FLUORECENT REACTIVE DYES, PROCESS FOR THE PRODUCTION THEREOF AND THEIR USE

Abstract

The present invention is directed to fluorescent reactive dyes of general formula (I)

##STR00001##

a process for the production thereof and their use.

Claims

1. A dye of formula (I) ##STR00148## wherein in each case independent from each other W is O, S or NH, R.sup.1 and R.sup.2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C.sub.1-C.sub.4)-alkanoyl, (C.sub.1-C.sub.4)-alkoxy and (C.sub.1-C.sub.4)-alkyl or benzyl, R.sup.3 and R.sup.4 is hydrogen, alkyl, hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, N-cinnamoylamino, halogen, cyano, SO.sub.3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy or SO.sub.2X, wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions, Z.sup. is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate, A.sup.1 and A.sup.2 is a spacer of formula (2c) or (2d) ##STR00149## whereby the respective spacer A.sup.1/A.sup.2 is attached to the chromophore at the * position and to the respective reactive anchor T.sup.1/T.sup.2 at the ** position, and wherein d is an integer from 1 to 4, e is an integer from 0 to 3, f is an integer from 0 to 3, g is an integer from 0 to 3, Q is O, NH or S, R.sup.6 is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, alkoxycarbonyl, acyl, arylol, acyloxy, aryloyloxy, cycloalkyl, aryl, SO.sub.3M or COOM, R.sup.8 and R.sup.9 is hydrogen, alkyl, alkoxy, aryl, hydroxyl, NHCH.sub.2CH.sub.2OSO.sub.3H, SO.sub.3M or COOM, T.sup.1 and T.sup.2 is a reactive anchor of formula (3d), (3e) or SO.sub.2X ##STR00150## whereby the respective reactive anchor T.sup.1/T.sup.2 is attached to the respective spacer A.sup.1/A.sup.2 at the *** position, and wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions, and M is hydrogen, lithium, sodium, potassium, ammonium, mono-, di-, tri- or tetra-(C.sub.1-C.sub.4)-alkylammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

2. The dye according to claim 1, wherein in each case independent from each other W is O or S, R.sup.1 and R.sup.2 is hydrogen, alkyl, alkyl substituted by one or more substituents selected from the group consisting of methoxy, hydroxy, sulfato, sulfo and chloro, aryl, aryl substituted by one or more substituents selected from the group consisting of chloro, acetylamino, sulfo, hydroxy, carboxy, (C.sub.1-C.sub.2)-alkanoyl, (C.sub.1-C.sub.2)-alkoxy and (C.sub.1-C.sub.2)-alkyl or benzyl, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.4)-alkyl, hydroxy, aryl, (C.sub.1-C.sub.4)-alkoxy, N-acylamino, halogen, SO.sub.3M, COOM, acyl, (C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-alkoxycarbonyl or SO.sub.2X, wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions, Z.sup. is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate, A.sup.1 and A.sup.2 is a spacer of formula (2c) or (2d) ##STR00151## whereby the respective spacer A.sup.1/A.sup.2 is attached to the chromophore at the * position and to the respective reactive anchor T.sup.1/T.sup.2 at the ** position, and wherein d is 1 or 2, e is 0 or 1, f is 0, g is 0 or 1, Q is O or S, R.sup.6 is hydrogen, (C.sub.1-C.sub.4)-alkyl, N-acylamino, (C.sub.1-C.sub.4)-alkoxy, acyl, benzyl, SO.sub.3M or COOM, R.sup.8 and R.sup.9 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, SO.sub.3M or COOM, T.sup.1 and T.sup.2 is SO.sub.2X, wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions and M is hydrogen, lithium, sodium, potassium, one equivalent of an alkali earth metal or a monovalent organic cation.

3. The dye according to claim 1, wherein in each case independent from each other W is oxygen, R.sup.1 and R.sup.2 is hydrogen, (C.sub.1-C.sub.4)-alkyl, aryl, or benzyl, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, halogen, SO.sub.3M, COOM or SO.sub.2X, wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions, Z.sup. is selected from the group consisting of halogen, sulfate, alkylsulfonate, benzolsulfonate, toluolsulfonate, tetraborofluorate and acetate, A.sup.1 and A.sup.2 is a spacer of formula (2c-1) or (2d-1) ##STR00152## whereby the respective spacer A.sup.1/A.sup.2 is attached to the chromophore at the * position and to the respective reactive anchor T.sup.1/T.sup.2 at the ** position, and wherein d is 1 or 2, e is 0 or 1, g is 0 or 1, Q is oxygen, R.sup.6 is hydrogen or (C.sub.1-C.sub.2)-alkyl, R.sup.8 and R.sup.9 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkoxy or SO.sub.3M, T.sup.1 and T.sup.2 is SO.sub.2X, wherein X is vinyl or CH.sub.2CH.sub.2Y, wherein Y is a group removable under alkaline conditions and M is hydrogen, lithium, sodium, potassium, one equivalent of an alkali earth metal or a monovalent organic cation.

4. A process for the production of dyes according to claim 1 comprising the steps of: a) Reacting one 3,6,9 substituted 9H-Xanthene, wherein the 3- and 6-substituents react as a leaving group, with two precursor-amines HNR.sup.1-A.sup.1-T.sup.1 and HNR.sup.2-A.sup.2-T.sup.2 of identical or different spacer-reactive-anchor-units on 3- and 6-position, and b) Sulfonating the OH-groups with concentrated sulfuric acid.

5. The process for the production of dyes according to claim 1 comprising the steps of: reacting one 3,6,9 substituted 9H-Xanthene, wherein the 3- and 6-substituents react as a leaving group, with a) two identical aliphatic-, aromatic- or mixed aliphatic/aromatic-amines symmetrically on both 3- and 6-position, or b) one aliphatic-, aromatic- or mixed aliphatic/aromatic-amine for the 3-position in a first step and one aliphatic-, aromatic- or mixed aliphatic/aromatic-amine, which is different to the first one, for the 6-position in a second step or c) one aliphatic-, aromatic- or mixed aliphatic/aromatic-amine for the 6-position in a first step and one aliphatic-, aromatic- or mixed aliphatic/aromatic-amine, which is different to the first one, for the 3-position in a second step and further reacting the products resulting from a), b) and c) respectively with reactive anchor groups.

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

7. An aqueous solution for dying comprising one or more chemical compounds according to claim 1.

8. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim 1.

9. An ink digital textile printing, comprising the dye according to claim 1.

10. A process for dying fibers which comprising contact the fibre or blends of the fibres 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 and 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.

11. Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and 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 comprising one or more dye(s) according to claim 1, either in chemically and/or physically bound form.

12. A process for dying fibers which comprising contact the fibre or blends of the fibres with the chemical composition according to claim 6 wherein the fibres are selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and 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.

13. A process for dying fibers which comprising contact the fibre or blends of the fibres with the aqueous solution according to claim 7 wherein the fibres are selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and 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.

Description

EXAMPLE 1

[0141] 50 parts of 2-sulfobenzoic acid anhydride were added to 246 parts of POCl.sub.3 under stirring. After 30 minutes 58 parts of resorcinol (3-hydroxy-phenol) were added and the mixture was heated to 95 C. and stirred for 2 hours. The reaction mixture was cooled down to 5 C. and added to 3000 parts of a 5 C. cold 20% ic aqueous NaCl solution. The suspension was stirred for 30 minutes at 0 to 5 C. and filtrated. The isolated wet press paste was suspended in 200 parts of acetone and stirred for 20 minutes at 5 C. After filtration and drying 27 parts of dichloro-sulfophenyl-xanthen were isolated.

##STR00010##

[0142] 1. Condensation: 10.13 parts of dichloro-sulfophenyl-xanthen were mixed together with 5.73 parts of n-ethyl-3 (-hydroxyethy)sulfonyl anilin/(2-(3-ethylamino-benzenesulfonyl)-ethanol) as amine 1 in 100 ml of water and the pH was adjusted to 5.0. The reaction mixture was heated to 60 C. and stirred and the pH was kept at 5.0 with a 15% ic Na.sub.2CO.sub.3 solution.

[0143] 2. Condensation: After 1 hour 4.9 parts of 2-(2-methylamino-ethanesulfonyl)-ethanol as amine 2 were added and the pH was adjusted to 9.0 and the reaction mixture was heated to 90 C. and stirred for 3 hours.

[0144] The reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 20.5 parts of Intermediate 1 after drying under vacuum conditions.

##STR00011##

[0145] Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110 parts sulfuric acid (98 to 100%) at 20 to 60 C. The reaction mixture was stirred for 3 h at 60 C. and then cooled to 0 to 5 C. This mixture was added to 300 parts of ice at 0 C., the pH was adjusted with CaCO.sub.3 to 5.3. The CaSO.sub.4 was filtered and the product in the filtrated solution was isolated by vacuum rotary evaporation and dried under vacuum conditions resulting in 16 parts of example 1 that dyes cotton in brilliant fluorescent red shades.

##STR00012##

Example 1

EXAMPLE 2

[0146] 1. Condensation: 10.13 parts of Dichloro-sulfophenyl-xanthen were mixed together with 5.73 parts of n-ethyl-3 (-hydroxyethy)sulfonyl anilin 2-(3-ethylamino-benzenesulfonyl)-ethanol as amine 1 in 100 ml of water and the pH was adjusted to 5.0. The reaction mixture was heated to 60 C. and stirred and the pH was kept at 5.0 with a 15% ic Na.sub.2CO.sub.3 solution.

[0147] 2. Condensation: After 1 hour 4.9 parts 2-(2-chloro-ethanesulfonyl)-ethylamine as amine 2 were added and the pH was adjusted to 9.0 and the reaction mixture was heated to 90 C. and stirred for 3 hours.

[0148] The reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 20.5 parts of Intermediate 1 after drying under vacuum conditions.

##STR00013##

[0149] Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110 parts sulfuric acid (98 to 100%) at 20 to 60 C. The reaction mixture was stirred for 3 h at 60 C. and then cooled to 0 to 5 C. This mixture was added to 300 parts of ice at 0 C., the pH was adjusted with CaCO.sub.3 to 5.3. The CaSO.sub.4 was filtered and the product in the filtrated solution was isolated by vacuum rotary evaporation and dried under vacuum conditions resulting in 16 parts of example 1 that dyes cotton in brilliant fluorescent red shades.

##STR00014##

Example 2

EXAMPLE 3 TO 39

[0150] According to example 1 or 2 the following amines can be used for 1. Condensation (Amine 1) and for 2. Condensation (Amine 2). After sulfonation and isolation according to example 1 or 2 dyes having the given colours are obtained when using amines 1 and 2 as indicated.

TABLE-US-00001 Shade Exam- on Amine 1 Amine 2 ple cotton [00015] [00016] 3 Red [00017] [00018] 4 Red [00019] [00020] 5 Red [00021] [00022] 6 Red [00023] [00024] 7 Red [00025] [00026] 8 Red [00027] [00028] 9 Red [00029] [00030] 10 Red [00031] [00032] 11 Bluish red [00033] [00034] 12 Bluish red [00035] [00036] 13 Bluish red [00037] [00038] 14 Bluish red [00039] [00040] 15 Bluish red [00041] [00042] 16 Bluish red [00043] [00044] 17 Bluish red [00045] [00046] 18 Bluish red [00047] [00048] 19 Bluish red [00049] [00050] 20 Bluish red [00051] [00052] 21 Bluish red [00053] [00054] 22 Bluish red [00055] [00056] 23 Bluish red [00057] [00058] 24 Red [00059] [00060] 25 Red [00061] [00062] 26 Red [00063] [00064] 27 Red [00065] [00066] 28 Violet [00067] [00068] 29 Violet [00069] [00070] 30 Violet [00071] [00072] 31 Violet [00073] [00074] 32 Violet [00075] [00076] 33 Violet [00077] [00078] 34 Violet [00079] [00080] 35 Violet [00081] [00082] 36 Violet [00083] [00084] 37 Violet [00085] [00086] 38 Violet [00087] [00088] 39 Violet

EXAMPLE 40

[0151] 1. Condensation: 10.13 parts of dichloro-sulfophenyl-xanthen were mixed together with 4.22 parts of 2-(2-chloro-ethanesulfonyl)-ethylamine as amine 1 in 100 ml of water and the pH was adjusted to 5.0. The reaction mixture was heated to 60 C. and stirred and the pH was kept at 5.0 with a 15% ic Na.sub.2CO.sub.3 solution.

[0152] 2. Condensation: After 1 hour 4.9 parts 2-(2-methylamino-ethanesulfonyl)-ethanol as amine 2 were added and the pH was adjusted to 9.0 and the reaction mixture was heated to 90 C. and stirred for 3 hours.

[0153] The reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 19.3 parts of Intermediate 1 after drying under vacuum conditions.

##STR00089##

[0154] Sulfonation: 17.52 parts of Intermediate 1 were added in portions to 110 parts sulfuric acid (98 to 100%) at 20 to 60 C. the reaction mixture was stirred for 3 h at 60 C. and then cooled to 0 to 5 C. This mixture was added to 300 parts of ice at 0 C., the pH was adjusted with CaCO.sub.3 to 5.3. The CaSO.sub.4 was filtered and the product in the filtrated solution was isolated by vacuum rotary evaporation and dried under vacuum conditions resulting in 16 parts of example 1 that dyes cotton in brilliant fluorescent red shades.

##STR00090##

Example 40

EXAMPLE 41 TO 43

[0155] According to example 40 and example 2 the following amines can be used for 1. Condensation (Amine 1) and for 2. Condensation (Amine 2), after sulfonation and isolation according to example 1 or 2 dyes having the given colours are obtained when using amines 1 and 2 as indicated.

TABLE-US-00002 Shade on Amine 1 Amine 2 Expl. cotton [00091] [00092] 41 Bluish red [00093] [00094] 42 Bluish red [00095] [00096] 43 Bluish red

EXAMPLE 44

[0156] 32.2 parts of phthalic anhydid were added to 246 parts of POCl.sub.3 under stirring. After 30 minutes 58 parts of Resorcinol (3-Hydroxy-phenol) were added and the mixture was heated to 95 C. and stirred for 2 hours. The reaction mixture was cooled down to 5 C. and added to 3000 parts of a 5 C. cold 20% ic aqueous NaCl solution. The suspension was stirred for 30 minutes at 0 to 5 C. and filtrated. The isolated wet press paste was suspended in 200 parts of acetone and stirred for 20 minutes at 5 C. After filtration and drying 24.6 parts of dichloro-carboxyphenyl-xanthen were isolated.

##STR00097##

[0157] 1. Condensation: 9.5 parts of dichloro-carboxyphenyl-xanthen were mixed together with 5.73 parts of n-ethyl-3 (-hydroyethy)sulfonyl anilin/(2-(3-ethylamino-benzenesulfonyl)ethanol) in 100 ml of water and the pH was adjusted to 5.0. The reaction mixture was heated to 60 C. and stirred and the pH was kept at 5.0 with a 15% ic Na.sub.2CO.sub.3 solution.

[0158] 2. Condensation: After 1 hour 4.9 parts of 2-(2-methylamino-ethanesulfonyl)-ethan were added and the pH was adjusted to 9.0 and the reaction mixture was heated to 90 C. and stirred for 3 hours.

[0159] The reaction mix was cooled to room temperature and the water was evaporated under reduced pressure delivering 19.8 parts of Intermediate 1 after drying under vacuum conditions.

##STR00098##

[0160] Sulfonation: 16.1 parts of Intermediate 1 were added in portions to 90 parts sulfuric acid (98 to 100%) at 20 to 60 C. The reaction mixture was stirred for 3 h at 60 C. and then cooled to 0 to 5 C. This mixture was added to 250 parts of ice at 0 C., the pH was adjusted with CaCO.sub.3 to 5.3. The CaSO.sub.4 was filtered and the product in the filtrated solution was isolated by vacuum rotary evaporation and dried under vacuum conditions resulting in 14.9 parts of example 1 that dyes cotton in brilliant fluorescent red shades.

##STR00099##

Example 44

EXAMPLES 45 TO 68

[0161] According to example 44 the following amines can be used for the first condensation (Amine 1) and for the second condensation (Amine 2). After sulfonation and isolation according to example 44 dyes having the given colours are obtained when using amines 1 and 2 as indicated.

TABLE-US-00003 Shade on Amine 1 Amine 2 Expl. cotton [00100] [00101] 45 Red [00102] [00103] 46 Red [00104] [00105] 47 Red [00106] [00107] 48 Red [00108] [00109] 49 Red [00110] [00111] 50 Red [00112] [00113] 51 Bluish red [00114] [00115] 52 Bluish red [00116] [00117] 53 Bluish red [00118] [00119] 54 Bluish red [00120] [00121] 55 Bluish red [00122] [00123] 56 Bluish red [00124] [00125] 57 Bluish red [00126] [00127] 58 Bluish red [00128] [00129] 59 Red [00130] [00131] 60 Red [00132] [00133] 61 Red [00134] [00135] 62 Red [00136] [00137] 63 Violet [00138] [00139] 64 Violet [00140] [00141] 65 Violet [00142] [00143] 66 Bluish red [00144] [00145] 67 Bluish red [00146] [00147] 68 Bluish red

DYEING EXAMPLE 1

[0162] 3 parts of the dye from example 1 of this invention and 60 parts of sodium chloride were dissolved in 1000 parts of water and 12 parts of sodium carbonate and 0.5 parts of a wetting agent were added. This dyebath was entered with 100 parts of bleached cotton knitted fabric. The temperature of the dye bath was raised to 30 C. at a gradient of 0.5 C./minute and held at this temperature for 30 minutes and then increased over 30 minutes to 60 C., this temperature being maintained for a further 60 minutes. Thereafter the dyed goods were initially rinsed with tapwater for 5 minutes. The dyed goods were neutralized at 50 C. using 60% strength acetic acid for 30 to 40 minutes. The goods were rinsed with boiling tapwater for 30 to 40 minutes followed by a final rinse at 40 to 50 C. for 20 minutes and dried.

[0163] The very brilliant fluorescent bluish red dyeing obtained has good overall fastness properties.