Claims
- 1. A process for the preparation of oxydiphthalic anhydride and acyloxyphthalic anhydrides comprising reacting, in a substantially anhydrous medium, a halophthalic anhydride with an alkali metal salt selected from the group consisting of potassium carbonate and sodium carbonate in the presence of at least a catalytically effective amount of a carboxylic acid or acid derivative, where said carboxylic acid or acid derivative does not contain a substituent that interferes with said reaction.
- 2. A process according to claim 1 wherein said carboxylic acid or acid derivative is selected from the group consisting of benzoic acid, substituted benzoic acids, benzoic acid salts, salts of substituted benzoic acids, hydrolyzable benzoyl esters, hydrolyzable substituted benzoyl esters, C.sub.2 to C.sub.12 straight, branched, and cyclic alkyl carboxylic acids, hydrolyzable esters of said alkyl carboxylic acids, and salts of said alkyl carboxylic acids.
- 3. A process according to claim 2 wherein said carboxylic acid or acid derivative is selected from the group consisting of benzoic acid, benzoic acids salts, substituted benzoic acids, and salts of substituted benzoic acids.
- 4. A process according to claim 2 wherein said carboxylic acid or acid derivative is selected from the group consisting of hydrolyzable benzoyl esters, and hydrolyzable substituted benzoyl esters.
- 5. A process according to claim 2 wherein said carboxylic acid or acid derivative is selected from the group consisting of alkyl carboxylic acids, hydrolyzable esters of alkyl carboxylic acids, and salts of alkyl carboxylic acids.
- 6. A process according to claim 1 wherein the process is conducted in an aprotic solvent.
- 7. A process according to claim 6 wherein said solvent is selected from a group consisting of dimethyl formamide, N-methyl pyrrolidone, dimethyl acetamide, hexamethylphosphoramide dimethyl sulfoxide, sulfolane, and dimethyl sulfone chlorobenzene, dichlorobenzene, trichlorobenzene, and benzonitrile.
- 8. A process according to claim 1 wherein said carboxylic acid or acid derivative is a Li, Na, K, Cs, or NH.sub.4.sup.+ salt of benzoic acid or of a substituted benzoic acid.
- 9. A process according to claim 6 wherein said solvent is non-polar and said reaction is conducted in the presence of a phase transfer catalyst.
- 10. A process according to claim 9 wherein said phase transfer catalyst is selected from the group consisting of tetraphenyl phosphonium benzoates, tetraphenyl phosphonium substituted benzoates, and tetraphenyl phosphonium halides.
- 11. A process for the preparation of oxydiphthalic anhydride and acyloxyphthalic anhydrides comprising reacting a halophthalic anhydride with an alkali metal salt selected from the group consisting of potassium fluoride and cesium fluoride in the presence of at least a catalytically effective amount of a carboxylic acid or acid derivative, where said carboxylic acid or acid derivative does not contain a substituent that interferes with said reaction.
- 12. A process according to claim 11 wherein said carboxylic acid or acid derivative is selected from the group consisting of benzoic acid, substituted benzoic acids, benzoic acid salts, salts of substituted benzoic acids, hydrolyzable benzoyl esters, hydrolyzable substituted benzoyl esters, C.sub.2 to C.sub.12 straight, branched, and cyclic alkyl carboxylic acids, hydrolyzable esters of said alkyl carboxylic acids, and salts of said alkyl carboxylic acids.
- 13. A process according to claim 12 wherein said carboxylic acid or acid derivative is selected from the group consisting of benzoic acid, benzoic acids salts, substituted benzoic acids, and salts of substituted benzoic acids.
- 14. A process according to claim 12 wherein said carboxylic acid or acid derivative is selected from the group consisting of hydrolyzable benzoyl esters, and hydrolyzable substituted benzoyl esters.
- 15. A process according to claim 12 wherein said carboxylic acid or acid derivative is selected from the group consisting of alkyl carboxylic acids, hydrolyzable esters of alkyl carboxylic acids, and salts of alkyl carboxylic acids.
- 16. A process according to claim 11 wherein the process is conducted in an aprotic solvent.
- 17. A process according to claim 16 wherein said solvent is selected from a group consisting of dimethyl formamide, N-methyl pyrrolidone, dimethyl acetamide, hexamethylphosphoramide, dimethyl sulfoxide, sulfolane, dimethyl sulfone, chlorobenzene, dichlorobenzene, trichlorobenzene, and benzonitrile.
- 18. A process according to claim 11 wherein said carboxylic acid or acid derivative is a Li, Na, K, Cs, or NH.sub.4.sup.+ salt of benzoic acid or of a substituted benzoic acid.
- 19. A process according to claim 16 wherein said solvent is a non-polar solvent and said reaction is conducted in the presence of a phase transfer catalyst.
- 20. A process according to claim 19 wherein said phase transfer catalyst is selected from the group consisting of tetraphenyl phosphonium benzoates, tetraphenyl phosphonium substituted benzoates, and tetraphenyl phosphonium halides.
- 21. A process according to claim 11 wherein the product is predominantly an acyloxyphthalic anhydride, and wherein said carboxylic acid or acid derivative is a reactant.
- 22. A process for the preparation of a product that is predominantly an acyloxyphthalic anhydride comprising reacting an halophthalic anhydride with an alkali metal salt selected from the group consisting of potassium carbonate and sodium carbonate in the presence of a carboxylic acid or acid derivative, where said acid or acid derivative does not contain a substituent that interferes with said reaction.
- 23. An acyloxyphthalic anhydride of the formula ##STR4## where X and Y are substituents independently selected from the group consisting of H, F, Cl, Br, NO.sub.2, CH.sub.3, CF.sub.3, CCl.sub.3 and CN, provided that X and Y may not both be H.
- 24. An acyloxyphthalic anhydride according to claim 23 namely 3-(4-chlorobenzoyloxy)phthalic anhydride.
- 25. An acyloxyphthalic anhydride according to claim 23 namely 4-(4-chlorobenzoyloxy)phthalic anhydride.
- 26. An acyloxyphthalic anhydride according to claim 23 namely 4-(3-chlorobenzoyloxy)phthalic anhydride.
- 27. An acyloxyphthalic anhydride according to claim 23 namely 4-(2-chlorobenzoyloxy)phthalic anhydride.
- 28. An acyloxyphthalic anhydride according to claim 23 namely 4-(3-bromobenzoyloxy)phthalic anhydride.
- 29. An acyloxyphthalic anhydride according to claim 23 namely 4-(2,4-dichlorobenzoyloxy)phthalic anhydride.
- 30. An acyloxyphthalic anhydride according to claim 23 namely 4-(2,5-dichlorobenzoyloxy)phthalic anhydride.
- 31. An acyloxyphthalic anhydride according to claim 23 namely 4-(2,6-dichlorobenzoyloxy)phthalic anhydride.
- 32. An acyloxyphthalic anhydride according to claim 23 namely 4-(3,4-dichlorobenzoyloxy)phthalic anhydride.
- 33. An acyloxyphthalic anhydride according to claim 23 namely 4-(3,5-dichlorobenzoyloxy)phthalic anhydride.
- 34. An acyloxyphthalic anhydride according to claim 23 namely 4-(3-methoxybenzoyloxy)phthalic anhydride.
- 35. An acyloxyphthalic anhydride according to claim 23 namely 4-(4-methylbenzoyloxy)phthalic anhydride.
- 36. An acyloxyphthalic anhydride according to claim 23 namely 4-(3-nitrobenzoyloxy)phthalic anhydride.
- 37. An acyloxyphthalic anhydride according to claim 23 namely 4-(4-nitrobenzoyloxy)phthalic anhydride.
- 38. An acyloxyphthalic anhydride according to claim 23 namely 4-(2-(trifluoromethyl)benzoyloxy)phthalic anhydride.
- 39. An acyloxyphthalic anhydride according to claim 23 namely 4-(3-(trifluoromethyl)benzoyloxy)phthalic anhydride.
- 40. An acyloxyphthalic anhydride according to claim 23 namely 4-(4-(trifluoromethyl)benzoyloxy)phthalic anhydride.
- 41. An acyloxyphthalic anhydride of the formula: ##STR5## where R is selected from the group consisting of C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.5 H.sub.11, C.sub.6 H.sub.13, C.sub.7 H.sub.15, C.sub.8 H.sub.17, C.sub.9, H.sub.19, C.sub.10, H.sub.21, and C.sub.11 H.sub.23, including branched isomers of those formulas and cyclic saturated hydrocarbon radicals containing 3 to 11 carbon atoms.
- 42. An acyloxyphthalic anhydride according to claim 41 wherein R is C.sub.2 H.sub.5.
- 43. A process according to claim 1 wherein no solvent is present during said reaction.
- 44. A process according to claim 1 wherein said process is conducted at a temperature of about 120.degree. to 275.degree. C.
- 45. A process according to claim 11 wherein said process is conducted at a temperature of about 120.degree. to 275.degree. C.
- 46. A method of making oxydiphthalic anhydride comprising
- (A) preparing a composition by mixing together
- (1) a halophthalic anhydride;
- (2) a basic alkali metal salt; and
- (3) a catalyst selected from the group consisting of benzoic acid, substituted benzoic acids, benzoic acid salts, substituted benzoic acid salts, hydrolyzable benzoyl esters, hydrolyzable substituted benzoyl esters, C.sub.2 to C.sub.12 straight, branched, and cyclic alkyl carboxylic acids, hydrolyzable esters of said alkyl carboxylic acids, and salts of said alkyl carboxylic acids; and
- (B) maintaining the total moisture content of said composition at less than 2000 ppm while reacting said composition at a temperature of about 120.degree. to about 275.degree. C., where said catalyst does not contain a substituent that interferes with said reaction.
- 47. A method according to claim 46 wherein said reaction is solventless.
- 48. A method according to claim 46 wherein an aprotic solvent is present during said reaction.
- 49. A method according to claim 48 wherein said basic alkali metal salt is potassium carbonate and said solvent contains about 0.05 to about 0.5 mole % total water, based on said halophthalic anhydride.
- 50. A method according to claim 49 wherein said aprotic solvent is non-polar and said catalyst is selected from the group consisting of nitrobenzoic acid, dinitrobenzoic acid, halobenzoic acids, dihalobenzoic acids, trihalobenzoic acids, cyanobenzoic acids, and trihalomethyl benzoic acids.
- 51. A method according to claim 48 wherein said aprotic solvent is polar and said catalyst is selected from the group consisting of benzoic acid, alkylbenzoic acids, alkoxybenzoic acids, and salts thereof.
- 52. A process for preparing oxydiphthalic anhydride comprising reacting, in 1,2-dichlorobenzene, 3-chlorophthalic anhydride or 4-chlorophthalic anhydride with potassium carbonate or sodium carbonate in the presence of a phase transfer catalyst and an added catalyst selected from the group consisting of 3-chlorobenzoic acid, 4-chlorobenzoic acid, salts of 3-chlorobenzoic acid, salts of 4-chlorobenzoic acid, and mixtures thereof.
Parent Case Info
This application is a continuation-in-part of application Ser. No. 07/535,259, filed Jun. 8, 1990, and now abandoned.
US Referenced Citations (4)
Number |
Name |
Date |
Kind |
4697023 |
Schwartz et al. |
Sep 1987 |
|
4952721 |
Fjare |
Aug 1990 |
|
5003031 |
Schwartz et al. |
Mar 1991 |
|
5003086 |
Stults et al. |
Mar 1991 |
|
Foreign Referenced Citations (4)
Number |
Date |
Country |
288974 |
Nov 1988 |
EPX |
1901028 |
Aug 1970 |
DEX |
56-74149 |
Jun 1981 |
JPX |
7408880 |
Jan 1976 |
NLX |
Non-Patent Literature Citations (2)
Entry |
Sato et al, Chem. Abst. 113-2128204u (1990). |
Von H. Muhlemann, Pharm. Acta. Helv. p. 257 (1948). |
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
535259 |
Jun 1990 |
|