EP0452406A1 - Substituierte semicarbazon-arthropodizide - Google Patents

Substituierte semicarbazon-arthropodizide

Info

Publication number
EP0452406A1
EP0452406A1 EP90902098A EP90902098A EP0452406A1 EP 0452406 A1 EP0452406 A1 EP 0452406A1 EP 90902098 A EP90902098 A EP 90902098A EP 90902098 A EP90902098 A EP 90902098A EP 0452406 A1 EP0452406 A1 EP 0452406A1
Authority
EP
European Patent Office
Prior art keywords
optionally substituted
phenyl
alkyl
independently selected
compound according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP90902098A
Other languages
English (en)
French (fr)
Inventor
John Powell Daub
George Philip Lahm
Bradford Senn Marlin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0452406A1 publication Critical patent/EP0452406A1/de
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
    • C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
    • C07C281/12—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones the carbon atom being part of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • U.S. 4,547,524 discloses benzoyl hydrazone derivatives as insecticides.
  • WO 8800197 discloses as part of a broader scope substituted semicarbazones derived' from chromanones and thiochromanones as intermediates used in the preparation of insecticides.
  • EP-3,913 discloses substituted oenzophenone hydrazones to be useful as insecticides.
  • EP-26,040 discloses a broad scope of
  • EP-254,461 discloses N-substituted hydrazones to be useful as insecticides.
  • This invention pertains to cImpounds of Formula I, including all geometric isomers, stereoisomers, and agronomically and nonagronomically suitable salts thereof, compositions containing them, and their use as agronomic and nonagronomic arthropodicides:
  • A is (CH 2 ) t , O, S(O) q , NR 7 , OCH 2 or S(O) q CH 2 , wherein, each carbon individually can be substituted with 1 to 2 substituents
  • R 1 and R 2 are independently R 8 , halogen, CN, NO 2 , N 3 , SCN, OR 8 , SR 8 , SOR 8 , SO 2 R 8 , NR 8 R 9 , C(O)R 8 , CO 2 R 8 , C(O)NR 8 R 9 , OC(O)R 8 , OCO 2 R 8 , OC(O)NR 8 R 9 , NR 9 C(O)R 8 , NR 9 C(O)NR 8 R 9 , OSO 2 R 8 , NR 9 SO 2 R 8 , or when m is 2, R 1 is optionally taken together to form a 5 or 6 membered fused ring as OCH 2 O, OCH 2 CH 2 O OR CH 2 CH 2 O each of which is optionally substituted with 1 to 4 halogen atoms or 1 to 2 methyl groups, or when n is 2, R 2 is optionally taken together to form a 5 or 6 membered fused ring as OCH 2 O, OCH 2
  • A is CH 2 ;
  • R 3 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 4 -C 6 alkylcycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6
  • R 4 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 cyanoalkyl, phenyl optionally substituted with (R 10 ) p or benzyl optionally substituted with 1 to 3 substituents independently selected from W;
  • R 5 and R 6 are independently H, C 1 -C 22 alkyl, C 2 -C 22 alkoxyalkyl, C 2 -C 22 alkylcarbonyl, C 2 -C 22 alkoxycarbonyl, C 2 -C 22 haloalkyl carbonyl, C 2 -C 22 haloalkoxycarbonyl, SR 11 ,
  • R 7 is H, C 1 -C 4 alkyl or phenyl optionally
  • R 8 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • halocycloalkylalkyl C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6
  • haloalkynyl C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C 1 -C 6 nitroalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, phenyl optionally substituted with 1 to 3
  • R 9 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, or R8 and R 9 is optionally taken together as (CH 2 ) 4 , (CH 2 ) 5 or
  • R 10 is R 8 , halogen, CN, NO 2 , N 3 , SCN, OR 8 , SR 8 , SOR 8 , SO 2 R 8 , NR 8 R 9 , COR 8 , CO 2 R 8 , CONR 8 R 9 ,
  • R 10 is optionally taken together to form a 5 or 6 membered fused ring as OCH 2 O, OCH 2 CH 2 O, or CH 2 CH 2 O each of which is optionally substituted with independently, 1 to 4 halogen atoms or 1 to 2 methyl groups;
  • R 11 is C 1 -C 22 alkyl, C 1 -C 22 haloalkyl,
  • R 11 is NR 12 C(O)R 13' NR 12 S(O) a R 13 ,
  • R 12 and R 16 are independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 4 -C 7 cycloa Iky1alkyl, C 2 -C 6 cyanoalkyl, C 2 -C 6 alkoxyalkyl, C 3 -C 8
  • alkoxycarbonylalkyl C 4 -C 8
  • dialkylaminocarbonylalkyl phenyl optionally substituted by 1 to 2 substituents selected from W, benzyl optionally substituted by 1 to 2 substituents selected from W and phenethyl optionally substituted by 1 to 2 substituents selected from W, or R 12 -R 16 is optionally taken together as (CH 2 ) 4 , (CH 2 ) 5 or (CH 2 ) 2 O(CH 2 ) 2 , each ring optionally substituted with 1 to 2 CH 3 ;
  • R 13 is F, C 1 -C 20 alkyl, C 1 -C 6 haloalkyl,
  • R 13 is C 1 -C 20 alkoxy C 1 -C 6 haloalkoxy or C 1 -C 4 alkoxy substituted with cyano, nitro, C 1 -C 4 alkoxy, C 4 -C 8
  • R 14 and R 15 are independently selected from
  • W is halogen, CN, NO 2 , C 1 -C 2 alkyl, C 1 -C 2
  • haloalkyl C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfonyl or C 1 -C 2 haloalkylsulfonyl; m is 1 to 5;
  • n 1 to 4.
  • t 0 to 3;
  • q 0 to 2;
  • p 1 to 3;
  • a 0 to 2;
  • V is 0 or S
  • Z is O or S.
  • Preferred Compounds (A) are those compounds of Formula I wherein;
  • R 3 or R 4 when R 3 or R 4 is H and A is oxygen then the remaining R 3 or R 4 is other than phenyl or phenyl optionally substituted with W and when t is 0 then R 3 or R 4 are other than Ph or phenyl optionally substituted with W.
  • Preferred Compounds (B) are Compounds of
  • R 1 , R 2 and R 10 are R 8 , halogen, CN, NO 2 , OR 8 , SR 8 , SOR 8 , SO 2 R 8 , NR 8 R 9 , CO 2 R 8 , SO 2 NR 8 R 9 , or when m, n or q is 2, then R 1 , R 2 or R 10 respectively is optionally taken together to form a 5 or 6 membered fused ring as OCH 2 O, OCH 2 CH 2 O or CH 2 CH 2 O each of which is optionally substituted with 1 to 4 halogens or 1 to 2 methyl groups; R 8 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • cycloalkyl phenyl optionally substituted with 1 to 2 substituents independently selected from W or benzyl optionally substituted with 1 to 2 substituents independently selected from W;
  • R 5 and R 6 are independently H, C 1 -C 3 alkyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4
  • alkoxycarbonyl CHO, SR 11 , phenyl
  • R 11 is C 1 -C 3 alkyl, phenyl optionally
  • R 12 and R 16 are independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 5 -C 6 cycloalkyl, C 3 -C 8 alkoxycarbonylalkyl, phenyl, benzyl and phenethyl or each phenyl, benzyl and phenethyl optionally substituted with 1 to 2 substituents independently selected from W, or R 12 and R 16 can be taken together as (CH 2 ) 4 ,
  • R 14 and R 15 are independently selected from
  • n 1 to 2;
  • n 1 to 2;
  • p 1 to 2;
  • V is S
  • Preferred Compounds (C) are Compounds B wherein:
  • R 3 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 4 is H, C 1 -C 3 alkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl;
  • R 5 is H, Me, CO 2 Me, CO 2 Et, SR 11 or phenyl optionally substituted with 1 to 2 substituents independently selected from W;
  • R 6 is H, Me, C(O)Me, CO 2 Me or SR 11 ;
  • R11 is C 1 -C 3 alkyl, NR 12 C(O)R 13 ,
  • R 12 is C 1 -C 4 alkyl or phenyl optionally
  • R 13 is C 1 -C 12 alkyl, C 1 -C 12 alkoxy,
  • A is CH 2 , CH 2 CH 2 , O, S, OCH 2 , NR 7 or SCH 2 , wherein, each carbon is optionally substituted with C 1 -C 3 alkyl or phenyl, wherein, the phenyl is optionally
  • R 7 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl or C 1 -C 4 alkylsulfonyl.
  • Preferred Compound (D) are Compounds C wherein:
  • R 1 and R 2 are independently selected from F, Cl, Br, CN, NO 2 , OMe, CF 3 , OCF 2 H, OCF 2 CF 2 H, SMe, SO 2 Me, SCF 2 H or when m or n is 2 R 1 or R 2 respectively is optionally taken together as CH 2 C(CH 3 ) 2 O or CF 2 CF 2 O; R 3 is C 1 to C 4 alkyl, allyl, propargyl, or phenyl optionally substituted with F, Cl, Br, CF 3 , OCF 2 H, OCF 3 , SCF 2 H, CN, NO 2 ,
  • R 4 is H or CH 3 ;
  • R 5 is H, CH 3 CO 2 CH 3 , CO 2 Et, or phenyl
  • R 6 is H, CH 3 , C(O)CH 3 or CO 2 CH 3 ;
  • A is O, S or CH 2 , optionally substituted with C 1 -C 3 alkyl or phenyl which may also be optionally substituted with W.
  • Preferred Compounds (E) are Compounds D wherein A is CH 2 ; and R 3 is optionally substituted phenyl or C 1 to C 4 alkyl.
  • Preferred Compounds (F) are
  • Preferred Compounds (G) are compounds of Formula I wherein Q is Q-2.
  • Preferred Compounds (H) are compounds of
  • Preferred Compounds (I) are compounds of Formula I wherein Q is Q 4 .
  • Preferred Compounds (J) are compounds of Formula I wherein Q is Q 5 .
  • Preferred Compounds (K) are
  • Compounds (L) are compounds of Formula I wherein Q is Q 7 .
  • Preferred Compounds (M) are compounds of Formula I wherein Q is Q 8 .
  • Preferred Compounds (N) are
  • the compounds of Formula I, where Q is Q-1 can be prepared by the reaction of hydrazones of Formula II with an aryl isocyanate of Formula III.
  • Compounds of Formula I, where Q is Q-2 through Q-8 can be prepared by procedures which are analogous to those for compounds where Q is Q-1; therefore, for brevity only the Q-1 compounds are described.
  • Typical reactions involve combination of equimolar amounts of II and III in a suitable solvent at temperatures generally in the range of -10 to 100°C. Although the reaction can be run neat, a solvent is generally preferred. Suitable solvents typically have
  • sufficient polarity to effect solution of the Formula II hydrazone include, but are not limited to, ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and polar aprotic solvents such as dimethylformamide and dimethylacetamide.
  • ethers such as diethyl ether, tetrahydrofuran and dioxane
  • halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • esters such as ethyl acetate and polar aprotic solvents such as dimethylformamide and dimethylacetamide.
  • Compounds of Formula I include both geometrical and optical isomers as well as syn and anti isomers around the nitrogen-nitrogen bond. These isomers may vary in their biological activity. In some
  • the generic formula (Formula I) encompasses certain compounds that may have long term stability problems and/or are difficult to prepare.
  • R 1 when R 1 is an OCO 2 R 8 group and R 8 is hydrogen the R 1 substituent is OCO 2 H which will decompose to the corresponding phenol and carbon dioxide.
  • haloalkylamines when R 1 is NR 8 R 9 and R 8 is C 1 to C 6 haloalkyl are unstable when the halo substituent is directly adjacent to nitrogen. These generally decompose to the corresponding hydrogen halides and imine.
  • the hydrazones of Formula II can be obtained by processes known in the art involving condensation of a ketone of Formula IV with either hydrazine or a substituted derivative thereof (Formula V). This reaction is typically conducted with equimolar amounts of IV and V although greater than
  • stoichiometric amounts of hydrazine (V) can be used.
  • Suitable solvents include the alcohols such as methanol, ethanol, propanol, butanol and the like at temperatures in the range of 0 to 150°C, with the reflux temperature of the solvent generally being a convenient reaction temperature.
  • Acid catalysis can also be useful, particularly for some of the more sterically hindered Formula IV compounds.
  • Typical acid catalysts include sulfuric, hydrochloric and p-toluene sulfonic acid.
  • An alternate process useful for the preparation of compounds of Formula I involves condensation of a phenyl substituted semicarbazide of Formula VI with a ketone of Formula III.
  • Preferred conditions for this reaction include an acid catalyst such as
  • hydrochloric, sulfuric or p-toluene sulfonic acid Reaction temperatures can range from 0 to 150°C with the reflux temperature of the solvent used generally preferred.
  • Suitable solvents include, but are not limited to, ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene and toluene; and especially preferred are alcohols such as methanol, ethanol and isopropanol.
  • Compounds of Formula I where R 5 and R 6 are other than hydrogen can generally be prepared from the corresponding compounds where R 5 and R 6 are hydrogen by reaction with electrophilic reagents such as alkyl halides, acyl halides, alkyl chloroformates and sulfenyl halides.
  • electrophilic reagents such as alkyl halides, acyl halides, alkyl chloroformates and sulfenyl halides.
  • the use of a base is generally preferred in these reactions but is dependent upon the specific nature of the reactants.
  • metal hydrides such as sodium hydride or
  • potassium hydride in solvents such as tetrahydrofuran or dimethylformamide are preferred.
  • solvents such as tetrahydrofuran or dimethylformamide.
  • amine bases such as
  • isochromanones isothiochromanones and others.
  • Example 1 illustrates the invention.
  • Step A 3-chloro- ⁇ -(4-chlorophenyl)benzene ⁇ ropanoic acid
  • the crude product was combined with 300 ml of methanol, 40 ml of water and 20 ml of 50% aqueous sodium hydroxide and refluxed overnight. After this time the reaction was concentrated and the crude residue partitioned between water and ether. The aqueous extracts were acidified with cone.
  • Step B 5-chloro-2-( 4-chlorophenyl)-2,3-dihydro- 1H-inden-1-one
  • Step A ethyl 2[5-fluoro-2-(4-fluorophenyl)-2,3- dihydro-1H-inden-1-ylidene]hydrazine carboxylate
  • Step B ethyl 2-[5-fluoro-2-(4-fluorophenyl)-2,3- dihydro-1H-inden-1-ylidenel-1-[[[4-(trifluoromethyl)phenyl]aminolcarbonyl]- hydrazine carboxylate
  • Step B methyl 5-chloro-2,3-dihydro-2-methyl-1-oxo- 1H-indene-2-carboxylate
  • Step A 3-(4-f luorophenyl)-1-phenyl-2-propen-1-one
  • Step A ethyl 4-fluoro- ⁇ -methylenebenzeneacetate
  • Step B ethyl 4-fluoro- ⁇ -[[(2-fluorophenyl)thio]- methyl]benzeneacetate
  • Step D 8-f luoro-3-(4-f luorophenyl)-2,3-dihydro-4H- 1-benzothiopyran-4-one
  • Step E 2-[8-fluoro-3-(4-fluorophenyl)-3,4-dihydro- 2H-1-benzothiopyran-4-ylidene]-N-r4-(trifluoromethyl) phenyl ]-hydrazinecarboxamide
  • the thiochromanone from Step D (1.1 g,
  • Step A methyl 6-fluoro-1,2,3,4-tetrahydro-1-oxo-2- naphthalenecarboxylate
  • Step B methyl 6-fluoro-1.2.3.4-tetrahydro-1-oxo-2- phenyl-2-naphthalenecarboxylate
  • Step C 6-fluoro-3.4-dihvdro-2-phenyl-1(2H)- naphthalenone
  • the tetralone from Step B (2.8 g, 9.4 mmole) was dissolved in 45 ml of dimethylformamide. To this solution was added lithium chloride (2.0 g, 47 mmole) and water (0.42 ml, 23 mmole). The reaction mixture was heated to 150°C for 2.5 hrs and then cooled and partitioned between ether and water. The aqueous phase was separated and extracted three times with ether. The combined organic phases were washed once with water, dried (MgSO 4 ), and concentrated (1.96 g, 87% yield).
  • Step D 2-(6-fluoro-1.2.3.4-tetrahvdro-2-phenyl-1- naphthalenylidene)-N-[4-(trifluoromethyl)- phenyl]hydrazinecarboxamide
  • Step A 4-Chloro-2-(2-methoxy-1-methyl-2-oxoethoxy)- benzoic acid, methyl ester
  • Step C (Z)-2-(6-chloro-2-methyl-3(2H)-benzofuranylidene)-N-[4-(trif luoromethyl)phenyl]- hydrazinecarboxamide
  • Step D (E)-2-(6-chloro-2-methyl-3(2H)-benzofuranylidene)-N-[4-(trifluoromethyl)phenyl)- hydrazinecarboxamide
  • the compounds of this invention will generally be used in formulation with a carrier comprising a liquid or solid diluent or an organic solvent.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, baits, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly. Sprayable
  • formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength
  • compositions are primarily used as intermediates for further formulation.
  • the formulations broadly, contain about 1% to 99% by weight of active
  • ingredient(s) and at least one of a) about.0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following
  • Agents Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. 3,060,084). Granules and pellets can be made by spraying the active
  • the ingredients are combined and stirred with gentle warming to speed solution.
  • a fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.
  • Example C The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer- mill, the material is re-blended and sifted through a 50 mesh screen.
  • Example C The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer- mill, the material is re-blended and sifted through a 50 mesh screen.
  • the wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged.
  • the product is suitable for use as a dust.
  • the active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged.
  • a volatile solvent such as acetone
  • the ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.
  • the ingredients are combined and stirred to produce a solution suitable for direct, low volume application.
  • Example H The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
  • the ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns.
  • the product can be used directly, extended with oils, or emulsified in water.
  • Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a
  • O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) ( S)-a-cyano-m-phenoxybenzyl ( 1R , 3R) -3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl-N',N'-dimethyl-N-C(methylcarbamoyl)oxy]-1- thioox amimidate (oxamyl)
  • Additional insecticides are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate,
  • the compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods which are pests of growing and stored agronomic crops, forestry, greenhouse crops,
  • Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting insects such as Western corn rootworm and other Diabrotica spp., Japanese beetle, European chafer and other coleopteran grubs, and wirew ⁇ rms; adults and larvae of the orders Hemiptera and
  • Homoptera including tarnished plant bug and other plant bugs (miridae), aster leafhopper and other leafhoppers (cicadellidae), rice planthopper, brown planthopper, and other planthoppers (fulgoroidea), psylids,
  • whiteflies (aleurodidae), aphids (aphidae), scales (coccidae and diaspididae), lace bugs (tinoidae), stink bugs (pentatomidae), cinch bugs and other seed bugs (lyoaeidae), cicadas (cicadidae), spittlebugs (cercopids).
  • squash bugs coreidae
  • red bugs and cotton stainers pyrrhocoridae
  • adults and larvae of the order acari including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feeding mites
  • adults and immatures of the order Orthoptera including grasshoppers
  • adults and immatures of the order Diptera including leafminers, midges, fruit flies (tephritidae). and soil maggots
  • Thysanoptera including onion thrips and other foliar feeding thrips.
  • the compounds are also active against
  • insect pests of the order Hymenoptera including carpenter ants, bees, hornets, and wasps
  • insect pests of the order Diptera including house files, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other
  • Brachycera mosquitoes, black flies, biting midges, sand flies, sciarids, and other
  • Nematocera insect pests of the order Orthoptera including cockroaches and crickets; insect pests of the order Isoptera including the Eastern subterranean termite and other termites; insect pests of the order Mallophaga and
  • Anoplura including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera
  • Macrosteles fascifrons southern corn rootworm
  • Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the Formula I compounds of this invention, in an effective amount, to the locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these
  • arthropod pest species many different methods of application are employed.
  • a preferred method of application is by spraying with equipment that
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • suitable carriers diluents, and surfactants
  • synergists such as piperonyl butoxide often enhance the efficacy of the compounds of Formula I.
  • Test units each consisting of an 8-ounce plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared. Ten third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into each cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed onto the cups, a single solution per set of three cups. Spraying was
  • Example 8 The test procedure of Example 8 was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. The results are tabulated below.
  • Test units were prepared from a series of 12-ounce cups, each containing oat (Avena sativa) seedlings in a 1-inch layer of sterilized soil. The test units were sprayed with individual solutions of the below-listed compounds. After the oats had dried from being sprayed, between 10 and 15 adult aster leafhoppers (Mascrosteles fascif rons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. The following table depicts the activity of the compounds tested on aster leafhopper.
  • Test units each consisting of an 8-ounce plastic cup containing 1 sprouted corn seed, were prepared. Sets of three tests units were sprayed as described in Example 8 with individual solutions of the below-listed compounds. After the spray on the cups had dried, five third-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. The results are tabulated below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Grinding And Polishing Of Tertiary Curved Surfaces And Surfaces With Complex Shapes (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
EP90902098A 1988-12-27 1989-12-20 Substituierte semicarbazon-arthropodizide Pending EP0452406A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US29040488A 1988-12-27 1988-12-27
US290404 1988-12-27
US43636189A 1989-11-13 1989-11-13
US436361 1989-11-13

Publications (1)

Publication Number Publication Date
EP0452406A1 true EP0452406A1 (de) 1991-10-23

Family

ID=26966165

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89313369A Expired - Lifetime EP0377304B1 (de) 1988-12-27 1989-12-20 Substituierte Semicarbazon-Arthropodizide
EP90902098A Pending EP0452406A1 (de) 1988-12-27 1989-12-20 Substituierte semicarbazon-arthropodizide

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89313369A Expired - Lifetime EP0377304B1 (de) 1988-12-27 1989-12-20 Substituierte Semicarbazon-Arthropodizide

Country Status (17)

Country Link
EP (2) EP0377304B1 (de)
JP (1) JP2894363B2 (de)
KR (1) KR910700231A (de)
CN (1) CN1043935A (de)
AT (1) ATE102606T1 (de)
AU (1) AU632093B2 (de)
BR (1) BR8907842A (de)
DE (1) DE68913706T2 (de)
DK (1) DK121991A (de)
ES (1) ES2062049T3 (de)
HU (1) HUT58695A (de)
IL (1) IL92870A (de)
NZ (1) NZ231999A (de)
PE (1) PE24491A1 (de)
RU (1) RU2067092C1 (de)
WO (2) WO1990007495A1 (de)
YU (1) YU245589A (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238941A (en) * 1988-03-25 1993-08-24 Ciba-Geigy Corporation Arylhydrazones and pharmaceutical compositions thereof
US5395855A (en) * 1990-05-07 1995-03-07 Ciba-Geigy Corporation Hydrazones
AU645799B2 (en) * 1990-05-07 1994-01-27 Novartis Ag Hydrazones
US5474998A (en) * 1990-08-17 1995-12-12 E. I. Du Pont De Nemours And Company Arthropodicidal pyrazolines, pyrazolidines and hydrazines
EP0553284A1 (de) * 1990-10-05 1993-08-04 E.I. Du Pont De Nemours And Company Semicarbazon arthropodiciden
US5462938A (en) * 1990-12-21 1995-10-31 Annus; Gary D. Arthropodicidal oxadiazinyl, thiadiazinyl and triazinyl carboxanilides
EP0586551A1 (de) * 1991-05-24 1994-03-16 E.I. Du Pont De Nemours And Company Arthropodizide anilide
US5514678A (en) * 1992-03-26 1996-05-07 E. I. Du Pont De Nemours And Company Arthropodicidal 1,2,4-triazinyl amides
IL105208A0 (en) * 1992-04-23 1993-07-08 Sumitomo Chemical Co Hydrazone derivatives,process for producing same,insecticides and/or acaricides containing same as active ingredient and intermediate compounds thereof
WO1993022289A1 (en) * 1992-05-06 1993-11-11 E.I. Du Pont De Nemours And Company Arthropodicidal imidazolidines
ES2103166B1 (es) * 1992-08-26 1998-04-01 Ciba Geigy Ag Procedimiento para la obtencion de amidinohidrazonas biciclicas.
US5328915A (en) * 1992-09-17 1994-07-12 E. I. Du Pont De Nemours And Company Arthropodicidal amidrazone ureas
AU5299493A (en) * 1992-10-19 1994-05-09 E.I. Du Pont De Nemours And Company Arthropodicidal semicarbazones
AU4953796A (en) * 1995-03-15 1996-10-02 Sanyko Company, Limited Dipeptide compounds having ahpba structure
AU2002952453A0 (en) 2002-11-01 2002-11-21 Novogen Research Pty Ltd Aminated isoflavonoid derivatives and uses thereof
CN101434595B (zh) * 2008-12-19 2014-06-25 沈阳药科大学 抗真菌剂-硫色满酮缩氨基(硫)脲系列物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL31161A (en) * 1968-01-02 1972-08-30 Bayer Ag Carbonic acid derivatives of 1,2-dicarbonylphenylhydrazones and their preparation,and their use as pesticides
GB1314899A (en) * 1970-07-28 1973-04-26 Sterling Winthrop Group Ltd Thiosemicarbazones processes for their preparations and compositions incorporating them
BE795111A (fr) * 1972-02-09 1973-08-07 Philips Nv Composes de benzylidene-semicarbazide et leur activite insecticide
US3920437A (en) * 1973-03-09 1975-11-18 Stauffer Chemical Co Biocidal active carbamyl hydrazones
NZ189705A (en) * 1978-03-01 1981-07-13 Boots Co Ltd Benzophenone-hydrazone derivatives and pesticidal compositions intermediates
DE3070271D1 (en) * 1979-08-31 1985-04-18 Fbc Ltd Substituted benzophenone hydrazones, pesticidal compositions containing them and method of combating pests
JPS5829297B2 (ja) * 1981-08-14 1983-06-22 北興化学工業株式会社 ベンゾイルヒドラゾン誘導体および殺虫剤
DE3624349A1 (de) * 1986-07-17 1988-01-28 Schering Ag Substituierte hydrazone, verfahren zu ihrer herstellung und ihre verwendung als schaedlingsbekaempfungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9007495A1 *

Also Published As

Publication number Publication date
DE68913706T2 (de) 1994-08-04
ATE102606T1 (de) 1994-03-15
IL92870A0 (en) 1990-09-17
DE68913706D1 (de) 1994-04-14
JP2894363B2 (ja) 1999-05-24
EP0377304A2 (de) 1990-07-11
ES2062049T3 (es) 1994-12-16
JPH05501556A (ja) 1993-03-25
DK121991D0 (da) 1991-06-21
IL92870A (en) 1994-05-30
PE24491A1 (es) 1991-08-22
AU632093B2 (en) 1992-12-17
EP0377304A3 (en) 1990-07-25
AU5024690A (en) 1990-08-01
NZ231999A (en) 1992-08-26
YU245589A (en) 1991-06-30
CN1043935A (zh) 1990-07-18
BR8907842A (pt) 1991-12-03
HUT58695A (en) 1992-03-30
EP0377304B1 (de) 1994-03-09
WO1991007382A1 (en) 1991-05-30
KR910700231A (ko) 1991-03-14
WO1990007495A1 (en) 1990-07-12
RU2067092C1 (ru) 1996-09-27
DK121991A (da) 1991-06-21

Similar Documents

Publication Publication Date Title
AU659121B2 (en) Arthropodicidal carboxanilides
AU632093B2 (en) Substituted semicarbazone arthropodicides
US5500438A (en) Arthropodicidal anilides
US5474998A (en) Arthropodicidal pyrazolines, pyrazolidines and hydrazines
WO1992006076A1 (en) Semicarbazone arthropodicides
EP0530264B1 (de) Arthropodizide tetrahydropyridazine
US5602126A (en) Arthropodicidal anilides
US5369121A (en) Arthropodicidal pyrazolines, pyrazolidines and hydrazines
US5182303A (en) Substituted semicarbazone arthropodicides
EP0363051A1 (de) Substituierte Indazole als Arthropodicide
US5428027A (en) Substituted semicarbazone arthropodicieds
EP0386892A2 (de) Tetrahydrobenzopyranopyrazole als Arthropodizide
WO1992012133A2 (en) Arthropodicidal carboxanilides
EP0506709A1 (de) Arthropodizidpyrazoline
WO1994024111A1 (en) Arthropodicidal and nematocidal triazoles
WO1993005024A1 (en) Arthropodicidal anilides

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 19910624

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

XX Miscellaneous (additional remarks)

Free format text: VERFAHREN ABGESCHLOSSEN INFOLGE VERBINDUNG MIT 89313369.4/0377304 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) VOM 20.05.92.