CA1091681A - Azamethine-cu complex compounds, process for their preparation and their use - Google Patents
Azamethine-cu complex compounds, process for their preparation and their useInfo
- Publication number
- CA1091681A CA1091681A CA282,755A CA282755A CA1091681A CA 1091681 A CA1091681 A CA 1091681A CA 282755 A CA282755 A CA 282755A CA 1091681 A CA1091681 A CA 1091681A
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen
- compound
- carbo
- formula
- azamethine
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- 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
- C09B55/002—Monoazomethine dyes
Abstract
Abstract of the Disclosure Compounds of the formula
Description
1~91 b;~
The pre~ent invention relates to azamethine-Cu complex compounds, to a proces3 for preparing them and their use as pigments.
The present in~ention provides azamethine-Cu complex compounds of the formula I
X~O--Cu--O ~
in which X represents hydrogen, chlorine, bromine, alkyl or alkoxy having 1 to 4 carbon atoms each, nitro, trifluoromethyl or a group of the formula -COOY, in which Y stands for ~ydro-gen or alkyl having 1 to 5 carbon atoms, and R1 and R2 are hydrogen, or one of the radicals R and R2 is hydrogen and the other represents -COOY, with the pro~iso that at lc~st one of the radicals X, Rl and R stands for -COOY.
If Y represents alkyl, it stands for example ror ethyl, n-propyl, isopropyl, n-butyl, i~obutyl, n-amyl or i~oamyl, however, preferably for methyl.
Thc invention also provides a proces~ for the preparation of the compounds of the formula I, which comprises metallizing an azamethine of the formula II
R~
N = CH ~ (II) OR HO
wherein R i~ hydrogen or a methyl group, with a copper-ylel-ding compound, i.e. an inorganic or organic, preferably bi-valent copper salt, as well a~ their use a~ pigments.
HOE ~6 ~ 1~2 X
As oopper salts, there are ~uitable, for example, copper(II)-chloride, copper(II)Yulfate, copper formate, copper(II)acetate or copper ~tearate.
The coppering of the compound II 9 in which R stand~ for hydrogen, may be carried out in water or organic solvents or aqueou~-organic ~olvent~ at a temperature in the range Or from 20 to 180C, preferably from 20 to 150C, e~pecially from 80 to 110C. As ~ol~ents for the coppering there are suitable, for e~ample, alcohol~, espeeially lower alkanol~, such a~ me-thanol~ ethanol, n-propanol, isopropanol, n-butanol or i~o-butanol; glycol-monomethylether; glacial acetic acid; form-amide or dipolar aprotic sol~ents, ~uch as dimethylformamide, N-methylpyrrolidone or tetramethylene-sulfone. For the coppe-ring reaction, use is made preferably of the same ~olvent, in which the copper salt has previously been di~sol~ed. The coppering m~y be effected in the presence Or a basic compound, such as sodium acetata.
The coppering of the ani~o~ derivati~ea (R=CH3) is carrisd `~
out in the prssence of a coppering agent in an inert organic solvent at a temperature in *he ranga of from 120 to 180C
with desalkylation, to give the azamethine compound of the formula I.
The azamethine compound of the formula II i3 prepared either separately , or the azamethine-Cu complex of the form-ula I is synthesized in a single reaction without isolating intermediate product~.
m e compound~ of the formula II are prepared by a con-densation of the correspondi~g 2-~minophenol or -anl~o~ or 29 their hydrochloride~ with th0 Z-hydroxynaphthaldehyde-(l) ~ IOE ~ 1 ~9 ~
~ optionally sub~tituted in the 3- or 6-position by the group -COOY9 Y optionally also being a cation, for example an al-kali metal, in which process equivalent amount~ of the two starting compounds are reacted in water, organic sol~ents or aqueous-organic sol~ents at a temperature in the range of from 20 to 150C, preferably fro~ 80 to 110C.
The reactivn may al80 be effected under an inert gas cover, such as in a nitrogen atmo~phere. If the reaction i8 carried out in water, the addition of surface-active agents, such as cationic, anionic or non-ionogenic compou~ds, is re-commended. If the hydrochloride of the 4-carbomethoxy-2-amino-phenol or -ani~ol~ is used, a basic compound, for example, sodium acetate, sodium hydrogencarbonate or pota~sium carbon-ate, should be added. As organic 601vents there are mentioned, for example: lower alcohols having 1 to 6 carbon atoms, gla-cial acetic acid, dimethylformamide or glycol-monomethylether.
After isolation and washing, the compound o~ the formula II
obtained may then be coppered as ha~ been described above.
According to another process the azamethine copper comple~ of the formula I can be prepared directly in a grinding device, in which the ~tarting compounds, for example, 4-carbometho~y-
The pre~ent invention relates to azamethine-Cu complex compounds, to a proces3 for preparing them and their use as pigments.
The present in~ention provides azamethine-Cu complex compounds of the formula I
X~O--Cu--O ~
in which X represents hydrogen, chlorine, bromine, alkyl or alkoxy having 1 to 4 carbon atoms each, nitro, trifluoromethyl or a group of the formula -COOY, in which Y stands for ~ydro-gen or alkyl having 1 to 5 carbon atoms, and R1 and R2 are hydrogen, or one of the radicals R and R2 is hydrogen and the other represents -COOY, with the pro~iso that at lc~st one of the radicals X, Rl and R stands for -COOY.
If Y represents alkyl, it stands for example ror ethyl, n-propyl, isopropyl, n-butyl, i~obutyl, n-amyl or i~oamyl, however, preferably for methyl.
Thc invention also provides a proces~ for the preparation of the compounds of the formula I, which comprises metallizing an azamethine of the formula II
R~
N = CH ~ (II) OR HO
wherein R i~ hydrogen or a methyl group, with a copper-ylel-ding compound, i.e. an inorganic or organic, preferably bi-valent copper salt, as well a~ their use a~ pigments.
HOE ~6 ~ 1~2 X
As oopper salts, there are ~uitable, for example, copper(II)-chloride, copper(II)Yulfate, copper formate, copper(II)acetate or copper ~tearate.
The coppering of the compound II 9 in which R stand~ for hydrogen, may be carried out in water or organic solvents or aqueou~-organic ~olvent~ at a temperature in the range Or from 20 to 180C, preferably from 20 to 150C, e~pecially from 80 to 110C. As ~ol~ents for the coppering there are suitable, for e~ample, alcohol~, espeeially lower alkanol~, such a~ me-thanol~ ethanol, n-propanol, isopropanol, n-butanol or i~o-butanol; glycol-monomethylether; glacial acetic acid; form-amide or dipolar aprotic sol~ents, ~uch as dimethylformamide, N-methylpyrrolidone or tetramethylene-sulfone. For the coppe-ring reaction, use is made preferably of the same ~olvent, in which the copper salt has previously been di~sol~ed. The coppering m~y be effected in the presence Or a basic compound, such as sodium acetata.
The coppering of the ani~o~ derivati~ea (R=CH3) is carrisd `~
out in the prssence of a coppering agent in an inert organic solvent at a temperature in *he ranga of from 120 to 180C
with desalkylation, to give the azamethine compound of the formula I.
The azamethine compound of the formula II i3 prepared either separately , or the azamethine-Cu complex of the form-ula I is synthesized in a single reaction without isolating intermediate product~.
m e compound~ of the formula II are prepared by a con-densation of the correspondi~g 2-~minophenol or -anl~o~ or 29 their hydrochloride~ with th0 Z-hydroxynaphthaldehyde-(l) ~ IOE ~ 1 ~9 ~
~ optionally sub~tituted in the 3- or 6-position by the group -COOY9 Y optionally also being a cation, for example an al-kali metal, in which process equivalent amount~ of the two starting compounds are reacted in water, organic sol~ents or aqueous-organic sol~ents at a temperature in the range of from 20 to 150C, preferably fro~ 80 to 110C.
The reactivn may al80 be effected under an inert gas cover, such as in a nitrogen atmo~phere. If the reaction i8 carried out in water, the addition of surface-active agents, such as cationic, anionic or non-ionogenic compou~ds, is re-commended. If the hydrochloride of the 4-carbomethoxy-2-amino-phenol or -ani~ol~ is used, a basic compound, for example, sodium acetate, sodium hydrogencarbonate or pota~sium carbon-ate, should be added. As organic 601vents there are mentioned, for example: lower alcohols having 1 to 6 carbon atoms, gla-cial acetic acid, dimethylformamide or glycol-monomethylether.
After isolation and washing, the compound o~ the formula II
obtained may then be coppered as ha~ been described above.
According to another process the azamethine copper comple~ of the formula I can be prepared directly in a grinding device, in which the ~tarting compounds, for example, 4-carbometho~y-
2-aminophenol and 2-hydroxynaphthaldehyde-(1), are ground in water together with a coppering agent, for example, copper(II)-sulfate, in the presence of an acid buffer, such as sodium acetate. As grinding de~ices there are suitable, for example, ball mills, bead mills or sand mill~. The grinding may also be carried out in the pre~ence o~ a salt and/or a surface-acti~e agent.
Z9 The azamethine-copper complex compounds of the formula I
HOE 76~F 159 K
hava ~aluable properties as pigments.
In order to obtain optimum coloristic properties of the pigm~nts of the invention, it is sometimes advantageous to convert ~he ready pigment into a finely divided form by heating it in a solYent, optionally in the presence of water or ~alt solutions.
A~ solvents suitable for this purpose there may be men-tioned those in which the pigment is insoluble, however, which promote und~r the finishing conditions a certain superficial dissol~ing action, for example, aliphatic alcohols, especially lower alkanols, such as ethanol, isopropanol, i80- or n-butanol, : chloro aromatic compounds, ~uch as chlorobenzene and -toluene, or dichlorobenzenes, as well as dipolar aprotic solvents, for axample, dimethylformamide, dimethylacetamide, dimethylsulfo~i-de, N-methyl-pyrrolidone, polyalkyl-ureas, such as tetramethyl-urea, and phosphoric acid amides, such a8 hexamethyl-phospho-ric acid-trisamide.
Also a fine division by grinding with salts or solvents may be advantageous, in which process in ths former case a dry grinding in vibration grinding mills is preferably effected and the salt is subsequently extracted with water, whereupon a wet grinding or a temperature treatment with solvents may optionally follow~
As salts there may be mentioned essentially alkali metal and alkaline earth metal salts of hydrohalic acids or of sul-furic acid, for example, ~odium or potassium chloride, as well as sodium or magnesium sulfate.
The sol~ents which may be used for the wet grinding pro-29 cess are essentially those mentioned above, for example, alcohols, acid amides or dimethyl sulfoxide.
The novel compounds represent valuable pigments which are used in printing inks, disper~ion dye~, varnishes, and which are suitable for pigm0nting high-molecular-weight organic material, for example, cellulose ethers and esters, polyamides, polyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resin~ or plastics, ~or example, aminoplasts, es-pecially urea and melamine formaldehyde resins~ alkyd resins, phenoplasts, polycarbonates, polyolefins, such a~ polyethylene or polypropylene, polystyrene, polyvinylchloride, polyacrylo-nitrile, polyacrylic acid esters, rubber, casein, siliconss and silicone resins. It is unimportant whether the above-men-tioned high-molecular-weight compounds are present as plaRtic masses, melts, or in the form of spinning solutions~ lacquers or printing paxtes. Depending on the application, it may be advantageous to use the novel pigments as toners or in the form of preparations.
The pigments of the invention have a high color intensity (tinctorial strength), a pure color shade, a good fastness to high temperatures in stove enamels and plastics, however, particularly an excellent fastness to overlacquering, to light and to weather, an extremely high fastness to light and to weathering, especially under the extreme conditions of an alu-minum metallic lacquering.
Z5 The following Examples ~erve to illu~trate the in~ention, the percentages being by weight, unless otherwise stated.
E X A M P L E 1:
17.2 Grams of 2-hydroxynaphthaldehyde-(1) are suspended 29 in 200 ml of ethanol, are heated to boiling temperature with ~ HOE 76~F 1~_K
21 . 5 g of the hydrochloride Or 4-carbomsthoxy-2-aminophenol and 10 g of anhydrous Podium acetate in 200 ml of ethanol, and the reaction mixture is maintained at this temperaturs for 1 hour. During the reaction time, nitrogen i6 led over the mix-ture. The orange-red precipitate of the aza~ethine i~ suction-filtered and washed with ethanol and w~ter. Yisld (after dry-ing)s 29.4 g (91.6 ~ of the theory)O
16 Grams of the azamethine thuo obtained are dissol~d in 150 ml of di~eth~lformamide and are treated for 3 ho~r~ at 100 C with 10 g of copper(II)acetate. Ths mi~ture is cooled to 50C~ i~ suction-filtered, and the yellow pigment is washed with ethanol and water. After drying7 17.8 g of the compound of the formula - -H3COCO ~ O-C~-are obtained.
--16.7 Grams of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydroxynaphthaldehyde-(1) are ~tirred for 5 minutes in 100 ml of water. Sub~equently 50 ml of 2N sodium hydro~ide solu-tion and 30 ml of a 40 % sodium hydrogen~ulfite solution are added, and the mixture ii stirred for 15 minutes at 95 C. The precipitate is filtered off with auction and is wa~hed with cold water. The press cake ia then stirred in 200 ml of water with an impeller.
Subsequently a solution of 27.S g of copper(II)sulfate pentahydrate in 100 ml of water and 50 g of concentrated ~ ~ ~ HOE 76/F ?~9 K
ammonia solution are added, the mixture i9 h0ated to 95 C and i9 maintainad at this -temperature for 1 hour. The pigmsnt i~
filtered off with suction, while hot, is washed with hot water and dried. 32.9 Grams of the compound Or Exampla 1 are ob-tained, A mixture of 16.7 g of 4-carbomethoxy-2-aminophenol, 17.2 g of 2-hydroxynaphthaldehyde-(1) and 200 ml of water is ground in a ball mill with 200 g of ceramic balls (diame~er of 10 mm) for 24 hours. Upon adding 25 g of 30dium acetate-trihydrate, 26 g of copper(II)sulfate pentahydrate and 100 ml of water, the mixture is continued to be ground for another 80 hDurs. The ground product obtained is wa~hed with water and dried.
Yield: 35.7 g of the yellow pigment of Example 1.
E X A M P L E 4:
16.7 Gram~ of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydroxynaphthaldehyde-(1) are dispersed with 400 ml of water by means of an impeller, and the disp0rsion is heated to a temperature in the range of from 95 to 98C and maintained at this temperature for 4 hours.
The product is suction-filtered, washed with hot water, and the moist press cake is stirred with 400 ml of water in which 26 g of copper(II)sulfate pentahydrate and 25 g of so-dium acetate are dissolved; thereafter the mixture is heatedto boiling temperature. After is has been heated to 100 C for g hours, the product i8 filtered off with Yuction, while hot, is washed with water and dried. 34.9 Grams of the yellow pig-29 ment of Example 1 are obtained.
~9~6~3~
E X_A M P L E 5:
18.1 Grams o~ 4-carbomethoxy-2-aminoaniso~ and 17.2 g of 2-hydroxynaphthaldehyde-(1) are heated i~ 400 ml of diethylene-glycol-monomethylether to 100C and are maintained at this temperature for 2 hours. During the reaction time, nitrogen is led over the mixture. 10 Grams Or copper(II)acetate dissolved in 100 ml of diglycol-monomethylether are added to the hot reaction mixture. Said mixture is heated to 150C and is main-tained at this temperature for 4 hours. After cooling, the yellow pigment is filtered off with suction, i6 thoroughly washed with ethanol and water and dried. 31.9 Grams of the compound of Example 1 are obtained.
E X A M
17.2 Grams of 2-hydroxy-1-naphthaldeh~de are suspended in 700 ml of n-propanol. Thereafter 24.3 g of the hydrochlori-de of 3-amino-4-hydroxybenzoic acid-n-propylester and 10 g of anhydrous sodium acatate are added. The mixture is rafluxed for 2 hours under a nitrogen atmo3phere. The yellow a~amethine of the formula n-C3H700 ~ OH HO ~
is suction-filtered, while hot, is washed with n-propanol and water and dried. Yield: 33 Grams.
17.45 Grams of the azamethine thus preparod are suspended in 250 ml of n-propanol. Subsequently 12.5 g of copper(II)-sulfate-pentahydrate dissolved in 30 ml of water are added dropwise within 15 minute~. The pH value is maintained at 5 by adding about 25 ml of a 4N sodium acetate solution. The ~OE 76/F 159 K
9~ 3.~
mixture is then h~ated under reflux for 3 hours under a nitro-gen atmosphere, ~ubsequently the product is suction-filtered, while hot, is washed with n-propanol and water and dried. Z3.3 Grams of the green pigment of the formula n-C3H700 are obtained.
L ~
17.2 Grams of 2-hydroxy-1-naphthaldahyde are su~pended in 500 ml of ethanol. Subsequently 23 g Or the hydrochloride of 3-amino-4-hydro~ybenzoic acid ethylaster and 10 g of an-hydrouq sodium acetate are added. The mixture is boiled under reflux for 2 hours in a nitrogen atmosphere. The precipitated orange azamethine of the formula C2H500C ~ OH HO ~
is filtered off with suction, while hot, is washed with etha-nol and water and dried. Yield: 28.4 Grams.
16.75 Grams of the azamethine thus prepared are su pended-in 250 ml of ethanol and are coppered, as has been described in Example 6. 24 Grams of the green pigment of the formula C2H500C ~ N ~ CH
Cu~
are obtained.
~ 8~ HOE 76/F 159 K
E X A M P_L E 8:
17.2 Grams of 2-hydroxy-1-naphthaldehyde are ~uapended in 500 ml of n-butanol, thereafter 25.75 g of the hydrochloride of 3-amino-4-hydroxybenzoic acid n-butyle~ter and 10 g of an-hydrous sodium acetate are added. Ihe mixture i~ heat~d to 90Cand i8 maint~ined at thi~ temperature for 2 hour~. Subsequently the product i9 filtered of~ with ~uction at about 70C, is washed with n-butanol and water and dried. 26.55 Grams of the ora~ge a~amethine of the ~ormuls n-C4HgOOC ~ N = CH
ara obtained.
18.15 Grams of the azamethine thu~ obtained are su~pended in 250 ml of n-butanol and are copp~red accordlng to the method describ~d in Example 6. 19.9~ Grams of the yellowi~h-green pig_ ment of the formula n-C4H900C ~ ~ Cu~
are obtained.
In a manner analogous to that described in Examples 6 through 8, the following pigments were obtained:
YOOC N = CH ~
Example Y Color Shade in book-prin-~ tin~s 9 H greenish-yellow H3C\
/ CH- greenish-yellow ~3c\
11 CH-CH - reddish-yellow CH3-CH2-CH- browni3h-yellow 13 3 2 2 2 2 reddish-yellow ~H3 14 CH -CH -CH-CH brownish-yellow 21.6 Grams of 2-hydroxy-1-naphthaldehyde-3-carboxylic acid ara re~luxed together with 11.4 g o~ Q-aminophenol in 300 ml of ethanol undar a nitrogen atmo~phere. Then the pre-cipitate of the azamethine is suction-filtered~ while hot, i~
washed with ethanol and water and dried.
10.2 Grams of the orange azamethine thus prepared are suspend~d in 300 ml of ethanol and are then heated to boiling temperature together with 7 g of copper acetate and maintained at $he boil for 3 hours. The pE value i~ maintained at 6.5 by adding 25 ml of 4N sodium acetat~ solution. The product is suction-filtered, while hot, is washed with ethanol and watur 1~9iiL6&~
and dried. Yield: 11.7 Gram~ of the greenish-yellow pigment of the formula Q
` Cu'O ~
COOH
~
21.6 Grams of Z-hydro~y-l-naphthaldehyde-6-carboxylic acid are suspend~d together wi$h 11. 4 g Or o-aminophenol in 300 ml of glacial acetic acid. The suspension is heated to the boiling point and is maintained at this temperature for
Z9 The azamethine-copper complex compounds of the formula I
HOE 76~F 159 K
hava ~aluable properties as pigments.
In order to obtain optimum coloristic properties of the pigm~nts of the invention, it is sometimes advantageous to convert ~he ready pigment into a finely divided form by heating it in a solYent, optionally in the presence of water or ~alt solutions.
A~ solvents suitable for this purpose there may be men-tioned those in which the pigment is insoluble, however, which promote und~r the finishing conditions a certain superficial dissol~ing action, for example, aliphatic alcohols, especially lower alkanols, such as ethanol, isopropanol, i80- or n-butanol, : chloro aromatic compounds, ~uch as chlorobenzene and -toluene, or dichlorobenzenes, as well as dipolar aprotic solvents, for axample, dimethylformamide, dimethylacetamide, dimethylsulfo~i-de, N-methyl-pyrrolidone, polyalkyl-ureas, such as tetramethyl-urea, and phosphoric acid amides, such a8 hexamethyl-phospho-ric acid-trisamide.
Also a fine division by grinding with salts or solvents may be advantageous, in which process in ths former case a dry grinding in vibration grinding mills is preferably effected and the salt is subsequently extracted with water, whereupon a wet grinding or a temperature treatment with solvents may optionally follow~
As salts there may be mentioned essentially alkali metal and alkaline earth metal salts of hydrohalic acids or of sul-furic acid, for example, ~odium or potassium chloride, as well as sodium or magnesium sulfate.
The sol~ents which may be used for the wet grinding pro-29 cess are essentially those mentioned above, for example, alcohols, acid amides or dimethyl sulfoxide.
The novel compounds represent valuable pigments which are used in printing inks, disper~ion dye~, varnishes, and which are suitable for pigm0nting high-molecular-weight organic material, for example, cellulose ethers and esters, polyamides, polyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resin~ or plastics, ~or example, aminoplasts, es-pecially urea and melamine formaldehyde resins~ alkyd resins, phenoplasts, polycarbonates, polyolefins, such a~ polyethylene or polypropylene, polystyrene, polyvinylchloride, polyacrylo-nitrile, polyacrylic acid esters, rubber, casein, siliconss and silicone resins. It is unimportant whether the above-men-tioned high-molecular-weight compounds are present as plaRtic masses, melts, or in the form of spinning solutions~ lacquers or printing paxtes. Depending on the application, it may be advantageous to use the novel pigments as toners or in the form of preparations.
The pigments of the invention have a high color intensity (tinctorial strength), a pure color shade, a good fastness to high temperatures in stove enamels and plastics, however, particularly an excellent fastness to overlacquering, to light and to weather, an extremely high fastness to light and to weathering, especially under the extreme conditions of an alu-minum metallic lacquering.
Z5 The following Examples ~erve to illu~trate the in~ention, the percentages being by weight, unless otherwise stated.
E X A M P L E 1:
17.2 Grams of 2-hydroxynaphthaldehyde-(1) are suspended 29 in 200 ml of ethanol, are heated to boiling temperature with ~ HOE 76~F 1~_K
21 . 5 g of the hydrochloride Or 4-carbomsthoxy-2-aminophenol and 10 g of anhydrous Podium acetate in 200 ml of ethanol, and the reaction mixture is maintained at this temperaturs for 1 hour. During the reaction time, nitrogen i6 led over the mix-ture. The orange-red precipitate of the aza~ethine i~ suction-filtered and washed with ethanol and w~ter. Yisld (after dry-ing)s 29.4 g (91.6 ~ of the theory)O
16 Grams of the azamethine thuo obtained are dissol~d in 150 ml of di~eth~lformamide and are treated for 3 ho~r~ at 100 C with 10 g of copper(II)acetate. Ths mi~ture is cooled to 50C~ i~ suction-filtered, and the yellow pigment is washed with ethanol and water. After drying7 17.8 g of the compound of the formula - -H3COCO ~ O-C~-are obtained.
--16.7 Grams of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydroxynaphthaldehyde-(1) are ~tirred for 5 minutes in 100 ml of water. Sub~equently 50 ml of 2N sodium hydro~ide solu-tion and 30 ml of a 40 % sodium hydrogen~ulfite solution are added, and the mixture ii stirred for 15 minutes at 95 C. The precipitate is filtered off with auction and is wa~hed with cold water. The press cake ia then stirred in 200 ml of water with an impeller.
Subsequently a solution of 27.S g of copper(II)sulfate pentahydrate in 100 ml of water and 50 g of concentrated ~ ~ ~ HOE 76/F ?~9 K
ammonia solution are added, the mixture i9 h0ated to 95 C and i9 maintainad at this -temperature for 1 hour. The pigmsnt i~
filtered off with suction, while hot, is washed with hot water and dried. 32.9 Grams of the compound Or Exampla 1 are ob-tained, A mixture of 16.7 g of 4-carbomethoxy-2-aminophenol, 17.2 g of 2-hydroxynaphthaldehyde-(1) and 200 ml of water is ground in a ball mill with 200 g of ceramic balls (diame~er of 10 mm) for 24 hours. Upon adding 25 g of 30dium acetate-trihydrate, 26 g of copper(II)sulfate pentahydrate and 100 ml of water, the mixture is continued to be ground for another 80 hDurs. The ground product obtained is wa~hed with water and dried.
Yield: 35.7 g of the yellow pigment of Example 1.
E X A M P L E 4:
16.7 Gram~ of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydroxynaphthaldehyde-(1) are dispersed with 400 ml of water by means of an impeller, and the disp0rsion is heated to a temperature in the range of from 95 to 98C and maintained at this temperature for 4 hours.
The product is suction-filtered, washed with hot water, and the moist press cake is stirred with 400 ml of water in which 26 g of copper(II)sulfate pentahydrate and 25 g of so-dium acetate are dissolved; thereafter the mixture is heatedto boiling temperature. After is has been heated to 100 C for g hours, the product i8 filtered off with Yuction, while hot, is washed with water and dried. 34.9 Grams of the yellow pig-29 ment of Example 1 are obtained.
~9~6~3~
E X_A M P L E 5:
18.1 Grams o~ 4-carbomethoxy-2-aminoaniso~ and 17.2 g of 2-hydroxynaphthaldehyde-(1) are heated i~ 400 ml of diethylene-glycol-monomethylether to 100C and are maintained at this temperature for 2 hours. During the reaction time, nitrogen is led over the mixture. 10 Grams Or copper(II)acetate dissolved in 100 ml of diglycol-monomethylether are added to the hot reaction mixture. Said mixture is heated to 150C and is main-tained at this temperature for 4 hours. After cooling, the yellow pigment is filtered off with suction, i6 thoroughly washed with ethanol and water and dried. 31.9 Grams of the compound of Example 1 are obtained.
E X A M
17.2 Grams of 2-hydroxy-1-naphthaldeh~de are suspended in 700 ml of n-propanol. Thereafter 24.3 g of the hydrochlori-de of 3-amino-4-hydroxybenzoic acid-n-propylester and 10 g of anhydrous sodium acatate are added. The mixture is rafluxed for 2 hours under a nitrogen atmo3phere. The yellow a~amethine of the formula n-C3H700 ~ OH HO ~
is suction-filtered, while hot, is washed with n-propanol and water and dried. Yield: 33 Grams.
17.45 Grams of the azamethine thus preparod are suspended in 250 ml of n-propanol. Subsequently 12.5 g of copper(II)-sulfate-pentahydrate dissolved in 30 ml of water are added dropwise within 15 minute~. The pH value is maintained at 5 by adding about 25 ml of a 4N sodium acetate solution. The ~OE 76/F 159 K
9~ 3.~
mixture is then h~ated under reflux for 3 hours under a nitro-gen atmosphere, ~ubsequently the product is suction-filtered, while hot, is washed with n-propanol and water and dried. Z3.3 Grams of the green pigment of the formula n-C3H700 are obtained.
L ~
17.2 Grams of 2-hydroxy-1-naphthaldahyde are su~pended in 500 ml of ethanol. Subsequently 23 g Or the hydrochloride of 3-amino-4-hydro~ybenzoic acid ethylaster and 10 g of an-hydrouq sodium acetate are added. The mixture is boiled under reflux for 2 hours in a nitrogen atmosphere. The precipitated orange azamethine of the formula C2H500C ~ OH HO ~
is filtered off with suction, while hot, is washed with etha-nol and water and dried. Yield: 28.4 Grams.
16.75 Grams of the azamethine thus prepared are su pended-in 250 ml of ethanol and are coppered, as has been described in Example 6. 24 Grams of the green pigment of the formula C2H500C ~ N ~ CH
Cu~
are obtained.
~ 8~ HOE 76/F 159 K
E X A M P_L E 8:
17.2 Grams of 2-hydroxy-1-naphthaldehyde are ~uapended in 500 ml of n-butanol, thereafter 25.75 g of the hydrochloride of 3-amino-4-hydroxybenzoic acid n-butyle~ter and 10 g of an-hydrous sodium acetate are added. Ihe mixture i~ heat~d to 90Cand i8 maint~ined at thi~ temperature for 2 hour~. Subsequently the product i9 filtered of~ with ~uction at about 70C, is washed with n-butanol and water and dried. 26.55 Grams of the ora~ge a~amethine of the ~ormuls n-C4HgOOC ~ N = CH
ara obtained.
18.15 Grams of the azamethine thu~ obtained are su~pended in 250 ml of n-butanol and are copp~red accordlng to the method describ~d in Example 6. 19.9~ Grams of the yellowi~h-green pig_ ment of the formula n-C4H900C ~ ~ Cu~
are obtained.
In a manner analogous to that described in Examples 6 through 8, the following pigments were obtained:
YOOC N = CH ~
Example Y Color Shade in book-prin-~ tin~s 9 H greenish-yellow H3C\
/ CH- greenish-yellow ~3c\
11 CH-CH - reddish-yellow CH3-CH2-CH- browni3h-yellow 13 3 2 2 2 2 reddish-yellow ~H3 14 CH -CH -CH-CH brownish-yellow 21.6 Grams of 2-hydroxy-1-naphthaldehyde-3-carboxylic acid ara re~luxed together with 11.4 g o~ Q-aminophenol in 300 ml of ethanol undar a nitrogen atmo~phere. Then the pre-cipitate of the azamethine is suction-filtered~ while hot, i~
washed with ethanol and water and dried.
10.2 Grams of the orange azamethine thus prepared are suspend~d in 300 ml of ethanol and are then heated to boiling temperature together with 7 g of copper acetate and maintained at $he boil for 3 hours. The pE value i~ maintained at 6.5 by adding 25 ml of 4N sodium acetat~ solution. The product is suction-filtered, while hot, is washed with ethanol and watur 1~9iiL6&~
and dried. Yield: 11.7 Gram~ of the greenish-yellow pigment of the formula Q
` Cu'O ~
COOH
~
21.6 Grams of Z-hydro~y-l-naphthaldehyde-6-carboxylic acid are suspend~d together wi$h 11. 4 g Or o-aminophenol in 300 ml of glacial acetic acid. The suspension is heated to the boiling point and is maintained at this temperature for
3 hours. The product is filtered off with suction, while hot, and is wa~hed with ~thanol and water. After drying, 30.5 g of the orange azamethine o~ the formula COOH
N = CH
OH HO
are obtained.
15.35 Grams of $he azaQethine thu~ prepared are dis~olved in 100 ml of dimathylformamid~ and are heated with 100 ml of diethylene-glycol-dimethylether and 15 g of copper acet~te to 100 C; then the mixture is maintained at thi~ temperature for 3 hour~. 16.7 Gram~ of the greeni3h~yellow pigment of the ~ormula ~ COOH
~ N - CH
are obtained.
E X A M P L E 1l.
If the proces~ i8 carried out according to the method - 13 _ described in Example 16, howevsr, while using 23.2 g Or the correspondlng methylester instead of the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid, 29.7 g of the orange azamethine of the formula N = CH ~ COOCH3 OH HO
are obtained.
20 Grams of the azamethine aro dissolved in a mixture o~
150 ml of dimethylformamide and 150 ml of diethylene-glycol-dimethylether and are heated with 13.5 g of copper(II)sulfate pentahydrate to 100C and maintained at this temperature for 3 hours. The product i9 then suction-filtered, while hot, is washed with ethanol and water and dried.
12 Grams o~ this crude pigment are ground for 10 hour~ to-gether with 50 g of sodium sulfate and 50 g of sodium acetate in a porcelain ball mill with 800 g of porcelain balls ha~ing a diameter of 10 m~. The contents of the mill are stirred in hot water, the greenish-yellow pigment is isolatad which is then washed until it is fres from Aalt and dried.
E X A_M P L E_ 18-If the proce~s is carried out as has been described inExample 17, however, while replacing the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid-methylester by 24.8 g Or 2-hydroxy-1-naphthaldehyde-3-carboxylic acid-ethylester, 31.5 g of the azamethine of the formula H HO ~
- ~4 _ :~"3~ 3 lL
are obtained.
15.4 Grams o~ the azamethine thus prepared are heated to 100C with 100 ml of dimethylformamide and 100 ml of diethylene-glycol-aimethylether and 9 g of copper acetate, and the mixture is maintained at this temperature for 3 hours. Subsequently the product is filtered off with suction, while hot, is washed with dimethylformamide, methanol and water and dried. 16.3 Grams of the yellowish-green azamethine-Cu complex compound of the formula ~ N--CH ~
are obtained.
According to the method described in Examples 15 through 18, the following further azamethine-Cu complex compounds are obtained:
~ 0~ 0 ~
Example Rl R2 Color Sh~de 19 COOCH3 H greenish-yellow C00-nC3H7 H greenish-yellow 21 COO-n~C~Hg H greenish-yellow 22 COOCH / 3 H yellow 23 COoCH-CH2CH3 H yellow 24 COO-n-C H H greenish-yellow CO0-CH2CH-CH2CH3 H yellow - 15a -~.
~3~
Example R1 R2 Color Shade 26 H COOC2H5 greenish-yellow 27 H COO-n-C3H7 greenish-yellow 28 H COO-n-C4Hg greenish-yellow 29 H COO-CH b H3 greenish-yellow H Coo-n-C5H11 greenish-yellow I~I3 31 H COOCH-CH2-CH3 yellow 32 H COOCH2CH-CH2-CH3 greeni8h~yellow E X A M P L E ~:
21.6 Gram~ of 2-hydroxy-1 naphthaldehyde-6-carboxylic acid are suspsnded with 21.5 g of the hydrochloride of 3-hydroxy-4-aminobenzoic acid-methylester in 300 ml of glacial acetic acid. The mixture is heated to the boiling psint and is maintained at this temperature for 3 hours. The product is filtered off with suction, while hot, is washed with ethanol and water. After drying, 35.Z g of the orange azamethine of the formula U3COOC ~ OH HO ~ CO~H
are obtained.
20 Grams of the azamethine are dissolved in a mixtura of 150 ml of dimethylformamide and 150 ml of diethylene-glycol-dimethylether and are heated to 100C with 15 g of copper(II)-sulfate pentahydrate, the mixture being maintained at this - 16 _ ~ ~ lg;~ OE ~6/F 159 X
temperature for 3 hours. Subseque~tly the product is sucti~n-filtered, while hot, is washed with ethanol and water and dried. Yield~ 23.5 Grams of the greenish-yellow pigment of the formula ~ COOH
~ Cu ' 12 Grams of this crude pigment are ground for 10 hours togsther with 50 g of sodium sulfate and 50 g of sodium aceta-te in a porcelain ball mill with 800 g of porcelain balls ha~ing a diameter o~ 10 ~m. The contents of the mill are then stirred in hot water, the greenish-yellow pigment is isolated, washed until it is saltfree and dried.
If the proces~ i~ carried out as ha~ been described in Example 33, however, while replaci~g the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid by 2-hydroxy-1-naphthaldehyde-3-carboxylic acid, 35.75 g of the a~amethine of the formula COOH
are obtained.
18.3 Grams of the azamethine thus prepared are heated to 100C with 100 ml of dimethylformamide and 100 ml of diethy-lene-glycol-dimethylether and 10 g of copper acetate, and the mixture is maintained at thi~ temperature for 3 hour~. Subse-quently the product is filtered off with suction, while hot, ~ HoE--~6/F 1~9 K
is wash~d with di~ethylfo~amide, ethanol and water and dried.
17.3 Grams of the yellowish-gr0en ~zamethine-Cu complex com-pound of the for~ula ~ 0~ 0 COO~
are obtained.
In a manner analogoua to that de3crib~d in Examples 33 and 34, the ~ollowing further a~amethine-Cu complex co~pounds are obtained~ .
~O Cu-O ~JR2 Example X R1 R2 Color Shade Cl COOH E reddish-brown 36 Cl H COOH yellow 37 NO2 COOH H reddish-yellow 38 NO2 H COOH reddish-yellow 39 Br COOH H greeni~h-yellow Br H COOH brownish-yellow 41 COOC2H5 COOH H yellowish-green 42 COOC2H5 H COOH green 43 CoOC3H7(n) COOH H brownish-green 44 COOC3H7(n) H COOH yellowish-green COOCH'' 3 COOH H brownish-green ~CH3 _ 18 -1~91~ HOE 76~F 159 K
Example X R1 R2 Color Shade 46 C CH ~ 3 H COOH yellowi~h-green c~3 47 COOC4Hg(n) COOH H yellowi~h green 48 COOC4Hg(~) H COOH bluish-green 49 CH3 COOH H reddi~h-yellow C~3 ~ COOH reddi~h-yellow 51 CF3 COOH H yellowi~h-green 52 CF3 H COOH yellow 53 OCH3 COOH H brownish-yellow 54 OCH3 H COOH reddish-yellow Cl COOCH3 H reddish-yellow 56 NO2 H COOCH3 reddish-yellow 57 CO2CH3 H COOCH3 yellow 58 COOH COOH H greenish-yellow 59 COOH H COOH greenish~yellow - 19 _
N = CH
OH HO
are obtained.
15.35 Grams of $he azaQethine thu~ prepared are dis~olved in 100 ml of dimathylformamid~ and are heated with 100 ml of diethylene-glycol-dimethylether and 15 g of copper acet~te to 100 C; then the mixture is maintained at thi~ temperature for 3 hour~. 16.7 Gram~ of the greeni3h~yellow pigment of the ~ormula ~ COOH
~ N - CH
are obtained.
E X A M P L E 1l.
If the proces~ i8 carried out according to the method - 13 _ described in Example 16, howevsr, while using 23.2 g Or the correspondlng methylester instead of the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid, 29.7 g of the orange azamethine of the formula N = CH ~ COOCH3 OH HO
are obtained.
20 Grams of the azamethine aro dissolved in a mixture o~
150 ml of dimethylformamide and 150 ml of diethylene-glycol-dimethylether and are heated with 13.5 g of copper(II)sulfate pentahydrate to 100C and maintained at this temperature for 3 hours. The product i9 then suction-filtered, while hot, is washed with ethanol and water and dried.
12 Grams o~ this crude pigment are ground for 10 hour~ to-gether with 50 g of sodium sulfate and 50 g of sodium acetate in a porcelain ball mill with 800 g of porcelain balls ha~ing a diameter of 10 m~. The contents of the mill are stirred in hot water, the greenish-yellow pigment is isolatad which is then washed until it is fres from Aalt and dried.
E X A_M P L E_ 18-If the proce~s is carried out as has been described inExample 17, however, while replacing the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid-methylester by 24.8 g Or 2-hydroxy-1-naphthaldehyde-3-carboxylic acid-ethylester, 31.5 g of the azamethine of the formula H HO ~
- ~4 _ :~"3~ 3 lL
are obtained.
15.4 Grams o~ the azamethine thus prepared are heated to 100C with 100 ml of dimethylformamide and 100 ml of diethylene-glycol-aimethylether and 9 g of copper acetate, and the mixture is maintained at this temperature for 3 hours. Subsequently the product is filtered off with suction, while hot, is washed with dimethylformamide, methanol and water and dried. 16.3 Grams of the yellowish-green azamethine-Cu complex compound of the formula ~ N--CH ~
are obtained.
According to the method described in Examples 15 through 18, the following further azamethine-Cu complex compounds are obtained:
~ 0~ 0 ~
Example Rl R2 Color Sh~de 19 COOCH3 H greenish-yellow C00-nC3H7 H greenish-yellow 21 COO-n~C~Hg H greenish-yellow 22 COOCH / 3 H yellow 23 COoCH-CH2CH3 H yellow 24 COO-n-C H H greenish-yellow CO0-CH2CH-CH2CH3 H yellow - 15a -~.
~3~
Example R1 R2 Color Shade 26 H COOC2H5 greenish-yellow 27 H COO-n-C3H7 greenish-yellow 28 H COO-n-C4Hg greenish-yellow 29 H COO-CH b H3 greenish-yellow H Coo-n-C5H11 greenish-yellow I~I3 31 H COOCH-CH2-CH3 yellow 32 H COOCH2CH-CH2-CH3 greeni8h~yellow E X A M P L E ~:
21.6 Gram~ of 2-hydroxy-1 naphthaldehyde-6-carboxylic acid are suspsnded with 21.5 g of the hydrochloride of 3-hydroxy-4-aminobenzoic acid-methylester in 300 ml of glacial acetic acid. The mixture is heated to the boiling psint and is maintained at this temperature for 3 hours. The product is filtered off with suction, while hot, is washed with ethanol and water. After drying, 35.Z g of the orange azamethine of the formula U3COOC ~ OH HO ~ CO~H
are obtained.
20 Grams of the azamethine are dissolved in a mixtura of 150 ml of dimethylformamide and 150 ml of diethylene-glycol-dimethylether and are heated to 100C with 15 g of copper(II)-sulfate pentahydrate, the mixture being maintained at this - 16 _ ~ ~ lg;~ OE ~6/F 159 X
temperature for 3 hours. Subseque~tly the product is sucti~n-filtered, while hot, is washed with ethanol and water and dried. Yield~ 23.5 Grams of the greenish-yellow pigment of the formula ~ COOH
~ Cu ' 12 Grams of this crude pigment are ground for 10 hours togsther with 50 g of sodium sulfate and 50 g of sodium aceta-te in a porcelain ball mill with 800 g of porcelain balls ha~ing a diameter o~ 10 ~m. The contents of the mill are then stirred in hot water, the greenish-yellow pigment is isolated, washed until it is saltfree and dried.
If the proces~ i~ carried out as ha~ been described in Example 33, however, while replaci~g the 2-hydroxy-1-naphthal-dehyde-6-carboxylic acid by 2-hydroxy-1-naphthaldehyde-3-carboxylic acid, 35.75 g of the a~amethine of the formula COOH
are obtained.
18.3 Grams of the azamethine thus prepared are heated to 100C with 100 ml of dimethylformamide and 100 ml of diethy-lene-glycol-dimethylether and 10 g of copper acetate, and the mixture is maintained at thi~ temperature for 3 hour~. Subse-quently the product is filtered off with suction, while hot, ~ HoE--~6/F 1~9 K
is wash~d with di~ethylfo~amide, ethanol and water and dried.
17.3 Grams of the yellowish-gr0en ~zamethine-Cu complex com-pound of the for~ula ~ 0~ 0 COO~
are obtained.
In a manner analogoua to that de3crib~d in Examples 33 and 34, the ~ollowing further a~amethine-Cu complex co~pounds are obtained~ .
~O Cu-O ~JR2 Example X R1 R2 Color Shade Cl COOH E reddish-brown 36 Cl H COOH yellow 37 NO2 COOH H reddish-yellow 38 NO2 H COOH reddish-yellow 39 Br COOH H greeni~h-yellow Br H COOH brownish-yellow 41 COOC2H5 COOH H yellowish-green 42 COOC2H5 H COOH green 43 CoOC3H7(n) COOH H brownish-green 44 COOC3H7(n) H COOH yellowish-green COOCH'' 3 COOH H brownish-green ~CH3 _ 18 -1~91~ HOE 76~F 159 K
Example X R1 R2 Color Shade 46 C CH ~ 3 H COOH yellowi~h-green c~3 47 COOC4Hg(n) COOH H yellowi~h green 48 COOC4Hg(~) H COOH bluish-green 49 CH3 COOH H reddi~h-yellow C~3 ~ COOH reddi~h-yellow 51 CF3 COOH H yellowi~h-green 52 CF3 H COOH yellow 53 OCH3 COOH H brownish-yellow 54 OCH3 H COOH reddish-yellow Cl COOCH3 H reddish-yellow 56 NO2 H COOCH3 reddish-yellow 57 CO2CH3 H COOCH3 yellow 58 COOH COOH H greenish-yellow 59 COOH H COOH greenish~yellow - 19 _
Claims (26)
1. A compound of the formula in which X is hydrogen, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, nitro, tri-fluoromethyl or a group of the formula -COOY , wherein Y is hydrogen or alkyl of 1 to 5 carbon atoms, R1 and R2 are hydrogen or one of the substituents R1 and R2 is hydrogen and the other is -COOY, with the proviso that at least one of the substituents X, R1 and R2 is -COOY.
2. A compound as defined in claim 1, wherein X is hydrogen or -COOY.
3. A compound as defined in claim 1, wherein X is -COOY with Y being alkyl of 1 to 5 carbon atoms and R1 and R2 are hydrogen.
4. A compound as defined in claim 1, wherein X is -COOY with Y being alkyl of 1 to 5 carbon atoms and one of the sub-stituents R1 and R2 is hydrogen and the other is -COOY with Y being hydrogen.
5. The compound as defined in claim 1, wherein X is carbo-methoxy and R1 and R2 are hydrogen.
6. The compound as defined in claim 1, wherein X is carbo-ethoxy and R1 and R2 are hydrogen.
7. The compound as defined in claim 1, wherein X is carbo-n-propoxy and R1 and R2 are hydrogen.
8. The compound as defined in claim 1, wherein X is carbo-n-butoxy and R1 and R2 are hydrogen.
9. The compound as defined in claim 1, wherein X and R1 are hydrogen and R2 is carboxy.
10. The compound as defined in claim 1, wherein X is carbo-methoxy, R1 is carboxy and R2 is hydrogen.
11. The compound as defined in claim 1, wherein X is carbo-ethoxy, R1 is carboxy and R2 is hydrogen,
12. The compound as defined in claim 1, wherein X is carbo-isopropoxy, R1 is carboxy and R2 is hydrogen.
13. The compound as defined in claim 1, wherein X is carbo-methoxy, R1 is hydrogen and R2 is carboxy.
14. The compound as defined in claim 1, wherein X is carbo-n-propoxy, R1 is hydrogen and R2 is carboxy.
15. Process for the preparation of a compound as defined in claim 1, which comprises metallizing an azamethine of the formula II
II
wherein R represents hydrogen or methyl and X, R1 and R2 are defined as in claim 1, with a copper-yielding compound.
II
wherein R represents hydrogen or methyl and X, R1 and R2 are defined as in claim 1, with a copper-yielding compound.
16. Process as claimed in claim 15, wherein the metallization is carried out at a temperature in the range of from 20 to 180°C.
17. Process as claimed in claim 15, which comprises metallizing an azamethine of the formula II, wherein R stands for hydrogen, at a temperature in the range of from 20 to 150°C.
18. Process as claimed in claim 17, wherein the temperature range is from 80 to 110°C.
19. Process as claimed in claim 17, wherein the metallization is carried out in water or in an aqueous-organic solvent.
20. Process as claimed in claim 15, which comprises metallizing an azamethine of the formula II, in which R represents methyl, at a temperature in the range of from 120 to 180°C.
21. Process as claimed in claim 20, wherein the metallization is carried out in an inert organic solvent.
22. Process as claimed in claim 21, wherein the solvent is an alcohol, a glycolether, glacial acetic acid, formamide or a dipolar aprotic solvent.
23. Process as claimed in claim 15, wherein the metallization is effected with a copper salt.
24. Process as claimed in claim 23, wherein the copper salt is a copper-(II) salt.
25. A process for pigmenting articles, which comprises incorporating into said article a compound as defined in claim 1.
26. A process as claimed in claim 25, wherein said article is a lacquer, a plastics material or a printing paste.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762631786 DE2631786C3 (en) | 1976-07-15 | 1976-07-15 | Azamethine-Cu complex, process for its preparation and its use |
| DEP2631786.2 | 1976-07-15 | ||
| DEP2653482.7 | 1976-11-25 | ||
| DE19762653482 DE2653482C2 (en) | 1976-11-25 | 1976-11-25 | Azamethine-Cu complexes, process for their preparation and their use |
| DE19762653483 DE2653483C2 (en) | 1976-11-25 | 1976-11-25 | Azamethine-Cu complexes, process for their preparation and their use |
| DE19762653481 DE2653481C2 (en) | 1976-11-25 | 1976-11-25 | Azamethine-Cu complexes, process for their preparation and their use |
| DEP2653481.6 | 1976-11-25 | ||
| DEP2653483.8 | 1976-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091681A true CA1091681A (en) | 1980-12-16 |
Family
ID=27432129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,755A Expired CA1091681A (en) | 1976-07-15 | 1977-07-14 | Azamethine-cu complex compounds, process for their preparation and their use |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS539832A (en) |
| AU (1) | AU508751B2 (en) |
| BR (1) | BR7704650A (en) |
| CA (1) | CA1091681A (en) |
| CH (1) | CH632525A5 (en) |
| DK (1) | DK319677A (en) |
| FR (1) | FR2358386A1 (en) |
| GB (1) | GB1532749A (en) |
| IT (1) | IT1082124B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW202231789A (en) * | 2021-02-03 | 2022-08-16 | 日商富士軟片股份有限公司 | Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound |
| WO2023228791A1 (en) * | 2022-05-25 | 2023-11-30 | 富士フイルム株式会社 | Coloring composition, film, optical filter, solid-state imaging element and image display device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700709A (en) * | 1970-05-20 | 1972-10-24 | Ciba Geigy Ag | Azomethine pigments |
| CH562301A5 (en) * | 1971-12-13 | 1975-05-30 | Ciba Geigy Ag |
-
1977
- 1977-07-12 CH CH863777A patent/CH632525A5/en not_active IP Right Cessation
- 1977-07-13 IT IT2571877A patent/IT1082124B/en active
- 1977-07-13 FR FR7721652A patent/FR2358386A1/en active Granted
- 1977-07-14 DK DK319677A patent/DK319677A/en unknown
- 1977-07-14 BR BR7704650A patent/BR7704650A/en unknown
- 1977-07-14 CA CA282,755A patent/CA1091681A/en not_active Expired
- 1977-07-14 AU AU27031/77A patent/AU508751B2/en not_active Expired
- 1977-07-14 JP JP8363577A patent/JPS539832A/en active Pending
- 1977-07-15 GB GB2979877A patent/GB1532749A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2703177A (en) | 1979-01-18 |
| JPS539832A (en) | 1978-01-28 |
| BR7704650A (en) | 1978-04-04 |
| FR2358386B1 (en) | 1983-12-09 |
| CH632525A5 (en) | 1982-10-15 |
| AU508751B2 (en) | 1980-04-03 |
| FR2358386A1 (en) | 1978-02-10 |
| IT1082124B (en) | 1985-05-21 |
| GB1532749A (en) | 1978-11-22 |
| DK319677A (en) | 1978-01-16 |
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