CA1260486A - Insecticidal styryl- and substituted- styrylcyclopropanecarboxylates - Google Patents

Abstract

ABSTRACT New insecticidal styryl- and substituted-styrylcyclo-propanecarboxylates of the formula: wherein X is halogen, cyano, nitro, aryl, aralkyl, aryloxy, arylthio, alkyl, alkoxy, alkylthio, haloalkyl, dialkylamino or methylenedioxy; Y is hydrogen, halogen, cyano, alkyl, haloalkyl, carbomethoxy or carboethoxy; n is 0, 1, 2 or 3 and R is an alcohol residue, the ester from which provides an insecticidally active cyclopropanecarboxylate.

Description

~60~6 This invention relates to new insecticidal styryl- and substituted-styrylcyclopropanecarboxylates which are useful in agriculture to protect crops and animals, and are also useful to control household pests.
Ever since the structures of naturally occurring pyrethroids were elucidated, synthesis 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 photo-oxidative degradation, for example, 3-phenoxybenzyl 3-~ -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 i8 provided new styryl- and substituted-styrylcyclopropane-1 ~6 ~4~U~

carboxylate compounds and a process for their production.
Typical styryl- and substituted-styrylcyclopropane-carboxylate compounds of the present invention include insecticidal esters of 2,2-dimethyl-3-(~-phenylvinyl)cyclo-propanecarboxylic acid, 2,2-dimethyl-3-[~-(substituted-phenyl)vinyl]cyclopropanecarboxylic acid, 2,2-dimethyl-3-(~-phenyl-~-substituted-vinyl)cyclopropanecarboxylic acid, and 2,2-dimethyl-3-[~-(substituted-phenyl)-~-(substituted)-vinyl]cyclopropanecarboxylic acid, and are characterized by the formula-CH3\~CH3 Xn ~ = CH- ~ COOR (I) in which X is halogen, such as fluoro, chloro, or bromo;
cyano; nitro: aryl, such as phenyl, thienyl, furyl, or pyridyl; aralkyl, such as benzyl; lower alkyl; lower halo-alkyl; lower alkoxy; lower alkylthio; aryloxy; arylthio;
di(lower alkyl)amino; and methylenedioxy; Y ls hydrogen;
halogen, for example, chloro, bromo, or fluoro; lower alkyl;
cyano; lower haloalkyl; carbomethoxy; or carboethoxy; n is 0, 1, 2, or 3, more commonly 0, 1, or 2; and R is the residue of an alcohol which in combination with an appropriate acid moiety yields an insecticidal cyclo-propanecarboxylate. A wide range of alcohol moieties are known in the insecticide art and are useful in the present invention, for example:

( 1 ) a benzyl-or phenoxy-substituted benzyl group of the formula: z -CH
~ A - ~

wherein z is hydrogen, methyl, cyano, ethynyl, or phenyl, and A is -0- or -CH2-;

(2) a benzyl-or phenoxy-substituted furylmethyl group such as 5-benzyl-3-furylmethyl;

(3) an imidomethyl group such as maleimidomethyl, phthalimidomethyl, and tetrahydrophthalimidomethyl;

(4) a benzyl group substituted in at least two ring positions with chloro, methyl, or methylenedioxy groups, for example 3,4-methylenedioxybenzyl,`
2-chloro-4,5-methylenedioxybenzyl, and 2,4-dimethylbenzyl7 (53 a substituted cyclopentenonyl group such as allethrolonyl.
The commonly used R groups which give active insecti-cides of the preqent invention are: 3-phenoxybenzyl, a-cyano-3-phenoxybenzyl, and 5-benzyl-3-furylmethyl.
In the substituents X and Y, lower, as applied to 2~ alkyl groups, means having 1-4 carbon atoms, preferably having one or two carbon atoms. Examples of haloalkyl substituents include trichloromethyl and trifluoromethyl groups.
One aspect of the present invention relates to a process for the preparation of insecticidal styryl- and 1~260486 substituted-st~rylcyclopr~panecarboxylates of formula I, above, which comprises reacting a compound of the formula:
CH~ ~ CH3 / \ (II) OHC ' - ` ~COOR' wherein R' is alkyl of Cl-C4, with a phosphonium salt of partial formula:
Xn ~ CH - P \ (III) wherein X, Y, and n are as defined above, in the presence of a strong base, preferably conducted in the presence of an essentially anhydrous inert solvent, preferably under an inert atmosphere to give an ester of the formula:
CH3 ~ H3 Xn ~ Cl = CH / \ COOR' (Ia) wherein X, Y! n, and R' are as defined above, hydrolyzing the ester and reesterifying by conversion to the acid halide and treatment with an alcohol of the formula R-OH
wherein R i8 as defined above.
In the above process, the phosphonium salt is con-verted in the presence of the strong base to the corre-spondlng phosphorane:

Xn ~ C = P''' (IIIa) which species reacts with the cyclopropanecarboxaldehyde.
The strong base used in the above process may be an alkyllithium such as n-butyllithium, or an alkali metal hydride, amide, or alcoholate.

The inert solvent employed in the reaction of the cyclopropanecarboxaldehyde may be any of the solvents commonly used in Wittig-type reactions, including benzene, tetrahydrofuran, dimethoxyethane, dimethylformamide, and the like. The reaction may suitably be carried out at 0-35C for 1-24 hours, The hydrolysis of the resulting ester in the above described process may be effected with base.
Reesterification of the resulting acid in the above 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 intermediates, those of formula Ia above, wherein Y i8 cyano or halo, may optionally be pre-pared by the following metho,ds. The compounds wherein Y is cyano may be readily prepared by the base catalyzed conden-sation of an appropriately substituted benzyl cyanide with a cyclopropanecarboxaldehyde of formula II, The compounds wherein Y i6 halo may be readily prepared by the treatment of a dialkyl benzylphosphonate, appropriately substituted on the phenyl ring, with a strong base such as n-butyl-lithium at low temperature (about -78), followed by the addition of first carbon tetrahalide then a cyclopropane-carboxaldehyde of formula II.

_5_ 48~

The preparation and insecticidal properties of the compounds of this invention are illustrated in the follow-ing specific examples. Unles otherwise specified all temperatures are in degrees centigrade, and concentration of liquid volume was carried out under the reduced pressure produced by a water aspirator.
Example l Synthesis of 3-Phenoxybenzyl 2,2-Dlmethyl-3-(~-phenylvinyl)-_ _ cyclopropanecarboxylate _ _ A. Preparation of Ethyl 2,2-dimethyl-3-(~-phenyl-vinyl)cyclopropanecarboxylate Under a nitrogen atmosphere and anhydrous conditions 43 ml of an approximately 2.5 M solution of n-butyllithium in hexane was added to a suspension of 41.81 g benzyl-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 n-butyllithium solution was completed, the 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 9 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 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 100 ml 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 amorphous white solid. The solid was triturated with 150 ml 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 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate.
B. Preparation of 2,2-dimethyl-3-(~-phenylvinyl)-cyclopropanecarboxylic acid A mixture of 30.68 g of ethyl 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate, 5 g of sodium hydroxide, 29 ml of ethanol and 300 ml of water was heated at 50~ for 35 hours. After ~tanding 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 pres-sure. The re~idue was shaken with a mixture containing 400 ml of water 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 ml ~:~6048~

portions o~ water and then dried over anhydrous magnesium chloride. The dried ethereal solution was filtered and the solvent removed to yield 22.34 9 of 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylic acid. The nmr and ir spectra were consistent with the expected isomeric mixture.
C. Preparation of 3-phenoxybenzyl 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate To a stirred mixture of 6.10 g of 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylic acid in 50 ml of dry benzene, under a nitrogen gas atmosphere and at ~5, 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.
coplous amount of white pyridine hydrochloride precipi-tated from the reaction mixture. Stirring at ambient tem-perature was continued for 7 hours. To the above suspension containing 2,2-dimethyl-3-(~rphenylvinyl)cyclopropane-carbonyl chloride and pyridine hydrochloride was added 1.7 ml of pyridine and 100 ml of dry benzene; then, with stirring, 3.07 g (7.0% excess) of 3-phenoxybenzyl alco-hol in 50 ml of dry benzene. The reaction mixture was stirred at ambient temperature for 13.3 hours. Thin layer chromatographic analysis of the reaction mixture indicated the reaction was complete. The reaction mixture was fil-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 , in 30 ml diethyl ether and washed with two 700 ml portions of water. The ether 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%) of 3-phenoxybenzyl 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate. The nmr and the ir spectra were consistent with the proposed structure.
Analysis calc'd for C27H2603: C 81.38; H 6.58 Found: C 81.30; H 6.59, D. Separation of Isomers A sample of 3-phenoxybenzyl 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate was separated into three isomers by use of a medium pressure liquid chroma-tographic unit. The separation, with 50 parts hexane, 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 of 3-phenoxybenzyl 2,2-dimethyl-cis-3-(~-(Z)-phenylvinyl) cyclopropanecarboxylate. In the same manner, fractions 30-37 were combined to give 0.94 g of 3-phenoxybenzyl 2,2-dimethyl-trans-3-(~-(E)-phenylvinyl)cyclopropanecarboxylate. Frac-tions 28-29 were combined to give 0.25 g of 3-phenoxybenzyl 2,2-dlmethyl-trans 3-(~-(Z)-phenylvinyl)cyclopropanecarboxy-late. The nmr and lr spectra were consistent with the struc-ture assigned to each isomer.

~260486 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. Tetramethyl-silane was used as an internal standard. Values reported are ppm for deuterated chloroform solutions. Hl and H3 are respectively on the 1- and 3- carbons of the cyclo-propane ring, and Hl and H3 are re~pectively on the vinyl group a and ~ to the cyclopropane ring.
trans (E) cis (Z) trans (z) Hld, 1.73) m 1.70-2.32 d, 1.60 H3dd, 2.21 dd, 2.43 Hadd, 5.90 dd, 5.96 dd, 5.40 H~d, 6.50 d, 6.58 d, 6.57 Ha H~16 Hz 11 Hz 11 Hz By the methods exemplified above may be prepared other insecticidal esters of 2,2-dlmethyl-3-(~-phenyl-vinyl)cyclopropanecarboxyliclacid ~uch as a-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(~-phenylvinyl~cyclopropane-carboxylate and 5-benzyl-3-furylmethyl 2,2-dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate.
Example 2 Synthesis of a-Cyano-3-phenoxybenzyl 3-[~-(4-chlorophenyl)-vinyl]-2,2-dimethylcyclopropanecarboxylate A. Preparation of Ethyl 3-1~-(4-chloropbenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate Under a nitrogen atmosphere and anhydrous con-ditions 81 ml of an approximately 2.5 M solution of n-butyl-~"/ -1 0--~ , ~260486 lithium in hexane was added to a suspension of 84.54 g of 4-chloroben~yltriphenylphosphonium chloride in 200 ml an-hydrous 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 n-butyllithium solution was completed, the reaction mixture was stirred at room temperature for 2.75 hours. This mix-ture was added, in 10-20 ml portions via a glass tube, to an anhydrous, ice cold, stirred solution of 32.20 9 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, then with two 100 ml portions of saturated,brine, and dried over anhydrous magnesium sulphate. The solvent was removed and the resi-due dried under reduced pressure to yield an amorphous white solid. The solid was triturated with 150 ml anhydrous hexane, filtered and concentrated to yield 44.88 g of viscous liquid. The nmr and ir spectra were consistent with the expected mixture of geometric isomers of ethyl 3-[~-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane-carboxylate.
B. Preparation of 3-[~-(4-Chlorophenyl)vinyll-2,2-dimethylcyclopropanecarboxylic acid A mixture of 37.90 g of ethyl 3-[~-(4-chloro-~OJ.~

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 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 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~[~-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid. The nmr and ir spectrum were consistent with the expected isomeric mixture.
C. Preparation of trans-3-[~-(E)-(4-Chlorophenyl)-__ _ vinyl]-2,2-dimethylcyclopropanecarboxylic acid A mixture (33.06 g) of geometric isomers, pre-pared as described above, was stirred for 15 min. at room 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 as trans-3-[~-(E)-(4-chloro-phenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid. An ~Z~04~36 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-[~-(E)-(4-chlorophenyl)vinyl]-2,2-dimethylcyclo-propanecarboxylate Trans-3-[~-(E)-(4-chlorophenyl)vinyl]-2,2-dimethyl--cyclopropanecarboxylic acid (8.34 g) was heated under reflux for 3 hours with 5 ml of thionyl chloride in 35 ml of benzene. The excess thionyl chloride and benzene was distilled from the reaction mixture. Additional benzene was added to the reaction mixture to bring the volume of the solution to 100 ml. A 24 ml portion of this solution containing 2.14 g of trans-3-[~-(E)-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarbonyl 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 ~.2604~6 ~71.0%) of ~-cyano-3-phenoxybenzyl trans-3-[~-( E ) - ( 4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28~24ClNO3: C 73.43; H 5.28; N 3.06 Found: C 73.18; H 5.32; N 2.98.
E. Preparation of a-cyano-3-phenoxybenzyl cis,trans-3-[~-(E,Z)-(4-chlorophenyl)vinyl]-2,2-dimethyl-cyclopropanecarboxylate The final filtrate of Example 2-C contained mixed isomeric acids depleted as to the trans (E~ isomer. A por-tion of thi~ acid, 5.60 9 of cis,trans-3-[~-(E,Z)-(4-chloro-phenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid, was esterified by the method of Example 2-D with 2.73 9 of thionyl chloride, 5.18 g of a-cyano-3-phenoxybenzyl alcohol, and 3.5 ml of pyridine in benzene. The crude product was pur~fied on a chromatographic column of 54.5 9 of silica gel. Elution was accomplished using 20% methylene chlor-ide - 80% pentane to give 6.~5 g (72%) of a-cyano-3-phenoxy-benzyl cls,trans-3-[~-(E,Z)-(4-chlorophenyl)vinyll-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28H24ClN03: 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-(~-Chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate A. Preparation of Ethyl 3-(~-chloro-~-phenylvinyl)-2, 2-dimethylcyclopropanecarboxylate To a solution of 28.35 g of diethyl benzylphospho-nate in tetrahydrofuran at -78 was added one equivalent of ~a~o 4~

n-butyllithium in hexane. After the reaction mixture was stirred at -70 for 40 minutes, 124 ml of carbon tetra-chloride 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 temp~rature, 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 -50, triturated, and the pentane decanted. The residue was treated with 200 ml of pentane at -30, tri-turated, 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 con-centrated 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-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate 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-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylic acid A mixture of 16.91 g of ethyl 3-(~-chloro-~-phenyl-vinyl)-2,2-dimethylcyclopropanecarboxylate, 2.57 g of 12~50 4~

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-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylic acid.
The nmr and ir spectra were ~onsistent with the assigned structure.
C. Preparation of 3-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarbonyl chloride A 14.57 g portion of 3-(~-chloro-~-phenylvlnyl)-2,2-dimethylcyclopropanecarboxylic 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 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-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate A 33.3 ml portion of the 3-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarbonyl chloride solution in ben-; zene of Example 3-C was added at 0C to a stirred solution of :
~ -16-.

.

1~;~48fi 4.0 g of 3-phenoxybenzyl alcohol and 4 ml of pyridine in 26 ml of benzene. The reaction mixture was stirred at ambient temperature for 14 hours. The pyridine hydro-chloride 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 chroma-tographic column of 42.5 9 silica gel. Elution was accomplished with 860 ml of 20~ methylene chloride/80%
pentane to give 6.41 g (77%) of 3-phenoxybenzyl 3-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropane-carboxylate.
Analysi~: Calc'd for C27H25C103: C 74.90; H 5.82;
Found: C 74.81; H 5.83.
Example 4 Synthesis of 5-benzyl-3-furylmethyl 3-(~-chloro-~-phenyl-_ _ vinYl)-2,2-dimethylcyclopropanecarboxylate This compound was prepared by the method of Example 3-D, with 33.3 ml of the 3-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarbonyl chloride/benzene solution from Example 3-C, 3.75 g of 5-benzyl-3-furylmethyl alcohol and 4 ml of pyridine in 26 ml of benzene. The yield was 6.14 g ~46%) of^5-benzyl-3-furylmethyl 3-(~-chloro-~-phenyl-vinyl)-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C26H25C103: C 74.19; H 5.99;
Found: C 74.10; H 6.03.

~, .~ '.

4~

Example 5 Synthesis of a-cyano-3-phenoxybenzyl 3-(~-chloro-~-phenyl-vinyl)-2,2-dimethylcyclo ropanecarboxylate This compound was prepared by the method of Example 3-D, with 33.3 ml of the 3-~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropanecarbonyl chloride/benzene solution of Example 3-C, 4.50 g of a-cyano-3-phenoxybenzyl alcohol and 4 ml of pyridine in 26 ml of benzene. The yield was 7.12 g (81%) of ~-cyano-3-phenoxybenzyl 3-(~-chloro-~-phenyl-vinyl)-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28H24ClN03: C 73.43; ~ 5.28; N 3.06;
Found: 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 dis-persed in 180 ml of water co,ntaining one drop of isooctyl-phenyl polyethoxyethanol. Aliquots of this solution, which corresponds 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 (Epilachna varivestis Muls.) and the southern armyworm (Spodoptera eridania [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 ~ O 4~5 dried; the activity against the pea aphid ~Acyrthosiphon ~isum ~Harris]) was evaluated on broad bean plants whose leaves were dipped before infestation with adult aphids;
the activity against two-spotted spider mites (Tetranychus urticae Koch) was evaluated on pinto bean plants whose leaves were dipped after infestation with adult mites; the activities against the milkweed bug (Oncopeltus fasciatus [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 80F 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 i2~iO4t36 the mites or insects. Results of these tests are summarized in Table 2.

Example 7 InsecticidaI Activity Against House Flies and German 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 ~ermanica (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 microliter of an acetone solution containing five micro-grams of the candidate insecticide, for the Level II test one microliter of an acetone solution containing one micro-gram 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. ~nockdown counts were recorded 10 minutes after treatment of house-flies 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 com-pounds of the present invention as insecticides, the com-pounds will usually not be employed free from admixture or :

1~41g6 dilution, but will ordinarily be used in a suitable formu-lated 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 toxi-cants 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 formu-lation 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 appli-cation 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, as solutions, and the like.
Dusts are admixtures of the active ingredients with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, cal-cium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as dispersants and 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-phenoxybenzyl 3-[~-(4-:, :

1:2604a6 chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate, 30.0 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

5-50~ toxicant, and 95-50~ inert material which includes dispersing agents, emulsifying agents, and wetting agents.
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 wet inorganic diluents. A solid concentrate formu-lation useful herein contains 1.5 parts each of sodium lignosulfonate and sodium laprylsulfate as wetting agents, 25.0 parts of a-cyano-3-phenoxybenzyl 3-~-chloro-~-phenyl-vinyl)-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 napbthas, iso-phorone and other nonvolatile organic solvents. For ~, .. .
~, ' , .
, ~2~04~36 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 in pesticidal formulations include, for example, the alkyl - and alkylaryl sulfonates and sulfates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sul-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 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 about 2% to about 0.001%, but the composition may con-tain up to 99.5% toxicant, from 0 to 99.5% of an agri-culturally acceptable extender, and up to 30% of a surface-active agent, the sum of these not to exceed 100%. Prior .~

~ 2604S6 to dilution formulations may contain like amounts. Many variations of spraying and dusting compositions in the art may be used, by substituting a compound of this invention into compositicns 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, fertilizers, etc. In applying the chemicals, it is obvious that an effective amount and concentration of the compound of the invention should be employed. For agricultural ap-plication 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.

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Claims (29)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An insecticidal compound characterized by the formula:
in which X is halogen, cyano, nitro, aryl, aralkyl, aryloxy, arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4, haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4, haloalkyl of C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or 3; and R is an alcohol residue selected from the group consisting of:
(a) a benzyl or phenoxy substituted benzyl group of the formula:

wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and (b) 5-benzyl-3-furylmethyl.

2. The compound of claim 1 characterized in that R is 3-phenoxybenzyl, .alpha. -cyano-3-phenoxybenzyl, or 5-benzyl-3-furylmethyl.

3. The compound of claim 1 characterized in that X is chloro, cyano, methyl, methoxy, or methylenedioxy; Y is hydrogen, chloro, bromo, cyano, methyl, carbomethoxy or carbethoxy; n is 0, 1 or 2, and R is 3-phenoxybenzyl, .alpha.-cyano-3-phenoxy-benzyl, or 5-benzyl-3-furylmethyl.

4. The compound of claim 3 characterized in that X is chloro, Y is hydrogen or chloro, and n is 0 or 1.

5. The compound of claim 1 characterized in that the compound is 3-phenoxybenzyl 2,2-dimethyl-3-(.beta.-phenylvinyl)-cyclopropane-carboxylate.

6. The compound of claim 5 characterized in that the predominant isomer is the cis (Z) form.

7. The compound of claim 1 characterized in that the compound is .alpha.-cyano-3-phenoxybenzyl 3-[3-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate.

8. The compound of claim 7 characterized in that the predominant isomer is cis.

9. The compound of claim, 1 characterized in that the compound is 3-phenoxybenzyl 3-(.beta.-chloro-3-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate.

10. The compound of claim 1 characterized in that the compound is 5-benzyl-3-furylmethyl 3-(.beta.-chloro-.beta.-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate.

11. The compound of claim 1 characterized in that the compound is .alpha.-cyano-3-phenoxybenzyl 3-(.beta.-chloro-.beta.-phenylvinyl)-2,2-dimethylcyclopropanecarboxylate.

12. A method of controlling insects characterized in applying to the locus where control is desired an insecticidally effective amount of a compound of claim 1.

13. A process for the preparation of insecticidal styryl-or substituted-styrylcyclopropanecarboxylates characterized by the formula:

wherein X is halogen, cyano, nitro, aryl, aralkyl, aryloxy, arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4, haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4, haloalkyl of C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or 3; and R is an alcohol residue selected from the group consisting of:
(a) a benzyl or phenoxy substituted benzyl group of the formula:

wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and (b) 5-benzyl-3-furylmethyl;
characterized by reacting a compound of the formula:

wherein R' is alkyl of C1-C4 with a phosphonium salt of partial formula:

wherein X, Y and n are as defined above in the presence of a strong base in an essentially anhydrous inert solvent under an inert atmosphere to give an ester of the formula:

wherein X, Y, n and R' are as defined above, hydrolyzing the ester and reesterifying by conversion to the acid halide and treatment with an alcohol of the formula R-OH wherein R is as defined above.

14. A compound of the formula:

in which X is hydrogen, halogen or methyl, Y is hydrogen or cyano and n is 1 or 2.

15. A compound of the formula:

16. A compound of the formula:

17. A process for the production of compounds as defined in claim 14 which comprises reacting a compound of the formula:

in which X and n are as defined in claim 14 and Hal is halogen with a compound of the formula:

in which Y is as defined in claim 14.

18. A method of controlling insects comprising applying an insecticidally effective amount of a compound of claim 14 to the insects or to a locus where control is desired.

19. A compound of the formula:

in which X is hydrogen, halogen or alkyl of 1 to 4 carbon atoms, Z is halogen, Y is hydrogen or cyano and n is 1, 2 or 3.

20. A compound of the formula:

21. A process for the production of a compound as defined in claim 19 which comprises reacting a compound of the formula:

in which X, Z and n are as defined in claim 19 and Hal is halogen with a compound of the formula.

in which Y is as defined in claim 19.

22. A method of controlling insects comprising applying an insecticidally effective amount of a compound of claim 19 to the insects or to a locus where control is desired.

23. A compound of the formula:

in which R3 is phenyl or phenyl carrying at least one alkyl group or halogen atoms and R4 is hydroxy or halogen.

24. A compound of the formula:

in which R3 is phenyl carrying at least one alkyl group or halogen atom and R4 is alkoxy of 1 to 4 carbon atoms.

25. A compound of the formula:

in which Z is halogen, R3 is phenyl or phenyl carrying at least one alkyl group or halogen atom R4 is hydroxy or halogen.

26. An insecticidal compound characterized by the formula:

in which X is cyano, nitro, aryl, aralkyl, aryloxy, arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4, haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4, haloalkyl of C1-C2, carbomethoxy, or carbethoxy; n is 1, 2 or 3;
and R is an alcohol residue selected from the group consisting of:
(a) a benzyl or phenoxy substituted benzyl group of the formula:

wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and (b) 5-benzyl-3-furylmethyl.

27. An insecticidal compound characterized by the formula:

in which X is halogen, cyano, nitro, aryl, aralkyl, aryloxy, arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4, haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or methylenedioxy; Y is halogen, cyano, alkyl of C1-C4, haloalkyl of C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or 3; and R is an alcohol residue selected from the group consisting of:
(a) a benzyl or phenoxy substituted benzyl group of the formula:

wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and (b) 5-benzyl-3-furylmethyl.

28. A method of controlling insects characterized in applying to the locus where control is desired an insecticidally effective amount of a compound of claim 26.

29. A method of controlling insects characterized in applying to the locus where control is desired an insecticidally effective amount of a compound of claim 27.