Claims
- 1. A method of producing a cyclopropanecarboxylic acid derivative which comprises:
- treating an ester selected from the group consisting of esters of general formula III, esters of general formula V and esters of general formula VIII: ##STR23## or a mixture of two or more of such esters with a basic reagent, and then, with an acid reagent to obtain a cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and/or a cyclopropanecarboxylic acid ester of general formula IV: ##STR24## and a .gamma.-lactone derivative of general formula I: ##STR25## and, thereafter, (i) treating said .gamma.-lactone derivative I together with said cyclopropanecarboxylic acid derivative with a hydrogen halide of general formula HX and an alcohol of general formula R.sup.4 OH, recovering a cyclopropanecarboxylic acid ester of general formula IV from the reaction mixture, and treating an ester of general formula III concomitantly produced with a basic reagent to obtain an additional amount of cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and/or an ester thereof IV,
- wherein the above formulas, R.sup.1 and R.sup.2, respectively, mean an alkyl group of 1 to 5 carbon atoms; R.sup.3 is a member selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms and cycloalkyl groups of 3 to 8 carbon atoms; R.sup.4 s are the same or different and each means an alcohol residue selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ##STR26## wherein R.sup.5 is selected from the group consisting of hydrogen and methyl, R.sup.6 is selected from the group consisting of alkenyl, alkadienyl, alkynyl and benzyl; ##STR27## wherein R.sup.7 is selected from the group consisting of hydrogen, ethynyl and cyano, R.sup.8 is selected from the group consisting of hydrogen, halogen and alkyl, R.sup.9 is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, benzyl, thenyl, furylmethyl, phenoxy and phenylthio, R.sup.8 and R.sup.9, taken together, may form a polymethylene chain which may be interrupted by a sulfur or oxygen atom, Q is a member selected from the group consisting of --O--, --NH--, --S-- and --CH=CH--, n is 1 or 2; A--CH.sub.2 -- wherein A is selected from the group consisting of phenoxyphenyl, phthalimido, thiophthalimido, di- or tetrahydrophthalimido and dialkylmaleimido; and ##STR28## wherein R.sup.10 is selected from the group consisting of phenyl, thienyl and furyl; B is a halogen atom; Y is selected from the group consisting of X and --CHX--CH.sub.3 ; and Xs are the same or different and each means a halogen atom.
- 2. The method according to claim 1, wherein the ester of general formula III concomitantly produced and treated with a basic reagent, is further treated with an acid reagent to obtain an additional amount of cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and/or an ester thereof IV.
- 3. A method of producing a cyclopropanecarboxylic acid ester which comprises:
- treating an ester selected from the class consisting of esters of general formula III, esters of general formula V and esters of general formula VIII: ##STR29## or a mixture of two or more of such esters with an alkali metal hydroxide, and then, with an acid reagent to obtain a cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX: ##STR30## and a cyclopropanecarboxylic acid ester of general formula IV: ##STR31## and a .gamma.-lactone derivative of general formula I: ##STR32## treating said cyclopropanecarboyxlic acid derivative together with said .gamma.-lactone derivative I with an alcohol of general formula R.sup.4 OH under heating in the presence of an acid catalyst, separating and recovering a cyclopropanecarboxylic acid ester of general formula IV and a .gamma.-lactone derivative of general formula I independently from the resultant reaction mixture, reacting said .gamma.-lactone derivative I with a hydrogen halide of general formula HX and an alcohol of general formula R.sup.4 OH to obtain an ester of general formula III, treating said ester III with an alkali metal hydroxide, and then, with an acid reagent to obtain a mixture of a cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid IX and an ester thereof IV and a .gamma.-lactone derivative I, treating said mixture with an alcohol of general formula R.sup.4 OH under heating in the presence of an acid catalyst, and separating and recovering an additional amount of cyclopropanecarboxylic acid ester IV,
- wherein the above formulas, R.sup.1 and R.sup.2, respectively, mean an alkyl group of 1 to 5 carbon atoms; R.sup.3 is a member selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms and cycloalkyl groups of 3 to 8 carbon atoms; R.sup.4 s are the same or different and each means an alcohol residue selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ##STR33## wherein R.sup.5 is selected from the group consisting of hydrogen and methyl, R.sup.6 is selected from the group consisting of alkenyl, alkadienyl, alkynyl and benzyl; ##STR34## wherein R.sup.7 is selected from the group consisting of hydrogen, ethynyl and cyano, R.sup.8 is selected from the group consisting of hydrogen, halogen and alkyl, R.sup.9 is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, benzyl, thenyl, furylmethyl, phenoxy and phenylthio, R.sup.8 and R.sup.9, taken together, may form a polymethylene chain which may be interrupted by a sulfur or oxygen atom, Q is a member selected from the group consisting of --O--, --NH--, --S-- and --CH.dbd.CH--, n is 1 or 2; A--CH.sub.2 wherein A is selected from the group consisting of phenoxyphenyl, phthalimido, thiophthalimido, di- or tetrahydrophthalimido and dialkylmaleimido; and ##STR35## wherein R.sup.10 is selected from the group consisting of phenyl, thienyl and furyl; B is a halogen atom; Y is selected from the group consisting of X and --CHX--CH.sub.3 ; and Xs are the same or different and each means a halogen atom.
- 4. A method according to claim 3 wherein the amount of said acid catalyst is in the range of 0.01 to 10 weight percent based on the weight of said cyclopropanecarboxylic acid derivative.
- 5. A method according to claim 1, 2, or 3 wherein said alcohol is an alkanol of 1 to 4 carbon atoms.
- 6. A method according to any of claims 1, 2, or 3 wherein said alcohol is used in an amount corresponding to 0.5 to 10 times the stoichiometric requirement for a ring-opening esterification of said .gamma.-lactone and an esterification of said cyclopropanecarboxylic acid.
- 7. A method according to any of claims 1, 2, or 3 wherein said hydrogen halide is used in an amount corresponding to 0.5 to 10 times the stoichiometric requirement for a ring-opening reaction of said .gamma.-lactone derivative.
- 8. A method according to claim 7 wherein the proportion of hydrogen halide is 1.3 to 5 times the stoichiometric requirement for a ring-opening reaction of said .gamma.-lactone derivative.
- 9. A method according to any of claims 1, 2, or 3 wherein the ring-opening reaction of said .gamma.-lactone derivative is conducted at temperatures in the range of 0.degree. to 150.degree. C.
- 10. A method according to any of claims 1, 2, or 3 wherein said basic reagent is used in a proportion of 0.3 to 7 moles per mole of the starting material ester.
- 11. A method according to any of claims 1, 2, or 3 the treatment with said acid reagent is conducted at temperatures not exceeding 40.degree. C.
- 12. A method of producing a cyclopropanecarboxylic acid derivative which comprises:
- treating an ester selected from the group consisting of esters of general formula III, esters of general formula V and esters of general formula VIII: ##STR36## or a mixture of two or more of such esters with a basic reagent, and then, with an acid reagent to obtain a cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and/or a cyclopropanecarboxylic acid ester of general formula IV: ##STR37## and a .gamma.-lactone derivative of general formula I: ##STR38## and, thereafter, separating and recovering said cyclopropanecarboxylic acid derivative from said .gamma.-lactone derivative of general formula I, reacting said .gamma.-lactone derivative of general formula I with a hydrogen halide of general formula HX and an alcohol of general formula R.sup.4 OH to obtain an ester of general formula III, and
- treating said ester III with a basic reagent to obtain an additional amount of cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and a cyclopropanecarboxylic acid ester IV,
- wherein the above formulas, R.sup.1 and R.sup.2, respectively, mean an alkyl group of 1 to 5 carbon atoms; R.sup.3 is a member selected from the group consisting of hydrogen, alkyl groups of 1 to 5 carbon atoms and cycloalkyl groups of 3 to 8 carbon atoms; R.sup.4 s are the same or different and each means an alcohol residue selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ##STR39## wherein R.sup.5 is selected from the group consisting of hydrogen and methyl, R.sup.6 is selected from the group consisting of alkenyl, alkadienyl, alkynyl and benzyl; ##STR40## wherein R.sup.7 is selected from the group consisting of hydrogen, ethynyl and cyano, R.sup.8 is selected from the group consisting of hydrogen, halogen and alkyl, R.sup.9 is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, benzyl, thenyl, furylmethyl, phenoxy and phenylthio, R.sup.8 and R.sup.9, taken together, may form a polymethyl chain which may be interrupted by a sulfur or oxygen atom, Q is a member selected from the group consisting of --O--, --NH--, --S-- and --CH.dbd.CH--, n is 1 or 2; A--CH.sub.2 -- wherein A is selected from the group consisting of phenoxyphenyl, phthalimido, thiophthalimido, di- or tetrahydrophthalimido an dialkylmaleimido; and ##STR41## wherein R.sup.10 is selected from the group consisting of phenyl, thienyl and furyl; B is a halogen atom; Y is selected from the group consisting of X and --CHX--CH.sub.3 ; and Xs are the same or different and each means a halogen atom.
- 13. The method of claim 12, wherein the ester of general formula III obtained upon reacting the .gamma.-lactone derivative of general formula I with a hydrogen halide of general formula HX and an alcohol of general formula R.sup.4 OH, and which is treated with a basic reagent, is further treated with an acid reagent to obtain an additional amount of a cyclopropanecarboxylic acid derivative comprising a cyclopropanecarboxylic acid of general formula IX and a cyclopropanecarboxylic acid ester IV.
- 14. A method according to claim 12 or 13 wherein said alcohol is a lower alkanol having from 1 to 4 carbon atoms.
- 15. A method according to claim 12 or 13 wherein said alcohol is used in a proportion of at least 0.5 times the stoichiometric requirement for a ring-opening esterification of said .gamma.-lactone derivative.
- 16. A method according to claim 15 wherein the amount of alcohol is 0.5 to 10 times the stoichiometric requirement for a ring-opening esterification of said .gamma.-lactone derivative.
- 17. A method according to claim 16 wherein the amount of alcohol is 1.5 to 7 times the stoichiometric requirement for a ring-opening esterification of said .gamma.-lactone derivative.
- 18. A method according to claim 12 or 13 wherein said hydrogen halide is used in an amount corresponding to 0.5 to 10 times the stoichiometric requirement for a ring-opening reaction of said .gamma.-lactone derivative.
- 19. A method according to claim 18 wherein the proportion of hydrogen halide is 1.3 to 5 times the stoichiometric requirement for a ring-opening reaction of said .gamma.-lactone derivative.
- 20. A method according to claim 12 or 13 wherein the ring-opening reaction of said .gamma.-lactone derivative is conducted at temperatures in the range of 0.degree. to 150.degree. C.
- 21. A method according to claim 12 or 13 wherein said basic reagent is used in a proportion of 0.3 to 7 moles per mole of the starting material ester.
- 22. A method according to claim 12 or 13 wherein the treatment with said acid reagent is conducted at temperatures not exceeding 40.degree. C.
Priority Claims (3)
Number |
Date |
Country |
Kind |
50-89507 |
Jul 1975 |
JPX |
|
50-158047 |
Dec 1975 |
JPX |
|
51-50595 |
Apr 1976 |
JPX |
|
Parent Case Info
This application is a division of application Ser. No. 840,279, filed Oct. 7, 1977, now abandoned which in turn is a division of application Ser. No. 705,176, filed July 14, 1976 now abandoned.
US Referenced Citations (7)
Foreign Referenced Citations (3)
Number |
Date |
Country |
2539895 |
Mar 1976 |
DEX |
2621835 |
Nov 1976 |
DEX |
7605172 |
Nov 1976 |
NLX |
Divisions (2)
|
Number |
Date |
Country |
Parent |
840279 |
Oct 1977 |
|
Parent |
705176 |
Jul 1976 |
|