DD285977A5 - PROCESS FOR THE PREPARATION OF AZOLI THIOETHERS - Google Patents

Abstract

The invention relates to a process for the preparation of novel substituted Azolthioethern of the general formula I ASR1 (I) wherein A and R1 have the meaning given in the description and in the claims. The invention further relates to pest control compositions containing compounds of formula (I) as an active ingredient and used for controlling nematodes, sucking and insect pests, insect eggs and mites. {Novel substituted azole thioethers; strong nematicidal action; good plant compatibility; Application of pesticides, also effective against sucking and insect insects, insect eggs, mites}

Description

Field of application of the invention

The invention relates to a process for the preparation of novel substituted azole thioethers and their use as pesticides, in particular against nematodes.

Characteristic of the known state of the art

Compounds of similar structure with nematicidal action are well known, such as e.g. Example from EP-PS 0217747,0263066 and US-PS 3781438.

However, the known compounds have the disadvantage that they are either not sufficiently plant compatible or not sufficiently effective.

Object of the invention

The aim of the invention is the provision of new compounds with a strong nematicidal action and good plant tolerance.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

It has now been found that azole thioethers of the general formula I

A-SR ¹ (I),

A the groups

R ²

a) R- ¹¹ W- b) KnS- ° * ° * °>

means, where

A) if the group is a)

X oxygen or sulfur and

i) R 'the radicals -CFjBr, -CH ₂ -CF ,, -CF ₇ -CF ₂ Br, -CHj-CF ₂ CF ₂ HOdOr -CHj-CHjF and R ^{1 is} optionally mono- or polysubstituted, identically or differently, by halogen , C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkylthio, halo-C 1 -C 4 -alkoxy, halogeno-C 1 -C 4 -alkylthio, nitro or cyano-substituted phenyl,

Or (ii) R ^{1 is} an optionally mono- or polysubstituted or polysubstituted by halogen-substituted C ¹ -, 2-alkyl-I or

Cj) j-alkenyl radical and R ^{2 is} the group

• Ν-

in the

Y oxygen or sulfur, R ^{3 is} a fluoro-C,..., - alkyl or fluoro-C ₂ , 2-alkenylrestund R ⁴ 'is hydrogen, halogen, C 1-6 -alkyl, C 1-4 -alkoxy, C 1-4 -alkylthio, halo-C 1-4 -alkyl, halo-C 1-4 -alkoxy,

Halogen-C, _, - alkylihio or nitro, and B) when A is the groups b) or c),

R ^{1 is} optionally mono- or polysubstituted by identical or different halogen, substituted Ci-u-alkyl or C ₂ -I j-alkenyl resi and

R ^{2 is} optionally mono- or polysubstituted, identically or differently, by halogen, C _1-4 -alkyl, C _1-4 -alkoxy, C _1-4 -alkylthio, halogeno-C _1-4 -alkyl, halogeno-C _1-4 -alkoxy , Halogeno-C-4-alkylthio, nitro or cyano, substituted phenyl, biphenyl or naphthyl radical,

have a surprisingly good nematicidal activity at the same time good plant tolerance. In addition, however, the compounds according to the invention also show good activity against biting and sucking insects as well as against insects and against mites.

The term "haloalkyl" means that one or more hydrogen atoms of the alkyl radical are replaced by halogen Preferred compounds of general formula I are those in which A is the group a)

i) R ^{1 is} bromodifluoromethyl and

R ³ is phenyl, which is optionally substituted by halogen, C ^ -alkoxy or Ci-4-alkyl, or ii) R 'fluoro-Ci-4-alkyl or fluoro-C ₂ _4 alkenyl, which is optionally substituted by bromine, and

R ^{3 is} phenyl, which is preferably substituted in the para-position by fluoro-C 1-4 alkoxy. Preferred compounds of ii) are those with difluoromethyl or bromodifluoromethyl in the meaning of R ¹ . The compounds of the formula I according to the invention can be prepared by methods known per se by reacting compounds of the formula II

A-SY (II),

wherein A has the meaning given in formula I and Y is hydrogen, ammonium or an alkali metal, with

Compounds of the formula Z - R ', where Z is a leaving group such as. As halogen, mesylate and tosylate and R ¹ in formula I.

has the meaning given, in an inert solvent or solvent mixture if necessary with increased

Temperature and optionally at elevated pressure in the presence of a base. As bases organic and inorganic bases can be used, such as. B. tertiary amines such as triethylamine and Tripropylamine, alkali and alkaline earth metal hydrides, hydroxides, carbonates and bicarbonates, but also alkali metal, such as. B. Sodium methylate or potassium tert-butoxide. For the preparation of the compounds of the invention suitable solvents are, for. For example, diethyl ether, dioxane and Tetrahydrofuran, aliphatic and aromatic hydrocarbons such as toluene and petroleum ether; halogenated Hydrocarbons such as chlorobenzene, methylene chloride, carbon tetrachloride, chloroform; Nitriles such as acetonitrile, propionitrile; N, N-dialkylated amides such as dimethylformamide; Ketones such as acetone, methyl ethyl ketone; Dimethyisulfoxid.Sulfolan and water

and alcohols, e.g. As methanol, ethanol, isopropanol or butanol and the mixtures of such solvents with each other.

As a catalyst comes z. 18-crown-6,15-crown-5 or a tetraalkylammonium salt such as tetra-n-butylammonium bromide, in

Question.

The reaction of the compounds of formula II to give compounds of formula I, depending on the reactants at Temperatures between -7O ⁰ C to 12O ⁰ C performed. Also, depending on the reactants, the application of Pressure be appropriate. The then turned-around pressure is in the range between 1 to 25 bar. The reaction time is approximately

0.5 to 48 hours. The reaction mixture is then poured onto ice / water, extracted and known per se

Way worked up. The resulting products can be in customary by recrystallization, vacuum distillation or Clean column chromatography. The compounds of the formula II used as starting materials are known in some cases or can be prepared analogously

produce known methods.

Due to the nematicidal activity with good plant tolerance, the compounds of the invention with Success in plant protection as pesticides in agriculture, viticulture, horticulture and gardening Forestry crops are used. The plant parasitic nematodes which can be controlled according to the invention include, for example, the Root-gland nematodes, such as Meloidogyne incognita, Meloidogyne hapla, Meloidogyne javanica, which form cysts Nematodes, such as Glcoodera rostochiensis, Meterodera schachtii, Heterodera avenae, Heterodera glycines, Heterodera trifolii, Cane and small-leaved veins, ie Ditylenchus dipsaci, Ditylenchus destructor, Aphelenchoidos ritzemabosi, Pratylonus noglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Tylenchorhynchus dubius, Tylenchorhynchus claytoni, Rotylenchus

robustus, Heliocotylenchus multicinctus, Radopholus similis, Belonolaimus lungicaudatus, Longidorus elcngatus and

Trichodorus primitivus. The compounds according to the invention likewise have an insecticidal and acaricidal action and are therefore to be controlled

a variety of insects and mites, including animal ectopic parasites. For example, be mentioned

Lepidoptera such as Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Pieris brassica; Dipteron like Musca

domestica, ceratitis capitata, Erioischia brassicae, Lucilia sericata and AedGS aegypti; Homoptera including aphids such as Megoura viciae and Nilaparvata lugens; Coleoptera such as Phaedon cochleariae, Anthonomus grandis and Cornrootworm (Diabrotica spp., Eg Diabrotica undecimpunctata); Orthoptera such as Blattella germanica; Ticks like Boophilus microplus and

Lice such as Damalinia bovis and Linognathus vituli as well as spider mites such as Tetranychus urticae and Panonychus ulmi. In addition, because of the insecticidal and acaricidal properties of the compounds of the invention, they provide Uses both in the treatment of pests in various stages of crops as

also against pests including nematodes on humans and animals.

The application of the active compounds according to the invention takes place in the form of their commercial formulations and / or from these Formulations prepared application forms. The Wirkstcffgehalt prepared from the commercial formulations forms of application can be widely used

vary. The rate of application of nematode control per hectare is from about 0.03 kg to about 10 kg, preferably from about 0.3 kg to about 6 kg.

The active compounds or mixtures thereof can be converted into the customary formulations such as solutions, emulsions, Wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension Emulsion contrasts, seed powders, active substance-impregnated natural and synthetic substances, ultra-fine encapsulation in

polymeric materials and in seed garbage, and also in fuel-burning formulations such as smoke cartridges, cans, spirals and the like. as well as ULV KaIt and warm mist formulations. These formulations are prepared in a known manner,

z. B. by mixing the active compounds with extenders, ie liquid solvents, liquefied under pressure

Gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers

and / or dispersants and / or foam-forming agents.

In the case of using water as an extender z. As well as organic solvents used as auxiliary solvents

become.

As liquid solvents are essentially in question aromatic hydrocarbons such as xylene, toluene or Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or Methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols such as butanol, Glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide and water. By liquefied gaseous diluents or carriers are meant those liquids which are normal Temperature and under atmospheric pressure are gaseous, z. As aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide. Suitable solid carriers are natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic)! Ground minerals such as highly-dispersed silicic acid. Alumina and Silicates and natural carriers such as calcite, marble, pumice, which are harvested and fractionated as solid carriers for granules, Sepiolite, dolomite and synthetic granules of inorganic and organic meals and granules of organic Material such as sawdust, coconut shells, corncobs and tobacco stalks. Emulsifiers or foam-forming agents which may be mentioned are nonionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyuxethylene fatty alcohol ethers, e.g. As alkylaryl polyglycol ether, alkyl sulfonates, arylsulfonato

as well as protein hydrolysates.

As dispersants z. As lignin, liquors and methyl cellulose called. Also suitable in the formulations are adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular

or latex-shaped polymers are used such as gum arabic. Polyvinyl alcohol and polyvinyl acetate.

Furthermore, dyes such as inorganic pigments, for. As iron dioxide, titanium oxide, ferrocyan blue and organic dyes

such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt,

Molybdenum and zinc are used. The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. embodiment The invention is explained in more detail below with reference to some examples. Examples of formulations are: I. Spray powder

10 parts by weight of the compounds according to the invention are intimately mixed and ground with 12 parts by weight of calcium salt of ligninsulfonic acid, 76 parts by weight of kaolin and 2 parts by weight of dialkylnaphthalenesulfonate.

II. Stable powder

2.5 parts by weight of the compounds of the invention are dissolved in 10 parts of methylene chloride and added to a mixture of 25 parts by weight of powdered silica and 71.5 parts by weight of talc and 1 part by weight Sudan red. The solvent is removed in vacuo and the residue finely ground.

III. granules

5 parts by weight of the compounds according to the invention are dissolved in 10 parts of methylene chloride and sprayed onto 95 parts by weight of granulated attapulgite of particle size 0.3-0.8 mm and dried.

IV. Emulsions concentrate

20 parts by weight of the compounds according to the invention are dissolved in a mixture of 75 parts by weight of isophorone and 5 parts by weight of a mixture of 30 parts of phenylsulfonate calcium salt, 30 parts of castor-polyglycolate with 40 mol% of ethylene oxide and 40 parts of a copolymer of propylene oxide and ethylene oxide.

The starting compounds are prepared as follows:

5- {4-Dlfluormethoxyph "nyl) -1,3,4-oxadlazol-2-thlol

14.0 g (0.069 mol) of 4-difluoromethoxybenzhydrazide are dissolved in 300 ml of ethanol and admixed with 3.87 g (0.069 mol) of potassium hydroxide dissolved in 17 ml of water. At room temperature, 7.6 g (0.1 omol) of carbon disulfide are added dropwise with stirring. The reaction mixture is then refluxed for 7 hours. Thereafter, the reaction mixture is concentrated to dryness, the residue taken up in about 500 ml of water and filtered. The clear solution is adjusted with stirring to pH = 2 with concentrated hydrochloric acid. The resulting crystals are filtered off with suction and washed twice with water.

Yield: 14.1g & 83.7% of theory

Mp: 155-157 ⁰ C

5- {4-D! Fluorm6thoxyphenyl) -1,3,4-thiad! Azol-2-thlol

9.7 g (0.031 mol) of 4-Difluormethoxvbenzoyl potassium dithiocarbazate are added in portions in 45 ml of concentrated sulfuric acid at 5 ⁰ C added. The mixture is stirred for 30 minutes at ⁰ ° C. Thereafter, the reaction solution is added to 300 ml of ice water and the resulting precipitate is filtered off with suction. The precipitate is washed 3 times with water.

Yield: 6,9g ώ 85,5% of the theory

Mp .: 178-179 ° C

In an analogous manner, the following starting compounds are prepared, wherein A is the group N N

R ¹ = hydrogen, X and R ^{2 have} the meaning given in the general formula I.

R ² = E

No. EE ¹ E "X Fp. I

3 -OCH ₂ CF, H H O 192 4 -OCH ₂ CF, H H S 214 5 -OCF ₂ -CHF ₂ H H O * 6 -OCF ₂ -CHF ₂ H H S • 7 OCF, H H O 8th OCF, H H S * 9 -OCH ₂ CFjCHF ₂ H H O 110 10 -OCH ₂ CF ₂ CHF ₂ H H S 138 11 H -OCF ₂ H H O 168-172 12 H -OCF ₂ H H S 180-183

* = not purified starting material

example 1

2-8romdifluormethylthio-5- (4-chlorophenyl) -1,3,4-thiadiazole

1.65 g (0.55 mol) of an 80% sodium hydride suspension in paraffin oil is washed once with 10 ml of toluene and suspended in 20 ml of dimethylformamide. At a temperature of 5-1O ⁰ C, a solution of 5.5 g (0.024 mol) of 5- (4-chlorophenyl) -1,3,4-thiadiazole-2-thiol is added dropwise in 40 ml of dimethylformamide. It is stirred for 30 minutes at 1O ⁰ C. Thereafter, 11.6 g (0,055mol) dibromodifluoromethane are then added dropwise and the reaction solution stirred for 3 hours at 1O ⁰ C. The reaction mixture is poured onto 400 ml of ice / water and extracted 3 times with 100 ml of ethyl acetate. The combined organic phases are washed twice with water, dried over magnesium sulfate and concentrated. Purification is by column chromatography (eluent: hexane / Essignster 4: 1).

Yield: 2.40g & 13.2% of theory

Mp .: 72 ⁰ C

Example 2

5-'4-difluoromethoxyphenyl) -2-difluormetiiylthio-1,3,4-thiadiazole

10.0 g (0.038 mol) of 5- (4-difluorotethoxyphenyl) -1,3,4-thiadiazole-2-thiol are dissolved or suspended in 50 ml of dioxane, and with vigorous stirring, 31 g of a 34% potassium hydroxide solution are added dropwise. The reaction mixture is heated to 60 ⁰ C to 70 ° C and initiated with good stirring for 3 hours, a weak stream of chlorofluoromethane. Then the reaction mixture is poured onto 300 ml of ice water and extracted 3 times with 100 ml of ethyl acetate. The combined organic phases are dried over magnesium sulfate and concentrated. Purification is carried out by column chromatography (eluent: hexane / ethyl acetate 4: 1)

Yield: 2.83 g & 22.8% of theory ng ^u : 1.5754

In an analogous manner, the following compounds are prepared, wherein A is the group N N

R ² -

and X, R ¹ and R ² are as defined in the general formula I.

R ² =

E-

Mp [° C | / nJ ⁰

3 --OCHF, H H O -CHF ₂ 23 1.5278 4 -OCHF ₂ H H O CF = CFCF, 5 -OCHF ₂ H H S -CF = CFCF ₃ 6 -OCHF ₂ H H O -CF ₃ 89 1.51086 7 -OCHF ₂ H H S CF, 77 8th -OCHF ₂ H H O -CF ₂ Br 111 9 -OCHF ₂ H H S -CF ₂ Br 69 10 -OCHF ₂ H H S -CF ₂ -CF ₂ Br 87 11 -OCH ₂ CF, H H S -CF ₂ Br 117 12 -OCH ₂ CF, H H O -CHF ₂ 48 13 -OCH ₂ CF, H H S -CHF ₂ 62 14 -OCH ₂ CF, H H O -CF ₂ Br 74 15 -OCH ₂ CF, H H O -CF ₃ 16 -OCH ₂ CF, H H S -CF ₃ 76 17 -OCHF ₂ H H O -CHr-CH ₂ -CF = CF ₂ 51 18 -OCH ₂ CF ₂ ChF ₂ H H O -CHF, 19 -OCH ₂ CF ₂ CHF ₂ H H S -CHF, 20 -OCH ₂ CFiCHF, H H O -CF ₂ Br 1.53082 21 -OCH ₂ CF ₂ CHF ₂ H H S -CF ₂ Br 22 -OCF ₂ Br H H S -CF ₂ Br 77.6 23 H -OCHF ₂ H O -CF ₂ Br 1.54696 24 H -OCHF ₂ H O -CHF, 1.52982 25 H -OCHF ₂ H O -CH ₂ CH ₂ CHjCF ₃ 1.50838 26 H --OCHF, H S -CHF, 1.57826 27 -OCH ₂ CF, H H O -CH ₁ CH ₂ CF = CF, 28 -OCHjCF, H H S -CHjCHjCF = CF, oil 29 OCF, H H O -CHF, 30 -OCF ₃ H H S -CHF, 73.0 31 OCF, H H O -CF ₂ Br 90.0 32 OCF, H H S -CF ₂ Br 48.0 33 -OCF ₂ Br H H O -CF ₂ Br 54.5 34 -OCHF ₂ H H , S -CHjCHjCF = CF, 93.0 35 Cl H H O -CF ₂ Br 60.0 36 Cl H H O -CH ₂ CF ₃ 94.0 37 H H Cl O -CF ₂ Br 73.8 38 F H H O -CFjBr 39 CH ₁ O- H H O -CF ₂ Br 40 F H H S -CF ₂ Br 41 CH ₁ O- H H S -CF ₂ Br 42 H H Cl S -CF ₂ Br

e e ' E- X R ¹ -7- 285,977 1.55998 No. H Cl H S -CF ₂ Br Mp [ ⁰ ClZn ⁰ 43 H H F S -CF ₂ Br 63.8 44 H H F O -CF ₂ Br 93.0 1.60328 45 H Cl H O -CF ₂ Br 71.5 46 CH ₃ H H S -CF ₂ Br 52.7 47 Cl H H • o -CF ₂ CF ₂ Br 93.0 48 CHi H H O -CF ₂ Br 49 Cl H H S -CF ₂ CF ₂ Br 105.0 50 Cl H Cl O -CF ₂ Br 59.0 51 Cl H Cl S -CF ₂ Br 52 ' H H H O -CF ₂ Br 63.0 53 H H H S -CF ₂ Br 79.0 54 H -CF ₃ H O -CF ₂ Br 70.0 55 oil

Example 56

5-difluoromethylthio-3-phenylisoxazol

7.0 g (0.032 mol) of potassium 3-phenylisoxazole-5-thiolate are suspended in 22 ml of dioxane and, while stirring vigorously, 20.0 g of a 25% potassium hydroxide solution are added dropwise. The reaction mixture is heated to 60 to 7O ⁰ C and während3 hours initiated a weak stream of chlorodifluoromethane. Subsequently, the reaction mixture to 300ml

Pour ice / water and extract 3 times with 100 ml of ethyl acetate. The combined organic phases are over Dried magnesium sulfate and concentrated. Yield: 5.6 g ώ 80.6% of theory

nl °: 1.5608

Example 57 and 58

5- (1,2,2,2-tetrafluoro-1-trifluormethylethylthio) -3-phenyl-isoxazole (No.57)

5- (2,2-difluoro-1-trifluormethylvinylthio) -3-phenylisoxazole (No.58)

In an autoclave, 6.4 g (0.03 mol) of potassium 3-phenylisoxazole-5-thiolate are dissolved in 60 ml of dimethylformamide. Man presses

26 g (0.17 mol) of 1,1,2,3,3,3-hexafluoropropane (3.5 bar) and the reaction mixture is heated to 7O ⁰ C for 25 hours After cooling and relaxation of the pressure, the solution is poured to 300 ml of ice / water and extracted 3 times with 100 ml of ethyl acetate. The combined organic phases are dried over magnesium sulfate and eingeongt. The accumulating

Products are separated by column chromatography and purified. Yield No.2: 2.35g & 22.7% of theory / oil Yield No.3: 2.65g & derTheorie 28.8% / m.p .: 35 ⁰ C In an analogous manner, the following compounds are prepared, where A is the group

"2

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

R ² = ^£ ~ V_y Y- R ¹ rp. I LJ / river No. v * ff E -CHF ₂ 40-42 59 Cl -CF ₂ Br 55-56 60 Cl -CF ₂ -CF ₂ Br 30-32 61 Cl 4-CF ₃ CF ₃ 55 62 H -CHF ₂ 68 63 F -CH ₂ -CH ₂ -CF = CF ₂ 43 64 Cl -CH ₂ -CH ₂ -CF = CF ₂ 65 H -CHF ₂ oil 66 F ₂ HCO

Example 67

2- (Bromdifluormethylthio) -5- (4-chlorophenyl) oxazole

2.14g (0.07mol) of an 80% sodium hydride spun in paraffin oil is washed once with 10ml of toluene and in 15ml

Dimethylformamide suspended. At a temperature of 20-3O ⁰ C, a solution of 7.50 g (0.035 mol) of 5- (4-chlorophenyl) -2-

oxazolthiolin 100 ml of dimethylformamide was added dropwise. It is stirred for 30 minutes at room temperature. Then 7.34 g

(0.035 mol) dibromodifluoromethane is added dropwise and the reaction solution is stirred at room temperature for 12 hours. The reaction mixture is poured onto 300 ml of ice / water and extracted three times with 100 ml of ethyl acetate. The combined organic phases are dried over magnesium sulfate and concentrated. Purification is carried out by column chromatography (eluent: hexane / ethyl acetate 4: 1)

Yield: 5.93 g Δ 49.7% of theory ng ⁰ : 1.6313

example

5- (4-chlorophenyl) -2-difluormethylthlo-oxazol

A solution of 5.0 g (0.024 mol) of 5- (4-chlorophenyl) -2-oxazol'.hiol in 22 ml of dioxane is mixed with a solution of 9, (g (0.24 mol) Sodium hydroxide in 22 ml of water and heated to 7O ⁰ C with stirring. At this temperature will be 60 minutes

uniform stream of chlorofluoromethane introduced. It is allowed to cool and poured into 11 ice-water, acidified weakly and extracted several times with dichloromethane. The organic phase is dried over magnesium sulfate, filtered and concentrated.

The remaining oil is chromatographed on silica gel. Yield: 5.16 g & 82.2% of theory

ng ⁰ : 1.5997

Example 69

5- (4-chlorophenyl) -2- (2,2,2-trifluoroethylthio) oxazole

To an O'C cooled suspension of 1.44 g (0.048 mol) of 80% sodium hydride in 30 ml of dry dimethylformamide

Slowly added dropwise is a solution of 10 g (0.048 mol) of 5- (4-chlorophenyl) -2-oxazolthiol in 50 ml of dimethylformamide. To

To stop the evolution of hydrogen, 6.1 g (0.024 mol) of trifluoroethyl tosylate in 20 ml of dimethylformamide are added dropwise. The mixture is then heated for 6 hours under nitrogen to 11O ⁰ C. After cooling, poured into about 1000ml Ice water, extracted several times with ether, washed well with water and the ether phase is dried over magnesium sulfate. That after

The resulting oil is chromatographed on silica gel.

Yield: 3.0 g 6 42.5% of theory. on tosylate

Mp: 92-94 ⁰ C

In an analogous manner, the following compounds are prepared, where A is the group

, ι- ^N

ο r'- ¹ I

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

R ² =

No.

e '

R '

Fp |. ° C | / nJ °

70 H H -CHF, 65.0 1.58316 71 Cl Cl -CHF, 40.0 1.6082 72 Cl H -CF = CF-CF, ' ¹ 35.0 1.59874 -C (CFj) = CF, 73 F ₁ HCO- H -CF ₂ Br 1.56478 74 F ₂ HCO- H -CHF ₂ 75 F H -CFjBr 76 F H -CHF ₂ 77 Cl H -CH ₂ CH ₂ CF = CF ₂ 1.57942 78 F H -CH ₂ CH ₂ CF = CF, 1.54430 M- 1: 1 mixture

The following application examples show the biological activity of the compounds according to the invention. Application Example A Control of root-knot nematodes (Meloidogyne incognita)

10% powdered preparations of active compound are uniformly mixed with soil, which is heavily contaminated with the test nematodes. Then fill the so treated soil in 0.5 liter Tonschalon, cucumber seeds and cultured at a soil temperature of 25-27 ⁰ C in the greenhouse. After a culture period of 25-28 days, the cucumber roots are washed out, examined in a water bath for nematode infestation (root galls) and the efficiency of the active ingredient in the

Comparison to contaminated control determined in%. If the nematode infestation completely avoided, the efficiency

as 100% stated.

At a dose of 25mg of active ingredient per liter of soil, nematode infestation by Meloidogyne incognita was observed Vorbindungen according to the examples 1,2,3,5,8,12,14-18,23,24,26,35,38-41,43-47,49,53,54,56,59,63,64, 68.70 and 74-76

completely (100%) avoided.

Application leaflet B

Effect of curative leaf treatment of bush bean (Phasaolus vulgaris nanus Aschers.) Against motile stages of common bean spider mite (Tetranychus urticae Koch)

In the warm greenhouse, seedlings of the bush bean are grown until the primary leaves have fully developed and then covered with pieces of leaf that have been infected by Tetf.nychus urticae. One day later, the leaf pieces are removed and sprayed the plants with a 0.1% active ingredient-containing aqueous preparation dripping wet. After 7 days at 22-24 ⁰ C, the proportion of dead movable stages of Tetranychus on the treated and on untreated plants was determined. From this, according to Abbott, the effect of the treatment is calculated.

The compounds according to Examples 2, 35, 55, 59 and 68 had a more than 80% action.

Application Table C *>

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

In the warm greenhouse seedlings of the bush bean are attracted to the complete development of the primary leaves and then occupied with adult females of Totranychus urticae. One day later, the plants with the now stored eggs with 0.1% active ingredient containing aqueous preparation dripping. injected. After 7 days at 22-24 ⁰ C, the proportion of dead eggs on treated and untreated plants is determined. From this, according to Abbott, the effect of the treatment is calculated.

The compounds according to the examples 2,37,38,42,56,61,68,70 and 74 had a more than 80% effect.

Application example D

Effect of prophylactic foliar treatment against the brown rice leafhopper (Nilaparvata Ugens Stäl) In the warm greenhouse, rice seedlings (about 15 per pot) are grown until the formation of the third leaf and then sprayed to drip point with an aqueous preparation containing 0.1% of active compound. After drying Spriubsläge wii d put a transparent cylinder over each pot. On each pot then about 30 individuals of the brown rice leafhopper (Nilap arvata lugens) are brought. After 2 days of installation at 26 ⁰ C in the greenhouse, the proportion of killed cicadas is detected. With respect to some untreated control pots, the effect is calculated according to Abbott.

The compounds according to Examples 3,11-18,20,26,35-38,40-46,56,59-62,64,67,68,7C and 72-75 had a 100% effect.

Application bullet E

Killing Effect on Eggs / I.arves of Corn Rootworm (Diabrotica and Eeimpunetata) The compounds according to the invention are used as aqueous emulsions having an active compound concentration of 0.1%. The soils of Polystyrolpetrischelen and contained therein maize seedlings (1 maize seedling / shell) and in each case about 50 eggs of the corn rootworm (Diabrotica undeeimpunetata) with 4 mg spray / cm ^{2 are} metered into these active ingredient preparations. The sealed dishes are set up at 25 ^° C. under long day conditions for 4 days. Criterion for the impact assessment is the killing of eggs or fresh hatching larvae at the end of the experiment.

The compounds of Examples 1-3, 23, 24, 35, 37, 38, 40-42, 48-51, 53, 54, 56 and 72-75 showed 80-100% activity.

Application Example F

Ovicidal activity on egg yolks of the Egyptian cotton worm (Spodoptera littoralis Boisd.) The compounds according to the invention are used as aqueous suspensions or emulsions having an active ingredient concentration of 0.1%. 1 day old egg shells, which had been deposited on fertilizer paper by female flies, are immersed in these preparations until completely wetted and placed in closed petri dishes for four days in the laboratory under long-term conditions. Criterion tv the impact assessment is the percentage of slippage prevention, compared to untreated egg yolks.

The compounds according to Examples 2,3,35,56,68,69,73 and 74 showed an 80-100% β mortality effect.

Application banner Q

Effect of prophylactic feed treatment against the common bean spider mite (Tetranychus urticae Koch) From primary bush bean primary leaves (Phaseolus vulgaris nanus Ascherr ..) round leaf discs with a diameter of 14 mm are punched and untreated or after immersion with 0.1% We ' fabric containing aqueous preparation placed on wet filter paper, the leaf underside is directed upward. After the samples thus treated are dried, six adult females of Tetranychus urticae are placed on each leaf disc and kept for 3 days at 25 ° C and 16 hours light per day. The experiment is repeated four times. Then the dead and living females are counted and removed. Likewise, the deposited eggs are counted. After another seven days the living larvae are counted, referring to o ^! In untreated control, the overall effect is calculated according to Abbott.

The compounds according to Examples 11-18, 20, 21, 23, 25, 26, 59-62, 64 and 72-74 showed an 80-100% activity.

Application Header H

Ovicidal effect on eggplant of the cotton owl (Heliothis virescens F.)

The erfindunnsgema'ßen compounds are used as aqueous preparations with the drug concentration 0.1% oinge. One day old ovipositions, which had been prepared by fertilized female butterflies on filter paper, are dipped into complete wetting and placed in closed petri dishes for four days at 25 ° C. under long day conditions Comparison to untreated eggs.

The compounds according to Examples Nos. 2,3,14,23,24,26,38,42,43,44,48,50-54,56,68,73 and 74 had an 80-100% action.

Application example I

Residual effect of the treatment of bush-bean leaf discs (Phaseolus vulgaris nanu "Aschers.) Against colonization by the common bean spider mite (Tetranychus urticae Koch)

Leaf discs [ ^{1 to} 14 mm) of the bush bean are dripping wet with an aqueous preparation of the active compound concentration 0.1% and placed downside down on wet blotting paper. After the liquid has dried on the free underside of the leaves, Tetranychus urticae adult females are placed in the same number per leaf and left there for at least 2 days at about 25 ° C under long-day conditions. After collecting the adults, the leaf discs are left for a week under the same experimental conditions; then the resulting population is determined.

With reference to the untreated control, the effect on treatment is calculated.

The compounds according to Examples Nos. 1,38,40-481 id 50-54 showed an 80-100% action.

Application sheet J

Effect of prophylactic feed treatment against black bean lice (Aphis fabae Scop.) From primary bush bean primary leaves (Phaseolus vulgaris nanus Aschers.), 24 mm diameter round leaf discs are punched and untreated, or after dipping with a 0.1% aqueous preparation of the drug deposited on wet Fließpiapier, the leaf underside is directed upward. After the samples have been soaked, wingless stages of Aphis fabae are applied (about 100 per leaf disc). The experiment was repeated three times. The leaf discs are placed on wet filter paper at 25 ⁰ C for two days at 16 hours of light per day. With reference to the untreated control, the effect is calculated according to Abbott.

The Verbinduni ^θη according to de> i examples 23.61 'JND 74 showed a more than 80% effective.

Applicant Bills K

Killing effect on larvae (L 1) of the cotton owl (Heliothis virescöüs)

The compounds according to the invention are used as aqueous preparation having an active substance concentration of 0.1%.

Each of these preparations of active ingredient is dipped in a DK.tfutterstück for 2 seconds. After draining, the treated sausages are placed in polystyrene petroleum shampoo. One hour later, 10 larvae of the cotton tree (Hsüoüiiv virescens) are counted into the shells. Then the sealed dishes are placed up to 7 days at 25 ^° C. under long day conditions. Criterion for the impact assessment is the mortality of the larvae in percent at the end of the experiment.

The compounds according to Examples 67, 68 and 75 showed an 80-100% action.

Application Example L

Insecticidal activity against Musca domestica

Aliquots of a solution of the test substance in acetone in various concentrations are applied to filter paper (9 cm 0) in Petri dishes (9 cm 0) with watch glass cover. After evaporation of the solvent, the thus treated surfaces, together with the control experiments treated with acetone alone, adult house flies (Musca domestica) and exposed for 24 hours at 22 ⁰ C. The percentage mortality is then determined by counting.

Boi Kontroiiversucheti the mortality was <5% whereas compounds of Examples 35,46,56,68 and 71, an LD _M in einor concentration of 1000mg / m ² exhibited odfir less.

Anwondungsbelspiel M

Insecticidal activity against Lucüia sericata

1 ml of an aliquot of a solution of the test substance in acetone at various concentrations is applied to cotton dental rollers (1 cm x 2 cm) placed in glass tubes (2 cm 0 and 5 cm in length). After drying, the material thus treated is soaked with 1 ml of a nutrient solution, which is interspersed with young larvae of the sheep's shy (Lu>; ilia sericata). Then the glass tubes are closed with a cotton plug and kept at 25 ⁰ C for 24 hours.

The evaluation of the experiments showed that in the control experiments the mortality was <5%, while the compounds according to Examples 16, V, 43,44,46,56,68,71 and 77 an LC ₆₀ at a concentration of 300 ppm or have less.

Application Example N

Insecticidal activity against Boophilus microplus

Filter paper (9 cm 0) is soaked with 1 ml of an aliquot of a solution of the test substance in acetone at various concentrations. After drying, the filter papers are folded into envelopes into which tick larvae (Boophüus microplus) are introduced. Subsequently, the percentage mortality of the larvae is determined and compared with the control experiments.

The control experiments resulted in a mortality of <5%, during which the compounds ι according to the example; 16,35,40, 42-44,46, 56,58 and 71 gave an LD ₆₀ at a concentration of 300ppm or less.

Claims (4)

-1- 285 Claims:
1. A process for the preparation of Azolthioethem of the general formula I. A - SR ¹ (I), A the groups Jl Ji _- iT a) R ² JI ^ _x JL _fb) Jl Ji _{- or c)} means, where A) if A is the group a), X oxygen or sulfur and i) R ^{1 is} the radicals CF ₂ Br, -CH ₂ -CF ₃ , -CF ₂ -CF ₂ Br, -CH ₂ -CF ₂ -CF ₂ H OdOr-CH ₂ -CH ₂ F and R ^{2 is} optionally mono- or polysubstituted, identically or differently, by halogen, C 1-6 -alkyl, C 1-4 alkoxy-C 1-4 -alkylthio, halogeno-C 1-4 -alkyl, halogeno-C 1-4 -alkoxy, haloC 1-4 -alkylthio, Nitro or cyano substituted phenyl, biphenyl or Naphthylrest mean or H) R ^{1 is} an optionally mono- or polysubstituted or differently halogen-substituted C ₁ -I ₂ -AlkVl- or C ₂ _ ₁₂ alkenyl radical and R ^{2 is} the group in the Y oxygen or sulfur, R ^{3 is} a fluorine-Ci - ^ - alkyl, or fluoro-C ₂ _ ₁₂ alkenyl, and R ⁴ is hydrogen, halogen, C ^ alkyl, _C1 ^ -alkoxy, C ^ alkylthio, halo-C ^ alkyl, Halo-Ci-4-alkoxy, halogen-C ₁ _ ₄ alkylthio, or represents nitro, and ß) if A represents the groups b) or c) is, R ^{1 is} optionally mono- or polysubstituted or differently by halogen, substituted C _1-12 -alkyl or C ₂ _ ₁₂ -alkenyl radical and R ^{2 is} optionally mono- or polysubstituted, identically or differently, by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, halogeno-C 1 -C 4 -alkyl, halogeno-C 1 -C 4 -alkoxy, halogeno-C Ⓒ, nitro or cyano, substituted phenyl, biphenyl or naphthyl radical,
characterized in that
A) Compounds of Formelll A-SY (II), where A has the meaning given in formula I and Y is hydrogen, ammonium or an alkali metal, with compounds of the formula Z - R ¹ , where Z is a leaving group such as halogen, mesylate and tosylate and R ^{1 is} the meaning given in formula I. has, in an inert solvent or solvent mixture at optionally elevated temperature and optionally at elevated pressure in the presence of a base. 2. The method according to claim 1, characterized in that compounds of general formula I are prepared, in the A is the group a) and Π R ^{1 is} bromodifluoromethyl and R ³ P nyl, which is optionally substituted by halogen, C, 4-alkoxy or Ci ^ j-alkyl is substituted, or
ii) R ^{1 is} fluoro-Ci-4-alkyl or fluoro-C ₂ -4 alkenyl, which is optionally substituted by bromine, and R ^{3 is} phenyl, which is preferably substituted in the para-position by fluoro-C 1-4 alkoxy. 3. Use of compounds according to claims 1 and 2, characterized in that they are used for controlling pests, in particular nematodes. 4. pesticides, characterized by a content of at least one compound according to claims 1 and 2 in admixture with carriers and / or excipients.