DE3931067A1 - New fluoro-cyclopropyl-alkyl carbamide cpds. - useful as pesticides, esp. insecticides and acaricides, for control of plant pests and human and animal ectoparasites - Google Patents

Abstract

Fluorocyclopropyl-aklyl carbamides (I) are new. R1 = H or 1-20 C alkyl, 2-20C alkenyl or 2-20C alkenyl opt. substd by -Y-R4, -CO2R4, -NR4R5, carbamoyl, guanidino or opt. substd. aryl or heteroaryl; and R2 = H; or NR1R2 = satd. or unsatd ring; R3 = H alkali metal; 1 equiv of divalent metal; ammonium or phosphate opt. mono- to tetra-substd. by alkyl, aryl or aralkyl; 1-20C alkyl: 2-20C alkenyl; 2-20C alkynyl; halo-1-10C alkyl; 1-6C alkyl substd. by halo-3-6C cycloalkyl, phenyl, 1-3C alkoxyphenyl, halophenoxy or naphthyl; 3-6C cycloalkyl opt. substd. by 1-3C alkyl: phenyl-2-6C alkenyl; halobenzyl: 1-4C alkylbenzyl; phenoxybenzyl; alpha-cyanophenoxybenzyl; aryl opt substd. by 1-20C alkyl, halo- or phenyl-1-6C alkyl, 1-16C alkoxy halo- or phenyl-1-6C alkoxy opt. halo-substd. 3-10C cycloalkoxy, opt. halo-substd. 3-6C cycloalkylalkoxy, opt halo-substd. 2-6C alkenyl, opt. halo-substd. 2-6C alkynyl, opt. halo-substd. alkylsulphonyloxy, alkylphenylsulphonyloxy, phenyl, halogen, amino, hydroxy, nitro, aryloxy, heteroaryloxy, haloaryloxy, arylamino, haloarylamino, opt halo substd. 1-6C alkoxycarbonyl, 1-6C alkoxycarbonyl=methyl, 1-2C alkylenedioxy, 1-6C alkylthio, halo-3-6C cycloalkylalkylamino, halo-3-6C cycloalk-ylalkyl-carbonyloxy, 1-6C alkylamino or di-1-6C alkylamino: or heteroaryl opt. substd. by halogen or opt halo-substd. 1-3C alkyl; R4, R5 = H or 1-6C alkyl; X = H;F, or Cl; Y = O or S n = 0,2,4 or 6. USE/ADVANTAGE:Cpds. (I) are pesticides, esp. insecticides and acaricides. They are formulated conventionally and are applied in concns. of 0.0005-5% (wt./vol). Cpds (I) have a better insecticidal and acaricidal activity than the cpds. described in EP-116889.

Description

The invention relates to new 2-fluorocyclopropylalkyl carbamides, their preparation and their use as pesticides, especially against Insects and mites.

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

The disadvantage of the known compounds, however, is that they are not sufficient insecticidal and acaricidal activity.

The object of the present invention is to provide connections to ask which insects and mites are better than those known for this purpose Fight connections.

It has now been found that 2-fluorocyclopropylalkylcarbamides of the general Formula I.

in the

X hydrogen, fluorine, chlorine,
R¹ is hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl or C _1-20 alkyl, C _2-20 alkenyl or C _2-20 alkynyl, which is represented by one of the groups -Y-R⁴, -CO₂R⁴, -NR⁴R⁵, -CONH₂ or

or is substituted by substituted or unsubstituted aryl or heteroaryl (where R⁴ and R⁵ are hydrogen or C _1-6 alkyl and Y is oxygen or sulfur) and
R² is hydrogen or
R¹ and R² together with the N atom for a saturated or unsaturated heterocyclic ring and
R³ represents hydrogen, an alkali metal or a corresponding equivalent of a divalent metal or an ammonium or phosphate cation with 0-4 alkyl, aryl or aralkyl radicals, or C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl , Halo-C _1-10 -alkyl, halo-C _3-6 -cycloalkyl-C _1-6 -alkyl, C _3-6 -cycloalkyl, C _1-3 -alkyl-C _3-6 -cycloalkyl, phenyl-C _1-6- alkyl, phenyl-C _2-6 -alkenyl, halobenzyl, C _1-6 -alkylbenzyl, C _1-3 -alkoxyphenyl-C _1-6 -alkyl, phenoxybenzyl, α-cyanophenoxybenzyl, halophenoxy-C _1-6 -alkyl, naphthyl-C _1-6 -alkyl, free aryl or by C _1-20 -alkyl, halogen-C _1-6 -alkyl, C _1-16 - alkoxy, halogen-C _1-6 -alkoxy, phenyl- C _1-6 alkyl, phenyl-C _1-6 alkoxy, C _3-10 cycloalkyloxy, halogen C _3-10 cycloalkyloxy, C _3-6 cycloalkyloxy, halogen C _3-6 cycloalkylalkoxy, C _{2 -6} -Alkenyloxy, halo-C _2-6 -alkenyloxy, C _2-6 -alkynyloxy, halo-C _2-6 -alkynyloxy, alkylsulfonyloxy, alkylphenylsulfonyloxy, haloalkylsulfonyloxy, phenyl, halogen, amino, cyano, hy droxy, nitro, aryloxy, heteroaryloxy, haloaryloxy, arylamino, haloarylamino, C _1-6 alkoxycarbonyl, C _1-6 alkoxycarbonylmethyl, halo-C _1-6 alkoxycarbonyl, C _1-2 -Alkyldioxy, C _1-6 alkylthio , Halo-C _3-6 -cycloalkylalkylamino, halo-C _3-6 -cycloalkylalkylcarbonyloxy, C _1-6 -alkylamino, or di-C _1-6 - alkylamino mono- or polysubstituted aryl, free heteroaryl, by halogen, C _{1 -3-} alkyl or halogen-C _1-3 -alkyl substituted heteroaryl and
n represents 0, 2, 4 or 6,
show an improved insecticidal and acaricidal activity compared to the known compounds.

The term "alkyl" stands for a straight or branched chain of Carbon atoms.

The term "alkenyl" stands for a straight or branched chain of Carbon atoms that are interrupted by double bonds one or more times is.

The term "alkynyl" stands for a straight or branched chain of Carbon atoms interrupted by triple bonds one or more times is.  

The term "aryl" stands for a mono- to trinuclear aromatic residue, such as B. phenyl, naphthyl or phenanthryl.

The term "heteroaryl" stands for a 5- or 6-membered ring, the one contains one or more nitrogen, oxygen and / or sulfur atoms saturated, can be partially saturated or unsaturated and optionally benzo is fused, such as B. pyridine, thiazole, imidazole or indole.

The term "heterocyclic ring" is e.g. B. for morpholino, piperidino, Pyrrolo, Imidazolo, Triazolo or Pyrrolidino.

The compounds of general formula I according to the invention are in the form of mixtures of the optically active isomers. The invention not only relates to Isomer mixtures, but also each individual isomer of the Ver bonds.

Compounds of the general type have proven particularly effective Formula I where

X fluorine or chlorine,
R¹ is hydrogen, C _1-4 -alkyl, benzyl or C _1-4 -alkyl, which is substituted by the group -Y-R⁴, where Y is sulfur and R⁴ is methyl,
R² is hydrogen,
R³ is hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, benzyl, m-phenoxybenzyl, p-phenoxybenzyl or naphthylmethyl and
n 0 or 2

mean.

The 2-fluorocyclopropylalkyl carbamides of the general formula I according to the invention can be made by either

• A) an acid halide of the general formula II wherein
  X and n have the meanings given in formula I and
  Y represents chlorine or bromine, with an amino acid or an amino acid ester of the general formula III wherein R¹, R² and R³ have the meaning given in formula I, if appropriate in a solvent in the presence of an acid acceptor, or
• B) an acid of the general formula IV wherein
  X and n have the meanings given in formula I, with an amino acid ester of the general formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, or
• C) an acid of the general formula V wherein
  n has the meanings given in formula I, with an amino acid ester of the general formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, to form an intermediate compound of the formula VI wherein
  n, R¹, R² and R³ have the meanings given in formula I, and implement these in the presence of an inert solvent with a carbene of the general formula VII wherein
  X has the meanings given in formula II, can react, or
• D) an acid halide of the general formula VIII wherein
  n has the meanings given in formula I and
  Y represents chlorine or bromine, with an amino acid or an amino acid ester of the general formula III, optionally in a solvent in the presence of an acid acceptor, to form an intermediate compound of the formula VI, and these react in the presence of an inert solvent with a carbene of the formula VII lets, or
• E) a free acid of the general formula IX wherein
  X, n, R¹ and R² have the meanings given in formula I, with an alcohol of the general formula XR³-OH (X) in which
  R³ has the meanings given in formula I, if appropriate using a solvent in the presence of a catalyst or dehydrating agent.

The acid halides of formula II and to be used as starting material VIII, the acid of formula IV and V, the amino acids or amino acid esters of Formula III and the alcohols of formula X are known per se or can be represent according to known methods.

Suitable as acid acceptors for carrying out reaction variants A) and D) the usual basic agents, especially aliphatic, aromatic and heterocyclic amines, such as. B. triethylamine, dimethylamine, piperidine, di methylaniline, dimethylbenzylamine, pyridine and dimethylaminopyridine or on organic bases such as oxides, hydroxides, 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 carbons Hydrogen, 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 Tue. ethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, Dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl iso propyl ketone and methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile and Benzonitrile; Esters such as ethyl acetate and amyl acetate; Acid amides such as dimethyl formamide and dimethylacetamide, and sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane.

Water or mixtures of water and the above are also suitable as solvents inert solvents mentioned.  

The reaction can be carried out within a wide temperature range will. In general, it is at a temperature between -20 ° C and Boiling point of the reaction mixture, preferably between 20 ° C and 200 ° C, carried out.

The implementation is done under the pressure of the environment, albeit it could also be carried out at elevated or reduced pressure.

Suitable catalysts for carrying out reaction variant B) are strong acids such as sulfuric acid, hydrogen halide, sulfonic acids and acid Ion exchanger. It is advantageous to remove the water from the reaction mixture pull, e.g. B. by azeotropic distillation or by binding the water Sulfuric or a hydrohalic acid.

Reaction variant B) can be obtained under the same reaction conditions on temperature and pressure in the same solvents or mixtures thereof be carried out as they were called for the reaction variant A).

The same are suitable for carrying out the reaction variants C) and E) acidic catalysts and inert solvents as used for reaction variant B) were mentioned. The is particularly suitable for esterification Binding of water through the combination of triphenylphosphine and azodi carboxylic acid esters (Synthesis 1981, 1). But the classic ones are also suitable 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. The carbene reaction of the Reaction variant C) is preferred in ethers such as diglyme, triglyme and tetraglyme carried out. The carbenes are produced in the specialist literature known methods (Burton and Hahnfeld, Fluorine Chem. Rev. 8 (1977), 119 ff .; Wakselmann et al. Synthesis 1985, 754).

Alkali metal chloride fluorine, for example, are suitable as difluorocarbon donors acetate such as sodium chlorodifluoroacetate; Halogen difluorocarbons such as Chlorodifluoromethane; Organotin compounds such as trimethyl (trifluoromethyl) tin;  Organomercury compounds such as phenyl (trifluoromethyl) mercury; Organo phosphorus compounds such as tris (trifluoromethyl) difluorophosphorane and triphenyl (bromide fluoromethyl) phosphonium bromide.

Halogen fluorocarbons are suitable, for example, as chlorofluorocarbons Hydrogen such as dichlorofluoromethane and alkali metal dichlorofluoroacetate such as Sodium dichlorofluoroacetate.

Reaction variant D) can be obtained under the same reaction conditions on temperature and pressure and in the same solvents or mixtures thereof be carried out as they are called for the reaction variant A) were.

The optical isomers of the compounds according to the invention can be prepared be carried out according to known methods, for example by Um setting of compounds of general formula II with an optically active Amino acid of the general formula III or with a chiral auxiliary reagent, such as e.g. B. an optically active amine or an optically active alcohol and closing separation of the diastereomers thus obtained with the aid of physical Methods (Tetrahedron 33, 2725 (1977)), such as. B. crystallization, distillation or solid-liquid chromatography. By hydrolytic cleavage of the chiral auxiliary reagent, which is carried out either acid or base catalytically can be obtained, the optical isomers of the free acids of the general Formula IV, according to process variant B) to the compounds of the invention can be implemented.

Furthermore, the mixtures of optical isomers formed in the synthesis the general formula I by chromatography on chiral stationary phases, such as B. to cyclodextrins, starch or bound to polymers optically active Amino acid derivatives into which enantiomers are separated (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,  for example by distilling off the solvent used in normal or reduced pressure, by precipitation with water or by extraction.

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

The compounds of the invention are usually almost colorless and odorless Liquids as well as crystals, which are mostly 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 carbons Hydrogen such as benzene, toluene and xylene, ethers such as diethyl ether, tetra hydrofuran and dioxane, carbonitriles such as acetonitrile, alcohols such as Methanol and ethanol, carboxamides such as dimethylformamide and sulfoxides such as Dimethyl sulfoxide.

The compounds according to the invention are notable for good insecticides and acaricidal effect and thus provide a valuable addition to the technology Because of their action against a wide range of absorbent arthropods The compounds according to the invention can be of very different kinship groups not only be used against pests on crops, but also to combat parasites of humans and farm animals. Special The action of the compounds according to the invention against parasites is important, who have developed resistance to other agents.

To the insects and mites, including animal ectoparasites, which he can be combated according to the invention include, for example, the 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; including the homopterans Aphids such as Megoura viciae and Nilaparvata lugens; the coleopteras like Phaedon cochleariase, 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 and spider mites such as Tetranychus urticae and Panoychus ulmi.

The compounds according to the invention can be used in concentrations of 0.00005 to 5.0%, preferably 0.0001 to 0.1%, including the weight in grams of active ingredient in 100 ml preparation.

The compounds according to the invention can be used either alone or in a mixture with one another or with other insecticidal agents. Possibly other pesticides or pesticides such as Example insecticides, acaricides or fungicides, depending on the desired purpose be added.

A promotion of the intensity and speed of impact can Example by adding additives such as organic solvents, mesh medium and oils can be achieved. Such additives may therefore have one Reduction of drug dosage too.

Phospholipids can also be used as mixing partners play those from the group phosphatidylcholine, the hydrogenated phosphatidyl cholines, phosphatidylethanolamine, the N-acylphosphatidylethanolamines, phosphate idylinositol, phosphatidylserine, lysolecithin and phosphatidylglycerol.

The active compounds according to the invention or their mixtures are expediently used in Form of preparations such as powders, sprinkling agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers substances or diluents and, if necessary, adhesives, wetting agents, Emulsifying and / or dispersing agents applied.

Suitable liquid carriers are, for example, aliphatic and aromatic Hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dime thylsulfoxide, dimethylformamide, 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, Phe nolsulfonic 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 different preparations can vary within wide limits. For example, the agents contain about 10 to 90 Weight percent active ingredient, about 90 to 10 weight percent liquid or solid Carriers and optionally up to 20 percent by weight surface-active Fabrics.

The funds can be applied in the customary manner, for example with Water as a carrier in spray liquor quantities of approximately 100 to 3000 liters / ha. A Use of the funds in the so-called low-volume and ultra-low-volume process is 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 wt .-% 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 concentration 20% by weight of active ingredient
  75% by weight isophorone
  5% by weight 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 compounds according to the invention.

example 1 N- [2- (2,2-difluorocyclopropyl) acetyl] phenylalanine methyl ester

To a solution of 2.2 g (10 mmol) of L-phenylalanine methyl ester hydrochloride and 50 mg (0.41 mmol) of 4-dimethylaminopyridine in 80 ml of absolute pyridine are added dropwise with ice bath cooling 1.6 g (10 mmol) of 2- (2,2-difluorocyclopropyl) acetic acid chloride and stirred for 14 hours at room temperature with the exclusion of moisture. The reaction mixture is poured onto ice water containing 250 ml of dilute hydrochloric acid poured and extracted with dichloromethane. The organic phase is over Dried sodium sulfate, filtered and concentrated in a rotary evaporator. The The residue is chromato over a silica gel with hexane / ethyl acetate (1: 1) graphed.

Yield: 1.8 g (60.5% of theory)
: 1.5001
R _f = 0.6 (in ethyl acetate)

Example 2 2- (2,2-difluorocyclopropyl) acetic acid glycine amide

To a solution of 1.1 g (15 mmol) glycine in 5 ml 2N aqueous sodium hydroxide Solution is cooled with ice, a solution of 2.3 g (15 mmol) of 2- (2,2- Difluorocyclopropyl) acetic acid chloride in 7.5 ml of toluene and 2.5 ml of 4 N aqueous Sodium hydroxide solution added dropwise at the same time. The mixture is stirred for 15 minutes and then separated the organic phase. The aqueous phase is with diluted hydrochloric acid to pH 2-3, saturated with sodium chloride and with Extracted ethyl acetate. The organic phase is dried over sodium sulfate, filtered and concentrated on a rotary evaporator. The residue is made from ether / Recrystallized ethyl acetate.

Yield: 2.2 g (75.9%)
M.p .: 88-89 ° C
R _f = 0.22 (in ethyl acetate)

The following compounds can be produced in an analogous procedure:

The following examples show the effectiveness of the ver bonds.

Example of use A Effect of the prophylactic feed treatment against the black bean louse (Aphis fabae Scop.)

From developed primary leaves of the bush bean (Phaseolus vulgaris nanus Aschers.) Round leaf discs with a diameter of 24 mm are punched and untreated or after immersion treatment with a 0.1% aqueous preparation of the active ingredient placed on wet blotting paper, with the underside of the sheet is directed upwards. After the samples treated in this way have dried, winged stages of Aphis fabae put on (about 100 per leaf disc). The The experiment is repeated three times. The leaf disks are kept wet Filter paper set up for two days at 25 ° C and with 16 hours of light per day. The percentage mortality is then estimated and with reference to the untreated Control is calculated according to Abbott's effect.

The compounds according to the examples had an activity of 80% or more Nos. 1-4, 7 and 9.

Example of use B Effect of prophylactic feed treatment against the brown rice leafhopper (Nilaparcata lugens Stål)

Rice seedlings (Oryza sativa L.) in the two-leaf stage (about 10 per polystyrene pot of 6.5 × 6.5 cm) are untreated or after immersion treatment with a 0.1% Active ingredient-containing aqueous preparation until the liquid dries set up in the laboratory. Then a polystyrene cylinder is put over each pot, through its upper opening about 30 individuals anesthetized with carbon dioxide by Nilaparvata lugens in the 4th-5th Stage. After closing The pots are left to open for two days after opening with a close-meshed sieve 28 ° C and kept at 16 hours light per day. Then the percentage Mortality is determined and referenced to the untreated control Abbott calculated the effect.  

The compounds according to the examples had an activity of 80% or more Nos. 2 and 7-9.

Example of use C Effect of the prophylactic feed treatment against the common bean spider mite (Tetraychus 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 0.1% active ingredient aqueous preparation placed on wet filter paper, with the underside of the leaf is directed upwards. After the samples treated have dried on six adult females of Tetranychus urticae placed on each leaf disc and kept for 3 days at 25 ° C and 16 hours of light per day. The attempts are repeated four times. Then the dead and living females counted and taken. The laid eggs are also counted. To The living larvae are counted for a further seven days and with reference to the untreated control is calculated according to Abbott's total effect.

The compounds according to the examples had an 80-100% activity Nos. 1 to 7 and 9-12.

Example of use D Effect of curative treatment against common spider mite eggs (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 placed on wet filter paper with the top down. Per leaf disc at least 5 adult Tetranychus urticae females are placed and for 2 days at about 25 ° C, 50-60% relative humidity and 16 hours Light kept per day. After collecting the adults, the leaf disks become with immersed eggs in aqueous preparations containing wetting agents.  As a control, leaf disks in water containing wetting agent submerged. After counting the eggs, the leaf disks are around for 7 days 25 ° C, 50-60% relative humidity and kept 16 hours a day. From the percentage of eggs and live larvae, calculated as a percentage the effect is calculated with reference to the Abbott control. The The average is three repetitions.

The compounds according to the examples had an activity of 80% or more No. 3-7.

Application example E Effect of prophylactic feed treatment against the green peach aphid (Myzus persicae Sulz.)

About 3 cm of developed broad bean leaves (Vicia faba L.) cut long pieces, ent for about 3 seconds into a 0.0004% active ingredient holding aqueous preparation dipped and upside down wet filter paper. After the samples treated have dried winged individuals of Myzus persicae are set up. The attempt will set up at 25-28 ° C and 16 hours of light per day. After a week it will the percentage mortality is determined and with reference to the untreated Control is calculated according to Abbott's effect.

The compounds according to the examples had an activity of 80% or more Nos. 2 and 9.

Example of use F Killing effect on eggs / larvae of the corn rootworm (Diabrotica undecimpunctata)

The compounds according to the invention are mixed with a 0.1% aqueous preparation of the active ingredient used. From this preparation of active ingredient  0.2 ml onto the bottom of a polystyrene petri dish and onto one contained therein Corn seedling and on the approx. 50 eggs in the husk center of the corn rootworm (Diabrotica undecimpunctata). The locked ones Trays are set up for 4 days at 25 ° C under long day conditions. The criterion for the effectiveness assessment is the killing of eggs or the freshly hatching larvae at the end of the experiment.

The compounds according to Example No. 7 had an activity of 80-100% and 11.

Application example G Ovicidal effect on the oviposition of the cotton (Heliothis virescens)

The compounds according to the invention are mixed with a 0.1% aqueous preparation of the active ingredient used. In this preparation of active ingredient Day-old egg-laying by the fertilized female butterfly on filter paper were discontinued, immersed until completely wetted and for four days 25 ° C deposited in closed petri dishes under long day conditions. The criterion for the effectiveness assessment is the percentage slip prevention compared to untreated egg laying.

The compounds according to Example No. 7 had an activity of 80-100%.

Claims (6)

1. 2-fluorocyclopropylalkyl carbamides of the general formula I in the
X hydrogen, fluorine, chlorine,
R¹ is hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl or C _1-20 alkyl, C _2-20 alkenyl or C _2-20 alkynyl, which is represented by one of the groups -Y-R⁴, -CO₂R⁴, -NR⁴R⁵, -CONH₂ or or is substituted by substituted or unsubstituted aryl or heteroaryl (where R⁴ and R⁵ are hydrogen or C _1-6 alkyl and Y is oxygen or sulfur) and
R² is hydrogen or
R¹ and R² together with the N atom for a saturated or unsaturated heterocyclic ring and
R³ represents hydrogen, an alkali metal or a corresponding equivalent of a divalent metal or an ammonium or phosphate cation with 0-4 alkyl, aryl or aralkyl radicals, or C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl , Halo-C _1-10 -alkyl, halo-C _3-6 -cycloalkyl-C _1-6 -alkyl, C _3-6 -cycloalkyl, C _1-3 -alkyl-C _3-6 -cycloalkyl, phenyl-C _1-6 alkyl, phenyl C _2-6 alkenyl, halobenzyl, C _1-4 alkylbenzyl, C _1-3 alkoxyphenyl, C _1-6 alkyl, phenoxybenzyl, α-cyanophenoxybenzyl, halophenoxy C _1-6 -alkyl, naphthyl-C _1-6 -alkyl, free aryl or by C _1-20 -alkyl, halogen-C _1-6 -alkyl, C _1-16 -alkoxy, halogen-C _1-6 -alkoxy, phenyl- C _1-6 alkyl, phenyl C _1-6 alkoxy, C _3-10 cycloalkyloxy, halo C _3-10 cycloalkyloxy, C _3-6 cycloalkyloxy, halo C _3-6 cycloalkylalkoxy, C _{2 -6} -Alkenyloxy, halogen- C _2-6 -alkenyloxy, C _2-6 -alkynyloxy, halogen-C _2-6 -alkynyloxy, alkylsulfonyloxy, alkylphenylsulfonyloxy, haloalkylsulfonyloxy, phenyl, halogen, amino, hydroxy , Nitro, aryloxy, heteroaryloxy, halo aryloxy, arylamino, haloarylamino, C _1-6 alkoxycarbonyl, C _1-6 alkoxy carbonylmethyl, haloC _1-6 alkoxycarbonyl, C _1-2 alkyldioxy, C _1-6 - Alkylthio, halo-C _3-6 -cycloalkylalkylamino, halo-C _3-6 -cycloalkyl alkylcarbonyloxy, C _1-6 -alkylamino, or di-C _1-6 -alkylamino mono- or polysubstituted aryl, free heteroaryl, by halogen, C _1-3 alkyl or halogen C _1-3 alkyl substituted heteroaryl and
n means 0, 2, 4 or 6. 2. 2-fluorocyclopropylalkylcarbamides according to claim 1, characterized in that
X fluorine or chlorine,
R¹ is hydrogen, C _1-4 -alkyl, benzyl or C _1-4 -alkyl, which is substituted by the group -Y-R⁴, where sulfur and R⁴ is methyl,
R² is hydrogen,
R³ is hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, benzyl, m-phenoxybenzyl, p-phenoxybenzyl or naphthylmethyl and
n is 0 or 2. 3. Process for the preparation of compounds of general formula I, characterized in that

• A) an acid halide of the general formula II wherein
  X and n have the meanings given in formula I and
  Y represents chlorine or bromine,
  with an amino acid or an amino acid ester of the general formula III wherein
  R¹, R² and R³ have the meaning given in formula I, if appropriate in a solvent in the presence of an acid acceptor, or
• B) an acid of the general formula IV wherein
  X and n have the meanings given in formula I, with an amino acid ester of the general formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, or
• C) an acid of the general formula V wherein
  n has the meaning given in formula I, with an amino acid ester of the general formula III, optionally in a solvent in the presence of a catalyst or dehydrating agent, to give an intermediate compound of the formula IV wherein
  n, R¹, R² and R³ have the meanings given in formula I, and implement these in the presence of an inert solvent with a carbene of the general formula VII wherein
  X has the meanings given in formula II, can react, or
• D) an acid halide of the general formula VIII wherein
  n has the meanings given in formula I and
  Y represents chlorine or bromine, with an amino acid or an amino acid ester of the general formula III, if appropriate in a solvent in the presence of an acid acceptor, to form an intermediate compound of the formula VI, and this in the presence of an inert solvent with a carbene of the formula VII can react, or
• E) a free acid of the general formula IX wherein
  X, n, R¹ and R² have the meanings given in formula I, with an alcohol of the general formula XR³-OH (X) in which
  R³ has the meanings given in formula I, optionally using a solvent in the presence of a catalyst or dehydrating agent.

4. pesticide, characterized by a content of at least a compound according to claims 1 and 2. 5. pesticide according to claim 4, in a mixture with carrier and / or Auxiliary materials. 6. Use of compounds according to claims 1 and 2 for combating Insects and mites.