CA2011832A1 - Heteroaryl-aryl-butene and -butane derivatives, process for their preparation, agents containing them, and their use as pesticides - Google Patents
Heteroaryl-aryl-butene and -butane derivatives, process for their preparation, agents containing them, and their use as pesticidesInfo
- Publication number
- CA2011832A1 CA2011832A1 CA002011832A CA2011832A CA2011832A1 CA 2011832 A1 CA2011832 A1 CA 2011832A1 CA 002011832 A CA002011832 A CA 002011832A CA 2011832 A CA2011832 A CA 2011832A CA 2011832 A1 CA2011832 A1 CA 2011832A1
- Authority
- CA
- Canada
- Prior art keywords
- compound
- oph
- formula
- alkyl
- formulae
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen 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
- 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
- A01N43/04—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 one hetero atom
- A01N43/06—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 one hetero atom five-membered rings
- A01N43/08—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 one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/04—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 one hetero atom
- A01N43/06—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 one hetero atom five-membered rings
- A01N43/10—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 one hetero atom five-membered rings with sulfur as the ring hetero atom
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/10—Anthelmintics
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Veterinary Medicine (AREA)
- Tropical Medicine & Parasitology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Furan Compounds (AREA)
- Pyridine Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Abstract of the disclosure Heteroaryl-aryl-butene and -butane derivatives, process for their preparation, agents containing them, and their use as pesticids Compounds of the fonmulae I and II, the stereoisomers thereof, and the mixtures of the latter (I)
Description
~OECHST AXTIE~G~S~LLSCHAF~ HO~ B9/FOB2 Dr.~O/PP
De~cription Heteroaryl-aryl-butene ~nd -but~ne derivatives, proc~
for their prep~ration, ngen~s cvntaining the~, ~nd their u~e as pe~ticides It i~ known that cex~in 1,4-diaxylbut~ne ~nd 1,4-di~ryl-butene compounds have inaecticidal or acari~idal prop~r-ties (GB 2,187,452 A or Ch0m. Ab~tr. ~ol. 109~73119z).
HoweYer, the activitie~ o~ these compound~ ~re insuffi~
~ient in ~ome case~, By introducing ~eteroaryl group~ in~o the arylbutene ~nd arylbutane ~tructure, ~t ~as pos~i~le ~o prepare novel a ~ lbutene and a~ylbutane d~ri~ative~ having advantageous p2sticidal, in particular in~cticidal and/or acaricidal propertie~.
The pre~ent invention therefore relate~ to the ~ompo~nd~
of the formulae I and II, the ~tereoisomera there~, and:
the ~ix~ure~ of the l~tter ~ C - C - ~ - C - ~ R5 R ~ ~3 R4 ~ (I) ~ ~ A ~ ~ ~5 (Il) whera Rl iB pyridyl, p~Ti~idyl, thienyl, ~hiazolyl, furanylJ
pyT~zolyl, 1,3-oxazolyl or i~ida~olyl, all of wh;ch can ba ~bs~ituted, R2 i8 ~t (Cl-c4) alkyl, (cl-c4)haloalk~l~ (Cl-C4 )~lkosy, tc3 C6)cycloalkyl~ -CH=C~2 vr -C~C~, , .
De~cription Heteroaryl-aryl-butene ~nd -but~ne derivatives, proc~
for their prep~ration, ngen~s cvntaining the~, ~nd their u~e as pe~ticides It i~ known that cex~in 1,4-diaxylbut~ne ~nd 1,4-di~ryl-butene compounds have inaecticidal or acari~idal prop~r-ties (GB 2,187,452 A or Ch0m. Ab~tr. ~ol. 109~73119z).
HoweYer, the activitie~ o~ these compound~ ~re insuffi~
~ient in ~ome case~, By introducing ~eteroaryl group~ in~o the arylbutene ~nd arylbutane ~tructure, ~t ~as pos~i~le ~o prepare novel a ~ lbutene and a~ylbutane d~ri~ative~ having advantageous p2sticidal, in particular in~cticidal and/or acaricidal propertie~.
The pre~ent invention therefore relate~ to the ~ompo~nd~
of the formulae I and II, the ~tereoisomera there~, and:
the ~ix~ure~ of the l~tter ~ C - C - ~ - C - ~ R5 R ~ ~3 R4 ~ (I) ~ ~ A ~ ~ ~5 (Il) whera Rl iB pyridyl, p~Ti~idyl, thienyl, ~hiazolyl, furanylJ
pyT~zolyl, 1,3-oxazolyl or i~ida~olyl, all of wh;ch can ba ~bs~ituted, R2 i8 ~t (Cl-c4) alkyl, (cl-c4)haloalk~l~ (Cl-C4 )~lkosy, tc3 C6)cycloalkyl~ -CH=C~2 vr -C~C~, , .
2 ~ 3 ~
R3 13 ~ or ~C~-C~)alkyl, R4 i0 ~ (Cl-C~ C~ or ~C~C~t A is CH2, O o~ 8, B is CH, N or C(CH3), R5 i~ }I or halogen and R6 i~ phenyl, phenoxy or ben~yl, ~ll of whi~h e~n be allonosub~titu~ed to pentasub~titu~ed by h~logen or ~ Cl-C3 ) haloalkyl .
Preferred c:ompounds of the ~orDIul~ nd I~ ars tho~e in which Rl ie a r~dical o~ ~he formul~e A, El, C, ~, ~S or P
~R7)~ ~5,(h7)~ _~R7)~ R7)~
~A), (B), ~C), (D), ~1~ )~ ( ~7 ) ~D
(E), ~F) in which R7 is H, h~logen, (C~ lkyl, (Cl-C4)-alko~y, (Cl-C~)hAloalXyl, (Cl-C")halo~lko~y ~ncl ~ i8 15 1 or 2, RZ i~ (Cl-C3)alkyl, cyclopropyl OI' CF
R3 iB H ox ~ethyl, B is CH, R" is H, ~nethyl, CN or -C~CH and 20 Rb is pheno~y whlch ca~ t tuted in the 4 tion by Cl, Br or CP3.
Particul~rly pr~ferred ~:ompounds of ~he ormulae I and II are tho~e in which R7 i~ Cl, Br, (C~ 3)alko~ OC:F3, -OCH2CF3 or -OCF2CFz~
25 The ~ubstituent R1 i8 prefer~bly the radic~l~ of ~he ..
.
.
,. : .. . .
~or~ulae A, E~ or C:, in p~rticular A.
The invention embracel3 all ~tereoisomer~ ~hich ~an occur in the fonnulae I nnd II, in part~cular the Z- and ~-diastereomer~ of the olef ill function ~ n ~on~lala I and 5 their mixture~, furthermore the indi~vidual enantiomer~
well a~ pair& of enanti~merE~ of the fonil~lae I ~nd II.
Alkyl i8 both straight-chain and branched ~lkyl.
The pre~ent invention furthermore r~l~te~ to . pxo~e~
for the prep~r~ion oiE compound~ of ~he formul~e I ~nd II, ~rhich comprises a) for compc~unds of th~ formula I, raacti~g a compound of ~he fo3mlula ~II
(III) C - O
R2~
where Rl and R2 are a~ defined in forllnula I, ~ h a compound o~ the formula IV
R~4 PR3 P~R )3 (IV) whera R3, ~, R~, R~, A and B are 118 defined in iEormula I hnd R~ is phenyll cyclohexyl or ~utyl, ~nd ~) ~or c:ompolmds of the fo~ula II ~ cat~lyticallly hydrogenating the olef;n function ~f the cosre~pond-ing ~ powld of the fonnala I wi th hydrogen or a hydrogen-liberating cGm~urld.
~he proc~ de~crib~d under ~ known ~ ~ittig reaction. The procedure and the reaction paraslleter~ ~are descri~d in khe lit~rature (H . J. }3e~nann, Topic:~ in Current Chemi~try 109 ( 1983 ); ~ouben-W~yl , ~thoden der : . -, . : .. . .. :, ~ . , . . ~ . ..
:,' ' ~ ~, ' ,. ..
': , .: ' :
R3 13 ~ or ~C~-C~)alkyl, R4 i0 ~ (Cl-C~ C~ or ~C~C~t A is CH2, O o~ 8, B is CH, N or C(CH3), R5 i~ }I or halogen and R6 i~ phenyl, phenoxy or ben~yl, ~ll of whi~h e~n be allonosub~titu~ed to pentasub~titu~ed by h~logen or ~ Cl-C3 ) haloalkyl .
Preferred c:ompounds of the ~orDIul~ nd I~ ars tho~e in which Rl ie a r~dical o~ ~he formul~e A, El, C, ~, ~S or P
~R7)~ ~5,(h7)~ _~R7)~ R7)~
~A), (B), ~C), (D), ~1~ )~ ( ~7 ) ~D
(E), ~F) in which R7 is H, h~logen, (C~ lkyl, (Cl-C4)-alko~y, (Cl-C~)hAloalXyl, (Cl-C")halo~lko~y ~ncl ~ i8 15 1 or 2, RZ i~ (Cl-C3)alkyl, cyclopropyl OI' CF
R3 iB H ox ~ethyl, B is CH, R" is H, ~nethyl, CN or -C~CH and 20 Rb is pheno~y whlch ca~ t tuted in the 4 tion by Cl, Br or CP3.
Particul~rly pr~ferred ~:ompounds of ~he ormulae I and II are tho~e in which R7 i~ Cl, Br, (C~ 3)alko~ OC:F3, -OCH2CF3 or -OCF2CFz~
25 The ~ubstituent R1 i8 prefer~bly the radic~l~ of ~he ..
.
.
,. : .. . .
~or~ulae A, E~ or C:, in p~rticular A.
The invention embracel3 all ~tereoisomer~ ~hich ~an occur in the fonnulae I nnd II, in part~cular the Z- and ~-diastereomer~ of the olef ill function ~ n ~on~lala I and 5 their mixture~, furthermore the indi~vidual enantiomer~
well a~ pair& of enanti~merE~ of the fonil~lae I ~nd II.
Alkyl i8 both straight-chain and branched ~lkyl.
The pre~ent invention furthermore r~l~te~ to . pxo~e~
for the prep~r~ion oiE compound~ of ~he formul~e I ~nd II, ~rhich comprises a) for compc~unds of th~ formula I, raacti~g a compound of ~he fo3mlula ~II
(III) C - O
R2~
where Rl and R2 are a~ defined in forllnula I, ~ h a compound o~ the formula IV
R~4 PR3 P~R )3 (IV) whera R3, ~, R~, R~, A and B are 118 defined in iEormula I hnd R~ is phenyll cyclohexyl or ~utyl, ~nd ~) ~or c:ompolmds of the fo~ula II ~ cat~lyticallly hydrogenating the olef;n function ~f the cosre~pond-ing ~ powld of the fonnala I wi th hydrogen or a hydrogen-liberating cGm~urld.
~he proc~ de~crib~d under ~ known ~ ~ittig reaction. The procedure and the reaction paraslleter~ ~are descri~d in khe lit~rature (H . J. }3e~nann, Topic:~ in Current Chemi~try 109 ( 1983 ); ~ouben-W~yl , ~thoden der : . -, . : .. . .. :, ~ . , . . ~ . ..
:,' ' ~ ~, ' ,. ..
': , .: ' :
3 ~
~ 4 --org~n. Chemie [~ethods of Organic Ch~i3try~, Yol. ~1 and 5/lb). The carbonyl func~ion of the compound III can be exchanged for th~ radical CP(E~.~)3 of the ~ mpouJld IV, and vice versa.
5 Furthermore " ~he rsd~cal Rl c:an bs converted into a corre~ponding c~rl~nyl c~mpound ~i~ an organomet~l compsund. The co}apo~nd of the 40rmul~ I then originate~
by eli~nination of water from ~he tertiary ~lcohol which has formed (Hou~en-Neyl ~ol. 6/1~/2).
Tha keton~s III ~hich ~re u~ed a~ ~t~rting ~aterial~ ~or the Wittig reaction ~) are obtllined by P~riedel-Craft~
acylation of ~romatic co~und~ containing suf ~Eicisnt electrons (Houben~ eyl~ Vol. 7/2a, 39, 83), or, al~er natively, by synthesizins~ ~he carbon ~truc~ure by react-ing arylmetal compounds with ~uitable carboxylic ~c~d derivatives, ~uch a~ carboxylic acid halide~, ~nhydride~, esters or nitriles (Houben-ldeyl 7/2a, 548-6~ Crearyd ~. Org. Chem. 52, 5026-30 (1987) ) .
The ylide ~:ompound~ IV arç3 forme~ from ~he c:orret3pondlJIg phosphonium ~alt~ or pho~phonlc ester~ by depro~c~nation with s~rong ba~eh, ~uch ns ~lkall D~lot~l hydri~e~, or~ano~
likhium co~pounds, ~llkali ~etal Amide~ and alk~ netal alcoholate~ in ethers or aromatic hydroa~rbons a~ ~he solvent, either be~oxe the ~ddil:ion o~ ketone or in the pre~ence of the ketone III, ~t tempex~ture~ of fro~-20t:
to ~100~C IHouben-Weyl, ~ol. E!l ~nd 5~1b~.
~he pho~phonium ~alts V ~re obtained by R 5~
R6 BJ~H ~ A - ~H.... PtR~)3 anicn~ ~ ~V) alkylating triphenylpho~phane or trial~ylphosphane with arylalkyl h21ides o~ the formNla YI undsr rea~tion 2i~:~3,~3~
condition~ known from the literature (~ouben-~eyl Vol~
Bl, 495-515, ~nd 12/1, 79-124~.
5~ ~ ICH - A ~ F~ - X x o cl, Br, J (VI~
The al~ylat~n~ agents VI ~re formed on ~he one hand; ~hen A = CH2, fro~ the correspondi~g 3-axylpropanol~ VII and hydrogen halîde or inor~anic acid halides, for axample thionyl chloride, on ~he other hand~ if ~ O or S, they are prepared from the corresponding benzyl alcohol and formaldehyde ~nd hydro~en halide (~o~ben-Weyl Vol. 5/3 10and 5/4, DE-A-3,1~5~338~. ~he 3-arylpropanol~ VII can be prbpared by reducing cinn~mic acid~ and their ester~ VIII
with aluminum hydrogen compound~ for example l~thium alanate (Houben-~eyl, Vol. 4/ld, 190-216).
R ~ ~
R6 B CH2CH2CH2OH (YIX) 15R6 ~ CH ~ CH - COOR' R' - H, Alkyl (VITI) The ~rylbutan~ co~pound~ of the formula II ~re ~ynthe-sized by hydrogenating the ol~fin functi3n ~n ~n ~ryl-butene of the formula I with hydrogen or ~ hydrogsn-llberating co~pound, or example hydrazine, cyclohe~ene vr formic ~c~d derivati~es, ~nder the c~t~lyt$c inf1uence of compound~ of palladium, pl&tinu~ nick~l or rhodium, under reaction conditiona known fr~m the literature ~Houb~n-Weyl, Vol. 4/lc).
,', ' . .
The ~ompound~ I I G~n ~urthexmore bs p~epared by ~n additiorl reac:t~on nf dibor~nes, borane ~dduc~s or ~
6ubs~itu~ad borane~ with lthe C:,C double bond o 1, . ollowed by hydroly~ of the boron~carbon bond u~ing water or ~lcohol~ (Houben-~eyl, Vol. 4/ld, p. ~9-593.
The active cc)mpound~ ~re ~ui~able ~or combating ~ni~nal pe~t~t in particular irl~ect~, ~ras:hnid~, }Ielminthe~ ~and mollu~k~, very p~rticularly preferably for comb~ting in~ect~ and ara~:hnid~, enc:ountered in agriculture, ln animal hu~bandry, in forestry, in the protection of ~tored produc~s and OI D~atexial~, ~nd in th6~ hygiene field, and ha~e spod plant tolerance ~nd favor~le toxicity to warm-blooded anim~ls. ~hey ~re ~tive again~t normally ~ensitive and r~ tant ~pecie~ and 10 again~t all or some 8t~ge8 OI de~elop~nent. The above-mentioned pe~t~ include:
From the order of ~he Acarina, for ~xample ~s:aru~ ~iro, Agra~ 8pp., Ornithrodoros ~pp. "9ermanyssu~ gallinae, ~rîophye~ ribis, Phyllocoptnl~a 012ivora, Boophilu~ ~pp., Rhipicephalus ~pp., Amblyomma 3pp- t ~yalo~a Bpp. ~ Ixode~
8pp. ~ P~oropt:eB ~3pp-~ Choriopte~ ~pp-, Sarcopte~ ~PE; , Tar~onemus 8pp- ~ Bryobia pr~etiosa, Panonychu~ ~pp., Tetranychu~ 8pp- ~ ISs:~tæltr~lnyt:huEI ~pp-, OligonyGhun 8pp- ~
E:ultetran~chu~ epp. From the order o~ the Isopeda, ~or example, Oni~cue ~sellu~, ArDa~dium vulg~re ~nd Porcellio scaber. From the order of the Diplopoda, for ex~ple, Blaniulus guttul~u~. From l:he o~der of 'che t:hilopod~, for exa~ple, I;eophilu~ rpophagus ~and Scutl~er~
Fro3~ ~he order of the Sy~phyla, for example, Scu~igerella immaculata. Prom the order of the Thy~anur~, for ~a~c-plQ, L`epi8ma ~accharina. ~rom the order o~ ~he Collembola, for example, ~ychiuru~ armatu~. ~x~ ~he s3rder of the Orthoptera, for example, Blatta orient~
Periplaneta amer~c~na, L~u~ophaea ~aderae~ tella germanica, acheta dome~ticu~, Gryllotalpa 8pp-, IJDt:uE;lta migratoria migratorioide~, ~lel~noplu~ differentiali~ ~nd Schi~ocerca gregaria. From the c~rd~r t~f the Dermaptera, for exa~ple, Forficula aur~ularia. Prom ~he order s3f 2 ~ 3 2 the Isopter~, for example, Reticul~tnrmes ~pp.. From ~he order of the Anoplura, for ex~mple, Phyllo~era va3tatrix, PemphigUB 8pp ., Pediculus h~manus corpori~ ~aeQ~topinus 8pp. and Lino~na~hus 8pp. From the order of the Nallo-phaga, for example, ~richndectes ~pp. ~nd Damalinea ~pp.
From the order of the Thysanoptera, for example~
Hercinothrip~ femoralis and ~hrip8 ~abari, Fro~ the order of ~he Heteroptera, for e~ample, ~ury~a~er æpp., Dysdercuæ interMediu~, Pie~ma qu~dra~a, Ci~ex lectularius, Rhodnius proli~u~ ~nd ~riato~a ~pp. Fro~
the order of ~he ~omoptera, for example, AlQurodes bra~icae, Bemi~ia ~abaci, Trialeurode~ vaporarium, ~phis gossypii, ~revicornyne brassicae, Cryptomyzus r~bis, Doralis fabae, Doralis pomi, Er~o~oma lani~erum, Hyalop-teru~ arundinis, ~acrosiphum ~ven~e, Nyzu~ ~pp., Phorodonhumuli, ~ opalo~iphum padi, ~mp4asca Bpp., ~u8c~1i8 bilobatus, Nephotettix ~incticep~, Le~anium ~orni, Sai~etia oleae, Laodelphax stri~tellu~ parvata lugens, Aonidiella aurantii, A~pidiotus hed~rae, P~eudo-20 COCCU8 ~pp. and Psylla Bpp. Fro~ ~he order of theLepidoptera, for example, Rectinophora ~os~ypiella, Bupalus piniarius, Che ~ atobia bru~ata, Lithocolleti3 bl~ncardella, Hyponomeuta p~della, Plutella maculipanaia, ~al~cosoma neu~tria, ~uprocti~ chryeorrhoea, ~mantrla ~pp., Bucculatrix thuxberiell~/ Phy~locni~ti~ citrell~
Agroti~ 8pp., Buxoa ~pp.~ Pelti~ ~pp., Earins in~ul~n~, Helio~hi~ 8pp. ~ L~phygm~ exigua, ~ame~tra bra~aic~e, Panolis ~lammea, ProdeniA litura, Spodoptera ~pp., ~richoplu~ia ni, Carpo~ap~ pomon011~, Pi2rls ~pp~, Chilo ~pp., Pyrau~ta nubilali~, ~phestia kuehniell~, Ga}leria ~ellonella, Cacoecia podana, Capua retic na, Chori~o-neura fu~iferana, Clysi~ ambigu~ mona ~agnanima ~nd Tortri~ viridana. Fro~ the order ~f ~he Coleop~era, forexa~ple, Anobiu~ punct~tum, ~hizopertha d~inicn, Bruchi-diu~ obtectus, A~antho3celides obtectus, ~ylotrup~ba~ulu~, Agela~tica alni, ~ep~inotar~a decemlineata, Phaedon cochleariae, Di~bro~iea ~pp., P~ylliode~ chry80-cephala, ~pilachna v~rivesti~, A~omaria ~pp., Oryzae-philu~ ~urinamen~s, Anthonomus ~pp~, Sitophilu3 8pp ., Otiorrhynchu~ ~UlCatUB ~ Co8~0polite~ sordidus, Ceuthor-rhynchu~ a88imi~ ra po81:ica~ Dermeste~ ~pp., Trogoderma Bpp., A~;threnuF~ ~pp. ~ Att~genu~ ~pp~ ctu8 epp., ~l~gethes ~eneus, Ptinu~ ~pp., ~iptus hololeucu~, Gibbium psylloides, Tribolium ~pp., Tenebrio molitor, Agriokes ~pp., Conoderu~ 8pp. ~ Melolontha ~elolonth~, Amphim~llon 801stitiali~ ~nd Co~telytra ~eal~ndi~a. From the order of t~e ~ymenopter~, for ex~mple, Diprion 8pp.~
~oplocampa ~pp~ Lasius ~pp. r ~on~mori phar~ni~ and ~e~pa 8pp. From the order of the Diptera, ~or exa~pl~, Aedes pp., Anoph~les ~pp., Culex ~pp~, Dro~ophila melanogast~r, ~usca ~pp., ~n~iR ~pp.~ C~lliphora eryth-rocephala, Lucilia ~pp. ~ chryBomyia 8pp. ~ Cuterebra 8pp.
Ga6trophilus ~pp., Hyppobo~ca 5pp. ~ St~moXyB ~pp. ~
Oestru~ 8pp. ~ Hypoderma 6pp. ~ Tabanu~ ~pp.; Tannia ~pp., Bibio hortulanu~, O~c~nell~ frit, Phorbia 8pp. ~ ~egomyia hyoscyami, Ceratiti~ capitata, Dacus oleae and ~ipula paludo~a. From the order of ~he 5iphon~ptera~ ~or example, ~enop~ylla cheopi~ an~ C~ra~ophyllus ~pp. From the order of ~he Arachnida, for example, ~corpio mauru und Latrodec~us mactan~. From the ~ of ~he Helminthe~, for example ~ae~onchus, Trichoatronyulus, Osterta~ia, Cooperia, Chabextia, Strcn~ylo~de~, Oesophagostomu~, ~yostrongulu~, Ancylostema, A~c~ri~ and Heterakis, ~ well ~8 F~cioln ~nd phytopAtho~enic nematoda0, ~or exzmple tho~e o~ khe ~enera ~eloido~yne, ~eteroder~, Ditylenchu~, ~phelenchoido~, RAdopholus, Globodora, Pratylen¢hus, Longidorua ~nd ~iphinem~. From the clAs~ o~ the ~stropoda, for example, Derocer~ ~pp., Ario~ ~pp., Lymn~ea 8pp. ~ Galb~ ~pp.,Succinea 8pp. ~
~iophalaria ~pp., Bulinu~ ~pp. and Onco~el~nia ~pp.. Fxom th~ clas~ of the Biv~lv~, for exa~ple, Drei~na ~pp..
The inv~ntion ~l~o relate~ to ~gent~ whi~h cont~$n the co~pounds o~ the foxmulAe I and II, be~id~ ~uitable formulation auxilierie~.
The agent~ according to the invention generally cont~in the active co~pound~ of the for~ulae I and ~ he 2 ~ 3 ~
g extent of 1 to 95~ by w~ight.
They can be formulated in a variaty of w.~y~, a~ preteter-mined by the biological ~nd/or ~hemi~ophy~ical para-meters. The ~ollowing po~ibilitie~ are therefore ~uit-able for ~ormulation~ ~ettable powders (~P), emulsifi~bl2 concen~rate~ (~C), aqu~ou~ ~olutions (SC), ~mulsion0, sprayable ~Glutions, disp~r~io~ on ~n oil or wa~er ba~e (SC), suspo-e~ul~ions (gC), du~t~ng .~gant~ (DP3, ~eed-dressiny agents~ granul~ in the form of ~icrogr~nules, ~pray granules, coated ~ranule~ and ad~orption granules, water-dispersible granule~ ~G), m.v for~ulations, microcapsul s, wa~es or baits.
The~e individual formulation typ4s are known in principle and are described, for exa~ple, ~n:
Winnacker-Ruchler, "Ch~mi~che Technologie tChemical 'I'echnology]", Volume 7, C. Hau~er Verl~g ~unich, 4th ~d., 1986; van Falkenberg, nPesticide~ Formulations n ~ Narcel Dekker N.Y., 2nd ~d. 1972-73; ~. ~artensJ "Spray Drying Handbook", 3rd Xd. 1979, G. Goodwin Ltd. London.
The formulation auxillarie~ xequix~d, ~uch ~ in~rt material~, surfac~nts, ~olvent~ and other ~dd~tive~/ are likewi~e known and are do w rlb~d, ~or exaMple, ln~
~atkin~ andbook of InseG~i~ide Du~t Dlluent~ and C~rrier~", 2nd ~d., D~rland ~cok8, Caldwell ~.J.;
~5 ~.v.Olphen, ~In~roduc~lon to Clay Colloid Chsmistry~, ~nd ~d., J. Wiley ~ Sons, N.Y.; ~rschen, ~Solvent~ Guide~, 2nd ~d., Interecience, ~OY. 1950; ~Cu~cheon'~, ~Detergents and ~mulsifier~ ~nnual~ Publ. Corp.
Ridgewood N.J.; Sialey end Woodt U~ncyclopedi~ of Surface Active A~ent~, Chem. P~bl. Co. Inc~ . 1964;
Sch~nfeldt, ~Grenzfl~chen~ktive ~thyleno~id~dduk~e~
tSurface~ac~ive ~thylene Oxide Adduc~]~, ~isa.
Verlsg~ge~ell.~ ~tuttg~rt 1976; ~nn~cker-R~chler, "Chemische T~chnologie ~Chemical Technology~n, Volu~e 7, C. ~auser ~erlag ~unich, 4th Ed. 1986.
~L3.~
~o Combina~ion~ wlth other pe~tlcldally ~ctive ~ub~t~nae~, fertili2er~ and/or grow~h regulator~ may a1BO be prepar~d on the ba8i~ of the~e formulations, ~or e~ample ~ n the form of a readymix or as a t~nk ~ix. ~ettable powder~ ~re preparations which are ~nifo~mly dispersible in water and which, be~ides the ac~ive subst~nce, also contain wett~ng agentR, for example polyoxethylated ~lkylphenol~, polyox-ethylated fatty alcohol~, alkyl~ulfonat~ or ~lXylph~nol-sulfonate~, and di~per ing agent~, for exæmple ~odium lignin~ulfona~, sodium 2,2'-dinzphthyl~ethane-6,6'-di~ulfonate, ~odium dibutylnaphthalene~ulfonat~, or alternatively sodium oleylmethyltaurinate~ in addition to a diluent or inert substance. ~mulsifiable concentrate~
are prepared by di~solving the actiY~ ~ub~tance in ~n organic ~olvent, for example butanol, cyclohexanone, dLmethylformamide, xylene ~nd alao higher-bQiling aromatic compounds or hy ~ ocarbons, with the addition of one or more emul~ifiers. ~xample~ of ~mulsifiers which can be used ares calcium ~alts of an alkylaryl~ulfonic acid such as Ca-dod~cylbenzenesulfonate~ or non-ionic emul~i~ier~, ~uch as fatty ac ~d polyglycol 0~ter~, alkylaryl polyglycol ~ther~, atty ~lcohol ~olygly~ol ether~, propylene oxide/ethylene oxide condenshtion produc~, alkyl poly0thers, sorbitan ~Atty ~cld e~ter~, polyoxyethylene ~orbit~n ~atty ~cid e~ters or polyo~y-ethylen~ ~orbitol e~t~r~.
Du~ting ~ge~ts ~n be obtained by ~rinding the ~c~i~e sub~t~n~e with ~ ly divid~d ~olid ~ub~tances, for example ~alc or n~tural clay~, ~uch ~8 kaolin, ~entonlte, pyrophlllite, or di~t~macaous earth. ~r~nule~ can be produced either :by spraying ths ~ctive ~ubstance onto ~d~orptive, granul~ted insrt mnt~ri~l or by ~pplying active ~ub~tance concentrato~ onto the surf~ce of carrier~, such ~ sand, kaoli~ite~ or granul~ted inert material, by ~ean~ o~ binder~, for example polyvinyl alcohol, ~odium polyacrylate or, ~lte~natively, ~ineral oil~. 5uit~b1e ~ctive 8ub~tance~ c~n ~1BO be ~ranul~ted ~n the manner which i~ convent~onal for the produe~ion of 2 ~ 3 ~
fertilizer granule~, if de~ired ~n ~ ~ixture with fextiliæ~rs.
The concentration of active ~ubstance in wet~able powder~
is, for axample, about 10 to 90% by w~ight; the r~m~inder to 100% by weight i8 composed of conventional ~onmul~tion component~. In the ca~e of Qmulsifiable concentrate~ the concentration of acti~ ~ub~t~ce can be abou~ 5 to 80%
by weight. Fonmulations in ~he form o dust~ u~ually con~ain 5 ~o 20% by weight of active sub~tanc2, ~prayable ~olutions about 2 ~o 20% by wei~ht. In the ca~e of ~ranule~, the activ~ ~ub~tance content depend~ parkly on whe~her the active c~mpound i8 liquid or solid and on which granul~tion ~uxiliaries, ~illers e~c~ are used.
In addition, the active ~ubstanca formulations m~n~ioned I5 contain, ~f appropriate, th~ ~dh~ives, wetting ~gents, disper~ing agent~, ~mul. ifi~r~, penetrant~, solvQnts, filler~ or carriers which are co~ve~tional in ~ach ca~e.
For use, the concentrate~, pre~ent in c~mmercially a~ailable form, are d~luted~ if ~ppropriate, i~ a eus-tomary ~anner, ~or example using water in the case of wektable powder~, emul~ifi~ble concentrate~, dl~p~r~ion0 and in ~ome c~se~, also in the ca~e o~ mlcrogranule0.
P~eparation~ in khe form of du~t~ or granulate~ prep~ra-tion~ and al~o ~prayable ~olutions ~re u~u~lly not ~urther diluted with other inert ~ub3tances bsfore u~e.
The ~pplication rate requir~d Yar~a3 wi~h ~he e~ternal ~onditions, ~uch ~ ter ali~0 t~mp~r~ture, ~umidity, et~etera. It ~:an ~ary within ~ d~ l~nit~, for e~ampl~
betw~en 0.005 ~nd 10.0 k~/ha or more of ~c~ive 8ub8t~nc2;
pre~erably, ho~0ver, lt i~ b0twe~n 0.01 ~nd 5 kgth~.
~he ~ctive eubstances ~ccording to the i~vention ~y be pre~ent in ~heir com~erci~lly avail~ble fo~mul~tion~ ~nd ln the application foxms pr~pared fr~m these for~u-lat~on~, a~ a mi~ture ~ith other ~ctiv~ compounds, such '' '' , ' ' ' , .
' 2~3.~
in~ecticide~, ~ttractan~æ, ~teri~i~iny ~gent~, ~c~r~
~ide~, nemati~idas, fungicide~, grow~h regul~tDr~ vr herbi~ide~.
The insecticide~ includ~, ~or example, phosphoric ~sters, carbamat2s, caxbo~ylic e~ere, formamidin~, tln ~om-pound~ and 8ub8tance~ produced by micro-organiæm~, inter alia.
Preferred ~ixture ~omponents are 1. from ~he group co~pri~ing the pho~phoru~ ~o~pound~
acephate, a~a~ethiphos, ~zinpho6-ethyl, ~zinphos methyl, bromophos, bro~opho~-~thyl, chlorfenvinphos, chlormepho~, chlorpyriphos-methyl, demeton, demeton-S-methyl, demeton-S-~ethyl~ulfone, dialifo~, di~2inon, dichlorvo~, dicrotophos/ 0,0-1,2J2,2-tatrachloroethyl pho~phothioate ~S~ 208,304) d~meth~a~e, diaulfoto~, ~PN, ethion, ~hoprophos t ~tri~fo~0 ~amphur, fenami-phos, ~enitrothion, fen~ulfothion, ~onthion, fonofos, formothion~ heptenopho~, iæa~ophos, ~30thioate, i~oxathion, malathion, mathacrifo~, ~ethamidophos, 2Q methida hion, ~alithion, ~evinphos, ~onocro~opho~, naled, o~ethoate, oxyd~eto~-~ethyl, p~rathion, p~rathion~methyl, ph~nthoat~, phora~e, pho~lone, pho~folan, pho~met, phoaph~midon, phoxim, pi~i~ophos-ethyl, pirimiphos-methyl, pro~enofo~, prDp~phos, proetampho~, prothio~o~, pyTaclofo~, pyrid~pant-hlon, . guinalphos/ sulprofos~ ~mephos, ter~ufos, tetra-chlorvinphos, thi~mQton, triazophos, trichlorp~on, vamidotllion;
2. from the group campr~n~ the c~r~a~e~
aldicar~, 2-~e~-butylphe~yl met~ylc~r~am~te (BP~
carbaryl, c~rbofuran, c~xb~sulf~n, ~lo~thocarb~ ~æn-furacarb, ethiofencarb, ~ur~thiocarb, isoprocarb, ~ethomyl,5~m~thyl~m-~umenylbuty$yl(mathyl)carbamate, oxamyl, pix~icarb, propoxur~ thiodic~rb, ~hio~anox, ethyl ~,6/9-~riaza-4~ yl 6,10-di~sth~1-8-oxa-7-o~o-_ 13 -5,11-dithi~-9~dodscenoate (OK 135), l-~ethylthio-(ethylideneamino) -~-methyl~ morpholi~othio3aa~
bamate (UC 51717) 3. fro~ ~he group compri~inq the c~rboxyl~c es~ers allethrin, ~lphametrin, 5-b~nzyl-3-furylmethyl (E3-~lR3 ci~-2,2-dime~hyl-3~(2-Qxothiol~n-3-ylidenQ-~ethyl)cyclopxopanecar~oxyl~e, bloallethrin, bio-a}le~hrin ((S)cyclopentyl i~omer~, ~iores~ethrin, biphenate (RS3-1-cyano-1-(6-phenoxy 2-py~idyl)me~hyl (l~S)-trans-3-(4-tert.butylphenyl)-2,2-dimethylcyclo-propanecarbo~yla~e (~CI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cypenmethrin, cyphenothrin, deltamethrin, em~nthrin, ~fe~v~ler~e~ fenfluthrin, fenpropathrin, fenvaler~te, flucythrinate, flumethrin, fluvalinate (D-~B~m~r), p~rmethrin, pheothrin ((R~ omer), d-pralet ~ in, pyrethrins (natural pro-ducts), re~methrin, tefluthrin, ~e~ramethrin, tralo-methrin; .--4. from the group comprising the amidine6 amitraz, chlordimefoxm;
~ 4 --org~n. Chemie [~ethods of Organic Ch~i3try~, Yol. ~1 and 5/lb). The carbonyl func~ion of the compound III can be exchanged for th~ radical CP(E~.~)3 of the ~ mpouJld IV, and vice versa.
5 Furthermore " ~he rsd~cal Rl c:an bs converted into a corre~ponding c~rl~nyl c~mpound ~i~ an organomet~l compsund. The co}apo~nd of the 40rmul~ I then originate~
by eli~nination of water from ~he tertiary ~lcohol which has formed (Hou~en-Neyl ~ol. 6/1~/2).
Tha keton~s III ~hich ~re u~ed a~ ~t~rting ~aterial~ ~or the Wittig reaction ~) are obtllined by P~riedel-Craft~
acylation of ~romatic co~und~ containing suf ~Eicisnt electrons (Houben~ eyl~ Vol. 7/2a, 39, 83), or, al~er natively, by synthesizins~ ~he carbon ~truc~ure by react-ing arylmetal compounds with ~uitable carboxylic ~c~d derivatives, ~uch a~ carboxylic acid halide~, ~nhydride~, esters or nitriles (Houben-ldeyl 7/2a, 548-6~ Crearyd ~. Org. Chem. 52, 5026-30 (1987) ) .
The ylide ~:ompound~ IV arç3 forme~ from ~he c:orret3pondlJIg phosphonium ~alt~ or pho~phonlc ester~ by depro~c~nation with s~rong ba~eh, ~uch ns ~lkall D~lot~l hydri~e~, or~ano~
likhium co~pounds, ~llkali ~etal Amide~ and alk~ netal alcoholate~ in ethers or aromatic hydroa~rbons a~ ~he solvent, either be~oxe the ~ddil:ion o~ ketone or in the pre~ence of the ketone III, ~t tempex~ture~ of fro~-20t:
to ~100~C IHouben-Weyl, ~ol. E!l ~nd 5~1b~.
~he pho~phonium ~alts V ~re obtained by R 5~
R6 BJ~H ~ A - ~H.... PtR~)3 anicn~ ~ ~V) alkylating triphenylpho~phane or trial~ylphosphane with arylalkyl h21ides o~ the formNla YI undsr rea~tion 2i~:~3,~3~
condition~ known from the literature (~ouben-~eyl Vol~
Bl, 495-515, ~nd 12/1, 79-124~.
5~ ~ ICH - A ~ F~ - X x o cl, Br, J (VI~
The al~ylat~n~ agents VI ~re formed on ~he one hand; ~hen A = CH2, fro~ the correspondi~g 3-axylpropanol~ VII and hydrogen halîde or inor~anic acid halides, for axample thionyl chloride, on ~he other hand~ if ~ O or S, they are prepared from the corresponding benzyl alcohol and formaldehyde ~nd hydro~en halide (~o~ben-Weyl Vol. 5/3 10and 5/4, DE-A-3,1~5~338~. ~he 3-arylpropanol~ VII can be prbpared by reducing cinn~mic acid~ and their ester~ VIII
with aluminum hydrogen compound~ for example l~thium alanate (Houben-~eyl, Vol. 4/ld, 190-216).
R ~ ~
R6 B CH2CH2CH2OH (YIX) 15R6 ~ CH ~ CH - COOR' R' - H, Alkyl (VITI) The ~rylbutan~ co~pound~ of the formula II ~re ~ynthe-sized by hydrogenating the ol~fin functi3n ~n ~n ~ryl-butene of the formula I with hydrogen or ~ hydrogsn-llberating co~pound, or example hydrazine, cyclohe~ene vr formic ~c~d derivati~es, ~nder the c~t~lyt$c inf1uence of compound~ of palladium, pl&tinu~ nick~l or rhodium, under reaction conditiona known fr~m the literature ~Houb~n-Weyl, Vol. 4/lc).
,', ' . .
The ~ompound~ I I G~n ~urthexmore bs p~epared by ~n additiorl reac:t~on nf dibor~nes, borane ~dduc~s or ~
6ubs~itu~ad borane~ with lthe C:,C double bond o 1, . ollowed by hydroly~ of the boron~carbon bond u~ing water or ~lcohol~ (Houben-~eyl, Vol. 4/ld, p. ~9-593.
The active cc)mpound~ ~re ~ui~able ~or combating ~ni~nal pe~t~t in particular irl~ect~, ~ras:hnid~, }Ielminthe~ ~and mollu~k~, very p~rticularly preferably for comb~ting in~ect~ and ara~:hnid~, enc:ountered in agriculture, ln animal hu~bandry, in forestry, in the protection of ~tored produc~s and OI D~atexial~, ~nd in th6~ hygiene field, and ha~e spod plant tolerance ~nd favor~le toxicity to warm-blooded anim~ls. ~hey ~re ~tive again~t normally ~ensitive and r~ tant ~pecie~ and 10 again~t all or some 8t~ge8 OI de~elop~nent. The above-mentioned pe~t~ include:
From the order of ~he Acarina, for ~xample ~s:aru~ ~iro, Agra~ 8pp., Ornithrodoros ~pp. "9ermanyssu~ gallinae, ~rîophye~ ribis, Phyllocoptnl~a 012ivora, Boophilu~ ~pp., Rhipicephalus ~pp., Amblyomma 3pp- t ~yalo~a Bpp. ~ Ixode~
8pp. ~ P~oropt:eB ~3pp-~ Choriopte~ ~pp-, Sarcopte~ ~PE; , Tar~onemus 8pp- ~ Bryobia pr~etiosa, Panonychu~ ~pp., Tetranychu~ 8pp- ~ ISs:~tæltr~lnyt:huEI ~pp-, OligonyGhun 8pp- ~
E:ultetran~chu~ epp. From the order o~ the Isopeda, ~or example, Oni~cue ~sellu~, ArDa~dium vulg~re ~nd Porcellio scaber. From the order of the Diplopoda, for ex~ple, Blaniulus guttul~u~. From l:he o~der of 'che t:hilopod~, for exa~ple, I;eophilu~ rpophagus ~and Scutl~er~
Fro3~ ~he order of the Sy~phyla, for example, Scu~igerella immaculata. Prom the order of the Thy~anur~, for ~a~c-plQ, L`epi8ma ~accharina. ~rom the order o~ ~he Collembola, for example, ~ychiuru~ armatu~. ~x~ ~he s3rder of the Orthoptera, for example, Blatta orient~
Periplaneta amer~c~na, L~u~ophaea ~aderae~ tella germanica, acheta dome~ticu~, Gryllotalpa 8pp-, IJDt:uE;lta migratoria migratorioide~, ~lel~noplu~ differentiali~ ~nd Schi~ocerca gregaria. From the c~rd~r t~f the Dermaptera, for exa~ple, Forficula aur~ularia. Prom ~he order s3f 2 ~ 3 2 the Isopter~, for example, Reticul~tnrmes ~pp.. From ~he order of the Anoplura, for ex~mple, Phyllo~era va3tatrix, PemphigUB 8pp ., Pediculus h~manus corpori~ ~aeQ~topinus 8pp. and Lino~na~hus 8pp. From the order of the Nallo-phaga, for example, ~richndectes ~pp. ~nd Damalinea ~pp.
From the order of the Thysanoptera, for example~
Hercinothrip~ femoralis and ~hrip8 ~abari, Fro~ the order of ~he Heteroptera, for e~ample, ~ury~a~er æpp., Dysdercuæ interMediu~, Pie~ma qu~dra~a, Ci~ex lectularius, Rhodnius proli~u~ ~nd ~riato~a ~pp. Fro~
the order of ~he ~omoptera, for example, AlQurodes bra~icae, Bemi~ia ~abaci, Trialeurode~ vaporarium, ~phis gossypii, ~revicornyne brassicae, Cryptomyzus r~bis, Doralis fabae, Doralis pomi, Er~o~oma lani~erum, Hyalop-teru~ arundinis, ~acrosiphum ~ven~e, Nyzu~ ~pp., Phorodonhumuli, ~ opalo~iphum padi, ~mp4asca Bpp., ~u8c~1i8 bilobatus, Nephotettix ~incticep~, Le~anium ~orni, Sai~etia oleae, Laodelphax stri~tellu~ parvata lugens, Aonidiella aurantii, A~pidiotus hed~rae, P~eudo-20 COCCU8 ~pp. and Psylla Bpp. Fro~ ~he order of theLepidoptera, for example, Rectinophora ~os~ypiella, Bupalus piniarius, Che ~ atobia bru~ata, Lithocolleti3 bl~ncardella, Hyponomeuta p~della, Plutella maculipanaia, ~al~cosoma neu~tria, ~uprocti~ chryeorrhoea, ~mantrla ~pp., Bucculatrix thuxberiell~/ Phy~locni~ti~ citrell~
Agroti~ 8pp., Buxoa ~pp.~ Pelti~ ~pp., Earins in~ul~n~, Helio~hi~ 8pp. ~ L~phygm~ exigua, ~ame~tra bra~aic~e, Panolis ~lammea, ProdeniA litura, Spodoptera ~pp., ~richoplu~ia ni, Carpo~ap~ pomon011~, Pi2rls ~pp~, Chilo ~pp., Pyrau~ta nubilali~, ~phestia kuehniell~, Ga}leria ~ellonella, Cacoecia podana, Capua retic na, Chori~o-neura fu~iferana, Clysi~ ambigu~ mona ~agnanima ~nd Tortri~ viridana. Fro~ the order ~f ~he Coleop~era, forexa~ple, Anobiu~ punct~tum, ~hizopertha d~inicn, Bruchi-diu~ obtectus, A~antho3celides obtectus, ~ylotrup~ba~ulu~, Agela~tica alni, ~ep~inotar~a decemlineata, Phaedon cochleariae, Di~bro~iea ~pp., P~ylliode~ chry80-cephala, ~pilachna v~rivesti~, A~omaria ~pp., Oryzae-philu~ ~urinamen~s, Anthonomus ~pp~, Sitophilu3 8pp ., Otiorrhynchu~ ~UlCatUB ~ Co8~0polite~ sordidus, Ceuthor-rhynchu~ a88imi~ ra po81:ica~ Dermeste~ ~pp., Trogoderma Bpp., A~;threnuF~ ~pp. ~ Att~genu~ ~pp~ ctu8 epp., ~l~gethes ~eneus, Ptinu~ ~pp., ~iptus hololeucu~, Gibbium psylloides, Tribolium ~pp., Tenebrio molitor, Agriokes ~pp., Conoderu~ 8pp. ~ Melolontha ~elolonth~, Amphim~llon 801stitiali~ ~nd Co~telytra ~eal~ndi~a. From the order of t~e ~ymenopter~, for ex~mple, Diprion 8pp.~
~oplocampa ~pp~ Lasius ~pp. r ~on~mori phar~ni~ and ~e~pa 8pp. From the order of the Diptera, ~or exa~pl~, Aedes pp., Anoph~les ~pp., Culex ~pp~, Dro~ophila melanogast~r, ~usca ~pp., ~n~iR ~pp.~ C~lliphora eryth-rocephala, Lucilia ~pp. ~ chryBomyia 8pp. ~ Cuterebra 8pp.
Ga6trophilus ~pp., Hyppobo~ca 5pp. ~ St~moXyB ~pp. ~
Oestru~ 8pp. ~ Hypoderma 6pp. ~ Tabanu~ ~pp.; Tannia ~pp., Bibio hortulanu~, O~c~nell~ frit, Phorbia 8pp. ~ ~egomyia hyoscyami, Ceratiti~ capitata, Dacus oleae and ~ipula paludo~a. From the order of ~he 5iphon~ptera~ ~or example, ~enop~ylla cheopi~ an~ C~ra~ophyllus ~pp. From the order of ~he Arachnida, for example, ~corpio mauru und Latrodec~us mactan~. From the ~ of ~he Helminthe~, for example ~ae~onchus, Trichoatronyulus, Osterta~ia, Cooperia, Chabextia, Strcn~ylo~de~, Oesophagostomu~, ~yostrongulu~, Ancylostema, A~c~ri~ and Heterakis, ~ well ~8 F~cioln ~nd phytopAtho~enic nematoda0, ~or exzmple tho~e o~ khe ~enera ~eloido~yne, ~eteroder~, Ditylenchu~, ~phelenchoido~, RAdopholus, Globodora, Pratylen¢hus, Longidorua ~nd ~iphinem~. From the clAs~ o~ the ~stropoda, for example, Derocer~ ~pp., Ario~ ~pp., Lymn~ea 8pp. ~ Galb~ ~pp.,Succinea 8pp. ~
~iophalaria ~pp., Bulinu~ ~pp. and Onco~el~nia ~pp.. Fxom th~ clas~ of the Biv~lv~, for exa~ple, Drei~na ~pp..
The inv~ntion ~l~o relate~ to ~gent~ whi~h cont~$n the co~pounds o~ the foxmulAe I and II, be~id~ ~uitable formulation auxilierie~.
The agent~ according to the invention generally cont~in the active co~pound~ of the for~ulae I and ~ he 2 ~ 3 ~
g extent of 1 to 95~ by w~ight.
They can be formulated in a variaty of w.~y~, a~ preteter-mined by the biological ~nd/or ~hemi~ophy~ical para-meters. The ~ollowing po~ibilitie~ are therefore ~uit-able for ~ormulation~ ~ettable powders (~P), emulsifi~bl2 concen~rate~ (~C), aqu~ou~ ~olutions (SC), ~mulsion0, sprayable ~Glutions, disp~r~io~ on ~n oil or wa~er ba~e (SC), suspo-e~ul~ions (gC), du~t~ng .~gant~ (DP3, ~eed-dressiny agents~ granul~ in the form of ~icrogr~nules, ~pray granules, coated ~ranule~ and ad~orption granules, water-dispersible granule~ ~G), m.v for~ulations, microcapsul s, wa~es or baits.
The~e individual formulation typ4s are known in principle and are described, for exa~ple, ~n:
Winnacker-Ruchler, "Ch~mi~che Technologie tChemical 'I'echnology]", Volume 7, C. Hau~er Verl~g ~unich, 4th ~d., 1986; van Falkenberg, nPesticide~ Formulations n ~ Narcel Dekker N.Y., 2nd ~d. 1972-73; ~. ~artensJ "Spray Drying Handbook", 3rd Xd. 1979, G. Goodwin Ltd. London.
The formulation auxillarie~ xequix~d, ~uch ~ in~rt material~, surfac~nts, ~olvent~ and other ~dd~tive~/ are likewi~e known and are do w rlb~d, ~or exaMple, ln~
~atkin~ andbook of InseG~i~ide Du~t Dlluent~ and C~rrier~", 2nd ~d., D~rland ~cok8, Caldwell ~.J.;
~5 ~.v.Olphen, ~In~roduc~lon to Clay Colloid Chsmistry~, ~nd ~d., J. Wiley ~ Sons, N.Y.; ~rschen, ~Solvent~ Guide~, 2nd ~d., Interecience, ~OY. 1950; ~Cu~cheon'~, ~Detergents and ~mulsifier~ ~nnual~ Publ. Corp.
Ridgewood N.J.; Sialey end Woodt U~ncyclopedi~ of Surface Active A~ent~, Chem. P~bl. Co. Inc~ . 1964;
Sch~nfeldt, ~Grenzfl~chen~ktive ~thyleno~id~dduk~e~
tSurface~ac~ive ~thylene Oxide Adduc~]~, ~isa.
Verlsg~ge~ell.~ ~tuttg~rt 1976; ~nn~cker-R~chler, "Chemische T~chnologie ~Chemical Technology~n, Volu~e 7, C. ~auser ~erlag ~unich, 4th Ed. 1986.
~L3.~
~o Combina~ion~ wlth other pe~tlcldally ~ctive ~ub~t~nae~, fertili2er~ and/or grow~h regulator~ may a1BO be prepar~d on the ba8i~ of the~e formulations, ~or e~ample ~ n the form of a readymix or as a t~nk ~ix. ~ettable powder~ ~re preparations which are ~nifo~mly dispersible in water and which, be~ides the ac~ive subst~nce, also contain wett~ng agentR, for example polyoxethylated ~lkylphenol~, polyox-ethylated fatty alcohol~, alkyl~ulfonat~ or ~lXylph~nol-sulfonate~, and di~per ing agent~, for exæmple ~odium lignin~ulfona~, sodium 2,2'-dinzphthyl~ethane-6,6'-di~ulfonate, ~odium dibutylnaphthalene~ulfonat~, or alternatively sodium oleylmethyltaurinate~ in addition to a diluent or inert substance. ~mulsifiable concentrate~
are prepared by di~solving the actiY~ ~ub~tance in ~n organic ~olvent, for example butanol, cyclohexanone, dLmethylformamide, xylene ~nd alao higher-bQiling aromatic compounds or hy ~ ocarbons, with the addition of one or more emul~ifiers. ~xample~ of ~mulsifiers which can be used ares calcium ~alts of an alkylaryl~ulfonic acid such as Ca-dod~cylbenzenesulfonate~ or non-ionic emul~i~ier~, ~uch as fatty ac ~d polyglycol 0~ter~, alkylaryl polyglycol ~ther~, atty ~lcohol ~olygly~ol ether~, propylene oxide/ethylene oxide condenshtion produc~, alkyl poly0thers, sorbitan ~Atty ~cld e~ter~, polyoxyethylene ~orbit~n ~atty ~cid e~ters or polyo~y-ethylen~ ~orbitol e~t~r~.
Du~ting ~ge~ts ~n be obtained by ~rinding the ~c~i~e sub~t~n~e with ~ ly divid~d ~olid ~ub~tances, for example ~alc or n~tural clay~, ~uch ~8 kaolin, ~entonlte, pyrophlllite, or di~t~macaous earth. ~r~nule~ can be produced either :by spraying ths ~ctive ~ubstance onto ~d~orptive, granul~ted insrt mnt~ri~l or by ~pplying active ~ub~tance concentrato~ onto the surf~ce of carrier~, such ~ sand, kaoli~ite~ or granul~ted inert material, by ~ean~ o~ binder~, for example polyvinyl alcohol, ~odium polyacrylate or, ~lte~natively, ~ineral oil~. 5uit~b1e ~ctive 8ub~tance~ c~n ~1BO be ~ranul~ted ~n the manner which i~ convent~onal for the produe~ion of 2 ~ 3 ~
fertilizer granule~, if de~ired ~n ~ ~ixture with fextiliæ~rs.
The concentration of active ~ubstance in wet~able powder~
is, for axample, about 10 to 90% by w~ight; the r~m~inder to 100% by weight i8 composed of conventional ~onmul~tion component~. In the ca~e of Qmulsifiable concentrate~ the concentration of acti~ ~ub~t~ce can be abou~ 5 to 80%
by weight. Fonmulations in ~he form o dust~ u~ually con~ain 5 ~o 20% by weight of active sub~tanc2, ~prayable ~olutions about 2 ~o 20% by wei~ht. In the ca~e of ~ranule~, the activ~ ~ub~tance content depend~ parkly on whe~her the active c~mpound i8 liquid or solid and on which granul~tion ~uxiliaries, ~illers e~c~ are used.
In addition, the active ~ubstanca formulations m~n~ioned I5 contain, ~f appropriate, th~ ~dh~ives, wetting ~gents, disper~ing agent~, ~mul. ifi~r~, penetrant~, solvQnts, filler~ or carriers which are co~ve~tional in ~ach ca~e.
For use, the concentrate~, pre~ent in c~mmercially a~ailable form, are d~luted~ if ~ppropriate, i~ a eus-tomary ~anner, ~or example using water in the case of wektable powder~, emul~ifi~ble concentrate~, dl~p~r~ion0 and in ~ome c~se~, also in the ca~e o~ mlcrogranule0.
P~eparation~ in khe form of du~t~ or granulate~ prep~ra-tion~ and al~o ~prayable ~olutions ~re u~u~lly not ~urther diluted with other inert ~ub3tances bsfore u~e.
The ~pplication rate requir~d Yar~a3 wi~h ~he e~ternal ~onditions, ~uch ~ ter ali~0 t~mp~r~ture, ~umidity, et~etera. It ~:an ~ary within ~ d~ l~nit~, for e~ampl~
betw~en 0.005 ~nd 10.0 k~/ha or more of ~c~ive 8ub8t~nc2;
pre~erably, ho~0ver, lt i~ b0twe~n 0.01 ~nd 5 kgth~.
~he ~ctive eubstances ~ccording to the i~vention ~y be pre~ent in ~heir com~erci~lly avail~ble fo~mul~tion~ ~nd ln the application foxms pr~pared fr~m these for~u-lat~on~, a~ a mi~ture ~ith other ~ctiv~ compounds, such '' '' , ' ' ' , .
' 2~3.~
in~ecticide~, ~ttractan~æ, ~teri~i~iny ~gent~, ~c~r~
~ide~, nemati~idas, fungicide~, grow~h regul~tDr~ vr herbi~ide~.
The insecticide~ includ~, ~or example, phosphoric ~sters, carbamat2s, caxbo~ylic e~ere, formamidin~, tln ~om-pound~ and 8ub8tance~ produced by micro-organiæm~, inter alia.
Preferred ~ixture ~omponents are 1. from ~he group co~pri~ing the pho~phoru~ ~o~pound~
acephate, a~a~ethiphos, ~zinpho6-ethyl, ~zinphos methyl, bromophos, bro~opho~-~thyl, chlorfenvinphos, chlormepho~, chlorpyriphos-methyl, demeton, demeton-S-methyl, demeton-S-~ethyl~ulfone, dialifo~, di~2inon, dichlorvo~, dicrotophos/ 0,0-1,2J2,2-tatrachloroethyl pho~phothioate ~S~ 208,304) d~meth~a~e, diaulfoto~, ~PN, ethion, ~hoprophos t ~tri~fo~0 ~amphur, fenami-phos, ~enitrothion, fen~ulfothion, ~onthion, fonofos, formothion~ heptenopho~, iæa~ophos, ~30thioate, i~oxathion, malathion, mathacrifo~, ~ethamidophos, 2Q methida hion, ~alithion, ~evinphos, ~onocro~opho~, naled, o~ethoate, oxyd~eto~-~ethyl, p~rathion, p~rathion~methyl, ph~nthoat~, phora~e, pho~lone, pho~folan, pho~met, phoaph~midon, phoxim, pi~i~ophos-ethyl, pirimiphos-methyl, pro~enofo~, prDp~phos, proetampho~, prothio~o~, pyTaclofo~, pyrid~pant-hlon, . guinalphos/ sulprofos~ ~mephos, ter~ufos, tetra-chlorvinphos, thi~mQton, triazophos, trichlorp~on, vamidotllion;
2. from the group campr~n~ the c~r~a~e~
aldicar~, 2-~e~-butylphe~yl met~ylc~r~am~te (BP~
carbaryl, c~rbofuran, c~xb~sulf~n, ~lo~thocarb~ ~æn-furacarb, ethiofencarb, ~ur~thiocarb, isoprocarb, ~ethomyl,5~m~thyl~m-~umenylbuty$yl(mathyl)carbamate, oxamyl, pix~icarb, propoxur~ thiodic~rb, ~hio~anox, ethyl ~,6/9-~riaza-4~ yl 6,10-di~sth~1-8-oxa-7-o~o-_ 13 -5,11-dithi~-9~dodscenoate (OK 135), l-~ethylthio-(ethylideneamino) -~-methyl~ morpholi~othio3aa~
bamate (UC 51717) 3. fro~ ~he group compri~inq the c~rboxyl~c es~ers allethrin, ~lphametrin, 5-b~nzyl-3-furylmethyl (E3-~lR3 ci~-2,2-dime~hyl-3~(2-Qxothiol~n-3-ylidenQ-~ethyl)cyclopxopanecar~oxyl~e, bloallethrin, bio-a}le~hrin ((S)cyclopentyl i~omer~, ~iores~ethrin, biphenate (RS3-1-cyano-1-(6-phenoxy 2-py~idyl)me~hyl (l~S)-trans-3-(4-tert.butylphenyl)-2,2-dimethylcyclo-propanecarbo~yla~e (~CI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cypenmethrin, cyphenothrin, deltamethrin, em~nthrin, ~fe~v~ler~e~ fenfluthrin, fenpropathrin, fenvaler~te, flucythrinate, flumethrin, fluvalinate (D-~B~m~r), p~rmethrin, pheothrin ((R~ omer), d-pralet ~ in, pyrethrins (natural pro-ducts), re~methrin, tefluthrin, ~e~ramethrin, tralo-methrin; .--4. from the group comprising the amidine6 amitraz, chlordimefoxm;
5. from the ~roup ~ompri~$n~ the t~n ~o~pound~
cyhexatin, ~enbu~atin cxide;
cyhexatin, ~enbu~atin cxide;
6. othex~
aba~ectin, nacillu~ thurin~ien~i~, b4n~ultap, bi~ap~-. cryl, bromopropylate, buprofezi~, camphechlor, ~r-tap, chlorobenzialRte, chlorflua2uron, 2~ ehloro-phenyl~-4,5-diphenylthiophene SUBI-T 930~, clofen-tezine~ 2-naphthylmethyl cyclopropanee~rbc~ylake ~Ro 12-0470), cyro~z~n, ~th~ 3~5-dichloro-4-(1,1,2,3,3,3~-hexafluoro-1propylo~y)phenylc~rbs~oyl-2-~hloroben~ocarboxi~ida~e, DDT 7 dicofol, ~ 3,5-dichloro~ 2,?-tetxafluoroe~ho~y)phenyl~mino~-c~rbonyl)-2~6-difluorobenzamide (~RD 473), diflu-benzuron, N-(2,3-dihydro-3-~et~yl-1,3-~h~ol-2-ylidene)-2,4-xylidi~e, dinobuton~ ocap, endo~ulf~n, ethofnnprox, (4-ethoxyphanyl)(dimethyl~3~(3-phenoxy~
phenyl)propyl)~ ne, (4-e~hoxyphenyl)(3-t~-fluoro~3-phenoxyph~nyl)propyl)dim~thyl~ilane, feno~ycarb, 2 fluoro-5-(4-(4-etho~yphe~yl)~4-me~hyl-1 pen~yl) diphenyl ~ther (~I 800~, gra~ulosis and nucle~r polyhedro~i~ viru~es, fenthiocarb, flu~enz~mine, flucycloxuronS fluf~no~uron, gamma-~C~, he~ythiazox, hydra~thylno~ (AC 217300~ exmec~in, 2~nitromethyl-4,5-dihydro-6H-thiazin2 (SD 52618), 2-~itromethyl-3,4-dihydrothi~zole (SD 35fi51)~ 2-nitromethy~ene-1,2-~hiazinan-3-ylcarbamaldehyde (WL 10~477~, propargite~
teflubenzuron; tetradifon, tetra~ul, thiocyclam, triflumuron.
The active Rubstance con~ent of the ~se form~ prepared from the commercially ~vail~ble formulationfi can be from 0.00000001 to 100% ~y w~i~ht of ~cti~e ~ub~tance, prefer-ably between 0.00001 and 1% b~ ~eight.
Application i8 sff~cted i~ a con~entional ~ashion, m~tched to the u~e ~orm~.
~he active ~ubstance~ aa~ording ~o the inven~i4n ~re ~l~o ~uitable for comba~in~ endo- ~nd ecto-para~i~e~, pre~er-~bly in the veterinary medici~0 ~re~ or in the ~r~a o animal hu~bandry~
The ~ct~e ~ub~t~nces ~ccording tn ~he inv~ntion ~re applied in ~ known f~hion, ~uch ~ b~ or~l ~pplic~tio~
in the ~orm o~, for ex~mpl~0 tablet~ cap~ule~, pot~on3 or ~ranules~ by denmal application in th~ for~ of, ~or example, dippi~g, ~praying, p~uring~o~ ~nd ~pottiny-on ~nd po~dering, ~nd ~l~o by paranteral ~pplic~tion in the form of, for e~ample, $n~ect~on.
The no~el c~mpound~, according to ~h~ invention~ ~f the formllla I can accordingly al~o be em~loyed particularly advantageou~ly in lives~ock hu~bandry ( or example cattle, ~heep, pig~ and poultry ~uch ~ chicken~, ~ee~e 2 ~
- 15 ~
etc.). In a preferred embodiment o~ the inrention, the novel compound~, if ~ppropriate in suitable ormul~tion~
(cf. above) and if ~ppropriate wi~h the drinking wator or feed, are ~dmfnistered orally to the ~nimals. Since excretion in the dropping~ occur~ in an 8f ~ecti7e fashion, the develop~ent of in~ects in tha animal dropping~ can b2 prevented very 8imply in thi ~a~hion.
The do~ges and formulation~ suitable in each cs~e are particularly dependent on the ~ype ~nd ~tage o~ davelop-ment of the product~ve ~ni~al~ ~nd also on the de~ree of infe~tation of the insect~, and can ea~ily be de~exmined and fixed by conventional ~eth~ds. In the ca~e of ~attle, the novel compounds can be employed, for example, in dosage~ of 0.01 to 1 mg/kg of ~ody weigh~.
The following e~amples ~erve to illu~trate the inventicn.
~. ~oD~Nlation ~aqples a) A dusting agent iB obtained by ~ixing 10 part~ by weight of astive ~ubstance and 90 part~ b~ ~eigh~ of talc a6 inert materi~l and comminuting the ~ixture in a hammer mill.
b) A wettablo powder which io eaaily di~par~ible in water i8 obtained by ~i~in~ 25 paxt~ by wei~ht of ~c~ive ~ubstance, 65 p~rts by w~ight of k~olln-cont~ining quartz ~ ~nert materi~l, 10 p~r~s ~y w~iyht of pota~u~ Iigninsulfon~te ~nd 1 p~rt by ~e~ght o~
sodium oleoylmethyltaurinate ~8 wetti~ ~nd dispersing agent, and grinding the mi~ture in a pin di~k mill.
c) A di~persion concentxate which i~ e~8ily di~per~ible in wat~r i3 prep~red ~y ~ixing 40 p~rt~ by ~alght 9~
activ~ sub~t~nce ~ith 7 p~rts by w~i~h~ o~ ~ sulfo-~uccinic monoe~r, 2 parts by weight of ~ ~odium liynin~ulfonate ~nd 51 p~rt~ by w~i~h~ o~ waker, ~nd grinding the mixture in a ball ~ill to ~ finenes~ of below 5 ~icron~.
2~:~3 ~
d3 An emul~ifinble concentr~e ~ n be prepared fro2l 15 part~ by weight c>f ~ tilre ~ubstance, 75 p~rt~ by ~eight of c:yc:lohexanone a~ ~olvent and 10 par~s by weight of oxethyl~ted nonylphenol ( 10 IZ0 emulsifier.
e) Granules can be prepared from 2 to î5 part~ by ~ight of active aubstance an~ n inert granule ~rrier material ~uch a~ att~pu~glte, granulated pumice ancl/or quartz sand.
AdvantageouE~ly, ~ ~u~pens~on of the wettabl0 pc~ler frcml Example b) haYing a ~olid~ con~ent of 30 % i~ used/ and this i~ ~prayed onto the surf~ce of ~tt~pulgite ~ranul~s, which are dlried and mixed inti~at~ly. ~he ~proporltion by weight of the we~table powder i~ ~out 5 ~ and ~h~t of ~he inert carrier ~atexial about g5 % oiE the fini~hed granules .
B. Ch~mic~l e ~ ples 1,1,1-~rifluoro-2-t2-ethoxy-5-pyridyl~-5;(3-pheno~y-phenyl~-2-p~ntene (No. 1, ex~mple of ~ormul~ I~
2~5 ~ ~11.4 ~mol) o~ 2-ethoxy-5-trifluoroac0tylpyrldlna, 6.0 g ~lb.8 mmol) of 3-(3-pheno~yphenyl)-pxopyltriphen~l-pho~phonium bromide ~nd 1.3 g (12.0 mmol~ of pot~s~ium tert.-butoxide ~r~ mixed in 50 ~1 o~ ~oluene under ~
protectiv0 ga~ a~o~phere, and the ~ixture i~ ~tirred ox 6 hour~ at 20-C. The pot~iu~ bromide 1~ then r~moved by wa~hing with water~ the toluene phd8R i8 ~oncentr~ted, and the ~oluene extract ~ sep~rated by colu~n ohro~a~o-graphy (eluents ethyl ~cet~te~hept~ne - 2~8, ~tationary pha~e: ~ilic ~el). Thi~ yives 3.50 g ~75 %) o~ the olefin product (1) a~ ~olorle~ liquid. ~olubility~
readily ~oluble in heptane ~nd toluene; in~oluble in water. ~he lH- ~ ~nd ~C ~ea~ur~ments ~onf~rm tha~ a ~ixture of diastereo~er~ (Z ~nd ~ i~omer~ pre~en~ in the xa~io 203sl, b.p.lol3~386 ~nd 395~ t~C ~easur~ent).
2~3.~3~
-- ~7 --1, 1 " 1 -Tr i 1uoro-2 - ( 2 -ethoxy- 5 -pyridyl ) - 5 - ( 3 -phenoxy~
phenyl)-pent~ne (No. 61, exa~ple of ~or~ula II~
1. 0 g of platinu~ on active carbon ~10 % ) i~ initiz~lly introduced into 100 ~1 of ethans)l under an al:mospher2 sf S hydrogen~ and 5.0 g (12.1 ~mol) of ole~in (1~ axe ~dded.
A~ter 4 hours at 1013 mbar, the r~action ~lxture i8 filter~d through ~ilica gel a~nd conce~tra~od. ~hi~ gi~
the compound ~o. 61 a~ ~ colorle~s liquid, the yield i~
4,9 g t97 %)-The compounds of thE3 formulae I ~nd II, which ~r~ ted below, may be prepared in accc~rdance with the~e proce-dures .
Abbreviation~: Ne = C~I3, l~t = C2H5, Ph = C:6H5, iPr = C~I ( CH3 ) 2 2 ~ 3 ~, Table 1 A ~ ~ ~ R5 ( I ~
l~x~ Rl R~ R3 ~ R4 B R5 R6 Phy~ic~l No. da~a (~-p- "C, ~C) 1013 lab r Et~ CF3 H C~2 H CH ~ OPh 386, 395 2 - CF3 H O H C~ El OPh 393, 1~01 3 " CF3 H S H C~ H OPh 4 CF3 H CH2 H Cq ~ OPh " CF3 H O H CH F OPh 389, 397 6 " CH3 H CH2 H aH H OPh 401, 410 7 " CH3 H O H CH H OPh 405, 415 8 n CH3 H S H CH H OPh 9 " H H CH2 ~1 0 H OPh " H H O H CH H OPh 1 1 " iPr H CH2 H CH H OPh 1l05, 409 12 " iPr H O H C~ H OPh CH3 H a~2 H CH ~ ûPb 14 n CH3 H O H CH F OPh ~J~V CF3 H C~2 H CH H OPh 372 ~ 382 16 n CF3 H O H t:H H O~h 377, 387 17 n CF3 H ~H2 ~ ~ F OPh 374, 385 18 n CF3 H O H !:~ F 0Ph 381, 390 9 9 n ~R3 H CH2 B ~ H OPh n CH3 }~ H CH H OPh 392, 398 21 n H H CH2 H ~ H ~h - . , ~ ,, . . ;, :
2 ~ 3 ~
~3kL~ntinua~n ~x .Rl RZ ~3 ~ R~ R5 R~ Phy~i aal No. data (b.p. C, t:C) 1013 ~r 22q"~ iPr H CH2 H CH H OPh 23 " iPr H O H C~ H OPh 24 n 7~ H O N CH H OPh 25~ a~3 H CH2 N CH H ~)Ph 26~ CF3 H O H CH H OPh 27 ~ CF3 H CHz H ~H N OPh 28CF3 H O N as~~ Hl ~Ph ClJ~ CF3 H CH2 N C~ H OPh n C:F3 H O H C~ H OPh 31 J~ 3 H CH~ ~ CH H OPh 32 ll CF3 H O H CH H OPh 33 " CF3 H CH2 H C;H F OPh 34 n CF3 H O H C~ F OPh n iPr H CH2 H ~ H O~h 36 n lPr H O H ~ H OPh . .
2 ~
Table 1 - s:ontinuation ~x. Rl R2 R3 A R'~ ~B R5 ~.0 Phy~ica ~ d~ta (b p C GC~
1013 a~ r EtO~g~ CF3 H CH2 H CE~ H OPh 38" CF3 H O H ~I H Ol~h 39~ CF 3 H CH2 H CH H OPh 40~ CF3 H O H ~ H OPh EtO~ CF3 CH3 C~2 H CH H OPh 42" CH3 ~3 CH2 H CH H OPh 3CF3 CH3 G~2 H .CH F ~Ph 44~ CF 3 H O ~ ~ H OPh 45 ~3~ CF3 H C~2 H CH H OE'h 46~ CF3 H O H t~l H OPh 47n CH3 H CH2 H CH H OPh 48n CH3 H H CH H OPh 49 ~ CF3 H CH~ H C~l H t)Ph EtO
50 n CP 3 H H S~3 H OPh 51~3~ ~3 H C~2 H C~ H t~h 364,3'72 52 ~ CH3 H O H CH H OPh 37 1~376 .:
.. ..
.
.
2 ~
~c. Rl R2 R3 A R~ B R5 R~ Phy~ical No. d~ta (~ P. C~
1013 D~ar ~N~ CF3 H C~2 ~ CH H OPh 54 " ::F3 H O ff CH H OPh N
~ ~ CF3 H CH2 H C~ H ûPh Me S
56 n CF3 H H a~ H OPh 57 ~ CF3 H C~2 H N H OPh EtO N
58 " ~F3 ~ O H N H OPh 59 ~ CF3 H CH2 ~ N H OPh n CP'3 ~ o N tl H C~h R d~t~ (eluen~ CDC1J, ~t~md~rds ~S, ~(H) tpp~D]) 1~ ~Olefin: 1,39, t (3H, OCH2t:H3, 7.3 Hz); 2,30, la t2H, CH2CH2CH); 2,61, t ~2H, llrC~12CH~, 7.0 H:z); 4,36, q, ~2H, OCI~CH3, 7.3 Hz); 6,42 tq (1H, C~CHCH2, 1~.7 Hz, 7~5 H~);
6,68-7,35, m (10N, Ar~rl-H); 7,86, d (1H~ 6-Pyridrl-H, 2.5 '~z).
~Ole~ln: 1,38, 'c (3H, ~H2C~3. 7.3 Hz); 2,73, Dl t4EI, ArCH2CH2CH); 4,36, ~ (2H, Ocg~2CH3- 7-3 ~); 5,959 ~q (1H, ~ 2, 6,9 Hz); 5,65, d (lH, 3-Pyridyl-H, 8.8 ~);
6,85~7,48, m (10H, ~l-H); 7,99, d (1H, 6-Pyridrl-H, 2.5 Mz).
: . . ' ' ''' , ' ' ,' ~
. .
~3 ~
T~le 2 Rl Q, R5 ( II ) R2 ~ R3 ~4 ~ R6 i~x. Rl R2 R3 A R~ B R5 EtG Phy~ical data ~b.p. t:, GC) 1013 Dlbar Et~ CF3 H ' H2 H CH H OPh 3g2 62 n ( @3 H O H a~ HOPb 390 63 n ~F3 H H CH F~)Ph 385 64 ~ C F3 H CH2 H CH E;'O~h 394 n CH3 H Q2 H CH HOPh 405 66 ~ CH3 H O H C~l HOPh 411 57 n H H CH2 H CH H OPh 68 ~I H H O tl CH H OPh 69 n iPr H O H CH H OPh n iPr H ~:H2 H M~ H OPh 71 CF3 CH3 CH2 H CH H QPh 7 CH3 CH3 CH2 H CH H OPh 73 ~F3 C~3 ~2 ~ aH F OPh 74 n CF3 M O CN Cfl H ~)Ph g~ OE3 ~ CH2 H CH Hl~h 3BO
~H2CF3 76 l1 ~F3 H O H a~ Ph 382 77 " CF3 H G~12 H l:H ~OPh 384 78 n t~3 H O ~I CH F O~h 378 79 n CH3 H ~2 H CH N~Ph 38h BO n lPr H a~2 ~
. . -~ - , . . ..
.
.
2 ~3 ~
-- ~3 --l~x. Rl RZ R3 A R~ B R5 R~ PhysiCal No. data t~p. ~C, ~C~
1013 ~bar 81 1J~ iPr H O H CH H O~h B2~ CF3 H CH2 H CH E~ OPh 83l~ CF3 H H C~ H OPh MeoJ~ CF3 H CH2 f~ CH H OPh 85n CF3 H H CH H OPh iPr~ CF3 H ~2 H CH H OPh B7~ CF3 H O H SH H O~h 8B" ~F3 H ~2 H CH F OPh 89n CF3 ~ H CH F OPh EtO~9~ ~3 H C~2 H CH H OPh 91~ CF3 H O H CH H 9Ph EtO~ ~3 H ~2 H CH H OPh 93 n CF~ ~3 0 H ~3 H O~h N
94 <(~ OE3 H 02 H CH H OPh h~
n CF3 U O lH C~l H QPh 2 ~ 3 2 ; 24 ~
13x. Rl R2 R3 ~ R4 B R5 R~ Phy~ical ~o. data (~.p. ~C, ~C) 1013 mbar N
96 ~ C F3 H CH2 H CH H ~)Ph 97" CF3 H O H Cff H OPh EtO~ ~3 H CH2 N N H OPh 99" CF3 H O H tl H OPh l~2~ ~F3 H ~U2 H N H OPh 101" CF3 H O H N H OPh 102~ a~3 N O N C~ H OPh 390 103 ~ CF3 N CH2 H C~ F QPh ~fCF3 \
~F3 104 n CF3 H N t::H F OPh . . ~ .~ -, ' ' .. ~ '.' : ' .
2 ~ 3 ~
- ~5 -UU~
Ex. Rl R2 ~3 A Rs B }~.g ~.0 Phy~ical . da~a ~b.p. C, GC3 1013 ~ibar 105 " CH3 H CH2 ~3 CH F ~h 106 n CH3 H 0 H CH F OE'h H-NMR data (eluents CDC13, Btand~rd~ tH) tppm] ) Ex.No. 75 :
1,48, m (2H, Cff2); 1,90, ~ (2H, ~l2~ 2,56, t (ArCH2.
2H, 7.3 Hz); 3,19, m 11H, F3CCH); 4,73, q (2~, OCH2CF3, 8,6 Hz); 6,75-7,36, m (10H, Azyl-~); 7~51, dd (1H, 4-Pyridyl-H, 8.8 Hz, 2.5 Hz); 7,98, d ~lH, 6-~gridyl-H, 2.5 Hz).
,. ..
, ' ' ;'"': ' ' ' ' ' , .
.
2 ~ 3 ~
C. Biologi~al Examples ple 1 The insideE of the li~ and the bottom o~ a Petri di~h ~re aach unifonnly coated with 1 ml of the formulation to be 5 te~tad, emulsified in water, ~nd ~ batch of 10 imaginq~s of the ~:ommvn house 1y (~usca domE~stica~ ~re ~ntroduc~d when ~he coa~ing has dried on. ~fter ~he di~h ha~ been ~ealed, i~ ie storad at room temparature, ~nd th~ mor-~ality of the test animals i3 deter~ined ziEter 3 hours.
aba~ectin, nacillu~ thurin~ien~i~, b4n~ultap, bi~ap~-. cryl, bromopropylate, buprofezi~, camphechlor, ~r-tap, chlorobenzialRte, chlorflua2uron, 2~ ehloro-phenyl~-4,5-diphenylthiophene SUBI-T 930~, clofen-tezine~ 2-naphthylmethyl cyclopropanee~rbc~ylake ~Ro 12-0470), cyro~z~n, ~th~ 3~5-dichloro-4-(1,1,2,3,3,3~-hexafluoro-1propylo~y)phenylc~rbs~oyl-2-~hloroben~ocarboxi~ida~e, DDT 7 dicofol, ~ 3,5-dichloro~ 2,?-tetxafluoroe~ho~y)phenyl~mino~-c~rbonyl)-2~6-difluorobenzamide (~RD 473), diflu-benzuron, N-(2,3-dihydro-3-~et~yl-1,3-~h~ol-2-ylidene)-2,4-xylidi~e, dinobuton~ ocap, endo~ulf~n, ethofnnprox, (4-ethoxyphanyl)(dimethyl~3~(3-phenoxy~
phenyl)propyl)~ ne, (4-e~hoxyphenyl)(3-t~-fluoro~3-phenoxyph~nyl)propyl)dim~thyl~ilane, feno~ycarb, 2 fluoro-5-(4-(4-etho~yphe~yl)~4-me~hyl-1 pen~yl) diphenyl ~ther (~I 800~, gra~ulosis and nucle~r polyhedro~i~ viru~es, fenthiocarb, flu~enz~mine, flucycloxuronS fluf~no~uron, gamma-~C~, he~ythiazox, hydra~thylno~ (AC 217300~ exmec~in, 2~nitromethyl-4,5-dihydro-6H-thiazin2 (SD 52618), 2-~itromethyl-3,4-dihydrothi~zole (SD 35fi51)~ 2-nitromethy~ene-1,2-~hiazinan-3-ylcarbamaldehyde (WL 10~477~, propargite~
teflubenzuron; tetradifon, tetra~ul, thiocyclam, triflumuron.
The active Rubstance con~ent of the ~se form~ prepared from the commercially ~vail~ble formulationfi can be from 0.00000001 to 100% ~y w~i~ht of ~cti~e ~ub~tance, prefer-ably between 0.00001 and 1% b~ ~eight.
Application i8 sff~cted i~ a con~entional ~ashion, m~tched to the u~e ~orm~.
~he active ~ubstance~ aa~ording ~o the inven~i4n ~re ~l~o ~uitable for comba~in~ endo- ~nd ecto-para~i~e~, pre~er-~bly in the veterinary medici~0 ~re~ or in the ~r~a o animal hu~bandry~
The ~ct~e ~ub~t~nces ~ccording tn ~he inv~ntion ~re applied in ~ known f~hion, ~uch ~ b~ or~l ~pplic~tio~
in the ~orm o~, for ex~mpl~0 tablet~ cap~ule~, pot~on3 or ~ranules~ by denmal application in th~ for~ of, ~or example, dippi~g, ~praying, p~uring~o~ ~nd ~pottiny-on ~nd po~dering, ~nd ~l~o by paranteral ~pplic~tion in the form of, for e~ample, $n~ect~on.
The no~el c~mpound~, according to ~h~ invention~ ~f the formllla I can accordingly al~o be em~loyed particularly advantageou~ly in lives~ock hu~bandry ( or example cattle, ~heep, pig~ and poultry ~uch ~ chicken~, ~ee~e 2 ~
- 15 ~
etc.). In a preferred embodiment o~ the inrention, the novel compound~, if ~ppropriate in suitable ormul~tion~
(cf. above) and if ~ppropriate wi~h the drinking wator or feed, are ~dmfnistered orally to the ~nimals. Since excretion in the dropping~ occur~ in an 8f ~ecti7e fashion, the develop~ent of in~ects in tha animal dropping~ can b2 prevented very 8imply in thi ~a~hion.
The do~ges and formulation~ suitable in each cs~e are particularly dependent on the ~ype ~nd ~tage o~ davelop-ment of the product~ve ~ni~al~ ~nd also on the de~ree of infe~tation of the insect~, and can ea~ily be de~exmined and fixed by conventional ~eth~ds. In the ca~e of ~attle, the novel compounds can be employed, for example, in dosage~ of 0.01 to 1 mg/kg of ~ody weigh~.
The following e~amples ~erve to illu~trate the inventicn.
~. ~oD~Nlation ~aqples a) A dusting agent iB obtained by ~ixing 10 part~ by weight of astive ~ubstance and 90 part~ b~ ~eigh~ of talc a6 inert materi~l and comminuting the ~ixture in a hammer mill.
b) A wettablo powder which io eaaily di~par~ible in water i8 obtained by ~i~in~ 25 paxt~ by wei~ht of ~c~ive ~ubstance, 65 p~rts by w~ight of k~olln-cont~ining quartz ~ ~nert materi~l, 10 p~r~s ~y w~iyht of pota~u~ Iigninsulfon~te ~nd 1 p~rt by ~e~ght o~
sodium oleoylmethyltaurinate ~8 wetti~ ~nd dispersing agent, and grinding the mi~ture in a pin di~k mill.
c) A di~persion concentxate which i~ e~8ily di~per~ible in wat~r i3 prep~red ~y ~ixing 40 p~rt~ by ~alght 9~
activ~ sub~t~nce ~ith 7 p~rts by w~i~h~ o~ ~ sulfo-~uccinic monoe~r, 2 parts by weight of ~ ~odium liynin~ulfonate ~nd 51 p~rt~ by w~i~h~ o~ waker, ~nd grinding the mixture in a ball ~ill to ~ finenes~ of below 5 ~icron~.
2~:~3 ~
d3 An emul~ifinble concentr~e ~ n be prepared fro2l 15 part~ by weight c>f ~ tilre ~ubstance, 75 p~rt~ by ~eight of c:yc:lohexanone a~ ~olvent and 10 par~s by weight of oxethyl~ted nonylphenol ( 10 IZ0 emulsifier.
e) Granules can be prepared from 2 to î5 part~ by ~ight of active aubstance an~ n inert granule ~rrier material ~uch a~ att~pu~glte, granulated pumice ancl/or quartz sand.
AdvantageouE~ly, ~ ~u~pens~on of the wettabl0 pc~ler frcml Example b) haYing a ~olid~ con~ent of 30 % i~ used/ and this i~ ~prayed onto the surf~ce of ~tt~pulgite ~ranul~s, which are dlried and mixed inti~at~ly. ~he ~proporltion by weight of the we~table powder i~ ~out 5 ~ and ~h~t of ~he inert carrier ~atexial about g5 % oiE the fini~hed granules .
B. Ch~mic~l e ~ ples 1,1,1-~rifluoro-2-t2-ethoxy-5-pyridyl~-5;(3-pheno~y-phenyl~-2-p~ntene (No. 1, ex~mple of ~ormul~ I~
2~5 ~ ~11.4 ~mol) o~ 2-ethoxy-5-trifluoroac0tylpyrldlna, 6.0 g ~lb.8 mmol) of 3-(3-pheno~yphenyl)-pxopyltriphen~l-pho~phonium bromide ~nd 1.3 g (12.0 mmol~ of pot~s~ium tert.-butoxide ~r~ mixed in 50 ~1 o~ ~oluene under ~
protectiv0 ga~ a~o~phere, and the ~ixture i~ ~tirred ox 6 hour~ at 20-C. The pot~iu~ bromide 1~ then r~moved by wa~hing with water~ the toluene phd8R i8 ~oncentr~ted, and the ~oluene extract ~ sep~rated by colu~n ohro~a~o-graphy (eluents ethyl ~cet~te~hept~ne - 2~8, ~tationary pha~e: ~ilic ~el). Thi~ yives 3.50 g ~75 %) o~ the olefin product (1) a~ ~olorle~ liquid. ~olubility~
readily ~oluble in heptane ~nd toluene; in~oluble in water. ~he lH- ~ ~nd ~C ~ea~ur~ments ~onf~rm tha~ a ~ixture of diastereo~er~ (Z ~nd ~ i~omer~ pre~en~ in the xa~io 203sl, b.p.lol3~386 ~nd 395~ t~C ~easur~ent).
2~3.~3~
-- ~7 --1, 1 " 1 -Tr i 1uoro-2 - ( 2 -ethoxy- 5 -pyridyl ) - 5 - ( 3 -phenoxy~
phenyl)-pent~ne (No. 61, exa~ple of ~or~ula II~
1. 0 g of platinu~ on active carbon ~10 % ) i~ initiz~lly introduced into 100 ~1 of ethans)l under an al:mospher2 sf S hydrogen~ and 5.0 g (12.1 ~mol) of ole~in (1~ axe ~dded.
A~ter 4 hours at 1013 mbar, the r~action ~lxture i8 filter~d through ~ilica gel a~nd conce~tra~od. ~hi~ gi~
the compound ~o. 61 a~ ~ colorle~s liquid, the yield i~
4,9 g t97 %)-The compounds of thE3 formulae I ~nd II, which ~r~ ted below, may be prepared in accc~rdance with the~e proce-dures .
Abbreviation~: Ne = C~I3, l~t = C2H5, Ph = C:6H5, iPr = C~I ( CH3 ) 2 2 ~ 3 ~, Table 1 A ~ ~ ~ R5 ( I ~
l~x~ Rl R~ R3 ~ R4 B R5 R6 Phy~ic~l No. da~a (~-p- "C, ~C) 1013 lab r Et~ CF3 H C~2 H CH ~ OPh 386, 395 2 - CF3 H O H C~ El OPh 393, 1~01 3 " CF3 H S H C~ H OPh 4 CF3 H CH2 H Cq ~ OPh " CF3 H O H CH F OPh 389, 397 6 " CH3 H CH2 H aH H OPh 401, 410 7 " CH3 H O H CH H OPh 405, 415 8 n CH3 H S H CH H OPh 9 " H H CH2 ~1 0 H OPh " H H O H CH H OPh 1 1 " iPr H CH2 H CH H OPh 1l05, 409 12 " iPr H O H C~ H OPh CH3 H a~2 H CH ~ ûPb 14 n CH3 H O H CH F OPh ~J~V CF3 H C~2 H CH H OPh 372 ~ 382 16 n CF3 H O H t:H H O~h 377, 387 17 n CF3 H ~H2 ~ ~ F OPh 374, 385 18 n CF3 H O H !:~ F 0Ph 381, 390 9 9 n ~R3 H CH2 B ~ H OPh n CH3 }~ H CH H OPh 392, 398 21 n H H CH2 H ~ H ~h - . , ~ ,, . . ;, :
2 ~ 3 ~
~3kL~ntinua~n ~x .Rl RZ ~3 ~ R~ R5 R~ Phy~i aal No. data (b.p. C, t:C) 1013 ~r 22q"~ iPr H CH2 H CH H OPh 23 " iPr H O H C~ H OPh 24 n 7~ H O N CH H OPh 25~ a~3 H CH2 N CH H ~)Ph 26~ CF3 H O H CH H OPh 27 ~ CF3 H CHz H ~H N OPh 28CF3 H O N as~~ Hl ~Ph ClJ~ CF3 H CH2 N C~ H OPh n C:F3 H O H C~ H OPh 31 J~ 3 H CH~ ~ CH H OPh 32 ll CF3 H O H CH H OPh 33 " CF3 H CH2 H C;H F OPh 34 n CF3 H O H C~ F OPh n iPr H CH2 H ~ H O~h 36 n lPr H O H ~ H OPh . .
2 ~
Table 1 - s:ontinuation ~x. Rl R2 R3 A R'~ ~B R5 ~.0 Phy~ica ~ d~ta (b p C GC~
1013 a~ r EtO~g~ CF3 H CH2 H CE~ H OPh 38" CF3 H O H ~I H Ol~h 39~ CF 3 H CH2 H CH H OPh 40~ CF3 H O H ~ H OPh EtO~ CF3 CH3 C~2 H CH H OPh 42" CH3 ~3 CH2 H CH H OPh 3CF3 CH3 G~2 H .CH F ~Ph 44~ CF 3 H O ~ ~ H OPh 45 ~3~ CF3 H C~2 H CH H OE'h 46~ CF3 H O H t~l H OPh 47n CH3 H CH2 H CH H OPh 48n CH3 H H CH H OPh 49 ~ CF3 H CH~ H C~l H t)Ph EtO
50 n CP 3 H H S~3 H OPh 51~3~ ~3 H C~2 H C~ H t~h 364,3'72 52 ~ CH3 H O H CH H OPh 37 1~376 .:
.. ..
.
.
2 ~
~c. Rl R2 R3 A R~ B R5 R~ Phy~ical No. d~ta (~ P. C~
1013 D~ar ~N~ CF3 H C~2 ~ CH H OPh 54 " ::F3 H O ff CH H OPh N
~ ~ CF3 H CH2 H C~ H ûPh Me S
56 n CF3 H H a~ H OPh 57 ~ CF3 H C~2 H N H OPh EtO N
58 " ~F3 ~ O H N H OPh 59 ~ CF3 H CH2 ~ N H OPh n CP'3 ~ o N tl H C~h R d~t~ (eluen~ CDC1J, ~t~md~rds ~S, ~(H) tpp~D]) 1~ ~Olefin: 1,39, t (3H, OCH2t:H3, 7.3 Hz); 2,30, la t2H, CH2CH2CH); 2,61, t ~2H, llrC~12CH~, 7.0 H:z); 4,36, q, ~2H, OCI~CH3, 7.3 Hz); 6,42 tq (1H, C~CHCH2, 1~.7 Hz, 7~5 H~);
6,68-7,35, m (10N, Ar~rl-H); 7,86, d (1H~ 6-Pyridrl-H, 2.5 '~z).
~Ole~ln: 1,38, 'c (3H, ~H2C~3. 7.3 Hz); 2,73, Dl t4EI, ArCH2CH2CH); 4,36, ~ (2H, Ocg~2CH3- 7-3 ~); 5,959 ~q (1H, ~ 2, 6,9 Hz); 5,65, d (lH, 3-Pyridyl-H, 8.8 ~);
6,85~7,48, m (10H, ~l-H); 7,99, d (1H, 6-Pyridrl-H, 2.5 Mz).
: . . ' ' ''' , ' ' ,' ~
. .
~3 ~
T~le 2 Rl Q, R5 ( II ) R2 ~ R3 ~4 ~ R6 i~x. Rl R2 R3 A R~ B R5 EtG Phy~ical data ~b.p. t:, GC) 1013 Dlbar Et~ CF3 H ' H2 H CH H OPh 3g2 62 n ( @3 H O H a~ HOPb 390 63 n ~F3 H H CH F~)Ph 385 64 ~ C F3 H CH2 H CH E;'O~h 394 n CH3 H Q2 H CH HOPh 405 66 ~ CH3 H O H C~l HOPh 411 57 n H H CH2 H CH H OPh 68 ~I H H O tl CH H OPh 69 n iPr H O H CH H OPh n iPr H ~:H2 H M~ H OPh 71 CF3 CH3 CH2 H CH H QPh 7 CH3 CH3 CH2 H CH H OPh 73 ~F3 C~3 ~2 ~ aH F OPh 74 n CF3 M O CN Cfl H ~)Ph g~ OE3 ~ CH2 H CH Hl~h 3BO
~H2CF3 76 l1 ~F3 H O H a~ Ph 382 77 " CF3 H G~12 H l:H ~OPh 384 78 n t~3 H O ~I CH F O~h 378 79 n CH3 H ~2 H CH N~Ph 38h BO n lPr H a~2 ~
. . -~ - , . . ..
.
.
2 ~3 ~
-- ~3 --l~x. Rl RZ R3 A R~ B R5 R~ PhysiCal No. data t~p. ~C, ~C~
1013 ~bar 81 1J~ iPr H O H CH H O~h B2~ CF3 H CH2 H CH E~ OPh 83l~ CF3 H H C~ H OPh MeoJ~ CF3 H CH2 f~ CH H OPh 85n CF3 H H CH H OPh iPr~ CF3 H ~2 H CH H OPh B7~ CF3 H O H SH H O~h 8B" ~F3 H ~2 H CH F OPh 89n CF3 ~ H CH F OPh EtO~9~ ~3 H C~2 H CH H OPh 91~ CF3 H O H CH H 9Ph EtO~ ~3 H ~2 H CH H OPh 93 n CF~ ~3 0 H ~3 H O~h N
94 <(~ OE3 H 02 H CH H OPh h~
n CF3 U O lH C~l H QPh 2 ~ 3 2 ; 24 ~
13x. Rl R2 R3 ~ R4 B R5 R~ Phy~ical ~o. data (~.p. ~C, ~C) 1013 mbar N
96 ~ C F3 H CH2 H CH H ~)Ph 97" CF3 H O H Cff H OPh EtO~ ~3 H CH2 N N H OPh 99" CF3 H O H tl H OPh l~2~ ~F3 H ~U2 H N H OPh 101" CF3 H O H N H OPh 102~ a~3 N O N C~ H OPh 390 103 ~ CF3 N CH2 H C~ F QPh ~fCF3 \
~F3 104 n CF3 H N t::H F OPh . . ~ .~ -, ' ' .. ~ '.' : ' .
2 ~ 3 ~
- ~5 -UU~
Ex. Rl R2 ~3 A Rs B }~.g ~.0 Phy~ical . da~a ~b.p. C, GC3 1013 ~ibar 105 " CH3 H CH2 ~3 CH F ~h 106 n CH3 H 0 H CH F OE'h H-NMR data (eluents CDC13, Btand~rd~ tH) tppm] ) Ex.No. 75 :
1,48, m (2H, Cff2); 1,90, ~ (2H, ~l2~ 2,56, t (ArCH2.
2H, 7.3 Hz); 3,19, m 11H, F3CCH); 4,73, q (2~, OCH2CF3, 8,6 Hz); 6,75-7,36, m (10H, Azyl-~); 7~51, dd (1H, 4-Pyridyl-H, 8.8 Hz, 2.5 Hz); 7,98, d ~lH, 6-~gridyl-H, 2.5 Hz).
,. ..
, ' ' ;'"': ' ' ' ' ' , .
.
2 ~ 3 ~
C. Biologi~al Examples ple 1 The insideE of the li~ and the bottom o~ a Petri di~h ~re aach unifonnly coated with 1 ml of the formulation to be 5 te~tad, emulsified in water, ~nd ~ batch of 10 imaginq~s of the ~:ommvn house 1y (~usca domE~stica~ ~re ~ntroduc~d when ~he coa~ing has dried on. ~fter ~he di~h ha~ been ~ealed, i~ ie storad at room temparature, ~nd th~ mor-~ality of the test animals i3 deter~ined ziEter 3 hours.
10 At 25û ppm (r~la~ive to the corl~ent of ac~ive ~ubslsan~e, preparations 1, 2d 6, 7, 11, 15" 16, 19, 20, 51, 52, 61, 64, 65, 75 and 79 8how a good ~ction ~100 ~ mort~lity~
again~t the common hou~e f ly R~ple 2 Batches of 10 larvae (I.4 ) of the German co~:krssach (Blst-tella germanica) ~re introduc~d in~o ~he Petri dish treated as in ~xampl~ he dishes are sealed, ~nd the mort~lity of the ta~t an~aal~ i~ cletexmined ta~er 5 d~y~.
At lû0 ppm (rel~tive to ths ~ont2nt c>~ ~!aCtiYÇ3 8ub8tanc0) '20 the pr~aparations 1, 2, 11, 15, 20, 61, 6S~ 65, 75 ~nd 79 showed A good action (100 % m~rtality) ~g~in~3t ~he Germ~n cockroach .
One layer of f ilter pa~r and on thi~ ~n ~Dount of 3 5 ml of a semi~ynthat~c diet ~re applied ts~ th~ ~n~ides of the ~ottom of a Petri d~h. Af~er cc~lill~, de~rea~ing concentration~ of the s~r~ul~tion to be ~es~ed ~re ~prayed with water onto the 3urface c)f the fee:l and the filter paper, and, when the spray coa'cing h~s drledl on, ba~che~ of 10 larvae (~3 - W) c~f the cs>tton w~rm (Prode-nia litura ) are in~roduced .
2 ~
_ ~7 -~he Petrl d$~he~ clre ~led wi~ch lld~ and ~ored for 7 day~ ~t room t~mperature, nIld the ~ort~ y o~ the ~e~t animal3 i~ then deter~ined.
At 1000 ppm (relative to the conten~ of ~cti;re ~
~tance), prep~ration~ 1, 2, 6, 150 16, 19~ 61, 64, 65, 75 and 79 ~how a good action ~gain~t lan7ae of the cotton worm .
ple ~
Lar~rae of the ~ex~can bea~ beetle (~pilachna variv~t~, IQ L ~ were treated ~ n a ~praying apparatuæ w$~h a prepara~ion of active ~ub~tance of ~he de~ired concen~cra-tion. ~t the same ~i~e, leav~ o~ dwarf bean~ (Phaseolu~
vulgari~) were dipped in~o ~he corre~pond~ng ~olution of active subs~ance. After ~he ~pr~y c:oating had dri2d on, the larvae of the b~etle were placed on the bean leavex.
Af ter 3 days, the de~truction of the larvae wa0 deter-mined as a percant~ge . ~t 1000 PE~ ( relative to the a~tive s~tance ), the prep~ra~ion~ 1, 2, 6; 7, 15 ~ 16, 19, 20, S1, 52, 61, 64, 65, 75 ~nd 79 showed a yood action again~t the ~exi~an bean beetle.
Bxa~ple 5 harv~e o the l~t l~ l 3t~ge c~f tha brown plant hclpper ( Nil~p~rvata lugens ~ ~re pl~aed ln Petri di~he~ where a treated, ~bsorbent piece o~ psper has ~aen placed on ~he bo~tom. ~fore the animal~ ~re illtroduced" eac~ filter paper i8 moi~tene~ ~ith 2 ml o~ dis~cilled water ~d s~seguerltly sprayad with decreasing dos~g~s of the te~
preparation, ~mul~ified in water correspond~n~ to 600 1 of wat~ar/ha. After the ~anilaals have ~Q~ roduced into the dishe~, the l~tt~r ~re ~ealed immediately and s~orad for 24 ~ours under l~boratory condition~ untll ~hey are evaluated . ~fter th~ B, the action ( 9~ ~or~ality) i8 evalu~t~d. At ~ con~eE~tr~tion of ~kive sub~tance in the spray ll~uor of 125 ppm~ the preparat$on~ 1, 6 ~ 51,, 64 y 2 ~ $ ~
65 and 79 ~how 100 ~ elction agains~ brown plant hoppexs, Field bean~ tVici~ faba) whic:h ~re heavily infe~t~d ~ith a cow pea ~phid (Aphis cracs:ivora) ~re ~pray~d with S aqueous dilution~ of con~entrations of wettable powder~
with an wtive ~ ns:e cos~ten~- of 100 ppm until the r-anoff point i~ reached. The ~s)r~ality o~ the aphids i~
determined ater 3 days. 100 % de~tructioll can be achieved with th2 compound~ of Examples 1, 15, 16, 19, 61, 64, 6S, 75 and 79.
again~t the common hou~e f ly R~ple 2 Batches of 10 larvae (I.4 ) of the German co~:krssach (Blst-tella germanica) ~re introduc~d in~o ~he Petri dish treated as in ~xampl~ he dishes are sealed, ~nd the mort~lity of the ta~t an~aal~ i~ cletexmined ta~er 5 d~y~.
At lû0 ppm (rel~tive to ths ~ont2nt c>~ ~!aCtiYÇ3 8ub8tanc0) '20 the pr~aparations 1, 2, 11, 15, 20, 61, 6S~ 65, 75 ~nd 79 showed A good action (100 % m~rtality) ~g~in~3t ~he Germ~n cockroach .
One layer of f ilter pa~r and on thi~ ~n ~Dount of 3 5 ml of a semi~ynthat~c diet ~re applied ts~ th~ ~n~ides of the ~ottom of a Petri d~h. Af~er cc~lill~, de~rea~ing concentration~ of the s~r~ul~tion to be ~es~ed ~re ~prayed with water onto the 3urface c)f the fee:l and the filter paper, and, when the spray coa'cing h~s drledl on, ba~che~ of 10 larvae (~3 - W) c~f the cs>tton w~rm (Prode-nia litura ) are in~roduced .
2 ~
_ ~7 -~he Petrl d$~he~ clre ~led wi~ch lld~ and ~ored for 7 day~ ~t room t~mperature, nIld the ~ort~ y o~ the ~e~t animal3 i~ then deter~ined.
At 1000 ppm (relative to the conten~ of ~cti;re ~
~tance), prep~ration~ 1, 2, 6, 150 16, 19~ 61, 64, 65, 75 and 79 ~how a good action ~gain~t lan7ae of the cotton worm .
ple ~
Lar~rae of the ~ex~can bea~ beetle (~pilachna variv~t~, IQ L ~ were treated ~ n a ~praying apparatuæ w$~h a prepara~ion of active ~ub~tance of ~he de~ired concen~cra-tion. ~t the same ~i~e, leav~ o~ dwarf bean~ (Phaseolu~
vulgari~) were dipped in~o ~he corre~pond~ng ~olution of active subs~ance. After ~he ~pr~y c:oating had dri2d on, the larvae of the b~etle were placed on the bean leavex.
Af ter 3 days, the de~truction of the larvae wa0 deter-mined as a percant~ge . ~t 1000 PE~ ( relative to the a~tive s~tance ), the prep~ra~ion~ 1, 2, 6; 7, 15 ~ 16, 19, 20, S1, 52, 61, 64, 65, 75 ~nd 79 showed a yood action again~t the ~exi~an bean beetle.
Bxa~ple 5 harv~e o the l~t l~ l 3t~ge c~f tha brown plant hclpper ( Nil~p~rvata lugens ~ ~re pl~aed ln Petri di~he~ where a treated, ~bsorbent piece o~ psper has ~aen placed on ~he bo~tom. ~fore the animal~ ~re illtroduced" eac~ filter paper i8 moi~tene~ ~ith 2 ml o~ dis~cilled water ~d s~seguerltly sprayad with decreasing dos~g~s of the te~
preparation, ~mul~ified in water correspond~n~ to 600 1 of wat~ar/ha. After the ~anilaals have ~Q~ roduced into the dishe~, the l~tt~r ~re ~ealed immediately and s~orad for 24 ~ours under l~boratory condition~ untll ~hey are evaluated . ~fter th~ B, the action ( 9~ ~or~ality) i8 evalu~t~d. At ~ con~eE~tr~tion of ~kive sub~tance in the spray ll~uor of 125 ppm~ the preparat$on~ 1, 6 ~ 51,, 64 y 2 ~ $ ~
65 and 79 ~how 100 ~ elction agains~ brown plant hoppexs, Field bean~ tVici~ faba) whic:h ~re heavily infe~t~d ~ith a cow pea ~phid (Aphis cracs:ivora) ~re ~pray~d with S aqueous dilution~ of con~entrations of wettable powder~
with an wtive ~ ns:e cos~ten~- of 100 ppm until the r-anoff point i~ reached. The ~s)r~ality o~ the aphids i~
determined ater 3 days. 100 % de~tructioll can be achieved with th2 compound~ of Examples 1, 15, 16, 19, 61, 64, 6S, 75 and 79.
Claims (9)
1. A compound of the formulae I and II, the stereo-isomers thereof, and the mixtures of the latter (I) (II) where R1 is pyridyl, pyrimidyl, thienyl, thiasolyl, furanyl, pyrazolyl, 1,3-oxazolyl or imid-azolyl, all of which can be substituted, R2 is H, (1-C4)alkyl, (c1-C4)haloalkyl, (C1-C4)alkoxy, (C3-C6)cycloalkyl, -CH=CH2 or -C=CH, R3 is H or (C1-C4)alkyl, R4 is H, (C1-C4)alkyl, -CN or -C=CH, A is CH2, O or S, B is CH, N or C(CH3), R5 is H or halogen and R5 is phenyl, phenoxy or benzyl, all of which can be monosubstituted to pentasubstituted by halogen or (C1-C3)haloalkyl.
2. A compound of the formulae I and II of claim 1, in which R1 is a radical of the fomulae A, B, C, D, E
or F
(A), (B), (C), (D), (E), (F) in which R7 is H, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C1-C4)halo-alkoxy and m is 1 or 2, R2 is (C1-C3)alkyl, cyclopropyl or CF3, R3 is H or methyl, B is CH, R4 is H, methyl, -CN or -C=CH and R5 is phenoxy which can be substituted in the 4-position by C1, Br or CF3.
or F
(A), (B), (C), (D), (E), (F) in which R7 is H, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C1-C4)halo-alkoxy and m is 1 or 2, R2 is (C1-C3)alkyl, cyclopropyl or CF3, R3 is H or methyl, B is CH, R4 is H, methyl, -CN or -C=CH and R5 is phenoxy which can be substituted in the 4-position by C1, Br or CF3.
3. A compound of the formulae I and II of claim 2, where R7 is C1, Br, (C1-C3)alkoxy, -OCF3, -OCH2CF3 or -OCF2CF2H.
4. A compound as claimed in one or more of claims 1 to 3, wherein R1 is a radical of the formula A, B or C.
5. A compound as claimed in one or more of claims 1 to 4, wherein R2 is radical of the formula A.
6. A process for the preparation of a compound of the formulae I and II as claimed in one or more of claims 1 to 5, which comprises a) for compounds of the formula I, reacting a compound of the formula III
(III) where R1 and R2 are as defined in formula I, with a compound of the formula IV
(IV) where R3, R4, R5, R6, A and B are as defined in formula I and R8 is phenyl, cyclohexyl or butyl, and b) for compounds of the formula II, catalyti-cally hydrogenating the olefin function of the corresponding compound of the formula I with hydrogen or a hydrogen-liberating compound.
(III) where R1 and R2 are as defined in formula I, with a compound of the formula IV
(IV) where R3, R4, R5, R6, A and B are as defined in formula I and R8 is phenyl, cyclohexyl or butyl, and b) for compounds of the formula II, catalyti-cally hydrogenating the olefin function of the corresponding compound of the formula I with hydrogen or a hydrogen-liberating compound.
7. An insecticidal or acaricidal agent, containing an effective amount of a compound of the formulae I and/or II.
8. The use of a compound of the formulae I and/or II for controlling insect pests or acarids.
9. A method of controlling insect pests or acarids, which comprises applying an effective amount of a compound of the formulae I and/or II to these insect pests or acarids, or the plants, areas or substrates infested with them.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3907784.5 | 1989-03-10 | ||
| DE3907784A DE3907784A1 (en) | 1989-03-10 | 1989-03-10 | HETEROARYL-ARYL-BUTEN AND BUTANE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF, CONTAINERS THEREOF AND THEIR USE AS A PEST CONTROL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2011832A1 true CA2011832A1 (en) | 1990-09-10 |
Family
ID=6376018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002011832A Abandoned CA2011832A1 (en) | 1989-03-10 | 1990-03-09 | Heteroaryl-aryl-butene and -butane derivatives, process for their preparation, agents containing them, and their use as pesticides |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0386715B1 (en) |
| JP (1) | JPH0774203B2 (en) |
| KR (1) | KR900014319A (en) |
| CN (1) | CN1046156A (en) |
| AT (1) | ATE118480T1 (en) |
| AU (1) | AU622292B2 (en) |
| CA (1) | CA2011832A1 (en) |
| DE (2) | DE3907784A1 (en) |
| ES (1) | ES2070200T3 (en) |
| HU (1) | HUT53082A (en) |
| IL (1) | IL93688A0 (en) |
| ZA (1) | ZA901846B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3810379A1 (en) * | 1988-03-26 | 1989-10-12 | Hoechst Ag | AZANEOPHYL AND SILAZANEOPHYL SULFIDES, METHOD FOR THE PRODUCTION THEREOF, CONTAINERS THEREOF AND THEIR USE AS A PEST CONTROL |
| RU2561729C2 (en) | 2009-07-08 | 2015-09-10 | Дермира (Канада), Инк. | Tofa analogues, applicable in treatment of dermatological disorders or conditions |
| CN103214413B (en) * | 2013-03-22 | 2015-05-13 | 郑州泰基鸿诺药物科技有限公司 | Heterocycle-containing trifluoromethyl ketone compound and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8520027D0 (en) * | 1985-08-09 | 1985-09-18 | Ici Plc | Insecticidal ethers |
| GB2187452A (en) * | 1986-03-04 | 1987-09-09 | Ici Plc | Insecticidal fluoroalkyl benzene derivatives |
| US4840971A (en) * | 1986-04-07 | 1989-06-20 | Sumitomo Chemical Company, Limited | Novel ether compound, a process for manufacturing the same, a composition containing the same and a use thereof |
| GB2199825B (en) * | 1987-01-08 | 1991-04-17 | Ici Plc | Insecticidal ethers |
| DE3712752A1 (en) * | 1987-04-15 | 1988-11-03 | Hoechst Ag | HETEROCYCLIC NEOPHANAL ANALOG, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL |
| US4808762A (en) * | 1987-04-23 | 1989-02-28 | Fmc Corporation | Insecticidal cyclopropyl-substituted di(aryl) compounds |
| RO108522B1 (en) * | 1987-04-23 | 1994-06-30 | Fmc Corp | Derivates of di(aryl)-cyclopropyl, its substitutes and intermediaries thereof |
-
1989
- 1989-03-10 DE DE3907784A patent/DE3907784A1/en not_active Withdrawn
-
1990
- 1990-03-07 EP EP90104312A patent/EP0386715B1/en not_active Expired - Lifetime
- 1990-03-07 AT AT90104312T patent/ATE118480T1/en not_active IP Right Cessation
- 1990-03-07 ES ES90104312T patent/ES2070200T3/en not_active Expired - Lifetime
- 1990-03-07 DE DE59008451T patent/DE59008451D1/en not_active Expired - Fee Related
- 1990-03-08 IL IL93688A patent/IL93688A0/en not_active IP Right Cessation
- 1990-03-09 KR KR1019900003116A patent/KR900014319A/en not_active Application Discontinuation
- 1990-03-09 CA CA002011832A patent/CA2011832A1/en not_active Abandoned
- 1990-03-09 AU AU51180/90A patent/AU622292B2/en not_active Ceased
- 1990-03-09 HU HU901378A patent/HUT53082A/en unknown
- 1990-03-09 JP JP2056770A patent/JPH0774203B2/en not_active Expired - Lifetime
- 1990-03-09 CN CN90101246A patent/CN1046156A/en active Pending
- 1990-03-09 ZA ZA901846A patent/ZA901846B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774203B2 (en) | 1995-08-09 |
| AU622292B2 (en) | 1992-04-02 |
| DE3907784A1 (en) | 1990-09-13 |
| ZA901846B (en) | 1990-11-28 |
| HUT53082A (en) | 1990-09-28 |
| KR900014319A (en) | 1990-10-23 |
| EP0386715B1 (en) | 1995-02-15 |
| ATE118480T1 (en) | 1995-03-15 |
| IL93688A0 (en) | 1990-12-23 |
| HU901378D0 (en) | 1990-05-28 |
| ES2070200T3 (en) | 1995-06-01 |
| EP0386715A3 (en) | 1991-12-18 |
| AU5118090A (en) | 1990-09-13 |
| EP0386715A2 (en) | 1990-09-12 |
| DE59008451D1 (en) | 1995-03-23 |
| CN1046156A (en) | 1990-10-17 |
| JPH02289547A (en) | 1990-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1069900C (en) | Pesticide | |
| SE442995B (en) | SUBSTITUTED PHENOXYBENZYLOXICARBONYL DERIVATIVES AND USE THEREOF TO FIGHT INSECTS AND / OR ACARIDS | |
| HU202368B (en) | Insecticide and acaricide compositions containing silane derivatives as active components and process for producing silane derivatives | |
| JPS60158154A (en) | Substituted malonic acid derivative, manufacture and use | |
| CS268533B2 (en) | Insecticide and acaricide and method of efficient substances production | |
| FI102374B (en) | 1-arylimidazolpesticider | |
| DE3628892A1 (en) | SUBSTITUTED 1-ARYL-3-TERT.-BUTYL-PYRAZOLE | |
| EP0248348A1 (en) | Pesticide based on aminopyrimidine derivatives, and aminopyrimidine compounds | |
| PL107560B1 (en) | INSECTICIDE | |
| CS241124B2 (en) | Insecticide and acaricide and method of active substances production | |
| CA2011832A1 (en) | Heteroaryl-aryl-butene and -butane derivatives, process for their preparation, agents containing them, and their use as pesticides | |
| KR840001888B1 (en) | Process for the preparing of n-phosphonyl carbonyl-carbamate | |
| JPS63156781A (en) | Substituted 4-amino-pyrimidines | |
| CA1280764C (en) | Tetramethylcyclopropanecarboxylates | |
| EP0126235A1 (en) | Five-membered nitrogen-containing heterocycles, process for their preparation and their use as pesticides | |
| JPS61271276A (en) | Dichlorocyclopropylalkyl-hydroxyalkyl-azole derivative | |
| JPH0231066B2 (en) | ||
| JPH03271207A (en) | Insecticidal antimicrobial agent composition | |
| EP0004642A1 (en) | Diaryl amines, process for their preparation and their use | |
| KR880001864B1 (en) | Process for preparing esters of phenoxyphyridil methyl | |
| EP0595125A1 (en) | Substituted aza(cyclo) alkanes and their use as pesticides | |
| DE3700916A1 (en) | HALOGENALKYL, ALKENYL AND ALKINYL AZOLES | |
| DE3545569A1 (en) | NEW PYRIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF, CONTAINERS THEREOF AND THEIR USE AS A PEST CONTROL | |
| US5075294A (en) | Pyridyl phosphates, compositions containing them and their use as pesticides | |
| CA1196922A (en) | N-sulphenylated oxime-carbamates, processes for their preparation and their use in pest combating agents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |