WO1993024464A1 - 1-(4-cyanophenylcarbamoyl)pyrazoline insecticides and acaricides - Google Patents

1-(4-cyanophenylcarbamoyl)pyrazoline insecticides and acaricides Download PDF

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Publication number
WO1993024464A1
WO1993024464A1 PCT/EP1993/001363 EP9301363W WO9324464A1 WO 1993024464 A1 WO1993024464 A1 WO 1993024464A1 EP 9301363 W EP9301363 W EP 9301363W WO 9324464 A1 WO9324464 A1 WO 9324464A1
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Prior art keywords
compounds
optionally substituted
percent
pyrazoline
pyrazoline derivative
Prior art date
Application number
PCT/EP1993/001363
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French (fr)
Inventor
Holger Hoffmann
Annegrit Bosum-Dybus
Andreas Von Almsick
Thomas Wegmann
Harribert Neh
Hartmut Joppien
Harald Von Keyserlingk
Geoffrey Briggs
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Schering Aktiengesellschaft
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Publication of WO1993024464A1 publication Critical patent/WO1993024464A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • This invention relates to new pyrazoline derivatives , processes for their preparation, as well as their use as pesticides .
  • X and Y are the same or different and are fluorine or
  • R is hydrogen or C ⁇ -alkyl, optionally substituted by fluorine.
  • the invention includes isomeric forms and as well as mixtures of isomer ⁇ .
  • R is hydrogen.
  • the optionally substitured haloalkoxy is preferably a fluoroalkoxy group, especially fluoroethoxy and particularly 2 , 2 , 2-trifluoroethoxy.
  • X is preferably fluoroalkoxy and Y is preferably fluoro.
  • the solvent is one which is inert to the reactants, e.g aliphatic, alicyclic or aromatic hydrocarbons, which are optionally chlorinated, e.g. pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene or chlorobenzene; ethers, such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert.
  • the reactants e.g aliphatic, alicyclic or aromatic hydrocarbons, which are optionally chlorinated, e.g. pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, chloroform,
  • -butyl ether dioxane or tetrahydrofuran
  • nitriles such as acetonitrile, propionitrile or benzonitrile
  • esters such as ethyl acetate or amyl acetate
  • amides such as dimethylforma ide, N-methylpyrrolidone or hexa ethylphosphoric triamide, as well as sulfones, such as dimethyl sulfoxide or sulfolane.
  • Bases that can be used include aliphatic, aromatic and heterocyclic a ine, e.g. triethyla ine, dimethylaniline or pyridine.
  • the reaction can be carried out over a wide temperature range.
  • the reaction temperature lies between -20 and +100°C, preferably at however at room temperature.
  • the reaction is preferably carried out at atmospheric pressure, although higher or lower pressures can be used
  • the preparation of the pyrazoline of general formula II used as starting material can be carried out in known manner for example as described in DE 25 29 689 and EP 227 055.
  • 4-Cyanophenyl isocyanate used as starting material, is a known compound.
  • the compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced pressure, by precipitation with water or by extraction. A higher level of purity can be achieved as a rule by column chromatography or recrystallisation.
  • the pyrazoline derivatives of the invention are colourless and odourless and in most cases are crystalline compounds. They have a low solubility in water and toluene, are more soluble in ethyl acetate and highly soluble in dimethyl- formamide
  • the compounds of the invention have insecticidal and acaricidal activity and are suitable for combating parasites of humans and domestic animals as well as plant pests.
  • Examples are Lepidoptera, such as Plutella xylo ⁇ tella , Spodoptera littoralis , Heliothis armigera , Heliothis virescens and Pieris brassicae ; Diptera, such as Gasterophilus , Cochliomyia , Mu ⁇ ca domestica , Ceratitis capitata , Erioischia brassicae, Lucilia sericata and Aedes aegypti ; Hemiptera, including aphids such as Megoura viciae and leafhoppers, such as Nilaparvata lugens and Nephotettix cincticeps; Coleoptera, such as Phaedon cochleariae, Anthonomus grandi ⁇ and corn rootworms (Diabrotica
  • Orthoptera such as Blattella germanica j ticks, such as Boophilus microplus and lice, such as Damalinia bovis and Linognathus vituli as well as mites such as Tetranychus urticae and Panonychus ulmi .
  • 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-acy1-phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, lysolecithin or phosphatidylglycerol.
  • phospholipids e.g. such as from the group phosphatidylcholine, hydrated phosphatidylcholine, phosphatidylethanolamine, N-acy1-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 sulfoxide, 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 lignosulfonate, polyoxyethylenealkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, as well as substituted benzenesulfonic acids and their salts.
  • Formulations can be prepared, for example, from the following ingredients.
  • EA ethyl acetate
  • the compounds were made up as aqueous preparations at a concentration of 0.1%. 0.2 ml of this preparation was pipetted onto feed material, in a polystyrene petri dish and 0.2 ml onto the bottom of the petri dish. After drying, 5 adult (2 day old) cotton boll-weevils (Anthonomus grandis) were counted into each dishes. The closed dishes were left for up to 7 days at 25°C under extended daylight conditions.
  • the % mortality of the weevils at the end of the test indicated the level of activity.
  • the compounds were tested in a similar manner to test example A, against 10 LI of the cotton bollworm (Heliothis viriscens) , and in which only the feed material was treated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Pyrazoline derivatives of general formula (I) in which X and Y are the same or different and are fluorine or C1-4-alcoxy, optionally substituted by halogen, and R is hydrogen or C1-4-alkyl, optionally substituted by fluorine, have insecticidal and acaricidal activity.

Description

1- ( 4- _YAN0PHENYI_CARBAM0Y ) PYRAZOLINE INSECTICIDES AND ACARICIDES
Field of the invention
This invention relates to new pyrazoline derivatives , processes for their preparation, as well as their use as pesticides .
Prior Art
1-Phenylcarbamoylpyrazolines with insecticidal activity are already well known. There are a number of patents describing such compounds, for example DE OS 2529689, EP 58424, EP 113213 and EP 227055. In all these patents, there are disclosed compounds in which there is a substituted phenyl group in the 3 and 4 positions of the pyrazoline ring. In certain of these patents, compounds are disclosed in which there is a 4-cyano group positioned on the phenylcarbamoyl ring, optionally substituted haloalkoxy on one of the other phenyl rings and halogen on the third phenyl ring. However, there are no compounds disclosed with the particular pattern of substituents of the present invention.
The disadvantage of many of the prior art compounds is the insufficient activity and/or high mammalian toxicity and we have found that the compounds of the present invention overcome these disadvantages.
Description of the Invention
According to the invention there is provided a pyrazoline derivative of general formula I
Figure imgf000004_0001
in which
X and Y are the same or different and are fluorine or
Cj^-alkoxy, optionally substituted by halogen, and R is hydrogen or C^-alkyl, optionally substituted by fluorine.
The invention includes isomeric forms and as well as mixtures of isomerε.
It is generally preferred that R is hydrogen. The optionally substitured haloalkoxy is preferably a fluoroalkoxy group, especially fluoroethoxy and particularly 2 , 2 , 2-trifluoroethoxy. X is preferably fluoroalkoxy and Y is preferably fluoro.
The compounds of the invention of general formula I, where R is hydrogen, can be prepared by reacting a pyrazoline of general formula II
Figure imgf000004_0002
with 4-cyanophenyl isocyanate in a solvent and optionally in the presence of a base.
The solvent is one which is inert to the reactants, e.g aliphatic, alicyclic or aromatic hydrocarbons, which are optionally chlorinated, e.g. pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene or chlorobenzene; ethers, such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert. -butyl ether, dioxane or tetrahydrofuran; nitriles, such as acetonitrile, propionitrile or benzonitrile; esters, such as ethyl acetate or amyl acetate; amides, such as dimethylforma ide, N-methylpyrrolidone or hexa ethylphosphoric triamide, as well as sulfones, such as dimethyl sulfoxide or sulfolane.
Bases that can be used include aliphatic, aromatic and heterocyclic a ine, e.g. triethyla ine, dimethylaniline or pyridine.
The reaction can be carried out over a wide temperature range. In general, the reaction temperature lies between -20 and +100°C, preferably at however at room temperature.
The reaction is preferably carried out at atmospheric pressure, although higher or lower pressures can be used
Compounds where R is optionally substituted alkyl can then be prepared by alkylating the compound of formula I in known manner.
The preparation of the pyrazoline of general formula II used as starting material can be carried out in known manner for example as described in DE 25 29 689 and EP 227 055.
4-Cyanophenyl isocyanate, used as starting material, is a known compound.
The compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced pressure, by precipitation with water or by extraction. A higher level of purity can be achieved as a rule by column chromatography or recrystallisation.
The pyrazoline derivatives of the invention are colourless and odourless and in most cases are crystalline compounds. They have a low solubility in water and toluene, are more soluble in ethyl acetate and highly soluble in dimethyl- formamide
The compounds of the invention have insecticidal and acaricidal activity and are suitable for combating parasites of humans and domestic animals as well as plant pests. Examples are Lepidoptera, such as Plutella xyloεtella , Spodoptera littoralis , Heliothis armigera , Heliothis virescens and Pieris brassicae ; Diptera, such as Gasterophilus , Cochliomyia , Muεca domestica , Ceratitis capitata , Erioischia brassicae, Lucilia sericata and Aedes aegypti ; Hemiptera, including aphids such as Megoura viciae and leafhoppers, such as Nilaparvata lugens and Nephotettix cincticeps; Coleoptera, such as Phaedon cochleariae, Anthonomus grandiε and corn rootworms (Diabrotica spp. , e.g. Diabrotica undecimpunctata) ; Orthoptera, such as Blattella germanica j ticks, such as Boophilus microplus and lice, such as Damalinia bovis and Linognathus vituli as well as mites such as Tetranychus urticae and Panonychus ulmi .
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-acy1-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 sulfoxide, 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 lignosulfonate, polyoxyethylenealkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, as well as substituted benzenesulfonic acids and their salts.
Formulations can be prepared, for example, from the following ingredients.
Al ETTABLE POWDER
80 percent by weight active ingredient 15 percent by weight kaolin
5 percent by weight of surfactant based on of the sodium salt of N-methyl-N-oleyltaurine and calcium lignosulfonate
A2 V7ETTABLE POWDER
20 percent by weight active ingredient 35 percent by weight fuller's earth
8 percent by weight calcium lignosulfonate
2 percent by weight sodium salt of N-methyl-N-oleyltaurine
35 percent by weight silicic acid
B PASTE
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 EMULSIFIABLE CONCENTRATE
20 percent by weight active ingredient 75 percent by weight isophorone 5 percent by weight of a mixture of ionic and nonionic surfactants
The following examples illustrate the preparation of compounds according to the invention.
Example 1
N-(4-Cvanophenyl —3—r4— f2 , 2 , 2-trifluoroethoxy)phenyl1 - 4-(4-fluorophenyl) -4 , 5-dihydropyrazole-l-carboxamide
3.6 g (10.6 mmol) 3-[4- (2, 2 , 2-Trifluoroethoxy)phenyl]- 4-(4-fluorophenyl) -4, 5-dihydropyrazole was dissolved in 40 ml dichloromethane and, at room temperature, treated with 1.73 g (120 mmol) 4-cyanophenyl isocyanate together with a drop of triethylamine. The mixture was stirred for 1 hour at room temperature and allowed to stand overnight. The resulting crystals were suction filtered washed with 5 ml dichloromethane and dried jln vacuo.
Yield: 3.76 g (74% of theory) m.p. : >250°C R... 0.84 (silica gel/EA)
Example 2
N-Methyl-N- (4-cvanophenyl) -3-T4- (2,2, 2-trifluoroethoxy) - henyl1-4- (4-fluorophenyl) -4 , S-dihvdrooyrazole- 1-carboxamide
1.00 g (2.0 mmol) of the product of Example 1 was added, with stirring under anhydrous conditions at room temperature, to a suspension of 180 mg (6.0 mmol) of sodium hydride (80% suspension in mineral oil) in 20 ml tetrahydrofuran. When gas evolution had ceased (30 in) 0.85 g (40.0 mmol) iodomethane in 10 ml tetrahydrofuran was added dropwise. The mixture was stirred for 3 hours at room temperature and allowed to stand overnight. It was then added to 20 ml ice-water and extracted 4 times, each time with 30 ml ethyl acetate. The crude product, obtained by concentration of the organic phases, was purified by silica gel column chromatography (ethyl acetate/hexane, 1:2) .
Yield: 210 mg (21% of theory) m.p. : 83-5°C
In a similar manner to Example 1 or 2, the following compounds of formula I were prepared:
Figure imgf000010_0001
EA = ethyl acetate The following examples illustrate the possibilities for use of the compounds of the invention.
Test Example Α Activity against adult cotton boll-weevil (Anthonomus grand is)
The compounds were made up as aqueous preparations at a concentration of 0.1%. 0.2 ml of this preparation was pipetted onto feed material, in a polystyrene petri dish and 0.2 ml onto the bottom of the petri dish. After drying, 5 adult (2 day old) cotton boll-weevils (Anthonomus grandis) were counted into each dishes. The closed dishes were left for up to 7 days at 25°C under extended daylight conditions.
The % mortality of the weevils at the end of the test indicated the level of activity.
The compounds of Examples 1 to 13 showed 80 - 100% activity.
Test Example B
Activity against larvae (LI) of the cotton bollworm (Heliothis viriscens)
The compounds were tested in a similar manner to test example A, against 10 LI of the cotton bollworm (Heliothis viriscens) , and in which only the feed material was treated.
The compounds of Examples 1 to 13 showed 80 - 100% activity.

Claims

A pyrazoline derivative of general formula I
Figure imgf000012_0001
in which
X and Y are the same or different and are fluorine or C -alkoxy, optionally substituted by halogen, and R is hydrogen or C -alkyl, optionally substituted by fluorine.
A pyrazoline derivative according to claim 1, in which R is hydrogen.
A pyrazoline derivative according to claim 1 or 2 , in which the optionally substituted haloalkoxy is a fluoroalkoxy group.
A pyrazoline derivative according to claim 3, in which the fluoroalkoxy group is 2,2, 2-trifluoroethoxy.
A pyrazoline derivative according to any one of the preceding claims in which X is fluoroalkoxy and Y is fluoro. 6. An insecticidal and acaricidal composition which comprises a compound claimed in any one of the preceding claims in admixture with an agriculturally acceptable diluent or carrier.
7. Use of a compound claimed in any one of the preceding claims, for combating insects or acarids.
8. A method of combating insects and acarids which comprises applying to the insect or acarid or their locus, an effective amount of a compound claimed in any one of the preceding claims.
PCT/EP1993/001363 1992-06-04 1993-05-28 1-(4-cyanophenylcarbamoyl)pyrazoline insecticides and acaricides WO1993024464A1 (en)

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DE4218745A DE4218745A1 (en) 1992-06-04 1992-06-04 1- (4-cyanophenylcarbamoyl) pyrazoline
DEP4218745.1 1992-06-04

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CN (1) CN1082537A (en)
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DE (1) DE4218745A1 (en)
IL (1) IL105778A0 (en)
WO (1) WO1993024464A1 (en)
ZA (1) ZA933961B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679644A1 (en) * 1994-04-29 1995-11-02 Bayer Ag Substituted pyrazoline derivatives

Citations (5)

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DE2529689A1 (en) * 1974-07-12 1976-01-29 Philips Nv NEW PYRAZOLINE COMPOUNDS
EP0058424A2 (en) * 1981-02-17 1982-08-25 Nissan Chemical Industries Ltd. Pyrazoline derivatives
US4464386A (en) * 1981-02-17 1984-08-07 Nissan Chemical Industries, Ltd. Insecticidal 3-difluoromethoxyphenyl-1-phenylcarbamoyl-2-pyrazolines
US4767779A (en) * 1985-09-24 1988-08-30 Fmc Corporation Pyrazoline-1-carboxamides, composition containing them, and insecticidal method of using them
EP0300692A1 (en) * 1987-07-17 1989-01-25 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines

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NL183400C (en) * 1976-01-09 1988-10-17 Duphar Int Res METHOD FOR PREPARING AN INSECTICIDE PREPARATION CONTAINING A PYRAZOLINE COMPOUND AND METHOD FOR PREPARING A PYRAZOLINE COMPOUND WITH INSECTICIDE ACTION
SU717991A3 (en) * 1975-07-25 1980-02-25 Н.В.Филипс Глойлампенфабрикен (Фирма) Insecticidic composition
SU722485A3 (en) * 1976-05-07 1980-03-15 Н.В.Филипс Глойлампенфабрикен (Фирма) Method of preparing pyrazoline derivatives
DE3264760D1 (en) * 1981-05-12 1985-08-22 Duphar Int Res New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal compositions on the basis of these compounds
DE3545786A1 (en) * 1985-12-21 1987-06-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides
DE3628647A1 (en) * 1986-08-22 1988-02-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides and acaricides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2529689A1 (en) * 1974-07-12 1976-01-29 Philips Nv NEW PYRAZOLINE COMPOUNDS
EP0058424A2 (en) * 1981-02-17 1982-08-25 Nissan Chemical Industries Ltd. Pyrazoline derivatives
US4464386A (en) * 1981-02-17 1984-08-07 Nissan Chemical Industries, Ltd. Insecticidal 3-difluoromethoxyphenyl-1-phenylcarbamoyl-2-pyrazolines
US4767779A (en) * 1985-09-24 1988-08-30 Fmc Corporation Pyrazoline-1-carboxamides, composition containing them, and insecticidal method of using them
EP0300692A1 (en) * 1987-07-17 1989-01-25 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679644A1 (en) * 1994-04-29 1995-11-02 Bayer Ag Substituted pyrazoline derivatives

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KR940005579A (en) 1994-03-21
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CN1082537A (en) 1994-02-23
DE4218745A1 (en) 1993-12-09
IL105778A0 (en) 1993-09-22

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