IE50932B1

IE50932B1 - Insecticidal ester derivatives of certain 4-substituted-2-indanols

Info

Publication number: IE50932B1
Application number: IE38081A
Authority: IE
Original assignee: Fmc Corp
Priority date: 1981-02-24
Filing date: 1981-02-24
Publication date: 1986-08-20
Also published as: IE50933B1

Description

The present invention is concerned with cyciopropanecarboxylate and related insecticides obtained irom a novel alcohol, which is claimed in Patent Specification No. 50933 Pyrethrins, naturally occurring extracts of chrysanthemum flowers, 5 have long been of interest as insecticides. Since elucidation of the structures of these compounds, synthesis efforts have been directed toward preparation of related compounds having enhanced insecticidal activity and improved stability towards air and light.' Since a prerequisite for insecticidal activity of pyrethroids is the presence of one molecule of an appropriate acid residue and an appropriate alcohol residue, research has been directed towards novel acid and/or alcohol radicals. Noteworthy advances in the area of alcohol research were the discovery of 5-benzyl-3-furylmethyI alcohol, then of the more photostable 3-phenoxybenzyl alcohol. Similarly significant advances have been made in pyrethroid acid research. The commercial 1? insecticide permethrin, the common name for 3-phenoxyphenylmethyI 3-(2,2-dichloroethenyJ)-2,2-dimethylcyciopropanecarboxyIate, exemplifies use of both newer acid and alcohol residues in a single compound. in this application, the term lower as applied to an aliphatic hydrocarbon group means having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The term halo or halogen means bromine, chlorine or fluorine. The term haloalkyl means an alkyl group of I to 3 carbon atoms substituted with 1 or more halogen atoms. The term insecticide is used in its broadest sense, and includes compounds possessing activity against true S0932 insects, acarids, and other household, veterinary or crop pests of the phylum Arthropoda. These definitions are applicable throughout the specification and claims except where a contrary meaning is dearly indicated.

The novel compounds of this invention have the general formula: in which R1 is phenyl, optionally substituted with halogen or # alkyl, and R3 is 2,2,3,3-tetramethylcyclopropylcarbonyl, l-(4-chlorophenyl)-2methylpropylcarbonyl, or a group of the formula \=CH ./ » cwhere each of Y anc 2, which are the same or different, is a hydrogen or halogen atom, a alkyl or Cj_2 perhaloalkyl radical, or a phenyl, or phenylthio radical, optionally substituted with halogen or Cj_4 alkyl, with the proviso that at least one of Y and Z is other than hydrogen and further provided that the isomer of S configuration at C-2 of the mdanol ring is not present in an enantiomeric excess of 25% or more over the isomer of R configuration at C-2 oi the indanol ring.

Specification PCT/U581/01690, published as WOS2/02321, discloses compounds in which the isomer of 5 configuration at C-2 of the indanol ring is present in an enantiomeric excess of 25% or more over the isomer of R configuration at C-2 of the indanol ring.

Particularly useful insecticides or acaricides of the present invention are the cydopropanecarboxylates in which one of Y and Z is halogen, such as chlorine or bromine, and the other, the same or different, is halogen or a perhaioalkyl group such as trihaiomethyl, and is phenyl.

The cydopropanecarboxylates having the acid residue of formula Π have cis and trans isomeric forms, i.e., the carboxy and the substituted vinyl groups at the 1 and 3 positions of the cyclopropane ring are either cis or trans with respect to each other. Preparation of these compounds will usually yield a mixture of the cis and trans isomers, designated herein as cis, trans, in which the ratio of cis to trans may vary over a wide range. The compounds where Y is different from Z may also exist as E or Z isomers or as mixtures of E an«^ Z isomers, designated E,ji, depending upon the spatial relationship of substituents on the α-carbon of the vinyl group to those on the &-carbon of the vinyl group.

In the cyclopropanecarboxylate art it is known there may be substantial differences in the level of insecticidal activity of the cis and trans isomers. In general, as between the cis and trans isomer of a given cyclopropanecarboxylate, the cis isomer is usually more active than the trans and also more active than the cis,trans mixture. Similar differences in activity may also occur with respect to the E and £ isomers.

Unless a contrary intent is specifically expressed, this invention embodies and includes both cis and trans isomeric forms of the claimed compounds as well as mixtures thereof wherein the cis to trans ratio is within the range of 0:100 to 100:0. Similarly, the individual E and Z isomers, as well as the mixtures, are contemplated by and within the scope of the invention. The various enantiomers of the claimed compounds and mixtures of them are also included within the scope of the invention.

The novel alcohols may be prepared in a number of ways. The schemata below for 4-phenyl-2-indanol is illustrative of methods by which the alcohols can be prepared.

CO-H (C) (E) (G) (I) C2115 011 boch.V (A) (B) CO2H KOH/H,O/C,HSOH I IfJI H2O This method of preparation (Method A) is described in greater detail in Example 1. Other methods include the hydroboration/oxidation (Method B) and the epoxidation/ reduction (Method C) of an appropriate indene, such as compound H in the schemata above. These additional methods are described in detail in Examples 2 and 3 respectively.

The insecticidal compounds having the acid residue of formula II may be prepared from alkanoates of the formula: III in which Y and Z are defined as above; R is lower alkoxy, such as methoxy or ethoxy, or a 4-substituted-2-indanyIoxy residue of formula: and X is chloro or bromo. Example 4 illustrates a method for preparation of 10 the aikanoate intermediate compounds of formula ΙΠ whereby a lower alkyl 3,3-dimethyl-4-pentenoate is allowed to react with a compound of the formula XjCtYXZ) where X, Y and Z are as defined above.

Dehydrohalogenation of the compound of formula 111 followed, if necessary, by hydrolysis of the ester and, also if necessary, halogenation of the resulting carboxyl group gives a compound of the formula: >COR IV in which R is lower alkoxy, hydroxy, halogen, or a 4-substituted-2indanyioxy moiety from an aicohol of formula I, and Y and Z are as defined above. The dehydrohalogenation reaction may proceed through one or more intermediates of the formulae: 832 XL, VII and may be conducted in a single step by elimination of two equivalents of hydrogen halide, HX, to give a compound of formula VI directly, or in multiple steps under conditions allowing a sequential elimination of the two equivalents of HX in separate reactions. These intermediates or mixtures thereof may be recovered if desired. The compound of formula IV is then converted to the compound of formula I by methods known to the art, for example, where R is lower alkoxy, hydroxy, or halogen, by esterifying or trans-ester if ying with a 4-r' -2-indanoi.

The examples which follow illustrate preparation of the insecticidal compounds and novel alcohol intermediates therefor in accordance with the general method described above. In the examples all temperatures are in degrees centigrade, all pressures are in Pascals, and reduced pressure for concentrations of liquid was produced by a water aspirator unless otherwise specified.

Examples 1-3 illustrate the preparation of 4-R^-2-indanols, which do not fall within the scope of the invention.

Example 1 SYNTHESIS OF 9-PHENYL-2-INDANOL (METHOD A) A. Preparation of 2-(bromomethyl)biphenyl A stirred solution of 58.9 g. (0.319 mole) of 2-biphenylmethanol and 6 mJ of concentrated sulfuric acid in 67 mi of aqueous 4896 hydrobromic acid was heated under reflux for 5 hours. The reaction mixture was cooled to ambient temperature, poured into ice-water, and the resulting mixture extracted with three portions ol 100 ml each of diethyl ether. The combined extracts were washed with 50 ml of a saturated aqueous solution of sodium bicarbonate, then with 50 ml of water. The organic layer was dried with magnesium sulfate, filtered and the filtrate concentrated under reduced pressure to give 76.8 g. of 2-(bromomethyl)biphenyl as a residual oil. The nmr and ir spectra were consistent with the proposed structure.

B. Preparation of diethyl (2-phenylbenzylJmalonate A stirred mixture of 12.5 g (0.54 mole) of sodium hydride (25 g of a 50% dispersion in mineral oil) in 300 ml of dimethylformamide and 900 ml of benzene was placed under a nitrogen atmosphere and cooled to 0*C. To this mixture, 104.3 g (0.9 mole) of diethyl malonate was added dropwise during a 5 minute period and the mixture was stirred until hydrogen evolution ceased. 2-(Bromomethyl)biphenyl (117 g, 0.47 mole) was then added at 0’C. Upon complete addition the reaction mixture was stirred at 0’C for 30 minutes, then was allowed to warm to ambient temperature with stirring for one hour. The reaction mixture was poured into 500 ml of water, the layers separated, and the aqueous layer washed with two portions of 250 ml e-ach of diethyl ether. The organic layer was combined with the ether washings, and the whole was washed with one portion of 500 ml of aqueous 5% hydrochloric acid, one portion of 500 ml of water, one portion of 300 ml of a solution saturated with sodium bicarbonate, and finally, one portion of 500 ml of water. The organic layer was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to an oil residue. The oil was distilled under reduced pressure to give 149.0 g of diethyl (2-phenylbenzyl)malonate; b.p. 175-18O’C/1O7-12O Pa. The nmr spectrum was consistent with the proposed structure.

C. Preparation of (2-phenylbenzyl)malonic acid A stirred solution of 149.0 g (0.456 mole) of diethyl (2-phenylbenzylJmalonate and 56.1 g (1.0 mole) of potassium hydroxide in 50 ml of water and 500 ml of ethanol was heated under reflux for 3 hours. The reaction mixture was allowed to cool to ambient temperature and stand for 60 hours. The ethanol was removed by distillation and the residue slurried in 400 ml of water. The mixture was extracted with one portion of 250 ml of diethyl ether. The aqueous phase was separated and acidified with concentrated hydrochloric acid, then extracted with two portions of 250 ml each of diethyl ether. The two extracts of the acidified aqueous phase were combined, dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to give (2-phenylbenzylJmalonic acid as a pale yellow oil. The oil was used directly in the next step of this reaction sequence.

D. Preparation of 3-(2-biphenylJpropionic acid A solution of 124.2 g (0.46 mole) of the oil from step C of this Example in 500 ml of water was heated under reflux for 16 hours. The reaction mixture was cooled, and the product was collected by filtration to give, after recrystallization from ethanol-water, 92.9 g of 3-(2-biphenylJpropionic acid. The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C 79.62, H 6.24 Found: C 79.84, H 5.98.

E. Preparation of 4-phenyl-1-indanone A solution of 92.9 g (0.41 mole) of 3-(2-biphenylJpropionic acid in 100 ml of thionyl chloride was stirred at ambient temperature for 16 hours. The excess thionyl chloride was removed by distillation followed by co-distillation with three 50 ml portions of benzene.

The residue was dissolved in 150 ml of benzene and was added dropwise at 10’C over 15 minutes to a stirred mixture of 71.0 g (0.53 mole) of aluminum chloride in 900 ml of benzene. Upon complete addition the reaction mixture was stirred at 10’C for 110 minutes then poured into 1000 ml of ice-water and stirred until the ice melted. The aqueous phase was separated and extracted with two portions of 100 ml each of diethyl ether. The ether extracts and the organic phase were combined and washed with a 10% aqueous solution of sodium hydroxide, then with two portions of water. The combined extracts were dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced S093S pressure to give, as a brown crystalline solid, 85.4 g of 4-phenyl-J-indanone, m.p. 85-90'C. The product was used without further purification.

A sample was recrystallized for analytical purposes. The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for CjjH^qO: C 86.50, H 5.81 Found: C 86.63, H 5.74.

F. Preparation of 4-phenyl-1-indanol To a stirred solution of 20.8 g (0.10 mole) of 4-phenyl-l-indanone in 150 ml of ethanol was added portionwise 2.0 g (0.06 mole) of sodium borohydride. During the addition the reaction temperature rose to 33*C. Upon complete addition the reaction mixture was allowed to cool to ambient temperature and was stirred for 16 hours. The reaction mixture was mixed in water and concentrated under reduced pressure. A precipitate, which developed during concentration of the aqueous solution, was collected, dried, then recrystallized from toluene-hexane to give 17.3 g of 4-phenyl-1-indanol; m.p. 80.5-81.5'C. The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C15H14O: C 85.68, H 6.71 Found: C 85.63, H 6.70.

G. Preparation of 7-phenyl~1H-indene A stirred solution of 16.7 g (0.08 mole) of 4phenyl-1-indanol and 0.1 g of £~toluenesulfonic acid in 180 ml of benzene was heated under reflux for one hour as by-product water was collected in a Dean-Stark trap. The reaction mixture was washed with two portions of 50 ml of a 5* aqueous solution of sodium bicarbonate, then with one portion of 50 ml of water. The organic phase was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure, keeping the temperature under 50’C., to give 14.6 g of 7-phenyl1H-indene. The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C 93.71, H 6.29 Found: C 93.47, H 6.31.

H. Preparation of 4-phenyl-2-indanone A stirred solution of 53.2 ml of formic acid and 10.5 ml of 30% hydrogen peroxide was heated to 35’C, and 14.5 g (0.075 mole) of 7-phenyl-1H-indene was added dropwise causing the reaction mixture temperature to rise to 41 °C. Upon complete addition the reaction mixture was allowed to cool to ambient temperature and was stirred for 16 hours. The reaction mixture was concentrated under reduced pressure to give a residual semi-solid which was subjected to steam distillation in the presence of aqueous dilute sulfuric acid. The steam distillates were filtered to give 1.84 g of 4-phenyl-215 indanone; m.p. 133-136’C. The nmr and the ir spectra were consistent with the proposed structure.

I. Preparation of 4-phenyl-2-indanol To a stirred mixture of 0.30 g (0.0014 mole) of 4-phenyl-2-indanone in 10 ml of ethanol was added portionwise 0.03 g (0.0008 mole) of sodium borohydride. The resulting yellow colored solution was stirred at ambient temperature for 1.5 hours, then concentrated, and 50 ml of water was added. The mixture was extracted with two portions of 50 ml each of diethyl ether. The extracts were combined, dried with sodium sulfate, filtered and the filtrate concentrated under reduced pressure to give, after recrystallization from hexane, 0.13 g of 4-phenyl-2-indanol. The nmr and ir spectra were consistent with the proposed structure.

Example 2 SYNTHESIS OF 4-PHENYL-2-INDANOI. (METHOD B) Under a dry argon atmosphere, a stirred solution of 32.9 g (0.391 mole) of 2,3-dimethyl-2-butene in 250 ml of tetrahydrofuran was cooled to 0’ to -5°C. To this was added during 30 minutes 372.5 ml of a 1.05M solution of borane (0.391 mole) in tetrahydrofuran, and the mixture was stirred for 1 3/4 hours. A solution of 168.2 g (0.355 mole) of 7-phenyl-1H-indene (which may be prepared as in Example 1G) in 250 ml of tetrahydrofuran was added over 30 minutes with continued cooling, and the mixture was stirred for 1 1/2 hours. The mixture was cooled to -15*C, and 71 ml of water was added over 30 minutes. A 3N aqueous solution of sodium hydroxide (213 ml) and 213 ml of a 30% aqueous solution of hydrogen peroxide were added dropwise in sequence, and the mixture was stirred at 0’ for 30 minutes, then filtered through a pad of diatomaceous earth. The aqueous phase of the two-phase filtrate was separated and extracted with diethyl ether. The extracts were combined with the organic phase of the filtrate, and the whole was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous potassium carbonate, and filtered. The filtrate was concentrated under reduced pressure to give 79.6 g of a yellow-green oil, which was shown by gas chromatographic analysis to contain 90% 4-phenyl-2-indanol and 8.4% 4-phenyl-1-indanol.

A solution of the 79.6 g of oil and 0.1 g of p-toluenesulfonic acid in 350 ml of toluene was heated at reflux for 15-20 minutes during which a toluene/water azeotrope collected in a Dean-Stark trap. The mixture was cooled, placed on a silica gel chromatography column, and eluted first with toluene, then with 1:1 toluene/ ethyl acetate. Appropriate fractions were combined and concentrated to give, after crystallization from toluene, 44.5 g of 4-phenyl-2-indanol, mp 71’-73°C. The nmr spectrum was consistent with the proposed structure.

Example 3 SYNTHESIS OF 4-PHENYL-2-INDANOL (METHOD C) A. Preparation of 1,2-epoxy-4-phenylindane A stirred solution of 47.5 g (0.234 mole) of mchloroperbenzoic acid (85% purity) in 390 ml of chloroform was cooled to O’C. To this was added dropwise a solution of 45 g (0.234 mole) of 7-phenyl-1H-indene (which may be prepared as in Example IG) in 110 ml of chloroform. After complete addition, the mixture was stirred for 2 1/2 hours, then was allowed to stand for 21 hours at 0“C, With the temperature in the range of O’-5°C, 100 ml of a 10% aqueous solution of sodium hydroxide, then 50 ml of a 10% aqueous solution of sodium sulfate, were added dropwise with stirring. After complete addition the two-phase mixture was stirred for 30 minutes. The organic phase was separated, washed first with a dilute aqueous solution of sodium bicarbonate, then with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to give 47.7 g of 1,2epoxy-4-phenylindane as a pale yellow oil, 97% purity by gas chromatographic analysis.

B. Preparation of 4-phenyl-2-indanol Under a dry argon atmosphere, a stirred solution of 9 g (0.067 mole) of aluminum chloride in 225 ml of anhydrous diethyl ether was cooled to 0°C. To this was added portionwise 9.4 g (0.245 mole) of lithium aluminum hydride. The cooling bath was removed, and the mixture stirred for 15 minutes. With the temperature being maintained at 25°C, a solution of 47.7 g (0.229 mole) of 1,2-epoxy-4-phenylindane in 175 ml of anhydrous diethyl ether was added dropwise. After complete addi25 tion, the mixture was heated at reflux for 18 hours, then cooled to 0°C. Water and an aqueous solution of sodium hydroxide were added to decompose the excess lithium aluminum hydride, and the mixture was filtered. The filter cake was washed with diethyl ether, and the filtrate and washes were combined and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate concentrated under reduced pressure to give an oil. The oil was subjected to column chromatography on silica gel, eluting with 98:2 toluene/ethyl acetate followed by 90:10 toluene/ethyl acetate to give 62.1 g of 4-phenyl-2-indanol, mp 72°-76°C. The nmr spectrum was consistent with the proposed structure. 50832 Example 4 illustrates the preparation of compounds of formula III.

Example 4 SYNTHESIS OF ETHYL 3,3-DIMETHYL-4,6,6-TRICHLORO-7,7,7TRIFLUOROHEPTANOATE A stirred solution of 44.G g (0.267 mole) of ethyl 3,3-dimethyl-4-pentenoate, 100 g (0.533 mole) of 1,1,1-triohlorotrifluoroethane, 0.27 g (0.0027 mole) of cuprous chloride, and 8.2 g (0.134 mole) of ethanolamine in 270 ml of tertiary butyl alcohol, under a nitrogen atmosphere, was heated at reflux for 16 hours. The reaction mixture was cooled to ambient temperature and extracted with three portions of 100 ml each of diethyl ether. A precipitate formed in the extracts, and was removed by vacuum filtration. The filter cake was washed with two portions of 25 ml each of diethyl ether. The ether extracts were combined with the washings, and the whole was concentrated under reduced pressure to an oily residue. Remaining volatile components were removed from the residue under further reduced pressure using a vacuum pump. The residue was subjected to distillation under reduced pressure to give 78.3 g of ethyl 3,3-d imethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate; bp 85-87* at 16-20 Pa. The nmr spectrum was consistent with the assigned structure.

Examples 5 and 6 illustrate preparation of the lower alkyl esters of formula IV. Example 5 is a two-step process via the intermediate of formula VII. Example 6 is a one-step process.

Example 5 SYNTHESIS OF METHYL CIS,TRANS-3-(2-CHLORO-3,3,3-TRIFLUORO-1 -PROPENYL) - 2,2-DIMETHYLCYCLOPROPANECARBOXYLATE A. Preparation of methyl cis,trans-3-(2,2-dichloro-3,3,3-tri fluoropropyl)-2,2-dimethylcyclopropanecarboxylate A stirred solution of 37.0 g (0.112 mole) of methyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro16 50S32 heptanoate, 50 ml of tert-butyl alcohol, 50 ml of dimethylformamide, and 50 ml of hexane, under an argon atmosphere, was cooled to -5°C. To the stirred solution was added dropwise a solution of 16.4 g (0.14 mole) of potassium tert-butoxide in 200 ml of tert-butyl alcohol at such a rate so as to maintain the reaction mixture temperature at -3 to -5°C. upon complete addition, the reaction mixture was stirred for 4 hours at -3 to -5’C, then poured into a solution of 8.0 g of ammonium chloride in 250 ml of water. The mixture was extracted with two portions of 200 ml each of diethyl ether. The combined ether extracts were washed with two portions of 200 ml each of water. The ether layer was dried with sodium sulfate and filtered. The filtrate was evaporated under reduced pressure to a residual oil. The oil was distilled under reduced pressure to give 19.8 g of methyl cis,trans-3-(2,2-d ichloro-3,3,3-trifluoropropyl)-2,2-dimethylcyclopropanecarboxylate; b.p. 55-57°C/12 Pa. The ir and the nmr spectra were consistent with the pro20 posed structure.

Analysis calc’d for C.nH,,C19F,O~: C 40.98; H 4.47 Found: C 41.50; H 4.41 B. Synthesis of methyl cis,trans-3-(2-chloro3,3,3-trifluoro-1-propenyl)-2,2-dimethyl25 cyclopropanecarboxylate.

A stirred solution of 30.6 g (0.105 mole) of me thyl cis,trans-3-(2,2-dichloro-3,3,3-tri fluoropropyl)2,2-dimethylcyclopropanecarboxylate and 17.6 g (0.116 mole) of 1,5-diazabicyclo(5.4.0)undec-5-ene in 100 ml of dimethylformamide was heated at 100“C for 4 hours. The reaction mixture was cooled and poured into a solution of 37.2 ml of concentrated hydrochloric acid in 300 ml of water. The mixture was extracted with three portions of 200 ml each of diethyl ether. The combined ether extracts were washed with an aqueous saturated solution of sodium chloride. The ether layer was dried with sodium sulfate and filtered. The filtrate was 50S32 evaporated under reduced pressure to give a residual oil. The oil was dissolved in hexane, treated with decolorizing carbon, and filtered. The filtrate was evaporated under reduced pressure to a residual oil. The oil was distilled under reduced pressure to give in three fractions 10.0 g of methyl cis,trans 3-(2-chloro3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate; b.p. 40-60*C/ 6.67 Pa. The ir and the nmr spectra were consistent with the proposed structure. The nmr spectra indicated an 88:12 mixture of cis:trans isomers.

Analysis calc’d for C^gH^ClFjOj! C 46.80; H 4.71; Found: C 46.91; H 4.79.

Example 6 SYNTHESIS OF ETHYL CIS,TRANS-3-(2-CHLORO-3,3,3-TRIFLUORO- 1 -PROPENYL) -2 ,2-DIMETHYLCYCLOPROPANECARBOXYLATE To a stirred solution of 78.3 g (0.228 mole) of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate in 200 ml of distilled ethanol was added dropwise at ambient temperature 500 ml of an ethanolic solution of sodium ethoxide prepared from 11.5 g of metallic sodium (0.50 mole). After complete addition, the reaction mixture was stirred for one hour at ambient temperature, then allowed to stand for 18 hours. The cloudy reaction mixture was filtered and the filtrate evaporated under reduced pressure to give a residue. The residue was slurried in 200 ml of water, and the mixture was extracted with three portions of 50 ml each of diethyl ether. The combined extracts were dried with sodium sulfate and filtered. The filtrate was evaporated under reduced pressure to give, as a residual oil, 58.5 g of ethyl cis,trans-3-(2-chloro-3,3,3-trifluoro-1-propenyl)2,2-dimethylcyclopropanecarboxylate. The nmr and the ir spectra were consistent with the assigned structure and indicated the product was a mixture of approximately equal parts of cis and trans isomers. v 50932 Examples 7 and 8 illustrate preparation of the individual cis and trans isomers of the free acids of formula IV.

Example 7 SYNTHESIS OF TRANS AND CIS,TRANS-3-(2-CHLORO-3,3,3-TRIFLOORO-1-PROPENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLIC ACID A solution of 16.2 g (0.06 mole) of ethyl cis, trans-3-( 2-chloro-3,3,3-trif luoro-1-propenyl )-2,2-dimethylcyclopropanecarboxylate in 94 ml (0.078 mole) of a stock solution containing 3.34 g of sodium hydroxide, 94 ml of ethanol and 6 ml of water was stirred while heating under reflux for a period of 18 hours. The reaction mixture was concentrated under reduced pressure, 25 ml of water was added, and the mixture was acidified to pH 1 using 6N hydrochloric acid. The acidified mixture was extracted with two portions of 50 ml each of diethyl ether. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to give a residue.

The residue was heated with 50 ml of hexane. The hot hexane was decanted from a tarry residue and cooled to yield a solid precipitate, which was collected by filtration, then dried to give 3.3 g of solid, m.p. 97-103“C. Concentration of the mother liquor provided a second fraction of solid weighing 0.8 g, m.p. 96-103*C. Nmr spectra of the two fractions indicated the solids were each trans-3-(2-chloro-3,3,3-trifluoro-1-propenyl)2,2-dimethylcyclopropanecarboxylic acid. The mother liquor was evaporated to a residue. The residue was taken up in 50 ml of hexane and the solution cooled in a freezer for 18 hours. A solid precipitate was collected by filtration and dried to give 4.3 g of a solid, m.p. 64-74°C. An nmr spectrum indicated the solid was a 50/50 mixture of cis and trans isomers of 3-(2-chloro35 3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid. 59832 Example 8 SYNTHESIS OF CIS AND CIS,TRANS-3-(2-CHLORO-3,3,3-TRIFLUORO-l-PROPENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLIC ACID A stirred solution of 90.0 g (0.35 mole) of methyl cis,trans-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (approximately 90% cis, prepared in accordance with Example 5B), 5.4 ml of concentrated sulfuric acid and 13.8 ml of water in 138 ml of acetic acid was heated under reflux for 1 hour. The reaction mixture was cooled and extracted with two portions of 100 ml each of diethyl ether. The combined extracts were dried with sodium sulfate, filtered, and the filtrate concentrated under reduced pressure to a solid residue. The residue was digested with 300 ml of hexane and the hexane solution was decanted from a dark, tarry residue and allowed to cool to ambient temperature. A solid precipitate formed and was collected by filtration to give 42.4 g of cis-3-(2-chloro-3,3,3trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid, as determined by NMR spectroscopy. A melting point was not determined. The melting point of another sample of cis acid prepared at a different time was 108-110*C. The filtrate was concentrated and cooled to give 5.1 g of solid, identified by NMR spectroscopy to be a 50:50 mixture of cis,trans-3-(2-chloro-3,3,3-trif 1 uo ro-1 -propeny 1)-2,2-d ime thyl cyclopropanecarboxyl ic acid. The filtrate was cooled in dry ice to give an additional 8.1 g of a 50:50 mixture of the cis,trans isomers.

Examples 9 and 10 illustrate preparation of the acid halides of formula IV.

Example 9 SYNTHESIS OF TRANS-3-(2-CHLORO-3,3,3-TRIFLUORO-1-PROPENYL)-2,2-DIMETHYLCYCLOPROPANECARBONYL CHLORIDE To a stirred solution of 4.1 g (0.0173 mole) of trans-3-( 2-chloro-3,3,3-trifluoro-1-propenyl)-2,250932 dimethylcyclopropanecarboxylic acid in 40 ml of toluene at ambient temperature was added 1.7 g (0.022 mole) of pyridine, then 2.6 g (0.022 mole) of thionyl chloride in 25 ml of toluene. Upon complete addition the reaction mixture was stirred at ambient temperature for 17 hours. The reaction mixture was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure to give 3.8 g of trans-3-(2-chloro-3,3,3-trif 1 uoro-1-propenyl)-2,2-dimethylcyclopropanecarbonyl chloride. The ir spectrum was consistent with the assigned structure.

Example 10 SYNTHESIS OF CIS-3-(2-CHLORO-3,3,3-TRIFLUORO-l-PROPENYL)-2,2-DIMETHYLCYCLOPROPANECARBONYL CHLORIDE a stirred solution of 10.0 g (0.04 mole) of cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid in 100 ml of toluene was heated to 80°C. To this solution at 80°C was added dropwise over 10 minutes a solution of 10.5 g (0.08 mole) of oxalyl chloride in 5 ml of toluene, and the whole heated at 80°C for 26 hours. The toluene and excess oxalyl chloride were removed by distillation to give a residual oil which was distilled under reduced pressure using a Kugelrohr distilling system to give 8.2 g of c_is-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2dimethylcyclopropanecarbonyl chloride; b.p. 85°C/12 Pa. The nmr and ir spectra were consistent with the proposed structure.

Examples 11 and 12 illustrate preparation of compounds of formula I.

Example 11 SYNTHESIS OF 4-PHENYL-2-INDANYL CIS-3-(2-CHLORO-3,3,3TRIFLUORO-1-PROPENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLATE A stirred solution of 0.25 g (0.0012 mole) of 35 4-phenyl-2-indanol and 0.11 g (0.0014 mole) of pyridine in 10 ml of toluene was cooled to 5°C, and a solution 50032 of 0.28 g (0.0011 mole) of cis-3-(2-chloro~3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarbonyl chloride, prepared in accordance with Example 10, in 5 ml of toluene was added portionwise. Upon complete addition the reaction mixture was stirred at ambient temperature for 2 hours. The reaction mixture was filtered and the filtrate concentrated under reduced pressure to a residual oil. The oil was placed on a silica gel pad, and the product was eluted with 50 ml of 1:1 hexane:toluene. The eluate was concentrated under reduced pressure at 100-115°C/2.67 Pa. using a Kugelrohr distilling system to give 0.12 g of 4-phenyl-2-indanyl cis-3-( 2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate. The nmr spectrum was consistent with the proposed structure.

Analysis eale'd for C ^6.28; H 5.10 Found: C 65.76; H 5.28.

Example 12 SYNTHESIS OF 4-PHENYL-2-INDANYL CIS,TRANS-3-(2,2-DICHLOROETHENYL)-2,2-DIMETHYLCYCLOPROPAKECARBOXYLATE A solution of 0.64 g (0.003 mole) of 4-phenyl2-indanol, 0.70 g (0.003 mole) of cis,trans 3-{2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride, and 0.24 g (0.003 mole) of pyridine, in 20 ml of benzene was stirred at ambient temperature for 16 hours, then mixed with 50 ml of water. The organic layer was separated and the aqueous layer was washed with 50 ml of diethyl ether. The combined organic layers were washed with 100 ml of agueous dilute hydrochloric acid, then with 100 ml of a 10% aqueous solution of sodium hydroxide, and finally, with water. The organic layer was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to a residual oil. The oil was subjected to column chromatography, eluting with benzene. The appropriate fractions were combined to give 1.1 g of 4-phenyl-2-indanyl cis,trans-3-(2,2-dichloroetheny1)-2,2-dimethylcyclopropanecarboxylate.

Analysis calc'd for ^23H22^^2°2! 68.83; H 5.53; Found; C 68.59; H 5.79.

In the method aspect of this invention, an effective insecticidal amount of the compound of formula I is applied to the locus where insect control is desired, i.e., to the insect itself or to the foliage or seeds of agricultural plants. The compounds are useful for the control of household, veterinary, arid crop insects and may be applied as technical material or as formulated product. Typical formulations include compositions of the active ingredient in combination with an agriculturally acceptable carrier or extender, preferably with a surface active agent, and optionally with other active ingred15 ients. Suitable formulations include granules, powders, or liquids, the choice varying with the type of pest and environmental factors present at the particular locus of infestation. Thus, the compounds may be formulated as granules of various sizes, as dusts, as wettable powders, as emulsifiable concentrates, as solutions, as dispersions, as controlled release compositions, and the like.

A typical formulation may vary widely in concentration of active ingredient depending upon the particular agent used, the additives and carriers used, other active ingredients, and the desired mode of application. With due consideration to these factors the active ingredient of a typical formulation may, for example, be suitably present at a concentration of about 0.01% up to about 99.5%, preferably 0.1% up to 90% or 95%, of the formula30 tion. An agriculturally acceptable carrier may comprise about 99.5% by weight to as low as about 0.5% by weight of the formulation. Compatible surface active agents, if employed in a formulation, may be present at various concentrations, suitably in the range of 1 to 30% by weight of the formulation.

The formulation may be used as such or diluted to S0932 a desired use dilution with a diluent or carrier suitable for facilitating dispersion of the active ingredients. A concentration of the active ingredient in the use dilution may be in the range of 0.001% to about 50%, preferably up to about 10%, by weight.

Many variations of spraying, dusting, and controlled or slow release compositions of a type known in the art may be used by substituting or adding an insecticidal compound or compounds of this invention into the compositions known or apparent to the art.

The insecticidal compounds of this invention may be formulated and applied with other compatible active agents including nematacides, insecticides, acaracides, fungicides, plant regulators, herbicides, fertilizers, and the like.

In applying these compounds, whether alone or with other agricultural chemicals, an effective insecticidal amount of the active ingredient must be applied. While the application rate will vary widely depending on the choice of compound, formulation, mode of application, plant species being protected, planting density and other like factors, a suitable use rate for agricultural crops may be in the range of 0.005 to 3 kg/ha, preferably 0.01 to about 1 kg/ha.

The insecticidal compounds of this invention were tested for insecticidal activity as described in Examples 13 and 14 below.

Example 13 Initial Contact Activity: The test compound was dissolved in 5-10 ml of acetone containing 0.25% acetylphenoxypolyethoxyethanol. This solution was dispersed in a solution of 90% water, 9.75% acetone, and 0.25% acetylphenoxypolyethoxyethanol to give a solution having 512 ppm (w/w) active ingredient. Aliquots of this solution were diluted with an appropriate amount of water to provide solutions containing various concentrations of active ingredient.

Test organisms and techniques were as follows: The activity against Mexican bean beetle (Epilachna varivestis Muls.) and southern armyworm (Spodoptera eridania [Cram.]) was evaluated by spraying the leaves of pinto 5 bean plants with the test solution and infesting with 3rd instar larvae after the foliage had dried. The activity against the pea aphid (Acyrthosiphon pisum [Harris]) was evaluated on broad bean plants whose leaves were sprayed before infestation with adult aphids. To prevent escape of the insects from the test site, the complete test plant or the incised leaves were placed in capped paper cups. The tests were transferred to a holding room at 80°C and 50% relative humidity for an exposure period of at least 48 hours. At the end of this time the dead and living insects were counted and the percent kill was calculated. Results of these tests are summarized in the table below. Also shown in the table below for comparison are insecticidal efficacy data from these tests for the commercial insecticide permethrin, 3-phenoxybenzyl (+) cis,trans-3-(2,2-dichloroethenyl)2,2-dimethylcyclopropanecarboxylate. Mortality figures in parentheses are from retests.

The compound of Example 12 was more active than permethrin against Mexican bean beetle and pea aphid, but less active than permethrin against Southern armyworm, The compound of Example 11 was superior in activity to permethrin against all three insect species. Relative to permethrin, the compounds of Examples 11 and 12 showed outstanding activity against pea aphid.

INITIAL CONTACT ACTIVITY Percent Kill at Indicated Concentration (ppm) Mexican Bean Beetle Compound of Example 11 12 Permethrin 16 8 6.5 100 Armyworm 3.2 100 100(100) 50( 55) 85(80) 35(25) Southern 10 11 - - 100 80 12 100 85 35 10 Permethrin - - 100 60(7) Pea Aphid 11 - - 100 100 15 12 80(100) 80(70) - - Permethrin 10( 30) - - - Example 14 Topical Application Test; The compounds of this invention were tested for insecticidal activity by applying to the insect appropriate amounts of a toxicant solution containing 5 mg/ml of toxicant in acetone. The tests were read twenty-four hours after application of the toxicant solution and the percent kill determined. The commercial insecticide per25 methrin, 3-phenoxybenzyl (+) cis-trans-3-(2,2-diohlorovinyl)-2,2-dimethylcyclopropanecarboxylate, was used as the standard for comparison. Relative potency, based on a value of 1.0 for permethrin was determined by comparing the LDgg for the test compound with that for the stan30 dard. The insects employed include southern armyworm (Spodoptera eridania (Cram.]), cabbage looper (Trichoplusia ni [Hubner]), Mexican bean beetle (Epilachna varivestis Muls.), beet armyworm (Spodoptera exigua [Hubner]), milkweed bug (Oncopeltus faciatus [Dallas]), tobacco bud35 worm (Heliothis virescens [Fabricius]), and corn earworm (Heliothis zea [Boddie]). The results of these tests are shown in the table below. The insect species above are 50832 designated in the table respectively, as SAW, CL, MBB, BAW, MWB, TBW, and CEW.

In these tests, the compound of Example 11 was generally superior to permethrin while the compound of Example 12 was generally inferior to permethrin. The compound of Example 11, which was not tested against beet armyworm, tobacco budworm or corn earworm, was less active than permethrin against Southern armyworm, and more active than permethrin against cabbage looper, Mexican bean beetle, and milkweed bug. The compound of Example 12 was less active than permethrin against Southern armyworm, cabbage looper, and corn earworm, more active than permethrin against milkweed bug, and about as active as permethrin against Mexican bean beetle, beet armyworm, and tobacco budworm.

TOPICAL APPLICATION TEST Relative Potency Against Compound of Example SAW CL MBB BAW MWB TBW CEW Permethrin 1.01 1.02 1.03 - 1.04 - - 11 0.55 1.50 3.31 - 1.58 - - Permethrin 1.05 1.06 1.07 1.08 1.09 1.010 1.011 12 0.47 0.65 1.04 0.96 1.68 0.93 0.72 1. 2.LD50 —50 — 18 130 nanograms/insect nanograms/insect 3. —50 = 17 nanograms/insect 4. -50 = 700 nanograms/insect 5. -50 = 24 nanograms/insect 30 6. -50 = 140 nanograms/insect 7. -50 = 21 nanograms/insect 8. -50 = 1300 nanograms/insect 9. -50 = 640 nanograms/insect 10. -50 = 750 nanograms/insect 35 11. -50 = 270 nanograms/insect

Claims

1. A compound oi the formula r 2 o in which is phenyl, optionally substituted with halogen or alkyl, and 5 is 2,2,3,3-tetramethylcyclopropylcarbonyl, l-(4-chlorophenyl)-2methylpropylcarbonyl, or a group of the formula where each of Y and 2, which are the same or different, is a hydrogen or 10 halogen atom, a Cj alkyi or Cj_ 2 perhaloalkyl radical, or a phenyl, or phenylthio radical, optionally substituted with halogen or Cj^ alkyl, with the proviso that at least one of Y and Z is other than hydrogen and further provided that the isomer of S configuration at C-2 of the indanol ring is not present in an enantiomeric excess of 25% or more over the isomer of R 15 configuration at C-2 of the indanol ring.

2. A compound as claimed in Claim 1 in which R^ is phenyl and R^ is a group of the formula ,C=CH Z II C50932

3. A compound as claimed in Claim 2 in which one of Y and Z is halogen and the other is halogen or perhaloalkyl.

4. A compound as claimed in Claim 3 in which both Y and Z are halogen.

5. A compound as claimed in Claim 4 in which both Y and Z are chlorine. 5

6. A compound as claimed in Claim 3 in which one of Y and Z is halogen and the other is trifluoromethyl.

7. A compound as claimed in Claim 6 in which one of Y and Z is chlorine and the other is trifluoromethyl.

8. A compound as claimed in Claim 1, when prepared by a method 10 substantially as hereinbefore described in Example 11 or 12.

9. An insecticidal or acaricidal composition containing an insecticidally or acaricidally effective amount of a compound as claimed in any one of Claims 1 to 8, in admixture with at least one additional component selected from compatible adjuvants, diluents, and carriers. gg

10. A method for controlling insects or acarids comprising applying to the insect or acarid or to the locus where control is desired from 0.005 to 3 kg/ha of a compound as claimed in any one of Claims 1 to 8.

11. A composition as claimed in Claim 9 containing 0.01% to 99.5% by weight of the said compound, the remainder being the additional 20 components.

12. A method for controlling insects or acarids comprising applying a composition as claimed in Claim 9 or 11 to the insect or acarid or to the locus where control is desired at a rate equivalent to 0.005 to 3 kg/ha of active ingredient. 50832

13. A compound of the first formula given and defined in Claim 1, substantially as hereinbefore described with reference to Examples 1-12 inclusive of the accompanying Examples. 5

14. A process for the preparation of a compound of the first formula given and defined in claim 1, substantially as hereinbefore described with reference to Examples 1-12 inclusive of the accompanying Examples.

15. A compound of the first formula given and defined in claim 1, whenever prepared by a process claimed in claim 14. IS. An insecticidal or acarioidal composition according to claim 9, substantially as hereinbefore 15 described with reference to Examples 13 and 14 of the accompanying Examples.

16.

17. A method according to Claim 10 or 12 for controlling insects or acarids, substantially as hereinbefore described with reference to Examples 2o 13 and 14 of the accompanying Examples.