CA1089869A - Metal-containing disazomethine compounds, process for preparing them and their use as colorants - Google Patents
Metal-containing disazomethine compounds, process for preparing them and their use as colorantsInfo
- Publication number
- CA1089869A CA1089869A CA258,057A CA258057A CA1089869A CA 1089869 A CA1089869 A CA 1089869A CA 258057 A CA258057 A CA 258057A CA 1089869 A CA1089869 A CA 1089869A
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- CA
- Canada
- Prior art keywords
- carboxylic acid
- group
- amide
- alkyl
- radical
- Prior art date
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Classifications
-
- 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
- C09B55/00—Azomethine dyes
- C09B55/005—Disazomethine dyes
Abstract
ABSTRACT OF THE DISCLOSURE
New metal-complex disazomethine compounds of the formulae (Ia) (Ib )
New metal-complex disazomethine compounds of the formulae (Ia) (Ib )
Description
~V~ 69 The present invention relates to metal-containing disazomethine com-pounds, to a process for preparing them and to their use as colorants.
The novel compounds have the general formulae ~Ia), (Ib), and (Ic) X ~ O - M - Z Z - M - O _ ~ X (Ia) CH = N A N = CH
X ~ O _ M _ O ~ (Ib) CH = N 1~ = CH
X ~ ,~ X
= ' ` CH
CH N N CH (Ic) X~ ~ X
wherein A is a straight-chain or branched alkylene radical which may be interrupted by one or more moieties selected from the group consisting of hetero atoms, isocyclic rings and other bivalent groups, or is a cycloalky-lene radical or an arylene radical, R is a covalent bond or is defined as A, Z as a group capable of forming a metal complex is an -O-, -COO-or a lower alkoxy group, for example a methoxy or ethoxy group, or an aminogroup optionally substituted by lower alkyl or aryl radicals such as phenyl
The novel compounds have the general formulae ~Ia), (Ib), and (Ic) X ~ O - M - Z Z - M - O _ ~ X (Ia) CH = N A N = CH
X ~ O _ M _ O ~ (Ib) CH = N 1~ = CH
X ~ ,~ X
= ' ` CH
CH N N CH (Ic) X~ ~ X
wherein A is a straight-chain or branched alkylene radical which may be interrupted by one or more moieties selected from the group consisting of hetero atoms, isocyclic rings and other bivalent groups, or is a cycloalky-lene radical or an arylene radical, R is a covalent bond or is defined as A, Z as a group capable of forming a metal complex is an -O-, -COO-or a lower alkoxy group, for example a methoxy or ethoxy group, or an aminogroup optionally substituted by lower alkyl or aryl radicals such as phenyl
-2-.
7~
.. , .,. -... . .. . ~ . .. .. . . .
: . . . ~ . :. .
1~89869 radicals, for example the -N~phenyl)-group, or a carboxylic acid- (Cl-C5)-alkyl ester radical, for example the carboxylic acid methyl ester group, or Z
stands for a carbonamide group or for a sulfonic acid amide radical optionally substituted at one or two nitrogens by lower alkyl or aryl groups (phenyl groups), X is a carboxylic acid group, carboxylic acid ester group, an option-ally substituted carboxylic acid amide or carboxylic acid hydrazide group and M is a bivalent copper, cobalt, nickel, zinc or manganese atom.
The invention especially concerns the compounds of the above-mention-ed formulae (Ia) to (Ic), in which the radicals X in the same molecule have the same meaning and each Z represents identical groups.
There are especially preferred compounds of the formulae (Ia) to (Ic), in which R is a covalent bond, or A and R each are an alkylene radical having 2 to 8 carbon atoms which may be interrupted by a phenylene or cyclohexylene radical, or is a cyclohexylene radical or a phenylene radical, which may be substituted preferably by 1 or 2 substituents thereof, by chlorine atoms, lower alkyl, especially methyl, ethyl, lower alkoxy, especially methoxy and ethoxy, nitro, trifluoromethyl, carboxylic acid-(C1-C5)-alkyl ester groups, carboxylic acid amide, carboxylic acid phenyl amide, acetylamino, benzoylamino, sulfonic acid amide, sulfonic acid-(Cl-C5)-alkylamide and/or sulfonic acid phenyl amide groups, or A or R represents a naphthylene, quinoline, benzimidazolone or phthalimide radical.
There are furthermore especially preferred compounds of the formula (Ia), wherein A stands for the diphenylene radical, Z is oxygen or the radical of the formula -C0-0-, the carbonyl group of it being bound to the radical A, the X groups are identical or different, preferably identical, and each stands for a carboxylic acid group, a carboxylic acid-(Cl-C4)-alkyl-ester group, car-boxylic acid amide or carboxylic acid methyl amide group, and M is a copper atom, furthermore compounds of the formula (Ib) wherein R is an alkylene radi-__ ~ , -3-.. . ~ .
. ~ - .
.. .. .
' . . . '- . - .. . . - :
.
10~9~9 cal having 2 to 6 carbon atoms which may be interrupted by, preferably 1 or 2, groups of the formula -NH- or -NtCH3)-, or is the ortho-phenylene radical which may be substituted by preferably 1 or 2, substituents selected from the group consisting of chlorine, methyl, ethyl, nitro, carboxy, carbomethoxy, carbeth-oxy, from the two last compounds preferably carbomethoxy, carboxylic acid amide, carboxylic acid phenylamide, acetylamino, benzoylamino, and sulfonic acid phenylamide, and the X are identical or different, preferably identical, and each of it represents the carboxylic acid group, a carboxylic acid-(Cl-C4-alkyl)-ester group, the carboxylic acid amide group, a carboxylic acid-tCl-C4-alkyl)-amide group, carboxylic acid-di-(Cl-C4-alkyl)-amide group, carboxylic acid phenylamide or carboxylic acid phenylhydrazide group, and M stands for nickel, as well as compounds of the formula (Ic) wherein the X are identical or different, preferably identical, and each of it stands for the carboxylic acid group, carboxylic acid amide, carbomethoxy or carbethoxy group and M is nickel.
Among these compounds, those of the formula ~ ..
CH = N N = CH
~ O -- Ni--O =
X X
are particularly interesting in which Y stands for hydrogen, methyl or carboxy, ant the X groups are identical or different, preforably identical, and each represents a carboxy, carboxylic acid amide or carboxylic acid phenylamide group; the nickel complex compounds of the Examples 24, 28, 32, 36 and 39 may ....,"~, - :- , : - .: . - :
~, . .~ . . . . .
.' . ~' ' ., '" .;, '' ' . :, ' .: . ' 1~)89~9 be particularly mentioned.
The compounds of the invention may be prepared by condensing one mol of one or several amines of the formula (IIa) or (IIb) H2N - A - NH2 (IIa) H2N - R - NH2 (IIb) wherein A and R have the above meaning and 2 groups ~ are bound to A, with 2 ls of one or several compour,ds of the formula (III) X ~ (!11) CHO
wherein X has the above meaning, and metallizing the disazomethine compounds simultaneously or in a following process step by means of a copper, cobalt, nickel, zinc or manganese-yielting agent.
The condensation of the diamines of the formulae (II) with compounts of the for~ula III m~y be carried out in water aDd iD
.
B~
. ~ . .. . - . .. . .
~ , ~ . ,. :. - : . :
10~ 9 HCE 75/F 190 an organic solvent, such as an aliphatic alcohol, an aliphatic carboxylic acid, dimethylformamide, xylene, chlorobenzene, o-di-chlorobenzene,nitrobenzene or glycol ethers. It generally proceeds fast and quantitatively, at a temperature of 50 to 100C. It may be useful to work in a solvent or in a mixture of solvents at a higher temperature, for example at 150C or above, and to ef-fect simultaneously an azeotropic distillation of the water set free by condensation.
The preparation of metal complex compounds may be carried out as follows: the condensation described above of the amine of the formula II with compounds of the formula III takes place in the presence or with the addition of the metal-yielding agents, or the metalfree dyestuff prepared first and optionally isolated is subsequently treated with the metal-yielding agents, using water or in an organic solvent or solvent mixture, for example one of the above solvents, and optionally maintaining exact pH
conditions and defined temperatures.
Metallization is generally carried out according to usual analogous processes, for example at temperatures between 60C
and ~20C and at a pH value of from 3 to 9, preferably 3,5 to 6; but in the preparation of the compounds of the formula (Ic) a pH value above 7, preferably fro~ 7 to 9 has to be observed.
Instead of the free amines of the formula (II), also their salts, for example the chlorhydrates or sulfates, may be used for the reaction with the compounds of the formula (III), option-ally in the presence of an acid-binding agent, such as an alka-line or alkaline earth carbonate or -hydroxide.
- The diamines of the formula (II) to be used as starting 2~ compounds are for example hydrazine, aliphatic diamines having a . : ; - .
, . . .
m~s~6s straight-chained or branched alkylene radical of 2 to 8 carbon atoms which may be interrupted by hetero atoms, such as oxygen, sulfur or nitrogen atoms, by isocyclic radicals, for example cycloalkylene or a phenylene radical or by other bivalent groups or are cycloaliphatic diamines, such as cyclopentylene or cyclo-hexylene diamines, aromatic diamines of the benzene, naphthalene or anthraquinone series as well as those of the general formulae NH2 ~ D ~ ~~- NH ~ NH2 wherein D is a single bond, an oxygen or sulfur atoms, a -NH-group, -N(alkyl-1-4)-, -C~2-, -CH-CH-, -CO-, -CONH-, -NHCONH-, -CO-NH-CO-NH-, -SO-, -SO2-, -SO2NH- or -N=N- group, E is an oxy-gen or sulfur atom, a -NH-, -N(alkyl 1-4)-, -CH2-, -CO-, -C~=CH-, -CONH-, -NHCONH-, -SO2-, -SO2NH- or -N=N- group and the aromatic nuclei , each may be substituted by one or several, preferably 1 or 2 substituents selected from a group consisting of halogen, such as chlorine, bromine, nitro, lower alkyl, cy ano, trifluoro-methyl, hydroxy, amino, lower alkylamino, arylamino such as phenyl-amino, lower alkoxy, carboxy, carboxylic acid -(C1-CS-alkyl)-ester, carboxylic acid hydrazide, hydroxamic acid, sulfonic acid ester, sulfonic acid amide optionally substituted/such as by lower alkyl and/or phenyl and acylamino of an aliphatic lower carboxylic acid or aromatic carboxylic acid, such as acetyl amin~, propionyl amino or benzoylamino; furthermore suitable amines are heterocyclic diamines, for example diaminopyridines.
Preferred diamines are diamines with carbonamide groups, especial-ly with cyclic carbonamide groups, especially diamines of the 10d9'd~
general formula ~[ (CO)3 wherein R2 is hydrogen, a lower alkyl or phenyl radical, and m and n, identical or different, are each 1 or 2, whereby the sum of m and n is 3 or 4, and the group of the formula L (NR2)n(CO)m~ in which -NR2- and -CO- are in any de-sired arrangement to each other, forms together with two ortho-standing carbon atoms of the ring system B a five- or six-membered heterocyclic ring; further-more there are especially preferred diamines of the formulae (II) which are substituted in o-position - to one of the amino groups by a ligand Z which is hydroxy, lower alkoxy, carboxy amino, amino substituted by lower alkyl ant/
or aryl radicals (phenyl radicals), a carboxylic acid-(Cl-C5)-ester group, carboxylic acid amide or a sulfonic acid amide unsubstituted or substituted st the one or two N-atoms by lower alkyl and/or aryl groups (phenyl groups).
As metals M are preferred zinc and cobalt and especially preferred are copper and nickel.
The aldehyde of the formula (III) used as starting compounds are compounds easy to prepare. For preparing them, for example compounds of the formula IV
~ -8-.. , - . . :, . -.: : ` `. .. :: , ., ` . . `.
` . . ` ~ .` . .. . .
. - . ~ ~ ; . , .
`, .
, X~
~ OH (IV) in which X has the above meaning, are reacted in lower aliphatic carboxylic acids with hexamethylene tetramine.
The novel compounds are valuable colorants, preferably as pigments, and are suitable, - especially after a conditioning usual for pigment dyestuffs - , for example for coloring plastic masses which are masses which either are free from solvents and contain a solvent or are free from softening agents or contain a softening agent of plastics or synthetic resins, for the pig-mentation of paints on an oily or aqueous base as well as of lacquers of different types, for the spin-dyeing of viscose and cellulose acetate or for the pigmentation of polyethylene, poly-styrene, polyvinyl chloride, caoutchouc and synthetic leather.
They may also be used in printing pastes for graphic industry, for coloring paper masses, for the coating of textiles or pig-ment printing.
The dyeings obtained have an excellent fastness to migration, to light, to weather and to solvents; they shows an excellent fastness to heat and are characterized by a high tinctorial strength, a good transparency and frequently by surprisingly pure shades.
The following Examples illustrate the invention. Parts and percentages are by weight unless stated otherwise.
E X A M P L E 1:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid are added, while stirring, to a solution of 3.0 parts of 1,2-diaminoethane, _ g _ . . - - - -. .-: . . - - . - . .
- . .
1()t~9~ 3 in 250 parts of ethanol and 10 parts of glacial acetic acid, and heated for 3 hours at the boil. After cooling the yellow compound is suction-filtered and washed well with ethanol. The moist product is then introcuded into 150 parts of dimethylform-amide, mixed with 9.0 parts of nickel diacetate and heated for 4 hours at 120C. The yellow pigment thus obtained is filtered hot, washed well, first with water, then with ethanol. After drying 30.2 parts of the yellow pigment of the formula C~ - N ~ (CH2)2- ~ ~ CH
~ ~ O - Ni 0 ~
HOOC COOH
with the analysis: Ni calculated: 11.4 %
found: 11.3 %, are obtained, which dyes polyvinyl chloride in a clear yellow shade having excellent fastness properties.
E X A M P L E 2:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid, 3.0 parts of diaminoethane and 9.0 parts of nickel diacetate are heated in 300 parts of ethanol for 5 hours at the boil. The yellow com-pound is then filtered hot and washed well with hot water and ethanol. The product is then heated in 150 parts of dimethyl-formamide for 1 hour at 120C, filtered hot and washed well with hot water and ethanol. After drying 31.0 parts of a yellow pigment are obtained which is identical with the pigment obtain-ed according to Example 1.
In similar and analogous manner as described in the above -- ~O --., .
.
' ' ~.
` HOE 75/F 190 i~8~8~i9 Examples 1 or 2, also the following nickel complex compounds listed in the subsequent Table 1 according to the following for-mula with R and X indicated therein, can be prepared:
T A B L E
Shade in ~olyvinyl Example R ~ chloride ~PVC) .: - .
7~
.. , .,. -... . .. . ~ . .. .. . . .
: . . . ~ . :. .
1~89869 radicals, for example the -N~phenyl)-group, or a carboxylic acid- (Cl-C5)-alkyl ester radical, for example the carboxylic acid methyl ester group, or Z
stands for a carbonamide group or for a sulfonic acid amide radical optionally substituted at one or two nitrogens by lower alkyl or aryl groups (phenyl groups), X is a carboxylic acid group, carboxylic acid ester group, an option-ally substituted carboxylic acid amide or carboxylic acid hydrazide group and M is a bivalent copper, cobalt, nickel, zinc or manganese atom.
The invention especially concerns the compounds of the above-mention-ed formulae (Ia) to (Ic), in which the radicals X in the same molecule have the same meaning and each Z represents identical groups.
There are especially preferred compounds of the formulae (Ia) to (Ic), in which R is a covalent bond, or A and R each are an alkylene radical having 2 to 8 carbon atoms which may be interrupted by a phenylene or cyclohexylene radical, or is a cyclohexylene radical or a phenylene radical, which may be substituted preferably by 1 or 2 substituents thereof, by chlorine atoms, lower alkyl, especially methyl, ethyl, lower alkoxy, especially methoxy and ethoxy, nitro, trifluoromethyl, carboxylic acid-(C1-C5)-alkyl ester groups, carboxylic acid amide, carboxylic acid phenyl amide, acetylamino, benzoylamino, sulfonic acid amide, sulfonic acid-(Cl-C5)-alkylamide and/or sulfonic acid phenyl amide groups, or A or R represents a naphthylene, quinoline, benzimidazolone or phthalimide radical.
There are furthermore especially preferred compounds of the formula (Ia), wherein A stands for the diphenylene radical, Z is oxygen or the radical of the formula -C0-0-, the carbonyl group of it being bound to the radical A, the X groups are identical or different, preferably identical, and each stands for a carboxylic acid group, a carboxylic acid-(Cl-C4)-alkyl-ester group, car-boxylic acid amide or carboxylic acid methyl amide group, and M is a copper atom, furthermore compounds of the formula (Ib) wherein R is an alkylene radi-__ ~ , -3-.. . ~ .
. ~ - .
.. .. .
' . . . '- . - .. . . - :
.
10~9~9 cal having 2 to 6 carbon atoms which may be interrupted by, preferably 1 or 2, groups of the formula -NH- or -NtCH3)-, or is the ortho-phenylene radical which may be substituted by preferably 1 or 2, substituents selected from the group consisting of chlorine, methyl, ethyl, nitro, carboxy, carbomethoxy, carbeth-oxy, from the two last compounds preferably carbomethoxy, carboxylic acid amide, carboxylic acid phenylamide, acetylamino, benzoylamino, and sulfonic acid phenylamide, and the X are identical or different, preferably identical, and each of it represents the carboxylic acid group, a carboxylic acid-(Cl-C4-alkyl)-ester group, the carboxylic acid amide group, a carboxylic acid-tCl-C4-alkyl)-amide group, carboxylic acid-di-(Cl-C4-alkyl)-amide group, carboxylic acid phenylamide or carboxylic acid phenylhydrazide group, and M stands for nickel, as well as compounds of the formula (Ic) wherein the X are identical or different, preferably identical, and each of it stands for the carboxylic acid group, carboxylic acid amide, carbomethoxy or carbethoxy group and M is nickel.
Among these compounds, those of the formula ~ ..
CH = N N = CH
~ O -- Ni--O =
X X
are particularly interesting in which Y stands for hydrogen, methyl or carboxy, ant the X groups are identical or different, preforably identical, and each represents a carboxy, carboxylic acid amide or carboxylic acid phenylamide group; the nickel complex compounds of the Examples 24, 28, 32, 36 and 39 may ....,"~, - :- , : - .: . - :
~, . .~ . . . . .
.' . ~' ' ., '" .;, '' ' . :, ' .: . ' 1~)89~9 be particularly mentioned.
The compounds of the invention may be prepared by condensing one mol of one or several amines of the formula (IIa) or (IIb) H2N - A - NH2 (IIa) H2N - R - NH2 (IIb) wherein A and R have the above meaning and 2 groups ~ are bound to A, with 2 ls of one or several compour,ds of the formula (III) X ~ (!11) CHO
wherein X has the above meaning, and metallizing the disazomethine compounds simultaneously or in a following process step by means of a copper, cobalt, nickel, zinc or manganese-yielting agent.
The condensation of the diamines of the formulae (II) with compounts of the for~ula III m~y be carried out in water aDd iD
.
B~
. ~ . .. . - . .. . .
~ , ~ . ,. :. - : . :
10~ 9 HCE 75/F 190 an organic solvent, such as an aliphatic alcohol, an aliphatic carboxylic acid, dimethylformamide, xylene, chlorobenzene, o-di-chlorobenzene,nitrobenzene or glycol ethers. It generally proceeds fast and quantitatively, at a temperature of 50 to 100C. It may be useful to work in a solvent or in a mixture of solvents at a higher temperature, for example at 150C or above, and to ef-fect simultaneously an azeotropic distillation of the water set free by condensation.
The preparation of metal complex compounds may be carried out as follows: the condensation described above of the amine of the formula II with compounds of the formula III takes place in the presence or with the addition of the metal-yielding agents, or the metalfree dyestuff prepared first and optionally isolated is subsequently treated with the metal-yielding agents, using water or in an organic solvent or solvent mixture, for example one of the above solvents, and optionally maintaining exact pH
conditions and defined temperatures.
Metallization is generally carried out according to usual analogous processes, for example at temperatures between 60C
and ~20C and at a pH value of from 3 to 9, preferably 3,5 to 6; but in the preparation of the compounds of the formula (Ic) a pH value above 7, preferably fro~ 7 to 9 has to be observed.
Instead of the free amines of the formula (II), also their salts, for example the chlorhydrates or sulfates, may be used for the reaction with the compounds of the formula (III), option-ally in the presence of an acid-binding agent, such as an alka-line or alkaline earth carbonate or -hydroxide.
- The diamines of the formula (II) to be used as starting 2~ compounds are for example hydrazine, aliphatic diamines having a . : ; - .
, . . .
m~s~6s straight-chained or branched alkylene radical of 2 to 8 carbon atoms which may be interrupted by hetero atoms, such as oxygen, sulfur or nitrogen atoms, by isocyclic radicals, for example cycloalkylene or a phenylene radical or by other bivalent groups or are cycloaliphatic diamines, such as cyclopentylene or cyclo-hexylene diamines, aromatic diamines of the benzene, naphthalene or anthraquinone series as well as those of the general formulae NH2 ~ D ~ ~~- NH ~ NH2 wherein D is a single bond, an oxygen or sulfur atoms, a -NH-group, -N(alkyl-1-4)-, -C~2-, -CH-CH-, -CO-, -CONH-, -NHCONH-, -CO-NH-CO-NH-, -SO-, -SO2-, -SO2NH- or -N=N- group, E is an oxy-gen or sulfur atom, a -NH-, -N(alkyl 1-4)-, -CH2-, -CO-, -C~=CH-, -CONH-, -NHCONH-, -SO2-, -SO2NH- or -N=N- group and the aromatic nuclei , each may be substituted by one or several, preferably 1 or 2 substituents selected from a group consisting of halogen, such as chlorine, bromine, nitro, lower alkyl, cy ano, trifluoro-methyl, hydroxy, amino, lower alkylamino, arylamino such as phenyl-amino, lower alkoxy, carboxy, carboxylic acid -(C1-CS-alkyl)-ester, carboxylic acid hydrazide, hydroxamic acid, sulfonic acid ester, sulfonic acid amide optionally substituted/such as by lower alkyl and/or phenyl and acylamino of an aliphatic lower carboxylic acid or aromatic carboxylic acid, such as acetyl amin~, propionyl amino or benzoylamino; furthermore suitable amines are heterocyclic diamines, for example diaminopyridines.
Preferred diamines are diamines with carbonamide groups, especial-ly with cyclic carbonamide groups, especially diamines of the 10d9'd~
general formula ~[ (CO)3 wherein R2 is hydrogen, a lower alkyl or phenyl radical, and m and n, identical or different, are each 1 or 2, whereby the sum of m and n is 3 or 4, and the group of the formula L (NR2)n(CO)m~ in which -NR2- and -CO- are in any de-sired arrangement to each other, forms together with two ortho-standing carbon atoms of the ring system B a five- or six-membered heterocyclic ring; further-more there are especially preferred diamines of the formulae (II) which are substituted in o-position - to one of the amino groups by a ligand Z which is hydroxy, lower alkoxy, carboxy amino, amino substituted by lower alkyl ant/
or aryl radicals (phenyl radicals), a carboxylic acid-(Cl-C5)-ester group, carboxylic acid amide or a sulfonic acid amide unsubstituted or substituted st the one or two N-atoms by lower alkyl and/or aryl groups (phenyl groups).
As metals M are preferred zinc and cobalt and especially preferred are copper and nickel.
The aldehyde of the formula (III) used as starting compounds are compounds easy to prepare. For preparing them, for example compounds of the formula IV
~ -8-.. , - . . :, . -.: : ` `. .. :: , ., ` . . `.
` . . ` ~ .` . .. . .
. - . ~ ~ ; . , .
`, .
, X~
~ OH (IV) in which X has the above meaning, are reacted in lower aliphatic carboxylic acids with hexamethylene tetramine.
The novel compounds are valuable colorants, preferably as pigments, and are suitable, - especially after a conditioning usual for pigment dyestuffs - , for example for coloring plastic masses which are masses which either are free from solvents and contain a solvent or are free from softening agents or contain a softening agent of plastics or synthetic resins, for the pig-mentation of paints on an oily or aqueous base as well as of lacquers of different types, for the spin-dyeing of viscose and cellulose acetate or for the pigmentation of polyethylene, poly-styrene, polyvinyl chloride, caoutchouc and synthetic leather.
They may also be used in printing pastes for graphic industry, for coloring paper masses, for the coating of textiles or pig-ment printing.
The dyeings obtained have an excellent fastness to migration, to light, to weather and to solvents; they shows an excellent fastness to heat and are characterized by a high tinctorial strength, a good transparency and frequently by surprisingly pure shades.
The following Examples illustrate the invention. Parts and percentages are by weight unless stated otherwise.
E X A M P L E 1:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid are added, while stirring, to a solution of 3.0 parts of 1,2-diaminoethane, _ g _ . . - - - -. .-: . . - - . - . .
- . .
1()t~9~ 3 in 250 parts of ethanol and 10 parts of glacial acetic acid, and heated for 3 hours at the boil. After cooling the yellow compound is suction-filtered and washed well with ethanol. The moist product is then introcuded into 150 parts of dimethylform-amide, mixed with 9.0 parts of nickel diacetate and heated for 4 hours at 120C. The yellow pigment thus obtained is filtered hot, washed well, first with water, then with ethanol. After drying 30.2 parts of the yellow pigment of the formula C~ - N ~ (CH2)2- ~ ~ CH
~ ~ O - Ni 0 ~
HOOC COOH
with the analysis: Ni calculated: 11.4 %
found: 11.3 %, are obtained, which dyes polyvinyl chloride in a clear yellow shade having excellent fastness properties.
E X A M P L E 2:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid, 3.0 parts of diaminoethane and 9.0 parts of nickel diacetate are heated in 300 parts of ethanol for 5 hours at the boil. The yellow com-pound is then filtered hot and washed well with hot water and ethanol. The product is then heated in 150 parts of dimethyl-formamide for 1 hour at 120C, filtered hot and washed well with hot water and ethanol. After drying 31.0 parts of a yellow pigment are obtained which is identical with the pigment obtain-ed according to Example 1.
In similar and analogous manner as described in the above -- ~O --., .
.
' ' ~.
` HOE 75/F 190 i~8~8~i9 Examples 1 or 2, also the following nickel complex compounds listed in the subsequent Table 1 according to the following for-mula with R and X indicated therein, can be prepared:
T A B L E
Shade in ~olyvinyl Example R ~ chloride ~PVC) .: - .
3 CH2C~2 -COOCH3 yellow
4 CH2CH2 , COOC~2C~2CH2CH3 yellow -CH2CH2- -CON~2 yellow CE2C~2 -CON~CH~ ye~Ilow~~~
7 C~2C~2 -CONXCH2CH2CH2CH3 yellow---8 C~2CH2 -CON (C4 ~ )2 yeilow 9 -C~2CX2- -CONHCH2C~2~(C~3)2 ~eilow -CH2CH2- -CONH ~ . _yeliow-g$een 11 - -C~2C~2- -CON~ . yellow-green 12 -(CH2)4- -COOH yeilow-grëer.
.
13 -(C~2)6- -COOH - yeiiow green . . .. .. . .
.. . . . . . . . . . . .
iO~869 ~xample R ~ vinyl chloride (PVC~
14 -(C~2)3NH(CH2)3 -COO~ y~llow-green Cl 3 ~(CH2)3N(CH2)3- -COOH yellow-green .
16 ~C~2)6 -COOCH~ yellow-~ree~
E X A M P L E 17:
22.9 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl amide are introduced, while stirring, to 12.2 parts of 3,3'-di-methoxy-4,4'-diaminodiphenyl in 200 parts of ethanol and 10 parts of gla~ial acetic acid, and the whole i9 refluxed for 4 hours.
The red compound is suction-filtered, washed well with ethanol and then introduced again into 300 parts of ethanol. 21.0 Parts of copper acetate are added and the mixture is heated for 6 hours at the boil. The yellow pigment is filtered hot and washed well with hot water and ethanol. After drying 34.6 parts of the com-pound of the formula ,,, . - 12 -,,, ': ' `'~ ~` ' ,., 10~9~
CH ~ N - C~.
~ O ~O . 'O~ ~0~
~ CO~HCH
H3CNHOC . 3 are obtained.
Analysis: Cu calculated: 16.7 %
found: 16.9 %
The pigment thus obtained dyes polyvinyl chloride in a dull yellow shade having very good fastness properties.
According to analogous processes as described above, the copper complex compounds listed in the following Table 2 cor-responding to the following general formula Cu~ ~z~CU; ~X
with X and Z indicated therein, can be prepared:
9l~69 _ Ex ~ e ~ z Shade ~n PVC
_ 18 -COOH ~ -O- yellow brown 19 -COOCH3 -O- n n --CONH2 ~C00~ ~~ n 21 --COO~I ~C00~ --- -22 -COOC~3 -COO- ~ n 23 -co-OC~2CX2CH2CH~ -COO-E X A M P L E 24:
7 C~2C~2 -CONXCH2CH2CH2CH3 yellow---8 C~2CH2 -CON (C4 ~ )2 yeilow 9 -C~2CX2- -CONHCH2C~2~(C~3)2 ~eilow -CH2CH2- -CONH ~ . _yeliow-g$een 11 - -C~2C~2- -CON~ . yellow-green 12 -(CH2)4- -COOH yeilow-grëer.
.
13 -(C~2)6- -COOH - yeiiow green . . .. .. . .
.. . . . . . . . . . . .
iO~869 ~xample R ~ vinyl chloride (PVC~
14 -(C~2)3NH(CH2)3 -COO~ y~llow-green Cl 3 ~(CH2)3N(CH2)3- -COOH yellow-green .
16 ~C~2)6 -COOCH~ yellow-~ree~
E X A M P L E 17:
22.9 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl amide are introduced, while stirring, to 12.2 parts of 3,3'-di-methoxy-4,4'-diaminodiphenyl in 200 parts of ethanol and 10 parts of gla~ial acetic acid, and the whole i9 refluxed for 4 hours.
The red compound is suction-filtered, washed well with ethanol and then introduced again into 300 parts of ethanol. 21.0 Parts of copper acetate are added and the mixture is heated for 6 hours at the boil. The yellow pigment is filtered hot and washed well with hot water and ethanol. After drying 34.6 parts of the com-pound of the formula ,,, . - 12 -,,, ': ' `'~ ~` ' ,., 10~9~
CH ~ N - C~.
~ O ~O . 'O~ ~0~
~ CO~HCH
H3CNHOC . 3 are obtained.
Analysis: Cu calculated: 16.7 %
found: 16.9 %
The pigment thus obtained dyes polyvinyl chloride in a dull yellow shade having very good fastness properties.
According to analogous processes as described above, the copper complex compounds listed in the following Table 2 cor-responding to the following general formula Cu~ ~z~CU; ~X
with X and Z indicated therein, can be prepared:
9l~69 _ Ex ~ e ~ z Shade ~n PVC
_ 18 -COOH ~ -O- yellow brown 19 -COOCH3 -O- n n --CONH2 ~C00~ ~~ n 21 --COO~I ~C00~ --- -22 -COOC~3 -COO- ~ n 23 -co-OC~2CX2CH2CH~ -COO-E X A M P L E 24:
5.4 Parts of 1.2-diaminobenzene are dissolved in 170 parts of ethanol and 10 parts of glacial acetic acid. While stirring~
21.6 parts of l-formyl-2-hydroxy-6-naphthoic acid are introduced, and the solution is heated at the boil for three hours.
The yellow bis-azomethine is filtered hot, washed well with ethanol and then introduced in the moist state into 200 parts of dimethylformamide. The mixture is heated to 100C, and then 9.0 parts of nickel diacetate are added. After heating for 3 hours, the red pigment prepared is filtered and washed well with hot water and ethanol. After drying 33.4 parts of the pig-ment of the formula .
: ' ` - ' ' .: .
lS)89~69 ~ .
C~ - N N = C~
,J~ o'~i~o ~
~IOOC COO~I
.... .
are obtained.
Analysis: Ni calculated: 10.5 ~
found: 10.3 %
The pigment dyes polyvinyl chloride in a brownish red hav-ing an excellent fastness to bleeding.
X A M P L E 2 5:
2.8 Parts of 1,2-diaminobenzene and 11.3 parts of 1-formyl-2-hydroxy-6-naphthoic acid are heated in 100 parts of dimethyl-formamide for one hour at 120C. Then 4.5 parts of nickel di-acetate are added and heated for 3 hours at 120C. The red com-pound is filtered hot and washed well with hot water and etha-nol. After drying 14.2 part of a red pigment are obtained, which is identical with the pigment prepared according to Ex-ample 24.
In corresponding way as described in the previous Examples the nickel comples compounds listed in the following Table 3 and correqponding to the following formula CH ~ N N - C~
Ni /
: - . ,, - . ` - j . . ' .
.. , .. . .: .
.
lV~
with X and Y indicated in the Table, are obtained.
ExampIe-z~ ~ Y ~hade ~ PVC
. ~ . . .
26 -COOCH~; H or~nge 27 -COOCR2CH2C~I2C~3 H orange 28 -C~2 H red 29 --CON}ICX3 H . red -CO~ICH2CH2C~2C~3 H red 31 -CO~CH CH2~ ~ 3 2 ~ CH3 re~~
32 -CON}I ~3 H . ora~ge 33 -CO~} ~3 ~ orange 34 . -COOH N02 ` r~d -COOH Cl . -r~d 36 -COOH 3 re~
1~9~69 ~x~mple- 2 y Shade -r_ _ in~PVC
37 -COO~ -NHCOCH3 red -38 -COOH -~HCO ~ n 39 -COOX -COO~ n -COO~ . -CON~2 ~ --4l -COOH -CON~
42 -COO~ -SO
43 -C~2 ~2 44 -CON~c~2cH2cH2c~3 -COOH n --CO~IC~2C~2CH2C~3 --COOC~I3 n -COOc~3 E X A M P L E 47:
11.5 Parts of formyl-2-hydroxy-6-naphthoic acid methyl ester are added, while stirring, to 1.5 parts of a 80 % b. w.
hydrazine hydrate in 150 parts of ethanol. The mixture is heated at the boil for 3 hours. The 3 parts of sodium-acetate and 4.5 parts of nickel diacetate are added, and the whole is heated again for S hours at the boil. The pH value is constantly ma~ntained above 7 with the aid of diluted aqueous sodium hydro-xide solution.
' ' ., ' . ~
. . - ` ~ , ' . ' - ~, .
The yellow compound is then filtered hot, washed well with hot water and ethanol. After drying 14.3 parts of a yellow pig-ment is obtained which corresponds to the formula Ic wherein R is a single bond, M is Ni and X is -COOCH3.
A lacquer pigmented therewith and having been used for coating shows a good fastness to overvarnishing and to light.
E X A M P L E 48:
11.5 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl ester are added, while stirring, to 1.5 parts of a 80 ~ b.w.
hydrazine hydrate in 150 parts of ethanol. The mixture is heat-ed at the ~oil for 3 hours, and the yellow compound is filtered hot, washed well with ethanol and introduced in the moist state into 100 parts of dimethylformamide. 5.0 Parts of nickel di-acetate and 30 parts of sodium acetate are added at 100C, and the mixture is stirred for 5 hours at this temperature. The yel-low complex compound thus obtained is filtered at 30 - 40C and washed well with hot water and ethanol. After drying, 9.8 parts of a yellow pigment are obtained which i5 identical to the pigment obtained according to Example 47.
If in Example 47 the 1-formyl-2-hydroxy-6-naphthoic acid methyl ester is replaced by one of the aldehydes listed in Table 4, the corresponding nickel complex compounds corresponding to the general formula (Ic) with R and X indicated therein, are obtained, - ~8 -HOE ?5/E 190 -` 108'38ti9 TA s LE 4 . . .
- '~ample_ ~ldeh~de R 2 Sha~e in - lacquer~
C~O ' H2NC ~ C~2 ~ ~ellow C~O
HO-C ~_ OH _ COOX yelI~
, . ~ ,, . , - - :
. -, .. : :
-~ ~. . . . ..
21.6 parts of l-formyl-2-hydroxy-6-naphthoic acid are introduced, and the solution is heated at the boil for three hours.
The yellow bis-azomethine is filtered hot, washed well with ethanol and then introduced in the moist state into 200 parts of dimethylformamide. The mixture is heated to 100C, and then 9.0 parts of nickel diacetate are added. After heating for 3 hours, the red pigment prepared is filtered and washed well with hot water and ethanol. After drying 33.4 parts of the pig-ment of the formula .
: ' ` - ' ' .: .
lS)89~69 ~ .
C~ - N N = C~
,J~ o'~i~o ~
~IOOC COO~I
.... .
are obtained.
Analysis: Ni calculated: 10.5 ~
found: 10.3 %
The pigment dyes polyvinyl chloride in a brownish red hav-ing an excellent fastness to bleeding.
X A M P L E 2 5:
2.8 Parts of 1,2-diaminobenzene and 11.3 parts of 1-formyl-2-hydroxy-6-naphthoic acid are heated in 100 parts of dimethyl-formamide for one hour at 120C. Then 4.5 parts of nickel di-acetate are added and heated for 3 hours at 120C. The red com-pound is filtered hot and washed well with hot water and etha-nol. After drying 14.2 part of a red pigment are obtained, which is identical with the pigment prepared according to Ex-ample 24.
In corresponding way as described in the previous Examples the nickel comples compounds listed in the following Table 3 and correqponding to the following formula CH ~ N N - C~
Ni /
: - . ,, - . ` - j . . ' .
.. , .. . .: .
.
lV~
with X and Y indicated in the Table, are obtained.
ExampIe-z~ ~ Y ~hade ~ PVC
. ~ . . .
26 -COOCH~; H or~nge 27 -COOCR2CH2C~I2C~3 H orange 28 -C~2 H red 29 --CON}ICX3 H . red -CO~ICH2CH2C~2C~3 H red 31 -CO~CH CH2~ ~ 3 2 ~ CH3 re~~
32 -CON}I ~3 H . ora~ge 33 -CO~} ~3 ~ orange 34 . -COOH N02 ` r~d -COOH Cl . -r~d 36 -COOH 3 re~
1~9~69 ~x~mple- 2 y Shade -r_ _ in~PVC
37 -COO~ -NHCOCH3 red -38 -COOH -~HCO ~ n 39 -COOX -COO~ n -COO~ . -CON~2 ~ --4l -COOH -CON~
42 -COO~ -SO
43 -C~2 ~2 44 -CON~c~2cH2cH2c~3 -COOH n --CO~IC~2C~2CH2C~3 --COOC~I3 n -COOc~3 E X A M P L E 47:
11.5 Parts of formyl-2-hydroxy-6-naphthoic acid methyl ester are added, while stirring, to 1.5 parts of a 80 % b. w.
hydrazine hydrate in 150 parts of ethanol. The mixture is heated at the boil for 3 hours. The 3 parts of sodium-acetate and 4.5 parts of nickel diacetate are added, and the whole is heated again for S hours at the boil. The pH value is constantly ma~ntained above 7 with the aid of diluted aqueous sodium hydro-xide solution.
' ' ., ' . ~
. . - ` ~ , ' . ' - ~, .
The yellow compound is then filtered hot, washed well with hot water and ethanol. After drying 14.3 parts of a yellow pig-ment is obtained which corresponds to the formula Ic wherein R is a single bond, M is Ni and X is -COOCH3.
A lacquer pigmented therewith and having been used for coating shows a good fastness to overvarnishing and to light.
E X A M P L E 48:
11.5 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl ester are added, while stirring, to 1.5 parts of a 80 ~ b.w.
hydrazine hydrate in 150 parts of ethanol. The mixture is heat-ed at the ~oil for 3 hours, and the yellow compound is filtered hot, washed well with ethanol and introduced in the moist state into 100 parts of dimethylformamide. 5.0 Parts of nickel di-acetate and 30 parts of sodium acetate are added at 100C, and the mixture is stirred for 5 hours at this temperature. The yel-low complex compound thus obtained is filtered at 30 - 40C and washed well with hot water and ethanol. After drying, 9.8 parts of a yellow pigment are obtained which i5 identical to the pigment obtained according to Example 47.
If in Example 47 the 1-formyl-2-hydroxy-6-naphthoic acid methyl ester is replaced by one of the aldehydes listed in Table 4, the corresponding nickel complex compounds corresponding to the general formula (Ic) with R and X indicated therein, are obtained, - ~8 -HOE ?5/E 190 -` 108'38ti9 TA s LE 4 . . .
- '~ample_ ~ldeh~de R 2 Sha~e in - lacquer~
C~O ' H2NC ~ C~2 ~ ~ellow C~O
HO-C ~_ OH _ COOX yelI~
, . ~ ,, . , - - :
. -, .. : :
-~ ~. . . . ..
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Metal-containing disazomethine compounds of the formulae (Ia) (Ib) (Ic) wherein A is a straight-chain or branched alkylene radical, which may be inter-rupted by one or more moieties selected from the group of hetero atoms, bivalent groups and isocyclic rings, or is a cycloalkylene radical or an arylene radical, R is a covalent bond or is defined as A, Z as a group capable of forming a metal complex is an -O-, -COO- or lower alkoxy group, or an amino group optionally sub-stituted by lower alkyl or aryl, or a carboxylic acid (C1 to C5) alkyl ester group, or Z stands for a carbonamide group or for a sulfonic acid amide radi-cal optionally substituted at one or two nitrogen atoms by alkyl or aryl groups, and X is a carboxylic acid group, carboxylic acid ester group, an optionally substituted carboxylic acid amide or carboxylic acid hydrazide group and M is a bivalent copper, cobalt, nickel, zinc or manganese atom.
2. Process for preparing metal-containing disazomethine compounds claim-ed in claim 1, which comprises condensing 1 mol of one or several diamines of the formula or wherein A and R have the meanings given in claim 1, 2 groups ? being bound to A, with 2 mols of one or several compounds of the formula wherein X has the meaning as stated in claim 1, and metallizing the disazo-methine compound obtained simultaneously or in a following separate reaction process by means of a copper, cobalt, nickel, zinc or manganese-yielding agent.
3. Compounds as claimed in claim 1 of the general formula wherein R stands for the diphenyl radical, Z is oxygen or a radical of the formula -CO-O-, the carbonyl group being bound to the radical R, each X stands for a carboxylic acid, carboxylic acid-(C1-C4-alkyl)-ester, carboxylic acid amide or carboxylic acid methylamide group, and M is a copper atom.
4. Compounds as claimed in claim 1 of the general formula wherein R is an alkylene radical having 2 to 6 carbon atoms, which may be in-terrupted by 1 or 2 groups of the formula -NH- or -N(CH3)-, or the ortho-pheny-lene radical, which may be substituted by chlorine, methyl, ethyl, nitro, carboxy, carbomethoxy, carbethoxy, carboxylic acid amide, carboxylic acid phenylamide, acetylamino, benzoylamino or sulfonic acid phenylamide, each X
stands for a carboxylic acid group, a carboxylic acid-(C1-C4-alkyl)-ester group, a carboxylic acid amide group, a carboxylic acid-(C1-C4-alkyl)-amide group, carboxylic acid-di-(C1-C4-alkyl)-amide group, carboxylic acid phenyl-amide or carboxylic acid phenylhydrazide group and M stands for nickel.
stands for a carboxylic acid group, a carboxylic acid-(C1-C4-alkyl)-ester group, a carboxylic acid amide group, a carboxylic acid-(C1-C4-alkyl)-amide group, carboxylic acid-di-(C1-C4-alkyl)-amide group, carboxylic acid phenyl-amide or carboxylic acid phenylhydrazide group and M stands for nickel.
5. Nickel complex compounds as claimed in claim 1 of the formula wherein each X stands for a carboxylic acid, carboxylic acid amide, carbometh-oxy or carbethoxy group.
6. A compound as claimed in claim 1 of the formula wherein Y stands for hydrogen or methyl or a carboxy group and each X repre-sents a carboxy, carboxylic acid amide or carboxylic acid phenyl amide group.
7. A compound as claimed in claim 6, wherein Y stands for hydrogen and each X for a carboxylic acid group.
8. A compound as claimed in claim 6, wherein Y stands for hydrogen and each X for a carboxylic acid amide group.
9. A compound as claimed in claim 6, wherein Y is hydrogen and each X
is a carboxylic acid phenylamide group.
is a carboxylic acid phenylamide group.
10. A compound as claimed in claim 6, wherein Y is methyl and each X is a carboxy group.
11. A compound as claimed in claim 6, wherein Y and X each represent a carboxy group.
12. A metal-complex disazomethine compound of formula (Ib) as defined in claim 1 wherein R is phenylene or phenylene substituted by 1 or 2 substi-tuents selected from the group consisting of chlorine, lower alkyl, lower al-koxy, nitro, trifluoromethyl, carboxylic acid (C1 - C5-alkyl)-ester, carbamoyl, N-phenyl-carbamoyl, acetylamino, benzoylamino, sulfamoyl, sulfonic acid (C1 -C5-alkyl)-amide and sulfonic acid phenyl amide, each X is carboxy, carboxylic acid (C1 -C4-alkyl) ester, carbamoyl, carboxylic acid N-(C1-C4-alkyl)-amide or carboxylic acid phenyl amide, and M is copper, nickel or zinc.
13. A metal-complex disazomethine compound of formula (Ib) as defined in claim 1 wherein R is ortho-phenylene or ortho-phenylene substituted by 1 or 2 substituents selected from the group consisting of chlorine, methyl, ethyl, nitro, carboxy, carbomethoxy, carbethoxy, carbamoyl, N-phenyl-carba_ moyl, acetylamino, benzoylamino and sulfonic acid phenyl amide, each X is carboxy, carboxylic acid (C1 - C4-alkyl) ester, carbamoyl, carboxylic acid (C1 - C4-alkyl)-amide, carboxylic acid-di-(C1 - C4-alkyl)-amide or carboxylic acid phenyl amide, and M is nickel.
14. Printing pastes, printing inks, high-molecular plastic masses, lac-quers, paints or spinning masses, containing a compound defined in claim 1 or prepared according to claim 2.
A process for coloring a material which comprises incorporating into the material as a colorant agent a compound according to claim 1.
A process for coloring a material which comprises incorporating into the material as a colorant agent a compound according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2533947.3 | 1975-07-30 | ||
| DE19752533947 DE2533947A1 (en) | 1975-07-30 | 1975-07-30 | METAL-CONTAINING DISAZOMETHINE COMPOUNDS, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS A COLORANT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089869A true CA1089869A (en) | 1980-11-18 |
Family
ID=5952763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,057A Expired CA1089869A (en) | 1975-07-30 | 1976-07-29 | Metal-containing disazomethine compounds, process for preparing them and their use as colorants |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5221030A (en) |
| BR (1) | BR7604962A (en) |
| CA (1) | CA1089869A (en) |
| CH (1) | CH611328A5 (en) |
| DE (1) | DE2533947A1 (en) |
| FR (1) | FR2319688A1 (en) |
| GB (1) | GB1532043A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2457388C2 (en) * | 1974-12-05 | 1982-12-02 | Bayer Ag, 5090 Leverkusen | Thermoelastomeric poly-segment copolymers |
| DE2801288C2 (en) * | 1978-01-13 | 1985-06-20 | Hoechst Ag, 6230 Frankfurt | Use of water-insoluble diazomethine compounds for dyeing thermoplastic polyesters in bulk and in spin dyeing of thermoplastic polyesters |
| AU2002361689A1 (en) | 2002-01-04 | 2003-07-30 | University Of Dayton | Non-toxic corrosion protection pigments based on cobalt |
| US20040011252A1 (en) | 2003-01-13 | 2004-01-22 | Sturgill Jeffrey A. | Non-toxic corrosion-protection pigments based on manganese |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2305071C2 (en) * | 1973-02-02 | 1975-04-17 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Water-insoluble disazomethine dyes, process for their preparation and their use |
| DE2343984A1 (en) * | 1973-08-31 | 1975-03-13 | Hoechst Ag | WATER-INSOLUBLE DISAZOMETHIN DYES, METHOD FOR THEIR MANUFACTURING AND USE |
| GB1439048A (en) * | 1973-09-11 | 1976-06-09 | Ciba Geigy Ag | Metal complexes of bis-azomethines and processes for their manufacture |
| DE2533960A1 (en) * | 1975-07-30 | 1977-02-17 | Hoechst Ag | NEW 2-HYDROXYNAPHTHALIN-1-ALDEHYDE, THE METHOD FOR MANUFACTURING IT AND ITS USE |
-
1975
- 1975-07-30 DE DE19752533947 patent/DE2533947A1/en not_active Withdrawn
-
1976
- 1976-07-27 CH CH961476A patent/CH611328A5/en not_active IP Right Cessation
- 1976-07-28 JP JP8928376A patent/JPS5221030A/en active Pending
- 1976-07-28 GB GB3143576A patent/GB1532043A/en not_active Expired
- 1976-07-29 CA CA258,057A patent/CA1089869A/en not_active Expired
- 1976-07-29 BR BR7604962A patent/BR7604962A/en unknown
- 1976-07-30 FR FR7623353A patent/FR2319688A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5221030A (en) | 1977-02-17 |
| GB1532043A (en) | 1978-11-15 |
| FR2319688A1 (en) | 1977-02-25 |
| FR2319688B1 (en) | 1980-06-06 |
| BR7604962A (en) | 1977-08-09 |
| DE2533947A1 (en) | 1977-02-17 |
| CH611328A5 (en) | 1979-05-31 |
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