IE45656B1 - Insecticidal styryl- and substituted-styryl-cyclopropanecarboxylates - Google Patents

Abstract

The insecticide contains, as active ingredient, a compound of the formula: in the form of a mixture with an agriculturally acceptable extender. The compounds of the formula I are prepared by 1) Reacting a compound of the formula: with a phosphonium salt of the sub-formula: 2) Hydrolysing the resulting ester of the formula: 3) Converting the free acid obtained into an acid halide and 4) Esterifying the acid-halide with an alcohol of the formula R-OH. In the formulae, R, X, Y and n have the meanings given in Patent Claim 1 and R' has the meaning given in Patent Claim 9.

Description

Ever since the structures of naturally occurring pyrethroids were elucidated, efforts have been directed toward the preparation of related compounds of enhanced insecticidal activity and improved stability toward air and light. A noteworthy advance in this area was the discovery by Elliott and co-workers of certain highly active compounds remarkably resistant to photooxidative degradation, for example, 3-phenoxybenzyl 3-(f5 ,β-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, Nature, 246, 169 (1973), Belgian Patents 800,006 and 818,811.

Despite extensive research in the field of insecticidal cyclopropanecarboxylates, insecticidal styrylcyclopropanecarboxylates of the type described herein have not been described prior to the present invention.

In accordance with the present invention there are provided new (styryl and substituted styryl)-cyclopropanecarboxylates having the formula: in which X is halogen, such as fluorine, Chlorihe or bromine; 20 cyano; nitro; aryl, such as phenyl, thienyl, furyl or pyridyl; aralkyl, such as benzyl; aryloxy; arylthio; Cj._4 alkyl; Cj_4 alkoxy; C2_4 alkylthio; C1-2 haloalkyl; di(C1_2 alkyl) amino or methylenedioxy; Y is hydrogen; halogen for example chlorine, bromine or fluorine; cyano; C^_4 alkyl, C^_2 halo25 alkyl, methoxycarbonyl or ethoxycarbonyl; n is 0, 1, 2 or 3, preferably Ο, 1 or 2; and R is the residue of an alcohol which in combination with an appropriate acid residue yields an insecticidal cyclopropanecarboxylate.

The (styryl and substituted styryl)-cyclopropanecarboxy5 late compounds of the present invention are insecticidal esters of 2,2-dimethy1-3-(β-phenylvinyl)cyclopropanecarboxylic acid, 2,2-dimethy1-3-/5-(substituted phenyl)viny17cyclopropanecarboxylic acids, 2,2-dimethy l-3~/Ji-phenyl-3-(substituted vinyl)/ cyclopropanecarboxylic acids, and 2,2-dimethyl-3-/B-(substituted phenyl)-β-(substituted vinyl)J7-cyclopropanecarboxylic acids.

A wide range of alcohol residues is known in the insecticide art and is useful in the present invention, for example: 456 5 6 \=Aa-O (1) a benzyl-or phenoxy-substituted benzyl group of the formulas where Z is hydrogen, methyl, cyano, ethynyl, or phenyl, .-0- or -CH2-j a benzyl-or phenoxy-substituted furylmethyl group such as 5-benzyl-3-furylmethylj an iraidomethyl group such as maleimidomethyl, phthalimidomethyl, and tetrahydrophthalimidomethyl; a benzyl group substituted in at least two ring positions with chloro, methyl, or methylenedioxy groups, for example 3,4-methylenedioxybenzyl, 2-ehloro-4,5-methylenedioxybenzyl# and 2,4dimethylbenzyl; a substituted cyclop?ntenonyl group such as allethrolonyl. commonly used R groups which give active insectithe present invention ares 3-phenoxybenzyl, α-cyano-3-phenoxybenzyl, and 5-behzyl-3-furylmethyl.

Hi tile substituents X and Y, the C£_4 alkyl groups, preferably v&ave cme or two carbon atoms. Examples of haloalkyl substituents include triehloromethyl and trifluoromethyl groups.

The present invention also provides a process for the preparation of insecticidal-(styryl.and ; and A is (2) (.3) (4) (5) The aides of - 4 45656 substituted styryl) oyclopropanecarboxylates of formula I, above, which comprises reacting a compound of the formula: CH3 ν >CH3 OHC .COOR' wherein· R' is C1-4 alkyl, with a phosphonium salt of partial formula: xy ,CH Y (XI) (III) where X, Y, and n are as defined above, in the presence of a Strong base and preferably in the presence of an essentially anhydrous inert solvent, preferably under an inert atmosphere,to give an ester of the formula: ch3. chs ,xy •C = CHy -COOR' (la) where X, Y, n and R' are as defined above, hydrolysing the ester and reesterifying by conversion to the acid halide and treatment with an alcohol of the formula R-OH where R is as defined above.

In the above process, the phosphonium salt is converted in the presence of the strong base to the corresponding phosphorane: λ -C = pR (Ilia) which reacts with the cyclopropanecarboxaldehyde.

The strong base used in the above process may be an alkyllithium such as rj-butyllithium, or an alkali metal hydride, .amide, or alcoholate. 48656 The inert solvent used in the reaction of the eyclopropanecarboxaldehyde may be any of the solvents commonly used in Wittig-type reactions, including benzene, tetrahydrofuran, dimethoxyethane·and'dimethylformamide. 5Ehe reaction may suitably be carried out at 0-35°C for 1-24 hours, •i The hydrolysis of the resulting ester in the above described process may be effected with base.

Reesterification of the resulting acid in the above 10 process may be accomplished by treatment with thionyl chloride in an anhydrous inert solvent under an inert atmosphere in the presence of a base such as pyridine at ambient temperature, followed by the addition of the alcohol R-OH.

Certain of the intermediate conpounds, viz, those of formula la above where Y is cyano or halogen, may optionally be prepared by the following methods. The compounds in which Y is cyano may be readily prepared by the base-catalysed condensation of an appropriately substituted benzyl cyanide with a eyclopropanecarboxaldehyde of formula II. The compounds in which Y is halo may be readily prepared by the treatment Cf a dialkyl benzylphosphonate, appropriately substituted on the phenyl ring, with a strong base such as rv-butyllithium at low temperature (about -7.8°), followed by the addition of’a carbon tetrahalide followed by a. eyclopropanecarboxaldehyde of formula II.

The preparation and insecticidal properties of the compounds of this invention are illustrated in the following specific examples. Unless otherwise specified all temperatures are in degrees centigrade, all parts and percentages axe by weight and concentration of liquid, volume was carried out under the reduced pressure produced by a water aspirator.

Example 1 Synthesis of 3-Phenoxybenzyl 2,2-Dimethyl-3-(0-phenylvinyl)cyclopropanecarboxylate A. Preparation of Ethyl 2,2-dimethyl-3-(0-phenylvinyl)cyclopropanecarboxylate Under a nitrogen atmosphere and anhydrous conditions 43 ml of an approximately 2.5 M solution of n_-butyl lithium in hexane was added to a suspension of 41.81 g benzyl15 triphenylphosphonium chloride in 200 ml anhydrous benzene.

During the addition of the n-butyllithium solution in small portions the reaction temperature was maintained at about 25* by intermittent cooling with an ice-water bath. After addition of the ιι-butyllithium solution was completed, the 2o reaction mixture was stirred at room temperature for 2.75 hours. The reaction mixture was then added, in 10-20 ml portions via a glass tube, to an anhydrous ice cold stirred solution of 16.7 g ethyl caronaldehyde in 50 ml of benzene. During the addition, the reaction mixture was cooled with an ice-water bath. The reaction mixture was allowed to warm to room temperature over a period of - 7 4 5 6 5 6 0.5 hr and then stirred for an additional hour. The reaction mixture was filtered, and the filtrate was washed sequentially with two 200 ml portions of water and two 100ml portions of saturated brine and then dried over anhydrous magnesium sulphate. The solvent was removed and the residue dried under reduced pressure to yield 27.71 g of amorphous white solid. The solid was triturated with' 150 ml of anhydrous hexane, filtered and concentrated to yield 20.59 g of viscous liquid. The nmr and ir spectra were consistent with the expected mixture of geometric isomers of ethyl 2,2dimethyl-3-ί β-phenylvinyl)cyclopropanecarboxylate.

B. Preparation of 2,2-dimethyl-3-(β-phenylvinyl)cyclopropanecarboxylic acid A mixture of 30.68 g of ethyl 2,2-dimethyl-3{β-phenylvinyl)cyclopropanecarboxylate, 5 g of sodium hydroxide, 29 ml of ethanol and 300 ml of water was heated at 50s for 35 hours. After standing at room temperature for 12 hours, the reaction mixture was concentrated under reduced pressure. The concentrate was diluted with 450 ml of dry benzene, then taken to dryness under reduced pressure. The residue was shaken with a mixture containing 400 ml of w^ter and 100 ml saturated brine, and the resulting mixture was then extracted with chloroform. The aqueous phase was made acidic (pH 3) with 320 ml of 3% hydrochloric acid and extracted with a 500 ml portion of diethyl ether followed by two 1200 ml portions of diethyl ether. The ethereal extracts were washed with four 300 ral - 8 45656 portions of water and then dried over anhydrous magnesium chloride. The dried ethereal solution was filtered and the solvent removed to yield 22.34 g of 2,2-dimethyl-3(β-phenylvinylJcyclopropanecarboxylic aeid. The nmr and ir spectra were consistent with the expected isomeric mixture.

C. Preparation of 3-phenoxybenzyl 2,2-dimethyl-3(3-phenylvinyl)cyclopropanecarboxylate To a stirred mixture of 6.10 g of 2,2-dimethyl-3(P-phenylvinyl)cyclopropanecarboxylic acid in 50 ml of dry lo benzene, under a nitrogen gas atmosphere and at 25°, was added 1.2 ml of pyridine (4.0% excess), then 1.1 ml of thionyl chloride (7.0% excess). The exothermic reaction caused the reaction mixture temperature to rise to 35-40°.

A copious amount of white pyridine hydrochloride precipi15 tated from the reaction mixture. Stirring at ambient temperature was continued for 7 hours. To the above suspension^, containing 2,2-dimethy1-3-(β-phenylvinyl) cyclopropanecarbonyl chloride and pyridine hydrochloride^ was added 1.7 ml of pyridine and 100 ml of dry benzene; then, with 2o stirring, 3.07 g (7.0% excess) of 3-phenoxybenzyl alcohol in 50 ml of dry benzene. The reaction mixture was stirred at ambient temperature for 13.3 hours. Thin-layerchromatographic analysis of the reaction mixture indicated the reaction was complete. The reaction mixture was fil25 tered, and the filtrate was concentrated, diluted with hexane, and refiltered. The filtrate was concentrated under reduced pressure to a pale yellow oil and then further concentrated by use of a vacuum pump. The oil was dissolved - 9 4 5 6 5 6 in 30 ml of diethyl ether and washed with two 700 ml portions of water. The ethereal layer was washed with a saturated brine solution, then dried over magnesium sulfate. The mixture was filtered and the filtrate evaporated to a residual 5.66 g of oil. The oil was filtered through a column containing 51 g of silica gel and with pentane and pentane-ether as eluent to give 4.1 g (72%J of 3-phenoxybenzyl 2,2-dimethyl-3(0-phenylvinyl)cyclopropanecarboxylate. The nmr and the ir spectra were consistent with the proposed structure.

Analysis calc'd for C27H26°3S C 8^,38j s 8,58 Found: C 81.30; B 6.59.

D. Separation of Isomers A sample of 3-phenOxybenzyl 2,2-dimethyl-3(0-phenylvinyl)cyclopropanecarboxylate was separated into three isomers by use of a medium pressure liquid chromatographic unit. The separation, with 50 parts hexane: and 1 part ethyl acetate as eluent, was carried out on a silica gel column and gave sixty 25 ml fractions. Fractions 24-27 were combined and evaporated under reduced pressure to give 0.40 g 2o of 3-phenoxybenzyl 2,2-dimethyl-cis-3-(S — (Z)-phenylvinyl) cyclopropanecarboxylate. In the same manner, fractions 30-37 were combined to give 0.94 g of 3-phenoxybenzyl 2,2-dimethyltrans-3-(0-(E)-phenylvinyl)cyclopropanecarboxylate. Fractions 28-29 were combined to give 0.25 g of 3-phenoxybenzyl 2,2-dimethyl-trans 3-(0-(iZ)-phenylvinyl)cyclopropanecarboxylate. The nmr and ir spectra were consistent with the structure assigned to each isomer. - 10 4S656 The structure assignments of the isomers were based on the following nmr data in which d means doublet, dd means doublet of doublets, and m means multiplet. Tetramethylsilane was used as an internal standard. Values reported are ppm for deuterated chloroform solutions. and Hg are respectively on the 1- and 3- carbons of the cyclopropane ring, and and Hg are respectively on the vinyl group a and β to the cyclopropane ring. trans (E) cis (Z) rt ' ' trans (Z)H1 d, 1.73 7 m 1.70-2.32 d, 1.60H3 dd, 2.21 J dd, 2.43Ha dd, 5.90 dd, 5.96 dd, 5.40 «β d, 6.50 d, 6.58 d, 6.57 16 Hz 11 Hz 11 HzΗαΗβ By the methods exemplified above may be prepared other insecticidal esters of 2,2-dimethyl-3-(β-phenylvinyl)cyclopropanecarboxylic acid such as a-cyano-3phenoxybenzyl 2,2-dimethy1-3-(O-phenylvinyl)oyclopropanecarboxylate and 5-benzyl-3-furylmethyl 2,2-dimethyl-3(β-phenylvinyl)cyclopropanecarboxylate.

Example 2 Synthesis of a-cyano-3-phenoxybenzyl 3-£β—(4-chlorophenyl)vinyl]-2,2-dlmethylcyclopropanecarboxylate A. Preparation of Ethyl 3-[0-(4-chlorophenyl)vinyl]2,2-dimethylcyclopropanecarboxylate Under a nitrogen atmosphere and anhydrous conditions 81 ml of an approximately 2.5 M solution of n-butyl11 45666 lithium in hexane was added to a suspension of 84.54 g of 4-chlorobenzyltriphenylphosphonium chloride in 200 ml anhydrous benzene over a period of 20 min. The n-butyllithium solution was added in small· portions, and the reaction temperature was maintained at about 25° by intermittent cooling with an ice-water bath. After addition of the nbutyllithium solution was completed, the reaction mixture was stirred at room temperature for 2.75 hours. This mixture was added, in 10-20 ml portions via a glass tube, to an 10 anhydrous ice cold stirred solution of 32.20 g ethyl caronaldehyde in 50 ml of.benzene. During the addition the reaction mixture was cooled in an ice-water bath. The reaction mixture was allowed to warm to room temperature over a period of 0.5 hr and then stirred for an additional hour. The reaction mixture was filtered, and the filtrate was washed with two 200 ml portions of water and then with two 100 ml portions of saturated brine, and dried over anhydrous magnesium sulphate. The solvent was removed and the residue dried under reduced pressure to yield an amorphous white solid. The solid was triturated with 150 ml of anhydrous hexane, filtered and concentrated to yield 44.88 g of viscous liquid. The nmr ahd ir spectra were consistent with the expected mixture of geometric isomers of ethyl 3-(β-{4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane25 carboxylate.

B. Preparation of 3-[P-(4-Chlorophenyl)vinyl]-2,2dimethylcyclopropanecarboxylic acid A mixture of 37.90 g of ethyl 3-[3-(4-chloro12 45636 phenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate, 6.56 g of sodium hydroxide, 371 ml of ethanol, and 21.5 ml of water was heated at 55° for 60 hours. After the mixture had stood at room temperature for 12 hours, the reaction mixture was concentrated under reduced pressure. The concentrate was diluted with 450 ml of dry benzene, then taken to dryness under reduced pressure. The residue was shaken with a mixture containing 400 ml of water and 100 ml saturated brine, then the resulting mixture was extracted with lo chloroform. The aqueous phase was made acidic (pH 3) with 320 ml of 3% hydrochloric acid, and extracted with a 500 ml portion of diethyl ether followed by two 1200 ml portions of diethyl ether. The ethereal extracts were washed with four 300 ml portions of water and then dried over anhydrous 15 magnesium chloride. The dried ethereal solution was filtered and the solvent removed under reduced pressure to yield as an oil 33.06 g of 3-(β-(4-chlorophenyl)vinyl]2,2-dimethylcyclopropanecarboxylic acid. The nmr and ir spectrum were consistent with the expected isomeric >0 mixture.

C. Preparation of trans-3- [3-(E)-(4-Chlorophenyl)~ vinyl]-2,2-dimethylcyclopropanecarboxylic acid A mixture (33.06 g) of geometric isomers, prepared as described above, was stirred for 15 min. at room 5 temperature in 200 ml of pentane and filtered. The residue was collected and dried to yield 5.75 g of solid, m.p. 106°, identified by its nmr spectrum ae trans-3-[β-(E)-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid. An .6 5 6 additional 2.79 g of this isomer was obtained by reducing the volume of the filtrate by about 1/2 and cooling the concentrated filtrate to 0°. (The filtrate, containing other isomeric acids, was reserved). The nmr spectrum was definitive for the assigned structure.

D. Preparation of a-cyano-3-phenoxybenzyl trans-3[β-(E)-(4-chlorophenyl) vinylJ-2,2-dimethylcyclopropanecarboxylate Trans-3-[β-(E)-(4-chlorophenyl) vinyl]-2,2-dimethylcyclopropanecarboxylic acid (8.34 g) was heated under reflux for 3 hours with 5 ml of thionyl chloride in 35 ml of benzene. The excess of thienyl chloride and benzene was distilled from the reaction mixture. Additional benzene was added to the reaction mixture to bring the volume of the solution fo 100 ml. A 24 ml portion of this solution containing 2.14 g of trans-3-Lg-(E)— (4-chlorophenyl)vinyl]2,2-ditoethyleyclopropaneearbonyl chloride was treated with a mixture of 1.79 g of a-cyano-3-phenoxybenzyl alcohol, and 1.59 ml of pyridine in 10 ml of benzene. The addition of the 'alcohol mixture to the acid chloride was done at 0°.

Upon complete addition the reaction mixture was stirred at ambient temperature for 24 hours; then was filtered to remove pyridine hydrochloride. The filtrate was evaporated under reduced pressure to a residual 3»50 g of oil. The oil was purified on a chromatographic column of 17.5 g of silica gel. Elution of the oil from the column was accomplished with diethyl ether/pentane mixtures. The yield was 2.60 g (71.0%) of a-cyano-3-phenoxybenzyl trans-3-[β-(Ε)-(4ohlorophenyl) vinyl]-2,2-dimethylcyclopropanecarboxylate. Analysis; Calc'd for C28H24C1NO3: C 73.43} H 5.28, M 3.06 Found: C 73.18; H 5.32; N 2.98.

E. Preparation of a-cyano-3-phenoxybenzyl cis,trans3-[β-(Ε,z)- (4-chlorophenyl) vinyl]-2,2-d imethy1cyolopropanecarboxylate The final filtrate of Example 2-C contained mixed isomeric acids depleted as to the trans (E) isomer. A por10 tion of this acid, 5.60 g of cis,trans-3-[β-(Ε,Ζ)-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid, was esterified by the method of Example 2-D with 2.73 g of thionyl chloride, 5.18 g of a-cyano-3-phenoxybehzyl alcohol, and 3.5 ml of pyridine in benzene. The crude product was purified on a chromatographic column of 54.5 g of silica gel. Elution was accomplished using 20% methylene chloride - 80% pentane to give 6.95 g (72%) of a-cyano-3-phenoxybenzyl cis,trans-3-[β-(Ε,Z)-(4-chlorophertyl)vinyl]-2,2dimethylcyclopropanecarboxylate.

Analysis! Calc'd for C28H24C1NO3! C 73.43, H 5.28; N 3.06 Found! C 73.20; H 5.32; N 3.01.

Example 3 Synthesis of 3-phenoxybenzyl 3-(0-Chloro-0-phenylvinyl)2,2-dimethylcyclopropanecarboxylate A. Preparation of Ethyl 3-(0-chloro-8-phenylvinyl)-2, 2-dimethylcyclopropanecarboxylate To a solution of 28.35 g of diethyl benzylphosphonate in tetrahydrofuran at -78° was added one equivalent of n-butyllithium in hexane. After the reaction mixture had been stirred at -70° for 40 minutes, 124 ml of carbon tetrachloride was added and stirring at -70° was continued for an additional 40 minutes. To this mixture was added 23.6 g of . ethyl caronaldehyde. The mixture was allowed to warm to room temperature, and 27 ml of water was added. The reaction mixture was extracted with diethyl ether. The ethereal extract was concentrated, treated with 200 ml of pentane at —5Q>° and triturated, and the pentane decanted. The residue was treated with 200 ml of pentane at -30° and triturated, and the pentane decanted. The combined decantates were concentrated to an oil, which was treated with 19 g of sodium bisulfite in 50 ml of water. The mixture was extracted with 50 ml of diethyl ether. The extract was washed with 50 ml of saturated aqueous sodium chloride solution, dried over anhydrous, magnesium sulfate, and concentrated to yield 19.71 g of oil. The oil was purified by chromatography on 98.5 g of silica gel, with 95:5 hexane:ether as eluent. The solvents were removed under reduced pressure to yield 14.4 g of ethyl 3-(P-chloro-0phenylvinyl)-2,2-dimethylcyelopropanecarboxylate as a mixture of isomers containing cis, trans, (E), and (Z) forms. The nmr and ir spectra were consistent with the assigned structure.

B. Preparation of 3-(P-chloro-β-phenylvinyl)-2,2dimethylcyclopropanecarboxylic acid A mixture of 16,91 g of ethyl 3γ’(β-chloro-β-phenylvihyl)-2,2-dimethylcyclopropanecarboxylate, 2.57 g of 6 2 6 sodium hydroxide, 4.6 ml of water, and 72 ml of ethanol was heated at 55° for 17 hours. The mixture was allowed to cool and was concentrated to near dryness. A saturated aqueous sodium chloride solution was added to the concentrate and the mixture thus formed was washed with chloroform. The aqueous phase was acidified with 3% hydrochloric acid and extracted with diethyl ether. The ethereal extract was concentrated to yield approximately 14.57 g of 3-(0-chloro-β -phenylvinyl)-2,2-diraethylcyclopropanecarboxylic acid.

The nmr and ir spectra were consistent with the assigned structure.

C. Preparation of 3-(p-chloro-p-phenylvinyl)-2,2dimethylcyclopropaneoarbonyl chloride A 14,57 g portion of 3-(P-chloro-β-phenylvinyl)2.2- dimethyloyclopropanecarboxylic acid was dried by twice azeotropically distilling the .contained water with benzene. The acid was then diluted with 52 ml of benzene, and 9 ml of thionyl chloride was added to the solution. The mixture was heated under reflux for 3 hours. The excess of thionyl chloride was removed by distillation. More benzene was added, and further distillation removed all traces of thionyl chloride. The reaction mixture was diluted to a volume of 100 ml with benzene.

D. Preparation of 3-phenoxybenzyl 3-(0-chloro-0phenylvinyl)-2,2-d ime thylcyclopropanecarboxylate A 33.3-ml portion of the 3-(0-chloro-0-phenylvinyl)2.2- dimethylcyclopropanecarbonyl chlptide solution in benzene of Example 3-C was added at 0°C to a stirred solution of - 17 I »· 4.0 g of 3-phenoxybenzyl alcohol and 4 ml of pyridine in 26 ml of benzene. The reaction mixture was stirred at k ambient temperature for 14 hours. The pyridine hydrochloride was removed by filtration. The filtrate was evaporated under reduced pressure to give 8.6 g of residual oil. The residual oil was purified on a chromatographic column of 42.5 g. silica gel. Elution was accomplished with 860 ml of 20% methylene chloride/80% pentane to give 6.41 g (77%) of 3-phenoxybenzyl 3-(0-chloro-0-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate.

Analysis: Calc'd for Cg^HggClOg: C 74.90; H 5.82; Found: C 74.81; H 5.83.

Example 4 Synthesis of 5-benzyl-3-furylmethyl 3-(0-chloro-0-phenylvinyl)-2,2-dlmethylcyclopropanecarboxylate This compound was prepared by the method of Example 3-D, with 33.3 ml of the 3-(0-chloro-0-phenylvinyl)-2,2dimethylcyclopropanecarbonyl chloride/benzene solution from 2o Example 3-C, 3.75 g of 5-benzyl-3-furylmethyl alcohol and ml of pyridine in 26 ml of benzene. The yield was 6.14 g (46%) of •S-benzyl-S-furylmethyl 3-(O-chloro-0-phenylvinyl )-2,2-dimethylcyclopropanecarboxylate, Analysis: Calc'd for C26H25C103! C 74.19; H 5.99; Found: C 74.10; H 6.03.

Example 5 Synthesis of a-cyano-3-phenoxybenzyl 3-(0-chloro-0-phenylvlnyl)-2,2-d imethylcyclopropanecarboxylate This compound was prepared by the method of Example 3-D, with 33.3 ml of the 3-(0-chloro-p-phenylvinyl)-2,2dimethylcyclopropanecarbonyl chloride/benzene solution of Example 3-C, 4.50 ή of a-cyano-3-phenoxybenzyl alcohol and 4 ml of pyridine in 26 ml of benzene. The yield was 7.12 g (81%) of a-cyano-3-phenoxybenzyl 3-(β-chloro-p-phenylvinyl )-2,2-dimethylcyclopropanecarboxylate.

Analysis; Calc'd for CggHj^ClNO^; C 73.43; H 5.28; N 3.06; Founds C 73.60; H 5.31; N 3.08.

Example 6 Toxicity to Insects and Mites Initial Contact Activity; One quarter gram of test compound was dissolved in 20 ml of acetone and this solution was dispersed in 180 ml of water containing one drop of isooctylphenyl polyethoxyethanol. Aliquot porticns of this solution which corresponded to 1250 ppm of active ingredient were diluted with an appropriate amount of water to provide solutions containing 312 ppm or 156 ppm of active ingredient. Test organisms and techniques were as follows: the activities against the Mexican bean beetle (Epllachna varlvestls Muls.) and the southern armyworm (Spodoptera erldanla (Cram.]) were evaluated by dipping the leaves of pinto bean plants into the test solution and infesting the leaves with the appropriate immature-form insects when the foliage had 6 S 6 dried; the activity against the pea aphid (Acyrthosiphon pisum [Harris]) was evaluated on broad bean plants whose leaves were dipped before infestation with adult aphids; the activity against two-spotted spider mites (Tetranyehus urticae Koch) was evaluated on pinto bean plants whose leaves were dipped after infestation with adult mites; the activities against the milkweed bug (Oncopeltus faseiatus [Dallas]), the boll weevil (Anthonomus grandis Boheman), and the plum curculio (Conotrochelus menuphar [Herbst]) were evaluated by spraying the test solutions into glass dishes or jars containing the adult insects; the activities against the confused flour beetle (Tribolium confusum [duVal]) and granary weevil [Sitophilus granarius (Linnaeus)] were evaluated by introducing the insects into glass dishes which had been previously sprayed with test solution and allowed to dry. All organisms in the-test were maintained in a holding room at 80°F and 50% relative humidity for an exposure period of 48 hours (96 hours for the confused flour beetle). At the end of this time, the dead and living insects or mites were counted, and the percent kill was calculated. Results of these tests are summarized in Table 1.

Residual Contact Activity; The residual contact activity of the compounds was determined on the same organisms using the techniques described above, except that in each case the treated surface was allowed to dry and was exposed to normal light and air for seven days‘before introduction of - 20 4ί5ΰ5ϋ the mites or insects. Results of these tests are summarized in Table 2.

Example 7 Insecticidal Activity Against House Flies and German 5 Cockroaches In this test the compounds of this invention were tested for insecticidal activity against three or four day old female houseflies (resistant) (Musca domestica Linnaeus) and male German cockroaches [Blattella germanica (Linnaeus)]. A number of insects was anesthetized with carbon dioxide and placed in a container for about 2 hours, during which time the insects recovered to normal activity. The container confining the insects was fitted with a plunger which is used to force the insects against a nylon mesh at one end of the container. For the Level I test one i microliter of an acetone solution containing five micrograms of the candidate insecticide, for the Level II test one microliter of an acetone solution containing one microgram of the candidate insecticide, was applied topically to each insect. The plunger was withdrawn and the insects were allowed to move freely about the container. Knockdown counts were recorded 10 minutes after treatment of houseflies and 30 minutes after treatment of cockroaches. Percent mortality readings were made after 18-24 hours. Test results are set forth in Table 3.

It is anticipated that, in the normal use of the compounds of the present invention as insecticides, the compounds will usually not be free fpm admixture or 48656 dilution, but will ordinarily be used in a suitable formulated state compatible with the method of application. The insecticidal cyclopropanecarboxylates of this invention may be formulated with the usual additives and extenders used in the preparation of pesticidal compositions. The toxicants of this invention, like most pesticidal agents, are incorporated with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of a toxicant may affect the activity of the material. The present compounds may be applied, for example, as a spray, dust, or granule, to the area in which pest control is desired, the choice of application varying of course with the type of pest and the environment* Thus, the compounds of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates and as solutions.

Dusts are admixtures of the active ingredients with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as dispersants arid carriers for the toxicant. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein contains 10.0 parts of a-cyano-3-pherroxybenzyl 3-(3-(422 chlorophenyl) vinyl]-2,2-dimethylcyclopropanecarboxylate, .0 parts of bentonite clay, and 60.0 parts of talc.

The compounds of the present invention may be made into liquid concentrates by solution or emulsion in suitable liquids, and into solid concentrates by admixtures with talc, clays, and other known solid carriers used in the pesticide art. The concentrates are compositions containing about -50% toxicant, and 95-50% inert material which includes dispersing agents, emulsifying agents, and wetting agents. '10 The concentrates are diluted for practical application, with water or other liquid for sprays or with additional solid carrier for use as dusts. Typical carriers for solid concentrates (also called wettable powders) include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wetted inorganic diluents. A solid concentrate formulation useful herein contains .1.5 parts each of sodium lignosulfonate and sodium laurylsulfate as wetting agents, 25.0 parts of u-cyano-3-phenoxybenzyl 3-(3-chloro-p-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate and 72.0 parts of bentonite clay.

Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other dispersant, and may consist entirely of the toxicant with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. For application, these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.

Typical wetting, dispersing or emulsifying agents used 5 in pesticidal formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylamide feulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sul10 fonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from,1-15% by weight of the pesticidal composition but may comprise up to 30%, Other useful formulations include simple solutions of the active ingredient in a solvent in which it is completely 2q soluble at the desired concentration, such as acetone or other organic solvents.

The concentration of the toxicant in the dilution generally used for application is normally in the range of 2% to 0.001%, but the composition may con25 tain up to 99,5% toxicant, from 0 to 99.5% of an agriculturally acceptable extender, and up to 30% of a surface' active agent, the sum of these not to exceed 100%. Prior - 24 4S656 to dilution formulations may contain like amounts. Many variations of spraying and dusting compositions may be used, by substituting a compound of this invention into compositions known or apparent to the art.

Pesticidal compositions may be formulated and applied with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators and fe«4±I4jfers. In applying the chemicals, it is obvious that an effective amount and concentration of the compound of the invention should be employed. Por agricultural application the active ingredient of the invention may be applied at a rate of 75 to 4000 g per hectare, preferably 150 to 3000 g per hectare. 45G5S ca tai Rl Ώ o © CJ σι oo in σι in Η tn te Ο sacs ss a ss Q ss Q Z o z o O' o rt o Q Q a z rt CO z z Z z si Sil u © © © a o O O © o ·* © o o o © O © rt rt rt rt rt rt rt rt © rt o rt © © • 0 * o 9) O rt CJ rt © rt rt © © © o © © © 0 O 0 o o © © © rt rt rt rt rt O O © © O O O © © O o o o © O O rt rt rt rt rt rt rt rt © © rt © o © © © © O © z © © © rt rt rt rt rt rt ύ o 1 H 1 rt CJ rt <* in tl Φ Φ tl tl rt Ci rt rt rt rt ft φ rt & & & & a M g B fi fi 19 9 Ό - A A !3 S H rt φ M M X x 63 Μ W rt U H w » MJ a & ca N w m IM 0 φ 0 0 o 0 M U Ό Φ 04 rn D] w* Ό in ό Ό Ό C 6 ci C C c a fi C s ο ω (3 «5 a 9 w 9 s » p to « M U rt Q i-l 0 0 p ft E H u Oi 04 CM ft 6 s e E 0 0 0 0 0 O U a o U α β Q Q ο in o S β 55 55 CM rt M cm © in cn O Q Q H in ffi ffi ffi Q o © rt Q D O JB M rt rt ffi ffi 55 Ο © in Ο Q Q Q S 53 ffi ffi Residual (7-Day) Toxicity to Insects and Mites S| ft X ω o £ I o in ο ο ο o m o rtrt in rt «0 μ φ Φ » ΜΗ 0 £·Η Ovrl 0 > rH rd Φ ra CO £ fa Φ ra □ ϊ > ό μ ό ο Φ £ Φ >Φ φ υ w μ ϊ > 3 Ιβ ta “ s •Η rt 0 W Ο Ο Ο ο Ο ra ο ffi ft U CS ο © 00 ο ra ο ra ra ra mums ffi ft ft 5 ο © ο ο ο © ο ο ο ο CN ο Η ra ra ra © Ο ο ο ο Ο ο © CN © ο ο ο ο ra ra ra ra ν o I H d 0 Ή μ £ Ό μ Φ μ μ φ Η & ι—1 Μ ρ e ο ** © οι Β ό 0) 0 ·Η Φ Φ ο j α ra ra . &Μ β* 0« β β _ ε β 19 Β Ό a § ω «ϋ οι Μ Η « _ +ί Μ ω β U (β β Μ Μ W Οί ca Ν μ μ μ μ Α Φ Φ Ρ*. 0 0 0 <9 0 Λ μ Μ Qrt 4J & W Φ Srt Ό Ό <α Μ £ c β β β β 0 0) 0 ω Α Α φ £ £ £ ffi £ w Α Μ U Η 0 0 δ ΕΗ U Οι Οι Οι α η ο: £ Β η < 436CC w φ £ί ω υ fi fi •Η Ο (0 Μ ς»Λί < υ ο •rt fi > fi •rt S 43 M Ο fi < Q HX3 fi fi Ό fi «rt υ w •rt fi 43 *rt OH Φ dP H H •rt tf © © © © ch o H H H fi C H 43 & fi fi 0 > fi Ό fi E4 © O o © tf O H 0 fi tf H H tn o © © dP •rt os © © © tf Η H H to H 43 fi fi > fi fi H >4 O »0 dP 34 fi tf in © ’tf tf u tf u WO HO fi fi O fi M fi O fi 0 •rtU iw a ω ω ta 0 1 «- 1 -H 0) IB CM Ot ta s Ή W Ό o fi G 0 K o S r-l IB Η M KU Q &ll ft-H & SE* β s II It E fi fi ** 0 M X Cq U U W H mu

Claims (25)

1. CLAIMS:1. An insecticidal compound having the formula: CH. CH. X, COOR n in which X is halogen, cyano, nitro, aryl, aralkyl, aryloxy, 5 arylthio, C^_ 4 alkyl, C^_ 4 alkoxy, C^_ 4 alkylthio, C^_ 2 halo· alkyl, di(C 1 _ 2 alkyl)amino or methylenedioxy; Y is hydrogen, halogen, cyano, γ_ 4 alkyl, C 1 _ 2 haloalkyl, methoxycarbonyl or ethoxycarbonyl; n is O, 1, 2 or 3; and R is an alcohol residue which, when combined with the acid residue, provides

2. A compound as claimed in claim 1 in which R is (a) a benzyl-substituted or phenoxy-substituted benzyl group of the formula: •CH· A

3. A compound as claimed in claim 1 in which R is 3-phenoxybenzyl, a-cyano-3-phenoxybenzyl or 5-benzyl-3-furylmethyl.

4. A compound as claimed in claim 2 hydrogen and n is 0. or 3 in which Y is 5. Or 10. 5 14. 5-Benzyl-3-furylmethyl 3-(g-chloro-g-phenylvinyl)-2,2dimethyl cy c 1 op ropane carboxylate.

5. A compound as and n is 1, 2 or 3 claimed in claim in which Y is hydrogen

6. A compound as claimed in claim 3 than hydrogen. in which Y is other

7. A compound as Claimed in claim 3 in which X is chlorine, 10 cyano, methyl, methoxy or methylenedioxy; Y is hydrogen, chlorine, bromine, cyano, methyl, methoxycarbonyl or ethoxycarbonyl and n is 0, 1 or 2.

8. A compound as claimed in claim 7 in which X is chlorine, Y is hydrogen or chlorine, and n is 0 or 1. 15

9. 3-Phenoxybenzyl-2,2-dimethy1-3-(0-phenylvinyl)oyclopropanecarboxylate. 10. And treatment with an alcohol of the formula R-OH where R is as defined in claim 1.

10. The compound claimed in claim 9 in which the predominant isomer is the cis (Z) form. 10 an insecticidally active cyclopropanecarboxylate.

11. α-Cyano-3-phenoxybenzyl 3-/B-(4-chlorophenyl)vinyl7”2»

12. The compound claimed in claim 11 in which the predominant isomer is cis.

13. 3-Phenoxybenzyl 3-(g-chloro-g-phenylvinyl)-2,2-dimethy1cyclopropanecarboxylate.

14. Or 15.

15. α-Cyano-3-phenoxybenzyl 3-(0-chloro-p-phenylvinyl)-2,2dimethylcyclopropanecarboxylate. 15 where Z is hydrogen, methyl, cyano, ethynyl or phenyl and A is —0- or CH 2 —; (b) 5-benzyl-3-furyImethyl; (o) maleimidomethyl, phthalimidomethyl or tetrahydrophthalimidomethyl;

16. An insecticidal composition containing an insecticidally 10 effective amount of a compound as claimed in claim 1 in admixture with an agriculturally acceptable extender.

17. A composition as claimed in claim 13 that also contains a surface-active agent.

18. A method of controlling insects comprising applying to 15 the locus where control is desired an insecticidally effective amount of a compound as claimed in claim 1.

19. A process for the preparation of a compound as claimed in claim 1 that comprises reacting a compound of the formulas CHg CHg OHC COOR / (II) 31 45 6 56 where r' is Cj_ 4 alkyl with a phosphonium salt of partial (III) where X, Y and n are as defined in claim 1 in the presence 5 of a strong base in an essentially anhydrous inert solvent under an inert atmosphere to give an ester of the formula: ί where X, Y, n and R are as defined above, hydrolysing the ester and reesterifying by conversion to the acid halide

20. A process for preparing a compound as claimed in claim 1 substantially as hereinbefore described in any one of Examples 1 to 5. 32 45656 20 2-dimethylcyclopropanecarboxylate. 30 45656 20 (d) 3,4-methylenedioxybenzyl, 2-chloro-4,5-methylenedioxybenzyl or 2,4-dimethylbenzyl; or (e) allethrolonyl. -2945656

21. A compound as claimed in claim 1 when prepared by a process as claimed in claim 19 or 20.

22. A composition as claimed in claim 16 or 17 in which the said compound is a compound as claimed in claim 4, 9

23. A composition as claimed in claim 16 or 17 in which the said compound is a compound as claimed in claim 5, 11 or 12.

24. A composition as claimed in claim 16 or 17 in which 10 the said compound is a compound as claimed in claim 6, 13,

25. A composition as claimed in claim 16 or 17 in which the said compound is a compound as claimed in any one of claims 2, 3, 7, 8 or 21.