CN1082537A - 1-(4-cyano-phenyl carbamyl) pyrazoline derivative - Google Patents

1-(4-cyano-phenyl carbamyl) pyrazoline derivative Download PDF

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Publication number
CN1082537A
CN1082537A CN93106877A CN93106877A CN1082537A CN 1082537 A CN1082537 A CN 1082537A CN 93106877 A CN93106877 A CN 93106877A CN 93106877 A CN93106877 A CN 93106877A CN 1082537 A CN1082537 A CN 1082537A
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China
Prior art keywords
pyrazoline derivative
compounds
fluorine
pyrazoline
formula
Prior art date
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Pending
Application number
CN93106877A
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Chinese (zh)
Inventor
H·霍夫曼
A·范阿尔锡克
H·奈
H·范凯泽林克
A·波森-戴巴斯
T·韦格曼
H·约皮恩
G·布里格斯
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Bayer Pharma AG
Merck Sharp and Dohme Corp
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Schering Corp
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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

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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

The pyrazoline derivative of formula I has desinsection and acaricidal activity, and among the formula I, X and Y are identical or different, is fluorine or C 1-4Alkoxyl group, the latter can at random be replaced by halogen, and R is hydrogen or C 1-4Alkyl, the latter can at random be replaced by fluorine.

Description

1-(4-cyano-phenyl carbamyl) pyrazoline derivative
The present invention relates to new pyrazoline derivative, they the preparation method and they are as the application of agricultural chemicals.
As everyone knows, many 1-phenylamino formyl radical pyrazoline derivatives have insecticidal activity.Some patents have been described such compound, for example, and DE OS 2529689, EP 58424, EP 113213 and EP 227055.In all these patents, the compound that wherein has the phenyl of replacement on 3 and 4 of pyrazoline ring is all disclosed.In some patent, disclose wherein and to have 4-cyano group on the phenylamino formyl basic ring, on the 3rd phenyl ring, to have the compound of fontanel element at the fontanel that has any replacement on the other phenyl ring for alkoxyl group.But these patents all do not disclose the substituent compound of specific type that has of the present invention.
The shortcoming of many prior art compounds is active deficiencies and/or has high mammalian toxicity that the applicant has had been found that The compounds of this invention has overcome these shortcomings.
According to the present invention, it provides the pyrazoline derivative of formula I:
Figure 931068770_IMG3
X and Y are identical or different in the formula, are fluorine or C 1-4Alkoxyl group, the latter can at random be replaced by the fontanel element,
R is hydrogen or C 1-4Alkyl, the latter can at random be replaced by fluorine.
The present invention includes each isomeric forms and mixture of isomers.
Usually preferred R is a hydrogen.Arbitrarily the fontanel that replaces is for alkoxyl group preferably fluoroalkyl, especially fluoro oxyethyl group, and particularly 2,2, the 2-trifluoro ethoxy.X is preferably fluoroalkyl, and Y is preferably fluorine.
Wherein R is that the formula I The compounds of this invention of hydrogen reacts by general formula II pyrazoline and isocyanic acid 4-cyanobenzene ester in the presence of alkali can and need in solvent the time and prepares:
Figure 931068770_IMG4
Described solvent is the hydro carbons of inert solvent such as aliphatic series, alicyclic or aromatics to each reactant, they can be chloros, for example, pentane, hexane, hexanaphthene, sherwood oil, benzene,toluene,xylene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trieline or chlorobenzene; Ethers such as ether, methyl ethyl ether, isopropyl ether, butyl ether, methyl tertiary butyl ether, diox or tetrahydrofuran (THF); Nitrile such as acetonitrile, propionitrile or benzonitrile; Ester class such as ethyl acetate or pentyl acetate; Amides such as dimethyl formamide, N-Methyl pyrrolidone or hexamethyl phosphoric triamide; And sulfone class such as dimethyl sulfoxide (DMSO) or tetramethylene sulfone.
Operable alkali comprises aliphatic amine, aromatic amine and heterocyclic amine, for example, and triethylamine, xylidine or pyridine.
This reaction can be carried out in very wide temperature range.Usually, temperature of reaction is between-20～+ 100 ℃, yet preferably at room temperature carries out.
This reaction is preferably carried out under barometric point, but also can use higher or lower pressure.
Then, by preparing the compound of R to described formula I alkylation for any alkyl that replaces by currently known methods.
Be used as starting raw material the general formula II pyrazoline preparation can by currently known methods for example described in DE 2529689 and EP 227055 method carry out.
The isocyanic acid 4-cyanobenzene ester that is used as starting raw material is a known compound.
The The compounds of this invention that makes by these methods can separate from reaction mixture by ordinary method, for example, under normal pressure or decompression, steam desolventize, water makes it precipitation or separate by extraction method.Usually, can reach higher purity by column chromatography or recrystallization.
Pyridine oxazole derivatives of the present invention is a colorless and odorless, in most of the cases is the crystalloid compound.They have low solubility in water and toluene, be soluble in ethyl acetate, and solvable at the dimethyl formamide camber.
Compound of the present invention has desinsection and acaricidal activity, is applicable to parasite and the plant insect of eliminating human body and domestic animal.Example comprises lepidopteran such as small cabbage moth, Spodoptera littoralis, bollworm, America Yan noctuid and large white butterfly; Diptera such as Gasterophilus, Callitroga, housefly, Mediterranean fruitfly, wild cabbage root flowerfly, lucilia sericata and Aedes aegypti; Hemiptera comprises that aphid such as broad bean repair tail aphid and leafhopper such as Nilaparvata lugen (brown planthopper) and rice green leafhopper; Coleoptera such as Phaedon cochleariae, anthonomus grandis and pumpkin 12 asterophyllite first (various chrysomelid for example 11 asterophyllite first); Orthoptera such as Groton bug; Tick class such as boophilus microplus and lice class such as Damaliniabovis and long-nosed cattle louse and mite class such as two-spotted spider mite and apple red spider.
The compounds of this invention can use separately and also can mix mutually or mix use with other sterilant.According to desirable result, can randomly add other plant protection component or pesticide composition such as sterilant, miticide or mycocide.
Can improve the intensity and the speed of effect by for example adding suitable auxiliary such as organic solvent, wetting agent and oils.These additives can allow to reduce dosage.
The suitable mixture partnership also can comprise phospholipid for example phosphatidylcholine, hydration phosphatidylcholine, phosphatidylethanolamine, N-acyl group-phosphatidylethanolamine, phosphatidylinositols, phosphatidylserine, lysolecithin or phosphatidyl glycerol.
Specified activeconstituents or their mixture can suitably use as for example powder, pulvis, granula, solution, emulsion or suspension, wherein be added with liquid and/or solid carrier and/or thinner, and, randomly be added with binding agent, wetting agent, emulsifying agent and/or dispersion agent.
Suitable liquid vehicle has for example aliphatic hydrocrbon and aromatic hydrocarbon such as benzene,toluene,xylene, pimelinketone, isophorone, dimethyl sulfoxide (DMSO), dimethyl formamide, other mineral oil fractions and vegetables oil.
Suitable solid carrier comprises mineral soil amygdala soil, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant prod such as flour.
As tensio-active agent, spendable Phenylsulfonic acid and the salt thereof that for example calcium lignosulfonate, polyoxyethylene alkyl phenyl ether, naphthene sulfonic acid and salt thereof, Phenylsulfonic acid and basic salt, formaldehyde condensation products, fatty alcohol sulfate and replacement are arranged.
Can use-case such as following composition prepare preparation.
The A1 wettable powder
80%(weight) activeconstituents
15%(weight) kaolin
5%(weight) based on the N-methyl-sodium salt of N-oil base taurine and the tensio-active agent of calcium lignosulfonate
The A2 wettable powder
20%(weight) activeconstituents
35%(weight) Fuller's earth
8%(weight) calcium lignosulfonate
2%(weight) sodium salt of N-methyl-N-oil base taurine
35%(weight) silicic acid
The B paste
45%(weight) activeconstituents
5%(weight) lagoriolite
15%(weight) with the cetyl polyglycol ether of 8 mole ethylene oxides
2%(weight) spindle oil
10%(weight) polyoxyethylene glycol
23 parts of water
C missible oil
20%(weight) activeconstituents
75%(weight) isophorone
5%(weight) ionic and honionic surfactant mixture
The preparation of the following example explanation The compounds of this invention
Embodiment 1
The N-(4-cyano-phenyl)-and 3-[4-(2,2, the 2-trifluoro ethoxy) phenyl]-the 4-(4-fluorophenyl)-4,5-pyrazoline-1-methane amide
With 3.6 gram (10.6 mmole) 3-[4-(2,2, the 2-trifluoro ethoxy) phenyl]-the 4-(4-fluorophenyl)-4, the 5-pyrazoline is dissolved in the 40ml methylene dichloride, and at room temperature handles with 1.73 gram (120 mmole) isocyanic acid 4-cyanobenzene esters and a triethylamine.Mixture was at room temperature stirred 1 hour, place then and spend the night.The crystallization that suction filtration goes out to produce, after 5 milliliters of washed with dichloromethane, vacuum-drying.
Yield 3.76 gram (theoretical amount 74%)
m.p.＞250℃
Rf 0.84(silica gel/EA)
Embodiment 2
N-methyl-N-(4-cyano-phenyl)-and 3-[4-(2,2, the 2-trifluoro ethoxy) phenyl]-the 4-(4-fluorophenyl)-4,5-pyrazoline-1-methane amide
At anhydrous condition with under stirring, 1.00 products that restrain (2.0 mmole) embodiment 1 are added under room temperature in the suspension of 180 milligrams of (6.0 mmole) sodium hydrides (dispersion in 80% mineral oil) in 20 milliliters of tetrahydrofuran (THF)s.Emit when gas stop (30 minutes) after, drip the methyl iodide of 0.85 gram (40.0 mmole) in 10 milliliters of tetrahydrofuran (THF)s.Mixture was at room temperature stirred 3 hours, place then and spend the night.Be added to then in 20 milliliters of frozen water, use ethyl acetate extraction 4 times, use 30 milliliters of ethyl acetate at every turn.By concentrating organic solvent, obtain crude product, by silica gel column chromatography (ethyl acetate/hexane 1: 2) purifying.
210 milligrams of yields (theoretical amount 21%)
m.p.83-5℃
According to embodiment 1 or 2 similar modes, prepare following formula I compound:
Ex X Y R m.p.(℃) R f(EA)
3 F F H >200 0.67
4 CF 3CH 2O CF 3CH 2O H 123-5
5 F CF 3CH 2O H 197-9
6 CHF 2O CHF 2O H 84-4
7 CHF 2O CHF 2O CH 370-2
8 F CF 3CH 2O CH 3123-7
9 CF 3CH 2O F CH 383-85
10 CF 3CH 2O CF 3CH 2O CH 3Spumescence 0.65
11 CF 2HCH 2O F H >200 0.83
12 CF 3CH 2O F CH 2CF 3153-9 0.80
13 CF 2HCF 2CH 2O F H spumescence
The EA=ethyl acetate
The possibility of its application of the following example explanation The compounds of this invention.
Experimental example A
The activity of the anti-anthonomus grandis (Anthonomus grandis) that grows up
It is 0.1% water preparation that The compounds of this invention is made concentration.0.2 milliliter of said preparation is drawn on the feed substances, places Petri dish, and with on 0.2 milliliter of end that is drawn onto Petri dish.After the drying, 5 adult anthonomus grandis (Anthonomus grandis) counting in 2 day age is put into each culture dish.Build culture dish, reach 7 days with following placement of the sunshine conditions that prolong in 25 ℃.
The percentage mortality ratio of anthonomus grandis when test-results shows activity level.
The compound exhibits of embodiment 1-13 goes out the 80-100% activity.
Experimental example B
The activity of bollworm resisting (Heliothis viriscens) larva (L1)
According to experimental example A similar methods compound being tested, 10 Ll of bollworm resisting (Heliothis viriscens) have wherein only handled feed substances.
The compound exhibits of embodiment 1-13 goes out the 80-100% activity.

Claims (8)

1, the pyrazoline derivative of formula I:
Figure 931068770_IMG2
X and Y are identical or different in the formula, are fluorine or C 1-4Alkoxyl group, the latter can at random be replaced by halogen, and R is hydrogen or C 1-4Alkyl, the latter can at random be replaced by fluorine.
2, according to the pyrazoline derivative of claim 1, wherein R is a hydrogen.
3, according to the pyrazoline derivative of claim 1 or 2, wherein the fontanel that replaces arbitrarily is a fluoroalkyl for alkoxyl group.
4, according to the pyrazoline derivative of claim 3, wherein fluoroalkyl is 2,2, the 2-trifluoro ethoxy.
5, according to the pyrazoline derivative of aforementioned any one claim, wherein X is a fluoroalkyl, and Y is a fluorine.
6, a kind of desinsection and miticide composition are comprising acceptable diluent or carrier on above-mentioned arbitrary claim claimed compounds and the agronomy.
7, above-mentioned arbitrary claim claimed compounds is used to destroy the insects or the application of mite class.
8, a kind of destroying the insects and the method for mite class is applied to insect or mite or its location comprising the above-mentioned arbitrary claim claimed compounds with significant quantity.
CN93106877A 1992-06-04 1993-06-04 1-(4-cyano-phenyl carbamyl) pyrazoline derivative Pending CN1082537A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4218745A DE4218745A1 (en) 1992-06-04 1992-06-04 1- (4-cyanophenylcarbamoyl) pyrazoline
DEP4218745.1 1992-06-04

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CN1082537A true CN1082537A (en) 1994-02-23

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CN (1) CN1082537A (en)
AU (1) AU4320293A (en)
DE (1) DE4218745A1 (en)
IL (1) IL105778A0 (en)
WO (1) WO1993024464A1 (en)
ZA (1) ZA933961B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4414974A1 (en) * 1994-04-29 1995-11-02 Bayer Ag Substituted pyrazoline derivatives

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL158178B (en) * 1974-07-12 1978-10-16 Philips Nv METHOD OF PREPARING INSECTICIDE PREPARATIONS CONTAINING A PYRAZOLINE DERIVATIVE, SO PREPARED PREPARATIONS, AND METHOD OF PREPARING PYRAZOLINE DERIVATIVES WITH INSECTICIDE ACTION.
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
US4464386A (en) * 1981-02-17 1984-08-07 Nissan Chemical Industries, Ltd. Insecticidal 3-difluoromethoxyphenyl-1-phenylcarbamoyl-2-pyrazolines
GB2093836B (en) * 1981-02-17 1984-09-05 Nissan Chemical Ind Ltd Insecticidal 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
US4767779A (en) * 1985-09-24 1988-08-30 Fmc Corporation Pyrazoline-1-carboxamides, composition containing them, and insecticidal method of using them
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
IL87131A0 (en) * 1987-07-17 1988-12-30 Du Pont Pyrazoline derivatives and their use as insecticides

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AU4320293A (en) 1993-12-30
KR940005579A (en) 1994-03-21
ZA933961B (en) 1994-01-05
DE4218745A1 (en) 1993-12-09
WO1993024464A1 (en) 1993-12-09
IL105778A0 (en) 1993-09-22

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