JPS60222444A - Cyclopropane derivative, manufacture and insecticidal tickicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel cyclopronoconic acids and derivatives thereof useful as intermediates, and to insecticidal active esters of the acids of and to compositions containing the same.

The present invention also relates to novel methods of making acids and derivatives and novel discoveries useful in such methods.

According to the first gist, the present invention provides the following formula (■): [in the formula 82
preferably represents an α-branched alkyl radical containing from 3 to 5 carbon atoms, aa (a) represents a hydroxy, halo (especially chloro or an alkoxy group of up to 6 carbon atoms) or (b) a group -0R1 (wherein R1 is the residue of the alcohol of 2ROH which forms an insecticidal ester when combined with hachrysanthemic acid, permethic acid or cyhalothric acid) is provided.

Nogu-metholinic acid is j-(J,,!-dichlorovinylnorco, nordimethylcyclopro/guncarzenic acid, and cyhalothric acid is 3-(2-chloro-3,,3,3-
Trifluorozolobu l-ene-/-ylno2. λ−
It is dimethylcyclopronozone cardinic acid.

More specifically, R is the following general formula: [wherein X is oxygen, sulfur, vinylylene, or the following formula:
=Y- (in the formula, Y is nitrogen or OR), and R
4 is hydrogen, methyl, cyan, or ethynyl group, each R5 is hydrogen, halogen, and an alkyl group optionally substituted with halogen and having up to μ carbon atoms f'L, R is hydrogen, halogen, and up to μ carbon atoms; Alkyl of carbon atoms is an alkenyl, phenyl, phenoxy or benzyl group of up to 1 carbon atoms, or a phenyl, phenoxy or benzyl group having halogen or alkyl as a substituent]
represents the group of

It will be appreciated that the compounds of formula (1) above can exist in various isomeric forms and as mixtures of isomers. That is, there are cis and trans isomers resulting from the substitution type of the cyclopropane group, and optical isomerization arises from the presence of λ asymmetric centers in the cyclopropane group, resulting in (+)-cis, (- )-cis, (+)-trans and (-)-)lance isomers are possible. Furthermore, isomerism may be present in the insecticidal active esters of the present invention if the alcohol moiety contains an alkenyl group or one or more asymmetric centers. The individual isomeric forms and mixtures thereof, including racemates, are within the scope of the invention.

Particular compounds of the above formula (I) (wherein R represents an alkoxy group of up to 6 carbon atoms) useful as intermediates include the above formula (■) (wherein R2 is propunoyl, buty-
2-yl, pentyl-λ-yl, pentyl-3-yl, cortacylprop-2-yl, -monomethylputinoyl,
cyclopropyl and cyclohexyl) acids. Particularly preferred compounds include ethyl(t)-trans-co, 2-dimethyl-3-<s-propunoylpyrimidine! -Irunocyclopropane calxylate.

Ethyl(t)-trans-29,2-dimethyl-3-[
-1(nomethylprop-2-ylnopyrimidine-j
-yl]-cyclopropane calxylate and the corresponding methyl and 2-methylprop-2-yl-esters.

Formula (1) where R is an alkoxy group of 4 or less carbon atoms
The above compound can be suitably converted into i-converted Lyc according to the following reaction sequence.
can be prepared from j-bromopyrimidine = (a) No α-branched alkyl group due to the formation of Grignard products!
-Compatible with bromopyrimidine! -conversion to the formyl derivative followed by treatment with dimethylformamide, i.e. (b) hydrogenation) in the presence of a base such as IJium.
- reacting formylpyrimidine with 0.0-dialkyl alkoxycarzenyl methyl phosphonate to give 3-(pyrimidine-!-ylnopropenoate; (c) in the presence of an organometallic reagent such as n-butyllithium; In an alternative method of reacting pyrimidinyl zolopenoate with an inpropyl triphenylphosphonium salt to obtain a cyclopropyl ester, i.e., to produce th:3-pyrimidin-y-yl-propenoate, nosoradium salts (e.g. palladium acetate), tetramethylethylenediamine and preferably phosphine derivative C example,
tb) in the presence of liphenylphosphine)! - Bromopyrimidines can be reacted directly with alkylpropenoates (in particular t,i-)methylethylnoropnoate), ie; some of the j-bromopyrimidines used as starting materials in this reaction sequence are new. These can be prepared by reacting a mucobromic acid derivative with a suitable amidine followed by decarboxylation of the pyrimidine carzene acid, i.e. when R is an alkoxy group of up to 6 carbon atoms and VR2 is An alternative method of preparing the above mentioned compounds of formula II) as described above uses the following reaction sequence; (a) of the following formula: and R7 and R8 are alkyl or aryl groups, preferably R7 is 6 such as mekyl or ethyl.
A phosphonium salt of a phosphonium salt of an alkyl group of fm or less carbon atoms, which is a phenyl group) is prepared by mixing sodium hydride with a strong base in an aprotic solvent, preferably in dimethylsulfoxyP. The ylide obtained by treatment with cr) (obtained) is reacted with a compound of the following formula: to obtain a compound of the following formula (m): 1.

lb) The compound of formula (ill) is treated with phosphorylchloride P and dimethylformamide P under Vilsmeier-Haack reaction conditions to form the following formula (IV) and/or the following formula (■ ): to obtain the compound.

(c) A compound of formula (IV) and/or fV) is reacted with an amidine of formula: in the presence of a base such as sodium methoxy P, preferably in methanol, so that R is an alkoxy group as defined above. A compound of formula (1) is provided.

The compounds of formulas (III), (IV) and (V) have not been previously described. Accordingly, in another aspect, the present invention provides compounds of formula (1) useful as intermediates for the preparation of compounds of formula (1).
ll), (IV) and (V3).

Preferred 11S sweets of the above formula ([1) include the following: 11 cis and out-trans isomers of compounds in which R is a methoxy or ethoxy group and B7 is an alkyl group of up to 6 carbon atoms Methyl(t)-trans-j-((E,z)-nomethoxyvinyl)-s, 2-dimethyl cyclopropane carboxylate, Methyl-trans-j-[, (g,z) -Nomethoxyvinyl]-2,2-4methyl cyclopropane carboxylate, ethyl-trans-3-[(E,Z)-2-methoxyvinyl]-2,2-dimethyl cyclopropane carboxylate, ethyl -Ta-cis-j((E+,Z)-nomethoxypinyl)-2,2-dimethyl cyclopropylcarboxylate.

Correspondence (D together with ethyl ester include the formula (
The corresponding compounds of ■) and (V) are also preferred: methyl-trans-3-((E,Z)-t-formyl-!-methoxyvinyl]-2,,!-))1 tyl
Cyclopropane carboxylate, methyl cyclopropane carboxylate, methyl cyclopropane-[(E,Z)-i-formyl-27methoxyvinyl]-2,2-1 methylcyclopropane carboxylate, methyl cyclopropane-C(E,Z) -2-dimethylamino-l-formylvinyl) -' *Nosimethylcyclopronogne carboxylate methyl(t)-cis-J-((E,z)-nodimethy/I/767-i-
Formylvinyl]-2,2-,)methylcyclopropylcarboxylate.

Details of all these methods are described below in the Examples. Compounds of the formula DJ in which R represents a hydroxyl group can be obtained by hydrolysis of alkyl esters, preferably alkaline hydrolysis, for example using an aqueous solution of alcoholic sodium hydroxide, and are useful for insecticidal purposes. When used directly in the synthesis, it can be used or it can be first converted by reaction with a suitable halogen agent such as thionyl chloride into a compound of formula fI) in which R is preferably chloro.

Particular compounds useful for insecticidal treatment according to the invention include, where appropriate, single isomers and racemic compounds thereof and formula +1
1 (in the form of a racemic mixture of lance isomers) or a single isomer thereof (where FL2 is a prop-2-
yl, but-2-yl, pent-2-yl, pent-3
l-methyl-2-yl, 2-methylpropylene, λ-methylbuty-2-yl, cyclozolopyl, and cyclohexyl). 3,! , l, -tetrafluorobenzyl alcohol, pentafluorobenzyl alcohol, aryl, 2,3. ! , 6-titrafluoropendyl alcohol, φ-methoxymethyl-2.3. j, 6-titrafluoropenzyl alcohol, 3-phenoxybenzyl alcohol, coquano-3
-phenoxybenzyl 7/I/col, t-phenoxybilyr-noylmethanol, l-cyano-1-(6-phninoxypyri)% J-yl)methanol, 3-(≠-chlorophenoxybenzyl)alcohol, α- Ethynyl-3-phenoxybenzyl alcohol, /-(A-phenoxybilyl-P-2-yl)ethanol, l-fluoro-3-phenoxybenzyl alcohol α-cyano-μm fluoro-3-phenoxybenzyl
alcohol, ! -Benzyru 3-Furyl methanol, Cope Riru 3
-Methyl-Hiro-HyProxy cyclopentonoenone, Cortacyl-3-phenylbenzyl alcohol.

Particularly preferred compounds include: methyl-
2,j,j,A-tetrafluorobenzyl fk3-)
9ns 2. Nodimethyl-3-[λ-(Nomethylpropcoyl)pyrimidine-! -yl]cyclozolono7ane carboxylate (hereinafter referred to as "Compound I").

μm allele-2,! ,! , t-tetrafluorobenzy-trans-2,λ-dimethyl-3-[no(J-
Methylpropinoyl)pyrimidine-! −yl] cyclopronocarboxylate (hereinafter referred to as “compound ■
)0 3-phenoxybenzyl-)? Nsuco, nodimethyl-3-[no(λ-methylprozo=noyl)pyrimidin-y-yl]cyclopropanecardixylate (hereinafter referred to as "compound m").

TA-α-cyano-3-phenoxybenzyl TA-trans-2,nodimethyl-j-(J-(2-methylprop-
2-yl)pyrimidine-! −il] cyclopronozone
Calyl? −? Sylate (hereinafter referred to as "compound ■").

6-FetoxypyriP-noylmethylta-trans-
2,2-dimethyl-3-[no (no methyl prozo 2
-yl)pyrimidine-! -yl]cyclopropane carboxylate (hereinafter referred to as "Compound ■").

(g)-7-cyano-/-(4-phenoxypyryr-2
-yl)methyl(t)-trans-λ,2-dimethyl-3-[no(2-methylpropinoyl)pyrimidine-j-ylcocyclopropane]ruzexylate (hereinafter referred to as "Compound ■").

Cortacyl-3-phenylbenzyl(t)-trans-
2,2-dimethyl-3-[cortacyl-prop-2-yl)pyrimidine-! -yl]cyclopropane carboxylate (hereinafter referred to as "Compound 1").

≠-Fluoro-3-phenoxybenzyl-trans-co, 42-dimethyl-3-[no-methylzolop-2-yl)pyrimidine-! -yl]cyclopropane carboxylate (hereinafter referred to as "Compound ■").

f33-/-cyano-/-(4-phenoxypyriP-noyl)methyl-trans-J,! --) Methyl-
3-(coprosonoyl-pyrimidin-1-yl)
Cyclopropane calgoxylate (hereinafter referred to as "Compound ■").

f5-/-cyano-1-(6-phenoΦcypyrir---
il) methyl ta-transuco, no dimethyl-j-(
, 2-cyclohexylpyrimidin-j-yl)cyclopropane (hereinafter referred to as "Compound X").

Ta-! -Cyano/, -(A-phenoxypyryP-2-
yl)methyl(i)-trans-2,2-dimethyl-3
-(2-cyclop-a-virpyrimidin-j-yl)cyclopropane calzexyle) (described as "Compound X" under IL).

Ta-1-(6-phenoΦcypyryp-x-yl)ethyl...
-trans-
(written as J).

Pentafluorobenzyl-transco, no methyl-3-[no(2-methylprop-λ-yl)pyrimidine-! -yl] cyclopropane calzexylate (hereinafter written as [compound XI[l J )].

α-ethynyl-3-phenoxybenzyl-transco, λ-dimethyl-3-[no(no-methylzolopukoyl)pyrimidin-j-yl]cyclopronogne carboxylate (hereinafter referred to as [Compound XP/J ).

≠-Methoxymethyl-2. j, jt, t-nato2fluorobenzyl-) t-nsu j, +2-,,) methyl-
j-(J-(λ-methylfurofu-λ-yl)hyrimidin-!-yl)cyclozolonozone calxylate (hereinafter referred to as [Compound XV J).

Cortatil-3-phenylbenzylta-transuco,
2-dimethyl-3-(2-propunoylhyrimidin-!-yl)cyclopropane carboxylate (hereinafter referred to as "compound XVIJ").

The insecticidal active compound of the present invention of the formula +11 is an ester, and can be prepared by a conventional esterification method, examples of which are as follows: (a) The following formula (■): (wherein Q is a hydroxyl group and R2 is as previously described) can be directly reacted with an alcohol of the formula Preferably it is carried out in the presence of hydrogen chloride or in the presence of a dehydrating agent such as, for example, dicyclohexylcardidiimide P.

(b) It is possible to react the acid H2P of the formula (■) (where Q represents a halogen atom, preferably a chlorine atom, and 2 is as described above) with the alcohol of the formula (Ill). The reaction is preferably carried out in the presence of a base such as pyridine, an alkali metal hydroxide or carbonate or an alkali metal alkoxy P.

(c) The acid of the above formula (■) (where Q represents a hydroxyl group or preferably an alkali metal salt thereof) is converted into an acid of the following formula (I
V) 1 Q-R(IV) (in the formula, Q1 represents a halogen atom, preferably a chlorine atom, and B1 is as described above), or a tertiary amine For example, it may be reacted with a μ-grade ammonium salt derived from pyridine or a chitrialkylamine, such as triethylamine.

) The lower alkyl ester of the formula (n) (wherein Q represents a lower alkoxy group containing 6 or less carbon atoms, preferably a methoxy or ethoxy group, and R2 is as described above) is converted into the lower alkyl ester of the formula (III) The transesterification reaction is carried out by heating with alcohol. The process is preferably carried out in the presence of a suitable catalyst, such as an alkali metal alkoxy such as sodium methoxy or an alkylated titanium derivative such as natho-2-methyl titanate.

All of these conventional methods of preparing esters can be carried out, if appropriate, using various anti-nuisance solvents and diluents, and when carried out at elevated temperatures or in the presence of suitable catalysts, e.g. phase transfer catalysts. Under-working can be accelerated and can result in higher yields of product.

The preparation of the individual isomers can be carried out in the same manner, but starting from the corresponding individual isomer of the compound of formula (II). These are obtained from mixtures of isomers by conventional isomer separation techniques. Thus, cis and trans isomers can be separated by fractional crystallization of carboxylic acids or their salts, whereas various optically active compounds can be separated by fractional crystallization of salts of said acids and optically active amines followed by optically pure crystallization. V is obtained by regeneration of acid.

The above acids (or their equivalent acid chlorides or esters)
The optically pure isomeric form of can then be reacted with a suitable lunol to produce a compound of formula II) in its individually pure isomeric form.

The compound of the formula (1) is a pest insect and other spineless and vertebrate pests,
For example, it is used to kill and control mite infestations. Xt) The pests and mites to be killed and controlled by the use of the compounds of the invention include agriculture (this term is meant to include the growing of crops for food and textile products, hardening and animal husbandry); , forestry, and the storage of products of plant origin, such as fruits, grains, and timber, as well as pests that transmit human and animal diseases.

In order to apply the compounds of the invention to pest-infested areas, they are usually combined with the insecticidal active ingredient of formula (1) (7M or more) plus a suitable inert diluent or carrier material, a preservative/or a surface treatment agent. Formulated into a composition containing an active agent. The composition may also contain other insecticidal substances, such as other insecticides or acaricides, or fungicides, such as insecticidal synergists such as r-decylimidazole, safroxane-coated piperonyl butoxy P. May contain.

The composition may be in the form of a powder for dispersion, in which the active ingredient is mixed with a solid diluent or carrier such as kaolin, bentonite, diatomaceous earth or talc, and the composition may be in the form of granules. in which the active ingredient is absorbed into a porous particulate material, such as pumice.

Alternatively, the compositions may take the form of liquid formulations for use as dips or sprays, which formulations are generally supplemented with one or more known wetting agents, dispersing agents, or emulsifying agents.
Aqueous dispersions or emulsions of active ingredients, including surfactants).

Wetting agents, dispersing agents and emulsifying agents may be of cationic, anionic or nonionic type. Suitable cationic agents include, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide.

Suitable anionic sacrificial agents include, for example, soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium P-decylbenzenesulfonate, sodium lignosulfonate, calcium nu7ammonium, butylnaphthalene. sulfonate salts, and mixtures of sodium diisopropylnaphthalene sulfonate and sodium triisopropylnaphthalene sulfonate. Suitable non-ionic sacrificial agents include the condensation products of e.g.

Other nonionic recreational agents include partial esters derived from long chain fatty acids and anhydrous hexitol, condensation products of the partial esters with ethylene oxyr, and lecithin.

Said composition is prepared by dissolving the active ingredient in a suitable solvent, for example a ketone solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene, and adding the resulting mixture to one or more known wetting agents. It is prepared by addition to water which may contain dispersants or emulsifiers.

Other suitable organic solvents are dimethylformamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylene, trichloroethylene, N-methyl-λ-pyro IJ l-'n's Tetraphyllofurfuryl Alcohol (THFA) T.

Compositions used in the form of aqueous dispersions or emulsions are generally supplied in the form of concentrates containing a high concentration of the active ingredients, which concentrates are diluted with water before use. be done. These concentrates can withstand long-term storage and can be diluted with water after such storage;
It is often necessary to produce an aqueous solution that remains homogeneous for a sufficient period of time so that it can be applied using conventional spray equipment. Concentrates Fi/species or more active ingredients can be on the order of 10-is π weight. When diluted to form an aqueous solution, the concentration of active ingredient in the solution can be varied depending on the intended use. For agricultural and gardening purposes, 0.0001, 0. Particularly useful are aqueous solutions containing t@ of active ingredients.

In use, the composition is applied to the pest, the pest's location, the pest's habitat, or the growing plants susceptible to pest infestation by any of the known means of applying insecticidal compositions, such as by spraying or spraying.

The compositions of the present invention can be applied to, for example, the following pests: Myzus pericae
(aphida) Caterpillar butterfly larva (Pieri)
s brassicae) (White butter)
fly, Iarvae) diamond back
moth, 1arvaQ) mustard captominus (Pha
edon cochleariae) (mustard
beetle) (carmine 5pider m1te) two-spotted spider mite (Tetranychus urticae) (re
d 5pider m1le) Aonidaeera (Aon
idiella spp, ) (scale 1nsec
ts) Blattella german
ica) (cockroaches) Spodozotella
Litoralis (Spodoptera toralis)
is) (cotton 1eaf worm)
obacco budworms) Cortiocetes terminifera (Ohortiocetes terminifera)
') (locusts) Diabrochi power (Diabr
otica spp,) (rootworms root-eater East) Root-cutting insect (Agrostis spp,) (cut
It is toxic to a wide range of pests, including worms and other vertebral pests.

The compounds of formula iI) and compositions containing them are themselves useful against plant mites such as the two-spotted spider mite and spider mites, as well as against costopterous pests of cotton, such as Sboroptera 1m (5p
odoptera spp, ) and Heliothis trace (H
eliothis spp.).

It was shown that The compounds are effective against soil-dwelling pests such as Diabrotica apI.
-) can be used to exterminate. The compounds may also be used to control insect pests and tick pests that infest livestock, such as the British cattle tick (Oophylata us spp.) Ixodes ticks (
Dermaceutor spp, ). The compounds described above are effective in combating susceptible and #i species of pests in adults, larvae and intermediate stages of growth and are suitable for topical, oral or parenteral administration. can be applied to infested host animals.

The following examples illustrate various aspects of the invention.

In manufacturing examples, the products are typically identified and characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy. In each case where the product was specified, its spectral characteristics were consistent with the assigned structure.

Example! This example describes the preparation of pipalamidine hydrochloride.

A mixture of trimethylacetonitrile (lA3f: 0.61 M) and dry ethanol (Kohiro, 0.6/M) was cooled using an ice/salt bath while dry hydrogen chloride gas was added for a period of 0 min. A total of 2/f Hot
is passed through the mixture until it has been absorbed.

The mixture is then kept at room temperature for 2 days before being diluted with dry diethyl ether (100 cd) to precipitate ethyl trimether acetemidate hydrochloride, which is collected by filtration (3p, jf). Add dry ethanol (s
Dry ammonia gas (6f
) solution little by little while stirring gently. During the addition, the solid gradually dissolves and the resulting solution is heated to 20°C.
After holding for an hour, the solvent is removed by evaporation under reduced pressure and the remaining solid is washed with diethyl ether to yield pivalamidine hydrochloride (27f).

Example 2 This example uses the promoter λ-(2-methylglob-2-
The production of pyrimidine-carboxylic acid will be explained.

A solution of sodium ethoxide in ethanol [sodium (/, j) in dry ethanol (-2≠ef/l)
ft) of the solution obtained by dissolving l≠,! −
], bivalamidine hydrochloride (j, /ffy) at ≠θ℃
and dry ethanol (<5tta) carefully added to the stirred mixture. After stirring the mixture for a further 10 minutes,
When a solution of mucobrome m(j,/4r) obtained by dissolving mucobromic acid (dry ethanol<10 cd), j, 44,43, is added to the mixture, an exothermic reaction occurs, during which The temperature is raised to 65°C. After a period of 20 minutes, the temperature is lowered to SO 0 C and the remainder of the sodium ethoxide solution and the remainder of the mucobromic acid are added. The reaction temperature is maintained at jO 0 C for a pi time by external heating, after which insoluble matter is removed by filtration at that temperature, washed with ethanol, and the washing liquid and p liquid are combined.

After removing the solvent by evaporation under reduced pressure, the remaining solid was washed with dilute hydrochloric acid (λM, /(116/l)') and with water.

When dried, j-promo 2 (2-methylprop-2-
Il) Pyrimidine-coucarvone e<3.8'? ＞, the melting point λ~/4'≠℃ (accompanied by decomposition) is obtained, and its N, M
, R and infrared spectra were consistent with this identification.

'HNMR (ODOI 3) point: /, 4'j (s
, PH)'*ROj(s , /H): Ri・Hiro≠(wide s
, /H) Infrared spectrum (halafinmal) = 2 170, 21
tO.

2!00 (wide), 1qio, 1s7o.

/370 /, 303 /2ri0 /220//ri0.
//73,7 to 0,610crn-'Example 3 This example is! -promo 2-(2-methylglob-λ-
The production of pyrimidine will be explained.

! -Promo 2-(2-methylglopnoyl)pyrimidine-≠-carboxylic acid (/, Of) without stirring 1
The decarboxylated product is obtained by heating to 413° C. followed by distillation using a Kugelrobr apparatus under water pump pressure. The distillate solidifies upon cooling to give promo-2-(2-methylprop-2-yl).
Pyrimidine (0, At) m, p, 10-31°C is obtained.

Its N, M, FL and infrared spectra were consistent with this identification.

'HNMR(ODOI3)a:/,jri(s,ri)()
:J', 7/ (8, uH).

Infrared spectrum (paraffin mar): , 2F110
,2160°/! 30 /4'zaQ /Hiroshi, 2o ii
'y.

1010.110,1. Hiroocm-'.

EXAMPLES This example describes the preparation of 2-(2-methylpropyl)pyrimidine-j-carboxaldehyde.

A solution of 1Vj91 of j-promo-2-(-1methylprop-λ-yl)pyrimidine (7,6?, 0.0.36M) in dry tetrahydrofuran (3061) was treated with magnesium in the presence of a few crystals of iodine. Scraps (0, rij2,
Grignard grade). The rate of addition is controlled by the exothermic reaction rate. After the addition is complete, the mixture is warmed to complete the reaction. the mixture
After cooling to ℃, tetrahydrofuran <tsmt')
A solution of dimethylformamide (2jlf) in solution is added dropwise to this. The mixture is warmed to room temperature with stirring over a period of 2 hours and kept without stirring for 16 hours. After adding water to the mixture, the tetrahydrofuran is removed by evaporation under reduced pressure and the residue is partitioned between a dilute aqueous solution of ammonium chloride and diethyl ether (/j Offl). The aqueous phase is extracted with ether (/60 cfl) and the extracts are combined with the ether phase, washed with water and dried over anhydrous magnesium sulfate. Evaporation of the ether under reduced pressure produced an oily solid residue (100 parts by volume) which was eluted with a mixture of methylene chloride (10 parts by volume) and ethyl acetate (1 parts by volume) on silica gel. When purified by dry column chromatography using a column, 2-(2-methylglob-λ-yl)pyrimidine-5-carboxaldehyde (3,≠f), m, p, J', 2-♂3℃ get.

Infrared spectrum (Harafinmal) = 2rihiro O2λ♂6
01/700 /jriOl≠30 /, 230itso
, rto, tsocrn-1 Example! This example describes the preparation of ethyl 3-[λ-(/,/-diethyl ether)pyrimidin-j-yl]propenoate.

Q dissolved in dry diethyl ether (20 otl).

O-diethyl ethoxycarbonyl methylphosphonate)
A solution of (j, 31) was added dropwise to a stirred suspension of water-volatile sodium (0 #1 Iy of 10% oil dispersion) in dry diethyl ether <30 cd> at -j °C. , the mixture is then allowed to stir for 0 minutes. A solution of λ-(λ-methylprop-2-yl)pyrimidine-j-carboxaldehyde (2,21?) in dry diethyl ether (Hiro 0,4) was added dropwise to this stirred mixture at 0 °C. The resulting mixture is allowed to warm to room temperature with stirring over 2 hours and then kept at room temperature for 76 hours.

The mixture was mixed with water (/j (117)) and diethyl ether (2
! θcrI) and the aqueous phase was partitioned between ether (2
j Ocd ) and the extract is combined with the ether phase. After washing with water (200 c4) and drying over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure and the residual oil was evaporated using a silica gel column and as eluent j volumes/
Ethyl 3-[λ
-(,2-methylprob-1-yl)pyrimidine-! −
yl]propenoate (3,6?), which solidified on standing, m, p, 413-4'j °C, and its N, M, R, and infrared spectral data indicate that the product is the trans isomer. It will be shown when the

1HNMR('CDCl6)δ:/, 3! (t, j
I():/:”(S + riH); 11.2≠(q, 2H
);6. ! Q(d,l■();7,aO(a,/H);
Za, za 2 (s, 2H).

Infrared spectrum (baraffin mar) = 2260°/7
30 /All! /! 90 /1716/μ≠0. /
320. //zas,ttjs,,'Example 6 This example describes the production of ethyl transco,-2-dimethyl-(J-(,2-methylprobyl-noyl)pyrimidin-j-ylcocyclopropanecarboxylate) Explain.

A solution of n-butyllithium (10.tcd of a 455M solution in hexane) was dissolved in prop-λ in dry tetrahydrofuran (2o cd!) at room temperature under a nitrogen atmosphere.
-yltriphenylphosphonium iodide (7,/
9) and the resulting mixture was allowed to stir for an additional 75 min before adding ethyltrans 3-[λ-<
2-methylprog-2-yl)pyrimidin-j-yl]
A solution of globenoate (3,+22) is added dropwise at -5°C. After stirring for 30 minutes (during which time the mixture warms to room temperature), it is kept at room temperature for 16 hours. The mixture was mixed with water (300 (:td)) and diethyl ether k (
The aqueous phase is extracted with ether (-2X 200 crd) and the extracts are combined with the ethereal phase.

After washing with water (COX/00 all) and drying over anhydrous magnesium sulfate, the ether was removed by evaporation under reduced pressure to give a residual oil, which was first eluted with dichloromethane to remove the triphenylphosphine. ) and then dry column chromatography using a silica gel column eluting with a mixture of dichloromethane (lθθ vol.) and ethyl acetate (j vol.) to give ethyltransco, 2-dimethyl-3-[2-(-2 -methylprop-[lambda]-yl)pyrimidin-5-yl]cyclopropanecarboxylate) (2,fr), whose identity was confirmed by infrared spectroscopy and N, M, R, spectroscopy.

'HNMR (ODOI3) δ: 0. Tata (s, jH);
/, j/(t, JH);/, 440(s, /2H);/
, ri A (d, /l-1): 2, j≠(d, /H)
: 'A2 (q +2H) ; zz (s, -2H) Infrared spectrum (liquid film): 260. /7j, 0. ／≠
ts.

l hiro 60 / 1A20 / 260 //10 1163cm.

Mass spectroscopy (M”): 27 was used in Example 7.
,2-no11-propinoyl)pyrimidi7-
The production of cyclopropanecarboxylic acid (j-i/l/) will be explained.

of ethyltrans-2,2-dimethyl-3-[no(,2-methylprop-λ-yl)pyrimidine-j-ylcocyclopropanecarboxylate (,2j f ) in ethanol (!0,d ). Solution wo, water (s
Sodium hydroxide (/, Of
) and the mixture is allowed to stir at room temperature for 5 hours. After removing most of the ethanol by evaporation under reduced pressure, the pH of the remaining mixture is adjusted to 3 with dilute hydrochloric acid. The mixture is extracted with diethyl ether (2×2006/l) and the combined extracts are washed with water and dried over anhydrous magnesium sulfate. Evaporation of the ether under reduced pressure yields transco, 2-dimethyl-3-[λ-(2-methylpropocoyl)pyrimidin-j-yl]cyclopronocarphonic acid (2,/f), m, p, iur Obtain ~ri°C.

'H, NMR (ODOI) δ:/, 0.3 (s,
3H): /, Hiro/(S, riH); 1, ≠za (s, JH)
';Jj72(d, /H):ko, &(d, /H);zaJ
7(s,,2H) infrared spectrum (paraffinyl):
, 2≠0. /700°/1111, /1130
, /333, /260.

/230 /210α-1 Mass spectroscopy (M+): not/-g Examples This example shows 3-phenoxybenzyltrans-22-dimethyl-J- yl)pyrimidin-j-yl]cyclopropanecarboxylate.

trans-2,2-dimethyl-3-[λ-(2-methylglob-λ-yl)pyrimidin-j-yl]cyclo'pronocarboxylic acid (j00■) and 3-phenoxybenzyl bromide (6322) and anhydrous Potassium carbonate (3
A mixture of acetone (10-mg) and acetone (10-) is heated at reflux temperature for 2 hours with stirring and then kept at room temperature for 16 hours. After removing the solid precipitate by filtration, The liquid is concentrated by evaporation under reduced pressure.The residual oil is purified using a silica column and dichloromethane (1
00 parts by volume) and ethyl acetate (2 parts by volume) using high performance liquid chromatography (Gilson). The product 3-phenoxybensylate-2-2-9.2-dimethyl-3-[λ-(2-methylprop-λ
-yl)-pyrimidine-j-ylcyclopropanecarboxylate<100%) was obtained as an oil, the identity of which was confirmed by N, M, R, and infrared spectroscopy.

'HNMR(ODO+6)δ:O0ri'(s+3H)
:'; Hiro O (S, /, 2H): 2, θ-2 (d, /H)
Knee, 2. J-7(d, /H):s,,ts,,(S,
+, J'H);4-' 7.1 (m+riH).

Infrared spectrum (liquid film) = Lid 60μF 30, /
jriO2l≠ri0 /260 /ko20 iitocr,,"'1 Mass spectroscopy (M):≠30 Example This example uses guaryl-λ, 3. J, t-tetrafluorobenzyl trans-λ, 2-dimethyl-3-[λ-(
2-Methylpropinoyl)pyrimidine-! −il]
The production of cyclopropane carboxylate will be described.

・Dicyclohexylcarbocyimide (4120mg
), trans-2,-2-dimethyl-3-[λ-(dimethylgrogunoyl)pyrimidin-y-yl]cyclopropa/carboxylene)(jO!■)tocouarylλl 31'l'-tetrafluorobenzyl Alcohol (≠62■, small amount of isomeric - monoallic acid 3.
II,! , t-tetrafluorobenzyl alcohol), ≠-dimethylaminopyridine (5■) and dry dichloromethane (lOcA) in small portions at room temperature, and the resulting mixture was stirred for an additional period of ios minutes. , followed by holding at room temperature for '/6 hours. The solid precipitate was removed by filtration, washed with ether, and the washings were
Combine with liquid. After removing the solvent by evaporation under reduced pressure, the residual oil was purified by HPLO (Gi I -5on)
trans-2,2-dimethyl-3-(,2-(
, 2-metherprobunoyl)pyrimidine-yoylcocyclopropanecarboxylic acid Hiro-aryl 2,3. j
, t-tetrafluorobenzyl ester tag wt% and 1-aryl3. Hiroshi.

! , A-f dorafluorobenzyl ester z% by weight
The product (1,j Omg) was obtained as an oil, which solidified on standing m+ p, 4! ~6
6℃.

Its identity was confirmed by N, M, R, infrared spectroscopy and mass spectrometry.

'HNMR (ODOI3) δ; O, Cotton (s, JH) 3 (s + "n): 1, Ri A (dl/H); -2, -t
J (d, /H): jJ (m, 2H); 44 ter jJ (m
, 4'H): J, A4. /(m, /H);g,4'I(
s, 2H)・＼ Infrared spectrum (paraffinyl) = 2 zO2λ 3
0°, 2za 1,0 /736 /≠90 /Hiroshi6014
L≠θ, lhiro, 20. /33θ, //60σ−1 Mass Spectroscopy (M”) Nige!O Example IO ≠-Methyl-2.3.j, t-tetrafluoro Penzyl transsuco, 2-dimethyl-3-[no(nomethylpropyrimidin-!-yl)]cyclopropane calxylate was obtained from cardanic acid and benzoyl bromide as a colorless oil.

'HNMFL (ODO13) δ: O, Pri (s, JH
):/, 39 (s, /JH);/ri4 (d,.

iH): 2,30<m, 3H); , 2J/; (d, /H): j, 2F(s
, 2H): Lul (s, JH) infrared spectroscopy (liquid film)
: +2rittO, /7guo, ihiroyz, iμ20゜l rich 0. //13,107!佽-1゜Mass Spectroscopy' (M”)
:≠21 Example // By using a method similar to that described in Example 2, the following esters were obtained: (a) 6- from cardanic acid and t-phenoxypyridolylmethanol Fethoxypyridonoylmethyltrans-2,2-dimethyl-3-(X-(X-methylprop-λ-ylnopyrimidin-!-yl)cyclopronoguncaldexylate.

'HNMR(ODO25)δ:/, O/(s, JH)
:/, G l (s, /, 2H); Ko, Olr (d.

IH): Ko, Or (d, /H) ;j, /♂(
s, +2H); A, 77-74 (, IrH):
ll0Cs, 2H infrared spectroscopy (liquid film): λ tθ, /
710. /100. /j♂0゜lgeta0. /jμo,
i+2to, ilt.

(Ml-1 Mass spectroscopy (M+): 4'J / (b) Cardic acid and 2-methyl-3-phenylpenzyl alcohol or lanaumethyl-3-phenylpenzyltrans-, -1dimethyl-3-[no( 2-Methylzolozonoyl nobilimidin-!-yl]cyclopropane calxylate.

'HNMTLCODO13) δ: 0. P ta (
s, jH) :/J(7(s,/jH):ko, 06 (
d e /H) : -2, Jj(a, JH) ;ko, 40
(d, IH) knee t, core (s, 2H): 7. / −7j (m.

IH): IJOCa, 2H).

Infrared spectroscopy (liquid film): 2YtO, /73.0. ilt
-16,/1720゜//lO,760,70jcIn
-' Mass spectroscopy (M''J: 4'co♂ (C) From cardanic acid and α-cyano-3-phenoxybenzyl alcohol to a-cyano-3-phenoxybenzyltrans-,2,nodimethyl-3-( --(No-methyl-prop-coyl-2-pyrimidin-!-yl)cyclopropane calxylate.

'HNMFL (ODO13) δ: O, Tata (s)
; ',' ” (s): ', 3j (s): 1
．． 3ri (s): /, lA j (s): 2. O
j (7:, 2j (c): t, Hiroshi λ (s): 6.μ
μ(S) Near, J A On): 1. II A (
s): za, j O(s).

(The whole corresponds to a 22l mixture of dilatational isomers) Infrared spectroscopy (liquid film): λ AO, /7≠O1/! ri0. I
I-8.

/+2!0. //4tO,191cm-1 mass spectroscopy (
M"):μ!! (d) From cardanic acid and /-cyano-7-(t-phenoxypyrid-2-ylnomethanol /-cyano-/
-(-phenoxypyridonoylnomethyltrans-+21+2-dimethyl-3~[--(2-methylpropinoylnobilimidin-!-yl)cyclozolonognecarboxylate.

1HNMR (ODOt3Jδ: /, 00(s):
/, OJ(s) : /, J j(s) : 8≠' (
s): ko, / (nj: , 2j (to); 1, II
(js): t, ri (d); 7. J (pd;
7, ♂ (dd): ♂,! 0 (kos).

(The whole is consistent with a /2/ mixture of polarized left and right isomers) Infrared spectroscopy (liquid membrane saw 2?tO, /7416./JriJ, /
Hiro O1/4tjO, /2AO, //4t, 0. A9j
, -1 Mass spectroscopy tpl'): 4Az g (e) Cardanic acid and methoxymethyl-co, 3°s
, A-f to 5 fluoropendyl alshidoka et al.≠−
Methoxymethyl-2,3. j,t-tetra°fluorobenzyl ω-trans-2,2-4methyl-3-[No C
Comethylprosocoylnobilimidine! -ilun-2,2-dimethylcyclopronoguncalcexylate.

'HNMR (ODOl3) δ: O, Tata (s
, J'H); /, 4(0(Ja, /, 2H);
1. Tani 1 (d.

/H): Ko, 1t(d, /H): j,! (7(8,jI(]; p, t θLm, 2H
):Lj0(m.

2H): J', 0 (s, 2H) infrared spectroscopy
: /731,132! ,/Hori o, i Kota! .

I”7 F7 Mar) / / jO,? / 0,
lr r O, 770ffi-1 mass spectroscopy (M”)
: IIj 4A (f) From calzenic acid and (t)-/-(t-phenoxypyridonoyl ethanol (t)-/-(A-phenoxypyrid-2-ylnoethyl (t)) once 2 O-
2,2-dimethyl-3-[no (no methyl f-
J-yl]pyrimidin-3-yl]cyclopropane calxylate.

'HNMFt(ODOl,)δ: /, o (s);
/, J j (s): 8 μ θ (S): 1,! (a
) : i, lr (s) : ,2. Or ldd)
;2J O(ko d); ter' j (q): t,
7(d); 7.2 fn): 7.6j (dd)
: Lj 0(-2S).

Infrared spectroscopy (t[[I): 2yro, /73o, /ao
o, tzro.

1aat, no 260. //70. Tata 0゜7006n
"Mass spectroscopy (MH"J: da4!6 (g) From calzenic acid and Hiro-fluoro-3-phenoxybenzyl alcohol≠-fluoro-3-phenoxybenzyl mountain-trans-2,2-dimethyl-3-[- 1 (2-Methylprosy λ-ilnovi vmi, :iin!-
yl, l cyclopropane carboxylate.

(h) One-trandome of topentafluoropenzyl carzenate alcohol or lahentafluorobenzyl --21
．． 2-dimethyl-J-[,z-(x-methylprop-2
-ilnovirimidine-yoichiil] cyclopronozoncal? Xylate.

'(i) Power k y! ? 7 Acid (!: (g)-α-
Engineering f::k -3-phenoxybenzyl alcohol and ω-α-ethynyl-3-phenoxybenzyl(t)-
Trance.

Nodimethyl-J-(J-(Nomethylprozo2-ylnopyrimidin-!-yl)cyclopropanecardixylate.

Example 12 This example shows (t)-〇-cyano-3-phenoxybenzyl(t)-trans-J-(J-(,2-methylzolozonoylfuvirimidin-!-yl)-21cordimethylcyclo The present invention relates to the preparation of pronozone carboxylate (f-hyperoxylate) and the separation of its component pairs of enantioisomers.

ω-trans-3-[no(,2-methylpropyrimidin-!-yl)-,2,2-dimethylcyclopropylcarboxylic acid (J, Jt) and 3-phenoxybenzaldehyde cyanohydrin (J,!rr, contaminated with about 20% 3-phenoxybenzaldehyde 7
m) A stirred mixture of dimethylaminopyridine (100η) and dichloromethane (ioo-) was heated to room temperature (approx.
dicyclohexylcalzediimide (JJ f
) in small portions. After stirring for an hour, the mixture is kept at room temperature for 76 hours, filtered and the collected solids washed with dichloromethane. After that, the liquid and washing liquid were concentrated by evaporation of the solvent under reduced pressure, and the residual oil was purified using a silica column dissolved in a mixture of dichloromethane (100 parts by volume 5) and ethyl acetate (! parts by volume λ). Liquid chromatography (h, p, 1. c, ) (Gi
Purify by 1son). The first fraction is 3-
A mixture of phenoxybenzaldehyde and the desired product is produced, the latter fraction being pure (t)-α- in the form of a gum consisting of a mixture of λ racemic pairs of enantiomers in a ratio of 2/2. Cyano-3-phenoxybenzyl(t)-trans-3-[no(cortacylprop-2-ylnobilimidi/-!-yl]-2, JJ methylcycloprono-ξ-encalxylene) (1,3t). Rechromatography of the first fraction using the same eluent at a rate of 30 ad/min on a 2,000 ml silica column results in a faster distillation of the enantiomers (the less polar two pairs (1 , 20~).The more polar (faster distillation) pair of enantiomers (, 21■)
, later fraction (2:l mixture of isomer pairs (A)
ffi-containing] by similar rechromatography. The product consists of a mixture of more polar isomers and less polar isomers. Recombination and evaporation of the discarded 7-lactone yields a 7:1 mixture (8) of less polar and more polar isomers.

Two-spotted spider mite + Tetranych on the leaves of kidney beans
In biological tests using adult insects of P. ursicae, the pair of enantiomers with higher mechanical properties 'o50 = ''
, J'1m) is the more polar pair of isomers (Lc5o
- Hiroppm) Yoshi is also about 7θ times more effective.

, a mixture of the less polar pair of enantiomers and the more polar pair of enantiomers in a ratio of 7:l was added to Improper Tools (o, 1 cr) containing triethylamine (j weight ratio).
d) and stir at room temperature.

, after 22.3 hours this ratio is the alcohol part no.a
'-The epilation induced by chlorine at carbon causes approximately l
:/ is.

'I(NMR(ODOt6)δ:(A)O,ta z (
s); 1. o (s): /,,? z (s)
: l, a (s) : 8g j (8) : ko,
OL, 2dノ: J, l, (-2d); t, Hiroshi [kos]: 76.2 (c): r, ≠ 1 (,2s) (the whole is a 2:l mixture of left-right isomers) matches (
B) /, O(s t 3 H) ”, / , 4A O
[s, ri) (J:/, ≠yo(s.

3H〕:,2,0jCd,/Hノ;2,j,t
(d, /H); +, 4t.

(s, / H): 7. -2 (m.

H): 1.4t O(s, 2H) infrared spectroscopy (liquid film): (A), 260. /7410. /jriO1/g20. / Gut! ,/koArO.

1i4Ao,tyz,,-1 (s) L2rittO, /74tO, ljJ'j.

/μrθ, January bow, /+211-! .

/ /4tO, J 9j--' Example/3 Production of methyl(t)-transuco, nodimethyl-3-formylcyclopropanecarboxylate Methyl λ,
λ-Dimethyl-3-(dimethoxymethyl)cyclopronognecarboxylate (ri!trans isomer, ao, or), glacial acetic acid (/, 20d), and acetone (/
& 0dl) and water (210cA) at room temperature! Stir for an hour, dilute with water (/!0OcI) and extract with diethyl ether <1ooOcD). The aqueous residue is washed with ether (2×!00 ad) and the washings and extracts are washed with a saturated solution of sodium I/ium bicarbonate until there is no total acidity. After drying the ethereal solution over anhydrous magnesium sulfate, the solvent was removed by evaporation to produce a residual oil, which was purified by distillation and purified at 10°C.
Methyl mono-trans-1,2-dimethyl-3-formylcyclozolonocalcexylate (J 1.j f ) as a fraction boiling at Oj rmnHf
'e collect.

Example/Preparation of 4t (to)-transmethyl J-[(E,Z)-2-methoxyvinyl-2-dimethylcyclopronog/carboxylate Sodium hydride [tO% oil dispersion (rej f )] n
- obtained by washing with hexane to remove the oil] was suspended in dry dimethyl sulfoxide (distilled from /!Od1 calcium hydride) and the suspension was mixed with 3 g -
Stir at ≠θ°C for 5 hours under dry nitrogen atmosphere. A solution of methoxymethyltriphenylphosphonium chloride (2♂, 2) in dry dimethyl sulfoxide (200 crl) is added over 7♂ minutes while maintaining the reaction temperature at about 20°C by external cooling. . The solution of the ylide thus prepared was mixed with dimethyl sulfoxide CjOcd.
Methyl ω-trans-2゜2-dimethyl-3-formylcyclopropanecarboxylate (co1) dissolved in
．． ! The reaction is carried out while maintaining the reaction temperature at about 2 O'CK over a period of 2 hours. The mixture is stirred for a further 30 minutes and then kept at room temperature for 72 hours. Water (/zoOcrl
) and the mixture was diluted with diethyl ether (/X1000
crl) (ko x 300ctd). The extracts are combined, washed with water (3 x 30 Ocrills) and dried over anhydrous magnesium sulfate. The solvent was removed by evaporation under reduced pressure and the residue was dissolved in petroleum ether (S range to, t).

℃, lyoOd) and stir. Undissolved solids.

was removed by filtration and the P solution was evaporated to give a yellow oil (2 ot), which was purified by Kugerol.
Distillation under reduced pressure using an Irohr J system yields methyl (
g)-Rikuyx-J-((E,Z)-λ-methoxyvinyl)-J,, 2-dimethylcyclopronocarzeki'
/V −) I 2/, lA t), boiling point 1. F
°C/0. Generate OjtwnHy.

'HNMRfODOt3)δ: /, / J (s)
;8,24t(s);/,2t(s):.

1, ≠ (c); /, ri (e); λ, 3 G111; 3
．． j(s): 3. A (s): j, A 6 (
s): 4', /(,2d):≠,j 7 (,2s;t, θ(dd);6,≠(d).

(Total is consistent with (E) and (Z) isomers and mixtures) Infrared spectroscopy (liquid film): 2 60./730./1 pjO
, /41410°/270. /, 23j, //70. +201 ctn ・Example 1 This example is methyl(t)-trans-J-(E,
Z)-Nodimethylamino/-formylvinyl]-X
. Explain the production of a mixture with.

A solution of phosphoryl chloride (1,0cA) in 1,+2-dichloroethane (io,o-) is added to a stirred mixture of dimethylformamide (2Jcrl) and/,2-dichloroethane (100cd) at room temperature. Add dropwise. After the addition is complete, the mixture is stirred for an additional 75 minutes and cooled to iz°C. To this mixture /, methyl(t)-trans-J-[(B,Z)-2-methoxyvinyl:]-, dissolved in J-dichloroethane (10c4),
Add portionwise to the solution of 2,,2-dimethylcyclopropane caldexylate. # Keep the mixture at room temperature for an hour and add solid anhydrous potassium carbonate (/30?). After the exothermic reaction has subsided, the mixture is extracted with methylene chloride (-2X J 00 d ), and the entire extract is washed with water (3θ064). After drying over anhydrous magnesium sulphate, the solvent was removed by evaporation under reduced pressure [7, residual oil fj 3°C and 0. The volatile components were removed by heating in a Kugelrohr apparatus at 10 mixture (A ) (/0.3 f).

'HNMR(ODOt3)δ: (A) /, o (s
); l, o, t (s); Ha27 (s);
i, 3o (s); -2,11;' 6n):
J-/r (s): 3.37 (S); L OJ'
(s): 3.7θ(s): 6.7j C width S; I,, 3j (wide S); ♂, J' (s) The entire C is (B> and (Z) isomer Infrared spectroscopy consistent with -2:l mixture: Body 60,2F20./F3σ,/10
0゜(nosorahui:/rfiv) /4AjO,/Hiro1
0. /21'0. /230°//7! c1n-' Example/This example describes the preparation of methyl(t)-trans-3-(nocyclohexylpyrimidine=!-ylnocycloprobancalzexylate).

Sodium methoxide (3.2 cd of !M solution in methanol)'k, methikcf)-trans-J-
((E.

Z)-X-,)methylamino-/-formylvinyl]-
2. +2-dimethylcyclopronocalxylene □
-)(/, 01P: small amount of methyl(t)-trans-3
The product of Example it containing -(:CB,Z)-/-formylunomethoxyvinyl)-,2,,2-dimethylcyclopronogyne caldexylate is in the form of cyclohexanoylamidine (/ , 01 r J and methanol (
♂−] dropwise at room temperature to obtain n
3. Heat to reflux temperature for j hours. The mixture was cooled to ambient temperature and poured into water (200 cr/I);
Extract with diethyl ether (2×-200 crJl). After washing the threatened extract with water (jOctd) and drying over anhydrous magnesium sulfate, the solvent was removed by evaporation under reduced pressure and the residual oil was dissolved in salt f methylene (3 parts by volume) and diethyl ether ( When prepared by column chromatography using a silica column eluting with a mixture of methyl(t)-trans-3-((B
'.

'z,)-x-dimethylamine-l-formylvinyl2. λ-dimethylcyclopropanecarboxylate (
7riQ~) is generated.

'HNMR(ODO43)δ:/, 0(s, 3H)
:/, ≠ (s.

,3H):/,,2-/,♂(b,10H):/,
? ! (d , /H): ko, t (d .

/)();J♂(b,/l-1)”, 3.7(s, JH
) : Lj (s,=2HI.

Infrared spectroscopy (liquid film: 22410.2 0./730
．． /600°/300. Hatao, i+2ri0. //7
6cM-1゜Example/7 Example 7 except that methanol is used instead of ethanol
Using a method similar to that described in Example K/
The product (720~) of l was converted into (t)-57, by -3-(
,2-cyclohexylpyrimidine-! -ilno=2,2
−． ) Methylcyclopropanecarzenic acid + 76 OF
ng, mip, /Jr ~/30℃) K-turn (B-turn.

Infrared spectroscopy: 3300-2200 (wide), /710
゜ (Nosorafuinil) /! jO, /34AO, /,
290.12AO.

//ri0. //+20. .

Mass spectroscopy (M+): , 27! .

Example 1 This example is (S)-/-cyano-/-(A-phenoxybilyP-λ-yl)methyl(/, R8゜trans)-
3-(x-cyclohexylpyrimidiy-j-yl)
-1. The production of JJ methyl cyclopanoson carboxylate will be explained.

DicyclohexylcardiimiY(iir?)wo, (t)-trans-3-(J, -cyclohexylpyrimidin-j-yl)-x, 2-dimethylcyclopronozone carboxyle)(/j (lJmg) and / -cyano-7-(6-phuninoxybylyr-2-yl)methanol (tjOirrg), Hiro-dimethylaminopyridine (j~) and dichloromethane<rcms), and The mixture was stirred at room temperature for 7 hours and then for an additional 16 hours.
Hold without stirring for an hour. The product was isolated by filtering through a silica column and eluting first with dichloromethane and then with a mixture of dichloromethane (20 parts by volume) and ethyl acetate (1 part by volume) to yield (R8)-t-Schiff/ -1-(6-F-x-yl)methyl(/R8,)lance)-3-(λ-cyclohexylpyrimidin-!-yl)-, z, 2-dimethylcyclopronoguncarxylate (λμt~), which was identified as a 1:1 mixture of λ pairs of enantiomeric stereoisomers N, M, R,.

'HNMR (ODO15) a: /, 0 (2s)
; /, 3! (s): /, 4'J(s): 1
, λ-2,0 (bm): 2.06 (m): J, j
[m) :2Jj [m) :A, 3j (bs);
6. Ri (d); 7. J, t(m) near, I fdd)
;Here, Hiro (λS).

(The whole corresponds to a l:l mixture of left and right isomers) Infrared spectroscopy (liquid film) = 22 references 0.2g 1,0,1711! .

t6oo, 14Lzo, 1iro.

The length is 10,700cm.

The following compounds are also prepared from the appropriate amidines using methods similar to those described in Example 1-6.

(1) Methyl(t)-trans-3-(l-prozonoylpyrimidin-!-yl)-2, cordimethylcyclopronogne carboxylate.

'H,NM几(ODOI,)5: 0. ri♂(s, J
H); i, 30 (a, JH); t, 1t (tr,
iH):t,ao(s,3H);1,rij(d,/H)
;λ, 2r (d, /H);j, J(m, /H);j,
77 (s, /H): ♂, Sanza (s, JH); Infrared spectroscopy (liquid film): , 2910. /73ta, /19
6° / 1jO, /4t4tO, /j4tO.

t2AO, t17j, 130 stories.

(11) Methyl-trans-3-(2-cyclozolopyl pyrimidin-yl)-2,2-dimethylcyclopropane carboxylate.

'HNMELtoDo+5)δ:O1riA (s,
j H): /, Oj(m + ”H) :tJO(
s, JH); t, rij(, d, zH); -2, -2(
m, /H): λ, t(d, zH): 3.71 (a,
jH); lr, Hiroshi (a, 2H).

Infrared spectroscopy (liquid film): 3oto, 2ri60. /730
゜1600.1110.14470゜/444t3', //71. Rir Taku.

Example 20 Using methods similar to those described in Example 17 and tr, the following insecticidal and acaricidal compounds of formula fl) are obtained.

1i) -2-Methyl-3-phenylbenzyl-trans-2,2-dimethyl-3-(coprob-/-ylhyrimidin-j-yl)cyclopropanecaroxylate.

1HNM几(ODOI5)J:θJ? (s, jH):t
, 30 (s, jH'): 1.3g (s + JH); t, a
2(s, 3H); λ, / (d, zH): L2j(s
, jHl :Co・6j(d,/H):3. −2(m,
/H): j, 27 (s, 2H) near, 3 (m, JH);
g, Hiroshi (8, KoH).

Infrared spectroscopy (liquid film 1: sqgo, 173o, i!9
3゜/jJ'0, /≠23', /2440゜ti
taj, 'y≠0,710ts' (II) t-l-cyano-no (A-phenoxybiliP
-Noyl) methyl trans-co, 2-dimethyl-
3-(Copropunoylpyrimidin-t-yl)cyclopropanecaroxylate.

1HNMEL (ODOI5) δ: t, oocm): t
,03c8):t,3t(s):1,jf(s);
/, jf (a) ;/, 4! J(s): x, Oj(m
); ko, 60 (m): 3,2 (m): 6.3j (
bs); A, ri (d) near, 3 (m); 7J
(dd): Lj (koS).

(The whole corresponds to an l:l-mixture of threshold left and right isomers) c
.

Infrared spectroscopy (liquid film): Kota 10, 17≠km/r9B1
110, /4AJ: 0,1210°t / 30.711r, lf 1θ, octn song) (
g)-1-cyano-/-(A-phenoxypyridonoyl)methyl-trans-co, -2-,)) Mef
Ru3-(,2-cyclopropylpyrimidy-!
-yl) cyclopronone carboxy V-t.

'HNMR(ODOI,) δ: z, 1(s);/,
Oj(m);/, (76(s):i,jll(s)
; i, 4A2 (s) :ko, Ot2d); 2.2
(m) :2 za (m); A, 4'(s); 6.2
(d); 7. j (m); 7. Za(c+d)
:, r-3t(2a).

(The total corresponds to a l:l mixture of left and right isomers) Infrared spectroscopy (liquid film): 3010,2≠0,17jO.

/ 600, /≠10,12ru O1 /110. ri/0, too.

700α.

Example 21 The insecticidal activity of compounds I to ■ is shown in the following table as a mortality rate grade of A, B, or C, which indicates that a mortality rate of A11 tro to ioo% was observed, and B! Indicates that a mortality rate of θ to 72π was observed, and 0 indicates that a mortality rate of Q−≠Ritsu was observed. In the insecticidal activity test, the test pest is carried on a medium (e.g. leaves of a suitable food plant or paper), and the pest and medium are sprayed (contact test - rOTJ in the table) or the pest is placed. Spray onto the previous medium (residual test -
("RT" in the table). Mortality rate is evaluated 72 hours after spraying, but after constant weight. In this test, the test compound is dissolved in a mixture of t - ≠ parts by volume of acetone, 1 part by volume of diacetone alcohol, and the same solvent, and the solution is mixed with 01O1 by weight π of a wetting agent (Rizapol N cr) manufactured by diluting with water containing zo
It is used in the form of an aqueous composition comprising oppm of the compound.

It can be seen in the above table that the compounds of the present invention exhibit useful insecticidal and acaricidal activity against a number of tested pests that harbor a variety of insects and mites of economic importance.

Claims (1)

[Claims] / The following formula (I): [In the formula, R2 represents an a-branched alkyl group containing 3 to 6 carbon atoms, and R is (a) hydroxy, or or fl
(b) Group -OR (provided that R1 hachrysanthemic acid,) -
A compound representing the alcohol residue of R10H which forms an insecticidal ester with methholic acid or cyhalothric acid. -LR2 represents an α-branched alkyl group containing 3 to 6 carbon atoms, R is of the formula: [wherein X is oxygen, sulfur, vinylylene or
=Y- (wherein Y is nitrogen or OR), and R
is hydrogen, methyl, cyan, or ethynyl, each R is selected from hydrogen, halogen, and an alkyl group of up to 100 carbon atoms optionally substituted with halogen, and R is hydrogen, halogen, or up to μ carbon atoms Alkyl is an alkenyl, phenyl, phenoxy or benzyl group of up to 1 carbon atoms, or a phenyl, phenoxy or nbenzyl group having halogen or alkyl as a substituent, a,! 1), provided that when R6 is hydrogen, halogen, alkyl or alkenyl group, R4 is hydrogen]. 3 R is prop-2-yl, but-2-yl, pentyl
2-yl, pentyl-3-yl, -methylprop-2-
2-methylbutynoyl, cyclopropyl and cyclohexyl. 44 R is pentafluorobenzyloxy, ≠-methyl-2. J,! , A-tetrafluorobenzyloxy, μ
mAllyl-2,3,j, t-tetrafluorobenzyloxy, goumethoxymethyl-2,3,! , t-tetrafluorobenzyloxy, 3-phenoxybenzyloxy, α-cyano-3-phenoxybenzyloxy, g-fluoro-3-phenoxybenzyloxy, α-cyano-
Hiro-fluoro-3-phenoxybenzyloxy, α-ethynyl-3-phenoxybenzyloxy,! Patent representing -methyl-3-phenylbenzyl, t-phenoxypyridonoylmethanol, /-cyano-/-(6-phynoxypyridonoyl)methanol or ij/-(A-phenoxypyridonoyl)methanol Compound 16 according to claim 2. ta-cyano-3-phenoxybenzyltrans-J-
(J-(2-methylpropinoylfupyrimidine-oyl)-X, Z-dimethylcyclopropane dioxylate. t,<8)-α- Cyano-3-phenoxybenzyl (/
R,) Lance)-3-Cnor(,2-MethylProcy2
-ylnopyrimidine-yyl]-2゜-mono-dimethylcyclopropane-ruzexylate and CR)-α-cyano-
3-phenoxybenzyl(/S,) Lancenow 3-[No(,2-methylpropinoylfupyrimidine!-
yl]-21,2-dimethylcyclopropane and ruzexylate. Attached to f in the section. Patent for phagia two/-(&-phenoxypyrido-2-yltumethyltrans-3-[no(,2-methylprocyλ-ylnobilimidin-!-yl]-J,J-dimethylcyclopronoguncarboxylate) The compound according to claim 1. t As an active ingredient in combination with a diluent or carrier for the active ingredient, the following formula (I): 16 of the branched alkyl group, B represents the group -OR' (wherein R1 is the residue of an alcohol of the formula R'OH which forms an insecticidal ester with chrysanthemic acid, permethric acid or cyhalothric acid); An insecticidal and acaricidal composition comprising the compound Y : FL'-OH (IID (in the formula, R1 is as shown below) is directly reacted with an alcohol, and the reaction is carried out in the presence of an acid catalyst or a dehydrating agent,
or ←) The acid halide of the formula (ff) (wherein Q is a halogen atom, preferably a chlorine atom, and R is as described below) is reacted with the alcohol of the formula (III), and the reaction is carried out in the presence of a base. or e→ The acid formula () of the above formula (ID (where Q represents a hydroxy group or an alkali metal salt thereof) (in the formula, Q1 represents a halogen atom and R1 is as shown below) or with a μ-class ammonium salt derived from such a halide and a tertiary amine; Represents a lower alkoxy group, FL
The following formula (I) consists of heating the lower alkyl ester of the formula (IID) with the alcohol of the formula (IID) to carry out the transesterification reaction: [wherein R is 3 to 3 carbon atoms] represents an α-branched alkyl group containing (a) hydroxy, halo or iA
(b) represents an alkoxy group of up to 3 carbon atoms;
The group OFL' (where R1 is a formula that forms an insecticidal ester with chrysanthemic acid, permethric acid or cyhalothric acid) L' represents an alcohol residue of OH]
A method for producing the compound. 10, The following formula: [In the formula, z is bromo, formyl, or the following formula: (In the formula, R9 is 4
is an alkyl group of up to 3 carbon atoms,
"2 is an α-branched alkyl group of 3 to 3 carbon atoms" compound of the following formula: (wherein R is an alkoxy group of t or less carbon atoms,
7 is an alkyl group of up to 4 carbon atoms). 12 The following formula: [wherein G is OR (wherein R7 is an alkyl group of up to 4 carbon atoms] or a dimethylamino group,
R is an alkoxy group of up to 4 carbon atoms.