USRE37087E1 - Insecticidal triffluormethyl alkane derivatives - Google Patents

Insecticidal triffluormethyl alkane derivatives Download PDF

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USRE37087E1
USRE37087E1 US07/720,091 US72009191A USRE37087E US RE37087 E1 USRE37087 E1 US RE37087E1 US 72009191 A US72009191 A US 72009191A US RE37087 E USRE37087 E US RE37087E
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fluoro
phenyl
phenoxyphenyl
trifluoromethylbutane
halo
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Helga Franke
Heinrich Franke
Hans-Rudolf Kruger
Hartmut Joppien
Dietrich Baumert
David Giles
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Bayer Pharma AG
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Schering AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/275—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having all ether-oxygen atoms bound to carbon atoms of six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
    • A01N29/10—Halogen attached to an aliphatic side chain of an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/06—Nitrogen directly attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom directly attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/08—Systemic pesticides

Definitions

  • the invention relates to new alkane and alkoxyalkane derivatives, processes for their preparation and insecticidal and acaricidal compositions containing these compounds.
  • the object of the present invention is the preparation of new compounds that combat insects and spider mites better than compounds known for this purpose.
  • alkane and alkoxyalkane derivatives of the invention are of the general formula I
  • R 1 is aromatic or aromatic substituted by C 1-4 alkyl, halo-C 1-4 alkyl, phenyl-C 1-4 alkyl, C 2-4 alkenyl, halo-C 2-4 alkenyl, phenyl-C 2-4 alkenyl, C 2-4 alkynyl, halo-C 2-4 alkynyl, phenyl-C 2-4 alkynyl, C 1-4 alkoxy, halo-C 1-4 alkoxy, phenyl-C 1-4 alkoxy, C 2-4 alkenyloxy, halo-C 2-4 alkenyloxy, phenyl-C 2-4 alkenyloxy, C 2-4 alkynyloxy, halo-C 2-4 alkynyloxy, phenyl-C 2-4 alkynyloxy, alkylsulphonyloxy, haloalkylsulphonyloxy, arylsulphonyloxy, halo, cyano,
  • R 2 is hydrogen or C 1-4 alkyl
  • R 3 is hydrogen, cyano or ethynyl
  • R 4 is phenyl or pyridyl or these groups substituted by one or more of C 1-6 alkyl, halo-C 1-6 alkyl, phenyl-C 1-6 alkyl, C 2-6 alkyl interrupted by an O-, N- or S-atom, C 2-4 alkenyl, halo-C 2-4 alkenyl, phenyl-C 2-4 alkenyl, C 1-4 alkoxy, halo-C 1-4 alkoxy, phenyl-C 1-4 alkoxy, C 2-4 alkenyloxy, halo-C 2-4 alkenyloxy, phenyl-C 2-4 alkenyloxy, C 2-4 alkynyloxy, halo-C 2-4 alkynyloxy, phenyl-C 2-4 alkynyloxy, aryloxy, haloaryloxy, C 1-4 alkylaryloxy, arylamino, haloarylamino, C 1-4 alkylaryla
  • A is C 2 or O.
  • the compounds of the invention are surprisingly highly active against a number of important plant pests, such as for example Plutella xylostella, Epilachna verivestis and Spodoptera littoralis.
  • highly active insecticides are known that can be used for combating these plant pests.
  • the compounds of the invention also have activity against a number of economically important animal ectoparasites and public health pests.
  • the aromatic group designated as R 1 in general formula I includes aryl and heteroaryl such as phenyl, 1-naphthyl, 2-naphthyl, benzofuran-5-yl, benzothiophen-5-yl, benzofuran-6-yl, benzothiophen-6-yl, benzoxazol-5-yl, benzoxazol-6-yl, indan-5-yl, indan-6-yl, 1,4-benzodioxan-6-yl, 1,3-benzodioxan-6-yl, 1,3-benzodioxan-7-yl, 1,3-benzodioxol-5-yl and 5,6,7,8-tetrahydronaphthyl.
  • aryl and heteroaryl such as phenyl, 1-naphthyl, 2-naphthyl, benzofuran-5-yl, benzothiophen-5-yl, benzofuran-6-
  • R 1 is chlorophenyl, bromophenyl, fluorophenyl, methylphenyl, methoxyphenyl, ethoxyphenyl, difluoromethoxyphenyl, fluorethoxyphenyl, or trifluoroethoxyphenyl,
  • R 2 is hydrogen or methyl
  • R 3 is hydrogen
  • R 4 is phenoxyphenyl, fluorophenoxyphenyl or phenoxypyridyl and
  • A is CH 2 or O.
  • the compounds of the invention exist as optional isomers.
  • the invention includes all isomers as well as mixtures of them.
  • R 1 , R 2 , R 3 and R 4 have the meanings given above and R 5 is alkyl or phenyl, R 6 is is alkyl and X is halogen.
  • R 1 , R 2 , R 3 and R 4 have the meanings given above and Z is halogen, methanesulphonate or toluenesulphonate.
  • the reaction with the phosphonium salts or the phosphonates of general formula II, III and VI can be carried out, for example in the presence of an inert solvent, such as that generally used in Wittig reactions.
  • suitable solvents include alaphatic or aromatic hydrocarbons, such as for example hexane, benzene or toluene, and ethers such as for example diethyl ether and tetrahydrofuran.
  • Other suitable solvents are amides, such as dimethylformamide or hexamethylphosphoric acid triamide. In some cases, alcohols or dimethyl sulphoxide can be used.
  • Suitable bases for the Wittig reaction include metal alcoholates, such as for example sodium ethanolate, metal hydrides, such as for example sodium hydride, metal amides, such as for example sodium amide and organometalic compounds, such as for example phenyllithium or butyllithium.
  • Suitable bases include metal alcoholates, such as for example potassium tert.-butylate, metal hydrides, such as for example sodium hydride, metal amides, such as for example lithium diisopropylamide and metal alkyl compounds, such as for example ethyl mangnesium bromide or butyllithium.
  • metal alcoholates such as for example potassium tert.-butylate
  • metal hydrides such as for example sodium hydride
  • metal amides such as for example lithium diisopropylamide
  • metal alkyl compounds such as for example ethyl mangnesium bromide or butyllithium.
  • Suitable solvents include inert substances such as aliphatic and aromatic hydrocarbons such as for example hexane, benzene or toluene and ethers such as for example diethyl ether, tetrahydrofuran or dimethoxyethane.
  • Suitable further amides include dimethylformamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
  • the etherification can further be carried out in a two phase system by using a catalyst and optionally a solvent.
  • Bases that can be used include alkali metal hydroxides or alkali metal carbonates, either as solids or an aqueous solution.
  • Suitable solvents are the reactants themselves as long as they are liquid. Otherwise they can be used in substances which are inert to the bases and which are immiscible with water, such as aliphatic or aromatic hydrocarbons, such as for example hexane, benzene of toluene.
  • Suitable catalysts include crown ethers and quaternary ammonium salts, such are described in Dehmlow and Dehmlow, Phase Transfer Catalysts, Weinheim 1980.
  • the reaction can be carried out at temperatures between ⁇ 78° and 140° C., preferably at 20°-80° C., generally at room temperature.
  • aldehyde compounds of formula IV used as starting materials, in which R 2 is H, can be prepared by reacting a compound of general formula XVIII
  • a cyanisation reagent such as for example trimethylsilyl cyanide
  • a Lewis acid such as for example TiCl 4 or SnCl 4
  • a solvent M. T. Reetz, I. Chatziiosifidis, Angew. Chem. 93. 1075 (1981); R. Davis, K. G. Untch, J. Drg. Chem. 46, 2987 (1981) and then reducing the resulting nitrile of general formula XIX
  • R 1 and R 2 have the meanings given above and Y is a hydroxy group or a leaving group, such as for example halogen.
  • the compounds of general formula XIX, in which the group R 1 is an alkoxyphenyl or haloalkoxyphenyl group etc. can be obtained also by treatment of the corresponding hydroxyphenyl derivatives, (which themselves can be prepared by hydrolysis of another alkoxyphenyl derivative), for example by using the corresponding alkyl halide.
  • the phosphonium salt or phosphonate starting material of general formula II, III and VI can be obtained by treatment of R 4 CH(R 3 )CH 2 X or R 4 CH(R 3 )CH 2 CH 2 X, wherein X is a halogen atom, with (R 5 ) 3 P or (R 6 O) 3 P.
  • the alcohols used as starting materials of general formula XIV and XVII can be prepared by reduction of the corresponding nitrile, aldehyde, carboxylic acid or carboxylic acid ester.
  • the reaction can be carried out according to known methods with metal hydride complexes, for example lithium aluminium hydride or alkyl aluminium hydrides for example diisobutylaluminium hydride.
  • metal hydride complexes for example lithium aluminium hydride or alkyl aluminium hydrides for example diisobutylaluminium hydride.
  • the halonide, tosylate and mesylates which are used, are known in themselves or can be prepared according to known methods (DE-OS No. 31 17 510, DE-OS No. 33 17 908, Houben-Wevl, Band 5/4, page 354; ibid. Band 9, page 663).
  • the compounds of the invention prepared by the above described processes can be isolated from the reaction mixture in conventional manner, for example by distillation of the solvent used at normal or reduced pressure or by extraction.
  • a higher degree of purity can be obtained as general rule by thin layer chromatography purification or by fractional distillation.
  • the compounds of the invention are, as a rule, colourless oils that are highly soluble in practically all organic solvents but are almost insoluble in water.
  • the compounds according to the invention can be used at a concentration of 0.005 to 5%, preferably from 0.001 to 1%, calculated as gram active material per 100 ml of the composition.
  • the compounds of the invention can be used either alone or in mixture with each other or another insecticide.
  • other plant protection or pesticidal compositions such as for example insecticides, acaricides or fungicides can be added depending on the desired result.
  • An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils.
  • suitable adjuvants such as organic solvents, wetting agents and oils.
  • Such additives may allow a decrease in the dose.
  • Suitable mixture partners may also include phospholipids, e.g. such as from the group phosphatidylcholine, hydrated phosphatidylcholine, phosphatidylethanolamine, N-acyl-phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
  • phospholipids e.g. such as from the group phosphatidylcholine, hydrated phosphatidylcholine, phosphatidylethanolamine, N-acyl-phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
  • active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.
  • Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, other mineral-oil fractions and plant oils.
  • Suitable solid carriers include mineral earths, e.g. tonsil, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
  • mineral earths e.g. tonsil, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
  • surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.
  • compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.
  • the agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 3,000 l/ha.
  • the agents can be applies using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
  • formulations can be carried out in a known manner, for example by milling or mixing processes.
  • individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.
  • Formulations can be prepared, for example, from the following ingredients.
  • Trimethylsilyl cyanide (65.1 ml; 423 mmol) was added at room temperature to 1-chloro-1-(4-methoxyphenyl)-1-trifluoromethylethane (77.6 g; 335.5 mmol) in methylene chloride (975 ml) followed by titanium tetrachloride (32.5 ml; 3.25 mmol).
  • 2N sodium hydroxide was added carefully, dropwise, until the mixture was neutral and the precipitate separated over celite.
  • 1,1,1-Trifluoroacetone (60.4 ml; 675 mmol) dissolved in absolute ether (80 ml) was added, dropwise, at 5° to 10° C. to an ethereal Grignard solution (prepared from p-bromoanisole (84.17 g; 450 mmol) and magnesium (10.9 g; 450 mmol) in ether (600 ml)) and the mixture stirred at room temperature for 20 hours. It was then added to saturated ammonium chloride solution, extracted with ether and the extract washed with water, dried over sodium sulphate and concentrated. The precipitate was filtered off washed with hexane and the filtrate concentrated.
  • an ethereal Grignard solution prepared from p-bromoanisole (84.17 g; 450 mmol) and magnesium (10.9 g; 450 mmol) in ether (600 ml)
  • n 20 D 1.5463.
  • the compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%.
  • Cabbage leaves (Brassica olearacea var. botrytis), placed in polystyrene petri dishes, were sprayed with these preparations (4 mg spray/cm 2 ). After the sprayed surface had dried, 10 young larvae of the diamond-backed moth (Plutella xylostella) were placed in each petri dish and thereby exposed to the treated food in the closed dishes for two days. The % mortality of the larvae after two days indicated the level of activity.
  • the compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%.
  • French bean plants Phaseolus vulgaris
  • two plant stems with in total four primary leaves were placed in glass vases filled with water and enclosed in plexiglass cylinders.
  • five larvae of the Mexican bean beetle (Epilachna varivestis) at the third larval stage were put in the glass cylinders and kept for three days under extended daylight conditions. The % mortality of the larvae after three days indicated the level of activity.
  • Compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%.
  • Leaflet pairs of beans (Vicia fabae) as well as 10 larvae (L2) of the cotton army worm (Spodoptera littoralis) per experiment were sprayed with 4 mg spray/cm 2 of these preparations in polystyrene petri dishes.
  • the closed petri dishes were left in the laboratory under extended daylight conditions for two days. The % mortality of the larvae after two days indicated the level of activity.
  • the compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%.
  • One day old eggs that had been laid on filter paper by fertilised female moths were dipped in the preparations until they were completely wet and then placed in closed petri dishes in the laboratory under extended daylight conditions for four days.
  • the % inhibition of hatching of the eggs in comparison with untreated eggs indicates the level of activity.
  • the controls gave a mortality of less than 5% whereas compounds of Examples 2, 3, 5, 9, 10, 11, 12, 13, 22, 25, 26, 28, 32, 33, 37-46, 48, 51-55, 57, 58, 60, 62-67, 69-72, 74, 76, 77 and 79-81. caused 50% mortality at a concentration of 300 ppm or less.

Abstract

There are provided new alkane and alkoxyalkane derivatives of the general formula Iin which R1, R2, R3, R4 and A have the meanings given in the description, processes for their preparation and insecticidal and acaricidal compositions containing these compounds.

Description

The invention relates to new alkane and alkoxyalkane derivatives, processes for their preparation and insecticidal and acaricidal compositions containing these compounds.
It is already known that certain alkane and alkoxyalkane derivatives possess insecticidal and acaricidal properties (DE-OS No. 31 17 510 and DE-OS No. 33 17 908).
The object of the present invention is the preparation of new compounds that combat insects and spider mites better than compounds known for this purpose.
The alkane and alkoxyalkane derivatives of the invention are of the general formula I
Figure USRE037087-20010306-C00002
in which
R1 is aromatic or aromatic substituted by C1-4 alkyl, halo-C1-4 alkyl, phenyl-C1-4 alkyl, C2-4 alkenyl, halo-C2-4 alkenyl, phenyl-C2-4 alkenyl, C2-4 alkynyl, halo-C2-4 alkynyl, phenyl-C2-4 alkynyl, C1-4 alkoxy, halo-C1-4 alkoxy, phenyl-C1-4 alkoxy, C2-4 alkenyloxy, halo-C2-4 alkenyloxy, phenyl-C2-4 alkenyloxy, C2-4 alkynyloxy, halo-C2-4 alkynyloxy, phenyl-C2-4 alkynyloxy, alkylsulphonyloxy, haloalkylsulphonyloxy, arylsulphonyloxy, halo, cyano, nitro, aryloxy, haloaryloxy, C1-4alkyl-aryloxy, or nitroaryloxy,
R2 is hydrogen or C1-4 alkyl,
R3 is hydrogen, cyano or ethynyl,
R4 is phenyl or pyridyl or these groups substituted by one or more of C1-6 alkyl, halo-C1-6 alkyl, phenyl-C1-6 alkyl, C2-6 alkyl interrupted by an O-, N- or S-atom, C2-4 alkenyl, halo-C2-4 alkenyl, phenyl-C2-4 alkenyl, C1-4 alkoxy, halo-C1-4 alkoxy, phenyl-C1-4 alkoxy, C2-4 alkenyloxy, halo-C2-4 alkenyloxy, phenyl-C2-4 alkenyloxy, C2-4 alkynyloxy, halo-C2-4 alkynyloxy, phenyl-C2-4 alkynyloxy, aryloxy, haloaryloxy, C1-4 alkylaryloxy, arylamino, haloarylamino, C1-4 alkylarylamino, aryl-N-C1-4 alkylamino, aryl-N-C1-4 acylamino, aroyl, haloaroyl, C1-4 alkylaroyl, aryl, haloaryl, C1-4 alkylaryl or halo, and
A is C2 or O.
It has been found that these compounds have a better insecticidal and acaricidal activity than structurally similar compounds.
The compounds of the invention are surprisingly highly active against a number of important plant pests, such as for example Plutella xylostella, Epilachna verivestis and Spodoptera littoralis. For this activity, highly active insecticides are known that can be used for combating these plant pests. The compounds of the invention also have activity against a number of economically important animal ectoparasites and public health pests.
The aromatic group designated as R1 in general formula I includes aryl and heteroaryl such as phenyl, 1-naphthyl, 2-naphthyl, benzofuran-5-yl, benzothiophen-5-yl, benzofuran-6-yl, benzothiophen-6-yl, benzoxazol-5-yl, benzoxazol-6-yl, indan-5-yl, indan-6-yl, 1,4-benzodioxan-6-yl, 1,3-benzodioxan-6-yl, 1,3-benzodioxan-7-yl, 1,3-benzodioxol-5-yl and 5,6,7,8-tetrahydronaphthyl.
Compounds of the invention showing particularly good insecticidal and acaricidal activity are those in which in general formula I
R1 is chlorophenyl, bromophenyl, fluorophenyl, methylphenyl, methoxyphenyl, ethoxyphenyl, difluoromethoxyphenyl, fluorethoxyphenyl, or trifluoroethoxyphenyl,
R2 is hydrogen or methyl,
R3 is hydrogen,
R4 is phenoxyphenyl, fluorophenoxyphenyl or phenoxypyridyl and
A is CH2 or O.
The compounds of the invention exist as optional isomers. The invention includes all isomers as well as mixtures of them.
The compounds of the invention, where A=CH2, can be prepared for example
(a) reacting a compound of general formula II
Figure USRE037087-20010306-C00003
or of general formula III
Figure USRE037087-20010306-C00004
first with a base and then with a compound of general formula IV
Figure USRE037087-20010306-C00005
to give a compound of general formula V
Figure USRE037087-20010306-C00006
and then reducing this to the desired product, or
(b) reacting a compound of general formula VI
Figure USRE037087-20010306-C00007
first with a base and then with a compound of general formula VII
Figure USRE037087-20010306-C00008
to give a compound of general formula VIII
Figure USRE037087-20010306-C00009
and then reducing this to the desired product, or
(c) condensing a compound of general formula IX
Figure USRE037087-20010306-C00010
with an aldehyde of general formula X
R4CHO   (X)
to given an α,β-unsaturated compound of general formula XI
Figure USRE037087-20010306-C00011
and then reducing this to the desired product or
(d) condensing a compound of general formula XII
Figure USRE037087-20010306-C00012
with an aldehyde of general formula IV
Figure USRE037087-20010306-C00013
to give an α,β-unsaturated compound of general formula XIII
Figure USRE037087-20010306-C00014
and then reducing this to the desired product, in which R1, R2, R3 and R4 have the meanings given above and R5 is alkyl or phenyl, R6 is is alkyl and X is halogen.
The compounds of the invention, where A=O, can be prepared for example
(a) reacting a compound of general formula XIV
Figure USRE037087-20010306-C00015
with a compound of general formula XV
Figure USRE037087-20010306-C00016
in the presence of a base and using a solvent, or
(b) reacting a compound of general formula XVI
Figure USRE037087-20010306-C00017
with a compound of general formula XVII
Figure USRE037087-20010306-C00018
in the presence of a base and using a solvent, in which R1, R2, R3 and R4 have the meanings given above and Z is halogen, methanesulphonate or toluenesulphonate.
The reaction with the phosphonium salts or the phosphonates of general formula II, III and VI can be carried out, for example in the presence of an inert solvent, such as that generally used in Wittig reactions. Suitable solvents include alaphatic or aromatic hydrocarbons, such as for example hexane, benzene or toluene, and ethers such as for example diethyl ether and tetrahydrofuran. Other suitable solvents are amides, such as dimethylformamide or hexamethylphosphoric acid triamide. In some cases, alcohols or dimethyl sulphoxide can be used.
Suitable bases for the Wittig reaction include metal alcoholates, such as for example sodium ethanolate, metal hydrides, such as for example sodium hydride, metal amides, such as for example sodium amide and organometalic compounds, such as for example phenyllithium or butyllithium.
The compounds of general formula I in which the group R1 is an alkoxyphenyl or haloalkoxyphenyl group etc., and A=CH2, can also be obtained by treatment of a hydroxyphenyl derivative that can be prepared by hydrolysis of another alkoxyphenyl derivative, for example with the corresponding alkyl halide.
The etherification is generally carried out in solution. Suitable bases include metal alcoholates, such as for example potassium tert.-butylate, metal hydrides, such as for example sodium hydride, metal amides, such as for example lithium diisopropylamide and metal alkyl compounds, such as for example ethyl mangnesium bromide or butyllithium.
Suitable solvents, as opposed to the reactants, especially the bases, include inert substances such as aliphatic and aromatic hydrocarbons such as for example hexane, benzene or toluene and ethers such as for example diethyl ether, tetrahydrofuran or dimethoxyethane. Suitable further amides include dimethylformamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
The etherification can further be carried out in a two phase system by using a catalyst and optionally a solvent. Bases that can be used include alkali metal hydroxides or alkali metal carbonates, either as solids or an aqueous solution. Suitable solvents are the reactants themselves as long as they are liquid. Otherwise they can be used in substances which are inert to the bases and which are immiscible with water, such as aliphatic or aromatic hydrocarbons, such as for example hexane, benzene of toluene. Suitable catalysts include crown ethers and quaternary ammonium salts, such are described in Dehmlow and Dehmlow, Phase Transfer Catalysts, Weinheim 1980.
The reaction can be carried out at temperatures between −78° and 140° C., preferably at 20°-80° C., generally at room temperature.
The carbonyl compounds starting materials of general formula IV in which R2=H, and those of general formula VII are known either as such or as their analogues (R1=phenyl) and can be prepared according to methods described in the literature (F. E. Herkes, D. J. Burton, J. Org. Chem. 32, 1316 (1967); R. Stewart, K. C. Teo, Can. J. Chem. 58, 2491 (1980); C. Aaron, D. Dull, J. L. Schmiegel, D. Jaeger, Y. Ohashi, H. S. Mosher J. Org. Chem. 32, 2797 (1967).
The aldehyde compounds of formula IV, used as starting materials, in which R2 is H, can be prepared by reacting a compound of general formula XVIII
Figure USRE037087-20010306-C00019
which can be themselves prepared by methods described in literature, with a cyanisation reagent, such as for example trimethylsilyl cyanide, in the presence of a Lewis acid, such as for example TiCl4 or SnCl4, optionally using a solvent (M. T. Reetz, I. Chatziiosifidis, Angew. Chem. 93. 1075 (1981); R. Davis, K. G. Untch, J. Drg. Chem. 46, 2987 (1981) and then reducing the resulting nitrile of general formula XIX
Figure USRE037087-20010306-C00020
to the desired aldehyde in conventional manner. R1 and R2 have the meanings given above and Y is a hydroxy group or a leaving group, such as for example halogen.
The compounds of general formula XIX, in which the group R1 is an alkoxyphenyl or haloalkoxyphenyl group etc. can be obtained also by treatment of the corresponding hydroxyphenyl derivatives, (which themselves can be prepared by hydrolysis of another alkoxyphenyl derivative), for example by using the corresponding alkyl halide.
The phosphonium salt or phosphonate starting material of general formula II, III and VI can be obtained by treatment of R4CH(R3)CH2X or R4CH(R3)CH2CH2X, wherein X is a halogen atom, with (R5)3P or (R6O)3P.
The alcohols used as starting materials of general formula XIV and XVII can be prepared by reduction of the corresponding nitrile, aldehyde, carboxylic acid or carboxylic acid ester. The reaction can be carried out according to known methods with metal hydride complexes, for example lithium aluminium hydride or alkyl aluminium hydrides for example diisobutylaluminium hydride. The halonide, tosylate and mesylates which are used, are known in themselves or can be prepared according to known methods (DE-OS No. 31 17 510, DE-OS No. 33 17 908, Houben-Wevl, Band 5/4, page 354; ibid. Band 9, page 663).
The compounds of the invention prepared by the above described processes can be isolated from the reaction mixture in conventional manner, for example by distillation of the solvent used at normal or reduced pressure or by extraction.
A higher degree of purity can be obtained as general rule by thin layer chromatography purification or by fractional distillation.
The compounds of the invention are, as a rule, colourless oils that are highly soluble in practically all organic solvents but are almost insoluble in water.
The compounds according to the invention can be used at a concentration of 0.005 to 5%, preferably from 0.001 to 1%, calculated as gram active material per 100 ml of the composition.
The compounds of the invention can be used either alone or in mixture with each other or another insecticide. Optionally other plant protection or pesticidal compositions, such as for example insecticides, acaricides or fungicides can be added depending on the desired result.
An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.
Suitable mixture partners may also include phospholipids, e.g. such as from the group phosphatidylcholine, hydrated phosphatidylcholine, phosphatidylethanolamine, N-acyl-phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
The designated active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.
Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, other mineral-oil fractions and plant oils.
Suitable solid carriers include mineral earths, e.g. tonsil, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.
As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.
The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.
The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 3,000 l/ha. The agents can be applies using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
The preparation of these formulations can be carried out in a known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.
Formulations can be prepared, for example, from the following ingredients.
(a)
80 percent by weight active ingredient
15 percent by weight kaolin
5 percent by weight surface-active agent based on the sodium salt of N-methyl-N-oleyltaurine and the calcium lignosulphonate
(b)
45 percent by weight active ingredient
5 percent by weight sodium aluminium silicate
15 percent by weight cetylpolyglycol ether with 8 moles ethylene oxide
2 percent by weight spindle oil
10 percent by weight polyethylene glycol
23 parts water
(c)
20 percent by weight active ingredient
35 percent by weight bentonite
8 percent by weight calcium lignosulphonate
2 percent by weight of the sodium salt of N-methyl-N-oleyltaurine
35 percent by weight silicic acid
(d)
20 percent by weight active ingredient
75 percent by weight isophorone
5 percent by weight of an emulsifier mixture of calcium phenylsulphonate and fatty alcohol polyglycol ether
The following examples illustrate the preparation of compounds according to the invention.
EXAMPLE 1 5-(4-Fluoro-3-phenoxyphenyl)-2-(4-methoxyphenyl)-2-trifluoromethylpentane
Figure USRE037087-20010306-C00021
1-(4-Fluoro-3-phenoxyphenyl)-4-(4-methoxyphenyl)-4-trifluoromethyl-2-pentene (15.12 g; 37.76 mmol) was hydrogenated in methanol (200 ml) with hydrogen using Raney nickel (5 g) at room temperature and under atmospheric pressure. After the calculated amount of hydrogen had been taken up, the catalyst was filtered off and the solvent removed under reduced pressure. After chromatography on silica gel using ethyl acetate/hexane as eluant, there was obtained a 10.1 g of product (=61.8% of theory).
nD 20:1.5434.
Preparation of the Starting Material
A solution of butyllithium in hexane (1.6 molar; 30 ml) was added, dropwise, under a nitrogen atmosphere to [2-(4-fluoro-3-phenoxyphenyl)ethyl]triphenylphosphonium bromide (26.76 g; 48 mmol) in absolute tetrahydrofuran (200 ml). After stirring for two hours, 2-(4-methoxyphenyl)-2-trifluoromethylpropionaldehyde (10.13 g; 43.63 mmol) dissolve in absolute tetrahydrofuran (80 ml) was added, dropwise. The mixture was heated at reflux for 3 hours and then added to ice-water, extracted with ethyl acetate, the extract dried over sodium sulphate and evaporated. After chromatography on silica gel using hexane/ethyl acetate as eluent, there was obtained 1-(4-fluoro-3-phenoxyphenyl)-4-(4-phenoxyphenyl)-4-trifluoromethyl-2-pentene (15.2 g=80.5% of theory).
A 1.2 molar solution of diisobutylaluminium hydride in toluene (46 ml) was added, dropwise, to 2-(4-methoxyphenyl)-2-trifluoromethylpropionitrile (10.0 g; 43.6 mmol) in absolute toluene (100 ml) at a temperature of 5° to 10° C. After stirring at room temperature for 3 hours, the mixture was added to ice-water, acidified with dilute hydrochloric acid, extracted with ethyl acetate, the organic phase was washed with water and dried over sodium sulphate. There was obtained 2-(4-methoxyphenyl)-2-trifluoromethylpropionaldehyde (9.5 g=93.7% of theory).
Trimethylsilyl cyanide (65.1 ml; 423 mmol) was added at room temperature to 1-chloro-1-(4-methoxyphenyl)-1-trifluoromethylethane (77.6 g; 335.5 mmol) in methylene chloride (975 ml) followed by titanium tetrachloride (32.5 ml; 3.25 mmol). After stirring for 20 hours at room temparature, 2N sodium hydroxide was added carefully, dropwise, until the mixture was neutral and the precipitate separated over celite. The aqueous phase was extracted with ethyl acetate and the extract dried over sodium suphate. After concentrating, there was obtained 2-(4-methoxyphenyl)-2-trifluoromethylpropionitrile (71.49 g=90% of theory).
Titanium tetrachloride (42.3 ml; 42.17 mmol) was added, dropwise, at room temperature to 1-(4-methoxyphenyl)-1-trifluoromethylethanol in methylene chloride (100 ml). After stirring for 1 hour, the mixture was added to ice-water, extracted with methylene chloride, washed first with saturated sodium hydrogen carbonate solution and then with water, dried over sodium sulphate and concentrated. Following distillation in a rotary evaporator at 150° C./0.5 ml, there was obtained 1-chloro-1-(4-methoxyphenyl)-2-trifluoromethylethane (77.67 g=76.7% of theory).
1,1,1-Trifluoroacetone (60.4 ml; 675 mmol) dissolved in absolute ether (80 ml) was added, dropwise, at 5° to 10° C. to an ethereal Grignard solution (prepared from p-bromoanisole (84.17 g; 450 mmol) and magnesium (10.9 g; 450 mmol) in ether (600 ml)) and the mixture stirred at room temperature for 20 hours. It was then added to saturated ammonium chloride solution, extracted with ether and the extract washed with water, dried over sodium sulphate and concentrated. The precipitate was filtered off washed with hexane and the filtrate concentrated. 1-(4-methoxyphenyl)-1-trifluoromethylethanol (93.35 g=94.2% of theory) was obtained as a brown oil that was used without further purification. (The alcohol can also be coverted direct to the nitrile in a one-pot reaction.
EXAMPLE 2 [2-(4-Ethoxyphenyl)-2-trifluoromethylpropyl](4-fluoro-3-phenoxybenzyl)ether
Figure USRE037087-20010306-C00022
Sodium hydride (144 mg; 6 mmol) was suspended in dimethoxyethane (16 ml) and then in turn, with stirring, there was added 2-(4-ethoxyphenyl)-2-trifluoromethyl-1-propanol (1.25 g; 5.044 mmol), a spatula of sodium iodide and 4-fluoro-3-phenoxybenzyl bromide (1.4 g; 5.04 mmol). After stirring for 5 hours at room temperature, the mixture was added to ice-water, extracted 3 times with ether and the extracts washed with water dried over sodium sulphate and evaporated. After chromatography on silica gel using a mixture of ethyl acetate and hexane, there was obtained 2.06 g of product (=91.1% of theory).
n20D; 1.5375.
Preparation of the Starting Material
2-(4-Ethoxyphenyl)-2-trifluoromethylpropionaldehyde (4.23 g; 17.18 mmol), prepared as described in Example 1 for 2-(4-methoxyphenyl)-2-trifluoromethylpropionaldehyde, was reduced with sodium borohydride in isopropanol (Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1976, page 616). After working up and chromatography on silica gel using hexane/ethyl acetate, there was obtaine 2.71 g of 2-(4-ethoxyphenyl)-2-trifluoromethyl-1-propanol (=63.7% of theory).
EXAMPLE 3 4-(3-Phenoxyphenyl)-1-phenyl-1-trifluoromethylbutane
Figure USRE037087-20010306-C00023
4-(3-Phenoxyphenyl)-1-phenyl-1-trifluoromethyl-1-butene (3.18 g; 8.6 mmol) was hydrogenated in ethanol (40 ml) with hydrogen with the addition of Raney nickel (0.4 g) at room temperature and under atmospheric pressures. After the calculated amount of hydrogen had been taken up, the catalyst was filtered off and the solvent removed under reduced pressure. After chromatography on silica gel with hexane/toluene, there remained 2.49 g of product (=78% of theory).
n20D: 1.5463.
Preparation of the Starting Material
A solution of butyllithium in n-hexane (8.5 ml of 1.6 molar) was added, dropwise, at room temperature and under a nitrogen atmosphere over 10 minutes to [3-(3-phenoxyphenyl)propyl]-triphenylphophonium bromide (7.67 g; 13.75 mmol) in absolute tetrahydrofuran (40 ml). After stirring for 2 hours, α,α,α-trifluoroacetophenone (2.18 g; 12.5 mmol) dissolved in absolute tetrahydrofuran (10 ml) was added dropwise. After stirring for 3 hours at room temperature, the mixture was added to ice-water, extracted with ether and the extract dried over sodium sulphate and evaporated. After chromotography on silica gel using hexane-toluene, there was obtained 4-(3-phenoxyphenyl)-1-phenyl-1-trifluoromethyl-1-butene (3.31 g=71.9% of theory).
EXAMPLE 4 3-Phenoxybenzyl 2-phenyl-2-trifluoromethylethyl ether
Figure USRE037087-20010306-C00024
Sodium hydride (138 mg; 5.75 mmol) was suspended in dimethoxyethane (20 ml). There was then added in turn, with stirring, 2-phenyl-2-trifluoromethylethanol (1.0 g; 5.25 mmol), a spatula full of sodium iodide and 3-phenoxybenzyl bromide (1.39 g; 5.25 mmol). After stirring for 4 hours at room temperature, the mixture was added to ice-water, extracted with ether, the extract washed with water, dried over sodium sulphate and concentrated. After chromatogrpahy on silica gel using a mixture of hexane and toluene, there was obtained 1.14 g of product (=58.3% of theory).
n20D: 1,546.
Preparation of the Starting Material
A 20% solution of diisobutylaluminium hydride in n-hexane (53.4 ml) was added, dropwise, to ethyl α-trifluoromethylphenylacetate (2.9 g; 12.5 mmol) (T. S. Everett, S. T. Purrington, C. L. Baumgardner, J. Org. Chem. 49, 3702 (1984)) in absolute tetrahydrofuran (50 ml) at about 60° C. The mixture was then allowed to rise to room temperature and stirred for an hour at this temperature. Then at a temperature of 5°-10° C., methanol (10.5 ml) followed by 10% aqueous potassium hydroxide (5.3 ml) was added, dropwise. After 1.5 hours, the mixture was filtered and the filtrate dried over sodium sulphate which was washed with ethyl acetate and the organic phase concentrated. There was obtained 2-phenyl-2-trifluoromethylethanol (2.07 g=87.1 of theory).
In a similar way the following compounds were prepared:
Exam- Physical
ple constant
No. Compound nD 20
5 2-(4-Ethoxyphenyl)-2-trifluoromethyl- 1.5451
propyl 3-phenoxybenzyl ether
6 2-(4-Ethoxyphenyl)-2-trifluoromethyl- 1.5542
propyl 3-(N-methylanilino)benzyl ether
7 2-(4-Methoxyphenyl)-2-trifluoromethyl- 1.5498
propyl 3-phenoxybenzyl ether
8 2,6-Dichlorobenzyl 2-(4-methoxyphenyl)-2- 1.5358
trifluoromethylpropyl ether
9 4-Fluoro-3-phenoxybenzyl 2-(4-methoxy- 1.5402
phenyl-2-trifluoromethylpropyl ether
10 2-(4-Difluoromethoxyphenyl)-2-trifluoro- 1.5239
methylpropyl 3-phenoxybenzyl ether
11 2-(4-Isopropoxyphenyl)-2-trifluoro- 1.5418
methylpropyl 3-phenoxybenzyl ether
12 4-Fluoro-3-phenoxybenzyl 2-(4-isopropoxy- 1.5331
phenyl)-2-trifluoromethylpropyl ether
13 2-(4-Isopropoxyphenyl)-2-trifluoromethyl- 1.5390
propyl 6-phenoxy-2-pyridylmethyl ether
14 2-(4-Butoxyphenyl)-2-trifluoro- 1.5380
methylpropyl 3-phenoxybenzyl ether
15 2-(4-Butoxyphenyl)-2-trifluoromethylpropyl 1.5305
4-fluoro-3-phenoxybenzyl ether
16 2-[4-(2-fluoroethoxy)phenyl]-2-trifluoro- 1.5422
methylpropyl 3-phenoxybenzyl ether
17 4-Fluoro-3-phenoxybenzyl 2-[4-(2-fluoro- 1.5350
ethoxy)phenyl]-2-trifluoromethylpropyl ether
18 2-(4-Ethoxyphenyl)-2-trifluoro- 1.5440
methylpropyl 6-phenoxy-2-pyridylmethyl ether
19 2-(4-Difluoromethoxyphenyl)-2-trifluoro- 1.5203
methylpropyl 4-fluoro-phenoxybenzyl ether
20 2-(4-Butoxyphenyl)-2-trifluoromethyl- 1.5542
propyl 3-(N-methylanilino)benzyl ether
21 2-(4-Difluoromethoxyphenyl)-2-trifluoro- 1.5256
methylpropyl 6-phenoxy-2-pyridylmethyl ether
22 2-(4-Ethoxyphenyl)-5-(4-fluoro-3-phenoxy- 1.5392
phenyl)-2-trifluoromethylpentane
23 5-(4-Fluoro-3-phenoxyphenyl)-2- 1.5350
(4-ispropoxyphenyl)-2-trifluoromethylpentane
24 2-(4-Difluoromethoxyphenyl)-5-(4-fluoro- 1.5223
3-phenoxyphenyl)-2-trifluoromethylpentane
25 2-(4-Methoxyphenyl)-5-(3-phenoxyphenyl)- 1.5505
2-trifluoromethylpentane
26 5-(3-Phenoxyphenyl)-2-trifluoromethyl-2- 1.5130
(4-trifluoromethylsulphonyloxyphenyl)pentane
27 2-(4-Ethoxyphenyl)-5-(3-phenoxyphenyl)- 1.5454
2-trifluoromethylpentane
28 2-(4-Isopropoxyphenyl)-5-(3-phenoxyphenyl)- 1.5410
2-trifluoromethylpentane
29 2-(4-Difluoromethoxyphenyl)-5-(3-phenoxy- 1.5280
phenyl)-2-trifluoromethylpentane
30 2-[4-(2,2-Dichlorovinyloxy)phenyl]-5- 1.5596
(3-phenoxyphenyl)-2-(trifluoromethylpentane
31 4-Fluoro-3-phenoxybenzyl 1.5380
2-phenyl]-2-trifluoromethylethyl ether
32 1-(4-Methoxyphenyl)-4-(3-phenoxyphenyl)- 1.5461
1-trifluoromethylbutane
33 1-(4-Ethoxyphenyl)-4-(3-phenoxyphenyl)- 1.5440
1-trifluoromethylbutane
34 1-(4-Isopropoxyphenyl)-4-(3-phenoxyphenyl)- 1.5391
1-trifluoromethylbutane
35 1-(4-Difluoromethoxyphenyl)-4-(3-phenoxy- 1.5264
phenyl)-1-trifluoromethylbutane
36 4-(3-Phenoxyphenyl)-1-trifluoromethyl-1- 1.5122
(4-trifluoromethylsulphonyloxyphenyl)butane
37 1-(Fluorophenyl)-4-(3-phenoxy- 1.5360
phenyl)-1-trifluoromethylbutane
38 1-(Methylphenyl)-4-(3-phenoxy- 1.5430
phenyl)-1-trifluoromethylbutane
39 4-(4-Fluoro-3-phenoxyphenyl)-1-(4-methoxy- 1.5393
phenyl)-1-trifluoromethylbutane
40 1-(4-Ethoxyphenyl)-4-(4-fluoro-3- 1.5350
phenoxyphenyl)-1-trifluoromethylbutane
41 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5303
(4-isopropoxyphenyl)-1-trifluoromethylbutane
42 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5048
trifluoromethyl-1-(4-trifluoromethyl-
sulphonyloxyphenyl)butane
43 1-(4-Difluoromethoxyphenyl)-4-(4-fluoro- 1.5178
3-phenoxyphenyl)-1-trifluoromethylbutane
44 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5356
(4-methylphenyl)-1-trifluoromethylbutane
45 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5278
(4-fluorophenyl)-1-trifluoromethylbutane
46 4-(4-Fluoro-3-phenoxyphenyl)-1-(3,4-methyl- 1.5460
enedioxyphenyl)-1-trifluoromethylbutane
47 2-(4-Fluoro-3-phenoxyphenyl)-2- 1.5385
(trifluoromethylpropyl) 3-phenoxybenzyl ether
48 2-(4-Fluoro-3-phenoxyphenyl)-2-(trifluoro- 1.5350
methylpropyl) 4-fluoro-3-phenoxybenzyl ether
49 2-(4-Ethoxy-3-fluorophenyl)-2- 1.5376
(trifluoromethylpropyl) 3-phenoxybenxyl ether
50 2-(4-Ethoxy-3-fluorophenyl)-2-(4-trifluoro- 1.5312
methylpropyl) 4-fluoro-3-phenoxybenzyl ether
51 2-(4-Methoxyphenyl)-2-(trifluoro- 1.5490
methylethyl) 3-phenoxybenzyl ether
52 4-Fluoro-3-phenoxybenzyl 2-(4-methoxy- 1.5400
phenyl)-2-trifluoromethylethyl ether
53 2-(4-Methoxyphenyl)-2-(trifluoro- 1.5422
methylethyl) 6-phenoxy-2-pyridylmethyl ether
54 4-(4-Fluoro-3-phenoxyphenyl)-1-[4-(2- 1.5319
fluoroethoxy)phenyl]-1-trifluoromethylbutane
55 1-[4-(2,2-Difluorocyclopropylmethoxy)phenyl]- 1.5244
4-(4-fluoro-3-phenoxyphenyl)-1-trifluoro-
methylbutane
56 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5060
[4-(2,2,3,3-tetrafluoropropoxy)phenyl]-
1-trifluoromethylbutane
57 1[4-(2,2-Dichlorocyclopropylmethoxy)- 1.5450
phenyl]-4-(4-(fluoro-3-phenoxyphenyl)-1-
trifluoromethylbutane
58 1-(4-Ethenyloxyphenyl)-4-(4-fluoro-3- 1.5408
phenoxyphenyl)-1-trifluoromethylbutane
59 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5101
[4-(2,2,2-trifluoroethoxy)phenyl]-
1-trifluoromethylbutane
60 1-[4-(2,2-Difluorocyclopropyloxy)phenyl]- 1.5240
4-(4-fluoro-3-phenoxyphenyl)-1-trifluoro-
methylbutane
61 1-[4-(2,2,2-Trichloro-1,1-difluoroethoxy)- 1.5236
phenyl]-4-(4-fluoro-3-phenoxyphenyl)-1-
trifluoromethylbutane
62 1-(3-Fluoro-4-methoxyphenyl]-4- 1.5420
(3-phenoxyphenyl)-1-trifluoromethylbutane
63 1-(4-tert.-Butylphenyl]-4-(3-phenoxyphenyl)- 1.5366
1-trifluoromethylbutane
64 2-(4-Ethoxyphenyl)-2-(trifluoro- 1.5444
methylethyl) 3-phenoxybenzyl ether
65 1-(4-Ethoxy-3-fluorophenyl)-4-(3-phenoxy- 1.5376
phenyl)-1-trifluoromethylbutane
66 2-(4-Ethoxyphenyl)-2-(trifluoromethyl- 1.5358
ethyl) 4-fluoro-3-phenoxy-benzyl ether
67 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5286
(3-fluorophenyl)-1-trifluoromethylbutane
68 1-(3-Fluorophenyl)-4-(3-phenoxyphenyl)- 1.5360
1-trifluoromethylbutane
69 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5210
(3,4-difluorophenyl]-1-trifluoromethylbutane
70 1-(3,4-Difluorophenyl)-4-(3-phenoxyphenyl)- 1.5290
1-trifluoromethylbutane
71 1-(4-tert.-Butylphenyl]-4-(4-fluoro-3- 1.5280
phenoxyphenyl)-1-trifluoromethylbutane
72 1-(3-Fluoro-4-methoxyphenyl)-4-(4-fluoro- 1.5330
3-phenoxyphenyl)-1-trifluoromethylbutane
73 1-(4-Ethoxy-3-fluorophenyl)-4-(4-fluoro- 1.5294
3-phenoxyphenyl)-1-trifluoromethylbutane
74 1-(4-Difluoromethoxy-3-fluorophenyl]-4- 1.5119
(4-fluoro-3-phenoxyphenyl)-1-
trifluoromethylbutane
75 1-(3-Fluoro-4-isopropoxyphenyl)-4-(4-fluoro- 1.5215
3-phenoxyphenyl)-1-trifluoromethylbutane
76 4-(3-Phenoxyphenyl)-1-(5,6,7,8-tetrahydro- 1.5534
2-naphthyl)-1-trifluoromethylbutane
77 1-(5-Indanyl)-4-(3-phenoxyphenyl)- 1.5541
1-trifluoromethylbutane
78 1-(4-Phenoxyphenyl)-4-(3-phenoxyphenyl)- 1.5694
1-trifluoromethylbutane
79 4-(4-Fluoro-3-phenoxyphenyl)-1-(5-Indanyl)- 1.5461
1-trifluoromethylbutane
80 4-(4-Fluoro-3-phenoxyphenyl)-1-(5,6,7,8- 1.5380
tetrahydro-2-naphthyl)-1-trifluoromethylbutane
81 1-(4-Fluorophenyl)-4-[3-(4-methoxyphenoxy- 1.5380
phenyl)-1-trifluoromethylbutane
82 4-(4-Fluoro-3-phenoxyphenyl)-1- 1.5585
(4-phenoxyphenyl)-1-trifluoromethylbutane
83 1-(4-Fluorophenyl)-(4-pentafluoro- 1.4587
phenyl)-1-trifluoromethylbutane
84 4-[3-(4-Chlorophenoxy)phenyl]-1- 1.5405
(4-fluorophenyl)-1-trifluoromethylbutane
85 4-[3-tert.-Butylphenoxy)phenyl]-1- 1.5272
(4-fluorophenyl)-1-trifluoromethylbutane
86 1-(4-Fluorophenyl)-1-trifluoromethyl-4- 1.5037
[3-(3-trifluoromethylphenoxy)phenyl]butane
87 1-(4-Fluorophenyl)-4-[3-(4-methylphenoxy)- 1.5340
phenyl)-1-trifluoromethylbutane
88 4-(4-Dimethylaminophenyl)-1- 1.5221
(4-fluorophenyl)-1-trifluoromethylbutane
89 4-[4-(1,1,2,2-tetrafluoroethoxy)phenyl]-1- 1.4580
(4-fluorophenyl)-1-trifluoromethylbutane
90 1-(4-Fluorophenyl)-4-(6-phenoxy)- 1.5316
2-pyridyl)-1-trifluoromethylbutane
91 4-(3-Anilinophenyl)-1-(4-fluorophenyl)- 1.5620
1-trifluoromethylbutane
92 1-(4-Fluorophenyl)-4-(2,6-difluoro- 1.4780
2-phenyl)-1-trifluoromethylbutane
93 4-(2-Fluorenyl)-1-(4-fluorophenyl)- 1.5648
1-trifluoromethylbutane
94 1-(4-Ethoxyphenyl)-1-trifluoromethyl- 1.5144
4-[3-(3-trifluoromethylphenoxyphenyl]butane
95 1-(4-Ethoxyphenyl)-4-[3-(4-methoxyphenoxy)- 1.5436
phenyl]-1-trifluoromethylbutane
96 4-(3-Anilino-4-fluorophenyl)-1-(4- 1.5550
fluorophenyl)-1-trifluoromethylbutane
97 1-(4-Fluorophenyl)-4-(3,4-methylenedioxy- 1.5120
phenyl)-1-trifluoromethylbutane
98 1-(4-Ethoxyphenyl)-4-(6-phenoxy- 1.5405
2-pyridyl)-1-trifluoromethylbutane
99 4-[3-(4-tert.-Butylphenoxy)phenyl]-1- 1.5356
(4-ethoxyphenyl)-1-trifluoromethylbutane
100 4-(3-Phenoxyphenyl)-1-trifluoromethyl- 1.5149
1-(3-trifluoromethylphenyl)butane
101 4-(4-Fluoro-3-phenoxy)phenyl)-1-trifluoro- 1.5078
methyl-1-(3-trifluoromethylphenyl)butane
102 1-(4-Fluorophenyl)-4-(2,3-methylenedioxy- 1.5094
phenyl)-1-trifluoromethylbutane
103 4-(4-Ethoxy-2,3,4,5-tetrafluorophenyl- 1.4669
1-(4-fluorophenyl)-1-trifluoromethylbutane
104 1-(4-Allyloxyphenyl)-4-(3-phenoxyphenyl)- 1.5465
1-trifluoromethylbutane
105 1-(4-Allyloxyphenyl)-4-(4-fluoro-3-phenoxy- 1.5391
phenyl)-1-trifluoromethylbutane
106 4-(3-Phenoxyphenyl)-1-(4-propargyloxy- 1.5502
phenyl)-1-trifluoromethylbutane
107 4-(4-Fluoro-3-phenoxyphenyl)-1-(4-propargyl- 1.5430
oxyphenyl)-1-trifluoromethylbutane
108 1-[4-(But-2-inyloxy)phenyl]-4-(3-phenoxy- 1.5510
phenyl)-1-trifluoromethylbutane
109 1-[ 4-(But-2-inyloxy)phenyl]-(fluoro- 1.5510
3-phenoxyphenyl)-1-trifluoromethylbutane
110 1-(4-Bromophenyl)-4-(3-phenoxy-
phenyl)-1-trifluoromethylbutane
111 1-(4-Chlorophenyl)-4-(3-phenoxy-
phenyl)-1-trifluoromethylbutane
112 1-(4-Bromophenyl)-4-(4-fluoro-3-phenoxy-
phenyl)-1-trifluoromethylbutane
113 1-(4-Chlorophenyl)-4-(3-phenoxy-
phenyl)-1-trifluoromethylbutane
114 1,4-Bis-(4-Fluorophenyl)- 1.4860
1-trifluoromethylbutane
115 1-(4-Fluorophenyl)-4-(3-methoxy- 1.5040
phenyl)-1-trifluoromethylbutane
116 1-(4-Fluorophenyl)-1-trifluoromethyl-4- 1.4660
(3-trifluoromethylphenyl)butane
117 4-[3-(3,4-Dichlorophenoxy)phenyl]-1- 1.5493
(4-Fluorophenyl)-1-trifluoromethylbutane
118 2-(4-Ethoxyphenyl)-2-(trifluoromethyl-
ethyl 4-(2-fluoroethoxy)benzyl ether
119 2-(4-Ethoxyphenyl)-2-(trifluoromethyl-
ethyl 3-(2-fluoroethooxy)benzyl ether
120 2-(4-Chlorophenyl)-2-(trifluoromethyl-
ethyl 4-(2-fluoroethooxy)benzyl ether
121 2-(4-Chlorophenyl)-2-(trifluoromethyl-
ethyl 3-(2-fluoroethooxy)benzyl ether
122 1-(4-Fluorophenyl)-4-[3-(2-fluoroethoxy)-
phenyl]-1-trifluoromethylbutane
123 1-(4-Fluorophenyl)-4-[4-(2-fluoroethoxy)-
phenyl]-1-trifluoromethylbutane
124 1-(4-Ethoxyphenyl)-4-[4-(2-fluoroethoxy)
phenyl]-1-trifluoromethylbutane
125 1-(4-Ethoxyphenyl)-4-[3-(2-fluoroethoxy)-
phenyl]-1-trifluoromethylbutane
126 1-(4-Chlorophenyl)-4-[3-(2-fluoroethoxy)-
phenyl]-1-trifluoromethylbutane
127 1-(4-Chlorophenyl)-4-[4-(2-fluoroethoxy)-
phenyl]-1-trifluoromethylbutane
The following test Examples illustrate the possible uses of the compounds of the invention that have been suitably formulated for use.
TEST EXAMPLE 1 Activity against Wingless Stages of Black Bean Aphids (Aphis fabae)
Compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%. Broad bean (Vicia fabae) plants (one plant per pot) that had previously been infested with wingless stages of the black bean aphid (Aphis fabae) were sprayed until dripping wet with these preparations. After this, the treated test samples were left in the laboratory under extended daylight conditions for 48 hours. The % mortality of the larvae after 48 hours from the start of the experiment in comparison with untreated controls indicated the level of activity.
In this experiment, the compounds of the preparative Examples 1-43, 44-46, 48-51, 53, 64, 66, 67, 69-75, 77, 79, 98 and 101 showed 100% activity.
TEST EXAMPLE 2 Activity against Larvae of the Diamond-Backed Moth (Plutella xylostella).
The compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%. Cabbage leaves (Brassica olearacea var. botrytis), placed in polystyrene petri dishes, were sprayed with these preparations (4 mg spray/cm2). After the sprayed surface had dried, 10 young larvae of the diamond-backed moth (Plutella xylostella) were placed in each petri dish and thereby exposed to the treated food in the closed dishes for two days. The % mortality of the larvae after two days indicated the level of activity.
In this experiment, the compounds of the preparative Examples 2, 3, 4, 9, 19, 22, 24, 31-54, 56, 58-60, 62, 72-75, 79-82, 84, 87, 90, 93, 95-98, 100 and 101 showed 100% activity.
TEST EXAMPLE 3 Activity against Larvae (L3) of the Mexican Bean Beetle (Epilachna varivestis)
The compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%. French bean plants (Phaseolus vulgaris) in the primary leaf stage were dipped in the preparations. For each test, two plant stems with in total four primary leaves were placed in glass vases filled with water and enclosed in plexiglass cylinders. Then five larvae of the Mexican bean beetle (Epilachna varivestis) at the third larval stage were put in the glass cylinders and kept for three days under extended daylight conditions. The % mortality of the larvae after three days indicated the level of activity.
In these experiments the compounds of Examples 2, 4, 5, 9, 11, 22, 24, 28, 33 and 62-66 showed 100% mortality.
TEST EXAMPLE 4 Activity against Larvae (L2) of the Cotton Army Worm (Spodoptera littoralis)
Compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%. Leaflet pairs of beans (Vicia fabae) as well as 10 larvae (L2) of the cotton army worm (Spodoptera littoralis) per experiment were sprayed with 4 mg spray/cm2 of these preparations in polystyrene petri dishes. The closed petri dishes were left in the laboratory under extended daylight conditions for two days. The % mortality of the larvae after two days indicated the level of activity.
In this experiment, the compounds of the preparative Examples 2, 3, 4, 9, 12, 17, 18, 21, 33-46, 49, 50, 52, 54, 58-60, 62, 64-70, 72, 75, 84, 90, 96, 98, 100 and 101 showed 100% activity.
TEST EXAMPLE 5 Ovicidal Activity against Eggs of the Cotton Army Worm (Spodoptera littoralis)
The compounds of the invention were made up as aqueous emulsions at a concentration of 0.1%. One day old eggs that had been laid on filter paper by fertilised female moths were dipped in the preparations until they were completely wet and then placed in closed petri dishes in the laboratory under extended daylight conditions for four days. The % inhibition of hatching of the eggs in comparison with untreated eggs indicates the level of activity.
In this experiment, the compounds of the preparative Examples 2, 4, 5, 64-66, 72, 73, 77, 87, 90 and 96 showed 100% activity.
TEST EXAMPLE 6 Activity against Motile Stages and Eggs of the Two Spotted Spider Mite (Tetranychus urticae)
Compounds of the invention were made up as an aqueous emulsion at a concentration of 0.1%. Dwarf bean plants (Phaseolus vulgaris) in the primary leaf stage, which had been infested with spider mites (Tetranychus urticae), were sprayed with these preparations until they were dripping wet and left in a laboratory for seven days under extende daylight conditions. After this, the % mortality of the motile stages on the one hand and the eggs on the other hand were estimated in comparison with untreated controls, using a magnifying glass.
In this experiment, the compounds of the preparative Examples 11, 12, 13, 19, 23, 24, 66, 69, 74, 75, 82, 84, 87 and 90-96 showed 100% activity.
TEST EXAMPLE 7 Activity in Prophylactic Treatment of Leaves against Brown Rice-Hoppers (Niliparvata lugens Stal)
In a heated greenhouse, rice seedlings (about 15 per pot) were grown until formation of the third leaf and then sprayed until dripping wet with an aqueous preparation containing 0.1% of active material. After drying the sprayed leaves, a transparent cylinder was placed over each pot. 30 Adult brown rice-hoppers (Niliparvata lugens) were introduced into each pot. After 2 days at 26° C. in the greenhouse, the amount of dead hoppers was determined. The activity was calculated according to Abbott in comparison with several untreated control pots.
Complete death was reached with the compounds of Examples 4, 12, 19, 22, 24, 33, 35-46, 49-55, 59-62, 64-81, 83, 84, 90, 94-96 and 114.
TEST EXAMPLE 8 Tickicidal Activity against Boophilus microplus
9 cm diameter filter papers were impregnated with 1 ml aliquots of acetone solutions of test compound at various concentrations. The papers were allowed to dry and then folded into envelopes in which cattle tick larvae, (Boophilus micoplus) were enclosed and held at 25° C. and 80% R.H. for 48 hours. The percentage mortality of tick larvae was then recorded and compared with controls.
The controls gave a mortality of less than 5% whereas compounds of Examples 2, 3, 5, 9, 10, 11, 12, 13, 22, 25, 26, 28, 32, 33, 37-46, 48, 51-55, 57, 58, 60, 62-67, 69-72, 74, 76, 77 and 79-81. caused 50% mortality at a concentration of 300 ppm or less.
TEST EXAMPLE 9 Insecticidal Activity against Lucilia sericata
1 ml aliquots of an acetone solution containing test compound at various concentrations were applied to cotton wool dental rolls 1 cm×2 cm, contained in glass vials (2 cm diameter×5 cm long). After drying, the treated materials were then impregnated with 1 ml of nutrient solution, infested with first instar larvae of sheep blowfly (Lucilia sericata), closed by a cotton wool plug and held at 25° C. for 24 hours.
For the controls the morality was <5% whereas the compounds of Examples 2, 5, 7, 9-18, 22, 23, 28, 32-35, 37-46, 51-55, 57, 58, 60-67, 69-72, 74, 76, 77 and 79-81 had an LC50 of 100 ppm or less.
TEST EXAMPLE 10 Insecticidal Activity against Musca domestica
Aliquots of acetone solutions of test compounds at various concentrations were applied to 9 cm diameter filter papers placed in the bottom of 9 cm diameter petri dishes closed by glass lids. After evaporation of solvent, the treated surfaces, together with control treated with acetone alone, were then infested with adult houseflies, (Musca domestica) and held at 22° C. for 24 hours.
The percentage mortality of the insects was then recorded. Less than 5% mortality resulted in the control treatments whereas the compounds of Examples 2, 5, 9, 10, 11, 12, 18, 32, 39, 40, 43, 44 and 66 had an LC50 of 400 mg/m2 or less.
TEST EXAMPLE 11 Insecticidal Activity against Blattella germanica
Aliquots of acetone solutions of test compounds at various concentrations were applied to glass plates (10 cm×10 cm). After evaporation of solvent, the treated surfaces, together with controls treated with acetone alone, were then infested with second instar nymphs of the German cockroach, (Blattella germanica), retained on the treated surface within PTFE-coated glass rings 6 cm in diameter and held for 24 hours at 22° C. The percentage mortality of the insects was then recorded.
Less than 5% mortality resulted in the control treatments whereas the compounds of Examples 2, 3, 5, 7, 9, 11-13, 16, 17, 22, 23, 25, 27, 29, 32, 33, 37-46, 51-55, 57, 58, 60-62, 67, 69-72, 74, 76, 77 and 79-81 had an LD50 of 100 mg/m2 or less.

Claims (15)

We claim:
1. An alkane or alkoxyalkane derivative of the formula
Figure USRE037087-20010306-C00025
in which
R1 is aryl or heteroaryl or these groups substituted by C1-4 alkyl, halo-C1-4 alkyl, phenyl-C1-4 alkyl, C2-4 alkenyl, halo-C2-4 alkenyl, phenyl-C2-4 alkenyl, C2-4 alkynyl, halo-C2-4 alkynyl, phenyl-C2-4 alkynyl, C1-4 alkoxy, halo-C1-4 alkoxy, phenyl-C1-4 alkoxy, C2-4 alkenyloxy, halo-C2-4 alkenyloxy, phenyl-C2-4 alkenyloxy, C2-4 alkynyloxy, halo-C2-4 akynyloxy, phenyl-C2-4 alkynyloxy, alkylsulphonyloxy, haloalkylsulphonyloxy, arylsulphonyloxy, halo, cyano, nitro, aryloxy, haloaryloxy, C1-4 alkylaryloxy, or nitroaryloxy, wherein heteroaryl is benzofuranyl, benzothiophenyl, benzoxazolyl, indanyl or benzodioxanyl
R2 is hydrogen or C1-4 alkyl,
R3 is hydrogen, cyano or ethynyl,
R4 is phenyl or pyridyl or these groups substituted by at least one of C1-6 alkyl, halo-C1-6 alkyl, phenyl-C1-6 alkyl, C2-6 alkyl interrupted by an O-, N- or S-atom, C2-4 alkenyl, halo-C2-4 alkenyl, phenyl-C2-4 alkenyl, C1-4 alkoxy, halo-C1-4 alkoxy, phenyl-C1-4 alkoxy, C2-4 alkenyloxy, halo-C2-4 alkenyloxy, phenyl-C2-4 alkenyloxy, C2-4 alkynyloxy, halo-C2-4 alkynyloxy, phenyl-C2-4 alkynyloxy, aryloxy, haloaryloxy, C1-4 alkylaryloxy, arylamino, haloarylamino, C1-4 alkylarylamino, aryl-N-C1-4 alkylamino, aryl-N-C1-4 acylamino, aroyl, haloaroyl, C1-4 alkylaroyl, aryl, haloaryl, C1-4 alkylaryl or halo, and
A is CH2 or O .
2. Alkane or alkoxyalkane derivative according to claim 1, in which
R1 is chlorophenyl, bromophenyl, fluorophenyl, methylphenyl, methoxyphenyl, ethoxyphenyl, difluoromethoxyphenyl, fluoroethoxyphenyl, or trifluoroethoxyphenyl,
R2 is hydrogen or methyl,
R3 is hydrogen,
R4 is phenoxyphenyl, fluorophenoxyphenyl or phenoxypyridyl and
A is CH2 or O .
3. Insecticidal and acaricidal composition which comprises a compound claimed in claim 1 in admixture with an agriculturally acceptable diluent.
4. A method of combating insects and acarids which comprises applying to the insects or acarids or their locus an effective amount of a compound claimed in claim 1.
5. The method of claim 4 in which said compound is [2-(4-ethoxyphenyl)-2-trifluoromethylpropyl](4-fluoro-3-phenoxybenzyl)ether, 2-phenoxybenzyl 2-phenyl-2-trifluoromethylethyl ether or 4-fluoro-3-phenoxybenzyl 2-(4-methoxyphenyl)-2-trifluoromethylpropyl ether.
6. The method of claim 4 in which said compound is 5-(4-fluoro-3-phenoxyphenyl)-2-(4-methoxyphenyl)-2-trifluoromethylpentane, 4-(3-phenoxyphenyl)-1-phenyl-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-methoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-isopropoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(6-phenoxy-2-pyridyl)-1-trifluoromethylbutane, 4-(3-phenoxyphenyl)-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane, or [4-(4-fluoro-3-phenoxy)phenyl]-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane.
7. A method of combatting insects and acarids which comprises applying to the insects or acarids or to their locus an effective amount of a compound claimed in claim 2.
8. Insecticidal and acaricidal composition according to claim 3 in which said compound is [2-(4-ethoxyphenyl)-2-trifluoromethylpropyl](4-fluoro-3-phenoxybenzyl)ether, 2-phenoxybenzyl 2-phenyl-2-trifluoromethylethyl ether or 4-fluoro-3-phenoxybenzyl 2-(4-methoxyphenyl)-2-trifluoromethylpropyl ether.
9. Insecticidal and acaricidal composition according to claim 3 in which said compound is 5-(4-fluoro-3-phenoxyphenyl)-2-(4-methoxyphenyl)-2-trifluoromethylpentane, 4-(3-phenoxyphenyl)-1-phenyl-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-methoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-isopropoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(6-phenoxy-2-pyridyl)-1-trifluoromethylbutane, 4-(3-phenoxyphenyl)-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane, or [4-(4-fluoro-3-phenoxy)phenyl]-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane.
10. Insecticidal and acaricidal composition which comprises a compound claimed in claim 2 in admixture with an agriculturally acceptable diluent.
11. Alkane or alkoxyalkane derivative according to claim 1 which is [2-(4-ethoxyphenyl)-2-trifluoromethylpropyl](4-fluoro-3-phenoxybenzyl)ether, 2-phenoxybenzyl 2-phenyl-2-trifluoromethylethyl ether or 4-fluoro-3-phenoxybenzyl 2-(4-methoxyphenyl)-2-trifluoromethylpropyl ether.
12. Alkane or alkoxyalkane derivative according to claim 1 which is 5-(4-fluoro-3-phenoxyphenyl)-2-(4-methoxyphenyl)-2-trifluoromethylpentane, 4-(3-phenoxyphenyl)-1-phenyl-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-methoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(3-fluoro-4-isopropoxyphenyl)-4-(4-fluoro-3-phenoxyphenyl)-1-trifluoromethylbutane, 1-(4-ethoxyphenyl)-4-(6-phenoxy-2-pyridyl)-1-trifluoromethylbutane, 4-(3-phenoxyphenyl)-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane, and [4-(4-fluoro-3-phenoxy)phenyl]-1-trifluoromethyl-1-(3-trifluoromethylphenyl)butane.
13. Alkane derivative according to claim 1 which is 1-( 4 -ethoxyphenyl)- 4 -( 4 -fluoro- 3 -phenoxyphenyl)- 1 -trifluoromethylbutane or 1 -( 4 -ethoxy- 3 -fluorophenyl)- 4 -( 3 -phenoxyphenyl)- 1 -trifluoromethylbutane.
14. Insecticidal and acaricidal composition which comprises a compound claimed in claim 13 in admixture with an agriculturally acceptable diluent.
15. A method of combating insects and acarids which comprises apply to the insects or acarids or their locus an effective amount of a compound claimed in claim 13.
US07/720,091 1986-01-22 1991-06-20 Insecticidal triffluormethyl alkane derivatives Expired - Lifetime USRE37087E1 (en)

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US20020058660A1 (en) * 2000-09-12 2002-05-16 Bentley Terence James 1,4 diaryl-2,3-difluoro-2-butene insecticidal and acaricidal agents

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8520027D0 (en) * 1985-08-09 1985-09-18 Ici Plc Insecticidal ethers
US5225607A (en) * 1985-08-09 1993-07-06 Imperial Chemical Industries Plc Insecticidal ethers
EP0390228A3 (en) * 1986-03-04 1991-03-13 Imperial Chemical Industries Plc Chemical intermediates
GB8605281D0 (en) * 1986-03-04 1986-04-09 Ici Plc Diphenyl ether derivatives
EP0276558B1 (en) * 1987-01-08 1992-07-08 Imperial Chemical Industries Plc Insecticidal ethers
GB8702717D0 (en) * 1987-02-06 1987-03-11 Ici Plc Insecticidal compounds
JPS6475437A (en) * 1987-09-14 1989-03-22 Sumitomo Chemical Co Optically active alcohols and their production
GB8822792D0 (en) * 1988-09-28 1988-11-02 Ici Plc Insecticidal compounds
GB8822793D0 (en) * 1988-09-28 1988-11-02 Ici Plc Insecticidal compounds
JP2767707B2 (en) * 1989-07-07 1998-06-18 三井化学株式会社 Solid insecticidal miticide
US5136080A (en) * 1989-12-04 1992-08-04 Burroughs Wellcome Co. Nitrile compounds
IL107161A0 (en) * 1992-10-15 1993-12-28 Schering Ag Process for the preparation of 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane derivatives and intermediates for use in the preparation thereof
DE4318370C1 (en) * 1993-05-28 1994-05-11 Schering Ag Prepn. of substd. 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-tri:fluoro-pentane derivs. - useful as insecticides, via new intermediates
TR27159A (en) * 1993-11-12 1994-11-10 Schering Ag Methods and intermediates for the preparation of substituted 2-phenyl-5- (3-phenoxyphelin (1,1,1-trifluoropentanes).
EP0780375B1 (en) 1995-12-21 2002-09-11 Pfizer Inc. 3-((5-substituted benzyl)amino)-2-phenylpiperidines as substance p antagonists
FR2779717B1 (en) * 1998-06-11 2001-06-22 Rhodia Chimie Sa PROCESS FOR THE CONDENSATION, IN AN ACID MEDIUM, OF ONE OR MORE CARBONYL COMPOUNDS ON CARBOCYCLIC AROMATIC ETHERS OR THIOETHERS
JP6670793B2 (en) * 2017-04-21 2020-03-25 信越化学工業株式会社 Method for producing 1-halo-6,9-pentadecadiene and (7Z, 10Z) -7,10-hexadecadienal

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998855A (en) 1972-01-14 1976-12-21 Ciba-Geigy Corporation Epoxyalkoxy substituted benzophenones
EP0008734A1 (en) 1978-08-28 1980-03-19 Bayer Ag Process for the preparation of 4-fluor-3-phenoxytoluene
JPS55154931A (en) 1979-05-22 1980-12-02 Ihara Chem Ind Co Ltd Trifluoromethylphenoxyisopropylbenzene and its preparation
US4266074A (en) 1972-07-11 1981-05-05 Sumitomo Chemical Company Limited Novel insecticidal composition
US4316994A (en) 1979-08-08 1982-02-23 Bayer Aktiengesellschaft Preparation of 4-fluoro-3-phenoxy-toluene
US4326087A (en) 1979-08-22 1982-04-20 Bayer Aktiengesellschaft 3-Bromo-4-fluoro-benzyl derivatives
JPS5829733A (en) 1981-08-14 1983-02-22 Kureha Chem Ind Co Ltd Phenoxy-(3,3,3-trifluoropropyl)benzene
US4397864A (en) 1980-05-02 1983-08-09 Mitsuitoatsu Chemicals Inc. 2-Arylpropyl ether or thioether derivatives and insecticidal and acaricidal agents containing said derivatives
JPS60193940A (en) 1984-03-16 1985-10-02 Mitsui Toatsu Chem Inc Novel aromatic alkene compound
EP0175377A2 (en) 1984-09-21 1986-03-26 Sumitomo Chemical Company, Limited An ether compound, its production and an insecticidal and acaricidal composition containing it as an active ingredient
US4661501A (en) 1982-05-18 1987-04-28 Mitsui Toatsu Chemicals, Inc. Certain aryl-alkane-2-pyridyloxy-phenyl derivatives having insecticidal and acaricidal activity
US4791139A (en) 1986-03-04 1988-12-13 Imperial Chemical Industries Plc Diphenyl ether derivatives and their use as insecticides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59501982A (en) * 1982-09-24 1984-11-29 コモンウエルス・サイエンテイフイツク・アンド・インダストリアル・リサ−チ・オ−ガニゼイシヨン Arthropod control composition
DE3438483A1 (en) * 1984-10-17 1986-04-17 Schering AG, Berlin und Bergkamen, 1000 Berlin SUBSTITUTED BENZYL ETHER, PEST CONTROL, CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF
DE3505370A1 (en) * 1985-02-14 1986-08-14 Schering AG, 1000 Berlin und 4709 Bergkamen AROMATIC ALKANE DERIVATIVES, PEST CONTROLS CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF
GB8520027D0 (en) * 1985-08-09 1985-09-18 Ici Plc Insecticidal ethers

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998855A (en) 1972-01-14 1976-12-21 Ciba-Geigy Corporation Epoxyalkoxy substituted benzophenones
US4266074A (en) 1972-07-11 1981-05-05 Sumitomo Chemical Company Limited Novel insecticidal composition
EP0008734A1 (en) 1978-08-28 1980-03-19 Bayer Ag Process for the preparation of 4-fluor-3-phenoxytoluene
JPS55154931A (en) 1979-05-22 1980-12-02 Ihara Chem Ind Co Ltd Trifluoromethylphenoxyisopropylbenzene and its preparation
US4316994A (en) 1979-08-08 1982-02-23 Bayer Aktiengesellschaft Preparation of 4-fluoro-3-phenoxy-toluene
US4326087A (en) 1979-08-22 1982-04-20 Bayer Aktiengesellschaft 3-Bromo-4-fluoro-benzyl derivatives
US4570005A (en) 1980-05-02 1986-02-11 Mitsuitoatsu Chemicals Inc. Process for the preparation of 2-arylpropyl ether or thioether derivatives
US4397864A (en) 1980-05-02 1983-08-09 Mitsuitoatsu Chemicals Inc. 2-Arylpropyl ether or thioether derivatives and insecticidal and acaricidal agents containing said derivatives
JPS5829733A (en) 1981-08-14 1983-02-22 Kureha Chem Ind Co Ltd Phenoxy-(3,3,3-trifluoropropyl)benzene
US4661501A (en) 1982-05-18 1987-04-28 Mitsui Toatsu Chemicals, Inc. Certain aryl-alkane-2-pyridyloxy-phenyl derivatives having insecticidal and acaricidal activity
JPS60193940A (en) 1984-03-16 1985-10-02 Mitsui Toatsu Chem Inc Novel aromatic alkene compound
EP0175377A2 (en) 1984-09-21 1986-03-26 Sumitomo Chemical Company, Limited An ether compound, its production and an insecticidal and acaricidal composition containing it as an active ingredient
US4664698A (en) 1984-09-21 1987-05-12 Sumitomo Chemical Company, Limited Ether compound, and an insecticidal and acaricidal composition containing it as an active ingredient
US4791139A (en) 1986-03-04 1988-12-13 Imperial Chemical Industries Plc Diphenyl ether derivatives and their use as insecticides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020058660A1 (en) * 2000-09-12 2002-05-16 Bentley Terence James 1,4 diaryl-2,3-difluoro-2-butene insecticidal and acaricidal agents
US6506800B2 (en) * 2000-09-12 2003-01-14 Basf Aktiengesellschaft 1,4 diaryl-2,3-difluoro-2-butene insecticidal and acaricidal agents

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IL81249A (en) 1995-03-15
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