DE3229661A1 - alpha -Allenyl-3-phenoxybenzyl cyclopropane carboxylate and alpha -allenyl- 3-phenoxybenzyl acetates, processes for their preparation, and their use in pest control - Google Patents

Abstract

alpha -Allenyl-3-phenoxybenzyl cyclopropane carboxylate and alpha -allenyl- 3-phenoxybenzyl acetates, of the formula <IMAGE> in which <IMAGE> X1 is methyl or halogen; X2 and X4 are in each case halogen; R1 is phenyl, cyano or trifluoromethyl; R2 is hydrogen, chlorine, cyano or -COO-C1-C3-alkyl; R3 is C1-C6-alkyl or phenyl; R4 is C1-C6-alkyl; X3 is oxygen or sulphur; Y1 and Y2 are in each case hydrogen, halogen, methyl or methoxy; R5 is isopropyl or cyclopropyl, and R6 is optionally monosubstituted or polysubstituted phenyl, phenoxy, phenylthio or phenylamine, or <IMAGE>. Processes for their preparation, and their use in pest control are described.

Description

MCyclopropane carboxylic acid - allenyl-3-phenoxybenzyl ester

and a-allenyl-3-phenoxybenzyl acetates, a process for their preparation and their use in pest control. α-Allenyl-3-phenoxybenzyl acetates, process for their preparation and their use in pest control. The cyclopropanecarboxylic acid-allenyl-3-phenoxybenzyl esters have the formula X1 methyl or halogen, X2 and X4 each halogen, R1 phenyl, cyano or trifluoromethyl, R2 hydrogen, chlorine, cyano or -COO-Cl-C3-alkyl, R3C1-C6-alkyl or phenyl, R4C1-C6-alkyl, X3 oxygen or sulfur, Y1 and Y2 each hydrogen, halogen, methyl or methoxy, R5 isopropyl or cyclopropyl and R6 optionally mono- or polysubstituted phenyl, phenoxy, phenylthio or phenylamine, mean.

Halogen includes fluorine, chlorine, bromine or iodine, and X1 in particular Fluorine, chlorine or bromine, with X2 chlorine or bromine, with Y1 fluorine and with Y2 fluorine, chlorine or bromine, to understand.

The alkyl groups in R2, R3 and R4 can be straight-chain or branched be. Examples of such groups are: methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-hexyl and their isomers.

Halogen, in particular, are substituents on the groups at R6 Chlorine, C1-C4-alkyl, especially methyl, haloalkyl, especially trifluoromethyl, C1-C4-alkoxy, especially methoxy, halogen-C 1-C4-alkoxy, especially trifluoromethoxy and difluoromethoxy into consideration.

Preference is given to compounds of the formula I in which X1 fluorine, chlorine or bromine; X2 chlorine or bromine; Y1 denotes hydrogen or fluorine and Y2 denotes hydrogen, fluorine, chlorine or bromine.

Also preferred are compounds of the formula I in which A R5 is isopropyl or cyclopropyl, R6 is p-chlorophenyl, Y1 is hydrogen or fluorine and Y2 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy.

The compounds of the formula I are prepared by methods known per se, for example as follows: 1) A-CH-CH-COX 'CH = C = CH2 acid-binding or zCX + // \ water-binding CH3 CH3 X-CH- -O-. ~~~~~~~~~~~~ CH3 cH3 medium 1 \><2 1 2 (11) (III) 2) A-CH-CR-COOR I CH = C = CH2 -RAW + + HO-CH-i il- ° -i il ~ o I 3 3 means <water-binding (Iv) (V) In formulas II to V, A, Y1 and Y2 have the meanings given for formula I.

In formulas II and III, one of the symbols X and X 'stands for a Hydroxyl group and the other for a halogen atom, especially for chlorine or bromine, and in formula IV, R stands for H or C1-C4-alkyl, in particular for methyl or Ethyl. In particular, tertiary amines, such as trialkylamines and pyridine, are used as acid-binding agents. also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals as well as alkali metal alcoholates such as potassium t-butylate and sodium methylate. As a water-binding agent, e.g.

Dicyclohexylcarbodiimide can be used. Procedures 1 and 2 are at a reaction temperature between -10 and 1200C, usually between 20 and 800C, at normal or elevated pressure and preferably in an inert solution or Diluent carried out. As a solution or Diluents e.g. ethers and ethereal compounds such as diethyl ether, dipropyl ether, Dioxane, dimethoxyethane and tetrahydrofuran; Amides, such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, Toluene, xylenes, chloroform and chlorobenzene; nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and ethyl ethyl ketone.

The starting materials of the formulas II and IV are known or can be prepared analogously to known methods. The starting materials of the formulas III and V can be prepared analogously to known methods, e.g. as described in Example IA will.

The compounds of formula I are available as mixtures of different optically active isomers are present if not uniformly optically during manufacture active starting materials are used.

The various isomer mixtures can be prepared by known methods be separated into the individual isomers. Under the compound of formula I. one understands both the individual isomers and their mixtures.

The compounds of the formula I are suitable for combating various types of disease Pests on animals and plants. So they can be used to control insects, e.g. of the order Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera and by mites and ticks of the order Acarina.

In particular, compounds of the formula I are suitable for combating plant-damaging insects, especially plant-damaging feeding insects, in ornamental and useful plants, especially in cotton and rice crops (e.g. against Spodoptera littoralis, Heliothis virescens, Chilo suppressalis and Laodelphax) as well Vegetable and fruit crops (e.g. against Leptinotarsa decemlineata, Myzus periscae, Laspeyresia pomonella and Adoxophyes reticulana).

Active ingredients of the formula I also show a very beneficial effect against Flies such as Musca domestica and mosquito larvae.

The acaricidal or insecticidal effect can be achieved by adding other insecticides and / or acaricides and in given circumstances adjust. Org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidine; Ureas; other pyrethrin-like compounds as well Carbamates and chlorinated hydrocarbons.

With particular advantage, compounds of the formula I are also with Combined substances that have a synergistic or reinforcing effect Exercise pyrethroids. Examples of such compounds include piperonyl butoxide, Propynyl ethers, propynyloximes, propynyl carbamates and propynylphosphonates, 2- (3,4-Nethylenedioxyphenoxy) -3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithionate, 1,2-ethylenedioxy-4- (2- (octylsulfinyl) propyl) benzene.

The compounds of the formula I are used in unchanged form or, preferably used together with the auxiliaries customary in formulation technology and are therefore e.g. emulsion concentrates that can be sprayed or thinned directly Solutions, diluted emulsions, wettable powders, soluble powders, dusts, Granules, including encapsulations in e.g. polymeric materials, processed in a known manner. The application methods such as spraying, misting, dusting, scattering or pouring become the same as the nature of the means, the desired goals and the given circumstances chosen accordingly.

The formulations, i.e. the active ingredient of the formula I and optionally agents, preparations or containing a solid or liquid additive Compositions are prepared in a known manner, for example by intimate mixing and / or grinding the active ingredients with extenders, such as solvents, solid carriers, and optionally surface-active compounds (surfactants).

The following solvents can be used: aromatic hydrocarbons, preferably the fractions C8 to C12, e.g.

Xylene mixtures or substituted naphthalenes, phthalic acid esters such as Dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or Paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, Ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar Solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. for dusts and dispersible Powder, natural rock flour are usually used, such as calcite, talc, Kaolin, montmorillonite or attapulgite.

To improve the physical properties, highly dispersed Silicic acid or highly dispersed absorbent polymers are added. As grained, adsorptive granulate carriers come from porous types, such as pumice stone, broken bricks, Sepiolite or bentonite, as non-sorptive carrier materials e.g. calcite or sand in question.

In addition, a large number of pregranulated materials can be more inorganic or of an organic nature such as in particular dolomite or comminuted plant residues be used.

As surface-active compounds, depending on the nature of the formulating active ingredient of the formula I nonionic, cationic and / or anionic Surfactants with good emulsifying, dispersing and wetting properties are suitable. Under Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be so-called water-soluble soaps like water soluble synthetic surface active compounds.

Suitable soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C1O-C22), such as the .Na- or K salts of oleic or stearic acid, or of natural fatty acid mixtures, the e.g. can be obtained from coconut or tallow oil. The fatty acid methyl taurine salts are also used to mention.

However, so-called synthetic surfactants are used more frequently, in particular Fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually as alkali, Alkaline earth or optionally substituted ammonium salts and have a Alkyl radical with 8 to 22 carbon atoms, where alkyl also represents the alkyl part of acyl radicals includes, e.g. the Na or Ca salt of ligninsulphonic acid, of the dodecylsulphuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with 8-22 C atoms. Alkylarylsulfonates are e.g. the Na-, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

There are also corresponding phosphates such as salts of the phosphoric acid ester a p-nonylphenol- (4-14) -ethylene oxide adduct in question.

Polyglycol ether derivatives are primarily used as nonionic surfactants of aliphatic or cycloaliphatic alcohols, saturated or unsaturated Fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms may contain in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the compounds mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, Polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned.

Furthermore, there are also fatty acid esters of polyoxyethylene sorbitan such as the polyoxyethylene sorbitan trioleate into consideration.

The cationic surfactants are mainly quaternary Ammonium salts which contain at least one alkyl radical with 8 to 22 as N-substituent Contain carbon atoms and, as further substituents, lower ones, optionally halogenated ones Have alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology include described in the following publication: "Mc Cutcheon's Detergents and Emulsifiers Annual "MC Publishing Corp., Ringwood, New Jersey, 1979.

The pesticidal preparations usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25%, of a surfactant.

While concentrated products are preferred as commodities, the end user usually uses diluted agents.

The agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, Binders, adhesives and fertilizers or other active ingredients to achieve special Effects included.

Formulation examples for liquid active ingredients of the formula I (% - percent by weight) 1. Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% calcium dodecylbenzene sulfonate 5% 8Z 6% castor oil polyethylene glycol ether (36 mol AeO) 5% - tributylphenol polyethylene glycol ether (30 mol AeO) - 12% 4% cyclohexanone - 15% 202 xylene mixture 65% 25% 20% of such Concentrates can be diluted with water to create emulsions of any desired concentration getting produced.

2. Solutions a) b) c) d) Active ingredient 80X 10% 5% 95% ethylene glycol monomethyl ether 20% - - -Polyethylene glycol M G 400 - 70% - -N-methyl-2-pyrrolidone - 20% - -Epoxidized Coconut oil - - 1% 5% gasoline (boiling limits 160-1900C) - - 94% -The solutions are suitable for use in the form of tiny drops.

3. Granules a) b) Active ingredient 5 10% kaolin 94% highly disperse silica 1% Attapulgite - 90% The active ingredient is dissolved in methylene chloride on the carrier sprayed on and the solvent then evaporated in vacuo.

4. Dusts a) b) Active ingredient 2% 5% Highly dispersed silica 1% 5% Talc 97X Kaolin - 90% By intimately mixing the carrier with the active ingredient ready-to-use dusts are obtained.

Formulation examples for solid active ingredients of the formula I (Z = weight percent) 5. Wettable powder a) b) c) Active ingredient 25X 50% 75% Na lignin sulfonate 5% 5Z Na lauryl sulfate 3% - 5% Na diisobutylnaphthalene sulfonate - 6Z 10 octylphenol polyethylene glycol ether (7-8 mol AeO) - 2% -Highly disperse silica 5% 10% 10% kaolin 62Z 27% -The active ingredient is mixed well with the additives and ground well in a suitable mill. This gives wettable powders which, with water, form suspensions of any desired concentration let it dilute.

6. Emulsion concentrate active ingredient 10% octylphenol polyethylene glycol ether (4-5 mol AeO) 3X calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (36 mol AeO) 4% cyclohexanone 30% xylene mixture 50% This concentrate can be diluted emulsions of any desired concentration can be made with water.

7. Dusts a) b) Active ingredient 5% 8% Talc 95X Kaolin - 92Z Man receives ready-to-use dusts by mixing the active ingredient with the carrier and ground on a suitable mill.

8. Extruder granulate active ingredient 10% Na-Ligninsulfonat 2Z Carobxymethylcellulose 1% kaolin 87X The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

9. Enveloping granulate active ingredient 3% polyethylene glycol (M G 200) 3% Kaolin 94% The finely ground active ingredient is mixed with polyethylene glycol in a mixer moistened kaolin applied evenly. In this way you get dust-free Wrapping cranulates.

10. Suspension concentrate active ingredient 40Z ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol AeO) 6% Na lignin sulfonate 10% carboxymethyl cellulose 1% 37% aqueous Formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% Water 32 X The finely ground active ingredient is intimately mixed with the additives. A suspension concentrate is obtained in this way, from which by diluting with water Suspensions of any desired concentration can be prepared.

Example 1: A) Preparation of α-allenyl-3-phenoxybenzyl alcohol 10 g of a-ethynyl-3-phenoxy-benzyl alcohol together with 2.1 g of paraformaldehyde, 5.3 g of diisopropylamine, 0.215 g of CuBr and 50 ml of dioxane for 2 hours under reflux cooked. The reaction mixture is cooled to 200 ° C. and poured into 2 N HCl solution and extracted with ether. The organic phase is mixed with 10% potassium carbonate and saturated sodium chloride solution, dried over magnesium sulfate and concentrated.

After the product has been chromatographed on silica gel with hexane / ether 7: 3 as the eluent, the compound of the formula is obtained 20 ° with a refractive index of nD - 1.5942. The following connections are also established in the same way: B) Preparation of a-allenyl-3-phenoxybenzyl-2,2-dimethyl-3- (1,2-dibromo-2,2-dichloroethyl) -cyclopropane-1-carboxylate.

5 g of a-allenyl-3-phenoxybenzyl alcohol dissolved in 20 ml of toluene are added dropwise one at 00C to a mixture of 8.1 g of 2,2-dimethyl-3- (1,2-dibromo-2,2-dichloroethyl) -cyclopropanecarboxylic acid chloride, 2.2 ml pyridine and 20 ml toluene. The reaction mixture is stirred for 18 hours at 200C, Poured into 2N hydrochloric acid and extracted with toluene. The organic phase is with Washed 10X potassium carbonate and saturated sodium chloride solution over magnesium sulfate dried and concentrated.

After the crude product has been chromatographed over silica gel with ether / hexane 1:10 as the eluent, compound no. 1 of the formula is obtained with a refractive index of nD0o - 1 5928.

The following connections are also established in the same way: Example 2: Preparation of α-allenyl-3-phenoxybenzyl-α-isopropyl-α2-4-chlorophenyl acetate 5 g of α-allenyl-3-phenoxybenzyl alcohol dissolved in 20 ml of toluene are added dropwise at 0 ° C. to a mixture of 4.7 g phenylacetyl chloride, 2.2 ml pyridine and 20 ml toluene. The reaction mixture is stirred for 18 hours at 200 ° C., poured into 2N hydrochloric acid and extracted with toluene. The organic phase is washed with 10% strength potassium carbonate and saturated sodium chloride solution, dried over magnesium sulfate and concentrated.

After the crude product has been chromatographed over silica gel with ether / hexane 1:10 as the eluent, compound no. 7 of the formula is obtained 20 ° with a refractive index of nD = 1.5768.

The following connections are also established in the same way: Example 3 Insecticidal Food Poison Effect Cotton plants are sprayed with a test solution containing 25, 50 and 100 ppm of the compound to be tested.

After the covering has dried on, the cotton plants are covered with Spodoptera littoralis larvae L3 occupied. The experiment is carried out at 240C and 60% relative humidity carried out.

Compounds according to Examples 1 and 2 show in the above test the feed poison effect against Spodoptera larvae listed in the following table.

Biological test results The table below shows test results based on the example above, with the following rating index With regard to the percentage death of the pests: A: 80-100% death at 25 ppm active ingredient concentration B: 80-100% destruction at 50 ppm active ingredient concentration C: 80-100% kill at 100 ppm active ingredient concentration. No effect against Spodoptera littoralis larvae L3 1 A 6 C 7 B 8 B 10 C 11 B

Claims (13)

Claims: 1. A cyclopropane carboxylic acid α-allenyl-3-phenoxybenzyl ester resp. α-Allenyl-3-phenoxyphenyl acetates of the formula X1 methyl or halogen, X2 and X4 each halogen, R1 phenyl, cyano or trifluoromethyl, R2 hydrogen, chlorine, cyano or -COO-C1-C3-alkyl, R3 C 1-C6-alkyl or phenyl, RC -C -alkyl, 416 X3 oxygen or sulfur, Y1 and Y2 each hydrogen, halogen, methyl or methoxy, R5 isopropyl or cyclopropyl and R6 optionally mono- or polysubstituted phenyl, phenoxy, phenylthio or phenylamine, mean. 2. A compound according to claim 1, wherein A X1 denotes fluorine, chlorine or bromine, X2 denotes chlorine or bromine, Y1 denotes hydrogen or fluorine and Y2 denotes hydrogen, fluorine, chlorine or bromine. 3. A compound according to claim 1, wherein R5 is isopropyl or cyclopropyl, R6 is p-chlorophenyl, Y1 is hydrogen or fluorine and Y2 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy. 4. The compound according to claim 2 of the formula 5. The compound according to claim 1 of the formula 6. The compound according to claim 3 of the formula 7. The compound according to claim 3 of the formula 8. The compound according to claim 3 of the formula 9. The compound according to claim 3 of the formula 10. A process for the preparation of compounds according to claim 1, characterized in that a compound of the formula in the presence of an acid-binding agent with a compound of the formula reacted, in which A, Y1 and Y2 have the meaning given in claim 1 and one of the symbols X and X 'stands for a hydroxyl group and the other for a halogen atom. 11. A pesticide that acts as an active component a compound according to claim 1 and auxiliaries customary in formulation technology contains. 12. Use of a compound according to Claiml for combating various pests on animals and plants. 13. Use according to claim 12 for combating insects and Representatives of the order Akarina.