WO1995021159A1 - Substituted pyrazoline - Google Patents

Substituted pyrazoline Download PDF

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Publication number
WO1995021159A1
WO1995021159A1 PCT/EP1995/000356 EP9500356W WO9521159A1 WO 1995021159 A1 WO1995021159 A1 WO 1995021159A1 EP 9500356 W EP9500356 W EP 9500356W WO 9521159 A1 WO9521159 A1 WO 9521159A1
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Prior art keywords
percent
weight
phenyl
dihydropyrazole
active ingredient
Prior art date
Application number
PCT/EP1995/000356
Other languages
French (fr)
Inventor
Thomas Wegmann
Andreas Van Almsick
Annegrit Bosum Dybus
Holger Hoffmann
Hartmut Joppien
Harald Von Keyserlingk
Original Assignee
Hoechst Schering Agrevo Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Schering Agrevo Gmbh filed Critical Hoechst Schering Agrevo Gmbh
Priority to AU16637/95A priority Critical patent/AU1663795A/en
Publication of WO1995021159A1 publication Critical patent/WO1995021159A1/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
    • 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 a new substituted pyrazoline derivative, namely N-(4-ethoxycarbonylphenyl - 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroetho y)phenyl]- 4,5-dihydropyrazole-l-carboxamide, to a process for its production and to its use as a pesticide, in particular as an insecticide and acaricide.
  • N-(4-ethoxy- carbonylphenyl)-4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoro ⁇ ethoxy)phenyl]-4,5-dihydropyrazole-l-carboxamide is superior, compared with the known compounds of the prior art, both in its biological effectiveness and in the parameter which is important for the environment, its rate of degradation in soil.
  • the pyrazoline according to the invention is obtained by reacting 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroethoxy)- phenyl]-4,5-dihydropyrazole with 4-ethoxycarbonylphenyl isocyanate in a solvent in the presence of a base.
  • the dihydropyrazole used as starting material is known, e.g. from EP 227 055.
  • the isocyanate used as starting compound is also known.
  • the reaction preferably takes place in an organic solvent or solvent mixture at a temperature from -20 to 150°C, preferably at room temperature.
  • Suitable solvents are those which are 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, dichloro ethane, 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 a yl acetate; amides, such as dimethylformamide
  • Aliphatic, aromatic and heterocyclic amines such as e.g. triethylamine, dimethylaniline and pyridine may be cited as bases.
  • the compound according to the invention can, however, also be produced by reacting the dihydropyrazole with phosgene to give 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroethoxy)- phenyl]-4,5-dihydropyrazole-l-carbonyl chloride, and then reacting this with ethyl 4-aminobenzoate, in the presence of triethylamine.
  • the compound of the invention prepared by the processes described above 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 new compound has a markedly pronounced effectiveness against animal pests, in partic ar against insects and spider mites. It shows a considerably better insecticidal effectiveness against plant-damaging and mammal- parasitizing insects and spider mites compared with known compounds which are chemically and biologically closely related.
  • Lepidoptera such as Plutella xylostella, Spodoptera littoralis, Heliothis armigera , Heliothis virescens and Pieris brassicae ; Diptera, such as Gasterophilus, ⁇ ..ochliomyia, Musca do estica, Ceratitis capitata, Erioischia brassicae , Lucilia sericata and Aedes aegypti ; Hemiptera, including aphids such as Megoura viciae and leafhoppers, such as Nilaparvata lugens and Nephotettix cincticep ⁇ ; Coleoptera, such as Phaedon cochleariae, Anthonomus grandis and corn rootworms (Diabrotica spp. , e.g. Diabrotica undecimpunctata) ; Orthoptera, such as
  • Blattella germanica 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 compound of the invention can be used either alone or in mixture with 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.
  • the active ingredient is suitably in the form of a preparation such as a powder, dust, granule, solution, emulsion or suspension, 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, dimethylforma ide, 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.
  • 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.
  • 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.
  • composition can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 3,000 1/ha.
  • the agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
  • the compound of the invention can be used in active ingredient concentrations of from 0.005 to 5% by weight, preferably from 0.01 to 0.5% by weight.
  • formulations can be carried out in known manner, for example by milling or mixing processes.
  • individual components can be mixed just before use for example by the commonly used so-called tank-mixing method.
  • Formulations can be prepared, for example, from the following ingredients.
  • N-methyl-N-oleyltaurine 35 percent by weight silicic acid
  • the compound of the invention and the listed homologous pyrazoline derivatives were used as an aqueous preparation with different active ingredient concentrations. 0.2 ml of these active ingredient preparations were pipetted onto a dietary feed in five polystyrene Petri dishes. After drying, 10 LI each of the cotton bollworm (Heliothis virescens) were counted into the dishes. The closed dishes were kept for up to 7 days at 25 ⁇ °C under long-day conditions. The criterion for assessing the activity was the mortality of the larvae at the end of the experiment.
  • the half-life value was determined under aerobic conditions in a biologically active soil using high pressure liquid chromatography. The following half-life values were obtained:

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

Abstract

There is described N-(4-ethoxycarbonylphenyl)-4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroethoxy)phenyl]-4,5-dihydropyrazole-1-carboxamide, a process for its preparation and its use as a pesticide.

Description

Case 94B001
Title: Substituted pyrazoline
Field of the invention
This invention relates to a new substituted pyrazoline derivative, namely N-(4-ethoxycarbonylphenyl - 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroetho y)phenyl]- 4,5-dihydropyrazole-l-carboxamide, to a process for its production and to its use as a pesticide, in particular as an insecticide and acaricide.
Pyrazolines with insecticidal action have been known for a long time. Thus, there is described for example in EP 58424 and EP 227 055, pyrazolines which generally have in the 1-position of the pyrazoline ring a phenylcarbamoyl group substituted by alkoxycarbonyl, and in the 3- and 4- positions of the pyrazoline ring a phenyl group substituted in the 4-position. In E? 58424, the ethoxycarbonyl group is specifically mentioned as an example of alkoxycarbonyl. In EP 227 055, the compound 4-(4-fluorophenyl)-N-(4-isopropoxycarbonylphenyl)- 3-[4-(2,2,2-trifluoroethoxy)phenyl]-4,5-dihydropyrazole- 1-carboxamide is disclosed.
The known pyrazolines do, however, have the disadvantage that they have an activity spectrum and environmental behaviour which seems to make them unsuitable for use as pesticides.
It was now surprisingly found that N-(4-ethoxy- carbonylphenyl)-4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoro¬ ethoxy)phenyl]-4,5-dihydropyrazole-l-carboxamide is superior, compared with the known compounds of the prior art, both in its biological effectiveness and in the parameter which is important for the environment, its rate of degradation in soil.
The pyrazoline according to the invention is obtained by reacting 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroethoxy)- phenyl]-4,5-dihydropyrazole with 4-ethoxycarbonylphenyl isocyanate in a solvent in the presence of a base.
The dihydropyrazole used as starting material is known, e.g. from EP 227 055.
The isocyanate used as starting compound is also known.
The reaction preferably takes place in an organic solvent or solvent mixture at a temperature from -20 to 150°C, preferably at room temperature.
Suitable solvents are those which are 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, dichloro ethane, 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 a yl acetate; amides, such as dimethylformamide, N-methylpyrrolidone or hexamethylphosphoric triamide, as well as sulfones, such as dimethyl sulfoxide or sulfolane.
Aliphatic, aromatic and heterocyclic amines such as e.g. triethylamine, dimethylaniline and pyridine may be cited as bases.
The compound according to the invention can, however, also be produced by reacting the dihydropyrazole with phosgene to give 4-(4-fluorophenyl)-3-[4-(2,2,2-trifluoroethoxy)- phenyl]-4,5-dihydropyrazole-l-carbonyl chloride, and then reacting this with ethyl 4-aminobenzoate, in the presence of triethylamine.
The compound of the invention prepared by the processes described above 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 new compound has a markedly pronounced effectiveness against animal pests, in partic ar against insects and spider mites. It shows a considerably better insecticidal effectiveness against plant-damaging and mammal- parasitizing insects and spider mites compared with known compounds which are chemically and biologically closely related.
Based on its insecticidal and acaricidal activity it is thus suitable for combating parasites of humans, domestic animals and plants. Examples of such parasites are
Lepidoptera, such as Plutella xylostella, Spodoptera littoralis, Heliothis armigera , Heliothis virescens and Pieris brassicae ; Diptera, such as Gasterophilus, ^..ochliomyia, Musca do estica, Ceratitis capitata, Erioischia brassicae , Lucilia sericata and Aedes aegypti ; Hemiptera, including aphids such as Megoura viciae and leafhoppers, such as Nilaparvata lugens and Nephotettix cincticepε; Coleoptera, such as Phaedon cochleariae, Anthonomus grandis and corn rootworms (Diabrotica spp. , e.g. Diabrotica undecimpunctata) ; Orthoptera, such as
Blattella germanica; 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 compound of the invention can be used either alone or in mixture with 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 active ingredient is suitably in the form of a preparation such as a powder, dust, granule, solution, emulsion or suspension, 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, dimethylforma ide, 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.
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 composition can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 3,000 1/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.
The compound of the invention can be used in active ingredient concentrations of from 0.005 to 5% by weight, preferably from 0.01 to 0.5% by weight.
The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the commonly used so-called tank-mixing method. Formulations can be prepared, for example, from the following ingredients.
Al WETTABLE 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 WETTABLE 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 Preparation example
N- (4-ethoxycarbonylphenyl) -4- (4-f luorophenyl) - 3- [4- (2 , 2 , 2-trif luoroethoxy) phenyl] -4 , 5-dihydropyrazole- 1-carboxamide
131.9 g (0.39 mol) 4-(4-Fluorophenyl)-
3-[4-(2,2,2-trifluoroethoxy)phenyl]-4,5-dihydropyrazole is dissolved in 1 1 dichloromethane and mixed at room temperature with 75 g (0.39 mol) 4-ethoxycarbonylphenyl isocyanate and one drop of triethylamine. The reaction mixture is stirred for 2 hours at room temperature and left to stand overnight. The mixture is then filtered over fine silica gel and the filtrate is evapc ated. The residual oil is crystallized using diisopropyl ether and a little isopropanol.
Yield: 184.75 g (89.5 % of the theory) white crystals Melting point: 135°C
Comparative example l
Activity aσainst larvae fLl) of the cotton bollworm (Heliothis virescens)
The compound of the invention and the listed homologous pyrazoline derivatives were used as an aqueous preparation with different active ingredient concentrations. 0.2 ml of these active ingredient preparations were pipetted onto a dietary feed in five polystyrene Petri dishes. After drying, 10 LI each of the cotton bollworm (Heliothis virescens) were counted into the dishes. The closed dishes were kept for up to 7 days at 25^°C under long-day conditions. The criterion for assessing the activity was the mortality of the larvae at the end of the experiment.
Figure imgf000010_0001
Active 0.001 0.0004 0.00016
R = ingredient concentration
[%]
% mortality after 7 days methyl* 100 50 25 ethyl 100 100 100 isopropyl* 100 100 25 tert.butyl* 100 100 30
* = comparison Comparative example 2
Determination of the rate of degradation in soil.
The half-life value was determined under aerobic conditions in a biologically active soil using high pressure liquid chromatography. The following half-life values were obtained:
Compound DT50 [days]
R = methyl* 60
R = ethyl 67
R = isopropyl* 165
R = tert. butyl* 193
* = comparison

Claims

Claims
1. N-(4-ethoxycarbonyIpheny1)-4-(4-fluorophenyl)- 3-[4-(2,2,2-trifluoroethoxy)phenyl]-4,5-dihydro- pyrazole-1-carboxamide.
2. Pesticidal compositions characterized in that they contain N-(4-ethoxycarbonyIpheny1)-4-(4-fluoro¬ phenyl)-3-[4-(2,2,2-trifluoroethoxy)phenyl]- 4,5-dihydropyrazole-l-carboxamide mixed with a diluent or carrier.
PCT/EP1995/000356 1994-02-03 1995-02-01 Substituted pyrazoline WO1995021159A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU16637/95A AU1663795A (en) 1994-02-03 1995-02-01 Substituted pyrazoline

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4403788A DE4403788C1 (en) 1994-02-03 1994-02-03 Substituted pyrazoline
DEP4403788.0 1994-02-03

Publications (1)

Publication Number Publication Date
WO1995021159A1 true WO1995021159A1 (en) 1995-08-10

Family

ID=6509686

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (5)

Country Link
AU (1) AU1663795A (en)
DE (1) DE4403788C1 (en)
IL (1) IL112472A0 (en)
WO (1) WO1995021159A1 (en)
ZA (1) ZA95887B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113213A2 (en) * 1982-12-30 1984-07-11 Schering Agrochemicals Limited Pyrazoline insecticides
DE3545786A1 (en) * 1985-12-21 1987-06-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides
EP0300692A1 (en) * 1987-07-17 1989-01-25 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2093836B (en) * 1981-02-17 1984-09-05 Nissan Chemical Ind Ltd Insecticidal pyrazoline derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0113213A2 (en) * 1982-12-30 1984-07-11 Schering Agrochemicals Limited Pyrazoline insecticides
DE3545786A1 (en) * 1985-12-21 1987-06-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides
EP0300692A1 (en) * 1987-07-17 1989-01-25 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines

Also Published As

Publication number Publication date
AU1663795A (en) 1995-08-21
DE4403788C1 (en) 1995-10-26
IL112472A0 (en) 1995-03-30
ZA95887B (en) 1995-11-13

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