NZ279591A

NZ279591A - 1,3-oxazoline or-thiazoline derivatives; arthropodicidal compositions therefrom

Info

Publication number: NZ279591A
Application number: NZ27959195A
Authority: NZ
Inventors: Victor Ekow Amoo; Renee Marie Lett; George Chihshu Chiang
Original assignee: Du Pont
Priority date: 1994-01-24
Filing date: 1995-01-17
Publication date: 1997-04-24
Also published as: WO1995019972A1; BR9506625A; MX9602949A; AU1676595A; EP0741714A1; JPH09508366A; CN1143957A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £79591 New Zealand No. 279591 International No. PCT/US95/00208 Priority D «!•(§): QIL.JL'.'Sil Comptet* Specification RM: Ctair.(®]LCB PuWJcitfon Date P.O. Joumtl No: .JjjJS. NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Arthropodicidal 2-oxa and thia-zolines Name, address and nationality of applicant(s) as in international application form: E. I. DU PONT DE NEMOURS AND COMPANY, of 1007 Market Street, Wilmington, Delaware 19898, United States of America , c* Q^S" C0/^v-Yp>0<"V^ BA-9036-A 2 79591 1 10 title ARTHROPODICIDAL 2-OXA AND THIA-ZOLINES The present invention comprises compounds useful for the control of arthropods. JP 05001060 discloses 4-thienyl-2-oxa(thia)zoline derivatives wherein the thienyl moiety is bonded directly to the oxa- or thia-zoline ring. U.S. 5.141,948 discloses oxa- and thia-zoline derivatives wherein the left hand phenyl ring is appended to the oxa- or thia-zoline ring either directly or through a lower alkylene bridge. Neither of these references suggests the compounds of the instant invention. J. Amer. Chem. Soc. (1964). 86. 4716-4720 discloses compounds IV and X. No biological activity for these compounds is disclosed. CH3CH2" H CH3CH2CH2" / NO2 IV Chem. Abstracts, vol. 113 (1990), no. 11,97490x discloses compound I. No biological 1 * activity for this compound is disclosed. 1 y h ch3' 20 EP-A-345,775 discloses compounds of Formula i as insecticides and acaricides. wherein X1 and X2 are independendy H, lower alkyl, lower alkoxy, halogen, trifluoromethyl or 25 trifluoromethoxv; r—-■ ~| \IZ. - 8 MAY 1996 Hi:.-. : ;v - a®*5* 279591 1A Yl and Y- arc independcndy H, lower alkyl. lower alkoxy, lower alkylthio, cyano, nitro. halogen or trifluoromethyl; Z is O or S; and n is 0 or 1. WO-A-93/24470 discloses compounds of Formula ii as aithropodicides and acaricides. wherein, inter alia, A is a direct bond or C1-C3 alkylene; E is CrC4 alkyl or Cj-C4 haloalkyi; Z is O or S; q is 0-3; Q is a 5- to 16- membered aromatic ring system selected from the group: (i) monocyclic aromatic ring containing 1 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, (ii) fused caibobicyclic ring containing 8 to 12 carbons; (iii) fused carbotricyclic ring containing 12 to 16 carbons; (iv) fused bicyclic ring containing 1 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur, (v) fused tricyclic ring containing 1 to 6 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; and (vi) phenyl substituted with M-J1; Q being optionally substituted with 1 to 6 subatituents; R1 and R2 are independently H, halogen, CpCg alkyl, C^-Cg haloalkyi, Cj-Cg haloalkoxy, C1-C5 alkylthio, CN or NO2; M is a direct bond, S, Ov C(=0), C(=0)0-C1-C2 alkylene, C1-C4 alkylene, O-C1-C4 alkylene or O-C2-C4 alkenylene, wherein when M is O-C1-C4 alkylene or O-C2-C4 alkenylene, the oxygen atom is attached to either ring and when M is €(=0)0-02-02, C(=0) is attached to either ring; and ii JaENDED SHEET - 8 MAY 1996 IB 2 7 9 5 9 1 J1 is a 5- membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, and a 6-membered ring containing 2 to 4 nitrogen atoms each ring optionally substituted with independently selected substituents. EP-A-432,661 discloses compounds of Formula iii as insecticides and acaricides. Rl and R2 are independently H, halogen, lower alkyl, lower alkoxy, nitro. lower haloalkyi or lower haloalkoxy, provided that Rj and R2 are not simultaneously H; R3 is H, halogen, lower alkyl or lower alkoxy; R4 is alkyl having 7 or more carbon atoms, alkoxy having 7 or more carbon atoms, alkylthio, lower alkoxy-lower alkyl, lower alkoxy-lower alkoxy, alkenyloxy having 3 or more carbon atoms, lower alkynyloxy, tri(lower alkyl)silyl, cycloalkyl which may be substituted by a lower alkyl, or B is a direct bond, O, lower alkylene, lower alkyleneoxy, lower alkylenedioxy or a di(lower alkyl)silyl; Q is CH or N; n is 0-5; each R5 is independently halogen, alkyl, alkoxy, lower haloalkyi, lower haloalkoxy or triQower alkyl)silyl; A is a direct bond or lower alkylene; and Z is 0 or S. wherein 0&5)n B- N.Z. FAT7 AMENDED SHEET 8 MAY 1S3B 1C 27959 1 SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments. The 5 compounds are: I wherein: 10 A is selected from the group A-1 A-2 O a-3 Q X2 and A-4 A-5 A-6 15 B is selected from the group O and N-Y; E is selected from the group C1-C4 alkyl and Cj-C4 haloalkyi; X1 and Z are independendy selected from the group O and S; IjBESDED sheet - 8 MAY 1338 PCT/US95/00208 X2 is selected from the group H, halogen, C--C4 alkyl, Cj-C4 haloalkyi, CJ-C4 alkoxy, C1-C4 haloalkoxy, CrC4 alkylthio, C(0)0R13 and CN; Y is selected from the group H, Cj-C6 alkyl, CrC6 haloalkyi, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, CHO, C(0)Rl6 C(0)0R16, C(S)R16, C(S)OR16, C(S)SR16, C(0)C(0)0Ri6, C(0)CH2C(0)0Rl6 S(0)tRl6, S(0)2CH2C(0)0R16, P(X)(OR18)2, S(0)tN(R13)C(0)0R'2, S(0)tN(R14)R15, NsCR^R1OR9, NR^R10; phenyl optionally substituted with 1-3 substituents independently selected from W1; and Cj-Cg alkyl substituted with 1-3 substituents independently selected from the group C]-C3 alkoxy, C1-C3 haloalkoxy, CN, N02, S(0)tR16, P(X)(OR18)2, C(0)R16, C(0)0R16 and phenyl optionally substituted with 1-3 substituents independently selected from W1; X is selected from the group O and S; G1 is selected from the group single bond, C(=X1), C(=X1)N(Y), C(=X1)0 and S(0)2; G2 is selected from the group single bond, O, S and N-Y; G3 is selected from the group single bond, O and N-Y; G4 is selected from the group single bond, O and N-Y; G5 is selected from the group single bond, O, S and N-Y; G6 is selected from the group C2-C4 alkenylene, C2-C4 alkynylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene; Q is selected from the group H and J; or Q is selected from the group CpCig alkyl, CrC16 haloalkyi, ^-C^ alkenyl, C2-Ci6 haloalkenyl, 02-C^ alkynyl, C2-C16 haloalkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W; J is a 5- or 6-membered aromatic ring containing 0 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur; or J is a 9- to 14-membered aromatic ring system selected from the, group fusui bicylic ring and fused tricyiic ring, each ring system containing 0 to 6 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; wherein J is optionally substituted with 1-4 substituents independently selected from the group R3; R1 is selected from the group halogen, Cj-Cg alkyl, CrC6 haloalkyi, CrC6 alkoxy, Cj-Cg haloalkoxy, S(0)tR16, CN and N02; R2 is selected from the group H, halogen, Cj-Cg alkyl, Cj-C6 haloalkyi, Cj-C6 alkoxy, C,-C6 haloalkoxy, S(0)tR16, CN and N02; R3 is selected from the group halogen, Cj-Cjg alkyl, C]-C16 haloalkyi, C2-C]6 alkenyl, C2-C16 haloalkenyl, C2-Cjg alkynyl, C2-C]6 haloalkynyl, C2-C]6 alkoxy alkyl, C2-C]6 alkylthioalkyl, C]-Ci6 nitroalkyl. C2-C16 cyanoalkyl, C3-CU WO 95/19972 WO 95/19972 PCT/US95/00208 3 alkoxycarbonylalkyl, C3~Cg cycloalkyl, C^-Cg halocycloalkyl, CN, N3, SCN. N02. SH, S(0)tR16, OCHO, OR20, CHO, C(0)R21, C(0)0R2', C(0)NRl6Rl7, S(0)2NR16R17, C(R4)=NR9, N=CR4R9, NR16R17, NR17C(0)R16, NR,7C(0)NHR16, NR17S(0)2R16, Si(R6)(R7)(R8), SF5 and M-J'; R4 is selected from the group halogen, Cj-Cg alkyl, CpCg haloalkyi, Cj-Cg alkoxy, Cj-Cg haloalkoxy and phenyl optionally substituted with R5; R5 is selected from the group halogen, CN, N02, Cj-Cg alkyl, CrCg haloalkyi, Cj-Cg alkoxy, CrC6 haloalkoxy, C(0)R16, C(0)0R16 and Si(R6)(R7)(R8); R6 and R7 are independently Cj-Cjo alkyl; R8 is selected from the group CpCjo alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1; R9 is selected from the group H, Cj-C4 alkyl, CpC4 haloalkyi, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(0)R>6, C(0)0R16, C(0)NR16R17, S(0)2NR16R17, S(0)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1; R10 is selected from the group H, C]-C4 alkyl, C(0)R16 and C(0)0R16; R11 is selected from the group H, CpC4 alkyl, CpC4 haloalkyi and phenyl optionally substituted with 1-3 substituents independently selected from W1; or R10 and R11 are taken together as (CH2)4 or (CH2)5; R12 is Cj-C18 alkyl; R13 is CrC4 alkyl; R14 and R15 are independently Cj-C4 alkyl; or R14 and R15 are taken together as (CH2)4, (CH2)s or CH2CH2OCH2CH2; R16 is selected from the group Cj-Cg alkyl, C]-Cg haloalkyi, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C2-Cg alkoxyalkyl, C2-Cg alkylthioalkyl, Cj-Cg nitroalkyl, C2-.Cg cyanoalkyl, C3-Cg alkoxycarbonylalkyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C4-C7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1; R17 is selected from the group H and C]-C4 alkyl; or R16 and R17, when attached to the same atom, are taken together as (CH2)4, (CH2>5 or CH2CH2OCH2CH2, each group optionally substituted with 1-3 CH3; R18 is selected from the group Cj-C3 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1; R19 is selected from the group halogen, CN, N02, CpCg alkyl, Cj-Cg haloalkyi, OR9, C(0)R!6 C(0)0R16 and Si(R6)(R7)(R8); ' WO 95/19972 PCMJS95/00208 R20 is selected from the group H, Cj-C4 alkyl, Cj-C4 haloalkyi, C2-C4 alkenyl. C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(0)R16, C(0)0R16, C(0)NR»6Rl7t S(0)2NR'6R17 and S(0)2R16; R21 is selected from the group Cj-Cg alkyl, CrC6 haloalkyi, C2-C6 alkenyl, C2-C6 5 haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, Cj-Cg nitroalkyl, C2-Cg cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl and C4-C7 cycloalkylalkyl; M is selected from the group direct bond, S, O, C(O), C(0)-Cj-C2 alkylene, C(0)0-CpC2 alkylene, C]-C4 alkylene, 0-C]-C4 alkylene, 0-C2-C4 alkenylene and 10 0-C2-C4 alkynylene; provided that when M is O-C \ -C4 alkylene, 0-C2-C4 alkenylene or 0-C2-C4 alkynylene, the oxygen atom is attached to the J ring; and when M is C(0)0-C]-C2 alkylene, the C(O) is attached to the J ring; J1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R19; or J1 is a 5-or 6-membered aromatic 15 ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-4 substituents independently selected from R19; W is selected from the group J, N02, CN, OH, C]-Cg alkoxy and Cj-Cg haloalkoxy; W1 is selected from the group, halogen, CN, N02, Cj-C2 alkyl, CrC2 haloalkyi, Cj-C2 20 alkoxy, C]-C2 haloalkoxy, Cj-C2 alkylthio, Ci-C2haloalkylthio,C]-C2 alkylsulfonyl, and Cj-C2 haloalkylsulfonyl; q is 0, 1 or 2; and t is 0, 1 or 2. Preferred compounds A are compounds of Formula I wherein: 25 A is A-1; Q is selected from the group J, Cj-Cjg alkyl and C2-C16 alkenyl; and J is selected from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R3. Preferred Compounds B are Compounds of Preferred A wherein: 30 Q is J; and J is phenyl optionally substituted with 1-3 substituents independently selected from the group R3. Preferred Compounds C are Compounds B wherein: G1 is C(O); 35 RJ is selected from the group F and CI in the 2-position; R2 is selected from the group H, F and CI in the 6-position; R3 is independently selected from the group, halogen, Cj-Cg alkyl, CpCg haloalkyi, OR20 and M-J1; WO 95/19972 PCT/US95/00208 5 R20 is selected from the group CrC4 alkyl and C]-C4 haloalkyi: and J1 is selected from the group phenyl, thienyl, pyridyl and furyl. Specifically preferred for biological activity is Compound D of Preferred C which is: /V-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoro-5 methyl)benzamide. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when anriched relative to the other stereoisomer(s) or when seperated from the other 10 stereoisomer(s). Additionally, the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof. The terms "aromatic ring" and "aromatic ring system" are defined as those rings or ring 15 systems which satisfy the Hiickel rule. Examples include: a 5- or 6- membered monocyclic aromatic ring containing 0 to 4 heteroatoms such as phenyl, furyl, fiirazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen. For example, when the aromatic ring system is furyl, 20 it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring system is i-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for pyridyl, the aromatic ring system is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other monocyclic aromatic rings; fused carbobicyclic rings containing at least one phenyl ring, examples include naphthyl and tetralinyl; fused carbotricyclic ring containing at least one phenyl ring, examples include fluorenyl and phenanthrenyl; fused bicyclic rings containing 1 to 4 25 heteroatoms and 1 or 2 aromatic rings, examples include quinolyl, isoquinolyl, quinoxalinyl, benzofiiiyl, isobenzofuranyl, benzothienyl, benzodioxolyl, chromanyl, indolinyl, isoindolyl, thienofuranyl, and purinyl; and fused tricyclic rings containing 1 to 6 heteroatoms and at least 1 aromatic ring, examples include acridinyl, phenanthridinyl, phenanthrolinyl, phenoxazinyl, and dibenzofuranyl. As with the monocyclic aromatic rings, the bicyclic and tricyclic aromatic ring 30 systems can be attached through any available carbon or nitrogen, for example, for naphthyl, the carbobicyclic aromatic ring system is 1-naphthyl or 2-naphthyl, for benzofuryl, the aromatic ring system can be 2-, 3-, 4-. 5-, 6-, or 7-benzofuryl, for fluorenyl, the aromatic ring system can be 1-, 2-, 3-, 4-, or 9-fluorenyl and similarly for the other bicyclic and tricyclic aromatic ring systems. 35 In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyi" denotes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different isomers through CJ6. Examples of "alkylene" include CH2. CHoCHb, CH2CH2CH2 and the different butylene isomers. "Alkenyl" denotes straight-chain or ^ WO 95/19972 PCT/US95/00208 6 branched alkenes such as ethenyl, l-propenyl, 2-propenyl, and the different isomers through C]f,. "Alkenyl" also denotes polyenes such as 1,3-hexadiene. Examples of "alkenylene" include CH=CH, CH2CH=CH, CH=CHCH2 and the different butenylene isomers. "Alkynyl" denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different 5 isomers through C)6. Examples of "alkynylene" include Q=C, CH2C=C, CsCCH2 and the different butynylene isomers. "Alkoxy" denotes, 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 CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2 and the different isomers 10 through Cj6. "Alkylthio" denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "Alkylthioalkyl" include CH3SCH2, CH3CH2SCH2, CH3SCH2CH2, CH3CH2CH2SCH2, CH3CH2SCH2CH2 and the different isomers through Cjg. "Alkylsulfonyl" denotes CH3S(0)2 and CH3CH2S(0)2. 15 "Cycloalkyl" denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C7 isomers bonded to straight-chain or branched alkyl groups. "Alkoxycarbonylalkyl" denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups. Examples of "alkoxycarbonylalkyl" include CH2C(0)0CH3, 20 CH2C(0)0CH2CH3, CH2CH2C(0)0CH3 and the different isomers through Cjg. The term "halogen", either alone or in compound words such as "haloalkyi", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyi", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyi" include F3C, C1CH2, CF3CH2 and CF3CC12. Examples of 25 "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HCsCCHCl, CF3CSC, CCI3OC and FCH2CsCCH2. Examples of "haloalkoxy" include CF3O, CCl3CH20, CF2HCH2CH20 and CF3CH20. Examples of "haloalkylthio" include CCI3S, CF3S, and CCI3CH2S. Examples of "haloalkylsulfonyl" include CF3S02, CCl3S02, CF3CH2S02 and CF3CF2S02. The total number of carbon atoms in a substituent 30 group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 18. For example, Cj-Cg alkyl designates methyl, ethyl, and propyl through hexyl isomers; C2 alkoxy designates CH3CH20-; and C3 alkoxy designates CH3CH2CH20- or (CH3)2CHO-. Nitroalkyl designates a straight or branched-chain alkyl group substituted with N02. Cyanoalkyl designates a straight or branched-chain alkyl group substituted with CN. 35 DETAILS OF THE INVENTION Compounds of Formula I (where A is A-1, G1 is C(O), S(0)2 or C(0)0. and Y is H) can be prepared by condensation of a compound of Formula II and a compound of Formula III. This transformation is illustrated in Scheme 1. A generally useful method is the reaction of the WO 95/19972 PCTAJS95/00208 7 Formula II compound with the Formula ID compound in the presence of an acid scavenger (usually a tertiary amine base such as triethylamine) at room temperature or below. The reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, chloroform, toluene and other solvents that will not react with acid chlorides or bases. The reaction is 5 normally completed in less than 24 h. Other useful methods for the formation of amides, sulfonamides and carbamates are discussed in Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York. Scteire 1 %cv-©c * ^ HnN n m G,= aO).S(0)2 or C(0)0. 10 As illustrated in Scheme 2, compounds of Formula I (where A is A-1, G1 is C(X,)N(Y) and Y is H) can be prepared by reaction of Formula II compounds with isocyanates of Formula IV. Typical reactions involve the combination of equimolar amounts of II and IV in an organic solvent such as ethyl acetate, methylene chloride, tetrahydrofuran, chloroform, benzene 15 or toluene. A base such as an alkali metal, tertiary amine, alkali metal hydroxide or metal hydride can be used. The reaction can be run at temperatt es ranging from about -20-100 °C with temperatures in the range of -10-30 °C being preferred. The reaction is completed within 24 h. Scheme 2 /~~\L>^r2 + QNCX " 1CA-A-1. /~N \ ' R G1=C(X1)N(Y). H2N and Y =H). . n iv (Qis other than II) 20 Compounds of Formula I (where A is A-1 and Y is H) can be prepared by reaction of a compound of Formula II with an aldehyde of Formula V as shown in Scheme 3. This reaction can be carried out in a solvent such as methanol or ethanol in the presence of a reducing agent such as sodium borohydride or sodium cyanoborohydride (Borch et al., J. Am. Chem. Soc. 25 (1971), 93,2897). The reaction temperature can vary from -30-200 °C and the reaction is completed in about 2-72 h. 1 (A=A-l.G1=QO). S(Ob 0rC(O)O,and Y=H). WO 95/19972 PCT/US95/00208 8 Scheme 3 (E)< hin + qcho reducing agent 1 (A = A-1 and Y=H). D V Alternatively, Foraiula 1 compounds (where A is A-1, A-1 is QCH2N(Y) and Y is H) can be prepared by the reduction of compounds of Formula I (where A is A-1, A-1 is QC(0)N(Y) 5 and Y is H) as shown in Scheme 4. Useful reducing agents are alkali metal hydrides. For example, treatment of a compound of Formula I (A is A-1, G1 is C(O) and Y is H) with lithium aluminum hydride at 0-50 °C in ethereal solvents such as tetrahydrofuran, ether or dimethoxyethane yields compounds of Formula I (A is A-1 and Y is H). The reduction is usually completed in 24 h. For alternative methods of reduction of amides to amines, see 10 March, Advanced Organic Chemistry 3rd Ed., (1985), pp 1099-1100. I A = A-1 A-1 =QQO)NY Y = H Compounds of Formula II can be prepared by the reaction of compounds of Formula VI 15 with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 5. A review of the Hofmann rearrangement can be found in Org. Rxns. (1946), 3, pp. 267-306. A typical reaction involves the addition of a compound of Formula VI to an aqueous solution of sodium hypobromite. The temperature of the reaction can range from 0-200 °C with the preferred temperature range between 30-100 °C. The reaction is usually 20 complete in 24 h. Alternatively, the transformation can be accomplished by treating a Formula VI compound with [hydroxy(tosyloxy)iodo]benzene in refluxing acetonitrile. (See J. Org. Chem. (1986), 51, pp 2669-2671). Scheme 4 reducing agent I (A=A-1,A-1=QCH2NOO and Y=H). Scheme 5 D O VI 1 WO 95/19972 PCT/US95/00208 Compounds of Formula VI can be prepared by reacting compounds of Formula VII with ammonia. This transformation is shown in Scheme 6. The reaction can be run in solvents such as methanol, ethanol, ether, benzene and toluene. Typical reactions are carried out at ambient temperature, and reactions are usually completed in 24 h. For reference, see D. W. Jones. J. Chem. Soc. (1969), 1729. Schemed MeO. Arrmonia VI 10 15 20 Compounds of Formula VII can be prepared by the reaction of commercially available serine derivatives (Formula VIII) with an imidate of Formula IX as shown in Scheme 7. The reaction can be carried out in solvents such as methanol, methylene chloride, chloroform, benzene, dioxane and tetrahydrofuran. Water can be added as a cosolvent. The reaction can be carried out at temperatures varying from 0 °C to the reflux temperature of the particular solvent being used, and the reaction is usually complete in 24 h. For reference, see Agric. Biol. Chem. (1986), 50, pp 615-623. One skilled in the art would recognize that this transformation can be extended to the preparation of compounds where A=A-3. Scheme 7 NH rI (E)o MeO. -ZH NH2 o vm br^ K L=Me, Et vn As depicted in Scheme 8, imidates of Formula IX can be prepared from commercially available amides of Formula X by reaction with a trialkyloxonium tetrafluoroborate in an inert solvent such as methylene chloride, benzene or toluene. The syntheses of imidates has been extensively reviewed by D. A. Neilson in The Chemistry of Amidines and Imidates, Patai and Rappoport. Eds., Vol. 2, (1991), pp 425-483. WO 95/19972 PCT/U S95/00208 Compounds of Formula I (where A is A-4 or A-5 and X2 is alkoxy or thioalkyl) can be prepared by the reaction of Formula I compounds (where A is A-4 or A-5 and X2 is CI or Br) 5 with sulfur or oxygen nucleophiles as illustrated in Scheme 9. Typical reactions involve the combination of equimolar amounts of the reactants in the presence of a base such as an alkali metal, tertiary amine, metal hydride and the like in conventional organic solvents including ether, tetrahydrofuran, 1,2-dimethoxyether, methylene chloride, chloroform, N.N-dimethylformamide and dimethylsulfoxide. The reaction can be conducted at temperatures ranging from -20-100 °C 10 with temperatures in the range of -10-30 °C preferred. One skilled in the art will recognize that the reactions of this general type can be extended to other nucleophilic reagents. Scheme 9 ^ i— z\ /> (I CJ) I (A = A-4 or A-5 and "N R2 X2=alko>y orthioalkyl). I A =A-4orA-5 X2=a, Br 15 As illustrated in Scheme 10, compounds of Formula I (where A is A-4 or A-5 and X2 is CI or Br) can be prepared by the reaction of Formula I compounds (where A is A-1 or A-2, G1 is C(O) or G2 = NH, X1 is O, and Y is H,) with an appropriate halogenating agent such as phosphorous trichloride, phosphorous tribromide, phosphorous pentachloride, phosphorous pentabromide, thionyl chloride, thionyl bromide, sulfuryl chloride, triphenylphosphorous and 20 carbon tetrachloride or carbon tetrabromide (Wolkoff, Can. J. Chem. (1975), 53, 1333). Typical reactions involve combination of the reactant with an excess of halogenating agent in the presence or absence of an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane. The preferred reaction temperature ranges from 35-100 °C and the reaction is generally complete within 24 h. WO 95/19972 PCT/US95/00208 11 Scheme 10 1 (A = A-4 or A-5 and X- = Q or Br). A = A-l.G1 =QO), X1 =Oand Y =H or A = A-2, Gr = NH, X1 = O and Y=H. Compounds of Formula I (where A is A-5 and X2 is H ) can be prepared by reaction of Formula II compounds with Formula V compounds. Typical reactions include the combination of equimolar amounts of Formula II compounds with Formula V compound in a suitable solvent such as acetonitrile, methanol, ethanol or benzene. The reaction can be run in the presence or absence of an acid catalyst. Typical acid catalysts include alkyl or arylsulfonic acids and mineral acids such as hydrochloric acid. The reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Scheme 11 illustrates tnis transformation. The reaction is normally completed within 24 h. Compounds of Formula I (where A is A-2, G2 is O, S or NH and X1 is O) can he prepared by condensation of Formula XI compounds with Formula XII compounds. A generally useful method is treatment of an acid chloride of Formula XI with an amine, alcohol or thiol of Formula XII in the presence of an acid scavenger such as triethylamine at room temperature or below. The reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, toluene, benzene and chloroform. An alternative method is treatment of an acid of Formula XI with a Formula XH compound in the presence of a condensation reagent such as dicyclohexylcarbodiimide in a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate. The temperature can range from 0-200 °C with the preferred temperature range from 20-100 °C. The reaction can be run in the presence of a catalyst such as dimethylaminopyridine (see Synthesis (1972), 453) and is completed in 30 min to 48 h. Scheme 11 + QCHO +■ I (A = A-5 and X2=H). h2n V WO 95/19972 PCT/US95/00208 12 Sctero? 13 Compounds of Formula XI (where L1 is OH) can be prepared by hydrolysis of a Formula VII compound as shown in Scheme 13. Typical reactions involve treating Formula VII 5 compounds with a base such as sodium hydroxide or potassium hydroxide in a suitable solvent such as water, methanol or ethanol. The reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Hydrolysis of esters have been thoroughly discussed in March, Advanced Organic Chemistry, 3rd Ed., (1985), pp 334-338. Typical reactions are completed in less than 24 h. Compounds of Formula I (where A is A-6 and G6 is alkenylene) can be prepared by reaction of compounds of Formula XIII with an aldehyde of Formula V in the presence of a strong base. This transformation is shown in Scheme 14. A typical reaction involves mixing a 15 compound of Formula XEI with a strong base such as an alkyllithium (e.g., butyllithium), a metal alkoxide (e.g., sodium methoxide), sodium amide or sodium hydride in a suitable solvent such as tetrahydrofuran, ether, benzene, methanol, ethanol, toluene, dimethoxyethane and dimethylsulfoxide, followed by the addition of an aldehyde of Formula V. The temperature of the reaction can vary from -70-200 °C. The Wittig reaction has been reviewed by Maercker in 20 Org. Rxns. (1965), 14, pp 270-490. The reaction is complete in 1-48 h. Scheme 13 10 O vn Scheme 14 Base / + QCHO >■ ! (A = A-6 and Or = alkenylene) .© xm V L2 = Br,Cl,I 'WO 95/19972 PCT/US95/00208 13 Formula XIII compounds can be prepared by reaction of equimolar amounts of a Formula XIV compound and triphenylphosphine. The transformation is shown in Scheme 15. The reaction can be run in a solvent such as benzene, toluene, xylene, ether, tetrahydrofuran, nitromethane, nitrobenzene, acetonitrile, ethyl acetate and dimethylformamide. The reaction temperature can vary from 0-200°C. For details see Maercker, Org. Rxn. (1965), 14, pp 270-490. The reaction is completed in 24 h. Scheme 15 Triphenylphosphine Xm (L- = Br, CI, I) 10 Compounds of Formula XTV can be prepared from compounds of XV as shown in Scheme 16. The reaction involves combination of an alcohol of Formula XV with a halogenating agent such as triphenylphosphine and carbon tetrachloride or carbon tetrabromide, triphenylphosphine, imidazole and iodine in a suitable solvent such as acetonitrile or methylene chloride. (Hooz et al., Can. J. Chem. (1968), 46, 86; Lange et al., Syn. Commun. (1990), 20, 15 1473). The reaction temperature may vary from 0-100 °C and is usually completed in 24 h. Scheme 16 20 HO. XV XIV (L2 = Br,a, I) Compounds of Formula XV can be prepared bv reduction of esters of Formula VII with alkali metal hydrides (Scheme 17). The reaction co^itions are as described for Scheme 4. MeO. reducing agent XV 25 Compounds of Formula I (where A is A-6, G6 is C2 alkylene, and Q is aryl) can be prepared by reaction of a compound of Formula XVI, first with thionyl chloride and then with sodium hydroxide in methanol as shown in Scheme 18. A typical reaction involves mixing a O 95/19972 PCT/US95/00208 14 compound of Formula XVI with thionyl chloride neat or with a suitable solvent such as toluene or carbon tetrachloride. The mixture is heated from 30-100°C for 0.25-4 h. The solvent and excess thionyl chloride are concentrated under vacuum and the resultant crude chloride is dissolved in methanol and treated with aqueous sodium hydroxide. This second reaction is then heated for 0.25-4 h at 30-65°C. Extraction of the cooled reaction mixture with an organic solvent enables the isolation of the product of Formula I where A is A-6 and G6 is Co alkylene. Scheme 18 O R1 DSOCb R1 2) NaOH. MeOH R2 OH XVI Q=aryl 10 Compounds of Formula XVI can be prepared from compounds of Formula XVII as shown in Scheme 19. Amino alcohols of Formula XVII are first converted to silyl ethers by reaction with trimethylsilyl cyanide at 0-30°C in a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran. (The alcohol group in compounds of Formula XVII is protected as the silyl ether so it does not react with the benzoyl chloride in the next step.) After 15 15-60 mill, the solution of silyl ether is treated with an organic base like triethylamine and then with an appropriate benzoyl chloride at 0-30°C for 0.5-4 h. The crude intermediate amide can be isolated by addition of water and extraction with an appropriate organic solvent. The silyl ether protecting group is removed by treatment of the crude intermediate (dissolved in an appropriate solvent like tetrahydrofuran) with a solution of tetrabutylammonium fluoride at 20 0-30°C for 5-60 min. Compounds of Formula XVI are then isolated by addition of water and extraction with an organic solvent like ethyl acetate. Scheme 19 UTMSCN 2a)El3N 3)Bu4NF 0H »- *- ► XVI 2b) R XVD 25 Compounds of Formula XVII can be prepared from compounds of Formula XVIII as shown in Scheme 20. A typical reaction involves treatment of a phthalimide of Formula XVIII. dissolved in an appropriate solvent like methanol or ethanol, with an excess of hydrazine al 40-80°C for 0.5-8 h. 'WO 95/19972 PCT/US95/00208 15 10 Scheme 20 NHo m2™2 t ^ A .OH xvn Compounds of Formula XVIII can in turn be prepared from compounds of Formula XIX as shown in Scheme 21. An epoxide of Formula XIX is dissolved in an appropriate solvent like tetrahydrofuran and treated with one equivalent of phthalimide and a catalytic amount (10 mol %) of an appropriate palladium catalyst like tetrakis-(triphenylphosphine) palladium (0) at 15-35°C for 0.5-4 h. XIX Pd[P(Ph)3]4 »- XVffl Compounds of Formula XIX can be prepared as shown in Scheme 22. Compounds of Formula XX are treated with trimethylsulfonium iodide under phase transfer conditions to give epoxides of Formula XIX (Syn. Commun. (1987), 17, 503-513). Compounds of Formula XX are available commercially or can be easily prepared by those skilled in the art. A useful 15 preparation can be found in J. Chem. Soc. Chem. Commun. (1984), 1287. Scheme 22 O XX XIX Compounds of Formula I (where A is A-1, Y is H, Q is J) can also be prepared by reaction 20 of a compound of Formula II with a triarylbismuth of Formula XXI in the presence of cupric acetate as shown in Scheme 23. This reaction can be carried out in a solvent such as methylene chloride at room temperature in less than 24 h (see Barton et al. Tetrahedron Letts. (1987), 28, pp 887-890). WO 95/19972 PCT/U S95/00208 10 16 Scheme 23 R1 Cu(OAc)t QjBi ^ I (A = A-1, Y=H,Q = J) XXI Compounds of Formula I (where R1 and R2 are halogens and R3 is alkyl or aryl) can be obtained by reaction of a compound of Formula XXII with a base. Compounds of Formula XXII are prepared by reacting substituted benzamide with 2-haloacetaldehyde dialkylacetal (see EP-A-594,129). The conversion of XXII to I takes place at room temperature over a period of several hours. Scheme 24 discloses this transformation. Scheme 24 base *- xxn One skilled in the art would recognized that the transformations described in Schemes 7 and 12 can be extended to the preparation of compounds of Formula I where A is A-3 by using appropriate commercially available serine derivatives. It is recognized that some reagents and reaction conditions described above for preparing 15 compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences into the synthesis will aid in obtaining the desired products. The use and choice of the protecting group will be apparent to one skilled in chemical synthesis. EXAMPLE 1 20 Step A: Methvl 2.6-difluorobenzenecarboximidate An amount of 10.62 g (0.068 mol) of 2,6-difluorobenzamide was added to a suspension of 10.0 g (0.068 mol) of trimethyloxonium tetrafluoroborate in 70 mL of methylene chloride. The reaction was stirred under nitrogen overnight. Saturated aqueous sodium bicarbonate was slowly added and the mixture extracted with methylene chloride. The combined extracts were 25 washed with brine, dried over MgS04 and evaporated. The residue was passed through a silica gel column eluting with EtOAc:hexane (1:6) to give 9.13 g of a pale yellow oil: 1H NMR (CDC13) 8 7.70 (br,lH), 7.73 (m,lH), 6.94 (t,2H), 3.94 (s,3H). Step B: Methvl 2-f2.6-difluorophenvn-4.5-dihvdro-4-oxazolecarboxvlate An amount of 9.09 g (0.058 mol) of serine methyl ester hydrochloride was added 30 portionwise to a 10.0 g (0.058 mol) solution of the product of Step A in 15 mL EtOH and 5 mL WO 95/19972 PCT/US95/00208 17 H2O. The mixture was stirred at reflux for 1.5 h. Volatiles were evaporated under reduced pressure and the residue partitioned between EtOAc and HnO. The EtOAc layer was washed with brine, dried over MgSC>4 and evaporated. The residue was passed through a silica gel column eluting with EtOAc:hexane (1:4) to give 6.0 g of a colorless oil: 'H NMR (CDCI3) 8 7.43 (m,lH), 6.98 (t,2 H) 5.00 (t,lH), 4.63-4.72 (2t,2H), 3.84 (s,3H). Step C: 2-(2.6-DifluorophenvD-4.5-dihvdro-4-oxazolecarboxvlic acid A solution of 24.37 g (0.101 mol) of the product of Step.6and 6.17 g (0.109 mol) of KOH in 100 mL of MeOH was stirred at room temperature for 5 h. The MeOH was evaporated under reduced pressure and the residur. dissolved in H2O. Hydrochloric acid was added to the 10 solution resulting in precipitation of a white solid. The solid was filtered and air dried to give 19.6 g of product: m.p. 149-150 °C; JH NMR (DMSO-d6) 8 13.10 (br,lH), 7.68 (m,lH), 7.28 (t,2H), 4.95 (t,lH), 4.59 (2 t,2H). Step D: 2-f2.6-Difluorophenvn-4.5-dihvdro-A/-(4-methoxvphenvl)-4- oxazolecarboxamide 15 The compound, 1,3-dicyclohexylcarbodiimide (0.433 g, 0.0021 mol), was added to a mixture of the product of Step C (0.500 g, 0.0021 mol), 4-dimethylaminopyridine (0.044 g, 0.00036 mol) and p-anisidine (0.259 g, 0.0021 mol) in 3.5 mL of methylene chloride. The mixture was stirred at reflux for 1.5 h. The solvent was evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:4) to give 0.881 g of a solid: m.p. k20 144-146.5 °C; ^H NMR (DMSO-d6) 8 10.17 (s,lH), 7.65 (m,lH), 7.58 (d,2H), 7.28 (t,2H), 6.90 (d,2H), 5.05 (t,lH), 4.69 (2t,2H), 3.73 (s,3H). EXAMPLE 2 Step A: 2-(,2.6-Difluorophenvtt-4.5-dihvdro-4-oxazoIecarboxamide A solution of 10.0 g (0.041 mol) of methyl 2-(2,6-difluorophenyl)-4,5-dihydro-^25 4-oxazolecarboxylate in 100 mL of a 2M solution of ammonia in MeOH was stirred at room temperature overnight. Evaporation of solvent afforded 9.04 g of a white powder: m.p. 148-149 °C; !H NMR (DMSO-d6) 8 7.67 (m,lH), 7.49 (br s,lH), 7.39 (br s,lH), 7.27 (t,2H), 4.85 (t,lH), 4.56 (2 t,2H). Step B: 2-f2.6-Difluorophenvn-4.5-dihvdro-4-oxazolamine 30 An amount of 0.386 g (0.0044 mol) of bromine was added dropwise to a cooled solution of 0.440 g (0.011 mol) of NaOH in 3.7 mL of H2O. 0.500 g (0.002 mol) of the product of Step A was added portionwise. The reaction was stirred at 80 °C for 0.5 h. Et20 and HoO was added and the mixture extracted with EtOAc. The combined extracts were washed with brine, dried MgS04 and evaporated to give 0.350 g of a white solid: m.p. 81-85 °C; 'H NMR 35 (DMSO-dg) 8 7.62 (m,lH), 7.24 (t,2H). 5.15 (t,lH), 4.70 (t,lH), 3.83 (t.lH). Step C: W-r2-f2.6-DifluoroDhenvlV4.5-dihvdro-4-oxazoIvllnonanamide The Compound, 1,3-dicyclohexylcarbodiimide (1.03 g, 0.005 mol) was added to a mixture of the product of Step B (1.00 g, 0.005 mol). 4-dimethylaminopyridine (0.106 g, 0.00087 mol). O 95/19972 PCT/U S95/00208 18 and nonanoic acid (0.756 g, 0.005 mol) in 9 mL of methylene chloride. The reaction was stirred at room temperature overnight. The solvent was evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:2) to give 1.28 g of a white solid: m.p. 55-58 °C; •H NMR CDC13 8 7.45 (m,lH), 7.10 (br,lH), 6.98 (t,2H), 6.09 (m,lH), 4.67 (t,lH), 4.20 (dd,lH), 2.20 (t,2H), 1.61 (m,2H), 1.26 (br,10H), 0.87 (t,3H). EXAMPLE 3 Ar-r2-f2.6-Difluorophenvn-4. 5-dihvdro-4-oxa7iolvll-2-fluoro-4-(trifluoromethvnbenzamide Thionyl chloride (2.008 g, 0.017 mol) was added to a cooled solution of 1.10 g 10 (0.005 mol) of 2-fluoro-4-trifluoromethylbenzoic acid in 5 mL of benzene. The mixture was refluxed for 1 h. The benzene was evaporated and fresh benzene added to azeotrope off excess thionyl chloride. The residue was dissolved in 2 mL of dry THF and added dropwise to a cooled solution of 0.952 g (0.0048 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine and 0.81 mL of Et3N in 3 mL of dry THF. The reaction was allowed to warm to room temperature 15 and stirred overnight. EtjO was added and the salts filtered. The filtrate was washed successively with IN HC1, brine, IN NaOH and brine. It was dried over MgSO^ filtered, and evaporated to give a light brown solid. This solid was triturated with hexanes to give 0.825 g of product: m.p. 146-147 °C; *H NMR (DMSO-dg) 8 9.39 (d,lH), 7.83 (t,2H), 7.69 (m,2H), 7.30 (t,2H), 6.26 (m,lH), 4.68 (t,lH), 4.30 (t,lH). ,20 EXAMPLE 4 2-f2.6-Difluorophenvn-4.5-dihvdro-N-r4-ftrifluoromethvn-phenvlmethvlenel-4- oxazQlamme A mixture of 1.00 g (0.005 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine, 0.870 g (0.005 mol) of 4-trifluoromethylbenzaldehyde and 0.530 g (0.005 mol) of Na2C03 in , 25 6 mL of MeOH was stirred at room temperature overnight. Solvents were evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:4) affording 0.560 g of a yellow solid: m.p. 85-87 °C; !H NMR (CDC13) 8 8.70 (s,lH), 7.91 (d,2H), 7.68 (d,2H), 7.45 (m,lH), 7.02 (t,lH), 6.18 (t,lH), 4.78 (t,lH), 4.39 (dd,lH). EXAMPLE 5 30 2-(2.6-DifluorophenvD-4.5-dihvdro-N-phenvl-4-oxazolamine A mixture of 2.98 g (0.015 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine, 7.79 g (0.018 mol) of triphenylbismuth (Alfa Research Chemicals) and 2.57 g (0.014 mol) of anhydrous cupric acetate (Aldrich Chemical Co.) in 48 mL of methylene chloride was stirred at room temperature for 2 h. Solvent was evaporated and the residue passed through a silica gel 35 column eluting with 30% EtOAc/hexane affording 1.76 g of the title compound as a light yellow solid, which was further purified by recrystallization from CHCl3-hexane: m.p. 109.5-110.5°C; 'H NMR (CDC13) 8 7.45 (m, 1H), 7.22 (m,2H), 7.00 (m.2H), 6.80 (m,3H), 5.90 (dd.lH), 4.69 (t,lH), 4.20 (dd.lH), 4.15 (bs,lH). WO 95/19972 PCT/US95/00208 19 EXAMPLE 6 2-f2.6-DifluorophenviM.5-dihvdro-4-methoxvoxazoline A mixture of 2.5 g (0.01 mol) of N-(l-methoxy-2-chloroethyl)-2,6-diflurobenzamide and 0.7 g (0.011 mol) of KOH pelletes (85%) in 30 mL methanol were stirred at room temperature overnight. The white slurry that formed was filtered, and the filtrate evaporated to remove residual solvent. The residue was extracted with water/methylene chloride. Upon evaporation of the methylene chloride, 1.5g (70% yield) of the title compound was obtained as an oil: >H NMR (CDC13) 8 7.42 (m,lH), 6.98 (m,2H), 5.59 (t.lH), 4.42 (d,lH), 4.27 (d,lH), 3.55 (s,3H). By the procedures described herein the following compounds of Tables 1-12 can be prepared. The compounds in Table l,line 1 can be referred to as 1-1, 1-2, 1-3, 1-4 , 1-5, 1-6 and 1-7 (as designated by line and column). All the other specific compounds covered in these Tables can be designated in an analogous fashion. The following abbreviations have been used in Tables 1-12: Me = methyl, Ph = phenyl, and pyr = pyridyl. Tabfcl R*=F: R^F: Z=0; Y=H; Xl=0\ R3= COLUMN 1 2 3 4 5 6 7 1 3-F 4-F 5-F 6-F H 4-SCF, 4-COPh 2 3-C1 4-Cl 5-Cl 6-CI 4-Br 4-SFs 4-OPh 3 3-CFi 4-CF^ 5-CF, 4-C(0)0Me 4-1 4-CH3 6-CF, 4 3-OCF3 4-OCF^ 5-OCF3 4-(4-Cl-Ph) 4-CN 4-OCH^ 4-Ph 5 3-OCH9CF3 4-OCH?CF3 5-OCH?CF3 6-OCH?CF3 4-NOt 4-COMe 6-OCF7 6 4-CH7CF3 4-t-Bu 4-nBu 4-sBu 4-nPr 4-CH9CH3 4-iPr r1 =F; ^2=C1; Z=0; Y=H; XJ=0; r3= 7 3-F 4-F 5-F 6-F H 4-SCF^ 4-COPh 8 3-C1 4-Cl 5-Cl 6-Cl 4-Br 4-SFs 4-OPh 9 3-CF, 4-CF, 5-CF3 6-CF3 4-1 4-CH, 4-C(0)0Me 10 3-OCF^ 4-OCF^ 5-OCF3 6-OCF3 4-CN 4-OCH^ 4-Ph 11 3-OCHiC3 4-OCH9CF3 5-OCHoCF^ 6-OCTbCF^ 4-NOo 4-COMe 4-(4-Cl-Ph) 12 4-CHICF^ 4-t-Bu 4-nBu 4-sBu 4-nPr 4-CH1CH3 4-iPr WO 95/19972 PCT/US95/00208 20 Rr=Cl: R2=C1: Z=0: Y=H; X1^: R3= 13 3-F 4-F 5-F 6-F H 4-SCF, 4-COPh 14 3-CI 4-Cl 5-Cl 6-Cl 4-Br 4-SF^ 4-OPh 15 3-CF, 4-CF, 5-CF-* 6-CF, 4-1 4-CHi, 4-C(0)0Me 16 3-OCFr, 4-OCF-, 5-OCF^ 6-OCF^ 4-CN 4-OCH^ 4-Ph 17 3-OCHoCF^ 4-OCHtiCF^ S-OCHbCF, 6-OCH?CFr< 4-NO-) 4-COMe 4-(4-Cl-Ph) 18 4-CH?CF-, 4-t-Bu 4-nBu 4-s-Bu 4-nPr 4-CHoCH^ 4~iPr R*=F; 19 4-Ph 4-CH^ 4-COPh 4-ochicf, 4-ocf, 4-scf^ 3-OCF^ 20 4-F 3-CF^ 4-CF, 4-(4-Cl-Ph) 4-COMe 4-CN 2-CF^ 21 4-Cl 4-sfs 4-OPh 4-CHoCF} 4-no5 4-OCH} 4-tBu R'=F; R2=F; Z=0; Y=I i; X'=S; R3= 22 4-CF, 4-CH,, 4-COPh 4-CN 4-OCF^ 4-OCH?CF-, 4-COMe 23 4-F 3-OCFt 4-Ph 2-CF, 4-OCH^ 4-CHoCF^ 4-SCF, 24 4-Cl 4-SFs 4-OPh 3-CF, 4-noi 4-(4-Cl-Ph) 4-tBu R]=F; R2=F: Z=S; Y=H; Xj=0; R3= 25 4-CF, 4-CH^ 2-CF, 4-CN 4-OCF^ 4-(4-Cl-Ph) 4-OCH^ 26 4-F 4-SCF, 4-Ph 3-OCF, 4-COMe 4-CHoCF-, 4-COPh 27 4-Cl 4-SF«; 4-OPh 3-cf^ 4-NO-, 4-OCHoCF^ 4-tBu RJ=F; R-=F; Z=0; Y=CH^: X!=0; R3 28 4-CF, 4-CH^ 4-OCH^ 4-CN 4-OCF, 4-(4-Cl-Ph) 4-COPh 29 4-F 2-CF-, 4-Ph 3-OCF^ 4-COMe 4-CHoCF-, 4-scf^ 30 4-Cl 4-sfs 4-OPh 3-CF^ 4-NOT 4-OCH2CF3 4-tBu rj=f; r2=F; Z=0; Y=COMe;X'=0; r3= - 31 4-CF, 4-CH-, 4-COPh 4-CN 4-OCF^ 4-(4-Cl-Ph) 3-ocfT 32 4-F 4-OCH^ 4-Ph 2-cf^ 4-COMe 4-ochocfi, 4-scf^ 33 4-Cl 4-SFs 4-OPh 3-CF^ 4-NOT 4-ch7cf, 4-tBu WO 95/19972 PCT/US95/00208 21 Ri=F; r2=f; Z=0; Y=C(0)0Me; X'=0; R3= 34 4-CF^ 4-CH^ 4-COPh 4-CN 4-OCF^ 4-OCHoCF^ 4-SCF^ 35 4-F 4-OCH-, 4-Ph 2-CF^ 4-COMe 4-CHoCF-, 3-OCF, 36 4-Cl 4-SFs 4-OPh 3-CFt, 4-NO-) 4-(4-CI-Ph) 4-tBu Tabfe 3 Q= COLUMN ] 2 3 4 37 (CH^CHT (CH,)10CH, CH=CH(CH?)fiCH-} CHoPh 38 (CH?)4CH^ (CH,)nCH, CH=CH(CH?)7CH, CHoCHoPh 39 (CH,)sCH^ CH=CHCH?CH^ CH=CH(CH-,)rCH^ 3-Pyr 40 (CH,)fiCH, CH=CH(CH?)9CHT CH=CH(CH,)qCH3 6-Cl-(3-Pyr) 41 (CH9)7CH? CH=CH(CH,)^CH^ CH=CH(CH5),OCH3 CH^»-4-CI-Ph 42 (CH5)rCH3 CH=CH(CH2)4CH1 CH=CHCFfoPh (CHo)o-4-Cl-Pn 43 (CH?)qCHT CH=CH(CH2)SCH3 CH=CHPh (CH5)3-4-Cl-Ph Table 4 Q= COLUMN 1 2 3 4 5 6 44 (CH?hCH:< rcH?)inCH3 4-Ph-Ph 3-Pyr (CHi)qCH^ CH-jCHiPh 45 (CHo)4CH3 fCH2)nCH^ 4-CN-Ph 2-Pvr 4-OCHoCF-^-Ph 4-CF^-Ph 46 (CHo)sCH^ 4-OCF^-Ph 3-CF^-Ph Ph (CH?)8CH, 4-F-Ph 47 fCH7)fiCH3 4-Cl-Ph (ch2)7ch3 ChbPh CH->-4-Cl-Ph 4-Pyr WO 95/19972 PCT/CS95/00208 ->-> X'=0; Y=H; R3= COLUMN 1 2 3 4 5 6 7 48 4-CF-; 4-CH} 4-COPh 4-CN 4-OCF-, 4-OCHoCF^ 4-OCH^ 49 4-F 2-CF, 4-Ph 4-SCFn 4-COMe 4-CH0CF3 3-OCF^ 50 4-Cl 4-SFs 4-OPh 3-CF^ 4-NOo 4-(4-Cl-Ph) 4-tBu Xl=S\ Y=H; r3= 51 4-CF, 4-CHs 4-COPh 4-CN 4-OCF3 4-CHoCF^ 3-OCF^ 52 4-F 4-OCH^ 4-Ph 4-SCF^ 4-COMe 4-(4-Cl-Ph) 4-NOt 53 4-Cl 4-SFs 4-OPh 3-CF-, 4-NOo 4-OCH'jCF^ 4-tBu x*=0; Y=CHv. r3= 54 4-CF, 4-CH, 4-COPh 4-CN 4-OCF3 4-(4-Cl-Ph) 3-OCF^ 55 4-F 4-OCH^ 4-Ph 4-SCF3 4-COMe 4-CHiCF^ 2-CF-, 56 4-Cl 4-SF, 4-OPh 3-CF, 4-NO? 4-OCHoCF^ 4-tBu x'=0; Y=COMe; r3= 57 4-CF, 4-CH„ 4-COPh 4-CN 4-OCF3 4-OCH9CF-< 3-OCF^ 58 4-F 4-OCH3 4-Ph 4-SCF^ 4-COMe 4-CH^CF^ 2-CF3 59 4-Cl 4-SFs 4-OPh 3-CF, 4-NOo 4-(4-Cl-Ph) 4-tBu X]=0; Y=C(0)0Me; r3= 60 4-CF-, 4-CH3 4-COPh '4-CN 4-OCFi 4-OCHoCF^ 3-OCF^ 61 4-F 4-OCH, 4-Ph 4-SCF3 4-COMe 4-CHoCF^ 2-CF^t 62 4-Cl 4-SF5 4-OPh 3-CFt, 4-NO? 4-(4-Cl-Ph) 4-tBu Table 6 WO 95/19972 PCT/US95/00208 23 Q= COLUMN 1 2 3 4 5 6 7 8 63 (CHo)^CH^ (CH7)rCH, (CH,)nCH, (CHobPh (CH?)fiCH, <CH,)inCH, 2-Pvr 3-Pyr 64 (CH9)4CHr, (CH5)qCH:, CHo-4-CI-Ph CH-jPh (CH5)7CH3 (CH,)SCH3 4-Pyr t-Bu table 7 Q= COLUMN 1 2 3 4 5 6 7 65 (CH^CH, (CH,)„CH, fCH7bPh 4-Cl-PhO 2-Pyr (CH2)nCH, 4-CFvPh 66 (CH7)4CH, (CH7)gCH^ (CHi)fiCH, 4-CFrPhO CHoPh CH-j-4-CI-Ph 4-Cl-Ph 67 (CH?_)sCH, (CH2)10CH3 (CH2)7^H^ Ph 4-Pyr 3-Pyr t-Bu Table 8 X2=H; Q= COLUMN 1 2 3 4 5 6 68 (CH7)^CH^ CCH7)ioCH3 4-OCFvPh 3-Pyr CHoCHoPh (CH7)„CH, 69 (CH,)4CH, (CH^JnCH, 4-CN-Ph 4-Ph-Ph 4-OCH7CF^-Ph (CH7)qCH^ 70 (CH7)sCH^ Ph 3-CF^-Ph 4-F-Ph CH>7-4-Cl-Ph 4-CF^-Ph 71 (CH7)fiCH3 2-Pyr OHhPh 4-Cl-Ph (CH,)7CH, 2-F-Ph X2=C1; Q= 72 (CH7),CHI, 4-OCFvPh 3-Pyr (CH7)qCH, CHo-4-Cl-Ph 73 (CH7)4CH^ (CH?>11CH, 4-CN-Ph 4-Ph-Ph 4-OCH7CFvPh CHoCH^Ph 74 (CH^CH, Ph 3-CFrPh 4-CF^-Ph 4-Cl-Ph (CH,)rCH, 75 (CH7)fiCH, 2-Pyr CHoPh 4-F-Ph (CH7)7CH, 2-F-Ph ^WO 95/19972 PCT/US95/00208 24 X2=OMe; Q= 76 (CHo)^CH^ fCH7),nCH^ 4-OCF^-Ph 3-Pyr (CHt)QCH^ CHi-4-CI-Ph 77 (CH7)4CH, (CH7)nCH, 4-CN-Ph 4-Ph-Ph 4-OCH?CFvPh CHoCHoPh 78 (CH?)SCH1 Ph 3-CF^-Ph 2-Pyr 4-CF-^-Ph (CHo)RCHr, 79 (CHoJfiCH^ 4-F-Ph CHoPh 2-F-Ph (CHo^CH^ 4-Cl-Ph X2=H; R3= COLUMN 1 2 3 4 5 6 7 80 3-F 4-F 5-F 6-F H 4-SCF-} 4-COPh 81 3-C1 4-Cl 5-Cl 6-Cl 4-Br 4-SFs 4-OCH^ 82 3-CF3 4-CF3 5-CF3 6-CF3 4-1 4-CH3 4-C(0)0Me 83 3-OCF^ 4-OCF^ 5-OCF-, 6-OCF3 4-CN 4-OPh 4-COM 84 3-OCH;CF^ 4-OCHtiCF^ 5-OCH-)CF^ 6-OCH?CF-} 4-NO*) 4-Ph 4-(4-CI-Ph) 85 4-CHoCF^ 4-CHoCH^ 4-nBu 4-sBu 4-nPr 4-tBu 4-iPr Tabfe 10 F 5 X2=H; R3= 86 3-CF^ 4-CH^ 4-OCF^ 4-CN 2-CF, 4-SCF^ 4-CHoCF^ 87 4-F 4-OCH3 4-COMe 3-OCF3 4-Ph 4-COPh' 4-OCHiCF^ 88 4-Cl 4-SF, 4-NO-> 4-CF-^ 4-OPh 4-tBu 4-(4-Cl-Ph) X2=C1; R3= 89 4-CF3 4-CH3 4-COPh 4-CN 4-OCF^ 4-SCF^ 4-OCH^CF^ 90 4-F 4-OCH^ 4-Ph 2-CF3 4-COMe 3-OCF, 4-CHoCF^ 91 4-Cl 4-SF^ 4-OPh 3-CF3 4-NO-) 4-tBu 4-(4-CI-Ph) WO 95/19972 PCT/US95/00208 X2=OMe: R3= 92 4-CF^ 4-CH^ 4-COPh 4-CN 4-OCF^ 3-OCFt, 4-CH-.CF1 93 4-F 4-OCH^ 4-Ph 4-SCF^ 4-COMe 2-CF:, 4-(4-Cl-Ph) 94 4-Cl 4-SF, 4-OPh 3-CF, 4-NO-> 4-tBu 4-OCHoCF-^ Table 11 F F X^=H; Q= COLUMN 1 2 3 4 5 6 95 (CH,hCH:t (CHo)RCH, (CHo)iPh 2-Pyr (CH9), ,0^ CHo-4-CI-Ph 96 (CH?)4CH, (CH2)qCH^ CHiPh 3-Pyr (CHo)fiCH^ (CH?)7CH, 97 (CH2)sCH^ (CH2>]f)CH^ 4-Pyr (CH,),Ph (CH2)4Ph (CH?)sPh X2=C1; Q= 98 (CHahCH, (CH,)RCH, (CH,bPh (CH,)7CH, (CH,)fiCHi 99 (CH2)4CH^ (CH9)qCHT 3-Pyr CHoPH (CH,)nCH, 100 (CH2)sCH^ (CH2)inCH^ 2-Pyr 4-Pyr CH?-4-Cl-Ph x2=OMe; Q= 101 (CH2),CH, (CH,)«CH, 4-Pvr (CH9hCH, (CHo)nCH, 102 (CH2)4CH, (CH?)„CH«, 2-Pyr (CH?bPh (CH,)fiCH, 103 (CH^CH, (CH,),nCH, CHoPH CH?-4-Cl-Ph 3-Pyr Table 12 WO 95/19972 PCT/US95/00208 26 0= COLUMN 1 2 3 4 5 6 104 (CH?),CH, (CH,)inCH, Ph 3-Pyr (CH^CH, CHo-4-Cl-Ph 105 (CH^CHi (CH2)nCH3 4-CN-Ph 4-Ph-Ph (CH3)RCH, 4-OCH?CFvPh 106 (CH^CH} 4-OCFvPh 3-CF^-Ph 2-Pyr CHoCHoPh 4-CFrPh 107 (CH?)fiCH, 4-Cl-Ph CHoPh 4-F-Ph (CH5)7CH, 2-F-Ph 10 Formulation/Utilitv Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent. Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 weight percent. Weight Percent Wettable Powders Oil Suspensions, Emulsions, Solutions, (including Emulsifiable Concentrates) Dusts Granules, Baits and Pellets High Strength Compositions Active Ingredient 5-90 5-50 1-25 0.01-99 90-99 Diluent 0-74 40-95 70-99 5-99.99 0-10 Surfactant 1-10 0-15 0-5 0-15 0-2 15 Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., lnterscience, New York, (1950). McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood. New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical 20 Publ. Co.. Inc., New York, (1964), list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, and the like. WO 95/19972 PCT/US95/00208 27 Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example. Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are 5 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, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pages 8-57 and following, and WO 91/13546. 10 For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15,39,41, 52,53, 58, 132,138 -140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; 15 and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989). In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-E. Example A 20 Wettable Powder Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% 25 montmorillonite (calcined) 23.0%. Example B Granule Compound 1 10.0% attapulgite granules (low volatile 30 matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. Example C Extruded Pellet Compound 1 25.0% 35 anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. WO 95/19972 PCT/US95/00208 28 Example p F.mulsifiahle Concentrate Compound 1 20.0% blend of oil soluble sulfonates i and polyoxyethylene ethers 10.0% isophorone 70.0%. The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" includes insects, mites and nematodes) which are pests of growing and stored 10 agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. Nevertheless, compounds of this invention display activity against one or more of the following pests: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, 15 root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, junveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders 20 Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabroiica undecimpunctata howardi), aster leafhopper . (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite {Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), 25 green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophiius), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice 30 stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (,Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus 35 cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi. Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus WO 95/19972 PCT/US95/00208 29 phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions. Compounds of this invention can also be mixed with one or more other insecticides, 5 fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as avermectin B, monocrotophos, 10 carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos. triflumuron. diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, 15 biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, imidacloprid, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimoiph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, 20 diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; 25 bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entomopathogenic bacteria, virus and fungi. In certain instances, combinations with other aithropodicides having a similiar spectrum of 30 control but a different mode of action will be particularly advantageous for resistance management. Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic 35 and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I. or WO 95/19972 PCT/US95/00208 30 compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic 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. Alternatively, granular formulations of these compounds can be applied to the plant 5 foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, m.croencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like. The compounds of this invention can be applied in their pure state, but most often 10 application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance 15 compound efficacy. The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active 20 ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. 25 The following TESTS demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-G for compound descriptions. The following abbreviations have been used in Index Tables A-G: Me = methyl, 30 Bu = butyl and Ph = phenyl. Index Table A WO 95/19972 PCTAJS95/00208 31 Compound 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 R1 A F C(0)0Me F C(0)NH2 F C(S)NH2 F C(0)Ph F C(0)0H F C(0)NHtBu F C(0)NH(CH2)ioCH3 F NH2 F OMe CI OMe F N(H)CH?(2-F-Ph) F CH=CH(Ph) F CH=CH(4-F-Ph) F m.p, (°C) oil* 148-149 138-139 oil* 149-150 67-70 54-55 81-85 oil* oil* oil* oil* wax* 125-130 oil" oil* 134-136 WO 95/19972 PCT/US95/00208 32 19 * see Index Table G for spectral data. Index Table B Compound G2 R3 m.D. (°C) 20 NH 4-Cl 123-129 2.1 NH 4-tBu 140-144 22 O 4-tBu 63-65 23 NH 4-CN 159-163 24 NH 4-OMe 144-147 25 NH 4-NO, 160-168 26 NH 4-CF3 144-147 27 NH 4-Me 101-103 28 NH 4-Br 135-138 29 NH 3-N02 158-160 30 NH 3-CN 170-172 31 NH 3-OMe 78-79 32 NH 3-CF3 130-133 33 NH 3-Me oil* * see Index Table G for spectral data. Index Tab)? C wax" WO 95/19972 PCT/US95/00208 33 Compound R3 nt,p- CO 34 4-tBu 117-120 35 2-F. 4-CF, 146-147 36 4-Ph 195-197 37 3-OPh 134-135 38 3-COPh 193-194 39 4-CF, 153-155 40 2-F 116-119 41 H 151-152 42 4-OMe 152-153 43 4-OPh 134-135 44 4-OCF3 145-146 45 4-CHO 174-175 46 4-1 168-173 47 4-{4-Cl-Ph) 168-170 48 2,4-diF 144-145 49 4-F 158-160 50 2-OMe 98-101 51 2-F, 4-(4-Cl-Ph) 138-139 52 2,5-diF 152-154 fcxtex Tafrte P *r N Compound R3 53 4-CJ 54 4-CF3 55 4-tBu oil * see Index Table G for spectral data oil* 85-87 * ®WO 95/19972 Compound 56 57 58 59 60 61 62 63 64 65 PCT/US95/00208 34 Index Table E q m.p. CO (CH2)7CH3 55-58 CH=CH(CH2)5CH3 59-60 CH=CH(4-CI-Ph) 152-154 N(HK4-Cl-Ph) 165-169 2-pyridyl 126-129 OMe 92-93 2-naphthyl 73-76 OC(Ph) 114-116 OsC(4-Cl-Ph) 134-135 168-170 Index Table F 5 WO 95/19972 PCT/US95/00208 35 Comoound Q m.p. f°C) 68 Ph 109.5-110.5 69 4-F-Ph 101.5-102 70 4-CI-Ph 111-113 71 4-Br-Ph 125 72 4-Me-Ph 81.5-82 73 4-F-3-Me-Ph 101-102 74 3-F-Ph 108 75 3,5-diF-Ph 128-129 76 4-tBu-Ph oil* 77 4-OCF3-Ph oil* 78 4-(4-Me-Ph>Ph 131-139 79 CH2(2-F-4-CF3-Ph) 61-63 CMPP I NMR (CDCI3): 4 *H NMR (CDCI3): 9 1HNMR(CDC13): 10 1HNMR(CDC13): II NMR (CDC13): 12 'H NMR (CDCI3): 13 1HNMR(CDC13): 16 !H NMR (CDCI3): 18 1HNMR(CDC13): 19 1HNMR(CDC13) * see Index Table G for spectral data. INDEX TABLE G Spectral Data 8 7.43 (m,lH); 6.98 (t,2H); 5.00 (ABq,lH); 4.63-4.72 (m,2H); 3.84 (s,3H). 8 8.24 (d,2H), 7.30-7.70 (m,4H), 6.93 (t,2H), 5.79 (t,lH), 5.14 (t,lH), 4.60 (t,lH). 8 7.42 (m,lH), 6.98 (m,2H), 5.59 (t,lH), 4.42 (d,lH), 4.27 (d.lH), 3.55 (s, 3H). 8 7.35 (m,lH), 7.25 (m,lH), 7.05 (m,lH), 5.60 (m,lH), 4.42 (m,lH), 4.30 (m, IH), 3.55 (s,3H). 84.10 (ABq,2H), 4.13 (t,lH), 4.52 (t.lH), 5.35 (t,lH), 6.92-7.45 (m,7H). 8 7.50-7.20 (m,6H), 6.98 (t,2H), 6.71 (d,lH), 6.28 (dd.lH), 5.08 (q.lH), 4.67 (t, IH), 4.24 (t,lH). 8 7.43 (m,lH), 7.37 (m,2H), 7.00 (m,4H), 6.65 (d,lH), 6.18 (dd,lH), 5.06 (q.lH), 4.66 (t,lH), 4.23 (t,lH). 8 3.71 (s,3H), 4.67 (m,2H), 6.99 (m,3H), 7.30-7.70 (m,4H). 84.05 (ABq,2H), 4.10 (t,lH), 4.55 (t,lH), 5.36 (t,lH), 6.95 (t,2H), 7.35-7.55 (m,9H). 8 7.55-7.35 (m,9H), 6.99 (t,2H). 6.73 (d,lH), 6.33 (dd,lH), 5.10 (q,lH), 4.68 (t,lH), 4.26 (t,lH). WO 95/19972 PCT/US95/00208 36 33 !H NMR (Me2SO-<*6): 8 10.20 (s,lH), 7.70 (m,lH), 7.30 (s.lH), 7.45 (d,lH), 7.20-7.32 (m,3H), 6.94 (d,lH), 5.06 (t,lH), 4.63-4.69 (m,2H), 2.29 (s,3H). 53 !H NMR (CDC13): 8 8.58 (s,lH), 7.72 (d.2H), 7.39 (m,3H), 7.01 (t,2H), 6.12 (t,lH), 4.75 (t,lH), 4.39 (t,lH). 55 *H NMR (CDCI3): 8 8.59 (s,lH), 7.72 (d,2H), 7.44 (m,3H), 6.99 (t,2H), 6.10 (t, IH), 4.72 (t,lH), 4.36 (t,lH), 1.33 (s,9H). 76 *H NMR (Me2SO): 8 7.62 (m,lH), 7.24 (t,2H), 7.16 (d,2H), 6.69 (d,2H), 6.2 (d,lH), 5.80 (q,lH), 4.65 (UH), 4.18 (t,lH), 1.22 (s,9H). 77 NMR (Me2SO): 8 7.62 (m,lH), 7.25 (t,2H), 7.14 (d,2H), 6.84 (d,2H), 6.75 (d,lH), 5.85 (q,lH), 4.70 (t,lH), 4.20 (t,lH). testa Spvthem Corn Rpotwgrm Test units, each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm2 plug (1 square inch) of a wheatgerm diet, were prepared. Solutions of each of the test compounds in 5 75/25 acetone/distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.). After the spray on the cups had dried, five second-instar larvae of the southern com rootworm ([Diabrotica undecimpunctata howardi) were placed 10 into each cup. The cups were held at 27°C and 50% relative humidity for 6-8 days. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 54. TESTS Two-Spotted Spiter Mite Pieces of kidney bean leaves, each approximately 2.54 cm2 (1 square inch) in area, that 15 had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75/25 acetone/distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kilograms of active ingredient per hectare (about 0.5 pounds per acre) at 20 207kPa (30 p.s.i.). The leaf squares were then placed underside-up on square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface. The test units were held at 27°C and 50% relative humidity for 7 days and read for larvacide/ovacide mortality Of the compounds tested, the following gave activity levels of 80% or higher: 5, 7, 12,13, 19,20 and 25 27. </div>

Claims

<div class="application article clearfix printTableText" id="claims"> WO 95/19972 PCT/US95/00208 . • i 37 testc Two-Spotted Spider Mite A solution of the test compound was prepared by dissolving it in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 100 ppm. Two-week old red kidney bean plants infested with two-spotted spider mite eggs (Tetranychus urticae}were sprayed to run-off with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity and scored for activity seven days after spray. Of the compounds tested, 80% or greater control was achieved using the following compounds: 7,11*, 12, 13, 16*, 18*, 19, 35,40*. 41*, 44*. 48*, 49*, 51*, 53,56, 57,58, 68*, 70*, 71*, 72*, 74*, 76*, 77* and 79*. * - tested at 50 ppm. WO 95/19972 PCT/US95/00208 Pn- 38 CLAIMS

1. A compound of the formula ®q —-z. 279591 'N R1 R2 5 wherein: A is selected from the group A-1 **x X1 A-2 S A A-3 ^2 ' and A-4 A-5 A-6 10 15 20 25 B is selected from the group O and N-Y; E is selected from the group C]-C4 alkyl and Cj-C4 haloalkyi; X1 and Z are independently selected from the group O and S\/ X2 is selected from the group H, halogen, CJ-C4 alkyl, CpC4 haloalkyi, Cj-C4 alkoxy, C1-C4 haloalkoxy, Ci-C4 alkylthio, C(0)0R13 and CN; Y is selected from the group H, Cj-Cg alkyl, Cj-C6 haloalkyi, C2-Cg alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, CHO, C(0)R16, C(0)0R16, C(S)R16, C(S)OR16, C(S)SR16, ccOCfOJOR1®, C(0)CH2C(0)0R16, S(0)tR16, S(0)2CH2C(0)0R16 P(X)(ORl8)2, S(O)tN(R13)C(O)0R12, S(0)tN(R^)Rl5, N=CR10RU, OR9, NR^R50; phenyl optionally substituted with 1-3 substituents independently selected from W1; and Cj-C6 alkyl substituted with 1-3 substituents independently selected from the group C,-C3 alkoxy, C,-C3 haloalkoxy, CN, N02, S(0)tR'6 P(X)(OR!8)2> C(0)R16, C(0)0R16 and phenyl optionally substituted with 1-3 substituents independently selected from W1; X is selected from the group O and S; 39 ' 9 5 9 1 G1 is seleaed from the group single bond. C(=X1). C(=X1)N(Y), C(=X1)0 and S(0)2: wherein the carbonyl or thiocarbonvl carbon is attached to B of A-1: G- is seleaed from the group single bond, O, S and N-Y; G- is selected from the group single bond, 0 and N-Y; G4 is selected from the group single bond, 0 and N-Y; G5 is selected from the group single bond, O, S and N-Y; G^ is seleaed from the group C2-C4 alkenylene. C2-C4 alkynylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene; Q is selected from the group H and J; or Q is selected from the group Cj-C^ alkyl, Cj-Cig haloalkyi, C2-CAg alkenyl, C2-Cig haloalkenyl, C2-Cjg alkynyl, C^-Cjg haloalkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W; J is a 5- or 6-membered aromatic ring containing Oto 4 heteroatoms independently seleaed from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur; or J is a 9- to 14-membered aromatic ring system selected from the group fused bicylic ring and fused tricylic ring, each ring system containing 0 to 6 heteroatoms independently seleaed from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; wherein J is optionally substituted with 1-4 substituents independently selected from the group R3; R1 is seleaed from the group halogen, CpCg alkyl, CpCg haloalkyi, Cj-Cg alkoxy, Cj-Cg haloalkoxy, S(0)tR16, CN and N02; R2 is seleaed from the group H, halogen, C^-Cg alkyl, C^Cg haloalkyi, Cj-Cg alkoxy, Cj-Cg haloalkoxy, S(0)tR16, CN and N02; R3 is seleaed from the group halogen, Cj-Cig alkyl, Cj-Cig haloalkyi, C2-Cjg alkenyl, C2-Cig haloalkenyl, C2-Cig alkynyl, C2-C1(5 haloalkynyl, C^-C^ alkoxyalkyl, C2-Cxg alkylthioalkyl, Cj-Cjg nitroalkyl, C2-Cjg cyanoalkyl, Cj-Cjg alkoxycarbonylalkyl. C3-Cg cycloalkyl, C3-C5 halocycloalkyl, CN, N3, SCN, N02, SH, S(0)tR16, OCHO, OR20, CHO, C(0)R21, C(0)0R21, C(0)NR16R17, S(0)2NR16R17, C(R4)=NR9, N=CR4R9, NR^RH, NR17C(0)R16, NR17C(0)NHR16, NR17S(0)2R16, Si(R6)(R7)(R8), SF5 and M-J1: R4 is selected from the group halogen, C^-Cg alkyl, Cj_-Cg haloalkyi, Cj-Cg alkoxy, Cj-Cg haloalkoxy and phenyl optionally substituted with R5; R5 is seleaed from the group halogen, CN, N02, Cj-Cg alkyl. Cj-Cg haloalkyi, CpCg alkoxy, CrCg haloalkoxy, C(0)R16, C(0)OR16 and Si(R6)(R7)(R8): R° and R~ are independendy C^-C^ alkyl; ^amended sheet t 2 7 94ULil WO 95/19972 # w ptfr/tf&5/0(fe08 i 40 R8 is selected from the group C]-Ci2 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1; R9 is selected from the group H, Cj-C4 alkyl, C]-C4 haloalkyi, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(0)R16, C(0)0R16, 5 C(0)NR16R17, S(0)2NR16R17, S(0)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1; R10 is selected from the group H, CrC4 alkyl, C(0)R16 and C(0)0R16; R11 is selected from the group H, C]-C4 alkyl, C]-C4 haloalkyi and phenyl 10 optionally substituted with 1-3 substituents independendy selected from W1; or R10 and R11 are taken together as (CH2)4 or ((^2)5; R12 is C,-C18 alkyl; R13 is C,-C4 alkyl; 15 R14 and R15 are independently Ci~C4 alkyl; or R14 and R15 are taken together as (CH2)4, (CH2)s or CH2CH2OCH2CH2; R16 is selected from the group CrC6 alkyl, CrCg haloalkyi, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C2-Cg alkoxyalkyl, Co-C^ alkylthioalkyl, CpC6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonyl-20 alkyl, C3-Q5 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1; R17 is selected from the group H and Cj-C4 alkyl; or 25 R16 and R17, when attached to the same atom, are taken together as (CH2)4, (CH2)5 or CH2CH2OCH2CH2, each group optionally substituted with 1-3 CH3; R18 is selected from th6 group C1-C3 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1; 30 R19 is selected from the group halogen, CN, N02, C \ -C$ alkyl, C j -C6 haloalkyi, OR9, C(0)R16, C(0)0R16 and Si(R6)(R7)(R8); R20 is selected from the group H, C]-C4 alkyl, Cj-C4 haloalkyi, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(0)Rl6, C(0)0R16, C(0)NR16R17, S(0)2NR,6R17 and S(0)2R16; 35 R21 is selected from the group Cj-C6 alkyl, Cj-Cg haloalkyi, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C^-Cg alkylthioalkyl, Cj-Cg nitroalkyl, C2-Cg cyanoalkyl, C3-C8 alkoxycarbonylalkyl, Cj-Cg cycloalkyl, C3-Cg halocycloalkyl and C4-C7 cycloalkylalkyl; 41 279591 M is selected from the group direct bond, S. O, C(O), C(0)-Cj-C2 alkylene, C(0)0-C1-C2 alkylene. C1-C4. alkylene, O-C1-C4 alkylene, O-C2-Q alkenylene and O-C2-C4 alkynylene; provided that when M is 0-C1-C4 alkylene, O-C2-C4 alkenylene or O-C2-C4 alkynylene. the oxygen atom is attached to the J ring; and when M is C(0)0-C1-C2 alkylene. the C(O) is attached to the J ring; J1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R19; or J1 is a 5-or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the 10 ring optionally substituted with 1-4 substituents independently selected from R19; W is selected from the group J, NO2, CN, OH, Q-Cg alkoxy and Cj-Cg haloalkoxy; W1 is selected from the group, halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyi, Ci-C2 alkoxy, Cj-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl, and C1-C2 haloalkylsulfonyl; 15 q is 0,1 or 2; and t is 0, 1 or 2; provided that, when A is A-2 and Q is unsubstituted C1-C3 alkyl, then R1 and R- are other than' nitro in the 4-position.

2. A compound according to Claim 1 wherein: 20 A is A-1; Q is selected from the group J, CpCjg alkyl and C2-Cig alkenyl; and J is seleaed from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R3.

3. A compound according to Claim 2 wherein: 25 S Q is J; and J is phenyl optionally substituted with 1-3 substituents independently selected from the group R3.

4. A compound according to Claim 3 wherein: G1 is C(O); 30 R1 is selected from the group F and CI in the 2-position; ^ R2 is selected frcrn the group H, F and CI in the 6-position; R3 is independendy selected from the group, halogen, C^-Cg alkyl.

Cj-Cg haloalkyi, OR20 and M-J1; R20 is seleaed from the group C|-C4 alkyl and CpC4 haloalkyi: and 35 J1 is seleaed from the group phenyl, thienyl, pyridyl and furyl- A compound according to Claim 4 which is: j..; - ■ 8 1W 1^3 AMENDED h": I 27 9 59 1 WO 95/19972 PCTAJS95/00208 42 N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoro-methyl)benzamide.

6. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to Claim 1 and a carrier therefor. 5

7. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound according to Claim 1.

8. A compound as claimed in claim 1 as specifically set forth herein.

9. A process for the preparation of a compound of claim 1 substantially as herein described with reference to Examples 1 to 6.

10. An arthropodicidal composition comprising a compound of claim 1 substantially as herein described with reference to Examples A to D.

11. A method as claimed in claim 7 substantially as herein described. END OF CLAIMS </div>