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 an aniline of the formula Ha or lib are diazotized or tetrazotized by a method known per se and coupled with an aminonaphthalene of the formula Ilia. PRICE: THIRTY RUPEES

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The present invention relates to a process for the eparation of a reactive dye of the formula I where n is 1 or 2, Ri is hydrogen or hydroxysulfonyl, R2 is hydrogen or hydroxy1, R3 is carboxymethyl, hydroxysulfonylmethyl, a radical of the formula WI-SO2-Y or W2(-S02-Y)2, where W^ is C1-C4-alky-lene or unsubstituted or substituted phenylene, W^ is a trivalent radical of a benzene ring which is unsxabsti-tuted or substituted and Y is vinyl or a radical of the formula C2H4-Q, where Q is a group which can be elimi¬nated under alkaline reaction conditions, Cs-CT-cyclo-alkyl or phenyl which is substituted by C1-C4-alkyl, C1-C4-alkoxy, carboxyl or a radical of the formula CONH-W--SO2-Y or SO2-Y, where W^ and Y each have the abovementioned meanings, or, if n is 2, R1 may further¬more be carboxy-C2-C4-alkyl or hydroxysulfonyl-C2-C4-al)cyl, R'^ is hydrogen or R1 and R'^, together with the nitrogen atom linking them, form a 5-membered or 6-membered saturated heterocyclic radical which may have further hetero atoms, and D, if n is 1, is a radical of the formula where R1, RS and R"^, independently of one another, are each hydrogen, C1-C4-alkyl, C1-C4-alkoxy or hydroxysul-fonyl, E1 is a heterocyclic anchor or a anchor from the aliphatic series, £2 is hydrogen or E1, and T is a bridge meraber, with the proviso that at least one anchor is present in D, :heir use for dyeing or printing hydroxyl-containing or nitrogen-containing organic substrates, and novel aminonaphthalenes. E:P-A-369 385 discloses azo-based reactive dyes which contain L—hydroxy-3-hydroxysulfonyl-7-(2-cyano—, 2-hydroxysulfonyl— or 2-carbamoylethylamino)naphthalene as a coupling component. Furthermore, Indian Patent Nos.138559 and 138633 describe reactive iyes of this class having 1—hydroxy-3-hydroxysulfonyl-7-methyl— sr phenylaminonaphthalene as a coupling component. It is an object of the present invention to provide novel reac¬tive dyes which are derived from phenylazonaphthalene dyes. The novel dyes should have advantageous performance characteristics. ;^e have found that this object is achieved by the reactive dyes of the formula I which are defined at the outset. The novel reactive dyes of the formula I are each present in the form of the free aC1d. Of course, the claims also relate to the salts thereof. Suitable cations are derived from metal or ammonium ions. Metal ions are in particular the lithium, sodium or potassium ions. For the purposes of the present invention, ammonium ions are to be understood as meaning unsubstituted or substituted ammonium cations. Substituted ammonium cations are, for example, mono-alkyl-, dialkyl—, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations or cations which are derived from nitrogen-containing 5— or 6-imembered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations or the N-monoalkyl- or N,N-dialkyl-substituted products thereof. Alkyl is to be understood in general as meaning straight-chain or branched C1-C2o-al} All alkyl and alkylene radicals occurring in the abovementioned formula I may be either straight-chain or branched. If substituted alkyl groups occur in the abovementioned formula I, they have, as a rule, 1 or 2 substituents. If substituted phenyl, phenylene or benzenetriyl groups occur in the abovementioned formula, suitable substituents are, for example, C1-C4-alkyl, C1-C4-alkoxy, halogen, hydroxysulfonyl, sulfamoyl or C1-C^-mono— or dialkylsulfamoyl, unless stated other¬wise. In this case, they have, as a rule, from 1 to 3, preferably 1 or 2, substituents. If R- and R1, together wiuh the nitrogen atom linking them, form a 5-membered or 6-membered saturated heterocyclic radical which may have further hetero atoms, suitable radicals of this type are, for example, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpho-linyl, thiomorpholinyl S,S-dioxide, piperazinyl or N-(C].-C4-al-kyDpiperazinyl, such as N-methyl- or N-ethylpiperazinyl. R1, RS and R' are each, for example, methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy. Wi is, for example, CH2, {CH2)2. (CH2)3, {CH2)4, CH(CH3)CH2, CH(CH3)CH(CH3) or 1,2-, 1,3- or 1,4-phenylene. W2 is, for example, benzene-1,2,3—, —1,3,4— or —1,3,5—triyl. R3 is, for example, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, carboxi'inethyl, 1— or 2-carboxyethyl, a radical of the formula C2H4-SO2-Y or C3H6-SO2-Y, cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-met1iylphenyl, 2-, 3- or 4-ethylphenyl, 2—, 3— or 4—pro-pylphenyl, 2—, 3— or 4—isopropylphenyl, 2-, 3— or 4—butylphenyl, where L^.^ L2 and L^, independently of one another, are each C1-C4-alkyl or benzyl and An® in each case is one equivalent of an anion. Suitable anions are, for example, fluoride, chloride, bromide, iodide, mono—, di- and trichloroacetate, methanesul-fonate, benzenesulfonate and 2— or 4-methylbenzenesulfonate. Anchors E1 and E1 are those which undergo a substitution or addi¬tion reaction with the hydroxy1-containing or nitrogen-containing groups of the substrates to be treated. That the anchor undergoes a substitution reaction with the rele¬vant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the leaving groups or leaving atoms (for example fluorine and chlorine) in the anchor are sub¬stituted by the hydroxyl groups of the cellulose according to the following scheme: heterocyclic anchors E1 and E2 are, for example, halogen-substi-:uted radicals of 1,3,5-triazine, quinoxaline, phthalazine, py-rimidine or pyridazone, or a 2-alkylsulfonylbenzothiazole radical. ixamples are the followina heterocyclic radicals: where X is hydrogen or C1-C4-alkyl, Hal is fluorine or chlorine, U^ is hydrogen or nitro and u2 and U^, independently of one another, are each hydrogen or C1-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 which may be interrupted by 1 or 2 oxygen atoms as an ether func¬tion, by imino or by C1-C^-alkylimine, or U^ and U^, together with the nitrogen atom linking them, form pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N-(C1-C4-alkyl)piper azinyl or U^ may furtherm.ore be a radical of the formula where the rings A and K may each be monosubstituted or disiobsti-tuted by hydroxysulfonyl and may each be benzofused and, indepen¬dently thereof, the ring K may be monosubstituted or disub-stituted by chlorine, nitro, C1-C^-alkyl, C1-C^-alkoxy, cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of the formula CH2-SO2-Y, SO2-Y, NH-CO-Y or NU2-C0-NU2-z-SO2-Y, where Y and u2 each have the abovementioned meanings, and Z is C2-Ce-alky lene which is unsubstituted or suibstituted by hydroxyl, chlorine, cyano, carboxyl, C1-C^-alkoxycarbonyl, C1-C4-alkanoyloxy or sul¬fate and may be interrupted by 1 or 2 oxygen atoms as an ether function or by imino or C1-C4-alkylimino. Anchors E1 and E2 from the aliphatic series are, for example, acryloyl, mono—, di— or trichloroacryloyl, mono-, di— or tri-bromoacryloyl, -C0-CC1=CH-C00H, -C0-CH=CC1-COOH, 2-chloropro-pionyl, 1,2—dichloropropionyl, 1,2-dibromopropionyl, 3—phenylsul fonylpropionyl, 3—methylsulfonylpropionyl, 2—sulfatoethylamino-sulf onyl , 2—fluoro-2-chloro-3,3-difluorocyclobut-1-ylcarbony1, 2,2,3,3-tetrafluorocyclobut-1-ylcarbonyl, 2,2,1 »3-tetrafluorocyclobut-l-ylsulfonyl, 2-(2,2,3,3-tetrafluoro-cyclobut-l-yl)acryloyl, 1- or 2-alkylsulfonylacryloyl or 1- or 2-arylsulfonylacryloyl, such as 1- or 2-methylsulfonylacryloyl, or a radical of the formula SO2-Y, CONH-WI-SO2-Y or NHCONH-WI-SO2-Y, where W^ and Y each have the abovementioned meanings. Where E1, E1 and T each have the abovementioned meanings. Preferred reactive dyes are those of the formula I where R1 is hydrogen. Reactive dyes of the formula I where R1 is hydroxyl are also preferred. Other preferred reactive dyes are those of the formula I where R3 is hydroxysulfonylmethyl. Reactive dyes of the formula I where R5, R6 and R7 are each hydro¬gen are furthermore preferred. Further preferred reactive dyes are those of the formula I where E1 is a halogen-substituted radical of 1,3,5-triazine or a radical of the formula SO2-Y, where Y has the abovementioned meanings. Reactive dyes of the formula I where T is a radical of the formu¬la CO or SO2 if n is 2 are also preferred. Reactive dyes of the formula I where n is 1 are furthermore preferred. R3, E1 and E2 each have the abovementioned meanings. Reactive dyes of the formula la, where E1 is a radical of the formula SO2-Y, are of particular interest. The novel reactive dyes of the formula I can be obtained by methods known per se. where R1 is hydrogen or hydroxysulfonyl, R2 is hydrogen or hydroxy1, R6 is carboxymethyl, hydroxysulfonylmethyl or a radical of the formula WI-SO2-Y or W2(-S02-Y)2, where W^ is C1-C4-alkylene or unsubstituted or substituted phenylene, W2 is a trivalent radical of a benzene ring which is unsubstituted or substi¬tuted and Y is vinyl or a radical of the formula C2H4-Q, where Q is a group which can be eliminated under alkaline reaction conditions, C5-C7-cycloalkyl or phenyl which is substituted by C1-C4-alkyl, C1-C4-alkoxy, carboxyl or a radical of the formu¬la CONH-WI-SO2-Y or SO2-Y, where W1 and Y each have the abo-vementioned meanings, and R4 is hydrogen or R4 and R6, together with the nitrogen atom linking them, form a 5-nembered or 6-membered saturated heterocyclic radical which may have further hetero atoms. Aminonaphthalenes of the formula III where R1 is hydrogen are preferred. Rm-inonaphthalencc of ^^e formula III where R2 -is hydro;r/l arc zl^f^ preferred. Other preferred aminonaphthalenes are those of the formula III where R1 is hydroxysulfonylmethyl. where R4 and R6 each have the abovementioned meanings, in the presence of an alkali metal sulfite, for example sodium sulfite or potassium sulfite. The novel reactive dyes of the formula I can be advantageously-used for dyeing or printing hydroxyl-containing or nitrogen-containing organic substrates. Examples of such substrates are leather or fiber material which contains predominantly natural or synthetic polyamides or natural or regenerated cellulose. The novel dyes can preferably be used for dyeing and printing textile material based on wool or in particular on cotton. Dyeings in red hues are obtained. Deep dyeings which have a very high fixation yield, very good lightfastness and excellent wet fastness properties, such as fastness to washing, to chlorine bleaches, to peroxide bleaches, to alkalis, to sea water or to perspiration, are obtained, par¬ticularly on substrates based on cellulose. Accordingly, the present invention provides a process for the preparation of a reactive dye of the formula I R' is carboxyrnethyl, hydrcxysulf cnylmethyl, a radical of the for-ula W--SO;-Y or W^(-SO,-Y);, where W' is C,-C,-alkylene or ur.subsC1tuted cr substituted phenylene, W' is a trivalent radical cf a benzene ring which is unsubstituted or subs-ituted and Y is vinyl or a radical of the formula C;K.-Q, where Q is a group which can be eliminated vinder alkaline reaction conditions, C5-C7-cycloalkyl or phenyl which is substituted by C^-C.-alkyl, C^-C^-alkoxy, carboxyl or a radical of the formula COM:-:— W'-S0:-Y or S0;-Y, where W' and Y each have the abovementioned meanings, or, if n is 2, R1 may furthermore be carboxy-C;-C.-alkyi or hydroxysulfonyl-C.-C^-alkyl, ?," is hvirrgen cr ?/ and ?/, together with the nitrcgen atom linking che~, fcriri a 5— membsred or £— merrbered saturated he'erocyclic radical which may have furclner hetero atoms, D, if n is 1, is a radical of the formula where R1 R2 R1 and R2 each have the abovementioned meanings. where R5 R6 and R7, independently of one another, are each hydrogen, C1-C8-alkyl, C^-C^-alkoxy or hydroxysulfonyl, E' is a heterocyclic anchor or a anchor from the aliphatic series, E" is hydrogen or E1, and T is a bridge member, with the proviso that at least one anchor is present in D, in the form of a 3 5% strength by weight aq-aeous solution was dia-zotized at from 0 to 5°C with 25 ml of 30% strength by weight hy¬drochloric aC1d and 3 0 ml (0.1 mol) of 23% strength by weight aq~jeous sodium nitrite solution. 33.1 g {0.1 mol) of the compound of the formula were then added, the pH being kept at from 2.5 to 3 by adding aqueous sodium acetate solution. After the end of the coupling, the pH was brought to 5—5.5 with sodium bicarbonate. The dye of the formula was isolated by salting out, filtering off and drying. Xroax (water): 52 3 nm Example 2 28.1 g (0.1 mol) of l-amino-2-(2-sulfatoethylsulfonyl)benzene were stirred in 300 ml of ice water and diazotized by adding 10 ml of- 3nsr strength by weight hydro^-hlori c aC1d and ^0 ml (0.1 mol) of 23% strength by weight aqueous sodium nitrite solu¬tion. A temperature of from 0 to 5°C was maintained for 1.5 hours. 34.3 g (0.103 mol) of the compound of the formula were then added, the pH being kept at 2.5 by adding aqueous so¬dium acetate solution. After the end of the coupling, the pH was brought to 5—5.5 with sodium bicarbonate. The dye of the formula was isolated by salting out, filtering off and drying. It can also be isolated by spray-drying, ^ax (water): 530 nm Example 3 0.1 mol of the compovmd of the formula ■/as stirred in 200 ml of ice water. Diazotization was effected at Erom 0 to 5°C by adding 25 ml of 30% strength by weight hydrochlo¬ric aC1d and 3 0 ml (0.1 mo1) of 23% strength by weight aqueous sodium nitrite solution. 33.3 g (0.1 mol) of the compound of the formula were then added, the pH being kept at 2.5—3 by adding aqueous so¬dium acetate solution. After the end of the coupling, the pH was ' brought to 5—5.5 with sodium bicarbonate. The dye of the formula WE CLAIM 1. Process fcr the preparation of a reactive dye of the formula I where n is 1 or 2, R1 is hydrogen or hydroxysulfonyl, R2 is hydrogen or hydroxyl, R3 is carboxyraethyl, hydroxysulfonylmethyl, a radical of the formula W1-SO2-Y or WM-SO2-Y)2 where W1 is C1-C4-alkylene or unsubstituted or substituted phenylene, W' is a trivalent radical of a benzene ring which is unsubstituted or substituted and Y is vinyl or a radical of the formula C2H4-Q, where Q is a group which can be eliminated under alkaline reaction conditions, C5-C7-cycloalkyl or phenyl which is substituted by C1-C4-alkyl, C1-C4-alkoxy, carboxyl or a radical of the formula CONH- W1-SO2-Y or SO2-Y, where w1 and Y each have the abovementioned meanings, or, if n is 2, R3 may furthermore be carboxy-Cj-C^-alkyl or hydroxysulfonyl-C2-C4-alkyl, R4 is hydrogen cr R3 and R4, together with the nitrogen atom linking them, form, a 5— membered or 6— membered saturated heterocyclic radical which may have further hetero atoms, and D, if n is 1, is a radical of the formula where R5 R6 and R7, independently of one another, are each hydrogen, C1-C4-alkyl, C1-C4-alkoxy or hydroxysulfonyl, E' is a heterocyclic anchor or a anchor from the aliphatic series, E' is hydrogen or E1, and T is a bridge member, with the proviso that at least one anchor is present in D, where R5 R6 R7, E1, E2 and T each have the abovementioned meanings, are diazotizsd or tetrazotized by a method known per se and coupled with an aminonaphthalene of the formula Ilia 2. The process as claimed in claim 1, wherein R1 is hydrogen. 3. The process as claimed in claim 1, wherein R is hydroxyl. 4. The process as claimed in claim I, wherein R3 is hydroxysulfonyhnethyl. 5. The process as claimed in claim 1, wherein R5, R6 and R7 are each hydrogen. 6. Tlie process as claimed in claim 1, wherein E' is a halogen-.substituted radical of 1,3,5-triazine or a radical of the formula SO2-Y, where Y has the meanings stated in claim 1. 7. The process as claimed in claim 1, wherein T is a radical of the formula CO or SO2 if n is 2. 8. The process as claimed in claim 1, wherein n is 1. 9. The process as claimed in claim 1, wherein F/ is a radical of the formula SO2- Y, where Y has the meanings stated in claim 1, and is ortho to the azo group. 10. A process for the preparation of a reactive dye substantially as herein described and exemplitied with reference to the accompanying drawings.

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1235-mas-1995 abstract.pdf

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