Claims
- 1. A process for the preparation of prophyrins or mixtures of porphyrins of the formula ##STR14## in which X, Y, Z independently of one another, are CH or N, but at least one of X, Y or Z represents N,
- R.sub.1 has the meaning given below and
- m is 0 to 8,
- characterized in that a compound of the formula ##STR15## wherein R denotes hydrogen, acetyl or benzoyl,
- R.sub.1 denotes hydrogen, C.sub.1 -C.sub.6 -alkyl, phenyl, biphenyl, naphthyl, a heterocyclic aromatic radical containing 1 or 2 five-, six- or seven-membered rings, at least one of which contains 1, 2 or 3 heteroatoms from the series comprising O, N, S or denotes C.sub.1 -C.sub.4 -alkylcarbonyl or substituted or unsubstituted phenylcarbonyl, C.sub.1 -C.sub.6 -alkoxy, halogen, carboxyl, carboxamido, cyano or nitro, or two adjacent substituents R.sub.1 can form a benzene ring together with the C-atoms on the benzene ring linking them,
- and it being possible for the phenyl, biphenyl, naphthyl radicals, the heterocyclic aromatic radicals and the benzene ring mentioned above to contain substituents from the series comprising F, Cl, Br, C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, unsubstituted amino, carboxyl, carboxamido, sulpho, sulphonamido, C.sub.1 -C.sub.6 -alkoxycarbonyl, sulphonylamino, C.sub.1 -C.sub.6 -alkylsulphonyl, C.sub.1 -C.sub.4 -alkylcarbonyl, phenylcarbonyl or aminocarbonyloxy and
- n denotes 0 to 2
- is heated to temperatures of about 100.degree.-300.degree. C.
- 2. A process for the preparation of porphyrins or mixtures of porphyrins of the formula ##STR16## in which X, Y, Z, independently of one another, are CH or N, but at least one X, Y or Z represents N,
- R.sub.1 has the meaning given below and
- m is 0 to 8,
- characterized in that a compound of the formula ##STR17## wherein R denotes hydrogen, C.sub.1 -C.sub.6 -alkyl, phenyl, biphenyl, naphthyl, a heterocyclic aromatic radical containing 1 or 2 five-, six- or seven-membered rings, at least one of which contains 1, 2 or 3 heteroatoms from the series comprising O, N, S or denotes C.sub.1 -C.sub.4 -alkylcarbonyl or substituted or unsubstituted phenylcarbonyl,
- and it being possible for the phenyl, biphenyl, and naphthyl radicals and for the heterocyclic aromatic radical mentioned above to contain substituents from the series comprising F, Cl, Br, C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, unsubstituted amino, carboxyl, carboxamido, sulpho, sulphonamido, C.sub.1 -C.sub.6 -alkoxycarbonyl, sulphonylamino, C.sub.1 -C.sub.6 -alkylsulphonyl, C.sub.1 -C.sub.4 -alkylcarbonyl, phenylcarbonyl or aminocarbonyloxy and
- R.sub.1 and n have the meaning given in claim 1
- is heated in a mixture with an effective amount of up to 20 mol of a compound ##STR18## in which R.sub.1 and n have the meaning given in claim 1 to temperatures of about 100.degree.-300.degree. C.
- 3. A process according to claim 1, wherein the reaction mixture is heated to a temperature of about 150.degree.-270.degree. C.
- 4. A process according to claim 2, wherein the reaction mixture is heated to a temperature of about 150.degree.-270.degree. C.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 3937716 |
Nov 1989 |
DEX |
|
Parent Case Info
This application is a continuation of application Ser. No. 600,033, filed Oct. 16, 1990 ABN.
The present invention relates to compounds of the formula ##STR4## in which R is H or a substituent
The substituents R.sub.1 can be identical or different.
Examples of suitable substituents R are alkyl, aryl, hetaryl, acyl.
Examples of suitable substituents R.sub.1 are R, alkoxy, halogen, carboxyl, carboxamido, cyano, NO.sub.2.
Two adjacent substituents R can also form a carbocylic or heterocyclic ring or ring system together with the C atoms on the benzene ring linking them.
Alkyl preferably represents C.sub.1 -C.sub.6 -alkyl, such as CH.sub.3, C.sub.2 H.sub.5, n-- and i--C.sub.3 H.sub.7 and n--, i-- and t--C.sub.4 H.sub.g.
Aryl preferably represents those carbocyclic-aromatic radicals containing 1, 2, 3 or 4, in particular 1 or 2, rings, such as phenyl, diphenylyl and naphthyl.
Hetaryl preferably represents those heterocyclic-aromatic radicals containing 1, 2, 3 or 4, in particular 1 or 2, five-, six- or seven-membered rings, at least one of which contains 1, 2 or 3, preferably 1 or 2, heteroatoms from the series comprising O, N, S. Examples of heterocyclic-aromatic radicals are:
pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thienyl, quinolyl, curarinyl, benzofuranyl, benzoimidazolyl, benzoxazolyl, dibenzofuranyl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, pyrazolyl, imidazoiyl, oxazolyl, isooxazolyl, thiazoiyl, indazoiyl, benzothiazoiyl, pyridazinyl, cinnolyl, quinazolyl, quinoxaiyl, phthalazinyl, phthalazinedionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho-sulphobenzimidyl, maleimidyl, naphtharidinyl, benzimidazolonyl, benzoxazolonyl, benzothiazoionyl, benzothiazolinyl, quinazolonyl, pyrimidonyl, quinoxalonyl, phthalozonyl, dioxapyrimidinyl, pyridonyl, isoquinolonyl, isoquinolinyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, thinoxalinedionyl, benzoxazinedionyl, benzoxazinonyl and naphthalimidyl.
The aryl and hetaryl radicals can have customary substituents, for example F, Cl, Br, alkyl, alkoxy, substituted or unsubstituted amino, carboxyl, carboxylate, carboxamido, sulpho, sulphonamido, alkoxycarbonyl, sulphonylamino, alkylsulphonyl, acylamino, aminocarbonyloxy. Halogen represents F, Cl, Br, I. Alkoxy is preferably C.sub.1 -C.sub.6 -alkoxy. Acyl preferably represents alkyl-(preferably C.sub.1 -C.sub.4 -alkyl) or substituted or unsubstituted phenylcarbonyl.
Preferred compounds (I) are those where n is 0 and those where n is 1 and R.sub.1 is phenyl or OCH.sub.3, R in each case representing H, acetyl, benzoyl, furthermore those where n is 2, two radicals R.sub.1 together with the C atoms linking them representing a benzene ring.
The reaction of (II) with (III) is preferably carried out in an inert diluent at temperatures of 20.degree. to 150.degree. C., if appropriate in the presence of inert gases.
Suitable diluents are in particular water-miscible organic solvents, such as alcohols or ethers thereof, for example ethanol, methanol, butanol, ethylene glycol mono-C.sub.1 -C.sub.4 -alkyl ether, carboxylic acids, such as acetic acid; dioxane, pyridine, cyclic amides, such as dimethylformamide.
Compounds (I) (the formula given is one of the possible tautomeric forms) are valuable intermediates for the preparation of pigments.
The invention also relates to a process for the preparation of porphyrins or mixtures of porphyrines of the formula ##STR6## in which X, Y, Z, independently of one another, denote CH or N, but at least one X, Y or Z represents N,
The process yields uniform compounds (IV) or mixtures of different compounds (IV).
The reaction is preferably carried out in a solvent. Examples of suitable solvents are alcohols, such as pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-butanol, furthermore dipolar aprotic solvents, such as dimethylformamide, dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone, and aliphatic or aromatic hydrocarbons, which can be unsubstituted or substituted by alkyl, alkoxy, halogen or nitro groups, such as decalin, xylene, metsitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-chloronaphthalene, 2-chloronaphthalene, and substituted or unsubstituted heterocyclic solvents, such as pyridine, picoline, quinoline.
The pigments of the type (IV) are obtained by the process described above in sufficient purity and can be used directly or after suitable formulation as pigments. Owing to their good pigment properties, pigments of the formula (IV) are suitable for a wide range of pigment applications and as organic photoconductors, for example for electrophotography.
Consequently, they can be used for the preparation of pigmented systems of very good fastness properties, such as mixtures with other substances, preparations, paints, printing inks, coloured paper and coloured macromolecular substances. A mixture with other substances can be understood to mean, for example, those containing inorganic white pigments, such as titanium dioxide (rutile). Examples are preparations of flush pastes containing organic liquids and, if appropriate, preservatives. The designation coating agent is understood to mean, for example, physically or oxidatively drying surface coatings, stoving enamels, reaction coatings, two-component coatings, emulsion paints for weather-resistant coatings and distempers. Printing inks are understood to mean those for paper, textile and metal sheet printing.
The novel pigments are in particular suitable for pigmenting macromolecular organic substances. The macromolecular substances can be of natural origin, such as rubber, can be obtained by chemical modification, such as acetylcellulose, cellulose butyrate or viscose, or produced synthetically, such as polymers, polyaddition products and polycondensation products. Examples are plastic materials, such as polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyolefins, for example polyethylene or polyamides, super polyamides, polymers and copolymers made of acrylic esters or methacrylic esters, acrylonitrile, acrylamide, butadiene, styrene and polyurethanes and polycarbonates. The substances pigmented with the claimed products can be present in any desired form. Owing to their high weather fastness, the pigments of the formula (I) are particularly suitable for use in automotive paints, in particular for metallic effect paints.
The pigments of the formula (IV) have excellent water fastness, oil fastness, acid fastness, lime fastness, alkali fastness, solvent fastness, overcoating fastness, overspray fastness, sublimation fastness, heat fastness, vulcanizing fastness, give high yields, have good distribution in plastic materials and have in particular excellent light fastness and migration fastness.
Some of the compounds of the formula (IV) are known (for example (IV) where m is 0 and X, Y, Z are N). Accordingly, GB Patent 494,738 describes the following process: methylenephthalimidinoacetic acid is reacted in the presence of magnesium turnings in chloronaphthalene to give magnesium tetrabenzotriazaporphin. The magnesium tetrabenzotriazaporphin is dissolved in concentrated sulphuric acid and then poured into water to give a metal-free tetrabenzotriazaporphin. The tetrabenzotriazaporphin prepared by this method is present in the .alpha.-modification, which shows strong bands in the X-ray diffraction photograph at the Bragg angles 6.7; 13.6; 15.0; 24.5 and 26.9.
This process for the preparation of compounds of the formula (IV) is very lengthy, since first the methylenephthalimidinoacetic acid has to be prepared in a two-step synthesis. Moreover the metal-free tetrabenzotriazaporphin can only be obtained via the magnesium complex by dissolution and reprecipitation from sulphuric acid, which results in an expensive work-up or disposal of the sulphuric acid solution.
A further process for the preparation of tetrabenzotriazaporphin is described by Barrett, Linstaed and Tuey (J. Chem. Soc. 1939, p. 1809-1822) by reaction of phthalodinitrile with methylmagnesium iodide or methyllithium in ether.
The tetrabenzotriazaporphin prepared by this method is present in the .beta.-modification, which shows strong bands in the X-ray diffraction photograph at the Bragg angles 7.0; 8.9; 17 9; 20.3; 23.7; 26.0; 26.8; 27.7 and 30.0.
A disadvantage of this process is the use of ether as solvent. Because of the low ignition point and the tendency to form explosive peroxides, the use of ether in industry as solvent is subject to stringent safety regulations. Moreover organometallic reagents, such as methyllithium and methylmagnesium iodide, due to their very high reactivity and the tendency to develop explosive gases upon contact with moisture, are expensive and can only be reacted in special equipment.
In contrast, the process according to the invention starts with readily available starting materials, and the products of the general formula (IV) can be prepared directly in a one-step synthesis in metal-free form.
Heating (I) where n is O and R is H or acyl with (V) where n is O and R is H or acyl in a molar ratio of about 1:1 gives the tetrabenzotriazaporphin ##STR8## in the known .beta.-modification.
Grinding the .beta.-modification of the compound of the formula (IVa), if appropriate in the presence of an inorganic or organic salt, gives the new .omega.-modification of the compound of the formula (IVa), which in the X-ray diffraction photograph shows strong bands at the Bragg angles 8.5; 10.2; 11.9; 14.4; 18.0; 20.4; 22.6; 24.0; 24.7 and 29.8 and to which the invention also relates.
The grinding is preferably carried out in the presence of salts, in particular inorganic salts, for example the alkali metal salts of strong inorganic acids, such as NaCl, preferably at room temperature.
A further process for the preparation of the .omega.-modification of the compound of the formula (IVa) consists in heating the .alpha.-modification of the compound of the formula (IVa) by heating to 100.degree. to 300.degree. C., preferably in the presence of a solvent.
Suitable solvents are organic solvents, for example alcohols, phenols, dipolar aprotic solvents, such as dimethylformamide, dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone, and preferably aliphatic or aromatic hydrocarbons, which can be unsubstituted or substituted by alkyl, acyl, alkoxy, halogen, ester or nitro groups, such as decalin, xylene, metsitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, naphthalene, 1-methylnaphthalene, methyl benzoate, 2-methylnaphthalene, 1-chloronaphthalene, 2-chloronaphthalene and unsubstituted or substituted heterocyclic solvents, such as pyridine, picoline, quinoline.
A further process for the preparation of the .omega.-modification of the compound of the formula (IVa) consists in carrying out the synthesis of the pigment by the preparation process according to the invention in the presence of preferably 0.001 to 0.1 mole of the .omega.-modification of the compound of the formula (IVa), relative to 1 mole of the compound of the formula (I).
The .omega.-modification of the compound of the formula (IVa) is usable for a wide range of the abovementioned pigment applications and as an organic photoconductor pigment, due to its particularly good pigment properties.
US Referenced Citations (4)
Foreign Referenced Citations (2)
| Number |
Date |
Country |
| 0428214 |
May 1991 |
EPX |
| 1169901 |
Nov 1969 |
GBX |
Non-Patent Literature Citations (3)
| Entry |
| Journal of the Chemical Society, 1939, pp. 1809-1820, The Chemical Society, Letchworth, GB P.A. Barrett et al. |
| "Justus Liebigs Annalen Der Chemie" vol. 529, 1937, pp. 205-211 Weinheim, DE J. H. Helberger. |
| Journal of the Chemical Society, 1940, pp. 1079-1092, The Chemical Society, Letchword, GB: P. A. Barrett et al. |
Continuations (1)
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Number |
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| Parent |
600033 |
Oct 1990 |
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Patent Grant
5162518
