Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Patent
1985-06-03
1987-10-20
Rotman, Alan L.
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
514277, 514352, 546300, 546302, 546312, 546342, C07D21355, A01N 4340
Patent
active
047014644
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to cyclopropanecarboxylate insecticides. More particularly it relates to cyclopropanecarboxylate insecticides in which the alcohol component is a substituted fluoropyridinylmethyl group, to a process for making them, to insecticidal compositions thereof, and to novel intermediates useful in the preparation of such insecticidal compounds.
In accordance with the present invention the insecticidal compounds of this invention are compounds of formula I: ##STR2## in which X is hydrogen, halogen, particularly chlorine or fluorine, C.sub.1-2 alkoxy, phenoxy, or di(C.sub.1-2 alkyl)amino;
These compounds have been found to be highly active for foliar or soil application for control of foliar insects or soil borne insects. Certain of the compounds of the invention are also highly active in controlling acarids. The wide versatility in uses for these compounds is highly unexpected and unusual for pyrethroid type compounds.
The invention includes compounds in which the carboxylate group is attached at position 2 or 4 of the pyridine ring, preferably position 4, or a mixture of compounds in which the carboxylate group is attached at positions 2 and 4.
It will be apparent to one skilled in the cyclopropanecarboxylate insecticide art that the insecticidal compounds have two asymmetric centers on the cyclopropane ring, thus providing the possibility for four isomers, two cis isomers and two trans isomers, and that various mixtures of these isomers, designated cis,trans also exist. It will also be apparent that some of the compounds also exist in the E and Z forms depending on the configuration about the vinyl group at the 3-position of the cyclopropane ring. Each of these isomers and configurations and all combinations of them are included in and form a part of the present invention.
Among the starting materials for preparation of the insecticides of this invention are tetrafluoropyridinylmethanols which may be made by the method of Sket and Zupan, J. Heterocycl. Chem., 15, 527 (1978). This method produces a mixture of 2-hydroxymethyl and 4-hydroxymethyl isomers of tetrafluoropyridine. The mixture can be esterified without separation of isomers to produce the insecticidal compound of the invention having a corresponding mixture of isomers.
The 4-hydroxymethyl tetrafluoropyridine may also be separated from the mixture of isomers and used as the starting material for preparation of the 4-pyridinylmethyl esters of the invention.
This invention provides several novel intermediates which may be represented by formula II: ##STR3## in which X is hydrogen, halogen, C.sub.1-2 -alkoxy, phenoxy, or di(C.sub.1-2 -alkyl)amino or hydrazino; R.sup.1 is hydrogen or a halogen; and Q is a leaving group. Suitable leaving groups, Q, in the aforesaid structural formula are known in the art today and include bromo, chloro, methylsulfonyl, and hydroxy. It is recognized that any leaving groups readily displaced by carboxylate anions are and will be functional equivalents for Q in the aforesaid formula. The insecticidal compounds of the invention may be prepared from these novel intermediates by esterification techniques, for example by reacting an acid chloride of the formula RCOCl or a carboxylic acid or salt of the formula RCOOM, in which R is as defined above and M is hydrogen or a cation, with an appropriately substituted fluoropyridinyl intermediate.
The following examples illustrate the foregoing methods of preparation.
EXAMPLE 1
SYNTHESIS OF A MIXTURE OF 2-HYDROXYMETHYL-3,4,5,6-TETRAFLUOROPYRIDINE AND
4-HYDROXYMETHYL-2,3,5,6-TETRAFLUOROPYRIDINE AS AN INTERMEDIATE
A mixture of 4.0 g (0.023 mole) of pentafluoropyridine and 8.8 g (0.048 mole) of benzophenone in 350 ml of nitrogen-degassed methanol was irradiated at room temperature in a Pyrex vessel for 48 hours using light between 300 nm and 350 nm in wavelength. The solution was concentrated under reduced pressure. The residue was dissolved in diethyl ether. This solution was successively washed twice with 50 ml of 5% aqueous sodium bicarbonate and once w
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Roberts et al., Basic Principles of Organic Chemistry, pp. 560-561, Benjamin pub. (1965).
Sket, et al., J. Heterocyclic Chem., 15, 527 (1978).
Engel John F.
Phillips Richard B.
Plummer Ernest L.
Andersen R. L.
Ertelt H. R.
FMC Corporation
Rotman Alan L.
Schmonsees W.
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