DE3916835A1 - Di:fluoro-cyclopropyl-ethyl ester(s) of aryl-vinyl acid(s) - useful as insecticides and acaricides - Google Patents

Abstract

Difluorocyclopropyl-ethane derivs. (I) are new. A = phenyl otp. substd. by fluorine, chlorine, bromine, cyano, nitro, hydroxy, 1-6C alkyl, fluoro-1-6C alkyl, chloro-1-6C alkyl, 2-6C alkenyl, fluoro-2-6C alkenyl, chloro-2-6C alkenyl, 1-6C alkoxy, fluoro-1-6C alkoxy, chloro-1-6C alkoxy, difluorocyclopropyl-1-6C alkoxy, 2-6C alkenylloxy, fluoro-2-6C alkenyloxy, chloro-2-6C alkenyloxy, 2-4C alkylyloxy, fluoro-2-4C alkynylloxy, chloro, 2-4C alkynyloxy, amino, 1-4C alkylamino, di-1-4C alkyl-amino or 1-4C alkoxycarbonyl, naphthyl, pyridyl, pyrimidinyl imidazolyl, or triazolyl, R1, R2 = H fluorine, chlorine, bromine, nitro, cyano, 1-4C alkyl opt. substd. by fluorine chlorine or bromine, or phenyl opt. substd. by fluorine, chlorine, bromine, cyano, nitro, 1-4C alkyl, chloro-1-4C alkyl, fluoro-1-4C alkyl or 1-4C alkoxycarbonyl, R3 = H, 1-4C alkyl opt. substd. by fluorine, chlorine, bromine, cyano, 1-4C alkoxy, or 1-4C alkylthio, phenyl opt. substd. by fluorine, bromine, cyano, nitro, 1-4C alkyl, trifluoromethyl 1-4C alkoxy, etc. USE?ADVANTAGE - Cpds. (I) are insecticides and acaricides. They can be used in concns. of 0.00005-5% (g/100ml) and can be applied e.g. as spray liquors at a rate of 100-3000 l/ha. Compared with the cpds. described in EP116889 cpds. (I) have an improved activity and are tolerated better by useful (predatory) mites.

Description

The invention relates to new difluorocylopropylethane derivatives, their preparation and their use as pesticides, in particular against insects and mites.

It is already known that cyclopropane compounds are acaricidal and insecticidal Have properties (EP 1 16 889).

A disadvantage of the known compounds, however, is that they are not sufficient insecticidal and acaricidal activity. Another disadvantage is that the known compounds are predominantly toxic to useful mites are.

The object of the present invention is to provide connections to ask which insects and mites are better than those for this purpose combat known compounds and beyond that for useful ones (predatory) mites are highly tolerated.

It has now been found that difluorocyclopropylethane derivatives of the general Formula I.

in the
A free phenyl or phenyl, which by fluorine, chlorine, bromine, cyano, nitro, hydroxy, C _1-6 alkyl, fluoro-C _1-6 alkyl, chloro C _1-6 alkyl, C _2-6 - Alkenyl, fluoro-C _2-6 -alkenyl, chloro-C _2-6 -alkenyl, C _1-6 -alkoxy, fluoro-C _1-6 -alkoxy, chloro-C _1-6 -alkoxy, difluorocyclopropyl-C _{1- 6} -alkoxy, C _2-6 -alkenyloxy, fluoro-C _2-6 -alkenyloxy, chloro-C _2-6 -alkenyloxy, C _2-4 -alkynyloxy, fluoro-C _2-4 -alkynyloxy, chloro-C _{2- 4} -alkynyloxy, amino, C _1-4 -alkylamino, di- (C _1-4 -alkyl) -amino or C _1-4 -alkoxycarbonyl, is substituted one or more times or free naphthyl or naphthyl, which by fluorine, chlorine , Cyano, nitro, amino or C _1-4 alkyl is substituted, or free pyridyl or pyridyl, which by fluorine, chlorine, bromine, C _1-4 alkyl, fluoro-C _1-4 alkyl or chloro-C _{1 -4-} alkyl is substituted,
or free pyrimidyl or pyrimidyl which is substituted by fluorine, chlorine or C _1-4 alkyl, or the imidazolyl or the triazolyl radical and
R¹ and R² are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, free C _1-4 alkyl, C _1-4 alkyl substituted by fluorine, chlorine or bromine, free phenyl or by fluorine, chlorine, , fluoro-C _1-4 -alkyl or C bromine, cyano, nitro, C _1-4 alkyl, chloro-C _1-4 -alkyl _1-4 alkoxycarbonyl-substituted phenyl and
R³ is hydrogen, free C _1-4 alkyl, C _1-4 alkyl substituted by fluorine, chlorine, bromine, cyano, C _1-4 alkoxy or C _1-4 alkylthio, free phenyl, by fluorine, bromine, cyano , Nitro, C _1-4 alkyl, trifluoromethyl, C _1-4 alkoxy, C _1-2 fluoroalkoxy, C _1-2 chlorofluoroalkoxy, C _1-4 alkylthio, di (C _1-3 alkyl) amino or C _1-3 alkoxycarbonyl substituted phenyl, free benzyl, benzyl, free pyridyl or fluorine, chlorine, C, substituted by fluorine, chlorine, cyano, nitro, C _1-4 alkyl, trifluoromethyl or C _1-4 alkoxycarbonyl _1-4 alkyl, trifluoromethyl or C _1-4 alkyloxy substituted pyridyl,
show an improved insecticidal and acaricidal activity compared to the known compounds, while at the same time being well tolerated by useful (predatory) mites.

The present invention relates to the individual Z and E isomers of general formula I above, all enantiomers and diastereomers as well their mixtures.

The difluorocyclopropylethane derivatives of the formula I according to the invention establish yourself by

• A) an alcohol of the general formula II wherein
  R³ has the meaning given in formula I, with an acid of the general formula IIIA-CR¹ = CR²-COOH (III), in which
  A, R¹ and R² have the meaning indicated in formula I, optionally using a solvent in the presence of a catalyst or dehydrating agent, or
• B) an alcohol of the general formula II with an acid halide of the general formula IV A-CR¹ = CR²-COX (IV) in the
  A, R¹ and R² have the meaning given in formula I and X represents chlorine or bromine, optionally in a solvent in the presence of an acid acceptor or
• C) an alcohol of the general formula VI in the
  R³ has the meaning given in formula I, with an acid of the general formula III, optionally using a solvent in the presence of a catalyst or dehydrating agent, to give an intermediate compound of the formula VII in the
  A, R¹, R², R³ have the meaning given in formula I, and reacting them in the presence of an inert solvent with difluorocarbons or
• D) an alcohol of the general formula VI with an acid halide general formula IV, optionally using a solvent and an acid acceptor, to an interconnection of the Formula VII and this in the presence of an inert solvent can react with difluorocarbons.

As an acid acceptor for carrying out reaction variants B) and D) the usual basic agents, in particular aliphatic, aromatic, are suitable and heterocyclic amines, such as. B. triethylamine, dimethylaniline, Dimethylbenzylamine, pyridine and dimethylaminopyridine or inorganic Bases such as oxides, carbonates, hydrogen carbonates and alcoholates of alkali and alkaline earth metals such as potassium hydroxide, sodium hydroxide, sodium and Potassium carbonate.

The aforementioned acid acceptors themselves or are suitable as solvents inert solvents or mixtures thereof.

Examples include aliphatic, alicyclic and aromatic Hydrocarbons, which may or may not 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 like Acetonitrile, propionitrile and benzonitrile; Esters such as ethyl acetate and Amyl acetate; Acid amides such as dimethylformamide and dimethylacetamide as well Sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane.  

The reaction can be carried out within a wide temperature range will. Generally, it is at a temperature between -20 ° C and 200 ° C.

The implementation is done under the pressure of the environment, albeit they can also be carried out under increased pressure or reduced pressure could.

As catalysts for carrying out reaction variants A) and C) strong acids such as sulfuric acid, hydrogen halide, sulfonic acids are suitable and acidic ion exchangers. It is advantageous to the reaction mixture to withdraw the water or the ester of formula I, e.g. B. by azeotropic Distillation or by binding the water to sulfuric or hydrohalic acid.

The reaction variants A) and C) can under the same reaction conditions in terms of temperature and pressure and in the same solvents or mixtures thereof as for the Reaction variants B) and D) were mentioned.

The binding of the water through is particularly suitable for the esterification the combination of triphenylphosphine and azodicarboxylic acid ester (Synthesis 1981, 1). The classic dehydrating agents are also suitable such as concentrated sulfuric acid, anhydrous salts of inorganic acids such as magnesium sulfate or calcium chloride, carbodiimides such as dicyclohexylcarbodiimide or zeolites.

The production of difluorocarbons is carried out according to specialist literature Methods (e.g. Burton and Hahnfeld, Fluorine Chem. Rev. 2, 8 (1977), 119 ff.).  

Suitable difluorocarbon donors are, for example, alkali metal chlorodifluoroacetates such as sodium chlorodifluoroacetate; Halogen difluorocarbons such as chlorodifluoromethane; Organotin compounds such as trimethyl (trifluoromethyl) tin; Organomercury compounds such as bis (trifluoromethyl) mercury; Organophosphorus compounds such as tris (trifluoromethyl) - difluorophosphorane and triphenyl (bromide fluoromethyl) phosphonium bromide.

The preparation of the optical isomers of the compounds according to the invention can be carried out according to methods known per se, for example by reacting compounds of general formula II with a chiral auxiliary reagent, such as. B. an optically active acid and subsequent Separation of the diastereomers thus obtained using physical Methods (Tetrahedron 33, 2725 (1977)), such as. B. crystallization, distillation or solid-liquid chromatography. By subsequent hydrolytic Cleavage, which can be carried out either acid or base catalytically, the optical isomers of the free alcohols of the general are obtained Formula II, according to process variant A) or B) to the invention Connections can be implemented.

Furthermore, the mixtures formed in the synthesis can be more optical Isomers of the general formula I by chromatography on chiral stationary phases, such as B. on cyclodextrins, starch or on polymers bound optically active amino acid derivatives, separated into the enantiomers (Angew. Chem. 92, 14 (1980)).

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

An increased degree of purity can usually be determined by column chromatography Purification and by fractional distillation or crystallization be preserved.  

The compounds of the invention are usually almost color and are odorless liquids and crystals that are sparingly soluble in water, conditionally 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, carboxamides such as dimethylformamide and sulfoxides such as dimethyl sulfoxide.

The acid halides of formula IV to be used as the starting material Acid of formula III, the alcohol of formula II, the alcohol of formula VI as well as the intermediate compound of formula VII are known or can according to known methods can be produced.

The compounds according to the invention are notable for good insecticides and Acaricidal effect with good tolerability for useful ones (predatory) mites and thus provide a valuable asset to the Technology. Because of its effect against a wide range of suction Arthropods of different kinship groups at the same time The tolerance according to the invention can be well tolerated by useful mites Compounds not only used against pests on crops but also to combat parasites of humans and the Farm animals. The action of the compounds according to the invention is of particular importance against parasites that develop resistance to other agents to have.

To insects and mites, including animal ectoparasites, that can be combated according to the invention include, for example Lepidoptera such as Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Pieris brassicae; the dipteras 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 coleopteras such as Phaedon cochleariae, Anthonomus grandis and Cornrootworm (Diabrotica spp., For example Diabrotica undecimpunctata); the othoptera such as Blattella germanica; 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 Panoychus ulmi.

The compounds according to the invention can be used in concentrations from 0.00005 to 5.0%, preferably from 0.001 to 0.1%, including the weight in grams of active ingredient in 100 ml preparation is to be understood.

The compounds of the invention can either be used alone or in a mixture with each other or with other insecticidal agents. Other pesticides or pesticides may be used such as insecticides, acaricides or fungicides, depending on the desired purpose can be added.

A promotion of the intensity and speed of impact can for example, through additives that increase the effects, such as organic solvents, Wetting agents and oils can be achieved. Such additives may therefore be left out a reduction in drug dosage.

Phospholipids can also be used as mixing parameters Example those from the group phosphatidylcholine, the hydrogenated Phosphatidylcholines, phosphatidylethanolamine, the N-acylphosphatidylethanolamines, Phosphatidylinositol, phosphatidylserine, lysolecithin and Phosphatidylglycerol.

The active compounds according to the invention or their mixtures are expediently used in Form of preparations such as powders, scattering agents, granules, solutions, Emulsions or suspensions, with the addition of liquid and / or solid Carriers or diluents and, if necessary, adhesives, Wetting, emulsifying and / or dispersing aids applied.

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.

Minerals are suitable as solid carriers, for example Tonsil,  Silica gel, talc, kaolin, attapulgite, limestone and herbal products, for example flour.

Examples of surface-active substances include calcium lignin sulfonate, Polyethylene alkylphenyl ether, naphthalenesulfonic acids and their Salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the different preparations can vary widely. For example, the funds include 10 to 90% by weight of active ingredient, about 90 to 10% by weight liquid or solid carriers and optionally up to 20% by weight surfactants.

The funds can be applied in the customary manner, for example with water as a carrier in spray liquor quantities of about 100 to 3000 liters / ha. An application of the funds in the so-called low-volume and ultra-low-volume Processes are just as possible as their application in the form of so-called Microgranules.

For example, the following ingredients are used to prepare the preparations used:

A wettable powder

20 wt .-% active ingredient
35% by weight of bleaching earth
8% by weight calcium salt of lignin sulfonic acid
2% by weight sodium salt of N-methyl-N-oleyl-taurine
35% by weight of silica

B paste

45% by weight of active ingredient
5% by weight sodium aluminum silicate
15% by weight of cetyl polyglycol ether with 8 moles of ethylene oxide
2% by weight spindle oil
10% by weight polyethylene glycol
23 parts of water

C emulsion concentrate

20 wt .-% active ingredient
75% by weight isophorone
5 wt .-% of a mixture based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid.

% By weight = percent by weight

The following examples describe the preparation of the invention Links.

Example 1 4-Hydroxycinnamic acid [2- (2,2-difluorocyclopropyl) ethyl] ester

To 51 g (0.31 mol) of 4-hydroxycinnamic acid and 49.3 ml (0.31 mol) of diethyl azodicarboxylate in 200 ml of tetrahydrofuran, a solution of 80.6 g (0.31 mol) of triphenylphosphine and 38 g ( 0.31 mol) of 2- (2,2-difluorocyclopropyl) ethyl alcohol in 200 ml of tetrahydrofuran and stirred for 8 hours at room temperature. After evaporation of the solvent, the reaction product is purified by column chromatography on silica gel with hexane / ethyl acetate 80:20 as the eluent and a sample is analyzed by thin layer chromatography with hexane / ethyl acetate 50:50 (R _f : 0.49).

46 g (55% of theory) of 4-hydroxycinnamic acid [2- (2,2-difluorocyclopropyl) ethyl] ester are obtained.
Melting point: 50-51 ° C.

The following compounds are produced in an analogous procedure:

The following compounds show the effectiveness of the invention Links.

Example of use A Effect of curative leaf treatment of the bush bean (Phaseolus vulgaris nanus Aschers.) Against movable stages of the common bean spider mite (Tetranychus urticae Koch)

In the warm greenhouse, seedlings of the bush bean are grown until complete Development of the primary leaves attracted and then covered with leaf pieces, which are affected by Tetranychus urticae. A day later they will Leaf pieces are removed and the plants are treated with a 0.1% active ingredient containing aqueous preparation sprayed to runoff. After 7 days at The percentage of dead mobile stages from Tetranychus to 22-24 ° C treated and determined on untreated plants. According to Abbott the effect of the treatment is calculated.

The compounds according to the examples had an activity of 80% or more No. 1-15.

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

In the warm greenhouse, seedlings of the bush bean are grown until complete Development of the primary leaves attracted and then with adult females of Tetranychus urticae occupied. A day later the plants are planted with meanwhile laid eggs with an aqueous containing 0.001% active ingredient Preparation sprayed soaking wet. After 7 days at 22-24 ° C the Percentage of dead eggs in treated and untreated plants determined. The effect of the treatment was calculated from this according to Abbott.

The compounds according to the examples had an activity of 80% or more No. 1-16.  

Example of use C Effect of prophylactic feed treatment against the common bean spider mite (Tetranychus urticae Koch)

From developed primary leaves of the bush bean (Phaseolus vulgaris nanus Aschers.) Round leaf disks with a diameter of 14 mm are punched and untreated or after immersion treatment with a 0.0025% active ingredient containing aqueous preparation placed on wet filter paper, wherein the underside of the sheet is facing upwards. After drying the so treated Samples are taken from six adult Tetranychus urticae females placed on each leaf disc and for 3 days at 25 ° C and 16 hours of light held per day. The experiments are repeated four times. Then they will dead and living females counted and removed. Likewise, the number of eggs laid. After another seven days, the living Larvae are counted and referenced to the untreated control Abbott calculated the overall effect.

The compound according to Example 16 had an 80-100% activity.

Example of use D Compatibility for useful arthropods

From developed primary leaves of the Phaseolus vulgaris nanus Aschers.) Round leaf disks with a diameter of 14 mm are punched and untreated or after immersion treatment with the desired active ingredient concentration an aqueous preparation placed on wet filter paper, with the underside of the sheet facing upwards. After drying The liquid contains around 20 predatory mite eggs per treatment Phytoseiulus persimilis Athias-Henriot using fine hair brush on the Leaf area set. Individuals are responsible for the care of predatory mites Bean spider mite (Tetranychus urticae Koch) added as prey. To 3 days incubation at 25 ° C and 16 hours of light per day count the hatched live and dead larvae as well as the hatched eggs.  

Abbott calculates the mortality for the untreated control. A concentration of 0.016% active ingredient against spider mites as an aqueous preparation with compounds according to Example No. 2, 3, 6, 11-13 and 15 showed 100% tolerance for eggs and larvae from Phytoseiulus persimilis. 15.

Application example E Killing effect on eggs / larvae of the corn rootworm (Diabrotica undecimpunctata)

The compounds of the invention are used as an aqueous preparation with the Active ingredient concentration 0.1% used. Of these drug preparations be 0.2 ml on the bottom of a polystyrene petri dish and on a contained in the corn seedling and on those in the switch center About 50 eggs of the corn rootworm pipetted. The closed shells are set up for 7 days at 25 ° C under long day conditions. criteria for the effectiveness assessment is the killing of eggs or the fresh hatching larvae at the end of the experiment.

The compound according to Example No. 13 had an activity of 100%.

Claims (5)

1. Difluorocyclopropylethane derivatives of the general formula I in the
A free phenyl or phenyl, which by fluorine, chlorine, bromine, cyano, nitro, hydroxy, C _1-6 alkyl, fluoro-C _1-6 alkyl, chloro C _1-6 alkyl, C _2-6 - Alkenyl, fluoro-C _2-6 -alkenyl, chloro-C _2-6 -alkenyl, C _1-6 -alkoxy, fluoro-C _1-6 -alkoxy, chloro-C _1-6 -alkoxy, difluorocyclopropyl-C _{1- 6} -alkoxy, C _2-6 -alkenyloxy, fluoro-C _2-6 -alkenyloxy, chloro-C _2-6 -alkenyloxy, C _2-4 -alkynyloxy, fluoro-C _2-4 -alkynyloxy, chloro-C _{2- 4} -alkynyloxy, amino, C _1-4 -alkylamino, di- (C _1-4 -alkyl) -amino or C _1-4 -alkoxycarbonyl, is substituted one or more times or free naphthyl or naphthyl, which by fluorine, chlorine , Cyano, nitro, amino or C _1-4 alkyl is substituted, or free pyridyl or pyridyl, which by fluorine, chlorine, bromine, C _1-4 alkyl, fluoro-C _1-4 alkyl or chloro-C _{1 -4-} alkyl, or free pyrimidyl or pyrimidyl which is substituted by fluorine, chlorine or C _1-4 alkyl, or the imidazolyl or triazolyl radical and
R¹ and R² are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, free C _1-4 alkyl, C _1-4 alkyl substituted by fluorine, chlorine or bromine, free phenyl or by fluorine, chlorine, Bromine, cyano, nitro, C _1-4 -alkyl, chloro-C _1-4 -alkyl, fluoro-C _1-4 -alkyl or C _1-4 -alkoxycarbonyl are substituted phenyl and
R³ is hydrogen, free C _1-4 alkyl, C _1-4 alkyl substituted by fluorine, chlorine, bromine, cyano, C _1-4 alkoxy or C _1-4 alkylthio, free phenyl, by fluorine, bromine, cyano , Nitro, C _1-4 alkyl, trifluoromethyl, C _1-4 alkoxy, C _1-2 fluoroalkoxy, C _1-2 chlorofluoroalkoxy, C _1-4 alkylthio, di- (C _1-3 alkyl) amino or C _1-3 alkoxycarbonyl substituted phenyl, free benzyl, benzyl, free pyridyl or fluorine, chlorine, C, substituted by fluorine, chlorine, cyano, nitro, C _1-4 alkyl, trifluoromethyl or C _1-4 alkoxycarbonyl _1-4 alkyl, trifluoromethyl or C _1-4 alkyloxy substituted pyridyl. 2. Process for the preparation of compounds of general formula I, characterized in that

• A) an alcohol of the general formula II wherein
  R³ has the meaning given in formula I, with an acid of the general formula IIIA-CR¹ = CR²-COOH (III), in which
  A, R¹ and R² have the meaning indicated in formula I, optionally using a solvent in the presence of a catalyst or dehydrating agent, or
• B) an alcohol of the general formula II with an acid halide of the general formula IV A-CR¹ = CR²-COX (IV) in which
  A, R¹ and R² have the meaning given in formula I and X represents chlorine or bromine, optionally in a solvent in the presence of an acid acceptor or
• C) an alcohol of the general formula VI in the
  R³ has the meaning given in formula I, with an acid of the general formula III, optionally using a solvent in the presence of a catalyst or dehydrating agent, to give an intermediate compound of the formula VII in the
  A, R¹, R², R³ have the meaning given in formula I, and reacting them in the presence of an inert solvent with difluorocarbons or
• D) reacting an alcohol of the general formula VI with an acid halide of the general formula IV, optionally using a solvent and an acid acceptor, to give an intermediate compound of the formula VII and allowing this to react with difluorocarbene in the presence of an inert solvent.

3. pesticide, characterized by a content of min at least one compound according to claim 1 of the general formula I. 4. pesticide according to claim 3, in admixture with carrier and / or auxiliary substances. 5. Use of compounds according to claim 1 of formula I for combating of insects and mites.