzyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nOCO-phenyl, (CH.sub.2).sub.nOCO-benzyl, COO(CH.sub.2).sub.n-2-furfuryl, COO(CH.sub.2).sub.n-2-dehydropyranyl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-dehydropyranyl, CHR.sup.2CH?CH.sub.2, CHR.sup.2(CH.sub.2).sub.pO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pO-phenyl, CHR.sup.2(CH.sub.2).sub.pO-benzyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-phenyl, CHR.sup.2(CH.sub.2).sub.pO(CH.sub.2).sub.mO-benzyl, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO-benzyl, CHR.sup.2(CH.sub.2).sub.pCN, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-benzyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pOCO-phenyl or CHR.sup.2(CH.sub.2).sub.pOCO-benzyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.

18. A chemical composition comprising one or more dye(s) according to claim 17.

19. A chemical composition consisting of two or more dyes according to claim 17.

20. An aqueous dispersion for dying comprising one or more dyes according to claim 17.

21. A process for dyeing or printing hydrophobic materials with the dye according to claim 17.

22. An ink for digital textile printing comprising the dye according to claim 17.

23. A process for dying fibers which comprises contacting the fibers with the dye according to claim 17, wherein the fibres are selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.

24. A dye of formula (III) ##STR00038## wherein independent from each other X is hydrogen, R.sup.1 is hydrogen, methyl or methoxy, R.sup.5 is methyl, R.sup.3 and R.sup.4 is hydrogen, C.sub.1-C.sub.2-alkyl, (CH.sub.2)-phenyl, CH.sub.2CH?CH.sub.2, (CH.sub.2).sub.2O(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2O-phenyl, (CH.sub.2).sub.2O-benzyl, (CH.sub.2).sub.2O(CH.sub.2).sub.mO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO-phenyl, (CH.sub.2).sub.nCOO-benzyl, (CH.sub.2).sub.nCN, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nCOO(CH.sub.2).sub.mCO-phenyl, (CH.sub.2).sub.nOCO(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.nOCO-phenyl, COO(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.mO(CH.sub.2).sub.n-2-furfuryl, CHR.sup.2(CH.sub.2).sub.pCOO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2)O(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.pCO(C.sub.1-C.sub.2)-alkyl, CHR.sup.2(CH.sub.2).sub.pCOO(CH.sub.2).sub.mCO-phenyl, CHR.sup.2(CH.sub.2).sub.pOCO(C.sub.1-C.sub.2)-alkyl or CHR.sup.2(CH.sub.2).sub.pOCO-phenyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1.

25. Fiber and blends comprising a fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers and comprising one or more dye(s) according to claim 17 either in chemically and/or physically bound form.

26. A chemical composition comprising one or more dye(s) according to claim 24.

27. A chemical composition consisting of two or more dyes according to claim 24.

28. An aqueous dispersion for dying comprising one or more dyes according to claim 24.

29. A process for dyeing or printing hydrophobic materials with the dye according to claim 24.

30. An ink for digital textile printing comprising the dye according to claim 24.

31. A process for dying fibers which comprises contacting the fibers with the dye according to claim 24, wherein the fibres are selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.

32. Fiber and blends comprising a fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6,6, aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers and comprising one or more dye(s) according to claim 24 either in chemically and/or physically bound form.

Description

EXAMPLES

(1) Intermediate 1:

(2) 192 ml (2 Mol) of m 3-Fluor-aniline are added to 200 ml of Toluidine and stirred. To this mixture is heated to 50? C. and 203 ml (2.1 Mol) of Acetanhydride are added while the temperature is kept at 50 to 60? C. After 2 h the mixture is evaporated under vacuum. The remaining product is mixed with 1000 ml of cold water filtrated and dried under vacuum, conditions delivering 292 g of intermediate 1

(3) ##STR00011##
Intermediate 2:

(4) 137.9 g (0.9 Mol) of Intermediate 1 are added slowly to a mixture of 259 g HNO.sub.3 and 630 g of H.sub.2SO.sub.4 at ?5 to 0? C. The mixture is stirred at 0 to 5? C. for 1 h and then added to a stirred mix of 4 l ice/water, isolated by filtration and dried under vacuum conditions to deliver 140 g of Intermediate 2

(5) ##STR00012##
Intermediate 3:

(6) 140 g of intermediate 2 are added to 545 ml 50% H.sub.2SO.sub.4 and heated for 3 h to 100? C. under stirring. The mixture is added to 5 l of ice/water, isolated by filtration and dried under vacuum conditions to deliver 107 g of intermediate 3

(7) ##STR00013##

(8) An alternative synthesis for intermediate 3 is shown below: (Organic Letters, 14(10), 2504-2507; 2012/Journal of Organic Chemistry, 27, 1910-11; 1962/Bioorganic & Medicinal Chemistry Letters, 21(14), 4189-4192; 2011)

(9) ##STR00014##
Intermediate 4:

(10) 38.8 g (0.193 Mol) of Intermediate 3 are dissolved in 200 ml of acetic acid and 40 ml of 37% HCl are added. The mixture is stirred at 25? C. and 21 ml of H.sub.2O.sub.2 35% are added slowly. This mixture is stirred at 25 to 30? C. for 3 days and then poured on 1000 ml of ice/water, isolated by filtration and dried under vacuum conditions to deliver 39.5 g of intermediate 4

(11) ##STR00015##
Intermediate 5:

(12) 38.8 g (0.193 Mol) of Intermediate 3 are dissolved in 200 ml of acetic acid and 11.6 ml Bromine (0.22 Mol) are added slowly at 25? C. This mixture is stirred at for 3 days at 25 to 30? C. and then the poured on 1000 ml of ice/water, isolated by filtration and dried under vacuum conditions to deliver 48.1 g of intermediate 5

(13) ##STR00016##
Coupling Components (K)/(2) and (2a)

(14) ##STR00017##
for disperse dyes are well known and described in chemical encyclopaedia literature like Ullmann's Encylopedia of Industrial Chemistry, Houben-Weyl, other scientific literature and numerous patents. Thus detailed synthesis is only given for a few coupling components.
Coupler 1:

(15) 80 g of Zn powder are activated by stirring it in 5% aqueous HCl, filtrated and washed with water. 54 g (0.3 Mol) of 3-Amino-4-methoxyacetanilid are stirred in 250 ml of acetic acid and 25 ml of water and 35.2 g (0.3 Mol) of Methyacetoacetat (CH.sub.3COCH.sub.2COOCH.sub.3). To this mixture the activated Zn-powder is added at 25? C. The temperature rises after the reaction starts and is kept at 80 to 90? C. for 12 h. The acetic acid is evaporated under vacuum and 300 ml water and 300 ml CH.sub.2Cl.sub.2 are added. The pH is adjusted to 7 with Ammonia solution and the 2 phases are mixed intensively, after phase-separation, the organic phase is isolated.

(16) The aqueous phase is extracted with 100 ml of CH.sub.2Cl.sub.2 and both organic phases are combined, washed with water, dried with MgSO.sub.4 and evaporated under vacuum resulting in 39.2 g of Coupler 1

(17) ##STR00018##

Dye Example 1

(18) Diazotation:

(19) 8.8 g of intermediate 3 are mixed with 85 ml of acetic-/propionic-acid (60/40) and cooled down to 0? C. 8.0 ml of nitrosylsulfuric acid is added slowly at 0? C. This mixture is stirred 4 h at 0? C. and the excess of Nitrite is destroyed the Amidosulfonic acid.

(20) Coupling:

(21) 9.4 g of 3-(N,N-diethyl)-aminoacetanilid are mixed with 140 ml of Methanol and 10 g of Sodium acetate and 2 g of urea and cooled down to 5? C. To this mixture the diazotation is added slowly and the reaction mixture is stirred for 30 min at 5? C.

(22) 100 ml of water are added and the resulting product is isolated by filtration.

(23) After re-crystallisation from Ethanol and drying under vacuum conditions, 10.6 g of the dye are obtained.

(24) ##STR00019##

(25) This dye of the invention was further formulated using dispersing agent, glass bead milling and dried via spray drying and gives deep violet dyeing's or prints, on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes with very good fastness properties.

Example 2

(26) Diazotation:

(27) 8.8 g of intermediate 5 are mixed with 85 ml of acetic-/propionic-acid (60/40) and cooled down to 0? C. 8.0 ml of nitrosylsulfuric acid is added slowly at 0? C. This mixture is stirred 4 h at 0? C. and the excess of Nitrite is destroyed the Amidosulfonic acid.

(28) Coupling:

(29) 11.04 g of 3-(N,N-dipropyl)mesylmetamin (N-(3-Dipropylamino-phenyl)metanesulfonamid) are mixed with 140 ml of Methanol and 10 g of Sodium acetate and 2 g of urea and cooled down to 5? C. To this mixture the diazotation is added slowly and the reaction mixture is stirred for 30 min at 5? C.

(30) 100 ml of water are added and the resulting product is isolated by filtration.

(31) After re-crystallisation from Acetone and drying under vacuum conditions, 10.6 g of the Example 2-dye are obtained.

(32) ##STR00020##

(33) The resulting dye of the invention was formulated using dispersing agent, glass bead milling and dried via spray drying and gives deep violet dyeing's or prints on polyester or polyester blends for example, under the dyeing conditions typical for disperse dyes with very good fastness properties.

Examples 3 to 5

(34) With the following annelated/substituted couplers (Coupler 2 to 4) and the diazo-component Intermediate 3 or Intermediate 5 also high wash fast dyes can be prepared following the procedure of Example 1.

(35) ##STR00021##
that dyes polyester in deep red shades,

(36) ##STR00022##
that dyes polyester in deep reddish blue shades,

(37) ##STR00023##
that dyes polyester in deep bluish-red shades.

Examples 6 to 63 of Formula (IIa)

(38) ##STR00024##
can be prepared according the procedure of example 1 or 2
using Intermediate 3 as a diazo-component and coupling components of formula (2) with:

(39) TABLE-US-00001 Shade on No: R.sup.1 R.sup.2 R.sup.3 R.sup.4 polyester 6 Hydrogen CH.sub.3 (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Red-violet 7 Hydrogen CH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Red-violet 8 Hydrogen CH.sub.3 C.sub.2H.sub.4 (CH.sub.2).sub.2COOCH.sub.3 Red-violet 9 Hydrogen Hydrogen C.sub.2H.sub.4 CH.sub.2COOCH.sub.3 Red-violet 10 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Bluish red 11 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 C.sub.2H.sub.4 Red-violet 12 Hydrogen Hydrogen CH.sub.2-phenyl CH.sub.2CH?CH.sub.2 Red-violet 13 Hydrogen Hydrogen CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Red-violet 14 Hydrogen COO(CH.sub.2).sub.2OCH.sub.3 C.sub.2H.sub.5 C.sub.2H.sub.5 Bluish red 15 Hydrogen COO(CH.sub.2).sub.2OCH.sub.3 Hydrogen CH.sub.2-phenyl Bluish red 16 Hydrogen Hydrogen (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Red-violet 17 Hydrogen Hydrogen Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 Bluish red 18 Hydrogen Hydrogen (CH.sub.2).sub.2O-phenyl (CH.sub.2).sub.2O-phenyl Red-violet 19 Hydrogen Hydrogen (CH.sub.2).sub.2O-benzyl CH.sub.3 Red-violet 20 Hydrogen Hydrogen CH.sub.2-phenyl CH.sub.2COOCH.sub.3 Red-violet 21 Hydrogen Cl Hydrogen (CH.sub.2).sub.2OCH.sub.3 Red 22 Hydrogen Cl CH.sub.2COOC.sub.2H.sub.5 CH.sub.2COOC.sub.2H.sub.5 Red-violet 23 Hydrogen Cl (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Bluish red 24 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Red-violet 25 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Bluish red 26 Hydrogen Hydrogen (CH.sub.2).sub.2COO-phenyl Hydrogen Bluish red 27 Hydrogen Hydrogen CH.sub.3 (CH.sub.2).sub.2COO-benzyl Red-violet 28 Hydrogen Hydrogen (CH.sub.2).sub.2CN (CH.sub.2).sub.2COO-benzyl Red-violet 29 Hydrogen Hydrogen (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Bluish red 30 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Red-violet 31 Hydrogen Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Bluish red 32 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl C.sub.2H.sub.5 Red-violet 33 Hydrogen COOH CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Bluish red 34 Hydrogen COOH CH.sub.3 CH.sub.3 Bluish red 35 Hydrogen COOH C.sub.2H.sub.5 (CH.sub.2).sub.2OCO-phenyl Bluish red 36 Hydrogen Hydrogen (CH.sub.2).sub.2OCO-phenyl C.sub.2H.sub.4 Red-violet 37 Hydrogen Hydrogen (CH.sub.2).sub.2OCH.sub.2-(2-furfuryl) C.sub.2H.sub.4 Red-violet 38 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.2-(2-furfuryl) Red-violet 39 Hydrogen Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.3 Bluish red 40 Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Red-violet 41 Hydrogen Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2CO-phenyl Bluish red 42 Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Bluish red 43 Hydrogen Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2OCO-phenyl Bluish red 44 Hydrogen Hydrogen C.sub.2H.sub.4 CH.sub.2-phenyl Red-violet 45 Hydrogen Hydrogen Hydrogen CH.sub.2-phenyl Violet 46 Hydrogen Hydrogen C.sub.2H.sub.4 C.sub.2H.sub.4 Red-violet 47 Hydrogen CH.sub.3 CH.sub.2COOC.sub.2H.sub.5 CH.sub.2COOC.sub.2H.sub.5 Red-violet 48 Hydrogen CH.sub.3 CH.sub.2COOCH.sub.3 Hydrogen Red-violet 49 Hydrogen CH.sub.3 C.sub.2H.sub.4 (CH.sub.2).sub.2OCOCH.sub.3 Red-violet 50 Hydrogen CH.sub.3 (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Red-violet 51 Hydrogen CH.sub.3 Hydrogen CH.sub.2-phenyl Red-violet 52 Hydrogen CH.sub.3 CH.sub.2-phenyl (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Red-violet 53 Hydrogen CH.sub.3 CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Red-violet 54 Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 (CH.sub.2).sub.2OCOCH.sub.3 Red-violet 55 Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 C.sub.2H.sub.4 Red-violet 56 Hydrogen Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Bluish red 57 Hydrogen COOCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Bluish red 58 Hydrogen COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Bluish red 60 Hydrogen COOCH.sub.3 CH.sub.2-phenyl C.sub.2H.sub.5 Bluish red 61 Hydrogen OH C.sub.2H.sub.5 C.sub.2H.sub.5 Violet 62 Hydrogen OH CH.sub.2-phenyl C.sub.2H.sub.5 Violet 63 Hydrogen OH (CH.sub.2).sub.2OC.sub.2H.sub.5 (CH.sub.2).sub.2OC.sub.2H.sub.5 Violet

Examples 64 to 95 of Formula (IIb)

(40) ##STR00025##
can be prepared according the procedure of example 1 or 2
using Intermediate 4 or intermediate 5 as a diazo-component and coupling components of formula (2) with:

(41) TABLE-US-00002 Shade on No: X R.sup.1 R.sup.2 R.sup.3 R.sup.4 polyester 64 Cl Hydrogen Hydrogen CH.sub.3 CH.sub.3 Violet 65 Br Hydrogen Hydrogen CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Violet 66 Br Hydrogen Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 (CH.sub.2).sub.2OC.sub.2H.sub.5 Violet 67 Br Hydrogen Hydrogen CH.sub.2COOCH.sub.3 Hydrogen Red-violet 68 Br Hydrogen Hydrogen CH.sub.2COOC.sub.2H.sub.5 CH.sub.2-phenyl Red-violet 69 Br Hydrogen Hydrogen C.sub.4H.sub.9 CH.sub.2COOC.sub.2H.sub.5 Red-violet 70 Br Hydrogen Hydrogen (CH.sub.2).sub.2COOC.sub.2H.sub.5 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Red-violet 71 Br Hydrogen Hydrogen C.sub.2H.sub.4 (CH.sub.2).sub.2COOCH.sub.3 Violet 72 Cl Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Violet 73 Cl Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Red-violet 74 Br Hydrogen Hydrogen Hydrogen (CH.sub.2).sub.2COO-phenyl Red-violet 75 Br Hydrogen Hydrogen (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Red-violet 76 Br Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Violet 78 Cl Hydrogen Hydrogen CH.sub.2phenyl (CH.sub.2)COOCH.sub.2COCH.sub.3 Red-violet 79 Cl Hydrogen Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Red-violet 80 Br Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 (CH2).sub.2OCOCH.sub.3 Red-violet 81 Br Hydrogen Hydrogen C.sub.2H.sub.4 (CH.sub.2).sub.2OCOCH.sub.3 Violet 82 Cl Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 CH.sub.2-phenyl Violet 83 Cl Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Hydrogen Red-violet 84 Cl Hydrogen CH.sub.3 (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Violet 85 Br Hydrogen CH.sub.3 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Red-violet 86 Br Hydrogen CH.sub.3 (CH.sub.2).sub.2COOC.sub.2H.sub.5 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Red-violet 87 Br Hydrogen CH.sub.3 C.sub.2H.sub.4 (CH.sub.2).sub.2COOCH.sub.3 Violet 88 Br Hydrogen CH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Violet 89 Br Hydrogen CH.sub.3 (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Red-violet 90 Br Hydrogen CH.sub.3 (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Violet 91 Br Hydrogen CH.sub.3 CH(CH.sub.3)CH.sub.2OCOC.sub.2H.sub.5 Hydrogen Red-violet 92 Br Hydrogen Cl CH.sub.2COOCH.sub.3 CH.sub.2COOCH.sub.3 Red-violet 93 Cl Hydrogen COOCH.sub.3 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Hydrogen Red-violet 94 Cl Hydrogen COOH C.sub.3H.sub.7 C.sub.3H.sub.7 Red-violet 95 Cl Hydrogen OH (CH.sub.2).sub.2OC.sub.2H.sub.5 (CH.sub.2).sub.2OC.sub.2H.sub.5 Red-violet

Examples 96 to 202 of Formula (IIc)

(42) ##STR00026##
i. e. structures, wherein R.sup.2 of general structure (II) is NHCOR.sup.5, and wherein the R.sup.5 is alkyl, i. e. R.sup.2 of (II) is NHCO(C.sub.1-C.sub.2)-alkyl and which
can be prepared according the procedure of example 1 or 2
using Intermediate 3 as a diazo-component and coupling components of formula (2a) with:

(43) TABLE-US-00003 Shade on No: R.sup.1 R.sup.3 R.sup.4 R.sup.5 polyester 96 Hydrogen (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 Methyl Violet 97 Hydrogen CH.sub.2COOCH.sub.3 CH.sub.2COOCH.sub.3 Methyl Violet 98 Hydrogen CH.sub.2-phenyl CH.sub.2COOCH.sub.3 Methyl Violet 99 Hydrogen C.sub.2H.sub.4 CH.sub.2COOCH.sub.3 Methyl Violet 100 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Methyl Violet 101 Hydrogen (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Methyl Violet 102 Hydrogen Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 Ethyl Violet 103 Hydrogen (CH.sub.2).sub.2O-phenyl (CH.sub.2).sub.2O-phenyl Methyl Violet 104 Hydrogen C.sub.2H.sub.4 (CH.sub.2).sub.2O-phenyl Methyl Violet 105 Hydrogen (CH.sub.2).sub.2O-benzyl Hydrogen Methyl Violet 106 Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 Hydrogen Methyl Violet 107 Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2CO-phenyl Methyl Violet 108 Hydrogen CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Methyl Violet 109 Hydrogen CH(CH.sub.3)CH.sub.2OCOC.sub.2H.sub.5 C.sub.2H.sub.4 Ethyl Violet 110 Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2OCO-phenyl Methyl Violet 111 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 C.sub.2H.sub.4 Methyl Violet 112 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Methyl Violet 113 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Methyl Violet 114 Hydrogen (CH.sub.2).sub.2COO-phenyl Hydrogen Ethyl Violet 115 Hydrogen Hydrogen CH.sub.2).sub.2COO-benzyl Methyl Violet 116 Hydrogen (CH.sub.2).sub.2OCH.sub.2-(2-furfuryl) C.sub.2H.sub.4 Methyl Violet 117 Hydrogen CH.sub.2COOCH.sub.2-(2-furfuryl) CH.sub.2COOC.sub.2H.sub.5 Ethyl Violet 118 Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.2-(2-furfuryl) Methyl Violet 119 Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.3 Methyl Violet 120 Hydrogen CH(CH.sub.3)CH.sub.2OCH.sub.3 Hydrogen Methyl Violet 121 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl Methyl Violet 122 Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 (CH.sub.2).sub.2OCOCH.sub.3 Methyl Violet 123 Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 CH.sub.2-phenyl Methyl Violet 124 Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Methyl Violet 125 Hydrogen (CH.sub.2).sub.2OCO-phenyl Hydrogen Ethyl Violet 126 Hydrogen (CH.sub.2).sub.2OCO-phenyl C.sub.2H.sub.4 Methyl Violet 127 Hydrogen (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Methyl Violet 128 Hydrogen Hydrogen (CH.sub.2).sub.2CN Ethyl Violet 129 Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Methyl Violet 130 Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Methyl Violet 131 Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Methyl Violet 132 Hydrogen C.sub.2H.sub.4 CH.sub.2-phenyl Methyl Violet 133 Hydrogen Hydrogen CH.sub.2-phenyl Methyl Violet 134 Hydrogen Hydrogen CH.sub.3 Ethyl Violet 135 Hydrogen C.sub.3H.sub.7 C.sub.3H.sub.7 Ethyl Violet 136 Hydrogen CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Methyl Violet 137 Methoxy C.sub.2H.sub.4 CH.sub.2-phenyl Methyl Blue 138 Methoxy Hydrogen CH.sub.2-phenyl Ethyl Blue 139 Methoxy Hydrogen CH.sub.3 Methyl Blue 140 Methoxy C.sub.2H.sub.4 C.sub.2H.sub.4 Methyl Blue 141 Ethoxy CH.sub.2-phenyl CH.sub.2CH?CH.sub.2 Methyl Blue 142 Methoxy CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Methyl Blue 143 Methoxy (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Methyl Blue 144 Methoxy (CH.sub.2).sub.2OC.sub.2H.sub.5 CH.sub.2).sub.2OC.sub.2H.sub.5 Ethyl Blue 145 Ethoxy Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 Methyl Blue 146 Methoxy (CH.sub.2).sub.2O-phenyl (CH.sub.2).sub.2O-phenyl Methyl Blue 147 Methoxy C.sub.2H.sub.4 (CH.sub.2).sub.2O-phenyl Methyl Blue 148 Methoxy Hydrogen (CH.sub.2).sub.2O-phenyl Ethyl Blue 149 Methoxy (CH.sub.2).sub.2O-benzyl (CH.sub.2).sub.2O-benzyl Methyl Blue 150 Ethoxy (CH.sub.2).sub.2O-benzyl CH.sub.3 Ethyl Blue 151 Methoxy (CH.sub.2).sub.2O-benzyl Hydrogen Methyl Blue 152 Methoxy (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 Methyl Blue 153 Ethoxy (CH.sub.2).sub.2O(CH.sub.2).sub.3OC.sub.2H.sub.5 (CH.sub.2).sub.2O(CH.sub.2).sub.3OC.sub.2H.sub.5 Methyl Blue 154 Methoxy CH.sub.2COOCH.sub.3 CH.sub.2COOCH.sub.3 Methyl Blue 155 Methoxy CH.sub.2-phenyl CH.sub.2COOCH.sub.3 Ethyl Blue 156 Methoxy C.sub.2H.sub.4 CH.sub.2COOCH.sub.3 Methyl Blue 157 Methoxy CH.sub.2COOC.sub.2H.sub.5 CH.sub.2COOC.sub.2H.sub.5 Methyl Blue 158 Methoxy (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Methyl Blue 159 Ethoxy (CH.sub.2).sub.2COOC.sub.2H.sub.5 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Blue 160 Methoxy (CH.sub.2).sub.2COOCH.sub.3 C.sub.2H.sub.4 Methyl Blue 161 Methoxy (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Methyl Blue 162 Ethoxy CH.sub.3 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Blue 163 Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Methyl Blue 164 Methoxy (CH.sub.2).sub.2COO-phenyl Hydrogen Ethyl Blue 165 Methoxy (CH.sub.2).sub.2COO-phenyl C.sub.2H.sub.4 Methyl Blue 166 Ethoxy (CH.sub.2).sub.2COO-phenyl (CH.sub.2).sub.2OCH.sub.3 Methyl Blue 167 Methoxy (CH.sub.2).sub.2COO-phenyl CH.sub.2-phenyl Methyl Blue 168 Methoxy Hydrogen (CH.sub.2).sub.2COO-benzyl Methyl Blue 169 Methoxy CH.sub.3 (CH.sub.2).sub.2COO-benzyl Ethyl Blue 170 Methoxy (CH.sub.2).sub.2CN (CH.sub.2).sub.2COO-benzyl Methyl Blue 171 Methoxy (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Methyl Blue 172 Methoxy Hydrogen (CH.sub.2).sub.2CN Ethyl Blue 173 Methoxy (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Methyl Blue 174 Methoxy (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Methyl Blue 175 Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Methyl Blue 176 Methoxy (CH.sub.2).sub.2COOCH.sub.2COC.sub.2H.sub.5 CH.sub.3 Methyl Blue 177 Methoxy (CH.sub.2).sub.2COOCH.sub.2CO-phenyl C.sub.2H.sub.5 Methyl Blue 178 Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl Methyl Blue 179 Ethoxy (CH.sub.2).sub.2COOCH.sub.2CO-benzyl C.sub.2H.sub.5 Methyl Blue 180 Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-benzyl Methyl Blue 181 Methoxy (CH.sub.2).sub.2OCOCH.sub.3 (CH.sub.2).sub.2OCOCH.sub.3 Methyl Blue 182 Methoxy (CH.sub.2).sub.2OCOC.sub.2H.sub.5 (CH.sub.2).sub.2OCOC.sub.2H.sub.5 Methyl Blue 183 Methoxy (CH.sub.2).sub.2OCOCH.sub.3 C.sub.2H.sub.4 Methyl Blue 184 Methoxy (CH.sub.2).sub.2OCOCH.sub.3 CH.sub.2-phenyl Methyl Blue 185 Ethoxy Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Ethyl Blue 186 Methoxy (CH.sub.2).sub.2OCO-phenyl Hydrogen Methyl Blue 187 Methoxy (CH.sub.2).sub.2OCO-phenyl C.sub.2H.sub.4 Methyl Blue 188 Methoxy (CH.sub.2).sub.2OCO-phenyl (CH.sub.2).sub.2OCH.sub.3 Methyl Blue 189 Methoxy (CH.sub.2).sub.2OCH.sub.2-(2-furfuryl) CH.sub.2-phenyl Methyl Blue 190 Methoxy (CH.sub.2).sub.2OCH.sub.2-(2-furfuryl) C.sub.2H.sub.4 Methyl Blue 191 Methoxy (CH.sub.2).sub.2OCH.sub.2-(2-furfuryl) (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Blue 192 Methoxy CH.sub.2COOCH.sub.2-(2-furfuryl) CH.sub.2COOC.sub.2H.sub.5 Methyl Blue 193 Methoxy (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.2-(2-furfuryl) Methyl Blue 194 Methoxy Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.3 Methyl Blue 195 Methoxy CH(CH.sub.3)CH.sub.2OCH.sub.3 Hydrogen Methyl Blue 196 Methoxy Hydrogen CH(CH.sub.3)CH.sub.2OC.sub.2H.sub.5 Methyl Blue 197 Methoxy CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 Hydrogen Methyl Blue 198 Methoxy CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Ethyl Blue 199 Methoxy Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2CO-phenyl Methyl Blue 200 Methoxy CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Methyl Blue 201 Methoxy CH(CH.sub.3)CH.sub.2OCOC.sub.2H.sub.5 C.sub.2H.sub.4 Methyl Blue 202 Methoxy Hydrogen CH(CH.sub.3)CH.sub.2OCO-phenyl Methyl Blue

Examples 203 to 312 of Formula (III)

(44) ##STR00027##
can be prepared according the procedure of example 1 or 2
using Intermediate 4 or Intermediate 5 as a diazo-component and coupling components of formula (2a) with:

(45) TABLE-US-00004 Shade on No: X R.sup.1 R.sup.3 R.sup.4 R.sup.5 polyester 203 Bromo Hydrogen (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 Methyl Blue 204 Chloro Hydrogen CH.sub.2COOCH.sub.3 CH.sub.2COOCH.sub.3 Methyl Reddish blue 205 Bromo Hydrogen C.sub.2H.sub.4 CH(CH.sub.3)COOC.sub.2H.sub.5 Methyl Blue 206 Bromo Hydrogen CH(CH.sub.3)COOCH.sub.3 CH.sub.2COOCH.sub.3 Methyl Reddish blue 207 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Methyl Reddish blue 208 Bromo Hydrogen (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Methyl Blue 209 Chloro Hydrogen Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 Ethyl Blue 210 Chloro Hydrogen (CH.sub.2).sub.2O-phenyl (CH.sub.2).sub.2O-phenyl Methyl Reddish blue 211 Bromo Hydrogen C.sub.2H.sub.4 (CH.sub.2).sub.2O-phenyl Methyl Blue 212 Bromo Hydrogen (CH.sub.2).sub.2O-benzyl Hydrogen Methyl Reddish blue 213 Bromo Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 Hydrogen Methyl Reddish blue 214 Chloro Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2CO-phenyl Methyl Reddish blue 215 Bromo Hydrogen CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Methyl Reddish blue 216 Bromo Hydrogen CH(CH.sub.3)CH.sub.2OCOC.sub.2H.sub.5 C.sub.2H.sub.4 Ethyl Blue 217 Bromo Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2OCO-phenyl Methyl Reddish blue 218 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.3 C.sub.2H.sub.4 Methyl Blue 219 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Methyl Blue 220 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Hydrogen Methyl Reddish blue 221 Chloro Hydrogen (CH.sub.2).sub.2COO-phenyl Hydrogen Ethyl Reddish blue 222 Chloro Hydrogen Hydrogen (CH.sub.2).sub.2COO-benzyl Methyl Blue 223 Bromo Hydrogen (CH.sub.2).sub.2OCH.sub.2(2-furfuryl) C.sub.2H.sub.4 Methyl Blue 224 Bromo Hydrogen CH.sub.2COOCH.sub.2(2-furfuryl) CH.sub.2COOC.sub.2H.sub.5 Ethyl Reddish blue 225 Chloro Hydrogen (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.2(2-furfuryl) Methyl Reddish blue 226 Bromo Hydrogen Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.3 Methyl Blue 227 Bromo Hydrogen CH(CH.sub.3)CH.sub.2OCH.sub.3 Hydrogen Methyl Reddish blue 228 Bromo Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl Methyl Reddish blue 229 Bromo Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 (CH.sub.2).sub.2OCOCH.sub.3 Methyl Reddish blue 230 Bromo Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 CH.sub.2-phenyl Methyl Blue 231 Chloro Hydrogen Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Methyl Blue 232 Bromo Hydrogen (CH.sub.2).sub.2OCO-phenyl Hydrogen Ethyl Reddish blue 234 Bromo Hydrogen (CH.sub.2).sub.2OCO-phenyl C.sub.2H.sub.4 Methyl Blue 235 Bromo Hydrogen (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Methyl Reddish blue 236 Chloro Hydrogen Hydrogen (CH.sub.2).sub.2CN Ethyl Reddish blue 237 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl C.sub.2H.sub.5 Methyl Blue 238 Bromo Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Methyl Blue 239 Bromo Hydrogen Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Methyl Reddish blue 240 Bromo Hydrogen C.sub.2H.sub.4 CH.sub.2-phenyl Methyl Blue 241 Chloro Hydrogen Hydrogen CH.sub.2-phenyl Methyl Reddish blue 242 Bromo Hydrogen Hydrogen CH.sub.3 Ethyl Reddish blue 243 Bromo Hydrogen C.sub.2H.sub.4 C.sub.2H.sub.4 Methyl Blue 244 Bromo Hydrogen CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Methyl Blue 245 Bromo Methoxy C.sub.2H.sub.4 CH.sub.2-phenyl Methyl Greenish blue 246 Bromo Methoxy Hydrogen CH.sub.2-phenyl Ethyl Blue 247 Bromo Methoxy Hydrogen CH.sub.3 Methyl Blue 248 Bromo Methoxy C.sub.2H.sub.4 C.sub.2H.sub.4 Methyl Greenish blue 249 Bromo Ethoxy CH.sub.2-phenyl CH.sub.2CH?CH.sub.2 Methyl Greenish blue 250 Bromo Methoxy CH.sub.2CH?CH.sub.2 CH.sub.2CH?CH.sub.2 Methyl Greenish blue 251 Bromo Methoxy (CH.sub.2).sub.2OCH.sub.3 (CH.sub.2).sub.2OCH.sub.3 Methyl Greenish blue 252 Bromo Methoxy (CH.sub.2).sub.2OC.sub.2H.sub.5 (CH.sub.2).sub.2OC.sub.2H.sub.5 Ethyl Greenish blue 253 Chloro Ethoxy Hydrogen (CH.sub.2).sub.2OC.sub.2H.sub.5 Methyl , Greenish blue 254 Bromo Methoxy (CH.sub.2).sub.2O-phenyl (CH.sub.2).sub.2O-phenyl Methyl Greenish blue 255 Bromo Methoxy C.sub.2H.sub.4 (CH.sub.2).sub.2O-phenyl Methyl Greenish blue 256 Bromo Methoxy Hydrogen (CH.sub.2).sub.2O-phenyl Ethyl Blue 257 Chloro Methoxy (CH.sub.2).sub.2O-benzyl (CH.sub.2).sub.2O-benzyl Methyl Greenish blue 258 Chloro Ethoxy (CH.sub.2).sub.2O-benzyl CH.sub.3 Ethyl Greenish blue 259 Chloro Methoxy (CH.sub.2).sub.2O-benzyl Hydrogen Methyl Blue 260 Bromo Methoxy (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 (CH.sub.2).sub.2O(CH.sub.2).sub.3OCH.sub.3 Methyl Greenish blue 261 Bromo Ethoxy (CH.sub.2).sub.2O(CH.sub.2).sub.3OC.sub.2H.sub.5 (CH.sub.2).sub.2O(CH.sub.2).sub.3OC.sub.2H.sub.5 Methyl Greenish blue 262 Bromo Methoxy CH.sub.2COOCH.sub.3 CH.sub.2COOCH.sub.3 Methyl Blue 263 Bromo Methoxy CH.sub.2-phenyl CH.sub.2COOCH.sub.3 Ethyl Greenish blue 264 Bromo Methoxy C.sub.2H.sub.4 CH.sub.2COOCH.sub.3 Methyl Greenish blue 265 Chloro Methoxy CH.sub.2COOC.sub.2H.sub.5 CH.sub.2COOC.sub.2H.sub.5 Methyl Blue 266 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.3 Methyl Blue 267 Chloro Ethoxy (CH.sub.2).sub.2COOC.sub.2H.sub.5 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Blue 268 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.3 C.sub.2H.sub.4 Methyl Greenish blue 269 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.3 CH.sub.2-phenyl Methyl Greenish blue 270 Bromo Ethoxy CH.sub.3 (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Greenish blue 271 Chloro Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.3 Methyl Blue 272 Bromo Methoxy (CH.sub.2).sub.2COO-phenyl Hydrogen Ethyl Blue 273 Bromo Methoxy (CH.sub.2).sub.2COO-phenyl C.sub.2H.sub.4 Methyl Greenish blue 274 Bromo Ethoxy (CH.sub.2).sub.2COO-phenyl (CH.sub.2).sub.2OCH.sub.3 Methyl Greenish blue 275 Chloro Methoxy (CH.sub.2).sub.2COO-phenyl CH.sub.2-phenyl Methyl Greenish blue 276 Chloro Methoxy Hydrogen (CH.sub.2).sub.2COO-benzyl Methyl Blue 278 Chloro Methoxy CH.sub.3 (CH.sub.2).sub.2COO-benzyl Ethyl Greenish blue 279 Chloro Methoxy (CH.sub.2).sub.2CN (CH.sub.2).sub.2COO-benzyl Methyl Blue 280 Bromo Methoxy (CH.sub.2).sub.2CN (CH.sub.2).sub.2CN Methyl Blue 281 Chloro Methoxy Hydrogen (CH.sub.2).sub.2CN Ethyl Blue 282 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 C.sub.2H.sub.5 Methyl Greenish blue 283 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Methyl Greenish blue 284 Bromo Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2COCH.sub.3 Methyl Blue 285 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.2COC.sub.2H.sub.5 CH.sub.3 Methyl Greenish blue 286 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.2CO-phenyl C.sub.2H.sub.5 Methyl Greenish blue 287 Bromo Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-phenyl Methyl Blue 288 Bromo Ethoxy (CH.sub.2).sub.2COOCH.sub.2CO-benzyl C.sub.2H.sub.5 Methyl Greenish blue 289 Chloro Methoxy Hydrogen (CH.sub.2).sub.2COOCH.sub.2CO-benzyl Methyl Blue 290 Bromo Methoxy (CH.sub.2).sub.2OCOCH.sub.3 (CH.sub.2).sub.2OCOCH.sub.3 Methyl Blue 291 Chloro Methoxy (CH.sub.2).sub.2OCOC.sub.2H.sub.5 (CH.sub.2).sub.2OCOC.sub.2H.sub.5 Methyl Blue 292 Bromo Methoxy (CH.sub.2).sub.2OCOCH.sub.3 C.sub.2H.sub.4 Methyl Greenish blue 293 Bromo Methoxy (CH.sub.2).sub.2OCOCH.sub.3 CH.sub.2-phenyl Methyl Greenish blue 294 Bromo Ethoxy Hydrogen (CH.sub.2).sub.2OCOCH.sub.3 Ethyl Blue 295 Bromo Methoxy (CH.sub.2).sub.2OCO-phenyl Hydrogen Methyl Blue 296 Bromo Methoxy (CH.sub.2).sub.2OCO-phenyl C.sub.2H.sub.4 Methyl Greenish blue 297 Chloro Methoxy (CH.sub.2).sub.2OCO-phenyl (CH.sub.2).sub.2OCH.sub.3 Methyl Greenish blue 298 Bromo Methoxy (CH.sub.2).sub.2OCH.sub.2(2-furfuryl) CH.sub.2-phenyl Methyl Greenish blue 299 Bromo Methoxy (CH.sub.2).sub.2OCH.sub.2(2-furfuryl) C.sub.2H.sub.4 Methyl Greenish blue 300 Bromo Methoxy (CH.sub.2).sub.2OCH.sub.2(2-furfuryl) (CH.sub.2).sub.2COOC.sub.2H.sub.5 Methyl Greenish blue 301 Bromo Methoxy CH.sub.2COOCH.sub.2(2-furfuryl) CH.sub.2COOC.sub.2H.sub.5 Methyl Blue 302 Bromo Methoxy (CH.sub.2).sub.2COOCH.sub.3 (CH.sub.2).sub.2COOCH.sub.2(2-furfuryl) Methyl Blue 303 Bromo Methoxy Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.3 Methyl Blue 304 Chloro Methoxy CH(CH.sub.3)CH.sub.2OCH.sub.3 Hydrogen Methyl Blue 305 Chloro Methoxy Hydrogen CH(CH.sub.3)CH.sub.2OC.sub.2H.sub.5 Methyl Blue 306 Chloro Methoxy CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 Hydrogen Methyl Blue 307 Bromo Methoxy CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 CH.sub.2-phenyl Ethyl Greenish blue 308 Bromo Methoxy Hydrogen CH(CH.sub.3)CH.sub.2COOCH.sub.2CO-phenyl Methyl Blue 309 Bromo Methoxy CH(CH.sub.3)CH.sub.2OCOCH.sub.3 Hydrogen Methyl Blue 310 Bromo Methoxy CH(CH.sub.3)CH.sub.2OCOC.sub.2H.sub.5 C.sub.2H.sub.4 Methyl Greenish blue 311 Bromo Methoxy Hydrogen CH(CH.sub.3)CH.sub.2OCO-phenyl Methyl Blue 312 Bromo Methoxy CH(CH.sub.3)CH.sub.2COOCH.sub.2COCH.sub.3 Hydrogen Methyl Blue