CA1098516A - Process for the manufacture of phthalocyanine azo dyestuffs - Google Patents
Process for the manufacture of phthalocyanine azo dyestuffsInfo
- Publication number
- CA1098516A CA1098516A CA276,284A CA276284A CA1098516A CA 1098516 A CA1098516 A CA 1098516A CA 276284 A CA276284 A CA 276284A CA 1098516 A CA1098516 A CA 1098516A
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
- C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
- C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/003—Cyclisation of azo dyes; Condensation of azo dyes with formation of ring, e.g. of azopyrazolone dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
- C09B47/26—Amide radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B56/00—Azo dyes containing other chromophoric systems
- C09B56/14—Phthalocyanine-azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
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- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
Abstract of the Disclosure Fiber reactive phthalocyanine azo dyes having at least one group of the formula wherein ar denotes a divalent aromatic or araliphatic radical, R3 and R4 denote hydrogen or optionally substituted alkyl radicals, A = the group -NH-, -CO-NH-, -S02-NH- or -S02-, B = the radical of an optionally substituted, mononuclear or dinuclear, aromatic hydrocarbon X = the vinyl group, the .beta.-hydroxyethyl group or an ethyl group which is substituted in the .beta.-position by a group which can be split off by means of alkalis, n = 0 or 1 and p = 0.1 or 2 are prepared by diazotizing phthalocyanine amines having at least one group of the formula S02-? -ar-NH2 wherein the amino group is linked to an aromatic C atom of the radical ar, coupling the diazonium compound with a succinic acid derivative of the formula V
(V) wherein Z denotes hydrogen or an optionally substituted hydrocarbon radical, treating the hydrazone interme-diate with alkali to obtain a phthalocyanine pyrazolone having at least one group of the formula and coupling this product with a diazotized amine of the formula wherein the group
(V) wherein Z denotes hydrogen or an optionally substituted hydrocarbon radical, treating the hydrazone interme-diate with alkali to obtain a phthalocyanine pyrazolone having at least one group of the formula and coupling this product with a diazotized amine of the formula wherein the group
Description
Re~. 3065 The present invention relates to a process for the m~nu-. factur~ of valuable, water-soluble~ green phthaloc~anine azo : dyestuf~s which can ha~e ~ibre-reactive properties~ o~ the ~ fo~mula I
j(S03H)k /
Pc (50 -N~
:`. : ~ ~ ~: :;:
\ COOR4 SD~ ar - N~ ~A~9-- (CII2,3 -SO2-~
R3~ ~ OH
wherein~ - the group -NH~ -CO-NH-, -$02~N~ or -S02-~ B =
the radical of:a~ optionally ~sub ituted, mono~uclear or ~
dinuclear~ aro~aatic hydro~arbo~,X = ~he vinyl group, the B- : :
:
hyd~o~yethyl group: or an ~ èthyl ~group which ~ is~ substituted in th~ B-po3itio~l by a group which ca~ b~ ~plit~:of~ by means o~ . ;
:: alkalis, such a~ an acyl or acyloxyethyl radlcal, for example ~ a ~-(arylsulphonyloxy) radical, such as phenylsulphonyloxy or ., ~, , .
' s~ :
~-(3-carboxyphenylsulphonyloxy), or a f~-(alkylsulphonyloxy) radical, such as ~:~-(methylsulphonyloxy), a ~-(arylsulphonyloxy) or ~-(alkylsulphonyloxy) radical, such as ~-ace-toxy or ~-(3-sulpho-benzoyloxy), a ~-chloro radical, ~-thiosulphato radical, ~-sulpha-to radical 9 ~-phosphato radical, ~-phenoxy radical, ~-~di-(lower alkyl.)-amino~ radical or a ~-[tri-(lower alkyl)-ammonium halide]-ethyl radical, but preferably the vinyl group, ~chloroethyl group, ~--thiosulphatoe-thyl group or ~-dialkylaminoethyl group having 1 to 4 C atoms in each alkyl radical, for example the ~-dimethylaminoethyl group and -the ~-diethylaminoethyl group, or the ~-sulphatoethyl group or the ~-phosphatoe-thyl group or the ~-hydroxyethyl group, Pc = the radical of a metal-containing or metal-free phthalooyanlne, ar = the radlcal of an optionally substitu-ted, mononuclear or dinuclear,~aromatic or araliphatic hydrocarbon, :the alkylene chain of which is linked to the S02-N- group~ R
R
hydrogen, optionally substituted alkyl having 1-6 C atoms, phenalkyl or naphthalkyl havlng 1-3 C atoms in the aliphatic chain, or phenyl or naphthyl, it be1ng possible for the aro-~:
matiG nuclel to carry further substituents if appropriate, Rz = hydrogen, optlonally substltuted alkyl having 1-6 C ato~s . .
Dr unsubstituted alkyl havine 7-20 C atoms, R3 = hydrogen or optionally substituted alkyl habing 1-6 C~atoms, R4 - hydrogen or optionally substi-tu-ted alkyl having 1-6 C atoms or unsub-stituted alkyl having 7-18 C atoms, k represents the numbers 0 9 1, 2 or 3, 1 represen-ts 0, L or 2, m represents 1, 2~ or 4, n represents 0 or 1 and p represen-ts 0, 1 or 2 and -the sum of ; 6 k, 1 and m is 2, 3 or 4, preferably 3 or 4, and o~ their salts, especially alkali metal salts9 su h as sodium salt or potas sium salt, the ammonium salt or the alkaline earth metal salt~, ~uch as calcium salts~ This process according ~o the inve~-tio~ is characterised in that an amine of a phthalocya~ine compound o~ the general ~ormula II
__ _ .... _ . . _ .. ... .. , . . ... ._ . _. . .. . . . .. ... .. . _ ...
(S03H)~
(502-N / ~
3 ] m ~ `' i~ which the amino group is linked to an aromatio C atom in the radical ar a~d wherein Pc, ar, R~, R2, R3, k, 1 and m have the abovementioned meanings, is dia~otlsed and coupled in an aqueous medium at a pH value between 3 and 8 with a succinic acid derivative of the ~ormula III
R5-OCC C~2-C~-CR 4 (III~
Co-z : wherein R~ denotes optio~ally substituted alkyl having 1-6 C
atoms or unsubstituted alkyl having 7-18 C atom~, R5 de~otes optionally sub~tituted alkyl having 1-6 C atoms or unsub~tituted alkyl having 7-18 C atoms and Z denotes hydrogen, an optionally substltuted alkyl radical having 1-10 C atoms, an optio~ally substituted ph~nyl radical or alkoxycarbonyl having 2-6 C
~toms, ~nd the resulting hydrazone~ of the formula IV
.'~, 5~ :
.
3E~)k Pc _- ( SO2-N ~ ~ ~ O
~21 / ~ IV
( SQ2-N--ar-N~-N-C
R3 COOR4 / m , ar, R1~ R2, R3, R4, R5, k, 1 and m have the above-mentioned meanings, are conver-ted by the action of alkalis into pyrazolones of the general formula V
,~ . .
~ ~( 3 k ':' ' /
~, (V), Pc ~ (S02-N / :
\ ~2 ~ 1 ~3 ~ 01 ~wh~rein Pc~ ar, Rl, R2, R3,:Rl~, k9;1 and m have the above~
mentioned meanings, and these pylrazolones are coupled with the diazonium compound o.~ an am me of the general formula VI
i . ~
: ~ B - (~C~2)p ~ So2X (VI) , :
wherein A, B, X, n and p have the abovementioned meanings.
B is pre~erably a radical of a mononuclear or dinuclear aromatlc hydrocarbon which can be substituted by a subs~ituent ~rom the group of alkyl having 1-4 C atoms, alkoxy havi~g 1-4 C atomsg halogen, such as, for example, chlorine or bromine, carboxyl, h~droxyl, nitro, phenylamino or sulph~
In particular, in the abovementio~ed general ~ormula a~d also in the amines which are to be employed according to the invent~on, of the phthalocyanine series of the general formula II, Pc denotes the radical o~ a metal-containi~g phthalocyani~e, such as copper phthalocyanine, cobalt phthalo~
cyanine or nickel phthalocyanine, ar denotes 9 ln partlcular~
the radical o~ a mononuclear or dinuclear, aromatic or arali-phatic hydrocarbon which is optionally substituted by a -SO3H
group ~d which can be substitute~, in each nucleu~, by one ~ub~tit.,uent from ~he group alkoxy having 1 to 4 C atoms, -S02-R~ or a~ additional --SO3H groupj by one or two identlcal or di~erent sub~tituents irom the group halogen, ~ 1 S2 N or -COOH, or denotes a phenyle~e radical which is optionally substituted by a -SO3~ group a~d which can be addltionally substituted by one to three identical or dif-~erent alkyl radicals having 1 to 4 C atoms, R1 a~d R1 inde-pende~tly o~ one a~other denote hydrogen, methyl, carboxymeth~l, sulphom~thyl, an alkyl radical which contains 2-6 C atoms and which i~ optionally ~u~tituted by Cl, Br9 OH7 alkoxy hav~ng 1-6 C atoms, alk~noylamino having 1-6 C atoms9 preferably acetylami~o or benzoylamino, alkanoyloxy having 1-6 C atoms, pre~erably acetoxy, - COOH or -S03H, a phenalkyl or naphthalk~l 5~6 radical having 1-3 C atoms in -the aliphatic chain, or phenyl or naphthyl, it 'being possib-le for the aromatic nuclei to be substituted by Cl, Br, OH, alkyl and/or alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C a~toms, -COOH or -S03H, R2 and R2 independently of one another denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains
j(S03H)k /
Pc (50 -N~
:`. : ~ ~ ~: :;:
\ COOR4 SD~ ar - N~ ~A~9-- (CII2,3 -SO2-~
R3~ ~ OH
wherein~ - the group -NH~ -CO-NH-, -$02~N~ or -S02-~ B =
the radical of:a~ optionally ~sub ituted, mono~uclear or ~
dinuclear~ aro~aatic hydro~arbo~,X = ~he vinyl group, the B- : :
:
hyd~o~yethyl group: or an ~ èthyl ~group which ~ is~ substituted in th~ B-po3itio~l by a group which ca~ b~ ~plit~:of~ by means o~ . ;
:: alkalis, such a~ an acyl or acyloxyethyl radlcal, for example ~ a ~-(arylsulphonyloxy) radical, such as phenylsulphonyloxy or ., ~, , .
' s~ :
~-(3-carboxyphenylsulphonyloxy), or a f~-(alkylsulphonyloxy) radical, such as ~:~-(methylsulphonyloxy), a ~-(arylsulphonyloxy) or ~-(alkylsulphonyloxy) radical, such as ~-ace-toxy or ~-(3-sulpho-benzoyloxy), a ~-chloro radical, ~-thiosulphato radical, ~-sulpha-to radical 9 ~-phosphato radical, ~-phenoxy radical, ~-~di-(lower alkyl.)-amino~ radical or a ~-[tri-(lower alkyl)-ammonium halide]-ethyl radical, but preferably the vinyl group, ~chloroethyl group, ~--thiosulphatoe-thyl group or ~-dialkylaminoethyl group having 1 to 4 C atoms in each alkyl radical, for example the ~-dimethylaminoethyl group and -the ~-diethylaminoethyl group, or the ~-sulphatoethyl group or the ~-phosphatoe-thyl group or the ~-hydroxyethyl group, Pc = the radical of a metal-containing or metal-free phthalooyanlne, ar = the radlcal of an optionally substitu-ted, mononuclear or dinuclear,~aromatic or araliphatic hydrocarbon, :the alkylene chain of which is linked to the S02-N- group~ R
R
hydrogen, optionally substituted alkyl having 1-6 C atoms, phenalkyl or naphthalkyl havlng 1-3 C atoms in the aliphatic chain, or phenyl or naphthyl, it be1ng possible for the aro-~:
matiG nuclel to carry further substituents if appropriate, Rz = hydrogen, optlonally substltuted alkyl having 1-6 C ato~s . .
Dr unsubstituted alkyl havine 7-20 C atoms, R3 = hydrogen or optionally substituted alkyl habing 1-6 C~atoms, R4 - hydrogen or optionally substi-tu-ted alkyl having 1-6 C atoms or unsub-stituted alkyl having 7-18 C atoms, k represents the numbers 0 9 1, 2 or 3, 1 represen-ts 0, L or 2, m represents 1, 2~ or 4, n represents 0 or 1 and p represen-ts 0, 1 or 2 and -the sum of ; 6 k, 1 and m is 2, 3 or 4, preferably 3 or 4, and o~ their salts, especially alkali metal salts9 su h as sodium salt or potas sium salt, the ammonium salt or the alkaline earth metal salt~, ~uch as calcium salts~ This process according ~o the inve~-tio~ is characterised in that an amine of a phthalocya~ine compound o~ the general ~ormula II
__ _ .... _ . . _ .. ... .. , . . ... ._ . _. . .. . . . .. ... .. . _ ...
(S03H)~
(502-N / ~
3 ] m ~ `' i~ which the amino group is linked to an aromatio C atom in the radical ar a~d wherein Pc, ar, R~, R2, R3, k, 1 and m have the abovementioned meanings, is dia~otlsed and coupled in an aqueous medium at a pH value between 3 and 8 with a succinic acid derivative of the ~ormula III
R5-OCC C~2-C~-CR 4 (III~
Co-z : wherein R~ denotes optio~ally substituted alkyl having 1-6 C
atoms or unsubstituted alkyl having 7-18 C atom~, R5 de~otes optionally sub~tituted alkyl having 1-6 C atoms or unsub~tituted alkyl having 7-18 C atoms and Z denotes hydrogen, an optionally substltuted alkyl radical having 1-10 C atoms, an optio~ally substituted ph~nyl radical or alkoxycarbonyl having 2-6 C
~toms, ~nd the resulting hydrazone~ of the formula IV
.'~, 5~ :
.
3E~)k Pc _- ( SO2-N ~ ~ ~ O
~21 / ~ IV
( SQ2-N--ar-N~-N-C
R3 COOR4 / m , ar, R1~ R2, R3, R4, R5, k, 1 and m have the above-mentioned meanings, are conver-ted by the action of alkalis into pyrazolones of the general formula V
,~ . .
~ ~( 3 k ':' ' /
~, (V), Pc ~ (S02-N / :
\ ~2 ~ 1 ~3 ~ 01 ~wh~rein Pc~ ar, Rl, R2, R3,:Rl~, k9;1 and m have the above~
mentioned meanings, and these pylrazolones are coupled with the diazonium compound o.~ an am me of the general formula VI
i . ~
: ~ B - (~C~2)p ~ So2X (VI) , :
wherein A, B, X, n and p have the abovementioned meanings.
B is pre~erably a radical of a mononuclear or dinuclear aromatlc hydrocarbon which can be substituted by a subs~ituent ~rom the group of alkyl having 1-4 C atoms, alkoxy havi~g 1-4 C atomsg halogen, such as, for example, chlorine or bromine, carboxyl, h~droxyl, nitro, phenylamino or sulph~
In particular, in the abovementio~ed general ~ormula a~d also in the amines which are to be employed according to the invent~on, of the phthalocyanine series of the general formula II, Pc denotes the radical o~ a metal-containi~g phthalocyani~e, such as copper phthalocyanine, cobalt phthalo~
cyanine or nickel phthalocyanine, ar denotes 9 ln partlcular~
the radical o~ a mononuclear or dinuclear, aromatic or arali-phatic hydrocarbon which is optionally substituted by a -SO3H
group ~d which can be substitute~, in each nucleu~, by one ~ub~tit.,uent from ~he group alkoxy having 1 to 4 C atoms, -S02-R~ or a~ additional --SO3H groupj by one or two identlcal or di~erent sub~tituents irom the group halogen, ~ 1 S2 N or -COOH, or denotes a phenyle~e radical which is optionally substituted by a -SO3~ group a~d which can be addltionally substituted by one to three identical or dif-~erent alkyl radicals having 1 to 4 C atoms, R1 a~d R1 inde-pende~tly o~ one a~other denote hydrogen, methyl, carboxymeth~l, sulphom~thyl, an alkyl radical which contains 2-6 C atoms and which i~ optionally ~u~tituted by Cl, Br9 OH7 alkoxy hav~ng 1-6 C atoms, alk~noylamino having 1-6 C atoms9 preferably acetylami~o or benzoylamino, alkanoyloxy having 1-6 C atoms, pre~erably acetoxy, - COOH or -S03H, a phenalkyl or naphthalk~l 5~6 radical having 1-3 C atoms in -the aliphatic chain, or phenyl or naphthyl, it 'being possib-le for the aromatic nuclei to be substituted by Cl, Br, OH, alkyl and/or alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C a~toms, -COOH or -S03H, R2 and R2 independently of one another denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains
2-6 C atoms and is optionally substituted by Cl, Br, OH, alkoxy . .
ha~ing 1-6 C atoms, alkanoylamino having 1 6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having 6-20 C atoms, R~ = hydro-gen, methyl, carboxymethyl, sulphome-thyl, or an al~yl r'~dical which contains 2-6 C atoms and is optionally s~bsti-tuted by Cl, Br, OH, alkoxy having~1-6 C atoms~ alkanoylamino having 1-6 C a-toms, benzoylamino, alkanoyloxy having 1-6 C
atoms, -COOH or ~S03H, and R6 = methyl,carboxyme-thyl, alkyl having 2 or 3 C atoms, or benzyl or phenyl, it being possible for the aromatic nuclei to be monosubstitu-ted or disubstituted :by -COOH or SO~H.
The symbol k repres~ents the numbers 0, 1, 2 or 3, 1 ~: :
represents 0, l or 2 and m represents 1, 2,3 or 4 and the su~
o~ k, l and m is 3 or 4.
' Preferred amines of -the general f'ormula II which are to : be employed according to the invention are those in which Pc denotes the radlcal of a metal-'c'ontalnlng ph-thalocyanine, such as, for example, cobalt ph-thalocyanine or copper phthalocyanine, but especially -the radical of nickel ph-thalocyanine~
Aral~pha-tlc radicals which are represented by ar are always linked by means of an aroma-tlc nucleus to the -NH2 group, consequent~Ly in formula I to -the pyrazolone nucleus.
Mononuclear, aroma-tic or aralipha-tic radicals which can be represen-ted by ar, are -the optionally substituted radicals phenylene and monomethylene-phenylene or polyme-thylene-phenylene of the general formula ~ . ~
(CH ) ~
in which b deno-tes an integer from 1 to 10.
Dinuclear, aromatic or araliphatic radicals which can be represented by ar are -the opti.onally substituted radicals naphthylene, monomethylene-naphthylene or polymethylene-naphthylene of the general formula in which b denotes an in-teger from 1 to 3, and the optionallly substituted radicals of the formulae , . ~ Cil,, ~ 2-C~2 ~CH--CH~, ~U~ , ~N~
CO ~ and ~ S~2-.
5~
The following are ~xamples of mononuclear or dinuclear, aromatic or araliphatic hydrocarbons whlch can be represented by ar in the arnines o~ the formula II: 1,4~phenylene, 1,3-phenylene, 2-sulpho-1,4-phenylene, 3-sulpho-1,4-phenylene, 4-or 5~sulpho-1,3-phenylene, 2-carboxy-1,4-phenylene, 3-carboxy 1,4-phenylene, 4-, 5- or 6-carboxy-1,3-phenylene, 2-carboxy-5-sulpho-1,4-phenylene, 2~carboxy-6-sulpho-1,4-phenylene, 3-carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-1,3-pheny-lene, 5-carboxy~2-sulpho-1,3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dicarboxy-1,3 phenylene, 2-chloro-5-sulpho-1,4-phenylene, 2-chloro-6-sulpho-1,4-phenylene, 3-chloro-6-sulpho-i',4-phenylene, 6-chloro-4-sulpho-1,3-phenylene, 2-chl~ro-5-'carboxy-1,4-phenylene, 2,6-disulpho-1,4-phen~ylene, 2,5-disulpho-1,4-phenylene, 4,6-disulpho-1,3-phenylene, 3-chloro-6-carboxy-1,4-phenylene, 6-chloro-4 carboxy-1,3-phenylene, 4-chloro-5-carboxy-1,3-phenylenej 2 methyl-5-carboxy-1,4-pheny-lene, 2~ethyl-6-carboxy-1,4-phenylene, 3-ethyl-6-sulpho-1,4-~phenylene, 6-ethyl-4-oarboxy-1,3-phenylene, 6-propyl-4-sulpho-1,3-phenylene, 5-isopropyl-4-sulpho-1,3-phenylene, 5-isopropyl-6-carboxy-1,3-phenylene,4-n-butyl-6-sulpho-1,3-phenylene, 3-n-butyl-6-sulpho-1,4-phenylene, 4-tert~-butyl-6-sulpho-1,3~
phenylene, 3-1sobutyl-6-sulpho-1,4-phenylene, 2,5-diisopropyl-6-sulpho-1,4 phenylene, 2j4-diethyl-5-carboxy-l~3-phenylene~ -'' 2,4,6-trimethyl-5-sulpho-1,3-phénylene, 2-cyano-1,4-phenylene, 4-cyano-1,3-phenylene, 2-cyano-5-sulp'ho-1,4-phenylene9 2-tri~luoromethyl-l 9 4-phenylene, 2-methylsulphonyl-1,4-phenylene, 2-ethylsulphonyl-1,4-phenylene, 4-sulpho-1,5-naphthylene, 8-sulpho-1,5-naphthylene, 4-sulpho-2,6-naphthylene, 2-carboxy !~
.. . . .
- .
1,4-naphthylene, 2-carboxy-1,5-naphthylene, 5-carboxy-1,4-naphthylene, 3 carboxy-1,8-naph-thylene, 3-carboxy-1,5-naphthylene, 4-carboxy-2,6-naphthylene, Lr-carboxy-2,7-naphthylene, l-sulpho-2,6-naph-thylene, 8-sulpho-1,3-naphthylene, 4,8 disulpho-2,6 naphthylene, 3,7-disulpho-1,5-naphthylene, l-sulpho-4-chloro~2,6-naphthylene, 1-chloro-5-sulpho-2,6-naphthylene, l-chloro-7-sulpho 2,6-naphthylene, 2-chloro-6-sulpho-1,4-naphthylene, 1-methyl~4-sulpho 2,6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene. The hydrazone group here is in each case in the l-position of the phenyl nucleus or in the l-position or 2 position of the naphthalene nucleus.
The ~ollowing list indlcates examples of compounds from which urther divalent radicals ~hich are represented by ar are derived. The positions of the two bonds by means of which the divalent radicals are linked, on the one side, in the 1-;position of the pyrazolone (the first posi-tional indication) and, on the other ~ide, to the group -N- (the second positional R~
indication) in the dyestuffs which can be manufaotured accor ding to the invention, are given in the second column o~ the -table.
Compound ~rom which -ar- is derived Position of the bonds in -ar-diphenyl ,1- ~,4' ~2,2'-dimethyl-diphenyl 4,4'
ha~ing 1-6 C atoms, alkanoylamino having 1 6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having 6-20 C atoms, R~ = hydro-gen, methyl, carboxymethyl, sulphome-thyl, or an al~yl r'~dical which contains 2-6 C atoms and is optionally s~bsti-tuted by Cl, Br, OH, alkoxy having~1-6 C atoms~ alkanoylamino having 1-6 C a-toms, benzoylamino, alkanoyloxy having 1-6 C
atoms, -COOH or ~S03H, and R6 = methyl,carboxyme-thyl, alkyl having 2 or 3 C atoms, or benzyl or phenyl, it being possible for the aromatic nuclei to be monosubstitu-ted or disubstituted :by -COOH or SO~H.
The symbol k repres~ents the numbers 0, 1, 2 or 3, 1 ~: :
represents 0, l or 2 and m represents 1, 2,3 or 4 and the su~
o~ k, l and m is 3 or 4.
' Preferred amines of -the general f'ormula II which are to : be employed according to the invention are those in which Pc denotes the radlcal of a metal-'c'ontalnlng ph-thalocyanine, such as, for example, cobalt ph-thalocyanine or copper phthalocyanine, but especially -the radical of nickel ph-thalocyanine~
Aral~pha-tlc radicals which are represented by ar are always linked by means of an aroma-tlc nucleus to the -NH2 group, consequent~Ly in formula I to -the pyrazolone nucleus.
Mononuclear, aroma-tic or aralipha-tic radicals which can be represen-ted by ar, are -the optionally substituted radicals phenylene and monomethylene-phenylene or polyme-thylene-phenylene of the general formula ~ . ~
(CH ) ~
in which b deno-tes an integer from 1 to 10.
Dinuclear, aromatic or araliphatic radicals which can be represented by ar are -the opti.onally substituted radicals naphthylene, monomethylene-naphthylene or polymethylene-naphthylene of the general formula in which b denotes an in-teger from 1 to 3, and the optionallly substituted radicals of the formulae , . ~ Cil,, ~ 2-C~2 ~CH--CH~, ~U~ , ~N~
CO ~ and ~ S~2-.
5~
The following are ~xamples of mononuclear or dinuclear, aromatic or araliphatic hydrocarbons whlch can be represented by ar in the arnines o~ the formula II: 1,4~phenylene, 1,3-phenylene, 2-sulpho-1,4-phenylene, 3-sulpho-1,4-phenylene, 4-or 5~sulpho-1,3-phenylene, 2-carboxy-1,4-phenylene, 3-carboxy 1,4-phenylene, 4-, 5- or 6-carboxy-1,3-phenylene, 2-carboxy-5-sulpho-1,4-phenylene, 2~carboxy-6-sulpho-1,4-phenylene, 3-carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-1,3-pheny-lene, 5-carboxy~2-sulpho-1,3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dicarboxy-1,3 phenylene, 2-chloro-5-sulpho-1,4-phenylene, 2-chloro-6-sulpho-1,4-phenylene, 3-chloro-6-sulpho-i',4-phenylene, 6-chloro-4-sulpho-1,3-phenylene, 2-chl~ro-5-'carboxy-1,4-phenylene, 2,6-disulpho-1,4-phen~ylene, 2,5-disulpho-1,4-phenylene, 4,6-disulpho-1,3-phenylene, 3-chloro-6-carboxy-1,4-phenylene, 6-chloro-4 carboxy-1,3-phenylene, 4-chloro-5-carboxy-1,3-phenylenej 2 methyl-5-carboxy-1,4-pheny-lene, 2~ethyl-6-carboxy-1,4-phenylene, 3-ethyl-6-sulpho-1,4-~phenylene, 6-ethyl-4-oarboxy-1,3-phenylene, 6-propyl-4-sulpho-1,3-phenylene, 5-isopropyl-4-sulpho-1,3-phenylene, 5-isopropyl-6-carboxy-1,3-phenylene,4-n-butyl-6-sulpho-1,3-phenylene, 3-n-butyl-6-sulpho-1,4-phenylene, 4-tert~-butyl-6-sulpho-1,3~
phenylene, 3-1sobutyl-6-sulpho-1,4-phenylene, 2,5-diisopropyl-6-sulpho-1,4 phenylene, 2j4-diethyl-5-carboxy-l~3-phenylene~ -'' 2,4,6-trimethyl-5-sulpho-1,3-phénylene, 2-cyano-1,4-phenylene, 4-cyano-1,3-phenylene, 2-cyano-5-sulp'ho-1,4-phenylene9 2-tri~luoromethyl-l 9 4-phenylene, 2-methylsulphonyl-1,4-phenylene, 2-ethylsulphonyl-1,4-phenylene, 4-sulpho-1,5-naphthylene, 8-sulpho-1,5-naphthylene, 4-sulpho-2,6-naphthylene, 2-carboxy !~
.. . . .
- .
1,4-naphthylene, 2-carboxy-1,5-naphthylene, 5-carboxy-1,4-naphthylene, 3 carboxy-1,8-naph-thylene, 3-carboxy-1,5-naphthylene, 4-carboxy-2,6-naphthylene, Lr-carboxy-2,7-naphthylene, l-sulpho-2,6-naph-thylene, 8-sulpho-1,3-naphthylene, 4,8 disulpho-2,6 naphthylene, 3,7-disulpho-1,5-naphthylene, l-sulpho-4-chloro~2,6-naphthylene, 1-chloro-5-sulpho-2,6-naphthylene, l-chloro-7-sulpho 2,6-naphthylene, 2-chloro-6-sulpho-1,4-naphthylene, 1-methyl~4-sulpho 2,6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene. The hydrazone group here is in each case in the l-position of the phenyl nucleus or in the l-position or 2 position of the naphthalene nucleus.
The ~ollowing list indlcates examples of compounds from which urther divalent radicals ~hich are represented by ar are derived. The positions of the two bonds by means of which the divalent radicals are linked, on the one side, in the 1-;position of the pyrazolone (the first posi-tional indication) and, on the other ~ide, to the group -N- (the second positional R~
indication) in the dyestuffs which can be manufaotured accor ding to the invention, are given in the second column o~ the -table.
Compound ~rom which -ar- is derived Position of the bonds in -ar-diphenyl ,1- ~,4' ~2,2'-dimethyl-diphenyl 4,4'
3,3'-dimetho~y-diphenyl 4,4' . .
3,3'-dichloro-diphenyl 4,4i 3~3'-dimethyl-diphenyl 4,4i _ 9 Compound from which -ar- is derived Position of the bonds in -ar-~ . ~
2,2'-disulpho-diphenyl L~ ~ 4 diphenyl-ethane 4 ,L~ ~
diphenyl ether 4,4' 2,2'-disulpho-diphenyl-methane ~,41 292'-disulpho-diphenyl-ethane 4,4' 3,3'-disulpho-diphenyl-ethane 4,4' 2~2'-disulpho-diphenyl e-ther L~ ~ 4 2~sulphamido-diphenyl-e-thane 4,L~
2,2' disulphamide-diphenyl ethane 474l 2,2~ di-~-hydroxyethylsulphamido-dlphenyl- 4,4' stilbene-2,2'-disulphonic acid 4,4' methyl-phenyl 4,~ .
methyl-phenyl-3-sulphonic acid : 4 9 l~ethyl-phenyl-2-sulphonic acid 4 ,~
propyl-phenyl-3-sulphonic acid 4,~
5-methyl-naphthalene-1-sulphonic acid 2,w d1phenylamine 4,4' 6~methoxy-diphenylamine-2'-sulphonlc ac1d 3,4'
3,3'-dichloro-diphenyl 4,4i 3~3'-dimethyl-diphenyl 4,4i _ 9 Compound from which -ar- is derived Position of the bonds in -ar-~ . ~
2,2'-disulpho-diphenyl L~ ~ 4 diphenyl-ethane 4 ,L~ ~
diphenyl ether 4,4' 2,2'-disulpho-diphenyl-methane ~,41 292'-disulpho-diphenyl-ethane 4,4' 3,3'-disulpho-diphenyl-ethane 4,4' 2~2'-disulpho-diphenyl e-ther L~ ~ 4 2~sulphamido-diphenyl-e-thane 4,L~
2,2' disulphamide-diphenyl ethane 474l 2,2~ di-~-hydroxyethylsulphamido-dlphenyl- 4,4' stilbene-2,2'-disulphonic acid 4,4' methyl-phenyl 4,~ .
methyl-phenyl-3-sulphonic acid : 4 9 l~ethyl-phenyl-2-sulphonic acid 4 ,~
propyl-phenyl-3-sulphonic acid 4,~
5-methyl-naphthalene-1-sulphonic acid 2,w d1phenylamine 4,4' 6~methoxy-diphenylamine-2'-sulphonlc ac1d 3,4'
4~methyI-diphenylamine-2'-sulphonic acid 3~4~
d1phenylketone-5,5'-disulphonic acid 3,3' diphenylketone-3'-sulphonic acid 3~,4' ; :. . ".
~: dlphenyl sulphone 494' 4,4'-dichloro-diphenyl sulphone 3,3' 4,~4'-disulpho-diphenyl sulphone 3,3' 4~methyl-5-sulpho-diphenyl sulphone 3,3' !~
- The optionally substituted radicals phenylene, naph-thy-lene, -CH2 ~ , -C~l2-C~12 ~ ,-CU2 ~ and ~ CH-C~ ~
are preferred for ar in -the amines of the formula II which are to ~ be employed according to -the invention. The optionally .
substituted, mononuclear or dinuclear, aroma-tic or araliphatic hydrocarbon radical which i5 represented by ar in the amines o~ the formula II which aretobeemployed according to the inven-t~on, appropriately contains at least one sulpho group or carboxyl group, but valuable dyestuffs according to the inven-tion can a1so be obtained with radicals which have the general : : defin1tion of ar and contain no:acid gro~ps which impart solu-bility in water. In addition., ar can be subs-tituted in ~ , :
each nucleus by one~substituent ~rom -the group -OH7 a1koxy :having 1-4 C atoms., -CN, -CF39 -S02~6 or an additional ~S03H
group, or by one or two identical or different substituents of the group halogen, S02-N / or -COOH I~ ar is derived ~rom a phenylene.
radical, it can-~be substituted,."additionally to a -S03H group Which may be present, by one tQ three identical or different:
alkyl radicaIs having 1-4 C atoms ;, .
: ~ Amlnes of the formula II in which ar is phenylene or s : phenylene substituted by one or:two carboxyl groups or by one - or two sulpho groups or a naphthylene radical which is .
substituted by one or two sulpho groups or a stilbenyl radi-cal which is subs-titu-ted by one or two sulpho groups, are employed par-ticularly preferen-tially, especially those amines in which ar is a radical of -the formula ' SO
~31~
~0311 . . ~ .
or S~311 ~1~3 ~ ~ ' wherein the position shown here corresponds to -the positlon in the general formula I.
Amongst the amines of -the formula II which contain a Rl 502-N \ group in ar, preferred amines are tho~e in which R2 ~ ~ :
Rl and Rl independently o~ one another denote hydrogen, an alkyl radical which con-tains:2 or 3 C a-tome and is optlonally~
substituted by OH, alko~y havlng 1-3 C atoms, -COOH:or S03H, methyl, carboxymethyl or sulphomet~yl, and also those ln which : R2 and R2 independently of one'ano-ther denote an alkyl radical . which contains 2 or 3 C atoms and which l.S optionally sub ~ .. ati-tuted by OH~ alkoxy having 1-3 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having l-20 C a-toms, bu-t especially hydrogen, methyl, carboxymethyl or an alk~l radical - 1.2 -.
.
d1phenylketone-5,5'-disulphonic acid 3,3' diphenylketone-3'-sulphonic acid 3~,4' ; :. . ".
~: dlphenyl sulphone 494' 4,4'-dichloro-diphenyl sulphone 3,3' 4,~4'-disulpho-diphenyl sulphone 3,3' 4~methyl-5-sulpho-diphenyl sulphone 3,3' !~
- The optionally substituted radicals phenylene, naph-thy-lene, -CH2 ~ , -C~l2-C~12 ~ ,-CU2 ~ and ~ CH-C~ ~
are preferred for ar in -the amines of the formula II which are to ~ be employed according to -the invention. The optionally .
substituted, mononuclear or dinuclear, aroma-tic or araliphatic hydrocarbon radical which i5 represented by ar in the amines o~ the formula II which aretobeemployed according to the inven-t~on, appropriately contains at least one sulpho group or carboxyl group, but valuable dyestuffs according to the inven-tion can a1so be obtained with radicals which have the general : : defin1tion of ar and contain no:acid gro~ps which impart solu-bility in water. In addition., ar can be subs-tituted in ~ , :
each nucleus by one~substituent ~rom -the group -OH7 a1koxy :having 1-4 C atoms., -CN, -CF39 -S02~6 or an additional ~S03H
group, or by one or two identical or different substituents of the group halogen, S02-N / or -COOH I~ ar is derived ~rom a phenylene.
radical, it can-~be substituted,."additionally to a -S03H group Which may be present, by one tQ three identical or different:
alkyl radicaIs having 1-4 C atoms ;, .
: ~ Amlnes of the formula II in which ar is phenylene or s : phenylene substituted by one or:two carboxyl groups or by one - or two sulpho groups or a naphthylene radical which is .
substituted by one or two sulpho groups or a stilbenyl radi-cal which is subs-titu-ted by one or two sulpho groups, are employed par-ticularly preferen-tially, especially those amines in which ar is a radical of -the formula ' SO
~31~
~0311 . . ~ .
or S~311 ~1~3 ~ ~ ' wherein the position shown here corresponds to -the positlon in the general formula I.
Amongst the amines of -the formula II which contain a Rl 502-N \ group in ar, preferred amines are tho~e in which R2 ~ ~ :
Rl and Rl independently o~ one another denote hydrogen, an alkyl radical which con-tains:2 or 3 C a-tome and is optlonally~
substituted by OH, alko~y havlng 1-3 C atoms, -COOH:or S03H, methyl, carboxymethyl or sulphomet~yl, and also those ln which : R2 and R2 independently of one'ano-ther denote an alkyl radical . which contains 2 or 3 C atoms and which l.S optionally sub ~ .. ati-tuted by OH~ alkoxy having 1-3 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having l-20 C a-toms, bu-t especially hydrogen, methyl, carboxymethyl or an alk~l radical - 1.2 -.
.
5~6 .
which contains 2 or 3 C atom~ and ~hich is optionally sub-sti-tuted by OH.
Hydrogen, methyl or ~-hydroxyethyl are par-ticularly preferred meanings for R1 and R2. In the same way, hydro-gen, methyl and ~-hydroxyethyl are particularly preferred meanings for Rl and R2 Amines of -the formula II which carry no further sub-stituents beyond carboxylic acid and sulphonic acid esters in the divalent radical ar are particularly preferred.
Further preferred groups of amines of the general ~ ., form~ula II whichare to be employed according to the inven-tion are characterised in that R3 denotes hydrogen9 methyl9 carboxy-~methyl, sulphomethyl~or an ethyl radical which is optionallysubstituted by Cl9 OH, alkoxy having 1 or 2 C atoms, -COOH or ~; -SO3H, and especially hydrogen or me-thyl.
Amonget the amines of the formula II which contain a O~-R6 gro~p in ar, preferred amines are those in which R6 is~ ~methyl, ethyl, phenyl or carboxymethyl.
, - :
Particularly preferred amines of the general for~ula II whichareto be employed accord m g to the mvention are -those in which 1 is O, k is 2 or 3 and m is l or 2 and the sum of k + m is 4. ,, ~
The substituents indicated in formula II can be in the 3~position or the 4-position of the phthalocyanine. The position is preferred for the substituents indica-tedO
3-positions are the 3-, 3'-, 3"- and 3"'-posi-tlons and ~i 4-positi.o~s are the 4~, 4'-, 411_ and 4 "'-positions of the phthalocy~nine.
In the case where l represents 0, the ~mines o~ the general ~ormula II which are required ~or the manu~acture, accordi~g to the i~vention, o~ the dyestuffs of the formula I, are obtained by reacting phthalocyanine 3 or 4-disulpho-chlorides, trisulphochlorides or~ pre~erably, tetrasulpho chloride~ with amines of the general ~ormula X
HN~-ar-NH2 R3 X ~ .
wherei~ R3 and ar have the meanings indicated aboYe. Instead o~ the ami~es o~ the ~ormula X, it is also possible to employ mo~oacylated amines, ~or example acetylated amines of the formula ~a H
~ar~N-1-CH3 Xa ~3 In this case, the resulting conde~satio~ product with phthalo-cyan1ne sulphoohloride is subsequently ~aponi~ied~
I~ 1 in ~o~mula I or IV represents the ~umber 1, the amines o~ the formula II are obtained by reacting the phthalo-cyani~e 3~ or 4-~ulphochloride in any desired sequence with an amine o~ the general formula XI
HN / ~
'~
5:~6 in which Rl and R2 have -the meanings indicated above, and with an amine of the formula X.
In addi-tion, however, it is aIso possible to use a mix-ture of the amines of the ~or~nulae X and XI as the starting material from the outset. The reaction of the phthalocyanine sulphochloride with the said amines is carried out in a manner which is in itself known by adding -the amines, either suc-cesively or as a mixture, to a concentrated aqueous suspension of the sulphochlorides in water or in a mixture of wa-ter with organic, wa-ter-miscible solvents. The reaction can, how-ever 3 also be carried out solely in organic solvents. The temperature of the reaction mixture is kept at O to 35C and.
the pH value, which is continuously displaced into the acid range during -thè reaction, is kept between 4 and 10, preferably be-tween 6 and 8, by gradual addition of alkali. Alkalis ~which can be used are the customary substances with an alka-~; line reaction, such as sodium hydroxide solution, sodium carbonate, potassium carbonate or trisodium phosphate, Sod~
um hydroxide solution is pre~erred, I-t is advantageous to add a tertiary aminej such as, for example, pyridine, in cata-.
lytic amounts in order to accelerate the reaction. It is possible to process further the aminesofthe formula II direct . .
~in the aqueous solution in which they are produced, but on the whole it is advan-tageous -to isolate them in order to free them from a proportion of unreacted amine of the formula X andlor XI which may still be present, The following should be men-tioned as amines o~ the formula XX which can be used for the manufacture of the amines of the formula II: ammonia, me-thylamine, dime-thy]amine, ethyl-amine, diethylamine, ~-hydroxyethylamine, ~-me-tho~yethylamine, bis-~-hydroxye-thylamine, aminoacetic acid, taurine, n-me-thyl-taurine, butylamine 9 caprylamine, laurylamine, aniline, tolui-dine, chloroaniline, aniline-o-, -m- or -p-sulphonic acid, aniline-o~, -m- or -p-carboxylic acid, N-methylaniline, N-ethyl-aniline-o-, -m- or -p-sulphonic acid, aniline-~-methane-sulphonic acid, benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-sulphonic acid and ~-acetylaminoethylamine.
The following should be mentioned as examples of amines o~ the formula X, which can also be employed in the form of the ,.
~^ monoacyl compound: p-phenylenediamine, N-methyl-p-phenylene-diamine, N-carboxymethyl-p-phenylenediamine, m-phenylenediamine, . , N-~-hydroxy~thyl-m-phenylenediaminesl,4-phenylenediamine-2-sulphonic acid, l-amino-4-N-sulphomethylamlno-phenylene-2-sulphonic acid7 1,4-phenylenediamine-2,5- or -2,6-disulphonic acid, 1-ami~o-4~N-methylamino-phenylene-2,6-disulphonic acid, 1,3-phenylenediamine-4-sulphonic acia, 1,3-phenylenediamine-496-disulphonic acid, 2,4 diamino-toluene-5- or -6-sulphonic ~acid, 2,6-dlam1no-toluene-4-sulphonic acid, 2,5-diamino-1,3,5-trimethylbenzene-4-sulphonic acid, 2,6-dlamino-1,3-diethyl-benzene-4-sulphonic acid, 274-diamino-1-chlorobenzene-6-, . . .
sulphonic acid, 2,4-diamino-1-tert.-bu-tyl-benzene-6-suIphonic acid, 2,4-dlaminotoluene-5- or -6-sulphamide, 2,6-diamino--toluene-4-e-thanol or -diethanolsulphamide, 1,4-diamino- ;
- phenylene-2~dime-thylsulphamide, 1,3-diaminophenylene-4-sulph-anilide 9 1,~-diaminophenylene-4-~-hydroxye-thyl sulphone, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-i - 16 -.. . : ' .
8~i~L6 p-phenylenediamine, N-pentyl-p-phenylenediamine, N hexyl-p-phenylenediamine, N-~-hydroxy-propyl-p-phenylenediamineg N-~-carboxy-propyl-p-phenylenediamine, N-y-chloro-butyl-p-pheny-lenediamine, N-~-me-thoxy-bu-tyl-p-phenylenediamine, N-~-propoxy-butyl-p-phenylenediamine, N-~-ace-tylamino ethyl-p-phenylenediamine, N-~-butyrylamino-ethyl-p-phenylerediamine, N-benzoylamino-ethyl-p-phenylenediamine, 1-N me-thyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl-4-amino-benzene-3-sulphonic acid, 2~4 diamino-phenol-6~sulphonic acid, 2,4-diamino-1-methoxybenzene-5-sulphonic acid, 1,5-diaminonaph-thalene, 1,5-dlaminonaph-thalene-3-sulphonic acid, 1,5-diaminonaphthalene-4-sùlphonic acid9 1,5-diaminonaphthalene-2-sulphonic acid7 1,6-diaminonaphthalene-4-sulphonic acid, 1,4-diaminonaphthalene-2-sulphonic acid, 1,4-diaminonaphthalene-5-sulphonic acid, 1,4-diaminonaphthalene-7-sulphonic acid, 1,8-diaminonaphthalene-4-sulphonic acld, 2j6-diaminonaphthalene-8-sulphonic acld, 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,5-diaminonaph-thalene-3,7-disulphonic acid, 1,4-dlaminonaphthalene-5-~carboxylic acid, 1,4-dlaminonaphthalene-2-carboxylic acid, 1,8-diaminonaphtha-lene-3-carboxyllc acid, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4'-dlaminodiphenyl-2,2~~disulphonic acid, 3,3'-dimethoxy-4,4'-~diaminodiphenyl, 1-amino-4-aminomethyl-benzene, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 1-amino-4~~-amlnoethyl-benzene-2-sulphonic acid, 1-amino-4 Y-aminopropyl-benzene-3- -ulphonlc acid, 2-amino~5-aminomethyl-naphthalene-1-sulphonic acid, 4,4'-diamino-diphenylmethane-2,2'-disulphonic acid, 4,4'- 1 -diamino-diphenylethane-2,2'-disulphonic acid, 4~4'-diamino-diphenyle-thane-mono-sulphamide~ 4,4' diamino-dlphenylethane-disulphamide, 4,4'-diaminostilbene-2,2'~disulpho~ic acid, 4,4'-dia~ino~diphenylmethane, 4~4'-diamino-diph~nylethane-di-B-hydroxyethylsulphamide, 4 9 4' diamino-diphenylamine-3-sulphonic acid, 3,4'~diamino-6-methoxy-diphenylamine-2'-~ulpho~io acid9 3,4'-diamino-4-methyl-diphenylamine-2'-sulphonlc acld, 393'-diaminobenzophenone 5~5'-disulphonic acid, ~,4'-diaminobenzo-phenone-3'-sulphonic acld, 4,4'-diamino-dlphenyl sulphone, 4~4'-dichloro-3,3'-diamino-diphenyl sulphone, 3,3'-diamino-4-methyl-diphe~yl-sulphone-5-sulpho~ic acid and 3,3'-diamino-diphe~yl~sulphone-4,4'-disulphonic acid.
In the manufaeture, according to the inve~tio~, of the dyestuf~s o~ the ge~eral ~ormula I, an amine of the phthalo r cyanine series of the general formula II wherein the free ~mino group is linked to an aromatic C atom i~ the radical ar / ~S03H)k /R~
PC~ S2 N\
R~J
3 ~ m and wherein Pcr ar, R1D R2,R39 k, 1 and m have the abo~e-m~ntioned meanings, is fir~t diazotised and coupled i~ an aqueous medium at a p~I value between 3 and 8 with a succinlc acid derlvati~e of the formula III
5~6 R5-OOC-C~ CIl-COOR~ III
CO-Z
wherein R4 and R5 have the abovementioned meanings and Z
denotes hydrogen, an alkyl radical which con-tains 1-10 C
a-toms and is op-tionally substituted by alkoxy having 1-4 C
atoms or alkoxycarbonyl having 2-6 C atoms, a phenyl radical which is optionally substi-tuted by Cl, Br or alkyl or alkoxy having 1-4 C a-toms, or alkoxycarbonyl having 2-6 C atoms.
Pre~erred succinic acid derivatives of the formula III
which can be used are those in which R4 denotes an alkyl radi-cal which contains 2-6, preferably 2, C atoms and which is substituted by Cl, OH or alkoxy having 1-~, preferably 1-2, C atoms, or an unsubs-tituted~al~yl radical having 1-18, pre-ferably 1-6, ~ atoms, R5 denotes an ethyl radlcal which is substituted b~ Cl, OH or alkoxy having 1-2 C atoms, or an :
unsubsti-tuted alkyl radical having 1-18 C a-toms, and Z denotes hydrogen, alkyl havlng 1-3 C atoms, phenyl, methylphen~l or alkoxycarbonyl having 2 or 3 C atomsO
Succinic acid derivatives of the formula III in which R4~and~R5 are 1dentical and denote methyl or ethyl and Z rep-resents a methyl group) are particularly preferred.
The amines of the general formula II are diazotis~d i.n "- :
a manner which is in itself known~in an aqueous, acid medium by reaction with nitrous acid or an agent which splits off nitrou~ acid. A sal~t of nitrous acid, especially an alkali metal salt, such as sodium nitrite or potassium nitrite, in a mineral acid medium is generally employed as -the agent which -- 19 - .
splits off nitrous acid. In a pre~erred embodiment, a solu-tion of sodium nitrite is added in a molar ratio of 1 : m to the neutral, aqueous solution of 1 mol of an amine of -the form-ula II and this mixture is then run, at tempera-tures between -5 and -~25C, preferably -2 -to ~5C, into at least 2.5 mols, preferably 3 mols, per mol of amino group present, of dilute, approximately 5-15% strength, hydrochloric acidp while stirring.
The diazo suspension obtained in -this way is then reacted with a succinic acid derivative of the general formula III at a pH value between 3 and 8, preferably between 4.5 and 5.5, by adding the succinic acid deriva-tive to the acid suspension of .
the diazonium compounds and -then adjusting the pH value to the desired value by adding alkali, for example sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, potas-sium carbonate or sodium phosphate. Af-ter stirring for 1-3 hours~ the diazotised amine can no longer be de-tected and the forma~ion of the hydrazone is complete. It can be sepa-rated out from the solution by salting-out, that is to say by adding a neutral~ water-soluble salt, such as, fvr example, sodium chloride~or potassium chloride. It is, however, by :
no means necessary to separate out the hydrazones for fur~her processing, on the con-trary, it is appropriate and advantage-..
ous to employ the reaction solutions obtained ln -the coupling ~process direct for fur-ther processing The aqueous medium in which the coupling reaction of ; the diazotised amines of the formula II with ~he succinic acid derivatives of the ~ormula III is carried out, can also con- t tain organic, wa-ter-miscible solvents, particularly lower .~ ..
.
aliphatic alcohols, such as, for example, methanol, ethanol or isopropanol. In -the same way, it is possible for known coupling accelerators, such as, for example, urea or pyridine, to be presen-t during -the coupling reaction.
The second reaction stage of the manuac-turing pro-cess according to the invention, the cyclisation of the hydrazone IV to givethepyrazolone V, is carried ou-t extremely easily by alkaline trea-tment of the aqueous solu-tion of -the hydrazones of the formula IV at tempera-tures be-tween O and 100C, preferably 15 to 30C, at a pH value between 8 and 14, with elimina-tion of the alcohol of the formula R50H. It is ,~ . , .
possible to couple the cyclisation with a saponification of the group -COOR4 of the resul-ting pyrazolone to give the free carboxyl group. For this purpose lt is only necessary to carry out the reac-tion near to the upper limlt of -the range of pH values indicated, for example at pH values of 10 to 14.
The cyclisation i5 appropriately carried out direc-t in the reaction solution of the hydrazones of the formula IV which is produced in the coupling reaction, by raising its pH value to 10 to 14,~and room -temperature is generally adequate.
A diazo ~olution of an amine of the formula VI
: . . .
::
H2~ 3 A--)~ B - (C~12)~p - S02 - X~ (VI) m which A, B, X, p and n have the abovementioned meanings, is appropriately added to the soIution of the pyrazolone V
obtained in this way~ without isolating -the pyrazolone and S~6 after cooling -to tempera-tures between -~ and +35C, pre-ferably +5 to ~20C, and stirring is continued until the coupling reaction is comple-te, at -tempera-tures be-tween -5 and +25C, preferably -~5 to -~15C, wi-th cooling if necessary.
During the progress of -the coupling reactlon, which is gener-ally comple-te after only a few minu-tes, the pH value is kept at values of 3 to 8, preferably 5 to 6, by successive additions of a buffer substance or an alkali.
The amines of the formula VI are diazotised in a man-ner which is in itself known in an a~ueous medium by reaction with 1 mol of nitrous acid or an agent which splits off nit-rous acid, in the presence of a-t least 2 equivalen-ts, preferably approxima-tely Z.5 equivalen-ts, relative to 1 mol of the amine, of a s-trong acid. A sal-t of nitrous acid, particularly an alkall me-tal salt, such~as sodium nltrl-te or potassium m t-rite, in a mineral acid medium is generally employed as -the , . . .
agent which splits off nitrous acid.
If the diazonium compound of an amine o~ the formula VI ~lS coupled in the manufacturine process according to the invention w1th~the pyrazolone V9 the manufacture, accordlng to -the inventlon, of the water-soluble9 fibre-reactive phthalo-cyanine azo dyestuffs is complete after the coupling reac~ion has taken pLace.~ Thls~embodlment of the prooess according~ ;
to the inven-tion is preferred~.
The dyestuff can then be isolated by salting-out;
from the aqueous solutions of the phthalocyanine azo dyestuffs obtained in this way, or it can be obtained in the form of a solid dyestuff prepara-tion by~spray-drying the solutions.
The water-soluble, fibre-reac-tive phthalocyanine dyestuffs which can be manufactured according -to the invention are outstandingly sui-table for dyeing and prin-ting cellulose materials, cellulose-containing ma-terials and natural and synthetic polyamide ma-terials. They are distinguished' by a high degree of fixation, particularly in'prin-ting processes and in fixing by means of dry heat, and by ease of washing-out the non-fixed portion of dyestuff and they give yellowish-tinged to bluish-tinged green dyeings and prints of high brilliance and depth of colour which have very good fastness ~-to light, good fastness -to wet processing, such as washing at~60C and 95C~ fastness to sea water, fastness to acid and alkaline perspiration, fastne~ss to chlorinatedpoolwater,fastness to peroxides and fastness to flue gases.
Mixtures of dyestuf~s which can be manufactured accor-~' .
ding to the invention, especially those in which the meanings of k and/or 1 and/or m are different in the individual com-ponents, are also outstandingly sui-ta'ble for dyeing and printing cel1ulose materials and display -the same advantageous '~ ~propèrties as the individual~dyestuffs. Mixtures of this ~; type are obtalned, .~or example,~lf mlxtures of amlnes of the '~ ~formula II, the mdlvidual oomponents of which dif~er from one ~another in respect~of the meanings o~ k and/or 1 and/or m, are used as starting materials in th'e manufacture according to the invention~ Mixtures of amines~of the ~ormula~II in which, ; in general, one componen-t is substantially predominant9 are normally obtained in the manu-f'acture thereof by reacting phthalocyanine sulphochlorides with amines.
281 g of 4- aminophenyl-B-sulphatoe~hyl ~ulphone are dissolved ln about 6,000 ml of water to ~orm a neutr~l solutio~.
70 g of sodium ~itrite are added to the neutral solution and the mixture is the~ s-tirred into 250 ml o~ 10 N hydrochloric acid at 0 - 3C. Whe~ the dlazoti~atio~ is complete 9 the diazo suspension is added to a solution of N~ 3'-(3~carboxy-5-hydroxy-1-pyraæolyl)-4l-sulpho-phe~yl - Ni-trisulpho-phthalo eyaninylsulpho~amide to which 100 g o~ sodium bicarbonate have previously been added. The coupling i5 complete within a ~ew mi~utes.
The resulting green phthalocya~ine azo dyestuff can be isolated by salting-out or spray-dryi~g~ It has the following structure:
( 3 )3 NiPc -- S02-NH,~ N'~ COOE3[ ~so2- C~2-C~2-0S03 S~
The solution o~ the phthalocya~ine-pyrazolone which i~ required ~or the coupling can be obt~ined in the ~ollowing manner:
19060 g of 3 (3-amino-4-sulpho-phenyl)-ami~o~s~ phohyl-nickel-phthalocyanlne-3'5 3~l, 3n l-trisulphonic acid, which has been prepared in ths customary manner by a co~den~ation reac~io~
of nickel phthalocyanine sulphochloride wi~h 15~-diamino~
benzene-4-sulphonic acid, are stirred with 79000 ml o~ water and are dissolved by addlng 400 ml o~ 10 N ~odium hydroxide ,':
' solution. 72 g of sodlum nitri-te are added -to -this solu-tion and -the mixture is then s-tirred in-to a mixture of 2,0QO
g of ice and 300 ml of concentra-ted h~drochloric acid in the course of 30 minutes. A temperature of O -to 5C is main-tained by adding a further 2,000 g of ice. After a shor-t time any excess of nitri-te which may be present is destroyed by adding aminosulphonic acid. 21 g o~ acetylsuccinic acid dimethyl ester are poured into the diazo suspension obtained in this way. The pH value is then kept, first at 5.5 by sprinkling in approxima-tely 13 g of sodium carbonate, and then at 5 to 6 using approxima-tely 21 g of sodium bicarbonate.
~Stirring is then continued for approximately 1 hour, The end of the reaction is recognised from -the fact that the pH
remains constart and tha-t no alteration in colour shade occurs when a sample is treated wi-th a solution of H~acid in 2 N
sodlum carbonate. ~
350 ml~o~lO N~ alkali~metal hydroxide solution are added~to the solutlon of oxalacetic acid dimethyl ester- 3-nickel-trlsulpho-phthalocyaninylsulphonylamino) -6-sulpho-phenylhydraz~one obtained in thls way~ as a result o~ whlch the pH~rises to values of 12 to 13. ~ The~mixture is stirred or~a~few hours,~best~overnight at~room~temperature. The~
rearrangement to give N-~3-(3-oarboxy~5-hydroxy-1-pyrazolyl)-4-sulpho~phenyl]-nickel-trlsulpho-phthalocyanlnyl-sulphonamide is then complete; the pH is reduced -to 8 with a llt-tle hydro-chloric acid and the resulting crude solution is employed direct ~or coupllng.
Dyestuffs ha~ing similar properties are obtained lf~
' '. . , : , 35:~6 instead of 4-aminophenyl-~-sulphatoethyl sulphone~ equivalen-t quantities of the following amines are used: 3-aminopheny]-~-sulphatoethyl sulphone, 3-amino-4-me-thoxyphenyl-~-sulphatoethyl sulphone, 4-amino-3-methoxyphenyl-~-sulphatoe-thyl sulphone, 3-amino-4-me-thylphenyl-~-sulphatoe-thyl sulphone, 3-amino 4'-sulphophenyl-~ sulphatoe-thyl sulphone, 4-amino-3-bromophenyl-~-sulphatoethyl sulphone, 4-amino-3,5-dichlorophenyl-~-sulphatoethyl sulphone, 3-amino-4-carboxyphenyl-~-sulphato-ethyl sulphone, 3-amino-4-hydroxyphenyl-~-sulphatoethyl sul-phone, 4-amino-3-hy~roxyphenyl-~-sulphatoethyl sulphone, 4-amino-2,5-dimethoxyphenyl-~-sulphatoethyl sulphone, 4-amino-2-methyl-5-methoxyphenyl-~-sulphatoethyl sulphone', 4-amino-phenyl-~-(N,N-dimethylamino)-ethyl sulphone, 4-aminophenyl-~-(N9N-diethylamino)-ethyl sulphone, 4-amlnophenyl-~-phosphato- . '' ' ethyl sulphone, 4-aminophenyl-~-thiosulphatoethyl sulphone, 4-aminophenyl-~ chloroethyl sulphone, 3-aminophenyl-~-chloro~
ethyl sulphone, 4-aminophenyl-vinyl sulphone, 4-amino-3-chloro-5-me-thylphenyl-~-sulphatoethyl sulphone, 3-aminobenzyl-~csulphatoethyl sulphone, ~-(4-aminophenyl)-ethyl-~-sulphato- .
ethyl sulphone, 3-nitro-4-(4'-aminophenyl)-aminophenyl-~-sulphatoethyl sulphone, 2-phenylamino-5-amlno-phenyl-~-sulphatoethyl sulphone, 4~(4'-aminophenylsulphonyl)-phenyl-~-sulphatoethyl sulphone, 3-(4'~aminobenzoyl)-amino-phenyl-~-'sulphatoethyl sulphone, 3-(3'-aminophenylsulphonyl)-amino phenyl-~-sulphatoethyl sulphone, 4-amino-1-naphthyl-~- :
~ulphatoethyl sulphone, 5-amino-1-naphthyl-~-sulphatoethyl sulphone, 6-amino-1-naphthyl-~-sulphatoethyl sulphone, 6- 1 ~
amino-2-naphthyl-~-sulphatoethyl sulphone, 6-amino-1-sulpho-2- 1 ' ' .
naphthyl-~-sulpha-toethyl sulphone, 8-amino-2-naphthyl-~-sulphatoethyl sulphone and 8-amino-6-sulpho-2-naph-thyl-~-sulphatoethy]. sulphone.
Valuable green reac-tive dyestuffs are also obtained if the condensation produc-t of nickel phthalocyanine sulpho-chloride and one of the amines mentioned in the following text is used for the preparation of the coupling component instead of -the abovemen-tioned condensation product of nickel phthalocyanine sulphochloride and 19 3-diaminobenzenesulphonic acid, and if -the procedure followed is in other respects as described: 1,4-phenylenediamine-2-sulphonic acid, 1,3-phenylenediamine-4,6-disulphonic acid, 1,4-phenylenediamine-2,5-di~ulphonlc acid, 1,4-pheny].enedi.amlne-2,6-disulphonic acid, 2,4-diaminotoluene-6-sulphonic acid, 2,6-diaminotoluene-4-sulphonic acid, 274-diamino-1,3,5-trimethylbenzene-6-sulphonLc acid, 2,6-diaminonaph-thalene-4,8-disulphonic acid, 1,5-diaminonaphthalene-2-sulphonic acid, 2,6-diaminonaphtha-:
lene-8-sulphonic acid, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 2-amlno-5-aminomethyl-naphthalene-1-sulphonic acid, ,~ :
474'~-diamino-diphenylamine-3-sulphonic acid, 3,3'-diamino-4-methyl-diphenyl-sulphone-5-sulphonic acid,~l,3-phenylenediamlne (acetyl deriva-tlve, subsequently saponified), 2,4-diami.no-toluene (acetyl derivative7 subsequently saponified), 1,4-phenylenediamine (acetyl derlvative, subsequen-tly saponifled), 4,4'-diamino-diphenyle-thane-2,2'-disulphonic acid, 4,4'-diamino-diphenylethane-mono-sulphamide, 474 ' -diamino-diphenyl-e'thane-diSUlphamide 3 4, 4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diamino-diphenylamine-3-sulphonic acid, ~,4' ~ 6 diamino-6-methoxy-diphenylamine-2'-sulphonic acid9 ~,41_ diamino-4-methyl-diphenylamine-2'~sulphonic acld; 3~
diami~obenzophenone-5,5'-disulphonic acid, 3,4'~diaminobenzo-phenone-3l-sulphonic acid~ 4~4'~diamino-diphenyl ~ulphone9 4,4' dichloro-3~3'-diamino-diphenyl sulphone, 3,3'-diamin~-4-methyl-diphenyl-sulphone-5 sulphcnic acid and 3,3'-diamino-diphe~yl sulphone-4,4'-disulphonic acid.
Example 2:
281 ~ of 4~aminophenyl-B-sulphatoethyl sulpho~e are dissolved in about 6,000 ml of water to give a neutral solu-: tion. After adding 70 g of sodium nitrite, th~ solution is run into 250 ml of 10 N hydrochloric acld and the diazo sus~
pension obtained in this way is the~ a~ded, as described in Example 1, to a solution of the bi.spyrazolo~e prepar~d as des--cribed further on in the text from 535 g of 3~,3'~-bis~- (4-aminophenyl)-amino-sulphonyl -nickel-phthalocyanine-3'i, 3'~'-disulphonic acid. The pH is then ad~usted with 4 N ssdium carbonate solution ~o 7 ~ 7.2 and the green dyestu~ which ha~ formed is isolated by salting-out or spray-drying. The dyestuff has the following structure: ~:
(S0 ~2 NiPc (S02-NH' ~ ~ -N ~ S02-CU2-c}12-Os03~)2 The bispyrazolone employed as the coupling compo~ent was pre-pared in the following manner: 535 g of 3,3'-bis~ r(4-amlno-phenyl)-amino-~ulphonyl]-nickel phthalocya~ine-3'1,3'~
~ 28 ~uh.
?S~L6 disulphonic acid, prepared in the cus-tomary manner by a con-densation reaction be-tween 0.5 mol of nickel phthalocyanine tetrasulphochloride and 1 mol of acetyl-p-phenylenediamine and saponifica-tion of -the condensa-tion product, are stirred with 3,500 ml of water and are dissolved by adding 200 ml of 10 N sodium hydroxide solu-tion. 70 g of sodium nitrite are added to this ~oluti~on and the mixture is then stirred into a mix-ture of 2,000 g of ice and 300 ml of concentrated HC1 in the course of about 30 minu-tes. The temperature is kept between 0 and 5C by adding a further 100 g of ice. Stir-ring is continued for about 10 minutes and any slight excess of nitrite which may be presen-t is then removed by means of amidosulphonic acid. 135 g of ace-tylsuccinic acid diethyl ester are added to the diazo suspension ob-tained in this way.
The pH is adjusted to about 6 with approximately 250 g of sodium carbonate and is kept at this value until the dlazo compound can no longer be detected. This gives a solution of the turqu~se-coloured 3,3'-bis-[4-(1,2-bis-ethoxycarbonyl-ethylidene)-hydrazino-phenyl-aminosulphonyl]-nickel-phthalo-cyanine-3",3"'-disulphonic acid, which is converted direct, ' by theaction of alkali~ into -the corresponding bispyrazolone, by adding about hOo ml of 10 N sodium hydroxide~solutlon to the mixture and~stirring for approximately 4 hours' at room , .
temperature.
Valuable ph-thalocyanine hydrazones are also obtained ;i~ the corresponding 4,4~ 941? ,4111 deri~ative is used instead o~ -the amine employed above. I
Green phthalocyanine azo d~estu~fs are also obtained ~ -.
i~ the condensation product of nlckel phthalocyanine sulpho~ -chloride with two mols of one o~ the amines me~tioned i~ the table which follows is used instead of the amine employ~d above as the diazo compo~ent ~or the pyrazolo~e stage a~d i~
the procedure followed i~ in other resp cts as described abo~:
1 ,3-phe~yle~ediamine (acetyl deri~ative, subseque~tly saponi-fied) 9 2,4-diaminotolue~e (açetyl derivativey subs~quently saponi~ied), 2,4-diaminoanisole (acetyl derivative, subse-quently saponified), 1,4~pheny.enediamine-2-sulphonic acid, 2,4-diaminotoluene 6-sulphonic acid, 4~amino-be~zylamine (4-ac~tyl derivative 9 subsequently saponified), 4,4'-diami~o-stilbenedisulpho~ic acid, 4,4'~diami~omethanedisulphonic ac~d and 4,4' diami~o-diphe~ylami~e-3-sulphonic acid.
Arylhydra~ones which can be processed accord~ng to the inve~tion to give valuable azophthalocyanine dyestuffs are also obtained if the acetylsuccinic acld diethyl ester employed as the coupllng component ~or the pyrazolone ~tage is replaced by one of the ~ollowing derivatives of ~uccinic acid:
:
R5 - OOC C~2 - CH ~ C~O - R14 _ z o ..
, . .
~o .~ ~
-~H3 -CH3 ~
-CH~ -C2H4Cl ~CH3 -CH3 -i-C3H~ -CH3 -~H3 -i-C4Hg -COO CH3 -CH~ i C6H11 ~COO-C2H5 -CH3 -C ~4-OH -CH3 -CH3 . C3~0~H3 -COO-C3H4 -CH3 ~ -C2H5 -COO-C3H4 qC3H7 -c2~5 -C3 ~
C5H1 1 -.c2~5 -CH2-C6~I5 gH19 ~CZ~s -COO-CH3 -C16~3~ ~C2H5 6H5 -~2H4-0-~2H5 -C2H5 -C6H4-CH~3 ~ ` , Valuable hydrazones of oxalacetic acid methyl ester which G~ be prooessed ~urther to give the correspondingly substituted pyrazolones, are also obtained if,~ instead of the amine indicated i~ Example 1~ 3- r(3-~m1~o-4-sulpho-phenyl) :
.
amino-sulpho~yl]-niokel~phthalocyanine-3' 9 3" 9 3"'~trisulphonic acid, the eorresponding molar quantity of one o~ the~amines men-: tloned i~ the table which ~ollows is used a~d th~ proc~dure ~ollowed i~ in other respects as indicated in Example ~:
S03E~)k Po--( ~02-N~ ~) ~SO~ ar-N~2)m - 31 _ ,~> , , , ~ . . __ _ _ _ _ ~
i ! c~ m~ m~
C_~ C.\ O
__ ~ _ _ m :~ _ . ~ , , , , ~ . . .
' . .
m~
m m c~ m ~ m --- - - ---- ~ _ ~n 3~n ~ W
l 1 .
- ~, . .
~, .
;~ t -- ~5 2 s~
~ . ~
. . ~
- , .
s.-; -o~ o o~ 4~ o~
,n ~7 o ~ ~
u ' ~' ' ` ~ I , ~ :
o ~, I ~ ' ~,. . ~ .
' '.
A~ . ~ m m ::q ~ ~ m p~
..
" ', ,~, ~!f f~ f,--'f ~' r~
~,f,~`, ~, f~ r~ ~, ,,,~,~, ,~"
,~r,~,;
o~
w f ~r, f~ ;sff ~ fxf ~ ~ .
X, m 'I' ~ ~ ~ r f '':: l l l ' . . ,'', .
' ~8~
.. . . . . .. .
I
i ~ I .
1~
, o o ' ~) CJ m o . . . ~ _ o o j~ o o - ~ o C~ ~ -~' I C.)C.) ~i ~i i~ ~ m m .
~ I ' . . , ~
V Y ~ ' ~1 I O C ~
~: ~. o ~ I ` m ~ ~ -a~ i I oo c; o ~
m I ~s ~ F
v c~
r :
o o ~ ~ o ~
~ :
h .
a9 _ O ' ::q `~ ~ f- ~ : ' , . ~ , . . .
: . .
~ ~n : ` tl::
P~ ~ m : ~ ~ : ~ ~
~ V~~ ~ oC~ "
~ ~ , : ~ ; :, ':
s~ ~
,- I , f~f ~' ff_ t ,,. I ,~ o o o __ . , ~
~C f-f ff_. o .
- ';rff ~ ~3 ~
,:~
~ f f: ~ ~ ' .
; ~ ?i - ; ~
, ~" ~ ~ ~',)f,l; ff-~ ' ' ' ' '. ' '~
' ~ ff' ' ~ "; , ' '' .
.
which contains 2 or 3 C atom~ and ~hich is optionally sub-sti-tuted by OH.
Hydrogen, methyl or ~-hydroxyethyl are par-ticularly preferred meanings for R1 and R2. In the same way, hydro-gen, methyl and ~-hydroxyethyl are particularly preferred meanings for Rl and R2 Amines of -the formula II which carry no further sub-stituents beyond carboxylic acid and sulphonic acid esters in the divalent radical ar are particularly preferred.
Further preferred groups of amines of the general ~ ., form~ula II whichare to be employed according to the inven-tion are characterised in that R3 denotes hydrogen9 methyl9 carboxy-~methyl, sulphomethyl~or an ethyl radical which is optionallysubstituted by Cl9 OH, alkoxy having 1 or 2 C atoms, -COOH or ~; -SO3H, and especially hydrogen or me-thyl.
Amonget the amines of the formula II which contain a O~-R6 gro~p in ar, preferred amines are those in which R6 is~ ~methyl, ethyl, phenyl or carboxymethyl.
, - :
Particularly preferred amines of the general for~ula II whichareto be employed accord m g to the mvention are -those in which 1 is O, k is 2 or 3 and m is l or 2 and the sum of k + m is 4. ,, ~
The substituents indicated in formula II can be in the 3~position or the 4-position of the phthalocyanine. The position is preferred for the substituents indica-tedO
3-positions are the 3-, 3'-, 3"- and 3"'-posi-tlons and ~i 4-positi.o~s are the 4~, 4'-, 411_ and 4 "'-positions of the phthalocy~nine.
In the case where l represents 0, the ~mines o~ the general ~ormula II which are required ~or the manu~acture, accordi~g to the i~vention, o~ the dyestuffs of the formula I, are obtained by reacting phthalocyanine 3 or 4-disulpho-chlorides, trisulphochlorides or~ pre~erably, tetrasulpho chloride~ with amines of the general ~ormula X
HN~-ar-NH2 R3 X ~ .
wherei~ R3 and ar have the meanings indicated aboYe. Instead o~ the ami~es o~ the ~ormula X, it is also possible to employ mo~oacylated amines, ~or example acetylated amines of the formula ~a H
~ar~N-1-CH3 Xa ~3 In this case, the resulting conde~satio~ product with phthalo-cyan1ne sulphoohloride is subsequently ~aponi~ied~
I~ 1 in ~o~mula I or IV represents the ~umber 1, the amines o~ the formula II are obtained by reacting the phthalo-cyani~e 3~ or 4-~ulphochloride in any desired sequence with an amine o~ the general formula XI
HN / ~
'~
5:~6 in which Rl and R2 have -the meanings indicated above, and with an amine of the formula X.
In addi-tion, however, it is aIso possible to use a mix-ture of the amines of the ~or~nulae X and XI as the starting material from the outset. The reaction of the phthalocyanine sulphochloride with the said amines is carried out in a manner which is in itself known by adding -the amines, either suc-cesively or as a mixture, to a concentrated aqueous suspension of the sulphochlorides in water or in a mixture of wa-ter with organic, wa-ter-miscible solvents. The reaction can, how-ever 3 also be carried out solely in organic solvents. The temperature of the reaction mixture is kept at O to 35C and.
the pH value, which is continuously displaced into the acid range during -thè reaction, is kept between 4 and 10, preferably be-tween 6 and 8, by gradual addition of alkali. Alkalis ~which can be used are the customary substances with an alka-~; line reaction, such as sodium hydroxide solution, sodium carbonate, potassium carbonate or trisodium phosphate, Sod~
um hydroxide solution is pre~erred, I-t is advantageous to add a tertiary aminej such as, for example, pyridine, in cata-.
lytic amounts in order to accelerate the reaction. It is possible to process further the aminesofthe formula II direct . .
~in the aqueous solution in which they are produced, but on the whole it is advan-tageous -to isolate them in order to free them from a proportion of unreacted amine of the formula X andlor XI which may still be present, The following should be men-tioned as amines o~ the formula XX which can be used for the manufacture of the amines of the formula II: ammonia, me-thylamine, dime-thy]amine, ethyl-amine, diethylamine, ~-hydroxyethylamine, ~-me-tho~yethylamine, bis-~-hydroxye-thylamine, aminoacetic acid, taurine, n-me-thyl-taurine, butylamine 9 caprylamine, laurylamine, aniline, tolui-dine, chloroaniline, aniline-o-, -m- or -p-sulphonic acid, aniline-o~, -m- or -p-carboxylic acid, N-methylaniline, N-ethyl-aniline-o-, -m- or -p-sulphonic acid, aniline-~-methane-sulphonic acid, benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-sulphonic acid and ~-acetylaminoethylamine.
The following should be mentioned as examples of amines o~ the formula X, which can also be employed in the form of the ,.
~^ monoacyl compound: p-phenylenediamine, N-methyl-p-phenylene-diamine, N-carboxymethyl-p-phenylenediamine, m-phenylenediamine, . , N-~-hydroxy~thyl-m-phenylenediaminesl,4-phenylenediamine-2-sulphonic acid, l-amino-4-N-sulphomethylamlno-phenylene-2-sulphonic acid7 1,4-phenylenediamine-2,5- or -2,6-disulphonic acid, 1-ami~o-4~N-methylamino-phenylene-2,6-disulphonic acid, 1,3-phenylenediamine-4-sulphonic acia, 1,3-phenylenediamine-496-disulphonic acid, 2,4 diamino-toluene-5- or -6-sulphonic ~acid, 2,6-dlam1no-toluene-4-sulphonic acid, 2,5-diamino-1,3,5-trimethylbenzene-4-sulphonic acid, 2,6-dlamino-1,3-diethyl-benzene-4-sulphonic acid, 274-diamino-1-chlorobenzene-6-, . . .
sulphonic acid, 2,4-diamino-1-tert.-bu-tyl-benzene-6-suIphonic acid, 2,4-dlaminotoluene-5- or -6-sulphamide, 2,6-diamino--toluene-4-e-thanol or -diethanolsulphamide, 1,4-diamino- ;
- phenylene-2~dime-thylsulphamide, 1,3-diaminophenylene-4-sulph-anilide 9 1,~-diaminophenylene-4-~-hydroxye-thyl sulphone, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-i - 16 -.. . : ' .
8~i~L6 p-phenylenediamine, N-pentyl-p-phenylenediamine, N hexyl-p-phenylenediamine, N-~-hydroxy-propyl-p-phenylenediamineg N-~-carboxy-propyl-p-phenylenediamine, N-y-chloro-butyl-p-pheny-lenediamine, N-~-me-thoxy-bu-tyl-p-phenylenediamine, N-~-propoxy-butyl-p-phenylenediamine, N-~-ace-tylamino ethyl-p-phenylenediamine, N-~-butyrylamino-ethyl-p-phenylerediamine, N-benzoylamino-ethyl-p-phenylenediamine, 1-N me-thyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl-4-amino-benzene-3-sulphonic acid, 2~4 diamino-phenol-6~sulphonic acid, 2,4-diamino-1-methoxybenzene-5-sulphonic acid, 1,5-diaminonaph-thalene, 1,5-dlaminonaph-thalene-3-sulphonic acid, 1,5-diaminonaphthalene-4-sùlphonic acid9 1,5-diaminonaphthalene-2-sulphonic acid7 1,6-diaminonaphthalene-4-sulphonic acid, 1,4-diaminonaphthalene-2-sulphonic acid, 1,4-diaminonaphthalene-5-sulphonic acid, 1,4-diaminonaphthalene-7-sulphonic acid, 1,8-diaminonaphthalene-4-sulphonic acld, 2j6-diaminonaphthalene-8-sulphonic acld, 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,5-diaminonaph-thalene-3,7-disulphonic acid, 1,4-dlaminonaphthalene-5-~carboxylic acid, 1,4-dlaminonaphthalene-2-carboxylic acid, 1,8-diaminonaphtha-lene-3-carboxyllc acid, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4'-dlaminodiphenyl-2,2~~disulphonic acid, 3,3'-dimethoxy-4,4'-~diaminodiphenyl, 1-amino-4-aminomethyl-benzene, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 1-amino-4~~-amlnoethyl-benzene-2-sulphonic acid, 1-amino-4 Y-aminopropyl-benzene-3- -ulphonlc acid, 2-amino~5-aminomethyl-naphthalene-1-sulphonic acid, 4,4'-diamino-diphenylmethane-2,2'-disulphonic acid, 4,4'- 1 -diamino-diphenylethane-2,2'-disulphonic acid, 4~4'-diamino-diphenyle-thane-mono-sulphamide~ 4,4' diamino-dlphenylethane-disulphamide, 4,4'-diaminostilbene-2,2'~disulpho~ic acid, 4,4'-dia~ino~diphenylmethane, 4~4'-diamino-diph~nylethane-di-B-hydroxyethylsulphamide, 4 9 4' diamino-diphenylamine-3-sulphonic acid, 3,4'~diamino-6-methoxy-diphenylamine-2'-~ulpho~io acid9 3,4'-diamino-4-methyl-diphenylamine-2'-sulphonlc acld, 393'-diaminobenzophenone 5~5'-disulphonic acid, ~,4'-diaminobenzo-phenone-3'-sulphonic acld, 4,4'-diamino-dlphenyl sulphone, 4~4'-dichloro-3,3'-diamino-diphenyl sulphone, 3,3'-diamino-4-methyl-diphe~yl-sulphone-5-sulpho~ic acid and 3,3'-diamino-diphe~yl~sulphone-4,4'-disulphonic acid.
In the manufaeture, according to the inve~tio~, of the dyestuf~s o~ the ge~eral ~ormula I, an amine of the phthalo r cyanine series of the general formula II wherein the free ~mino group is linked to an aromatic C atom i~ the radical ar / ~S03H)k /R~
PC~ S2 N\
R~J
3 ~ m and wherein Pcr ar, R1D R2,R39 k, 1 and m have the abo~e-m~ntioned meanings, is fir~t diazotised and coupled i~ an aqueous medium at a p~I value between 3 and 8 with a succinlc acid derlvati~e of the formula III
5~6 R5-OOC-C~ CIl-COOR~ III
CO-Z
wherein R4 and R5 have the abovementioned meanings and Z
denotes hydrogen, an alkyl radical which con-tains 1-10 C
a-toms and is op-tionally substituted by alkoxy having 1-4 C
atoms or alkoxycarbonyl having 2-6 C atoms, a phenyl radical which is optionally substi-tuted by Cl, Br or alkyl or alkoxy having 1-4 C a-toms, or alkoxycarbonyl having 2-6 C atoms.
Pre~erred succinic acid derivatives of the formula III
which can be used are those in which R4 denotes an alkyl radi-cal which contains 2-6, preferably 2, C atoms and which is substituted by Cl, OH or alkoxy having 1-~, preferably 1-2, C atoms, or an unsubs-tituted~al~yl radical having 1-18, pre-ferably 1-6, ~ atoms, R5 denotes an ethyl radlcal which is substituted b~ Cl, OH or alkoxy having 1-2 C atoms, or an :
unsubsti-tuted alkyl radical having 1-18 C a-toms, and Z denotes hydrogen, alkyl havlng 1-3 C atoms, phenyl, methylphen~l or alkoxycarbonyl having 2 or 3 C atomsO
Succinic acid derivatives of the formula III in which R4~and~R5 are 1dentical and denote methyl or ethyl and Z rep-resents a methyl group) are particularly preferred.
The amines of the general formula II are diazotis~d i.n "- :
a manner which is in itself known~in an aqueous, acid medium by reaction with nitrous acid or an agent which splits off nitrou~ acid. A sal~t of nitrous acid, especially an alkali metal salt, such as sodium nitrite or potassium nitrite, in a mineral acid medium is generally employed as -the agent which -- 19 - .
splits off nitrous acid. In a pre~erred embodiment, a solu-tion of sodium nitrite is added in a molar ratio of 1 : m to the neutral, aqueous solution of 1 mol of an amine of -the form-ula II and this mixture is then run, at tempera-tures between -5 and -~25C, preferably -2 -to ~5C, into at least 2.5 mols, preferably 3 mols, per mol of amino group present, of dilute, approximately 5-15% strength, hydrochloric acidp while stirring.
The diazo suspension obtained in -this way is then reacted with a succinic acid derivative of the general formula III at a pH value between 3 and 8, preferably between 4.5 and 5.5, by adding the succinic acid deriva-tive to the acid suspension of .
the diazonium compounds and -then adjusting the pH value to the desired value by adding alkali, for example sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, potas-sium carbonate or sodium phosphate. Af-ter stirring for 1-3 hours~ the diazotised amine can no longer be de-tected and the forma~ion of the hydrazone is complete. It can be sepa-rated out from the solution by salting-out, that is to say by adding a neutral~ water-soluble salt, such as, fvr example, sodium chloride~or potassium chloride. It is, however, by :
no means necessary to separate out the hydrazones for fur~her processing, on the con-trary, it is appropriate and advantage-..
ous to employ the reaction solutions obtained ln -the coupling ~process direct for fur-ther processing The aqueous medium in which the coupling reaction of ; the diazotised amines of the formula II with ~he succinic acid derivatives of the ~ormula III is carried out, can also con- t tain organic, wa-ter-miscible solvents, particularly lower .~ ..
.
aliphatic alcohols, such as, for example, methanol, ethanol or isopropanol. In -the same way, it is possible for known coupling accelerators, such as, for example, urea or pyridine, to be presen-t during -the coupling reaction.
The second reaction stage of the manuac-turing pro-cess according to the invention, the cyclisation of the hydrazone IV to givethepyrazolone V, is carried ou-t extremely easily by alkaline trea-tment of the aqueous solu-tion of -the hydrazones of the formula IV at tempera-tures be-tween O and 100C, preferably 15 to 30C, at a pH value between 8 and 14, with elimina-tion of the alcohol of the formula R50H. It is ,~ . , .
possible to couple the cyclisation with a saponification of the group -COOR4 of the resul-ting pyrazolone to give the free carboxyl group. For this purpose lt is only necessary to carry out the reac-tion near to the upper limlt of -the range of pH values indicated, for example at pH values of 10 to 14.
The cyclisation i5 appropriately carried out direc-t in the reaction solution of the hydrazones of the formula IV which is produced in the coupling reaction, by raising its pH value to 10 to 14,~and room -temperature is generally adequate.
A diazo ~olution of an amine of the formula VI
: . . .
::
H2~ 3 A--)~ B - (C~12)~p - S02 - X~ (VI) m which A, B, X, p and n have the abovementioned meanings, is appropriately added to the soIution of the pyrazolone V
obtained in this way~ without isolating -the pyrazolone and S~6 after cooling -to tempera-tures between -~ and +35C, pre-ferably +5 to ~20C, and stirring is continued until the coupling reaction is comple-te, at -tempera-tures be-tween -5 and +25C, preferably -~5 to -~15C, wi-th cooling if necessary.
During the progress of -the coupling reactlon, which is gener-ally comple-te after only a few minu-tes, the pH value is kept at values of 3 to 8, preferably 5 to 6, by successive additions of a buffer substance or an alkali.
The amines of the formula VI are diazotised in a man-ner which is in itself known in an a~ueous medium by reaction with 1 mol of nitrous acid or an agent which splits off nit-rous acid, in the presence of a-t least 2 equivalen-ts, preferably approxima-tely Z.5 equivalen-ts, relative to 1 mol of the amine, of a s-trong acid. A sal-t of nitrous acid, particularly an alkall me-tal salt, such~as sodium nltrl-te or potassium m t-rite, in a mineral acid medium is generally employed as -the , . . .
agent which splits off nitrous acid.
If the diazonium compound of an amine o~ the formula VI ~lS coupled in the manufacturine process according to the invention w1th~the pyrazolone V9 the manufacture, accordlng to -the inventlon, of the water-soluble9 fibre-reactive phthalo-cyanine azo dyestuffs is complete after the coupling reac~ion has taken pLace.~ Thls~embodlment of the prooess according~ ;
to the inven-tion is preferred~.
The dyestuff can then be isolated by salting-out;
from the aqueous solutions of the phthalocyanine azo dyestuffs obtained in this way, or it can be obtained in the form of a solid dyestuff prepara-tion by~spray-drying the solutions.
The water-soluble, fibre-reac-tive phthalocyanine dyestuffs which can be manufactured according -to the invention are outstandingly sui-table for dyeing and prin-ting cellulose materials, cellulose-containing ma-terials and natural and synthetic polyamide ma-terials. They are distinguished' by a high degree of fixation, particularly in'prin-ting processes and in fixing by means of dry heat, and by ease of washing-out the non-fixed portion of dyestuff and they give yellowish-tinged to bluish-tinged green dyeings and prints of high brilliance and depth of colour which have very good fastness ~-to light, good fastness -to wet processing, such as washing at~60C and 95C~ fastness to sea water, fastness to acid and alkaline perspiration, fastne~ss to chlorinatedpoolwater,fastness to peroxides and fastness to flue gases.
Mixtures of dyestuf~s which can be manufactured accor-~' .
ding to the invention, especially those in which the meanings of k and/or 1 and/or m are different in the individual com-ponents, are also outstandingly sui-ta'ble for dyeing and printing cel1ulose materials and display -the same advantageous '~ ~propèrties as the individual~dyestuffs. Mixtures of this ~; type are obtalned, .~or example,~lf mlxtures of amlnes of the '~ ~formula II, the mdlvidual oomponents of which dif~er from one ~another in respect~of the meanings o~ k and/or 1 and/or m, are used as starting materials in th'e manufacture according to the invention~ Mixtures of amines~of the ~ormula~II in which, ; in general, one componen-t is substantially predominant9 are normally obtained in the manu-f'acture thereof by reacting phthalocyanine sulphochlorides with amines.
281 g of 4- aminophenyl-B-sulphatoe~hyl ~ulphone are dissolved ln about 6,000 ml of water to ~orm a neutr~l solutio~.
70 g of sodium ~itrite are added to the neutral solution and the mixture is the~ s-tirred into 250 ml o~ 10 N hydrochloric acid at 0 - 3C. Whe~ the dlazoti~atio~ is complete 9 the diazo suspension is added to a solution of N~ 3'-(3~carboxy-5-hydroxy-1-pyraæolyl)-4l-sulpho-phe~yl - Ni-trisulpho-phthalo eyaninylsulpho~amide to which 100 g o~ sodium bicarbonate have previously been added. The coupling i5 complete within a ~ew mi~utes.
The resulting green phthalocya~ine azo dyestuff can be isolated by salting-out or spray-dryi~g~ It has the following structure:
( 3 )3 NiPc -- S02-NH,~ N'~ COOE3[ ~so2- C~2-C~2-0S03 S~
The solution o~ the phthalocya~ine-pyrazolone which i~ required ~or the coupling can be obt~ined in the ~ollowing manner:
19060 g of 3 (3-amino-4-sulpho-phenyl)-ami~o~s~ phohyl-nickel-phthalocyanlne-3'5 3~l, 3n l-trisulphonic acid, which has been prepared in ths customary manner by a co~den~ation reac~io~
of nickel phthalocyanine sulphochloride wi~h 15~-diamino~
benzene-4-sulphonic acid, are stirred with 79000 ml o~ water and are dissolved by addlng 400 ml o~ 10 N ~odium hydroxide ,':
' solution. 72 g of sodlum nitri-te are added -to -this solu-tion and -the mixture is then s-tirred in-to a mixture of 2,0QO
g of ice and 300 ml of concentra-ted h~drochloric acid in the course of 30 minutes. A temperature of O -to 5C is main-tained by adding a further 2,000 g of ice. After a shor-t time any excess of nitri-te which may be present is destroyed by adding aminosulphonic acid. 21 g o~ acetylsuccinic acid dimethyl ester are poured into the diazo suspension obtained in this way. The pH value is then kept, first at 5.5 by sprinkling in approxima-tely 13 g of sodium carbonate, and then at 5 to 6 using approxima-tely 21 g of sodium bicarbonate.
~Stirring is then continued for approximately 1 hour, The end of the reaction is recognised from -the fact that the pH
remains constart and tha-t no alteration in colour shade occurs when a sample is treated wi-th a solution of H~acid in 2 N
sodlum carbonate. ~
350 ml~o~lO N~ alkali~metal hydroxide solution are added~to the solutlon of oxalacetic acid dimethyl ester- 3-nickel-trlsulpho-phthalocyaninylsulphonylamino) -6-sulpho-phenylhydraz~one obtained in thls way~ as a result o~ whlch the pH~rises to values of 12 to 13. ~ The~mixture is stirred or~a~few hours,~best~overnight at~room~temperature. The~
rearrangement to give N-~3-(3-oarboxy~5-hydroxy-1-pyrazolyl)-4-sulpho~phenyl]-nickel-trlsulpho-phthalocyanlnyl-sulphonamide is then complete; the pH is reduced -to 8 with a llt-tle hydro-chloric acid and the resulting crude solution is employed direct ~or coupllng.
Dyestuffs ha~ing similar properties are obtained lf~
' '. . , : , 35:~6 instead of 4-aminophenyl-~-sulphatoethyl sulphone~ equivalen-t quantities of the following amines are used: 3-aminopheny]-~-sulphatoethyl sulphone, 3-amino-4-me-thoxyphenyl-~-sulphatoethyl sulphone, 4-amino-3-methoxyphenyl-~-sulphatoe-thyl sulphone, 3-amino-4-me-thylphenyl-~-sulphatoe-thyl sulphone, 3-amino 4'-sulphophenyl-~ sulphatoe-thyl sulphone, 4-amino-3-bromophenyl-~-sulphatoethyl sulphone, 4-amino-3,5-dichlorophenyl-~-sulphatoethyl sulphone, 3-amino-4-carboxyphenyl-~-sulphato-ethyl sulphone, 3-amino-4-hydroxyphenyl-~-sulphatoethyl sul-phone, 4-amino-3-hy~roxyphenyl-~-sulphatoethyl sulphone, 4-amino-2,5-dimethoxyphenyl-~-sulphatoethyl sulphone, 4-amino-2-methyl-5-methoxyphenyl-~-sulphatoethyl sulphone', 4-amino-phenyl-~-(N,N-dimethylamino)-ethyl sulphone, 4-aminophenyl-~-(N9N-diethylamino)-ethyl sulphone, 4-amlnophenyl-~-phosphato- . '' ' ethyl sulphone, 4-aminophenyl-~-thiosulphatoethyl sulphone, 4-aminophenyl-~ chloroethyl sulphone, 3-aminophenyl-~-chloro~
ethyl sulphone, 4-aminophenyl-vinyl sulphone, 4-amino-3-chloro-5-me-thylphenyl-~-sulphatoethyl sulphone, 3-aminobenzyl-~csulphatoethyl sulphone, ~-(4-aminophenyl)-ethyl-~-sulphato- .
ethyl sulphone, 3-nitro-4-(4'-aminophenyl)-aminophenyl-~-sulphatoethyl sulphone, 2-phenylamino-5-amlno-phenyl-~-sulphatoethyl sulphone, 4~(4'-aminophenylsulphonyl)-phenyl-~-sulphatoethyl sulphone, 3-(4'~aminobenzoyl)-amino-phenyl-~-'sulphatoethyl sulphone, 3-(3'-aminophenylsulphonyl)-amino phenyl-~-sulphatoethyl sulphone, 4-amino-1-naphthyl-~- :
~ulphatoethyl sulphone, 5-amino-1-naphthyl-~-sulphatoethyl sulphone, 6-amino-1-naphthyl-~-sulphatoethyl sulphone, 6- 1 ~
amino-2-naphthyl-~-sulphatoethyl sulphone, 6-amino-1-sulpho-2- 1 ' ' .
naphthyl-~-sulpha-toethyl sulphone, 8-amino-2-naphthyl-~-sulphatoethyl sulphone and 8-amino-6-sulpho-2-naph-thyl-~-sulphatoethy]. sulphone.
Valuable green reac-tive dyestuffs are also obtained if the condensation produc-t of nickel phthalocyanine sulpho-chloride and one of the amines mentioned in the following text is used for the preparation of the coupling component instead of -the abovemen-tioned condensation product of nickel phthalocyanine sulphochloride and 19 3-diaminobenzenesulphonic acid, and if -the procedure followed is in other respects as described: 1,4-phenylenediamine-2-sulphonic acid, 1,3-phenylenediamine-4,6-disulphonic acid, 1,4-phenylenediamine-2,5-di~ulphonlc acid, 1,4-pheny].enedi.amlne-2,6-disulphonic acid, 2,4-diaminotoluene-6-sulphonic acid, 2,6-diaminotoluene-4-sulphonic acid, 274-diamino-1,3,5-trimethylbenzene-6-sulphonLc acid, 2,6-diaminonaph-thalene-4,8-disulphonic acid, 1,5-diaminonaphthalene-2-sulphonic acid, 2,6-diaminonaphtha-:
lene-8-sulphonic acid, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 2-amlno-5-aminomethyl-naphthalene-1-sulphonic acid, ,~ :
474'~-diamino-diphenylamine-3-sulphonic acid, 3,3'-diamino-4-methyl-diphenyl-sulphone-5-sulphonic acid,~l,3-phenylenediamlne (acetyl deriva-tlve, subsequently saponified), 2,4-diami.no-toluene (acetyl derivative7 subsequently saponified), 1,4-phenylenediamine (acetyl derlvative, subsequen-tly saponifled), 4,4'-diamino-diphenyle-thane-2,2'-disulphonic acid, 4,4'-diamino-diphenylethane-mono-sulphamide, 474 ' -diamino-diphenyl-e'thane-diSUlphamide 3 4, 4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diamino-diphenylamine-3-sulphonic acid, ~,4' ~ 6 diamino-6-methoxy-diphenylamine-2'-sulphonic acid9 ~,41_ diamino-4-methyl-diphenylamine-2'~sulphonic acld; 3~
diami~obenzophenone-5,5'-disulphonic acid, 3,4'~diaminobenzo-phenone-3l-sulphonic acid~ 4~4'~diamino-diphenyl ~ulphone9 4,4' dichloro-3~3'-diamino-diphenyl sulphone, 3,3'-diamin~-4-methyl-diphenyl-sulphone-5 sulphcnic acid and 3,3'-diamino-diphe~yl sulphone-4,4'-disulphonic acid.
Example 2:
281 ~ of 4~aminophenyl-B-sulphatoethyl sulpho~e are dissolved in about 6,000 ml of water to give a neutral solu-: tion. After adding 70 g of sodium nitrite, th~ solution is run into 250 ml of 10 N hydrochloric acld and the diazo sus~
pension obtained in this way is the~ a~ded, as described in Example 1, to a solution of the bi.spyrazolo~e prepar~d as des--cribed further on in the text from 535 g of 3~,3'~-bis~- (4-aminophenyl)-amino-sulphonyl -nickel-phthalocyanine-3'i, 3'~'-disulphonic acid. The pH is then ad~usted with 4 N ssdium carbonate solution ~o 7 ~ 7.2 and the green dyestu~ which ha~ formed is isolated by salting-out or spray-drying. The dyestuff has the following structure: ~:
(S0 ~2 NiPc (S02-NH' ~ ~ -N ~ S02-CU2-c}12-Os03~)2 The bispyrazolone employed as the coupling compo~ent was pre-pared in the following manner: 535 g of 3,3'-bis~ r(4-amlno-phenyl)-amino-~ulphonyl]-nickel phthalocya~ine-3'1,3'~
~ 28 ~uh.
?S~L6 disulphonic acid, prepared in the cus-tomary manner by a con-densation reaction be-tween 0.5 mol of nickel phthalocyanine tetrasulphochloride and 1 mol of acetyl-p-phenylenediamine and saponifica-tion of -the condensa-tion product, are stirred with 3,500 ml of water and are dissolved by adding 200 ml of 10 N sodium hydroxide solu-tion. 70 g of sodium nitrite are added to this ~oluti~on and the mixture is then stirred into a mix-ture of 2,000 g of ice and 300 ml of concentrated HC1 in the course of about 30 minu-tes. The temperature is kept between 0 and 5C by adding a further 100 g of ice. Stir-ring is continued for about 10 minutes and any slight excess of nitrite which may be presen-t is then removed by means of amidosulphonic acid. 135 g of ace-tylsuccinic acid diethyl ester are added to the diazo suspension ob-tained in this way.
The pH is adjusted to about 6 with approximately 250 g of sodium carbonate and is kept at this value until the dlazo compound can no longer be detected. This gives a solution of the turqu~se-coloured 3,3'-bis-[4-(1,2-bis-ethoxycarbonyl-ethylidene)-hydrazino-phenyl-aminosulphonyl]-nickel-phthalo-cyanine-3",3"'-disulphonic acid, which is converted direct, ' by theaction of alkali~ into -the corresponding bispyrazolone, by adding about hOo ml of 10 N sodium hydroxide~solutlon to the mixture and~stirring for approximately 4 hours' at room , .
temperature.
Valuable ph-thalocyanine hydrazones are also obtained ;i~ the corresponding 4,4~ 941? ,4111 deri~ative is used instead o~ -the amine employed above. I
Green phthalocyanine azo d~estu~fs are also obtained ~ -.
i~ the condensation product of nlckel phthalocyanine sulpho~ -chloride with two mols of one o~ the amines me~tioned i~ the table which follows is used instead of the amine employ~d above as the diazo compo~ent ~or the pyrazolo~e stage a~d i~
the procedure followed i~ in other resp cts as described abo~:
1 ,3-phe~yle~ediamine (acetyl deri~ative, subseque~tly saponi-fied) 9 2,4-diaminotolue~e (açetyl derivativey subs~quently saponi~ied), 2,4-diaminoanisole (acetyl derivative, subse-quently saponified), 1,4~pheny.enediamine-2-sulphonic acid, 2,4-diaminotoluene 6-sulphonic acid, 4~amino-be~zylamine (4-ac~tyl derivative 9 subsequently saponified), 4,4'-diami~o-stilbenedisulpho~ic acid, 4,4'~diami~omethanedisulphonic ac~d and 4,4' diami~o-diphe~ylami~e-3-sulphonic acid.
Arylhydra~ones which can be processed accord~ng to the inve~tion to give valuable azophthalocyanine dyestuffs are also obtained if the acetylsuccinic acld diethyl ester employed as the coupllng component ~or the pyrazolone ~tage is replaced by one of the ~ollowing derivatives of ~uccinic acid:
:
R5 - OOC C~2 - CH ~ C~O - R14 _ z o ..
, . .
~o .~ ~
-~H3 -CH3 ~
-CH~ -C2H4Cl ~CH3 -CH3 -i-C3H~ -CH3 -~H3 -i-C4Hg -COO CH3 -CH~ i C6H11 ~COO-C2H5 -CH3 -C ~4-OH -CH3 -CH3 . C3~0~H3 -COO-C3H4 -CH3 ~ -C2H5 -COO-C3H4 qC3H7 -c2~5 -C3 ~
C5H1 1 -.c2~5 -CH2-C6~I5 gH19 ~CZ~s -COO-CH3 -C16~3~ ~C2H5 6H5 -~2H4-0-~2H5 -C2H5 -C6H4-CH~3 ~ ` , Valuable hydrazones of oxalacetic acid methyl ester which G~ be prooessed ~urther to give the correspondingly substituted pyrazolones, are also obtained if,~ instead of the amine indicated i~ Example 1~ 3- r(3-~m1~o-4-sulpho-phenyl) :
.
amino-sulpho~yl]-niokel~phthalocyanine-3' 9 3" 9 3"'~trisulphonic acid, the eorresponding molar quantity of one o~ the~amines men-: tloned i~ the table which ~ollows is used a~d th~ proc~dure ~ollowed i~ in other respects as indicated in Example ~:
S03E~)k Po--( ~02-N~ ~) ~SO~ ar-N~2)m - 31 _ ,~> , , , ~ . . __ _ _ _ _ ~
i ! c~ m~ m~
C_~ C.\ O
__ ~ _ _ m :~ _ . ~ , , , , ~ . . .
' . .
m~
m m c~ m ~ m --- - - ---- ~ _ ~n 3~n ~ W
l 1 .
- ~, . .
~, .
;~ t -- ~5 2 s~
~ . ~
. . ~
- , .
s.-; -o~ o o~ 4~ o~
,n ~7 o ~ ~
u ' ~' ' ` ~ I , ~ :
o ~, I ~ ' ~,. . ~ .
' '.
A~ . ~ m m ::q ~ ~ m p~
..
" ', ,~, ~!f f~ f,--'f ~' r~
~,f,~`, ~, f~ r~ ~, ,,,~,~, ,~"
,~r,~,;
o~
w f ~r, f~ ;sff ~ fxf ~ ~ .
X, m 'I' ~ ~ ~ r f '':: l l l ' . . ,'', .
' ~8~
.. . . . . .. .
I
i ~ I .
1~
, o o ' ~) CJ m o . . . ~ _ o o j~ o o - ~ o C~ ~ -~' I C.)C.) ~i ~i i~ ~ m m .
~ I ' . . , ~
V Y ~ ' ~1 I O C ~
~: ~. o ~ I ` m ~ ~ -a~ i I oo c; o ~
m I ~s ~ F
v c~
r :
o o ~ ~ o ~
~ :
h .
a9 _ O ' ::q `~ ~ f- ~ : ' , . ~ , . . .
: . .
~ ~n : ` tl::
P~ ~ m : ~ ~ : ~ ~
~ V~~ ~ oC~ "
~ ~ , : ~ ; :, ':
s~ ~
,- I , f~f ~' ff_ t ,,. I ,~ o o o __ . , ~
~C f-f ff_. o .
- ';rff ~ ~3 ~
,:~
~ f f: ~ ~ ' .
; ~ ?i - ; ~
, ~" ~ ~ ~',)f,l; ff-~ ' ' ' ' '. ' '~
' ~ ff' ' ~ "; , ' '' .
.
Claims (26)
The Embodiments of the Invention in which an excluslve Property or Privilege is claimed are defined as follows:
1. A process for the preparation of a phthalocyanine azo dyestuff compound of the general formula I
(I) wherein A is a group -NH-, -C0-NH-, -S02 -NH- or -S02-, B is a radical of a mononuclear or dinuclear, aromatic hydrocarbon, optionally substituted by a substituent from the group of alkyl having 1-4 C atoms, alkoxy having 1-4 C atoms, halogen, carboxyl, hydroxy, nitro, phenylamino or sulpho, X is a vinyl group, .beta.-hydroxyethyl group or an ethyl group which is substituted in the .beta.-position by a group which can split off by means of an alkali, k represents an number 0, 1, 2 or 3, q represents 0, 1 or 2, m represents 1, 2, 3 or 4, n repre-sents 0 or 1 and p represents 0, 1 or 2 and the sum of k, q and m is 2, 3 or 4, Pc is the radical of a matal-contai-ning or metal-free phthalocyanine, ar is the radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by a -S03H group and each nucleus being optionally further substituted by alkoxy having 1 to 4 C atoms; -S02R6 or additional -S03H group, by one or two identical or different substituents selected from halogen, and -COOH, or denotes a phenylene radical which is optionally substituted by a -SO3H group and which can be additionally substituted by one to three identical or different alkyl radicals having 1-4 C atoms, R1 and R'1 can be the same or different and each represents hydrogen, methyl, carboxy-methyl, sulphomethyl, an alkyl radical which contains 2-6 C
atoms and which is optionally substituted by C1, Br, OH, alkoxy having 1-6 C atoms, alkanoylamlno having 1-6 C atoms, alkanoyl-oxy having 1-6 atoms, -COOH or -SO3H, a phenalkyl or naphth-alkyl radical having 1-3 C atoms in the aliphatic chain or phenyl or naphthyl, the aromatic nuclei being optionally substituted or further substituted by one or more of C1, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms, alkanoylamino having 1-6 C atoms, -COOH or -SO3H, R2 and R'2 can be the same or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains 2-6 C atoms and is optionally substituted by C1, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms, benzoyiamino, alkanoyl-oxy having 1-6 C atoms, -COOH or -SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 is hydrogen, methyl, carboxymethyl, sulphomethyl, or an alkyl radical which contains 2-6 C atoms and is optionally substituted by C1, Br, OH, alkoxy having 1-6 C atoms, -COOH or -S03H, R4 is hydrogen or alkyl having 2-6 C atoms substituted by C1, Br, OH or alkoxy having 1-4 C atoms, or unsubstituted alkyl having 1-18 C atoms, and Z denotes hydrogen and R6 is methyl, carboxymethyl, alkyl having 2 or 3 C atoms, or benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by -COOH or -SO3H or a salt thereof, in which process: a) an amine of the general formula II
(II) in which the amino group substituent on the ar radical is linked to an aromatic C atom of said radical ar wherein Pc, ar, R1, R2, R3, k, q and m have the same meaning as defined in formula I, is diazotised and coupled in an aqueous medium at a pH value from 3 to 8 with a succinic acid derivative of the formula III
(III) wherein R'4 and R5 are the same or different and each is alkyl having 2-6 C atoms substituted by C1, Br, OH, or alkoxy having 1-4 C atoms, or substituted alkyl having 1-18C atoms and Z denotes hydrogen, alkyl having 1-10 C atoms optionally substituted by alkoxy having 1-4 C atoms, or alkoxycarbonyl having 2-6 C atoms, a phenyl radical optionally substituted by C1, Br or alkyl or alkoxy having 1-4 C atoms, or alkoxy-carbonyl having 2-6 C atoms, so as to form a hydrazone of the formula IV
(IV) wherein R5 has the same meaning as defined above in formula III
and Pc, ar, R1, R2, R3, R'4, k, q, and m have the same meaning as defined above in formula I; b) the compound of formula IV
is converted by the action of an alkali into a pyrazolone of the general formula V
(V) wherein Pc, ar, R1, R2, R3, R4, k, q, and m have the same meaning as defined above in formula I; and c) the pyrazolone of formula V is coupled with the diazonium compound of an amine of general formula VI
(VI) wherein A, B, X, n and p have the same meaning as defined above in formula I, so as to form the dyestuff compound of formula I.
(I) wherein A is a group -NH-, -C0-NH-, -S02 -NH- or -S02-, B is a radical of a mononuclear or dinuclear, aromatic hydrocarbon, optionally substituted by a substituent from the group of alkyl having 1-4 C atoms, alkoxy having 1-4 C atoms, halogen, carboxyl, hydroxy, nitro, phenylamino or sulpho, X is a vinyl group, .beta.-hydroxyethyl group or an ethyl group which is substituted in the .beta.-position by a group which can split off by means of an alkali, k represents an number 0, 1, 2 or 3, q represents 0, 1 or 2, m represents 1, 2, 3 or 4, n repre-sents 0 or 1 and p represents 0, 1 or 2 and the sum of k, q and m is 2, 3 or 4, Pc is the radical of a matal-contai-ning or metal-free phthalocyanine, ar is the radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by a -S03H group and each nucleus being optionally further substituted by alkoxy having 1 to 4 C atoms; -S02R6 or additional -S03H group, by one or two identical or different substituents selected from halogen, and -COOH, or denotes a phenylene radical which is optionally substituted by a -SO3H group and which can be additionally substituted by one to three identical or different alkyl radicals having 1-4 C atoms, R1 and R'1 can be the same or different and each represents hydrogen, methyl, carboxy-methyl, sulphomethyl, an alkyl radical which contains 2-6 C
atoms and which is optionally substituted by C1, Br, OH, alkoxy having 1-6 C atoms, alkanoylamlno having 1-6 C atoms, alkanoyl-oxy having 1-6 atoms, -COOH or -SO3H, a phenalkyl or naphth-alkyl radical having 1-3 C atoms in the aliphatic chain or phenyl or naphthyl, the aromatic nuclei being optionally substituted or further substituted by one or more of C1, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms, alkanoylamino having 1-6 C atoms, -COOH or -SO3H, R2 and R'2 can be the same or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains 2-6 C atoms and is optionally substituted by C1, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms, benzoyiamino, alkanoyl-oxy having 1-6 C atoms, -COOH or -SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 is hydrogen, methyl, carboxymethyl, sulphomethyl, or an alkyl radical which contains 2-6 C atoms and is optionally substituted by C1, Br, OH, alkoxy having 1-6 C atoms, -COOH or -S03H, R4 is hydrogen or alkyl having 2-6 C atoms substituted by C1, Br, OH or alkoxy having 1-4 C atoms, or unsubstituted alkyl having 1-18 C atoms, and Z denotes hydrogen and R6 is methyl, carboxymethyl, alkyl having 2 or 3 C atoms, or benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by -COOH or -SO3H or a salt thereof, in which process: a) an amine of the general formula II
(II) in which the amino group substituent on the ar radical is linked to an aromatic C atom of said radical ar wherein Pc, ar, R1, R2, R3, k, q and m have the same meaning as defined in formula I, is diazotised and coupled in an aqueous medium at a pH value from 3 to 8 with a succinic acid derivative of the formula III
(III) wherein R'4 and R5 are the same or different and each is alkyl having 2-6 C atoms substituted by C1, Br, OH, or alkoxy having 1-4 C atoms, or substituted alkyl having 1-18C atoms and Z denotes hydrogen, alkyl having 1-10 C atoms optionally substituted by alkoxy having 1-4 C atoms, or alkoxycarbonyl having 2-6 C atoms, a phenyl radical optionally substituted by C1, Br or alkyl or alkoxy having 1-4 C atoms, or alkoxy-carbonyl having 2-6 C atoms, so as to form a hydrazone of the formula IV
(IV) wherein R5 has the same meaning as defined above in formula III
and Pc, ar, R1, R2, R3, R'4, k, q, and m have the same meaning as defined above in formula I; b) the compound of formula IV
is converted by the action of an alkali into a pyrazolone of the general formula V
(V) wherein Pc, ar, R1, R2, R3, R4, k, q, and m have the same meaning as defined above in formula I; and c) the pyrazolone of formula V is coupled with the diazonium compound of an amine of general formula VI
(VI) wherein A, B, X, n and p have the same meaning as defined above in formula I, so as to form the dyestuff compound of formula I.
2. A process as claimed in claim 1 wherein R1 and/or R'1 is alkyl having 2 to 6 carbon atoms and substituted by acetyl-amino, benzoylamino or acetoxy.
3. A process as claimed in claim 1 wherein, in the amine of formula II, Pc is the radical of cobalt phthalocyanine, copper phthalocyanine or nickel phthalocyanine.
4. A process as claimed in claim 3 wherein Pc is the radical of nickel phthalocyanine.
5. A process as claimed in claim 1, wherein, in the amine of formula II, ar is a phenylene, mono-methylene-phenylene or polymethylene-phenylene radical of the general formula wherein b denotes an integer from 1 to 10, or naphthylene or monomethylene-naphthylene or polymethylene-naphthylene radical of the general formula wherein b denotes an integer from 1 to 3, or an optionally substituted radical of formula of the formula , , , , or optionally substituted as given in claim 1.
6. A process as claimed in claim 1, wherein, in the amine of formula II, ar is a phenylene or naphthylene radical or an optionally substituted radical of the formula , , or optionally substituted as given in claim l.
7. A process as claimed in claim 1, wherein, in the amine of formula II, ar is a phenylene radical which is optionally substituted by one or two carboxyl groups or by one or two sulpho groups, or a naphthyl radical which is substituted by one or two sulpho groups, or a stilbenylene radical which is substituted by one or two sulpho groups.
8. A process as claimed in claim 7 wherein, in the amine of formula II, ar is a radical of the formula , , , , , or
9. A process as claimed in claim 1, wherein, in the amine of formula II, R1 and R'1 are the same or different and each is hydrogen, alkyl having 2 or 3 C atoms, optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH or -SO3H, methyl, carboxymethyl or sulphomethyl.
10. A process as claimed in claim 1 wherein, in the amine of the phthalocyanine series of the formula II, R2,and R'2 are the same or different and each is hydrogen, methyl, carboxymethyl, alkyl having 2 or 3 C atoms optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH or -SO3H, or unsubstituted alkyl having 1-20 C atoms.
11. A process as claimed in claim 10 wherein R2 and R'2 are the same or different and each is hydrogen, methyl, carboxy-methyl or alkyl having 2 or 3 C atoms optionally substituted by OH.
12. A process as claimed in any of claims 9 to 11 wherein R1 and R2 as well as R'1 and R'2 are the same or different and each is hydrogen, methyl, or .beta.-hydroxyethyl.
13. A process as claimed in claim 1 wherein, in the amine of formula II, R3 is hydrogen, methyl, carboxymethyl, sulpho-methyl or an ethyl radical which is optionally substituted by C1, OH, alkoxy having 1 or 2 C atoms, -COOH or -SO3H.
14. A process as claimed in claim 1 wherein, in the amine of the phthalocyanine series of the formula II, q is O, k is 2 or 3 and m is 1 or 2 and the sum of k + m is 4.
15. A process as claimed in claim 1 wherein , in the amine of formula II, the substituents on the Pc radical are in the 3-positions or 4-positions of the phthalocyanine.
16. A process as claimed in claim 15 wherein the substituents on the Pc radical are in the 3-positions of the phthalocyanine.
17. A process as claimed in claim 1 wherein R'4 denotes ethyl substituted by C1, OH or alkoxy having 1-2 C atoms, or unsubstituted alkyl having 1-6 C atoms.
18. A process as claimed in claim 1 or claim 17 wherein R5 is ethyl substituted by C1, OH or alkoxy having 1-2 C atoms, or unsubstituted alkyl having 1-18 C atoms.
19. A process as claimed in claim 1 wherein R'4 and R5 are identical and denote methyl or ethyl.
20. A process as claimed in claim 1 wherein Z denotes hydrogen,alkyl having 1-3 C atoms, phenyl, methyl-phenyl or alkoxycarbonyl having 2 or 3 C atoms.
21. A process as claimed in claim 20 wherein Z denotes methyl.
22. A process as claimed in claim 1 wherein, in the diazonium compound of an amine of the general formula VI, n and p are each 0.
23. A process as claimed in claim 1 wherein, in the diazonium compound of an amine of the general formula VI, B denotes a phenylene or naphthylene radical.
24. A process as claimed in claim 1 wherein, in the diazonium compound of an amine of the general formula VI, X is a .beta.-sulphato-ethyl group.
25. A process for the preparation of a phthalocyanine azo dyestuff compound of the general formula I as defined in claim 1 in which a hydrazone of the formula IV as defined in claim 1 is converted by the action of an alkali into a pyrazolone of the general formula V as defined in claim 1 and said pyrazolone of formula V is coupled with the diazonium compound of an amine of the general formula VI as defined in claim 1 so as to form the dyestuff compound of formula I.
26. A method of dyeing and printing a cellulose material, cellulose-containing material, or a natural or synthetic poly-amide material wherein is used a water-soluble, fibre-reactive phthalocyanine azo dyestuffs compound of the general formula I
as defined in claim 1, produced according to the process of claims 1 and 25.
as defined in claim 1, produced according to the process of claims 1 and 25.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2617087A DE2617087C3 (en) | 1976-04-17 | 1976-04-17 | Process for the production of phthalocyanine azo dyes and their use for dyeing and printing cellulosic materials, cellulosic materials, and natural and synthetic polyamide materials |
| DEP2617087.6 | 1976-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098516A true CA1098516A (en) | 1981-03-31 |
Family
ID=5975707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA276,284A Expired CA1098516A (en) | 1976-04-17 | 1977-04-15 | Process for the manufacture of phthalocyanine azo dyestuffs |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS52127926A (en) |
| BE (1) | BE853677A (en) |
| BR (1) | BR7702427A (en) |
| CA (1) | CA1098516A (en) |
| CH (1) | CH619480A5 (en) |
| DE (1) | DE2617087C3 (en) |
| ES (1) | ES457851A1 (en) |
| FR (1) | FR2348253A1 (en) |
| GB (1) | GB1551680A (en) |
| IN (1) | IN143936B (en) |
| IT (1) | IT1143649B (en) |
| NL (1) | NL7704038A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254219U (en) * | 1988-10-13 | 1990-04-19 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1289206B (en) * | 1964-07-29 | 1969-02-13 | Hoechst Ag | Process for the preparation of water-soluble azophthalocyanine dyes |
| JPS4936076A (en) * | 1972-08-11 | 1974-04-03 |
-
1976
- 1976-04-17 DE DE2617087A patent/DE2617087C3/en not_active Expired
-
1977
- 1977-04-11 IN IN542/CAL/1977A patent/IN143936B/en unknown
- 1977-04-13 NL NL7704038A patent/NL7704038A/en not_active Application Discontinuation
- 1977-04-15 JP JP4273577A patent/JPS52127926A/en active Granted
- 1977-04-15 BE BE176787A patent/BE853677A/en unknown
- 1977-04-15 CA CA276,284A patent/CA1098516A/en not_active Expired
- 1977-04-15 BR BR7702427A patent/BR7702427A/en unknown
- 1977-04-15 GB GB15759/77A patent/GB1551680A/en not_active Expired
- 1977-04-15 ES ES457851A patent/ES457851A1/en not_active Expired
- 1977-04-15 IT IT22534/77A patent/IT1143649B/en active
- 1977-04-18 FR FR7711587A patent/FR2348253A1/en active Granted
- 1977-04-18 CH CH477977A patent/CH619480A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2348253A1 (en) | 1977-11-10 |
| CH619480A5 (en) | 1980-09-30 |
| DE2617087C3 (en) | 1979-09-27 |
| DE2617087A1 (en) | 1977-10-27 |
| BR7702427A (en) | 1978-05-09 |
| NL7704038A (en) | 1977-10-19 |
| FR2348253B1 (en) | 1980-02-01 |
| IT1143649B (en) | 1986-10-22 |
| BE853677A (en) | 1977-10-17 |
| ES457851A1 (en) | 1978-03-01 |
| GB1551680A (en) | 1979-08-30 |
| DE2617087B2 (en) | 1979-02-08 |
| JPS614423B2 (en) | 1986-02-10 |
| IN143936B (en) | 1978-03-04 |
| JPS52127926A (en) | 1977-10-27 |
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