DD292446A5 - PROCESS FOR THE PREPARATION OF 2-HALOGENIC CYCLOPROPYLETHANE DERIVATIVES AND THEIR USE AS SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to processes for the preparation of 2-Halogencyclopropylethanderivaten the general formula * in which R1, R2, R3, A and X have the meanings mentioned in the description, and their use as pesticides, especially against insects and mites. Formula (I) {2-Halogencyclopropylethane Derivative Preparation; Schaedlingsbekaempfungsmittel; Insects; mites}

Description

CH ₂ -CH-CH-CH ₂ - BH _{(χ) #}

in the _N

B and R ^{2 have} the meaning given in formula I, with an acid of general formula VIII, optionally using a solvent and a catalyst, to form an intermediate compound of formula XI

Il 3

CH ₂ -CH-CH-CH ₂ -BCR ( _X 1) ₍

R ²

in the

B, D, R ² and R ^{3 have} the meaning given in Formal I, reacting and reacting in the presence of an inert solvent with chlorofluorocarbene, or

g) reacting an alcohol of the general formula X with an acid halide of the general formula IX, if appropriate using a solvent and an acid acceptor, to give an intermediate compound of the formula XI and reacting this with chlorofluorocarbene in the presence of an inert solvent.

2. Pesticides, characterized by a content of at least one compound according to claim 1 of the general formula I in admixture with carriers and / or excipients.

3. Use of compounds according to claim 1 of the formula I, characterized in that they are used for controlling insects and mites.

Field of application of the invention

The invention relates to a process for the preparation of 2-Halogencyclopropylethanderivaten and their use as pest control agents, in particular against insects and mites.

Characteristic of the known state of the art

It is already known that cyctopropane compounds have acaricidal and insecticidal properties (EP 116889). However, the disadvantage of the known compounds is their insufficient insecticidal and acaricidal activity.

Object of the invention

By the method according to the invention are insecticidal and acaricidal new 2-Halogencyclopropylethanderivate to

Provided.

Explanation of the essence of the invention

The object of the present invention is to provide processes for the preparation of compounds which control insects and mites better than the compounds known for this purpose.

-4- 792 446

It has now been found that 2-HalogencycIopropytethanderivate the general formula I.

.1

in the

R ^{1 is} hydrogen or chlorine,

R ^{2 is} hydrogen, C ₁ -C ₆ -alkyl, aryl or aryl-C ₁ -C -alkyl,

A represents the group -CHB-C- or -C-E-

0 D

D Il

(Here B ^- C ^- or b ^- are connected to R ³ , where B and D are oxygen or sulfur), E is oxygen, sulfur or the radical NR ⁴ and

R ³ and R ⁴ are each independently hydrogen, an alkali metal atom or equivalent of a divalent metal, C 1 to C 6 alkyl, C 1 to C 2 alkenyl, C 1 to C 1 alkyno, halo C 1 to C 1 alkyl, C 6 to C 6 cycloalkyl, C 1 -C 3 -alkyl, C 1 -C 3 -cycloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkyL, halogeno-C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, bicycloalkyl, chlorofluorocyclopropylmethylcarbonyloxy-C 1 -C 10 -alkyl, chlorofluorocyclopropylcarbonyloxy Ci-Ca-alkoxy-Ci-Ca-alkyl,

_AΓyl-C) -C _(, alkyl, aryl-C _^ C6-alkenyl, HalogθnaΓyl-C, -C - alkyl, C, -C _{<-Alkylaryi-C,} -C ₄ alkyl,

Haloaryl-Cr-C -alkenyl halo-C 1 -C 4 -alkylaryl-C 1 -C 6 -alkyl.Cj-Cs-alkoxyaryl-C ₁ -C 6 -alkyl-aryloxybenzyl, halophenyl (cyclopropyl) C 1 -C ₃ -alkyl, halophenoxy-C 1 C6-alkyl, naphthyl-Ci-Ce-alkyl, free or aryl C ₁ -C ₂₀ -alkyl, halo-C, -C _e alkyl, d-CKwuvoxy.H.ioa.n-ciCVe-alkoxy, phenyl -C ^ Ce-alkyl, phenyl-C, -C ₆ alkoxy, C ₃ -C ₀ -CyClOaIkOXy, halo-Cj-Cio-cycloalkoxy.Cj-Ce-Cycloalkylalkyloxy.Halogen-Cr-Ce-cycloalkylalkyloxy, Cj-Ce alkenyloxy, halo-C2-C _e alkenyloxy, C2-C _e alkynyloxy, halo-Cz-Cj-alkinyloxy.Alkylsulfonyloxy, Alkylphenylsulfonyloxy, haloalkylsulfonyloxy, phenyl, halogen, amino, cyano, hydroxy. Nitro, aryloxy, heteroaryloxy, haloaryloxy, arylamino, haloarylamino, C ₁ -C ₀ -alkoxycarbonyl, C ₎ -CE-alkoxycarbonylmethyl, halogeno-C ₁ -C _e -alkoxycarbonyl, C ₁ -C ₂ -alkyldioxy, C ₁ -C 6- alkylthio, halo-C3-C _e -cycloalkylalkylamino, halo-Cj-Ce-cycloalkyl-alkylcarbonyloxy, Ci-Ce-alkylamino, or di-Ci-Ce-alkylamino mono- or poly-substituted aryl, heteroaryl free, by halogen, Ci- C ₃ alkyl or halogeno-C ₁ -C 8 -alkyl-substituted heteroaryl,

show improved compared to the known compounds insecticidal and acaricidal activity.

The term "alkyl" represents a straight or branched chain of carbon atoms. The term "alkenyl" represents a straight-chain or branched chain of carbon atoms through double bonds

one or more times interrupted.

The term "alkynyl" represents a straight or branched chain of carbon atoms through triple bonds

one or more times interrupted.

The term "aryl" represents a mono- to trinuclear aromatic radical, such as, for example, phenyl, naphthyl or phenanthryl. The term "heteroaryl" means a 5- or 6-membered ring containing one or more nitrogen, oxygen and / or Contains sulfur atoms, may be saturated, partially saturated or unsaturated and optionally benzoanellated, such as. Pyridine, Thiazole or chromene. R ³ and R ⁴ may optionally together with the N atom represent saturated or unsaturated heterocyclic rings,

such as As morpholino, piperidino, pyrrolo, imidazolo or triazoles

The compounds of the general formula I according to the invention are present as mixtures of the optically active isomers. The

The invention relates not only to the mixtures of isomers, but also to any individual isomer of the compounds of the invention

 The invention further relates to compounds of general formula II

(II)

in the

R ¹ and R ^{1 have} the meaning given in the formula I and

X is hydroxy, chlorine or bromine, as intermediates for the preparation of compounds of formula I.

The new intermediates are particularly advantageous for the preparation of the compounds of the formula I according to the invention, in which

A represents the group -C-E.

The inventive 2-Halogencyclopropylethanderivate of formula I, wherein A represents the group -C-E-, can be prepared by either

A) An acid halide of the general formula II

- R ¹

0 (, J)

Il.

CH C X

R ¹ and R ^{2 have} the meaning given in formula I and

X is chlorine or bromine,

with an alcohol or amine of general formula III

HER ³ (III),

in the

E and R ^{3 have} the meaning given in formula I, if appropriate in a solvent in the presence of an acid acceptor, or

B) a free acid of general formula IV

Il (IV).

CH-C-OH

in the

R ¹ and R ^{2 have} the meaning given in formula I, with an alcohol or amine of formula II, optionally using a solvent in the presence of a catalyst, or

C) an acid of the general formula V

0 II CH ₂ = CH-CH-C-OH _(v)

II ²

in the

R ^{3 has} the meaning given in formula I, with an alcohol or amine of formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, to form an intermediate compound of formula VI

CH ₂ = CH-CH-CER ³ (VI),

R ²

in the

E, R ² and R ^{3 have} the meaning given in formula I, and reacting in the presence of an inert solvent with chlorofluorocarbene, or if

AdieGroup -q \\ _b-C- means

² Il ο

D) an alcohol of the general formula VII

"1

R ²

in the

R ¹ , R ² and B have the meaning given in formula I, with an acid of general formula VIII

R ³ - j - BH. (VIII)

in the

B, D and R ³ are as defined in formula I, optionally with the use of a solvent and

a catalyst, converts, or

E) an alcohol of the general formula VII with an acid halide of the general formula IX

R ³ - jj - x (ix),

in the

Xis chlorine or bromine and

R ^{3 has} the meaning given in formula I, if appropriate using a solvent and a

Acid acceptors, metabolizes, or F) an alcohol of the general formula X. CH "= CH - CH - CH _n - BH

CH - CH, - BH _{(χ) /}

in the

B and R ^{2 have} the meaning given in formula I, with an acid of general formula VIII, optionally under Use of a solvent and a catalyst, to an intermediate of the formula XI CH ₂ = CH - CH - CH ₂ --B - C - R ³ < ^XI >'

R ²

B, D, R ² and R ^{3 have} the meaning given in formula I, reacting and reacting these in the presence of an inert solvent with chlorofluorocarbene, or

G) reacting an alcohol of the general formula X with an acid halide of the general formula IX, if appropriate using a solvent and an acid acceptor, to give an intermediate compound of the formula XI and reacting this with chlorofluorocarbene in the presence of an inert solvent.

Suitable acid acceptors for carrying out the reaction variants A), E) and G) are the customary basic agents,

in particular aliphatic, aromatic and heterocyclic amines, such as. Triethylamine, dimethylaniline, dimethylbenzylamine,

Pyridine and dimethylaminopyridine or inorganic bases such as oxides, carbonates, bicarbonates and alcoholates of Alkali and alkaline earth metals such as potassium hydroxide, sodium hydroxide, sodium and potassium carbonate. Suitable solvents are the abovementioned acid acceptors themselves or inert solvents or mixtures thereof

among themselves.

Examples which may be mentioned are aliphatic, alicyclic and aromatic hydrocarbons which may be chlorinated

such as hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride,

Ethylene chloride, trichlorethylene and chlorobenzene; Ethers, such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, Propylene oxide, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile and benzonitrile; Esters such as ethyl acetate and amyl acetate; Sa'ureamide like

Dimethylformamide and dimethylacetamide sowio sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane.

The reaction can be carried out within a wide temperature range. In general, she will be at one Temperature between -20 ° C and 200 ⁰ C performed. The reaction is carried out under the pressure of the environment, albeit at elevated or reduced pressure Printing could be done. Suitable catalysts for carrying out the Roactionvariants B), D) and F) are strong acids such as sulfuric acid, Hydrogen halide, sulfonic acids and acidic ion exchangers. It is advantageous, the reaction mixture, the water or the To withdraw esters of the formula I, z. B. by azeotropic distillation or by binding the water to sulfur or Hydrohalic acid. The reaction variant B) can under the same reaction conditions with respect to temperature and pressure and in the same Solvents or mixtures thereof are carried out, as they were called for the reaction variant A). For carrying out reaction variant C), the same acids are suitable for the preparation of intermediate compound VI Catalysts and inert solvents such as those mentioned for Reaction B). Especially suitable for the Esterification is the binding of the water by the combination of triphenylphosphine and azodicarboxylic acid ester (Synthesis

1981.1). However, suitable are also the classical dehydrating agents such as concentrated sulfuric acid, anhydrous salts of inorganic acids such as magnesium sulfate or calcium chloride, carbodiimides such as dicyclohexylcarbodiimide or zeolites.

Chlorofluorocarbene is produced by methods known in the art (e.g., Wakselman et al., Synthesis 1985, 754). However, the representations of chlorofluorocarbene are preferred from salts of dichlorofluoroacetic acid in high-boiling Solvents such as diglyme, triglyme and tetraglyme. Suitable chlorofluorocarbon donors are, for example, halofluorocarbons such as dichlorofluoromethane and Alkali metal dichlorofluoroacetates such as sodium dichlorofluoroacetate. The preparation of the optical isomers of the compounds according to the invention can be carried out by processes known per se

be carried out, for example, by reacting compounds of general formula II with a chiral

Auxiliary reagent, e.g. an optically active amine or an optically active alcohol and then separating the so

obtained diastereomers by means of physical methods (Tetrahedron 33,2725 [1977]), such as. Crystallization, distillation or solid-liquid chromatography. By a subsequent hydrolytic cleavage, which can be performed either acid or base catalysis, we obtain the optical isomers of the free acids of the general formula IV, according to

Process variant B) can be converted to the compounds of the invention.

Furthermore, the resulting in the synthesis mixture '; optical isomers of general formula I by chromatography on chiral stationary Ph ?. on, such. B. on cyclodextrins starch or polymers bound optically active amino acid derivatives were separated into the enantiomers (Angew Chem.92,14 [1980]).

The compounds according to the invention which can be prepared by the above-mentioned processes can be isolated from the reaction mixture by the customary processes, for example by distilling off the solvent used under normal or reduced pressure, by precipitation with water or by extraction.

An increased degree of purity can usually be achieved by column chromatographic purification as well as by fractional purification Distillation or crystallization can be obtained. The compounds of the invention are usually almost colorless and odorless liquids and crystals, which

sparingly soluble in water, moderately soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, aromatic

Hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carbonitriles

such as acetonitrile, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide and sulfoxides such as

Dimethylsulfoxide. The acid halides of the formula IX to be used as starting material, the acid of the formula VIII, the alcohol and the amine

of the formula III are known or can be prepared by methods known per se.

The compounds of the invention are characterized by good insecticidal and acaricidal activity and thus provide a

valuable addition to the art. Because of their action against a wide range of sucking arthropods of the most diverse kinetic groups, the compounds according to the invention can not only be used against pests

Crop plants are used, but also to combat parasites of humans and livestock. Special Significance has the effect of the compounds of the invention against parasites that are resistant to other agents

have developed.

The insects and mites, including animal ectoparasites, which can be controlled according to the invention include

for example, the lepidopterans such as Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Pieris brassicae; the

Dipterans such as Musca domestica, Ceratitis capitata, Erioischia brassicae, Lucilia sericata and Aedes aegypti; the homoptera

including aphids such as Megoura viciae and Nilaparvata lugens; the Coleoptera such as Phaedon cochleariae, Anthonomus grandis and Cornrootworm (Diabrotica spp., for example Diabrotica and Eeimpunetata); the Othopteras like Blattellagermanica; the ticks like Boophilus microplus and the lice like Damalinia bovis and Linognathus vituli as well as the

Spider mites such as Tetranychus urticae and Panonychus ulmi. The use of the compounds according to the invention can be carried out in concentrations of 0.0005 to 5.0%, preferably of 0.001

to 0.1%, which is the weight in grams of active ingredient in 100ml preparation to understand.

The compounds of the invention may be used either alone, in admixture with each other or with other insecticides Active ingredients are applied. If necessary, other plant protection products or pesticides such as For example, insecticides, acaricides or fungicides may be added according to the desired purpose. A promotion of the intensity of action and the rate of action, for example, by effect-enhancing additives

how organic solvents, wetting agents and oils are achieved. Such additives may therefore allow for a reduction in drug dosage.

In addition, phospholipids, for example those from the group, can be used as the mixing partner Phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acylphosphatidylethanolamines, Phosphatidylinositol, phosphatidylserine, lysolecithin and phosphatidylglycerol. The active compounds according to the invention or mixtures thereof are expediently used in the form of preparations such as powders, Dispersants, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers

or diluents and optionally adhesion, wetting, emulsifying and / or dispersing aids.

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, Cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, further mineral oil fractions and vegetable oils. Suitable solid carriers are minerals, for example tonsil, silica gel, talc, kaolin, attapulgite, limestone and vegetable Products, for example flours. Surfactants include, for example, calcium lignosulfonate, polyethylene alkylphenyl ethers, Naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates

and substituted benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example

contain the agents about 10 to 90 parts by mass in% active ingredient, about 90 to 10 parts by mass in% liquid or solid carriers and optionally up to 20 parts by mass in% surfactants.

The application of the agents can be carried out in a customary manner, for example with water as carrier in Spritzbrühmengen of about 100 to 3000 liters / ha. An application of the funds in the so-called low-volume and ultra-low-volume method is just as possible as their application in the form of so-called microgranules.

For the preparation of the preparations, for example, the following constituents are used: A spray powder

20 mass fractions in% active ingredient

35 mass fractions in% bleaching earth

8 mass% of calcium salt of lactin sulfonic acid

2 mass fractions in% sodium salt of N-methyl-N-oleyl-taurine 35% by weight of silica

B paste

45 mass fractions in% active ingredient

5 mass fractions in% sodium aluminum silicate 15 mass fractions in% Cetylpolyglycolether with

8 moles of ethylene oxide

2 mass fractions in% spindle oil 10 mass fractions in% polyethylene glycol 23 parts water _s

C emulsion concentrate 20 mass fractions in% active substance 75 mass fractions in% isophorone

5 mass fractions in% of a mixture based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignosulfonic acid.

AusfOhrungsbelsplele

The following examples describe the preparation of the compounds of the invention.

Example 1 4- (2-Propyloxy) benzoic acid [2- (2-chloro-2-fluorocyclopropyl) ethyl] ester

1. To 25 g (0.14 mol) of 4- (2-propyloxy) benzoic acid and 22.5 ml (0.14 mol) of diethyl azodicarboxylate in 150 ml of tetrahydrofuran are added dropwise, while cooling, a solution of 35.9 g (0.14 mol) of triphenylphosphine and 15.5 ml (0 , 18mol) of 3-buten-1-ol in 150 ml of tetrahydrofuran and stirred for 5 hours at room temperature. After evaporation of the solvent, the reaction product is purified by column chromatography on silica gel, eluted with hexane / ethyl acetate 95: 5 and analyzed by thin layer chromatography with hexane / ethyl acetate 8: 2 as eluent (hV 0.61).

This gives 29 g (89% of theory) of 4- (2-propyloxy) -benzoic acid-3-buten-1-yl-ester.

2. Into a vigorously stirred mixture of 21 g (0.09 mol) of 4- (2-propyloxy) -benzoic acid-3-buten-1-yl ester, 100 ml of 50% sodium hydroxide solution, 150 ml of dichloromethane and 1 g (4.4 mmol). Triethylbenzylammonium chloride are introduced at 5 to 10 ° C 60 g (0.58 mol) of dichlorofluoromethane (Freon 21) over a period of 1 to 2 hours. The mixture is then stirred at 5 ⁰ C for 3 hours. The reaction mixture is poured into 500 ml of water and extracted twice with 100 ml of methylene chloride. The combined organic phases are washed with water and dried over magnesium sulfate. After evaporation of the solvent, the crude product is purified by column chromatography on silica gel, using hexane / ethyl acetate 95: 5 as eluent, and a sample is analyzed by thin-layer chromatography with hexane / ethyl acetate = 8: 2 as eluent (R ₍ = 0.53).

There are obtained 4.5 g (16% of theory) of 4- (2-propyloxy) benzoic acid - [- 2- (2-chloro-2-fluorocyclopropyl) ethyl] ester.

ng ⁰ : 1.5139

Example 2

2- (2-chloro-2-fluorocyclopropyl) -acetic acid (2-naphthylmethyl) ester

A solution of 3.61 g (0.016 mol) of 3-butenoic acid (2-naphthylmethyl) ester in 40 ml of diglyme is heated to 162 ° C. At this temperature, a solution of 8.1 g (0.048 mol) of sodium dichlorofluoroacetate in 60 ml of diglyme over a period of 1 hour

hinzuyptropft. Then allowed to cool, the solvent is distilled off in an oil pump vacuum, the residue is taken up in Ess! Wash twice with water, dry over magnesium sulfate and concentrate on a rotary evaporator. The crude product is purified by column chromatography on silica gel, with hexane / ethyl acetate 99: 1 as eluent, and a sample is analyzed by thin layer chromatography, with hexane / ethyl acetate 8: 2 as eluent (R ₁ = 0.39).

There are obtained 1.7 g (36% of theory) of 2- (2-chloro-2-fluorocyclopropyl) -acetic acid (2-naphthylmethyl) ester.

In an analogous procedure, the following compounds can be prepared.

FR '

R ¹ = Cl

R ² . H

process

3 20 '

Example variant AR η or Fp. [ ⁰ C]

x> ° o

-c- ° - / "vVv \

C -C -O-

Il

-C-O-

Il

Cl

 2 "-jj- Ni ^ N ^^. 1.5576

Procedure example variant

n _Q or Fp. [ ⁰ C]

,

y%

, 5385

-C-O-

Il O (R = O ₁ 15 ^f in ethyl acetate)

-C-O-

Il

1.5338

-C-O-

Il ο

Cl

Cl

1.5303

-C-O-IIO

egg

1, 5313

-C-O

Il

1.5695

-C-O-

Il ο 1, 5A97

-C-O-Il

1.4584

*) Z shape

**) E-shape

Process »Example Variant A20

or Fp. [ ⁰ C]

·

-C-O

Il ο1, U17

-C-O-

Il

1.4 809

C-O

Il ο

-C-O-IIO

, C = C _x

- O-CO-CHj, -

1.4585

1.4579

C-NH-

Il ο

Cl

Cl

101,

-C-NH-Il 0

Cf

Cl79,6

-CH ₂ -OC-

) 1.5118

v ^r

1.5150

The following examples show the effectiveness of the compounds according to the invention.

Application Example A

Effect of prophylactic feed treatment against the swarm bean louse (Aphis fabae Scop.) From primary leaves of the bush bean (Phaseotus vulgaris nanus Aschers.) Round leaf discs are punched with a diameter of 24 mm and untreated or after immersion with a 0.1%! Prepare the active ingredient on wet blotting paper with the underside of the leaf facing upwards. After the samples have been soaked, wingless stages of Aphis fabae are applied (about 100 per leaf disc). The experiment is repeated three times. The Blat.'scheiben be placed on wet filter paper held for two days at 25 ⁰ C and at 16 hours of light per day. Then we estimated the percent mortality and J with reference to the untreated control according to Abbott the effect is calculated

 An effect of 80% or more had the compounds according to Examples Nos. 2,4,6,7,8 and 11 to 22.

Application Example B

Effect of prophylactic feed treatment against the brown rice leafhopper (Nilaparvata lugens Stäl) Rice seedlings (Oryza sativa L.) in the two-leafed stalk (about 10 per polysyryl pot of 6.5 cm x 6.5 cm) are left untreated or after immersion treatment with a 0.1% active substance aqueous preparation until the liquid in the

Set up laboratory. Then a polystyrene cylinder is slipped over each pot, about 30 with its upper opening Carbon dioxide anesthetized individuals of Nilaparvata lugens in the 4th-5th cent. Stage are introduced. After closing the opening

with a close-meshed sieve, the pots are held at 28 ^° C. for two days and at 16 hours of light per day. Then the percentage mortality is determined and with respect to the untreated control the effect is calculated after abboe.

An effect of 80% or more had the compounds according to Examples Nos. 1 to 7, 11, 12, 18 and 23. Application Example C Effect of prophylactic feed treatment against common bean spider mite (Totraychus urticae Koch) From developed primary leaves of the bush bean (Phaseolus vulgaris nanus Aschers.) Are round leaf discs with a Diameter of 14mm punched and untreated or after immersion treatment with a 0.1% active ingredient containing

aqueous preparation placed on wet filter paper, the leaf underside is directed upward. After drying the samples sobehandelten with six adult female Tetranychus be placed on each leaf disk and for 3 days at 25 ⁰ C and maintained at 16 hours light per day urticae. The experiments are repeated four times. Then the dead and surviving females are counted and removed. Likewise, the deposited eggs are counted. After a further seven days, the living larvae are counted and with reference to the untreated control, Abbott calculates the total effect.

An 80-100% effect had the compounds according to Examples Nos. 1 to 9 and 11 to 24. Application sheet D

Effect of curative leaf treatment of the bush bean (Phaseolus vulgaris nanus Aschers.) Against eggs of the common bean spider mite (Tetraychus urticae Koch)

In the warm greenhouse seedlings of the bush bean are attracted to complete development of the primary leaves and then occupied with adult females of Tetranychus urticae. One day later, plants are sprayed to drip point with the eggs, which have since been deposited, with an aqueous preparation containing 0.1% of active substance. After 7 days, measured at about 25 ⁰ Cwird the proportion of dead eggs on treated and untreated Pflanzon. This became after Abbott the

Effect of treatment calculated. An 80-100% effect had the compounds according to Examples Nos. 1,3,8 and 11 to 22. Application example E Killing effect on eggs / larvae of corn rootworm (Diabrotica undeeimpunetata) The compounds of the invention are used as an aqueous preparation with an active compound concentration of 0.1%. Of these preparations, 0.2 ml are placed on the bottom of a Polystyrolpetrischale and on the therein Maize seedling and about 50 eggs of the mallow root worm (Diabrotica undeeimpunetata) in the shell center

Pipette. The sealed dishes are placed up to 7 days at 25 ° C under long day conditions. The criterion for the impact assessment is the killing of eggs or the newly hatching larvae at the end of the experiment. The compounds according to Preparation Examples 8, 16, 22 and 23 achieved an 80-100% activity.

Application Example F Ovizlde effect on egg deposits of the cotton owl (Heliothis virescens) The compounds of the invention are used as an aqueous preparation with an active compound concentration of 0.1%. One day old ovipositions are deposited in these preparations of active ingredient, which are deposited on fertilized filter paper by fertilized female females

were immersed to complete wetting and closed for four days at 25 ⁰ C under long-day conditions

Deposited Petri dishes. The criterion for the impact assessment is the percentage of slip prevention compared to

untreated ovipositions.

The compounds according to Preparation Examples 2,5,6,7,8,11,13,16,19,22 and 23 achieved an 80-100% effect.

Claims (1)

R ^{1 is} hydrogen or chlorine, R ^{2 is} hydrogen, C ₁ -C ₆ -alkyl, aryl or aryl-C ₁ -C -alkyl, A represents the group -CH-B-C- or -C-E. (Here, Bc- or E- are connected to R ³ , where B and D are oxygen or sulfur
mean), E is oxygen, sulfur or the radical NR ⁴ and R ³ and R ⁴ independently represent hydrogen, an alkali metal atom or a corresponding equivalent of a divalent metal, C ₁ -C ₂ -alkyl-O, C2 "C ₂ o-alkenyl, _{C2-C2o-alkynyl,}
Halo-C ^^ - alkyl, C ₃ -C ₆ -CyClOaIkYhC ₁ -C ₃ -alkyl-C ₃ -C ₆ -CyClOaIkYl,
C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -silyl, halo-C ₁ -C -cycloalkyl-C ₁ -C ₄ -alkyl-bicycloalkyl,
Chlorofluorocyclopropylmethylcarbonyloxy-C! -C ₁₀ -alkyl,
Chlorofluorocyclopropylcarbonyloxy-C ₁ -C 3 -alkoxy-C ₁ -C ₃ -alkyl, aryl-C ₁ -C ₆ -alkyl,
Aryl-C ₂ -C ₆ -alkenyl, haloaryl-Cj -C ₆ -alkyl, C ₁ -C -alkylaryl-Cj-C ₄ -alkyl
~ Harogenaryl-C 2 -C ₆ -alkenyl, halo-C 1 -C 4 -alkyl-1-aryl-C 1 -C 4 -alkyl,
C ^ Ca-alkoxyaryl-C ^ ^ Ce-alkyl.Aryloxybenzyl.aC Ca Alkylphenoxybenzyl,
HalogenphenyUcyclopropyD-Ci-Ca-alkyl, halophenoxy-Cr-Ce-alkyl,
Naphthyl-C ₁ -C ₂₀ -alkyl / free aryl or by C ₁ -C ₂₀ -alkyl, halogeno-C ₁ -C 6 -alkyl, C ₁ -C ₁₆ -alkoxy, halogeno-C ₁ -C ₄ -alkoxy, phenyl-C ₁ -C ₄ -alkyl, alkyl, phenyl-CT-Ce-alkoxy, C ₃ -C ₁₀ -cycloalkyl, C ₁ -C ₆ -alkenyloxy, halogeno-C 1 -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, halogeno-C 1 -C ₆ -alkynyloxy, Alkylsulfonyloxy, alkylphenylsulfonyloxy, haloalkylsulfonyloxy, phenyl, halogen, amino, cyano, hydroxy, nitro, aryloxy, heteroaryloxy, haloaryloxy, arylamino,
Haloarylamino ^ r-Ce-alkoxycarbonyl ^ -Ce-alkoxycarbonylmethyl '
Halogeno-C ₁ -alkoxycarbonyl, C ₁ -C ₂ -alkyl-cyano, C ₁ -C ₆ -alkyl, Halo-Ca-Ce-cycloalkylalkylamino.Halogen-Ca-Ce-cycloalkyl-alkylcarbonyloxy,
C ^ Ce-alkylamino, or di-C ₁ -C ₆ -alkylamino mono- or polysubstituted aryl, free Heteroaryl, halogen, C ₁ -C ₃ alkyl or heteroaryl which is substituted by halogen-C ₁ -C ₃ -alkyl (alkyl represents a straight-chain or branched carbon chain, alkenyl represents a straight-chain or branched carbon chain which is bonded by double bonds or interrupted several times, alkynyl represents a straight or branched carbon chain which is interrupted by triple bonds one or more times, aryl stands for a one-to
trinuclear aromatic radical, heteroaryl represents a 5 or 6 membered ring
or containing several nitrogen, oxygen and / or sulfur atoms, is saturated, partially saturated or unsaturated and is optionally benzoanellated), characterized in that 0
a) if A is the group -ce-, an acid halide of the general formula II (ID, in which R ¹ and R ^{2 have} the meaning given in formula I and X is chlorine or bromine, with an alcohol or amine of general formula III HER ³ (III), E and R ^{3 have} the meaning given in formula I, if appropriate in a solvent in the presence of an acid acceptor, or b) a free acid of general formula IV R ¹ , _Cl j-OH in which R ¹ and R ^{2 have} the meaning given in the formula I, with an alcohol or amine of the formula III, if appropriate using a solvent in the presence of a catalyst, or c) an acid of the general formula V ο Il CH ₂ = CH-CH-C-OH (V), I ² in which R ^{2 has} the meaning given in formula I, with an alcohol or amine of formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, to form an intermediate compound of formula VI Il CH ₂ = CH - CH - C - E - R ( _V |), R ² in the E, R ² and R ^{3 have} the meaning given in formula I, reacting and reacting in the presence of an inert solvent with chlorofluorocarbene, or d) if A is the group -ch-b-c-, an alcohol of the general formula VII C. it CH-CH.-BH I ₂ R ² in which R ¹ , R ² and B have the meaning given in formula I, with an acid of general formula VIII ^r3 - yy - ^BH (Viii), in which B, D and R ^{3 have} the meaning given in formula I, if appropriate using a solvent and a catalyst, or e) an alcohol of the general formula VII with an acid halide of the general formula IX R ³ - C - X
0 in the X is chlorine or bromine and R ^{3 has} the meaning given in formula I, if appropriate using a solvent and an acid acceptor, or f) an alcohol of the general formula X.