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WO1999046266A1 - Arthropodicides a base de benzoxadiazocinyle - Google Patents

Arthropodicides a base de benzoxadiazocinyle Download PDF

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Publication number
WO1999046266A1
WO1999046266A1 PCT/US1999/000882 US9900882W WO9946266A1 WO 1999046266 A1 WO1999046266 A1 WO 1999046266A1 US 9900882 W US9900882 W US 9900882W WO 9946266 A1 WO9946266 A1 WO 9946266A1
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Prior art keywords
come
alkyl
pyridinyl
haloalkyl
column
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PCT/US1999/000882
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English (en)
Inventor
Stephen Frederick Mccann
Bruce Lawrence Finkelstein
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E.I. Du Pont De Nemours And Company
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Priority to AU23213/99A priority Critical patent/AU2321399A/en
Publication of WO1999046266A1 publication Critical patent/WO1999046266A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/08—Bridged systems
    • 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
    • A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems

Definitions

  • This invention relates to certain benzoxadiazocinyl arthropodicides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
  • arthropod pests The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action. Jan Svetlik in J. Chem. Soc, Perkin I (1988) pp.2053-8 discloses
  • This invention is directed to a compound of Formula I including all geometric and stereoisomers, N-oxides, agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides,
  • A is CR 7 R 8 ;
  • E is O, S, CR 16 R 17 or NR 17 ;
  • G is a fused 5- or 6-membered ring which may be aromatic or non-aromatic, optionally containing one or two heteroatoms selected from the group nitrogen, oxygen and sulfur: each R 1 is independently selected from the group halogen, cyano, nitro, formyl, Cj-Cg alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 6 alkoxy, C r C 6 haloalkyl, C2-C haloalkenyl, C 2 -C6 haloalkynyl, C Cg haloalkoxy; C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C Cg haloalkylsulfinyl, Cj-Cg alkylsulfonyl, C j -Cg haloalky
  • each R 2 is independently selected from the group halogen, nitro, Ci-Cg alkyl, Cj-Cg haloalkyl and C Cg alkoxy; or R 1 and R 2 , when on adjacent atoms, can be taken together along with the atoms to which they are attached to form a 5- or 6- membered ring which may be aromatic or non-aromatic, optionally containing one or two hetero atoms selected from nitrogen, oxygen and sulfur, and optionally substituted with (R 10 ) q ; R 3 and R 4 are each independently selected from the group H; C3-C6 cycloalkyl; Ci-Cg haloalkyl; C2-Cg alkenyl; C2-C6 alky
  • R 5 and R 6 are each independently selected from the group H; C ⁇ -Cg cycloalkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl;
  • R 7 is H, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, C2-Cg alkylcarbonyl, C 2 -C ⁇ alkoxycarbonyl, C -Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, Q or C j -Cg alkyl optionally substituted with Q; or R 3 and R 7 can be taken together along with the carbon atoms to which they are attached to form a 4-, 5-, 6- or 7-membered ring; or
  • R 4 and R 7 can be taken together along with the carbon atoms to which they are attached to form a 4-, 5-, 6- or 7-membered ring;
  • each R 9 is independently selected from the group H, C Cg alkyl, Cj-Cg haloalkyl, C j -C 6 alkoxy, C Cg haloalkoxy or phenyl optionally substituted with (R 10 ) p ;
  • each R 10 is independently selected from the group halogen, cyano, nitro, formyl, SF 5 , C j -Cg alkyl, C 3 -C 6 cycloalkyl, C -C 6 alkenyl, C -C 6 alkynyl, C ⁇ -C 6 alkoxy, Cj-C 6 haloalkyl, C2-Cg haloalkenyl, C
  • R 13 , R 14 and R 15 are each independently Cj-Cg alkyl or phenyl;
  • R 16 is H or C C 6 alkyl;
  • R 17 is H; C 3 -C 6 cycloalkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; C2-Cg alkylcarbonyl; C2-Cg alkoxycarbonyl; C2-Cg alkylaminocarbonyl; C3-Cg dialkylaminocarbonyl; Q; and Cj-Cg alkyl optionally substituted with cyano, Cj-Cg alkoxy, C r C 6 haloalkoxy or Q; R 18 is H or C ! -C 6 alkyl;
  • R 19 is H, C r C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy or phenyl optionally substituted with (R 10 ) p ; m and n are each independently 0, 1 or 2; each p is 0, 1, 2, 3, 4 or 5; and q is O, 1, 2, 3 or 4; provided that a compound of Formula I is other than
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, M-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as ethenyl, 1 -propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkylamino and dialkylamino are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • G is "a fused 5- or 6-membered ring which may be aromatic or non-aromatic, optionally containing one or two heteroatoms selected from the group nitrogen, oxygen and sulfur" includes, for example, cyclohexyl, cyclopentyl, phenyl, thienyl and pyridinyl.
  • R 1 and R 2 are taken together to "form a 5- or 6- membered ring which may be aromatic or non-aromatic, optionally containing one or two hetero atoms selected from nitrogen, oxygen and sulfur, and optionally substituted with (R 10 ) q " include, for example, naphthalenyl and quinolinyl.
  • aromatic ring denotes a fully unsaturated ring in which the ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring).
  • non-aromatic ring denotes a fully saturated ring as well as partially or fully unsaturated ring (where non-aromatic indicates that the H ⁇ ckel rule is not satisfied for the ring).
  • the heterocydic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • aromatic and non-aromatic ring systems containing 1 to 4 heteroatoms selected from the group nitrogen, oxygen and sulfur, containing no more than 2 oxygens and no more than 2 sulfurs include, pyrrolidinyl; piperidinyl; tetrahydrofuranyl; tetrahydro-2H-pyranyl; 1,3-dioxanyl; 1,3-dithianyl; 4,5-dihydrooxazolyl; 4,5-dihydrothiazolyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; 1H- 1,2, 3 -triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazol
  • halogen either alone or in compound words such as “haloalkyl” includes 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.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfmyl include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • haloalkoxyalkoxy examples include CF 3 OCH 2 O, CICH2CH2OCH2CH2O, CI3CCH2OCH2O as well as branched alkyl derivatives.
  • C j -C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred compounds for reasons of better activity and/or ease of synthesis are:
  • R 3 is H or Cj-Cg alkyl optionally substituted with 1-3 halogen or R 3 is phenyl optionally substituted with (R 10 ) p ;
  • R 7 is H or C r C 6 alkyl
  • R 8 is H
  • R 17 is H or C r C 3 alkyl;
  • R 18 is H, C r C 3 alkyl;
  • R 19 is H, C r C 3 alkyl.
  • G is a fused cyclohexyl, cyclopentyl, phenyl, naphthalenyl, thienyl, pyridinyl or quinolinyl ring;
  • R 3 is H or C r C 6 alkyl;
  • R 4 is H or CH 3 .
  • Preferred 3 Compounds of Preferred 2 wherein: G is a fused phenyl ring; each R 1 is independently selected from the group consisting of halogen, C j -C3 alkyl, C1-C3 haloalkyl and C1-C3 haloalkoxy;
  • R 5 and R 6 are each independently H, C j -Cg alkyl, C alkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C3 alkylsulfonyl, 3-pyridinylmethyl 7 optionally substituted with 1-2 halogens or 5-thiazolylmethyl optionally substituted with halogen; and p and q are each independently 0, 1 or 2.
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of (2 ⁇ ,6 ⁇ )-(3,6-dihydro-2-methyl-2,6-methano-2H-l,3,5-benzoxadiazocin-4-yl)cyanamide and at least one of a surfactant, a solid diluent or a liquid diluent.
  • This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount (2 ⁇ ,6 ⁇ )-(3,6-dihydro-2-methyl-2,6-methano-2H-l,3,5-benzoxadiazocin-4-yl)cyanamide (e.g., as a composition described herein).
  • Compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • a compound of Formula I may exist as geometric isomer I or la, or both I and la.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • a compound of Formula I wherein R 5 is H may exist as tautomer lb or Ic, or both lb and Ic; and a compound of Formula I wherein R 6 is H may exist as tautomer Id or Ie, or both Id and Ie.
  • the present invention comprises all tautomeric forms of compounds of Formula I.
  • compounds of Formula I can exist as syn or anti isomers.
  • a compound of Formula I may exist as isomers I or If, or both I and If.
  • the present invention comprises all syn and anti isomeric forms of compounds of Formula I.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-14.
  • the definitions of R ! -R 19 , G, E, X and X 1 in the compounds of Formulae 1-25 are as defined above in the Summary of the Invention or as defined below in the Schemes.
  • Compounds of Formulae Ia-If are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-If are as defined above for Formula I.
  • X is halogen, alkylsulfonate, arylsulfonate, or R -X is an anhydride of a carboxylic acid or sulfonic acid or R -X is an alkyl or aryl isocyanate.
  • Compounds of Formula 1 can be highly varied and include alkylating agents such as alkyl halides, alkyl sulfonates and the like; acylating agents such as acyl halides and acyl anhydrides and pyrocarbonates; sulfonylating agents such as sulfonyl halides and sulfonic anhydrides; and carbamoylating reagents such as alkyl and aryl isocyanates.
  • Typical Scheme 1 reactions involve mixing a compound of Formula I (R 6 is H) with one to ten molar equivalents of a compound of Formula 1 in the presence of one molar equivalent of a proton acceptor.
  • Typical proton acceptors include sodium hydride, potassium hydride, potassium carbonate, sodium carbonate, alkyl lithiums, lithium amides (such as lithium diisopropylamide) amines (such as pyridine, triethylamine and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU)) and hydroxide bases (such as sodium hydroxide and potassium hydroxide).
  • lithium amides such as lithium diisopropylamide
  • amines such as pyridine, triethylamine and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
  • hydroxide bases such as sodium hydroxide and potassium hydroxide.
  • Scheme 1 reactions are usually carried out in a solvent, including polar aprotic solvents (such as tetrahydrofuran, NN-dimethylformamide, NN-dimethylacetamide and 1 -methyl-2-pyrrolidinone), alcohols such as methanol, ethanol and 2-propanol, or water. In some cases, a solvent is not used.
  • Scheme 1 reactions are typically run at temperatures ranging from 0 °C to the reflux temperature of the solvent and the reactions are usually complete within 2 to 48 hours.
  • the products of Formula I (R 6 is other than H) can be isolated by chromatography, crystallization or, in some cases, by the addition of water to the reaction followed by filtration of the product.
  • Compounds of Formula I where R 5 is other than H can be prepared by the reaction of a compound of Formula I (where R 5 is H) with a compound of Formula 2 in the presence of a proton acceptor as depicted in Scheme 2. 10 Scheme 2
  • Step i of Scheme 3 is an example of a Scheme 1 reaction using di-tert-butyl pyrocarbonate (3) as the compound of Formula 1.
  • the product of Step i reacts with a compound of Formula 2 as described in Scheme 2.
  • the product of Step ii reacts with an acid, which results in the removal of the 11 t-butoxy carbonyl group and the formation of compounds of Formula I (R 5 is other than H, R 6 is H).
  • Acids used in Step iii reactions include trifluoroacetic and hydrochloric acids.
  • Reaction temperatures can range from 20 °C to the reflux temperature of the solvent and the reactions are usually complete in 2 to 48 hours.
  • a great number of the compounds of Formula 5 can be obtained from commercial sources (for example, when G forms a phenyl ring, then compounds of Formula 5 [where E is O] are comprised of the well-known salicylaldehydes [R 3 is H], o-hydroxyacetophenones [R 3 is Me] and o-hydroxybenzophenones [R 3 is optionally substituted phenyl].
  • Salicylaldehydes of Formula 5 (E is O, R 3 is H), can be prepared by the 13
  • ⁇ -Hydroxy phenyl alkyl ketones of Formula 5 (E is O, R 3 is optionally substituted alkyl) and o-hydroxy phenyl aryl ketones of Formula 5 (E is O, R 3 is optionally substituted aryl) can be prepared by a number of methods, including the Friedel-Crafts acylation (see Chem. Revs., (1955), vol. 55, p. 229) depicted in Scheme 7. Phenols of Formula 7 may be obtained from commercial suppliers.
  • Step i of Scheme 8 the methoxy thiophenes of Formula 9 are acylated using either the Nilsmeier reagent (POC ⁇ /NN-dimethylformamide ) to give compounds of Formula 10 (R 3 is H) or by a Friedel-Crafts acylation procedure (R 3 COCl/AlCl3) to give compounds of Formula 10 (R 3 is other than H).
  • Procedures for conducting Step i of Scheme 8 are well-known to those skilled in the art (see, e.g., Chem. Rev., (1955), vol. 55, p. 229 and J. Chem. Soc, Section C (1967), p. 779).
  • Step ii of Scheme 8 the methyl ether is removed using boron tribromide in a solvent such as dichloromethane (for an example, see Org. Synth., Collect, vol. V, (1973), p. 412).
  • a solvent such as dichloromethane
  • Formula 5b (R 3 is H) using an oxidant such as activated manganese dioxide in a solvent such as methylene chloride or toluene at temperatures ranging from ambient to the refluxing temperature of the solvent.
  • an oxidant such as activated manganese dioxide in a solvent such as methylene chloride or toluene at temperatures ranging from ambient to the refluxing temperature of the solvent.
  • aldehydes of Formula 5b (R 3 is H) react with a compound of Formula 14 to form secondary alcohols of Formula 13.
  • keto-esters of Formula 15 are reduced to alcohols of Formula 16 using sodium borohydride in a polar solvent such as ethanol at temperatures 17 ranging from 0 °C to 78 °C for times ranging from 1 hour to 3 days.
  • a polar solvent such as ethanol
  • alternative reduction procedures are available for the conversion of a compound of Formula 15 to a compound of Formula 16 (using, e.g., aluminum triisopropoxide, Baker's yeast or hydrogen with a platinum or nickel catalyst, see Helv. Chim. Acta, (1952), vol. 35, p. 2406).
  • the esters of Formula 17 are reduced to primary alcohols of Formula 18 using preferably lithium aluminum hydride in an ethereal solvent, or diisobutylaluminum hydride in dichloromethane, tetrahydrofuran or toluene as depicted in Step iii of Scheme 10.
  • Numerous procedures for analogous ester reductions are available in the chemical literature (see, e.g., Tetrahedron Lett. (1995), p. 2097 and Synlett, (1993), p. 27).
  • Step iv of Scheme 10 the primary alcohols of Formula 18 are oxidized to aldehydes of Formula 19 using oxidants such as the Swera reagent (dimethyl sulfoxide, oxalyl chloride), pyridinium chlorochromate (PCC) or (rc-Pr ⁇ NRuO ⁇ These are standard procedures for organic synthesis and are well-known to those skilled in the art (for two examples, see J. Org. Chem., (1992), vol. 57, p. 4512 and Tetrahedron-Asymmetry, (1995), p. 2131).
  • silyl ethers of Formula 19 are converted to alcohols of
  • Formula 5c using a fluoride-ion source such as tetrabutylammonium fluoride, potassium fluoride, aqueous hydrofluoric acid or pyridine- hydrofluoric acid.
  • a fluoride-ion source such as tetrabutylammonium fluoride, potassium fluoride, aqueous hydrofluoric acid or pyridine- hydrofluoric acid.
  • non-fluoride-ion de-silylation procedures are available as well (see, e.g., J. Am. Chem. Soc, (1985), vol. 107, p. 4577).
  • the preparation of compounds of Formula 5d (compounds of Formula 5 where E is O and R 3 is other than H) can be achieved using procedures depicted in Scheme 11.
  • Step iii of Scheme 11 removal of the silyl protecting group from compounds of Formula 21 to form alcohols of Formula 5 is realized via procedures which are completely analogous to those already described for Scheme 10, Step v reactions.
  • X is a leaving group such as halogen, alkoxy or dialkylamino, or the compound of Formula 23 is an acid anhydride 19
  • Scheme 12 reactions involve the reaction of mercaptans of Formula 22 with typically 2 molar equivalents of n-butyllithium and 2 molar equivalents of N,N,N,N-tetramethylenediamine (TMEDA) in a solvent such as tetrahydrofuran or cyclohexane at temperatures ranging from -78 °C to the refluxing temperature of the solvent for 0.25 to 12 hours, followed by treatment with compounds of Formula 23 (1-2 molar equivalents) at 0 °C to ambient temperature.
  • the products of Formula 5e are typically isolated by acidification of the reaction medium followed by extractive work-up.
  • compounds of Formula 23 are typically N,N-dimethylformamide or N-formylpiperidine.
  • compounds of Formula 5e may be prepared via nitriles of Formula 24 as shown in Scheme 13.
  • Scheme 14 reactions are usually performed in a solvent such as an alcohol (e.g., -propanol or ethanol), tetrahydrofuran or aromatic hydrocarbon (e.g., benzene or toluene).
  • a solvent such as an alcohol (e.g., -propanol or ethanol), tetrahydrofuran or aromatic hydrocarbon (e.g., benzene or toluene).
  • Reactions are typically carried out at temperatures ranging from O °C to 150 °C, with the reflux temperature of the solvent being preferred. Reactions are typically complete in 1 to 72 hours.
  • Diamines of Formula 25 can be prepared by known methods (e.g., Chem. Pharm. Bull, (1966), vol. 14, p. 324) or by methods known to one skilled in the art.
  • Step B Preparation of re/-r(2R,6R)-3.6-dihvdro-2-methyl-2.6-methano-2H-l.3.5- benzoxadiazocin-4-vncyanamide
  • cyanamide 0.25 g (1.5 mmol) of the product of the previous step, cyanamide (0.3 g, 3.1 mmol), 1 ,2-dimethoxyethane (2 mL) and piperidine (two drops) was heated at reflux for 5 h, cooled to ambient temperature, diluted with 1, 2 -dimethoxy ethane (5 mL) and filtered.
  • aqueous layer was extracted with ethyl acetate (3 X 100 mL) and the combined organic layers were washed with water (4 X 100 mL), dried over anhydrous magnesium sulfate and concentrated to give 0.21 g of a crude product that was chromatographed on silica gel using 1:1 hexane-ethyl acetate to give 60 mg of the title compound as a solid, mp 216 °C (dec).
  • Aqueous sodium hydroxide (10.5 mL, 1.0 N) was added to a solution of 5-chlorosalicylaldehyde (1.5 g, 9.6 mmol) and acetone (7 mL) at ambient temperature. After 18 h, the reaction was cooled to 5 °C and then 12.5 mL of 1 N aqueous hydrochloric acid was added dropwise. The resulting solid product was removed by filtration and washed with 1 N aqueous hydrochloric acid. After drying, 1.7 g of the title compound was isolated as a tan solid, mp 157 °C (dec). !
  • Step B Preparation of re/-r(2R.6R)-8-chloro-3,6-dihydro-2-methyl-2.6-methano-2H- 1 ,3 ,5-benzoxadiazocin-4-yl]cyanamide
  • 1,3-naphthalenediamine prepared according to Chem. Pharm. Bull, (1966), vol. 14, p. 324) in 70 mL of 2-propanol was added 1.87 g (7.93 mmol) of diphenyl cyanocarbonimidate. The mixture was refluxed for 4 h. After cooling 0.93 g of the title compound was filtered off, mp > 250 °C. !H ⁇ MR (300 MHz, Me 2 SO- ⁇ / 6 ) ⁇ 8.16 (br s,lH), 7.83 (br s,lH), 7.20 (m,4H), 4.40 (br s,lH), 3.94 (br s,lH), 2.84 (m,2H), 2.02 (m,2H).

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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

Cette invention se rapporte à des composés représentés par la formule (I), et à leurs N-oxydes et sels utilisables en agriculture et qui servent d'arthropodicides. Dans cette formule, A représente CR7R8; E représente O, S, CR?16R17 ou NR17¿; G représente un cycle à 5 ou 6 éléments fusionné, qui peut être aromatique ou non aromatique et contenant éventuellement un ou deux hétéroatomes choisis dans le groupe de l'azote, de l'oxygène et du soufre; et R?1-R8, R16 et R17¿ sont définis dans les pièces descriptives de l'invention. Cette invention présente également des compositions contenant ces composés de formule (I) et un procédé de lutte contre les arthropodes qui consiste à mettre en contact les arthropodes ou leur milieu ambiant avec une quantité efficace d'un composé de formule (I).
PCT/US1999/000882 1998-03-13 1999-01-13 Arthropodicides a base de benzoxadiazocinyle WO1999046266A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23213/99A AU2321399A (en) 1998-03-13 1999-01-13 Benzoxadiazocinyl arthropodicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7791698P 1998-03-13 1998-03-13
US60/077,916 1998-03-13

Publications (1)

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WO1999046266A1 true WO1999046266A1 (fr) 1999-09-16

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PCT/US1999/000882 WO1999046266A1 (fr) 1998-03-13 1999-01-13 Arthropodicides a base de benzoxadiazocinyle

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AU (1) AU2321399A (fr)
WO (1) WO1999046266A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292574A (zh) * 2020-02-21 2021-08-24 四川大学 一类手性多环的托品烷化合物及其制备方法和用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580553A2 (fr) * 1992-07-22 1994-01-26 Ciba-Geigy Ag Dérivés d'oxadiazine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580553A2 (fr) * 1992-07-22 1994-01-26 Ciba-Geigy Ag Dérivés d'oxadiazine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292574A (zh) * 2020-02-21 2021-08-24 四川大学 一类手性多环的托品烷化合物及其制备方法和用途

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