EP0393120A1 - Carboxanilides de pyrazoline heterocycliques - Google Patents

Carboxanilides de pyrazoline heterocycliques

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Publication number
EP0393120A1
EP0393120A1 EP19890900538 EP89900538A EP0393120A1 EP 0393120 A1 EP0393120 A1 EP 0393120A1 EP 19890900538 EP19890900538 EP 19890900538 EP 89900538 A EP89900538 A EP 89900538A EP 0393120 A1 EP0393120 A1 EP 0393120A1
Authority
EP
European Patent Office
Prior art keywords
phenyl
alkyl
ocf
haloalkyl
substituted
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
EP19890900538
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German (de)
English (en)
Inventor
Thomas Martin Stevenson
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
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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 EP0393120A1 publication Critical patent/EP0393120A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • R/Ar are C 6 ,H 5 /C 6 H 5 ,
  • R 1 Is optionally substituted phenyl
  • R 2 and R 3 are independently optionally substituted pyridyl, thieny or phenyl groups and X is O or S.
  • EPA 0153127 discloses insecticidal compounds of the formula
  • a and B are unsubstituted or substituted aryl; U is O, S or NR; Y is alkyl, carbonyl or unsubstituted or substituted aryl, and Z is cycloalkyl or an unsubstituted or substituted aryl group.
  • A is H, C 1 to C 6 alkyl, phenyl, phenyl substituted by (R 5 ) p , CN, CO 2 R 3 , C(O)R 3 , C(O)NR 3 R 4 , C(S)NR 3 R 4 , C(S)R 3 or C(S)SR 3 ;
  • B is H, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 2 to C 6 Alkoxyalkyl, C 2 to C 6 cyanoalkyl, C 3 to C 8 alkoxycarbonylalkyl, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl, C 2 to C 6 alkoxycarbonyl, phenyl, phenyl substituted with 1 to 3 substituents independently selected from W, benzyl or benzyl substituted with 1 to 3 substituents independently selected from W.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers thereof, agriculturally suitable salts thereof, agricultural compositions containing said compounds and salts, and their use as insecticides:
  • X is O or S;
  • Y is selected from the group H, C 1 to C 4 alkyl, C 2 to C 4 alkoxyalkyl, C 1 to C 4 alkylthio, C 1 to C 4 haloalkylthio, SX', phenylthio, or phenylthio substituted with 1 to 3 substituents independently selected from W, C 2 to C 4 alkoxycarbonyl, C(O)H,
  • A is selected from the group H, C 1 to C 6 alkyl, phenyl, phenyl substituted by (R 5 ) p , CN, CO 2 R 3 , C(O)R 3 , C(O)NR 3 R 4 ,
  • B is selected from the group H, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 2 to C 6 alkoxyalkyl, C 2 to C 6 cyanoalkyl, C 3 to C 8 alkoxycarbonylalkyl, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl, C 2 to C 6 alkoxycarbonyl, phenyl, phenyl substituted with 1 to 3 substituents independently selected from W, benzyl and benzyl substituted with 1 to 3 substituents independently selected from W;
  • W is selected from the group halogen, CN, NO 2 , C 1 to C 2 alkyl, C 1 to C 2 haloalkyl, C 1 to C 2 alkoxy, C 1 to C 2 haloalkoxy, C 1 to C 2 alkylthio, C 1 to C 2 haloalkyl
  • R is or K, being K when A is other than J;
  • R 1 , R 2 and R 5 are independently selected from the group R 3 , halogen, CN, N 3 , SCN, NO 2 , OR 3 ,
  • R 1 , R 2 or R 5 can be taken together as -OCH 2 O-, -OCF 2 O-, -OCH 2 CH 2 O-, -CH 2 C(CH 3 ) 2 O-, -OCF 2 CF 2 O-, or -CF 2 CF 2 O- to form a 5- or 6-membered ring;
  • R 3 is selected from the group H, C 1 to C 4 alkyl, C 1 to C 4 haloal
  • C 4 haloalkenyl C 2 to C 4 alkynyl, C 2 to C 4 haloalkynyl, C 2 to C 4 alkoxyalkyl, C 2 to C 4 alkylthioalkyl, C 1 to C 4 nitroalkyl, C 1 to C 4 cyanoalkyl, C 3 to C 6 alkoxycarbonylalkyl, C 3 to C g cycloalkyl, C 3 to C 6 halocycloalkyl, phenyl, benzyl, or phenyl or benzyl substituted with 1 to 3 substituents independently selected from W;
  • R 4 is H or C 1 to C 4 alkyl, or when R 3 and R.
  • J and K are independently selected from a 5- or 6- membered heteroaromatic rings independently con taining 1 or 2 heteroatoms independently select from 0 to 1 oxygen, 0 to 1 sulfur and 0 to 2 nitrogen atoms, attached via carbon and optiona substituted by one or more substituents indepen dently selected from W;
  • R 6 and R 10 are independently selected from C 1 to C 6 alkyl, C 1 -C 8 haloalkyl, C_-C 8 cycloalkyl, C 4 -C 7 cycloalkyl- alkyl/ C 2 to C g cyanoalkyl, C 2 to C 6 alkoxyalkyl, C 3 to C 8 alkoxycarbonylalkyl, C 4 to 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 6 and R 10 can be taken together as (CH 2 ) 4 , (CH 2 ) 5 or (CH 2 ) 2 O(CH 2 ) 2 , each ring being optionally substituted with 1 to 2 CH 3 ;
  • R 7 is F, C 1 -C 20 alkyl, C 1 -C 8 haloalkyl, C 2 -C 8
  • dialkylamino each ring being optionally substituted with 1 to 2 CH 3 ; phenyl optionally substituted by 1 to 2 substituents selected from W, or R 7 is C 1 -C 20 alkoxy, C 1 -C 6 alkoxy substituted by cyano, nitro, C 1 -C 6 alkoxy, C 4 -C 8 alkoxyalkoxy, C 1 -C 2 alkylthio, C 2 -C, alkoxycarbonyl, C 3 -C 5 dialkylaminocarbonyl, phenyl or 1 to 6 halogens, or R 7 is phenoxy optionally substituted by 1 to 2 substituents selected from W, R 8 and R 9 are independently selected from C 1 -C 4 alkyl, C 2 -C 4 haloalkyl or phenyl optionally substituted by 1 to 2 substituents selected from W or R 8 and R 9 may be taken together as (CH 2 ) 2 ,
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl”, includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl, hexyl isomers.
  • Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy or pentoxy isomers.
  • Alkenyl includes straight chain or branched alkenes, e.g., vinyl, 1- ⁇ ropenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers.
  • Alkynyl includes straight chain or branched alkynes, e.g, ethynyl, 1-propynyl, 2-pro ⁇ ynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkylthio includes methylthio, ethylthio and the different propylthio and butylthio isomers.
  • Alkylsulfinyl, alkylsulfonyl, alkylamino, etc., are used analogously to the above examples.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halogen either alone or in compound words such as “haloalkyl” means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl” said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH 2 CH 2 F, CF 2 CF 2 and CH 2 CHFCl.
  • halocycloalkyl haloalkenyl
  • haloalkynyl are used analogously to "haloalkyl.
  • compound(s)" employed herein includes all isomers and agriculturally suitable salts thereof.
  • C i to C j The total number of carbon atoms in a substituent group is indicated by the "C i to C j " prefix where i and j are numbers from 1 to 8.
  • C 1 to C 3 alkylsulfonyl would designate methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkoxy would designate OCH 2 OCH 3
  • C 4 alkoxyalkoxy would designate the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH 2 OCH 2 CH 2 CH 3 and OCH 2 CH OCH 2 CH 3
  • C 2 cyanoalkyl would designate CH 2 CN and C 3 cyanoalkyl would designate CH 2 CH 2 CN and CH(CN)CH 3
  • C 2 alkylcarbonyl would designate C(O)CH 3 and C 4 alkylcarbonyl would include C(0)CH 2 CH 2 CH 3 and C
  • Group B of preferred Group A wherein: X is O; Y is H, CH 3 , SCH 3 , SCCl 3 , SC 6 H 5 , 2-(NO 2 )C 6 H 4 S,
  • R 6 and R 1 0 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 or phenethyl each optionally substituted with W or R 6 and R 10 may be taken together as (CH 2 ) 4 , (CH 2 ) 5 or (CH 2 ) 2 O(CH 2 ) 2 ; R 8 and R 9 are independently selected from
  • R 3 is C 1 to C 4 alkyl, C 1 to C 2 haloalkyl, C 2 to C 4 alkenyl, C 2 to C 4 haloalkenyl, propargyl, phenyl, benzyl; or phenyl or benzyl substituted with one of F, Cl, Br, CF 3 ,
  • B is H, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl,
  • R 1 is halogen, CN, SCN, NO 2 , R 3 , OR 3 , SR 3 , S(O) 2 R 3 , CO 2 R 3 or C(O)R 3 , or when m is 2, R 1 can be taken together as -OCH 2 CH 2 O-,
  • R 2 is halogen, CN, SCN, NO 2 , R 3 , OR 3 , SR 3 , S(O) 2 R 3 , OC(O)R 3 , OS(O) 2 R 3 , CO 2 R 3 , C(O)R 3 , C(O)NR 3 R 4 , S(O) 2 NR 3 R 4 or NR 3 R 4 ;
  • R 3 is C 1 to C 4 alkyl, C 1 to C 2 haloalkyl,
  • R 4 is H or C 1 to C 2 alkyl;
  • W is halogen, CN, CO 2 CH 3 , C(O)NHCH 3 , C(O)N(CH 3 ) 2 . NO 2 , CH 3 , CF 3 , OCH 3 , OCF 2 H, OCF 2 CF 2 H, SCH 3 , SCF 2 H, SCF 2 CF 2 H or S(O) 2 CH 3 ;
  • B is H, C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, or C 3 to C 4 alkenyl;
  • R 1 1 is H or C 1 to C 2 alkyl.
  • Y is H, CH 3 , C(O)CH 3 , CO 2 CH 3 or SX';
  • X ' is X 1 , X 2 , X 3 or X 5 ;
  • R 6 is C 1 -C 4 alkyl, CF 3 , cyclohexyl, phenyl optionally substituted by W, or benzyl optionally substituted by W;
  • R 7 is F, C 1 -C 12 alkyl, C 1 -C 6 haloalkyl, phenyl or phenoxy each optionally substituted by W, Cl"C12 alko ⁇ y' dimethylamino or C 1 -C 4 alkoxy substituted with NO 2 , C 1 -C 4 alkoxy or 1-6 halogens; m is 1 or 2 and one substituent is in the 4-position of the phenyl ring; n is 0, 1 or 2 and one substituent is in the 4-position of the phenyl ring; R 1 is F, Cl, Br, CF 3 , OCF 2 H, OCF 3 , CN, or when m is 2, R 1 can be taken together as -CH 2 C(CH 3 ) 2 O- or -CF 2 CF 2 O-; R 2 is F, Cl, Br, CN, NO 2 , CF 3 , CH 3 , OCH 3 , OCF 2 H, OCF 3 , SCH 3 , SCF 2
  • B is H or CH 3 .
  • A is C 1 to C 6 alkyl, phenyl, phenyl substituted by (R 5 ) p .
  • Y is H, CH 3 , SCH 3 , SCCl 3 , SC 6 H 5 , 2-(NO 2 )C 6 H 4 S, C(O)CH 3 , C(O)H, C(O)CF 3 , CO 2 CH 3 , CO 2 C 2 H 5 or SX';
  • X is X 1 , X 2 , X 3 , X 4 , X 5 or X 7 ;
  • R 6 and R 10 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 or phenethyl each optionally substituted with W or R 6 and R 10 may be taken together as (CH 2 ) 4 , (CH 2 ) 5 or (CH 2 ) 2 O(CH 2 ) 2 ; R 8 and R 9 are independently selected from C 1 -C 3 alkyl and Phenyl; a is 2; R is C 1 to C 4 alkyl, C 1 to C 2 haloalkyl, C 2 to C 4 alkenyl, C 2 to C 4 haloalkenyl, propargyl, phenyl, benzyl, or phenyl or benzyl each substituted with one of F, Cl, Br, CF 3 , OCF 2 H, OCF 3 or NO 2
  • R 1 is halogen, CN, SCN, NO 2 , R 3 , OR 3 , SR 3 , SO0) 2 R 3 , CO 2 R 3 or C(O)R 3 , or when m is 2, R. can be taken together as -OCH 2 CH 2 O-, -CH 2 C(CH 3 ) 2 O-, -OCF 2 CF 2 O- or -CF 2 CF 2 O-;
  • R 3 is C 1 to C 4 alkyl, C 1 to C 2 haloalkyl, C 2 to C 4 alkenyl, C 2 to C 4 haloalkenyl or propargyl;
  • R 4 is H or C 1 to C 2 alkyl
  • R 5 is halogen, CN, SCN, NO 2 , R 3 , OR 3 , SR 3 , S(O) 2 R 3 , OC(O)R 3 , OS(O) 2 R 3 , CO 2 R 3 , C(O)R 3 , C(O)NR 3 R 4 , S(O) 2 NR 3 R 4 or NR 3 R 4
  • W is halogen, CN, CO 2 CH 3 , C(O)NHC H3 , C(O)N(CH 3 ) 2 ,
  • A is C 1 to C 4 alkyl, phenyl, phenyl substituted with (R 5 ) p , CO 2 R 3 , C(O)R 3 , C(O)NR 3 R 4 or C(O)N(R 4 )phenyl said phenyl optionally substituted with F, Cl, Br, CF 3 , OCF 2 H, OCF or NO 2 ;
  • B is H, C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, or C 3 to C 4 alkenyl;
  • R 11 is H or C 1 to C 2 alkyl.
  • Y is H, CH3, C(0)CH3, C02CH3 or SX'; X' XS X 1 , X 2 , X 3 or X 5 ;
  • R 6 is C 1 -C 4 alkyl, CF 3 cyclohexyl, phenyl optionally substituted by W, or benzyl optionally substituted by W;
  • R 7 is F, C 1 -C 12 alkyl, C 1 -C 6 haloalkyl, phenyl or phenoxy optionally substituted by W, C 1 -C 12 alkoxy, dimethylamino or C 1 -C 4 alkoxy substituted with NO 2 , C 2 -C 4 alkoxy or 1-6 halogens;
  • R 1 is F, Cl, Br, CF 3 , OCF 2 H, OCF 3 , CN, or when m is 2, R 1 can be taken together as -CH 2 C(CH 3 ) 2 O- or -CF 2 CF 2 O-;
  • R 5 is F, Cl, Br, CN, NO 2 , CF 3 , CH 3 , OCH 3 , OCF 2 H, OCF 3 , SCH 3 , SCF 2 H, S(O) 2 CH 3 ,
  • A is phenyl or phenyl substituted with (R 5 ) p ;
  • B is H or CH 3 ;
  • m is 1 or 2 and one substituent is in the 4- position of the phenyl ring; and
  • p is 0, 1 or 2 and one substituent is in the
  • Y is H, CH 3 , C(O)CH 3 or CO 2 CH 3 ;
  • X' is X 1 , X 2 or X 5 ;
  • R 6 is C 1 -C 4 alkyl or phenyl optionally substi- tuted with CH 3 or Cl;
  • R 7 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 - C 1 2 alkoxy, dimethylamino or phenyl optionally substituted with CH 3 or Cl;
  • R 1 is F, Cl, Br, CF 3 , OCF 2 H, OCF 3 or CN;
  • A is CO 2 CH 3 , CO 2 C 2 H 5 , C(O)NHCH 3 or
  • Specifically preferred compounds are:
  • Suitable solvents for the chlorination reaction are inert to hydrogen chloride and include benzene, toluene, and dichloromethane.
  • Preferred temperatures for this process are from 20° to 100°C with temperatures between 20° and 80°C being particularly preferred.
  • the latter reaction can be carried out in many different inert solvents such as dialkylethers, chlorinated hydrocarbons, and aromatic hydrocarbons. While temperatures at or below 25°C are preferred, higher temperatures can also be employed. These reactions are normally run at atmospheric pressure, but can also be carried out at elevated pressures.
  • anilines react readily with esters of Formula II.
  • the reaction is best carried out at room temperature to 120°C Suitable solvents include dichloromethane, 1,2-dichloroethane, and toluene.
  • Coupling agents include dicyclohexylcarbodiimide (DCC), N-hydroxysuccinimide, 2-chloro-N-methylpyridinium iodide, carbonyl diimidazole, or other agents capable of activating an acid function or acting as a dehydrating agent.
  • the cyclization reaction is best carried out on an unsaturated keto-acid derivative (IV) in refluxing alcoholic media, in refluxing lower carboxylic acids, or in polar aprotic solvents such as dimethylformamide or dimethyl sulfoxide.
  • Ethanol containing acetic acid or acetic acid alone are the preferred solvents although other protic or aprotic solvents and mixtures are also applicable.
  • phenyl hydrazones can be isolated prior to final cyclization and these can be refluxed further in order to complete the cyclization.
  • unsaturated acid derivatives (IV) are preferred, saturated compounds with a reactive group such as a halogen beta to the carbonyl can be employed in certain instances.
  • the most Preferred Z substituents for the cyclization are the acids and anilides.
  • Compounds of Formula I and intermediates of Formula II can also be obtained by the dipolar cyclo-addition reaction of nitrile-imines, generated from substituted phenylhydrazones of Formula VI, with appropriately substituted alkenes.
  • an acid acceptor generally an amine base, for example, triethylamine
  • the alkene is used in a two- to five-fold molar excess and the amine base in a three- to five-fold excess based on the hydrazone (VI).
  • Suitable solvents include but are not restricted to benzene, toluene, 1,2-dichloroethane, chloroform, and tetrahydrofuran.
  • the reaction can be carried out at temperatures ranging from 20° to 120°C with the relative reactivity of the alkene (VII) governing the required temperature for a given example.
  • the required hydrazones (VI) for the synthesis of compounds of Formula I and II can be prepared by methods known in the art or by modifications thereof; see, e.g., Shawali et al., Tetrahedron, 20 (1971), 2517.
  • alkenes such as (VII) used in cycloaddition reactions are generally available commercially.
  • Other alkenes can be synthesized by many methods such as those described in March, "Advanced Organic Chemistry", 3rd Edition, Wiley, New York, pages 1149 to 1151.
  • Nitrile-imines may also be generated by other methods which may be better suited for basic nitrogen containing heterocycles such as pyridine.
  • the thermal or photolytic decomposition of 2,5-disubstituted tetrazoles produces nitrile-imines.
  • Tetrazoles (VIII) suitable for use in the present invention may be obtained by the general route of Lippmann et al.
  • thermolysis of tetrazoles generally requires high temperatures from 200° to 400°C.
  • Photolysis with high intensity lamps can be performed on these compounds at room temperature to 120°C.
  • Suitable solvents include benzene, dioxane, and toluene.
  • the reaction is best performed in dilute solutions in the presence of one or more equivalents of an alkene.
  • Use of CuSO 4 solution or a pyrex filter in the photolysis apparatus is preferred.
  • the photolysis of syndnones is another method of nitrile-imine generation. Irradiation of a dilute solution of the sydnone (IX) (about 0.05 M) in the presence of an excess of the alkene at or near room temperature gives the compounds of the present invention.
  • Sydnones (IX) of the desired structures can be obtained by the metallation of the sydnones (X) and subsequent reaction with phenylisocyanates, chloroformates, or carbon dioxide.
  • Metallation and trapping of the sydnones is best performed at temperatures lower than -20°C. Typical solvents used are diethyl ether and tetrahydrofuran. Metallation can be accomplished with n-butyl lithium and other alkyl lithium bases.
  • Certain reactions can be used to convert various functional groups into heterocycles on already formed pyrazolines (I or II).
  • TOSMIC p-toluene sulfonyl- isocyanide
  • the reaction is carried out in polar organic solvents such as alcohols.
  • the preferred bases are inorganic salts such as potassium carbonate, sodium carbonate or potassium bicarbonate.
  • Reaction of compounds of Formula I in the presence of an acid acceptor with electrophilic agents results in substitution on nitrogen.
  • electrophilic agents such as sodium hydride, potassium t-butoxide, potassium hydride, and other bases known in the art to deprotonate amides are preferred in the process.
  • Suitable electrophiles include, but are not restricted to alkyl halides, acyl halides, acid anhydrides, carbonates, chloroformates, disulphides, and sulphenyl halides.
  • This reaction is normally run in the temperature range of 0° to 25°C, but can be run at temperatures up to 120°C if unreactive electrophiles are used. Solvents not deprotonated under the reactions conditions such as tetrahydrofuran, dimethylformamide, dimethoxyethane, and diethyl ether are preferred.
  • Phosphorous pentasulfide either alone or in combination with organic or inorganic bases is a preferred reagent to effect this conversion. When phosphorous pentasulfide is used alone, organic bases such as pyridine are the preferred solvents. When it is used in conjunction with inorganic bases such as sodium bicarbonate, the preferred solvents are ethers such as diglyme.
  • Example 2 The compound of Example 1 (2.0 g) was suspended in benzene (20 ml) and heated to reflux in the presence of 2-vinylfuran (2.5 ml). Triethylamine was added and the mixture was allowed to reflux for 1 hour longer. The mixture was partitioned between water and ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate and concentrated. Chromatography on silica gel (5:1 hexanes/ethyl acetate) gave the title compound (1.8 g). NMR
  • Example 2 The compound of Example 2 (1.4 g) was heated to reflux in methanol (20 ml) with 50% sodium hydroxide (1.0 ml) for 1 hour. The mixture was cooled and acidified with IN HCl. Extraction with ethyl acetate, drying, and evaporation gave the acid. The acid was suspended in benzene (10 ml) and heated to reflux with thionyl chloride (1.5 ml). After heating for 2 hours, the mixture was evaporated and azeotroped with toluene (10 ml). The residue was dissolved in tetrahydrofuran (20 ml) and divided in two.
  • Example 4 1-(6-Chloro-3-Pyridazinyl)-5-(4-fluorophenyl)-4,5- dihvdro-N-[4-(trifluoromethyl)phenyl]-1H-pyrazole- 3-carboxamide Part A: To make potassium 4-(4-fluorophenyl)- 2-oxo-3-butenoate, a solution of pyruvic acid and p-fluorobenzaldehyde (24.8 g) in methanol (20 ml) were cooled to 15°C and treated with a solution of potassium hydroxide (16.8 g) in (50 ml) methanol.
  • Part B The compound of Part A was converted to the corresponding carboxylic acid by the general method of Stecher (J. Am. Chem. Soc., 1952, 74,
  • Part C The compound of Part B (0.9 g) was dissolved in dimethylformamide (8 ml) and treated with 6-chloro-3-hydrazinopyridazine (0.3 g) and then heated for 2 hours at reflux. The solvent was evaporated under reduced pressure. The residue was chromatographed on silica gel (hexane/ethyl acetate (3:1)). The main fraction was crystallized by addition of hexane to give the title compound (0.53 g).
  • Example 4 The procedure for Example 4 was used and 5-chloro-2-pyridyl hydrazine (0.34 g) was substituted in Part C to yield the title compound (0.49 g). m.p.: 175 to 177 (MeOH); NMR (CDCl 3 ); 8.6 (NH), 8.0 to 7.0 (m, ArH); 5.8 (m, CH); 3.8 (m, CH); 3.2 (m, CH).
  • the starting material 1H-pyrazole-3- carboxamide, 1-(4-fluorophenyl)-5-formyl- 4,5-dihydro-5-methyl-N-((4-(trifluoromethyl)- phenyl)), was synthesized by the general procedures for Examples 1 to 3 using p-fluoroaniline instead of p-chloroaniline in Example 1 and methacrolein in place of 2-vinylfuran in Example 2.
  • the starting material (0.5 g) and p-toluenesulfonylisocyanide (0.24 g) were suspended in methanol (5 ml) and stirred at room temperature for 4 hours.
  • 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, 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 approximate proportions:
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
  • 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 material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration”, Chemical Engineering. December 4, 1967, pages 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.
  • spray oils usually have these characteristics: they are not phytotoxic to the crop sprayed, and they have appropriate viscosity. Petroleum based oils are commonly used for spraying. In some areas, crop oils are preferred such as the following:
  • oils also meet the criteria for a spray oil: mineral, fish and cod liver oil.
  • Spray oil concentrates comprise a spray oil together with one or more additional ingredients such as emulsifiers and wetting agents.
  • additional ingredients such as emulsifiers and wetting agents.
  • 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.
  • a volatile solvent such as acetone
  • the acetone is then driven off by heating.
  • the granules are then allowed to cool and are packaged,
  • 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.
  • Example 13 Agueous Suspension 5-(5-chloro-2-thienyl)-1-(4-fluorophenyl)-4,5-dihydro- N-[4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carboxamide 40% polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% 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.
  • Example 15 Bait Granules 1-(5-chloro-2-pyridinyl)-5-(4-fluorophenyl)-4,5-dihydro- N-[4-(triflyoromethyl)phenyl]-1H-pyrazole-3-carboxamide 3. o% blend of polyethoxylated nonyl- 9.0% phenols and sodium dodecyl- benzene sulfonates ground up corn cobs 88.0%
  • Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of ef fective ag ricultura l protection .
  • suitable solvent such as acetone
  • Additional insecticides are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphos-methyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, profenofos, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone.
  • Fungicides methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)
  • Bactericides tribasic copper sulfate streptomycin sulfate.
  • Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 6-methyl-1,3-dithiolo[4,5- ⁇ ]quinoxalin-2-one
  • the compounds of the present invention exhibit activity against a wide spectrum of foliar and soil inhabiting insects. Those skilled in the art will recognize that not all compounds are equally effective against all insects, but the compounds of this invention display activity against economically important pest species, such as grasshoppers and cockroaches; thrips; hemipterans; plant bugs
  • tarnished plant bug such as lace bugs (Tingidae), seed bugs (Lygaeidae) such as cinch bugs, stink bugs (Pentatomidae), leaf-footed bugs (Coreidae), such as squash bug, and red bugs and stainers (Pyrrhocoridae) such as cotton stainer; also homopterans such as whiteflies, aphids such as the green peach ap-hid r greenbug and cotton aphid, leafhoppers, spittlebugs and plant hoppers such as aster leafhopper, potato leafhopper and rice planthoppers, psyllids such as pear psylla, scales
  • coleopterans including weevils, such as boll weevil and rice water weevil, grain borers, chrysomellid beetles, such as Colorado potato beetle, flea beetles and other leaf beetles, coccinellid beetles such as Mexican bean beetle, and soil insects such as southern corn rootworm and wireworm; lepidopterous larvae including noctuids such as fall armyworm, beet armyworm, other Spodoptera spp., Heliothis virescens, Heliothis zea, cabbage looper, green cloverworm, velvetbean caterpillar, cotton leafworm, black cutworm, and other noctuid cutworms and including pyralids such as European corn borer, navel orangeworm, and stalk/stem borers and including tortricids like codling moth and grape berry moth as well as other lepidopterous larvae, such
  • Insects are controlled and agricultural crops are protected by applying one or more of the Formula I compounds of this invention, in an effective amount, to the locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying with spray equipment that distributes the compound on the foliage, in the soil, or to the plant part that is infested or needs to be protected.
  • granular formulations of these compounds can be applied to soil or foliage or, optionally, incorporated into the soil. Either aerial or ground application can be used.
  • the pyrazoline compound(s) of this invention can be applied directly, but most often application will be of a formulation comprising one or more compounds of this invention, in an agriculturally suitable carrier or diluent.
  • a most preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils and spray oil concentrations often enhance the efficacy of the compounds of Formula I.
  • the rate of application of the Formula I compounds required for effective control will depend on such factors as the species of insect to be controlled, the pest's life stage, its size, its loction, the host crop, time of year of application, ambient moisture, temperature conditions, and the like.
  • Example 16 Fall Armyworm 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 frugjperda) 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 accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time readings were taken. Of the compounds tested on fall armyworm, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 5, 6, 7, 8, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and 31.
  • Example 16 The test procedure of Example 16 was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Of the compounds tested on tobacco budworm, the following resulted in greater than or equal to 80% mortality: 7, 8, 10, 11, 12, 13, 14, 17, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 and 29.
  • Example 18 European Corn Borer Test units each consisting of an 8-ounce plastic cup containing one-inch square of wheat germ/soyflour diet, were prepared. Five third-instar larvae of the European corn borer (Ostrinia nubilalis) were placed into each cup. Sets of three test units were sprayed as described in Example 16 with individual solutions of the test compounds. The cups were then covered and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested on European corn borer, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 6, 7, 8, 9 and 10.
  • Test units each consisting of an 8-ounce plastic cup containing 1 sprouted corn seed (Zea mays). were prepared. Sets of three test units were sprayed as described in Example 16 with individual solutions of the test 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. Of the compounds tested on southern corn rootworm, the following resulted in greater than or equal to 80% mortality: 4, 7, 11, 13, 15, 19, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 31.
  • Example 20 Boll Weevil
  • boll weevils Five adult boll weevils (Anthonomus grandis) were placed into each of a series of 9-ounce cups. The test procedure employed was then otherwise the same as in Example 16 with three cups per treatment. Mortality readings were taken 48 hours after treatment. Of the compounds tested on boll weevil, the following resulted in greater than or equal to 80% mortality: 1, 2, 7, 9, 10, 27, 28, 29 and 30.
  • 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. Sets of three test units were sprayed as described in Example 16 with individual solutions of the test compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested on aster leafhopper, the following resulted in greater than or equal to 80% mortality: 7, 8, 19, 20, 21, 23, 24 and 27.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Insecticides à base de carboxanilide de pyrazoline hétérocyclique de formule générale (I) comprenant tous leurs isomères géométriques et leurs stéréo-isomères, ainsi que compositions les contenant utilisées pour l'agriculture.
EP19890900538 1987-11-30 1988-11-30 Carboxanilides de pyrazoline heterocycliques Pending EP0393120A1 (fr)

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US126619 1987-11-30

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EP88311325A Withdrawn EP0322126A1 (fr) 1987-11-30 1988-11-30 Pyrazoline-carboxanilides hétérocycliques

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DE3931786A1 (de) * 1989-09-23 1991-04-04 Basf Ag Pyrazol-3-carbonsaeureamide
FR2665898B1 (fr) * 1990-08-20 1994-03-11 Sanofi Derives d'amido-3 pyrazole, procede pour leur preparation et compositions pharmaceutiques les contenant.
EA005216B1 (ru) * 1999-03-12 2004-12-30 Басф Акциенгезельшафт Синергетические инсектицидные композиции
WO2007009690A1 (fr) * 2005-07-15 2007-01-25 Laboratorios Del Dr. Esteve, S.A Composes de pyrazoline a substitution heterocyclyle, preparation et utilisation de ceux-ci comme medicaments
EP1947088A1 (fr) * 2007-01-17 2008-07-23 Laboratorios del Dr. Esteve S.A. Composés de pyrazoline substitués présentant une activité inhibitrice de l'ACAT, leur composition et utilisation en tant que médicaments
EP1950203A1 (fr) * 2007-01-24 2008-07-30 Laboratorios del Dr. Esteve S.A. Composés de pyrazoline substitués avec ACAT, leur composition et utilisation en tant que médicaments
WO2008087030A1 (fr) * 2007-01-17 2008-07-24 Laboratorios Del Dr. Esteve, S.A. Composés de pyrazoline substituée présentant une activité inhibitrice de l'acat, leur préparation et utilisation comme médicaments

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NL158178B (nl) * 1974-07-12 1978-10-16 Philips Nv Werkwijze ter bereiding van insekticide preparaten die een pyrazolinederivaat bevatten, aldus verkregen gevormde preparaten, en werkwijze ter bereiding van pyrazolinederivaten met insekticide werking.
US4496391A (en) * 1980-05-19 1985-01-29 Basf Aktiengesellschaft Herbicides containing 3-aryl-5-methylpyrazole-4-carboxylic acid esters, their manufacture and use
DE3633840A1 (de) * 1986-10-04 1988-04-14 Hoechst Ag Phenylpyrazolcarbonsaeurederivate, ihre herstellung und verwendung als pflanzenwachstumsregulatoren und safener
AU1154488A (en) * 1987-01-05 1988-09-26 E.I. Du Pont De Nemours And Company 1-sub-phenyl-3-sub-phenylamino(thio) carbonyl-pyrazolines as insecticides

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See references of WO8905300A1 *

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EP0322126A1 (fr) 1989-06-28

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