FLUOROPYRIDINYLMETHYL CYCLOPROPANECARBOXYLATE INSECTICIDES AND INTERMEDIATES

Abstract: Insecticidal compounds of formula (I), formulations thereof, their use for control of foliar or soil-borne insects, their method of preparation and certain novel intermediates for their preparation are disclosed and exemplified.

Description: FLUOROPYRIDINYLMETHYL CYCLOPROPANECARBOXYLATE INSECTICIDES AND INTERMEDIATES The present invention relates to cyclopropanecar¬ boxylate 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 prepara¬ tion of such insecticidal compounds. In accordance with the present invention the insecti¬ cidal compounds of this invention are compounds of formula in which X is hydrogen, halogen, particularly chlorine or fluorine, C, 2 alkoxy, phenoxy, or di(C,_ 2 alkyl)amino; R is 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethyl- cyclopropyl; 3-(2,2-dihaloethenyl)-2,2-dimeth lcyclopropyl ; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimeth lcyclopropyl ; 2,2,3,3-tetramethylcyclopropyl; or l-(4-chlorophenyl)- 2-methylpropyl; and R is hydrogen or a halogen, particularly chlorine or fluorine. 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 cyclopro- panecarboxylate 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 mix¬ tures of these isomers, designated " cis,trans als.o 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 cyclopro¬ pane 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 tetrafluoropyridinyl- methanols which may be made by the method of Sket and Zupan, J. Heterocycl. Chem. , 15, 527 (1978). This method produce-s a mixture of 2-hydroxymethyl and 4-hydroxymeth l isomers of tetrafluoropyridine. The mixture can be esterified without separation of isomers to produce the insecticidal compound of the invention having a corre¬ sponding mixture of isomers. The 4-hydroxymeth l 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: in which X is hydrogen, halogen, C, 2 -alkoxy, phenoxy, or di(C, --alkyDamino or hydrazino; R 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, ethylsulfonyl, 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 RC0C1 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-HYDROXY- METHYL-2,3,5,6-TETRAFLUOROPYRIDINE AS AN INTERMEDIATE A mixture of 4.0 g (0.023 mole) of penta luoropyri¬ dine and 8.8 g (0.048 mole) of benzophenone in 350 ml of nitrogen-degassed methanol was irradiated at room tempera¬ ture in a Pyrex vessel for 48 hours using light between 300 nm and 350 nra in wavelength. The solution was concen¬ trated 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 with 50 ml of water. After being dried over anhydrous sodium sulfate the solution was filtered and evaporated under reduced pressure, leaving a yellow oil as residue. This yellow oil was distilled to give 2.2 g of colorless oil, b.p. 56-60°C/9 mm of Hg. Gas chromatographic analysis revealed that this oil consisted of 87% 4-hydroxymethyl-2,3,5,6-tetrafluoropyridine and 13% 2-hydroxymeth l-3,4,5,6-tetrafluoropyridine. EXAMPLE 2 SYNTHESIS OF A MIXTURE OF (2,3,5,6-TETRAFLU0R0- 5 PYRIDIN-4-YDMETHYL AND (3,4,5,6-TETRAFLU0R0- PYRIDIN-2-YDMETHYL CIS-3-(2-CHL0R0-3,5,3- TRIFLUOROPROPENYL)-2,2-DIMETHYLCYCLOPROPANE- CARBOXYLATES To a solution of 0.61 g (0.0025 mole) of cis-3-(2- 10 chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropane- carboxylic acid in 20 ml of dry diethyl ether containing one drop of dry dimethylformamide was added an ether solu¬ tion of 0.55 g (0.0044 mole) of oxalyl chloride during a twenty minute period. The reaction mixture was stirred at 5 room temperature for 0.5 hour. The solvent was evaporated under reduced pressure. Additional anhydrous diethyl ether (15 ml) was added to the residue, and this solvent * was evaporated to remove excess oxalyl chloride. The crude product was dissolved in 20 ml of dry diethyl * ether, 0 and to this solution was added 0.5 g (0.003 mole) of the mixture o£ 4-hydroxymethyl-2,3,5,6-tetrafluoropyridine and 2-hydroxymethyl-3,4,5,6-tetrafluoropyridine (from Example 1) followed by the addition of 1 ml of anhydrous triethyl- amine. The reaction mixture was stirred at room tempera- 5 ture for twelve hours after which it was poured into 5% hydrochloric acid. This mixture was extracted three times with 35 ml of diethyl ether. The combined extracts were washed twice with 30 ml of water and once with 25 ml of a saturated aqueous sodium chloride solution. The extract 0 was dried over anhydrous magnesium sulfate, filtered, and the solvent evaporated under reduced pressure, leaving an oil. This crude product was chromatographed on a Chroma- totron (2mm SiO- plate, 15% diethyl ether/hexane) and the higher R f material as illuminated by UV light was 5 collected. The material collected was 90% (2,3,5,6-tetra- fluoropyridin-4-yl)me h l cis-3-(2-chloro-3,3,3-trifluoro- propenyl)-2,2-dimethyl-cyclopropanecarboxylate and 10% (3,4,5,6-tetrafluoropyridin-2-yl)methyl cis-3-(2-chloro- 3,3,3-trifluoropropenyl)-2,2-diraethylcyclopropanecar- boxylate, Compound No. 1 of the tables below. Analysis calc'd for C ls H n ClF 7 N0 2 : C 44.41; H 2.73; N 3.45; Found: C 44.32; H 2.66; N 3.18. EXAMPLE 3 SYNTHESIS OF A MIXTURE OF (2,3,5,6-TETRAFLUORO- PYRIDIN-4-YL)METHYL AND (3,4,5,6-TETRAFLUORO- PYRIDIN-2-YDMETHYL CIS-3-(2, 2-DICHL0R0ETHENYL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATES By the method of Example 2, 0.50 g (0.0024 mole) of cis-3-(2,2-dichloroethenyl)-2,2-dimeth 1cyclopropane- carboxylic acid was reacted with 0.55 g (0.0044 mole) of oxalyl chloride. The resulting cis-3-(2,2-dichloro- ethenyl)-2,2-dimethylcyclopropanecarbonyl chloride was reacted with 0.53 g (0.0029 mole) of a mixture of 4-hy- droxyraethyl-2,3,5,6-tetrafluoropyridine and 2-hydroxy- methyl-3,4,5,6-tetrafluoropyridine. Chromatographic separation (Chromatotron) of the reaction residue, a yellow oil, yielded 0.56 g of a white solid, mp 69-71°C. This white solid was a mixture composed of 90% (2,3,5,6- tetrafluoropyridin-4-yl)meth l cis-3-(2,2-dichloroeth- enyl)-2,2-dimethylcyclopropanecarboxylate and 10% (3,4,5,6-tetrafluoropyridin-2-yl)meth l cis-3-(2,2-di- chloroethenyl)-2,2-dimethylcyclopropanecarbox late, Compound No. 4 of the tables below. Analysis calc'd for C 14 H 1;L C1 2 F 4 N0 2 : C 45.19; H 2.98; N 3.76 Found: C 45.42; H 2.78; N 3.65 EXAMPLE 4A SYNTHESIS OF A MIXTURE OF (2,3,5,6-TETRAFLU0R0- PYRIDIN-4-YDMETHYL AND (3,4,5,6-TETRAFLU0R0- PYRIDIN-2-YDMETHYL CIS-3-(2,2-DIFLUOROETHENYL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATES By the method of Example 2, 1.0 g (0.005 mole) of cis, trans-3-(2,2-difluoroethenyl)-2,2-dimethylcyclopro- panecarbonyl chloride was reacted with 0.91 g (0.005 mole) of a mixture of 4-hydroxymethyl-2,3,5,6-tetra luoro- pyridine and 2-hydroxymethyl-3,4,5,6-tetrafluoropyridine. The crude residue recovered from the reaction, weighing 1.6 g, was passed through a silica column using ether: hexane (1:49) to elute the fractions. The residue remaining after evaporation of solvent from the first fraction weighed 0.5 g and was shown by gas chromatography to contain 84% (2,3,5,6-tetrafluoropyridin-4-yl)methyl cis-3-(2,2-difluoroethenyl)-2,2-dimethylcyclopropanecar- boxylate and 16% (3,4,5,6-tetrafluoropyridin-2-yl)methyl cis-3-(2,2-difluoroethenyl)-2,2-dimethylcyclopropanecar- boxylate, Compound No. 7 of the tables below. Analysis calc'd for C 14 H 11 F 6 N0 2 : c 49 -. 56 » H 3.24; N 4.13 Found: C 50.46; H 3.32; N 4.45 • EXAMPLE 4B SYNTHESIS OF A MIXTURE OF (2,3,5,6-TETRAFLU0R0- PYRIDIN-4-YL)METHYL AND (3,4,5,6-TETRAFLU0R0- PYRIDIN-2-YL)METHYL TRANS-3-(2,2-DIFLU0R0ETHENYL)- 2,2-DIMETHYLCYCL0PR0PANECARB0XYLATES The residue from the second fraction (of Example 4A) weighed 0.4 g and was shown by gas chromatography to contain 50% (2,3,5,6-tetrafluoropyridin-4-yl)methy1 trans- 3-(2,2-di luoroethenyl)-2,2-dimeth lcyclopropanecarboxylate and 50% (3,4,5,6-tetrafluoropyridin-2-yl)methyl trans-5- (2,2-difluoroethenyl)-2,2-dimethylcyclopropanecarboxylate, Compound 9 of the tables below. Analysis calc'd for c i H nF6 N0 2 : C 49 - 56 '> H 3.24; N 4.13; Found: C 50.36; H 3.29; N 4.50. EXAMPLE 5 SYNTHESIS AND ISOLATION OF 4-HYDR0XYMETHYL- 2,3,5,6-TETRAFLUOROPYRIDINE By the method of Example 1, 20.g (0.12 mole) of pentafluoropyridine and 33 g (0.18 mole) of benzophenone were irradiated in 1700 ml of methanol for approximately ninety hours. A brown oil weighing 26 g was recovered from the reaction mixture. Flash distillation of the brown oil produced 20 g of yellow oil which was redis¬ tilled under vacuum, yielding the following fractions: Fraction Head Temperature (°C) Pressure (mm of Hg) 1 50-54 1.-2 2 55-55 1.3 3 57-58 1.3 4 58 1.3 Fraction 4 was found to contain essentially pure 4-hydroxymethyl-2,3,5,6-tetrafluoropyridine. EXAMPLE 6 SYNTHESIS OF (4-HYDR0XYMETHYL-2,3,5-TRIFLU0R0- PYRIDIN-6-YDHYDRAZINE AS AN INTERMEDIATE To a solution of 1.0 g (0.0055 mole) of 4-hydroxy- methyl-2,3,5,6-tetrafluoropyridine (from Example 5) in 50 ml of ethanol was added 0.2 g (0.004 mole) of hydrazine hydrate. This mixture was stirred for approximately twent.y-four hours during which a white precipitate formed. The reaction mixture was filtered, and the filtrate was concentrated by evaporating the solvent under reduced pressure. Water and ether were added to this residue. The ether layer was separated, dried, and the solvent evaporated, leaving a yellow solid, (4-hydroxy- meth 1-2,3,5-trifluoropyridin-6-yl) ydrazine. The structure and nmr data are set forth in Table 1C. EXAMPLE 7 SYNTHESIS OF 2-CHLORO-4-HYDROXYMETHYL-3,5,6- TRIFLUOROPYRIDINE AS AN INTERMEDIATE To a solution of 0.35 g (0.0026 mole) of copper (II) chloride in 25 ml of concentrated hydrochloric acid was added slowly at room temperature 0.5 g (0.0026 mole) of (4-hydroxymeth l-2,3,5-trifluoropyridin-6-yl)hydrazine (from Example 6). This mixture was stirred at ambient temperature for two hours and was then refluxed for one hour. After being cooled, the reaction mixture was poured into water and was extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate, filtered, and the solvent evaporated under reduced pressure, leaving a brown, oily residue. This residue was passed through a short column of silica gel using a hexane/diethyl ether (50/50) mixture as eluant. The appropriate fractions were combined, and the solvent evaporated under reduced pressure, yielding 0.31 g of 2-chloro-4-hydroxymethyl-3,5,6-trifluoropyridine as a yellowish-brown liquid. The structure and nmr spectra are set forth in Table IC. Analysis calc'd for C 6 H 3 C1F 3 N0: C 36.46; H 1.52; N 7.09; Found: C 36.18; H 1.88; N 7.87 ' EXAMPLE 8 SYNTHESIS OF (2-CHL0R0-3,5,6-TRIFLU0R0PYRIDIN- 4-YL)METHYL CIS-3-(2-CHL0R0-3,3,3-TRIFLU0R0PR0- PENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLATE By the method of Example 2, 0.4 g (0.002 mole) of 2-chloro-4-hydroxymethyl-3,5,6-trifluoropyridine (from - Example 7) was reacted with 0.54 g (0.002 mole) of cis-3- (2-chloro-3,3,3-trifluoropropenyl)-2,2-dimeth lcyclopro- panecarbonyl chloride to produce 0.35 g of (2-chloro- 3,5,6-trifluoropyridin-4-yl)methyl cis_-3-(2-chloro-3,3,3- trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate as a light yellow oil, Compound 14 in the Tables below. Analysis calc'd for C 15 H n Cl 2 F 6 N0 2 : C 42.65; H 2.61; N 3.32; Found: C 42.67; H 3.22; N 2.60. EXAMPLE 9 SYNTHESIS OF 4-HYDR0XYMETHYL-2,3,5-TRIFLU0R0PYRIDINE To a suspension of 0.7 g (0.0036 mole) of (4-hydroxy- methyl-2,3,5-trifluoropyridin-6-yl)hydrazine (from Example 6) in 25 ml of distilled water was added a solution of 2.5 g (0.016 mole) of copper (II) sulfate during a 1.5 hour period. Nitrogen evolution continued while the reaction mixture was stirred at ambient temperature for two hours and while it refluxed for an additional two hours. After being cooled, the reaction mixture was extracted with diethyl ether. This extract was dried over anhydrous magnesium sulfate, filtered, and the solvent was evap¬ orated under reduced pressure, leaving a brown oil. This oil was passed through a short column of silica gel using a mixture of diethyl ether and hexane (50/50) as eluant. The appropriate fractions were combined and the solvent evaporated under reduced pressure, yielding 0.3 g of 4-hydroxymethyl-2,3,5-trifluoropyridine as a yellow oil. The structure and nmr spectra for this compound are set forth in Table lC. Analysis calc'd for C 6 H 4 F 3 N0: C 44.17; H 2.45; N 8.59; ' Found: C 44.70; H 2.99; N 8.55. EXAMPLE 10 SYNTHESIS OF (2,3,5-TRIFLUOROPYRIDIN-4-YL)METHYL CIS_-3-(2-CHLORO-3,3,3-TRIFLU0R0PR0PENYL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATE By the method of Example 2, 0.3 g (0.002 mole) of 4-hydroxymethyl-2,3,5-trifluoropyridine (from Example 9) was reacted with 0.5 g (0.002 mole) of cis-3-(2-chloro- 3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecar- bonyl chloride to produce 0.35 g of (2,3,5-trifluoro¬ pyridin-4-yl)methyl cis-3-(2-chloro-3,3,3-trifluoro- propenyl)-2,2-dimethylcyclopropanecarboxylate as a clear, yellow oil, Compound 15 of the tables below. Analysis calc'd for C 15 H 12 C1F 6 N0 2 : C 46.45; H 3.10; N 3.6; Found: C 46.37; H 3.22; N 3.0. EXAMPLE 11 SYNTHESIS OF 4-HYDROXYMETHYL-2-METHOXY-3,5,6- TRIFLUOROPYRIDINE AS AN INTERMEDIATE A mixture of 1.0 g (0.0055 mole) of 4-hydroxymethyl- 2,3,5,6-tetrafluoropyridine (from Example 5) and 0.30 g (0.0055 mole) of sodium methoxide in.25 ml of methanol was refluxed for approximately twenty hours. After being cooled, the reaction mixture was poured into water. The aqueous solution was extracted with diethyl ether. The diethyl ether extract was dried over anhydrous magnesium sulfate, filtered, and the solvent evaporated under reduced pressure, yielding 0.85 g of 4-hydroxymeth l- 2- ethoxy-3,5,6-trifluoropyridine as a yellow oil. The structure and nmr spectra are set forth in Table 1C below. Analysis calc'd for C 7 H 6 F 3 N0 2 : C 43.52; H 3.11; N 7.25; Found: C 43.10; H 3.11; N 7.12. EXAMPLE 12 SYNTHESIS OF (2-METHOXY-3,5,6-TRIFLU0R0PYRIDIN- 4-YL)METHYL CIS-3-(2-CHL0R0-3,3,3-TRIFLU0R0- PROPENYL)-2,2-DIMETHYLCYCL0PR0PANECARB0XYLATE By the method of .Example 2, 0.5 g (0.003 mole) of 4-hydroxymethyl-2-methoxy-3,5,6-trifluoropyridine (from Example 11) was reacted with 0.7 g (0.003 mole) of cis-3- (2-chloro-3,3,3-trifluoropropenyl)-2,2-dimeth lcyclopro- panecarbonyl chloride to produce as a clear oil, Compound 16 of tables below. Analysis calc'd for C 16 H 14 C1F 6 N0 3 : C 45.98; H 3.35; N 3.35; Found: C 45.89; H 3.51; N 3.00. EXAMPLE 13 SYNTHESIS OF 2-DIMETHYLAMIN0-4-HYDR0XYMETHYL- 3,5,6-TRIFLUOROPYRIDINE AS AN INTERMEDIATE A mixture of 1.0 g (0.0055 mole) of 4-hydroxymethyl- 2,3,5,6-tetrafluoropyridine (from Example 5) and 0.23 g (0.0050 mole) of dimethylamine in 25 ml of ethanol was refluxed for approximately twenty hours. The reaction mixture was cooled and was poured into water. This mixture was extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate, filtered, and the solvent evaporated under reduced pressure, yielding 0.9 g of 2-dimethylamino-4-hydroxymethyl-3 , 5, 6-trifluoropyridine as a yellow oil. The structure and nmr spectra are set forth in Table 1C below. Analysis calc'd for CgHgF^O: C 46.60; H 4.37; N 13.59; Found: C 47.18; H 4.42; N 14.51. EXAMPLE 14 SYNTHESIS OF (2-DIMETHYLAMINO-3, 5,6-TRIFLUORO- PYRIDIN-4-YL)METHYL CIS-3-(2-CHLORO-3 , 3,3-TRIFLUORO- PROPENYL)-2, 2-DIMETHYLCYCLOPROPANECARBOXYLATE By the method of Example 2 , 0.5 g (0.002 mole) of 2-dimethylamino-4-hydroxymethyl-3, 5,6-trifluoropyridine (from Example 13) was reacted with 0.6 g (0.002 mole) of cis-3-(2-chloro-3 , 3, 3-trifluoropropenyl)-2, 2-dimethyIcyclo • propanecarbonyl chloride to produce, after purification through a short silica gel column and the Chromatotron, 0.45 g of (2-methoxy-3 ,5, 6- trifluoropyridin-4-yl) methyl cis-3-(2-chloro-3 , 3,3-trifluoropropenyl)-2, 2-dimethyIcyclo propanecarboxylate as an oil, Compound No. 20 of the. tables below. Analysis calc'd for C 17 H 17 C1F 6 2 0 2 : C 47.38; H 3.95; N 6.50 Found: C 47.69; H 4.09; N.6.55 EXAMPLE 15 SYNTHESIS OF 3,5-DICHLORO-2, 6-DIFLUORO 4-HYDROXYMETHYLPYRIDINE AS AN INTERMEDIATE Step A Synthesis of 4-Cyano-3,5-dichloro-2, 6-di- fluoropyridine To a mixture of 40.4 g (0.200 mole) of 3, 5-dichloro- 2,4, 6-trifluoropyridine in 50 ml of dimethylformamide that had been cooled to 0°C was added slowly 10 g (0.20 mole) of sodium cyanide. After addition was complete the reaction was stirred at 0°C for two hours and at room temperature for two hours. The dimethylformamide was distilled from the reaction mixture under reduced pressure, and the black residue was mixed with 200 ml of water. This mixture was extracted with ethyl acetate. The extracts were combined, and the ethyl acetate was evaporated, leaving a black residue weighing approximately 15 g. This residue was distilled, yielding approximately 10 g of 4-cyano-3,5-dichloro-2,6-difluoropyridine as a white solid. The ir and nmr spectra were consistent with the proposed structure. Step B Synthesis of 3,5-dichloro-2,6-difluoro- pyridine-4-carboxaldehyde To a mixture of 10.1 g (0.048 mole) of 4-cyano-3 , 5-dichloro-2, 6-di luoropyridine (from Step A) in 50 ml of toluene that had been cooled to 0°C was added 6.9 g (0.049 mole) of diisobut laluminum hydride. After complete addition the reaction mixture was allowed to warm to room temperature and was stirred for approximately seventeen hours. A mixture of methanol and petroleum ether (2:1) was added to the reaction mixture which was then acidified with dilute sulfuric acid. The organic layer was separated from the aqueous layer and was dried over anhydrous sodium sulfate. After being filtered, the solvent was evaporated under reduced pressure, leaving 6.0 g of 3,5-dichloro-2,6-difluoropyridine-4-carboxaldehyde as a residue. The ir and nmr spectra were consistent with the proposed structure. Step C Synthesis of 3,5-dichloro-2,6-difluoro- 4-hydroxymethylpyridine To a mixture of 5.0 g (0.024 mole) of 3,5-dichloro-2, 6-di- fluoropyridine-4-carboxaldehyde (from Step B) in 100 ml of ethanol that had been cooled to 0°C was added slowly 1.4 g (0.037 mole) of sodium borohydride. After complete addition the reaction mixture was allowed to warm to room temperature and was stirred for approximately seventeen hours . The reaction mixture was quenched with a stoichiometric amount of glacial acetic acid, and the ethanol was evaporated under reduced pressure, leaving a residue. This residue was mixed with dilute hydrochloric acid, and this mixture was extracted with diethyl ether. The combined extracts were washed repeatedly with a 5% aqueous solution of sodium bicarbonate. The extract was dried over anhydrous sodium sulfate and filtered. The solvent was evaporated under reduced pressure, leaving 3.0 g of 3,5-dichloro-2 , 6-difluoro4-hydroxymethylpyridine as a residue. The ir and nmr spectra were consistent with the proposed structure. . EXAMPLE 16 SYNTHESIS OF (3,5-DICHLORO-2, 6-DIFLUOROPYRIDIN- 4-YL)METHYL CIS-3-(2-CHLORO-3 , 3, 3-TRIFLUOROPROPENYL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATE By the method of Example 2 0.6 (0.002 mole) of 3,5-di- chloro2, 6-difluoro-4-hydroxymethylpyridine (Example 15) was reacted with 0.61 g (0.002 mole) of cis-3-(2-chloro- 3,3,3-trifluoropropenyl)-2, 2-dimethylcyclopropanecarbonyl chloride to produce, after purification using the Chromatotron, 0.5 g of (3, 5-dichloro-2, 6-difluoropyridin- 4-yl)methyl cis-3-(2-chloro-3 , 3, 3-trifluoropropenyl)- 2,2-dimethylcyclopropanecarboxylate as a clear, white liquid, compound 21 in the Tables below. The ir and nmr spectra were consistent with the proposed structure. Analysis calc'd for C 1 H 11 C 1 3 F 5 N0 2 : c 41.05; H 2.51; N 3.19 Found: C 41.54: H 2.32; N 2.89 EXAMPLE 17 SYNTHESIS OF (3, 5-DICHLORO-2, 6-DIFLUOROPYRIDIN-4-YL)- METHYL CIS-3-(2,2-DICHLOROETHENYL)-2, 2-DIMETHYL- CYCLOPROPANECARBOXYLATE By the method of Example 2, 0.5 g (0.002 mole) of 3,5-dichloro-2,6-di luoro-4-hydroxymethylpyridine (Example 15) was reacted with 0.5 g (0.002 mole) of cis-3-(2,2-di- chlσroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride to produce, after purification using the Chromatotron, 0.3 g of (3,5-dichloro-2,6-difluoropyridin-4-yl)methyl cis_-3-(2,2-di-chloroethenyl ) -2 ,2-dimethylcyclopropanecarb- oxylate, compound 22 in the Tables below. The ir and nmr spectra were consistent with the proposed structure. EXAMPLE 18 SYNTHESIS OF 4-HYDR0XYMETHYL-2-PHEN0XY- 3,5,6-TRIFLUOROPYRIDINE AS AN INTERMEDIATE To a solution of 5.0 g (0.028- ole) of 4-hydroxymethyl- 2,3,5,6-tetrafluoropyridine in 50 ml of tetrahydrofuran was added 0.64 g (0.028 mole) of sodium metal. The reaction mixture was stirred at room temperature for three hours after which 2.6 g (0.028 mole) of phenol was added, and the mixture refluxed for twenty-one hours . The reaction was cooled to room temperature and then acidified with 10% hydrochloric acid. The resulting solution was extracted with diethyl ether. The combined extracts were dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure, leaving a yellow oil. This yellow oil was chromatographed through silica gel, yielding 4-hydroxymethyl-2-phenoxy-3 ,5, 6-trifluoropyridine as a clear, yellow liquid. The proton nmr and ir spectra were consistent with the proposed structure. EXAMPLE 19 SYNTHESIS OF (2-PHENOXY-3, 5,6-TRIFLUOROPYRIDIN-4-YL)- METHYL CIS-3-(2-CHLORO-3 ,3,3-TRIFLUOROPROPE YL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATE By the method of Example 2,0.5 g (0.0019 mole) of cis-3-(2-chloro-3, 3, 3-trifluoropropenyl)-2, 2-dimethylcyclo propanecarbonyl chloride was reacted with 0.5 g (0.0020 mole) of 4-hydroxymethyl-l-phenoxy-3 ,5,6-trifluoropyridine to produce 0.6 g of (2-phenoxy-3 , 5, 6-trifluoropyridin- -4-yl)methyl cis-3-(2-chloro-3 ,3, 3-trifluoropropenyl)- 2, 2-dimethylcyclopropanecarboxylate as a colorless oil compound 23 in the Tables below. The ir and nmr spectra were consistent with the proposed structure. EXAMPLE 20 SYNTHESIS OF 2-BROMOMETHYL-6-FLUOROPYRIDINE AS AN INTERMEDIATE A mixture of 10 g (0.09 mole) of 2-fluoro-6-methylpyridine and 16 g (0.09 mole) of N-bromosuccinimide in 90 ml of carbon tetrachloride was refluxed for one hour using a sunlamp as heat and light source. The reaction mixture was cooled and filtered. The solvent was evaporated from the filtrate under reduced pressure, leaving 16 g of a brown liquid as residue. This brown liquid was distilled into the following fractions: Fraction Head " emperature Pressure 1 25-35 * C <1 mm 2 80-82 C 0.9 mm 3 83-91 * C 0.9 mm 4 91-92 % C <1 mm Fractions 2 and 3 were >96% pure 2-bromomethyl-6-fluoro- pyridine and were therefore combined. Fraction 4 was composed of a 1:1 mixture of 2-bromomethyl-6-fluoropyridine and 2-dibromomethyl-6-fluoropyridine. The nmr spectra was consistent with the proposed structure for Fractions 2 and 3. EXAMPLE 21 SYNTHESIS OF (6-FLUOROPYRIDIN-2-YL)METHYL CIS-3-(2-CHLORO-3,3,3-TRIFLUOROPROPENYL)-2, 2-DIMETHYL- CYCLCPRO NECARBOXYLATE To a mixture 0.970 g (0.004 mole) of cis-3-(2-chloro- 3,3, 3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylic acid and 0.609 g (0.004 mole) of 1,8-diazabicyclo[5.4.0]- undec-7-ene in 15 ml of acetonitrile was added under nitrogen 0.75 g (0.004 mole) of 2-bromomethyl-6-fluoro¬ pyridine (Example 20). The reaction mixture was stirred for approximately sixteen hours after hich it was diluted with diethyl ether. This mixture was extracted twice with 150 ml of IN hydrochloric acid and once with 150 ml of a saturated aqueous solution of sodium chloride. After drying the organic phase over anhydrous sodium sulfate, it was filtered, and the solvent was evaporated under reduced pressure, leaving an orange oil as residue. This oil was purified on a Chromatotron using methylene chloride/hexane (3/1) as eluant. The proper fractions were combined, and the solvent was evaporated, leaving 0.92 g of (6-fluoro¬ pyridin-2-yl)methyl cis-3-(2-chloro-3, 3,3-trifluoro- propenyl) -2 , 2-dimethylcyclopropanecarboxylate, compound 26 in the Tables below. The ir and nmr spectra were consistent with the proposed structure. Analysis calc'd for C 15 H 14 C1F 4 0 2 N: C.51.23; H.4.01 Found: C:48.04; H:3.45 EXAMPLE 22 SYNTHESIS OF 4-BROMOMETHYL-2-FLUOROPYRIDINE AS AN INTERMEDIATE By the method of Example 20, 10 g (0.09 mole) of 2-fluoro- 4-methylpyridine and 16 g (0.09 mole) of N-bromosuccinimide were reacted in 90 ml of carbon tetrachloride to produce 4.18 g 4-bromomethy1-2-fluoropyridine. The ir, proton nmr, aand 19 nd FF nnimr spectra were all consistent with the proposed structure, EXAMPLE 23 SYNTHESIS OF (2-FLUOROPYRIDIN-4-YL)METHYL CIS-3-(2-CHLORO-3, 3,3-TRIFLUOROPROPENYL)- 2,2-DIMETHYLCYCLOPROPANECARBOXYLATE (Compound 37) By the method of Example 21, 0.970 g (0.004 mole) of cis-3-(2-chloro-3, 3, 3-trifluoropropenyl)-2, 2-dimethylcyclo- propanecarboxylic acid and 0.75 g (0.004 mole) of 4-bromo- methyl-2-fluoropyridine (Example 22) were reacted in the presence of 0.609 g (0.004 mole) of 1, 8-diazabicyclo[5.4.0]- undec-7-ene in 20 ml of acetonitrile to produce 1.09 g of (2-fluoropyridin-4-yl) methyl cis-3-(2-chloro-3 ,3,3- trifluoropropenyl)-2, 2-dimethylcyclopropanecarboxylate, compound 28 in the Tables below. The ir, proton nmr, and 19F nmr spectra were all consistent with the proposed structure. Analysis calc'd for C^H ClF 4 O.N: C:51.23; H.-4.01 Found: C:50.47; H:3.83 The compounds of the invention were tested for biological activity as described below. Initial Southern Corn Rootwor Activity A stock solution of the test compound was prepared by dissolving 4.8 mg in 10 ml of acetone and diluting with 90 ml of acetone/water (1:9). The addition of 5 ml of this stock solution to 30 g of air-dried, clay loam soil in a 3 oz plastic cup provided a concentration of 8 ppm of the test compound in the soil. Serial dilution of the stock solution was used to provide concentrations of the test compound in soil of 4, 2, 1, 0.5, and 0.125 ppm. In all cases 5 ml of a solution having the required concentration was added to 30 g of soil. The treated soil was allowed to stand uncovered in a' hood for 0.5 hour to evaporate the acetone. Before infesting the soil with southern corn rootworm larvae, the soil was mixed thoroughly and two three-day-old corn sprouts were placed in the cup. Ten early third-stage (9-10 days old) southern corn rootworm larvae (Diabratica undecimpunctita howardi Barber) were placed in the cup which was then covered with a plastic lid and placed in a closed plastic bag. After storage at 74-78°F for 48 hours, the mortality of the larvae was determined by removing the cup from the plastic bag, removing the cover, and placing the cup in a modified Berlese polyethylene funnel fitted with an 18-mesh. screen. The funnels were placed over containers of an aqueous detergent solution. Incandescent lights (100 watts) were placed 36 cm above the soil samples. The heat from these lights slowly dried the soil causing ' larvae that had not been affected by the test compound to emerge from the soil and drop into the detergent solution. The percent mortality was determined in this manner for each concentration. Duplicate tests were run at each concen¬ tration. The results of these tests, shown in Table 2, demonstrate outstanding initial activity against southern corn rootworm. Residual Southern Corn Rootworm Activity The residual activity of the test compounds was determined in the same manner as the initial activity except that treated soil was not infested with larvae 5 until 7, 14, 28, and 42 days after treatment, the usual concentration of test compound being 4 ppm. Whenever the mortality dropped below 20% at 7 or 14 days, the remainder of the test was not run. Many of the compounds had excel¬ lent residual activity as shown by the results in Table 3. ° Foliar Insecticide Activity Test compounds were dissolved in a mixture containing 10% acetone, 0.25% octylphenoxypolyethoxyethanol, and 89.75% water to give a solution containing 1000 ppm of the compound. This solution was sprayed on the upper and lower surfaces of the leaves of the green test plants to run-off. After spraying, the plants were allowed to dry. Two replicates of each com- pound were run for each species. Insecticidal activity against the pea aphid (Acyr- thosiphon pisum) was tested by placing a broad bean plant which had been sprayed and had dried into a 1400 ml cup. Each plant was infested with ten aphids, and the cups were then capped. Mortality was determined 48 hours after treatment. Pinto bean plants were used for tests against the Mexican bean beetle (Epilachna varivestis) and the southern armyworm (Spodoptera eridania). For both species treated leaves were removed from the plants and placed in paper cups. Ten individuals of one species were placed in a cup and the cup was then capped. Mortality was recorded 48 hours after treat¬ ment. The twospotted spider mite (Tetranychus urticae) was also tested on pinto beans. The plants were infested by placing a section of a leaf taken from an infested plant onto the test plant to be infested. Approximately 75 mites were used. The test plants were sprayed after infestation and were placed on a shelf at ambient conditions for 48 hours. Mortality was determined at the conclusion of this period. The results shown in Table 4 show the compounds are highl .active against each species against which they were tested. In accordance with the composition aspect of the invention, the compounds are generally not applied full strength but are typically applied as formula¬ tions which may be applied as such or further diluted for application. Typical formulations include com¬ positions of the active ingredient in combination with one or more agriculturally acceptable adjuvants, carriers or diluents, preferably with a surface active agent, and optionally with other active ingre¬ dients. Suitable formulations include solid composi¬ tions such as dusts, wettable powders, and granules or liquid compositions such as solutions, disper¬ sions f suspensions, and emulsifiable concentrates, the choice varying with the type of pest and environ¬ mental factors present at the particular locus of infestation. A typical formulation may vary widely in concen¬ tration of active ingredient and other ingredients depending upon the particular agent used, the addi¬ tives and carriers used, other active ingredients, the desired mode of application, and numerous other factors well known to those skilled in formulating compositions for use in agriculture. With due consideration to these factors, the active ingredient of a typical formulation may, for example, comprise 0.01 percent to 1 percent by weight up to about 95 percent by weight, preferably 1 per- cent up to 90 or 95 percent by weight, of the for¬ mulation. Agriculturally acceptable carriers, diluents, adjuvants, surface active agents, and optionally other suitable active ingredients comprise the balance of the formulation. Thus a typical for¬ mulation may contain from 0.01 to 95 (preferably 1 to 95) percent by weight active ingredient, from 0 to 30 percent by weight surface active agent, and from 5 to 99.99 (preferably 5 to 99) percent by weight of an inert agriculturally acceptable carrier or diluent. Provided below is a general description of exem¬ plary types of formulations which may be employed for application of the compounds of the present invention. SOLID OR DRY FORMULATIONS Dry formulations are mixtures of a liquid or solid active ingredient with a solid carrier to form a particulate product comprising discrete solid par¬ ticles of various sizes. Solid or dry compositions may take the form of dusts, wettable powders and granules having average particle sizes varying from about.5 microns to about 5000 microns. These compositions employ solid or dry carriers and/or diluents which may be selected from one or more of the following: 1. Attapulgite Clay: Characterized as hydrated aluminum-magnesium silicate, with or without free water, and possessing sorptive capacity of at least 35% w/w. 2. Kaolin or Kaolinite Clay: Characterized as hydrated aluminum silicate, and including the species dickite, nakrite, and halloysite, and further charac¬ terized by having low values for cation exchange capacity. 3. Montmorillonite: Characterized as hydrous aluminum silicate derived by natural modification of mica and pyrophyllite, and further sub-divided into swelling (sodium form) and non-swelling (calcium form). 4. Pyrophyllite (Talc): Characterized as hydrous magnesium or aluminum silicate and having neutral to basic pH, and further characterized by low to moderate sorptive capacity. 5. Diatomite: Class of opaline silica skeletal remains of aquatic species which includes diatoma- ceous earth, tripolite, kieselguhr, and fossil flour, characterized by high (85-93%) silica content, and having high absorptive and low adsorptive capacity. 6. Silica: Diverse origin materials charac¬ terized by very high (98-100%) silica content and high (75-100%) sorptive capacity (synthetic), or low sorptive capacity, such as sand. .7. Botanicals: Any material of plant origin capable of being processed into particles of the desired size, including nut shell flours, wood and cellulose flours, corncobs, and the like. 8. Calcium Carbonate Dust formulations are finely divided solid compositions of active ingredient in admixture with a solid carrier. In most cases dust formulations have an average particle size of less than about 50 microns, typically 5 to 40 microns, an active ingred¬ ient content of 1 to 30 percent by weight, and from 70 to 99 percent by weight of one or more of the solid diluents or carriers described above. Since dust formulations are generally applied as such or mixed with other solids for application, they generally do not require a surface active agent or other adjuvants. The following exemplify typical dust formulations: - 1% Dust % W/W Active Ingredient 1.0 Finely Divided Silica 99.0 100.0 10% Dust Active Ingredient 10.0 Kaolin 90.0 100.0 30% Dust Activ.e Ingredient 30.0 Montmorillonite 30.0 Talc 40.0 100.0 Wettable powders are finely divided solid com- positions which disperse readily in water or other liquid vehicles. The wettable powder may be applied as a dry dust or as a dispersion in water or other liquid. Thus, wettable powders are essentially a dust or powder formulation containing a surface active agent in addition to the active ingredient and solid- carrier normally employed in dusts. A wettable powder may thus typically contain from 1 to 95 percent by weight active ingredient, from 1 to 15 percent surface active agent, and from 4 to 98 percent by weight of one"or more of the inert solid or dry carriers or diluents described above. Suitable surface active agents may be selected from the following: 1. Salts or esters of sulfated or sulfonated fatty acids. 2. Salts or esters of ethylene oxide conden¬ sates of sulfated or sulfonated fatty acids. 3. Salts of amine derivatives of various resin and fatty acids including, but not restricted to, palmitic and myristic acids, tall oils, and taurine. 4. Salts of alkylarylsulfonates including alkylnapthalenesulfonates and dialkylnaphthalenesul- fonates. 5. Ethylene oxide condensates of mixed fatty and resin acids. 6. Ethylene oxide condensates of linear or branched chain glycols, secondary alcohols, or alkyl- aryl alcohols. 7. Mixed ethylene oxide and propylene oxide condensates of linear and branched chain glycols. 8. Salts of sulfonated napthalene-formaldehyde condensates. 9. Salts of carboxylated poly-electrolytes. 10. Salts of polymerized alkylnap thalenesul- fonic acids. 11. Salts of lignin sulfonates. 12. Fatty alcohol polyglycol ethers.. 13. Materials of .classes 1, 2, 5, 6, 7 above when sorbed onto a sorptive, wate^r compatible carrier. 14; " Inorganic salts such as tripolyphosphate and hexametaphosphate. 15. Salts and esters of orthophosphoric acid. 16. Fatty acid esters of sorbitan. 17. Ethylene oxide condensates with fatty acid esters of sorbitan. 18. Alkylated alkene mono- and polyhydric alcohols. 19. Sulfonated castor oil. 20. Ethylene oxide condensate with lanolin. 21. Coconut alkanolamides. 22. Sulfated sperm oil. 23. Salts of linear alkyl sulfonates 24. Tall oil ethoxylates. The following are typical wettable powders: 1% Powder % W/W Active Ingredient 1.0 Sodium lignosulfonate 7.5 Sodium laurylsulfate 1.5 Talc 96.0 Total 100.0 5% Powder Active Ingredient 5.0 Sodium lignosulfonate 1.5 Sodium alkylnaphthylene 1.5 sulfonate Attaclay 92.0 Total 100.0 25% Powder Active Ingredient 25.0 Sodium lignosulfonate 1.5 Sodium laurylsulfate 1.5 Montmorillonite 72.0 Total 100.0 90% Powder % W/W Active Ingredient 90.0 Sodium dibutylnaphthalene- sulfonate 0,5 Sodium lignosulfonate 3.5 Kaolin clay 6.0 Total 100.0 Granules are solid or dry compositions of active ingredient deposited on or in a large particle. Granules usually have an average particle size in the range of 150 to 5000 microns, typically 425 to 850 microns. Granular formulations generally contain from 1 to 50 percent by weight of active ingredient, from 1 to 15 percent by weight of one or more of the surface active agents described above, and from 50 to 98 percent by weight of one or more of the inert solid or dry carriers or diluents described above. Granular formulations may be of several types. Impregnated granules are those in which the active ingredient is applied, normally as a solution, to large particles of an absorbent diluent or carrier such as attapulgite or kaolin clay, corncobs or expanded mica. Surface coated granules are granules produced by adhering an active ingredient in finely divided form on the surface of a generally non-absor¬ bent particle or by applying a solution of active ingredient to the surface of such a carrier. The carrier or core may be water soluble, such as prilled fertilizer or urea, or insoluble., such as sand, marble chips, corncobs, or coarse talc, as described above. Particularly useful are granules wherein a wettable powder is adhered as a surface coating to a sand or other insoluble particle, so that the wettable powder may be dispersed on contact of the granule with mois¬ ture. Granules may also be produced by agglomeration of dusts or powders, by compaction, by extrusion through a die, or by use of a granulation disk. The following are typical granular formulations: 1% Granule % W/W Active Ingredient 1.0 Attapulgite 99.0 Total 100.0 5% Granule Active Ingredient 5.0 Attapulgite 95.0 Total 100.0 The granules above may be prepared by dissolving the active ingredient in a volatile solvent such as methylene chloride, coating large particles of attapulgite clay with the solution, then allowing the solvent to evaporate. As indicated above, granules may also be adhered to a nonabsorbent core material. The following are typical formulations: 5% Sand-Core Granule % W/W 75% Powder Base 6.64 Active compound 75. .0 Sodium alkylnaphthalene- sulfonate 1. .0 Sodium lignosulfonate 4. ,0 Barden clay 20. ,0 Dilute Polyvinylacetate 1.75 Silica (425-850) 91.61 Total • . ,100.00 47.5% Sand-Core Granule % W/W 95% Powder Base 50.0 Active compound 95.0 Sodium alkylnaphthalene- sulfonate 1.0 Sodium lignosulfonate 4.0 Dilute Polyvinylacetate 2.0 adherent Silica (425-850) 48.00 Total 100.00 The foregoing sand-core granules may be prepared by incorporating the active compound into the base, then adhering the base to sand, utilizing an adhesive such as polyvinylacetate to assure adhesion. LIQUID AND SEMI-LIQUID FORMULATIONS Liquid formulations are those which contain the active ingredient dissolved or dispersed in one or more inert liquid carriers or diluents, containing from 0.01 to about 95% active ingredient. Carriers suitable for use in liquid formulations may be selected from the following: 1. Water 2. Aliphatic petroleum solvents including kero- sene, light refined mineral oils, and diesel oils. 3. Aromatic petroleum solvents including coal tar fractions yielding xylene, toluene, and benzene; light, medium, and heavy aromatic naphthas; and alkylated mixed naphthenics. 4. Alcohols such as ethanol and isopropyl alcohol. 5. Alkyl ethers of glycols. 6. Esters including dibutyl phthalate, di-2- ethylhexyl phthalate, and ethyl acetate. 7. Ketones including cyclohexanone, methyl iso- butyl ketone, acetone, diacetone, and isophorone. 8. Chlorinated hydrocarbons including ethylene dichloride, methylene chloride, chlorobenzene, chlo¬ rinated toluene, and chlorinated xylene. 9. Vegetable oils including cottonseed, soy¬ bean, pine, sesame, and palm oils. 10. Aqueous solutions of natural origin such as liquors obtained in processing natural sugar pro¬ ducts, and fermentation broths. Solutions are liquid compositions containing from about 0.01 to 95 percent by weight active ingredient and from 1 to 99.99 percent by weight of one or more of the inert liquid diluents or carriers described above. These may be applied as such or further di- luted for application. Suspensions or dispersions (also sometimes called flowable formulations) are liquid formulations con¬ taining from 0.01 to 95 percent by weight active ingredient and from 1 to 99.99 percent by weight of an inert liquid diluent or carrier, in which the active ingredient is wholly or partially insoluble in the diluent or carrier at the concentration level employ¬ ed. Suspension or dispersion is frequently facilitated by incorporating from 1 to 30 percent by weight of one or more surface active agents described above, alone or together with a thickner or suspending agent. Like solutions, dispersions may be used as such or further diluted with a liquid carrier for application. The following illustrate suspensions suitable for use in the present invention: 25% Oil Suspension: % W/W Active ingredient . 25.0 polyoxyethylene sorbitol hexaeleate 5.0 aliphatic hydrocarbon oil 70.0 Total 100.0 1% Aqueous Suspension: % W/W Active ingredient 1.0 Polyacrylic acid thickener 0.3 Sodium alkylnapthalenesulfonate 1.0 Sodium lignosulfonate 4.0 Polyvinyl alcohol suspending agent 1.0 Water 92.7 Total 100.0 20% Aqueous Suspension: Active ingredient 20.0 Polyacrylic acid thickener 0.3 Sodium alkylnapthalenesulfonate 1.0 Sodium lignosulfonate 4.0 Polyvinyl alcohol suspending agent 1.0 Water 73.7 Total 100.0 40% Aqueous Suspension: Active ingredient 40. , 0 Polyacrylic acid thickener 0. , 3 Dodecylphenol polyethylene glycol ether 0. , 5 Disodiura phosphate 1. , 0 Monosodium phosphate 0. , 5 Polyvinyl alcohol 1. , 0 Water 56. 7 Total 100.0 E ulsifiable concentrates (EC's) are homogeneous liquid compositions, containing the active ingredient dissolved in a liquid carrier. Commonly used liquid carriers include xylene, heavy aromatic naphthas, isophorone, and other nonvolatile or slightly volatile organic solvents. For application these concentrates are dispersed in water, or other liquid vehicle, forming an emulsion, and are normally applied as a spray to the area to be treated. The concentration of the essential active ingredient in EC's may vary according to the manner in which the composition is to be applied, but, in general, is in the range of 0.01 to 95 percent by weight of active ingredient. Also included in the composition are from 1 to 30 percent by weight surface active agent and from 4 to 97.99 percent of one or more of the inert liquid carriers described above. The following are typical EC compositions: 1% Emulsifiable Concentrate % W/W Active Ingredient 1.0 Anionic calcium dodecylbenzene- sulfonate 4.2 Nonionic polyethoxylated nonylphenol (Mol. Wt. 450-500) 0.4 Nonionic polyethoxylated nonylphenol (Mol. Wt. 1400-1600) 1.1 Nonionic paste of 100% poly- alkalene glycol ether 0.4 Xylene 92.9 Total 100.0 5% Emulsifiable Concentrate Active Ingredient 5.0 Anionic calcium dodecylbenzene- ' sulfonate 4.2 Nonionic polyethoxylated .nonylphenol (Mol. Wt. 450-500) 0.4 Nonionic polyethoxylated nonylphenol (Mol. Wt. 1450-1600) 1.1 Nonionic paste of 100% poly- alkylene glycol ether 0.4 Xylene 88.9 Total 100.0 10% Emulsifiable Concentrate % W/W Active Ingredient 10.0 Blend of alkyInaphthalenesulfonate and polyoxyethylene ethers 4.0 Xylene 86.0 Total 100.0 50% Emulsifiable Concentrate Active Ingredient 50.0 Blend of alkylnaphthalenesulfonate and polyoxyethylene ethers 6.0 Epoxidized soybean oil 1.0 Xylene 43.0 Total 100.0 75% Emulsifiable Concentrate Active Ingredient 75.0 Blend of alkylnaphthalenesulfonate and polyoxyethylene ethers 4.0 Xylene 21.0 Total 100.0 Other useful formulations include simple solu¬ tions of the active ingredient in a relatively non-volatile solvent such -as corn oil, kerosene, propylene glycol, or other organic solvents. This type of formulation is particularly useful for ultra low volume application. The concentration of the active ingredient in use dilution is normally in the range of about 2% to about 0.1%. Many variations of spraying, dusting, and con- trolled or slow release compositions in the art may be used by substituting or adding a compound of this invention into compositions known or apparent to the art. These compositions may be formulated and applied with other suitable active ingredients, including nematicides, insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc. In applying the foregoing chemicals, an effective insect controlling amount of active ingredient must be applied, sometimes referred to herein as an insectici- dal amount. While the application rate will vary widely depending on the choice of compound, the formulation and mode of application, the plant species being protected and the planting density, a suitable use rate may be in the range of 0.10 to 0.50 kg per hectare, preferably 0.25 to about 1.5 kg/hectare. The compounds of this invention may be applied by incorporating or applying a formulation thereof to a food source for the insects to be controlled, i.e. the locus where control is required, including application to the above ground portions of plants on which the insects feed, to the soil in which plants are or are about to be planted in order to provide control of soil-borne insects, or in a bait-type formulation for application to surfaces on which insects normally do not feed. When applying the compounds to the soil, the compounds may be broadcast broadly over the planted area or the area to be planted or by .limiting the application to a small area or band in the root zone where plants are or are to be planted. When either method of soil application is used, sufficient compound must be applied to provide an insect con¬ trolling concentration of the compound in the soil in the root zone. For the present a suitable concentra- tion is about 0.2 to about 50 parts by weight of com¬ pound per million parts of soil. TABLE 1A COMPOUNDS OF FORMULA I Compound No. R J (b ) R 1 X Isomer Ratio 1 A F F 90/10 2 A F F 0/100 3 B F F 95/5 4 C F F 90/10 5 D F F 93/7 6 E F F 100/0 7 F F F 85/15 8 G F F 90/10 9 G F F 50/50 10 H F F 100/0 11 I F F 62/38 12 J F F 100/0 13 K F F 100/0 14 A ' F Cl 100/0 15 A F H 100/0 16 A F OCH 3 100/0 17 C F OCH 3 100/0 22 C Cl F 100/0 23 A F phenoxy 100/0 24 C F phenoxy 100/0 25 C F F 30/70 26 A H H 0/100 27 C H H 0/100 28 A H H 100/0 29 C H H 100/0 Footnotes: (a) A = cis-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2- dimethyl cyclopropyl B = trans-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2- dimeth 1cyclopropyl C = cis-3-(2,2-dichloroethenyl)-2,2-dimethylcyclo- propyl D = trans-3-(2.2-dichloroethenyl)-2,2-dimethyl- cyclopropyl E = cis-3-(2,2-dibromoethenyl)-2,2-dimeth lcyclo- propyl F = cis-3-(2,2-difluoroethenyl)-2,2-dimethylcyclo- propyl G = trans-3-(2,2-difluoroethenyl)-2,2-dimethyl- cyclopropyl H = cis-3-(l,2-dibromo-2,2-dichloroethyl)-2,2- dimeth 1cyclopropyl I ■ trans-3-(l,2-dibromo-2,2-dichloroethyl)-2,2- dimethy1cyclopropyl J = 2,2,3,3-tetramethylcyclopropyl K = l-(4-chlorophenyl)-2-methylpropyl (b) Isomer ratio = substituted-pyridin-4- lmethyl ester substituted-pyridin-2- lmeth l ester TABLE IB Cmpd. No. Proton NMR a > 19 F NMR b > c 1 1.31(s,6H), -69.3(s,3F), 1.90-2.25(m,2H), -90.7(m,2F), 5.32(t,2H, -144.5(m,2F) JHF=1-5), 6.89 (dt,lH, HH=8» JHF=1-5) 2 1.30(s,3H), -69.3(s,3F), 1.33(s,3H), -89.3(m,lF), 2.00-2.40(m,2H), -138.9(m,lF), 5.20(d,2H, -146.2(m,lF), J H F=2), 6.90 -157.2(m,lF). (dt,lH,J H H=8, J HF =1.5) 3 1.27(s,3H), 1.35(s,3H), 1.82(d,lH,J H H=5), 2.43(m,lH), 5.32(t,2H,J H F β l-5), 6.17(dt,lH,JHH=S, J H F=1.S) 4 1.30(s,6H), -90.41(m,2F), 1.75-2.20(m,2H), -143.70(m,2F). 5.30(t,2H,J H F=l-5), 6.20(d,lH,J H H=8)- 5 1.23(s,3H), 1.30(s,3H), 1.65(d,lH,J=6), 2.00-2.40(m,lH), 5.30(t,2H,JHF=1.5), 5.63(d,lH,J=8) 6 1.20(s,6H), -90.8(m,2F), 1.60-2.10(m,2H), -143.5(m,lF), 5.20(t,2H, ■ -145.8(m,lF). J{jp=l.5) , 6.63 (d,lH,J HH =S) TABLE IB (Continued) Cmpd. No. ProtonJNMRa , b 19p NMR b > c 7 8 1.18(s,3H), 1.27(s,3H), 1.52(dd,lH,J H H e 6) ) 2.03(m,lH), 4.10(ddd, 1H,J H H=6, J HF =8 and 24), 5.32(t,2H,JHF=l-5). 9 1.18(s,3H),1.28(s,3H), 1.68(m,lH), 2.03(m,lH), 4.10(ddd,lH,JHH=6 JHF=8 and 24), 5.22-5.30(d and t, 2H, JHF=2)- 10 1.30(m,6H), 1.60(m,lH), 1.90-2.30(m,lH), 4.40(t,lH,J=10), 5.30(m,2H). 11 1.30(m,6H), 1.90-2.10(m,2H), 5.00-5.20(m,lH), 5.30(m,2H). 12 1.22(s,6H), 1.27(s,6H), 1.20-1.30(s,lH), 5.27(t,2H,JHF=l-5). 13 0.75(d,3H,J=6), 1.06(d,3H,J=6), 2.00-2.30(m,lH), 3.20(m,lH), 5.28(t,2H,JHF=l-5), 7.28(s,4H). TABLE IB (Continued) Cmpd. No. Proton NMR a > D l^F NMR b »c 14 1.30(bs,6H), -69.3(s,3F), 1.80-2.30(m,2H), -89.1(dd,lF, 5.20(t,2H, JFF= 6 and 30), J HF =1.5),6.92 -132.1(d,lF, (bd,lH,J=8) JFF=30), -139.2(d,lF, JpF β 26). 15 1.33(s,6H), -69.2(s,3F), 1.80-2.40(m,2H), -87.7(dd,lF, 5.30(t,2H, JpF=22 and 30), JHF SS 1«5),6.80 -122.37(dd,lF, (bd,lH,J=8), JpF = 30,JHF = 2.5) 7.97(m,lH). -140.42(dd,lF, JFF=22,JHF = 2.5) 16 1.32(s,6H), -69.28(s,3F), 1.90-2.40(m,2H), -94.15(dd,lF, 4.00(s,3H), Jpp=22 and 31) , 5.27(bs,2H), -144.38(dd,lF, 6.90(bd,lH) JFF=31,JHF=2), -154.1(dd,lF ; JpF=22, JHF = 3 . 17 1.25(s,6H), -94.23(dd,lF, 1.60-2.20(m,2H), JFF= 2 and 31), 4.00(s,3H), -144.28(dd,lF, 5.28(bs,2H), JFF=31, HF=2) , 6.25(d,lH,J=8). -153.98(dd,lF, JFF=22,JHF=3 . 18 1.23(s,6H) 1.60-2.10(m,2H), 4.00(s,3H), 4.20-4.90(m,lH), 5.25(t,2H,J H F=l-5). Table IB (continued) Compd No. Proton NMRa,b 19F NMRb,c 20 1.28(s,6H) , -69.37(s,3F) , 1.90-2.40 (m,2H) -92.61(dd,1F) , 3.05(d,6H,J=2) , J p _=25 and 33) , 5.20t,2H,J=1.5) , -137.00(dt,lF, 6.55(d,lH,J=8) . ^ σp = 33.J- j _=2 , -l59.12(c!cl,1F, J FF =25,J HF =6) ' 21 1.35(s,6H), 1.7- -69.22 (3F) , 2.2(m,2H) , 5.42 -70.67 (2F) (d,2H) , 6.93 (bd,lH) . 22 1.32(s,6H), 1. 6- -70.80 2.25(m,2H) , 5, 38 (d,2H), 6.22 (d,lH). 3 1.42(d,6H), 2.0- -69.12(d,3F) , 2.5( ,2H), 5.32 -94.5(m,lF) , (s,2H) , 6.8-7.8 -146.50(m,1P) , (m,5H) . -155.6(m,1F) . 4 1.31(s,6H), 2.0- -94.6(ra,1F) , 2.35( ,2H) , -146.50(m,1F) , 5.31(s,2H), 6.2- -155.8(m,1F) . -6.4(m,lH), 7.0- 7.6(m,5H) . 5 1.28(s,6H) , 1.85- -83.22(m,0.7F) , 2.3(m,2H), 5.35 -90.43(m,0.6F) , (dt,2H), 6.38 -138.7(m,0.7F) , (m,1H) . -143.59(m,0.6F) -146.11 (m,0.7F) -157.10(m,0.7F) 6 1.33(bs,6H),2.0- -67.33(d,lF, 2.4(m,2H)-, 5.2 J=8Hz) , -69.16 (bs,2H) , 6.8- (s,3F). 8.0(m,4H) . 7 1.28(s,6H) , 2.0- -67.40(d,1F, (m,3H) . Table 1B ( continued ) Co pd No. Proton NMRa,b 19F NMRb c 28 1.33(d,6H), 1.8- -67.97(d,lP) r 2.2(m,2H) , 5.15 -69.3(s,3F) . (bs,2H), 6.8-7.3 (m,3H), 8.27 (d,1H). 29 1.30(bs,6H) , -€8.0(d,1P) 1.75-2.2(m,2H) , 5.15(bs,2H) , 6.2 (bd,1H) , 6.8-8.2(m,3H) TABLE 1C COMPOUNDS OF FORMULA II Cmpd. of Example R 1 X 9. Proton NMR(a) 19F NMR(a) 6 F NHNH2. OH -94.95 (dd, IF, JpF=4 and 32) -148.85(d,lF, J FF =32), 160..69(d,lF, FF=4) 7 F Cl OH 2.50(bs,lH), -88.01(dd,lF, 4.90(bs,2H). JFF=24 and 29) -124.40(dd,lF, JFF=4 and 29), -142.51(dd,lF, JpF=4 and 24). 9 F H OH 2.55(bm,lH), -89.50(t,lF, 4.90(bs,2H), JFF=28), 7.20-7.90 -133.95(dd,lF, (m,lH), JpF = 30 and 2), -141.34(d,lF, JFF=28). 11 F 0CH 3 OH 3.07(bs,lH), -94.80(dd,lF, 4.00(s,3H), JpF=22 and 30), 4.83(bs,2H).- -146.36(d,lF, FF'30), -155.86(d,lF, JpF=22). 13 F N(CH 3 ) 2 OH 3.05(dd,7H, -93.35(dd,lF, J=2 and 4), JFF=25 and 29) 4.75(t,2H, -138.45(d,lF, J=l). JpF=32) , -160.43(dd,lF, JpF=3 and 25). 15 Cl F C&≠ 2.67(t,lH), -71.19(s,2F) e 4.92(d,2H). 18 F phenoxy O≠ 4.8-4.9(t, -93.0(m,0.2F), lH),5.5(bs, -93.42(m,0.8F), 2H), 6.7- -140.9(m,0.2F), 7.4(m,5H). -142.5(ra,0.8F), -145.3(m,o.2F), Cmpd. of Example Rl X 1 Proton NMR(a) 19p NMR(a) 20 H H Brg 4.47(s,2H), -66.9(d,lF) 6.75-8.0(m,3H). 22 H H Br h 4.77(s,2H), -68.13(s,lF). 7.05-7.30 (m,2H), 8.23 (d,lH). (a) See footnotes for Table IB. (d) 100% 4-hydroxymethyl substituent (e) Reference compound was hexafluorobenzene and solvent was CDCI3 (f) Ratio 4-hydroxymeth l compound/2-hydroxymethylcompound was 80/20, however, esters prepared from this mixture were isolated by chromatography and consisted 100% of the pyridin-4-ylmethyl isomer. (g) 100% 2-bromomethyl-6-fluoropyridine (h) 100% 4-bromometh 1-2- luoropyridine TABLE 2 INITIAL ACTIVITY AS SOIL INSECTICIDES Percent Mortal i ty Cmpd. No. 4 ppm 2 ppm 1 ppm 0.5 ppm 0.25 ppm 1 100 a 100 a 90 a 93 a 40 2 85 50 35 20 15 3 100 a 100 85 40 15 4 100 b 93 b 45 45 5 5 6 7 100 100 a 85 65 15 8 95 a 90 a 55 25 30 9 100 70 65 30 20 10 45 30 20 5 11 90 65 30 35 25 12 95 30 10 5 5 13 14 100 90 30 15 10 15 100 85 45 5 0 16 95 90 90 50 5 17 73 17 7 0 0 18 90 55 10 0 0 19 80 10 5 0 0 20 100 100 45 5 5 21 100 90 75 70 50 22 95 80 40 30 10 23 100 90 65 65 55 24 95 65 35 25 10 25 100 85 60 50 35 26 90 85 85 65 55 27 100 60 50 45 25 a . Average of 2 results b . Average of 3 results TABLE 3 RESIDUAL ACTIVITY AS SOIL INSECTICIDES Percent Mortali ty 7 Days 14 Days 28 Days 42 Days Cmpd. No. 8 ppm 4 ppm 4 ppm 4 ppm 2 ppm 1 100 100 a 90 a 80 a 80 2 0 3 100 90 a 80 a 25 a 4 100 a 85 a 75 a 0 7 100 95 a 100 a 90 a 15 8 100 50 0 0 9 20 5 a 11 20 12 10 14 20 15 5 16 90 90 40 . 17 16 18 37 33 19 0 - 20 10 21 95 55 20 22 75 70 25 23 65 45 - 24 100 65 - 25 100 95 90 .26 90 95 45 27 65 50 40 Footnotes : See Table 2 TABLE 4 RESULTS OF FOLIAR INSECTICIDE SCREEN AT 1000 ppm Percent Mortality Mexican Cmpd. * Bean Pea Southern Twospotted No. Beetle 3 Aphidb Armyworm c Spider Mited 1 100 100 100 0 2 0 0 0 0 3 100 100 100 0 4 100 100 100 0 5 100 100 100 0 6 100 100 100 0 7 0 0 20 0 8 0 0 0 0 9 0 50 40 0 10 100 40 45 0 11 100 100 100 0 12 0 .0 0 0 13 95 100 0 0 14 50 100 100 0 15 100 0 0 0 16 100 100 100 0 17 100 100 100 0 18 100 100 100 0 19 65 95 50 80 20 0 100 100 100 21 100 100 50 0 22 100 100 50 0 23 0 0 ' 0 0 24 0 0 0 0 25 100 100 60 100 26 0 0 0 0 27 0 0 0 0 a. Epilachna varivestis b. Acyrthosiphon pisum c. Spodoptera eridania d. Tetranychus urticae

Claims: Claims : 1. A compound characterized by the formula in which X is hydrogen, halogen, C, 2 a ^ c ox , phenoxy, or amino; R is 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimeth Icyclo- propyl; 3-(2,2-dihaloethe yl)-2,2-dimeth lcyclopropyl; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimeth lcyclopropyl; 2,2,3,3-tetramethylcyclopropyl; or l-(4-chlorophenyl)-2- methylpropyl; and R is hydrogen or a halogen. 2. The compound of claim 1 characterized in that X is at position 2 and the carboxylate moiety is attached at position 4.. 3. An insecticidal composition characterized by an insecticidal amount of a compound of the .formula in which X is hydrogen, halogen, C,_ 2 alkoxy, phenoxy, or di(C-,_2 a lk l)amino; ^ i- s 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopro- pyi; 3-(2,2-dihaloethenyl)-2,2-dimethylcyclopropyl; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimeth lcyclopropyl; 2,2,3,3-tetramethylcyclopropyl; or l-(4-chlorophenyl)-2- ethylpropyl; and R is hydrogen or a halogen, in admixture with at least one agriculturally acceptable carrier, vehicle, or adjuvant. 4. The insecticidal composition of claim 3 charac¬ terized in that X is at position 2 and the carboxylate moiety is attached at position 4. 5. A method for controlling insects characterized by applying to the locus where control is desired an insec¬ ticidal amount of a compound of the formula in which X is hydrogen, halogen, C,_-alkoxy, phenoxy or di(C, 2 alkyl)amino; R is 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimeth Icyclo- propyl; 3-(2,2-dihaloethenyl)-2,2-dimeth lc cloprop l; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropyl; 2,2,3,3-tetramethylcyclopropyl; or l-(4-chlorophenyl)-2- methylpropyl; and R is hydrogen or a halogen. 6. The method of claim 5 characterized by applying to the locus where control is desired an insecticidal amount of the compound in which X is at position 2 and the carboxylate moiety is attached at position 4. 7. A method for preparing a compound of the formula: characterized by reacting a fluoropyridinylmethanol of the formula in which X is hydrogen, halogen, C, -alkoxy, phenoxy, or di(C, _--alkyl)amino and R is hydrogen or a halogen, with a compound of the formula RC0C1 in which R is 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimeth lcyclo¬ propyl; 3-(2,2-dihaloethenyl)-2,2-dimeth lcyclopropyl; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropyl; 2,2,3,3-tetramethylcyclopropyl; or l-(4-chlorophenyl)-2- methylpropyl. 8. A method for preparing a compound of the formula: characterized by reacting a fluoropyridinylmethylbromide of the formula in which X is hydrogen, halogen, C, 2 alkoxy, phenoxy, or di(C. 2 -alkyl)amino and R is hydrogen or a halogen, with a compound of the formula RCOOM in which R is 3-(2-chloro-3,3,3-tri luoropropenyl)-2,2-dimeth Icyclo- propyl; 3-(2,2-dihaloethenyl)-2,2-dimethylcyclopropyl ; 3-(l,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropyl ; 2,2,3,3-tetramethylcyclopropyl ; or l-(4-chlorophenyl)-2- raethylpropyl and M is hydrogen or a cation. 9. A compound of the formula in which X is hydrogen, chloro, ethoxy, dimethylamino, phenoxy or hydrazino; R is hydrogen or halogen; and Q is a leaving group, readily displaced by carboxylate anions. 10. The compound of claim 9 characterized in that Q is hydroxy or bromo. 11. The compound of claim 9 characterized in that Q is hydroxy, RI is chlorine, X is fluorine, the carboxylate group is attached at position 4 of the pyridinyl ring, and X is at position 2 of the pyridinyl ring. 12. A method for controlling acarids characterized by applying to the locus where control is desired an acaricidal am of the formula in which X is methoxy and R is trans-3-(2,2-difluoro- ethenyl)-2,2-dimethylcyclopropyl or X is dimethylamino and R is 3-(2-chloro-3,3,3-tri luoropropenyl)-2,2-dimethyl- cyclopropyl. 13. A method for controlling acarids characterized by applying to the locus where control is desired an acaricidal amount of a compound of the formula where R is cis-3-(2 yl)-2, 2-dimethylcyclo- propyl.

Inventors: ENGEL JOHN FRANCIS, PHILLIPS RICHARD BENTON, PLUMMER ERNEST LOCKHART, ENGEL, JOHN, FRANCIS, PHILLIPS, RICHARD, BENTON, PLUMMER, ERNEST, LOCKHART
Applicants: FMC CORP, FMC CORPORATION
Application year: 1985
Main classification: A01N43
IPC codes: A01N43, A01N53, C07D213