Title of Invention

A PROCESS FOR THE PREPARATION OF A REACTIVE DYE

Abstract The present invention relates to a process for the preparation of a reactive dye of the formula I wherein n is 1 or 2, R 1 is hydrogen or hydroxyl, D is, when n is 1, is a mdical of the formula or, when n is 2, is a radical of the formula wherein ring A can be benzo-fused, R2,R3 and R4 are each, independently of one another, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or an anchor from the aliphatic series, Y is vinyl or a radical of the formula C2~-Q where Q is a group which can be eliminated under alkaline conditions, and T is a linker, with the proviso that, when n is 1, R I is hydroxyl and R2, R3 and R4 are each hydrogen, E is neither hydrogen nor a radical of the formula 802- Y, Wl-802- Y or CONX-Wl-80z- Y where Y has in each case the above mentioned meaning, and WI is in each case CI-C4-alkylene and X is hydrogen or CI-C4-alkyl, which process comprising diazotizing an aniline of the formula lIa by a method known per se or tetrazotizing an aniline of the formula lIb by a method per se wherein ring A, R2, R3, R4, E, Y and T each have the above mentioned meanings, are diazotized or tetrazotized by a method known per se and coupling with an aminonaphthalene of the formula III wherein R I has the above mentioned meanings in each case.
Full Text



The present invention relates to reactive dye^ of the for-nula I

where ring A can be benzo-fused, R^, R3 and R'* are each, inde¬pendently of one another, hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or an anchor radical from the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q where Q is a group which can be eliminated under alkaline conditions, and T is a linker,
ith the proviso that, when n is 1, R^ is hydroxyl and R^, R3 and K* are each hydrogen, E is neither hydrogen nor a radical of the formula SO2-Y, WI-SO2-Y or CONX-WI-SO2-Y where Y has in each case

the abovementioned meanings, and W^ is in each case Ci-C4-alk.ylene and X is hydrogen or Ci-C4-alk:yl,
and to the use thereof for dyeing or printing organic substrates j having hydroxyl groups or nitrogen atoms.
EP-A 637 615 discloses dyes which have a similar structure to those of the formula I (n = 1, Ri = hydroxyl). However, the dyes described therein differ in the substitution pattern in the diazo i component.
Earlier German Patent Application P 44 34 989.0 relates, inter alia, to reactive dyes with a coupling component from the 3-hydroxysulfonylnaphthalene series which have a substituted ami-• no group in ring position 7 and may additionally have a hydroxyl and sulfo group.
It is an object of the present invention to provide novel reac¬tive dyes derived from phenyl- or naphthaleneazonaphthalene dyes. The intention is that the novel dyes be distinguished by an ad¬vantageous profile of use properties.
We have found that this object is achieved by the reactive dyes of the formula I defined at the outset.
The novel reactive dyes of the formula I are in each case indi¬cated in the form of the free acid.
Suitable cations are derived from metal or ammonium ions. Metal ions are, in particular, lithium, sodium or potassium ions. Ammoni^uin ions mean, for the purpose of the invention, unsubsti-tuted or substituted ammonium cations. Examples of substituted ammonium cations are monoallcyl-, dialkyl-, trialkyl-, tetraalkyl-or benzylrrialkylammonium cations or cations derived from nitrogen-containing 5- or 6-membered saturated heterocycles such as pyrrclidini'um, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. In this connection, alkyl generally means straight-chain or branched Ci-C2o-alkyl which may be substituted by hydroxyl groups and/or interrupted by oxygen atoms in ether func¬tionality.
All the alkyl and alkylene radicals occurring in the present ap¬plication may be either straight-chain or branched.

When substituted alkyl groups occur in the present application, as a rule they have 1 or 2 substituents,
When substituted phenylene groups occur in the present applica¬tion, possibly suitable substituents are, unless otherwise indi¬cated, for example Ci-C4-alkyl, Ci-C4-alkoxy, halogen, hydroxy-sulfonyl, sulfamoyl or Ci-C4-mono- or dialkylsulfamoyl. As a rule, they then have from 1 to 3, preferably 1 or 2, substituents.
Examples of R2 , R3 and R" radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
The radical Q is a group which can be eliminated under alkaline conditions. Examples of such groups are chlorine, bromine, Ci-C4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, 0P(0)(0H)2, Cj-C4-alkylsulfonyloxy, unsubstituted or substituted phenylsulfonyloxy, Ci-C4-alkanoyloxy, Ci-C4-dialkylamino or a radical of the formula

where L^, L^ and L^ are each, independently of one another, Ci-C4-alkyl or benzyl and An® is in each case one equivalent of an anion. Examples of suitable anions in this connection are fluoride, chloride, bromide, iodide, mono-, di- or trichloro-acetate, methanesulfonate, benzenesulfonate or 2- or 4-methyl-benzenesulfonate.
The radicals E within a molecule can be identical or different. Anchor radicals E are those which react by displacement or addi¬tion with the hydroxyl groups or nitrogen-containing groups on the substrates to be treated. Moreover, C2H4-Q reacts to give vinyl under the alkaline reaction conditions.
Reaction by displacement of the anchor radical with the relevant groups in the substrates, eg. with the hydroxyl groups on cellu¬lose, means that the leaving groups or atoms (eg. fluorine or chlorine) in the anchor radical are displaced by the hydroxyl groups of the cellulose as shown in the following diagram:


Reaction by addition of the anchor radical with the relevant groups in the substrates, eg. with hydroxyl groups on cellulose, means that the hydroxyl groups of the cellulose add on to the an¬chor radical as shown in the following diagram:

Exau-iples of heterocyclic anchor radicals E are halogen-substi¬tuted radicals of 1,3,5-triazine, quinoxaline, phthalazine, pyrimidine or pyridazine, or the 2-alkylsulfonylbenzothiazole radical.
The following heterocyclic radicals rr^.ay be mentioned by way of example.




where
X is hydrogen or Ci-C4-alkyl,
Sal is fluorine or chlorine,
J^ is hydrogen or nitro and
J2 and U^ are each, independently of one another, hydrogen,
Ci-Cg-alkyl which is unsubstituted or substituted by hydroxyl, halogen, cyano, hydroxysulfonyl or a radical of the formula -SO2-Y where Y has the abovementioned meanings, and can be interrupted in each case by 1 or 2 oxygen atoms in ether functionality, imino or Ci-C4-alkylimino groups, or U^ and U^ are, together with the nitrogen atom connecting them, pyrro-lidinyl, piperidinyl, morpholinyl, piperazinyl or N-{Ci-C4-alkyl)pipera2inyl or U^ is also a radical of the formula

where the rings B and K can each be substituted once or twice by hydroxysulfonyl and can be benzp-fused, and ring K can, indepen-
I dently thereof, be substituted once or twice by chlorine, nitro, Cx-C^-alkyl, Ci-C4-alkoxy, cyano, carboxyl, acetylamino, hydroxy-sulfonylmethyl or a radical of the formula CH2-SO2-Y, SO2-Y, NH-CO-Y or NU2-CO-NU2-Z-S02-Y where Y and U^ each have the abovementioned meanings, and Z is C2-C6-alkylene which is
' unsubstituted or substituted by hydroxyl, chlorine, cyano, carboxyl, Ci-C4-alkoxycarbonyl, Ci-C4-alkanoyloxy or sulfate and can be interrupted by in each case 1 or 2 oxygen atoms in ether functionality or imino or Ci-C4-alkylimino groups.
I Examples of anchor radicals E from the aliphatic series are acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tribromoacryloyl, -CO-CCl=CH-COOH, -C0-CH=CC1-C00H, 2-chloropropionyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl,
' 2-sulfatoethylaminosulfonyl, 2-chloro-2,3,3-trifluorocyclobutylcarbonyl, 2,2,3,3-tetrafluorocyclobutylcarbonyl, 2,2,3,3-tetrafluoro-

cyclobutylsulfonyl, 2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or -arylsulfonylacryloyl such as 1- or 2-methylsulfonylacryloyl, or a radical of the formula S02-y, WI-SO2-Y, CONX-W2-S02~Y or NXCONX-W2-S02-Y where X and Y each have the abovementioned meanings, W^ is Ci-C4-alkylene and W^ is Ci-C4-alkylene or unsubstituted or substituted phenylene.
Examples of W^ and W^ radicals are CH2, (CH2)2, (CH2)3, (CH2)4, CH(CH3)CH2 or CH(CH3)CH(CH3).
Further examples of W^ radicals are 1,2-, 1,3- or 1,4-phenylene.
T in formula I is a linker. Suitable linkers obey, for example, the formula


Further preferred reactive dyes of the formula I are those where R2, R3 and R4 are each hydrogen.
Further preferred reactive dyes of the formula I are those where E is hydrogen, an anchor radical from the 1,3,S-triazine series or a radical of the formula SO2-Y where Y has the abovementioned meanings.
Further preferred reactive dyes of the formula I are those where, when n is 2, T is a radical of the formula CO or SO2.
Further preferred reactive dyes of the formula I are those where n is 1.
Further preferred reactive dyes of the formula I are those where ring A is not benzo-fused.
Particularly preferred reactive dyes of the formula I are those where E is hydrogen or a radical of the formula SO2-Y where Y has the abovementioned meanings.
Further particularly preferred reactive dyes of the formula I are those where the radical of the formula SO2-Y is in the position ortho to the azo group.
Further particularly preferred reactive dyes are those of the formula la

where R^ and R^ are each, independently of one another, hydrogen or hydroxysulfonyl, and E and Y each have the abovementioned meanings.
Particularly interesting reactive dyes are those of the formula
la where E is hydrogen or a radical of the formula SO2-Y, with hy¬
drogen being particularly important, and R^ and R^ are each hy¬
droxysulf onyl. ^

The novel reactive dyes of the rormuxa I can be obtained by con¬ventional methods.
For example, an aniline of the formula IIa or IIb

where R1 has the abovementioned meanings in each case.
The anilines of the formula IIb can be obtained by conventional methods, for example as described in the earlier German Patent Application P 195 08 311.3.
The novel reactive dyes of the formula I are advantageously suit¬able for the dyeing or printing of organic substrates having hy-droxyl groups or nitrogen atoms. Examples of substrates of this type are leather or fiber material which predominantly contains natural or synthetic polyamides or natural or regenerated cellu¬lose. The novel dyes are preferably suitable for dyeing and printing textile material based on wool or, in particular, cotton. Dyeings in red hues are obtained.
Dyeings in particular on cellulose-based substrates have intense colors and very high.fixation yields and display very good light fastness and excellent wet fastness properties such as fastness

to washing, chlorine bleaches, peroxide bleaches, alkalis, sea water or sweat.
Accordingly the present invention provides a process for the preparation of a reactive dye of the formula I

wherein ring A can be benzo-fused, R2,R3 and R4 are each, independently of one another, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen or

hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or an anchor from the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q where Q is a group which can be eliminated under alkaline conditions, and T is a linker, with the proviso that when n is 1, R1 is hydroxy and R2, R3 and R4 are each hydrogen, E is neither hydrogen nor a radical of the formula SO2-Y, W'-S02-Y or C0NX-W'-S02-Y where Y has in each case the above mentioned meaning, and W1 is in each case C1-C4-alkylene and X is hydrogen or C1-C4-alkyl, which process comprising diazotizing an aniline of the formula IIa by a method known per se or tetrazotizing an aniline of the formula IIb by a method per se


The following examples are intended to explain the invention in detail.
Example 1
33.1 g of 3-(2-sulfatoethylsulfonyl)aniline-4,6-disulfonic acid were stirred in 100 ml of ice-water, 10 ml of 10 N hydrochloric acid were added and, while stirring at 0-5°C, diazotization was carried out by dropwise addition of 15 ml of 23 % by weight aqueous sodium nitrite solution. After stirring at 0-5°C for 2 h, the small excess of free nitrous acid was decomposed by adding sulfamic acid, and the diazoniiom salt solution was maintained at 0-5°C until the coupling.
16.9 g of l-hydroxy-7-aminonaphthalene-3,6-disulfonic acid were stirred in 100 ml of ice-water. The diazonium salt solution was added dropwise to this solution while keeping the pH at 2.5-3 with sodium acetate. After the reaction was complete, the mixture was allowed to warm to room temperature and then the pH was ad¬justed to 4.5-5 using sodium bicarbonate. 50 g of sodium chloride were then added to the solution, which was then stirred for 4 h. The precipitate which had formed was filtered off and dried to result in 24.6 g of the dye of the formula

15.5 g of 3-(2-sulfatoethylsulfonyl)aniline were stirred in 100 ml of ice-water, 10 ml of 10 N hydrochloric acid were added ind, while stirring at 0-5°C, diazotization was carried out by dropwise addition of 15 ml of 23 % by weight aqueous sodium litrite solution. After stirring at 0-5°C for 2 h, the small ex-:ess of free nitrous acid was decomposed by adding sulfamic acid, and the diazonium salt solution was maintained at 0-5*C until the :oupling.

27.6 g of 2-aminonaphthalene-3,6-disulfonic acid were stirred in 100 ml of ice-water. The diazonium salt solution was added drop-wise to this solution while keeping the pH at 2.5-3 with aqueous sodium carbonate solution. After the reaction was complete, the mixture was allowed to warm to room temperature and then the pH was adjusted to 4.5-5 using sodium bicarbonate. 25 g of sodium chloride were then added to the solution, which was then stirred for 4 h. The precipitate which had formed was filtered off and dried to result in 24.2 g of the dye of the formula



30.2 g of 3, 3'-diainino-4 , 4'-bis( 2-sulf atoethylsulf onyl )benzo-phenone were stirred in 200 ml of ice-water, 30 ml of 10 N lydrochloric acid and 100 ml of glacial acetic acid were added and, while stirring at 0-5°C, tetrazotization was carried out with 31 ml of 23 % by weight aqueous sodium nitrite solution. After stirring at 0-5°C for 3 h, the slight excess of free nitrous acic was decomposed by adding sulfamic acid. 57.5 g of 2-aminonaphtha-Lene-3,6-disulfonic acid were added, and the pH was kept at 3-3. E with sodium carbonate. After the reaction was complete, the mix¬ture was allowed to warm to room temperature and the pH was ad¬justed to 5-5.5 with sodium carbonate. 50 g of sodium chloride were added to the solution, which was then stirred for 4 h. The red precipitate was filtered off and dried to result in the dye of the formula


Example 10
The procedure was similar to Example 9 but an equivalent amount of 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid was used, re¬sulting in the dye of the formula

Example 11
The procedure was similar to Example 9 but the carbonyl compound was replaced by the corresponding sulfonyl compound as tetrazo component, and the naphthalene derivative mentioned in Example 10 was used as coupling component, resulting in the dye of the for¬mula



WE CLAIM:
1. A process for the preparation of a reactive dye of the formula I
wherein
n is 1 or 2,
R' is hydrogen or hydrox>'l,
D is, when n is 1, is a radical of the formula

wherein ring A can be benzo-fused, R2,R3 and R4 are each, independently of one another, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen or

hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or an anchor from the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q where Q is a group which can be eliminated under alkaline conditions, and T is a linker, with the proviso that, when n is 1, R' is hydroxyl and R^, R^ and R' are each hydrogen, E is neither hydrogen nor a radical of the formula SO2-Y, W'-S02-Y or C0NX-W^-S02-Y where Y has in each case tlie above mentioned meaning, and W' is in each case Ci-C4-alkylene and X is hydrogen or Ci-C4-alkyI, which process comprising diazotizing an aniline of the formula Ila by a method known per se or tetrazotizing an aniline of the formula lib by a method per se

wherein ring A, R~, R^ R'*, E, Y and T each have the above mentioned meanings, are diazotized or tetrazotized by a method known per se and coupling with an aminonaphthalene of the formula III

wherein R' has the above mentioned meanings in each case.

The process as claimed in claim 1, wherein R1 is hydroxyl.
The process as claimed in claim 1, wherein R2, R3 and R4 are each
hydrogen.
The process as claimed in claim 1, wherein when n is 2, T is a
radical of the fonnula CO or SO2.
The process as claimed in claim 1, wherein n is 1.
The process as claimed in claim 1, wherein E is hydrogen or a
radical of the formula SO2-Y where Y has the meanings specified
in claim 1.
The process as claimed in claim 1, wherein the radical of the
formula SO2-Y is in the position ortho to the azo group.
A process for the preparation of a reactive dye of the formula I
substantially as herein described and exemplified.


Documents:

0486-mas-1996 abstract.pdf

0486-mas-1996 claims.pdf

0486-mas-1996 correspondence-others.pdf

0486-mas-1996 correspondence-po.pdf

0486-mas-1996 description(complete).pdf

0486-mas-1996 form-1.pdf

0486-mas-1996 form-26.pdf

0486-mas-1996 form-4.pdf

0486-mas-1996 form-9.pdf

0486-mas-1996 petition.pdf


Patent Number 192882
Indian Patent Application Number 486/MAS/1996
PG Journal Number 30/2009
Publication Date 24-Jul-2009
Grant Date 18-Mar-2005
Date of Filing 26-Mar-1996
Name of Patentee M/S. BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN
Inventors:
# Inventor's Name Inventor's Address
1 MANFRED PATSCH FRITZ WENDEL-STR4, 67157 WACHENHEIM
2 HEIKE KILBURG SCHUBERTSTR4, 67346 SPEYER
3 ANDREA ZAMPONI LEISBERG 36, 69124 HEIDELBERG
PCT International Classification Number C09B 62/507
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA