WO1997042169A2 - Agents a base d'hydrazones benzophenoniques, destines a la lutte contre les arthropodes - Google Patents

Agents a base d'hydrazones benzophenoniques, destines a la lutte contre les arthropodes Download PDF

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WO1997042169A2
WO1997042169A2 PCT/US1997/005955 US9705955W WO9742169A2 WO 1997042169 A2 WO1997042169 A2 WO 1997042169A2 US 9705955 W US9705955 W US 9705955W WO 9742169 A2 WO9742169 A2 WO 9742169A2
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alkyl
haloalkyl
och
compounds
compound
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PCT/US1997/005955
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WO1997042169A3 (fr
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Jeffrey Keith Long
Thomas Martin Stevenson
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E.I. Du Pont De Nemours And Company
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Publication of WO1997042169A3 publication Critical patent/WO1997042169A3/fr

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    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms

Definitions

  • This invention relates to certain benzophenone hydrazones, their 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.
  • EP-3913-A1 discloses insecticidal benzophenones containing thioether moieties wherein the sulfur atom is bonded directly to a benzophenone phenyl ring. This reference does not disclose or suggest the present benzophenones wherein the sulfur atom is bonded to phenyl through a chain of at least two carbon atoms.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides:
  • I is a single bond of E or Z configuration
  • R 1 and R 2 are independently selected from H, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl, C 4 -C 8 alkylcycloalkyl, C 4 -C 8 halo(alkylcycloalkyl), phenyl optionally substituted with W 1 , formyl, C(Y)R 6 , benzoyl optionally substituted with W 2 , phenoxycarbonyl optionally substituted with W 3 , benzyloxycarbonyl optionally substituted with W 4 , C j -Cg alkylsulfonyl, C j -Cg haloalkylsulfonyl,
  • R 5 is selected from C 2 -C 6 alkyl and C 2 -C 6 haloalkyl, each substituted with S(O) p R 18 , S(O) q OR 19 and S(O) 2 N(R 20 )(R 21 ), provided there is a chain of at least two carbon atoms between the sulfur atom of the S(O) p R 18 , S(O) q OR 19 or S(O) 2 N(R 20 )(R 21 ) substituent and the phenyl ring to which R 5 is attached;
  • R 6 is selected from Q-C5 alkyl, Q-C5 haloalkyl, C3-C7 cycloalkyl, C3-C 7 halocycloalkyl, C 4 -Cg cycloalkylalkyl, C 4 -Cg halocycloalkylalkyl, C 2 -C 5 alkenyl, C 2 -C 5 haloalkenyl, C 2
  • Y is selected from O or S
  • R 7 is selected from H, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 alkoxy and C ⁇ -C 6 haloalkoxy;
  • R 8 is independently selected from H, Cj-C 6 alkyl and C ⁇ -C 6 haloalkyl;
  • R 9 is C,-C 6 alkyl;
  • R 10 is C!-C 6 alkyl
  • R 11 and R 12 are independently selected from C ⁇ -C 4 alkyl; or R 1 1 and R 12 are taken together as -(CH 2 ) 5 - or -CH 2 CH 2 OCH 2 CH 2 -; R 13 is selected from H, halogen, C ⁇ C 6 alkyl, C j -C 6 alkoxy, SH, C ⁇ -C 6 alkylthio and phenyl optionally substituted with W 7 ;
  • R 14 is selected from H, C,-C 6 alkyl, C,-C 6 haloalkyl, C 3 -C 6 alkylcarbonylalkyl, C j -Cg alkylamino, C 2 -Cg dialkylamino, C j -Cg alkoxyamino, C1-C5 alkylsulfonylamino and phenyl optionally substituted with W 8 ;
  • R 21 and R 24 are independently selected from H, C j -Cg alkyl and C j -Cg haloalkyl;
  • R 20 and R 23 are independently selected from H, C ⁇ -C 6 alkyl, C!-C 6 haloalkyl, C ⁇ -C 6 alkoxy and C ⁇ -C ⁇ haloalkoxy;
  • R 18 is selected from C j -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 cyanoalkyl and phenyl optional
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, rc-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as vinyl, 1 -propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • 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, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkynyloxy includes straight-chain or branched alkynyloxy moieties.
  • 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 hexylsull ⁇ nyl 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.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group.
  • Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Alkylamino “dialkylamino”, and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • Alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl.
  • 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. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfmyl examples 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 .
  • C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyi include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I 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.
  • 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: Preferred 1.
  • R 1 is selected from C(Y)R 6 , C ⁇ -C 4 alkylsulfonyl, C j -C 4 alkylaminosulfonyl and C 2 -C 4 dialkylaminosulfonyl;
  • R 3 and R 4 are independently selected from H, halogen, C ⁇ -C 4 haloalkyl and
  • R 5 is selected from CH 2 CH 2 S(O) p R 18 ;
  • R 6 is selected from C j -C 4 alkyl and C,-C 4 alkoxy;
  • R 18 is selected from C ⁇ -C 4 alkyl and C ⁇ -C 4 haloalkyl; m is 1 or 2, and one substituent is in the para position; and n is 0 or 1.
  • Preferred 2. Compounds of Preferred 1 wherein: p is 2; and
  • R 18 is selected from CH 3 or CF3.
  • Preferred 4 Compounds of Formula I above and agriculturally suitable salts thereof, wherein:
  • R 1 is selected from C(Y)R 6 , C,-C 4 alkylsulfonyl, C j -C 4 alkylaminosulfonyl and C 2 -C 4 dialkylaminosulfonyl; R 3 and R 4 are independently selected from H, halogen, C ⁇ -C 4 haloalkyl and
  • R 5 is selected from CH 2 CH 2 S(O) p R 18 ;
  • R 6 is selected from Cj-C 4 alkyl and C ⁇ -C 4 alkoxy;
  • R 18 is selected from C ⁇ -C 4 alkyl and C ⁇ -C 4 haloalkyl;
  • m is 1 or 2, and one substituent is in the para position; and
  • n is O or 1.
  • R 18 is selected from CH3 or CF 3 .
  • 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.
  • 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.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-12.
  • X 2 , X 3 and Y in the compounds of Formulae 1-16 below are as defined above in the Summary of the Invention unless otherwise indicated.
  • Compounds of Formulae la-Id are various subsets of the compounds of Formula I, and all substituents for Formulae la-Id are as defined above for Formula I.
  • Solvents, reagents, catalysts and reaction conditions given are illustrative of the best methods available to prepare the compounds of this invention but are not meant to be either an exhaustive list of possible conditions nor to in any way limit this invention to those listed.
  • the intermediates and compounds of this invention are mixtures of E and Z isomers and/or tautomers that can be used as such mixtures to either carry out further reaction steps or for utilization as useful final compounds.
  • the E and Z isomers, their tautomers, and mixtures of these are believed to possess useful biological activity.
  • many of the compounds of Formula I can be prepared by condensation of a ketone of Formula 1 with a hydrazine of Formula 2.
  • the reaction can be carried out optionally in an inert solvent such as benzene, toluene, acetonitrile, or alcohols such as methanol, ethanol, 2-propanol, etc., at ambient temperature to the boiling point of the solvent for 30 minutes to five days and optionally employing a basic catalyst or preferably an acid catalyst such as acetic acid, propionic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, monosodium hydrogen phosphate, an acidic ion-exchange resin, etc., and optionally with removal of water by forming an azeotrope with solvent or by abso ⁇ tion by a zeolite or other water-binding material.
  • the hydrazines or hydrazine derivatives 2 are known or are prepared in analogy to corresponding known reagents.
  • compounds of this invention can be prepared as shown in Scheme 2 from compounds of Formula I in which at least one of R 1 and R 2 is H, which are known or can be prepared in analogy to corresponding known compounds, by further reaction with reagents that are known in the art or are prepared by analogy to corresponding known reagents and that are known to react with hydrazones, amines, acylhydrazones, etc., to add alkyl, benzyl, phenyl, acyl, alkoxycarbonyl, sulfonyl, sulfenyl, sulfenylamino, carbamoyl, thiocarbamoyl groups, etc.
  • reaction can be carried out optionally in an inert solvent or mixture of solvents such as benzene, toluene, dichloromethane, water, tetrahydrofuran, ethyl acetate, N ⁇ V-dimethylformamide, etc., and optionally in the presence of an acid-binding agent such as pyridine, triethylamine, potassium carbonate, sodium hydroxide, sodium hydride, lithium diisopropylamide, a basic polymer-bound resin, etc., at a temperature of -80 °C to the boiling point of the solvent(s), preferably at about -20 to 80 °C.
  • an inert solvent or mixture of solvents such as benzene, toluene, dichloromethane, water, tetrahydrofuran, ethyl acetate, N ⁇ V-dimethylformamide, etc.
  • an acid-binding agent such as pyridine, triethylamine, potassium carbonate, sodium hydro
  • R 14 is an amino-containing substituent
  • Scheme 1 or alternatively as shown in Scheme 3 by reaction of a compound in which R 1 and R 2 are both H with the reagents shown, which are known or can be prepared in analogy to corresponding known reagents, optionally in the presence of an inert solvent such as toluene, xylene, JV,N-diethylaniline, etc., but preferably in the presence of excess reagent as solvent, at temperatures from ambient to, preferably, the boiling point of the reagent.
  • an inert solvent such as toluene, xylene, JV,N-diethylaniline, etc.
  • compounds of Formula Ia in which R 14 contains a substituted amino group can be prepared as shown in Scheme 6 from compounds of Formula I in which R l and R 2 are H by reaction of the shown reagent 5, which is known or prepared by analogy to corresponding known compounds, optionally in an inert solvent or mixture of solvents such as benzene, toluene, dichloromethane, water, tetrahydrofuran, ethyl acetate, N ⁇ V-dimethyl- formamide, etc., and optionally in the presence of an acid-binding agent such as pyridine, triethylamine, sodium hydroxide, potassium carbonate, a basic polymer-bound resin, etc., at a temperature of -80 °C to the boiling point of the solvent(s), preferably at about -20 to 80 °C.
  • an acid-binding agent such as pyridine, triethylamine, sodium hydroxide, potassium carbonate, a basic polymer-bound resin, etc.
  • E is alkyl, alkoxy, alkylsulfonyl.
  • Compounds of Formula 1 can be prepared as shown in Scheme 8 from compounds of Formula 7 or Formula 8, which are known or are prepared by analogy to corresponding known compounds, and in which X 1 and X 2 are halogen, preferably chlorine, by the conditions of a Friedel-Crafts reaction with aromatic compounds substituted with the appropriate R 3 , R 4 or R 30 groups.
  • R 30 is R 5 or a group which can be converted into an R 5 group.
  • R 30 being an appropriately protected hydroxyalkyl group (see, for example, Greene, Protective Groups in Organic Synthesis, 2nd ed., John Wiley & Sons, New York, 1991) can be converted directly into R 5 by reactions well known in the art (see, for example, March, Advanced Organic Chemistry, 3rd ed., John Wiley & Sons, New York, 1985; S. Fujisaki et al., Bull. Chem. Soc. Jpn. 1985, 58(8), 2429; M. Yamoto et al., Synthesis 1982, 1014).
  • R 30 being hydroxyalkyl can be converted into an alkyl group substituted by such leaving groups as halogen, methanesulfonate, trifluoromethanesulfonate, etc., and thus can also be converted into R 5 groups, by procedures well known in the art, such as by displacement of the leaving group by mercaptans or their salts or by thiourea followed by hydrolysis to form mercaptans, followed by alkylation, etc., to form R groups (see, for example, March, ibid.). If a mercaptan is prepared, it is well known in the art that mild oxidation yields disulfides (see, for example, March, ibid.). Disulfides can then be converted to compounds in which R 18 is haloalkyl by reaction with halocarbons under the conditions of Wakselman et al. (J Chem. Soc, Perkin Trans. 1 1992, 3371).
  • hydrazone derivatives of Formula Id as shown in Scheme 9 can be converted to compounds of Formula I by the same means as described for Scheme 8.
  • Compounds of Formula 1 can alternatively be made as shown in Scheme 10 by the reaction of a compound of Formula 10, substituted by (R 3 ) m» w i tn an arylmagnesium halide, aryl copper reagent, aryllithium reagent, etc. of Formula 11, which is substituted with (R 4 ) n and R 30 , in which R 30 is R 5 or a group which can be converted into R 5 , as described previously.
  • the intermediate compound of Formula 9 can be prepared by the reaction of a compound of Formula 12 which is substituted by (R 4 ) n and R 5 or R 30 with an arylmagnesium halide or aryllithium reagent which is substituted with (R 3 ) m .
  • R 30 in a compound of Formula 9 is converted to an alkyl halide as described for Scheme 8, formation of a Grignard reagent is possible, as shown in Scheme 11.
  • the Grignard reagent can then, by procedures well known in the art, react to form R 5 groups containing S(O) p R 18 , S(O) q OR l9 , or S(O) 2 N(R 20 )(R 21 ), either by direct reaction with reagents known in the art or prepared by analogy to corresponding known reagents, or through intermediate sulfonyl chlorides, sulfinic acids, or mercaptans formed by known reactions of Grignard reagents with sulfuryl chloride, sulfur dioxide, or sulfur, respectively (see March, ibid.).
  • the benzophenone carbonyl group must be protected by an appropriate protecting group (see, for example, Greene, Protective Groups in Organic Synthesis, 2nd ed., John Wiley & Sons, New York, 1991).
  • each R 3 !, R 32 , R 33 , R 34 is independently H, alkyl, haloalkyl;
  • R 30 is an alkenyl group
  • it can be converted into R groups by reactions known in the art (see, for example, N. Kamigata et al., J. Org. Chem. 1985, 50(25) 5045; G. Glaros et al., Syn. Comm. 1976, 6, 495; M. Thiel et al., Chem. Berichte 1965, 98, 685; E. Block et al., J. Am. Chem. Soc. 1986, 705(19), 4568), F. Bellesia et al., Synthetic Comm. 1992, 22(8), 1101-1108).
  • Such alkenes can also be converted to a protected mercaptan (see, for example, B. Hache et al., Tetrahedron Lett. 1994, 55(12), 1837), and thus to an R group as described for Scheme 8.
  • compounds of this invention and intermediates in their preparation in which sulfur is present at one oxidation state can be converted, by procedures well known in the art, to compounds and intermediates in which sulfur is in a higher or lower oxidation state (see, for example, March, ibid., Hudlicky, Oxidations in Organic Chemistry, ACS Monograph 186, American Chemical Society, Washington DC, 1990, and Hudlicky, Reductions in Organic Chemistry, Halsted Press (John Wiley & Sons), New York, 1986). Conversion of one R 5 group to another is also possible by halogenation, alkylation, etc.
  • R 5 groups containing S(O) p R 18 in which p is 0 or 1 can be fluorinated on a carbon next to the sulfur atom by reaction with diethylaminosulfur trifluoride (see, for example, McCarthy et al., J. Am. Chem. Soc. 1985, 707, 735-737).
  • R 5 groups containing sulfoxide, sulfone or sulfonamide groups can be halogenated or alkylated on a carbon atom adjacent to these functional groups by procedures well known in the art.
  • the desired product can be subjected to conventional post- treatments such as organic solvent extraction and concentration to isolate the desired compound. If necessary, the resulting compound can be purified by a method such as chromatography or recrystallization.
  • Step A Preparation of l-bromo-4-[2-(ethoxymethoxy)ethyl]benzene
  • sodium hydride 50% in mineral oil, 4.4 g, 110 mmol
  • THF tetrahydrofuran
  • 4-bromobenzeneethanol 14 mL, 20 g, 100 mmol
  • THF trifluorohydrofuran
  • This mixture was stirred at ambient temperature for one hour and recooled to 0-5 °C, and a solution of chloromethyl ethyl ether (10.2 mL, 10.4 g, 110 mmol) in THF (5 mL) was added dropwise.
  • Step B Preparation of (4-chlorophenyl)[4-(2-hydroxyethyl)phenyl]methanone To a solution of l-bromo-4-[2-(ethoxymethoxy)ethyl]benzene (5.45 g, 21.0 mmol) in
  • the aqueous phase was extracted with ethyl ether and the combined organic phase was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, dried (MgSO 4 ), and concentrated under vacuum.
  • the oily residue was dissolved in THF (10 mL), aqueous hydrochloric acid (IN, 2 mL) was added, and this mixture was heated at reflux for one hour, at which point aqueous hydrochloric acid (6N, 1 mL) was added. After a further three hours at reflux, THF (10 mL) was added, and the reaction mixture was heated at reflux overnight.
  • reaction mixture Upon cooling to ambient temperature, the reaction mixture was extracted with ethyl acetate and the combined organic phase was washed with water, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution, dried (MgSO 4 ), and concentrated under vacuum.
  • the oily residue was redissolved in dichloromethane (110 mL), activated manganese (IN) oxide (Aldrich, 16 g) was added, and this mixture was stirred at ambient temperature for three days. The mixture was filtered through Celite® diatomaceous filter agent and absorbed onto silica gel, which was then applied to a column of silica gel.
  • Step C Preparation of ethyl [(4-chlorophenyl)[4-(2-hydroxyethyl)phenyl]methylene]- hydrazinecarboxylate
  • 4-chlorophenyl)[4-(2-hydroxyethyl)phenyl]methanone (0.42 g, 1.6 mmol) in absolute ethyl alcohol (3 mL) was added ethyl carbazate (0.50 g, 4.8 mmol) and glacial acetic acid (0.43 mL, 7.2 mmol), and this mixture was stirred and heated at reflux overnight.
  • reaction mixture Upon cooling to ambient temperature, the reaction mixture was treated with two drops of 50% aqueous sodium hydroxide solution, and volatiles were removed under vacuum. The residue was partitioned between ethyl acetate and water, and the organic phase was washed with water, saturated aqueous sodium hydrogen carbonate solution, water, and saturated aqueous sodium chloride solution, dried (MgSO 4 ), and concentrated under vacuum to afford the title compound, a resinous solid, as a mixture of geometric isomers (0.31 g, 56% yield).
  • Step D Preparation of ethyl [[4-(2-chloroethyl)phenyl](4-chlorophenyl)methylene]- hydrazinecarboxylate
  • Step E Preparation of ethyl [(4-chlorophenyl)[4-[2-(methylthio)ethyl]phenyl]methylene]- hydrazinecarboxylate
  • CH 2 C CCH 2 C1 C(S)On-pentyl S(0) 2 NH(CH 2 CF 3 ) cyclopropyl C(0)OCH 2 Cl SMe cyclobutyl C(0)0CH 2 CH 2 CH 2 C1 S(i-Pr)
  • TABLg 16 Compounds of Formula I where R 2 is H, R 3 is 4-Cl, m is 1, n is 0, R 5 is 4-(CH 2 CH 2 S(0)CF 3 )
  • R-> is in the para positioi 1

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit des composés de la formule (I), ainsi que leurs sels acceptables sur le plan agricole, utiles en tant qu'agents de lutte contre les arthropodes. Dans cette formule, R?1, R2, R3, R4, R5¿, m et n possèdent les notations données dans la description. On décrit également des compositions contenant les composés de la formule (I) ainsi qu'un procédé de lutte contre les arthropodes, lequel consiste à mettre en contact ces arthropodes ou leur environnement avec une dose efficace d'un composé de la formule (I).
PCT/US1997/005955 1996-05-09 1997-04-10 Agents a base d'hydrazones benzophenoniques, destines a la lutte contre les arthropodes WO1997042169A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24529/97A AU2452997A (en) 1996-05-09 1997-04-10 Benzophenone hydrazone arthropodicides

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US1722696P 1996-05-09 1996-05-09
US60/017,226 1996-05-09

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WO1997042169A2 true WO1997042169A2 (fr) 1997-11-13
WO1997042169A3 WO1997042169A3 (fr) 1997-12-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387572C (zh) * 2006-06-09 2008-05-14 浙江工业大学 一种二苯甲酮腙的合成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006076A1 (fr) * 1990-10-05 1992-04-16 E.I. Du Pont De Nemours And Company Arthropodicides a base de semi-carbazone
EP0662472A1 (fr) * 1994-01-05 1995-07-12 Ciba-Geigy Ag Dérivés d'hydrazone comme pesticides
EP0684229A1 (fr) * 1994-05-27 1995-11-29 Nihon Bayer Agrochem K.K. Dérivés sulfamides
WO1996033168A1 (fr) * 1995-04-19 1996-10-24 Kumiai Chemical Industry Co., Ltd. Derive de sulfure de benzyle, son procede de production et pesticide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006076A1 (fr) * 1990-10-05 1992-04-16 E.I. Du Pont De Nemours And Company Arthropodicides a base de semi-carbazone
EP0662472A1 (fr) * 1994-01-05 1995-07-12 Ciba-Geigy Ag Dérivés d'hydrazone comme pesticides
EP0684229A1 (fr) * 1994-05-27 1995-11-29 Nihon Bayer Agrochem K.K. Dérivés sulfamides
WO1996033168A1 (fr) * 1995-04-19 1996-10-24 Kumiai Chemical Industry Co., Ltd. Derive de sulfure de benzyle, son procede de production et pesticide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387572C (zh) * 2006-06-09 2008-05-14 浙江工业大学 一种二苯甲酮腙的合成方法

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WO1997042169A3 (fr) 1997-12-18
AU2452997A (en) 1997-11-26

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