CA1104565A - Hydrazone compounds, their preparation and use - Google Patents
Hydrazone compounds, their preparation and useInfo
- Publication number
- CA1104565A CA1104565A CA276,287A CA276287A CA1104565A CA 1104565 A CA1104565 A CA 1104565A CA 276287 A CA276287 A CA 276287A CA 1104565 A CA1104565 A CA 1104565A
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- CA
- Canada
- Prior art keywords
- atoms
- radical
- denotes
- alkoxy
- optionally substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
- G11C11/21—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements
- G11C11/44—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements using super-conductive elements, e.g. cryotron
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/30—Devices switchable between superconducting and normal states
- H10N60/35—Cryotrons
- H10N60/355—Power cryotrons
Abstract
Astract of the Disclosure New phthalocyanine hydrazones having at least one group of the formula wherein R3, R4 and R5 denote optionally substituted alkyl, and R3 additionally denotes hydrogen and ar is a divalent aromatic or araliphatic radical, are prepared by diazotizing phthalocyanine amines having at least one group of the formula wherein the amino group is linked to an aromatic C atom of the radical ar and coupling the diazonium compound with a succinic acid derivatives of the formula V
Description
The present invention relates to new water-soluble hy-drazones of the ph-thalocyanine series of the general formula I
/ (S03H)k \ < R2 ) fH \ (I) (S2-~ - -ar-NH-N=C ¦
3 COOR~ /
/m ~:
wherein Pc denotes the radical of cobalt ph-thalocyanine, copper phthalocyanine or nickel phthalocyanine, ar denotes a phenylene radical, which is optionally substituted by a -S03H group and optionally further substituted by an alkoxy having 1 to 4 C
atoms, -CN, -CF3, -S02R6 or additional -S03~ suhstituent, or by one or two iclentical, or different substituents selected from halogen, -S02-N \ R 1 and -COOH, or by from one to three identi~
cal or different alkyl radicals having 1 to 4 C atoms, a mono~
methylene-phenylene or methylene-phenylene radical of the general :~
formula : -(C 2)n ~
wherein n denotes an in-teger from 1 to 10, a naphthylene radical ~:
or a monomethylene-naphthylene or polymethylene-naphthylene radi-cal of the general formula ~~cH2)nJ~
wherein n denotes an inte~er from 1 to 3, or an optionally sub-20 stituted radical of the formula ~;
.
~ .j - - :
S~
,~CH2C~
CH=C~ ~ , ~ O ~ , ~ N
~ CO ~ or ~ - S2 which is optionally substituted by a -SO3H group and each nucleus be:ing op-tlonally further subst:ituted by an alkoxy hav:ing :l to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or di~-ferent substituents selected from halogen, / R l and -COOH, whereby the alkylene cha.in of the mono- or polymethylene-phenylene and -naphthylene radicals are linked to the -SO2-X- group, Rl and R'l can be the same or dif-ferent and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOII or -SO3H, a phenalkyl or :~
naphthalkyl radical having 1-3 C atoms in the aliphatic chain, or phenyl or naphthyl, the aromatic nuclei being optionally substituted or further sub- :
stituted by one or re of Cl, 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 identical or different and denote hydrogen, methyl, carboxymethyl, suIpho- :
methyl, an alkyl radical which has 2-6 C atoms and which is optionally substi-tuted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C
atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 denotes hydrogen, methyl, ,~ .,r s carboxymethyl, s~llphomethyl, or an alkyl radical which has 2-6 C atoms and which is optionally substitu~ed by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C
atoms, -COOII or SO3~-l, R~ denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, Oll or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes an alky] radi-cal which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C
atoms, R6 denotes methyl, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 .
C atoms and which is optionally substituted by Cl, OH, alkoxy having 1-3 C
atoms, acetylamino, acetoxy, -COOII or -S03H, or clenotes benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstitute~d by -COO~I or -SO3~l, k represents tl-e numbers 1, 2 or 3, q represents O, 1 or 2 ancl m represents 1, 2, 3, or 4 and the sum of k, q and m is 3 or 4, or an alkali metal, ammonium or alkaline earth metal salt thereof. :
The new hydrazones according to the invention of the general form-ula I are obtained by cliazotising an amine of the phthalocyanine series of the general formula IV
~So3H)k ~ :
I'c ~-- (502-N~ ) (IV) (SO2-1 - ar-NH~
wherein the amino group is linked to an aromatic C atom of the radical ar and wherein Pc, ar, Rl, R2, R3, k, 1 and m have the abovementioned meanings, and coupling the product in an aqueous medium at a pH value between 3 and 8 with a succinic acid derivative of the formula V
5 2 f 4 (V) CO-Z
wherein R4 and R5 have the abovementioned meanings and Z denotes hydrogen, an alkyl radical having 1-10 C atoms and optionally subs~ituted by alkoxy having _,~
'~ ' .
~4~
1 to 4 C atoms, a phenyl radical optionally substituted by Cl~ Br or alkyl or alkoxy eacll having 1-4 C atoms or alkoxycarbony]. having 2-6 C atoms, and, optionally, converting the resulting hydrazones into the alkali metal, ammon-ium or alkaline earth metal salts.
The new hydrazones according to the invention are valuable inter- :
mediate products for the manufacture, which is technically extremely simple, .~:
of green phthalocyanine azo dyestuffs of the formula VI ~ : :
(S03H)k :~
/ / Rl \
Pc ~S02-N
\ 2 ~1 (VI) \ HO N=N-D\
\ (sO~-N - 5r-~ ~ ) R3 COOR~
wherein D is the radi.cal of a diazo component and Pc, ar, Rl, R2, R3, k, 1 and m have the abovementioned meanings and R~, in addition to the abovemen~
tioned meaning, also has the meaning of a hydrogen atom.
The present invention relates in particular to new water-soluble hydrazones of the phthalocyanine series of the general formula I wherein Pc denotes the radical of a metal-containing or metal-free phthalocyanine, ar denotes the radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by a -S03H group and which can be substituted in each nucleus by one substituent of the group alkoxy having 1 :~
to 4 C atoms, -CN, -CF3 or -S02R6 or an additional -S03H group, by one or two identical or different subs~ituents of the groups halogen, -S02-N \R' or -COOH or denotes a phenylene radical which is optionally substituted by a -S03H group and w7nich csn be additionally substituted by one to three identi-cal or different alkyl radicals having 1 to 4 C atoms, Rl and Rl can be iden-tical or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by :~
Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino - : . . , ~ . :
having 1-6 C atoms, preferably acetylamino, be~zoylamino, alkanoyloxy having 1-6 C a-toms, preferably acetoxy~ -COOH
or -S03H, a phenalkyl or naphthalkyl radical having 1-3 C
atoms in the aliphatic chain, or phenyl or naphthyl~ it being possible 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 atoms, -COOH or -S03H, R2 and R2 can be identical or dif~erent and denote hydrogen, methyl, carboxymethyl, sulpho- ~-methyl, an alkyl radical which contains 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms~ benzoylamino, a1kan- ;
oyloxy having 1-6 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having 6-20 C a toms, R3 denotes hydrogen, me-thyl, carboxymethyl, sulphomethyl or an alkyl radical which contains
/ (S03H)k \ < R2 ) fH \ (I) (S2-~ - -ar-NH-N=C ¦
3 COOR~ /
/m ~:
wherein Pc denotes the radical of cobalt ph-thalocyanine, copper phthalocyanine or nickel phthalocyanine, ar denotes a phenylene radical, which is optionally substituted by a -S03H group and optionally further substituted by an alkoxy having 1 to 4 C
atoms, -CN, -CF3, -S02R6 or additional -S03~ suhstituent, or by one or two iclentical, or different substituents selected from halogen, -S02-N \ R 1 and -COOH, or by from one to three identi~
cal or different alkyl radicals having 1 to 4 C atoms, a mono~
methylene-phenylene or methylene-phenylene radical of the general :~
formula : -(C 2)n ~
wherein n denotes an in-teger from 1 to 10, a naphthylene radical ~:
or a monomethylene-naphthylene or polymethylene-naphthylene radi-cal of the general formula ~~cH2)nJ~
wherein n denotes an inte~er from 1 to 3, or an optionally sub-20 stituted radical of the formula ~;
.
~ .j - - :
S~
,~CH2C~
CH=C~ ~ , ~ O ~ , ~ N
~ CO ~ or ~ - S2 which is optionally substituted by a -SO3H group and each nucleus be:ing op-tlonally further subst:ituted by an alkoxy hav:ing :l to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or di~-ferent substituents selected from halogen, / R l and -COOH, whereby the alkylene cha.in of the mono- or polymethylene-phenylene and -naphthylene radicals are linked to the -SO2-X- group, Rl and R'l can be the same or dif-ferent and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOII or -SO3H, a phenalkyl or :~
naphthalkyl radical having 1-3 C atoms in the aliphatic chain, or phenyl or naphthyl, the aromatic nuclei being optionally substituted or further sub- :
stituted by one or re of Cl, 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 identical or different and denote hydrogen, methyl, carboxymethyl, suIpho- :
methyl, an alkyl radical which has 2-6 C atoms and which is optionally substi-tuted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C
atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 denotes hydrogen, methyl, ,~ .,r s carboxymethyl, s~llphomethyl, or an alkyl radical which has 2-6 C atoms and which is optionally substitu~ed by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C
atoms, -COOII or SO3~-l, R~ denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, Oll or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes an alky] radi-cal which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C
atoms, R6 denotes methyl, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 .
C atoms and which is optionally substituted by Cl, OH, alkoxy having 1-3 C
atoms, acetylamino, acetoxy, -COOII or -S03H, or clenotes benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstitute~d by -COO~I or -SO3~l, k represents tl-e numbers 1, 2 or 3, q represents O, 1 or 2 ancl m represents 1, 2, 3, or 4 and the sum of k, q and m is 3 or 4, or an alkali metal, ammonium or alkaline earth metal salt thereof. :
The new hydrazones according to the invention of the general form-ula I are obtained by cliazotising an amine of the phthalocyanine series of the general formula IV
~So3H)k ~ :
I'c ~-- (502-N~ ) (IV) (SO2-1 - ar-NH~
wherein the amino group is linked to an aromatic C atom of the radical ar and wherein Pc, ar, Rl, R2, R3, k, 1 and m have the abovementioned meanings, and coupling the product in an aqueous medium at a pH value between 3 and 8 with a succinic acid derivative of the formula V
5 2 f 4 (V) CO-Z
wherein R4 and R5 have the abovementioned meanings and Z denotes hydrogen, an alkyl radical having 1-10 C atoms and optionally subs~ituted by alkoxy having _,~
'~ ' .
~4~
1 to 4 C atoms, a phenyl radical optionally substituted by Cl~ Br or alkyl or alkoxy eacll having 1-4 C atoms or alkoxycarbony]. having 2-6 C atoms, and, optionally, converting the resulting hydrazones into the alkali metal, ammon-ium or alkaline earth metal salts.
The new hydrazones according to the invention are valuable inter- :
mediate products for the manufacture, which is technically extremely simple, .~:
of green phthalocyanine azo dyestuffs of the formula VI ~ : :
(S03H)k :~
/ / Rl \
Pc ~S02-N
\ 2 ~1 (VI) \ HO N=N-D\
\ (sO~-N - 5r-~ ~ ) R3 COOR~
wherein D is the radi.cal of a diazo component and Pc, ar, Rl, R2, R3, k, 1 and m have the abovementioned meanings and R~, in addition to the abovemen~
tioned meaning, also has the meaning of a hydrogen atom.
The present invention relates in particular to new water-soluble hydrazones of the phthalocyanine series of the general formula I wherein Pc denotes the radical of a metal-containing or metal-free phthalocyanine, ar denotes the radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by a -S03H group and which can be substituted in each nucleus by one substituent of the group alkoxy having 1 :~
to 4 C atoms, -CN, -CF3 or -S02R6 or an additional -S03H group, by one or two identical or different subs~ituents of the groups halogen, -S02-N \R' or -COOH or denotes a phenylene radical which is optionally substituted by a -S03H group and w7nich csn be additionally substituted by one to three identi-cal or different alkyl radicals having 1 to 4 C atoms, Rl and Rl can be iden-tical or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by :~
Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino - : . . , ~ . :
having 1-6 C atoms, preferably acetylamino, be~zoylamino, alkanoyloxy having 1-6 C a-toms, preferably acetoxy~ -COOH
or -S03H, a phenalkyl or naphthalkyl radical having 1-3 C
atoms in the aliphatic chain, or phenyl or naphthyl~ it being possible 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 atoms, -COOH or -S03H, R2 and R2 can be identical or dif~erent and denote hydrogen, methyl, carboxymethyl, sulpho- ~-methyl, an alkyl radical which contains 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms~ benzoylamino, a1kan- ;
oyloxy having 1-6 C atoms, -COOH or -S03H, or an unsubstituted alkyl radical having 6-20 C a toms, R3 denotes hydrogen, me-thyl, carboxymethyl, sulphomethyl or an alkyl radical which contains
2-6 C atoms and is optionally subs-titu-ted by Cl, Br~ OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoyl~
amino, alkanoyloxy having 1-6 C a-toms, -COOH or -S03H,~ R
denotes an alkyl radical which has 2-6 C atoms and is substi-tuted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes~ ;
an alkyl radical which has 2-6 C atoms and is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsub-stituted alkyl radical having 1-18 C atoms, R6 denotes methyi, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 C atoms and is op-tionally substituted by Cl, OH, alko~y having 1-3 C
atoms, acetylamlno, acetoxy, -COOII or -SO~H, benzyl or phenyl~
it being possible for the aromatic nuclei to be mono-substitu-ted or di-substituted by -COOH or -SO~H, k represents the number~
:
~: _ 4 _ ~45~
O, 1, 2 or 3, 1 represents 0, 1 or 2 and m represents 1, 2, 3 or 4 and the sum of k, 1 and m is 3 or 49 and to their alkali metal, ammonium or alkaline earth metal salts.
The substitueDts lndicated in ~ormula I can be in the
amino, alkanoyloxy having 1-6 C a-toms, -COOH or -S03H,~ R
denotes an alkyl radical which has 2-6 C atoms and is substi-tuted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes~ ;
an alkyl radical which has 2-6 C atoms and is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsub-stituted alkyl radical having 1-18 C atoms, R6 denotes methyi, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 C atoms and is op-tionally substituted by Cl, OH, alko~y having 1-3 C
atoms, acetylamlno, acetoxy, -COOII or -SO~H, benzyl or phenyl~
it being possible for the aromatic nuclei to be mono-substitu-ted or di-substituted by -COOH or -SO~H, k represents the number~
:
~: _ 4 _ ~45~
O, 1, 2 or 3, 1 represents 0, 1 or 2 and m represents 1, 2, 3 or 4 and the sum of k, 1 and m is 3 or 49 and to their alkali metal, ammonium or alkaline earth metal salts.
The substitueDts lndicated in ~ormula I can be in the
3-position and/or the 4-position o~ ths pht:halooyanlne. The 3-position o~ the subst~tuents lndicated i~; pre~erred.
Hydrazones according to the invention of the general ~ormula I in which Pc denotes the radioal o~ a metal-contai~ing phthalocyanine, such as9 for example, cobalt phthalocyanine or copper phthalocyanine, but especially the radical o~ nickel phthalocyanine, are pre~erred.
Araliphatic radicals which represent ar are always linked to the nitrogen o~ the hydrazone bridge by means o~ an aromatic nucleus. Mononuclear aromntic or araliphatlc radicals wh~eh can represent ar are the optionally substitutefl radicals phenylene and monomethylene-phenylene or polymethylene-phenylene of the general formula (CH2)n in which n denotes an integer ~rom 1 to 10.
Dinuclear aromatic or araliphatic radicals wh~ch can represent ar are the optionally substituted radicals naphthy-lene or monomethylene-naphthylene or polymethylene-naphthylene oi the general ~ormu}a ( 2)n in which n denot~s an integer from 1 to 3, and the optionally substituted radlcals o~ the ~ormulae ''1'" ' : . . ' ;
915~6~i , ~H2~S , ~C:H2-C~I2-~ :
CH=CH ~ , ~ O-~ N {
~O ~ and ~ SV2 ~
The op*ionally substitutsd radica]Ls phenylene, naphthy-lene, CH~ CH2-CH2 ~ ~ -CH~ ~ and ~ C~CH
are pre~erred for ar in the hydrazones accordlng to the inven-tion. The optionally substituted, mononuclear or di nuclear, aromatic or ara].iphatlc hydrocarbon radical which repres~nts ar appropriately contains at least one sulpho group or carboxyl group, but valuable hydrazones according to the invention can also be obtained with radicals which have the general de~inition o~ ar and which contain no acid group whlch imparts solubllity ~n water. In addition, the hydro-carbon radical can be substituted in each nucleus by one substituent of the group -OH, alkoxy having 1 to 4 C atoms -CN, -CF~ or -so2n6 or an additlonal -SO3H group, or by one or two identical or di~erent substituent~ oi the groups halogen , -SO2N ~ 1 or -COQH. If ar is deri~ed ~rom a phenyle~e radical, it can be substituted, additionally to a -SO3H group whtch may perhaps be present, by one to three identi¢al or di~erent alkyl radicals having 1 to 4 C atoms.
~ydrazones, according to the invention, in whlch ar ,~' , ' is phenylene or pheny~ene substituted by one or ~wo carboxyl groups or by one or two sulpho groups or a naphthylene radical which is substituted by ona or two sulpho groups or a stil-benyl radical which is substituted by two sulpho groups,~and especially those hydrazones in whlch ar i9 a radical Q~ the ~ormula 50 H S0 H S0 H ::
3 ~ 3 :
SO~H
{~ or ~C -C
wherein the position shown here corresponds to the position in the general ~ormula I, are particularly pre~erred. ~.
The ~ollowing are examples o~ mononuclear or dl-nuclear, aromatic or araliphatic hydrocarbon radicals which can represent ar in the hydrazones according to the invention:
~ phenylene, 1,3-phenylene, 2-sulpho-1,4-phenylene, 3-sulpho-l,~-phenylene, 4- or 5-sulpho-1,3 phenylene, 2-carboxy-1,4-phenylene, 3-carboxy-1,4-phenylene, 4-, 5- or 6 carb~xy-1,3-~henylene 2-carboxy-5-su~pho-1,4-phanylene, 2-carboxy-8-sulpho-1,4-phenylene, 3-carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-1,3-phenylene, 5-carboxy-2-sulpho-1,3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dlcarboxy-1,3-phenylene, 2-chloro-5-sulpho-1,4-phenylene, 2-chloro-6-sulpho-1,4-phenylene, 3-chloro-6-sulpbo-1,4-phenylene, 6-chloro-4- ~.
sulpho-1,3-phcnylene, 2-chloro-5-carboxy-1,4-phenylene, 2,6- ~
~: ~7~
.. .
i6~
disulpho-1,4-phenylene, 2,5-disulpho-174-phenylene9 496-di-sulpho-1,3-phenylene, 3-chloro-6--carboxy-l,L~phenylene, 6-chloro-L~carboxy-1,3-phenylene, ~chloro-5-carboxy-1,3-phenylene, 2-methyl-5-carboxy-13~phenylene, 2-ethyl-6-carboxy-l,4-phenylene1 3-ethyl-6-sulpho-1,4-phenylene, 6-ethyl-
Hydrazones according to the invention of the general ~ormula I in which Pc denotes the radioal o~ a metal-contai~ing phthalocyanine, such as9 for example, cobalt phthalocyanine or copper phthalocyanine, but especially the radical o~ nickel phthalocyanine, are pre~erred.
Araliphatic radicals which represent ar are always linked to the nitrogen o~ the hydrazone bridge by means o~ an aromatic nucleus. Mononuclear aromntic or araliphatlc radicals wh~eh can represent ar are the optionally substitutefl radicals phenylene and monomethylene-phenylene or polymethylene-phenylene of the general formula (CH2)n in which n denotes an integer ~rom 1 to 10.
Dinuclear aromatic or araliphatic radicals wh~ch can represent ar are the optionally substituted radicals naphthy-lene or monomethylene-naphthylene or polymethylene-naphthylene oi the general ~ormu}a ( 2)n in which n denot~s an integer from 1 to 3, and the optionally substituted radlcals o~ the ~ormulae ''1'" ' : . . ' ;
915~6~i , ~H2~S , ~C:H2-C~I2-~ :
CH=CH ~ , ~ O-~ N {
~O ~ and ~ SV2 ~
The op*ionally substitutsd radica]Ls phenylene, naphthy-lene, CH~ CH2-CH2 ~ ~ -CH~ ~ and ~ C~CH
are pre~erred for ar in the hydrazones accordlng to the inven-tion. The optionally substituted, mononuclear or di nuclear, aromatic or ara].iphatlc hydrocarbon radical which repres~nts ar appropriately contains at least one sulpho group or carboxyl group, but valuable hydrazones according to the invention can also be obtained with radicals which have the general de~inition o~ ar and which contain no acid group whlch imparts solubllity ~n water. In addition, the hydro-carbon radical can be substituted in each nucleus by one substituent of the group -OH, alkoxy having 1 to 4 C atoms -CN, -CF~ or -so2n6 or an additlonal -SO3H group, or by one or two identical or di~erent substituent~ oi the groups halogen , -SO2N ~ 1 or -COQH. If ar is deri~ed ~rom a phenyle~e radical, it can be substituted, additionally to a -SO3H group whtch may perhaps be present, by one to three identi¢al or di~erent alkyl radicals having 1 to 4 C atoms.
~ydrazones, according to the invention, in whlch ar ,~' , ' is phenylene or pheny~ene substituted by one or ~wo carboxyl groups or by one or two sulpho groups or a naphthylene radical which is substituted by ona or two sulpho groups or a stil-benyl radical which is substituted by two sulpho groups,~and especially those hydrazones in whlch ar i9 a radical Q~ the ~ormula 50 H S0 H S0 H ::
3 ~ 3 :
SO~H
{~ or ~C -C
wherein the position shown here corresponds to the position in the general ~ormula I, are particularly pre~erred. ~.
The ~ollowing are examples o~ mononuclear or dl-nuclear, aromatic or araliphatic hydrocarbon radicals which can represent ar in the hydrazones according to the invention:
~ phenylene, 1,3-phenylene, 2-sulpho-1,4-phenylene, 3-sulpho-l,~-phenylene, 4- or 5-sulpho-1,3 phenylene, 2-carboxy-1,4-phenylene, 3-carboxy-1,4-phenylene, 4-, 5- or 6 carb~xy-1,3-~henylene 2-carboxy-5-su~pho-1,4-phanylene, 2-carboxy-8-sulpho-1,4-phenylene, 3-carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-1,3-phenylene, 5-carboxy-2-sulpho-1,3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dlcarboxy-1,3-phenylene, 2-chloro-5-sulpho-1,4-phenylene, 2-chloro-6-sulpho-1,4-phenylene, 3-chloro-6-sulpbo-1,4-phenylene, 6-chloro-4- ~.
sulpho-1,3-phcnylene, 2-chloro-5-carboxy-1,4-phenylene, 2,6- ~
~: ~7~
.. .
i6~
disulpho-1,4-phenylene, 2,5-disulpho-174-phenylene9 496-di-sulpho-1,3-phenylene, 3-chloro-6--carboxy-l,L~phenylene, 6-chloro-L~carboxy-1,3-phenylene, ~chloro-5-carboxy-1,3-phenylene, 2-methyl-5-carboxy-13~phenylene, 2-ethyl-6-carboxy-l,4-phenylene1 3-ethyl-6-sulpho-1,4-phenylene, 6-ethyl-
4-carboxy-1,3-phenylene, 6-propyl-L~suipho-1,3-phenylene, 5-isopropyl-4-sulpho-1,3-phenylène, 5-isopropyl-6-carboxy-1,3-phenylene, 4-n-butyl-6-sulpho-ly3-phenylene3 3-n-butyl-6~
sulpho-l,4-phenylene, L~tert.-butyl-6-sulpho-1,3-phenylene, 3-lsobutyl-6-sulpho-1,4-phenylene, 2,5-diisopropyl--6-sulpho-1,4-phenylene, 2,L~diethyl-5-carboxy-1,3-phenylene, 2,4,6-trimethyl-5-sulpho-1,3-phenylene, 2-cyano-1,4-phenylene, L~
cyano-1,3-phenylene, 2-cyano 5-sulpho-1,4-phenylene, 2-tri-fluoromethyl-1,4-phenylene~ 2-methylsulphonyl-l,L~phenylene, 2-ethylsulphonyl-1,L~phenylene, L~sulpho-1,5-naphthylene, 8- -~sulpho-1,5-naphthylene, 4-sulpho-2,6-naphthylene, 2-carboxy-1,4_naphthylene, 2-carboxy~1,5~naph-thylene, 5-carboxy-l,L~
naphthylene, 3-carboxy-1,8-naphthylene, 3-carboxy-1,5-naphthy-lene, 4-carboxy-2,6-naphthylene, L~carboxy-2,7-naphthylene, l-sulpho-2,6-naphthylene, 8-sulpho-I,3-naphthylene, 4,8-di-sulpho-2,6-naphthylene, 3,7-disulpho-1,5-naph-thylene, l-sulpho-L~chloro-2,6-naphthylene, l-chloro-5-sulpho-2,6-naphthylene3 l-chloro-7-sulpho-2,6-naphthylene, 2-chloro-6-sulpho-1,4-naphthylene, l-me-thyl-4-sulpho-2~6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene. In each case the hydrazone group is in the l-position of the phenyl nucleus or~in the l-position or 2-position of the naphthalene nucleus, The list which followsindlca-tesexamples of compounds ~rom whichl :
.
further divalent radicals which represent ar, ~re derived.
The second column of the table indica-tes -the posltions of -the two bonds by means of which -the divalent radicals are linked, on the one hand, to the hydrazone g~oup (the ~irst position -:
number) and, on the other hand, to the group -S02-M- (the ~ ~3 second posi~on number) o~ the hydrazones according to the invention. ~
Compound ~rom which -ar- Posltion o~ the bonds of is derived ~ar-,, Diphenyl L~,4 2,2'-Dimethyl-diphenyl 3,3'-Dimethoxy-diphenyl 4,4 3,31~-Dichloro-diphenyl 4, 4 3,3'-Dimethyl-diphenyl ~, 4 2J2' Disulpho~diphenyl 4,4~ :
phenyl-ethane 4,4 Diphenyl ether 4,4' 2,2'-Disulpho-diphenyl-methane L~14-2,2'-Di6ulpho-diphenyl-ethane 4,4' 3p3'-Disulpho-diphenyl-ethane 4,4 2~2'~isulpho-diphenyl ether 4,4~
2-Sulphamido-diphenyl-ethane 4,4' 2,2'-Disulphamido-diphenyl-ethane 4,4 2,2'-Di-~-hydroxye-thylsulphamido-diphenyl-ethane 4,4' . ~:
Stilbene-2,2'-disulphonic acid 4,4~
Methyl-phenyl 4,~ :
9 _ ' r, 4~
Compound ~rom whlch -ar- Pos~tion of the bonds in is derived -ar-l-Methyl-phenyl-3-sulphonic acid 4,~
l~Ethyl-phenyl-2-sulpbonic acid 4, l-Propyl-phenyl-3-sulphonlc acld 4,~
sulpho-l,4-phenylene, L~tert.-butyl-6-sulpho-1,3-phenylene, 3-lsobutyl-6-sulpho-1,4-phenylene, 2,5-diisopropyl--6-sulpho-1,4-phenylene, 2,L~diethyl-5-carboxy-1,3-phenylene, 2,4,6-trimethyl-5-sulpho-1,3-phenylene, 2-cyano-1,4-phenylene, L~
cyano-1,3-phenylene, 2-cyano 5-sulpho-1,4-phenylene, 2-tri-fluoromethyl-1,4-phenylene~ 2-methylsulphonyl-l,L~phenylene, 2-ethylsulphonyl-1,L~phenylene, L~sulpho-1,5-naphthylene, 8- -~sulpho-1,5-naphthylene, 4-sulpho-2,6-naphthylene, 2-carboxy-1,4_naphthylene, 2-carboxy~1,5~naph-thylene, 5-carboxy-l,L~
naphthylene, 3-carboxy-1,8-naphthylene, 3-carboxy-1,5-naphthy-lene, 4-carboxy-2,6-naphthylene, L~carboxy-2,7-naphthylene, l-sulpho-2,6-naphthylene, 8-sulpho-I,3-naphthylene, 4,8-di-sulpho-2,6-naphthylene, 3,7-disulpho-1,5-naph-thylene, l-sulpho-L~chloro-2,6-naphthylene, l-chloro-5-sulpho-2,6-naphthylene3 l-chloro-7-sulpho-2,6-naphthylene, 2-chloro-6-sulpho-1,4-naphthylene, l-me-thyl-4-sulpho-2~6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene. In each case the hydrazone group is in the l-position of the phenyl nucleus or~in the l-position or 2-position of the naphthalene nucleus, The list which followsindlca-tesexamples of compounds ~rom whichl :
.
further divalent radicals which represent ar, ~re derived.
The second column of the table indica-tes -the posltions of -the two bonds by means of which -the divalent radicals are linked, on the one hand, to the hydrazone g~oup (the ~irst position -:
number) and, on the other hand, to the group -S02-M- (the ~ ~3 second posi~on number) o~ the hydrazones according to the invention. ~
Compound ~rom which -ar- Posltion o~ the bonds of is derived ~ar-,, Diphenyl L~,4 2,2'-Dimethyl-diphenyl 3,3'-Dimethoxy-diphenyl 4,4 3,31~-Dichloro-diphenyl 4, 4 3,3'-Dimethyl-diphenyl ~, 4 2J2' Disulpho~diphenyl 4,4~ :
phenyl-ethane 4,4 Diphenyl ether 4,4' 2,2'-Disulpho-diphenyl-methane L~14-2,2'-Di6ulpho-diphenyl-ethane 4,4' 3p3'-Disulpho-diphenyl-ethane 4,4 2~2'~isulpho-diphenyl ether 4,4~
2-Sulphamido-diphenyl-ethane 4,4' 2,2'-Disulphamido-diphenyl-ethane 4,4 2,2'-Di-~-hydroxye-thylsulphamido-diphenyl-ethane 4,4' . ~:
Stilbene-2,2'-disulphonic acid 4,4~
Methyl-phenyl 4,~ :
9 _ ' r, 4~
Compound ~rom whlch -ar- Pos~tion of the bonds in is derived -ar-l-Methyl-phenyl-3-sulphonic acid 4,~
l~Ethyl-phenyl-2-sulpbonic acid 4, l-Propyl-phenyl-3-sulphonlc acld 4,~
5-Methyl-naphthalene-l-sulphonlc 2,~
acid ~iphenylamine 4,4'
acid ~iphenylamine 4,4'
6-Methoxy-diphenylamine-2'-sulphonic acid 3,4' 4-Methyl-dlphenylamine-2'-sulphonic acid 3,4' Diphenylketone-5,5'-disulphonic acid 3,3' Diphenylketone-3'-sulphonic acid 3,4' Diphenylsulphone 4,4' 4,4'-dichloro-diphenyl-sulphone 3,3' 4,4'-disulpho-diphenyl-sulphone 3,3' 4-methyl-5 sulpho-diphenylsulphone ~
Water-soluble hydrazones,accordlng to the invention, o~ the phthalocyanine ser~es o~ the general ~ormula I in which Rl denotes hydrogen, an alkyl radical which contains 2 or 3 atoms and is optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH or SO3H, methyl, carboxymethyl or sulphomethyl, are pre~erred.
Water-soluble hydrazones,according to the invention, o~ the phthaloeyanine series of the general ~ormula I in which R denotes an alkyl radical which has 2 or 3 C atoms and which Ll !
56~
:
is optionally substituted by OH, alkoxy havlllg 1~3 C akoms, ~-COOH or ~S03~, or denote~ an unsubstituted alkyl radlcal having 1~20 C atoms, but especlally denotes hydro~en, methyl, carboxymethyl or an alkyl radical which has 2 or 3 C atoms and which is optionally substituted by OH, are also pre~erred.
Particularly pre~erred meallings ~or Rl and R2 are hydrogen, methyl or ~-hydroxyethyl. In thP same way hydrogen, methyl and ~-hydroxyethyl are particularly pre~erred meanings o~ Rl and R~ .
~ urther preferred groups o~ hydrazones, according to the invention, o~ the phthalocyanine series o~ the ~eneral ~ormula I are characterised in that R3 denotes hydrogell, methyl, carboxymethyl, sulphomethyl or an etllyl radical which is optionally substituted by Cll OH, alkoxy having 1 or ~ C atoms, :~
-COOH or -S03H, and particularly denotes hydrogen or methyl, R4 denctes an ethyl radlcal whtch ls substituted by Cl, OH or alkoxy havlng ~-2 C atoms, or denotes an un~ubsti-tuted alkyl~:
radical having 1-6 C atoms, and R5 denotes an ethyl radical which ls substituted by Cl, OH or alkoxy having 1-2 C atom~
or denotes an unsubstituted alkyl radical having 1-18 C atoms.
Water-soluble hydrazones, accordin~ to the ~nvention, :
of the phthalocyanine serles o~ the general formula I in which R4 and R5 are identical and denote methyl or ethyl, ar~ parti- :
cularly advantageous. :~
Those hydrazones, according to the invention, of the phthalocyanine serles of the general ~ormula I in which l = O, k = 2 or 3 a~d m 3 1 or 2 and the sum o~ k ~ m = 4, are par~
cularly pre~erred.
- 11 - ~:.''-~'' - ~ :
~4~iS
The individual hydrazones according to the lnvention can in ~ach case contain small proportions of hydrazone~, according to the ~nv~ntion, in which k and/ or l and/or m have a meaning di~erent ~rom that in the main component.
These mlxtures o~ hydrazones are also very valuable starting materials ~or the mnnu~acture o~ phthalocyanine azo dyestuf~s.
The water-soluble hydrazones, according to the inven-tion, o~ the phthalocyanine series o~ the general formula I
are manu~actured by diaxotlsing an amine o~ the phthalocyanine series o~ the general ~ormula IV
(S0311)k Pc . _ (S02-N ll (IV) :
\ 2~
(S02-N~ar~NH2)m R~
wherein *he ~ree amino grou~ is linked to an aromatic C atom o~ the radical ar and wherein Pc, ar, Rl, R2, R3, k, l and m have the abovementioned meanlngs, and the product is coupled in an aqueous medium at a p~1 value between 3 and 8 with a succinic acid derivative o~ the ~ormula V
R5-OOC-CH2-C~-C~OR4 ( V) CO-Z
wherein R4 and R5 have tbe abovementioned meanings and Z
denotes hydrogen, an alkyl radlcal whlch has l~lO C atoms and which is optionally substituted by alkoxy having l-4 C atoms ' ~
or alkoxycarbonyl having 2-6 C atoms, a phenyl radïcal which is optionally substituted by Cl~ Br "llkyl or aIkoxy having 1-4 C atoms, or alkoxycarbonyl h!ving 2-6 C atoms, and~ if appropria-te, converting the resu~-ting hycLrazones into the alkali metal, ammonlum or alkaline ea:rth metal salts.
Amines of the general formula IV in which the radicals Pcj ar, Rl, R2, R3, k, 1 and m have the meanings characterised above as preferred and in which the substi-tuents indicated in ;
formula IV are in -the 3-pcsi-tion~ are preferred for the manu-facture of the hydrazones, according to -the invention9 of the general formula I.
Possible succlnic acid deriva-tives of t~he ~ormula V
which are preferred are those in which Z denotes hydro~gen, alkyl having 1-3 C atoms, phenyl, me-thylphenyl or alkoxy-. ~ .
carbonyl having 2 or 3 C a-toms. The methyl group:is particularly preferred for Z. :
~ The amines of the general formula IV are diazotlsed : in a manner which is in itself known in an aqueous acid medium by reaction with nitrous acid or an agent which splits off nitrous acid. A salt of nitrous acid, especially an alkali metal salt, such as sodium or potassium nitrite, is generally ~: .
-: employed in a mineral acid medium as an agent which~plits off nitrous acid. In a preferred embodiment, the neutral : : a~ueous solution of an amine of the formula IV is treated ~ with a solution of sodium ni-trite in a molar ratio of 1 : m : and thls mixture is then run, whilst stirring, into at least 2.5 molsg preferably 3 mols 3 0~ dilute, approximately 5-15% ~ -strength hydrochloric acid per mol of amino group pre~ent~ at , .
s temperatures between -5 and ~25C, preferably -2 to +5C.
The diazo suspension thus obtained is -then reacted wi-th a succinic acid derivative of the general formula V at a pH
value between 3 and 8p preEerably between 4 . 5 and 5.5, for example by adding the succinic acid derivativ~ to -the acid suspension of the diazoni~un compounds and then adjusting the pH value to the desired ~igure by the addition of alkali, for exarnple sodium hydroxide, sodium carbonate, sodium bicar-bonate, sodium acetate, potassium carbonate or sodium phosphate.
After stirring for 1 to 3 hours the diazotised amine can no longer be detected and -the formation of the hydrazone accord-ing to the invention is complete. I-t can be separated out from the solu-tion by salting out, that is to say by adding a neutral, water-soluble salt9 such as, ~or example, sodium chloride or potassium chloride. Separation lS, however, in no way necessary for the further processlng of the hydra~
zones according to the invention, on -the o-ther hand it is .
appropriate and advantageous -to employ the reaction solutions obtained in -the coupling reac-tion direct for further processing.
The a~ueous medium in which the coupling reaction of the diazotised amines of the formula IV with -the succinic acid derivatives of the formula V is carried out can also contain organic, water-mlscible solvents, especially lower aliphatic alcohols, such as, for example, methanol, ethanol or lsopro-panolO In the same way, known coupling accelerators, such as, for example, urea or pyridine, can be present during the coupling reaction.
The hydrazones according -to the invention are valuabIe ~ !
i5 interm~diate products ~or the manu~acture, which is te~hni~
cally simple, o~ excellent green phthalocyanine azo dyestu~s o~ the formula VI.
The phthalocyanlne azo dyestu~s of the formula VI
are manu~actured ~rom the hydrazones accordlng to tAe inven-tion in accordancu with the ~ollowing equation (S03~)~
PC --(S02-N\ ) o~
~50-C-C~12 \
(S2 ~ N ~ ar - N~ - N ~ C
m ) lo~
j R (VII~
Pc - (S~2 N ~ ~ ) \ 2 l : :
~T ~ , ~SO~-N - ar-N
C09~4 m :~
[D-N-N ~] Z ~
"1 .
Phthalocyanine a~o dyestu~ (VI) The cyclisation o~ the hydrazone to giYe th~ pyra-: zolone, which is indicated in th~ reaction step I in the . .
.... . . .
~ ~J~
above equationl is carried out extremely easlly by stirring an aqueous solution of the hydraz~nes, according to the inven-tion, of -the formula I a-t temperatures be-tween O and 100C, pre~erably 15 to 30C, at a pH value be-twe~n 8 and 141 with elimination of the alcohol of ~ormula R50H. The cyclisa-tion can be coupled wi-th a saponi~ication of the group -COOR4 of the resulting pyrazolone, -to give the free carboxyl group.
To achieve this i-t is only necessary to carry out t:he reac-tion near to the upper limit of the range o~ pH values indi-cated, for example at pH values ~rom 10 to 14. The cyclisa-tion is appropria-tely carr:led ou-t direct in the reac-tion solution o~ the hydrazones, according to the invention~
of the ~ormula I, which is produced in -the coupling reaction, by increasing its pH value -to 10 to 14, room temperature generally being sufficient. A diazo solu-tion of an amine of the formula DNH2 is appropriatel~ added, af-ter cooling to temperatures between -5 and +25C, to the solution of the pyrazolone VII obtalned in -this way, withou-t isolating the pyrazolone, and stirring is continued at -temperatures between -5 and +25C until the coupling reaction is complete.
During the progress of the coupling reaction, the pH value is kept at figures of ~ to 8, preferably 5 to 6, by successive additions of a buffer substance or of an alkali. The phthalocyanine azo dyes-tu~fs whlch can be manu~actured in this way from the hydrazones, according -to -the invention, of the formula I have clear green shades and are distinguished by high molar tinctorial strength. ~
Dyestuf~s in which D contains a reactive radical, that is to say a radical capable o~ reactlng wlth the cellulose ~ibre, are particularly valuable. These dyestu~s are distlnguished by high tinctorial strength, bri1liance o~
shade, high degree o~ ~ixatioll and ease o~ washing out the non-fixed portion. The other fastness properties, such as ~astness to light, ~astness to wet processing, ~astness to perspiration and ~astness tv water, are also excellent.
The amines of the general f~rmula IV which are required ~or the manu~acture o~ the compounds according to the inven-tion are obtained, in the case where l represents 0, by reac- :
ting phthalocyanine 3- or 4-di-~ulphochlorides, tri-sulpho-chlorldes or 9 pre~erably, tetra-sulphochlorides with amines o~ the general ~ormula VIII
HN-ar-NH2 ~ .
I (V~
. wherein R3 and ar have the meanings indicated above. Mono-acylated amines, for example acetylated amines of the ~ormula :~
VIIIa H
HN-ar-N-C-CH3 (VIIIa) R O
can also be employed instead o~ the ami~es o~ the ~ormula VIII.
In this case the resulting condensation product with phthalo-cyanine sulphochloride is subsequently saponi~ied.
I~ l ln ~ormula I or IV represents the number 1, the amines o~ the iormula IV are obtained by reacting the phthalo- ~ ~
cyan~ne 3-sulphochloride or 4-sulphochloride in any desired ~ -sequence with an amine o~ the general ~ormula IX ; :~
.:~, ":
, ~
s : : ~
HN /
in which Rl and R2 have the rneanings indicated above, and with an amine of the formu]a VIIl. ;~
In addition, it is, however, possible to use a mixture~
of amines of the formulae VI[I ar,d IX as star-ting materials from the beginning. The reaction of the phthalocyanlne sulphochloride with the said amines is carried ou-t in a manner which is in itself known by adding the amines9 ~either successively or as a mix-ture to a concentrated aqueous sus-pension of the sulphochlorides in water or a mixture o~ wa-ter and organic, water-miscible solven-ts. The reac-tion can, however, also be carried out in organic solvents alone.
The temperature of the reac-tion mix-ture is kep-t at O to 35C
and the pH value, which is continuously displaced into the acid range during the reaction, is kept between 4 and 10, pre~erably between 6 and 8, hy gradual addition o~ alkali.
Alkalis which can be used are the customary substances;with an alkaline reaction~such as sodillm hydroxide solution, sodium carbonate, po-tassium carbonate or trisodium phosphate.
Sodium hydroxide solution is preferred. It is advantageous to add a tertiary amine, such as, for e~ample, pyridine, in catalytic quantities in order to accelerate the reaction.
It is possible to process further the amines o~ the formula IV
n a direct manner in the aqueous solution in whioh they are produced, but it is advantageous in all respects to isolate them, in order to ~ree them from a proportion o~ unreacted i l~;
' 5~iS
amine o~ the ~ormula VIII and/or IX which may still be present.
The following may be m~ntloned a~ amines of the .~or- :-mula IX which can be ~sed for the manu~acture o~ the amines of the formula IV: ammonia, methylamine, dimethylam~ne, ethylamine, diethylamine, ~-hydroxyethylamlne, ~-methoxy-ethylamine, bis-~-hydroxyethylamine, aminoacetic acid, taurine, N-methyltaurine, butylamine, caprylamine, laurylamine, anilinep toluidine, chloroaniline, aniline-o-, -m- or -p-sulphonic acid, aniline-o-, -m- or p-carboxylic acid, N-methylaniline, N-ethylaniline-o-, -m- or -p-sulphonic acid, aniline- ~ -methane- ;
sulphonic acid, benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-sulphonic acid and ~-acetylaminoethylamine.
The ~ollowing may be mentioned as examples of amines o~ the ~ormula VII~, which can also be used in the ~orm o~ the mono-acyl compound: p-phenylenediamine, N-methyl-p-phenylene-diamine, N-carboxymethyl-p-phenylenediamine, m-phenylenediam1ne, N-~-hydroxyethyl-m-phenylenediam1ne, l,4-phenylenediamine-2-sulphonic acld, l-amino-4-N-sulphomethylamino-phenylene-2-sulphonic acid, 1,4-phenylenediamine-2,5- or 2,6-disulphonic acld, l-amino-4-N-methylamino-phenylene-2,6-disulphonic acid, l~3-phenylenediamine-4-sulphonic acid, l,3-phenylen0diamine-4,6-disulphonic acid, 2,4-diamino-toluene-5- or -6-sulphonic :
acid, 2,~-diamino-toluene-4-sulphonic acid, 2,5-diamino-1,3,5- ; ~
trimethylbenzene-4-sulphonic acid, 2,6-diamlno-~,3-diethyl-~ ~ -benzene-~-sulphonic acid, 2,4-diamino-l-chlorobenzene-6 sulphonic acid, 2,4-diamino-l-tert.-butyl-benzene 6-sulphonic acid, 2,4-diaminotoluene-5- or -6-sulphamide, 2,6-diamino-toluene-~9 6S ~:
. . .
4~ethanol- ~ ~mide or 2,6-diaminoto:Luene-die~hanolsulphamide,. 1~4-diaminophenylene-2-dimethylsulphamide, 1,3-diaminophenylene-4-sulphanilide, 1 9 3-diaminophenylene L~ ~-hydroxyethylsulphone,~
N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, N-pentyl-p-E)heny:Lenediam.ine, N-hex~l-p-phenylenediamine~ N-~-hydroxy-propyl-p-phenylene-diamine, N-~-carboxy-propyl-p-phenylenediamine, N-r-c~loro~
butyl-p-phenylenediamine, N-~-methoxy-bUtYl.-p-phen~lenediamine 9 N-~-propoxy-butyl p-phenylenediamine, N-~-ace-tylamino-ethyl p-phenylcnediamine, N-~-butyr~lamino-ethyl-p-phen~le~ediamine, N-benzoylamino-ethyl-p-phenylenediamine, l-N-methyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl-L~amino-benzene-3-sulphonic acid, 2,L~diamino-phenol-6-sulphonic acid, 2,4- ~ ~
diamino-l-methoxybenzene-5-sulphonic acid, 1,5~diaminonaphtha-~ :
lene, l,5-diaminonaphthalene-3-sulphonic acld,~l,5-diamino-naphthalene-L~sulphonic acid, 1,5-dîaminonaphthalene-2-sulphonic acid, 1~6-diaminonaphthalene-4-sulphonic acid, 1,L~diamino-. :. ~:.
naphthalene-2-sulphonic acid, 1,4-diaminonaphthalene-5- :
sulphonic acid, 1,4-diaminonaphthalene-7-sulphonic acid, 1,8-diaminonaphthalene-L~sulphonic acid, 2,6-diaminonaphthalene--8-sulphonic acid, 2,6-diaminonaphthalene-4~8-dlsulphonic acid, 1,5-dlamlnonaphthalene-3,7-disulphonic acid, 1,4-diamino-naphthalene-5-carboxylic acid, 1,4-diaminonaphthalene-2-carbo~ylic acid, 1,8-diaminonaphthalene-3-carboxylic acid, :
4,4'-diaminodiphenyl, 2,2'-dimethyl-~,4'-diaminodiphenyl? 3,3'- .
dichloro-4,4'~diaminodiphenyl, 4,4'-diaminodiphenyl-2,2'~
dlsulphonic acid, 3,3'-dimethoxy-4,4'-diaminodLphenyl, 1-amino-~ ;
4-aminomethyl-benzene, 1-amlno-4~aminomethyl-benzene 3-sulphanl~o - 20 ~
, acid, l~amino-4-p-aminoethyl-benzene-2-sulphonic acid, 1-amino-4-y-aminopropyl-benx~ne-3~sulphonic ac~d, 2-amino-5- :~
aminomethyl-naphthalene-1-sulphonic acid, 4~4'-diamino-dlphenylmethane-2,2'-disulphonic acid, 4,4'-diamino-dlphenyl-ethane-2,2' disulphonic acid, 4l4'-d1amino-diphenylethane-mono-~ulphamlde, 4 J 4 I -diamino-diphenylethane-disulp}lamid~
4,4~-diaminostilbene-2,2~-disulphonic acid, 4,4'-diamino-diphenylmethane, 4~4'-d~amino-d~phenylethane-di-~-hydroxy-`ethylsulphamide,4,4'-diamino-diphenylamine-3-sulphon~c acid, 3,4'-diamina-6-methoxy-diphenylamine-2'-sulphonic acid, 3,4'-diamino-4-methyl-diphenylamlne~ ulphonic acicl, 3,3'-diamino-benzophenone-5,5'-disulphonlc acld, 3,4'-diaminobenzoph~none-3'-sulphonic acid, 4,4'-diamino-diphenyl sulphone, 4,4'-dl-chloro-3,3'-diamino-diphenyl sulphone, 3,3'-diamino-4-methyl- :
diphenyl-sulphone-5-sulphoni~ acid and 3,3'-diamino-diphenyl-sulphone-4,4l-disulphonic acid. ~-~1 106 g o~ 3 (3-amlno-4-sulpho-phenyl)-amino-sulphonyl-nickel-phthalocyanine-37, 3", 3"'-trisulphonic acidy prepared in the usual way by a condensation reactlon between nickel phthalocyanine sulphochloride and 1,3-diaminobenzene-4-sul-phonic acid, are stirred wi$h 700 ml o~ water and are dissolved by adding 40 ml of 10 N sodium hydroxide solution. 7.2 g of sodium nitrite are added to this solution and it is then stirred , in the course o~ 30 minutes, into a mixture of 200 g o~ ice and 30 ml of concentrated hydrochloric acid. A
temperature G~ 0 to 5C is maintalned by adding a ~urther 200 g of ice. A~ter a short time, any excess o~ nitrite which D~
: ` .
may be presen-t is destroyed by adding aminosulphonic acid.
21 g of acetylsuccinic acid dimethyl ester are poured into the diazo suspension obtained in this way. The pH value is then kept, first a-t 5.5 by ~prink:ling in appro~imately 13 g of sodium carbonate and then at 5 to 6 by means of approxi-mately 21 g of sodium bicarbonate. Stirring is then con-tinued f`or approximately 1 hour. The end of the reaction is recognised from the ~act -that the pH remains constant~and that no alterat1on o~ colour shade takes place when a solution of H-acid in 2 N sodium carbona-te is added to a sample.
A solution o~ oxalacet:Lc ac:ld dlmethyl es-ter 5-(Ni-trisulpho-phthalocyaninylsulphonylamino)-~-,ulpho-phenylhydrazone is obtained in this way, which has an in-tense blue-gréen colour and which can be processed further direct for the manufacture of N-[3-(3-carboxy-5-hydroxy-1 pyrazolyl)-4-sulpho-phenyl~-Ni-trlsulphophthalocyaninylsulphonamide.
Hydrazones, accordlng to -the in~en-tion, of the phthalo-cyanine series which have a deep colour and are very valuable are also obtained if, instead o~ the abovementioned amine, the condensation product o~ nickel phthalocyanine sulphochloride with one o~ the amines mentioned in thetable whioh~ollows is used as the diazo component: 1,4-pheny1enediamine-2-sulphonic acid~ 1,3-phenylenediamine-4,6-disulphonic acid9 1,4-phenylene-diamine-2,5-disulphonic acid~ 1,L~phenylenediamine-2~6-~disulphonic acid, 2,4-diamlnotoluene-6-sulphonic acid, 2,6~
diaminotoluene-L~su1phonic acid, 2,5-diamino 1,3,5-trimethyl-benzene-4-sulphonic acid, 2,6-diaminonaph-thalene-4,8-disu1- ~:
phonic acid, 1,5~diaminonaphthalene-3,7-disulphonic acid9 .i l~ -;~ .
:
6~ ~ ~
`~
1,5-diaminonaphthalene-2-sulphonic acid, 2,6-diaminonaphtha-lene~8-sulphonic acid, 1-amino-4-aminome-thyI-benzene-3- :
sulphonic acid, l-amino-5-aminomethy1.-naphthalene-2-sulphonic acidJ 4,4'-diamino-dipheny1amine--3-sulphonic acid~ 4,4'-diamino-stilbene-disulphonic aci(l, 3,3'-diamino-4-methyl- :~
diphenyl-su1phone-5-sulphonic ac:id, 1,3-phenylened1amine (acetyl derivative, subsequently saponifled), 2,4-diam1no~
toluene (acetyl derivative, subsequently saponified~, l,4-phenylenediamine (acetyl derivati~ve, subsequently ~aponi~ied), 4,4'-benzidine, 3,3'-4,4'-dichlorobenzidine and 494~-diamino-diphenyl sulphone, Example o~ the preparation o~` a d~estu~
35 ml of lO N alkali metal hydroxide solution are added ~.
to the solution, obtained accordi.ng to Example l, of oxaIacetic `` ~:-acid dimethyl ester C3-(nickel-trisu1pho-phtha10cy~ninylsulpho~
nylamino)~-6-sulpho-phenylhydrazone, as a result o~which the ~ ~ ;
pH rises to values from 12 to 13~ The mixture 1s stirred for a ~ew hours, best overnight at room -temperature. ; The rearrangement to give N~[3-(3-carboxy-5-hydroxy-l-pyrazolyl)~
4-sulpho-phenyl]-niokel-trisuIpho-phthalocyaninyl-sulphonamide i9 then complete; the pH is restored to 8 with a little hydrochloric acid. In order to prepare a green:reactive azo-phthalocyani~e dyestuff, 25:ml of 4 N sodium nitrite~s:olu-,:.-tion are added to a neutral solution of 48 g of the condensa~
tion product prepared in the usual way from aniline 3-sulphonic .:~
~: acid, cyanuric chloride and 2,4-diaminobenzenesulphonic acid and the produot is stirred into a mixture of~25 ml of 10 N ~
hydrochloric aoid and ice, so that the temperature remains l ~ :
, : - 23 -~ ' :
between 0 ~nd 5C~ Stirring is continued ~or a short time and any excess o~ nitrite which may be present 1s then removed by means of aminosulphonlc acid.
For the coupling reaction, the cliazo suspension thus obtained is added to the solution of the pyrazolone and the pH
value is adjusted to a figure of 6 to 7 with approximately 10 g o~ bicarbonate. The coupllng is cc>mplete after a few minutes.
The resulting azo dyestuff can be isolated by salting out or by spray drying.
It is distinguished by its uniformly good degree of fixation in all the one-phase printing processes. Its good degree of fixation when fixed by dry heat should be singled out particularly. Furthermore, for a phthalocyanine deri-vative, it has remarkably good washing-of~ prolperties, as well as good fastness to light and very good properties in use.
Example 2 107 g o~ 3,3'-bis-~(4-aminophenyl)-amino-sulphonyl7-nickel-phthalocyanine-3", 3"'-disulphonie acid,prepared in the usual way by a condensation reaction between 0.1 mol of nickel phthalocyanine tetr~sulphochloride and 0.2 mol of acetyl-p-phenylenediamine and saponification of the condensation pro-duct, are stirred with 700 ml of water and are dissolved by addtng 40 ml o~ 10 N sodium hydroxide solution. 14 g of sodium nitrite are added to this solu~ion and the mixture is then stirred, ~n the course of about 30 minutes, into a mix-ture oi 400 g o~ ice and 60 ml o~ coneentrated HCl. The temperature is Icept between 0 and 5C ~y adding a further `~:
~ ;
200 g of ice. Stirring is continued for about lO~minutes and any small excess of ni-trite ~hich may be present is then removed with aminosulphonic acid. 27 g of acetylsuccinic acid diethyl ester are added to -the clia~o suspension obtained in this way. The pH is adjus-ced -to about 6 with approxi-mately 50 g of sodium carbonate -md is kept at thls value until the diazo compound can no :Longer be detected ~ A
solution of turquoise-coloured 3~3'-bis-[L~(1,2-bis-ethoxy-carbonyl-ethylidene)-hydrazino-phenyl-aminosulphonyl]-nickel-phthalocyanine-3",3"'-disulphonic acid is obtained in this way, which can be converted direct in-to the corresponding bispyrazolone by the action of alkall.
Valuable phthalocyanine hydrazones are also obtained if the corresponding 4,4',4",4"'-deriva-tive i.~ used instead o~
the amine employed above. ;~
Very valuable, turquoise-coloured phthalocyanlne-bls-arylhydrazones according -to -the inven-tion are also obtained if the condensation product of nickel ph-thaIocya~lne~sulpho-:
chloride with two mols of one of the amines mentioned~in thetable which~follows is employed clS the diazo component instead o~ the amine employed above~ phenylenediamine (acetyl derivative, subsequently saponifi.ed), 2,4-diaminotoluene (acetyl derivative, subsequently saponified)~ 2~4-diamino-.
anisole ~acetyl derivative, subsequently saponi~ied),;l~4phenylenediamine-2-sulphonic acid, 2,4-diaminotoluene-6-~; sulphonic acid, 4-~mino-benzylamine (4-acetyl derivative, subse~uently saponi~ied), 1,4-phenylenedic~mine-2,6-disulphonic cid~ 4,4'-diaminostilbenedisulphonic acid, 4~' diamino~
.
-~ethanedisulphonlc acid and 4,4'-diamino-diphenyl~mine~3-sulphonic acid, Arylhydrazone~, accorcling to the invelltlon, which can be processed ~urther to give valunble ]pyrazolon~s, are al~o obtained i~ the acetylsuccinic acid diiethyl ester empIoyed as the coupling component is replaced by one of the following derivatives o~ succinic acid:
R5 - OOC - CH2 - CH - COO - R~
O
-c~3 -CH3 -H
-CH3 -C2H4Cl -CH3 -CH3 -i-C3H~ -CH3 -CH3 i C6Hl3 _COO-C2H5 -CH3 C2 ~ 0~1 -CII3 :
-C3H7 -C2i~5 -C3H7 C5Hll -C2H5 2 6 5 CgHlg C2HS -COO-CH3 C16H33 -C2H5 C6f~5 ~;
-C2H~-Q-C2H5 C2H5 -C6H4-C~I3 - 2~
: , , ~Q~$~6~9 ~ ~
Exam~le 3 Valuable hydrazones Qf oxalacetic acid m~thyl ester, which can be processe~ further to give the correspondingly substituted pyrazolones are also obtained i~, instead o~ the :
amine indicated in Example 1, 3~~(3-amino-4-sulpho-phenyl)~
amino-sulphonyl~-nickel-phthalocyanin~-3',3",3"'-trisulphonic acid, the corresponding amount in ~olar terms Or one of the amines mentioned in the table which ~ollows is used and the ~ -process is in other respects as indicated in that Example.
~ 1 Pc -- ( S02-N
\ 2 1 \ (S02-1N-ar-NH2)m _ ~ ~_ ~
~ - :
os ~ o~
. _ . . . W __ ,, ~, ~
. ' , , ..
_ ~ U "~ ~
. :
.. ~ U~
1~ ~ u~ ,~ u~ u~ ~ ~
_ ~ .:
~: : :
. ~ ~. .
æ ~ ~ ~w t~
~ ~ .
_ 2~
~:
,................. .... ... .... ..... ... .... ... .......... ...... ... .... ........... ~ `
s ~ ::
~4 s~ W e~
: :
d o~ o~ ~D o~ w~ m p~
~0~ a~p ~ . .. . ...... _ .
.
: ~N C~
qD ~ . :
C~ ~ ~
::: : : ~ ~:
:
: ~ : ::
6~i ~ ~ ,, ,~ " ,, ,, ,, ~ ~ ,, .Y ~ C~ C`~ N C`J C~
.
~ S~ o~ o~ o~
mC`' P~
. _ _ . ... _ ~ . . _ ... ;. _ P~ :
, ~ ~
' ' ' :
.
., ~ ~ ~ N N C~l N
_ ,~
: ~ ' ~ ~ ' aP
`,.
E
_ _ _ : ~' ' ~ ~
~ ~ ' : :
~ . ~ ~) ~I h O O
. _ _ .
:
' tl~
O C~ .. ' Q~ O /~ C'3 : :
~I N
W q tr~
.
. `' ' , ' ' `
. ~ .
:~a o ~ 8 ` ::: ~:
:: : ~ ~., " C~ V
: . 'q m P: P~ o :
~ ~ ~ I~o ~ w 8~ . d' ~ ~C' d' ~ ~ . . i , ~
: ~ ~ ~ C~ U~ ` U~ V~ ~ ~ :~
31~
. .
E c~
_ ~
~ C~ o : , _ ~
' ,:
. ~,.
~ ~C~
~ ,~
C~
- ~C
.
_ .... _ ,' - -P4 ~ .. 1 ' C9~
6~ : .
E c~
,1 ,, o O
,, ,~ o - ~ -. , ' ';, . .~
. 1~
U~
~ 'n`~3 i;~) '' _ _ , - ' '::
. , ':
: `
, ~ ,. .
' C~
~;
X :~ ~q ~ : ,.
-.
: .
~ . _ .. ~ .:
. ' ' ~
:, ~ ~ : ~ ' :
; :
i ,' ~
~.
Water-soluble hydrazones,accordlng to the invention, o~ the phthalocyanine ser~es o~ the general ~ormula I in which Rl denotes hydrogen, an alkyl radical which contains 2 or 3 atoms and is optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH or SO3H, methyl, carboxymethyl or sulphomethyl, are pre~erred.
Water-soluble hydrazones,according to the invention, o~ the phthaloeyanine series of the general ~ormula I in which R denotes an alkyl radical which has 2 or 3 C atoms and which Ll !
56~
:
is optionally substituted by OH, alkoxy havlllg 1~3 C akoms, ~-COOH or ~S03~, or denote~ an unsubstituted alkyl radlcal having 1~20 C atoms, but especlally denotes hydro~en, methyl, carboxymethyl or an alkyl radical which has 2 or 3 C atoms and which is optionally substituted by OH, are also pre~erred.
Particularly pre~erred meallings ~or Rl and R2 are hydrogen, methyl or ~-hydroxyethyl. In thP same way hydrogen, methyl and ~-hydroxyethyl are particularly pre~erred meanings o~ Rl and R~ .
~ urther preferred groups o~ hydrazones, according to the invention, o~ the phthalocyanine series o~ the ~eneral ~ormula I are characterised in that R3 denotes hydrogell, methyl, carboxymethyl, sulphomethyl or an etllyl radical which is optionally substituted by Cll OH, alkoxy having 1 or ~ C atoms, :~
-COOH or -S03H, and particularly denotes hydrogen or methyl, R4 denctes an ethyl radlcal whtch ls substituted by Cl, OH or alkoxy havlng ~-2 C atoms, or denotes an un~ubsti-tuted alkyl~:
radical having 1-6 C atoms, and R5 denotes an ethyl radical which ls substituted by Cl, OH or alkoxy having 1-2 C atom~
or denotes an unsubstituted alkyl radical having 1-18 C atoms.
Water-soluble hydrazones, accordin~ to the ~nvention, :
of the phthalocyanine serles o~ the general formula I in which R4 and R5 are identical and denote methyl or ethyl, ar~ parti- :
cularly advantageous. :~
Those hydrazones, according to the invention, of the phthalocyanine serles of the general ~ormula I in which l = O, k = 2 or 3 a~d m 3 1 or 2 and the sum o~ k ~ m = 4, are par~
cularly pre~erred.
- 11 - ~:.''-~'' - ~ :
~4~iS
The individual hydrazones according to the lnvention can in ~ach case contain small proportions of hydrazone~, according to the ~nv~ntion, in which k and/ or l and/or m have a meaning di~erent ~rom that in the main component.
These mlxtures o~ hydrazones are also very valuable starting materials ~or the mnnu~acture o~ phthalocyanine azo dyestuf~s.
The water-soluble hydrazones, according to the inven-tion, o~ the phthalocyanine series o~ the general formula I
are manu~actured by diaxotlsing an amine o~ the phthalocyanine series o~ the general ~ormula IV
(S0311)k Pc . _ (S02-N ll (IV) :
\ 2~
(S02-N~ar~NH2)m R~
wherein *he ~ree amino grou~ is linked to an aromatic C atom o~ the radical ar and wherein Pc, ar, Rl, R2, R3, k, l and m have the abovementioned meanlngs, and the product is coupled in an aqueous medium at a p~1 value between 3 and 8 with a succinic acid derivative o~ the ~ormula V
R5-OOC-CH2-C~-C~OR4 ( V) CO-Z
wherein R4 and R5 have tbe abovementioned meanings and Z
denotes hydrogen, an alkyl radlcal whlch has l~lO C atoms and which is optionally substituted by alkoxy having l-4 C atoms ' ~
or alkoxycarbonyl having 2-6 C atoms, a phenyl radïcal which is optionally substituted by Cl~ Br "llkyl or aIkoxy having 1-4 C atoms, or alkoxycarbonyl h!ving 2-6 C atoms, and~ if appropria-te, converting the resu~-ting hycLrazones into the alkali metal, ammonlum or alkaline ea:rth metal salts.
Amines of the general formula IV in which the radicals Pcj ar, Rl, R2, R3, k, 1 and m have the meanings characterised above as preferred and in which the substi-tuents indicated in ;
formula IV are in -the 3-pcsi-tion~ are preferred for the manu-facture of the hydrazones, according to -the invention9 of the general formula I.
Possible succlnic acid deriva-tives of t~he ~ormula V
which are preferred are those in which Z denotes hydro~gen, alkyl having 1-3 C atoms, phenyl, me-thylphenyl or alkoxy-. ~ .
carbonyl having 2 or 3 C a-toms. The methyl group:is particularly preferred for Z. :
~ The amines of the general formula IV are diazotlsed : in a manner which is in itself known in an aqueous acid medium by reaction with nitrous acid or an agent which splits off nitrous acid. A salt of nitrous acid, especially an alkali metal salt, such as sodium or potassium nitrite, is generally ~: .
-: employed in a mineral acid medium as an agent which~plits off nitrous acid. In a preferred embodiment, the neutral : : a~ueous solution of an amine of the formula IV is treated ~ with a solution of sodium ni-trite in a molar ratio of 1 : m : and thls mixture is then run, whilst stirring, into at least 2.5 molsg preferably 3 mols 3 0~ dilute, approximately 5-15% ~ -strength hydrochloric acid per mol of amino group pre~ent~ at , .
s temperatures between -5 and ~25C, preferably -2 to +5C.
The diazo suspension thus obtained is -then reacted wi-th a succinic acid derivative of the general formula V at a pH
value between 3 and 8p preEerably between 4 . 5 and 5.5, for example by adding the succinic acid derivativ~ to -the acid suspension of the diazoni~un compounds and then adjusting the pH value to the desired ~igure by the addition of alkali, for exarnple sodium hydroxide, sodium carbonate, sodium bicar-bonate, sodium acetate, potassium carbonate or sodium phosphate.
After stirring for 1 to 3 hours the diazotised amine can no longer be detected and -the formation of the hydrazone accord-ing to the invention is complete. I-t can be separated out from the solu-tion by salting out, that is to say by adding a neutral, water-soluble salt9 such as, ~or example, sodium chloride or potassium chloride. Separation lS, however, in no way necessary for the further processlng of the hydra~
zones according to the invention, on -the o-ther hand it is .
appropriate and advantageous -to employ the reaction solutions obtained in -the coupling reac-tion direct for further processing.
The a~ueous medium in which the coupling reaction of the diazotised amines of the formula IV with -the succinic acid derivatives of the formula V is carried out can also contain organic, water-mlscible solvents, especially lower aliphatic alcohols, such as, for example, methanol, ethanol or lsopro-panolO In the same way, known coupling accelerators, such as, for example, urea or pyridine, can be present during the coupling reaction.
The hydrazones according -to the invention are valuabIe ~ !
i5 interm~diate products ~or the manu~acture, which is te~hni~
cally simple, o~ excellent green phthalocyanine azo dyestu~s o~ the formula VI.
The phthalocyanlne azo dyestu~s of the formula VI
are manu~actured ~rom the hydrazones accordlng to tAe inven-tion in accordancu with the ~ollowing equation (S03~)~
PC --(S02-N\ ) o~
~50-C-C~12 \
(S2 ~ N ~ ar - N~ - N ~ C
m ) lo~
j R (VII~
Pc - (S~2 N ~ ~ ) \ 2 l : :
~T ~ , ~SO~-N - ar-N
C09~4 m :~
[D-N-N ~] Z ~
"1 .
Phthalocyanine a~o dyestu~ (VI) The cyclisation o~ the hydrazone to giYe th~ pyra-: zolone, which is indicated in th~ reaction step I in the . .
.... . . .
~ ~J~
above equationl is carried out extremely easlly by stirring an aqueous solution of the hydraz~nes, according to the inven-tion, of -the formula I a-t temperatures be-tween O and 100C, pre~erably 15 to 30C, at a pH value be-twe~n 8 and 141 with elimination of the alcohol of ~ormula R50H. The cyclisa-tion can be coupled wi-th a saponi~ication of the group -COOR4 of the resulting pyrazolone, -to give the free carboxyl group.
To achieve this i-t is only necessary to carry out t:he reac-tion near to the upper limit of the range o~ pH values indi-cated, for example at pH values ~rom 10 to 14. The cyclisa-tion is appropria-tely carr:led ou-t direct in the reac-tion solution o~ the hydrazones, according to the invention~
of the ~ormula I, which is produced in -the coupling reaction, by increasing its pH value -to 10 to 14, room temperature generally being sufficient. A diazo solu-tion of an amine of the formula DNH2 is appropriatel~ added, af-ter cooling to temperatures between -5 and +25C, to the solution of the pyrazolone VII obtalned in -this way, withou-t isolating the pyrazolone, and stirring is continued at -temperatures between -5 and +25C until the coupling reaction is complete.
During the progress of the coupling reaction, the pH value is kept at figures of ~ to 8, preferably 5 to 6, by successive additions of a buffer substance or of an alkali. The phthalocyanine azo dyes-tu~fs whlch can be manu~actured in this way from the hydrazones, according -to -the invention, of the formula I have clear green shades and are distinguished by high molar tinctorial strength. ~
Dyestuf~s in which D contains a reactive radical, that is to say a radical capable o~ reactlng wlth the cellulose ~ibre, are particularly valuable. These dyestu~s are distlnguished by high tinctorial strength, bri1liance o~
shade, high degree o~ ~ixatioll and ease o~ washing out the non-fixed portion. The other fastness properties, such as ~astness to light, ~astness to wet processing, ~astness to perspiration and ~astness tv water, are also excellent.
The amines of the general f~rmula IV which are required ~or the manu~acture o~ the compounds according to the inven-tion are obtained, in the case where l represents 0, by reac- :
ting phthalocyanine 3- or 4-di-~ulphochlorides, tri-sulpho-chlorldes or 9 pre~erably, tetra-sulphochlorides with amines o~ the general ~ormula VIII
HN-ar-NH2 ~ .
I (V~
. wherein R3 and ar have the meanings indicated above. Mono-acylated amines, for example acetylated amines of the ~ormula :~
VIIIa H
HN-ar-N-C-CH3 (VIIIa) R O
can also be employed instead o~ the ami~es o~ the ~ormula VIII.
In this case the resulting condensation product with phthalo-cyanine sulphochloride is subsequently saponi~ied.
I~ l ln ~ormula I or IV represents the number 1, the amines o~ the iormula IV are obtained by reacting the phthalo- ~ ~
cyan~ne 3-sulphochloride or 4-sulphochloride in any desired ~ -sequence with an amine o~ the general ~ormula IX ; :~
.:~, ":
, ~
s : : ~
HN /
in which Rl and R2 have the rneanings indicated above, and with an amine of the formu]a VIIl. ;~
In addition, it is, however, possible to use a mixture~
of amines of the formulae VI[I ar,d IX as star-ting materials from the beginning. The reaction of the phthalocyanlne sulphochloride with the said amines is carried ou-t in a manner which is in itself known by adding the amines9 ~either successively or as a mix-ture to a concentrated aqueous sus-pension of the sulphochlorides in water or a mixture o~ wa-ter and organic, water-miscible solven-ts. The reac-tion can, however, also be carried out in organic solvents alone.
The temperature of the reac-tion mix-ture is kep-t at O to 35C
and the pH value, which is continuously displaced into the acid range during the reaction, is kept between 4 and 10, pre~erably between 6 and 8, hy gradual addition o~ alkali.
Alkalis which can be used are the customary substances;with an alkaline reaction~such as sodillm hydroxide solution, sodium carbonate, po-tassium carbonate or trisodium phosphate.
Sodium hydroxide solution is preferred. It is advantageous to add a tertiary amine, such as, for e~ample, pyridine, in catalytic quantities in order to accelerate the reaction.
It is possible to process further the amines o~ the formula IV
n a direct manner in the aqueous solution in whioh they are produced, but it is advantageous in all respects to isolate them, in order to ~ree them from a proportion o~ unreacted i l~;
' 5~iS
amine o~ the ~ormula VIII and/or IX which may still be present.
The following may be m~ntloned a~ amines of the .~or- :-mula IX which can be ~sed for the manu~acture o~ the amines of the formula IV: ammonia, methylamine, dimethylam~ne, ethylamine, diethylamine, ~-hydroxyethylamlne, ~-methoxy-ethylamine, bis-~-hydroxyethylamine, aminoacetic acid, taurine, N-methyltaurine, butylamine, caprylamine, laurylamine, anilinep toluidine, chloroaniline, aniline-o-, -m- or -p-sulphonic acid, aniline-o-, -m- or p-carboxylic acid, N-methylaniline, N-ethylaniline-o-, -m- or -p-sulphonic acid, aniline- ~ -methane- ;
sulphonic acid, benzylamine, N-~-hydroxyethyl-benzylamine, benzylamine-sulphonic acid and ~-acetylaminoethylamine.
The ~ollowing may be mentioned as examples of amines o~ the ~ormula VII~, which can also be used in the ~orm o~ the mono-acyl compound: p-phenylenediamine, N-methyl-p-phenylene-diamine, N-carboxymethyl-p-phenylenediamine, m-phenylenediam1ne, N-~-hydroxyethyl-m-phenylenediam1ne, l,4-phenylenediamine-2-sulphonic acld, l-amino-4-N-sulphomethylamino-phenylene-2-sulphonic acid, 1,4-phenylenediamine-2,5- or 2,6-disulphonic acld, l-amino-4-N-methylamino-phenylene-2,6-disulphonic acid, l~3-phenylenediamine-4-sulphonic acid, l,3-phenylen0diamine-4,6-disulphonic acid, 2,4-diamino-toluene-5- or -6-sulphonic :
acid, 2,~-diamino-toluene-4-sulphonic acid, 2,5-diamino-1,3,5- ; ~
trimethylbenzene-4-sulphonic acid, 2,6-diamlno-~,3-diethyl-~ ~ -benzene-~-sulphonic acid, 2,4-diamino-l-chlorobenzene-6 sulphonic acid, 2,4-diamino-l-tert.-butyl-benzene 6-sulphonic acid, 2,4-diaminotoluene-5- or -6-sulphamide, 2,6-diamino-toluene-~9 6S ~:
. . .
4~ethanol- ~ ~mide or 2,6-diaminoto:Luene-die~hanolsulphamide,. 1~4-diaminophenylene-2-dimethylsulphamide, 1,3-diaminophenylene-4-sulphanilide, 1 9 3-diaminophenylene L~ ~-hydroxyethylsulphone,~
N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, N-pentyl-p-E)heny:Lenediam.ine, N-hex~l-p-phenylenediamine~ N-~-hydroxy-propyl-p-phenylene-diamine, N-~-carboxy-propyl-p-phenylenediamine, N-r-c~loro~
butyl-p-phenylenediamine, N-~-methoxy-bUtYl.-p-phen~lenediamine 9 N-~-propoxy-butyl p-phenylenediamine, N-~-ace-tylamino-ethyl p-phenylcnediamine, N-~-butyr~lamino-ethyl-p-phen~le~ediamine, N-benzoylamino-ethyl-p-phenylenediamine, l-N-methyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl-L~amino-benzene-3-sulphonic acid, 2,L~diamino-phenol-6-sulphonic acid, 2,4- ~ ~
diamino-l-methoxybenzene-5-sulphonic acid, 1,5~diaminonaphtha-~ :
lene, l,5-diaminonaphthalene-3-sulphonic acld,~l,5-diamino-naphthalene-L~sulphonic acid, 1,5-dîaminonaphthalene-2-sulphonic acid, 1~6-diaminonaphthalene-4-sulphonic acid, 1,L~diamino-. :. ~:.
naphthalene-2-sulphonic acid, 1,4-diaminonaphthalene-5- :
sulphonic acid, 1,4-diaminonaphthalene-7-sulphonic acid, 1,8-diaminonaphthalene-L~sulphonic acid, 2,6-diaminonaphthalene--8-sulphonic acid, 2,6-diaminonaphthalene-4~8-dlsulphonic acid, 1,5-dlamlnonaphthalene-3,7-disulphonic acid, 1,4-diamino-naphthalene-5-carboxylic acid, 1,4-diaminonaphthalene-2-carbo~ylic acid, 1,8-diaminonaphthalene-3-carboxylic acid, :
4,4'-diaminodiphenyl, 2,2'-dimethyl-~,4'-diaminodiphenyl? 3,3'- .
dichloro-4,4'~diaminodiphenyl, 4,4'-diaminodiphenyl-2,2'~
dlsulphonic acid, 3,3'-dimethoxy-4,4'-diaminodLphenyl, 1-amino-~ ;
4-aminomethyl-benzene, 1-amlno-4~aminomethyl-benzene 3-sulphanl~o - 20 ~
, acid, l~amino-4-p-aminoethyl-benzene-2-sulphonic acid, 1-amino-4-y-aminopropyl-benx~ne-3~sulphonic ac~d, 2-amino-5- :~
aminomethyl-naphthalene-1-sulphonic acid, 4~4'-diamino-dlphenylmethane-2,2'-disulphonic acid, 4,4'-diamino-dlphenyl-ethane-2,2' disulphonic acid, 4l4'-d1amino-diphenylethane-mono-~ulphamlde, 4 J 4 I -diamino-diphenylethane-disulp}lamid~
4,4~-diaminostilbene-2,2~-disulphonic acid, 4,4'-diamino-diphenylmethane, 4~4'-d~amino-d~phenylethane-di-~-hydroxy-`ethylsulphamide,4,4'-diamino-diphenylamine-3-sulphon~c acid, 3,4'-diamina-6-methoxy-diphenylamine-2'-sulphonic acid, 3,4'-diamino-4-methyl-diphenylamlne~ ulphonic acicl, 3,3'-diamino-benzophenone-5,5'-disulphonlc acld, 3,4'-diaminobenzoph~none-3'-sulphonic acid, 4,4'-diamino-diphenyl sulphone, 4,4'-dl-chloro-3,3'-diamino-diphenyl sulphone, 3,3'-diamino-4-methyl- :
diphenyl-sulphone-5-sulphoni~ acid and 3,3'-diamino-diphenyl-sulphone-4,4l-disulphonic acid. ~-~1 106 g o~ 3 (3-amlno-4-sulpho-phenyl)-amino-sulphonyl-nickel-phthalocyanine-37, 3", 3"'-trisulphonic acidy prepared in the usual way by a condensation reactlon between nickel phthalocyanine sulphochloride and 1,3-diaminobenzene-4-sul-phonic acid, are stirred wi$h 700 ml o~ water and are dissolved by adding 40 ml of 10 N sodium hydroxide solution. 7.2 g of sodium nitrite are added to this solution and it is then stirred , in the course o~ 30 minutes, into a mixture of 200 g o~ ice and 30 ml of concentrated hydrochloric acid. A
temperature G~ 0 to 5C is maintalned by adding a ~urther 200 g of ice. A~ter a short time, any excess o~ nitrite which D~
: ` .
may be presen-t is destroyed by adding aminosulphonic acid.
21 g of acetylsuccinic acid dimethyl ester are poured into the diazo suspension obtained in this way. The pH value is then kept, first a-t 5.5 by ~prink:ling in appro~imately 13 g of sodium carbonate and then at 5 to 6 by means of approxi-mately 21 g of sodium bicarbonate. Stirring is then con-tinued f`or approximately 1 hour. The end of the reaction is recognised from the ~act -that the pH remains constant~and that no alterat1on o~ colour shade takes place when a solution of H-acid in 2 N sodium carbona-te is added to a sample.
A solution o~ oxalacet:Lc ac:ld dlmethyl es-ter 5-(Ni-trisulpho-phthalocyaninylsulphonylamino)-~-,ulpho-phenylhydrazone is obtained in this way, which has an in-tense blue-gréen colour and which can be processed further direct for the manufacture of N-[3-(3-carboxy-5-hydroxy-1 pyrazolyl)-4-sulpho-phenyl~-Ni-trlsulphophthalocyaninylsulphonamide.
Hydrazones, accordlng to -the in~en-tion, of the phthalo-cyanine series which have a deep colour and are very valuable are also obtained if, instead o~ the abovementioned amine, the condensation product o~ nickel phthalocyanine sulphochloride with one o~ the amines mentioned in thetable whioh~ollows is used as the diazo component: 1,4-pheny1enediamine-2-sulphonic acid~ 1,3-phenylenediamine-4,6-disulphonic acid9 1,4-phenylene-diamine-2,5-disulphonic acid~ 1,L~phenylenediamine-2~6-~disulphonic acid, 2,4-diamlnotoluene-6-sulphonic acid, 2,6~
diaminotoluene-L~su1phonic acid, 2,5-diamino 1,3,5-trimethyl-benzene-4-sulphonic acid, 2,6-diaminonaph-thalene-4,8-disu1- ~:
phonic acid, 1,5~diaminonaphthalene-3,7-disulphonic acid9 .i l~ -;~ .
:
6~ ~ ~
`~
1,5-diaminonaphthalene-2-sulphonic acid, 2,6-diaminonaphtha-lene~8-sulphonic acid, 1-amino-4-aminome-thyI-benzene-3- :
sulphonic acid, l-amino-5-aminomethy1.-naphthalene-2-sulphonic acidJ 4,4'-diamino-dipheny1amine--3-sulphonic acid~ 4,4'-diamino-stilbene-disulphonic aci(l, 3,3'-diamino-4-methyl- :~
diphenyl-su1phone-5-sulphonic ac:id, 1,3-phenylened1amine (acetyl derivative, subsequently saponifled), 2,4-diam1no~
toluene (acetyl derivative, subsequently saponified~, l,4-phenylenediamine (acetyl derivati~ve, subsequently ~aponi~ied), 4,4'-benzidine, 3,3'-4,4'-dichlorobenzidine and 494~-diamino-diphenyl sulphone, Example o~ the preparation o~` a d~estu~
35 ml of lO N alkali metal hydroxide solution are added ~.
to the solution, obtained accordi.ng to Example l, of oxaIacetic `` ~:-acid dimethyl ester C3-(nickel-trisu1pho-phtha10cy~ninylsulpho~
nylamino)~-6-sulpho-phenylhydrazone, as a result o~which the ~ ~ ;
pH rises to values from 12 to 13~ The mixture 1s stirred for a ~ew hours, best overnight at room -temperature. ; The rearrangement to give N~[3-(3-carboxy-5-hydroxy-l-pyrazolyl)~
4-sulpho-phenyl]-niokel-trisuIpho-phthalocyaninyl-sulphonamide i9 then complete; the pH is restored to 8 with a little hydrochloric acid. In order to prepare a green:reactive azo-phthalocyani~e dyestuff, 25:ml of 4 N sodium nitrite~s:olu-,:.-tion are added to a neutral solution of 48 g of the condensa~
tion product prepared in the usual way from aniline 3-sulphonic .:~
~: acid, cyanuric chloride and 2,4-diaminobenzenesulphonic acid and the produot is stirred into a mixture of~25 ml of 10 N ~
hydrochloric aoid and ice, so that the temperature remains l ~ :
, : - 23 -~ ' :
between 0 ~nd 5C~ Stirring is continued ~or a short time and any excess o~ nitrite which may be present 1s then removed by means of aminosulphonlc acid.
For the coupling reaction, the cliazo suspension thus obtained is added to the solution of the pyrazolone and the pH
value is adjusted to a figure of 6 to 7 with approximately 10 g o~ bicarbonate. The coupllng is cc>mplete after a few minutes.
The resulting azo dyestuff can be isolated by salting out or by spray drying.
It is distinguished by its uniformly good degree of fixation in all the one-phase printing processes. Its good degree of fixation when fixed by dry heat should be singled out particularly. Furthermore, for a phthalocyanine deri-vative, it has remarkably good washing-of~ prolperties, as well as good fastness to light and very good properties in use.
Example 2 107 g o~ 3,3'-bis-~(4-aminophenyl)-amino-sulphonyl7-nickel-phthalocyanine-3", 3"'-disulphonie acid,prepared in the usual way by a condensation reaction between 0.1 mol of nickel phthalocyanine tetr~sulphochloride and 0.2 mol of acetyl-p-phenylenediamine and saponification of the condensation pro-duct, are stirred with 700 ml of water and are dissolved by addtng 40 ml o~ 10 N sodium hydroxide solution. 14 g of sodium nitrite are added to this solu~ion and the mixture is then stirred, ~n the course of about 30 minutes, into a mix-ture oi 400 g o~ ice and 60 ml o~ coneentrated HCl. The temperature is Icept between 0 and 5C ~y adding a further `~:
~ ;
200 g of ice. Stirring is continued for about lO~minutes and any small excess of ni-trite ~hich may be present is then removed with aminosulphonic acid. 27 g of acetylsuccinic acid diethyl ester are added to -the clia~o suspension obtained in this way. The pH is adjus-ced -to about 6 with approxi-mately 50 g of sodium carbonate -md is kept at thls value until the diazo compound can no :Longer be detected ~ A
solution of turquoise-coloured 3~3'-bis-[L~(1,2-bis-ethoxy-carbonyl-ethylidene)-hydrazino-phenyl-aminosulphonyl]-nickel-phthalocyanine-3",3"'-disulphonic acid is obtained in this way, which can be converted direct in-to the corresponding bispyrazolone by the action of alkall.
Valuable phthalocyanine hydrazones are also obtained if the corresponding 4,4',4",4"'-deriva-tive i.~ used instead o~
the amine employed above. ;~
Very valuable, turquoise-coloured phthalocyanlne-bls-arylhydrazones according -to -the inven-tion are also obtained if the condensation product of nickel ph-thaIocya~lne~sulpho-:
chloride with two mols of one of the amines mentioned~in thetable which~follows is employed clS the diazo component instead o~ the amine employed above~ phenylenediamine (acetyl derivative, subsequently saponifi.ed), 2,4-diaminotoluene (acetyl derivative, subsequently saponified)~ 2~4-diamino-.
anisole ~acetyl derivative, subsequently saponi~ied),;l~4phenylenediamine-2-sulphonic acid, 2,4-diaminotoluene-6-~; sulphonic acid, 4-~mino-benzylamine (4-acetyl derivative, subse~uently saponi~ied), 1,4-phenylenedic~mine-2,6-disulphonic cid~ 4,4'-diaminostilbenedisulphonic acid, 4~' diamino~
.
-~ethanedisulphonlc acid and 4,4'-diamino-diphenyl~mine~3-sulphonic acid, Arylhydrazone~, accorcling to the invelltlon, which can be processed ~urther to give valunble ]pyrazolon~s, are al~o obtained i~ the acetylsuccinic acid diiethyl ester empIoyed as the coupling component is replaced by one of the following derivatives o~ succinic acid:
R5 - OOC - CH2 - CH - COO - R~
O
-c~3 -CH3 -H
-CH3 -C2H4Cl -CH3 -CH3 -i-C3H~ -CH3 -CH3 i C6Hl3 _COO-C2H5 -CH3 C2 ~ 0~1 -CII3 :
-C3H7 -C2i~5 -C3H7 C5Hll -C2H5 2 6 5 CgHlg C2HS -COO-CH3 C16H33 -C2H5 C6f~5 ~;
-C2H~-Q-C2H5 C2H5 -C6H4-C~I3 - 2~
: , , ~Q~$~6~9 ~ ~
Exam~le 3 Valuable hydrazones Qf oxalacetic acid m~thyl ester, which can be processe~ further to give the correspondingly substituted pyrazolones are also obtained i~, instead o~ the :
amine indicated in Example 1, 3~~(3-amino-4-sulpho-phenyl)~
amino-sulphonyl~-nickel-phthalocyanin~-3',3",3"'-trisulphonic acid, the corresponding amount in ~olar terms Or one of the amines mentioned in the table which ~ollows is used and the ~ -process is in other respects as indicated in that Example.
~ 1 Pc -- ( S02-N
\ 2 1 \ (S02-1N-ar-NH2)m _ ~ ~_ ~
~ - :
os ~ o~
. _ . . . W __ ,, ~, ~
. ' , , ..
_ ~ U "~ ~
. :
.. ~ U~
1~ ~ u~ ,~ u~ u~ ~ ~
_ ~ .:
~: : :
. ~ ~. .
æ ~ ~ ~w t~
~ ~ .
_ 2~
~:
,................. .... ... .... ..... ... .... ... .......... ...... ... .... ........... ~ `
s ~ ::
~4 s~ W e~
: :
d o~ o~ ~D o~ w~ m p~
~0~ a~p ~ . .. . ...... _ .
.
: ~N C~
qD ~ . :
C~ ~ ~
::: : : ~ ~:
:
: ~ : ::
6~i ~ ~ ,, ,~ " ,, ,, ,, ~ ~ ,, .Y ~ C~ C`~ N C`J C~
.
~ S~ o~ o~ o~
mC`' P~
. _ _ . ... _ ~ . . _ ... ;. _ P~ :
, ~ ~
' ' ' :
.
., ~ ~ ~ N N C~l N
_ ,~
: ~ ' ~ ~ ' aP
`,.
E
_ _ _ : ~' ' ~ ~
~ ~ ' : :
~ . ~ ~) ~I h O O
. _ _ .
:
' tl~
O C~ .. ' Q~ O /~ C'3 : :
~I N
W q tr~
.
. `' ' , ' ' `
. ~ .
:~a o ~ 8 ` ::: ~:
:: : ~ ~., " C~ V
: . 'q m P: P~ o :
~ ~ ~ I~o ~ w 8~ . d' ~ ~C' d' ~ ~ . . i , ~
: ~ ~ ~ C~ U~ ` U~ V~ ~ ~ :~
31~
. .
E c~
_ ~
~ C~ o : , _ ~
' ,:
. ~,.
~ ~C~
~ ,~
C~
- ~C
.
_ .... _ ,' - -P4 ~ .. 1 ' C9~
6~ : .
E c~
,1 ,, o O
,, ,~ o - ~ -. , ' ';, . .~
. 1~
U~
~ 'n`~3 i;~) '' _ _ , - ' '::
. , ':
: `
, ~ ,. .
' C~
~;
X :~ ~q ~ : ,.
-.
: .
~ . _ .. ~ .:
. ' ' ~
:, ~ ~ : ~ ' :
; :
i ,' ~
~.
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A water-soluble hydrazone of the general formula I
(I) wherein Pc denotes the radical of cobalt phthalocyanine, copper phthalocyanine or nickel phthalocyanine, ar denotes a phenylene radical, which is optionally substituted by a -SO3H group and optionally further substituted by an alkoxy having 1 to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or different substituents selected from halogen, and -COOH, or by from one to three identical or different alkyl radicals having 1 to 4 C atoms, a monomethylene-phenylene or methylene-phenylene radical of the general formula wherein n denotes an integer from 1 to 10, a naphthylene radical or a monomethylene-naphthylene or polymethylene-naphthylene radical of the general formula wherein n denotes an integer from 1 to 3, or an optionally substituted radical of the formula , , , , or which is optionally substituted by a -SO3H group and each nucleus being optionally further substituted by an alkoxy having 1 to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or different substituents selected from halogen, and -COOH, whereby the alkylene chain of the mono- or polymethylene-phenylene and -naphthy-lene radicals are linked to the group, R1 and R'1 can be the same or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOH or -SO3H, a phenalkyl or naphthalkyl 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 Cl, 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 identical or different and denote hydrogen, methyl, carboxymethyl, sulpho-methyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 denotes hydrogen, methyl, carboxymethyl, sulphomethyl, or an alkyl radical which has 2-6 C
atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, R4 denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R6 denotes methyl, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 C atoms and which is optionally substituted by Cl, OH, alkoxy having 1-3 C atoms, acetylamino, acetoxy, -COOH or -SO3H, or denotes benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by -COOH or -SO3H, k represents the numbers 1, 2 or 3, q represents 0, 1 or 2 and m represents 1, 2, 3, or 4 and the sum of k, q and m is 3 or 4, or an alkali metal, ammonium or alkaline earth metal salt thereof.
(I) wherein Pc denotes the radical of cobalt phthalocyanine, copper phthalocyanine or nickel phthalocyanine, ar denotes a phenylene radical, which is optionally substituted by a -SO3H group and optionally further substituted by an alkoxy having 1 to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or different substituents selected from halogen, and -COOH, or by from one to three identical or different alkyl radicals having 1 to 4 C atoms, a monomethylene-phenylene or methylene-phenylene radical of the general formula wherein n denotes an integer from 1 to 10, a naphthylene radical or a monomethylene-naphthylene or polymethylene-naphthylene radical of the general formula wherein n denotes an integer from 1 to 3, or an optionally substituted radical of the formula , , , , or which is optionally substituted by a -SO3H group and each nucleus being optionally further substituted by an alkoxy having 1 to 4 C atoms, -CN, -CF3, -SO2R6 or additional -SO3H substituent, or by one or two identical, or different substituents selected from halogen, and -COOH, whereby the alkylene chain of the mono- or polymethylene-phenylene and -naphthy-lene radicals are linked to the group, R1 and R'1 can be the same or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoyl-amino, alkanoyloxy having 1-6 C atoms, -COOH or -SO3H, a phenalkyl or naphthalkyl 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 Cl, 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 identical or different and denote hydrogen, methyl, carboxymethyl, sulpho-methyl, an alkyl radical which has 2-6 C atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 denotes hydrogen, methyl, carboxymethyl, sulphomethyl, or an alkyl radical which has 2-6 C
atoms and which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C
atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOH or SO3H, R4 denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R5 denotes an alkyl radical which has 2-6 C atoms and which is substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or denotes an unsubstituted alkyl radical having 1-18 C atoms, R6 denotes methyl, carboxymethyl, sulphomethyl, alkyl which has 2 or 3 C atoms and which is optionally substituted by Cl, OH, alkoxy having 1-3 C atoms, acetylamino, acetoxy, -COOH or -SO3H, or denotes benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by -COOH or -SO3H, k represents the numbers 1, 2 or 3, q represents 0, 1 or 2 and m represents 1, 2, 3, or 4 and the sum of k, q and m is 3 or 4, or an alkali metal, ammonium or alkaline earth metal salt thereof.
2. A water-soluble hydrazone as claimed in claim 1 wherein Pc denotes the radical of nickel phthalocyanine.
3. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein ar denotes an optionally substituted phenylene or naphthylene radical or an optionally substituted radical of the formula , , or
4. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein ar is a phenylene radical which is optionally substituted by one or two carboxyl groups or by one or two sulpho groups or is a naphthyl radical which is substituted by one or two sulpho groups or a stilbenylene radical which is substituted by two sulpho groups.
5. A water-soluble hydrazone of the general formula I, as claimed in claim 4, wherein ar denotes a radical of the formula , , , , , or
6. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein R1 denotes hydrogen, an alkyl radical which has 2 or 3 C
atoms and is optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH
or -SO3H, methyl, carboxymethyl or sulphomethyl.
atoms and is optionally substituted by OH, alkoxy having 1-3 C atoms, -COOH
or -SO3H, methyl, carboxymethyl or sulphomethyl.
7. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein R2 denotes hydrogen, carboxymethyl, an alkyl radical which has 2 or 3 C atoms and is optionally substituted by OH, alkoxy having 1-3 C
atoms, -COOH or -SO3H, or an unsubstituted alkyl radical having 1-20 C atoms.
atoms, -COOH or -SO3H, or an unsubstituted alkyl radical having 1-20 C atoms.
8. A water-soluble hydrazone of the general formula I, as claimed in claim 7, wherein R2 denotes hydrogen, methyl, carboxymethyl or an alkyl radical which has 2 or 3 C atoms and is optionally substituted by OH.
9. A water-soluble hydrazone of the general formula I, as claimed in any of claims 1, 6 or 8, wherein R1 and R2 each denote hydrogen, methyl or .beta.-hydroxyethyl.
10. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein R3 denotes hydrogen, methyl, carboxymethyl, sulphomethyl or an ethyl radical which is optionally substituted by Cl, OH, alkoxy having 1 or 2 C atoms, -COOH or -SO3H.
11. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein R4 denotes an ethyl radical which is substituted by Cl, OH
or alkoxy having 1-2 C atoms, or cm unsubstituted alkyl radical having 1-6 C
atoms.
or alkoxy having 1-2 C atoms, or cm unsubstituted alkyl radical having 1-6 C
atoms.
12. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein R5 denotes hydrogen, ethyl substituted by Cl, OH or alkoxy having 1-2 C atoms, or unsubstituted alkyl having 1-18 C atoms.
13. A water-soluble hydrazone of the general formula I, as claimed in claim 1, 11 or 12, wherein R4 and R5 are identical and each denotes methyl or ethyl.
14. A water-soluble hydrazone of the general formula I, as claimed in claim 1, wherein q = 0, k = 2 or 3 and m = 1 or 2 and the sum of k + m = 4.
15. A process for the manufacture of a new water-soluble hydrazone of the general formula I as defined in claim 1 wherein an amine of the phthalocyanine series of the general formula IV
(IV) wherein the free amino group is linked to an aromatic C atom of the radical ar, and Pc, ar, B, R1, R2, R3, k, q and m have the meaning as defined in formula I in claim 1, is diazotised and is coupled in an aqueous medium at a pH value from 3 to 8 with a succinic acid derivative of the formula V
(V) wherein R4 and R5 have the same meaning as defined above in formula I and Z
denotes hydrogen, an alkyl radical having 1-10 C atoms and optionally substituted by alkoxy having 1 to 4 C atoms, or alkoxycarbonyl having 2-6 C
atoms, a phenyl radical optionally substituted by Cl, Br, or alkyl or alkoxy each having 1-4 C atoms, or alkoxy carbonyl having 2-6 C atoms.
(IV) wherein the free amino group is linked to an aromatic C atom of the radical ar, and Pc, ar, B, R1, R2, R3, k, q and m have the meaning as defined in formula I in claim 1, is diazotised and is coupled in an aqueous medium at a pH value from 3 to 8 with a succinic acid derivative of the formula V
(V) wherein R4 and R5 have the same meaning as defined above in formula I and Z
denotes hydrogen, an alkyl radical having 1-10 C atoms and optionally substituted by alkoxy having 1 to 4 C atoms, or alkoxycarbonyl having 2-6 C
atoms, a phenyl radical optionally substituted by Cl, Br, or alkyl or alkoxy each having 1-4 C atoms, or alkoxy carbonyl having 2-6 C atoms.
16. A process as claimed in claim 15, wherein coupling is carried out with a succinic acid derivative of formula V wherein Z denotes hydrogen, alkyl having 1-3 C atoms, phenyl, methylphenyl or alkoxycarbonyl having 2 or 3 C
atoms.
atoms.
17. A process as claimed in claim 15 or 16, wherein coupling is carried out with a succinic acid derivative of the formula V wherein Z
denotes methyl.
denotes methyl.
18. A process as claimed in claim 15 wherein the resulting free hydrazone is converted into the corresponding alkali metal, ammonium or alkaline earth metal salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2617062A DE2617062C2 (en) | 1976-04-17 | 1976-04-17 | Water-soluble hydrazones of the phthalocyanine series, their production and use |
| DEP2617062.7 | 1976-04-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104565A true CA1104565A (en) | 1981-07-07 |
Family
ID=5975687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA276,287A Expired CA1104565A (en) | 1976-04-17 | 1977-04-15 | Hydrazone compounds, their preparation and use |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4204056A (en) |
| JP (1) | JPS52127924A (en) |
| BE (1) | BE853675A (en) |
| BR (1) | BR7702431A (en) |
| CA (1) | CA1104565A (en) |
| CH (1) | CH638524A5 (en) |
| CS (1) | CS192578B2 (en) |
| DD (1) | DD129912A5 (en) |
| DE (1) | DE2617062C2 (en) |
| ES (1) | ES457849A1 (en) |
| FR (1) | FR2348216A1 (en) |
| GB (1) | GB1550527A (en) |
| IN (1) | IN145692B (en) |
| IT (1) | IT1143650B (en) |
| NL (1) | NL7704034A (en) |
| PL (1) | PL104271B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4304242A1 (en) * | 1993-02-12 | 1994-08-18 | Sandoz Ag | Phthalocyanine reactive dyes |
| US7074301B2 (en) * | 2002-06-11 | 2006-07-11 | Rayonier Products And Financial Services Company | Chemically cross-linked cellulose fiber and method of making same |
| US20040177935A1 (en) * | 2003-03-14 | 2004-09-16 | Hamed Othman A. | Method for making chemically cross-linked cellulosic fiber in the sheet form |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2413224A (en) * | 1945-07-11 | 1946-12-24 | Gen Aniline & Film Corp | Phthalocyanine sulfonhydrazides |
| FR1165425A (en) * | 1955-10-11 | 1958-10-24 | Bayer Ag | Water-insoluble phthalocyanine-sulfone-or-carbonamides and phthalocyanic dyes, and process for their production |
| US3047582A (en) * | 1957-04-20 | 1962-07-31 | Bayer Ag | Phthalocyanine-sulfonamides and-carbonamides |
| GB874355A (en) * | 1958-08-07 | 1961-08-02 | Cassella Farbwerke Mainkur Ag | New azo dyestuffs of the phthalocyanine series |
| FR1469360A (en) * | 1965-02-24 | 1967-02-10 | Eastman Kodak Co | New process for preparing magenta dye-forming couplers |
| FR1471148A (en) * | 1965-03-17 | 1967-02-24 | Gen Aniline & Film Corp | Azo dyes obtained from 2-hydroxy-5-nitrometanilic acid |
| CH478211A (en) * | 1966-04-05 | 1969-09-15 | Bayer Ag | Process for the preparation of azophthalocyanine reactive dyes |
| FR1530577A (en) * | 1967-05-17 | 1968-06-28 | Ugine Kuhlmann | New soluble azo dyes derived from phthalocyanine |
| US3625936A (en) * | 1967-08-12 | 1971-12-07 | Hoechst Ag | Azophthalocyanine dyestuffs and process for preparing them |
| US3632805A (en) * | 1967-12-08 | 1972-01-04 | Sumitomo Chemical Co | Process for producing 1-aminoalkyl-benzodiazepine derivatives |
| BE794330A (en) * | 1972-01-20 | 1973-07-19 | Pechiney Ugine Kuhlmann | LIPOPHILIC PHTHALOCYANINS |
-
1976
- 1976-04-17 DE DE2617062A patent/DE2617062C2/en not_active Expired
-
1977
- 1977-04-11 IN IN540/CAL/77A patent/IN145692B/en unknown
- 1977-04-13 NL NL7704034A patent/NL7704034A/en not_active Application Discontinuation
- 1977-04-14 CS CS772454A patent/CS192578B2/en unknown
- 1977-04-15 GB GB15757/77A patent/GB1550527A/en not_active Expired
- 1977-04-15 CA CA276,287A patent/CA1104565A/en not_active Expired
- 1977-04-15 JP JP4273377A patent/JPS52127924A/en active Pending
- 1977-04-15 ES ES457849A patent/ES457849A1/en not_active Expired
- 1977-04-15 BR BR7702431A patent/BR7702431A/en unknown
- 1977-04-15 DD DD7700198423A patent/DD129912A5/en unknown
- 1977-04-15 IT IT22542/77A patent/IT1143650B/en active
- 1977-04-15 PL PL1977197426A patent/PL104271B1/en unknown
- 1977-04-15 BE BE176785A patent/BE853675A/en unknown
- 1977-04-18 FR FR7711586A patent/FR2348216A1/en active Granted
- 1977-04-18 CH CH477877A patent/CH638524A5/en not_active IP Right Cessation
-
1978
- 1978-09-21 US US05/944,641 patent/US4204056A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CS192578B2 (en) | 1979-08-31 |
| CH638524A5 (en) | 1983-09-30 |
| DE2617062C2 (en) | 1985-07-04 |
| IN145692B (en) | 1978-12-02 |
| US4204056A (en) | 1980-05-20 |
| IT1143650B (en) | 1986-10-22 |
| BE853675A (en) | 1977-10-17 |
| JPS52127924A (en) | 1977-10-27 |
| BR7702431A (en) | 1978-05-09 |
| NL7704034A (en) | 1977-10-19 |
| PL104271B1 (en) | 1979-08-31 |
| DE2617062A1 (en) | 1977-10-20 |
| GB1550527A (en) | 1979-08-15 |
| DD129912A5 (en) | 1978-02-15 |
| ES457849A1 (en) | 1978-03-01 |
| FR2348216A1 (en) | 1977-11-10 |
| FR2348216B1 (en) | 1981-01-16 |
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