Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms

Definitions

• This invention relates to certain oxazolines and thiazolines, their N-oxides, agriculturally-suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
• A is a direct bond or a lower alkylene group
• R l and R 2 are independently H, lower alkyl, lower alkoxy, halogen, ⁇ O 2 , lower haloalkyl or lower haloalkoxy;
• R3 is H, lower alkyl, lower alkoxy or halogen;
• R 4 is broadly defined and includes a group of the formula
• B is a direct bond, O or a variety of carbon chains;
• Q is CH or N;
• R5 is H, alkyl, alkoxy, halogen, haloalkyl, haloalkoxy or a tri(lower alkyl)silyl group; Z is O or S; and n is 0-5.
• US 4,977,171 discloses insecticidal and acancidal oxa- or thia-zoline derivatives of the formula:
• X 1 and X 2 are independently H, lower alkyl, lower alkoxy, halogen, CF3 or OCF3
• Y 1 and Y 2 are independently H, lower alkyl, lower alkoxy, lower alkylthio, CN, NO 2 , halogen or CF 3
• Z is O or S
• n is 0 or 1.
• This invention is directed to compounds of Formula I including all geometric an stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides in both agronomic and nonagronomic environments:
• R 4 and R 5 are independently selected from the group H; halogen; CN; NO ;
• alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-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. "Alkylene” denotes a straight-chain or branched alkanediyl. Examples of “alkylene” include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH2, and CH 2 CH(CH 3 ).
• Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
• Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
• halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine.
• 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
• sai 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 .
• C 1 -C 3 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 .
• alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
• R 1 is selected from the group F and Cl in the 2-position
• R 2 is selected from the group H, F and Cl in the 6-position
• R 5 is H;
• X is O.
• 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 Formula I (e.g., as a composition described herein).
• the preferred methods of use are those involving the above preferred compounds.
• DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-21. The definitions of A, E, Z, R---R 15 , X, W, m, n and q in the compounds of Formulae I-XXXVI below are as defined above in the Summary of the Invention.
• the second step carried out is the ring closure. This can be accomplished by treating the intermediate amide of Formula m with a dehydrating agent.
• Some useful reagent systems for this transformation include but are not limited to triphenylphosphine carbon tetrachloride, diethyl azodicarboxylate/triphenylphosphine, and thionyl chloride.
• An especially useful method for ring closure involves treatment of the amide with thionyl chloride in benzene or another inert solvent at reflux until the starting material is consumed (usually 30 min to 3 h).
• compounds of Formula III can be prepared in two steps as shown in Scheme 2.
• compounds of Formula IV are amidoalkylated with a compound of Formula V to form Formula VI compounds.
• a typical reaction involves the combination of compounds of Formulae IV and V in an aci such as sulfuric acid, methanesulfonic acid, trifluoroacetic acid, polyphosphoric acid or perchloric acid.
• the reaction can be run in a cosolvent such as acetic acid.
• the reaction temperature can range from -10° to 200 °C with 0° -100 °C being preferred.
• amino alcohols of Formula ⁇ can be produced by the direct reduction of oximino acids and esters of Formula X with boranes or alkali metal hydrides.
• the reaction conditions with lithium aluminum hydride are as described for Scheme 4.
• Scheme 12 shows that the ketones of Formula XV can also be made by the reaction of vinyl ethers of Formula XX with compounds of Formula XVL .
• Optimal reaction conditions for the arylation of vinyl ethers with aryl halides and sulfonates have been described by Cabri (J. Org. Chem., 57, 3558-3563 (1992)).
• the reaction proceeds best in dipolar aprotic solvents such as dimethylformamide when tethered phosphine ligands are employed.
• Bis(diphenylphosphino)propane is the preferred ligand.
• W ile organic bases may be employed as acid acceptors in this process, inorganic bases such as silver or thallium salts are preferred.
• R v one carbon less than R 7
• RX alkyl
• compounds of Formula XX VII can be prepared by the palladium catalyzed reaction of compounds of Formula XVLTI with unsaturated alcohols of Formula XXVI.
• Larock has studied the reaction of aryl halides with unsaturated alcohols and published a convement procedure for carrying out the process (Tetrahedron Lett., 30, 6629-6632 (1989)).
• the reaction is best carried out in a dipolar aprotic solvent such as dimethylformamide or acetonitrile in the presence of a phase transfer agent such as tetrabutylammonium chloride or the like.
• a phase transfer agent such as tetrabutylammonium chloride or the like.
• an inorganic base such as sodium bicarbonate, potassium carbonate, lithium acetate, or sodium acetate is required.
• the reaction may be carried out at 25 °C to 150 °C. In some cases the reaction is improved by the addition of a lithium salt such as lithium chloride.
• R? H, halogen, haloalkyl, alkyl, CN
• the compounds of Formula XXXi ⁇ can be made by the means of the Wittig or Horner-Emmons reaction as shown in Scheme 18. Reaction between phosphonium salts or phosphonates of Formula XXXV with strong base followed by reaction with compounds of Formula XXVHI give the alkenes. A compendium of conditions and references for these reactions can be found in Larock, loc. cit. pp 173-185 and 295-296. A convenient version of the reaction for making dichloroalkenes of Formula XXXm from compounds of Formula XXVIII is carried out by reaction of phosphines with carbon tetrahalides. Salmond (Tetrahedron Lett. 14, 1239-1240 (1977) has described conditions for carrying out this reaction. Typically the reaction is carried out in dichloromethane as solvent at 25 °C.
• Compounds of Formula XXXVI can be made by reaction of compounds of Formula XXVIII with the anion of (trimethylsilyl)diazomethane as shown in Scheme 1 .
• the anion is formed in an ether or tetrahydrofuran solvent system by reaction of the diazomethane with a strong base such as lithium diisopropylamide and then is treated with the compound of Formula XXVIII at low temperature (-20 to -70 °C). The mixture is then heated to 65 °C to effect the Colvin rearrangement.
• the reaction has been described by Shioiri and coworkers in Syn. Lett. (1994), 107-108.
• compounds of Formula XXXIV can be made from the compounds of Formula XXXI ⁇ substituted by 2 halogens.
• the reaction is best carried out at low temperature (-30 to -80 °C) in ethereal solvents. Conditions for this transformation can be found in Villieras et al., Synthesis, 458-461, (1975).
• organometallic reagents can be made from commercially available or known aryl halides by methods disclosed in the references above.
• Lithium borohydride (55 mL, 2 in tetrahydrofuran, 0.11 mol) was added slowly and, after completion of he addition, the mixture was heated at reflux for 1 h. The mixture was cooled and quenched by slow addition of aqueous hydrochloric acid (200 mL, IN). The mixture was extracted with dichloromethane (200 mL), dried over magnesium sulfate and evaporated under reduced pressure. The residue was then treated with toluene (100 mL) and thionyl chloride (23 mL, 0.3 mol). The mixture was heated to reflux for 45 min and then evaporated under reduced pressure.
• Example 1 (0.30 g) were suspended in methanol (30 mL) and stirred for 4 h at 25 °C. The methanol was removed by evaporation at reduced pressure and the residue was partitioned between dichloromethane and water. The organic layer was dried and evaporated. The residue was subjected to silica gel chromatography with hexanes/ethyl acetate (4:1) to give the title compound of Example 1 (0.16 g), a compound of the invention, as a solid melting at 140-141 °C.
• Example 2 The residue was subjected to silica gel chromatography with hexanes ethyl acetate (6:1) as eluent to give the title compound of Example 2 (0.11 g), a compound of the invention, as a white solid melting at 156-157 °C. !H NMR (CDC1 3 ): ⁇ 7.6(m,6H), 7.4(m,3H), 7.0(m,2H), 6.9(m,lH), 5.5(m,lH), 4.9(m,lH), 4.3(m,lH).
• Example 2 The title compound of Example 2 (0.25 g) was dissolved in tetrahydrofuran (8 mL) and treated with lithium diisopropylamide (0.6 mL, 1.5M in hexanes). The cooling bath was removed and the reaction was allowed to come to 25 °C. The reaction mixture was treated with saturated aqueous ammonium chloride solution (5 mL) and water (20 mL). The ether phase was dried over magnesium sulfate and evaporated to give 0.2 g of the tide compound of Example 4, a compound of the invention, as a solid melting at 120-123 °C.
• Step B 1 - 4-[2-(2.6-Difluoropheny ⁇ -4.5-dihydro-4-oxazolynphenyllethanone O- fphenylmethvnoxime
• the title compound of Step A 0.5 g
• 0-benzylhydroxylamine hydrochloride (0.36 g) were suspended in methanol (15 mL) and treated with sodium acetate (0.23 g). The mixture was stirred at 25 °C for 2.5 h. More O-benzylhydroxylamine hydrochloride (0.1 g) was added and the mixture was heated to reflux for 10 min and allowed to stir at 25 °C for 1 h. The reaction mixture was partitioned between ether and water. The organic layer was dried over magnesium sulfate.
• Step A Ethyl 4-r2-(2.6-difluorophenyD-4.5-dihydro-4-oxazolyllbenzoate
• Step B 4-f2-(2.6-Difluorophenyl)-4.5-dihydro-4-oxazolynbenzenemethanol
• Step C 1 -Phenylethanone Q-. f4-.2-(2.6-difluorophenyl ⁇ -4.5-dihvdro-4- oxazolyl1phenyl]methynoxime
• the title compound of Step B was dissolved in toluene (50 mL), cooled in an ice bath and treated with thionyl chloride (1.5 mL) in toluene (20 mL). The mixture was stirred for 3 h and then evaporated to dryness under reduced pressure. The unstable oil (2.0 g) was immediately dissolved in dimethylformamide (10 mL).
• Step B 2-(2.6-Difluorophenyn-4.5-dihvdro-4-r4'-rrtris(l-methylethvnsUyllthioiri.l'- biphenyll-4-ynoxazole
• Step A The title compound of Step A (4.3 g) was dissolved in 15 mL of THF under a nitrogen atmosphere and cooled below -65°C, and then n-BuLi in hexanes (4.7 mL of 2.5M solution) was added dropwise. After 15 minutes, 26 mL of a 0.5M solution of ZnCl 2 in THF was added dropwise. In a separate reaction flask, 67 mg of Pd(OAc) 2 was added to a solution of 201 mg of tri(o-tolyl)phosphine in 5 mL of THF, and this mixture was stirred for 5 min before its addition, via cannula, to the main reaction mixture.
• Step C rr4'- .2-f 2.6-DifluorophenyD-4.5-dihydro-4-oxazolyll f 1.1 '-biphenyl -4- yllthiolacetonitrile
• a solution of 0.54 g of the title compound of Step B in 10 mL of THF was added 1.0 mL of a 1.1 M THF solution of «-Bu 4 NF at 15 to 20 °C (water bath cooling) under a nitrogen atmosphere. After 5 min, 0.9 mL of iodoacetonitrile was added and th reaction mixture was stirred overnight at room temperature.
• Liquid diluents include, for example, water, N-N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
• Example A Wettable Powder Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
• Example B
• Compound 4 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
• Test compounds were prepared by dissolving in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 50 ppm.
• Two- week old red kidney bean plants infested with two-spotted spider mites eggs were sprayed to run-off (equivalent to 28 g/ha) with the test solution using a turntable sprayer. Plants were held in a chamber at 25 °C and 50% relative humidity.
• the following gave mortality levels of 80% or higher seven days after spraying: 1, 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 23* and 24*.
• Treated plants were dried, and fall armyworm (Spodopterafrugiperda) larvae were exposed to excised, treated leaves. Test units were held at 27°C and 50% relative humidity, and evaluated for larval mortality 120 h post-infestation. Of the compounds tested, the following gave mortality levels of 80% or higher: 2, 3, 4, 7*, 8**, 10*, 11*,

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• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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• 1995
  • 1995-11-28 AU AU42437/96A patent/AU4243796A/en not_active Abandoned
  • 1995-11-28 JP JP8522237A patent/JPH10512859A/ja active Pending
  • 1995-11-28 BR BR9510149A patent/BR9510149A/pt unknown
  • 1995-11-28 EP EP95940807A patent/EP0804423A1/en not_active Withdrawn
  • 1995-11-28 WO PCT/US1995/015234 patent/WO1996022283A1/en not_active Application Discontinuation
  • 1995-11-28 CN CN95197382A patent/CN1173172A/zh active Pending
• 1996
  • 1996-01-08 IL IL11669396A patent/IL116693A0/xx unknown
  • 1996-01-11 ZA ZA96210A patent/ZA96210B/xx unknown

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