Title of Invention

A PROCESS FOR PREPARING REACTIVE DYES

Abstract

The present invention relates to a process for producing reactive dyes of the formula I wherein n is 1 or 2, G' is hydrogen or hydroxyl, g2 is hydrogen or hydroxysulfonyl, g3 is hydrogen or a radical of the formula R1 is hydrogen or hydroxysulfonyonyl,methyl, R2 is hydrogen or hydroxysulfonymethyl, and D is, when n is 1, a radical of the formula or, when is 2, a radical of the formula wherein the ring A may be benzofused, r3, R4 and R5 are each independently of the other hydrogen c1-c4-alkyl, C1-C4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen; a heterocyclic anchor radical or a anchor radical of the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q, where Q is an alkali-detachable group, and T is a bridge member, with the proviso that at least one hydroxysulfonylmethyl group shall be present in the molecule and that dyes of the formula wherein n, D and G2 are each as defined above, are excluded, comprising the steps of diazotizing aniline of the formula IIa or tetraazohizing an aniline of formula IIb in a known manner and then coupling with aminonaphthalene of the formula III wherein G1, G2, R1 and R2 are each as defined above to obtain the reactive dyes of formula I.

Full Text

dyes The present Invention relates to a process for preparing reactiv Reactive azo dyes with an aminonaphthalenesulfonic acid coupling component and intermediates therefor The present invention relates to novel reactive dyes of the for¬mula I where n is 1 or 2, G^ is hydrogen or hydroxyl, G2 is hydrogen or hydroxysulfonyl, G3 is hydrogen or a radical of the formula Ri is hydrogen or hydroxysulfonylmethyl, R2 is hydrogen or hydroxysulfonylmethyl, and D is, when n is 1, a radical of the formula or, when n is 2, a radical of the formula where the ring A may be benzofused, R^, R^ and R^ are each independently of the others hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or a anchor radical of the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q, where Q is an alkali-detachable group, and T is a bridge member, with the proviso that at least one hydroxysulfonylmethyl group shall be present in the molecule and that dyes of the formula where n, D and G^ are each as defined above, shall be excluded, to their use for dyeing or printing hydroxyl-containing or ni¬trogenous organic substrates and to naphthylamines as intermedi¬ates therefor. The above-excluded dyes and intermediates are known from prior patent application WO 9610610. It is an object of the present invention to provide novel reactive dyes derived from phenyl- or naphthalene-azo-naphthalene dyes. The novel dyes shall have an advantageous application property profile. We have found that this object is achieved by the reactive dyes of the formula I defined at the beginning. The novel reactive dyes of the formula I are each indicated in the form of the free acid, but salts thereof are also encompassed "by the claims, of course. Suitable cations are derived from metal or ammonium ions. Metal ions are in particular the lithium, sodium or potassium ions. Ammonium ions for the purposes of the present invention are sub¬stituted or unsubstituted ammonium cations. Substituted ammonium cations include for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations or cations derived/ from nitrogenous five- or six-membered saturated heterocycles, (_ such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted prod¬ucts. Alkyl is generally to be understood as meaning straight-chain or branched C1-C2o-alkyl which may be substituted by 1 or 2 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms in ether function. Any alkyl or alkylene herein can be straight-chain or branched. Any substituted alkyl herein generally contains 1 or 2 substitu-ents. Any substituted phenylene herein contains for example, unless otherwise stated, C1-C4-alkyl, C1-C4-alkoxy, halogen, hydroxysulfonyl, sulfamoyl or mono- or di-C1-C4-alkylsulfamoyl as substituents. Substituted phenylene then generally contains from 1 to 3, preferably 1 or 2, substituents. R3, R4 and R5 are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, fluorine, chlorine or bromine. Q is an alkali-detachable group. Such groups include for example chlorine, bromine, C1-C4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, 0P(0){0H)2/ C1-C4-alkylsulfonyloxy, substituted or unsubstituted phenylsulfonyloxy, C1-C4-alkanoyloxy, C1-C4-dialkyl-amino or a radical of the formula where L^, L^ and L^ are each independently of the others C1-C4-alkyl or benzyl and An® is in each case one equivalent of an anion. Suitable anions include for example fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methane-sulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate. Anchor radical E undergo substitutive or additive reactions with the hydroxyl or nitrogenous groups of the substrates to be treated. The fact that the anchor radical reacts substitutively with the relevant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the leaving groups or atoms (eg. fluorine or chlorine) in the anchor radical are replaced by the hydroxyl groups of the cellulose as per the following scheme: The fact that the anchor radical reacts additively with the rele¬vant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the hydroxyl groups of the cellu¬lose are added to the anchor radical as per the following scheme: Heterocyclic anchor radicals E include for example halogen-con¬taining radicals derived from the following basic heterocyclic species: 1,3,S-triazine, quinoxaline, phthalazine, pyrimidine or pyridazine or the 2-alkylsulfonylbenzothiazole radical. The following are particularly suitable heterocyclic radicals: where X is hydrogen or C4-alkyl, Hal is fluorine or chlorine, iji is hydrogen or nitro, and , U2 and U^ are each independently of the other hydrogen, Ce-alkyl with or without substitution by hydroxyl, halogen, cyano, hydroxysulfonyl or a radical of the formula -SO2-Y, where Y is as defined above, and with or without interruption by one or two oxygen atoms in ether function or nonadjacent imino or C4-alkylimino groups, or U2 and U3 are together with the nitrogen atom joining them together pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N-(C4-alkyl)piperazinyl, or else U^ may also be a radical of the formula f in which case the rings B and K may each be singly or doubly hydroxysulfonyl-substituted and/or benzofused and ring K may independently be monosubstituted or disubstituted by chlo¬rine, nitro, C4-alkyl, C4-alkoxy, cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of the formula CH2-SO2-Y, SO2-Y, NH-CO-Y or NU2-CO-NU2-Z-SO2-Y, where Y and U^ are each as defined above and Z is C2-C6-alkylene with or without substitution by hydroxyl, chlorine, cyano, carboxyl, C4-alkoxycarbonyl, C4-alkanoyloxy or sulfate and with or without interruption by 1 or 2 oxygen atoms in ether function or nonadjacent imino or C4-alkylimino groups. Aliphatic anchor radicals E include for example acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tribromoacryloyl, -CO-CC1=CH-C00H, -C0-CH=CC1-C00H, 2-chloropropionyl, Wi and w2 are each for example CH2, (CH2)2/ (CH2)3, (CH2)4, CH(CH3)CH2 or CH(CH3)CH(CH3) . W2 may further be for example 1,2-, 1,3- or 1,4-phenylene. T in the formula I is a bridge member. Suitable bridge members conform for example to the formula where E, Y and T are each as defined above. Preference is given to reactive dyes of the formula I where R^ and R^ are each hydrogen. Preference is further given to reactive dyes of the formula I where E is hydrogen, a anchor radicals of the 1,3,5-triazine se¬ries or a radical of the formula SO2-Y, where Y is as defined above. Preference is further given to reactive dyes of the formula I where T is a radical of the formula CO or SO2 when n is 2. Preference is further given to reactive dyes of the formula I where n is 1. Preference is further given to reactive dyes of the formula I where the ring A is not benzofused. Particular preference is given to reactive dyes of the formula I where E is hydrogen or a radical of the formula SO2-Y, where Y is as defined above. Particular preference is further given to reactive dyes of the formula I, in particular of the formulae I a-d, where the radical of the formula SO2-Y is disposed ortho to the azo group. The novel reactive dyes of the formula I are obtainable in a con¬ventional manner. For example, an aniline of the formula lla or lib The novel naphthylamines of the formula III are obtainable in a conventional manner. For example, a naphthylene derivative of the formula IV where G^ and G^ are each as defined above, can be reacted in a basic medium with the addition product of an alkali metal bisulfite with formaldehyde, eg. formaldehyde sodium bisulfite of the formula HOCHaSOaNa. By partial hydrolysis in the alkaline region the hydroxysulfonyl-amino group can also be converted back into the free amino group. The novel reactive dyes of the formula I are advantageously use¬ful for dyeing or printing hydroxyl-containing or nitrogenous or¬ganic substrates. Such substrates include for example leather or fiber material predominantly comprising natural or synthetic polyamides or natural or regenerated cellulose. The novel dyes are preferably useful for dyeing and printing textile material based on wool and in particular on cotton. The dyeings obtained have red shades. Cellulose-based substrates in particular are dyed with a very high yield of fixation in strong dyeings having very good light-fastness and also excellent wetfastness properties, such as wash, chlorine bleach, peroxide bleach, alkali, seawater or perspira¬tion fastness properties. wherein the ring A may be benzofused, R^, R"^ and R^ are each independently of the other hydrogen, C4-alkyl, CrC4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen; a heterocyclic anchor radical or a anchor radical of the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q, where Q is an alkali-detachable group, and T is a bridge member, with the proviso that at least one hydroxysulfonylmethyl group shall be present in the in a known manner and then coupling with aminonaphthalene of the formula III wherein G",G%R"AND R" are each as defined above to obtain the reactive dyes of formula I. The invention will now be described more in detail with reference to embodiments given by way of example, in which; Example 1 a) 149 g (0.5 mol) of 2-aminonaphthalene-5-sulfonic acid were suspended in 750 ml of water and dissolved by adding sodium hydroxide solution. 106 g (0.75 mol) of formaldehyde sodium bisulfite were added at PH 6.5 a little at a time and the mixture was stirred at 60°C for 4 h. 200 g of sodium chloride were added to precipitate the product of the formula to obtain 449 g (0.4 mol) of a moist paste. )) 15 g (0.05 mol) of 4-(2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 15 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at O-S"c for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 56 g (0.05 mol) of the compound described under a), and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with so¬dium carbonate. 300 ml of methanol and 2 1 of acetone were added to obtain 27 g (0.044 mol) of the scarlet dye of the formula c) 25 g (0.05 mol) of 3-(2-sulfatoethylsulfonyl)aniline-4,6-di-sulfonic acid were suspended in 200 ml of ice-water, admixed with 15 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at from 0 to 5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 25 g (0.05 mol) of the compound described under b), and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was ad¬justed to 5-5.5 with sodium bicarbonate. Precipitation with a methanol/ acetone mixture yielded 38.3 g (0,044 mol) of a reddish violet dye of the formula 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 55 g (0.05 mol) of the compound described under a), and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with sodium bicarbonate. Precipitating with the methanol/acetone mixture yielded 37.9 g (0.047 mol) of a reddish violet dye of the formula a) 129 g (0.5 mol) of 2-amino-8-hydroxynaphth.alene-6-sulfonic acid were suspended in 7 50 ml of water and dissolved with sodium hydroxide solution. 176,3 g (1.25 mol) of formaldehyde sodium bisulfite were added a little at a time at pH 8-8.5 and the mixture was stirred at eo"c for 9 h. After the reaction had ended, 137.5 ml (2.5 mol) of 50 % strength by weight sodium hydroxide solution were added and the mixture was heated at go-Q for 1.5 h. Thereafter it was adjusted to pH 5 with dilute hydrochloric acid, and the precipitate was filtered off. The paste was suspended in 800 ml of water and admixed with 100 ml of saturated aqueous sodium chloride solution to obtain 208 g (0.358 mol) of a moist paste of the formula b) 13.5 g (0.045 mol) of 2 -(2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5""c by the dropwise addition of 13.5 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5°C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 31 g (0.045 mol) of the compound prepared under a), and the reaction solution was held at a pH of from 3.5 to 4 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with sodium bicarbonate. The product was precipitated by adding 100 g of sodium chloride to obtain 34 g (0.041 mol) of a red dye of the formula The following dyes were obtained in a similar manner: a) 386 g (1.5 mol) of 2-amino-5-hydroxynaphthalene-7-sulfonic acid were suspended in 2250 ml of water and dissolved with sodium hydroxide solution. 318 g (2.25 mol) of formaldehyde sodium bisulfite were added at pH 5 and the mixture was stirred at 60°C for 4 h. After the reaction had ended, the resulting product of the formula was not isolated but used as a coupling component in solu¬tion. b) 14.5 g (0.05 mol) of 3 -(2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addi¬tion of 15 ml of 23 % strength by weight aqueous sodium ni¬trite solution with stirring. After stirring at 0-5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid. 106 ml (0.053 mol) of the solution described under a) were admixed with ice and adjusted to pH 3 with dilute hydrochlo¬ric acid. The diazonium salt solution was added dropwise to this solution while a pH of 2.5-3 was maintained with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. The dye was precipitated by adding 150 g of potassium chloride and 50 g of sodium chloride. Filtration left 37,5 g (0.048 mol) of a scarlet dye of the formula a) 2 1 (1.0 mol) of the solution described in Example 19a) were adjusted to pH 8.5 with sodium hydroxide solution and heated to eo"c. At that temperature, 70.5 g (0.05 mol) of formalde¬hyde sodium bisulfite were added and the mixture was stirred at 60°C for 2 hours. After the reaction had ended, the re¬sulting compound of the formula b) 14.5 g (0.05 mol) of 3 -(2-sulfatoethylsulfonyl)aniline were suspended in 2 00 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addi¬tion of 15 ml of 23 % strength by weight aqueous sodium ni¬trite solution with stirring. After stirring at 0-5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid. 112 ml (0.053 mol) of the solution described under a) were admixed with ice and adjusted to pH 3 with dilute hydrochlo¬ric acid. The diazonium salt solution was added dropwise to this solution while a pH of 2.5-3 was maintained with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. The dye was precipitated by adding 200 g of sodium chloride. Filtration left 47.8 g (0.045 mol) of a scarlet dye of the formula a) 1.05 1 (0.5 mol) of the solution described in Example 22 a) were heated to 60°C and admixed a little at a time at that reaction temperature with a total of 137.5 ml (2.5 mol) of 50 % strength by weight sodium hydroxide solution. After the reaction had ended, the pH was adjusted to 5 with dilute hydrochloric acid and 200 g of sodium chloride were added to isolate 497 g (0.33 mol) of moist paste of the formula b) 14.5 g (0.05 mol) of 3 -(2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5""c by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5"c for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 74 g (0.05 mol) of the compound prepared under a) and the reaction solution was held at pH 3.5-4 with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. Precipitating with a methanol/ethanol mixture yielded 35.1 g (0.042 mol) of the dye of the formula 35.3 g (0.075 mol) of 3-{2-sulfatoethylsulfonyl)aniline-4,6-di-sulfonic acid were suspended in 300 ml of ice-water, admixed with 30 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addition of 22.5 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5°C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. 70 ml (0.035 mol) of the solution described in Example 19 a) were admixed with ice and adjusted to pH 3 with dilute hydrochloric acid. Half the diazonium salt solution was added dropwise to this solution while the pH was held within the range from 2.5 to 3 with sodium acetate. After the coupling in " the ortho position to the amino group was complete, the pH was raised to 5-5.5 and the rest of the diazonium salt solution was added dropwise. Precipitating with methanol/ethanol mixture yielded 50.3 g (0.034 mol) of a scarlet dye of the formula 1 WE CLAIM: 1. A process for producing reactive dyes of the formula I wherein n is 1 or 2, G is hydrogen or hydroxyl, G is hydrogen or hydroxysulfonyl, G is hydrogen or a radical of the formula R is hydrogen or hydroxysulfonylmethyl, R is hydrogen or hydroxysulfonymethyl, and D is, when n is 1, a radical of the formula or, when n is 2, a radical of the formula wherein the ring A may be benzofused, R3 R4 and R5 are each independently of the other hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxysulfonyl, E is hydrogen; a heterocyclic anchor radical or a anchor radical of the aliphatic series, Y is vinyl or a radical of the formula C2H4-Q, where Q is an alkali-detachable group, and T is a bridge member, with the proviso that at least one hydroxysulfonylmethyl group shall be present in the molecule and that dyes of the formula in a known manner and then coupling with aminonaphthalene of the formula III wherein G1,G2,R1ANDR2 are each as defined above to obtain the reactive dyes of formula I. 2. The method as claimed in claim 1, wherein R3, R4 and R5 are each hydrogen. 3. The method as claimed in claim 1, wherein T is a radical of the formula CO or SO2 when n is 2. 4. The method as claimed in claim 1, wherein n is 1. 5. The method as claimed in claim 1, wherein E is hydrogen or a radical of the formula SO2-Y, where Y is as defined in claim 1. 6. The method as claimed in claim 1, wherein the radical of the formula SO2-Y is disposed ortho to the azo group. 7. A process for producing reactive dyes substantially as herein described and exemplified.

Documents:

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24-mas-1997 others.pdf

24-mas-1997 petition.pdf

24-mas-1997 abstract.pdf

24-mas-1997 claims duplicate.pdf

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24-mas-1997 correspondence-others.pdf

24-mas-1997 correspondence-po.pdf

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