Claims
- 1. A method for manufacturing a halogen-substituted pyrethroid intermediate compound which comprises: reacting in acetic solution:
- an olefin having the structure ##STR16## wherein each R" is hydrogen or an organyl group, an adductable organic compound selected from the group consisting of a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol, said adductable compound having two abstractable hydrogen atoms on a carbon atom alpha to said group,
- and a stoichiometric amount of an oxidizing ion of manganese, said reaction being conducted in the presence of fluoride, chloride or bromide ion;
- and recovering the fluorine-, chlorine-, or bromine-substituted adduct of said olefin.
- 2. The method of manufacture described in claim 1 wherein said adductable organic compound is an organic carbonyl compound and said ion of manganese is trivalent manganic ion.
- 3. The method of manufacture described in claim 2 wherein said organic carbonyl compound is an ester.
- 4. The method of claim 3 wherein said ester is dimethylmalonate.
- 5. The method of manufacture described in claim 2 wherein said organic carbonyl compound is an aldehyde.
- 6. The method of manufacture described in claim 2 wherein said organic carbonyl compound is a ketone.
- 7. The method of manufacture described in claim 6 wherein said ketone is acetone.
- 8. The method of manufacture described in claim 6 wherein said ketone is acetylacetone.
- 9. The method described in claim 1 wherein said reaction is conducted in the presence of chloride ion and said recovered adduct is chlorine-substituted.
- 10. The method described in claim 2 wherein said reaction is conducted in the presence of chloride ion and said recovered adduct is chlorine-substituted.
- 11. The method described in claim 2 wherein said olefin contains from 2 (two) to about 12 (twelve) carbon atoms.
- 12. The method described in claim 2 wherein there is also present during said reaction a concentration of 10.sup.-3 to 10.sup.-5 mols/liter cupric chloride or ferric chloride.
- 13. The method of manufacture described in claim 1 wherein said adductable organic compound is selected from the group consisting of dialkylmalonate, a malononitrile, a .beta.-ketoester, a cyanoacetic ester, a cyanoacetic acid and a .beta.-dicarbonyl compound; and said olefin contains as additional functional group a double bond, a halogen, or a hydroxyl group.
- 14. The method described in claim 11 wherein the olefin is a diene and contains at least one halogen substituent or hydroxyl group substituent.
- 15. The method described in claim 14 wherein the olefin is selected from the group consisting of 1,1-dichloro-4-methylbutadiene, 1,1-dichloro-4,4-dimethylbutadiene, 1,1-dibromo-4-methylbutadiene, 1,1-dibromo-4,4-dimethylbutadiene, 1-carbomethoxy-1-methyl-4-methylbutadiene, 1-carbomethoxy-1-methyl-4,4-dimethylbutadiene, 1-carboethoxy-1-methyl-4-methylbutadiene, 1-carboethoxy-1-methyl-4,4-dimethylbutadiene, 1,1-dibromoethylene, 1,1-dichloroethylene, 3-hydroxy-3-methylbutene-1, vinylcyclohexane, 1-hydroxy-1-vinylcyclohexane, vinylcyclopentane, and 1-hydroxy-1-vinylcyclopentane.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 775,145 filed Mar. 7, 1977, now abandoned, which, in turn, is a continuation-in-part of Ser. No. 400,484, Sept. 24, 1975, now U.S. Pat. No. 4,011,239 issued Mar. 8, 1977, which in turn was a continuation-in-part of copending Application Ser. No. 755,732, filed Aug. 27, 1968, now abandoned. This latter application was a continuation-in-part of copending application Ser. No. 714,447 filed Mar. 20, 1968, now abandoned.
US Referenced Citations (3)
Foreign Referenced Citations (1)
Number |
Date |
Country |
1269119 |
Apr 1972 |
GBX |
Non-Patent Literature Citations (2)
Entry |
Elliott, Bulletin of World Health Organization, 44, No. 1-3, pp. 315-323, (1970). |
March, Advanced Organic Chemistry, pp. 287-290, (1965). |
Continuation in Parts (4)
|
Number |
Date |
Country |
Parent |
775145 |
Mar 1977 |
|
Parent |
400484 |
Sep 1973 |
|
Parent |
755732 |
Aug 1968 |
|
Parent |
714447 |
Mar 1968 |
|