WO2001042196A1

WO2001042196A1 - Ester compounds, intermediates for the ester compounds and pesticidal methods

Info

Publication number: WO2001042196A1
Application number: PCT/JP2000/008308
Authority: WO
Inventors: Kazuya Ujihara; Kazunori Tsushima
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 1999-12-10
Filing date: 2000-11-24
Publication date: 2001-06-14
Also published as: JP4474745B2; JP2001226338A; WO2001042196A8; AU1551201A

Abstract

The present invention provides an ester compound encompassed by formula (I) wherein R1 represents a hydrogen atom, a C¿1? to C5 alkyl group which may be substituted with at least one halogen atom, a C4 to C5 cycloalkyl group which may be substituted with at least one halogen atom, a C3 to C5 alkenyl group which may be substituted with at least one halogen atom, a C3 to C5 alkynyl group which may be substituted with at least one halogen atom, a (C3 to C5 cycloalkyl)methyl group which may be substituted with at least one halogen atom or a C2 to C5 (alkoxyalkyl) group which may be substituted with at least one halogen atom. Further, the present invention provides an aldehyde compound encompassed by formula (II) Furthermore, the present invention provides pesticidal methods.

Description

DESCRIPTION

ESTER COMPOUNDS,

INTERMEDIATES FOR THE ESTER COMPOUNDS

AND PESTICIDAL METHODS

FIELD OF THE INVENTION

The present invention relates to ester compounds, intermediates for the ester

compounds and pesticidal methods.

BACKGROUND ART(S)

Pesticidal compounds have been widely utilized to control pests. 4-hydroxy-3-

methyl-2-(2-propynyl)-2-cyclopenten-l-one is known as a pesticidal compound (Pest. Soc.

52,21(1998)). However, such pesticidal compounds have failed to regularly provide an

effective control over the pests.

SUMMARY OF THE INVENTION

The present invention provides an ester compound encompassed by formula (I):

wherein R¹ represents a hydrogen atom, to C₅ alkyl group which may be substituted with at least one halogen atom, a C₄ to C₅ cycloalkyl group which may be substituted with at least

one halogen atom, a C₃ to C alkenyl group which may be substituted with at least one

halogen atom, a C₃ to C₅ alkynyl group which may be substituted with at least one halogen

atom, a (C₃ to C₅ cycloalkyl)methyl group which may be substituted with at least one

halogen atom or a C₂ to C₅ (alkoxyalkyl) group which may be substituted with at least one

halogen atom. Further, the present invention provides pesticidal methods of utilizing the

ester compound encompassed by formula (I). Furthermore, the present invention provides

as an intermediate for producing the ester compound encompassed by formula (I), an

aldehyde compound encompassed by formula (II):

DFTATT Fn DESCRIPTION OF THE INVENTION

In the present invention, there is mentioned as R¹ in formula (I), a hydrogen atom,

a to C₅ alkyl group which may be substituted with at least one halogen atom, a C₄ to C₅

cycloalkyl group which may be substituted with at least one halogen atom, a C₃ to C₅ alkenyl

group which may be substituted with at least one halogen atom, a C₃ to C₅ alkynyl group

which may be substituted with at least one halogen atom, a (C to C₅ cycloalkyljmethyl

group which may be substituted with at least one halogen atom or a C to C₅ (alkoxyalkyl)

group which may be substituted with at least one halogen atom. Examples of the to C₅ alkyl group which may be substituted with at least one halogen atom include a methyl group,

an ethyl group, a propyl group, a butyl group, a 1-methyl propyl group, a t-butyl group, a 2,2-

dimethylpropyl group, a 2,2,2-trifluoroethyl group, an isopropyl group, an isobutyl group and

the like. Examples of the C₄ to C₅ cycloalkyl group which may be substituted with at least

one halogen atom include a cyclobutyl group, an a cyclopentyl group and the like. Examples

of the C to C₅ alkenyl group which may be substituted with at least one halogen atom

include an allyl group, a 3-chloro-2-propenyl group and the like. Examples of the C₃ to C₅

alkynyl group which may be substituted with at least one halogen atom include a propargyl

group and the like. Examples of the (C₃ to C₅ cycloalkyl)methyl group which may be

substituted with at least one halogen atom include a cyclopropylmethyl group, a

cyclobutylmethyl group and the like. Examples of the C₂ to C₅ (alkoxyalkyl) group which

may be substituted with at least one halogen atom include a 2-methoxyethyl group and the

like.

The ester compounds encompassed by formula (1) include various pesticidal

isomeric forms thereof such as an optical isomer or a geometrical isomer form thereof.

Examples of such isomers of the ester compounds encompassed by formula (I) include an

optical isomer based on asymmetric carbon atoms therein (R,S), a geometrical isomer based

on the C=N double bond therein (E,Z), a geometrical isomer based on the cyclopropane ring

moiety therein (cis, trans) and the like.

The ester compounds encompassed by formula (I) may be produced according to

the following methods, Production Methods A and B.

Production Methods A These Production Methods A generally involve reacting a carboxylic acid

compound or a reactive derivative thereof with an alcohol compound or a sulfonate ester

derivative thereof. The carboxylic acid compound is encompassed by the following formula

(UT), as shown below:

The alcohol compound is encompassed by the following formula (TV), as shown below:

The carboxylic acid compound encompassed by formula (HI) or the reactive

derivatives thereof can be produced according to the methods described in J. Chem. Soc.

Perkin Trans.l 2470(1971) or in Japanese unexamined patent Sho54-160343.

The alcohol compound encompassed by formula (IV) or the reactive sulfonate

ester derivatives thereof can be produced according to the methods described in Tetrahedron

47, 8701(1991).

The poroduction of the ester compound encompassed by formula (I) may be

carried out according to the following conditions described in Production Methods A-1, A-2

and A-3.

Production Method A-1 This Production Method A-1 involves reacting the carboxylic acid compound

encompassed by formula (HI) with the alcohol compound encompassed by formula (IV).

Usually, the reaction is carried out in a solvent in the presence of a condensing agent. If so

desired, the reaction may be optionally carried out in the presence of a base.

Examples of condensing agents which can be utilized in the reaction include

dicyclohexylcarbodiimide (DCC), 1 -ethyl-3-(3-dimethylaminopropyl)carbodiimide

hydrochloride (WSC), an agent prepared from diethylazocarboxylate and

triphenylphosphine and the like.

The solvent utilized in the reaction can be an inert solvent in the condensation

reaction. Examples of solvents which can be utilized in the reaction include hydrocarbons

such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated

hydrocarbons such as dichloromethane, 1,2-dichloroethane and the like.

Examples of bases which can be utilized in the reaction include organic bases such

as triethylamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyridine,

diisopropylethylamine and the like.

The reaction time for such a reaction is usually within a range of from immediately

to 72 hours.

The reaction temperature for such a reaction is usually within a range of from -

20 °C to 100 °C. In such cases, it is preferable to have the reaction temperature below the

boiling point of the utilized solvent, particularly when the boiling point of the utilized solvent

in the reaction is below 100 °C.

In such a reaction, 1 mole of the carboxylic acid compound encompassed by formula (HI) may be utilized thei εin for every 1 mole of the alcohol compound encompassed

by formula (IV), such that there is a 1:1 molar ratio of the carboxylic acid compound

encompassed by formula (ID) to the alcohol compound encompassed by formula (IV).

However, it should be noted that in the reaction, the molar ratio of the carboxylic acid

compound encompassed by formula (HI) to the alcohol compound encompassed by formula

(IV) can be from 1:0.5 to 1:1.5.

Further, 1 mole of the condensing agent may be utilized in the reaction for every 1

mole of the carboxylic acid compound encompassed by formula (HI), such that there is a 1:1

molar ratio of the condensing agent to the carboxylic acid compound encompassed by

formula (HI). However, it should be noted that the amount of the condensing agent may vary

with the reacting environment of the reaction.

When utilized, the amount of the base in the reaction may vary with the reacting

environment of the reaction.

After the reaction, typical work-up procedures may be conducted with the reaction

mixture, such as work-up procedures including pouring the reaction mixture into water,

extracting the resulting reaction mixture with an organic solvent and then concentrating the

extracted layer therefrom. In addition to the work-up procedures, there may be conducted

purification methods such as chromotagraphy, distillation and the like, if so desired.

Production Method A-2

This Production Method A-2 involves reacting the reactive derivative of the

carboxylic acid compound encompassed by formula (HI) with the alcohol compound

encompassed by formula (TV). Usually, the reaction is carried out in a solvent in the presence of a base.

Examples of reactive derivatives of the carboxylic acid compound encompassed by

formula (EH) which can be utilized in such a reaction include an acid hydrochloride derivative

thereof, acid anhydride derivative thereof and the like. As the acid anhydride derivative of the

carboxylic acid compound encompassed by formula (HI), there can be utilized in such a

reaction, a mixed anhydride of the acid, such as a mixed anhydride of 2,4,6-trichlorobenzoic

acid as well as the acid anhydride of the carboxylic acid compound encompassed by formula

(m).

as triethylamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyridine and

diisopropylethylamine and the like.

The solvent utilized in the reaction can be an inert solvent therein. Examples of

solvents which can be utilized in the reaction include hydrocarbons such as toluene and

hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as

dichloromethane and 1,2-dichloroethane and the like.

to 72 hours.

in the reaction is below 100 °C.

In such a reaction, 1 mole of the alcohol compound encompassed by formula (IV) may be utilized therein for every 1 mole of the reactive derivative of the carboxylic acid

compound encompassed by formula (HI), such that there is a 1:1 molar ratio of the alcohol

compound encompassed by formula (IV) to the reactive derivative of the carboxylic acid

compound encompassed by formula (HI). However, it should be noted that the molar ratio of

the alcohol compound encompassed by formula (IV) to the reactive derivative of the

carboxylic acid compound encompassed by formula (HI) can be from 0.5:1 to 1.5:1.

Further, 1 mole of reactive derivative of the carboxylic acid compound

encompassed by formula (HI) may be utilized in the reaction for every 1 mole of the base,

such that there is a 1:1 molar ratio of the reactive derivative of the carboxylic acid compound

encompassed by formula (HI) to the base. However, it should be noted that the molar ratio of

reactive derivative of the carboxylic acid compound encompassed by formula (HI) to the base

can vary with the reacting environment of the reaction.

purification methods such as chromatography, distillation and the like, if so desired.

Production Method A-3

This Production Method A-3 involves reacting the carboxylic acid compound

encompassed by formula (HI) with the sulfonate ester derivative of the alcohol compound

encompassed by formula (IV). Usually, the reaction is carried out in a solvent in the

presence of a base. Examples of bases which can be utilized in the reaction include alkali metal

alkoxides such as sodium t-butoxide, inorganic bases such as potassium hydroxide and

sodium hydride and the like.

solvents which can be utilized in the reaction include water, organic sulfur compounds such

as dimethyl sulfoxide, organic phosphorous compounds such as

hexamethylphosphorotriamide and the like.

Examples of sulfonate ester derivatives of the alcohol compound encompassed by

formula (TV) include 4-methanesulfonyloxy-3-methyl-2-prop-2-ynyl-cyclopent-2-none and

the like.

to 24 hours.

in the reaction is below 100 °C.

In such a reaction, 1 mole of the sulfonate ester derivative of the alcohol compound

encompassed by formula (TV) may be utilized therein for every 1 mole of the carboxylic acid

compound encompassed by formula (HI), such that there is a 1:1 molar ratio of the sulfonate

ester derivative of the alcohol compound encompassed by formula (IV) to the carboxylic acid

compound encompassed by formula (HI). However, it should be noted that the molar ratio

of the sulfonate ester derivative of the alcohol compound encompassed by formula (IV) to the carboxylic acid compound .ncompassed by formula (HI) can be from 0.5:1 to 1.5:1.

The amount of the b..se in the reaction may vary with the reacting environment of

the reaction.

Production Methods B

These Production Methods B generally involve reacting the aldehyde compound

encompassed by formula (H) with a hydroxylamine compound or a protonic acid salt thereof.

The hydroxylamine compound is encompassed by the following formula (V), as shown

below:

R¹ONH₂ (V)

wherein R¹ represents the same as above.

Examples of the protonic acid salts of the hydroxylamine compound include O-

methylhydroxylamine hydrochloride, O-ethylhydroxylamine hydrosulfate, O-

allylhydroxylamine hydrochloride and the like.

Such reactions may be carried out according to the following conditions described

in Production Methods B-l and B-2.

Production Method B-l This Production Methcd B-l involves reacting the aldehyde compound

encompassed by formula (H) with the hydroxylamine amine compound encompassed by

formula (V). Usually, the reaction is carried out in a solvent.

Examples of solvents which can be utilized in such a reaction include water,

hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and

tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane,

amides such as N,N-dimethylformamide, alcohols such as methanol, organic sulfur

compounds such as dimethyl sulfoxide, carboxylic acids such as acetic acid and the like.

to 72 hours.

60 'C to 200 ^*C. In such cases, it is preferable to have the reaction temperature below the

in the reaction is below 200 D.

In such a reaction, 1 mole of the hydroxylamine compound encompassed by

formula (V) may be utilized therein for every 1 mole of the aldehyde compound

encompassed by formula (H), such that there is a 1:1 molar ratio of the hydroxylamine

compound encompassed by formula (V) to the aldehyde compound encompassed by formula

(H). However, it should be noted that the molar ratio of the hydroxylamine compound

encompassed by formula (V) to the aldehyde compound encompassed by formula (H) can be

from 0.5:1 to 1.5:1.

After the reaction, typical work-up procedures may be conducted with the reaction mixture, such as work-up procedures including pouring the reaction mixture into water,

Production Method B-2

This Production Method B-2 involves reacting the aldehyde compound

encompassed by formula (H) with the protonic acid salt of the hydroxylamine amine

compound encompassed by formula (V). Usually, the reaction can be carried out in a solvent

or without the solvent. If so desired, the reaction may be optionally carried out in the

presence of a base.

Examples of bases which may be utilized in such a reaction include tertiary amines

such as triethylamine and diisopropylethylamine, nitrogen-containing aromatic compounds

such as pyridine and 4-dimethylaminopyridine, alkali metal alkoxides such as sodium

methoxide, alkali metal salts of organic acids such as sodium acetate, inorganic bases such as

sodium hydroxide and potassium carbonate and the like.

Examples of solvents which can be utilized in such a reaction include water,

amides such as N,N-dimethylformamide, alcohols such as methanol and 2-propanol, organic

sulfur compounds such as dimethyl sulfoxide, carboxylic acids such as acetic acid and the

like.

The reaction time for such a reaction is usually within a range of from immediately to 72 hours.

60 °C to 200 °C. In such cases, it is preferable to have the reaction temperature below the

in the reaction is below 200 "C.

In such a reaction, 1 mole of the protonic acid salt of the hydroxylamine compound

encompassed by formula (V) may be utilized therein such a reaction for every 1 mole of the

aldehyde compound encompassed by formula (H), such that there is a 1:1 molar ratio of the

protonic acid salt of the hydroxylamine compound encompassed by formula (V) to the

aldehyde compound encompassed by formula (H). However, it should be noted that the

molar ratio of the protonic acid salt of the hydroxylamine compound encompassed by

formula (V) to the aldehyde compound encompassed by formula (IT) can be from 0.5:1 to

1.5:1.

When utilized, the amount of the base in such a reaction is from a catalytic amount

to a large excess.

The aldehyde compound encompassed by formula (H) can be produced according

to the following Production Method C. Production Method C

This Production Method C generally involves producing the aldehyde compound

encompassed by formula (H) by ozone decomposing an ester compound encompassed by

formula (VI), as shown below:

and by treating the resulting ozone decomposed product with a reducing agent.

The ester compound encompassed by formula (VI) can be produced according to

the methods described in Pest. Sci. 11, 202 (1980).

Such reactions may be carried out according to the following Reaction C-a and

Reaction C-b.

Reaction C-a

This Reaction C-a involves the reaction in which the ester compound of formula

(VI) is decomposed by ozone.

Such a reaction is typically carried out in a solvent.

Examples of solvents which can be utilized in such a reaction include water,

hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as

dichloromethane and 1,2-dichloroethane, esters such as ethyl acetate, alcohols such as methanol and the like.

100 °C to room temperature.

The reaction time for the reaction is usually within a range of from 5 minutes to

100 hours.

In such a reaction, it is preferable to react 1 mole of the ozone utilized in the ozone

decomposition for every 1 mole of the ester compound encompassed by formula (VI), such

that there is a 1:1 molar ratio of the ozone to the ester compound encompassed by formula

(VI). Typically, the 1:1 molar ratio of the ozone to the ester compound encompassed by

formula (VI) in the reaction restrains the ozone therein from producing unwanted side

products.

Reaction C-b

This Reaction C-b involves the reaction in which the resulting ozone decomposed

product is treated with a reducing agent.

Examples of reducing agents which can be utilized in such a reaction include

sulfides such as dimethyl sulfide and diphenyl sulfide, zinc phosphate esters such as zinc

trimethyl phosphate and zinc triphenyl phosphate, phosphines such as trioctylphosphine and

triphenylphosphine, tertiary amines such as triethylamine and diisopropylethylamine, metal

hydride compounds such as sodium borohydride and aluminum lithium hydride and the like.

After the reaction in C-a, the resulting reaction mixture may have the reducing

agent added thereto to carry out Reaction C-b in a one pot method.

The reaction time for such a reaction is usually within a range of from immediately to 100 hours.

The reaction temperature for such a reaction may vary with the type of reducing

agent utilized therein. However, the reaction temperature for the reaction is usually within a

range of from -100 °C to room temperature.

In such a reaction, 1 mole to a large excess of the reducing agent may be utilized

for every 1 mole of the ester compound encompassed by formula (VI), such that there is a 1:1

to large excess :1 molar ratio of the reducing agent to the ester compound encompassed by

formula (VI). It is more preferable in the reaction that the molar ratio of the reducing agent

to the ester compound encompassed by formula (VI) is from 1:1 to 5:1.

After the reaction, the aldehyde compounds of formula (H) can be isolated by

conducting the typical work-up procedures. As one example, such a work-up procedure

may include pouring the reaction mixture into water, extracting the resulting reaction mixture

with an organic solvent and then concentrating the extracted layer therefrom. As another

example, such a work-up procedure may include concentrating the resulting reaction mixture

in a one pot method. In addition to the work-up procedures, there may be conducted

purification methods such as chromatography and the like, if so desired.

The ester compounds encompassed by formula (I) may be utilized as an active

ingredient in a pesticidal composition. In such cases, the pesticidal compositions can be used

to control pests, such as by killing or repelling the pests.

In this regard, the pesticidal compositions of the present invention exhibit a

pesticidal control over arthropods such as acarina and insects. As examples of such

arthropods, the following are provided. Hemiptera :

Delphacidae (planthoppers) such as Laodelphax striatellus (small brown

planthopper), Nilaparvata lugens (brown planthopper) and Sogatella furcifere (white backed

rice planthopper), Deltocephalidae (leafhoppers) such as Nephotettix cincticeps (green rice

leafhopper) and Nephotettix virescens (green rice leafhopper), Aphididae (aphids),

Heteroptera (plant bugs), Aleyrodidae (whiteflies), scales, Tingidae (lace bugs), Psyllidae

(jumping plantlice) and the like,

Lepidoptera :

Pyralidae such as Chilo suppressalis (rice stem borer), Cnaphalocrocis medinalis

(rice leafroller) and Plodia interpunctella (Indian meal moth), Noctuidae such as Spodoptera

litura (tobacco cutworm), Pseudaletia separata (rice armyworm) and Mamestra brassicae

(cabbage armyworm), Pieridae (sulfur butterflies) such as Pieris rapae crucivora (common

cabbageworm), Tortricidae (tortricids) such as Adoxophyes spp, Caφosinidae, Lyonetiidae,

Lymantriidae (tussock moths), Plusiinae^grotts spp. such as Agrotis segetum (turnip

cutworm) and Agrotis ipsilon (black cutworm), Helicoverpα spp., Heliotis spp., Plutellα

xylostellα (diamondback moth), Pαrnαrα guttαtα (rice skipper), Tinea pellionella

(casemaking clothes moth), Tineola bisselliella (webbing clothes moth) and the like,

Diptera : mosquitoes [for example, Culexspp. such as Culex pipiens pollens (common

mosquito) and Culex tritaeniorhynchus,Aedes spp. such as Aedes αegypti (yellow fever mosquito) and Aedes αlbopictus, Chtronomidae (midges) and Anopheles spp. such as

Anopheles sinensis], Calliphoridae (nlow flies), Sarcophagidae (flesh flies), Anthomyiidae

such as Delia platura (seedcorn maggots), Fannia canicularis (little houseflies) and Delia

antiqua (onion maggots), Tephritidae (fruit flies), Drosophilidae (vinegar flies), Psychodidae

(moth flies), Tabanidae (breeze flies), Simuliidae (black flies), Stomoxyidae (stable flies),

Phoridae and the like,

Coleoptera (beetles):

corn rootworms such as Diabrotica virgifera (western com rootworm) and

Diabrotica undecimpunctata howardi (southern com rootworm), Scarabaeidae (scarabs)

such asAnomala cuprea (cupreous chafer) and Anomala rufocuprea (soybean beetle),

Curculionidae (weevils) such as Sitophilus zeamais (maize weevil), Lissorhoptrus

oryzophilus (ricewater weevil), ball weevil and Collosobruchus chinensis (adzuki bean

weevil), Tenebrionidae (darkling beetles) such as Tenebrio molitor (yellow mealworm) and

Tribolium castaneum (red flour beetle), Chrysomelidae (leaf beetles) such as Oulema oryzae

(rice leaf beetle), Phyllotreta striolata (striped flea beetle) and Aulacophora femoralis

(cucurbit leaf beetle), Anobiidae (deathwatch beetles), Epilachna spp. such as Epilachna

vigintioctopunctata (twenty-eight spotted ladybirds), Lyctidae (powdeφost beetles),

Bostrychidae (false powdeφost beetles), Cerambycidae (longicom beetles), Paederus

fuscipes (robe beetle) and the like,

Dictyoptera : Blattella germanica (German cockroach), Periplaneta fuliginosa (smokybrown

cockroach), Periplaneta americana (American cockroach), Periplaneta brunnea (brown

cockroach), Blatta orientalis (oriental cockroach) and the like,

Thysanoptera (thrips):

Thrips palmi, western flower thrips, Thrips hawaiiensis (flower thrip) and the like

Hymenoptera:

Formicidae (ants), Vespidae (hornets), Bethylidae (Bethylid wasp), Tenthredinidae

(sawflies) such as Athalis rosae ruficornis (cabbage sawfly) and the like,

Orthoptera:

Gryllotalpidae (mole crickets), Acrididae (grasshoppers) and the like,

Siphonaptera:

Pulex irritans (human flea), Ctenocephalides felis (cat flea) and the like,

Anoplura (lice):

Pediculus humanus and Pthirus pubis (crab louse) and the like,

Isoptera :

Reticulitermes speratus, Coptotermes formosanus (Formosan subterranean termite) and the like,

Isopoda (pill bugs):

Porcellionides pruinosus, Porcellio scaber,Armadillidium vulgar e (pillbug) and

the like,

Diplopoda:

Oxidus gracilis (hot house millipede) and the like,

Chilopoda:

Scolopendra subspinipes multilans, Scolopendra subspinipes multoidens and the

like,

Symphyla:

Scutigerella spp. and the like,

Acarina :

Dermanyssidae such as Dermatophagoides farinae (American house dust mite) and

Dermatophagoides pteronyssinus, Acaridae (acarid mites) such as Tyrophagus putrescentiae

(mold mite) and Aleuroglyphus ovatus (brown legged grain mite), Glycyphagidae such as

Glycyphagus privatus, Glycyphagus domesticus and Glycyphagus destructor (groceries mite),

Cheyletidae such as Chelacaropsis malaccensis and Cheyletusfortis, Tarsonemidae, Chortoglyphus spp.,Haplochthonius simplex, Tetranychidae such as Tetranychus urticae

(two-spotted spider mite), Tetranychus kanzawai (Kanzawa spider mite), Panonychus citri

(citrus red mite), Panonychus ulmi (European red mite), Ixodidae such as Haemaphysalis

longiconis and the like.

Further, the pesticidal compositions of the present invention can also effectively

control pests which have a resistance to well-known pesticidal compositions.

When utilizing the ester compounds encompassed by formula (I) as an active

ingredient in the pesticidal compositions of the present invention, the pesticidal compositions

are usually utilized as a formulation thereof. Examples of formulations of the pesticidal

compositions include oil solutions, emulsifiable concentrates, wettable powders, flowables

such as aqueous suspensions and aqueous emulsions, granules, dusts, aerosols, heating

volatile formulations for heating such as mosquito-coils, mosquito-mats for electric heaters

and liquids for electric heaters, fumigants such as combustible fumigants, chemical

fumigants and porous ceramic plate fumigants, non-heating volatile formulations such as

those applied on resin or paper, fogging formulations, ULV formulations (formulations for

ultra low volume application) and pesticidal baits.

As methods of formulating the ester compounds encompassed by formula (I), the

following methods from (D) to (F) may be utilized to formulate the ester compounds

encompassed by formula (I).

(D) a formulation method comprising mixing the ester compound encompassed by

formula (I) with a solid carrier, a liquid carrier, a gaseous carrier or a baiting agent. In such

cases, there can be optionally utilized therein a surfactant or a formulation auxiliary. (E) a formulation method comprising impregnating the ester compound encompassed

by formula (I) to a mosquito-coil component or a mosquito-mat component.

(F) a formulation method comprising mixing the ester compound encompassed by

formula (I) with a mosquito-coil component or a mosquito-mat component.

When formulated, the pesticidal compositions of the present invention may

comprise the ester compound encompassed by formula (I) in an amount of from 0.001 to

95 % by weight, wherein said percentage by weight is based on the total weight of the

provided pesticidal composition.

Examples of solid carriers which may be utilized in the present invention include

fine powder or granules of clays such as kaolin clay, diatomaceous earth, synthetic hydrated

silicon oxide, bentonite, Fubasami clay and acid clay, talc, ceramics, other inorganic minerals

such as sericite, quartz, sulfur, active carbon, calcium carbonate and naturally-occurring

hydrated silicon oxide and the like.

Examples of liquid carriers which may be utilized in the present invention include

water, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl

ketone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and

methylnaphthalene, aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and gas

oil, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and

isobutyronitrile, ethers such as diisopropyl ether and dioxane, acid amides such as N,N-

dimethylformamide and N,N-dimethylacetamide, halogenated hydrocarbons such as

dichloromethane, trichloroethane and carbon tetrachloride, dimethyl sulfoxide, vegetable oils

such as soybean oil and cottonseed oil and the like. Examples of gaseous carriers ( i.e. propellants) which may be utilized in the

present invention include freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl

ether, carbon dioxide and the like.

Examples of baiting agents which may be utilized in the present invention include

bait components such as a grain powder, vegetable oil, sugar and crystalline cellulose,

antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such

as dihydroacetic acid, substances for preventing erroneous eating such as red pepper powder,

attractants such as cheese flavor, onion flavor and peanut oil and the like.

Examples of surfactants which may be utilized in the present invention include

alkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethers, polyoxyethylenealkyl

aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives

and the like.

Examples of formulation auxiliaries which may be utilized in the present invention

include casein, gelatin, polysaccharides such as starch, gum arabic, cellulose derivatives and

alginic acid, lignin derivatives, bentonite, sugars and synthetic water-soluble polymers such

as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid, PAP (acid isopropyl

phosphate), BHT (2,6-di-tert-butyl-4-methyphenol), BHA (mixture of 2-tert-butyl-4-

methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids,

esters of fatty acids and the like.

The mosquito coil components which can be utilized in the present invention may

be mixtures containing a raw plant powder and a binding agent. Examples of the raw plant

powder include wood powders, Pyrethrum marcs and the like. Examples of the binding agent include Tabu powders (powder oiMachilus thunbergii), starches, glutens and the like.

The mosquito-mat components which can be utilized in the present invention may

be a plate of compacted fibrils. Examples of such fibrils include cotton linters, mixtures of

pulp with a cotton linter and the like.

When formulated as the combustible fumigants, the pesticidal compositions of the

present invention may utilize therein a combustible fumigant component. Examples of the

combustible fumigant component therein includes exothermic agents such as nitrate, zinc

nitrate, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood powder,

pyrolytic stimulating agents such as alkali metal salt, alkaline earth metal salt, dichromate

and chromate, oxygen sources such as potassium nitrate, combustion assistants such as a

melanin and wheat starch, bulk fillers such as diatomaceous earth, binding agents such as

synthetic glue and the like.

When formulated as the chemical fumigants, the pesticidal compositions may

utilize therein a chemical fumigant component. Examples of the chemical fumigant

component include an exothermic agents such as alkali metal sulfide, polysulfide,

hydrogensufide, hydrated salt and calcium oxide, catalytic agents such as carbonaneous

substance, iron carbide and activated clay, organic foaming agents such as azodicarbonamide,

benzenesulfonylhydrazide, dinitrosopentamethylene tetramine, polystyrene and polyurethane,

fillers such as a natural fiber and synthetic fiber and the like.

When formulated as the non-heating volatile formulations, the pesticidal

compositions of the present invention may utilize therein a non-heating volatile formulation

component. Examples of such a non-heating volatile formulation component include thermoplastic resins such as polyester, polyamide, ethylene-vinyl chloride copolymer,

ethylene-vinyl acetate copolymer and ethylene-methyl metacylate copolymer, papers such as

filter paper, Japanese paper, high quality printing paper, notebook paper, tissue paper and

cardboard, cloths such as unwoven cloth and the like.

In utilizing the pesticidal compositions, the preferred pesticidal methods may vary

with the form of formulation thereof, location in which the pesticidal composition is utilized

and the like. The following are provided as examples of pesticidal methods which utilize

the pesticidal compositions of the present invention.

(G) a method comprising applying the pesticidal composition to the pest.

(H) a method of diluting the pesticidal composition with a solvent such as water and applying

the diluted pesticidal composition at the habitat of a pest

(I) a method of heating the pesticidal composition, such that the ester compound

encompassed by formula (I) is applied to a habitat of a pest

Further, the ester compounds encompassed by formula (1) may be used in

combination with other pesticides such as an insecticide, an acaricide, a nematicide, a soil

disinfectant, a fungicide, a herbicide, a plant growth regulator, a pest repellant, a synergist, a

fertilizer, a soil improving agent and the like.

Examples of such insecticides, nematocides, acaricides and soil disinfectants

include organophosphorus compounds such as fenitrothion [O,O-dimethyl O-(3-methyl-4-

nitrophenyl) phosphorothioate], fenthion [O,O-dimethyl O-(3-methyl-4-(methythio)phenyl)

phosphorothioate], diazinon [O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl

phosphorothioate], chloφyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O,S-dimethyl acetylph sphoramidothioate], methidathion [S-2,3-dihydro-5-

methoxy-2-oxo-l,3,4-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate], disulfoton

[O,O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP [2,2-dichlorovinyl dimethyl

phosphate], sulprofos [O-ethyl O-4-(methylthio)phenyl S-propyl phosphorodithioate],

cyanophos [O-4-cyanophenyl O,O-dimethyl phosphorothioate], dimethoate [O,O-dimethyl

S-(N-methylcarbamoylmethyl) dithiophosphate], phenthoate [ethyl 2-

dimethoxyphosphinothioylthio(phenyl) acetate], malathion [diethyl

(dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro-l-

hydroxyethylphosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-l,2,3-benzotriazin-3-

ylmethyl O,O-dimethyl phosphorodithioate], monocrotophos [dimethyl (E)-l-methyl-2-

(methylcarbamoyl)vinyl phosphate] and ethion [O,O,O',O'-tetraethyl S,S'-methylene

bis(phosphorodithioate)], carbamate compounds such as BPMC [2-sec-butylphenyl

methylcarbamate], benfracarb [ethyl N-[2,3-dihydro-2,2-dimethylbenzofuran-7-

yloxycarbonyl(methyl) aminothio]-N-isopropyl-(.-alaninate], propoxur [2-isopropoxyphenyl

N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl N-

dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl N-methylcarbamate], methomyl

[S-methyl N-[(methylcarbamoyl) oxyjthioacetimidate], ethiofencarb [2-

(ethylthiomethyl)phenyl methylcarbamate], aldicarb [2-methyl-2-(methylthio)

propionaldehyde O-methylcarbamoyloxime], oxamyl [N,N-dimethyl-2-

methylcarbamoyloxyimino-2-(methylthio)acetamide] and fenothiocarb [S-4-phenoxybuthyl

N,N-dimethylthiocarbamate], pyrethroid compounds such as etofenprox [2-(4-

ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether], fenvalerate [(RS)- a -cyano-3- phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], esfenvalerate [(S)- a -cyano-3-

phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin [(RS)- a -cyano-3-

phenoxybenzyl 2,2,3,3-tetramethylcyclopropane-carboxylate], cypermethrin [(RS)- -cyano-

3-phenoxybenzyl (lRS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-

cyclopropanecarboxylate], permethrin [3-phenoxybenzyl (lRS)-cis,trans-3-(2,2-

dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate], cyhalothrin [(RS)- a -cyano-3-

phenoxybenzyl (Z)-(lRS)-cis-3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-

dimethylcyclopropanecarboxylate], deltamethrin [(S)- a -cyano-3-phenoxybenzyl (lR)-cis-3-

(2,2-dibromovinyl)-2,2-dimethyl-cyclopropanecarboxylate], cycloprothrin [(RS)- ot -cyano-3-

phenoxybenzyl (RS)-2,2-dichloro-l-(4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate

[ a -cyano-3-phenoxybenzyl N-(2-chloro- , , a -trifluoro-p-tolyl)-D-valinate], bifenthrin

[2-methylbiphenyl-3-ylmethyl (Z)-(lRS)-cis-3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-

dimethyl-cyclopropanecarboxylate], halfenprox [2-(4-bromodifluoromethoxyphenyl)-2-

methylpropyl 3-phenoxybenzyl ether], tralomethrin [(S)- a -cyano-3-phenoxybenzyl (1R)-

cis-3-(l,2,2,2-tetrabromoethyl)-2,2-dimethylcyclopropane-carboxylate], silafluofen [(4-

ethoxyphenyl)(3-(4-fluoro-3-phenoxyphenyl)propyl)dimethylsilane], d-phenothrin [3-

phenoxybenzyl (lR)-cis,trans-2,2-dimethyl-3-(2-methyl-l-

propenyl)cyclopropanecarboxylate], cyphenothrin [(RS)- a -cyano-3-phenoxybenzyl (1R)-

cis,trans-2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate], d-resmethrin [5-

benzyl-3-furylmethyl (lR)-cis,trans-2,2-dimethyl-3-(2-methyl-l-

propenyl)cyclopropanecarboxylate], acrinathrin [(S)- a -cyano-3-phenoxybenzyl (lR,3Z)-cis-

(2,2-dimethyl-3-(3-oxo-3-(l,l,l,3,3,3- hexafluoropropyloxy)propenyl)cyclopropanecarboxylate], cyfluthrin [(RS)- a -cyano-4-

fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],

tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (lRS,3Z)-cis-3-(2-chloro-3,3,3-trifluoro-l-

propenyl)-2,2-dimethylcyclopropanecarboxylate], transfluthrin [2,3,5,6-tetrafluorobenzyl

(lR)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tetramethrin

[3,4,5,6-tetrahydrophthalimidomethyl (lRS)-cis,trans-2,2-dimethyl-3-(2-methyl-l-

propenyl)cyclopropanecarboxylate], allethrin [(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl

(lR,3RS;lRS,3SR)-2,2-dimethyl-3-(2-methylprop-l-enyl)cyclopropanecarboxylate,

empenthrin [(RS)-l-ethynyl-2-methyl-2-pentenyl (lR)-cis,trans-2,2-dimethyl-3-(2-methyl-l-

propenyljcyclopropanecarboxylate], imiprothrin [2,5-dioxo-3-(2-propynyl)imidazolidin-l-

ylmethyl (lR)-cis,trans-2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate], d-

furamethrin [5-(2-propynyl)furfuryl (lR)-cis,trans-2,2-dimethyl-3-(2-methyl-l-

propenyljcyclopropanecarboxylate] and 5-(2-propynyl)furfuryl 2,2,3,3-

tetramethylcyclopropanecarboxylate, thiadiazine derivatives such as buprofezin [2-tert-

butylimino-3-isopropyl-5-phenyl-l,3,5-thiadiazinan-4-one], nitroimidazolidine derivatives,

nereistoxin derivatives such as cartap [S,S'-(2-

dimethylaminotrimethylene)bis(thiocarbamate)], thiocyclam [N,N-dimethyl-l,2,3-trithian-5-

ylamine] and bensultap [S,S'-2-dimethylaminotrimethylene di(benzenethiosulfonate)], N-

cyanoamidine derivatives such as N-cyano-N'-methyl-N'-(6-chloro-3-

pyridylmethyl)acetamidine, chlorinated hydrocarbons such as endosulfan [6,7,8,9,10,10-

hexachloro-l,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine 3-oxide], T -

BHC [1,2,3,4,5,6-hexachlorocyclohexane] and dicofol [1,1-bis (chlorophenyl)-2,2,2- trichloroethanol], benzoylphenylurea compounds such as chlorfluazuron [l-(3,5-dichloro-4-

(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea],

teflubenzuron [l-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea] and

flufenoxuron [ 1 -(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-

difluorobenzoyl)urea], formamidines such as amitraz [N-methylbis(2,4-

xylyliminomethyljamine, thiourea derivatives such as diafenthiuron [N-(2,6-diisopropyl-4-

phenoxyphenyl)-N'-tert-butylthiourea], N-phenylpyrazole compounds, metoxadiazone [5-

methoxy-3-(2-methoxyphenyl)-l,3,4-oxadiazol-2-(3H)-one], bromopropylate [isopropyl

4,4'-dibromobenzilate], tetradifon [4-chlorophenyl 2,4,5-trichlorophenyl sulfone],

chinomethionate [S,S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargite [2-(4-tert-

butylphenoxy)cyclohexyl prop-2-ynyl sulfite], fenbutatin oxide [bis[tris(2-methyl-2-

phenylpropyl)tin] oxide], hexythiazox [(4RS,5RS)-5-(4-chlorophenyl)-N-cyclohexyl-4-

methyl-2-oxo-l,3-thiozolidine-3-carboxamide], clofentezine [3,6-bis(2-chlorophenyl)-

1,2,4,5-tetrazine], pyridaben [2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-

3(2H)-one], fenpyroximate [tert-butyl (E)-4-[(l,3-dimethyl-5-phenoxypyrazol-4-

yl)methyleneaminooxymethyl]benzoate], tebufenpyrad [N-(4-tert-butylbenzyl)-4-chloro-3-

ethyl-l-methyl-5-pyrazolecarboxamide], polynactins complex [tetranactin, dinactin and

trinactin], pyrimidifen [5-chloro-N-[2-(4-(2-ethoxyethyl)-2,3-dimethylphenoxy)ethyl]-6-

ethylpyrimidin-4-amine], milbemectin, abamectin, ivermectin, azadirachtin [AZAD] and the

like.

Examples of the pest repellants include 3,4-caranediol, N,N-diethyl-m-toluamide,

l-methylpropyl 2-(2-hydroxyethyl)-l-piperidinecarboxylate, p-menthane-3,8-diol, botanical essential oils (e.g. hyssop oil) i nd the like.

Examples of the synorgists include S-421 [bis-(2,3,3,3-tetrachloropropyl) ether],

MGK-264 [N-(2-ethylhexyl)bicyclo [2.2.1]hept-5-ene-2,3-dicarboximide], piperonyl

butoxide [ -[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene] and the like.

EXAMPLES

The following examples are provided to describe the present invention in more

detail with production examples, formulation examples and test examples. However, the

present invention is not limited thereto.

Production Examples

The following Production Examples 1 to 5 set forth examples of producing the

ester compound encompassed by formula (I).

It should be noted that the following Production Examples use therein Compound

numbers (such as Compound 1, Compound 2 and the like) to refer to particular forms of the

ester compounds encompassed by formula (I), as expressed in Tables 1 to 16. Further, the

following Production Examples use therein an intermediate numbers (such as Intermediate 1,

Intermediate 2 and the like) to refer to a particular forms of the aldehyde compound

encompassed by formula (H), as represented in Table 17.

Production Example 1

Into 10ml of toluene, there was added 0.23g of pyridine and 0.45g of a mixture containing at a 1:1 molar ratio (lR)-trans-3-((E)-methoxyimino)-2,2-

dimethylcyclopropanecarboxylate and (lR)-trans-3-((Z)-methoxyimino)-2,2-

dimethylcyclopropanecarboxylate. An acid chloride solution was then produced therefrom by

adding under stirring conditions 0.34g of thionyl chloride to the mixture, and then by stirring

and heating the mixture at 80°C for 1 hour. After allowing the acid chloride solution to cool

to room temperature, there was added a mixture containing 3ml of toluene, 0.40g of pyridine

and 0.55g of (S)-4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentan-l-one. The resulting

reaction mixture was then stirred at room temperature for 1 hour. Subsequently, the reaction

mixture was poured into water and was extracted with tert-butyl methyl ether. The organic

layer therefrom was dried with anhydrous sodium sulfate and was concentrated under

reduced pressure. The resulting residue was subjected to silica gel chromatography (the

eluent: hexane/ethyl acetate =4/1) to provide 0.15g of (S) -2-methyl-4-oxo-3-(2-propynyl)-2-

cyclopentan-l-yl (lR)-trans-3-((E)-methoxyimino)-2,2-dimethylcyclopropanecarboxylate

(Compound 2, yield of 19%) and (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-yl

(lR)-trans-3-((Z)-methoxyimino)-2,2-dimethylcyclopropanecarboxylate (Compound 22,

yield of 19%).

Production Example 2

In 200ml of ethyl acetate, 6.90g of (S)-2-methyl-4-oxo-3-(2-propynyl)-2-

cyclopentan-lyl (lR)-trans-2,2-dimethyl-3-(2-methyl-l-propenyl)-cyclopropanecarboxylate

and O.Olg of Sudan HI [l-[4-(phenylazo)phenylazo]-2-naphthol] were dissolved. At -78°C

under stirring conditions, oxygen which contained ozone was blown to the reaction mixture until the red color of Sudan HI sufficiently disappeared to become colorless. Subsequently,

nitrogen was blown thereto. After the superfluous ozone was removed therefrom, 4.1g of

dimethylsulfide was added to the reaction mixture and the reaction mixture was then warmed

to room temperature. Two (2) days thereafter, the reaction solution was concentrated under

reduced pressure. The resulting residue was subjected to silica gel chromatography (eluent

of hexane/ethyl acetate = 2/1) to provide 5.47g of (S)-2-methyl-4-oxo-3-(2-propynyl)-2-

cyclopentan-1-yl (lR)-trans-3-formyl-2,2-dimethyl-cyclopropanecarboxylate (Intermediate 1,

yield of 87%).

In 3ml of methanol, 0.29g of (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-

yl (lR)-trans-3-formyl-2,2-dimethyl-cyclopropanecarboxylate and 0.17g of pyridine were

dissolved. Subsequently, 0.13g of O-allylhydroxylamine hydrochloride was then added

thereto to produce a reaction mixture. Three days thereafter, the reaction mixture was poured

into water and was extracted with tert-butyl methyl ether. The organic layer therefrom was

dried with magnesium sulfate and was concentrated under reduced pressure. The resulting

residue was subjected to silica gel chromatography (eluent of hexane/ethyl acetate =4/1) to

provide 0.08g of (S)-2-methyl-4-oxo-3-(2-proppynyl)-2-cyclopentan-l-yl (lR)-trans-3-((E)-

allyloxyimino)-2,2-dimethylcycloρropanecarboxylate (Compound 12, yield of 23%) and

0.07g of (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-yl (lR)-trans-3-((Z)-allyl

oxyimino)-2,2-dimethylcyclopropanecarboxylate (Compound 32, yield of 20%).

Production Example 3

In 10ml of tetrahydrofuran, there was dissolved 0.16g of (S)-4-hydroxy-3-methyl- 2-(2-propynyl)-2-cyclopentan-l-one, 0.15g of triethylamine and 0.20g of a mixture

containing at a 1:1 molar ratio (lR)-trans-3-((E)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate and (lR)-trans-3-((Z)-allyloxyimino-2,2-

dimethylcyclopropanecarboxylate. After cooling the resulting mixture, 0.26g of 2,4,6-

trichlorobenzoate was added over 5 minutes to the mixture under stirring conditions and that

was stirred for 2 hours. Subsequently, 4ml of a toluene solution containing 0.24g of 4-

dimethylaminopyridine was added thereto to produce a reaction mixture. The reaction

mixture was heated to 80 and was stirred for 1 hour. The reaction mixture was then

poured into water and was extracted with tert-butyl methyl ether. The organic layer

therefrom was washed with saturated brine, was dried with anhydrous sodium sulfate and

was concentrated under reduced pressure. The resulting residue was subjected to silica gel

chromatography (eluent: hexane/ethyl acetate=4/l) to provide 0.28g of a mixture containing

at a 1:1 molar ratio (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-yl (lR)-trans-3-((E)-

allyloxyimino)-2,2-dimethylcyclopropanecarboxylate (Compound 12) and (S)-2-methyl-4-

oxo-3-(2-propynyl)-2-cyclopentan- 1-yl (1 R)-trans-3-((Z)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate (Compound 32) (yield of 85%).

Production Example 4

In 130ml of tetrahydrofuran, there was dissolved 12.0g of (S)-4-hydroxy-3-methyl-

2-(2-propynyl)-2-cyclopentan-l-one, 2.0g of 4-dimethylaminopyridine and 13.0g of a

mixture containing at a 1:1 molar ratio (lR)-trans-3-((E)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate and (lR)-trans-3-((Z)-allyloxyimino)-2,2- dimethylcyclopropanecarboxylate. While stirring under ice cooled conditions, 18.1g of 1-

ethyl-3-(3-dimethylaminoprcpyl)carbodiimide hydrochloride were then added thereto over

10 minutes to produce a reaction mixture. After stirring the reaction mixture at room

temperature for 12 hours, the reaction mixture was poured into water and was extracted with

tert-butyl methyl ether. The organic layer therefrom was washed with saturated brine, was

dried with anhydrous magnesium sulfate and was concentrated under reduced pressure. The

resulting residue was subjected to silica gel chromatography (eluent: hexane/ethyl

acetate=4/l) to provide 16.5 g of a mixture containing at a 1:1 molar ratio (S)-2-methyl-4-

oxo-3-(2-propynyl)-2-cyclopentan-l-yl (lR)-trans-3-((E)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate (Compound 12) and (S)-2-methyl-4-oxo-3-(2-propynyl)-2-

cyclopentan-l-yl (lR)-trans-3-((Z)-allyloxyimino)-2,2-dimethylcyclopropanecarboxylate

(Compound 32) (yield of 76%).

Further, there were similarly produced according to the procedures above in

Production Method 4, Compounds 3, 4, 5, 13, 14, 15, 17, 19, 20, 23, 24, 25, 32, 33, 34, 35,

37, 39 and 40, as well as a mixture containing at a 1:1 molar ratio Compounds 9 and 29, a

mixture containing at a 1:1 molar ratio Compounds 47 and 67 and a mixture containing at a

1:1 molar ratio Compounds 50 and 70.

Production Example 5

In 10ml of tetrahydrofuran, there was dissolved 0.40g of (S)-4-hydroxy-3-methyl-

2-(2-propynyl)-2-cyclopentan-l-one, 0.03g of 4-dimethylaminopyridine and 0.35g of a

mixture containing at a 1:1 molar ratio (lR)-cis-3-((E)-allyloxyimino)-2,2- dimethylcyclopropanecarboxylate and (lR)-cis-3-((Z)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate. While stirring under ice-cooled conditions, 0.62g of N,N'

dicyclohexylcarbodiimide was added thereto over 5 minutes to produce a reaction mixture.

After stirring the reaction mixture at room temperature for 4 hours, the reaction mixture was

at a 1:1 molar ratio (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-yl (lR)-cis-3-((E)-

allyloxyimino)-2,2-dimethylcyclopropanecarboxylate (Compound 52) and (S)-2-methyl-4-

oxo-3-(2-propynyl)-2-cyclopentan- 1 -yl (1 R)-cis-3-((Z)-allyloxyimino)-2,2-

dimethylcyclopropanecarboxylate (Compound 72) (yield of 42%).

Further, there were similarly produced according to the procedures above in

Production Method 5, a mixture containing at a 1:1 molar ratio Compounds 42 and 62, a

mixture containing at a 1:1 molar ratio Compounds 43 and 63, a mixture containing at a 1:1

molar ratio Compounds 45 and 65, a mixture containing at a 1:1 molar ratio 46 and 66 and a

mixture containing at a 1:1 molar ratio Compounds 48 and 68.

Various forms of the ester compounds encompassed by formula (I) are expressed

in the following Tables 1 to 16 in connection with formula (I) and compound numbers. As

such, the groups provided in the R¹ columns in Tables 1 to 16 refer to R¹ as set forth in

formula (I). In addition, the compound numbers provided in the above Production Examples

1 to 5 are expressed in Tables 1 to 16 with the according compound number. In Tables 1 to 16, "the alcohol moiety configuration" means the absolute

configuration at the 1 position in the 2-cyclopentanone ring moiety of the ester compounds

encompassed by formula (I), such as a R or S configuration. Further, in Tables 1 to 16, the

"acid moiety configuration" means the absolute configuration at the 1 position in

cyclopropane ring moiety of the ester compounds encompassed by formula (I), such as a R or

S configuration, the relative configuration of the substituent at the 3 position of the

cyclopropane ring moiety in relation with the substituent at the 1 position of cyclopropane

ring moiety of the ester compounds encompassed by formula (I), such as a cis or trans

configuration, and the relative configuration based on the C=N double bond in the ester

compounds encompassed by formula (I), such as an E or Z configuration. Furthermore, as

used in Tables 1 to 16, an "RS" configuration means that the provided form of the ester

compounds encompassed by formula (I) is a mixture containing at a 1:1 molar ratio the R

configuration thereof and the S configuration thereof. Formula (I) is provided below with

additional notations showing example configurations of the alcohol moiety configuration and

the acid moiety configuration in the ester compounds encompassed by formula (I).

Further, in the R¹ column of Tables 1 to 16, "Me" means a methyl group, "Et"

means an ethyl group, "Pr" means a propyl group, "Bu" means a butyl group, "i-Pr" means an isopropyl group, "sec-Bu" means a CH₃CH₂(CH₃)CH group, "t-Bu" means a (CH)₃C

group and "i-Bu" means a (CH)CHCH₂ group.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

Table 14

Table 15

Table 16

The following sets forth certain characteristics of particular ester compounds

encompassed by formula (I), such as the NMR data thereof, the melting point thereof and the

index of refraction thereof.

Compound 2 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) <5 1.23 (3H,s), 1.30(3H,s), 1.92(lH,d,J=5.4), 2.00(lH,t,J=2.7), 2.18(3H,s),

2.23(lH,dd,J=7.3,5.4), 2.24(lH,dd,J=18.7,2.0), 2.91(lH,dd,J=18.7,6.4), 3.16(2H,d,J=2.7),

3.84(3H,s), 5.67(lH,dd,J=6.4,2.0), 7.23(lH,d,J=7.3)

Compound 4 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 0.93(3H,t,J=7.4), 1.23(3H,s), 1.29(3H,s), 1.66(2H,dd,J=7.4,6.9), 1.91(lH,d,J=5.4),

2.00(lH,t,J=2.8), 2.18(3H,s), 2.23(lH,dd,J=7.2,5.4), 2.24(lH,dd,J=18.7,2.0),

2.91(lH,dd,J=18.7,6.3), 3.15(2H,d,J=2.8), 3.98(2H,t,J=6.9), 5.66(lH,dd,J=6.3,2.0),

7.24(lH,d,J=7.2)

Compound 5 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 0.93(3H,t,J=7.4), 1.23(3H,s), 1.29(3H,s), 1.38(2H,sex,J=7.4), 1.62(2H,tt,J=7.4,6.7),

1.91(lH,d,J=5.5), 2.00(lH,t,J=2.8), 2.18(3H,s), 2.24(lH,dd,J=7.3,5.5),

2.25(lH,dd,J=18.7,1.8), 2.91(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 4.03(2H,t,J=6.7),

5.68(lH,dd,J=6.3,1.8), 7.23(lH,d,J=7.3)

Compound 12 C α J _D ^{2 7} =+8.0° (CHC1₃, c=5.2) 1H-NMR(CDC1₃, TMS

standard, values: δ is in ppm and J is in Hz) δ 1.23(3H,s), 1.29(3H,s), 1.91(lH,d,J=5.5),

1.99(lH,t,J=2.8), 2.18(3H,s), 2.25(lH,dd,J=18.7,2.0), 2.25(lH,dd,J=7.3,5.5),

2.91(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 4.54(2H,br d,J=5.8), 5.23(lH,br d,J=10.4),

5.30(lH,br d,J=17.2), 5.67(lH,dd,J=6.3,2.0), 5.98(lH,ddt,J=17.2,10.4,5.8), 7.28(lH,d,J=7.3) Compound 13 1H-NMR (CDC1 , TMS standard, values: δ is in ppm and J is

in Hz) δ 1.22(3H,s), 1.29(3H,s), 1.73(3H,br d,J=6.4), 1.90(lH,d,J=5.5), 2.00(lH,t,J=2.8),

2.18(3H,s), 2.25(lH,dd,J=7.3,5.5), 2.25(lH,dd,J=18.7,2.0), 2.91(lH,dd,J=18.7,6.3),

3.16(2H,d,J=2.8), 4.48(2H,d,J=6.6), 5.67(lH,dd,J=6.3,2.0), 5.60~5.86(2H,m),

7.25(lH,d,J=7.3)

Compound 14 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.16(3H,s), 1.30(3H,s), 1.93(0.5H,d,J=5.5), 1.94(0.5H,d,J=5.5), 2.01(lH,t,J=2.8),

2.19(3H,s), 2.21~2.28(2H,m), 2.25(lH,dd,J=18.7,1.9), 2.91(lH,dd,J=18.7,6.3),

3.16(2H,d,J=2.8), 4.51(lH,dd,J=6.5,l.l), 4.78(lH,dd,J=6.5,1.7), 5.67(lH,dd,J=6.3,1.9), 6.00

~6.30(2H,m), 7.26(0.5H,d,J=7.2), 7.27(0.5H,d,J=7.2)

Compound 15 1H-NMR (CDC1₃, TMS standard, values: <5 is in ppm and J is

in Hz) δ 1.24(3H,s), 1.30(3H,s), 1.95(lH,d,J=5.6), 2.00(lH,t,J=2.7), 2.18(3H,s), 2.21 ~

2.29(2H,m), 2.49(lH,t,J=2.4), 2.92(lH,dd,J=18.8,6.3), 3.16(2H,d,J=2.7), 4.64(2H,d,J=2.4),

5.67(lH,br d,J=6.3), 7.30(lH,d,J=7.2)

Compound 17 1H-NMR (CDC1 , TMS standard, values: δ is in ppm and J is

in Hz) δ 1.23(3H,s), 1.29(3H,s), 1.50~1.85(8H,m), 1.90(lH,d,J=5.5), 2.00(lH,t,J=2.8),

2.18(3H,s), 2.25(lH,dd,J=7.4,5.5), 2.25(lH,dd,J=18.7,2.0), 2.92(lH,dd,J=18.7,6.3),

3.16(2H,d,J=2.8), 4.65(lH,m), 5.68(lH,dd,J=6.3,2.0), 7.19(lH,d,J=7.4)

Compound 19 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.22(3H,s), l,29(3H,s), 1.76~2.10(7H,m), 2.18(3H,s), 2.21~2.287(2H,m),

2.64(lH,sept,j=7.0), 2.91(lH,dd,j=18.7,6.3), 3.16(lH,d,j=2.1), 4.02(lH,d,J=7.0), 5.66(1H, br,

d,J=6.3), 7.23(lH,d,J=7.6) Compound 20 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.24(3H,s), 1.31(3H,s), 1.91(lH,d,J=5.3), 2.01(lH,t,J=2.8), 2.20(3H,s), 2.23~

2.30(2H,m), 2.93(lH,d,J=18.8,6.3), 3.17(2H,d,J=2.8), 3.41(3H,s), 3.64(2H,t,J=4.8),

4.21(2H,t,J=4.8), 5.68(lH,dd,J=6.3,1.9), 7.31(lH,d,J=7.6)

Compound 22 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.25(3H,s), 1.30(3H,s), 1.79(lH,d,J=5.5), 2.01(lH,t,J=2.8), 2.18(3H,s),

2.22(lH,dd,J=18.7,2.0), 2.70(lH,dd,J=7.8,5.5), 2.92(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8),

3.90(3H,s), 5.70(lH,dd,J=6.3,2.0), 6.35(lH,d,J=7.8)

Compound 24 1H-NMR (CDC1 , TMS standard, values: δ is in ppm and J is

in Hz) δ 0.95(3H,t,J=7.5), 1.24(3H,s), 1.31(3H,s), 1.69(qt,J=7.5,6.7), 1.77(lH,d,J=5.5),

2.00(lH,t,J=2.8), 2.18(3H,s), 2.26(lH,dd,J=18.7,2.0), 2.71(lH,dd,J=7.5,5.5),

2.92(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 4.05(2H,t,J=6.7), 5.70(lH,dd,J=6.3,2.0),

6.36(lH,d,J=7.5)

Compound 25 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 0.95(lH,t,J=7.4), 1.24(3H,s), 1.30(3H,s), 1.40(2H,sex,J=7.4), 1.66(2H,tt,J=7.4,6.7),

1.77(lH,d,J=5.5), 2.01(lH,t,J=2.8), 2.18(3H,s), 2.26(lH,dd,J=18.7,1.9),

2.69(lH,dd,J=7.5,5.5), 2.91(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 4.09(2H,t,J=6.7),

5.70(lH,dd,J=6.3,1.9), 6.36(lH,d,J=7.5)

Compound 32 ( αϋ _D ^{2 7} =-6.7° (CHC1₃, c=3.1) 1H-NMR (CDC1₃, TMS

standard, values: δ is in ppm and J is in Hz) δ 1.25(3H,s), 1.31(3H,s), 1.78(lH,d,J=5.4),

2.00(lH,t,J=2.7), 2.18(3H,s), 2.26(lH,dd,J=18.7,2.0), 2.73(lH,dd,J=7.6,5.4),

2.91(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.7), 4.60(2H,br d,J=5.6), 5.23(lH,br d,J=10.5), 5.30(lH,br d,J=17.5), 5.70(lH,dd,J=6.3,2.0), 6.00(lH,ddt,J=17.5,10.5,5.6), 6.39(lH,d,J=7.6)

Compound 33 1H-NMR (CDC1₃, TMS standard, values: f5 is in ppm and J is

in Hz) _ 1.25(3H,s), 1.31(3H,s), 1.74(3H,br d,J=6.9), 1.77(lH,d,J=5.6), 2.00(lH,t,J=2.8),

2.18(3H,s), 2.26(lH,dd,J=18.7,1.9), 2.73(lH,dd,J=7.7,5.6), 2.91(lH,dd,J=18.7,6.3),

3.16(2H,d,J=2.8), 4.53(2H,d,J=6.0), 5.70(lH,dd,J=6.3,1.9), 5.62~5.85(2H,m),

6.37(lH,d,=7.7)

Compound 34 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.25(3H,s), 1.31(3H,s), 1.80(lH,d,J=5.3), 2.00(lH,t,J=2.8), 2.18(3H,s),

2.26(lH,dd,J=18.7,1.8), 2.69(lH,dd,J=7.7,5.3), 2.71(lH,dd,J=7.7,5.3),

2.92(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 4.57(lH,dd,J=6.1,1.0), 4.82(lH,dd,J=6.1,1.7),

5.70(lH,dd,J=6.3,1.8), 6.01~6.30(2H,m), 6.40(0.5H,d,J=7.7), 6.40(0.5H,d,J=7.7)

Compound 35 1H-NMR (CDC1 , TMS standard, values: δ is in ppm and J is

in Hz) δ 1.26(3H,s), 1.31(3H,s), 1.81(lH,d,J=5.3), 2.00(lH,t,J=2.9), 2.26(lH,dd,J=18.7,1.8),

2.50(lH,t,J=2.4), 2.72(lH,dd,J=7.8,5.3), 2.92(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.9),

4.70(2H,d,J=2.4), 5.70(lH,dd,J=6.3,1.8), 6.46(lH,d,J=7.8)

Compound 37 1H-NMR (CDC1 , TMS standard, values: δ is in ppm and J is

in Hz) δ 1.23(3H,s), 1.29(3H,s), 1.50~1.85(9H,m), 2.01(lH,t,J=2.8), 2.18(3H,s),

2,26(lH,dd,J=18.7,2.0), 2.64(lH,dd,J=7.3,5.6), 2.93(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8),

4.69(lH,m), 5.69(lH,dd,J=6.3,2.0), 6.39(lH,d,J=7.3)

Compound 39 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.23(3H,s), 1.30(3H,s), 1.75~2.10(7H,m), 2.18(3H,s), 2.26(lH,dd,J=18.7,1.9),

2.60~2.70(2H,m), 2.92(lH,dd,J=l 8.7,6.2), 3.16(2H,d,J=2.1), 4.07(2H,d,J=6.7), 5.69(lH,dd,J=6.2,1.9), 6.36(lH,d,J=7.2)

Compound 40 1H-NMR (CDC1₃, TMS standard, values: δ is in ppm and J is

in Hz) δ 1.25(3H,s), 1.30(3H,s), 1.74(lH,d,J=5.3), 2.00(lH,t,J=2.6), 2.18(3H,s),

2.26(lH,dd,J=18.6,1.9), 2.75(lH,dd,7.8,5.3), 2.91(lH,dd,J=18.6,6.3), 3.16(2H,d,J=2.6),

3.40(3H,s), 3.65(2H,t,J=4.8), 4.25(2H,t,J=4.8), 5.69(lH,d,J=6.3,1.9), 6.37(lH,d,J=7.8)

Mixture containing at a 1:1 molar ratio Compounds 9 and 29 1H-NMR

(CDC1₃, TMS standard, values: δ is in ppm and J is in Hz) δ 0.92(3H,d,J=6.7),

0.94(3H,d,J=6.7), 1.23(1.5H,s), 1.24(1.5H,s), 1.29(1.5H,s), 1.31(1.5H,s,), 1.77(0.5H,d,J=5.5),

1.91(0.5H,d,J=5.5), 1.94~2.02(lH,m), 2.00(lH,t,J=2.3), 2.17(3H,s), 2.15~2.30(1.5H,m),

2.70(0.5H,dd,J=7.4,5.5), 2.92(lH,dd,J= 18.7,6.3), 3.16(2H,d,J=2.3), 3.81(lH,d,J=6.8),

3.87(lH,d,J=6.8), 5.65~5.70(lH,m), 6.37(0.5H,d,J=7.4), 7.25(0.5H,d,J=7.4)

Mixture containing at a 1:1 molar ratio Compounds 47 and 67 1H-

NMR(CDC1₃, TMS standard, values: δ is in ppm and J is in Hz) δ 0.89~0.95(3H,m), 1.20

~1.26(6H,m), 1.32(1.5H,s), 1.34(1.5H,s), 1.45~1.75(2H,m), 1.87(0.5H,d,J=8.6),

1.91(0.5H,d,J=8.7), 2.00(lH,t,J=2.8), 2.06(0.5H,t,J=8.6,8.2), 2.15(3H,s), 2.28'IH, br

s,J=18.6), 2.51(0.5H,t,J=8.7,7.4), 2.93(lH,dd,J=18.6,6.5), 3.15(2H, br s), 4.13(lH,m),

5.68(lH,m), 6.95~6.99(0.5H,m), 7.67(0.5H,d,J=8.2)

Mixture containing at a 1:1 molar ratio Compounds 50 and 70 ¹H-NMR(CDC1 ,

TMS standard, values: δ is in ppm and J is in Hz) δ 0.94(4.5H,s), 0.96(4.5H,s),

1.25(1.5H,s), 1.28(1.5H,s), 1.31(1.5H,s), 1.34(1.5H,s), 1.87(0.5H,d,J=8.6),

1.91(0.5H,d,J=8.5), 1.99(lH,t,J=2.8), 2.04(0.5H,dd,J=8.8,8.6), 2.16(3H,s), 2.20(lH,br, d,

J=18.7), 2.49(0.5H,dd,J=8.5,7.1), 2.90(lH,dd,J=18.7,6.3), 3.16(2H,d,J=2.8), 3.77(lH,s), 3.83(lH,s), 5.66~5.69(lH,m), 6.96(0.5H,d,J=7.1), 7.71(0.5H,d,J=8.8)

Compound 3 Index of refraction Tin 1.5056

Compound 23 melting point 98.1°C

Mixture containing at a 1:1 molar ratio Compounds 42 and 62 Index of

refraction n_D 2(^o5 1.5079

Mixture containing at a 1:1 molar ratio Compounds 43 and 63 Index of

refraction no 2ό 1.5037

Mixture containing at a 1:1 molar ratio Compounds 45 and 65 Index of

refraction nn 26° 1.5074

Mixture containing at a 1:1 molar ratio Compounds 48 and 68 Index of

refraction n_D ²⁶ 1.5101

Mixture containing at a 1:1 molar ratio Compounds 52 and 72 Index of

refraction n_D ²⁶ 1.5153

Various forms of the aldehyde compound encompassed by formula (H) are

expressed in the following Tablel7 in connection with formula (H) and intermediate numbers.

As such, Intermediate 1 provided in the above Production Example 2 is expressed in Table

17 with the according Intermediate number.

In Table 17, "the alcohol moiety configuration" means the absolute configuration

at the 1 position in the 2-cyclopentanone ring moiety of the aldehyde compound

encompassed by formula (H), such as a R or S configuration. Further, in Table 17, the "acid

moiety configuration" means the absolute configuration at the 1 position in cyclopropane

ring moiety of the aldehyde compound encompassed by formula (H), such as a R or S configuration, and the relative configuration of the substituent at the 3 position of the

ring moiety of the aldehyde compound encompassed by formula (H), such as a cis or trans

configuration. Furthermore, as used in Table 17, an "RS" configuration means that the

provided form of the aldehyde compound encompassed by formula (H) is a mixture

containing at a 1:1 molar ratio the R configuration thereof and the S configuration thereof.

Table 17

The following sets forth the NMR data of Intermediate 1.

Intermediate 1 1H-NMR (CDC1₃, TMS) δ 1.31(3H,s), 1.36(3H,s),

2.00(lH,t,J=2.7), 2.18(3H,s), 2.25(lH,dd,J=18.7,2.0), 2.50(lH,d,J=5.6),

2.55(lH,dd,J=5.6,3.1), 2.92(lH,dd,J=18.7,6.3), 3.17(2H,d,J=2.7), 5.67(lH,dd,J=6.3,2.0),

9.64(lH,d,J=3.1)

Formulation Examples

The following Formulation Examples 1 to 16 set forth examples of formulating the

ester compounds encompassed by formula (I). In Formulation Examples 1 to 16, "parts"

means parts by weight, wherein the parts by weight are based on the total weight of the provided formulation. Further, in Formulation Examples 1 to 16, Compound numbers are

used therein to refer to particular forms of the ester compounds encompassed by formula (I),

as expressed in Tables 1 to 16.

Formulation Example 1 emusifiable concentrates

Ten (10) parts of Compounds 1 to 320 are dissolved, respectively, in a mixture

containing 35 parts of xylene and 35 parts of dimethylformamide. Fourteen (14) parts of

polyoxyethylenestyryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are

added, respectively, thereto. The resulting mixtures are then stirred to provide 10%

emulsifiable concentrates.

Formulation Example 2 wettable powders

Twenty (20) parts of Compounds 1 to 320 are mixed, respectively, with 4 parts of

sodium laurylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of a synthetic powder of

silicon hydroxide and 54 parts by weight of diatomaceous earth. The resulting mixtures are

stirred with a blender to provide 20% wettable powders.

Formulation Example 3 granules

Five (5) parts of Compounds 1 to 320 are stirred and mixed, respectively, with 5

parts of a synthetic powder of silicon hydroxide, 5 parts of sodium dodecylbenzenesulfonate,

30 parts of bentonite and 55 parts of clay. Appropriate amounts of water are added thereto

and then stirred. After producing granules with a granulator, the granules are air dried to provide 5% granules.

Formulation Example 4 dusts

One (1) part of Compounds 1 to 320 is dissolved, respectively, in an appropriate

amount of acetone. Five (5) parts of a synthetic powder of silicon hydroxide, 0.3 parts of

PAP and 93.7 parts of clay are added, respectively, thereto. The resulting mixtures are mixed

and stirred. The acetone in the mixture is then removed therefrom to provide 1% dusts.

Formulation Example 5 flowables

Ten (10) parts of Compounds 1 to 320 are mixed, respectively, with 35 parts of a

white carbon containing sulfateammonium polyoxyethylenealkyl ether and 55 parts of water.

The resulting mixtures are pulverized by the humid pulverization method to provide 10%

flowables.

Formulation Example 6 oil formulations

One-tenth (0.1) part of Compounds 1 to 320 are dissolved, respectively, in 10 parts

of dichloroethane. Eighty-nine and nine-tenths (89.9) parts of deodorized kerosene are mixed,

respectively, into the mixtures to provide 0.1% oil formulations.

Formulation Example 7 oil formulations

of trichloroethane. Eighty-nine and nine-tenths (89.9) parts of deodorized kerosene are mixed, respectively, into the mixtures to provide 0.1% oil formulations.

Formulation Example 8 oil-based aerosols

One (1) part of Compounds 1 to 320 are stirred and mixed, respectively, with 5

parts of dichloromethane and 34 parts of deodorized kerosene. The resulting mixtures are

packed into aerosol vessels. After valves are attached to the aerosol containers, 60 parts of a

propellant (liquid petroleum gas) are packed, respectively, into the aerosol vessels through

the valve attached thereto to provide oil-based aerosols.

Formulation Example 9 water-based aerosols

Six-tenths (0.6) parts of Compounds 1 to 320 are mixed and dissolved,

respectively, with 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of an

emulsion [Atmos 300 (a registered trade name, Atlas Chemical Coφ.)]. The resulting

mixtures and 50 parts of water are packed, respectively, into aerosol vessels. After valves

are attached to the aerosol vessels, 40 parts of a propellant (liquid petroleum gas) are packed,

respectively, into the aerosol vessels through the valves attached thereto to provide water-

based aerosols.

Formulation Example 10 mosquito-coils

Mosquito-coil components are produced by uniformly mixing Tabu powder,

Pyrethrum marc and wood powder at a 4:3:3 weight ratio, adding 120ml of water to 99.5g of

the resulting mixture, sufficiently kneading the mixture, forming the mixture into a plurality of components and drying each of the components.

Acetone solutions which contain, respectively, Compounds 1 to 320 are added to

the mosquito-coil components and dried to provide mosquito-coils.

Formulation Example 11 mosquito-mats for electric heaters

Mosquito-mat components are produced by compacting a fibril mixture containing

cotton linter and pulp into a plate having the dimensions of 2.5cm x 1.5cm with a thickness

of 0.3cm.. Eight-tenths grams (0.8g) of Compounds 1 to 320 and 0.4g of piperronylbutoxide

are dissolved, respectively, in acetone to amount to 10ml. Five-tenths milliliters (0.5ml) of

the acetone solutions are uniformly impregnated onto mosquito-mat components to provide

mosquito-mats for electric heater.

Formulation Example 12 liquids for electric heaters

Three (3) parts of Compounds 1 to 320 are dissolved, respectively, in 97 parts of

deodorized kerosene and are transferred to vinyl chloride containers. Heat-tolerant wicks are

then added thereto to provide liquids for electric heaters. The heat-tolerant wicks are

produced by assembling together an inorganic powder with a binder and sintering the

inorganic powder.

Formulation Example 13 fumigants

One hundred milligrams (lOOmg) of Compounds 1 to 320 are dissolved,

respectively, in appropriate amounts of acetone. The resulting acetone solutions are impregnated onto porous ceramic plates having the dimensions of 4.0cm x 4.0cm with a

thickness of 1.2cm to provide fumigants.

Formulation Example 14 pesticidal baits

Ten milligrams (lOmg) of Compounds 1 to 320 are dissolved, respectively, in

0.5ml of acetone. The resulting acetone solutions are applied, respectively, to 5g of pet food

granules (solid feed powder for breeding CE-2, CLER Japan, Inc.) and are uniformly mixed.

The resulting mixtures are allowed to dry to remove the acetone therein to provide 2%

pesticidal baits.

Formulation Example 15 acaricidal sheets

Compounds 1 to 320 are dissolved, respectively, in acetone and are uniformly

applied dropwise to unwoven cloths to amount to lg per lm . The resulting unwoven cloths

are allowed to dry to provide acaricidal sheets.

Formulation Example 16 microcapsules

Ten (10) parts of Compounds 1 to 320 are mixed, respectively, with 10 parts of

phenylxylylethane and 0.5 parts of Sumidur 1A5 (tolylenediisocyanate provided by

Sumitomo Bayer Urethane Co., Ltd.). Subsequently, 0.5 parts of the mixtures are added,

respectively, to 20 parts of a 10% aqueous solution of gum arabic. The mixtures are mixed

with a homoginizer to produce emulsions in which the mean droplet diameter therein is

20μm. The emulsions are further mixed, respectively, with 2 parts of ethylene glycol and are allowed to react for 24 hours at 60°C to produce microcapsule slurries.

A thickening solution is prepared by dispersing 0.2 parts of xanthan gum and 1.0

part Beagum R (aluminum magnesium silicate ; trademark of Sanyo Chemical Co., Ltd.) in

56.3 parts of ion-exchanged water.

Forty two and five-tenths (42.5) parts of the microcapsule slurries are mixed,

respectively, with 57.5 parts of the thickening agent to provide 10% micocapsules.

Test Examples

The following Test Examples 1 to 7 set forth examples of utilizing the ester

compounds encompassed by formula (I) as an active agent for controlling pests. In Test

Examples 1 to 8, Compound numbers are used therein to refer to particular forms of the ester

compounds encompassed by formula (I) as expressed in Tables 1 to 16.

Further, the following control compounds provided in Test Examples 1 to 8 are

referred to as Control Compounds A, B or C as shown below.

(S)-2-methyl-4-oxo-3-(2-propynyl)-2-cyclopentan-l-yl (lR)-trans-2,2-dimethyl-3-

(2-methyl-l-propenyl)cyclopropanecarboxylate is referred to as Control Compound A.

(S)-2-methyl-4-oxo-3-(2-proρynyl)-2-cylopentan-l-yl (lR)-cis-2,2-dimethyl-3-(2-

methyl-l-propenyl)cyclopropanecarboxylate is referred to as Control Compound B.

A mixture containing at a 8:2 molar ratio (S)-2-methyl-4-oxo-3-(2-propynyl)-2-

cyclopentan- 1 -yl (1 R)-trans-2,2-dimethyl-3-(2-methyl- 1 -propenyl)cyclopropanecarboxylate

and (S)-2-methyl-4-oxo-3-(2-propynyl)-2-cylopentan-l-yl (lR)-cis-2,2-dimethyl-3-(2-

methyl-l-propenyl)cyclopropanecarboxylate is referred to as Control Compound C. The Control Compounds A, B and C above may be produced according to the

methods described in J. Labelled Compd. Radiopharm. 23, 995 (1986).

Test Example 1 Pesticidal test with common cutworm

The mixture containing at a 1:1 molar ratio Compounds 42 and 62, the mixture

containing at a 1:1 molar ratio Compounds 43 and 63, the mixture containing at a 1:1 molar

ratio Compounds 45 and 65, the mixture containing at a 1:1 molar ratio Compounds 48 and

68 as well as the mixture containing at a 1:1 molar ratio Compounds 52 and 72 were

formulated as flowables according to Formulation Example 5. The flowables were then

diluted so that the concentration therein of the ester compounds encompassed by formula (I)

was 500ppm. Synthetic baiting agents (inselectorLF, Nihon Nosan Kogyo, K.K.) placed in

polyurethane cups having a diameter of 11cm were impregnated, respectively, with 2ml of

the diluted flowables. The polyethylene cups were each infested with 5 fourth instar larvae of

common cutworm (Spodoptera litura). The mortality rate of the common cutworm was

observed 6 days thereafter.

It was observed that the mortality rate for each of the tested compounds above was

100%.

Test Example 2 Pesticidal test with housefly

The mixture containing at a 1:1 molar ratio Compounds 42 and 62, the mixture

containing at a 1:1 molar ratio Compounds 45 and 65, the mixture containing at a 1:1 molar

ratio Compounds 48 and 68 as well as the mixture containing at a 1:1 molar ratio Compounds 52 and 72 were formulated as flowables according to Formulation Example 5.

The flowables were then diluted so that the concentration therein of the ester compounds

encompassed by formula (I) was 500ppm. Filter papers having a diameter of 5.5cm were

placed in polyethylene cups having a diameter of 5.5cm. Seven-tenths milliliters (0.7ml) of

the diluted flowables and 30mg of sucrose were added, respectively to the filter papers.

Subsequently, the cups were infested, respectively, with 10 female adult houseflies (Musca

domestica) and were covered. The mortality rate of the houseflies was observed 24 hours

thereafter.

100%.

Test Example 3 Pesticidal test with German cockroach

The mixture containing at a 1:1 molar ratio Compounds 43 and 63 as well as the

mixture containing at a 1:1 molar ratio Compounds 45 and 65 were formulated as flowables

according to Formulation Example 5. The flowables were then diluted so that the

concentration therein of the ester compounds encompassed by formula (I) was 500ppm.

Filter papers having a diameter of 5.5cm were placed in polyethylene cups having a diameter

of 5.5cm. Seven-tenths milliliters (0.7ml) of the diluted flowables and 30mg of sucrose were

added, respectively, to the filter papers. Subsequently, the cups were infested, respectively,

with 2 male adult German cockroaches (Blattella germanica) and were covered. The

mortality rate of the German cockroaches was observed 6 days thereafter.

It was observed that the mortality rate for each of the tested compounds was 100%. Test Example 4 Pesticidal test with common mosquito

The mixture containing at a 1:1 molar ratio Compounds 42 and 62, the mixture

was 500ppm. Seven-tenths milliliters (0.7ml) of the diluted flowables were further diluted,

respectively, in 100ml of ion exchange water. Twenty (20) final instar larvae of common

mosquito (Culex pipiens pollens) were infested, respectively, into the resulting ion exchange

water. The mortality rate of the common mosquitoes was observed 6 days thereafter.

It was observed that the mortality rate for each of the tested compounds was 100%.

Test Example 5 Knock down test with German cockroach

According to Formulation Example 7, there were formulated oil formulations of

the compounds shown in Table 18, i.e. Control Compound C, Compound 3, Compound 23,

a mixture containing at a 1:1 molar ratio Compounds 42 and 62, a mixture containing at a 1:1

molar ratio Compounds 43 and 63, a mixture containing at a 1:1 molar ratio Compounds 46

and 66 as well as a mixture containing at a 1:1 molar ratio Compounds 52 and 72. The

concentrations of the compounds shown in Table 18 in the flowables were as shown in Table

18. Vaseline was spread on the inner wa) 1 of polyethylene cups having a diameter of

9cm. The polyethylene cups were then infested, respectively, with 5 male and 5 female adult

German cockroaches and were covered with nylon nets of 16 mesh. The polyethylene cups

were placed in plastic cylinders having an inner diameter of 10cm and a height of 37cm. Six-

tenths milliliters (0.6ml) of the oil formulations were then sprayed, respectively, onto the

German cockroaches at a pressure of 5.9xl0⁴ Pa from the top portion of the plastic cylinders.

The number of knocked down German cockroaches were periodically counted up until 10

minutes thereafter. From such data, the times need to knock down 50% of the German

cockroaches were calculated (hereinafter referred to as KT₅₀). The results are shown in Table

18.

Table 18

Test Example 6 Knock down test with German cockroach

According to Formulation Example 6, there were formulated oil formulations of

the compounds shown in Table 19, i.e. Control Compound C, Compound 2, Compound 12,

Compound 15, Compound 22, Compound 32, Compound 35 and a mixture containing at a 1:1 molar ratio Compounds 3 and 23. The concentration of the compounds shown in Table

19 in the oil formulations were as shown in Table 19.

Margarine was spread onto the inner wall of cylinders to which metal nets of 16

mesh were attached to one of the ends thereof. Subsequently, the cylinders were infested,

respectively, with 5 male and 5 female adult German cockroaches.

In 46cm x 46cm x 70cm metal chambers, a metal net was placed on the bottom

surface of each of the metal chambers and square pieces of paper having a side length of

20cm was placed on the metal nets therein. The cylinders were then placed on the square

pieces of paper therein such that the metal net attached on the cylinders was on the bottom.

One and five-tenths milliliters (1.5ml) of the oil formulations then were sprayed, respectively,

onto the German cockroaches from the top portion of the metal chambers at a pressure of

4.1xl0⁴ Pa with a spray gun. Thirty (30) seconds thereafter, the cylinders were removed from

the chambers and the German cockroaches were transferred to second plastic cups having a

lower diameter 8cm, upper diameter of 9.3cm and a height of 4.5cm. The knocked down

German cockroaches were periodically counted up until 10 minutes after the spraying. From

such data, the KT₅₀ of the German cockroaches were calculated. The results are shown in

Table 19.

Table 19

Test Example 7

According to Formulation Example 6 or 7 as shown in Table 20, there were

formulated oil formulations of the compounds shown in Table 20, i.e. Control Compound A,

Control Compound B, Control Compound C, Compound 4, Compound 12, Compound 15,

Compound 24, Compound 32, Compound 35 Compound 40, a mixture containing at a 1:1

molar ratio Compounds 3 and 23, a mixture containing at a 1:1 molar ratio Compounds 9

and 29. a mixture containing at a 1:1 molar ratio Compounds 47 and 67, a mixture

containing at a 1:1 molar ratio Compounds 42 and 62, a mixture containing at a 1:1 molar

ratio Compounds 43 and 63, a mixture containing at a 1:1 molar ratio Compounds 46 and 66

as well as a mixture containing at a 1:1 molar ratio Compounds 52 and 72. The concentration

of the compounds shown in Table 20 in the oil formulations were as shown in Table 20.

Polyhedral glass chambers, having a side length of 70cm, were infested,

respectively, with 10 female adult common mosquitoes. Seven-tenths milliliters (0.7ml) of

the oil formulations were then sprayed, respectively, into the glass chambers from a window thereof at a pressure of 8.8x10 Pa. The number of knocked down common mosquitoes were

periodically counted up until 10 minutes thereafter. From such data, the KT₅₀ of the common

mosquitoes were calculated. The results are shown in Table 20.

Table 20

Test Example 8

According to Formulation Example 6 or 7 as shown in Table 21, there were

formulated oil formulations of the compounds shown in Table 21, i.e. Control Compound A,

Control Compound B, Control Compound C, Compound 4, Compound 12, Compound 24, Compound 32, a mixture containi ig at a 1:1 molar ratio Compounds 3 and 23 as well as a

mixture containing at a 1:1 molar ratio Compounds 46 and 66. The concentration of the

compounds shown in Table 21 in the oil formulations were as shown in Table 21.

Polyhedral glass chambers, having a side length of 70cm, were infested,

respectively, with 5 female and 5 male adult houseflies. Seven-tenths milliliters (0.7ml) of

the oil formulations were then sprayed, respectively, into the glass chambers from a window

thereof at a pressure of 8.8xl0⁴ Pa. The number of knocked down houseflies were

periodically counted up until 10 minutes thereafter. From such data, the KT₅₀ of the

houseflies were calculated. The results are shown in Table 21.

Table 21

Claims

CLAIMS:

An ester compound encompassed by formula (I):

wherein R represents a hydrogen atom, a to C₅ alkyl group which may be substituted

with at least one halogen atom, a C₄ to C₅ cycloalkyl group which may be substituted with at

least one halogen atom, a C to C₅ alkenyl group which may be substituted with at least one

halogen atom.

2. The ester compound according to claim 1, wherein the absolute configuration at

the 1 position of the cyclopropane ring moiety is a R configuration.

3. The ester compound according to claim 1, wherein in formula (I) the substituent at

the 1 position of the cyclopropane ring moiety and the substituent at the 3 position of the

cyclopropane ring moiety are in a trans configuration.

4. The ester compound according to claim 1, wherein the substituent at the 1 position of the cyclopropane ring moiety and the substituent at the 3 position of the cyclopropane ring

moiety are in a cis configuration.

5. The ester compound according to claim 1, wherein the absolute configuration at

the 1 position of the 2-cyclopentanone ring moiety is a S configuration.

6. The ester compound according to claim 1, wherein in formula (I) R¹ represents a

to C₃ alkyl group.

7. The ester compound according to claim 1, wherein in formula (I) R¹ represents a

methyl group.

8. The ester compound according to claim 1, wherein in formula (I) R¹ represents an

ethyl group.

9. The ester compound according to claim 1, wherein in formula (I) R¹ represents a

propyl group.

10. The ester compound according to claim 1, wherein in formula (I) R¹ represents an

allyl group.

11. The ester compound according to claim 1, wherein in formula (I) R¹ represents a propargyl group.

12. A pesticidal composition comprising as an active ingredient the ester compound of

claim 1.

13. An aldehyde compound encompassed by formula (H):

14. The aldehyde compound according to claim 13, wherein the absolute configuration

at the 1 position of the cyclopropane ring moiety is a R configuration.

15. The aldehyde compound according to claim 13, wherein the substituent at the 1

position of the cyclopropane ring moiety and the substituent at the 3 position of the

cyclopropane ring moiety are in a trans configuration.

16. The aldehyde compound according to claim 13, wherein the absolute configuration

at the 1 position of the 2-cyclopentanone ring moiety is a S configuration.

17. A method of controlling a pest, comprising applying the ester compound of claim 1 to at least one location selected from the pest and a habitat of the pest.