EP0367796A1 - Pyrazolines insecticides - Google Patents

Pyrazolines insecticides

Info

Publication number
EP0367796A1
EP0367796A1 EP19880906671 EP88906671A EP0367796A1 EP 0367796 A1 EP0367796 A1 EP 0367796A1 EP 19880906671 EP19880906671 EP 19880906671 EP 88906671 A EP88906671 A EP 88906671A EP 0367796 A1 EP0367796 A1 EP 0367796A1
Authority
EP
European Patent Office
Prior art keywords
och
alkyl
compound according
methyl
halogen
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP19880906671
Other languages
German (de)
English (en)
Inventor
George Philip Lahm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0367796A1 publication Critical patent/EP0367796A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • triphenylpyrazolines and agricultural compositions containing them are useful as insecticides.
  • R 1 is a phenyl group
  • R 2 is a halogenalkoxy, halogenalkenyloxy, halogenalkylthio, halogenalkenylthio, halogenalkylsulfonyl or halogenalkenylsulfonyl group having 1 to 6 carbon atoms;
  • X and Y represent hydrogen or halogen.
  • R is alkoxycarbonyl
  • X and Y are hydrogen or halogen, and n is 2, 3, or 4.
  • R 1 is phenyl
  • R 4 is hydrogen or lower alkyl
  • X is hydrogen or halogen
  • Y and Z are hydrogen, halogen, lower alkyl, lower alkoxy, nitro, trifluoromethyl, lower alkylthio, acyl, nitrile, lower alkyl- sulfonyl, lower alkoxycarbonyl, A-R 5 or Y and Z form
  • A is O, S, SO, or SO 2 and R 5 is halogen- substituted lower alkyl.
  • R 1 is hydrogen, alkyl or alkenyl;
  • X is oxygen or sulfur;
  • R 2 is halogen, alkyl, haloalkyl, cyano, nitro, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyloxy, alkylsulfonyl, alkoxycarbonyl or acyl, or two adjacent R 2 groups may form a ring;
  • m is 0 to 4;
  • R c is phenyl, para substituted by R 4 ;
  • R 4 and R 5 are R 8 SO 2 O, hydrogen, halogen, alkyl, haloalkoxy, alkylthio or alkylsulfonyl, wherein R 8 is alkyl or haloalkyl; at least one of R 4 and R 5 is R 8 SO 2 O, or R 4 is haloalkoxy.
  • R 4 -Q is broadly defined.
  • U.S. Patent 4,156,007 discloses insecticidal compounds of the formula
  • R 1 is phenyl or substituted phenyl
  • R 2 and R 3 are equal or different and have the meanings of an alkyl group, a cycloalkyl group, a pyridyl or thienyl group which may be substituted with halogen, alkyl or nitro, a phenyl group or a phenyl group substituted with 1-2 substituents selected from the group consisting of a halogen atom, an alkyl group possibly Substituted with halogen, a cycloalkyl group, an alkylthio group, an alkoxy group, a mono or dialkylamino group, a nitro group, a phenyl group possibly substituted with halogen, and a cyano group;
  • R 4 is hydrogen or alkyl; and X is oxygen or sulfur.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as insecticides:
  • R 1 , R 2 and R 3 are independently selected from R 8 , halogen, CN, N 3 , SCN, NO 2 , OR 8 , SRg, S(O)R 8 , S(O) 2 R 8 , OC(O)R 8 , OS(O) 2 R 8 , C(O)OR 8 , C(O)R 8 , C(O)NR 8 R 9 , S(O) 2 NR 8 R 9 , NR 8 R 9 , NR 9 C(O)R 8 , OC(O)NHR 8 , NR 9 C(O)NHR 8 and NR 9 S(O) 2 R 8 , or when m, n or p is 2, R 1 , R 2 or R 3 can be taken together as OCH 2 O, OCH 2 CH 2 O or CH 2 CH 2 O, to form a 5 or 6 membered ring, each of which can be substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups;
  • R 5 is selected from C(O)OR 10 , C(O)R 10 ,
  • R 7 is H or CH 3 ;
  • R 8 and R 10 are independently selected from H, C 1 to C 4 alkyl, C 3 to C 4 alkenyl, C 3 to C 4 alkynyl, C 1 to C 4 haloalkyl, C 3 to C 4 haloalkenyl, C 1 to C 4 alkyl substituted with CN, C(O)OCH 3 , C(O)OCH 2 CH 3 , OCH 3 , OCH 2 CH 3 , SCH 3 , SCH 2 CH 3 and NO 2 , and phenyl or benzyl, either optionally substituted with W, or R 8 and R 9 can be taken together as (CH 2 ) 4 ,
  • R 9 and R 11 are independently selected from H, C 1 to C 4 alkyl, C 3 to C 4 alkenyl, C 3 to C 4 alkynyl, and C 1 to C 4 haloalkyl, or R 10 and R 11 can be taken together as (CH 2 ) 4 , (CH 2 ) 5 or CH 2 CH 2 OCH 2 CH 2 ; m and n are independently 0 to 5; p is 0 to 4; W is selected from halogen, CN, NO 2 , C 1 to C 2 alkyl, C 1 to C 2 haloalkyl, C 1 to C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 to C 2 alkylthio, C 1 to C 2 haloalkylthio, C 1 to C 2 alkylsulfonyl or C 1 to C 2 haloalkyl- sulfonyl; X is O or S; and
  • Y is selected from H, C 1 to C 6 alkyl, C 2 to C 6 alkoxyalkyl, CHO, C 2 to C 6 alkylcarbonyl, C 2 to C 6 alkoxycarbonyl, C 2 to C 6 haloalkylcarbonyl, C 1 to C 6 alkylthio, C 1 to C 6 haloalkylthio, phenylthio, and phenylthio substituted with 1 to 3 substituents independently selected from W.
  • Preferred compounds A are those of Formula I wherein: R 6 is H;
  • R 7 is H; n and p are independently 0 to 2; and m is 1 to 2.
  • Preferred compounds B are preferred compounds A wherein:
  • R 1 is halogen, CN, NO 2 , OCF 2 H, OCF 3 OCF 2 CF 2 H, CF 3 or when m is 2 then R 1 may be taken together as CH 2 C(CH 3 ) 2 O or CF 2 CF 2 O to form a 5 membered ring.
  • R 2 is H, halogen, CN, N0 2 , OCH 3 , OCF 2 H,
  • R 10 is C 1 to C 3 alkyl, C 2 to C 3 haloalkyl, propargyl or allyl; and one of R 3 or R 5 is in the para-position and one of R 1 is in the para-position; and Y is H, CH 3 C(O)CH 3 , C(O)OCH 3 or CHO.
  • a compound of Preferred D which is methyl 4-[3-(4-chlorophenyl)-1-[(4-chlorophenyl) aminocarbonyl]-4,5-dihydro-1H-pyrazol-4- yl] benzoate; G. A compound of Preferred D which is methyl
  • R 1 or R 2 substitutents designated as disubstituted with two open termini are bound to phenyl to form a bicyclic ring such that the first numerical designation defines the position of the first listed terminus and the second numerical designation defines the position of the other terminus.
  • the formulations broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • Emulsions, Solutions, (including Emulsifiable Concentrates) are Emulsions, Solutions, (including Emulsifiable Concentrates).
  • compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.
  • the ingredients are combined and stirred with gentle warming to speed solution.
  • a fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.
  • the active ingredient is blended with the inert materials in a blender. After grinding in a hammermili, the material is reblended and sifted through a U.S.S. 50 mesh screen and packaged.
  • Example 4 Dust wettable powder of Example 2 5% pyrophyllite (powder) 95%
  • the active ingredient is dissolved in a suitable solvent and sprayed onto dedusted attapulgite granules in a double cone blender. The granules are warmed to drive off solvent, cooled and packaged.
  • Example 6 Granule wettable powder of Example 2 15% gypsum 69% potassium sulfate 16%
  • the ingredients are blended in a rotating mixer and water is sprayed on to accomplish granulation.
  • the desired range 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves)
  • the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 12% active ingredient.
  • the ingredients are ground together in a sand mill until the solid particles have been reduced to under 5 microns.
  • the resulting thick suspension may be applied directly, but preferable after being extended with oils or emulsified in water.
  • the active ingredient is blended with the inert materials in a blender. After griding in a hammermill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. 50 mesh screen and packaged.
  • Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a multi- component pesticide giving an even broader spectrum of effective agricultural protection.
  • Examples of other agricultural protectants with which compounds of the present invention can be mixed or formulated are:
  • Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 6-methy1-1,3-dithiolo[4,5- ⁇ ]quinoxalin-2-one (oxythioquinox) ethyl 4,4'-dichlorobenzilate (chlorobenzilate) 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide (hexythiazox) amitraz propargite fenbutatin-oxide bisclofentezin.
  • the compounds of the present invention exhibit activity against a wide spectrum of foliar and soil inhabiting insects. Those skilled in the art will recognize that not all compounds will be equally effective against all insects, but compounds of this invention display control of many of the economically important pest species of the insect orders
  • Lepidoptera Lepidoptera, Homoptera, and Coleoptera among many others.
  • the specific species for which control is exemplified below are: fall armyworm, Spodoptera frugjperda; boll weevil, Anthonomus grandis; European corn borer, Ostrinia nubilalis; southern corn rootworm, Diabrotica undecimpunctata howardi; aster leafhopper, Macrosteles fascifrons.
  • the pest control afforded by the compounds of the present invention is not limited, however, to these species.
  • Insects are controlled and agricultural crops are protected by applying one or more of the Formula I compounds of this invention, in an effective amount, to the locus of infestation, to the area to be protected (the environment of the pests), or directly on the pests to be controlled.
  • a preferred method of application is by spraying with spray equipment that distributes the compound on the foliage, in the soil, or to the plant part that is infested or needs to be protected.
  • granular formulations of these compounds can be applied to soil or foliage or, optionally, incorporated into the soil. Either aerial or ground application can be used.
  • the pyrazoline compound(s) of this invention can be applied in its (their) pure state, but most often application will be of a formulation comprising one or more compounds of this invention, in an agriculturally suitable carrier or diluent.
  • a most preferred method of application involves spraying a water dispersion or refined oil solution of the compounds.
  • the rate of application of the Formula I compounds required for effective control wi ll depend on such factors as the insect species population size, the pest's life stage, insect size, its location, the host crop, the host stage, time of year of application, placement of the insecticide, temperature conditions, and others. In general, application rates of 0.05 to 2 kg of active ingredient per hectare are sufficient to provide effective control in large scale field operations under normal circumstances, but as little as 0.01 kg/hectare may be sufficient or as much as 8 kg/hectare may be required, depending upon the factors listed above.
  • Example 10 Fall Armvworm A test unit consisted of an 8-ounce plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick infested with ten third-instar larvae of fall armyworm (Spodoptera frugiperda). Solutions of each of the above-listed test compounds were made by combining the compound in an acetone/distilled water 75/25 solvent and then sprayed onto the cups; a single solution per cup replicated three times. Spraying was accomplished by passing the cups, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time mortality readings were taken. Tested compounds which killed 80% or more of the larvae are listed below:
  • Example 11 Tobacco Budworm The test procedure of Example 10 was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Tested compounds which killed 80% or more of the larvae are listed below:
  • Example 13 Southern Corn Rootworm A test unit consisted of an 8-ounce plastic cup containing 1 sprouted corn seed. The test units were sprayed as described in Example 10. After the treated cup had dried it was infested with five third-instar larvae of the Southern corn rootworm (Diabrotica undecimpunctata howardi) and replicated three times. A moistened dental wick was inserted into each cup to prevent drying and the cups were covered. The cups were then held at 27°C and 50% humidity for 48 hours, after which time mortality readings were taken. Tested compounds which killed 80% or more of the larvae are listed below: 8
  • Example 14 Boll Weevil The test unit consisted of five adult boll weevils (Anthonomus grandis) in a 9-ounce cup. The test procedure employed was the same as in Example 10. Mortality readings were taken 48 hours after treatment. Tested compounds which killed 80% or more of the adults are listed below: 1 15
  • Example 15 Aster Leafhopper A test unit was a 12-ounce cup containing oat (Avena sativa) seedlings in a 1-inch layer of sterilized soil. Test units were sprayed as described in Example 10. After the treated oats had dried between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, and evaluated for mortality. Tested compounds which killed 80% or more of the insects are 22, 49, 50, 58 and 91.

Landscapes

  • 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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Des dérivés de pyrazoline de formule (I) dans laquelle R1, R2 et R3 sont indépendamment sélectionnés à partir de l'hydrogène ou de substituants organiques ou inorganiques définis; R5 représente un substituant d'acide, d'ester ou d'amide carboxylique ou un groupe sulfonamide; R6 et R7 représentent H ou un alkyl; m, n et p représentent zéro ou des nombres entiers; X représente O ou S; Y représente H ou un substituant organique; présentent une activité contre une large variété d'insectes foliaires ou habitant dans le sol, et peuvent donc être utilisés pour protéger les cultures.
EP19880906671 1987-07-17 1988-07-15 Pyrazolines insecticides Pending EP0367796A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7479587A 1987-07-17 1987-07-17
US74795 1993-06-10

Publications (1)

Publication Number Publication Date
EP0367796A1 true EP0367796A1 (fr) 1990-05-16

Family

ID=22121740

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880906671 Pending EP0367796A1 (fr) 1987-07-17 1988-07-15 Pyrazolines insecticides

Country Status (4)

Country Link
EP (1) EP0367796A1 (fr)
JP (1) JPH02504273A (fr)
AU (1) AU1993988A (fr)
WO (1) WO1989000562A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7884691A (en) * 1990-05-15 1991-12-10 E.I. Du Pont De Nemours And Company Arthropodicidal tetrahydropyridazines
JP5164510B2 (ja) * 2006-10-06 2013-03-21 日本曹達株式会社 含窒素複素環化合物および有害生物防除剤
JP5164525B2 (ja) * 2006-11-01 2013-03-21 日本曹達株式会社 含窒素へテロ環化合物および有害生物防除剤
WO2010093595A1 (fr) 2009-02-10 2010-08-19 E. I. Du Pont De Nemours And Company 2‑pyridones fongicides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL158178B (nl) * 1974-07-12 1978-10-16 Philips Nv Werkwijze ter bereiding van insekticide preparaten die een pyrazolinederivaat bevatten, aldus verkregen gevormde preparaten, en werkwijze ter bereiding van pyrazolinederivaten met insekticide werking.
DE3064749D1 (en) * 1979-07-03 1983-10-13 Duphar Int Res New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal composition on the basis of these new compounds
US4663341A (en) * 1984-02-16 1987-05-05 Rohm And Haas Company Insecticidal n-aryl-3-aryl-4,5-dihydro-1h-pyrazole-1-carboxamides
AU556949B2 (en) * 1984-10-25 1986-11-27 Fmc Corporation Pyrozoline insecticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8900562A1 *

Also Published As

Publication number Publication date
AU1993988A (en) 1989-02-13
WO1989000562A1 (fr) 1989-01-26
JPH02504273A (ja) 1990-12-06

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