CA1155122A - 1:1 nickel complexes of isoindolinazines, process for their preparation and use - Google Patents
1:1 nickel complexes of isoindolinazines, process for their preparation and useInfo
- Publication number
- CA1155122A CA1155122A CA000372758A CA372758A CA1155122A CA 1155122 A CA1155122 A CA 1155122A CA 000372758 A CA000372758 A CA 000372758A CA 372758 A CA372758 A CA 372758A CA 1155122 A CA1155122 A CA 1155122A
- Authority
- CA
- Canada
- Prior art keywords
- group
- formula
- alkoxy
- alkylcarbamoyl
- chlorine
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C09B26/00—Hydrazone dyes; Triazene dyes
- C09B26/02—Hydrazone dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract:
1:1 nickel complexes of isoindolinazines of the formula 1) in which R' is a cyano, carbamoyl, benzylcarbamoyl or thiocarbamoyl group, an alkylcarbamoyl or alkylthiocar-bamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl group having 4 - 23 C or a group of the formula 2) or 3) in which Z is an oxygen or sulfur atom, V is an oxygen or sulfur atom or the radical -NH-, X1 is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl group having 2 - 22 C, or a phenoxy, phenylcarbamoyl or phenyl-sulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X2 is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1 - 4 C, R1 is an H or chlorine atom, a sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or phenylsulfamoyl group which is unsubstituted or substituted by halogen atoms or alkyl or alkoxy groups having 1 - 22 C, or an alkanoylamino group having 2 - 22 C, and, in the case where R1 and R2 are H or chlorine atoms, methyl groups or alkoxy groups having 1 - 4 C, R' is an alkylcarbamoyl or alkylthiocarbamoyl group having 7 - 22 C, an alkoxy-alkylcarbamoyl group having 7 - 23 C or a radical of the formula 2) in which X1 is an alkyl, alkoxy, alkyl-sulfamoyl or alkanoylamino radical having 6 - 22 C or an alkylcarbamoyl radical having 7 - 23 C.
The novel pigments colour plastic masses in intense, brilliant orange to red shades with good fastness properties.
1:1 nickel complexes of isoindolinazines of the formula 1) in which R' is a cyano, carbamoyl, benzylcarbamoyl or thiocarbamoyl group, an alkylcarbamoyl or alkylthiocar-bamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl group having 4 - 23 C or a group of the formula 2) or 3) in which Z is an oxygen or sulfur atom, V is an oxygen or sulfur atom or the radical -NH-, X1 is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl group having 2 - 22 C, or a phenoxy, phenylcarbamoyl or phenyl-sulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X2 is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1 - 4 C, R1 is an H or chlorine atom, a sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or phenylsulfamoyl group which is unsubstituted or substituted by halogen atoms or alkyl or alkoxy groups having 1 - 22 C, or an alkanoylamino group having 2 - 22 C, and, in the case where R1 and R2 are H or chlorine atoms, methyl groups or alkoxy groups having 1 - 4 C, R' is an alkylcarbamoyl or alkylthiocarbamoyl group having 7 - 22 C, an alkoxy-alkylcarbamoyl group having 7 - 23 C or a radical of the formula 2) in which X1 is an alkyl, alkoxy, alkyl-sulfamoyl or alkanoylamino radical having 6 - 22 C or an alkylcarbamoyl radical having 7 - 23 C.
The novel pigments colour plastic masses in intense, brilliant orange to red shades with good fastness properties.
Description
3 12760 +
1:1 Nickel complexes of isoindolinazines, process for their preparation and use -The invention relates to 1:1 nickel complexes of isoindolinazines of the formula N--NaC~ qEI
ao/ ~ \ ~ 1) NC/~R ' .
in which Ri is a cyano, carbamoyl, benzylcarbamoyl or thiocarbamoyl group, an alkylcarbamoyl or alkylthiocar-bamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl group having 4 - 23 C or a group of the formula C-N~ 2) or _. ~ ~ 3) in which Z is an oxygen or sulfur atom, V is an oxygen or sulfur atom or the radical -NH-, X1 is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, a.n alkyl, alkoxy or alkylsulfamoyl group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl group having 2 - 2.2 C, or a phenoxy, phenylcarbamoyl, .
55~z benzoylamino or phenylsulfamoyl group which is unsubstitu-ted or substituted by chlorine or bromine atoms or methyl groups, and X2 is an H, chlorine or bromine atom or an alkyl or alkoxy group having l - 4 C, R2 is an H or chlorine atom or a methoxycarbonyl group, Rl is a H or chlorine atom, a sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or phenylsulfamoyl group which is unsubstituted or substituted . by halogen, atoms or alkyl or alkoxy groups having l - 22 C, or an alkanoylamino group having 2 - 22 C, and, in the case where Rl and R2 are H or chlorine atoms, methyl groups or alkoxy groups having l - 4 C, R' is an alkylcarbamoyl or alkylthiocarbamoyl group having 7-22 C, an alkoxyalkylcarb-amoyl group having 7 - 23 C or a radical of the formula 2) in which Xl is an alkyl, alkoxy, alkylsulfamoyl or alkanoyl-amino radical having 6 - 22 C or an alkylcarbamoyl radical having 7 - 23 C.
Nickel complexes of the formula l) in which Rl is a radical of the formula -C-NH~ 1 2a) . O 2 are very fast pigments with a particularly pure colour shade and are therefore preferred. Xl and X2 are as defined above.
Nickel complexes of the ~ormula l) in which Rl is an alkylcarbamoyl or alkoxyal~ylcarbamoyl group are distl.n-guished by being particularly easlly accessible.
Preferred Ni complexes are those of the formula NC CONHQ
.... , .. ~
' :~
'.
., ' l~S5iZZ
in which Q is an alkyl or alkoxyalkyl group having 8 - 22 C
or a group of the formula . ~ ~ 3 in which Y3 is an alkoxy, alkylsulfamoyl or alkanoylamino group having 8-22 C.
The formulae 1) and 4) represent only one of the possible isomeric or tautomeric forms.
The nickel complexes according to the invention are obtained by a) treating an azine of the formula 1) with nickel donors or b) heating a hydrazone of the formula H 2 N - N =
HO ~N \. ~
in which Rl and R2 are as defined, with an isoindolinone of the formula .~ ~./ \
! 11 /NH 6) ~'b NC R' in which R' is as defined, in the presence of nickel donors, ln a polar organic solvent.
The azines of the formula 1) are obtained, for example, by the process described ln British Patent Speci-flcation 1,467,595, wherein a hydrazone of the formula 5) ls condensed with an imino-isoindoline of the formula . ~
:
..
lZZ
.
. I!
.~ \./
!~ ,1!, jN~ 7 -in which R' is as defined above.
The imino-isoindolines of the formula 7) are in turn obtained by condensing l-amino-3-imino-isoindolenine with the acetonitrile of the formula NCCH2R', in which R' is as defined. Examples are the acetonitriles men-tioned on page 7 of British Patent Specification 1,467,595 and also cyanoacetic acid hexylamide, 2-ethylhexylamide,
1:1 Nickel complexes of isoindolinazines, process for their preparation and use -The invention relates to 1:1 nickel complexes of isoindolinazines of the formula N--NaC~ qEI
ao/ ~ \ ~ 1) NC/~R ' .
in which Ri is a cyano, carbamoyl, benzylcarbamoyl or thiocarbamoyl group, an alkylcarbamoyl or alkylthiocar-bamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl group having 4 - 23 C or a group of the formula C-N~ 2) or _. ~ ~ 3) in which Z is an oxygen or sulfur atom, V is an oxygen or sulfur atom or the radical -NH-, X1 is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, a.n alkyl, alkoxy or alkylsulfamoyl group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl group having 2 - 2.2 C, or a phenoxy, phenylcarbamoyl, .
55~z benzoylamino or phenylsulfamoyl group which is unsubstitu-ted or substituted by chlorine or bromine atoms or methyl groups, and X2 is an H, chlorine or bromine atom or an alkyl or alkoxy group having l - 4 C, R2 is an H or chlorine atom or a methoxycarbonyl group, Rl is a H or chlorine atom, a sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or phenylsulfamoyl group which is unsubstituted or substituted . by halogen, atoms or alkyl or alkoxy groups having l - 22 C, or an alkanoylamino group having 2 - 22 C, and, in the case where Rl and R2 are H or chlorine atoms, methyl groups or alkoxy groups having l - 4 C, R' is an alkylcarbamoyl or alkylthiocarbamoyl group having 7-22 C, an alkoxyalkylcarb-amoyl group having 7 - 23 C or a radical of the formula 2) in which Xl is an alkyl, alkoxy, alkylsulfamoyl or alkanoyl-amino radical having 6 - 22 C or an alkylcarbamoyl radical having 7 - 23 C.
Nickel complexes of the formula l) in which Rl is a radical of the formula -C-NH~ 1 2a) . O 2 are very fast pigments with a particularly pure colour shade and are therefore preferred. Xl and X2 are as defined above.
Nickel complexes of the ~ormula l) in which Rl is an alkylcarbamoyl or alkoxyal~ylcarbamoyl group are distl.n-guished by being particularly easlly accessible.
Preferred Ni complexes are those of the formula NC CONHQ
.... , .. ~
' :~
'.
., ' l~S5iZZ
in which Q is an alkyl or alkoxyalkyl group having 8 - 22 C
or a group of the formula . ~ ~ 3 in which Y3 is an alkoxy, alkylsulfamoyl or alkanoylamino group having 8-22 C.
The formulae 1) and 4) represent only one of the possible isomeric or tautomeric forms.
The nickel complexes according to the invention are obtained by a) treating an azine of the formula 1) with nickel donors or b) heating a hydrazone of the formula H 2 N - N =
HO ~N \. ~
in which Rl and R2 are as defined, with an isoindolinone of the formula .~ ~./ \
! 11 /NH 6) ~'b NC R' in which R' is as defined, in the presence of nickel donors, ln a polar organic solvent.
The azines of the formula 1) are obtained, for example, by the process described ln British Patent Speci-flcation 1,467,595, wherein a hydrazone of the formula 5) ls condensed with an imino-isoindoline of the formula . ~
:
..
lZZ
.
. I!
.~ \./
!~ ,1!, jN~ 7 -in which R' is as defined above.
The imino-isoindolines of the formula 7) are in turn obtained by condensing l-amino-3-imino-isoindolenine with the acetonitrile of the formula NCCH2R', in which R' is as defined. Examples are the acetonitriles men-tioned on page 7 of British Patent Specification 1,467,595 and also cyanoacetic acid hexylamide, 2-ethylhexylamide,
2-ethylhexyloxypropylamide, dodecylamide or stearylamide, cyanoacetic acid octylthioamide, cyanoace-tic acid p-dodecyl-phenylamide, cyanoacetic acid p-octyloxy-phenylamide, cyanoacetic acid m-octylsulfamoyl-phenylamide, cyanoacetic acid p-stearylcarbamoyl-phenylamide, cyanoacetic acid p-stearoylami~o-phenylamide or dodecylsulfamoyl-acetonitrile.
However, the azines of the formula 1) can also be obtained by condensing an acetyl compound of the formula 9) with a hydrazonoisoindoline of the formula 8) N-N~72 i ~ 8) ~-'b N~ ~' in which R' is as defined above. The compounds of the formula 8) required for -this prupose are obtained by reacting imino-isoindolines of the formula 7) with hydrazine hydrate.
1: l5512Z
The hydrazones of the formula 5) are obtained by the known process of condensing the quinoline of the formula : . OH
C~3Co\.~
! '! ! 9) HO~ ~ \-~
in which R1 and R2 are as defined, with hydrazine hydrate.
Examples are the following quinolines: 2,4-dihy-droxy-3-acetyl-7-carbomethoxy-quinoline, 2,4-dihydroxy-3-acetyl-7-carbamoyl-quinoline, 2,4-dihydroxy-3-acetyl-7-methylcarbamoyl-quinoline, 2,4-dihydroxy_3-acetyl-6- or -7-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-phenoxy-8-chloroquinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methyl-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methoxy-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-benzoyl-amino-quinoline, 2,4-dihydroxy-3-acetyl-7-phenylcarbamoyl-quinoline~ 2,4-dihydroxy-3-acetyl-6- or -7-phenylsulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-phenylsul-famoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-benzo~-amino-quinoline, 2,4-dihydroxy-3-acetyl-6-methoxy-7-ben-zoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-benzoylamino-quinoline~ 2,4-dihydroxy-3-acetyl-6-p-methyl-benzoyla~ino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methoxybenzoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-or -7-acetylamino-quinoline, Z,4-dlhydroxy-3-acetyl-6- or -7-stearoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-(2'-ethyl-hexanoyl)-amino-quinoline, 2,4-dihydroxy-3-acetyl-6-or -7-p-toluenesulfonylamino-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-nitro-quinoline, 2,4-dihydroxy-3-acetyl-6-p-dodecylphenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-phenylthio-quinoline, 2,4-dihydroxy-3-acetyl-6-sulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methylsulfamoyl-quin-oline, 2,4-dihydroxy-3-acetyl-6-phenylsulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-7-stearylcarbamoyl-quinoline, , . . . .
- . ., -- - .
1~L55i2Z
2,4-dihydroxy-3-acetyl-7-(2'-ethylhexyl)-carbamoyl-quinoline and 2,4-dihydroxy-3-acetyl-7-phenoxycarbonyl-quinoline.
The nickel donors used are preferably nickel formates, acetates or stearates. The reactions take place in a polar solvent, in particular one of a hydro-philic nature, for example an amide, such as dimethyl-formamide, formamide, dimethylacetamide or N-methyl-pyrrolidone, or also dimethyl sulfoxide, acetonitrile or an alcohol, for example ethylcellosolve. It is also possible to use a mixture of polar solvents.
m e reaction temperature is advantageously between 100 and 200C.
m e metal complex obtained is isolated in the customary manner by filtration. The material on the suction filter is washed thoroughly with solvent. It is obtained in good yield and purity and can be used without further purification, in finely divided form, for colour-ing high-molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, acetylcellulose and nitrocellulose, polyamides, polyurethanes or polyesters, and natural resins or synthetic resins, for example amino-plasts, in particular urea/formaldehyde and melamine/
formaldehyde resins, alkyd resins, phenoplasts, polycarbon-ates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile and poly-acrylic acid esters, thermoplastic or curable acrylic resins, rubber, casein, silicone and silicone resins, individually or in mi~tures, The high-molecular com-pounds mentioned can be in the form of plastic masses or melts or in the form of spinning solutions, surface coat-ings or printing inks. Depending on the intended use, it proves advantageous to use the novel pigments as toners or in the form of preparations.
The pigment can be employed in the form in which it is obtained in the synthesis, or in a lightly ground form, in which case it produces opaque final colourations.
.
-- --: ;' ' ~ . , 1~S~l2Z
However, it can also be subjected tomoreintensive grinding, in which case transparent final colourations, for example intensely coloured metallic-effect coatings, are obtained.
Pastes of the pigments in surface coatings are distinguished by favourable flow properties.
The colourations obtained, for example in plastics, fibres and surface coatings, are distinguished by colour intensity, high purity of colour shade, good dis-persion of the pigment and good fastness to overcoating, migration, heat, light and weather, and also by a good gloss.
Those pigments which possess an alkyl radical having 6 or more C atoms in the radicals R' or R2 of the formula 1) have a particularly high tinctorial strength and easy dispersibility, especially in plastics. In addition, final colourations of these pigments already have an unexpectedly high transpar~ncy in the crude state in plastics.
In the following examples, percentages are by weight and degrees a~e degrees centigrade. In each case, only one of the possible isomeric and tautomeric forms is indicated.
Example 1: A suspension of 24.8 g (0,09 mol) of the hydrazone of 3-acetyl-7-carbomethoxy-2,4-dihydroxyquinol-ine and 23.6 g (0.0945 mol) of nickel acetate tetrahydrate in 1,400 ml of N-methylpyrrolidone is warmed to 60 and treated with 26 g (0.09 mol) of 1-(cyano-N-phenylcarba-moylmethylene)-isoindolin-3-one, The mixture ls heated to 150 in the course of one hour and stirred for 3 hours at this temperature. The product precipitates out in the form of orange needles. It is filtered off at 100, washed thoroughly with N-methylpyrrolidone, methanol and acetone and dried at 80 in vacuo. ~ weight of 38.1 g of the metal co~plex of the composition C30H20N6NiO5 is obtained, which still contains 2% of water.
, .
' : ' , . ~
::
llSS12Z
The microanalYsis:
C H N Ni % calculated 58.54 3.50 13.65 9.45 % found 58.4 3.6 14.0 9.79 confirms the formula:
oa c~3 COOC ~ NC CON~
Only one of the possible tautomeric formulae has been considered.
, , Exampl~ _51: Equally valuable pigments;are obtained in an analogous procedure by condensing a hydrazone of the formula o~ j 3 - ~H2 ~-/ ~ ~0~ ~
in which R1 and R2 are as defined in columns 2 and 3 of Table 1 below, with an isoindolinone of the fo~mula o NC~ ~CONH-~
in which X1 and X2 are as defined in columns 4 and 5, in the presence of nickel acetate. When finely dispersed in plastics, sheets and surface coatings, the 1:1 nickel complexes produce very brilliant and fast final colour-ations, the colour shade of which is represented in column 5.
..
. .
: ' ~ . ' . ' ' , ~
' :
.
' 1:l551ZZ
_ g _ Table 1 .
ample¦RI l R2 xl ¦ shade .
2 H -COOCH3 2-Cl H orange
However, the azines of the formula 1) can also be obtained by condensing an acetyl compound of the formula 9) with a hydrazonoisoindoline of the formula 8) N-N~72 i ~ 8) ~-'b N~ ~' in which R' is as defined above. The compounds of the formula 8) required for -this prupose are obtained by reacting imino-isoindolines of the formula 7) with hydrazine hydrate.
1: l5512Z
The hydrazones of the formula 5) are obtained by the known process of condensing the quinoline of the formula : . OH
C~3Co\.~
! '! ! 9) HO~ ~ \-~
in which R1 and R2 are as defined, with hydrazine hydrate.
Examples are the following quinolines: 2,4-dihy-droxy-3-acetyl-7-carbomethoxy-quinoline, 2,4-dihydroxy-3-acetyl-7-carbamoyl-quinoline, 2,4-dihydroxy-3-acetyl-7-methylcarbamoyl-quinoline, 2,4-dihydroxy_3-acetyl-6- or -7-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-phenoxy-8-chloroquinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methyl-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methoxy-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-benzoyl-amino-quinoline, 2,4-dihydroxy-3-acetyl-7-phenylcarbamoyl-quinoline~ 2,4-dihydroxy-3-acetyl-6- or -7-phenylsulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-phenylsul-famoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-benzo~-amino-quinoline, 2,4-dihydroxy-3-acetyl-6-methoxy-7-ben-zoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-benzoylamino-quinoline~ 2,4-dihydroxy-3-acetyl-6-p-methyl-benzoyla~ino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methoxybenzoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-or -7-acetylamino-quinoline, Z,4-dlhydroxy-3-acetyl-6- or -7-stearoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-(2'-ethyl-hexanoyl)-amino-quinoline, 2,4-dihydroxy-3-acetyl-6-or -7-p-toluenesulfonylamino-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-nitro-quinoline, 2,4-dihydroxy-3-acetyl-6-p-dodecylphenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-phenylthio-quinoline, 2,4-dihydroxy-3-acetyl-6-sulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methylsulfamoyl-quin-oline, 2,4-dihydroxy-3-acetyl-6-phenylsulfamoyl-quinoline, 2,4-dihydroxy-3-acetyl-7-stearylcarbamoyl-quinoline, , . . . .
- . ., -- - .
1~L55i2Z
2,4-dihydroxy-3-acetyl-7-(2'-ethylhexyl)-carbamoyl-quinoline and 2,4-dihydroxy-3-acetyl-7-phenoxycarbonyl-quinoline.
The nickel donors used are preferably nickel formates, acetates or stearates. The reactions take place in a polar solvent, in particular one of a hydro-philic nature, for example an amide, such as dimethyl-formamide, formamide, dimethylacetamide or N-methyl-pyrrolidone, or also dimethyl sulfoxide, acetonitrile or an alcohol, for example ethylcellosolve. It is also possible to use a mixture of polar solvents.
m e reaction temperature is advantageously between 100 and 200C.
m e metal complex obtained is isolated in the customary manner by filtration. The material on the suction filter is washed thoroughly with solvent. It is obtained in good yield and purity and can be used without further purification, in finely divided form, for colour-ing high-molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, acetylcellulose and nitrocellulose, polyamides, polyurethanes or polyesters, and natural resins or synthetic resins, for example amino-plasts, in particular urea/formaldehyde and melamine/
formaldehyde resins, alkyd resins, phenoplasts, polycarbon-ates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile and poly-acrylic acid esters, thermoplastic or curable acrylic resins, rubber, casein, silicone and silicone resins, individually or in mi~tures, The high-molecular com-pounds mentioned can be in the form of plastic masses or melts or in the form of spinning solutions, surface coat-ings or printing inks. Depending on the intended use, it proves advantageous to use the novel pigments as toners or in the form of preparations.
The pigment can be employed in the form in which it is obtained in the synthesis, or in a lightly ground form, in which case it produces opaque final colourations.
.
-- --: ;' ' ~ . , 1~S~l2Z
However, it can also be subjected tomoreintensive grinding, in which case transparent final colourations, for example intensely coloured metallic-effect coatings, are obtained.
Pastes of the pigments in surface coatings are distinguished by favourable flow properties.
The colourations obtained, for example in plastics, fibres and surface coatings, are distinguished by colour intensity, high purity of colour shade, good dis-persion of the pigment and good fastness to overcoating, migration, heat, light and weather, and also by a good gloss.
Those pigments which possess an alkyl radical having 6 or more C atoms in the radicals R' or R2 of the formula 1) have a particularly high tinctorial strength and easy dispersibility, especially in plastics. In addition, final colourations of these pigments already have an unexpectedly high transpar~ncy in the crude state in plastics.
In the following examples, percentages are by weight and degrees a~e degrees centigrade. In each case, only one of the possible isomeric and tautomeric forms is indicated.
Example 1: A suspension of 24.8 g (0,09 mol) of the hydrazone of 3-acetyl-7-carbomethoxy-2,4-dihydroxyquinol-ine and 23.6 g (0.0945 mol) of nickel acetate tetrahydrate in 1,400 ml of N-methylpyrrolidone is warmed to 60 and treated with 26 g (0.09 mol) of 1-(cyano-N-phenylcarba-moylmethylene)-isoindolin-3-one, The mixture ls heated to 150 in the course of one hour and stirred for 3 hours at this temperature. The product precipitates out in the form of orange needles. It is filtered off at 100, washed thoroughly with N-methylpyrrolidone, methanol and acetone and dried at 80 in vacuo. ~ weight of 38.1 g of the metal co~plex of the composition C30H20N6NiO5 is obtained, which still contains 2% of water.
, .
' : ' , . ~
::
llSS12Z
The microanalYsis:
C H N Ni % calculated 58.54 3.50 13.65 9.45 % found 58.4 3.6 14.0 9.79 confirms the formula:
oa c~3 COOC ~ NC CON~
Only one of the possible tautomeric formulae has been considered.
, , Exampl~ _51: Equally valuable pigments;are obtained in an analogous procedure by condensing a hydrazone of the formula o~ j 3 - ~H2 ~-/ ~ ~0~ ~
in which R1 and R2 are as defined in columns 2 and 3 of Table 1 below, with an isoindolinone of the fo~mula o NC~ ~CONH-~
in which X1 and X2 are as defined in columns 4 and 5, in the presence of nickel acetate. When finely dispersed in plastics, sheets and surface coatings, the 1:1 nickel complexes produce very brilliant and fast final colour-ations, the colour shade of which is represented in column 5.
..
. .
: ' ~ . ' . ' ' , ~
' :
.
' 1:l551ZZ
_ g _ Table 1 .
ample¦RI l R2 xl ¦ shade .
2 H -COOCH3 2-Cl H orange
3 H do 3-Cl a orange-red
4 H do 4-Cl H ditto H do 2-Methyl H ditto 6 H do 3-~ethyl H ditto 7 H to 4-~ethyl H red 8 H do 2-MethoxyH red 9 H do 4-OCX3 . H orange-red H to 4-Phenylazo H red 11 H do 4-Benzoylamino H . red 12 H do 4-Car~amoyl H red 13 a do 3-CF3 H orange 14 H to 4-N02 H ditto .
15. H do 4-Phenoxy H red 16 H do 2-Cl 4-Cl orange 17 H do 2-Cl 5-Cl ~ ditto 18 H: do 3-Cl 4-Cl ditto 19 H do 3-Methyl 4-Methyl orange-red H do do 5-~Iethyl red 21 H -COOCH3 3-Cl 4-C~3 orange 22 H to 2-~ethoxy 5-OCH3 orange-red 23 H to 4-Sulfamoyl H r~d 24 H do 4-Carbamoyl 3-Cl orange-red 8 to 4-Dimethyl- H ditto maleinimido 26 H do 4-p-Methoxy- 2 ~ s-di-oca3 red phenoxy 27 H do 4-Phthal- H orange-red imido 28 H to 4-o-Methyl- 2-CH3 ditto . :. _ phenylazo , :.
-'' ,. . .. .
~15512 _ 10 -Table l = Rl R2 ~ --- ~ -- Colour No. _ . _ . .
29 H -COOCH 4-p-Aceeyl- a orange-red 3 aminophenyl-carbamoyl H do 2-Cl S-CF3 ditto 31 yl~amino H 2-Cl H orange-red 32 do H 3-Cl H red 33 do H 4-Cl H red 34 do H 4-oCH3 H red do a 4-Carbamoyl H red 36 do H 3-CF3 H orange-red 37 do H 4-Acetyl- H red amino 38 do H 4-CH3 H red 39 H -COOCH3 3-CF3 4-Cl red H do 3-CF3 6-Cl red 41 Phenoxy H H H red 42 do H 2-Cl H orange-red 43 do H 3-Cl a ditto 44 do H 4-Cl H red do 3-CF3 ~1 orange-red 46 do 4-CH3 H red 47 p-Meth- 2-Cl H red phenoxy 48 do 3-Cl H red 49 do 4-Cl H red do 3-CF3 H red 51 do amino H red ~.. . . . . _ 11~5~22 Example 52: 1.52 g (0.007 mol) of 2,4-dihydroxy-3-acetylquinoline-hydrazone and 1.84 g (0.0074 mol) of nickel acetate tetrahydrate are warmed to 60 in 80 ml of N-methylpyrrolidone. The brown suspension is treated with 4.0 g (0.007 mol) of 1-(cyano-N-p-stearoylamino-phenyl-carbamoylmethylene)-isoindolin-3-one, heated to 155-160 and stirred for 4 hours. During this process, the product precipitates out as red needles. It is isol-ated by filtration at 100, washed with dimethylformamide, methanol and acetone and dried at 80 in vacuo. 2.8 g of the metal complex of the formula i.l/~i ' , .
~ \CON~ ~COC17~35 are obtained.
Microanalysis:
C H N Ni % calculated 66.83 6.46 11.86 7.10 % found ~ 66.8 6.6 11.6 6.83 The product colours surface-coatings, sheets and plastics in strong bluish red shades with excellent fast-ness to light, weather, heat and migration.
Examples 53-64: Equally valuable pigments are obtained starting from a hydrazone of the formula ~ 2 R ~ ~t~ ~ \OH
in which R1 to R3 are as defined in columns 2-4 of Table 2, and an isoindolinone of the formula ., 1~55~2 .~-\./-\
.~ \./
N~ CONH-Q
in which Q is as defined in column 5, following an analo-gous procedure to that of Example 52. The colour shade of final colourations in PVC is represented in column 6.
1Y ~5~ZZ
Table 2 ~ R3 _ Cohouder ¦
, 53 H H H -~CH2) l7Ca3 orange~ed 54 H H H 2 t 2 ;)(CX2)3C~3 orang~red Cl H Cl -(CX2)17CH3 orange 56 H COOCH3 ~ -(CH2)17CH3 orange ;7 CH3 H H ~ Hco(cH2)l6cH3 reldiSh 8 ~:1 a C1 ditto ditto 9 a COOCH3 H ditto ditto ¦;Q ¦H ~ --(CIIz 11C~I3 ~ed ~1 H El EI \ , / 8al7 red . So2Na(cH2)7cH3 3 H H H --~ C0OC H red 64 H H H \ /--CONHC18H37 ~ed .~
i~5~1Z2 Example 65: 2.75 g (0.01 mol) of the hydrazone of 3-acetyl- 7-carbomethoxy-2,4-dihydroxyquinoline and 2.6 g of nickel acetate tetrahydrate (0.0105 mol) are suspended in 60 ml of N-methylpyrrolidone and the suspension is warmed to 60. 3.03 g (0.01 mol) of 1-(cyano-N-benzyl-carbamoyl-methylene)-isoindolin-3-one are added to the brown suspension. The mixture is warmed to 155 and stirred for 3 hours. After cooling to 100, it is filtered and the material on the filter is washed with N-methylpyrrolidone and methanol. By drying at 80 in vacuo, 2.7 g of a red pigment of the composition C31H22N6Ni5 are obtained.
Microanalysis:
C H N Ni % calculated 60.32 3.59 13.62 9.51 % found 59 9 3.6 13.8 9.50 In PVC sheets and stoving lacquers, a sample of the pig-ment converted into a fine form by grinding with salt produces intense, brilliant orange final colourations with very good fastness to migration, light and weather.
Exanrple 66: An equally valuabIe pigment is obtained from (cyano-N-methylcarbamoylmethylene)-isoindolin-3-one, following the procedure indicated in Example 65.
Example 67: 25 parts of the pigment prepared according to Example 1, 100 parts of finely ground sodi~m chloride and 30 parts of diacetone-alcohol are initially intro-duced into a laboratory kneader with a capacity of 250 parts by volume. The mixture ls kneaded for 5 hours, with cooling, and then inl;roduced into 4,000 parts by volume of water. The sodium chloride and diacetone-alcohol dissolve and the pigment precipitates out. The suspension is filtered and the material on the suction filter is washed thoroughly with water and dried in a vacuum drying cabinet at 80.
Example 68: 56.5 g (0.5 mol) of ethyl cyanoacetate and 64.6 g (0.5 mol) of 2-ethylhexylamine are stirred for l hour at 130-140 and the ethanol Iiberated is distilled ., : ~ ' ,'~ .
~L~lr55~ 2Z
- 15 ~
off. 61.6 g of the acid amide of the following formula:
2 2IH(CH2)3CH3 ' CllH20N2 are obtained from the reaction mixture by distillation at 130/0.1 mm Hg.
calcuiated 67.3 ~0 C 10.3 % H 14.3 % N
found 67.~ % C 10.4 % H 14.1 % N
19.6 g (0.1 mol) of this acid amide, 18.2 g (0.1 mol) of 1-imino-isoindolin-3-one hydrochloride and 11.1 g (0.135 mol) of sodium aceta-te are stirred in 100 ml of ethylcellosolve for 4 hours at 110. This suspension is left to cool, with stirring, and diluted with 100 ml of isopropyl alcohol. By filtration, washing with iso-propyl alcohol and water and drying, 19.5 g of a product melting at 121 to 122 are obtained, the microanalysis of which agrees with the methine-isoindolinone of the follow-ing formula:
o , jNH 19 23 3 2 NC c0NHCH2CH(CH2)3CH3 calculated 70.1 % C 7.1 % H 12.9 % N
found 69.7 % C 7.1 % H 13.3 % N
1.52 g (0.007 mol) of the hydrazone obtained by reacting 3-acetyl-2,4-dihydroxy-quinoline and hydrazine hydrate in alcohol, and 1 84 g (0.00735 mol) of nickel acetate tetrahydrate are stirred in 60 ml of N-methylpyrrolidone for 1/2 hour at 60. After the addition of 2.28 g (0.007 mol) of the above methine-isoindolinone, the .. .
~5S~Z2 - 16 ~
mixture is heated to 150 to 155 and stirred for 3 hours.
The orange-coloured suspension is cooled to 70, diluted with 50 ml of methanol and left to cool, with stirring.
The product is filtered off, washed with methanol and dried. Weight: 2.0 g. The product is the compound of the following formula or of a tautomeric formula:
N~ CONHCH2CH(CH2)3cH3 C30H30N6Ni3 calculated 62.0 % C 5.2 % H 14.5 % N 10.1 ~ Ni found 62.0 % C 5.4 % H 14.7 % N 9.9 % Ni In PVC sheets and surface coatings, the product produces strong orange final colourations with very good fastness properties.
Example 69: 1.52 g (0.007 mol) of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 1.84 g (0.00735 mol) of nickel acetate tetrahydrate are stirred in 60 ml of N-methylpyrrolidone for 1/2 hour at 60. After the addition of 2.93 g (0.007 mol) of 1-(cyano-N-p-n-octyl-oxyphenylcarbamoyl-methylene)-isoindolin-3-one, the mixture is heated and stirred for 3 hours at 150 to 155.
The product of the following formula (only one of the possible tautomeric forms has been considered) precipi-tates out as red needles. It is filtered off at 100, washed with dimethylformamide and methanol and dried at 80 in vacuo. Weight: 2.6 g.
l~S5 ,~X
- 17 ~
OH C~3 O ~.~/ ; 36 34N6Nio4 ~-~ NC/ CONH--\ /- C8H17 (n) calculated 64.2 ~ C 5.1 % H 12.5 % N 8.7 % Ni found 64.6 % C 5.4 % H 12.7 % N 8.6 % Ni When finely dispersed, the product colours plastics and surface coatings in strong, pure bluish red shades with excellent fastness to migration and light.
Ex~es70-92: Equally valuable pigments are obtained, following an analogous procedure, by reacting a hydrazone of the formula R2 T '~ OH
in which R1 to R3 are as defined in columns 2 to 4 of Table 3, in the presence of a nickel salt, with an iso-indolinone of the formula .~ \./
! I!
NC/ CON~-Q
in which Q is as defined in column 5. The colour shade of final colourations in polyvinyl chloride is indicated in column 6.
~55~2Z
Table 3 Ex- _ _ 2 R ¦ Q Colour ample 3 ! shade H -COOCH3 H -CH2CHtCH2)3CH3 orange 71 H H H -(CH2)30cH2 Cll(CH2) 3 orange 72 H -COOCH3 H ditto orange 73 H -COOCH3 H \ ~ C8Hl7(n) red 74 Cl H Cl \ / red . 2 8 17 .
H -COOCH3 a ditto orange 76 H H H ~~ COCH(CH2)3CH~ red 77 H -COOCX3 H dit~o red 78 -~ HCO--~ ~- H H H orange I ~
79 -NHCO--~ ~- H H -CH2CH(CE12)3CH3 orange . C2H5 ditto H H -(CH2)17CH3 orange 81 ditto H . H -(cH2)3ocH2-cH(cH2)3cH3 orarge . . . _ _. . . __ _ C2H5 .. ___ 11~5~ zz - 19 _ (continuation) _ _ . .. ~
~pi~ Rl R2 --R3-- Colour No shade . . __ ~_ .. .. ... ... _ 82 H -COOCH3 H H range 83 -NHCOCH3~ H H H range .
84 -NHCOCH3 I H 2)17 3 range 85 -NHCOCH~ H H ~ .. red 86 -NHCOC13 H H ~~ CH - red 87 -S2NH2 H ~ H orange 88 -52N82 H H Cl range 89 -52NH2 H I ~ ~--C1 red H :H ~-OC13 -(CH2~17C13 red 91 H I -OCH3: ~ \ /- C8H17(n) red 92 H H -OCH3 \ ./ o~ange . 2 8 17( ) . .
~ , .
.
': '. : ~ , ~, .
1~55 Example 9~: If the procedure described in Example 65 is repeated, except that 2.85 g of 1-(cyano-benzimidazolyl-methylene)-isoindolin-3-one are used in place of the 1-(cyano-N-benzylcarbamoyl-methylene)-isoindolin-3-one, a very fast, orange pigment is likewise obtained.
Example 94: Following an analogous procedure to that of Example 69, a pigment which colours plastics and surface coatings in fast, bluish red shades is obtained from 1.92 g of 3-acetyl-6-acetylamino-2,4-dihydroxy-quinoline-hydrazone, 1.84 g of nickel acetate tetrahydrate and 1.6 g of 1-(cyano-thiocarbamoyl-methylene)-isoindolin-3-one.
Example_25: 65 parts of stabilised polyvinyl chloride, 35 parts of dio~tyl phthalate and 0.2 part of the pigment obtained according to Example 67 are stirred with one another and then worked on a twin-roll mill for 7 minutes at 140. An orange-red _coloured sheet with very good fastness to light and migration is obtained.
Example 96: 10 g of titanium dioxide ~nd 2 g of the pig-ment prepared according to Example 1 are ground with ~8g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine/formaldehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene, for 48 hours in a ball mill.
If this surface coating is sprayed onto analumin-ium foil, predried for 30 minutes at room temperature and then stoved for 30 minutes at 120, a red coating is obtained, which has good colour intensity and is distin-guished by a very good fastness to overcoa~ing, light and weather.
Example 97: 4 parts of the finely divided pigment accord-ing to Example 67 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture of aromatic hydrocarbons), 15 parts of butyl acetate, 5 parts of Exkin II (ketoxime-based levelling agent), 25 parts of methyl isobutyl ketone and 5 parts of silicone oil (1% in Solvesso 150).
After complete fine dispersion has been reached ~L~l551~Z
_ 21 -(in about 15-60 minu-tes, depending on the type of stirring), the binders are added, i.e. 48.3 parts of . Baycryl L 530 (acrylic resin) (51% in xylene/butanol 3:1) and 27.7 parts of Maprenal TTX (melamine resin) (55% in butanol).
After a short period of homogenisation, the sur-face coating is applied by customary methods, such as spraying and dipping or, especially for the continuous coating of metal sheets, by the "coil-coating" process, and stoved (stoving: 30 minutes, 130). The red coatings obtained are distinguished by very good level-ling, high gloss and excellent fine dispersion of the pigment, and also by excellent fastness to weather.
Example 98: If the procedure described in Example 76 is repeated, except that 2.78 parts of Staybelite Resin (HERCULES) are added to the kneading mixture, a pigment containing 10% of resin is obtained, which is distin-guished by being easier to incorporate and by better dispersibility.
15. H do 4-Phenoxy H red 16 H do 2-Cl 4-Cl orange 17 H do 2-Cl 5-Cl ~ ditto 18 H: do 3-Cl 4-Cl ditto 19 H do 3-Methyl 4-Methyl orange-red H do do 5-~Iethyl red 21 H -COOCH3 3-Cl 4-C~3 orange 22 H to 2-~ethoxy 5-OCH3 orange-red 23 H to 4-Sulfamoyl H r~d 24 H do 4-Carbamoyl 3-Cl orange-red 8 to 4-Dimethyl- H ditto maleinimido 26 H do 4-p-Methoxy- 2 ~ s-di-oca3 red phenoxy 27 H do 4-Phthal- H orange-red imido 28 H to 4-o-Methyl- 2-CH3 ditto . :. _ phenylazo , :.
-'' ,. . .. .
~15512 _ 10 -Table l = Rl R2 ~ --- ~ -- Colour No. _ . _ . .
29 H -COOCH 4-p-Aceeyl- a orange-red 3 aminophenyl-carbamoyl H do 2-Cl S-CF3 ditto 31 yl~amino H 2-Cl H orange-red 32 do H 3-Cl H red 33 do H 4-Cl H red 34 do H 4-oCH3 H red do a 4-Carbamoyl H red 36 do H 3-CF3 H orange-red 37 do H 4-Acetyl- H red amino 38 do H 4-CH3 H red 39 H -COOCH3 3-CF3 4-Cl red H do 3-CF3 6-Cl red 41 Phenoxy H H H red 42 do H 2-Cl H orange-red 43 do H 3-Cl a ditto 44 do H 4-Cl H red do 3-CF3 ~1 orange-red 46 do 4-CH3 H red 47 p-Meth- 2-Cl H red phenoxy 48 do 3-Cl H red 49 do 4-Cl H red do 3-CF3 H red 51 do amino H red ~.. . . . . _ 11~5~22 Example 52: 1.52 g (0.007 mol) of 2,4-dihydroxy-3-acetylquinoline-hydrazone and 1.84 g (0.0074 mol) of nickel acetate tetrahydrate are warmed to 60 in 80 ml of N-methylpyrrolidone. The brown suspension is treated with 4.0 g (0.007 mol) of 1-(cyano-N-p-stearoylamino-phenyl-carbamoylmethylene)-isoindolin-3-one, heated to 155-160 and stirred for 4 hours. During this process, the product precipitates out as red needles. It is isol-ated by filtration at 100, washed with dimethylformamide, methanol and acetone and dried at 80 in vacuo. 2.8 g of the metal complex of the formula i.l/~i ' , .
~ \CON~ ~COC17~35 are obtained.
Microanalysis:
C H N Ni % calculated 66.83 6.46 11.86 7.10 % found ~ 66.8 6.6 11.6 6.83 The product colours surface-coatings, sheets and plastics in strong bluish red shades with excellent fast-ness to light, weather, heat and migration.
Examples 53-64: Equally valuable pigments are obtained starting from a hydrazone of the formula ~ 2 R ~ ~t~ ~ \OH
in which R1 to R3 are as defined in columns 2-4 of Table 2, and an isoindolinone of the formula ., 1~55~2 .~-\./-\
.~ \./
N~ CONH-Q
in which Q is as defined in column 5, following an analo-gous procedure to that of Example 52. The colour shade of final colourations in PVC is represented in column 6.
1Y ~5~ZZ
Table 2 ~ R3 _ Cohouder ¦
, 53 H H H -~CH2) l7Ca3 orange~ed 54 H H H 2 t 2 ;)(CX2)3C~3 orang~red Cl H Cl -(CX2)17CH3 orange 56 H COOCH3 ~ -(CH2)17CH3 orange ;7 CH3 H H ~ Hco(cH2)l6cH3 reldiSh 8 ~:1 a C1 ditto ditto 9 a COOCH3 H ditto ditto ¦;Q ¦H ~ --(CIIz 11C~I3 ~ed ~1 H El EI \ , / 8al7 red . So2Na(cH2)7cH3 3 H H H --~ C0OC H red 64 H H H \ /--CONHC18H37 ~ed .~
i~5~1Z2 Example 65: 2.75 g (0.01 mol) of the hydrazone of 3-acetyl- 7-carbomethoxy-2,4-dihydroxyquinoline and 2.6 g of nickel acetate tetrahydrate (0.0105 mol) are suspended in 60 ml of N-methylpyrrolidone and the suspension is warmed to 60. 3.03 g (0.01 mol) of 1-(cyano-N-benzyl-carbamoyl-methylene)-isoindolin-3-one are added to the brown suspension. The mixture is warmed to 155 and stirred for 3 hours. After cooling to 100, it is filtered and the material on the filter is washed with N-methylpyrrolidone and methanol. By drying at 80 in vacuo, 2.7 g of a red pigment of the composition C31H22N6Ni5 are obtained.
Microanalysis:
C H N Ni % calculated 60.32 3.59 13.62 9.51 % found 59 9 3.6 13.8 9.50 In PVC sheets and stoving lacquers, a sample of the pig-ment converted into a fine form by grinding with salt produces intense, brilliant orange final colourations with very good fastness to migration, light and weather.
Exanrple 66: An equally valuabIe pigment is obtained from (cyano-N-methylcarbamoylmethylene)-isoindolin-3-one, following the procedure indicated in Example 65.
Example 67: 25 parts of the pigment prepared according to Example 1, 100 parts of finely ground sodi~m chloride and 30 parts of diacetone-alcohol are initially intro-duced into a laboratory kneader with a capacity of 250 parts by volume. The mixture ls kneaded for 5 hours, with cooling, and then inl;roduced into 4,000 parts by volume of water. The sodium chloride and diacetone-alcohol dissolve and the pigment precipitates out. The suspension is filtered and the material on the suction filter is washed thoroughly with water and dried in a vacuum drying cabinet at 80.
Example 68: 56.5 g (0.5 mol) of ethyl cyanoacetate and 64.6 g (0.5 mol) of 2-ethylhexylamine are stirred for l hour at 130-140 and the ethanol Iiberated is distilled ., : ~ ' ,'~ .
~L~lr55~ 2Z
- 15 ~
off. 61.6 g of the acid amide of the following formula:
2 2IH(CH2)3CH3 ' CllH20N2 are obtained from the reaction mixture by distillation at 130/0.1 mm Hg.
calcuiated 67.3 ~0 C 10.3 % H 14.3 % N
found 67.~ % C 10.4 % H 14.1 % N
19.6 g (0.1 mol) of this acid amide, 18.2 g (0.1 mol) of 1-imino-isoindolin-3-one hydrochloride and 11.1 g (0.135 mol) of sodium aceta-te are stirred in 100 ml of ethylcellosolve for 4 hours at 110. This suspension is left to cool, with stirring, and diluted with 100 ml of isopropyl alcohol. By filtration, washing with iso-propyl alcohol and water and drying, 19.5 g of a product melting at 121 to 122 are obtained, the microanalysis of which agrees with the methine-isoindolinone of the follow-ing formula:
o , jNH 19 23 3 2 NC c0NHCH2CH(CH2)3CH3 calculated 70.1 % C 7.1 % H 12.9 % N
found 69.7 % C 7.1 % H 13.3 % N
1.52 g (0.007 mol) of the hydrazone obtained by reacting 3-acetyl-2,4-dihydroxy-quinoline and hydrazine hydrate in alcohol, and 1 84 g (0.00735 mol) of nickel acetate tetrahydrate are stirred in 60 ml of N-methylpyrrolidone for 1/2 hour at 60. After the addition of 2.28 g (0.007 mol) of the above methine-isoindolinone, the .. .
~5S~Z2 - 16 ~
mixture is heated to 150 to 155 and stirred for 3 hours.
The orange-coloured suspension is cooled to 70, diluted with 50 ml of methanol and left to cool, with stirring.
The product is filtered off, washed with methanol and dried. Weight: 2.0 g. The product is the compound of the following formula or of a tautomeric formula:
N~ CONHCH2CH(CH2)3cH3 C30H30N6Ni3 calculated 62.0 % C 5.2 % H 14.5 % N 10.1 ~ Ni found 62.0 % C 5.4 % H 14.7 % N 9.9 % Ni In PVC sheets and surface coatings, the product produces strong orange final colourations with very good fastness properties.
Example 69: 1.52 g (0.007 mol) of the hydrazone of 3-acetyl-2,4-dihydroxyquinoline and 1.84 g (0.00735 mol) of nickel acetate tetrahydrate are stirred in 60 ml of N-methylpyrrolidone for 1/2 hour at 60. After the addition of 2.93 g (0.007 mol) of 1-(cyano-N-p-n-octyl-oxyphenylcarbamoyl-methylene)-isoindolin-3-one, the mixture is heated and stirred for 3 hours at 150 to 155.
The product of the following formula (only one of the possible tautomeric forms has been considered) precipi-tates out as red needles. It is filtered off at 100, washed with dimethylformamide and methanol and dried at 80 in vacuo. Weight: 2.6 g.
l~S5 ,~X
- 17 ~
OH C~3 O ~.~/ ; 36 34N6Nio4 ~-~ NC/ CONH--\ /- C8H17 (n) calculated 64.2 ~ C 5.1 % H 12.5 % N 8.7 % Ni found 64.6 % C 5.4 % H 12.7 % N 8.6 % Ni When finely dispersed, the product colours plastics and surface coatings in strong, pure bluish red shades with excellent fastness to migration and light.
Ex~es70-92: Equally valuable pigments are obtained, following an analogous procedure, by reacting a hydrazone of the formula R2 T '~ OH
in which R1 to R3 are as defined in columns 2 to 4 of Table 3, in the presence of a nickel salt, with an iso-indolinone of the formula .~ \./
! I!
NC/ CON~-Q
in which Q is as defined in column 5. The colour shade of final colourations in polyvinyl chloride is indicated in column 6.
~55~2Z
Table 3 Ex- _ _ 2 R ¦ Q Colour ample 3 ! shade H -COOCH3 H -CH2CHtCH2)3CH3 orange 71 H H H -(CH2)30cH2 Cll(CH2) 3 orange 72 H -COOCH3 H ditto orange 73 H -COOCH3 H \ ~ C8Hl7(n) red 74 Cl H Cl \ / red . 2 8 17 .
H -COOCH3 a ditto orange 76 H H H ~~ COCH(CH2)3CH~ red 77 H -COOCX3 H dit~o red 78 -~ HCO--~ ~- H H H orange I ~
79 -NHCO--~ ~- H H -CH2CH(CE12)3CH3 orange . C2H5 ditto H H -(CH2)17CH3 orange 81 ditto H . H -(cH2)3ocH2-cH(cH2)3cH3 orarge . . . _ _. . . __ _ C2H5 .. ___ 11~5~ zz - 19 _ (continuation) _ _ . .. ~
~pi~ Rl R2 --R3-- Colour No shade . . __ ~_ .. .. ... ... _ 82 H -COOCH3 H H range 83 -NHCOCH3~ H H H range .
84 -NHCOCH3 I H 2)17 3 range 85 -NHCOCH~ H H ~ .. red 86 -NHCOC13 H H ~~ CH - red 87 -S2NH2 H ~ H orange 88 -52N82 H H Cl range 89 -52NH2 H I ~ ~--C1 red H :H ~-OC13 -(CH2~17C13 red 91 H I -OCH3: ~ \ /- C8H17(n) red 92 H H -OCH3 \ ./ o~ange . 2 8 17( ) . .
~ , .
.
': '. : ~ , ~, .
1~55 Example 9~: If the procedure described in Example 65 is repeated, except that 2.85 g of 1-(cyano-benzimidazolyl-methylene)-isoindolin-3-one are used in place of the 1-(cyano-N-benzylcarbamoyl-methylene)-isoindolin-3-one, a very fast, orange pigment is likewise obtained.
Example 94: Following an analogous procedure to that of Example 69, a pigment which colours plastics and surface coatings in fast, bluish red shades is obtained from 1.92 g of 3-acetyl-6-acetylamino-2,4-dihydroxy-quinoline-hydrazone, 1.84 g of nickel acetate tetrahydrate and 1.6 g of 1-(cyano-thiocarbamoyl-methylene)-isoindolin-3-one.
Example_25: 65 parts of stabilised polyvinyl chloride, 35 parts of dio~tyl phthalate and 0.2 part of the pigment obtained according to Example 67 are stirred with one another and then worked on a twin-roll mill for 7 minutes at 140. An orange-red _coloured sheet with very good fastness to light and migration is obtained.
Example 96: 10 g of titanium dioxide ~nd 2 g of the pig-ment prepared according to Example 1 are ground with ~8g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine/formaldehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene, for 48 hours in a ball mill.
If this surface coating is sprayed onto analumin-ium foil, predried for 30 minutes at room temperature and then stoved for 30 minutes at 120, a red coating is obtained, which has good colour intensity and is distin-guished by a very good fastness to overcoa~ing, light and weather.
Example 97: 4 parts of the finely divided pigment accord-ing to Example 67 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture of aromatic hydrocarbons), 15 parts of butyl acetate, 5 parts of Exkin II (ketoxime-based levelling agent), 25 parts of methyl isobutyl ketone and 5 parts of silicone oil (1% in Solvesso 150).
After complete fine dispersion has been reached ~L~l551~Z
_ 21 -(in about 15-60 minu-tes, depending on the type of stirring), the binders are added, i.e. 48.3 parts of . Baycryl L 530 (acrylic resin) (51% in xylene/butanol 3:1) and 27.7 parts of Maprenal TTX (melamine resin) (55% in butanol).
After a short period of homogenisation, the sur-face coating is applied by customary methods, such as spraying and dipping or, especially for the continuous coating of metal sheets, by the "coil-coating" process, and stoved (stoving: 30 minutes, 130). The red coatings obtained are distinguished by very good level-ling, high gloss and excellent fine dispersion of the pigment, and also by excellent fastness to weather.
Example 98: If the procedure described in Example 76 is repeated, except that 2.78 parts of Staybelite Resin (HERCULES) are added to the kneading mixture, a pigment containing 10% of resin is obtained, which is distin-guished by being easier to incorporate and by better dispersibility.
Claims (9)
1. A 1:1 nickel complex of an isoindolinazine of the formula 1) in which R' is a cyano, carbamoyl, benzylcarbamoyl or thio-carbamoyl group, an alkylcarbamoyl or alkylthiocarbamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl group having 4 - 23 C or a group of the formula or 3) in which Z is an oxygen or sulfur atom, V is an oxygen or sulfur atom or the radical -NH-, X1 is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulf-amoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl group having 2 - 22 C, or a phenoxy, phenylcarbamoyl, benzoyl-amino or phenylsulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X2 is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1 - 4 C, R2 is an H or chlorine atom or a methoxycarbonyl group and R1 is an H or chlorine atom, a sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or phenylsulfamoyl group which is unsubstituted or substi-tuted by halogen atoms or alkyl or alkoxy groups having 1 - 22 C, or an alkanoylamino group having 2 - 22 C, and, in the case where R1 and R2 are H or chlorine atoms, methyl groups or alkoxy groups having 1 - 4 C, R' is an alkylcarbamoyl or alkylthiocarbamoyl group having 7 - 22 C, an alkoxyalkylcarbamoyl group having 7 - 23 C or a radical of the formula 2) in which X1 is an alkyl, alkoxy, alkylsulfamoyl or alkanoylamino radical having 6 - 22 C or an alkylcarbamoyl radical having 7 - 23 C.
2. A nickel complex according to claim 1, in which is a radical of the formula in which X1 and X2 are as defined in claim 1.
3. A nickel complex according to claim 1, in which R' is an alkylcarbamoyl group having 2 - 22 C or an alkoxy-alkylcarbamoyl group having 4 - 23 C.
4. A nickel complex according to claim 1, of the formula 4) in which Q is an alkyl or alkoxyalkyl group having 8 - 22C
or a group of the formula in which Y3 is an alkoxy, alkylsulfamoyl or alkanoylamino group having 8 - 22 C.
or a group of the formula in which Y3 is an alkoxy, alkylsulfamoyl or alkanoylamino group having 8 - 22 C.
5. The compound according to claim 1 of the formula .
6. The compound according to claim 1 of the formula .
7. The compound according to claim 1 of the formula .
8. A process for the preparation of a nickel complex according to claim 1, which comprises a) treating an azine of the formula 1) with nickel donors or b) heating a hydrazone of the formula 5) in which R1 and R2 are as defined, with an isoindolinone of the formula 6 ) in which R' is as defined, in the presence of nickel donors, in a polar organic solvent.
9. High-molecular organic material containing a nickel complex according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1980/80-4 | 1980-03-13 | ||
| CH198080 | 1980-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155122A true CA1155122A (en) | 1983-10-11 |
Family
ID=4223096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372758A Expired CA1155122A (en) | 1980-03-13 | 1981-03-11 | 1:1 nickel complexes of isoindolinazines, process for their preparation and use |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0037372A1 (en) |
| JP (1) | JPS56143250A (en) |
| CA (1) | CA1155122A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4529804A (en) * | 1982-06-24 | 1985-07-16 | Ciba-Geigy Corporation | Naphthostyril Ni or Cu complexes, a process for their preparation, and high molecular weight organic material pigmented with these metal complexes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2142245C3 (en) * | 1971-08-24 | 1980-09-04 | Basf Ag, 6700 Ludwigshafen | Dyes based on imino-isoindoline, their production and use as pigments for lacquers and for coloring polyester materials |
| CH597324A5 (en) * | 1974-02-06 | 1978-03-31 | Ciba Geigy Ag |
-
1981
- 1981-03-09 EP EP19810810086 patent/EP0037372A1/en not_active Withdrawn
- 1981-03-11 CA CA000372758A patent/CA1155122A/en not_active Expired
- 1981-03-13 JP JP3643481A patent/JPS56143250A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0037372A1 (en) | 1981-10-07 |
| JPS56143250A (en) | 1981-11-07 |
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