CA1160248A

CA1160248A - Cyclopropane compounds

Info

Publication number: CA1160248A
Application number: CA000335721A
Authority: CA
Inventors: Steven A. Roman
Original assignee: Shell Canada Ltd
Current assignee: Shell Canada Ltd
Priority date: 1978-10-23
Filing date: 1979-09-17
Publication date: 1984-01-10
Also published as: JPS6338973B2; CH643232A5; IT7926699A0; AU528724B2; DE2942618A1; DK445779A; AU5202479A; NL7907718A; GB2048242B; BE879451A; GB2048242A; ZA795634B; FR2439771A1; FR2439771B1; IL58521A; IT1125554B; IL58521A0; JPS5557532A; DE2942618C2

Abstract

A B S T R A C T
Cyclopropane compounds of the formula (I) wherein R1 represents an acetyl or acetoxy group; an alkoxy group containlng 2 to 10 carbon atoms optional-ly-substituted by one or more halogen atoms; a (cyclo-alkyl)alkoxy group containing 3 to 7 ring carbon atoms, a total of 4 to 9 carbon atoms and optionally ring-substituted by one or more halogen atoms; a cycloalkoxy group containing 3 to 7 ring carbon atoms; an alkenyl-oxy group containing 2 to 4 carbon atoms optionally-substituted by one or more halogen atoms; an alkynyloxy group containing 2 to 4 carbon atoms; an aryloxy group containing 6 to 12 carbon atoms; an aralkyloxy group containing 7 to 10 carbon atoms; and wherein X is -CH2CH(OCH3)2; -CH2CHO; -CH=CHOR2 in which R2 is an acyl group containing 2 to 5 carbon atoms; -CHO; -COCL;
-COBr; -COOR in which R represents a hvdrogen atom, a salt-forming cation, an alkyl group containing from 1 to 20 carbon atoms; or a phenoxybenzyl or alpha-cyano-phenoxybenzyl group; with the proviso that when R1 is an acetoxy group, X is not a -CH2CH(OCH3)2 group. Some of the compounds have pesticidal activity and others are useful as intermediates in the manufacture of these and other pesticides.

Description

The present invention relates to cyclopropane com?ounds. Some of the compounds are useful as pesticides and the remainder can be used as intermediates in the manufacture of these and other pesticides.
The present invention relates to new cyclopropane co~npounds of the formula:-CH2 - Rl / \ (I) C113 ~ - \ - X
C~13 11 wherein Rl represents an acetyl or acetoxy group; an alkoxy group containing 2 to lO carbon atoms optionally-substituted by one or more halogen atoms; a (cycloalkyl)alkoxy group containing 3 to 7 ring carbon atoms, a total of 4 to 9 carbon atoms and optionally ring-substituted by one or more halogen atoms e.g.
a cyclopropylmethoxy group; a cycloalkoxy group, containing 3 to 7 ring carbon atoms, for example a cyclopropyloxy group; an alkenyloxy group containing 2 to 4 carbon atoms, e.g. a vinyloxy group, optionally-substituted by one or more halogen atoms; an alkynyloxy group containing 2 to 4 carbon atoms, e.g. a pro-pynyloxy group; an aryloxy group containing 6 to 12 carbon atoms, e.g. a phenoxy group; an aralkyloxy group containing 7 to lO carbon atoms, e.g. a benzyloxy group; and wherein X is -CH2CH(OCH3)2; -CH2CHO; -CH=CHOR2 in which R is an acyl group containing 2 to 5 carbon atoms; -CHO; -COCl; -COBr; -COOR in which R
represents a hydrogen atom, a salt-forming cation, e.g. an alkali metal, ammonium or substituted ammonium cation, an alkyl group containing from l to 20 carbon atoms, e.g. a tertiary butyl group, or a phenoxybenzyl or alpha-cyano-phenoxybenzyl group; with the proviso that when R is an acetoxy group, X is not a -CH2CH(OCH3)2 or a -Cll2CIIO group, and when R is an acetyl group X is not a -CH=CHOR , -CHO, -COOR, or a -CH2CH(OCH3)2 group.
The esters according to the invention, i.e. those of the general formu-la ~I) in which ~ is -COOR wherein R is an alkyl group or a phenoxybenzyl or alpha-cyano-phenoxybenzyl group, are useful pest control agents. The remaining cyclopropane compolmds of general formula (I) are useful intermediates for the production of these and other pest control esters.
A preferred subclass of compounds of the invention are those wherein R is an acetyl or acetoxy group; an alkoxy group containing from 1 to 6 carbon atoms; a (cycloalkyl)alkoxy group containing from 3 to 6 ring carbon atoms and 4 to 8 carbon atoms, in the alkoxy group; a cycloalkyloxy group containing :Erom 3 to 6 carbon atoms; an alkenyloxy or alkynyloxy group contailling :Erom 2 to ~1 carbon atoms; an aryloxy group containing from 6 to 12 carbon atoms or an aralkyl-oxy group containing from 7 to 10 carbon atoms; and X is -CH2CH(OCH3)2;
-CH2CHO: -CH=CHOR in which R is an acyl group containing 2 to 5 carbon atoms;
-CHO; -COCl; -COBr; -COOR in which R is a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, or a phenoxybenzyl or ~ -cyano-phenoxybenzyl group.
Particularly preferred are those compounds of general formula I wherein Rl is an acetyl or acetoxy group; an alkoxy group containing 1 to ~ carbon atoms;
a benzyloxy group; and X is -CH2CHO; -CH=CIIO.CO.CH3; -CHO; or -COOR in which R

is hydrogen or a phenoxybenzyl or alpha-cyano-phenoxybenzyl group.
The cyclopropane compounds exhibit stereo-isomerism by vir-tue of two asymmetric centres in the cyclopropane ring and consequently can be prepared in optically-active forms, which can subsequently be mixed together, or as racemic mixtures, which can subsequently be resolved into optically-active forms. Be-cause they usually provide the highest degree of pest control, the (lR, c esters are preferred although the (lR, trans) esters are also active. In the . - 2 -esters of alpha-substituted alcohols, there is a further possibility oE optical isomerism, i.e. as R or as S stereo-isomeric configuration.
The preferred compounds having pesticidal activity are those of formu-la (1) in which R is acetyl or acetoxy group or an alkoxy group containing 1 to 3 carbon atoms or a benzyloxy group and X is the group -COOR in which R is 3-phenoxybenzyl or alpha-cyano-3-phenoxybenzyl; the most preferred compounds be-ing those in the ~lR, cis)-form. Examples of such compounds are:-~a) alpha-cyano-3-phenoxybenzyl (lR, cis)-2,2,-dimethyl-3-(ethoxymethyl)-cyclopropanecarboxylate;
(b) ~ -cyano-3-phenoxybenzyl (lR, cis)-2,2-dimethyl-3-(methoxymethyl)-cyclopropanecarboxylate;
(c) 3-phenoxybenzyl (lR, cis)-2,2-dimethyl-3-(ethoxymethyl)cyclopropane-carboxylate;
(d) alpha-cyano-3-phenoxybenzyl (lR, cis)-2,2-dimethyl-3-(propoxymethyl)-cyclopropanecarboxylate;
(e) ~ -cyano-3-phenoxybenzyl (lR, cis)-2,2-dimethyl-3-(benzyloxymethyl)-cyclopropanecarboxylate.
The pesticidal esters and intermediates according to the invention are preferably in the (lR, cis) stereo-isomeric form as they prossess or impart the most potent pesticidal activity.
All the compounds according to the invention may be derived from 3-carene which, in its naturally occurring form exists as (+)-3-carene and in this latter form gives rise to compounds according to the invention in the (lR, cis)-form. Accordingly, these (lR, cis) compounds derived from (~)-3-carene con-stitute a preferred aspect of the invention.
The compounds according to the invention o:E general formula I wherein Rl has the meaning hereinbefore defined and X is -CH2CH(OCH3)2, -CH2CHO;

2 ~8 -CH=CHOR ; -CHO may be prepared by or as intermediate products in the following route.

3-Carene having the general formula III:-p (III) can be ozonized and treated with dimethyl sulfide in methanol to form 1-(2,2-dimethoxyethyl)-2,2-dimethyl-3-~2-oxopropyl)cyclopropane, a compound having the formula IV:-V C~l2C(O)CH3 / \ ~IV) 3 ~ ~ / 3 \ OCH

which can be oxidized to (2-~2,2-dimethoxyethyl)-3,3-dimethylcyclopropyl~-methyl-10acetate having the formula V:-H CH2OC(o)cH3 / \ (V) CH3 ~ OCH3 / \ \ OCH3 ~L~L61Uf~

Hydrolysis Of the above acetate derivative yields (2~2-dimcthyl-3-~2,2-dimethyl-oxyethyl)cyclopropyl)-methanol having the formula VI:-~

3 ~ - CH CH ~ 3 (VI) Compound VI can be converted to a compound having thC formula VII:-CH / \ ~ OC~13 ~VII) wherein Rl has the meaning hereinbefore defined except that acetyl and acetoxy are excluded. Hydrolysis of the compound VII yields an aldehyde derivative having the formula VIII:-\/

3 ~ CH2CHo ~VIII) 2 ~ ~

whieh can react with a carboxylic acid anhydride containing ~ to 10 caTbon atoms, e.g., acetic anhydride, to produce a compound having the formula IX:-z ~ ~IX) CH ~ \ CH=CHOR

wherein R is an acyl group containing 2 to 5 carbon atoms. Ozonolysis of thevinyl ester derivative and treatment with zinc forms an aldehyde having the formula X:-A (X) CH ~ \ CHO

Oxidation of the compound of formula X yields the corresponding carboxylic acid, useful for the preparation of ester pest control agents of the invention for example in which X is -COOR and R is 3-phenoxybenzyl or alpha-cyano-3-phenoxy-benzyl.
Compounds according to the invention having the general formula I
wherein R is acetoxy and X is -CH=CHOCOCH3 or -CHO may be prepared by or as an intermediate in the following route.

.~ .
,o.~ , B

Compound V can be hydrolyzed in the presence of acid to ~2,2-dimethyl-3-~2-oxoethyl)cyclopropyl)methyl acetate havlng the formula XI:-CH ~ CH2CHO ~XI) Treatment of the compound XI with an acid anhydride e.g. acetic anhydride inthe presence of a base produced 2-~3-acetoxymethyl-2,2-dimethylcyclopropyl)vinyl acetate having the formula XII:-CH3 ~ ~ CH=c~oc~o)CH3 ~XII) Ozonolysis and treatment with zinc of the above vinyl acetate derivative yields3-acetoxymethyl-2,2-dimethylcyclopropanecarboxaldehyde having the formula XIII:-CH3 ~ CHO ~XIII) , ~ ~

Oxidation of the above compound yields 3-acetoxymethyl-2,2-dimethyl-cyclopro-panecarboxylic acid, useful for the preparation of ester pest control agents of the invention wherein Rl is acetoxy and X is -C~O)OR in which R is 3-phenoxy-benzyl or alpha-cyano-3-phenoxybenzyl. In this route compounds XII and XIII
are novel compounds.
The ozonolysis reactions are conducted with a gaseous mixture compris-ing ozone and oxygen or ozone and air~ The mixture of ozone and oxygen is suitably diluted with an inert gas, such as nitrogen or argon. The ozonolysis is carried out at a temperature from -80C to ~20C, preferably from -20C to t20C. It is useful in certain cases to use a solvent. Suitable solvents include aromatic hydrocarbons such as benzene and toluene, halogenated hydro-carbons, such as methylene dichloride and chloroform, lower aliphatic car-boxylic acids and esters tllereof such as glacial acetic acid and ethyl acetate,aliphatic hydrocarbons, such as n-hexane, and los~er alkanols such as methanol.
Oxidation of composmds of :Eormula IV, X and XIII can be conducted using reagents which convert an aldehyde into an ester or acid group as required.
For example, the compound of formula IV is oxidized by hydrogen peroxide~ or a peracid, such as m-chloro-perbenzoic acid, perbenzoic acid, perphthalic acid, ina suitable solvent such as chlorinated hydrocarbon, e.g., chloroform or dichloro-ethylene, or an ether, e.g., diethyl ether, and the compounds of formulae X
and XIII are oxidized using potassium permanganate, chromic acid, or po-tassium dichromate. Such oxidations are conveniently carried out in the liquid phase by agitating, e.g., stirring a mixture of the reactants, preferably in a solventsuch as an acetone-water mixture, the reaction is conducted at a temperature of from 0C to 60C at normal pressures. Preferably, the reactions are conductecl at a temperature of from 10C to ~0C.
The acetate derivative of formula V can be converted into the cyclo-propylmethanol derivative of formula VI by hydrolysis, preferably under basic conditions, for example Usillg an alkali or alkaline earth metal hydroxide or carbonate, such as sodiwm hydroxide, potassium hydroxide, sodium carbonate or the like, in an aqueous alcoholic reaction medium, such as aqueous methanol, or ethanol.
The hydroxy group of compound VI can be converted into an ether group by treatment with an optionally-substituted hydrocarbyl llalide, in which the halogen atom is chlorine, bromine or iodine. Such treatment is suitably in the presence of an alkali metal hydride, such as sodiwn hydride or potassium hy-dride, preferably in the presence of an inert solvent, such as tetrahydrofuran, dimethylformamide, or in the presence of a hydrocarbyl lithiuDl compound, such as an alkyl, aryl or aralkyl lithium compound, e.g., n-butyl lithium~ preEer-ably i~n the presence of an inert solvent, such as tetrahydrofuran.
The acetals V and VII can be converted into the aldehydes of formulae XI and VII, respectively, by treatment with an acidic material in an aqueous environment. Preferred acidic materials are acetic acid or hydrochloric acid used in the form of an aqueous solution thereof.
The compounds of formulae XI and VIII are converted into ester deriva-tives of formulae XII and IX, respectively, by treatment with the appropriate carboxylic acid anhydride, e.g. acetic anhydride in the presence of a basic material. Suitable basic materials include tertiary amines, and alkali ace~ates.
Preferred amines are pyridine and especially triethylamide.
The acetate derivatives of formulae XII and IX can be converted to the aldehydes of formulae XIII and XJ respectively, by ozonolysis as previously described an~ by treatment with zinc in the presence of acetic acid or with a basic material, preferably triethylamine, usually in an inert solvent, such as methylene chloride.
The alcohols from which the pesticidally-active esters are formed are - _ g _ known in the art, for example in Elliott et al. ~nited States patent 3,922,269 or Belgian patent 839,360. The pest control esters of the present invention can be prepared by esterification involving the reaction of an alcohol or derivàtive thereof of formula RQ, wherein R is 3-phenoxy-benzyl or alpha-cyano-3-phenoxyben~yl, and a cyclopropanecarboxylic acid or derivative of formula Il CH2 - Rl CH3 ~ COP (XIV) CH3 ~1 wherein Q and COP are functional groups or atoms whlch will react to Eorm an ester linkage, and R is an acetyl or acetoxy group or an alkoxy group contain-ing l to 3 carbon atoms or a benzyloxy group.
It is usually convenient in practice either to treat the acid or acid halide with the alcohol (COP=COOH or CO-halide and Q=OH) or to treat a halogeno compound ~Q=halogen) with a salt of the carboxylic acid (COP =COO-M) where M is, for example, a silver or ammonium cation.
It can be useful to prepare the intermediate alkyl ester as tert-butyl ester (R=tert-butyl), which can be selectively converted under acid conditions as mentioned earlier to give the free acid which can be esterified, e.g. after conversion to the acid halide, to a pesticidal ester.
As stated earlier, the esters wherein Rl is an acetyl or acetoxy group or an alkoxy group containing l to 3 carbon atoms or a benyloxy group are useful pest control agents having the ability to knockdown insects, such as houseflies, or repel mites and/or to kill insects or mites. The particular mode of pest con-.. .~

trol activity (high knockdown, repelling or killing action) can vary with the individual cyclopropanecarboxylate ester of the invention and thus depends on the specific combination of acid and alcohol moieties. In general, the pest control mode of action of the esters of the invention wherein Rl is acetyl is knockdown or mite repelling rather than a killing action. In the esters wherein Rl is alkoxy or benzyloxy, high knockdown is present and often mite repelling, insecticidal and acaricidal activity as well.
The invetion includes, within its scope, pest control compositions comprising an agriculturally acceptable adjuvant - that is, at least one carrier or a surface-active agent - and, as active ingredient, a pesticidally-eE:Eective amount of a pest control ester of this invention. Likewise, the invention includes also a method of controlling insect, acarine or other arthropod pests at a locus which comprises applying to the pests or to their habitat a pesti-cidally effective amount of at least one ester of the invention.
With respect to the spectrum of pesticidal activity, the compounds of this invention exhibit a selective or non-selective activity as insecticides or acaricides against one or more species of such orders as Coleoptera, Lepidoptera (especially Larvae), Diptera, Orthoptera, Hemiptera, Homoptera and Acarina depending upon the specific combination of acid and alcohol moieties according to the present invention. The compositions according to the present invention are useful for controlling one or more disease carrying insects such as mosquitos, flies and cockroaches, grain insects such as rice weevil ( i~ lus oryzae) and mites as well as agricultural noxious insects such as planthoppers, green rice leafhopper (Nephotettix bipuntatus c_ ticepts Uhler), diamond-back moths (Plutella maculipennis Curtis), imported cabbage worm (Pieris rapae Linne), rice stem borers (chillo suppressalis Walker), corn earworm larvae (Heliothis zea Boddie), aphids, tortrixes, leaf-miners and the like.

.~, .

The pesticidal esters of the invention are used for harvested crops, horticultural application, forests, cultures in greenhouse, and packaging ma-terials for foodstuffs.
The term "carrier" as used herein means a material that may be in-organic or organic and of synthetic or natural origin with which the active compounds is mixed or formulated to facilitate its application to the plant, seed, soil and other object to be treated, or its storage, transport or handling.
The carrier may be a solid or a liquid.
Suitable solid carriers may be natural and synthetic clays and silicates~ for example, natural silicas such as diatomaceous earths; magnesium silicates, for example, talcs; magnesium al~ninum silicates, For example, atta-pulgites and vermiculites; aluminum silicates for example, kaolinites, montmoril-lonites and micas; calcium carbonate; calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; elements such as for example, carbon and sulfur; natural and synthetic resins such as, for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid poly-chlorophenols; bitumen, waxes such as beeswax, paraffin wax, and chlorinated mineral waxes; degradable organic solids, such as ground corn cobs and walnut shells; and solid fertilizers, for example super-phosphates.
Suitable liquid carriers include solvents for the compounds of this invention and liquids in which the toxicant is insoluble or only slightly soluble.
Example of such solvents and liquid carriers, generally, are water, alcohols, for example, isopropyl alcohol, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydro-carbons such as benzene, toluene and xylene; petroleum fractions, such as kerosene, light mineral oils, chlorinated hydrocarbons, such as methylene Z ~ ~

chloride, perchloroethylene, trichloroethane, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suit-able.
If used, the surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent. It may be nonionic, ionic or preferably, mixtures of both. Surface-active agents usually applied in formulating pesti-cides may be used. Examples of such surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; the condenstion products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; fatty acids salts of low molecular weight, mono-, di-, and trialkyl-amines; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example, p-octylphenol or p-octylcresol, with ethylcne oxide and/or propylene oxide; sulfates or sulfonates of -these condensation products; alkali or alkaline earth metal salts, preferably sodium salts of sulfonated castor oil, and sodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may be formulated as wettable powders, dusts, gr~nules, solutions, emulsifiable concentrates, emulsions, sus-pension concentrates or aerosols. Encapsulated formulations and controlled release formulations are also contemplated, as are bait formulations. Wettable powders are usually compounded to contain 25, 50 or 75%w of toxicant and usually contain, in addition to solid carrier, 3 - 10%w of stabilizer~s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable ... .

powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 1/2 - 10%w of toxicant.
Granules may be manufactured by extrusion of plastics, agglomeration or im-pregnation techniques. Generally, granules will contain 1/2 - 25%w toxicant and 0 - 10%w of additives such as stabilizers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent, and when necessary, cosolvent, 10 - 50%w/v toxicant, 2 - 20%w/v emul-sifiers and 0 - 20%w/v of appropriate additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to ob-tain a stable, nonsedimenting, flowable product and usually contain 10 - 75%w toxicant, 0 - 5%w of dispersing agents, 0.1 - 10%w of suspend:ing agents such as protective colloids and thixotropic agents, 0 - 10%w o:E appropriate addi-tives such as defoamers, corrosion in]libitors, stabilizers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble; certain organic additives or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as anti-freeze agents for water.
Aqueous dispersions and emulsions, for example, compositions ob-tained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, also lie within the scope of the present invention.
The compositions of the invention can also contain other ingredi-ents, for example other compounds possessing pesticidal, herbicidal or fungicidal properties, or attractants, such as pheromones, attractive food ingredients, and the like, for use in baits and trap formulations.
Particularly useful compositions can be obtained by using a mix-ture of two or more kinds of the present compounds, or by the use of synergists, such as those known for use with the general class of "pyrethroid" compounds, especially ~-[2-~2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene also known as piperonyl butoxide, 1,2-methylenedioxy-4-[2-~octyl-sul-Einyl)propyl]-benzene, 4-~3,4-methylene-dioxyphenyl)-5-methyl-1,3-dioxane also known as safroxane, N-(2-ethylhexyl)bicyclo-[2,2,1]hept-5-ene-2,3-dicarboximide, octa-chlorodipropyl ether, isobornyl thiocyanoacetate, and other synergists used for allerthrin and pyrethrin. Useful compositions can be prepared with other bio-logical chemicals including other cyclopropanecarboxylates, organic phosphate type insecticides and carbamate type insecticides.
The compositions of the invention are applied in suEficient amount to supply the effective dosage of active ingredient at the locus to be protected.
This dosage is dependent upon many factors, including the carrier employed, the method and conditions of application, whether thc formulation is present at the locus in the form of an aerosol, or as a film, or as discrete particles, the thickness of film or size of particles, the insect or acarine species to be controlled and the like, proper consideration and resolution of these factors to provide the necessary dosage of active material at the locus being within the skill of those versed in the art. In general, however, the effective dosage of active ingredient of this invention at the locus to be protected - i.e., the applied dosage - is of the order of 0.01% to 0.5% based on the total weight of the formulation, though under some circumstances the effective concentration will be as little as 0.001% or as much as 2%, on the same basis.
The invetion is illustrated by the following examples which describe the preparation of typical species of the invention. The identity of -the pro-ducts, including intermediates, was confirmed by elemental, infrared and nuclear magnetic resonance spectral ~NMR) analyses as necessary.

,, 7 , t Example 1 ~lR,cis)-3-~Ethoxymethyl)-2,2-dimethyl-1-~2,2-dimethoxyethyl)cyclopropane To a stirred mixture of sodium hydride, from 5.8 g of 50% dispersion of sodium hydride in mineral oil washed with pentane, and 200 ml of dry di-methylformamide was added dropwise, at room temperature, 22.6 g o~ ~lR,cis)-2,2-dimethyl-3-~2,2-dimethoxyethyl)cyclopropyl)methanol; mild gas evolution took place. Subsequently, 37.4 g of ethyl iodide was added dropwise at 10 -25C over a period of 1/2 ho-ur during which time vigorous gas evolution was observed. After stirring for about 18 hours at room temperature, an additional 6 g of sodium hydride in 100 ml oE dimethylformamide was added and the reaction mix~ure was stirred at room temperature for 3 days. The mixture was quenched with water after decomposing any excess sodi~m hydride with ethanol. Tlle aqueous solution was extracted with ether and the ether phase was washed wi-th water. The ether phase was then dried with magnesium sulfate and stripped to give 30 g of an oil. This oil was distilled to give 20.3 g of desired product, bp 69 - 70C at 0.2 mm.
Examples 2 - 4 Using procedures similar to those of Example 1 above, the following cyclopropane derivatives were prepared: 3-methoxy-methyl-2,2-dimethyl-1-~2,2-dimethoxyetnyl)cyclopropane, bp 60C at 0.3 mm Hg; 3-propoxymethyl-~2,2-di-methoxyethyl)cyclopropane, bp 75 - 77C at 0.2 mm Hg; and 3-benzyloxymethyl-1-(2,2-dimethoxyethyl)cyclopropane, bp 125 - 130C at 0.2 mm Hg.
Example 5 (lR,cis)-2,2-Dimethyl-3-(ethoxymethyl)cyc]opropaneacetaldehyde A 30 g solution of the acetal from Example 1 above in 500 ml of a 2:1 mixture of acetic acid and water was stirred at room temperature for about 6 hours. The reaction mixture was poured into 1 litre of water. The aqueous mixture was extracted with methylene chloride, and the methylene chloride phase was washed with water, then with a saturated sodium bicarbonate solution and finally with a saturated sodium chloride solution. The methylene chloride phase was dried with magnesium sulfate and stripped to give 2~ g of an oil.
The oil was distilled to give 21.6 g of product~ bp 64 - 66C at 0.5 mm and [~]D 5 -' 25-6 (CHC13); c=0.02 g/cc.
Examples 6 - 8 Using procedures similar to those of Example 5 above, the following cyclopropane derivatives were prepared: 2,2-dimethyl-3-(methoxymethyl)cyclo-propaneacetaldehyde, bp 55 - 57C at 0.3 mm Hg; 2,2-dimethyl-3-(propoxymethyl)-cyclopropaneacetaldehyde, bp 75 - 78C at 1 mm IIg; and 2,2-dimethyl-3-(benzyl-oxymethyl)cyclopropaneacetaldehyde, bp 115 - 124C at 0.15 - 0.25 mm IIg.
Example 9 ((lR~cis)-2~2-Dimethyl-3-(e~hoxymethyl)-cy _opropyl) vinyl acetate A solution of 20.5 g of the aldehyde from Example 5 above, 60 ml of acetic anhydride and 12.8 g of triethylamine was stirred at room temperature for 10 hours. The reaction mixture was diluted with ether, washed with ice water, ice cold lN hydrochloric acid, ice cold solution of sodium bicarbonate, and finally with saturated sodium chloride solution. The ether phase was dried with magnesium sulfate, and stripped to give 52 g of an oil. After removal of acetic anhydride at 40C and 10 mm Hg. the oil was distilled -to give 15.2 g of product, bp 78 - 80C at 0.3 mm Hg and [~]D25 -36.2 (CHC13); c=0.02 g/cc.
Examples 10 to 12 Using procedures similar to those of Example 9 above) the following cyclopropane derivatives were prepared: 2,2-dimethyl-3-(methoxymethyl)cyclo-propyl vinyl acetate, bp 5C at 0.5 mm Hg; 2,2-dimethyl-3-(propoxymethyl)cyclo-propyl vinyl acetate, bp 85 - 8SC at 0.2 mm Hg; and 2,2-dimethyl- 3-(benzyl-oxymethyl)cyclopropyl vinyl acetate, bp 121 - 127C at 0.03 mm Hg.

r Example 13 ~lR,cis)-2,2-Dimethyl-3-(ethoxymethyl)cyclopropanecarboxaldehyde Ozone was passed through a stirred solution of 14.5 g of the acetate from Example 9 above in 120 ml of methylene chloride at -70C at a rate of 1 litre/min for 2 hours until the appearance of a blue colour indicated the pre-sence of excess ozone. The reaction mixture was purged with air to remove ex-cess ozone and the methylene chloride stripped below 20C. The resulting product was diluted with 200 ml of ether containing 50 ml glacial acetic acid.
The solution was treated at 15 - 25C with 25 g of zinc dust added portionwise over 1 hour. This reaction mixture was stirred for 1 hour at 25C, filtered to remove salts and the solids were washed with ether. l`he combined ether filtrates were washed with water, saturated sodium bicarbonate solution and finally with saturated sodium chloride solution, dried with magnesium sulfate, and s-tripped to give 11 g of an oil. This oil was distilled to give 8.4 g of product, bp 63 - 66C at 1.5 mm Hg and [~]D -46.7 (CHC13); c=0.02 g/cc.
Examples 14 - 16 .

Using procedures similar to those of Example 13 above, the following cyclopropane compounds were prepared: 2,2-dimethyl-3-(methoxymethyl)cyclopropane-carboxaldehyde, bp 55 - 85C at 1.5 mm Hg: 2,2-diemthyl-3-(propoxymethyl)cyclo-propanecarboxaldehyde, bp 65 - 67C at 0.5 mm Hg: and 2,2-dimethyl-3-~benzyloxy-methyl)cyclopropanecarboxaldehyde, bp 120 - 123C at 0.3 mm Hg.
Example 17 (lR,cis)-2,2-Dimethyl-3-(2-ethoxymethyl)cyclopropanecarboxylic acid To a stirred solution containing 7.7 g of the aldehyde from Example 13 above in 100 ml of acetone and 20 ml of water was added portionwise, over 1/2 hour~ 6 g of potassium permanganate while maintaining the temperature at 5 - 10C.
The resulting reaction mixture was allowed to warm to room temperature while stirring for 4 hours. The mixture was filtered~ and the filtrate was decolour-ized with a 10% sodium bisulfite, and, after filtration adjusted to a pH of 4 by addition of concentrated hydrochloric acid. The solution was extracted wi~h methylene chloride and the extract was washed with water, and dried with magnesi-um sulfate. The solvent was stripped to give ~.4 g of a thick oily liquid.
Crystallization from hexane gave 4.9 g of product as a colourless solid; mp 40 - 40.5C.
Examples 18 - 20 Using procedures similar to Example 17 above, the following (lR,cls)2, 2-dimethyl-3-~hydrocarbyloxymethyl)cyclopropanecarboxylic acids were prepared:
2,2-dimethyl-3(methoxymethyl)cyclo~ropanecarboxylic acid,mp 42 - 43C; 2,2-dimethyl-3-(propoxymethyl)cyclopropanecarboxylic acid, bp 100C at 0.05 mm Hg;
and 2,2-dimethyl-3-(benzyloxymethyl)-cyclopropanecarboxylic acld, bp 110 - 120C
at 0.05 mm Hg.
Example 21 (lR,cis)-3-(ace~oxymethyl)-2,2-diemthylcyclopropanecarboxaldehyde Ozone was passed through 25 g of (lR,cis)-2-(3-acetoxymethyl-2,2-dimethylcyclopropyl)vinyl acetate in 150 ml methylene chloride at a rate of 3 l/min until appearance of a blue colour indicated an excess of ozone was present in the reaction mixture. Ozone treatment was continued at a rate of 1 l/min for an additional ~0 minutes. The reaction mixture was purged with air to remove excess ozone and stripped below 25 to clear pale yellow oil. This oil was dissolved in 250 ml acetic acid and 40 g of zinc dust was added portion-wise over a 2 hour period at 10 - 20C. The resulting mixture was stirred 2 additional hours and then filtered through CELITE (Trademark~. The filtrate was washed with water, then with saturated sodium bicarbonate solution and finally with a saturated sodium chloride solution. The resulting solution was -- -i dried with magnesium sulfate and stripped to give 16.1 g of product as a colour-less oil, bp 58 - 60C at 0.1 mm.
Example 22 (lR,cis)-2,2-Dimethyl-3-~acetoxymethyl)cyclopropanecarboxylic acid To a solution of 21.0 g of the product of Example 21 above, 250 ml of ace~one and 50 ml of water at 5C, was added 14.8 g of potassium permanganate portionwise over 40 minutes at 5 - 10C. The reaction mixture was then warmed to room temperature while stirring for 6 hours. The mixture was filtered and the filtrate was treated with 10~ sodium bisulfite solution to destroy excess permanganate and, after filtration, stripped to remove acetone and adjusted to a pH of 4 with concentrated hydrochloric acid. The resulting solution was extract-ed three times with 100 ml methylene chloride. The combined Inethylene chloride extracts were washed with water, then with saturated sodium chloride solution, dried with magnesium sulfate and stripped to give 19 g of a thic~ oil which crystallized upon cooling overnight. This product was triturated with cold pentane and filtered to give 13.7 g of product as a solid; mp 78 - 79C.
Example 23 ~-Cyano-3-phenoxybenzyl ~lR,cis)-2,2-dimethyl-3-~acetoxymethyl)cyclopropane-carboxylate A mixture of 1.1 g of the product from ~xample 22 above, 0.6 g of triethylamine, 1.7 g of ~-cyano-3-phenoxybenzyl bromide in 10 ml of ethyl acetate was refluxed for 1.5 hours to form a white precipitate. The reaction mixture was cooled, washed with water and dried with magnesium sulfate. The resulting mixture was chromatographed on silica gel using 5:1 pentane-ether as eluent to give 1.3 g of product as a viscous pale yellow oil; [~]D25 ~ 4.2 (CHC13);
c=0.024 g/cc.

,-Example 2~
~-Cyano-3--phenoxybenzyl (lR,cis)-2,2-dimethyl~3-~ethoxymethyl)--cyclopropanecarboxylate A mixture of 1.7 g of 2,2-dimethyl-3-ethoxymethylcyclopropanecarboxylic acid ~as prepared in Example 17), 2.9 g of ~-cyano-3-phenoxybenzyl bromide and 1 g of triethylamine in 25 ml of ethyl acetate was re~luxed for 3 hours. The reactiGn mixture was lef~ standing at room temperature overnight. The mixture was diluted with ether, washed with water and then with saturated sodium chloride solution. The ether phase was dried with magnesium sulfate and strip-ped to give 3.6 g of a thick oil. This oil was chromatographed on silica gel using a 5:1 pentane-ether solution as eluent to give 2.8 g of the desired product as a thick yellow oil; [~]D 5 ~ 23.8 ~C~IC13); c=0.02 g/cc.
Examples 25 - 28 Using procedures similar to those described in Example 2~ the ~ollow-ing cyclopropanecarboxylates were prepared: ~-cyano-3-phenoxybenzyl ~lR,c )-2,2-dimethyl-3-~methoxymethyl)cyclopropanecarboxylate, 3-phenoxybenzyl ~lR,c )-2,2-dimethyl-3-~ethoxymethyl)cyclopropanecarboxylate, ~-cyano-3-phenoxybenzyl ~lR, _ )-2,2-dimethyl-3-~propoxymethyl)cyclopropanecarboxylate and ~-cyano-3-phenoxybenzyl ~lR,c )-2,2-dimethyl-3-~benzyloxymethyl)cyclopropanecarboxylate.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:- (I) wherein Rl represents an acetyl or acetoxy group; an alkoxy group containing 2 to carbon atoms optionally substituted by one or more halogen atoms; a (cycloalkyl) alkoxy group containing 3 to 7 ring carbon atoms, a total of 4 to 9 carbon atoms and optionally ring-substituted by one or more halogen atoms; a cycloalkoxy group containing 3 to 7 xing carbon atoms; an alkenyloxy group containing 2 to 4 carbon atoms optionally substituted by one or more halogen atoms; an alkynyloxy group containing 2 to 4 carbon atoms; an aryloxy group containing 6 to 12 carbon atoms; an aralky-loxy group containing 7 to 10 carbon atoms; and where X is -CH2CH(OCH3)2; -CH2CHO; -CH=CHOR2 in which R2 is an acryl group containing 2 to 5 carbon atoms; -CHO; -COC1; -COBr; -COOR in which R represents a hydrogen atom; a salt-forming cation, an alkyl group containing 1 to 20 carbon atoms or a phenoxybenzyl or alpha-cyano-phenoxy-benzyl group; with the proviso that when R1 is an acetoxy group, X is not a -CH2CH(OCH3)2, or a -CH2CHO group, and when R1 is an acetyl group X is not a -CH2CH(OCH3)2' -CH=CHOR2 , -CHO, or -COOR group.

2. A compound according to claim 1 wherein Rl is an acetyl or acetoxy group; an alkoxy group containing 1 to 4 carbon atoms;
a benzyloxy group; and X is -CH2CHO; -CH=CHO.CO.CH3; -CHO; or -COOR in which R is hydrogen or a phenoxybenzyl or alpha-cyano-phenoxybenzyl group.

3. A compound according to claim 1 wherein R1 is an acetyl or acetoxy group, an alkoxy group containing 1 to 3 carbon atoms or a benzyloxy group and X is -COOR in which R is 3-phenoxy-benzyl or alpha-cyano-3-phenoxybenzyl.

4. A compound according to claim 1 in the (1R,cis)-form.

5. A method of controlling pests which comprises applying to the pests or their habitat a pesticidally-effective amount of a compound according to claim 3 or 4.