CH647224A5 - SUBSTITUTED BENZYL ESTER OF A 2,2-DIMETHYL-3- (2,2-DIHALOGENVINYL) CYCLOPROPANCARBONIC ACID. - Google Patents

Description

The invention relates to new pyrethroid compounds, namely substituted benzyl esters of a 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acid of the general formula (I)

x x

CH- CH-

^ / C = CH

\ C '1

, C = CH / \ CH

SC - CH-C-0 / "H O

: h ä

(i)

wherein each X is a halogen atom and R represents a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group, further a pesticidal agent containing such a compound as an active ingredient, and a method for controlling pests using such pyrethroid compounds.

Known as viral diseases of rice plants are dwarfism, rot, a dwarfism associated with black stripes and a dwarfism associated with yellowing, which are transmitted by green rice leafhopper (Nephotettix cincticeps Uhler) and small brown plant hoppers (Lao-delphax striatellus Fallén), as well as the Burn mosaic disease due to soil infection. Grass debris growth, which has recently been reported on rice crops in the tropics and in Asia, is also a viral disease transmitted by the brown plant hopper. Rice plants that are affected by grass debris growth give rice of poor quality. In order to prevent outbreak and spread of such viral diseases, it is necessary to timely control pests such as the brown plant hopper, the smaller brown plant hopper and the green rice leaf hopper, which are carriers of viruses which cause these diseases. However, none of the pesticides currently available can effectively combat the brown plant hop. Pesticides, which are able to fight these virus-transmitting pests thoroughly and effectively, are not yet known.

Some benzyl esters of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid are known. For example, a general formula is given in JP-OS 35332/80, which includes a-substituted or unsubstituted benzyl esters by-15, which on the benzene ring a lower alkyl, lower al-kenyl, cycloalkenyl, lower alkynyl, benzyl - Or phen-oxygruppe or a halogen atom or halogen atoms. 3-propargyl-a-ethynylbenzyl ester, 3-allyl-a-ethynylbenzyl ester and 3,4-dichloro-a-ethynylbenzyl ester (compound 20 (A), which is explained below by a structural formula) are the only compounds which specifically disclosed which carry an aliphatic hydrocarbon group or halogen atoms on the benzene ring. Other known cyclopropanecarboxylic acid benzyl esters are the 25 compounds (B), (C), (D), (E), (F), (G), (H), (J), (K) and (L), which are given below will. However, the pesticidal activity of each of these compounds is unsatisfactory for practical use (see JP-OS 28103/71, JP-OS 28532/73), JP-OS 45674/80 and the publication regarding the 5th meeting by Nippon Noyaku Gakkai (Pesticide Science Society of Japan) Abstracts of Papere, No. 115).

Clx A C = CH Cl

, v (hereinafter referred to as compound (A))

Cl '^ * COOCH- ^ ^ C1

cl \ A çn qi / V \ coqch - ^^ Yç 1 (hereinafter referred to as compound (B))

Cl.

Cl / \ / \ COOCH2 (hereinafter referred to as compound (c))

Cl '

Cl / \ Z - ^ - COOCH ^ - ^ VnO ^, (hereinafter referred to as compound (D))

Cl \ A Br

0] _ \ COQC ^ - ^ S (hereinafter referred to as compound (E))

C = CH I

COOCH - ^ "" ^ (hereinafter referred to as compound (F))

C = CH Cl

COOCH - ^ "^ (hereinafter referred to as compound (G))

5

647224

ChCH COOCH - ^ - Cl

C = CH CH, | 3rd

COOCH-

v-i

"O

C = CH CF. 1

■ Ö

COOCH

ChCH COOCH - ^^ - CF.

(hereinafter referred to as compound (H))

(hereinafter referred to as compound (J))

(hereinafter referred to as compound (K))

(hereinafter referred to as compound (L))

The invention creates new pyrothroid compounds, namely substituted benzyl esters of 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acids of the general formula (I), by means of which pests which are effective in the cultivation of Rice occur, can be controlled, such as the brown plant hopper, the smaller brown plant hopper and the green rice leaf hopper, which are carriers of viruses that cause viral diseases of the rice plants. Furthermore, pesticides which contain these pyrethroid compounds as active substances and a method for controlling these pests which occur when rice is grown using these pyrethroid compounds fall within the scope of the invention.

The invention provides substituted benzyl esters of the general formula (I) indicated, which have a significantly more pronounced pesticidal activity against various pests than the previously known benzyl cyclopropanecarboxylates.

Furthermore, substituted benzyl esters of the general formula (I) are provided by the invention, which can be produced cheaper than the conventional pyrothroids, typically permethrin and fenvalerate.

It has been found that substituted benzyl esters of 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acids of the general formula (I) are very effective against plant hoppers, such as the brown plant hoppers and the smaller brown plant hoppers, such as is evident from the following examples 1 and 2. This finding is extremely surprising in view of the fact that the known pyrothroids, typically permethrin and fenvalerate, have in practice no suitable activity against plant hoppers.

The substituted benzyl esters of the general formula (I) exert an excellent pesticidal action not only against pests in rice cultivation which are carriers for viruses which cause viral diseases of rice plants, but are also effective against pests in agriculture, horticulture and forestry that damage rice fields, dry field crops, cotton, fruit trees, forest trees, etc. They also show excellent pesticidal effects on pests that occur during grain storage and on household pests. In particular, the substituted benzyl esters of the general formula (I) develop an excellent pesticidal activity against both the susceptible and the resistant strains of pests belonging to the following orders (the

20 compounds are active against such pests during all or part of their growth stages):

Order Thysanura, for example Ctenolepisma villosa Escherich;

25 order Collembola, for example Anurida trioculata Kinoshita Onychiurus pseudarmatus yagii Miyoshi, Smin-thurus viridis Linné, Bourletiella hortensis Fitch;

Order Orthoptera, for example Homorocoryphus jezoensis Matsumura et Shiraki, P. sapporensis Shiraki, Te-30 leogryllus emma Ohmachi et Matsuura, Loxoblemmus doe-nitzi Stein, Blattella germanica Linné, Gryllotalpa africana Palisot de Beauvois, Serviplaneta fuligin;

Order Isoptera, for example Coptotermes formosa-nus Shiraki;

35 order Mallophaga, for example Menopon gallinae Linné, Damalinia equi Denny, Trichodectes canis De Geer;

Order Anoplura, for example Haematopinus eury-sternus Nitzsch;

Order Thysanoptera, for example Thrips tabaci 40 Lindeman, Hercinothrips femoralis Reuter;

The order Hemiptera, for example Sogatella furcifera Horvath, Nilapervata lugens Stai, Laodelphax striatellus Fallén, Nephtettix cincticeps Uhler, Inazuma dorsalis Mot-schulsky, Scotinophara lurida Burmeister, Lagynotomus 45 elongatus Dallas, Leptocorixa corbett China, Nezara viridu-la Linnaeus, Rhopalosiphum padi Linnaeus, Macrosiphum akebiae Shinji, Rhopalosiphum maidis Fitch, Myzus persicae Sulzer, Aphis goosypii Glover, Aulacorthum solani Kaltenbach, Aphis glycines Matsumura, Chauliops fallax Scott, Riptor-50 tus clavatus Thunberg, Nezara antennata Scott, Piezodorusiusiusinnacivoruscorcorcoruscorcorcorcorcorcorcorcorcorcorcorcorcorcorus Okajima, Ceratovacuna lanigera Zehnner, Brevicoryne brassicae Linné, Lygus lucorum Meyer-Dür, Neotoxoptera formosana Takahashi, Unaspis yano-55 nensis Kuwana, Aonidiella aurantii Maskell, Viteus vitifolii Fitch, Erythroneaburauicalusanaanaoanobu , Macrosiphum ibar ae Matsumura, Stepha-nitis pyrioides Scott, Pinnaspis aspidistrae Signoret; 60 order Trichoptera, for example Oecetis nigropunc-tata Ulmer;

Order Diptera, for example Chlorops oryzae Matsumura, Agromyza oryzae Munakata, Hydrellia griseola Fallén, Hydrellia sasakii Yuasa et Ishitani, Meromyza salta-65 trix Linné, Sitodiplosis mosellana Géhin, Melanagromyza dolichostigzen DE soijagya Melia, Melia. Hylemya platu-ra Meigen, Hylemya antiqua Meigen, Phytobia cepae He-

647 224

ring, Lampetia equestris Fabricius, Musca domestica vicina, Culex pipiens;

Order Aphaniptera, for example Xenopsylla cheo-pis Rothschild, Pulex irritans Linné;

Order Hymenoptera, for example Dolerus hordei Rohwer, Takeuchiella pentagona Malaise;

Order Lepidoptera, for example Chilo suppressalis Walker, Tryporyza incertulas Walker, Sesamia inferens Walker, Pelopidas mathias oberthüri Evans, Cnaphalocrocis me-dinalis Guénée, Susumia exigua Butler, Naranga aenescens Moore, Leucania separate Walker, Ostrinia furiachellella, Ostrinia furvachellais som-mulentella Zeller, Aedia leucomelas Linné, Heliothis viripla-ca adaucta Butler, Pyrrhia umbra Hufnagel, Syllepte ruralis Scopli, Grapholitha glycinivorélla Matsumura, Matsumu-raeses phaseoli Matsumura, Etiellazinckenella Tropschonia Helpa, Guia Heliopolis , Eucosma schistaceana Snel-len, Mamestra brassicae Linné, Plodenia litura Fabricius, Agrotis fucosa Butler ,, Pieris rapae cruvivora Boisduval, Me-sographe forficalis Linné, Plutella maculipennis Curtis, Mar-garonia indica Saunders, Acrolepov allisella-niyll-semistella citrella Stainton, Papilio xuthus Linné, Carposina niponensis Walsingham, Grapholitha molesta Busck, Adoxophyes orana Fischer von Röslerstamm, Ly-mantria dispar Linné, Malacosoma eustria testacea Mot-schulsky, Stenoptilia vitis Sasaki, Stathmopoda flavofasciata Nagano, Hyphantria cunea Druryusidiidina, urula poreusidia rina;

Order Coleoptera, for example Oulema oryzae Ku-wayama, Henosepilachna vigintioctomaculata Motschulsky, H. vigintioctopunctata Fabricius, Atrachya menetriesi Faidermann, Paraluperodes nigrobilineatus Motschulsky, Col-poscelis signata Motschuloky, Eugnathus Arrowadupolomulululufolomululufulomululufulomusulupululofalulufolomululofulo schoolofa exanthematica Wiedemann, Hylobius cribripennis Matsumura et Kono, Li-stroderes obliquus Klug, Aulacophora femoralis Motschulsky, Anthonomus grandis Boh., Sitophilus zeamais Motschulsky, Lissorhoptrus oryzophilus, Rhizopertha dominica Fabricius, Callosobrinnochinuseaisoneanonochinnus-phinuse-chinasea-chinisea-pha-lisono-chinis-pha-liso-chinas-phobis-chinaso-learon-phos-lina-chinaso-learon-phi-liso-chinas-phobus

Order Acarina, e.g. Penthaleus major Du-gés, Tetranychus urticaeKoch, Tetranychus telarius Linné etc.

The substituted benzyl esters of the general formula (I) have a distinctly more pronounced pesticidal activity compared to the various pests mentioned above compared to the known cyclopropanecarboxylic acid benzyl esters mentioned above.

Of the substituted benzyl esters of the general formula (I), those compounds in which R represents a hydrogen atom or a halogen atom or a nitro, methyl-10 or trifluoromethyl group are preferred in view of the pesticidal activity, where the substituent R in the m- or p-position of the benzene ring. Substituted benzyl esters of 2,2-dimethyl-3- (2,2-dichlorovinylcyclopropanecarboxylic acid of the general formula (10

15

20th

ch ch,

Cl </ 3

c = ch r / \ / \ cl c — ch-c-0

/

. h o c5ch f ch

'Xh-

(I. ')

where R 'is in the m or p position of the benzene ring for a hydrogen atom or a nitro or tri-25 fluoromethyl group, a strong pesticidal activity.

Other characteristic features of the substituted benzyl esters of the general formula (I) are (1) a high vapor pressure and thus good volatility or vaporizability, (2) a quick action, (3) a high stability to light or oxidation, but what nonetheless, does not pose any environmental residue problems as in the case of organochlorine pesticides, and (5) very low toxicity to humans and animals. 35 Of the substituted benzyl esters of the general formula (I), the 4-chloro-a-ethynylbenzyl ester and the 4-trifluoromethyl-a-ethynylbenzyl ester have a trans-2,2-dimethyl-3- (2,2-dihalo-vinyl) cyclopropanecarboxylic acid at the same time low toxicity to fish. 40 Typical examples of substituted benzyl esters of the general formula (I) given above are those given below. These esters include geometric isomers due to various configurations in the acid moiety and optical isomers due to asymmetric carbon atoms in the acid and alcohol moieties.

Connection no.

Structural formula

Elemental analysis

Found (%) Calculated (%)

(1)

(2)

(3)

(4)

C: 63.10 H: 5.02

C: 55.36 H: 4.06

C: 44.52 H: 3.24

C: 60.77 H: 4.55

63.17 4.99

55.45 4.11

44.67 3.31

60.90 4.51

7

647 224

Compound No. Structural Formula Elemental Analysis

Found (%) Calculated (%)

(5) cl \ _ Av - (rCIL C: 55'52 55'45

Cl

'\ C00CH- ^ f ^ yN02 H: 4> 00 4.11

(6) BrN A CHCH C: 44.52 44.67

\ C00CH- ^ Q-N02 H: 3.29 3'31

(7) Cl \ _, / \ CF3 C: 55.30 55.26 C1 ^ ~ V \ COOCHhQ H: 3.96 3.86

m C1W / \ f0 * C: 55'34 55'26

C] / V A_C00CH- (3-CP3 H: 3'90 3'86

(9) • C: 45.17 45.03

H: 3.08 3.15

(10) C: 45.15 45.03

H: 3.21 3.15

(11) C: 60.26 60.34

H: 4.25 4.22

(12) C: 60.30 60.34

H: 4.27 4.22

(13) C: 57.07 57.09

H: 4.18 4.23

(14) Cl V C = CH F C: 59.90 59.84

/ = \ / \ I W, H: 4.48 4.43

Cl ^ AZ ^ COOCH-Zj

(15) C: 50.83 50.78

H: 3.81 3.76

(16) C: 45.57 45.46

H: 3.43 3.37

(17) / \ I W C: 45.79 45.72

H: 3.34 3.38

(18) Br. X C = CH F C: 47.41 47.47

H: 3.45 3.52

647 224

8th

Connection no.

Structural formula

Elemental analysis

Found (%) Calculated (%)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28)

(29)

Br Br

\>

■ COOCH

\,

■ Ö '

h c;

■ -Ö

ChCH F

': -Ö

ChCH CH3 • COOCH <5.

C: 41.48 H: 3.02

C: 62.85 H: 4.60

C: 66.28 H: 4.95

C: 55.42 H: 4.04

C: 57.13 H: 4.29

C: 64.08 H: 5.44

C: 64.06 H: 5.30

C: 50.82 H: 4.31

C: 50.68 H: 4.18

C: 71.13 H: 6.06

C: 70.98 H: 5.92

41.58 3.08

62.87 4.66

66.23 4.90

55.30 4.10

57.09 4.23

64.11 5.38

64.11 5.38

50.73 4.26

50.73 4.26

71.04 5.96

71.04 5.96

The substituted benzyl esters of the general formula (I) can easily be obtained by reacting a substituted benzyl alcohol of the formula

C = CH

HO-CH- <Qf

, R

(II)

55

60

ch3 / ch3

Xs \, C = CH

X

\ / \ C — C-COOH

(III)

wherein R has the meaning given in connection with the formula (I), or a functional derivative thereof with a carboxylic acid of the general formula

H H

wherein X has the meaning given in connection with the formula (I), or with a functional derivative thereof. The functional derivative of the substituted benzyl alcohol includes halides and aryl sulfonates. The functional derivative of the carboxylic acid consists, for example, of a lower alkyl ester, an acid halide, an acid anhydride, an alkali metal salt, an

9

647 224

Silver salt or a salt with an organic tertiary base. Typical embodiments of the manufacturing method given above are as follows:

Procedure a

Reaction of an alcohol with a carboxylic acid halide The substituted benzyl alcohol of the formula (II) is reacted with a carboxylic acid halide of the general formula ch

X

\ /

c = ch

0 ch

</ 3

C.

\ / \ c — c-cox '

1 1 hh in which X has the meaning given in connection with the formula (I) and X 'represents a halogen atom, preferably a carboxylic acid chloride, in an inert solvent, for example benzene, toluene, ether, hexane or chloroform, in the presence of a tertiary amine ( for example pyridine or triethylamine) in an amount of 1 to 3 molar equivalents per mole of the substituted benzyl alcohol at room temperature or with heating to obtain the desired substituted benzyl ester.

Procedure b

Reaction of an alcohol with a carboxylic anhydride The substituted benzyl alcohol of the formula (II) is mixed with a carboxylic anhydride of the general formula x.

\

: c = ch ch_ ch,

V

x

\ / \ c — c-co 1 I hh where X has the meaning given in connection with the general formula (I), in an inert solvent such as benzene, toluene, xylene, hexane or acetone, preferably in the presence of an acid, for example Sulfuric acid, p-toluenesulfonic acid, or a tertiary amine, for example pyridine or triethylamine, reacted at room temperature or with heating to obtain the desired substituted benzyl ester.

Procedure c

Reaction of an alcohol with a carboxylic acid The substituted benzyl alcohol of the formula (II) is mixed with the carboxylic acid of the general formula (III) in an inert solvent, such as benzene, toluene or xylene, in the presence of a dehydration / condensation agent, for example dicyclohexylcarbodiimide, 2 -Chlor-l-methylpyri-dinium iodide plus triethylamine, implemented at room temperature or i5 with heating to obtain the desired substituted benzyl ester.

Process d reaction of an alcohol with a low 2o alkyl carboxylate

The substituted benzyl alcohol of formula (II) is reacted with a lower alkyl ester of the carboxylic acid of general formula (III) in the presence of a suitable ester exchange catalyst, e.g. an alkali metal alkoxide, Na-25 triumhydride, a titanium compound such as tetramethyl titanate, and heating in an inert solvent such as Toluene or xylene, the low-boiling alcohol which is formed being removed from the reaction system by means of a fractionation column, is reacted to obtain the substituted ben-30-cyl ester sought.

Lost

Reaction of a halide or an aryl sulfonate, an alcohol with an alkali metal salt of a carboxylic acid 35 A halide or aryl sulfonate of the substituted benzyl alcohol of the formula (II) is reacted with an alkali metal salt of the carboxylic acid of the general formula (III) in a solvent such as dimethylformamide, benzene or Acetone, at room temperature or with heating to obtain 40 of the substituted benzyl ester sought.

The substituted benzyl alcohol of formula (II), which is the alcohol component, can be bright and cheaply prepared according to the following reaction scheme:

OHC- ^ ~ ^ (iv)

R

Ethinylierurxg where R has the meaning given in connection with the formula (I).

In this way, a substituted benzaldehyde of formula (IV) with sodium acetylide in liquid ammonia as a solvent or with ethynyl magnesium bromide or ethynyl lithium in tetrahydrofuran as a solvent to obtain the substituted benzyl alcohol of formula (II).

On the other hand, the 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acid, which is the acid component, or a known lower alkyl ester thereof, and the above-mentioned functional derivatives can be prepared in a conventional manner from a lower alkyl ester of the corresponding carboxylic acid will.

In practice, the compounds according to the invention can be used even without other constituents.

c = ch

HO-CH- ^ y (II)

r

For use as pesticides, however, it is generally expedient to formulate them with a carrier and to apply the formulation obtained, if appropriate after sufficient dilution. To prepare a formulation, the compound according to the invention is mixed with a carrier in the form of a liquid, a solid or a liquefied gas by conventional formulation methods, optionally using a surface-active agent which acts as an emulsifying and / or dispersing and / or foaming agent , wherein any desired formulation in the form of an emulsifiable concentrate, a wettable powder, dust, 65 a granular formulation, a micro-granular formulation, an oil preparation, an aerosol, a thermal fumigane, for example a smoking snake, an electric smoking mat, a misting formulation

647224

tion, a non-thermal fumigane or a bait, to name just a few examples. The formulation can be applied selectively depending on the intended purpose. If water is used as a carrier, then, for example, an organic solvent can be used as the cosolvent or auxiliary solvent.

Aromatic hydrocarbons, for example xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, for example chlorobenzene, chlorethylene, methylene or methylene chloride, aliphatic or alicyclic hydrocarbons, for example cyclohexane, paraffin (for example a mineral oil fraction), alcohols, for example butanol, glycols and ethers or esters thereof, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide or acetonitrile, and water are in most cases suitable liquid carriers.

Preferred solid carriers are powdered natural minerals, such as kaolin, clay, talc, lime, quartz, attapulgite, montmorrilonite and diatomaceous earth, and also powdered synthetic minerals, such as aluminum oxide and silicates.

The liquefied gas carrier consists of liquids which are gases at normal temperature and pressure, for example aerosol propellants, such as dichlorodifluoromethane and trichlorofluoromethane.

Preferred examples of emulsifiers and foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene aliphatic carboxylic acid esters, polyoxyethylene aliphatic alcohol ethers, for example alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolyzates. Preferred examples of dispersants are lignin sulfite waste and methyl cellulose.

Natural and synthetic macromolecules in the form of powders, granules or latices, for example rubber arabic, carboxymethyl cellulose, polyvinyl alcohol and polyvinyl acetate, can be used as binders in the formulations. Furthermore, inorganic pigments, for example iron oxide or titanium oxide, and organic dyes, for example alizarin dyes, azo dyes or metal phthalocyanine dyes, can be used as colorants in the formulations.

In contrast to conventional chrysanthemum acid esters, the compounds according to the invention are extremely stable to light, heat and oxidation. If necessary, however, under extreme oxidative conditions, a corresponding amount of an antioxidant and / or a UC absorber can be added as a stabilizing agent for obtaining a pesticidal agent which has a more stable activity. Such a stabilizing agent is, for example, a phenol derivative, such as 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, a bisphenol derivative, an arylamine, for example phenyl-a-naph -thylamine, phenyl-ß-naphthylamine or a phenetidine / acetone condensate, or a benzophenone compound.

A pesticidal agent according to the invention may contain not less than 1 x 10 "7% by weight of the substituted benzyl ester of the general formula (I) given above. However, in general the formulation contains 0.01 to 95% by weight and preferably 0.1 up to 90% by weight of the compound according to the invention.

The compounds according to the invention can either be in the form of a large number of formulations, as mentioned above, or in various application forms, which are obtained by processing such formulations in order to adapt them to the particular purpose

10th

be administered. In such application forms, the content of the compounds according to the invention can fluctuate within a very wide range. So can. . the concentration of the compound in an application form is 1 × 10-7 to 100% by weight and preferably 0.001 to 10% by weight.

The pesticidal compositions according to the invention can be applied by conventional methods in accordance with the respective form of application. The following synthesis examples, test examples, formulation examples and usage examples illustrate the invention without restricting it. In the formulation examples, all parts are based on weight. The compounds identified by the numbers correspond to the aforementioned substituted benzyl esters (1) to (29) of the general formula (I).

20 Synthesis example Î

2.28 g (0.01 mol) of cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride and 1.77 g (0.01 mol) of a-ethynyl are placed in 20 ml of dried benzene -3-nitrobenzyl alcohol dissolved. Then 1.58 g (0.02 mol) of pyridine 25 are added dropwise to this solution at room temperature. The mixture is stirred at room temperature overnight. The reaction mixture is then poured into water and extracted with diethyl ether and the extract is washed with dilute hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low-boiling fraction is distilled off under reduced pressure. The remaining viscous oil is purified by liquid chromatography with high efficiency on 35 silica gel (solvent system: n-hexane / isopropyl ether = 85/15 by volume), 3.30 g (90% yield) of a-ethynyl-3- nitrobenzyl-cis-2,2-dimethyl-3- (2,2-dîchlorvinyl) cyclopropanecarboxylate (compound (2), cis-isomer) can be obtained.

40 If 2.28 g (0.01 mol) of trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride are used instead of 0.01 mol of cis-2,2-dimethyl-3- (2, 2-dichlorvinyI) cyclopropancar-bonyl chloride and repeats the method described above, then 3.39 g (92% yield) of a-ethi-45nyl-3-nitrobenzyl-trans-2,2-dimethyl-3- (2 , 2-dichlorovinyl) cy-clopropanecarboxylate (compound (2), trans-isomer).

The NMR spectra of the cis isomer and the transisomer of the compound (2) obtained in the manner described above are as follows: see NMR spectrum (90 MHz) 5hc ^:

cis isomer:

1.13-1.26 (m, 6H); 1.79-2.21 (m, 2H); 2.67-2.72 (m, 1H); 6.13, 6.17 (each d, 1H); 6.45-6.53 (m, 1H); 7.68 (d. 2H); 8.22 (d, 2H)

55 trans isomer:

1.10-1.28 (m, 6H); 1.62,1.64 (each d, 1H); 2.10-2.33 (m, 1H); 2.67-2.76 (m, 1H); 5.58, 5.60 (each d, 1H); 6.48-6.57 (m, 1H); 7.43-8.44) m, 4H)

60

Synthesis Examples 2 to 6 Following the procedure described in Synthesis Example 1, the cis isomer and the trans isomer of the compound (3), the cis isomer and the trans isomer of the compound (5) and the cis isomer of the compound (6) received. The yield and the NMR spectrum of each product are shown in Table I.

11

Table I

647 224

Synthesis example

product

Yield (%)

MMR spectrum (90 MHz) 8hms13

Compound (3) (cis isomer)

Compound (3) (trans isomer)

Compound (5) (cis isomer)

Compound (6) (cis isomer)

88

91

87

Compound (5) (trans isomer) 90

90

1.13-1.27 (m, 6H), 1.79-2.14 (m, 2H), 2.67-2.74 (m, 1H),

6.44-6.53 (m, 1H), 6.59-6.77 (m, 1H), 7.43-8.44 (m, 4H), 1.13-1.28 (m, 6H); 1.64-1.66 (each d, 1H) -2.02-2.30 (m, IH); 2.67-2.77 (m, IH); 6.13, 6.14 (each d, IH); 6.47-6.57 (m, IH); 7.43-8.45 (m, 4H)

1.13-1.26 (m, 6H); 1.79-2.21 (m, 2H); 2.67-2.72 (m, 1H); 6.13.6.17 (d, 1H);

6.45-6.53 (m, 1H);

7.68 (d. 2H); 8.22 (d, 2H) 1.10-1.27 (m, 6H); 1.62 1.64 (each d, 1H); 2.08-2.36 (m, IH); 2.67-2.74 (m, 1H); 5,57,5,59 (each d, IH); 6.47-6.54 (m, 1H);

7.67 (d. 2H); 8.19 (d. 2H)

1.14-1.27 (m, 6H), 1.77-2.12 (m, 2H), 2.66-2.72 (m, 1H), 6.43-6.52 (m, 1H), 6.58-6.76 (m, 1H),

7.68 (d, 2H), 8.21 (d, 2H)

Synthesis example 7

2.28 g (0.01 mol) of cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride and 2.00 g (0.01 mol) of a-ethynyl are placed in 200 ml of dried benzene -3-trifluoromethyl-benzyl alcohol dissolved. Then 1.58 g (0.02 mol) of pyridine are added dropwise to this solution at room temperature. The mixture is stirred at room temperature overnight. The reaction mixture is then poured into water and extracted with diethyl ether and the extract is washed with dilute hydrochloric acid and a saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low-boiling fraction is distilled under reduced pressure. The remaining viscous oil is obtained by liquid chromatography with high efficiency on silica gel (solvent system: n-hexane / isopropyl ether = 85/15, by volume) to obtain 3.53 g (90% yield) of a-ethynyl-3-trifluor -methylbenzyl-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropancarboxylate (compound (7), cis-isomer).

If 2.28 g (0.01 mol) of trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride are used instead of 0.01 mol of cis-2,2-dimethyl-3- (2.2 dichlorovinylcyclopropanecarbonyl chloride and repeats the method described above, then 3.60 g (92% yield) of α-ethynyl-3-trifluoromethylbenzyl-trans-2,2-dimethyl-3- (2,2-di-

chlorovinyl) cyclopropane carboxylate (Compound (7), trans isomer).

45 The NMR spectra for the cis isomer and the trans isomer of the compound (7) obtained in the above-described manner are as follows: NMR spectrum (90 MHz)

cis isomer:

so 1.10-1.27 (m, 6H); 1.76-2.15 (m, 2H); 2.60-2.68 (m, 1H); 6.17.6.20 (each d, 1H); 6.40-6.52 (m, 1H); 7.36-7.84 (m, 4H)

trans isomer:

1.08-1.29 (m, 6H); 1.61,1.59 (each d, 1H); 2.11-2.37

55 (m, 1H); 2.60-2.70 (m, 1H); 5.56, 5.58 (each d, 1H); 6.46-6.55 (m, 1H); 7.34-7.86 (m, 4H)

A 40:69 mixture of the cis isomer and the transisomer of compound (7) has a boiling point of 157 ° C / 1.4 mmHg.

60

Synthesis Examples 8 to 13 According to the method described in Synthesis Example 7, the cis isomer and the trans isomer of the compound (8), the trans isomer of the compound (9), the cis-

65 isomers of compound (10) and the cis isomer and the trans isomer of compound (1) were obtained. The yield and the NMR spectrum of each product are shown in Table II.

647224

12

Table II

Synthesis product example

Yield (%)

MMR spectrum (90 MHz) 8§ ^

8th

Compound (8) (cis isomer)

10th

11

12

Compound (1) (cis isomer)

13

92

Compound (8) (trans isomer) 94

Compound (9) (trans isomer) 90

Compound (10) (cis isomer) 92

92

Compound (1) (trans isomer) 91

1.10-1.27 (m, 6H); 1.74-2.15 (m, 2H);

2.58-2.63 (m, 1H); 6.14, 6.18 each d, 1H) 6.40-6.48 (m, 1H); 7.62 (s, 4H);

1.07-1.27 (m, 6H); 1.58.1.60 (each d, 1H); 2.10-2.33 (m, 1H);

2.59-2.67 (m, 1H); 5,54,5,56 (each d, 1H); 6.44-6.51 (m, 1H);

7.62 (s, 4H)

1.09-1.27 (m, 6H); 1.60, 1.62 (each d, 1H);

2.03-2.26 (m, 1H); 2.58-2.67 (m, 1H); 6.08, 6.10 (each d, 1H); 6.43-6.52 (m, 1H);

7.34-7.83 (m, 4H) 1.12-1.27 (m, 6H); 1.74-2.08 (m, 2H); 2.58-2.65 (m, 1H); 6.40-6.53 <m, 1H);

6.60-6.79 (m, 1H); 7.64 (s, 4H)

1.08-1.21 (M, 6H); 1.70-2.11 (m, 2H); 2.51-2.59 (m, IH); 6.18, 6.20 (each d, 1H);

6.35-6.45 (m, 1H); 7.23-7.56 (m, 5H)

1.04-1.26 (m, 6H); 1.54.1.56 (each d, 1H); 2.08-2.33 <m, 1H); 2.54-2.61 (m, 1H); 5.51, 5.53 (each d, 1H); 6.39-6.47 (m, 1H); 7.23-7.59 (m, 5H)

Synthesis example 14

2.28 g (0.01 mol) of trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarbonyl chloride and 1.67 g (0.01 mol) of 3-chlorine are added to 20 ml of dried benzene -A-ethynyl-benzyl alcohol dissolved. Then 1.58 g (0.02 mol) of pyridine are added dropwise to the solution at room temperature. The mixture is stirred at room temperature overnight. The reaction mixture is then poured into water and extracted with diethyl ether and the extract is washed with dilute hydrochloric acid and saturated aqueous sodium chloride solution. The organic layer is dried over anhydrous magnesium sulfate and the low-boiling fraction is submerged The viscous oil obtained is purified by liquid chromatography with high efficiency on silica gel (solvent system: N-hexane / isopropyl ether = 90/10, by volume) to obtain 3.30 g (92% yield) of 3-chlorine -a-ethynylbenzyl-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate (compound (13), trans-isomer purified.

If 2.28 g (0.01 mol) of cis-2,2-dimethyl-3- (2,2-di-chlorovinyl) cyclopropanecarbonyl chloride are replaced in place of 0.01 mol of trans-2,2-dimethyl-3- (2nd , 2-dichlorovinyl) cyclopropancar

bonyl chloride and repeats the method described above, then 3.21 g (90% yield) of 3-chloro-a-ethinylbenzyl-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate ( Compound (13), cis isomer). so The NMR spectra for the cis isomer and the trans isomer of the compound (13) obtained in the manner described above are as follows: NMR spectrum (90 MHz) 8 ^ '3:

cis isomer *

55 1.10-1.24 (m, 6H); 1.74-2.13 (m, 2H); 2.57-2.64 (m, 1H); 6.17, 6.19 (each d, 1H); 6.32-6.40 (m, 1H); 7.19-7.54 (m, 4H)

trans isomer:

1.08-1.28 (m, 6H); 1.58.1.60 (each d, 1H); 2.09-2.32 60 (m, 1H); 2.57-2.66) m, 1H); 5.58, 5.60 (each d, 1H); 6.35-6.42 (m, 1H); 7.20-7.56) m, 4H)

A 40:60 mixture of the cis isomer and the transisomer of compound (13) has a boiling point of 175 ° C / 1.3 mmHg.

65

Synthesis Examples 15 to 29 According to the manner described in Synthesis Example 14, the cis isomer and the trans isomer of the compound

tion (14), the cis isomer and the trans isomer of the compound (15), the 50:50 mixture of the cis isomer and the trans isomer of the compound (16), the trans isomer of the compound (18 ), the trans isomer of compound (19), the cis isomer and the trans isomer of compound (23),

647 224

the cis isomer and the trans isomer of the compound (24), the cis isomer and the trans isomer of the compound (25), the trans isomer of the compound (26) and the trans isomer of the compound (27). The yield and ass NMR spectrum of each product are shown in Table III.

13

Table III

Synthesis example

product

Yield (%)

MMR spectrum (90 MHz) 5hms'3

15

Compound (14) (cis isomer) 93

16

Compound (14) (trans isomer) 92

17th

Compound (15) {cis isomer) 90

18th

Compound (15) (trans isomer) 91

19th

20th

Compound (16) (50:50 mixture 88 of the cis isomer and the transisomer)

Compound (18) (trans isomer) 90

21st

Compound (19) (trans isomer) 90

22

Compound (23) (cis isomer) 92

1.10-1.23 (m, 6H);

1.74-2.13 (m, 2H);

2.57-2.63 (m, 1H);

6.16.6.18 (each d, 1H);

6.33-6.44 (m, 1H);

6.86-7.45 (m, 4H)

1.07-1.27 (m, 6H);

1.58.1.60 (each d, 1H);

2.08-2.33 (m, 1H);

2.58-2.65 (m, 1H);

5.53, 5.55 (each d, 1H); 6.38-6.46 (m, 1H);

6.85-7.45 (m, 4H)

1.10-1.24 (m, 6H);

1.74-2.13 (m, 2H);

2.58-2.65 (m, 1H);

6,18,6,20 q each d, 1H); 6.30, 6.41 (m, 1H);

7.09-7.70 (m, 4H)

1.03-1.26 (m, 6H);

1.55, 1.57 (each d, 1H);

2.06-2.30 (m, 1H);

2.58-2.67 (m, 1H);

5,52,5,54 (each d, 1H);

6.34-6.43 (m, 1H);

7.03-7.69 (m, 4H)

1.10-1.27 (m, 6H);

1.50-2.34 (m, 2H);

2.60-2.64 (m, 1H);

5.53, 5.55, 6, 18, 6.20 (each d, 1H); 6.28-6.40 (m, 1H); 6.96-8.04 (m, 4H)

1.08-1.28 (m, 6H);

1.60 1.62 (each d, 1H); 2.01-2.25 (m, 1H);

2.57-2.64 (m, 1H);

6.09.6.11 (each d, 1H); 6.37-6.46 (m, 1H);

6.85-7.46 (m, 4H)

1.07-1.27 (m, 6H);

1.58, 1.60 (each d, 1H); 2.00-2.24 (m, 1H);

2.56-2.63 (m, 1H);

6.10 (d. 1H);

6.34-6.43 (m, 1H);

7.07-7.69 (m, 4H)

1.08-1.24 (m, 6H);

1.72-2.12 (m, 2H);

2.54-2.62 (m, 1H);

6.15, 6.18 each d, 1H); 6.32-6.46 (m, 1H);

7.19-7.52 (m, 4H)

647 224

14

Table III (continued)

Synthesis product example

Yield (%)

MMR spectrum (90 MHz) 8hms'3

23

Compound (23) (trans isomer) 94

24th

Compound (24 (cis isomer)

91

25th

Compound (24) (trans isomer) 93

26

Compound (25) (cis isomer) 92

27th

Compound (25) (trans isomer) 94

28

Compound (26) (trans isomer) 89

29

Compound (27) (trans isomer) 90

1.07-1.28 (m, 6H); 1.56.1.58 (each d, 1H); 2.07-2.32 (m, 1H); 2.56-2.63 (m, 1H); 5,53,5,55 (d, 1H each); 6.37-6.45 (m, 1H); 7.21-7.53 (m, 4H) 1.10-1.24 (m, 6H); 1.74-2.10 (m, 2H); 2.33 (s, 3H);

2.54-2.60 (m, 1H); 6,20,6,22 each d, 1H); 6.33-6.40 (m, 1H);

7.04-7.34 (m, 4H)

1.05-1.26 (m, 6H); 1.56, 1.58 (each d, 1H); 2.07-2.35.2.32 (m, s, 4H);

2.53-2.60 (m, 1H); 5.52, 5.54 each d, 1H); 6.37-6.43 (m, 1H); 7.03-7.34 (m, 4H) 1.10-1.23 (m, 6H); 1.72-2.10 (m, 2H);

2.30 (s, 3H);

2.52-2.58 (m, 1H); 6.19.6.21 (each d, 1H) 6.33-6.40 (m, 1H) -

7.12 (d, 2H); 7.38 (d. 2H)

1.03-1.25 (m, 6H); 1.55, 1.57 (each d, 1H); 2.07-2.32 2.30 (m, s, 4H); 2.52-2.59 (m, 1H); 5.51, 5.53 each d, 1H); 6.37-6.43 (m, 1H);

7.13 (d. 2H); 7.39 (d. 2H)

1.06-1.27 (m, 6H); 1.59.1.61 each d, 1H); 2.02-2.36.2.32 (m, s, 4H);

2.54-2.62 (m, 1H); 6.08, 6.10 (each d, 1H); 6.37-6.44 (m, 1H);

7.04-7.37 (m, 4H) 1.06-1.27 (m, 6H); 1.58.1.60 (each d, 1H); 2.00-2.34.2.30 (m, s, 4H); 2.54-2.62 (m, 1H);

6.07, 6.09 (each d, 1H); 6.37-6.44 (m, 1H);

7.14 (d. 2H); 7.39 (d. 2H)

Test Example 1 Mortality test with domestic flies (Musca domestica) by the surface application method Each of the compounds according to the invention and the comparison compounds (Table IV) are precisely weighed out and dissolved in acetone to produce a solution with a predetermined concentration. Female adult house flies (Musca domestica) are anesthetized with ether, followed by 1 μl of the above solution

60 is micro-pipetted onto the back part at the chest level of each insect. The insects are then placed in a tall bowl with food. The bowl is covered with a wire mesh lid and kept at a temperature of 25 ° C. The test insects are used in 65 groups of 30 animals each. After 24 hours, the insects are examined for the death trap and the percentage of mortality is calculated. The results are shown in Table IV.

15

647 224

Table IV

Test connection

% Mortality

1 ng / female animal

0.1 ng female. animal

Connection (2) Connection (3) Connection (5) Connection (7) Connection (9) Connection (23)

Connection (A) Connection (B) Connection (D) Connection (E) Connection (G) Connection (H) Connection (K) Connection (L)

Cl Cl

Cl Cl

Cl Cl

.CF.

■ COOCH

OK

100 100 100 100 100 100

100 67 63 53 20 20 10 53

47

87 70 83 80 60 73

0 0 0 0 0 0 0 0

> = Ä

> = \ Ä.

CN

■ C00CII - <(3rd

CN

C00CH- {3 ~ N0;

C = CH

0 0

C00CH- {3-Br 10 0

Phenothrin allethrin

100 57

30 0

Test Example 2 Mortality test with Prodenia litura Fabricius by the surface application method Each of the compounds according to the invention and the comparison compound (Table V) are precisely weighed out and dissolved in acetone to prepare a solution with a predetermined concentration. Using a microsyringe, 0.5 μl of the above solution is dripped onto the abdominal part at the breast level of Prodenia litura Fabri-cius larvae in the third form. The larvae are then placed together with food on a filter paper in a bowl with a diameter of 9 cm and kept at a temperature of 25 ° C. The test larvae are used in groups of 20 animals each. After 24 hours, the insects are examined for death cases and the percentage of mortality is calculated. The results are shown in Table V.

Compound (13) Compound (16) Compound (A) Compound (C) s Compound (D) Compound (G) Compound (K) Compound (L)

100 100 80 0

40 20 65 30

65 70 20 0 0 0 0 0

10 Cl Cl

Cl

15 cl

> = \ X

CN I

COOCH COOCII

<5.

2-ÖC

30th

C = CH T

COOCH- ^ 3

C = CH I

45

• COOCH -Q-Br phenothrin 100

25th

25th

Formulation Example 1 30 parts of each of the compounds (1) to (29) are prepared. To each is added 50 parts of xylene and 20 parts of a 30 anionic surfactant (New Kargen ST- '50, an alkyl aryl sulfonate manufactured by Takemoto Oil & Fat Co., Ltd.). Each mixture is stirred well to produce emulsifiable 30% concentrates of the respective active ingredients.

35

Formulation Example 2 30 parts of each of the compounds (1) to (29) are prepared. To each of these compounds are added 50 parts of xylene and 20 parts of a 40 nonionic surfactant (Sorpol SM-200, a mixture of about 45% by weight of an alkylarylsulfonate as an anionic surfactant and about 55% by weight of a nonionic surfactant Mixture of long and short chain alkylaryl ethers of polyoxyethyl 45 lenglycol and a polyoxyethylene ester of a fatty acid, manufactured by Toho Chemical Co., Ltd.). The mixture is stirred well to produce an emulsifiable 30% concentrate of the respective active ingredient.

see formulation example 3

0.5 part of each of the compounds (1) to (29) are dissolved in 20 parts of acetone, followed by the addition of 99.5 parts of clay. After thorough stirring, the acetone is evaporated from each mixture and the residue is further stirred in a comminution device to produce a 0.5% dust of the respective active ingredient.

Table V

Test connection

Formulation Example 4 60 0.2 parts of each of the compounds (1) to (29) are dissolved in kerosene with stirring to prepare 100 parts. The above method provides oil preparations lug / larva 0, lng / larva of the respective active ingredients.

% Mortality

Connection (2) Connection (3) Connection (7) Connection (9)

100 100 100 100

65 75 95 80

65 Formulation example 5

To 20 parts of each of the compounds (1) to (29) are added 5 parts of a nonionic surfactant (Sorpol SM-200 as mentioned above)

647 224

16

ben. After thorough mixing, 75 parts of talc are added to each mixture, followed by stirring well in a grinder. The above method provides wettable powders of the respective active ingredients.

Example of use 1

A 30% emulsifiable concentrate of each test compound made by the method described in Formulation Example 1 is diluted with water to prepare a test solution at a concentration of 40 ppm. Rice plants are sprayed 4 weeks after sowing (grown in a 6 cm diameter pot, 7 seedlings) with 7 ml per pot of the test solution. After drying in air, a glass cylinder is placed on the pot. Then 20 adult brown plant hoppers (Nilaparvata lugens Stài) are placed in the cylinder and the cylinder is covered with a gauze. The pot is kept in a chamber at a constant temperature of 25 ° C. After 24 hours, the insects are examined for death cases and the mortality is determined. The insecticidal activity of each compound is determined according to the following criteria. The results are summarized in Table VI.

Criteria for the investigation:

A - Mortality: not less than 90%;

B - mortality: less than 90% but not less than 60%;

C - mortality: less than 60% but not less than 30%;

D - mortality not more than 30%.

Table VI

Insecticidal activity

Test connection

In;

Connection {1)

A

Connection (2)

A

Connection (7)

A

Connection (8)

A

Connection (9)

B

Connection (13)

A

Connection (14)

A

Connection (18)

A

Connection (23)

A

Connection (24)

A

Connection (25)

B

Connection (A)

C.

Connection (B)

D

Compound (C)

D

Connection (D)

D

Connection (E)

D

Connection (F)

D

Connection (G)

C.

Connection (H)

C.

Connection (J)

D

Connection (K)

D

Connection (L)

D

CHCH COOCH (

C = CH F

1 _rC

cooch cooch

ChCH Br I

<s

D

D

D

c = ch • cooch-q-ch,

Phenothrin permethrin fenvalerate v cn

D

D C D

hf

(AC-222705)

15

Cl Cl

CN

jQr ^ coo / Sr ^ rO

20th

KC00 '^ kj

5 z (nk-s116)

D

chjnhcoo

25th

-P

3chc, (bpmc)

ch3chc2h5

O

30th

(ch3CH2ch20) 2p-0- ^ 3 ~ scht c

(Propaphos)

Use Example 2 A 30% emulsifiable concentrate of each 35 test compound, prepared by the method described in Formulation Example 1, is diluted with water to make a test dilution at a concentration of 40 ppm. Rice plants are sprayed 4 weeks after sowing (grown in a pot with a diameter of 40 6 cm, 7 seedlings) with 7 ml per pot of the test solution. After allowing to air dry, a glass cylinder is placed on the pot. Then 20 adult smaller brown plant hoppers (Laodelphax stria-tellus Fallén) are placed in the cylinder and cylinder 45 is covered with a gauze. The pot is kept in a chamber at a constant temperature of 25 ° C. After 24 hours, the insects are examined for death cases and the mortality is determined. The insecticidal activity of each compound is examined according to the criteria described in Use Example 1-50. The results are shown in Table VII.

Table VII

55

Test connection

Insecticidal activity

60

Connection (7) Connection (8) Connection (9) Connection (13) Connection (15) Connection (18) Connection (23) Connection (24)

65 Compound (A) Compound (H) Compound (K) Fenvalerat

A A A A A A A A

B

C C C

17th

647 224

Use Example 3 A 30% emulsifiable concentrate of each test compound, prepared by the method described in Formulation Example 1, is diluted with water to prepare a test compound at a concentration of 40 ppm. Rice plants are sprayed 4 weeks after sowing (grown in a 6 cm diameter pot, 7 seedlings) with 7 ml per pot of the test solution. After allowing to air dry, a glass cylinder is placed on the pot. Then 20 adult green rice leaf hoppers (Nephotettix cincticeps Uhler) are placed in the cylinder and the cylinder is covered with a gauze. The pot is kept in a chamber at a constant temperature of 25 ° C. After 24 hours, the insects are examined for deaths and mortality is determined. The insecticidal activity of each compound is determined according to the criteria described in use example 1. The results are shown in Table VIII.

Table VIII

Test connection

Insecticidal activity

Connection (1) Connection (2) Connection (7) Connection (8) Connection (9) Connection (13) Connection (14) Connection (15) Connection (16) Connection (18) Connection (19) Connection (23) Connection ( 24) Connection (25) Connection (A) Connection (F) Connection (G) Connection (K) Connection (L)

XÄ

COOCH

C = CH F l

■ Ö

ChCH Br COOCH-

<-Ö

A

A

A

A

A

A-

A

A

A

A

A

A

A

A

C.

D

C.

C.

D

D

D

C = CH I

COOCH

■ O

CH.

Example of Use 4 A 30% emulsifiable concentrate of each test compound, prepared by the method of Formulation Example 2, is diluted with water to a concentration of 20 ppm. Cabbage leaves are immersed in the dilution, air dried, and placed in a plastic container approximately 6 cm in diameter and approximately 60 cm3 in volume. Then 10 diamond butterfly larvae (3rd to 4th stage) are added to the container. The container is kept in a chamber with a constant temperature of 25 ° C. After 2 days, the larvae are examined for deaths and mortality is determined. Two containers are used for each test connection. The results are shown in Table IX.

Table IX

Test connection

Mortality (%)

io connection (1) connection (2) connection (7) connection (8) connection (13) 15 connection (14) connection (15)

Permethrin

95 100 100 100 95 100 90

90

20th

Use Example 5 A 30% emulsifiable concentrate of each test compound, prepared by the method of Formulation Example 2, is diluted with water to a concentration of 20 ppm. Tea plant leaves are immersed in the solution and air dried, and then placed in a plastic container approximately 6 cm in diameter and approximately 60 cm3 in volume. Then 10 smaller tea wrapper larvae (3rd to 4th stage) are added to the container. The container is kept in a chamber with a constant temperature of 25 ° C 30. After 2 days, the larvae are examined for deaths. Two containers are used for each test connection. The results are shown in Table X.

Table X

35

Test connection

Mortality (%)

Connection (7) Connection (8)

1 permethrin fenvalerate

100 90

85 65

Use Example 6 45 A 30% emulsifiable concentrate of each test compound is prepared according to the method described in Formulation Example 2 and diluted with water to a concentration of 20 ppm. Cabbage leaves are immersed in the dilution, air dried, and placed in a plastic container approximately 6 cm in diameter and approximately 60 cm3 in volume. Then 10 Plodenia litura Fabricius larvae in the third form are placed in the container. The container is kept in a chamber with a constant temperature of 25 ° C. After 2 days, the larvae are examined for deaths and mortality is determined. Two containers are used for each test connection. The results obtained are shown in Table XI.

60

Table XI

Test connection

Mortality (%)

65

Connection (7) Connection (8)

Permethrin fenvalerate

90 100

90 95

18th

647 224

Test Example 3 Fish Toxicity Test with Carp (Cyprinus carpio L)

An acetone solution of a test compound selected from the group consisting of the trans isomer of compound (8), the trans isomer of compound (23), permethrin and fenvalerate, and a nonionic surfactant (Tween-20: polyethylene sorbitan monolaurate) produced. The above-mentioned acetone solution is added to 501 waters (30 cm deep) in a glass vessel. The mixture is stirred thoroughly to prepare an aqueous solution containing the test compound at a predetermined concentration. This is used as test water. Five carp (Cyprinus carpio L) with a body weight of approximately 6 g and a body length of approximately 6 cm are placed in each test water, which is kept at 21 + 1 ° C. After 48 hours, the test fish are examined for deaths. The TLm (mean tolerance limit, ppm) is determined. The test water is moderately aerated. The results are shown in Ta-5 belle XH.

Table XII

Test compound TLm (ppm)

Connection (8)> 1

Connection (23)> 1

Permethrin 0.015

i5 fenvalerate 0.0032

20th

25th

30th

35

40

45

55

65

Claims (34)

647 224 2nd PATENT CLAIMS 1. Substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acid of the general formula X x ch3 CH ^ \ / ^ ■ C / C = CH C = CH \ / \; / CH " C CH-C-0 H / H 0 R wherein each X is a halogen atom and R represents a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group. 2. Ester according to claim 1, characterized in that it has the general formula X X ch3 ch, \ / \ c c = ch / n / N / \ / c ch-c-0 / n H O CHCH l CH corresponds, where each X represents a halogen atom. 3. Ester according to claim 1, characterized in that it has the general formula 6. Ester according to claim 4, characterized in that it consists of a-ethynyl-3-nitro- or 4-nitrobenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate. 7. Ester according to claim 4, characterized in that it consists of a-ethynyl-3-trifluoromethyl or 4-trifluoromethylbene. zyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane carboxylate. 8. Ester according to claim 1, characterized in that it consists of a-ethynyl-4-chlorobenzyl-trans-2,2-dimethyl-3- (2,2- lo dihalogenvinyl) cyclopropanecarboxylate. 9. Ester according to claim 1, characterized in that it consists of a-ethyl-4-trifluoromethylbenzyl-trans-2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropane carboxylate. 10. Pesticidal agent, characterized in that it (i) 15 as an active ingredient is a substituted benzyl ester of a 2,2-di- methyl-3- (2,2-dihalovinyl) cyclopropanecarboxylic acid of the general formula 20th 25th X X CK CH, \ / > c \ / C \ C CH-C-0 / tl H O CsCH I. CH R wherein each X is a halogen atom and R represents a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group, and (ii) contains a support therefor. 11. Agent according to claim 10, characterized in that the active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acid of the general formula 35 x X CH. CH., </ > C \ / \ C CH-C-0 / U H O CsCH r CH R " 40 X C = CH X CH, CH- \ / C. \ / \ C CH-C-0 / U H O CsCH f CH 45 where X is a halogen atom and R "represents a halogen atom or a nitro, methyl or trifluoromethyl group, and the substituent R" is in the m or p position of the benzene ring. 4. Ester according to claim 1, characterized in that it is of the general formula, wherein each X is a halogen atom. 12. Composition according to claim 10, characterized in that the active ingredient is a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalogenvinyl) cyclopropanecarboxylic acid of the general formula Cl he C = CH \ CH, </ C. / \ CH. CHCH I CH H / CH-C-0 II O x> - 55 ch3, ch3 xn \ / C = CH X \ / \ C CH-C-0 / H ChCH CH / H R " where R 'represents a hydrogen atom or a nitro or trifluoromethyl group in the m or p position of the benzene ring. 5. Ester according to claim 4, characterized in that it consists of a-ethynylbenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate. in which each X represents a halogen atom and R "represents a halogen atom or a nitro, methyl or trifluoro-65 methyl group, and the substituent R" is in the m or p position of the benzene ring. 13. Composition according to claim 10, characterized in that the active ingredient is a substituted benzyl ester of a 2,2- 3rd 647224 Dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid of the general formula CH3 .CH3 Ck \ C = CH / v / V / \ Cl \ '✓ C CH-C-0 / II - H 0 CHCH 1 CH T> ' X X CH CH- \ /) C = CH \ C = CH 1 CH / H CH-C-0 II O Ì3: r x. C = CH X CH, CH, A / C. / \ C CH-C-0 / ri H O C = CH I CH corresponds, where each X represents a halogen atom. 24. The method according to claim 22, characterized in that the ester of the general formula used X 10th X CH, CH, \ / > CH. / ° \ is wherein R 'represents a hydrogen atom or a nitro or trifluoromethyl group in the m or p position of the benzene ring. 14. Composition according to claim 13, characterized in that the ester consists of a-ethynylbenzyl-2,2-dimethyl-3- (2,2-di-chlorovinyl) cyclopropanecarboxylate. 15. Composition according to claim 13, characterized in that the ester consists of a-ethynyl-3-nitro or 4-nitrobenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane carboxylate. 16. Composition according to claim 13, characterized in that the ester consists of a-ethynyl-3-trifluoromethyl- or 4-tri-fluoromethylbenzyl-2,2-dimethyl-3- (2,2-dichloro vinyl) cyclo-propane carboxylate. 17. Composition according to claim 10, characterized in that the active ingredient consists of a-ethynyl-4-chlorobenzyl-trans-2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropanecarboxylate. 18. Composition according to claim 10, characterized in that the active ingredient consists of a-ethynyl-4-trifluoromethylbenzyl-trans-2,2-dimethyl-3- (2,2-dihalo-vinyl) cyclopropane carboxylate. 19. Agent according to one of claims 10 to 18, characterized in that the content of the active ingredient is not less than 1 x 10-7 wt .-%, based on the total weight of the agent. 20. Composition according to claim 19, characterized in that the content of the active ingredient is 0.01 to 95 wt .-%. 21. Composition according to claim 20, characterized in that the content of the active ingredient is 0.1 to 90 wt .-%. 22. A method for combating pests, characterized in that in the area in which the pests live, an effective amount of a substituted benzyl ester of a 2,2-dimethyl-3- (2,2-dihalogenovinyl) cyclopropane carboxylic acid of the general formula \ ( / H C = CH I CH CH-C-0 II O R " 15 corresponds to, in each of which X stands for a halogen atom and R "represents a halogen atom or a nitro, methyl or trifluoromethyl group, the substituent R" being in the m or p position of the benzene ring. 25. The method according to claim 22, characterized in that the ester of the general formula 25th 30th Cl Cl CH3 xCH3 \ / / C = CIl / C \ / H CH-C-0 II O C = CH I CH R1 is applied, wherein each X is a halogen atom and R represents a hydrogen or halogen atom or a nitro, methyl or trifluoromethyl group. 23. The method according to claim 22, characterized in that the ester corresponds to the general formula in which R 'represents a hydrogen atom or a nitro or trifluoromethyl group in the m or p position 35 of the benzene ring. 26. The method according to claim 25, characterized in that the ester used consists of a-ethynylbenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate. 27. The method according to claim 25, characterized in that the ester used consists of a-ethynyl-3-nitro- or 4-nitrobenzyl-2,2-dimethyl-3- (2,2-diehIorvinyl) cyclopropane carboxylate. 28. The method according to claim 25, characterized in that the ester used is composed of a-ethynyl-3-triftuorme- there is thyl- or 4-trifluoromethylbenzyl-2,2-dimethyl-3- (2,2-di-chlorovinyl) cyclopropanecarboxylate. 29. The method according to claim 22, characterized in that the ester used from a-ethynyl-4-chlorobenzyl trans-2,2-dimethyl-3- (2,2-dihalogenovinyl) cyclopropanecarboxoxide exists. 30. The method according to claim 22, characterized in that the ester used from a-ethynyl-4-trifluorme- 55 thyl-benzyltrans-2,2-dimethyl-3- (2,2-dihalovinyl) cyclo-propane carboxylate. 31. The method according to any one of claims 22 to 30, characterized in that the ester in a concentration 6o of 1 x 10 "7 to 100 wt .-% is applied. 32. The method according to claim 31, characterized in that the order quantity is 0.001 to 10% by weight. 33. The method according to any one of claims 22 to 32, characterized in that the ester is applied to a paddy field. 647 224