CN1231663A - Arthropodicides and fungicides cyclic amides - Google Patents

Abstract

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful as fungicides and arthropodicides, wherein A is O; S; N; NR<5>; or CR<14>; G is C or N; provided that when G is C, then A is O, S or NR<5> and the floating double bond is attached to G; and when G is N, then A is N or CR<14> and the floating double bond is attached to A; W is O; S; NH; N(C1-C6alkyl); or NO(C1-C6alkyl); X is OR<1>; S(O)mR<1>; or halogen; R<1> is C1-C6alkyl; C1-C6haloalkyl; C2-C6alkenyl; C2-C6haloalkenyl; C2-C6alkynyl; C2-C6haloalkynyl; C3-C6cycloalkyl; C2-C4alkylcarbonyl; or C2-C4alkoxycarbonyl; R<2> is H; C1-C6alkyl; C1-C6haloalkyl; C2-C6alkenyl; C2-C6haloalkenyl; C2-C6alkynyl; C2-C6haloalkynyl; C3-C6cycloalkyl; C2-C4alkylcarbonyl; C2-C4alkoxycarbonyl; hydroxy; C1-C2alkoxy; or acetyloxy; m is 0, 1 or 2; and E, R<5>, Y, Z and R<14> are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling plant diseases caused by fungal plant pathogens which involves applying an effective amount of a compound of Formula (I). Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling arthropods which involves contacting the arthropods or their environment with an effective amount of a compound of formula (I).

Description

Arthropodicides and fungicides cyclic amides

Background of the invention

This invention relates to certain cyclic amides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides and arthropodicides.

Control of plant diseases caused by fungal phytopathogens is extremely important for obtaining high yields. Plant diseases that damage ornamental, vegetable, pasture, cereal and fruit crops can cause significant reductions in productivity and thus increased costs to consumers. Control of arthropod pests is also extremely important for high yields. Arthropods that cause damage to the growth and storage of agricultural crops cause significant reductions in productivity and thus increased costs to consumers. Control of arthropod pests is also important in forestry, greenhouse crops, ornamental plants, nursery crops, stored food and fiber products, livestock, household, public and animal health. Many products for these purposes are commercially available, but there is still a need for new compounds that are highly effective, low-cost, low-toxic, environmentally safe, or have different modes of action.

SUMMARY OF THE INVENTION

The present invention relates to compounds of formula I, including all geometric isomers and stereoisomers thereof, N-oxides and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides and arthropodicides the use of: wherein E is selected from: i) 1,2-phenylene optionally substituted by one of R ³ , R ⁴ , or both R ³ and R ⁴ ; ii) a naphthalene ring provided that when G and Y are attached to the same When on a ring, G and Y are attached to adjacent members of the ring, said naphthalene ring being optionally substituted by one of R ³ , R ⁴ , or both R ³ and R ⁴ ; and III) the ring system, Selected from 5-12 membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1-6 heteroatoms independently selected from nitrogen, oxygen and sulfur, provided that each heterocyclic ring system contains Up to 4 nitrogen atoms, up to 2 oxygen atoms and up to 2 sulfur atoms, each fused bicyclic ring system optionally contains one non-aromatic ring optionally including one or two Q as ring members and Optionally includes one or two ring members independently selected from C(=O) and S(O) ₂ provided that G is attached to the aromatic ring, and when G and Y are attached to the same ring, then G and Y is attached to adjacent members of the ring, and each aromatic heterocyclic ring system is optionally substituted by one of R ³ , R ⁴ , or both R ³ and R ⁴ ; A is O, S, N, NR ⁵ or CR ¹⁴ ; G is C or N, provided that when G is C, then A is O, S or NR ⁵ and floating (floating) double bonds are connected on G; and when G is N, then A is N or CR ¹⁴ And the floating double bond is connected to A; W is O, S, NH, N(C ₁ -C ₆ alkyl) or NO(C ₁ -C ₆ alkyl); X is OR ¹ , S(O) _m R ¹ or halogen; R ¹ is C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkylcarbonyl or C ₂ -C ₄ alkoxycarbonyl; R ² is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ halo Alkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, hydroxyl, C ₁ -C ₂ alkoxy or acetoxy; R ³ and ^R4 is each independently halogen, cyano, nitro, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl , C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, formyl, C ₂ -C ₆ alkylcarbonyl , C ₂ -C ₆ alkoxycarbonyl; NH ₂ C(O), (C ₁ -C ₄ alkyl) NHC(O), (C ₁ -C ₄ alkyl) ₂ NC(O), Si(R ²⁵ ) ₃ , Ge(R ²⁵ ) ₃ , (R ²⁵ ) ₃ Si-C≡C-, or phenyl, phenylethynyl, benzoyl or phenylsulfonyl, each substituted by R ⁸ and optionally Substituted by one or more R ¹⁰ ; or when E is 1,2-phenylene and R ³ and R ⁴ are attached to adjacent atoms, R ³ and R ⁴ can be taken together as C ₃ -C ₅ alkylene C ₃ -C ₅ haloalkylene, C ₃ -C ₅ alkenylene or C ₃ -C ₅ haloalkenylene, each optionally substituted by 1-2 C ₁ -C ₃ alkyl ; R ⁵ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl , C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkylcarbonyl or C ₂ -C ₄ alkoxycarbonyl; Y is -O-, -S(O ) _n -, -NR ¹⁵ -, -C(=O)-, -CH(OR ¹⁵ )-, -CHR ⁶ -, -CHR ⁶ CHR ⁶ -, -CR ⁶ =CR ⁶ -, -C≡C- , -CHR ¹⁵ O-, -OCHR ¹⁵ -, -CHR ¹⁵ S(O) _n -, -S(O) _n CHR ¹⁵ , -CHR ¹⁵ ON=C(R ⁷ )-, -(R ⁷ )C= N-OCH(R ¹⁵ )-, -C(R ⁷ )=NO-, -ON=C(R ⁷ )-, -CHR ¹⁵ OC(=O)N(R ¹⁵ )-, -CHR ¹⁵ OC(= S)N(R ¹⁵ )-, -CHR ¹⁵ OC(=O)O-, -CHR ¹⁵ OC(=S)O-, -CHR ¹⁵ OC(=O)S-, -CHR ¹⁵ OC(=S) S-, -CHR ¹⁵ SC(=O)N(R ¹⁵ )-, -CHR ¹⁵ SC(=S)N(R ¹⁵ )-, -CHR ¹⁵ SC(=O)O-, -CHR ¹⁵ SC(= S)O-, -CHR ¹⁵ SC(=O)S-, -CHR ¹⁵ SC(=S)S-, CHR ¹⁵ SC(=NR ¹⁵ )S-, CHR ¹⁵ (R ¹⁵ )C(=O)N (R ¹⁵ )-, CHR ¹⁵ ON(R ¹⁵ )C(=O)N(R ¹⁵ )-, CHR ¹⁵ ON(R ¹⁵ )C(=S)N(R ¹⁵ )-, CHR ¹⁵ ON=C( R ⁷ )NR ¹⁵ -, CHR ¹⁵ ON=C(R ⁷ )OCH ₂ -, CHR ¹⁵ ON=C(R ⁷ )-N=N-, CHR ¹⁵ ON=C(R ⁷ )-C(=O) -, CHR ¹⁵ ON=C(R ⁷ )-C(=NA ² -Z ¹ )-A ¹ -, CHR ¹⁵ ON=C(R ⁷ )-C(R ⁷ )=NA ² -A ³ -,- CHR ¹⁵ ON=C(-C(R ⁷ )=NA ² -Z ¹ )-, CHR ¹⁵ ON=C(R ⁷ )-CH ₂ O-, CHR ¹⁵ ON=C(R ⁷ )-CH ₂ S- , -O-CH ₂ CH ₂ ON=C(R ⁷ )-, -CHR ¹⁵ OC(R ¹⁵ )=C(R ⁷ )-, -CHR ¹⁵ OC(R ⁷ )=N-, -CHR ¹⁵ SC( R ⁷ )=N-, -C(R ⁷ )=N-NR ¹⁵ , -CH=NN=C(R ⁷ )-, -CHR ¹⁵ N(R ¹⁵ )-N=C(R ⁷ )-, - CHR ¹⁵ N(COCH ₃ )-N=C(R ⁷ )-, -OC(=S)NR ¹⁵ C(=O)-, -CHR ⁶ -C(=W ¹ )-A ¹ -, -CHR ⁶ CHR ⁶ -C(=W ¹ )-A ¹ -, -CR ⁶ =CR ⁶ -C(=W ¹ )-A ¹ -, -C≡CC(=W ¹ )-A ¹ -, -N=CR ⁶ -C(=W ¹ )-A ¹ -, or a direct bond, and the directionality of the Y bond is defined as: the part connected to the left side of the bond is connected to E, and the part on the right side of the bond is connected to Z; Z ¹ is H or -A ³ -Z ² -; W ¹ is O or S; A ¹ is O, S, NR ¹⁵ or a direct bond; A ² is O, NR ¹⁵ or a direct bond; A ³ is -C(= O)-, -S(O) ₂ - or a direct bond; Z ² is selected from: i) C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl and C ₂ -C ₁₀ alkynyl, each Optionally substituted by one or more R ¹⁰ ; ii) C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkenyl and phenyl, each optionally substituted by one or more R ¹⁰ ; iii) ring System, selected from 3-14 membered monocyclic, fused bicyclic and fused tricyclic non-aromatic heterocyclic ring systems, and 5-14 membered monocyclic, fused bicyclic and fused tricyclic aromatic Heterocyclic systems each containing 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur, provided that each heterocyclic system contains up to 4 nitrogen atoms, up to 2 oxygen atoms and up to 2 sulfur atoms , each non-aromatic or aromatic heterocyclic ring system is optionally substituted by one or more R ¹⁰ ; iv) polycyclic ring systems selected from 8-14 membered fused bicyclic and fused tricyclic systems, these systems are An aromatic carbocyclic ring system, a non-aromatic carbocyclic ring system, or a ring system containing one or two non-aromatic rings, each non-aromatic ring including one or two Q as ring members and one or two independent Ring members selected from C(=O) and S(O) ₂ , and any other remaining rings that are aromatic carbocycles, each polycyclic ring system is optionally substituted by one or more R ¹⁰ ; and v) any Selected by one or more R ¹⁰ substituted adamantyl (adamantyl); each R ⁶ is independently H, 1-2CH ₃ , C ₂ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₃ - C ₆ cycloalkyl, formylamino, C ₂ -C ₄ alkylcarbonylamino, C ₂ -C ₄ alkoxycarbonylamino, NH ₂ C(O)NH, (C ₁ -C ₃ alkyl) NHC ( O)NH, (C ₁ -C ₃ alkyl) ₂ NC(O)NH, N(C ₁ -C ₃ alkyl) ₂ , piperidinyl, morpholinyl, 1-2 halogen, cyano or nitro ; each R ⁷ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylthio group, C ₁ -C ₆ haloalkylsulfinyl group, C ₁ -C ₆ haloalkyl group Sulfonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkane radical, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, halogen, cyano, nitro, hydroxyl, amino, NH(C ₁ -C ₆ alkyl), N(C ₁ -C ₆ alkyl) ₂ or morpholinyl; Z is selected from: i) C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkenyl and phenyl, each substituted by R ^and optionally substituted by one or more ^R10 is substituted; ii) the ring system is selected from 3-14 membered monocyclic rings, fused bicyclic rings and fused tricyclic non-aromatic heterocyclic ring systems, and 5-14 membered monocyclic rings, fused bicyclic rings and fused tricyclic aromatic heterocycle systems each containing 1 to 6 heteroatoms independently selected from nitrogen, oxygen and sulfur, provided that each heterocycle system contains up to 4 nitrogen atoms, up to 2 Oxygen atom and up to 2 sulfur atoms, each non-aromatic or aromatic heterocyclic ring system is substituted by R ⁹ and optionally one or more R ¹⁰ ; iii) polycyclic ring system selected from 8-14 membered fused Bicyclic and fused tricyclic ring systems, which are aromatic carbocyclic ring systems, non-aromatic carbocyclic ring systems, or ring systems containing one or two non-aromatic rings, each non-aromatic ring including one or two Q as ring members and one or two ring members independently selected from C(=0) and S(0) ₂ , and any remaining rings as aromatic carbocycles, each ^polycyclic ring system consisting of R substituted and optionally substituted by one or more R ¹⁰ ; and iv) adamantyl substituted by R ⁹ and optionally substituted by one or more R ¹⁰ ; each Q is independently selected from -CHR ¹³ -, -NR ¹³ -, -O- and -S(O) _p -; R ⁸ is H, 1-2 halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyloxy, CO ₂ (C ₁ -C ₆ alkyl), NH(C ₁ -C ₆ alkyl), N(C ₁ -C ₆ alkyl) ₂ , cyano, nitro, SiR ¹⁹ R ²⁰ R ²¹ or GeR ¹⁹ R ²⁰ R ²¹ ; R ⁹ is C ₁ -C ₆ alkyl substituted by 2-3 C ₁ -C ₃ alkoxy groups, C ₂ -C ₄ alkyne substituted by one hydroxyl group or 1-3 C ₁ -C ₄ alkoxy groups Base, C ₂ -C ₆ haloalkynyl, selected from 1-4 halogen, 1-2 C ₁ -C ₃ alkyl, 1-2 C ₁ -C ₃ alkoxy and a Z ³ C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl or C ₃ -C ₆ cycloalkoxy substituted by at least one member of C 3 -C 6 cycloalkoxy, each optionally consisting of at least one member selected from 1-2 halogen, 1 -2 C ₁ -C ₃ alkyl, 1-2 C ₁ -C ₃ alkoxy and a Z ³ member substitution, adamantyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylthioalkyl, C ₂ -C ₆ cyanoalkyl, C ₃ -C ₆ alkoxyalkenyl, C ₇ -C ₁₀ tetrahydropyranyloxyalkynyl, from cyano, C (=O)OR ²⁶ or C(=O)N(R ²⁶ ) ₂ substituted C ₁ -C ₃ alkoxy, C ₃ -C ₆ haloalkenyloxy, C ₃ -C ₆ alkynyl Oxygen, C ₃ -C ₆ haloalkynyloxy, C ₂ -C ₆ alkoxyalkoxy, C ₅ -C ₉ trialkylsilylalkoxyalkoxy, C ₂ -C ₆ Alkylthioalkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₆ haloalkylsulfinyl substituted by cyano, C(=O)OR ²⁶ or C(=O)N(R ²⁶ ) ₂ Acyl, C ₁ -C ₆ Haloalkylsulfonyl, C ₃ -C ₆ Alkenylthio, C ₅ -C ₆ Haloalkenylthio, C ₃ -C ₆ Alkynylthio, C ₃ -C ₆ Halo Alkynylthio, C ₂ -C ₆ alkoxyalkylthio, C ₂ -C ₆ alkylthioalkylthio, thiocyanoxy, hydroxyl, mercapto, amino, N(R ²⁶ )(R ²⁸ ), SiR ²² R ²³ R ²⁴ , GeR ²² R ²³ R ²⁴ , (R ²⁵ ) ₃ Si-C≡C-, OSi(R ²⁵ ) ₃ , OGe(R ²⁵ ) ₃ , C(=O)R ²⁹ , C(=S)R ²⁶ , C(=O)OR ³⁰ , C(=S)OR ²⁶ , C(=O)SR ²⁶ , C(=S)SR ²⁶ , C(=O)N(R ²⁶ ) ₂ , C(=S)N(R ²⁶ ) ₂ , C(=NR ²⁶ )OR ²⁷ , OC(=O)R ²⁶ , OC(=S)R ²⁶ , SC(=O)R ²⁶ , SC(= S)R ²⁶ , N(R ²⁶ )C(=O)R ²⁶ , N(R ²⁶ )C(=S)R ²⁶ , OC(=O)OR ²⁷ , OC(=O)SR ²⁷ , OC(= O)N(R ²⁶ ) ₂ , SC(=O)OR ²⁷ , SC(=O)SR ²⁷ , S(O) ₂ OR ²⁶ , S(O) ₂ N(R ²⁶ ) ₂ , OS(O) ₂ R ²⁷ or N(R ²⁶ )S(O) ₂ R ²⁷ ; or R ⁹ is benzyloxy, benzyloxymethyl, phenylethynyl, phenoxymethyl, phenylthio, phenylsulfonyl, Benzylthio, pyridylmethyl, pyridylmethoxy, pyridyloxymethyl, pyridylethynyl, pyridylthio, thienylmethyl, thienylthio, furylmethyl, furyloxy Base, furylthio, pyrimidinylmethyl or pyrimidinylthio, each optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² on the aromatic ring; or R ⁹ is substituted by 1 -2 C 2 -C ₆ alkyl, C ₂ -C ₆ alkoxy substituted by phenyl, naphthyl, phenoxy, benzyloxy, pyridyl, pyrimidinyl, thienyl or furyl, _each aromatic ring Optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; or R ⁹ is -A ⁴ -Z ⁴ ; each R ¹⁰ is independently halogen, and is replaced by 1-3 C ₁ -C ₃ Alkoxy-substituted C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkylthioalkyl, C ₂ -C ₆ cyanoalkane radical, C ₃ -C ₆ alkoxyalkynyl, C ₇ -C ₁₀ tetrahydropyranyloxyalkynyl, benzyloxymethyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ Haloalkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ haloalkenyloxy, C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy C ₃ -C ₆ Cycloalkoxy, C ₂ -C ₆ Alkoxyalkoxy, C ₅ -C ₉ Trialkylsilylalkoxyalkoxy, C ₂ -C ₆ Alkylthioalkoxy Oxygen, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ alkyl Sulfonyl, C ₁ -C ₄ Haloalkylsulfonyl, C ₃ -C ₆ Alkenylthio, C ₃ -C ₆ Haloalkenylthio, C ₃ -C ₆ Alkynylthio, C ₃ -C ₆ Haloalkynylthio, C ₂ -C ₆ alkoxyalkylthio, C ₂ -C ₆ alkylthioalkylthio, nitro, cyano, thiocyanoxy, hydroxyl, mercapto, N(R ²⁶ ) ₂ , SF ₅ , Si(R ²⁵ ) ₃ , Ge(R ²⁵ ) ₃ , (R ²⁵ ) ₃ Si-C≡C-, OSi(R ²⁵ ) ₃ , OGe(R ²⁵ ) ₃ , C(R ¹⁸ )=NOR ¹⁷ , C(=O)R ²⁶ , C(=S)R ²⁶ , C(=O)OR ²⁶ , C(=S)OR ²⁶ , C(=O)SR ²⁶ , C(=S )SR ²⁶ , C(=O)N(R ²⁶ ) ₂ , C(=S)N(R ²⁶ ) ₂ , C(=NR ²⁶ )OR ²⁷ , OC(=O)R ²⁶ , OC(=S) R ²⁶ , SC(=O)R ²⁶ , SC(=S)R ²⁶ , N(R ²⁶ )C(=O)R ²⁶ , N(R ²⁶ )C(=S)R ²⁶ , OC(=O) OR ²⁷ , OC(=O)SR ²⁷ , OC(=O)N(R ²⁶ ) ₂ , SC(=O)OR ²⁷ , SC(=O)SR ²⁷ , S(O) ₂ OR ²⁶ , S(O ) ₂ N(R ²⁶ ) ₂ , OS(O) ² R ²⁷ , N(R ²⁶ )S(O) ₂ R ²⁷ , or phenyl, benzyl or phenoxy, each optionally represented on the phenyl ring by One of R ¹¹ and R ¹² or both R ¹¹ and R ¹² are substituted; or when Y and one R ¹⁰ are connected to the adjacent atom on Z and Y is CHR ¹⁵ ON=C(R ⁷ )-, -ON= C(R ⁷ )-, -O-CH ₂ CH ₂ ON=C(R ⁷ )-, -CHR ¹⁵ OC(R ¹⁵ )=C(R ⁷ )-, CH=NN=C(R ⁷ )-, -CHR ¹⁵ N(R ¹⁵ )-N=C(R ⁷ )- or -CHR ¹⁵ N(COCH ₃ )-N=C(R ⁷ )-, then R ⁷ and the adjacently connected R ¹⁰ can be Together -(CH ₂ ) _r -J-, so J is also connected to Z; J is -CH ₂ -, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -N(R ¹⁶ )CH ₂ - or -CH ₂ N(R ¹⁶ ), each CH ₂ group of J is optionally substituted by 1-2 CH ₃ ; Z ³ is benzene Base, naphthyl, 1H-pyrrolyl, furyl, thienyl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1H-1,2,3 -Triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-oxadiazole Base, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1H-tetrazolyl, 2H-tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl , pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl or 1,2,4,5-tetrazinyl, each optionally represented by one of R ¹¹ , R ¹² Or both R ¹¹ and R ¹² are substituted; R ⁴ is O, S, linear or branched C ₁ -C ₆ alkylene, or a direct bond; Z ⁴ is selected from: i) 1H-pyrrolyl, 1H- Pyrazolyl, 1H-imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H -1,2,4-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5 -oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-Thiadiazolyl, 1H-tetrazolyl, 2H-tetrazolyl, pyridazinyl, pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl and 1,2,4,5-tetrazinyl, each optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; ii) a ring system selected from 3-14 membered monocyclic rings , fused bicyclic and fused tricyclic non-aromatic heterocyclic ring systems, and 8-14 membered fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each containing 1-6 independent Heteroatoms selected from nitrogen, oxygen and sulfur, provided that each heterocyclic ring system contains up to 4 nitrogen atoms, up to 2 oxygen atoms and up to 2 sulfur atoms, each non-aromatic or aromatic heterocyclic system optionally Substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; and iii) polycyclic ring systems selected from 8-14 membered fused bicyclic and fused tricyclic systems, which are aromatic carbon Ring systems, non-aromatic carbocyclic ring systems, or ring systems containing one or two non-aromatic rings, each non-aromatic ring comprising one or two Q as ring members and one or two independently selected from C (=O) and S(O) _ring members, and any remaining rings that are aromatic carbocycles, each polycyclic ring system optionally consists of one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² Substitution; each R ¹¹ and each R ¹² is independently 1-2 halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ halo Alkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₂ -C ₆ alkoxyalkyl, C ₁ -C ₆ alkylthioalkyl, C ₃ -C ₆ alkoxyalkynyl, C ₇ -C ₁₀ tetrahydropyranyloxyalkynyl, benzyloxymethyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ haloalkenyloxy, C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ haloalkynyloxy, C ₂ -C ₆ alkoxyalkoxy, C ₅ -C ₉ trialkylsilylalkoxyalkoxy, C ₂ -C ₆ alkylthioalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfinyl, C ₃ - C ₆ alkenylthio, C ₃ -C ₆ haloalkenylthio, C ₂ -C ₆ alkylthioalkylthio, nitro, cyano, thiocyanoxy, hydroxyl, mercapto, N(R ²⁶ ) ₂ , SF ₅ , Si(R ²⁵ ) ₃ , Ge(R ²⁵ ) ₃ , (R ²⁵ ) ₃ Si-C≡C-, OSi(R ²⁵ ) ₃ , OGe(R ²⁵ ) ₃ , C(= O)R ²⁶ , C(=S)R ²⁶ , C(=O)OR ²⁶ , C(=S)OR ²⁶ , C(=O)SR ²⁶ , C(=S)SR ²⁶ , C(=O) N(R ²⁶ ) ₂ , C(=S)N(R ²⁶ ) ₂ , OC(=O)R ²⁶ , OC(=S)R ²⁶ , SC(=O)R ²⁶ , SC(=S)R ²⁶ , N(R ²⁶ )C(=O)R ²⁶ , N(R ²⁶ )C(=S)R ²⁶ , OC(=O)OR ²⁷ , OC(=O)SR ²⁷ , OC(=O)N( R ²⁶ ) ₂ , SC(=O)OR ²⁷ , SC(=O)SR ²⁷ , S(O) ₂ OR ²⁶ , S(O) ₂ N(R ²⁶ ) ₂ , OS(O) ₂ R ²⁷ or N (R ²⁶ )S(O) ₂ R ²⁷ , or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridylethynyl, each optionally on the aromatic ring It consists of 1-2 independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro and cyano Group substitution; each R ¹³ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or optionally composed of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano substituted phenyl; R ¹⁴ is H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl , C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl or C ₃ -C ₆ cycloalkyl; Each R ¹⁵ is independently H, C ₁ -C ₃ alkyl, C ₃ -C ₆ cycloalkyl, or phenyl or benzyl, each of which is optionally composed of halogen, C ₁ -C ₄ alkane on the benzene ring C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano; or when Y is -CHR ¹⁵ N(R ¹⁵ )C(= When O)N(R ¹⁵ )-, two R ¹⁵ connected to the nitrogen atom of the group can be taken together as -(CH ₂ ) _s -; or when Y is -CHR ¹⁵ ON=C(R ⁷ )NR ¹⁵ -, R ⁷ and adjacently connected R ¹⁵ can be together as -CH ₂ -(CH ₂ ) _s -, -O-(CH ₂ ) _s -, -S-(CH ₂ ) _s - or N(C ₁ -C ₃ alkyl)-(CH ₂ ) _s -, and the directionality of the bond is defined as such that the part next to the left side of the bond is connected to carbon, and the part on the right side of the bond is connected to nitrogen; R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently H, C ₁ -C ₃ alkyl, C ₃ -C ₆ cycloalkyl or optionally composed of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano substituted phenyl; R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently C ₁ -C ₆ Alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₄ alkoxy or phenyl; R ²⁴ is C ₁ -C ₄ haloalkyl; each R ²⁵ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ alkoxy or phenyl; each R ²⁶ is independently H, C ₁ -C ₆ alkane C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl or phenyl or benzyl, each of which on the benzene ring is optionally composed of 1-2 independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro and cyano group substitution; each R ²⁷ is independently C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl or phenyl Or benzyl, each on the benzene ring is optionally composed of 1-2 independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ haloalkoxy, nitro and cyano group substitution; each R ²⁸ is independently C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl or phenyl or benzyl, each of which is optionally selected from 1-2 independently selected Substituted from halogen, C _{1 -C 4} alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C 4 alkoxy, C ₁ -C ₄ haloalkoxy, nitro and cyano; each R ²⁹ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, or on the benzene ring, optionally 1-2 independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl , C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro and cyano groups substituted benzyl; each R ³⁰ is H, C ₁ -C ₆ haloalkyl, C ₂ - C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl or phenyl or benzyl Each group on the benzene ring is optionally composed of 1-2 independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ Haloalkoxy, nitro and cyano group substitution; m, n and p are each independently 0, 1 or 2; r is 0 or 1; and s is 2 or 3; provided that when Y is -CH(OR ¹⁵ )-, -CHR ⁶ -, -CHR ⁶ CHR ⁶ -, -CR ⁶ =CR ⁶ -, -C≡C-, -CHR ¹⁵ O-, -OCHR ¹⁵ -, -S(O) _n CHR ¹⁵ - , -(R ⁷ )C=N-OCH(R ¹⁵ )-, -CHR ¹⁵ ON=C(R ⁷ )-CH ₂ O-, -CHR ¹⁵ OC(R ¹⁵ )=C(R ⁷ )-, - CHR ⁶ -C(=W ¹ )-A ¹ -, -CHR ⁶ CHR ⁶ -C(=W ¹ )-A ¹ -, -CR ⁶ =CR ⁶ -C(=W ¹ )-A ¹ -or- When C≡CC(=W ¹ )-A ¹ -, then Z is not phenyl, furyl, thienyl, pyridyl and pyrimidyl.

Detailed description of the invention

In the above description, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl" refers to straight chain or branched chain alkyl, such as methyl, ethyl, n-propyl, iso - Propyl or the different butyl, pentyl or hexyl isomers. The term "1-2 methyl groups" means that a substituent may be methyl, or when one hydrogen is attached to the same atom, both the substituent and the hydrogen may be methyl. The term "1-2 alkyl groups" refers to positions where one or two substituents are available, which may be independently selected alkyl groups. "Alkenyl" includes straight or branched chain 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 or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" also includes multiple triple bond moieties such as 2,5-hexadiynyl. "Alkylene" means a straight chain (or branched chain when noted) alkanediyl group. Examples _of "alkylene _" include _{CH2CH2 ,} CH( _{CH3 ) , CH2CH2CH2 , CH2CH} ( _CH3 ) _{, CH2CH2CH2CH2 ,} and _{CH2CH2CH2CH 2CH2 .} "Alkenylene" means a straight-chain alkenediyl group containing one olefinic bond. Examples _of "alkenylene" include _CH2CH =CH, _CH2CH2CH =CH, _CH2CH = _CHCH2 and _CH2CH = _{CHCH2CH2 .} "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, alkoxy and hexyloxy isomers. The term "1-3 alkoxy groups" refers to the position where one to three substituents can be independently selected, and the substituents may be alkoxy groups, and the term "1-2 alkoxy groups" is defined similarly. "Alkoxyalkyl" means an alkoxy group substituted on an alkyl group. _{Examples of " alkoxyalkyl " include CH3OCH2 , CH3OCH2CH2 , CH3CH2OCH2 , CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2 . _} "Alkoxyalkoxy" means an alkoxy group substituted on an alkoxy group. "Alkenyloxy" means a straight or branched alkenyloxy moiety. Examples of "alkenyloxy" include H ₂ C=CHCH ₂ O, (CH ₃ ) ₂ C=CHCH ₂ O, (CH ₃ )CH=CHCH ₂ O, (CH ₃ )CH=C(CH ₃ ) _CH2O and _CH2 = _{CHCH2CH2O .} "Alkynyloxy" means a straight or branched chain alkynyloxy moiety. Examples _{of "} alkynyloxy" include _HC≡CCH2O , _CH3C≡CCH2O and _{CH3C≡CCH2CH2O .} "Alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio and the different propylthio, butylthiopentylthio and hexylthio isomers. "Alkylthioalkyl" means an alkylthio group substituted on an alkyl group. _{Examples of " alkylthioalkyl " include CH3SCH2 , CH3SCH2CH2 , CH3CH2SCH2 , CH3CH2CH2CH2SCH2 , and CH3CH2SCH2CH2 .} "Alkylthioalkylthio" means an alkylthio group substituted on an alkylthio group. Similarly, "alkoxyalkylthio" means an alkoxy group substituted on an alkylthio group, and "alkylalkoxy" means an alkylthio group substituted on an alkoxy group. "Alkylsulfinyl" includes both enantiomers of alkylsulfinyl. Examples of "alkylsulfinyl" include _CH3S (O), _{CH3CH2S (} O) _{, CH3CH2CH2S} (O) _, ( _CH3 ) _2CHS (O) and different butyl isomers of sulfinyl, pentylsulfinyl and hexylsulfinyl. Examples of "alkylsulfonyl" include CH ₃ S(O) ₂ , CH ₃ CH ₂ S(O) ₂ , CH ₃ CH ₂ CH ₂ S(O) ₂ , (CH ₃ ) ₂ CHS(O) ₂ and Different isomers of butylsulfonyl, pentylsulfonyl and hexylsulfonyl. "Cyanoalkyl" refers to an alkyl group substituted with a cyano group. Examples _of "cyanoalkyl" include _NCCH2 , _NCCH2CH2 and _CH3CH (CN) _CH2 . "Alkenylthio", "alkoxyalkynyl" and the like are defined similarly to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkoxy" includes the same groups attached through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups having more than one double bond such as 1,3- and 1,4-cyclohexadienyl. "Trialkylsilylalkoxyalkoxy" means a trialkylsilylalkoxy group substituted on an alkoxy group. Examples of "trialkylsilylalkoxyalkoxy" include, for example, (CH ₃ ) ₃ SiCH ₂ CH ₂ OCH ₂ O. The term "1-2 phenyl" refers to the position where one or two substituents that are phenyl are available. The term "aromatic carbocyclic ring system" includes entirely aromatic rings and carbocycles in which at least one ring in the polycyclic ring system is aromatic (herein aromatic means satisfying Huckel's rule). The term "non-aromatic carbocyclic ring system" refers to fully saturated carbocyclic rings as well as partially or fully unsaturated carbocyclic rings, wherein none of the rings in the ring system satisfy Huckel's rule. The term "aromatic heterocyclic ring system" includes entirely aromatic heterocyclic rings and carbocyclic rings in which at least one ring in the polycyclic ring system is aromatic (herein aromatic means satisfying Huckel's rule). The term "non-aromatic heterocyclic ring system" refers to fully saturated heterocyclic rings as well as partially or fully unsaturated heterocyclic rings, wherein none of the rings in the ring system satisfy Huckel's rule. The heterocyclic ring system is attached through any available carbon or nitrogen replacing a hydrogen on the carbon or nitrogen. Those skilled in the art will understand that not all nitrogen-containing heterocycles are capable of forming N-oxides, since the nitrogen requires an available lone pair of electrons for oxidation to oxides; those skilled in the art will recognize that nitrogen-containing heterocycles Rings can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Those skilled in the art are well aware of synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines, including the use of peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl peroxidation Hydrogen such as tert-butyl hydroperoxide, sodium perborate and dioxanes such as dimethyldioxane to oxidize heterocycles and tertiary amines. These methods of preparing N-oxides are extensively described and reviewed in the literature, see for example: TL Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, SV Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnikin Comprehensive Heterocyclic Chemistry, Vol.3, pp18-20, AJ Boulton and A. McKillop, Eds., Pergamon Press; MR Grimmett and BRT Keene in Advances in Heterocyclic Chemistry, Vol.43, pp149-161, ARKatritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, Vol.9, pp 285-291, ARKatritzky and AJ Boulton, Eds., Academic Press; and GWH Cheeseman and ESG Werstiuk in Advances in Heterocyclic Chemistry, Vol.22, pp 390-392, ARKatritzky and AJ Boulton Eds., Academic Press.

The term "halogen", alone or as a compound word such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halo" refers to a position where one or two substituents, which may be halo, are independently optionally available. Also, when a compound word such as "haloalkyl" is used, the alkyl group may be partially or completely substituted with halogen atoms which may be the same or different. Examples _of "haloalkyl" include _F3C , _ClCH2 , _CF3CH2 and _{CF3CCl2 .} The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", etc. are defined similarly to the term "haloalkyl". Examples of "haloalkenyl" include (Cl) ₂ C=CHCH ₂ and CF ₃ CH ₂ CH=CHCH ₂ . Examples of "haloalkynyl" include HC≡CCHCl, _CF3C≡C , _CCl3C≡C and _{FCH2C≡CCH2 .} Examples _of "haloalkoxy" include _{CF3O , CCl3CH2O , HCF2CH2CH2O} and _{CF3CH2O .} Examples _of "haloalkylthio" _{include CCl3S} , _CF3S , _CCl3CH2S and _{ClCH2CH2CH2S .} Examples of "haloalkylsulfinyl" include CF ₃ S(O), CCl ₃ S(O), CF ₃ CH ₂ S(O) and CF ₃ CF ₂ S(O). Examples of "haloalkylsulfonyl" include CF ₃ S(O) ₂ , CCl ₃ S(O) ₂ , CF ₃ CH ₂ S(O) ₂ and CF ₃ CF ₂ S(O) ₂ .

The total number of carbon atoms in a substituent is indicated by the "C _i -C _j " prefix, where i and j are numbers from 1-10. For example, C ₁ -C ₃ alkylsulfonyl refers to methylsulfonyl to propylsulfonyl. Examples of "alkylcarbonyl" include C(O) _CH3 , C(O) _CH2CH2CH3 and C( _O )CH( _{CH3 ) 2} . Examples of "alkoxycarbonyl" include CH ₃ OC(=O), CH ₃ CH ₂ OC(=O), CH ₃ CH ₂ CH ₂ OC(=O), (CH ₃ )CHOC(=O) and different The butoxy- or pentyloxycarbonyl isomers. In the above description, when the compound of formula I is composed of one or more heterocyclic rings, all substituents are connected through any available carbon atom or nitrogen atom, by replacing the hydrogen on the carbon atom or nitrogen atom on these rings.

When a group contains a substituent which is hydrogen, eg ^R8 or ^R13 , then (when the substituent is taken as hydrogen) it is understood that this is equivalent to the said group being unsubstituted.

The compounds of the invention may exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those skilled in the art will appreciate that one stereoisomer may be more potent and/or exhibit Beneficial effect. Furthermore, the skilled artisan knows how to separate, enrich and/or selectively prepare said stereoisomers. Accordingly, the present invention includes compounds selected from formula I, N-oxides and agriculturally acceptable salts. The compounds of the invention may also exist as mixtures of stereoisomers, as individual stereoisomers or as optically active forms.

Salts of compounds of the present invention include acid addition salts of inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid , propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or the acid addition salts of valeric acid. When the compound contains an acidic group such as phenol, the salts of the compounds of the present invention also include sodium, potassium and organic bases (such as pyridine, ammonia or triethylamine) or inorganic bases (such as hydride, hydroxide or salt, lithium salt, calcium salt, magnesium salt or barium salt).

In order to obtain better activity and/or easy synthesis, preferred compounds are:

Preferred 1. The above compounds of formula I and their N-oxides and agriculturally suitable salts: wherein E is selected from 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2- and 2,3-naphthalenediyl; 1H-pyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3 ,4-furandiyl; 2,3- and 3,4-thienediyl; 1H-pyrazole-1,5-, 3,4- and 4,5-diyl; 1H-imidazole-1,2- , 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazoldiyl; 3,4- and 4,5-isothiazolediyl ; 4,5-thiazoldiyl; 1H-1,2,3-triazole-1,5- and 4,5-diyl; 2H-1,2,3-triazole-4,5-diyl; 1H-1,2,4-triazole-1,5-diyl; 4H-1,2,4-triazole-3,4-diyl; 1,2,3-oxadiazole-4,5- Diyl; 1,2,5-oxadiazole-3,4-diyl; 1,2,3-thiadiazole-4,5-diyl; 1,2,5-thiadiazole-3,4 -diyl; 1H-tetrazole-1,5-diyl; 2,3- and 3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl ; 2,3-pyrazine-diyl; 1,2,3-triazine-4,5-diyl; 1,2,4-triazine-5,6-diyl; 1H-indole-1,4 -, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6 -, 3,7-, 1,2-2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2, 7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo [b] Thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 1H-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5 -, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 1H-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; 1,2-benzoisoxine Azole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2 ,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazole diyl; 1,2-benzisothiazole-3,4-, 3,5-, 3 ,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5- , 5,6- and 6,7-benzothiazyldiyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7- , 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7- and 7,8- Quinoline diyl; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-isoquinoline diyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-meat phenidinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and 7,8-phthalazindiyl; 2,5-, 2, 6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-quinazolines Diyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7- and 7,8-quinoxalinediyl; 1, 8-Naphthyridine-2,5-, 2,6-, 2,7-, 3,5-, 3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6 -, 2,7-, 4,6-, 4,7-, 6,7-pteridinediyl; pyrazolo[5,1-b]thiazole-2,6-, 2,7-, 3, 6-, 3,7-, 2,3- and 6,7-diyl; thiazolo[2,3-c]-1,2,4-triazole-2,5-, 2,6-, 5 ,6-diyl; 2-oxo-1,3-benzodioxol-4,5- and 5,6-diyl; 1,3-dioxo-1H-isoindole -2,4-, 2,5-, 4,5- and 5,6-diyl; 2-oxo-2H-1-benzopyran-3,5-, 3,6-, 3,7 -, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-diradicals; [1,2,4 ]triazolo[1,5-a]pyridine-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl; 3,4-Dihydro-2,4-dioxo-2H-1,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-, 5,6- , 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; Thieno[3,2-d]thiazole-2,5-, 2,6- and 5,6-diyl; 5,6,7,8 -Tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4 ,6-, 4,7-, 4,8-, 2,3- and 3,4-quinoline diyl; 2,3-dihydro-1,1,3-trioxo-1,2-benzene Aisothiazole-2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; 1,3-benzodioxyl Heterocyclopentene-2,4-, 2,5-, -4,5- and 5,6-diyl; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; 2,3-di Hydrogen-1,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and 5 ,6,7,8-Tetrahydro-4H-cyclohepta[b]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3 ,5-, 3,6-, 3,7-, 3,8- and 2,3-diyl; each aromatic ring system optionally consists of one of R ³ , R ⁴ or both R ³ and R ⁴ Substitution; W is O; R ¹ is C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl; R ² is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or C ₃ -C ₆ cycloalkyl; R ³ and R ⁴ are each independently halogen, cyano, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfonyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, (C ₁ -C ₄ alkane base) NHC(O), (C ₁ -C ₄ alkyl) ₂ NC(O), benzoyl or phenylsulfonyl; Y is -O-, -S(O) _n -, -NR ¹⁵ -, -C(=O)-, -CH(OR ¹⁵ )-, -CH ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, -OCH ₂ - , -CH ₂ S(O) _n -, -S(O) _n CH ₂ -, -CH ₂ ON=C(R ⁷ )-, -(R ⁷ )C=N-OCH(R ¹⁵ )-, - C(R ⁷ )=NO-, or a direct bond; R ⁷ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkane Thio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, halogen or cyano; or when Y and one R ¹⁰ are attached to the adjacent atom on Z And when Y is -CH ₂ ON=C(R ⁷ )-, then R ⁷ and the adjacent connection R ¹⁰ can be -(CH ₂ ) _r -J- together, so J is also connected to Z; Z is selected From C ₃ -C ₈ cycloalkyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, 1H-pyrrolyl, furyl, thienyl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, oxa Azolyl, isothiazolyl, thiazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1, 2,4-Triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl base, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1H-tetrazole Base, 2H-tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5- Tetrazinyl, 1H-indolyl, benzofuryl, benzo[b]thienyl, 1H-indazolyl, 1H-benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolinyl , isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthyridinyl, pteridinyl, 2,3-dihydro-1H-indenyl, 1, 2,3,4-tetrahydronaphthyl, 6,7,8,9-tetrahydro-5H-benzoheptenyl, 5,6,7,8,9,10-hexahydrobenzocyclooctenyl , 2,3-dihydro-3-oxobenzofuryl, 1,3-dihydro-1-oxoisobenzofuryl, 2,3-dihydro-2-oxobenzofuryl, 3,4-Dihydro-4-oxo-2H-1-benzopyranyl, 3,4-dihydro-1-oxo-1H-2-benzopyranyl, 3,4-dihydro -3-oxo-1H-2-benzopyranyl, 3,4-dihydro-2-oxo-2H-1-benzopyranyl, 4-oxo-4H-1-benzopyranyl Pyranyl, 2-oxo-2H-1-benzopyranyl, 2,3,4,5-tetrahydro-5-oxo-1-benzoxepinyl (benzoxepinyl), 2,3 ,4,5-tetrahydro-2-oxo-1-benzoxepeptyl, 2,3-dihydro-1,3-dioxo-1H-isoindolyl, 1,2,3 ,4-tetrahydro-1,3-dioxoisoquinolinyl, 3,4-dihydro-2,4-dioxo-2H-1,3-benzoxazinyl, 2-oxo- 1,3-benzodioxolyl, 2,3-dihydro-1,1,3-trioxo-1,2-benzisothiazolyl, 9H-fluorenyl, azulenyl and Thiazolo[2,3-c]-1,2,4-triazolyl, each group is substituted by R ⁹ and optionally substituted by one or more R ¹⁰ ; and R ¹⁵ is H, C ₁ -C ₃ alkyl or C ₃ -C ₆ cycloalkyl.

Preferred 2. Compounds of preferred 1, wherein: E is selected from 1,2-phenylene; 1,6-, 1,7-, 1,2- and 2,3-naphthalenediyl; 2,3- and 3,4- Furandiyl; 2,3- and 3,4-thiophenediyl; 2,3- and 3,4-pyridinediyl; 4,5-pyrimidinediyl; 2,4-, 2,7-, 3, 5-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; and benzo[b]thiophene-2,4-, 2,7-, 3,5- , 2,3-, 4,5-, 5,6- and 6,7-diyl; each aromatic ring system is optionally substituted by one of R ³ , R ⁴ or both R ³ and R ⁴ ; Z selected from phenyl, naphthyl, 2-thiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3, 4-Thiadiazolyl, pyridyl and pyrimidinyl, each group is substituted by ^R9 and optionally substituted by one or more ^R10 ; ^R7 is H, _C1 - _C6 alkyl, _C1 -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, cyclopropyl, halogen or cyano; R ⁹ is C ₃ -C ₆ substituted by at least one member selected from 1-2 halogen, 1-2 C ₁ -C ₃ alkyl, 1-2 C ₁ -C ₃ alkoxy and one Z ³ Cycloalkyl, C optionally substituted by at least one member selected from 1-2 halogen, 1-2 C ₁ -C ₃ alkyl, 1-2 C ₁ -C ₃ alkoxy and ^one Z ₃ -C ₆ cycloalkoxy, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ haloalkylsulfonyl, thiocyanooxy, SiR ²² R ²³ R ²⁴ , GeR ²² R ²³ R ²⁴ , (R ²⁵ ) ₃ Si-C≡C-, C(=O)R ²⁹ , C(=O)OR ³⁰ , S(O) ₂ OR ²⁶ , S(O) ₂ N(R ²⁶ ) ₂ or OS( O) ₂ R ²⁷ ; or R ⁹ is benzyloxy, phenylethynyl, phenoxymethyl, phenylthio, phenylsulfonyl, benzylthio, pyridylmethoxy, pyridyloxymethyl Base, pyridylethynyl or furyloxy, each optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² on the aromatic ring; or R ⁹ is substituted by 1-2 phenyl, C ₂ -C 6 alkyl or C ₂ -C ₆ alkoxy substituted by naphthyl, phenoxy, benzyloxy, pyridyl, pyrimidinyl _, thienyl or furyl, each aromatic ring is optionally represented by R ¹¹ , one of R ¹² or both R ¹¹ and R ¹² are substituted; or R ⁹ is -A ⁴ -Z ⁴ ; each R ¹⁰ is independently halogen, C ₁ -C ₄ haloalkyl, C ₂ -C ₆ alkyne group, nitro group, cyano group, Si(R ²⁵ ) ₃ or (R ²⁵ ) ₃ Si-C≡C-; or when Y and one R ¹⁰ are connected to the adjacent atom on Z and Y is -CH ₂ ON=C (R ⁷ )-, then R ⁷ and the adjacently connected R ¹⁰ can be -(CH ₂ ) _r -J- together, so that J is also connected to Z; J is -CH ₂ - or -CH ₂ CH ₂ -; Z ³ is phenyl, furyl, thienyl or pyridyl, each of which is optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; A ⁴ is a direct bond; Z ⁴ is 1,3-benzodioxolyl optionally substituted by one of R ¹¹ , R ¹² , or both R ¹¹ and R ¹² ; and r is 1.

Preferred 3. Preferred 2 compounds, wherein: E is selected from 1,2-phenylene; 2,3- and 3,4-thiophenediyl and 2,3- and 3,4-pyridinediyl; each aromatic ring system is any Optionally substituted by one of R ³ , R ⁴ or both R ³ and R ⁴ ; A is O or N; X is OR ¹ ; R ¹ is C ₁ -C ₃ alkyl; R ² is H or C ₁ - C ₂ alkyl; Y is -O-, -S(O) _n -, -NR ¹⁵ -, -C(=O)-, -CH(OR ¹⁵ )-, -CH ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S(O) _n -, -S(O) _n CH ₂ -, -CH ₂ ON= C(R ⁷ )-, -(R ⁷ )C=N-OCH(R ¹⁵ )-, -CH ₂ OC(=O)NH-, -CH ₂ SC(R ⁷ )=N- or a direct bond; Z is selected from phenyl, 2-thiazolyl, 1,2,4 ^{-thiadiazolyl, pyridyl and pyrimidinyl, each group is substituted by R and optionally substituted by one or more R 10 ;} R ⁷ is H, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio or cyclopropyl; and R ¹⁵ is H, C ₁ - C ₃ alkyl or cyclopropyl.

Preferred 4. The compound of preferred 3, wherein: R ¹ is methyl; R ² is methyl; Y is -O-, -CH ₂ O-, -CH ₂ ON=C(R ⁷ )- or -(R ⁷ )C= N-OCH(R ¹⁵ )-; R ⁹ is C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkoxy, SiR ²² R ²³ R ²⁴ , GeR ²² R ²³ R ²⁴ substituted by one Z ³ , (R ²⁵ ) ₃ Si-C≡C-, S(O) ₂ OR ²⁶ , S(O) ₂ N(R ²⁶ ) ₂ or OS(O) ₂ R ²⁷ ; or R ⁹ is benzyloxy, pyridine methoxy, each optionally substituted on the aromatic ring by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; or R ⁹ is C ₂ -C ₆ alkyl substituted by phenyl, so The phenyl group is optionally substituted by one of R ¹¹ and R ¹² or both R ¹¹ and R ¹² ; or R ⁹ is -A ⁴ -Z ⁴ ; each R ¹⁰ is independently halogen, C ₁ -C ₄ haloalkyl , C ₂ -C ₆ alkynyl or Si(R ²⁵ ) ₃ ; and Z ³ is a phenyl group optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ;

Preferred 5. The compound of preferred 4, wherein: Y is -O- or -CH ₂ ON=C(R ⁷ )-; and R ⁹ is C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ ring substituted by one Z ³ Alkoxy, SiR ²² R ²³ R ²⁴ , GeR ²² R ²³ R ²⁴ or (R ²⁵ ) ₃ Si-C≡C-; or R ⁹ is optionally selected from one of R ¹¹ , R ¹² on the aromatic ring or Benzyloxy substituted by both R ¹¹ and R ¹² ; or R ⁹ is -A ⁴ -Z ⁴ .

Most preferred are compounds selected from preferred 5 of the following: 4-[2-[[3-(1,3-benzodioxol-5-yl]-1,2,4-thiadi Azol-5-yl]oxy]phenyl]-2,4-5 dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; 4-[2 -[[[[1-[3-[Dimethyl(3,3,3-trifluoropropyl)silyl]phenyl]ethylene]amino]oxy]methyl]phenyl]-2, 4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; 4-[2-[3-[(2-chlorophenyl)methoxy Base]phenoxy]phenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; 4-[2-[[ 3-[1-(4-Chlorophenyl)cyclopropyl]-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5-methoxy -2-Methyl-3H-1,2,4-triazol-3-one; 4-[2-[[3-[1-(4-chlorophenyl)cyclopropyl]-1,2, 4-thiadiazol-5-yl]oxy]-6-methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazole- 3-keto; 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[1-[3-[tris(trifluoromethyl)germyl]benzene base]ethylene]amino]oxy]methyl]phenyl]-3H-1,2,4-triazol-3-one; and 2,4-dihydro-5-methoxy-2-methyl -4-[2-[3-[2-(Trimethylsilyl)ethynyl]phenoxy]phenyl]-3H-1,2,4-triazol-3-one.

The present invention also relates to fungicidal compositions comprising a fungicidally effective amount of a compound according to the invention and at least one surfactant, solid diluent or liquid diluent. Preferred compositions of the invention are those comprising the preferred compounds described above.

The present invention also relates to a method of controlling plant diseases caused by fungal plant pathogens, comprising applying to the plant or plant part, or to the seed or seedling, a fungicidally effective amount of a compound of the present invention (eg, a composition as described above). Preferred methods of use are those involving the preferred compounds described above.

The present invention also relates to arthropodicidal compositions comprising an arthropodicidally effective amount of a compound of the present invention and at least one surfactant, solid diluent or liquid diluent. Of note are the arthropodicidal compositions of the present invention comprising the preferred compounds described above.

The invention also relates to methods of controlling arthropods comprising contacting said arthropods or their environment with an arthropodicidally effective amount of a compound of the invention (eg, the compositions described above). It is worth noting that the arthropodicidal method used involves the preferred compounds described above.

Compounds notable for their arthropodicidal activity include: 4-[2-[[[[1-[3-[dimethyl(3,3,3-trifluoropropyl)silyl]phenyl ]ethylene]amino]oxy]methyl]phenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; 4 -[2-[[3-[1-(4-Chlorophenyl)cyclopropyl]-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro -5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; and 4-[2-[[3-[1-(4-chlorophenyl)cyclopropane Base]-1,2,4-thiadiazol-5-yl]oxy]-6-methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1, 2,4-Triazol-3-one.

Notable compounds are those wherein ^R9 is not N( ^R26 )( ^R28 ) and pyridyloxymethyl, and ^R9 is not _C2 - _C6 alkyl substituted by naphthyl, phenoxy, benzyloxy , each aromatic ring is optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² ; and R ⁹ is not substituted by 1-2 phenyl, naphthyl, phenoxy, benzyloxy, pyridyl , pyrimidyl, thienyl or furyl substituted C ₂ -C ₆ alkoxy, each aromatic ring is optionally substituted by one of R ¹¹ , R ¹² or both R ¹¹ and R ¹² .

Compounds of formula I can be prepared by one or more of the methods and modifications described in Schemes 1-41 below. E, A, G, W, X, R ¹ -R ³⁰ , Y, Z ¹ -Z ⁴ , W ¹ , A ¹ -A ⁴ , Z, Q, J, m, n, p, r and s are as defined above in the Summary of the Invention. Compounds of Formulas Ia-In are various subgroups of compounds of Formula I, and all substituents in Formulas Ia-In are as defined in Formula I above.

Those skilled in the art will recognize that certain compounds of formula I may exist in one or more tautomeric forms. For example, compounds of formula I wherein ^R2 is H may exist as tautomers Ia or Ib, or both Ia and Ib. The present invention includes all tautomeric forms of the compounds of formula I:

Compounds of formula I can be prepared as described in the following steps 1) to 5). Steps 1) to 4) describe the synthesis of the amide ring structure involving the formation of the aryl moiety (E-Y-Z). Step 5) describes the synthesis of the aryl moiety (E-Y-Z) with the amide ring already formed in situ.

1) Alkylation step

Compounds of formula I are prepared by treating compounds of formula 1 with an appropriate transalkylation reagent in an inert solvent with or without additional acidic or basic reagents or other reagents (Scheme 1). Suitable solvents are selected from polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide, ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether, ketones such as acetone or 2-butanone, hydrocarbons such as Toluene or benzene, and halogenated hydrocarbons such as methylene chloride or chloroform.

Process 1

X ¹ =OH,SH,NH ₂ , X=OR ¹ ,SR ¹

NH(C ₁ -C ₆ alkyl) or

NH(C ₁ -C ₆ alkoxy)

Method 1: U-CH=N ₂ (U=Hor(CH ₃ ) ₃ Si)

2

Method 3: (R ¹ ) ₃ O ⁺ BF ₄ ^-

4

Method 4: (R ¹ ) ₂ SO ₄ ; R ¹ OSO ₂ V; or R ¹ -halogen;

Optional base

(Halogen = F, Cl, Br, or I)

(V=C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or 4-CH ₃ -C ₆ H ₄ )

For example, the dicarbonyl compound of formula 1 can be prepared by the action of diazomethane reagent of formula 2 such as diazomethane (U=H) or trimethylsilane diazomethane (U=(CH ₃ ) ₃ Si) compound. The use of trimethylsilyldiazomethane requires a protic co-solvent such as methanol. See, for example, Chem. Pharm. Bull., (1984), 32, 3759 for examples of these procedures.

Compounds of formula I can also be prepared by contacting carbonyl compounds of formula 1 with alkyl trichloroacetimidates of formula 3 and a Lewis acid catalyst, as shown in Method 2. Suitable Lewis acids include trimethylsilyl triflate and tetrafluoroboric acid. Alkyl trichloroacetimidates were prepared from the appropriate alcohol and trichloroacetonitrile as described in the literature (J. Danklmaier and H. Honig, Synth. Commun., (1990), 20, 203).

Compounds of formula I can also be prepared from compounds of formula 1 by treatment with a trialkyloxonium tetrafluoroborate of formula 4 (ie, Meerwein's salt) (Method 3). The use of trialkyloxonium salts as strong alkylating agents is well known in the art (see U. Scholkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl., (1981), 20, 798) .

Other alkylating agents capable of converting carbonyl compounds of formula 1 into compounds of formula I are dialkyl sulfates such as dimethyl sulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alkyl halides such as iodine methane and propargyl bromide (Method 4). These alkylations can be carried out with or without an additional base. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undecyl -7-ene (DBU), triethylenediamine (see R.E. Benson, T.L. Cairns, J. Am. Chem. Soc., (1948), 70, 2115), such reagents were used in the alkylation examples.

Compounds of Formula 1a (compounds of Formula 1 where G=C, W=O and X'=OH) are prepared by condensing a malonate or a malonate derivative of Formula 5 with an amphiphilic nucleophile of Formula 6 (Process 2). The nucleophiles of Formula 6 are N-substituted hydroxylamines (HO-NHR ² ) and substituted hydrazines (HN(R ⁵ )-NHR ² ). Examples of such nucleophiles are N-methylhydroxylamine and methylhydrazine. Malonates of formula 5 can be prepared by methods described hereinafter. The corresponding carboxylic acid is formed by first hydrolyzing the ester, which is then converted to the acid chloride (T=Cl) with thionyl chloride or oxalyl chloride, or to the acyl imidazole by treatment with 1,1'-carbonyldiimidazole (T=1-imidazolyl) to activate the ester of formula 5. Compounds of formula 1aa can be prepared by reacting a cyanoester of formula 5b with an amphiphilic nucleophile of formula 6 (see: M.Scobie and G.Tennant, J.Chem.Soc., Chem.Comm., (1994), 2451 ). Alkylation of laa with an alkyl halide in the presence of a base provides compounds of formula 1ab. Alternatively, treatment of 1aa with alkylamines or alkoxyamines can provide compounds of formula 1ab.

Process 2

T=O(C ₁ -C ₄ alkyl), Cl, 1-imidazolyl

W=N(C ₁ -C ₆ alkyl) or NO(C ₁ -C ₆ alkyl)

According to A.Osuka, T.Kobayashi and H.Suzuki (Synthesis, (1983), 67) and M.S.Malamas, T.C.Hohman and J.Millen (J.Med.Chem., 1994, 37, 2043-2058) and process 3 Esters of formula 5a can be prepared by the copper(I)-catalyzed reaction of malonates of formula 7 with substituted aryl halides of formula 8 as illustrated. Methods for the preparation of compounds of formula 8 are described below (see Scheme 33).

Malonates of Formula 5a can also be prepared from diester carboxylic acids of Formula 5c by modifying their carboxylic acid functional groups with appropriate Y and Z groups. As shown in Scheme 3, the coupling reaction of copper (I)-catalyzed malonate of formula 7 with o-bromocarboxylic acid of formula 8a (see A.Bruggink, A.McKillop, Tetrahedron, (1975), 31 , 2607) can be used to prepare compounds of formula 5c. Methods for preparing compounds of formula 8a are common in the art (see P.Beak, V.Snieckus, Acc.Chem.Res., (1982), 15,306 and Org.React., (1979), 26,1 and references therein literature).

Process 3 R=C ₁ -C ₄ alkyl

Alternatively, aryl acetates of formula 5a can also be prepared by treating aryl acetates of formula 9 with dialkyl carbonate or alkyl chloroformate in the presence of a suitable base such as, but not limited to, sodium metal or sodium hydride. Malonate (Scheme 4). See, eg, J. Am. Chem. Soc., (1928), 50, 2758. Nitrile esters of formula 5b can be prepared analogously from compounds of formula 10.

R=C₁-C₄烷基

R=C₁-C₄烷基Process 4

R=C ₁ -C ₄ alkyl

R=C ₁ -C ₄ alkyl

According to scheme 5 described (see Org.Synth., Coll.Vol.I, (1941), 270), by the acid-catalyzed alcoholysis of formula 10 aryl acetonitrile or the esterification of formula 11 aryl acetic acid can prepare formula 9 ester.

Additionally, esters of formula 9 were prepared by palladium(0)-catalyzed cross-coupling reactions with aryl iodides of formula 8 with Reformatsky reagents or alkoxy(trialkylstannyl)acetylenes, followed by hydration (Scheme 5). See, for example, T. Sakamoto, A. Jutard, Yasuhara, Y. Kondo, H. Yamanaka, Synlett, (1992), 502, and J.F. Fauvarque, A. Jutard, J. Organometal. Chem., (1977), 132, C17.

R=C₁-C₄烷基Process 5

R=C ₁ -C ₄ alkyl

Aryl acetates of formula 9a can be prepared by subjecting an aryl halide of formula 12 to a compound of formula 13 in a copper(I) catalyzed condensation reaction as shown in EP-A-307103 and Scheme 6 below.

Process 6

R=C ₁ -C ₄ alkyl

Y1=O,S,OCHR ¹⁵ ,SCHR ¹⁵ ,ON=C(R ⁷ ),NR ¹⁵

Certain esters of Formula 9 (Formula 9b) can also be prepared by forming the Y ^bridge using conventional nucleophilic substitution chemistry (Scheme 7). Substitution of an appropriate leaving group (Lg) on a nucleophile of formula 15 or 16 with a nucleophilic ester of formula 14 provides a compound of formula 9b. The corresponding alkoxide or thiolate of the compound of formula 14 is generated using a base such as sodium hydride.

Process 7

R=C ₁ -C ₄ alkyl

Y ³¹ =OH,SH,CHR ^15OH ,CHR ^15SH ,NHR ¹⁵

Y ² =O,S,OCHR ¹⁵ ,SCHR ¹⁵ ,CHR ¹⁵ O,CHR ¹⁵ S,NR ¹⁵

Lg=Br,Cl,I,OSO ₂ CH ₃ ,OSO ₂ (4-Me-Ph)

Certain esters of formula 9 (formula 9a) can also be prepared by forming a ^Y3 bridge from a substituted hydroxylamine of formula 9a and a carbonyl compound of formula 14a. Hydroxylamine 9d can in turn be prepared from ester 9c. This method is described in EP-A-600835 and is illustrated in Scheme 8.

Process 8

9cB=CHR ¹⁵ Br R=C ₁ -C ₄ alkyl

9dB=CHR ¹⁵ ONH ₂ ·HCl Y ³ =CHR ¹⁵ ON=C(R ⁷ )

2) Substitute and conjugate addition/elimination methods

Compounds of formula I may also be prepared by reacting compounds of formula 17 with alkali metal alkoxides (R ¹ O ^- M ⁺ ), alkali metal thiolates (R ¹ S ^- M ⁺ ) or derivatives of amines in a suitable solvent (Process 9). The leaving group Lg ¹ of the amide of formula 17 is any group known in the art that is subject to such a substitution reaction. Examples of suitable leaving groups include chloro, bromo and sulfonyl and sulfonate groups. Examples of suitable inert solvents include dimethylformamide or dimethylsulfoxide, dimethoxyethanemethanol.

Process 9

X=OR ¹ , SR ¹ , NH ₂ , NHR ¹ ,

N(C ₁ -C ₆ alkyl) R ¹ , NH(C ₁ -C ₆ alkoxy) or

N(C ₁ -C ₆ alkoxy)R ¹

Lg ¹ = Cl, Br, -SO ₂ V or OSO ₂ V

V=C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or 4-CH ₃ -C ₆ H ₄

M=K or Na

Compounds of formula 17a can be prepared from compounds of formula 1b (compounds of formula 1 where X is OH) by reaction with a halogenating agent such as thionyl chloride or phosphorus oxybromide to form the corresponding β-halo-substituted derivatives (Scheme 10). Alternatively, treatment of compounds of formula 1b with alkylsulfonyl halides or haloalkylsulfonic anhydrides such as methanesulfonyl chloride, p-toluenesulfonyl chloride and trifluoromethanesulfonic anhydride can form the corresponding β-alkylsulfonate esters of formula 17a. The reaction with the sulfonyl halide can be carried out in the presence of a suitable base such as triethylamine.

Process 10

Lg ² =Cl, Br or -OSO ₂ V

V=C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or 4-CH ₃ -C ₆ H ₄

Halogen = Br, Cl or F

As shown in scheme 11, adopt the well-known oxidation method of sulfur (see Schrenk, K.In TheChemistry of Sulphones and Sulphoxides; Patai, S. et al., Eds.; Wiley: New York, 1988), make the corresponding formula 18 The sulfonyl compound of formula 17b can be prepared by oxidation of the thio compound. Suitable oxidizing agents include m-chloro-perbenzoic acid, hydrogen peroxide and Oxone ^_ (KHSO ₅ ).

Process 11

V=C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or 4-CH ₃ -C ₆ H ₄

Alternatively, as shown in Scheme 12, halogenated compounds of formula 17c (compounds of formula 17a where A=N, G=N and W=O) can be prepared from hydrazides of formula 19. When R ³² =C(=S)S(C ₁ -C ₄ alkyl), the diacyl compound of formula 19 is treated with an excess of thionyl halide, eg, excess thionyl chloride. The first product formed is a ring-closed compound of formula 20, which can be isolated or converted in situ to a compound of formula 17c (see P.Molina, A.T'arraga, A.Espinosa, Synthesis, (1989), 923 for this description of the method).

Alternatively, when ^R32 = ^R2 as defined above, hydrazides of formula 19 can be cyclized with phosgene to form cyclic ureas of formula 17c where halogen = Cl. This method is described in detail in J.Org.Chem., (1989), 54,1048.

Process 12

Hydrazides of formula 19 can be prepared as shown in Scheme 13. Condensation of an isocyanate ^{of formula 21 with a hydrazine of formula H2NNR2R32} _in ^an inert solvent such as tetrahydrofuran provides the hydrazide.

Process 13

R ³² =C(=S)S(C ₁ -C ₄ alkyl) or R ²

3) Conjugate addition/cyclization method

In addition to the methods described above, treatment of ketene dithioacetals of formula 22 with an amphinucleophile of formula 6 can prepare compounds of formula I where X = SR ¹ and G = C (formula Ic) (Scheme 14). The nucleophile of formula 6 is as described above.

Process 14

R=C ₁ -C ₄ alkyl

The ketene dithioethanol acetal of formula 22a or 22b can be prepared by condensing the aryl acetate of formula 9 or the amide of formula 9f respectively with carbon disulfide in the presence of a suitable base, followed by two equivalents of R ¹ -halide such as Prepared by reaction of iodomethane or propargyl bromide (Scheme 15). Conversion of 22b to 22c can be achieved by reaction with trialkyltetrafluoroborate.

Process 15

Compounds of formula 1d (compounds of formula 1 where A=N, G=N) can be prepared by condensation of N-amino-ureas of formula 23 with carbonylating reagents of formula 24 (Scheme 16). The carbonylating reagent of formula 24 is a carbonyl or thiocarbonyl transfer reagent such as phosgene, thiophosgene, diphosgene (ClC(=O)OCCl ₃ ), triphosgene (Cl ₃ COC(=O)OCCl ₃ ), N , N'-carbonyldiimidazole, N,N'-thiocarbonyldiimidazole and 1,1'-carbonylbis(1,2,4-triazole). Alternatively, the compound of formula 24 may be an alkyl chloroformate or a dialkyl carbonate. Some of these carbonylation reactions may require the addition of a base to facilitate the reaction. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, tertiary amines such as triethylamine and triethylenediamine, pyridine or 1,8-diazabicyclo [5.4. 0] Undec-7-ene (DBU). Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide, ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether, ketones such as acetone or 2-butanone, hydrocarbons such as toluene Or benzene, and halogenated hydrocarbons such as methylene chloride or chloroform. The reaction temperature can be varied from 0°C to 150°C and the reaction time can be varied from 1 to 72 hours according to the selection of base, solvent, temperature and substrate.

Process 16

T ¹ and T ² are independently Cl, OCCl ₃ , O(C ₁ -C ₄ alkyl), 1-imidazolyl, 1,2,4-triazolyl

X=OH or SH

X ¹ =O or S

N-amino-ureas of formula 23 can be prepared as described in Scheme 17. Treatment of arylamines of formula 25 with phosgene, thiophosgene, N,N'-carbonyldiimidazole or N,N'-thiocarbonyldiimidazole affords isocyanates or isothiocyanates of formula 26. Alkali can be added to react with phosgene or thiophosgene. Isocyanates of formula 26 can also be prepared by heating acyl azides of formula 25a in a solvent such as toluene or benzene (Curtius rearrangement). According to methods well known in the art (see March, J. Advanced Organic Chemistry; 3rd Edition, John Wiley: New York, (1985), pp 428, 637 and see Chem. Pharm. Bull (1977), 25, 165, and references therein) The corresponding acyl azides can be prepared. Subsequent treatment of the iso(thio)cyanate with an R ^substituted hydrazine yields the N-amino-urea of formula 23.

Process 17

CWCl ₂ , or

Compounds of formula 1e (compounds of formula 1 where A=CR ¹⁴ , G=N and X=O) can be prepared by any of the methods described in Scheme 18. Ureas of formula 27 can be reacted with activated 2-halocarboxylic acid derivatives such as 2-haloformyl chloride, 2-haloformate or 2-haloacyl imidazole. After the initial acylation on the arylamino nitrogen, intramolecular substitution of the 2-halo group proceeds to facilitate cyclization. A base may be added to accelerate acylation and/or subsequent cyclization. Suitable bases include triethylamine and sodium hydride. Alternatively, compounds of formula le can be prepared by reacting an iso(thio)cyanate of formula 26 or a carbodiimide of formula 26a with an ester of formula 28a. As mentioned above, a base may be added to accelerate the reaction and subsequent cyclization to compounds of formula le. Carbodiimides of formula 26a can be prepared as described in Scheme 18 starting from compounds of formula 26.

Process 18

23a 26a

W=O,S W=NT ⁵

T ⁵ =C ₁ -C ₆ alkyl; C ₁ -C ₆ alkoxy

(Thio)ureas or amidines of formula 27 can be prepared by one of the methods shown in scheme 19. As described above, an arylamine of formula 25 can be contacted with an isocyanate or isothiocyanate of formula ^R2N =C=W. Alternatively, iso(thio)cyanates of formula 26 or carbodiimides of formula 26a can be condensed with amines of formula ^R2 - ^NH2 to form ureas or amidines. Arylamines of formula 25 and iso(thio)cyanates of formula 26 are commercially available or prepared by well-known methods. For example, isothiocyanates can be prepared by the method described in J. Heterocycl. Chem., (1990), 27,407. Isocyanates can be found, for example, in March, J., Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp944, 1166 and in Synthetic Communications, (1993), 23(3), 335 and references therein Prepared by the method described. Can refer to MSGibsonin The Chemistry ofthe AminoGroup for the preparation method of the arylamine of the formula 25 that can not be bought commercially; Patai, S., Ed.; Interscience Publishers, 1968; P37 and TetrahedronLett.(1982), 23(7), 699 and references therein.

26:W=O,S26a:W=NT⁵ Process 19

26:W=O,S26a:W=NT ⁵

T ⁵ =C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy 4) The method of vulcanization is shown in scheme 20 (see Bull.Soc.Chim.Belg., (1978), 87,229; and Tetrahedron Lett. (1983), 24, 3815), by sulfuration reagents such as P ₂ S ₅ or Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3-dithio-2,4- diphosphetane-2,4-disulfide) to prepare compounds of formula Ie (compounds of formula I where W=S) by treating compounds of formula Id (I where W=O).

Process 20

Reaction of a compound of formula Iea with an alkyl halide in the presence of a base provides a compound of formula Ieb which can be reacted with a compound of formula ^T5NH2 which is then alkylated with ^R2- (Br, _Cl or I) to provide formula Iec compounds.

Process 20a

5) Synthetic method of aryl part (E-Y-Z)

Compounds of formula If (compounds of formula I wherein Y is CHR ¹⁵ O, CHR ¹⁵ S or CHR ¹⁵ ON=CR ⁷ ) can be prepared by contacting halides of formula 29 with various nucleophiles (Scheme 21). Treatment of the appropriate alcohol or thiol with a base such as sodium hydride forms the corresponding alkoxide or thiolate which can act as a nucleophile.

Process 21

Certain aromatic compounds of formula 29 are prepared by free radical halogenation of the corresponding alkyl compound (i.e., H in place of halogen in formula 29) or by acidic cleavage of the corresponding methyl ether (i.e., OMe in place of halo in compound of formula 29). base halides. Other aryl halides of formula 29 can be derived from formula 30 by halogenation methods well known in the art (see Carey, F.A.; Sundberg, R.J. Advanced Organic Chemistry; 3rd ed, Part B, Plenum: New York, (1990), p122). of suitable alcohols.

As shown in Scheme 22, compounds of formula I wherein Y is ^CR6 = ^CR6 or ^CHR6 - ^CHR6 (formulas Ig and Ih, respectively) can be prepared. Treatment of halides of formula 29a with triphenylphosphine or trialkylphosphite yields the corresponding phosphonium salt (formula 31) or phosphonate (formula 32), respectively. Condensation of a phosphorus-containing compound with a base and a carbonyl compound of formula Z(R ⁶ )C=O provides an alkene of formula Ig.

Process 22

Alkenes of formula Ig can be converted to saturated compounds of formula Ih by hydrogenation over metal catalysts such as palladium on charcoal according to methods well known in the art (see Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).

Alkynes of formula Ii can be prepared by halogenation/dehalogenation of alkenes of formula Ig using methods well known in the art (March, J. Advanced organic Chemistry; 3rd ed., John Wiley: New York, (1985), p924). Alternatively, alkynes of formula Ii are prepared by well-known reactions of aryl halides with derivatives of alkynes (see J. Organomet. Chem., (1975), 93 253-257) in the presence of catalysts such as nickel or palladium.

Alkenes of formula Ig can also be prepared by the reverse reaction of the reactants in a Wittig or Horner-Emmons condensation. For example, 2-alkylaryl derivatives of formula 33 can be converted to the corresponding dibromo compounds of formula 34 as shown in Scheme 23 (see Synthesis, (1988), 330). The dibromo compound can be hydrolyzed to a carbonyl compound of formula 35 which in turn is condensed with a phosphorus-containing nucleophile of formula 36 or 37 to provide an alkene of formula Ig. Alternatively, compounds of formula 35 can be prepared by oxidation of the corresponding alcohols of formula 30.

Vinyl halides of formula Ij are prepared by reacting a phosphorus-containing reagent of formula 37a or 37b with a carbonyl compound of formula 35 (Scheme 23). McKenna and Khawli in J. Org. Chem., (1986), 51, 5467 describe the preparation of halides of formula 37a from the appropriate diethyl phosphonoacetate. Thiocarbonyl esters of formula 37b can be prepared from esters of formula 37a by converting the carbonyl oxygen of the ester to a thiocarbonyl group (see Chem. Rev., (1984), 84, 17 and Tetrahedron Lett., (1984), 25, 2639 ).

Process 23

Oximes of formula Ik (wherein Y is C(R ⁷ )=NO compound of formula I) (Scheme 24). Alternatively, the O-substituted hydroxylamines can be condensed with carbonyl compounds of formula 38 to directly produce oximes of formula Ik.

Process 24

Carbamates of formula Il can be prepared by reacting alcohols of formula 30 with isocyanates of formula 39 (Scheme 25). A base such as triethylamine can be added to catalyze the reaction. As shown, carbamates of formula Il can be further alkylated to provide carbamates of formula Im.

Process 25

Compounds of formula I, wherein Y is -CHR ¹⁵ ON=C, can be prepared by methods known in the art or various modifications (see, for example, WO95/18789, WO95/21153 and references therein) combined with the methods disclosed herein. (R ⁷ )-C(=NA ² -Z ¹ )-A ¹ -, -CHR ¹⁵ ON=C(R ⁷ )-C(R ⁷ )=NA ² -A ³ -or-CHR ¹⁵ ON=C( -C(R ⁷ )=NA ² -Z ¹ )-.

Compounds of formula I wherein Y is -CHR ¹⁵ OC(=O)O- , -CHR ¹⁵ OC(=S)O-, -CHR ¹⁵ OC(=O)S-, -CHR ¹⁵ OC(=S)S-, -CHR ¹⁵ SC(=O)N(R ¹⁵ )-, - CHR ¹⁵ SC(=S)N(R ¹⁵ )-, -CHR ¹⁵ SC(=O)O-, -CHR ¹⁵ SC(=S)O-, -CHR ¹⁵ SC(=O)S-, -CHR ¹⁵ SC(=S)S-, -CHR ¹⁵ SC(=NR ¹⁵ )S-, or -CHR ¹⁵ N(R ¹⁵ )C(=O)N(R ¹⁵ )-.

In the presence of a suitable base (such as potassium carbonate, KO-t-Bu or sodium hydride), in a suitable solvent (for example, acetone, dimethylformamide, dimethylsulfoxide or tetrahydrofuran), the compound of formula 40 Compounds of formula In (wherein Y is (CH ₂ ) _x O (compound of formula Ia where x = 0 or 1)) (see Scheme 26).

Process 26

Can prepare formula Lg-Z compound according to the method of literature, for example, according to ComprehensiveHeterocyclic Chemistry, Pergamon Press, Vol.6,1984, pp463-511 or J.Org.Chem.(1973), 38,469 or J.Het.chem.( 1979), the method for preparing 1,2,4-thiadiazole described in 961, according to U.S.5166165 or J.Chem.Soc.Perkin Trans.1 (1983), described in 967, prepare 1,3,4-oxo The method of oxadiazole and 1,3,4-thiadiazole is prepared according to the method for preparing 1,2,4-oxadiazole described in EP446010 or J.Med.Chem.(1992), 35,3691.

Compounds of the invention are prepared by combinations of reactions described in Schemes 1-26, wherein Z is a moiety as defined in the Summary. A person skilled in the art can accomplish ^{the reaction sequence containing the group Z 5 (} Z as described in the overview, and L ( defined as any group attached to Z, as in The preparation of said compounds where ) is substituted) is described in each individual scheme. This reaction sequence can be formed on the basis of known reactions available in the art. For a general reference see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985) and references therein. See the following paragraphs and schemes for the preparation of certain embodiments defined by L in a single scheme, and representative examples of ^Z5 -L. Noting that ^Z is given as the following group in Schemes 27-41, such compounds represented by the methods set forth in Schemes 1-26 can be further modified by the chemistry described to provide Formula I as described in the Summary compound. Z ⁵ =Z

Compounds of formula 42 in Scheme 27 can be prepared by reacting compounds of formula 41 with hydroxylamine or hydroxylammonium salts (see method in Sandler and Karo, Organic Functional Group Preparations, Vol.3 Academic Press, New York, (1972) 372-381 review). The compound of formula 42 corresponds to the compound of formula 13 in scheme 6 (when Y ¹ =ON=C(R ⁷ )) and the reagent HO-N=CR ⁷ in scheme 21.

Process 27

Compounds of formula 41 can be prepared from compounds of formula 43 (Scheme 28) by Friedel-Crafts acylation with compounds of formula 44 (see Olah, G. "Friedel-Crafts and Related Reactions," Interscience, New York ((1963-1964) Review of ).The compound of formula 41 can also be prepared by reacting acyl halide, acid anhydride, ester or amide of formula 47 with an organometallic reagent of formula 46 (see March, J., Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp433-435 and references therein). By using, for example, magnesium or organolithium reagents to carry out reductive metal substitution or halogen-metal exchange of nitrogen-containing compounds of formula 45, or by using strong bases such as lithium amide or Organolithium reagents deprotonate compounds of formula 43 followed by transmetallation to prepare organometallic compounds of formula 46. Compounds of formula 41a correspond to compounds of formula 14a in scheme 8 and compounds of formula 41 in scheme 27, while compounds of formula 41b correspond to O=C(R ⁶ )Z in Scheme 22 and compound 41c correspond to compound 93 in Scheme 41 (where T ¹⁸ =R ²⁶ ).

Process 28

Halogen=Cl,Br,I M ¹ =MgX T ⁶ =Cl

CuLiZ OCOR ³³

CdZ OR

SnR ₃ NR ₂

R ³³ =R ⁶ ,R ⁷ ,R ²⁹ orR ²⁶

R=C ₁ -C ₄ alkyl

Compounds of formula 45 can be prepared by reacting compounds of formula 43 (Scheme 29) with eg bromine or chlorine under free radical or aromatic electrophilic halogenation conditions (depending on the nature of Z), with or without an additional catalyst. Additional halogen sources such as N _- halosuccinimide, t-butylhypohalite or _SO2Cl2 can also be used (see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985 ), pp 476-476, 620-626, and references therein). For a review of free radical halogenation, see Huyser, in Patai, "The Chemistry of the Carbon-Halogen Bond," Part 1, Wiley: New York, (1973), pp 549-607. For electrophilic substitution, see de la Mare, "Electrophilic Halogenation," Cambridge University Press, London (1976). Compounds of formula 45 correspond to compounds of formula 15 in scheme 7 (where Lg=Br, Cl or I) and reagent Z-halogen in scheme 24. Compounds of formula 49 can be prepared from compounds of formula 48 by similar methods. Compounds of formula 49 correspond to compounds of formula 16 in Scheme 7 (wherein Lg=Br, Cl or I). Compounds of formula 36 or 37 in Scheme 23 can be prepared by reacting compounds of formula 49 with triphenylphosphine or trialkylphosphite, respectively, followed by deprotonation with a base (see Cadogen, "Organophosphorus Reagents in Organic Synthesis," Academic Press, Proceedings on these reagents in New York (1979)).

Process 29

Compounds of formula 50 are prepared by treating compounds of formula 41d with a peracid such as perbenzoic acid or peracetic acid, or other peroxy compounds in the presence of an acidic catalyst, followed by hydrolysis of the resulting ester (Scheme 30). For a review thereof, see Plesnicar, in Trahanovsky, "Oxidation in Organic Chemistry", pt. C, Academic Press, New York (1978) pp254-267. Formula 50 corresponds to Formula 13 in Scheme 6 (when Y ¹ =0) and reagent HO-Z in Scheme 21. Compounds of formula 54 can be prepared by conversion of compounds of formula 50 to dialkylthiocarbamates of formula 52 followed by rearrangement to formula 53 and subsequent hydrolysis. See MS Newman and HA Kames, J. Org. Chem. (1966), 31, 3980-4. Formula 54 corresponds to Formula 13 in Scheme 6 (when Y ¹ =S) and reagent HS-Z in Scheme 21.

Process 30

Compounds of formula 55 can be converted to compounds of formula 45, 50 or 54 by treatment of diazonium compound 56 with nitrous acid followed by subsequent reaction (Scheme 31). See reviews by Hegarty (pt. 2, pp 511-91) and Schank (pt. 2, pp 645-657, in Patai): "The Chemistry of Diazonium and Diazo Groups," Wiley: New York, (1978). Treatment of compounds of formula 56 with cuprous halide or iodide ion affords compounds of formula 45. Treatment of compounds of formula 56 with cuprous oxide in the presence of excess copper nitrate affords compounds of formula 50 (Cohen, Dietz and Miser, J. Org. Chem., (1977), 42, 2053). Treatment of compounds of formula 56 with ( _S2 ) ^-2 affords compounds of formula 54. Treatment of compounds of formula 56 with sulfur dioxide and chlorine provides compounds of formula 54a.

Process 31

Compounds of formula 55 can be prepared from compounds of formula 43 by nitration followed by reduction (Scheme 32). A wide variety of nitrating agents are available (see Schofield "Aromatic Nitration," Cambridge University Press, Cambridge (1980). Reduction of nitro compounds can be accomplished in a variety of ways (see March, J., Advanced Organic Chemistry; 3rd Edition. John Wiley: New York, (1985), pp1103-4, and references therein). When Y ¹ =NR ¹⁵ and R ¹⁵ =H, Formula 55 corresponds to Formula 13 in Scheme 6.

Process 32

Iodides of formula 8 can be prepared from compounds of formula 60 by the methods described above in Schemes 21-26 for various Y-Z combinations. Compounds of formula 60 can in turn be prepared from compounds of formula 59 by functional group interchange well known to those skilled in the art. Compounds of formula 59 can be prepared by treating compounds of formula 58 with organolithium reagents such as tert-butyllithium or LDA, followed by trapping the intermediate with iodine (Beak, P., Snieckus, V.Acc.Chem.Res., (1982), 15, 306). Alternatively, lithiation (lithiation) by halo-metal interchange of compounds of formula 58 (wherein H is replaced by Br) will generate intermediates that can be trapped by iodine to prepare compounds of formula 59 (Parham, W.E., Bradsher, C.K. Acc .Chem.Res., (1982), 15,300 (Scheme 32).

Process 33 CH ₂ OH,OMe,OCH ₂ OMe t=1or2

Compounds of formula 63 can be prepared by reacting compounds of formula 61 with an acylating agent of formula 62 with or without an optional base. Suitable alkylating agents are, for example, alkyl chloroformates, acid anhydrides, carbamoyl chloride or carbonylimidazole. Alternatively, the compound of formula 61 can be reacted with a compound of formula 24 (such as phosgene, diphosgene, triphosgene, thiophosgene, N,N'-carbonyldiimidazole or N,N'-thiocarbonyldiimidazole), followed by Reaction with a compound of formula 64 with or without an optional base. Compounds of formula 68 can be prepared by reacting compounds of formula 66 with a sulfonylating agent of formula 67, such as methanesulfonyl chloride or trifluoromethanesulfonic anhydride, with or without an optional base. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, tertiary amines such as triethylamine and triethylenediamine, pyridine or 1,8-diazabicyclo [5.4. 0] Undec-7-ene (DBU). Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide, ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether, ketones such as acetone or 2-butanone, hydrocarbons such as toluene Or benzene, or halogenated hydrocarbons such as methylene chloride or chloroform. According to the choice of base, solvent, temperature and substrate, the reaction temperature can be varied from 0°C to 150°C and the reaction time can be varied from 1 to 72 hours.

Process 34 T ⁹ =Cl,OCCl ₃ ,OCO(C ₁ -C ₄ alkyl), 1-imidazolyl, 1,2,4-triazolyl T ¹⁰ =R ²⁶ ,OR ²⁷ ,SR ²⁷ ,N(R ²⁶ ) ₂

X ¹ =O,S

T ¹ and T ² are independently Cl, OCCl ₃ , O(C ₁ -C ₄ alkyl),

            1-imidazolyl, 1,2,4-triazolyl

T ¹¹ =OR ²⁷ ,SR ²⁷ ,N(R ²⁶ ) ₂

Q ² =O,NR ²⁶

T ¹² =Cl,R ²⁷ SO ₂ O

Compounds of formula 71 can be prepared by reacting compounds of formula 69 with isocyanates of formula 70. A base such as triethylamine can be added to catalyze the reaction. Compounds of formula 73 can be prepared by reacting compounds of formula 69 with a silylating or germylating agent of formula 72a or 72b in the presence of a base such as, but not limited to, pyridine or imidazole.

Process 35

R ²⁶ =R ²⁶ , except H

Q ³ =Si or Ge

Compounds of formula 76 can be prepared by reacting compounds of formula 74 with alkylating agents of formula 75, including alkyl-, haloalkyl- or aryl-sulfonates such as ethyl lactate mesylate, 2- Methoxyethyl triflate or cyanotosylate and alkyl halides such as benzyl bromide and propargyl bromide (Scheme 36). These alkylations can be carried out with or without the presence of an additional base. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undecyl -7-ene (DBU) and triethylenediamine. Note that when ^Q4 =NH, two equivalents of the same compound of formula 75 or two different parts of the compound of formula 75 can be reacted sequentially.

Process 36

Q ⁴ =O,S,NH Q ⁵ =O,S,NR ²⁸

Lg ^1a =Cl,Br,I,=OSO ₂ V ²

V ² =C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, phenyl, 4-MeC ₆ H ₄ -

T ¹³ =C ₃ -C ₆ haloalkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ haloalkynyl,

C ₂ -C ₆ alkoxyalkyl, C ₅ -C ₉ trimethylsilylalkoxyalkyl,

C ₂ -C ₆ alkylthioalkyl, cyano substituted C ₁ -C ₃ alkyl,

C(=O)OR ²⁶ or C(=O)N(R ²⁶ ) ₂

Compounds of formula 78 can be prepared from compounds of formula 77 by nucleophilic substitution with alkali metal alkoxides, alkali metal thiolates (M ⁺ -T ¹⁴ ) (Scheme 37). Similar substitution of compounds of formula 80 with compound M ⁺ -T ¹⁵ provides compounds of formula 81 . Compounds of formula 79 can be prepared by reaction with an amine derivative in a suitable solvent. The leaving group Lg ¹ of compounds of formulas 77 and 80 is any group known in the art that is subject to such a substitution reaction. Examples of suitable leaving groups include chloro, bromo and sulfonyl and sulfonate groups. Examples of suitable inert solvents include dimethylformamide or dimethylsulfoxide, dimethoxyethane and methanol.

M=K or Na

Lg=Cl,Br,-SO ₂ V or OSO ₂ V

V=C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or 4-CH ₃ -C ₆ H ₄

T ¹⁴ =SCN, benzyloxy, phenylthio, benzylthio, pyrimidinylmethoxy,

  Pyridylthio, thienylthio, furyloxy, furylthio, pyrimidine

Pyridylthio, each optionally substituted

T ¹⁵ = benzyloxy, phenylthio, each optionally substituted

Compounds of formula 84 can be prepared from compounds of formula 82 by reaction with a nucleophile of formula 83 in the presence of added base (Scheme 38). Similarly, reacting a compound of formula 54a with a nucleophile of formula 85 can result in the formation of a compound of formula 86. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undecyl -7-ene (DBU) and triethylenediamine. Acid chlorides of formula 82 can be prepared from carboxylic acids of formula 87 by various methods (see March, J. Advanced Organic Chemistry; 3rd ed, John Wiley: New York, (1985), pp388-9 and references therein). Carboxylic acids are available from a variety of sources and synthesized by various methods by those skilled in the art. In addition to the method described in Scheme 31, compounds of formula 54a can also be prepared by sulfonating compounds of formula 43 with chlorosulfonic acid (for a review, see Gilbert, Sulfonation and Related Reactions, Interscience, New York (1965) pp62-83, 87- 124). Compounds of formula 54a can also be prepared by oxidative chlorination of thiols of formula 52 with chlorine gas and water. Sulfide, disulfide and thioacetate derivatives etc. of Formula 52 (Formula 52a) can be used to affect the same reaction (for a review, see Gilbert, Sulfonation and Related Reactions, Interscience, New York (1965) pp202- twenty one).

T ¹⁷ =OR ²⁶ ,N(R ²⁶ ) ₂

Q ⁶ =C ₁ -C ₄ alkyl, benzyl, S(C ₁ -C ₄ alkyl), S-benzyl, SCOCH ₃

Compounds of formula 90 (Scheme 39) can be prepared by methods well known in the art (for primary references in the art on the preparation of silyl- and germyl-substituted compounds see The Organic Compounds of Germanium, Michel Lesabre, Piere Mazerolles, and Jacques Satge, Dietmar Seyferth, Ed., John Wiley & Sons, New York; C. Eaborn and K.C. Pande, J. Chem. Soc. (1960) 3200-3203; M. Wieber and M. Schmidt, J. Organometal. Chem. (1963) 93-94; and WO94/08976). See Scheme 39 for two approaches, one is to subject a compound of formula 88 to a reductive metal substitution or halogen-metal exchange process using magnesium or organolithium reagents, followed by silyl- or germyl-substitution of formula 89 halide treatment. The second method is to deprotonate the compound of formula 43 using a strong base such as lithium amide or an organolithium reagent, followed by treatment with a compound of formula 89.

Process 39

Q ⁷ =SiR ²² R ²³ R ²⁴ or GeR ²² R ²³ R ²⁴

R ³¹ =C ₁ -C ₄ alkyl or Si(C ₁ -C ₄ alkyl) ₃

Oxidation of the corresponding thio compound of formula 91 can Compounds of formula 92 were prepared (Scheme 40). One equivalent of oxidizing agent provides sulfinyl moieties (n=1), while two equivalents of oxidizing agent provide sulfonyl moieties (n=2). Suitable oxidizing agents include m-chloro-perbenzoic acid, hydrogen peroxide and Oxone ^_ (KHSO ₅ ).

Process 40

Q ⁸ =C ₁ -C ₆ haloalkyl, phenyl (optionally substituted)

n=1 or 2

As shown in Scheme 41 (see Bull. Soc. Chim. Belg., (1978), 87, 229; and Tetrahedron Lett. (1983), 24, 3815), by using a sulfurizing reagent such as P ₂ S ₅ or Lawesson's reagent (2 , 4-bis(4-methoxyphenyl)-1,3-dithio-2,4-diphosphetane-2,4-disulfide) can prepare the compound of formula 94 by treating the compound of formula 93.

Process 41

T ¹⁸ =R ²⁶ ,OR ²⁶ ,SR ²⁶ ,N(R ²⁶ ) ₂

Additionally, when Z is substituted by iodine or ^Lg (defined in Scheme ¹⁰ ), palladium ( 0) Catalyzed cross-coupling reactions can introduce certain ^R9 moieties.

It should be recognized that some of the reagents and reaction conditions described above for the preparation of compounds of formula I may not be compatible with certain functional groups present in the intermediates. In these cases, the introduction of protection/deprotection sequences or functional group interchange into the synthesis will help to obtain the desired product. The use and choice of protecting groups will be apparent to those skilled in chemical synthesis (see, e.g., Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that in some cases, following the introduction of a given reagent illustrated in any individual scheme, it is possible to perform other, not detailed, conventional synthetic steps to complete the synthesis of the compound of formula I. synthesis. Those skilled in the art will also recognize that it is possible to perform combinations of steps illustrated in the above schemes in an order other than the specific order presented to prepare compounds of formula I.

Those skilled in the art will also recognize that the compounds of Formula I and intermediates described herein may be subjected to a variety of electrophilic, nucleophilic, radical, organometallic, oxidative and reductive reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art, using the above description, can fully utilize the present invention. Therefore, the following examples are for illustration only, and in no way limit the content of the present disclosure. Percentages are by weight unless chromatographic solvent mixtures or otherwise indicated. Parts and percentages of chromatographic solvent mixtures are by volume unless otherwise indicated. ¹ H NMR spectrum is expressed in ppm from tetramethylsilane to downfield; s=singlet, d=doublet, t=triplet, q=quadruplet, ABq=“AB” quadruplet, m=multiplet, dd= Double doublet, ddd=double double doublet, br=broad, brs=broad unimodal, brm=broad multimodal.

Example 1

Step A: Preparation of N-(2-methoxyphenyl)-2,2-dimethylhydrazine carboxamide

7.65 ml of 1,1-dimethylhydrazine in 10 ml of toluene was slowly added to a stirred solution of 15.0 g of 2-methoxyphenylisocyanate in 100 ml of toluene at 5°C under nitrogen. The cooling bath was then removed and the reaction was stirred for an additional 10 minutes, then concentrated under reduced pressure. The resulting material was dissolved in ether and concentrated again. Trituration of the resulting solid with hexanes provided 21 g of the title compound of Step A as a white solid. ¹ HNMR(CDCl ₃ )δ8.6(brs,1H),8.24(m,1H),6.95(m,2H),6.85(m,1H),5.35(brs,1H),3.89(s,3H), 2.60(s,6H).

Step B: Preparation of 5-chloro-2,4-dihydro-4-(2-methoxyphenyl)-2-methyl-3H-1,2,4-triazol-3-one

To a stirred solution of 21 g of the title compound from Step A in 800 mL of dichloromethane was added 29.85 g of triphosgene under nitrogen. The reaction was heated to reflux and allowed to reflux overnight, cooled, then concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate and washed with distilled water and then with saturated aqueous sodium chloride. The organic layer was dried (magnesium sulfate), filtered and concentrated under reduced pressure. Recrystallization of the solid from dichloromethane and trituration of the resulting solid with ether provided 10 g of the title compound of Step B as a white solid, mp 152-154°C. ¹ H NMR (CDCl ₃ ) δ 7.45 (t, 1H), 7.25 (d, 1H), 7.05 (m, 2H), 3.84 (s, 3H), 3.53 (s, 3H).

Step C: Preparation of 5-chloro-2,4-dihydro-4-(2-hydroxyphenyl)-2-methyl-3H-1,2,4-triazol-3-one

Under nitrogen, the title compound of Step B (7.7 g) was dissolved in 65 mL of dichloromethane, cooled to -78°C, and then 34 mL of a 1.0M solution of boron tribromide in dichloromethane was added with stirring over 30 minutes. After the addition, it was kept in a cold bath (dry ice/acetone) for an additional 30 minutes, then the reaction was allowed to warm to room temperature. Ice was added to the reaction mixture, diluted with ether, and the product was extracted with 1N aqueous sodium hydroxide solution. The aqueous layer was acidified with 6N aqueous hydrochloric acid and extracted with dichloromethane and then ethyl acetate. The organic layers were combined, dried (magnesium sulfate), filtered and concentrated under reduced pressure. Trituration of the resulting residue with ether provided 5.54 g of the title compound of Step C as a white solid. ¹ H NMR (CDCl ₃ ) δ 8.18 (s, 1H), 7.11 (s, 2H), 6.91 (t, 1H), 6.76 (d, 1H), 3.56 (s, 3H).

Step D: Preparation of 2,4-dihydro-4-(2-hydroxyphenyl)-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

Under nitrogen, 18.6 mL of 30% sodium methoxide in methanol was added to a stirred solution of 5.54 g of the title compound from Step C in 50 mL of methanol and 25 mL of 1,2-dimethoxyethane. The reaction mixture was heated at reflux for 5.5 hours and then cooled to room temperature. The mixture was diluted with ether and the product was extracted with 1N aqueous sodium hydroxide solution. The aqueous layer was acidified with 6N aqueous hydrochloric acid and extracted with dichloromethane. The organic layer was dried (magnesium sulfate), filtered and concentrated under reduced pressure. Trituration of the resulting residue with ether provided 3.85 g of the title compound of Step D as a white solid (85% purity). ¹ H NMR (CDCl ₃ ) δ8.40 (brs, 1H), 7.20 (m, 2H), 7.03 (d, 1H), 6.94 (t, 1H), 4.00 (s, 3H), 3.48 (s, 3H).

Step E: 2,4-Dihydro-4-[2-[(3-iodo-1,2,4-thiadiazol-5-yl)oxy]phenyl]-5-methoxy-2- Preparation of methyl-3H-1,2,4-triazol-3-one

Potassium carbonate (2.44 g) and 3-iodo-5-(methylsulfonyl)-1,2,4-thiadiazole (J. Org. Chem. (1973), 38, 469) (4.33 g) were added to the step A solution of the title compound of D (3.0 g, 13.6 mmol) in acetone (27 ml). The mixture was stirred at room temperature for 36 hours, then diluted with water. The resulting mixture was extracted twice with dichloromethane and the combined extracts were dried over magnesium sulfate. The solution was concentrated to a solid and triturated with hot ethanol to afford the title compound of Step E (2.8 g, 48%). ¹ H NMR (CDCl ₃ ) δ 7.55 (m, 2H), 7.46 (m, 2H), 3.86 (s, 3H), 3.40 (s, 3H).

Step F: 2,4-Dihydro-5-methoxy-1-methyl-4-[2-[[3-[(2-pyridyl)ethynyl]-1,2,4-thiadiazole Preparation of -5-yl)oxy]phenyl]-3H-1,2,4-triazol-3-one

Add copper(I) iodide (14mg), triethylamine (0.347ml), 2-ethynylpyridine (186mg, 1.78mmol) and bis(triphenylphosphine)palladium(II) chloride (25mg) to step E The title compound (307mg, 0.71mmol) was dissolved in DMF (4ml). The mixture was stirred at room temperature for 16 hours, then diluted with ethyl acetate and washed twice with water. The aqueous phase was extracted with ethyl acetate and the combined organic phases were dried over magnesium sulfate. The solution was concentrated and the residue was purified by column chromatography (silica gel, diethyl ether, then ethyl acetate) to give the title compound of Step F, a compound of this invention. ¹ HNMR(CDCl ₃ )δ8.65(d,1H),7.7(m,1H),7.65-7.5(m,3H),7.5-7.4(m,2H),7.3(m,1H),3.84(s ,3H), 3.40(s,3H).

Example 2

Step A: Preparation of 1-(4-chlorophenyl)cyclopropaneformimidate (carboximidate) ethyl ester hydrochloride

Absolute ethanol (3.4ml) was added to a solution of 1-(4-chlorophenyl)cyclopropanenitrile (10g, 56.3mmol) in ether (56ml). The solution was cooled to 0°C and saturated with dry HCl gas. The reaction mixture was then allowed to stand at room temperature for 11 days after which it was filtered under a stream of dry nitrogen to afford the title compound of Step A (11.60 g) as a white solid. ¹ H NMR (Me ₂ SO-d ₆ ) δ 7.45 (s, 4H), 4.47 (q, 2H), 1.84 (m, 2H), 1.48 (m, 2H), 1.30 (t, 3H).

Step B: Preparation of 1-(4-chlorophenyl) cyclopropanecarboximidamide hydrochloride

Ammonia (9.0 mL, 7N in methanol) was added to a solution of the title compound of Step A (11.60 g, 44.6 mmol) in methanol (15 mL). The mixture was stirred for two days, then concentrated to give the title compound of Step B (9.78 g). ¹ H NMR (Me ₂ SO-d ₆ ) δ 9.2-9.0 (br, 4H), 7.52-7.43 (m, 4H), 1.52 (m, 2H), 1.29 (m, 2H).

Step C: Preparation of 5-chloro-3-[1-(4-chlorophenyl)cyclopropyl]-1,2,4-thiadiazole

Dichloromethane (200ml), benzyltriethylammonium chloride (0.79g) and perchloromethanethiol (4.62ml, 42.3mmol) were added to the title compound of Step B (9.78g, 42.3mmol) in water (100ml) solution and cooled the mixture on an ice bath. Under thorough stirring, a solution of sodium hydroxide (6.77 g) in water (100 ml) was added dropwise at such a rate that the internal temperature did not exceed 10°C. After the addition was complete, the cooling bath was removed and the reaction mixture was stirred for an additional 1.5 hours. The organic layer was then separated, dried over magnesium sulfate and concentrated. The yellow/brown tar was extracted with boiling hexanes and the hot solution was filtered through a pad of silica gel. The silica gel was washed with hexanes and the solution was concentrated to give a yellow solid which was recrystallized from ethanol to give 3.97 g of the title compound of Step C as a white solid. ¹ H NMR (CDCl ₃ ) δ 7.39-7.32 (m, 4H), 1.75 (m, 2H), 1.42 (m, 2H).

Step D: 4-[2-[[3-[1-(4-chlorophenyl)cyclopropyl]-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2, Preparation of 4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

Freshly ground potassium carbonate (244mg) and the title compound from Step C (368mg, 1.36mmol) were added to a solution of the title compound from Example 1, Step D (300mg, 1.36mmol) in acetone (3ml). The mixture was stirred at room temperature for 2 days, then diluted with water. The resulting mixture was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated. Recrystallization of the resulting residue from ethanol afforded the title compound of Step D, a compound of the invention, as an off-white solid, mp 123-124°C. ¹ HNMR(CDCl ₃ )δ7.52(m,2H),7.44(m,2H),7.36(m,2H),7.33(m,2H),3.82(s,3H),3.41(s,3H), 1.65(m,2H),1.30(m,2H).

Example 3

Step A: Preparation of ethyl 1,3-benzodioxol-5-carboximide hydrochloride

Absolute ethanol (3.99ml) was added to a solution of piperonylonitrile (10g, 68.0mmol) in diethyl ether (68ml) and dichloromethane (30ml). The solution was cooled to 0°C and saturated with dry HCl gas. The reaction mixture was then left standing at room temperature for 5 days after which it was concentrated and the residue was triturated with diethyl ether to give the title compound of Step A (6.38 g) as a white solid. ¹ H NMR (Me ₂ SO-d ₆ ) δ 7.80 (m, 2H), 7.18 (d, 1H), 6.23 (s, 2H), 4.61 (q, 2H), 1.47 (m, 3H).

Step B: Preparation of 1,3-benzodioxol-5-carboximide amide hydrochloride

Ammonia (5.6 ml, 7N in methanol) was added to a solution of the title compound of Step A (6.38 g, 29.3 mmol) in ethanol. The mixture was stirred for 6 days, then concentrated to give the title compound of Step B (5.60 g). ¹ H NMR (Me ₂ SO-d ₆ ) δ 9.30 (s, 2H), 9.17 (s, 2H), 7.50-7.45 (m, 2H), 7.16 (d, 1H), 6.20 (m, 2H).

Step C: Preparation of 5-chloro-3-(benzo1,3-dioxol-5-yl)-1,2,4-thiadiazole

Dichloromethane (136ml), benzyltriethylammonium chloride (0.52g) and perchloromethanethiol (3.05ml, 27.9mmol) were added to the title compound of Step B (5.60g, 27.9mmol) in water (68ml) solution and cooled the mixture on an ice bath. With full stirring, sodium hydroxide (68ml, 1.66N aqueous solution) was added dropwise at such a rate that the internal temperature did not exceed 10°C. After the addition was complete, the cooling bath was removed and the reaction mixture was stirred for an additional 1 hour. The organic layer was then separated, dried over magnesium sulfate and concentrated. The yellow/brown tar was extracted with boiling hexanes and the hot solution was filtered through a pad of silica gel. The silica gel was washed with hexanes and the solution was concentrated to give a yellow solid which was recrystallized from ethanol to give the title compound of Step C as a white solid. ¹ H NMR (CDCl ₃ ) δ 7.84 (d, 1H), 7.70 (s, 1H), 6.90 (d, 1H), 6.06 (s, 2H).

Step D: 4-[2-[[3-(1,3-benzodioxol-5-yl]-1,2,4-thiadiazol-5-yl]oxy]phenyl Preparation of ]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

Freshly ground potassium carbonate (244mg) and the title compound from Step C (327mg, 1.36mmol) were added to a solution of the title compound from Example 1, Step D (300mg, 1.36mmol) in acetone (3ml). The mixture was stirred at room temperature for 2 days, then diluted with water. The resulting mixture was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated. Crystallization of the resulting residue from diethyl ether afforded the title compound of Step D, a compound of the invention, as an off-white solid, mp 168-169°C. ¹ HNMR(CDCl ₃ )δ7.70(d,1H),7.63(m,2H),7.55(m,1H),7.48(m,2H),6.86(d,1H),6.02(s,2H), 3.78(s,3H),3.37(s,3H).

Example 4

Step A: Preparation of 2-(methylthio)-5-(tricyclo[ ^3.3.1.13,7 ]decac-1-yl)1,3,4-oxadiazole

Potassium hydroxide (1.08ml, 10N aqueous solution, 10.8mmol) and carbon disulfide (0.682ml) were added dropwise to a solution of 1-adamantanecarbohydrazide (2.0g, 10.3mmol) in ethanol (16ml). The mixture was further diluted with ethanol (10 ml) and the mixture was heated at reflux overnight. Methyl iodide (0.705ml) was then added and the mixture was cooled on an ice bath and stirred for a further 30 minutes. The solution was concentrated and redissolved in dichloromethane. The solution was filtered through a pad of silica gel and concentrated to give the title compound of Step A (2.15 g) as a white solid.

Step B: Preparation of 2-(methylsulfonyl)-5-(tricyclo[ ^3.3.1.13,7 ]decac-1-yl)1,3,4-oxadiazole

Potassium permanganate (60ml, 0.3M in water, 16.0mmol) was added dropwise to a solution of the title compound of Step A (2.15g, 7.62mmol) in acetic acid (17ml). A slightly exothermic reaction was controlled with an ice bath. After the addition was complete, sodium bisulfite (80 mL, 40% in water) was added and the resulting precipitate was filtered to give 1.84 g of the title compound of Step B. ¹ H NMR (CDCl ₃ ) δ 3.47 (s, 3H), 2.2-1.6 (brm, multiple H).

Step C: 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[5-(tricyclo[ ^3.3.1.13,7 ]decac-1-yl)1, Preparation of 3,4-oxadiazol-2-yl]oxy]phenyl]-3H-1,2,4-triazol-3-one

Potassium carbonate (406 mg) and the title compound from Step B (383 mg) were added to a solution of the title compound from Example 1 Step D (0.5 g, 2.26 mmol) in acetone (5 ml). The mixture was stirred overnight, then diluted with dichloromethane and washed with water. The aqueous phase was re-extracted with dichloromethane, the combined organic layers were dried over magnesium sulfate and the solution was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, 80% diethyl ether in petroleum ether, then diethyl ether) to give the title compound of Step C, a compound of the present invention. ¹ HNMR(CDCl ₃ )δ7.8(d,1H),7.5(t,1H),7.42(m,2H),3.86(s,3H),3.44(s,3H),2.1(brs,3H), 2.04 (brm, 6H), 1.79 (brm, 6H).

Example 5

Step A: 3-[(2-Chlorophenyl)methoxy]-5-(methylthio)-1,2,4-thiadiazole

Potassium carbonate (1.12g) and 2-chlorobenzyl bromide were added to 3-hydroxyl-5-thiomethyl-1,2,4-thiadiazole (J.Het.Chem., (1979), 961 ) (0.8g) in DMF (10ml) solution. The mixture was stirred at room temperature for 3 days, then diluted with ethyl acetate. The resulting mixture was washed twice with water and dried over magnesium sulfate. The solution was concentrated. The residue was purified by column chromatography (silica gel, 20% then 40%, then 60%, then 80% diethyl ether in petroleum ether). The previous fractions were combined, concentrated and repurified by column chromatography (silica gel, 5% then 10% diethyl ether in petroleum ether) to afford the title compound of Step A. ¹ H NMR (CDCl ₃ ) δ 7.45 (m, 2H), 7.3 (m, 2H), 5.03 (s, 2H), 2.71 (s, 3H).

Step B: 4-[2-[[3-[(2-Chlorophenyl)methoxy]-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4- Preparation of Dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

Hydrogen peroxide (0.17ml of a 30% solution in water) was added to a solution of the title compound of Step A (0.23g) in acetic acid (1ml) and acetic anhydride (1ml) and the solution was allowed to stand overnight. Another portion of hydrogen peroxide (0.085ml) was then added and allowed to stand for a further 2 hours before diluting with diethyl ether. The resulting mixture was washed with sodium sulfate (10% in water), aqueous sodium bicarbonate and dried over magnesium sulfate. The solution was concentrated to obtain 0.32 g of the compound. This material was redissolved in acetone (5ml) and potassium carbonate (0.218g) and the title compound from step D of Example 1 (0.232g) were added. The mixture was stirred at room temperature for 2 hours, then diluted with water and extracted twice with dichloromethane. The organic extracts were dried over magnesium sulfate and concentrated. Crystallization of the residue from diethyl ether afforded the title compound of Step B (240 mg), a compound of the present invention, as a solid, mp 107-108°C. ¹ HNMR(CDCl ₃ )δ7.6-7.5(m,3H),7.5-7.35(m,3H),7.3(m,2H),5.49(s,2H),3.82(s,3H),3.4(s ,3H).

Example 6

Step A: Preparation of Dimethylmalononitrile

Iodomethane (28.3ml, 0.45mol) and potassium carbonate (52.23g, 379mmol) were added to a solution of malononitrile (10.0g, 151.4mmol) in DMF (300ml) and the reaction mixture was stirred overnight. The mixture was then diluted with ether, washed with water and saturated aqueous sodium chloride, and the organic layer was dried over magnesium sulfate. Concentration afforded the title compound of Step A (4.84 g) as an oil containing 20 mole % DMF. ¹ HNMR (CDCl ₃ ) δ 1.84 (s).

Step B: Preparation of α-cyano-α-methylpropanimidamide

(see Tet. Lett., 1990, 31, 1969). Ammonium chloride (2.20 g) was added in small portions to a solution of trimethylaluminum (20.6 ml, 2M in toluene) in toluene (41 ml) at 0°C. After the addition was complete, the cooling bath was removed and the mixture was stirred for an additional 2 hours. This mixture was then added to a solution of the title compound from Step A (4.84g) in toluene (20ml) and the mixture was heated at 85°C overnight. The mixture was then cooled and poured into a slurry of silica gel (200g) in dichloromethane (300ml). The mixture was stirred for 5 minutes and filtered, washing the filter cake with methanol. The filtrate was concentrated to give the title compound of Step B (3.52 g). ¹ H NMR (Me ₂ SO-d ₆ ) δ 8.7-8.3 (brs, 3H), 1.75 (s, 6H).

Step C: Preparation of 5-chloro-α,α-dimethyl-1,2,4-thiadiazole-3-acetonitrile

Perchloromethanethiol (3.4ml) was added to a solution of the title compound from Step B (3.52g, 31.4mmol) in dichloromethane (75ml) and the mixture was cooled on an ice bath. Triethylamine (17.5 ml) was added at such a rate that the internal temperature did not exceed 10°C. After the addition was complete, the cooling bath was removed and the mixture was stirred for an additional 1.5 hours. The mixture was then washed with water, 1N hydrochloric acid and dried over magnesium sulfate. The mixture was concentrated and the residue was extracted with hot hexanes, filtered through a pad of silica gel and concentrated to give the title compound of Step C (1.3 g). ¹ HNMR (CDCl ₃ ) δ 1.84 (s).

Step D: 5-[2-(1.5-Dihydro-3-methoxy-1-methyl-5-oxo-4H-1,2,4-triazol-4-yl]phenoxy]- Preparation of α,α-Dimethyl-1,2,4-thiadiazole-3-acetonitrile

Potassium carbonate (406 mg) and the title compound from Step C (426 mg) were added to a solution of the title compound from Example 1 Step D (0.5 g, 2.26 mmol) in acetone (5 ml). The mixture was stirred at reflux overnight, then diluted with water, the mixture was extracted three times with dichloromethane, and the organic extracts were dried over magnesium sulfate. The solution was concentrated, and the residue was purified by column chromatography (silica gel, ether) to obtain the title compound of Step D (100 mg), a compound of the present invention, as a brown solid. ¹ H NMR (CDCl ₃ ) δ 7.57 (m, 2H), 7.48 (m, 2H), 3.83 (s, 3H), 3.40 (s, 3H), 1.77 (s, 6H).

Example 7

Step A: Preparation of 5-(methylthio)-3-(phenylmethoxy)-1,2,4-thiadiazole

Potassium carbonate (5.7g) and benzyl bromide (3.56ml) were added to 3-hydroxyl-5-thiomethyl-1,2,4-thiadiazole (J.Het.Chem., (1979), 961) (4.06g) in DMF (50ml) solution. The mixture was stirred at room temperature for 3 days, then diluted with ether, the resulting mixture was washed twice with water and the organic layer was dried over magnesium sulfate. The solution was concentrated. The residue was purified by column chromatography (silica gel, 5% then 10% diethyl ether in petroleum ether) to afford the title compound of Step A (2.0 g). ¹ H NMR (CDCl ₃ ) δ 7.5-7.4 (m, 2H), 7.45-7.3 (m, 3H), 5.43 (s, 2H), 2.68 (s, 3H).

Step B: 2,4-Dihydro-5-methoxy-2-methyl-4-[2-[[3-(phenylmethoxy)-1,2,4-thiadiazole-5- Preparation of yl]oxy]phenyl]-3H-1,2,4-triazol-3-one

Hydrogen peroxide (4.0 mL, 30% in water) was added to a solution of the title compound of Step A (2.0 g) in acetic acid (20 mL) and acetic anhydride (20 mL) and the solution was allowed to stand at room temperature. After 6 hours, the solution was diluted with ether and the resulting mixture was washed with sodium sulfite (10% in water), water and aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated to obtain 1.95 g of the compound. This material was used without purification. This material was dissolved in acetone (18ml) and potassium carbonate (1.3g) and the title compound from Example 1, Step D (1.6g) was added. The mixture was stirred overnight at room temperature, then diluted with ethyl acetate. The resulting mixture was washed twice with water and saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate and concentrated to give the title compound of Step B (2.75 g), a compound of the present invention. ¹ H NMR (CDCl ₃ ) δ 7.6-7.3 (m, 9H), 5.37 (s, 2H), 3.79 (s, 3H), 3.40 (s, 3H).

Example 8

2,4-Dihydro-4-[2-[(3-hydroxy-1,2,4-thiadiazol-5-yl)oxy]phenyl]-5-methoxy-2-methyl-3H Preparation of -1,2,4-triazol-3-one

Aluminum chloride (1.74g) was added to a solution of the title compound of Example 7, Step B (2.68g, 6.52mmol) in benzene (35ml) and the mixture was stirred at room temperature overnight. An additional 0.87 g of aluminum chloride was added and the mixture was stirred for an additional 4 hours. It was then quenched with water, extracted with ethyl acetate, twice with dichloromethane and twice with 20% methanol in dichloromethane. The combined organic phases were dried over magnesium sulfate, concentrated and triturated with petroleum ether to give the title compound of Example 8 (1.78 g), a compound of the invention, as an oil. ¹ H NMR (CDCl ₃ ) δ 7.3-7.1 (m, 4H), 3.98 (s, 1H), 3.89 (s, 3H), 3.41 (s, 3H).

Example 9

[5-[2-(1,5-Dihydro-3-methoxy-1-methyl-5-oxo-4H-1,2,4-triazol-4-yl)phenoxy]- Preparation of 1,2,4-thiadiazol-3-yl]trifluoromethanesulfonate

Triethylamine (0.182ml), catalytic amount of dimethylaminopyridine and trifluoromethanesulfonic anhydride (0.176ml) were added to a solution of the title compound of Example 8 (0.28g, 0.87mmol) in dichloromethane (4ml) , and the solution was allowed to stand overnight. The mixture was then diluted with ether and washed with 1N hydrochloric acid and aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (silica gel, 60% then 80% diethyl ether in petroleum ether) to give the title compound of Example 9 (compound of the invention), mixed with an equal amount of the title compound of Example 1, Step D. ¹ H NMR (CDCl ₃ ) δ 7.6-7.4 (m, 4H), 3.84 (s, 3H), 3.41 (s, 3H).

Example 10

Step A: Preparation of 2,2-diethoxyethylimine amide (ethanimidamide) hydrochloride

Sodium methoxide (2.7g, 50mmol) was added to a solution of diethoxyacetonitrile (6.46g, 50.0mmol) in methanol (50ml), and the mixture was stirred at room temperature for 24 hours. Ammonium chloride (5.35 g, 0.1 mol) was then added and the mixture was stirred at room temperature for an additional 24 hours, then concentrated to give the title compound of Step A (13.14 g) in admixture with sodium chloride as a white solid. ¹ H NMR (Me ₂ SO-d ₆ ) δ 9.0-8.4 (br s, 4H), 5.32 (s, 1H), 3.62 (q, 4H), 1.19 (t, 6H).

Step B: Preparation of 5-chloro-3-(diethoxymethyl)-1,2,4-thiadiazole

Dichloromethane (240ml), benzyltriethylammonium chloride (0.5g) and perchloromethanethiol (5.46ml) were added to a solution of the title compound (13.14mmol) of step A in water (120ml) and the mixture was Cool on an ice bath. Then, sodium hydroxide (120 ml, 1.66N aqueous solution) was added dropwise under sufficient stirring at a rate such that the internal temperature did not exceed 10°C. After the addition was complete, the cooling bath was removed and the reaction mixture was stirred for an additional 0.5 hours. The organic layer was then separated, dried over magnesium sulfate and concentrated. The yellow/brown tar was extracted with boiling hexanes and the hot solution was filtered through a pad of silica gel. Wash the silica gel with 5% ether in hexanes, then concentrate the solution to give the title compound of Step B. ¹ H NMR (CDCl ₃ ) δ 5.68 (s, 1H), 3.8-3.65 (q, 4H), 1.28 (t, 6H).

Step C: 4-[2-[[3-(diethoxymethyl)-1,2,4-thiadiazol-5-yl]oxy]phenyl]2,4-dihydro-5-methanol Preparation of Oxy-2-methyl-3H-1,2,4-triazol-3-one

Freshly ground potassium carbonate (278 mg) and the title compound from Step B (345 mg, 1.53 mmol) were added to a solution of the title compound from Example 1 Step D (345 mg, 1.53 mmol) in acetone. The mixture was stirred at room temperature for 16 hours, then diluted with water. The resulting mixture was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated. This material was purified by column chromatography (silica gel, 80% diethyl ether in petroleum ether, then diethyl ether) to give the title compound of Step C, a compound of this invention. ¹ HNMR(CDCl ₃ )δ7.6-7.4(m,4H),5.53(s,1H),3.81(s,3H),3.8-3.65(m,4H),3.40(s,3H),1.23(t ,6H).

Example 11

Step A: Preparation of 1-methoxy-3-(2-nitrophenoxy)benzene

At room temperature, 3-methoxyphenol (11.52g, 95.2mmol) was added to a suspension of potassium carbonate (13.1g, 95.2mmol) in 100ml of anhydrous N,N-dimethylformamide, and then The reaction was stirred for 10 minutes. Then 2-fluoronitrobenzene (12.2 g, 86.5 mmol) was added. The reaction was stirred at room temperature for 16 hours. The reaction mixture was diluted with ice water and the solid was filtered. The filter cake was washed with water and sucked dry to give 15.3 g of the title compound of Step A as a solid, mp 50-52°C. ¹ HNMR (CDCl ₃ ; 300MHz) δ3.80(s, 3H), 6.60(m, 2H), 6.75(m, 1H), 7.05(m, 1H), 7.2-7.3(m, 2H), 7.5(m ,1H), 8.0(m,1H).

Step B: Preparation of 2-(3-methoxyphenoxy)aniline

A solution of 1-methoxy-3-(2-nitrophenoxy)benzene (15.0g, 61.2mmol) and 15ml of water in 150ml of acetic acid was heated to 65°C on a steam bath, and divided at this temperature Iron powder (11.3 g, 202 mmol) was added (note exotherm after each addition). The reaction temperature was maintained between 65-85°C by controlling the rate of addition and cooling the bath with water. After stirring for an additional 10 minutes at 85°C, the reaction mixture was cooled to room temperature, diluted with dichloromethane and filtered through ^Celite® . The filtrate was washed once with water, then once with saturated sodium bicarbonate, and dried over magnesium sulfate. The solvent was then removed under reduced pressure to afford 12.1 g of the title compound of Step B as an oil. ¹ HNMR (CDCl ₃ ; 300MHz) δ3.8 (s, 5H total), 6.6-6.7 (m, 3H), 6.7 (m, 1H), 6.81 (dd, J=1.5, 7.8Hz, 1H), 6.89 ( d,J=7.9,Hz,1H),7.0(m,1H),7.2(m,1H).

Step C: Preparation of 2,2-dimethyl-N-[2-(3-methoxyphenoxy)phenyl]hydrazine carboxamide

The title compound of Step B (11.8 g, 55.0 mmol) was dissolved in 120 ml of dry toluene, and to this solution was added diphosgene (10.8 g, 55.0 mmol). The mixture was then refluxed for 4 hours with a water scrubber. The reaction mixture was cooled to room temperature, concentrated under reduced pressure to an oil, which was then dissolved in anhydrous THF (100ml). To this solution was added 1,1-dimethylhydrazine (4.0 g, 66 mmol) at room temperature. The reaction was then stirred at room temperature for 16 hours. The reaction mixture was concentrated under reduced pressure to a solid, which was then washed with water and sucked dry to give 16.5 g of the title compound of Step C as a solid, mp 93-95°C. ¹ HNMR (CDCl ₃ ; 300MHz) δ2.40(s,6H),3.80(s,3H),5.2(s,1H),6.7-6.8(m,2H),6.85(m,1H),7.0(m , 2H), 7.1-7.3 (m, 2H), 8.29 (d, J=7.9Hz, 1H), 8.6 (s, 1H).

Step D: 5-Chloro-2,4-dihydro-4-[2-(3-methoxyphenoxy)phenyl]-2-methyl-3H-1,2,4-triazole- Preparation of 3-keto

The title compound of Step C was dissolved in 600ml of dichloromethane and cooled to 0°C, at which temperature triphosgene (15.9g, 53.5mmol) was added. The reaction mixture was refluxed for 16 hours, cooled to room temperature and washed once with water. The organic layer was then dried over magnesium sulfate and concentrated under reduced pressure to give a crude oil which was purified by silica gel chromatography using 3:2 hexane:ethyl acetate as eluent to afford 14.7 g of the title compound of Step D as an oil. ¹ HNMR(CDCl ₃ ; 300MHz)δ3.47(s,3H),3.77(s,3H),6.61(m,2H),6.70(m,1H),7.01(dd,J=1.2,8.2 Hz,1H ), 7.2-7.3 (m, 2H), 7.34-7.42 (m, 2H).

Step E: 5-Chloro-2,4-dihydro-4-[2-(3-hydroxyphenoxy)phenyl]-2-methyl-3H-1,2,4-triazole-3- Preparation of ketones

The title compound of Step D (12.6g, 38.0mmol) was dissolved in 300ml of anhydrous toluene, and aluminum chloride (30g, 228mmol) was added to the solution at room temperature (slightly exothermic reaction, the temperature could reach 35°C) . The reaction mixture was then refluxed for 4 hours, cooled to room temperature, and crushed ice was added carefully. The crude slurry was then extracted twice with ether, and the combined extracts were washed once with saturated aqueous sodium chloride and dried over magnesium sulfate. The solvent was removed under reduced pressure to give an oil, which was subsequently purified by silica gel chromatography using 3:2 hexane:ethyl acetate as eluent to give 9.50 g of the title compound of Step E, a compound of the present invention, mp 135-138 ℃ solid. ¹ HNMR (CDCl ₃ ; 300MHz) δ3.46(s, 3H), 6.46(t, J=2.2Hz, 1H), 6.50-6.59(m, 3H total), 6.99(dd, J=1.3, 8.3Hz, 1H), 7.11(t, J=8.1, Hz, 1H), 7.20(dd, J=1.2, 7.6Hz, 1H), 7.32-7.40(m, 2H).

Example 12

2,4-Dihydro-4-[2-(3-hydroxyphenoxy)phenyl]-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one preparation

The title compound of Step E of Example 11 (8.7 g, 27.4 mmol) was dissolved in 300 ml of methanol, and to this solution was added sodium methoxide (7.4 g, 137 mmol) at room temperature (slight exotherm). The reaction mixture was then refluxed for 16 hours, cooled to room temperature, and concentrated under reduced pressure to a semi-solid. The semisolid was diluted with 1N hydrochloric acid, extracted twice with ether, washed with saturated aqueous sodium chloride, and dried over magnesium sulfate. The solvent was removed under reduced pressure to obtain a crude solid, which was purified by silica gel column chromatography using 1:1 hexane:ethyl acetate as eluent to obtain 5.80 g of the title compound of Example 12, the compound of the present invention, with a melting point of 153 Solid at -155°C. ¹ H NMR (CDCl ₃ ; 300MHz) δ3.37(s,3H),3.87(s,3H),6.4-6.5(m,2H),6.55(m,1H),6.9(brs,1H),7.0( m,1H), 7.1-7.2(m,2H), 7.3-7.4(m,2H).

Example 13

4-[2-[3-[(2-Chlorophenyl)methoxy]phenoxy]phenyl]-5-methoxy-2-methyl-3H-1,2,4-triazole Preparation of -3-one

The title compound of Example 12 (0.30g, 0.95mmol), 2-chlorobenzyl bromide (0.21g, 1mmol) and potassium carbonate (0.14g, 1mmol) were mixed in 10ml of anhydrous acetonitrile at room temperature. The resulting mixture was stirred for 16 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to a solid, which was triturated with hexane and sucked dry to give 0.32 g of the title compound of Example 13 (compound of the present invention) as a solid with a melting point of 112-114°C. ¹ HNMR (CDCl ₃ ; 300MHz) δ3.38(s,3H),3.85(s,3H),5.13(s,2H),6.6-6.8(m,3H),7.0(m,1H),7.2-7.4 (m,7H),7.5(m,1H).

Example 14

Step A: Preparation of 1-(4-chlorophenyl)cyclopropanecarboximide amide hydrochloride

Ammonium chloride (3.01 g, 56.3 mmol) was added in small portions to a solution of trimethylaluminum (56.3 mmol) in toluene (70 ml) at 0°C. After the addition was complete, the mixture was warmed to room temperature and stirred for 1.5 hours, then a solution of 1-(4-chlorophenyl)-1-cyclopropanenitrile (10.0 g, 56.3 mmol) in toluene (30 ml) was added dropwise. The mixture was heated to 80°C for 15 hours, cooled to room temperature and stirred overnight. The reaction mixture was then poured into a slurry of silica gel (250 g) and dichloromethane (300 ml). The resulting mixture was stirred for 10 minutes and filtered, washing the silica gel with methanol (300ml). Concentration of the combined filtrates provided 11.1 g of the title compound of Step A as a white solid. ¹ H NMR (Me ₂ SO-d ₆ ) δ 9.08 (m, 2H), 7.40 (m, 5H), 1.77 (m, 1H), 1.52 (m, 2H), 1.27 (m, 1H).

Step B: Preparation of 5-chloro-3-[1-(4-chlorophenyl)cyclopropyl]-1,2,4-thiadiazole

The title compound of Step A (11.1 g, 48.1 mmol) was dissolved in water (100 ml) and mixed with perchloromethanethiol (8.94 g, 48.1 mmol) and benzyltriethyl chloride in dichloromethane (200 ml). Ammonium (0.55 g, 2.4 mmol) was mixed. The resulting biphasic mixture was stirred vigorously, cooled to 0 °C and treated dropwise with a solution of sodium hydroxide (7.70 g, 193 mmol) in water (100 mL), maintaining the reaction temperature below 12 °C. The mixture was allowed to warm to room temperature and stirring was continued for 1 hour. The layers were separated, the organic phase was washed with water, dried over magnesium sulfate, filtered and concentrated. The residual oil was purified by flash column chromatography on silica gel with 2% ethyl acetate/hexanes to give 3.68 g of the title compound of Step B as a light yellow solid. ¹ H NMR (Me ₂ SO-d ₆ ) δ 7.41 (m, 4H), 1.62 (m, 2H), 1.42 (m, 2H).

Step C: Preparation of N-(2-methoxy-6-methylphenyl)-2,2-dimethylhydrazine carboxamide

At 0°C, 2-methoxy-6-methylaniline (125.0 g, 911 mmol) dissolved in ethyl acetate (250 ml) was added into ethyl acetate (750 ml) of phosgene (108 g, 1.09 mole) over 20 minutes. ) in a stirred solution. The reaction mixture was slowly warmed to room temperature, then heated to reflux for 1 hour. The solution was allowed to cool to room temperature and concentrated under reduced pressure to provide the crude isocyanate as a dark red liquid which was redissolved in ethyl acetate (1 L) and cooled to 0°C. 1,1-Dimethylhydrazine (55.0 g, 911 mmol) was added dropwise over 30 minutes, then the mixture was warmed to room temperature and stirred overnight. The mixture was cooled, filtered, the solid washed with ethyl acetate and dried to provide 200.0 g of the title compound of Step C as a white solid, mp 151-153°C. ¹ HNMR(CDCl ₃ )δ7.58(brs,1H),7.10(t,1H),6.84(d,1H),6.74(d,1H),5.22(brs,1H)3.80(s,3H),2.63 (s,6H), 2.31(s,3H).

Step D: 5-Chloro-2,4-dihydro-4-(2-methoxy-6-methylphenyl)-2-methyl-3H-1,2,4-triazole-3- Preparation of ketones

The title compound of Step C (100.0 g, 447.9 mmol) was suspended in ethyl acetate (1 L) and added dropwise to phosgene (177 g, 1.79 mole) in ethyl acetate (1.5 L) via a mechanical pump over 3.5 hours (heated into the stirred solution at reflux). After the addition was complete, the mixture was heated at reflux for an additional 3 hours, cooled to room temperature and stirred overnight. The solution was concentrated under reduced pressure and the residue was dissolved in ethyl acetate and water and extracted 4 times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride, dried (magnesium sulfate), filtered and concentrated to afford 111.4 g of the title compound of Step D as a pale yellow solid, mp 132-134°C. ¹ H NMR (CDCl ₃ ) δ 7.34 (t, 1H), 6.93 (d, 1H), 6.85 (d, 1H), 3.79 (s, 3H), 3.54 (s, 3H), 2.20 (s, 3H).

Step E: 5-Chloro-2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-2-methyl-3H-1,2,4-triazol-3-one preparation

At 0°C, aluminum chloride (23.7g, 178mmol) was added in small portions to a solution of the title compound (15.0g, 59.3mmol) in Step D in benzene (200ml). The mixture was stirred at room temperature for 2 days. The mixture was poured into ice and water. Extracted 4 times with ethyl acetate, washed the combined organic phases with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated to an oil, then purified by flash silica gel column chromatography to give 13.6 g of the title compound of Step E, It is a light orange solid with a melting point of 175-178°C. ¹ H NMR (CDCl ₃ ) δ 8.11 (s, 1H), 6.92 (t, 1H), 6.71 (d, 1H), 6.41 (d, 1H), 3.56 (s, 3H), 2.12 (s, 3H).

Step F: 2,4-Dihydro-4-(2-hydroxy-6-methylphenyl)-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one preparation of

Sodium methoxide (25% by weight in methanol, 382ml, 1.67mol) was added dropwise to a stirred solution of the title compound from Step E (133.5g, 557.0mmol) in tetrahydrofuran (1.5L). The mixture was heated at reflux for 3 hours, cooled to room temperature, then diluted with aqueous ammonium chloride and ethyl acetate. The aqueous layer was acidified (pH 4-5) with 1N hydrochloric acid and extracted 3 times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride, dried (magnesium sulfate), filtered and concentrated to a dark brown solid which was triturated with ethyl acetate to provide 75.0 g of the title compound of Step F as a white solid, mp 194 -196°C. ¹ HNMR(Me ₂ SO-d ₆ )δ9.91(s,1H),7.17(t,1H),6.78(m,2H),3.84(s,3H),3.30(s,3H),2.03(s ,3H).

Step G: 4-[2-[[3-[1-(4-Chlorophenyl)cyclopropyl]-1,2,4-thiadiazol-5-yl]oxy]-6-methylbenzene Preparation of ]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

Potassium carbonate (1.41 g, 10.2 mmol) was added to the title compound of step B (2.30 g, 8.50 mmol) and the title compound of step F (2.00 g, 8.50 mmol) in N,N-dimethylformamide (100 ml). ) in the solution. The mixture was stirred at room temperature for 16 hours, then diluted with water and extracted 3 times with ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium chloride, dried (magnesium sulfate), filtered and concentrated. The residual oil was purified by flash column chromatography on silica gel using 40% ethyl acetate/hexane as eluent to provide 2.99 g of the title compound of Step G, a compound of the present invention, as a pale yellow solid, mp 119-121 ℃. ¹ H NMR (CDCl ₃ ) δ 7.34 (m, 7H), 3.82 (s, 3H), 3.42 (s, 3H), 2.28 (s, 3H), 1.65 (m, 2H), 1.31 (m, 2H).

Example 15

Step A: Preparation of N-[2-(bromomethyl)phenyl]-2,2-dimethylhydrazine carboxamide

A solution of o-cresyl isocyanate (50.4 g) and 75.2 g of N-bromosuccinamide in 800 ml of carbon tetrachloride was heated to reflux. Benzoyl peroxide (1.1 g) was added and the mixture was heated to reflux for 1.5 hours. The solution was allowed to cool to room temperature and the precipitate was removed by filtration. The filtrate was concentrated in vacuo and redissolved in 500ml toluene, cooled to 5°C. 1,1-Dimethylhydrazine (30ml) in 20ml toluene was added dropwise. The reaction mixture was stirred overnight at room temperature. The precipitated solid was collected by filtration and redissolved in 1 L of dichloromethane. The organic solution was washed with 500 ml of water and then with 500 ml of saturated aqueous sodium chloride solution. The organic phase was dried (magnesium sulfate), filtered and concentrated to afford 58 g (56% yield) of the title compound of step A as a beige solid. ¹ HNMR(CDCl ₃ )δ 8.6(brs,1H),8.00(d,1H),7.30(m,2H),7.04(t,1H),5.70(brs,1H),4.52(s,2H),2.67 (s,6H). This material was used in the next step without further characterization.

Step B: 5-Chloro-4-[2-(chloromethyl)phenyl]-2,4-dihydro-2-methyl-3H-1,2,4-triazol-3-one preparation

The title compound of Step A (58 g) was dissolved in 800 ml of dichloromethane, and 86 g of triphosgene was added in one portion. A slight exotherm was observed and the mixture was heated to reflux overnight. The reaction mixture was cooled and the solvent was removed in vacuo. The resulting solid was dissolved in 1 L of ethyl acetate, washed with 500 mL of water, 500 mL of saturated aqueous sodium bicarbonate, and then 500 mL of saturated aqueous sodium chloride. The organic phase was dried (magnesium sulfate), filtered and concentrated to a dark oil which solidified on standing. This solid was triturated with 2:1 hexane:n-butyl chloride to give 32 g of a beige solid. Recrystallization of this solid from 150 mL of hot methanol yielded 21 g of the title compound of Step B as a white fluffy solid, mp 122-124°C. A second product was obtained by recrystallization from the mother liquor. ¹ H NMR (CDCl ₃ ) δ 7.45-7.6 (m, 3H), 7.25 (m, 1H), 4.68 (d, 1H), 4.46 (d, 1H), 3.56 (s, 3H). About ¹⁰ % of 4-[2-(bromomethyl)phenyl]-5-chloro-2,4-dihydro-2-methyl-3H-1,2, 4-Triazol-3-one.

Step C: Preparation of 1-(3-hydroxyphenyl)acetoxime

Under nitrogen, 3.5 g of hydroxylamine hydrochloride were added to a solution of 6.8 g of 3'-hydroxyacetophenone in 50 ml of pyridine. The solution was refluxed for 5 hours, then the solvent was removed in vacuo. The residue was dissolved in 1N aqueous hydrochloric acid, extracted twice with 50 mL of ethyl acetate, the combined organic phases were dried (magnesium sulfate), filtered and concentrated in vacuo to afford 7.8 g of the title compound of Step C as a light amber oil, ¹ HNMR(CDCl ₃ )δ7.25(d,1H),7.23(s,1H),7.2(m,2H),7.10(d plus advanced coupling,1H),6.84(ddd,1H),2.24(s,3H ).

Step D: 5-Chloro-2,4-dihydro-4-[2-[[[[1-(3-hydroxyphenyl)ethylidene]amino]oxy]methyl]phenyl]-2- Preparation of methyl-3H-1,2,4-triazol-3-one

Potassium carbonate (7 g, 51 mmol) was added to a solution of the title compound from Step C (3.9 g, 25.8 mmol) and the title compound from Step B (6.6 g, 25.8 mmol) in acetonitrile (100 ml). The mixture was heated to reflux for 4 hours, then stirred at room temperature overnight, and after reheating (7 hours) and standing at room temperature (72 hours), the mixture was diluted with water and extracted with ethyl acetate (3 x 50ml). The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure to give an oil which was chromatographed on silica gel (3:2 hexane:ethyl acetate as eluent) to provide 5.47 g of the title compound of Step D, the present The compound of the invention is an oil. ¹ HNMR(CDCl ₃ )δ8.09(brs,1H),7.62(d,1H),7.51(m,2H),7.22(m,4H),6.9(d,1H),5.08(q,2H), 3.44(s,3H),2.25(m,4H). This material was used in Example 16 without further characterization.

Example 16

2,4-2 Dihydro-4-[2-[[[[1-(3-hydroxyphenyl)ethylidene]amino]oxy]methyl]phenyl]-5-methoxy-2- Preparation of methyl-3H-1,2,4-triazol-3-one

A 30% solution of sodium methoxide in methanol (6.8ml, 36mmol) was added to a solution of the title compound (5.4g, 14.5mmol) of Step D of Example 15 in THF (350ml), and the resulting mixture was stirred at room temperature overnight, The mixture was diluted with ¹ N HCl in ether (20 mL) and concentrated under reduced pressure to provide a semi-solid. The residue was dissolved in ethyl acetate, and the insoluble portion was removed by filtration. Concentration of the organic phase under reduced pressure provided 4.36 g of the title compound of Example 16, a compound of the invention, as an oil. ¹ HNMR(CDCl ₃ )δ7.6(dd,1H),7.45(m,2H),7.25(m,3H),7.19(m,2H),6.85(dd,1H),5.08(AB q,2H) ,3.92(s,2H),3.39(s,3H),2.24(s,3H). This material was used in Example 17 without further characterization.

Example 17

[3-[1-[[[2-(1,5-Dihydro-3-methoxy-1-methyl-5-oxo-4H-1,2,4-triazol-4-yl] Preparation of 1,1-dimethylethyl phenyl]methoxy]imino]ethyl]phenoxy]acetate

A 60% oil dispersion of sodium hydride (35 mg) was added to a solution of the title compound of Example 16 (260 mg, 0.7 mmol) in tetrahydrofuran (20 ml), followed by tert-butyl bromoacetate (0.10 ml, 0.7 mmol) . The mixture was stirred at room temperature for 2 hours, then diluted with water and extracted with three 20 mL portions of ethyl acetate. The combined organic phases were dried (magnesium sulfate) and concentrated under reduced pressure to provide 290 mg of the title compound of Example 17, a compound of the invention, as an oil. ¹ HNMR(CDCl ₃ )δ7.6(m,1H),7.45(m,2H),7.23(m,4H),6.87(m,1H),5.09(AB q,2H),4.63(s,2H) ,3.91(s,3H),3.39(s,3H),2.28(s,3H),1.48(s,9H).

Example 18

Step A: the preparation of (2-bromomethyl) methyl phenylacetate

Mix o-methyl phenylacetate (24g), N-bromosuccinimide (27.2g) and benzoyl peroxide (about 50mg) in 200ml of carbon tetrachloride, heat to reflux with a high-intensity light source up to 1.5 hours. After cooling, the precipitate was removed by filtration and the filtrate was concentrated in vacuo to afford 36 g (ca. 100% yield) of the title compound of Step A as an amber oil. ¹ H NMR (CDCl ₃ ) δ 7.34 (m, 1H), 7.26 (m, 2H), 7.16 (m, 1H), 4.57 (s, 2H), 3.80 (s, 2H), 3.69 (s, 3H).

Step B: Preparation of 2-[[(benzoylamino)oxy]methyl]phenylacetic acid methyl ester

Phenylhydroxamic acid (17 g) and potassium carbonate (18.7 g) were suspended in 200 ml of acetonitrile, and the mixture was stirred at 60°C for 30 minutes. A solution of 28 g of the title compound from Step A in 100 mL of acetonitrile was added dropwise over 30 minutes. The mixture was stirred at 60°C for 3 hours, then cooled to room temperature overnight. Continue heating for another 4 hours. The mixture was cooled and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in 200 ml ethyl acetate and washed with 100 ml 6% aqueous potassium carbonate. The aqueous washes were extracted with 100 ml of ethyl acetate. The combined organic phases were washed with 100 ml of water. The organic phase was dried (magnesium sulfate), filtered and concentrated in vacuo to afford 31.5 g (93% yield) of the title compound of Step B as an orange oil. ¹ HNMR(CDCl ₃ )δ9.09(brs,1H),7.60(m,2H),7.47(m,1H),7.37(m,3H),7.29(m,3H),5.14(s,2H), 3.88(s,2H),3.71(s,3H).

Step C: Preparation of 2-[(aminooxy)methyl]phenylacetic acid methyl ester hydrochloride

The title compound of Step B (31.5 g) was added to a methanolic HCl solution (prepared by slowly adding 20 mL of acetyl chloride to 200 mL of methanol). The mixture was heated at 60°C for 1.5 hours. Solvent was removed in vacuo. The residue was dissolved in 100 ml ether and stirred at room temperature for 30 minutes. The ether layer was decanted, the solid dissolved in 100 mL THF and heated to about 50°C. The mixture was cooled in an ice-water bath and the solid was collected by filtration to provide 11.5 g (47% yield) of the title compound of Step C as a white solid, mp 169-170°C.

Step D: Preparation of 2-[[[[1-(4-hydroxyphenyl)ethylidene]amino]oxy]methyl]phenylacetate

4'-Hydroxyacetophenone (817mg) and the title compound of Step C (1.39g) were dissolved in 40ml of pyridine. The solution was heated to 90 °C overnight and then cooled to room temperature. Pyridine was removed in vacuo, the residue was dissolved in 40ml 1N hydrochloric acid and extracted with ethyl acetate (3 x 50ml). The combined organic layers were dried (magnesium sulfate), filtered and concentrated in vacuo to afford 1.96 g of the title compound of Step D as an amber oil. ¹ HNMR(CDCl ₃ )δ7.51(d,2H),7.45(m,1H),7.28(m,3H),6.78(d,2H),5.25(s,2H),3.82(s,2H), 3.68(s,3H), 2.19(s,3H). About 20% of the Z-isomer was also observed and this material was used in the next step without further purification.

Step E: Preparation of [2-[[[[1-(4-hydroxyphenyl) ethylidene] amino] oxygen] methyl] phenyl] dimethyl malonate

The title compound from Step D (1.87 g, 6 mmol) was dissolved in 10 mL of dimethyl carbonate. A slurry of 480 mg of sodium hydride (60% oil dispersion) in 10 ml of tetrahydrofuran was added and the mixture was heated to reflux for 1 hour. The mixture was then allowed to cool to room temperature overnight, quenched with 15 ml of 1N hydrochloric acid solution, washed with ethyl acetate Ester (3 x 25ml) was extracted. The combined organic layers were dried (magnesium sulfate), filtered and concentrated in vacuo to afford 2.33 g of crude, the title compound of Step E, as an amber oil. ¹ HNMR(CDCl ₃ )δ7.5(m,3H),7.4(m,3H),6.79(d,2H),5.25(s,2H),5.10(s,1H),3.68(s,6H), 2.18(s,3H). This material was used in the next step without further purification.

Step F: 4-[2-[[[[1-(4-Hydroxyphenyl)ethylidene]amino]oxy]methyl]phenyl]-5-methoxy-2-methyl-3(2H )- Preparation of isoxazolone

N-Methylhydroxylamine hydrochloride (1.5 g) was dissolved in 25 ml methanol. Under cooling in an ice bath, a solution of 2.0 g of potassium hydroxide dissolved in 25 ml of methanol was added. After 15 minutes, precipitated potassium chloride was removed by filtration. To this filtrate was added a solution of 2.2 g of the title compound from Step E in 10 mL of methanol. The resulting mixture was stirred overnight at room temperature. The mixture was diluted with water, acidified with hydrochloric acid and extracted with dichloromethane (3 x 30ml). The combined organic layers were dried (magnesium sulfate), filtered and concentrated in vacuo to give 1.95 g of an amber oil which was dissolved in 30 mL of toluene and 3 mL of methanol. A 10% solution of trimethylsilyldiazomethane in hexane (3 ml) was added dropwise, and the solution was stirred at room temperature for 2 hours. The solvent was removed in vacuo and the residue was purified by flash chromatography (1:1 hexane:ethyl acetate as eluent). Pooling of the third eluted fractions afforded 200 mg of the title compound of Step F, a compound of the invention, as an amber oil. ¹ HNMR(CDCl ₃ )δ7.52(d,1H),7.42(m,2H),7.32(m,3H),6.72(m,3H),5.24(AB q,2H),3.94(s,3H) , 3.44(s,3H), 2.16(s,3H). Very small amounts of the Z-isomer were also observed.

Example 19

[3-[2-(1,5-Dihydro-3-methoxy-1-methyl-5-oxo-4H-1,2,4-triazol-4-yl)phenoxy]benzene Preparation of base] trifluoromethanesulfonate

Trifluoromethanesulfonic anhydride (0.17ml, 1mmol) and pyridine (0.08ml, 1mmol) were added to a solution of the title compound of Example 12 (313mg, 1mmol) in dichloromethane (10ml), and the mixture was stirred at room temperature overnight, Dilute with water, acidify with 1N hydrochloric acid, and extract with 3 portions (20ml/part) of dichloromethane. The combined organic phases were dried (magnesium sulfate), filtered and concentrated in vacuo to an oil which was purified by flash chromatography (1:1 hexane:ethyl acetate as eluent). Pooling of the first eluted fractions afforded 100 mg of the title compound of Example 19, a compound of the present invention, as an amber oil. ¹ H NMR (CDCl ₃ ) δ 7.42 (m, 3H), 7.3 (m, 1H), 7.04 (m, 3H), 6.96 (t, 1H), 3.83 (s, 3H), 3.38 (s, 3H).

Example 20

Step A: Preparation of 2-(3-bromophenyl)-2-methyl-1,3-dioxolane

Dissolve 1-(4-bromophenyl)ethanone (60.6g, 0.3mole), ethylene glycol (83.7ml, 1.5mole) and p-toluenesulfonic acid (0.15g) in benzene (250ml), use The Dean-Stark apparatus was heated to reflux overnight. The water and some ethylene glycol were separated, the mixture cooled to room temperature was poured into water (300ml) and the resulting mixture was extracted with 1-chlorobutane (2x100ml). The combined organic phases were dried (magnesium sulfate) and concentrated to give the crude product as a yellow oil. The oil was purified by vacuum distillation (64-74 °C/19 Pa (0.14 mmHg)) to afford 70.1 g of the title compound of Step A as a colorless oil (96% yield).

Step B: Preparation of 1-[3-[three(trifluoromethyl)germyl]phenyl]ethanone

Magnesium turnings (0.61 g, 0.025 mol) suspended in 5 ml THF were charged into a 250 ml 4-necked flask. A solution of the title compound from Step A in 35 ml THF was added dropwise and after addition of a small portion of this solution, a small amount of iodine crystals were added to the mixture. Heating to reflux was required to initiate the reaction. After the addition of the title compound from Step A was complete, the reaction was refluxed for 2 hours. After cooling the mixture to 63 °C, a solution of tris(trifluoromethyl)germanium iodide (3.9 ml, 0.02 mole) in THF (20 ml) was added in small portions, allowing each addition to exotherm to maintain the temperature at 62 °C. Between -69°C. The mixture was refluxed for an additional 3 hours, then stirred overnight at room temperature. The mixture was poured into saturated ammonium chloride solution (100ml). The organic layer was then removed and extracted with ethyl acetate, the combined organic phases were dried (magnesium sulfate) and concentrated to give 8.9 g of a dark oil. The oil was then dissolved in acetone (400ml), and 1N hydrochloric acid (3ml) was added to the oil. The resulting solution was refluxed overnight. The mixture was concentrated, followed by a second addition of acetone (300ml) and 1N hydrochloric acid (2ml), followed by further reflux for 6 hours. The mixture was concentrated, then the residue was dissolved in ether and washed with saturated sodium bicarbonate. The organic layer was then dried (magnesium sulfate) and concentrated. The resulting dark brown oil was purified by filtration through a 1.5 inch silica gel column eluting with 15% ethyl acetate/hexanes to afford 2.95 g (37% over two steps) of the title compound of Step B as a colorless oil. ¹ H NMR (CDCl ₃ ) δ 8.284 (s, 1H), 7.9-8.0 (m, 2H), 7.2 (t, 1H), 2.586 (s, 3H).

Step C: Preparation of 1-[3-[tri(trifluoromethyl)germyl]phenyl]ethanone oxime

Sodium acetate trihydrate (1.22g, 9mmol) was added to a solution of hydroxylamine hydrochloride (0.62g, 9mmol) in water (7ml) and this solution was added to the title compound of Step B (2.95g, 7.4mmol) in methanol (20ml) solution. The mixture was then refluxed overnight and concentrated in vacuo. The mixture was treated with water and extracted with dichloromethane (3 x 120ml). The combined organic layers were dried (magnesium sulfate) and concentrated to give 2.74 g of a brown oil. The oil was chromatographed eluting with 15% ethyl acetate/hexanes to afford 1.72 g (56% yield) of the title compound of step C as a colorless oil. The oil crystallized on standing to give a solid m.p. 69-72°C.

Step D: 2,4-Dihydro-5-methoxy-2-methyl-4-[2-[[[[1-[3-[tris(trifluoromethyl)germyl]phenyl Preparation of ]ethylene]amino]oxy]methyl]phenyl]-3H-1,2,4-triazol-3-one

In a 125 ml 4-neck flask, sodium hydride (0.18 g, 4.5 mmol, 60% dispersion in mineral oil) was suspended in 8 ml dry THF. The title compound from Step C (2.0 g, 6.9 mmol) was dissolved in anhydrous THF (5 ml) and added dropwise causing gas evolution. The mixture was stirred at room temperature for 20 minutes, then a solution of the title compound from Example 15, Step B (0.39 g, 1.5 mmol) dissolved in anhydrous THF (5 mL) was added dropwise. To make it viscous, additional anhydrous THF (3ml) was added. The mixture was heated to reflux overnight, then cooled to room temperature. Additional sodium hydride (0.18 g, 4.5 mmol) was added and reflux was resumed for 6 hours. The mixture was allowed to cool, then stirred overnight at room temperature. Sodium hydride (0.06 g, 1.5 mmol) was added again, followed by careful dropwise addition of anhydrous methanol (0.5 ml, 1.5 mmol), causing gas evolution. The mixture was refluxed for an additional 3 hours, then cooled to room temperature. A few drops of 2-propanol were added and the mixture was concentrated until only a small amount of liquid remained. Hexanes (100 mL) were added and the mixture was purified by filtration through a 1 inch silica gel column eluting with a 1:1 mixture of dichloromethane/ethyl acetate (500 mL) to give 0.72 g of a yellow oil after concentration. The crude oil was purified by medium pressure liquid chromatography (MPLC) using 20% ethyl acetate/hexanes to afford the title compound of Step D, a compound of this invention, as an oil (0.27 g, 28%). ¹ HNMR(CDCl ₃ )δ7.941(s,1H),7.7(d,1H),7.55(m,2H),7.4-7.5(m,2H),7.4-7.5(m,2H),7.1(t ,2H), 5.2-5.4(q,2H), 3.889(s,3H), 3.413(s,3H), 2.152(s,3H).

Example 21

Step A: Preparation of 1-[3-[dimethyl(3,3,3-trifluoropropyl)silyl]phenyl]ethanone

Magnesium turnings (1.09 g, 0.041 mol) suspended in 8 ml THF were charged to a 125 ml 4-necked flask. A solution of the title compound from Example 20, Step A in 20 ml THF was added dropwise and after addition of a small portion of this solution, a small amount of crystalline iodine was added to the mixture. Heating to reflux was required to initiate the reaction. After the addition of the title compound from Step A was complete, the reaction was refluxed for 3 hours. After cooling the mixture to 48 °C, a solution of 3,3,3-trifluoropropyldimethylchlorosilane (7.82 g, 0.041 mole) in THF (8 ml) was added in small portions, allowing each addition to cool. The heat maintenance temperature is between 48-64°C. The mixture was refluxed for a further 5 hours, then cooled and poured into saturated ammonium chloride solution (200ml). The organic layer was then removed and extracted with diethyl ether, the combined organic phases were dried (magnesium sulfate) and concentrated to give 12.27 g of a yellow oil. The oil was then dissolved in acetone (500ml), and 1N hydrochloric acid (6ml) was added to the oil. The resulting solution was refluxed overnight. Concentration followed by partitioning between water and ether, then drying (magnesium sulfate) of the organic phase gave 10.79 g (94% over two steps) of the title compound of Step A as a yellow oil. ¹ HNMR(CDCl ₃ )δ8.078(s,1H),7.9(d,1H),7.7(d,1H),7.484(t,1H),2.625(s,3H),1.9-2.1(m,2H ), 1.0(m,2H), 0.359(s,6H).

Step B: Preparation of 1-[3-[dimethyl[3,3,3-trifluoropropyl)silyl]phenyl]ethanone oxime

Sodium acetate trihydrate (7.76 g, 0.057 mole) was added to a solution of hydroxylamine hydrochloride (3.96 g, 0.057 mole) in water (59 ml) and this solution was added to the title compound of Step A (10.7 g, 0.039 mole) methanol (78ml) solution. The mixture was then refluxed overnight and concentrated in vacuo. The mixture was treated with water and extracted with dichloromethane (3 x 120ml). The combined organic layers were dried (magnesium sulfate) and concentrated to give 11.34 g of a yellow oil. Chromatography of the oil eluting with 10% ethyl acetate/hexanes afforded 9.41 g (83% yield) of the title compound of Step B as a colorless oil. ¹ HNMR(CDCl ₃ )δ9.0(s,1H),7.748(s,1H),7.6(d,1H),7.5(d,1H),7.4(t,1H),2.310(s,3H), 2.0(m,2H),1.0(m,2H),0.338(s,5H).

Step C: 4-[2-[[[[1-[3-[Dimethyl-(3,3,3-trifluoropropyl)silyl]phenyl]ethylene]amino]oxy]methanol Preparation of base]phenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

In a 250 ml 4-neck flask, sodium hydride (0.84 g, 0.021 mole, 60% dispersion in mineral oil) was suspended in 50 ml dry THF. The title compound from Step B (2.0 g, 6.9 mmol) was dissolved in anhydrous THF (15 ml) and added dropwise causing gas evolution. The mixture was stirred at room temperature for 1 hour, then a solution of the title compound of Example 15, Step B (1.78 g, 6.9 mmol) dissolved in anhydrous THF (15 mL) was added dropwise. The mixture was heated to 35°C overnight, then methanol (2.2ml, 55mmol) was carefully added dropwise causing gas evolution. The mixture was refluxed overnight. A few drops of 2-propanol were added and the mixture was concentrated until only a small amount of liquid remained. Hexanes (100 mL) were added and the mixture was filtered through a 1 inch silica gel column eluting with a 1:1 mixture of dichloromethane/ethyl acetate (1500 mL) to give 3.35 g of an orange oil. Purification by MPLC (using 1.2% methanol/dichloromethane) afforded the title compound of Step C (1.31 g, 37%), a compound of the invention, as an oil. ¹ HNMR(CDCl ₃ )δ7.7(s,1H),7.6(m,2H),7.4-7.5(m,3H),7.4(t,1H),7.2(d,2H),5.2-5.3(q ,2H),3.882(s,3H),3.401(s,3H),2.201(s,3H),2.0(m,2H),1.0(m,2H),0.32(s,5.5H).

By combining the procedures described herein with methods known in the art, the compounds in Tables 1-7 below can be prepared. The following abbreviations are used in the tables below: t = tertiary, n = normal, i = iso, c = ring, Me = methyl, Et = ethyl, Pr = propyl, i-Pr = isopropyl, Bu = butyl Hex = hexyl, Ph = phenyl, OMe = methoxy, OEt = ethoxy, SMe = methylthio, CN = cyano, SCN = thiocyanate, NO ₂ = nitro, TMS = trimethyl Silyl group, Bzl=benzyl group, ada=1-adamantyl group, TMG=trimethylgermyl group and THP=2-tetrahydropyranyl group.

R³=H，和R⁹                R⁹               R⁹               R⁹3-CH₂OCH₃    3-OCH₂OCH₂TMS  4-SCH₂CH=CH₂    3-S(O)CF₂CF₃3-C≡C-OCH₃   4-SCN             3-C≡C-TMS        3-(1-Ph-2,2-Di-Cl-c-Pr)3-C≡C-I       3-Ge(Me)₂CF₃    3-OSi(Me)₂Ph     3-(2-Me-4-Ph-c-Hex)3-ada          3-Si(Me)₂CF₃    2-OH              3-C≡C-OTHP3-CH₂S-n-Pr   3-Ge(CF₃)₃      2-N(Me)Bzl        3-OCH₂CF=CF₂3-SC≡CEt      3-SCH₂C≡C-I     3-SCH₂OMe        3-SCH₂SEt3-OGe(Me)₂Ph      3-(C(=O)(3-Me-    4-C(=S)Me           4-((4-F-Bzl)-OC(=O))Bzl))4-C(=S)OEt         4-C(=S)SCHF₂     2-C(=O)N(Me)₂      2-C(=S)N(Et)₂4-CH₂CN           3-OC(=O)Me        3-OC(=S)Me          4-SC(=O)Me4-NHC(=O)Me        4-NHC(=S)Ph       4-OC(=O)O-c-Hex     4-OC(=O)S-n-Pr3-SC(=O)OCH₂CF₃  2-SC(=O)SMe       4-S(O)₂OCH₂CF₃  4-S(O)₂N(Me)₂4-(NHSO₂(4-Me-    4-(OCH₂(4-TMS-   2-CH₂OCH₂(2,4-Di-4-((4-TMS-Ph)-C≡C)Ph))               Ph))              F-Ph)3-(S-(4-TMG-Ph))   4-S(O)₂Ph        3-(SCH₂(3-Me-Ph))  3-(4-吡啶基-CH₂)3-(4-吡啶基-C≡C)  3-(2-吡啶基-S)    4-(2-噻吩基-CH₂)   4-(2-噻吩基-S)4-(2-呋喃基-O)     4-(3-呋喃基-S)    2-(4-嘧啶基-CH₂)   2-(2-嘧啶基-S)4-OC≡CCH₃        4-OCH₂CH₂OMe   3-OCH₂SMe          3-S(O)₂CH₂CH₂CF₃3-S(O)₂CF₃       2-NH₂           4-C(=S)OEt           2-C(=NH)OMe4-SC(=S)-i-Pr      2-OC(=O)N(Me)Ph   3-OS(O)₂CH₃       3-((4-CN-Ph)-OCH₂)3-(2-呋喃基-CH₂)  3-(2-噻唑基-CH₂) 3-((3-CF₃-4-吡啶基-OCH₂)R³=3-Me，和R⁹                      R⁹              R⁹              R⁹3-CH₂OCH₃       3-OCH₂OCH₂TMS  4-SCH₂CH=CH₂      3-S(O)CF₂CF₃3-C≡C-OCH₃      4-SCN             3-C≡C-TMS           3-(1-Ph-2,2-Di-Cl-c-Pr)3-C≡C-I          3-Ge(Me)₂CF₃    3-OSi(Me)₂Ph       3-(2-Me-4-Ph-c-Hex)3-ada             3-Si(Me)₂CF₃    2-OH                3-C≡C-OTHP3-CH₂S-n-Pr      3-Ge(CF₃)₃      2-N(Me)Bzl          3-OCH₂CF=CF₂3-SC≡CEt         3-SCH₂C≡C-I     3-SCH₂OMe          3-SCH₂SEt3-OGe(Me)₂Ph     3-(C(=O)(3-Me-    4-C(=S)Me           4-((4-F-Bzl)-OC(=O))Bzl))4-C(=S)OEt        4-C(=S)SCHF₂     2-C(=O)N(Me)₂      2-C(=S)N(Et)₂4-CH₂CN          3-OC(=O)Me        3-OC(=S)Me          4-SC(=O)Me4-NHC(=O)Me       4-NHC(=S)Ph       4-OC(=O)O-c-Hex     4-OC(=O)S-n-Pr3-SC(=O)OCH₂CF₃     2-SC(=O)SMe      4-S(O)₂OCH₂CF₃   4-S(O)₂N(Me)₂4-(NHSO₂(4-Me-       4-(OCH₂(4-TMS-  2-CH₂OCH₂(2,4-Di- 4-((4-TMS-Ph)-C≡C)Ph))                  Ph))              F-Ph)3-(S-(4-TMG-Ph))      4-S(O)₂Ph        3-(SCH₂(3-Me-Ph))  3-(4-吡啶基-CH₂)3-(4-吡啶基-C≡C)     3-(2-吡啶基-S)    4-(2-噻吩基-CH₂)   4-(2-噻吩基-S)4-(2-呋喃基-O)        4-(3-呋喃基-S)    2-(4-嘧啶基-CH₂)   2-(2-嘧啶基-S)4-OC≡CCH₃           4-OCH₂CH₂OMe   3-OCH₂SMe          3-S(O)₂CH₂CH₂CF₃3-S(O)₂CF₃          2-NH₂           4-C(=S)OEt          2-C(=NH)OMe4-SC(=S)-i-Pr         2-OC(=O)N(Me)Ph   3-OS(O)₂CH₃      3-((4-CN-Ph)-OCH₂)3-(2-呋喃基-CH₂)     3-(2-噻唑基-CH₂) 3-((3-CF₃-4-吡啶基Table 1

R ³ =H, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C -OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi( Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge (CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3 -(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl)-OC(=O))Bzl))4-C(=S)OEt 4- C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3-OC(=O)Me 3-OC(=S )Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4-OC(=O)Sn-Pr3-SC(=O )OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4-(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-( 4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C ) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S) 4-(2-furyl-O) 4-(3-furyl- S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(=S)-i-Pr 2-OC(=O) N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl-OCH ₂ )R ³ =3-Me, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-Pr )3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C≡ CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl)- OC(=O))Bzl))4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3-OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O )Oc-Hex 4-OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4-(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di- 4-((4-TMS-Ph)-C ≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-( 4-pyridyl-CH ₂ )3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S )4-(2-furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4- OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH )OMe4-SC(=S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-( 2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )R ³ =6-Me, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )R ³ =6-TMG, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )R ³ =4-S(O) ₂ CH ₃ , and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S (O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ )3-((3-CF3-4-pyridyl

-OCH ₂ )

D=CH,R³=7-Cl,R⁴=H，和R⁹                 R⁹               R⁹                R⁹3-CH₂OCH₃        3-OCH₂OCH₂TMS  4-SCH₂CH=CH₂      3-S(O)CF₂CF₃3-C≡C-OCH₃       4-SCN             3-C≡C-TMS          3-(1-Ph-2,2-Di-Cl-c-Table 2

D=CH, R ³ =7-Cl, R ⁴ =H, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S( O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )D=N, R ³ =7-I, R ⁴ =5-Cl, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH= CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ ( ₄ -Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di- 4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )D=N, R ³ =6-I, R ⁴ =H, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di-4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )

R³=H，和R⁹                R⁹                   R⁹                 R⁹3-CH₂OCH₃        3-OCH₂OCH₂TMS     4-SCH₂CH=CH₂      3-S(O)CF₂CF₃3-C≡C-OCH₃       4-SCN                3-C≡C-TMS          3-(1-Ph-2,2-Di-Cl-c-table 3

R ³ =H, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C -OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di- 4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )R ³ =6-C≡C-Si(Me) ₃ , and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH _{3 3} -OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3 -S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di- 4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )R ³ =3-(2-CN-Ph-C≡C-), and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH= CH ₂ 3S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4-Di- 4-((4-TMS-Ph)-C≡C)Ph)) Ph)) F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me-Ph)) 3-(4-pyridyl-CH ₂ ) 3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2- Furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3 -OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC(= S)-i-Pr 2-OC(=O)N(Me)Ph 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridyl

-OCH ₂ )

R⁹                 R⁹                   R⁹                 R⁹3-CH₂OCH₃         3-OCH₂OCH₂TMS      4-SCH₂CH=CH₂      3-S(O)CF₂CF₃3-C≡C-OCH₃        4-SCN                 3-C≡C-TMS          3-(1-Ph-2,2-Di-Cl-c-Table 4

R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

base-OCH ₂ )

D³=CH,D²=CH,D¹=CH,R³=H，和R¹¹              R¹¹             R¹¹              R¹¹4-Cl             2,4-Di-Cl        4-C≡C-I          4-C≡C-O-THP3-F              2-Me             3-CH₂OEt         3-CH₂OBzl2-I              3-CF₃           4-CH₂SMe         3-O-n-Pr4-CH=CH₂        3-C≡CH          3-C≡C-OMe        4-OCH₂CF₃4-S(O)₂CF₃     2-CN             2-NO₂            4-SCN4-SF₅           3-TMS            3-TMG             3-C≡C-TMS3-O-Ge(i-Pr)₃   4-C(=O)Me        4-C(=S)Me         3-C(=O)OBzl4-C(=O)N(Me)₂   4-C(=S)N(Me)₂   3-OC(=O)Ph        3-OC(=S)Ph4-NHC(=O)CH₃    4-NHC(=S)Me      3-OC(=O)-O-t-Bu   3-OC(=O)N(Me)₂2-OS(O)₂CF₃    4-N(Me)S(O)₂CH₃2-Ph              2-(2-CN-Ph)3-((3-CF₃-Ph)-  3-S(O)₂Ph       3-C≡C-Ph         4-(4-吡啶基-C≡C)CH₂O)4-OCH₂CH=CH₂   4-SEt            3-C(=O)SMe        2-(2-CN-Bzl)4-OCH₂CF=CF₂   4-OH             3-SC(=O)-n-戊基   3-SCHF₂3-OCH₂OCH₂-TMS 3-O-Si(i-Pr)₃   3-S(O)₂OCH₂CF₃3-S(O)CH₃3-S(O)CHF₂      3-S(O)₂CH₃      3-N(Me)₂         3-C(=S)SMe3-SC(=S)Bzl      2-S(O)₂N(Me)₂   3-((2-F-Ph)-O)     3-CH₂CH=C(Cl)₂D³=N,D²=N,D¹=CH,R³=3-Me，和R¹¹              R¹¹             R¹¹                R¹¹4-Cl             2,4-Di-Cl         4-C≡C-I           4-C≡C-O-THP3-F              2-Me              3-CH₂OEt          3-CH₂OBzl2-I              3-CF₃            4-CH₂SMe          3-O-n-Pr4-CH=CH₂        3-C≡CH           3-C≡C-OMe         4-OCH₂CF₃4-S(O)₂CF₃     2-CN              2-NO₂             4-SCN4-SF₅           3-TMS             3-TMG              3-C≡C-TMS3-O-Ge(i-Pr)₃   4-C(=O)Me         4-C(=S)Me          3-C(=O)OBzl4-C(=O)N(Me)₂   4-C(=S)N(Me)₂    3-OC(=O)Ph         3-OC(=S)Ph4-NHC(=O)CH₃    4-NHC(=S)Me       3-OC(=O)-O-t-Bu    3-OC(=O)N(Me)₂2-OS(O)₂CF₃    4-N(Me)S(O)₂CH₃ 2-Ph               2-(2-CN-Ph)3-((3-CF₃-Ph)-  3-S(O)₂Ph        3-C≡C-Ph          4-(4-吡啶基-C≡C)CH₂O)4-OCH₂CH=CH₂   4-SEt             3-C(=O)SMe         2-(2-CN-Bzl)4-OCH₂CF=CF₂   4-OH              3-SC(=O)-n-戊基    3-SCHF₂3-OCH₂OCH₂-TMS 3-O-Si(i-Pr)₃    3-S(O)₂OCH₂CF₃ 3-S(O)CH₃3-S(O)CHF₂      3-S(O)₂CH₃      3-N(Me)₂          3-C(=S)SMe3-SC(=S)Bzl      2-S(O)₂N(Me)₂   3-((2-F-Ph)-O)     3-CH₂CH=C(Cl)₂ table 5

D ³ =CH, D ² =CH, D ¹ =CH, R ³ =H, and R ¹¹ R ¹¹ R ¹¹ R ¹¹ 4-Cl 2,4-Di-Cl 4-C≡CI 4-C≡CO- THP3-F 2-Me 3-CH ₂ OEt 3-CH ₂ OBzl2-I 3-CF ₃ 4-CH ₂ SMe 3-On-Pr4-CH=CH ₂ 3-C≡CH 3-C≡C-OMe 4 -OCH ₂ CF ₃ 4-S(O) ₂ CF ₃ 2-CN 2-NO ₂ 4-SCN4-SF ₅ 3-TMS 3-TMG 3-C≡C-TMS3-O-Ge(i-Pr) ₃ 4-C(=O)Me 4-C(=S)Me 3-C(=O)OBzl4-C(=O)N(Me) ₂ 4-C(=S)N(Me) ₂ 3-OC (=O)Ph 3-OC(=S)Ph4-NHC(=O)CH ₃ 4-NHC(=S)Me 3-OC(=O)-Ot-Bu 3-OC(=O)N(Me ) ₂ 2-OS(O) ₂ CF ₃ 4-N(Me)S(O) ₂ CH ₃ 2-Ph 2-(2-CN-Ph)3-((3-CF ₃ -Ph)- 3- S(O) ₂ Ph 3-C≡C-Ph 4-(4-pyridyl-C≡C)CH ₂ O)4-OCH ₂ CH=CH ₂ 4-SEt 3-C(=O)SMe 2- (2-CN-Bzl)4-OCH ₂ CF=CF ₂ 4-OH 3-SC(=O)-n-pentyl 3-SCHF ₂ 3-OCH ₂ OCH ₂ -TMS 3-O-Si(i- Pr) ₃ 3-S(O) ₂ OCH ₂ CF ₃ 3-S(O)CH ₃ 3-S(O)CHF ₂ 3-S(O) ₂ CH ₃ 3-N(Me) ₂ 3-C( =S)SMe3-SC(=S)Bzl 2-S(O) ₂ N(Me) ₂ 3-((2-F-Ph)-O) 3-CH ₂ CH=C(Cl) ₂ D ³ = N, D ² =N, D ¹ =CH, R ³ =3-Me, and R ¹¹ R ¹¹ R ¹¹ R ¹¹ 4-Cl 2,4-Di-Cl 4-C≡CI 4-C≡CO-THP3 -F 2-Me 3-CH ₂ OEt 3-CH ₂ OBzl2-I 3-CF ₃ 4-CH ₂ SMe 3-On-Pr4-CH=CH ₂ 3-C≡CH 3-C≡C-OMe 4- OCH ₂ CF ₃ 4-S(O) ₂ CF ₃ 2-CN 2-NO ₂ 4-SCN4-SF ₅ 3-TMS 3-TMG 3-C≡C-TMS3-O-Ge(i-Pr) ₃ 4 -C(=O)Me 4-C(=S)Me 3-C(=O)OBzl4-C(=O)N(Me) ₂ 4-C(=S)N(Me) ₂ 3-OC( =O)Ph 3-OC(=S)Ph4-NHC(=O)CH ₃ 4-NHC(=S)Me 3-OC(=O)-Ot-Bu 3-OC(=O)N(Me) ₂ 2-OS(O) ₂ CF ₃ 4-N(Me)S(O) ₂ CH ₃ 2-Ph 2-(2-CN-Ph)3-((3-CF ₃ -Ph)- 3-S (O) ₂ Ph 3-C≡C-Ph 4-(4-pyridyl-C≡C)CH ₂ O)4-OCH ₂ CH=CH ₂ 4-SEt 3-C(=O)SMe 2-( 2-CN-Bzl)4-OCH ₂ CF=CF ₂ 4-OH 3-SC(=O)-n-pentyl 3-SCHF ₂ 3-OCH ₂ OCH ₂ -TMS 3-O-Si(i-Pr ) ₃ 3-S(O) ₂ OCH ₂ CF ₃ 3-S(O)CH ₃ 3-S(O)CHF ₂ 3-S(O) ₂ CH ₃ 3-N(Me) ₂ 3-C(= S)SMe3-SC(=S)Bzl 2-S(O) ₂ N(Me) ₂ 3-((2-F-Ph)-O) 3-CH ₂ CH=C(Cl) ₂

D³=CH,D²=CH,D¹=CH,R³=H，和R¹¹              R¹¹               R¹¹               R¹¹4-Cl              2,4-Di-Cl         4-C≡C-I           4-C≡C-O-THP3-F               2-Me              3-CH₂OEt          3-CH₂OBzl2-I               3-CF₃            4-CH₂SMe          3-O-n-Pr4-CH=CH₂         3-C≡CH           3-C≡C-OMe         4-OCH₂CF₃4-S(O)₂CF₃      2-CN              2-NO₂             4-SCN4-SF₅            3-TMS             3-TMG              3-C≡C-TMS3-O-Ge(i-Pr)₃    4-C(=O)Me         4-C(=S)Me          3-C(=O)OBzl4-C(=O)N(Me)₂    4-C(=S)N(Me)₂    3-OC(=O)Ph         3-OC(=S)Ph4-NHC(=O)CH₃     4-NHC(=S)Me       3-OC(=O)-O-t-Bu    3-OC(=O)N(Me)₂2-OS(O)₂CF₃     4-N(Me)S(O)₂CH₃2-Ph               2-(2-CN-Ph)3-((3-CF₃-Ph)-   3-S(O)₂Ph        3-C≡C-Ph          4-(4-吡啶基-C≡C)CH₂O)4-OCH₂CH=CH₂    4-SEt             3-C(=O)SMe         2-(2-CN-Bzl)4-OCH₂CF=CF₂    4-OH              3-SC(=O)-n-戊基    3-SCHF₂3-OCH₂OCH₂-TMS  3-O-Si(i-Pr)₃    3-S(O)₂OCH₂CF₃ 3-S(O)CH₃3-S(O)CHF₂       3-S(O)₂CH₃      3-N(Me)₂          3-C(=S)SMe3-SC(=S)Bzl       2-S(O)₂N(Me)₂   3-((2-F-Ph)-O)     3-CH₂CH=C(Cl)₂D³=N,D²=N,D¹=CH,R³=3-Me，和R¹¹              R¹¹               R¹¹               R¹¹4-Cl              2,4-Di-Cl         4-C≡C-I           4-C≡C-O-THP3-F               2-Me              3-CH₂OEt          3-CH₂OBzl2-I               3-CF₃            4-CH₂SMe          3-O-n-Pr4-CH=CH₂         3-C≡CH           3-C≡C-OMe         4-OCH₂CF₃4-S(O)2CF₃           2-CN             2-NO₂             4-SCN4-SF₅                3-TMS            3-TMG              3-C≡C-TMS3-O-Ge(i-Pr)₃        4-C(=O)Me        4-C(=S)Me          3-C(=O)OBzl4-C(=O)N(Me)₂        4-C(=S)N(Me)₂   3-OC(=O)Ph         3-OC(=S)Ph4-NHC(=O)CH₃         4-NHC(=S)Me      3-OC(=O)-O-t-Bu    3-OC(=O)N(Me)₂2-OS(O)₂CF₃         4-N(Me)S(O)₂CH₃2-Ph              2-(2-CN-Ph)3-((3-CF₃-Ph)-       3-S(O)₂Ph        3-C≡C-Ph         4-(4-吡啶基-C≡C)CH₂O)4-OCH₂CH=CH₂        4-SEt            3-C(=O)SMe         2-(2-CN-Bzl)4-OCH₂CF=CF₂        4-OH             3-SC(=O)-n-戊基    3-SCHF₂3-OCH₂OCH₂-TMS      3-O-Si(i-Pr)₃   3-S(O)₂OCH₂CF₃ 3-S(O)CH₃3-S(O)CHF₂           3-S(O)₂CH₃     3-N(Me)₂          3-C(=S)SMe3-SC(=S)Bzl           2-S(O)₂N(Me)₂  3-((2-F-Ph)-O)     3-CH₂CH=C(Cl)₂表7

R²=OH,R³=6-Me,R⁴=H,R¹⁰=H,Y=CH₂SC(=S)NH-、和R⁹                   R⁹              R⁹                R⁹3-CH₂OCH₃           3-OCH₂OCH₂TMS 4-SCH₂CH=CH₂     3-S(O)CF₂CF₃3-C≡C-OCH₃          4-SCN            3-C≡C-TMS         3-(1-Ph-2,2-Di-Cl-c-Table 6

D ³ =CH, D ² =CH, D ¹ =CH, R ³ =H, and R ¹¹ R ¹¹ R ¹¹ R ¹¹ 4-Cl 2,4-Di-Cl 4-C≡CI 4-C≡CO- THP3-F 2-Me 3-CH ₂ OEt 3-CH ₂ OBzl2-I 3-CF ₃ 4-CH ₂ SMe 3-On-Pr4-CH=CH ₂ 3-C≡CH 3-C≡C-OMe 4 -OCH ₂ CF ₃ 4-S(O) ₂ CF ₃ 2-CN 2-NO ₂ 4-SCN4-SF ₅ 3-TMS 3-TMG 3-C≡C-TMS3-O-Ge(i-Pr) ₃ 4-C(=O)Me 4-C(=S)Me 3-C(=O)OBzl4-C(=O)N(Me) ₂ 4-C(=S)N(Me) ₂ 3-OC (=O)Ph 3-OC(=S)Ph4-NHC(=O)CH ₃ 4-NHC(=S)Me 3-OC(=O)-Ot-Bu 3-OC(=O)N(Me ) ₂ 2-OS(O) ₂ CF ₃ 4-N(Me)S(O) ₂ CH ₃ 2-Ph 2-(2-CN-Ph)3-((3-CF ₃ -Ph)- 3- S(O) ₂ Ph 3-C≡C-Ph 4-(4-pyridyl-C≡C)CH ₂ O)4-OCH ₂ CH=CH ₂ 4-SEt 3-C(=O)SMe 2- (2-CN-Bzl)4-OCH ₂ CF=CF ₂ 4-OH 3-SC(=O)-n-pentyl 3-SCHF ₂ 3-OCH ₂ OCH ₂ -TMS 3-O-Si(i- Pr) ₃ 3-S(O) ₂ OCH ₂ CF ₃ 3-S(O)CH ₃ 3-S(O)CHF ₂ 3-S(O) ₂ CH ₃ 3-N(Me) ₂ 3-C( =S)SMe3-SC(=S)Bzl 2-S(O) ₂ N(Me) ₂ 3-((2-F-Ph)-O) 3-CH ₂ CH=C(Cl) ₂ D ³ = N, D ² =N, D ¹ =CH, R ³ =3-Me, and R ¹¹ R ¹¹ R ¹¹ R ¹¹ 4-Cl 2,4-Di-Cl 4-C≡CI 4-C≡CO-THP3 -F 2-Me 3-CH ₂ OEt 3-CH ₂ OBzl2-I 3-CF ₃ 4-CH ₂ SMe 3-On-Pr4-CH=CH ₂ 3-C≡CH 3-C≡C-OMe 4- OCH ₂ CF ₃ 4-S(O)2CF ₃ 2-CN 2-NO ₂ 4-SCN4-SF ₅ 3-TMS 3-TMG 3-C≡C-TMS3-O-Ge(i-Pr) ₃ 4- C(=O)Me 4-C(=S)Me 3-C(=O)OBzl4-C(=O)N(Me) ₂ 4-C(=S)N(Me) ₂ 3-OC(= O)Ph 3-OC(=S)Ph4-NHC(=O)CH ₃ 4-NHC(=S)Me 3-OC(=O)-Ot-Bu 3-OC(=O)N(Me) ₂ 2-OS(O) ₂ CF ₃ 4-N(Me)S(O) ₂ CH ₃ 2-Ph 2-(2-CN-Ph)3-((3-CF ₃ -Ph)- 3-S( O) ₂ Ph 3-C≡C-Ph 4-(4-pyridyl-C≡C)CH ₂ O)4-OCH ₂ CH=CH ₂ 4-SEt 3-C(=O)SMe 2-(2 -CN-Bzl)4-OCH ₂ CF=CF ₂ 4-OH 3-SC(=O)-n-pentyl 3-SCHF ₂ 3-OCH ₂ OCH ₂ -TMS 3-O-Si(i-Pr) ₃ 3-S(O) ₂ OCH ₂ CF ₃ 3-S(O)CH ₃ 3-S(O)CHF ₂ 3-S(O) ₂ CH ₃ 3-N(Me) ₂ 3-C(=S )SMe3-SC(=S)Bzl 2-S(O) ₂ N(Me) ₂ 3-((2-F-Ph)-O) 3-CH ₂ CH=C(Cl) ₂ Table 7

R ² =OH, R ³ =6-Me, R ⁴ =H, R ¹⁰ =H, Y=CH ₂ SC(=S)NH-, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3 -OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2 ,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

group-OCH ₂ )R ² =OMe, R ³ =3-OMe, R ⁴ =H, R ¹⁰ =H, Y=CH ₂ ON=C(H)OCH ₂ -, and R ⁹ R 9 R ^{9 R 9} 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3 -(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

base-OCH ₂ )R ² =Et, R ³ =5-NO ₂ , R ⁴ =H, R ¹⁰ =H, Y=CH ₂ ON=C(CH ₃ )-C(=NOC(=O)(4 -CF ₃ -2-pyridyl))-, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

group-OCH ₂ )R ² =Me, R ³ =H, R ⁴ =H, R ¹⁰ =H, Y=CH(CH ₃ )SC(Et)=N-, and R ⁹ R ^{9 R 9 R 9} 3 -CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3- (1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

-OCH ₂ ) R ² =Me, R ³ =3-Me, R ⁴ =6-Me, R ¹⁰ =H, Y=-O-, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph- 2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

group-OCH ₂ ) R ² =Me, R ³ =6-Me, R ⁴ =H, R ¹⁰ =2-Me.Y=-O-, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C-TMS 3-(1-Ph- 2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

-OCH ₂ )R ² =Me, R ³ =H, R ⁴ =H, R ¹⁰ =H, Y=CH ₂ N(COCH ₃ )-N=C(CH ₃ )-, and R ⁹ R ⁹ R ⁹ R ⁹ 3-CH ₂ OCH ₃ 3-OCH ₂ OCH ₂ TMS 4-SCH ₂ CH=CH ₂ 3-S(O)CF ₂ CF ₃ 3-C≡C-OCH ₃ 4-SCN 3-C≡C -TMS 3-(1-Ph-2,2-Di-Cl-c-

Pr)3-C≡CI 3-Ge(Me) ₂ CF ₃ 3-OSi(Me) ₂ Ph 3-(2-Me-4-Ph-c-Hex)3-ada 3-Si(Me) ₂ CF ₃ 2-OH 3-C≡C-OTHP3-CH ₂ Sn-Pr 3-Ge(CF ₃ ) ₃ 2-N(Me)Bzl 3-OCH ₂ CF=CF ₂ 3-SC≡CEt 3-SCH ₂ C ≡CI 3-SCH ₂ OMe 3-SCH ₂ SEt3-OGe(Me) ₂ Ph 3-(C(=O)(3-Me- 4-C(=S)Me 4-((4-F-Bzl) -OC(=O))

Bzl)) 4-C(=S)OEt 4-C(=S)SCHF ₂ 2-C(=O)N(Me) ₂ 2-C(=S)N(Et) ₂ 4-CH ₂ CN 3 -OC(=O)Me 3-OC(=S)Me 4-SC(=O)Me4-NHC(=O)Me 4-NHC(=S)Ph 4-OC(=O)Oc-Hex 4- OC(=O)Sn-Pr3-SC(=O)OCH ₂ CF ₃ 2-SC(=O)SMe 4-S(O) ₂ OCH ₂ CF ₃ 4-S(O) ₂ N(Me) ₂ 4 -(NHSO ₂ (4-Me- 4-(OCH ₂ (4-TMS- 2-CH ₂ OCH ₂ (2,4- 4-((4-TMS-Ph)-C≡C)Ph)) Ph) ) Di-F-Ph)3-(S-(4-TMG-Ph)) 4-S(O) ₂ Ph 3-(SCH ₂ (3-Me- 3-(4-pyridyl-CH ₂ )

Ph))3-(4-pyridyl-C≡C) 3-(2-pyridyl-S) 4-(2-thienyl-CH ₂ ) 4-(2-thienyl-S)4-(2 -furyl-O) 4-(3-furyl-S) 2-(4-pyrimidinyl-CH ₂ ) 2-(2-pyrimidinyl-S)4-OC≡CCH ₃ 4-OCH ₂ CH ₂ OMe 3-OCH ₂ SMe 3-S(O) ₂ CH ₂ CH ₂ CF ₃ 3-S(O) ₂ CF ₃ 2-NH ₂ 4-C(=S)OEt 2-C(=NH)OMe4-SC( =S)-i-Pr 2- 3-OS(O) ₂ CH ₃ 3-((4-CN-Ph)-OCH ₂ )

OC(=O)N(Me)Ph3-(2-furyl-CH ₂ ) 3-(2-thiazolyl-CH ₂ ) 3-((3-CF ₃ -4-pyridine

base-OCH ₂ )

Preparation/Use

The compounds of the invention are generally employed as formulations or compositions comprising an agriculturally suitable carrier comprising at least one liquid diluent, solid diluent or surfactant. The ingredients of the formulation or composition are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsified concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), and the like, which optionally can be thickened into gels. Useful formulations also include solids such as dusts, powders, granules, pellets, tablets, films and the like, which may be water-dispersible ("wettable") or water-soluble. The active ingredient may be (micro)encapsulated and may be further formed into a suspension or solid formulation; alternatively, the complete formulation of the active ingredient may be encapsulated (or "coated"). Encapsulation allows controlled or delayed release of active ingredients. Sprayable formulations can be dispersed in a suitable medium and used at spray volumes of from about 1 to several hundred liters per hectare. High-potency compositions are mainly used as intermediates for further formulations.

Described preparation usually contains the active ingredient of effective amount, diluent and tensio-active agent, and their amount roughly ranges as follows by total percentage (weight):

weight percentage

Active ingredients Diluents Surfactants Water-dispersible and water-soluble 5-90 0-94 1-15 Granules, tablets and powder suspensions, emulsions, solutions 5-50 40-95 0-15 (including Emulsified Concentrate) Powder 1-25 70-99 0-5 Granules and Pellets 0.01-99 5-99.99 0-15 High Potency Composition 0 - 2 0 - 1

Common solid diluents are described in Watkins et al Handbook of Insecticide Dust Diluents and Carriers 2nd Ed., Dorland Book, Caldwell, New Jersey. Common liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents (Chemical Publ. Co., Inc., New York, 1964) list surfactants and their recommendations usage. All formulations may contain minor amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organic Silicon compounds, N,N-dialkyltaurines, lignosulfonates, naphthalenesulfonate formaldehyde condensates, polycarboxylates and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin, starch, sucrose, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate, and sodium bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidones, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, Castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy - Methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by mixing and comminuting, usually with a hammer mill or fluid energy mill. Suspensions are usually prepared by wet-milling methods (see, eg, U.S. 3060084). Granules and pellets can be prepared by spraying the active ingredient onto preformed granular carriers or by gelling techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp. 8-57, etc., and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as described in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets may be prepared as described in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as described in GB2095558 and U.S.3299566.

For more information about the preparation field, see U.S.3235361, column 6, line 16 to column 7, line 19 and Examples 10-41; U.S.3309192, column 5, line 43 to column 7, line 62 and Example 8 , 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2891855 column 3 line 66 to column 5 line 17 and examples 1-4; Klingman, Weed Control as a Science , John Wiley and Sons, Inc., NewYork, 1961, pp81-96; 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 were prepared by conventional methods. Compound numbers refer to compounds in Tables A-C Index.

Example A

wettable powder

Compound 39 65.0%

Laurylphenol polyethylene glycol ether 2.0%

Sodium Lignosulfonate 4.0%

Sodium aluminosilicate 6.0%

Montmorillonite (calcined) 23.0%

Example B

particles

Compound 39 10.0%

Attapulgite particles (low volatile matter, 90.0%

0.71/0.30mm; U.S.S.25-50 sieve)

Example C

Squeeze pill

Compound 39 25.0%

Anhydrous Sodium Sulfate 10.0%

Crude Calcium Lignosulfonate 5.0%

Sodium alkylnaphthalene sulfonate 1.0%

Calcium/magnesium bentonite 59.0%

Example D

emulsifiable concentrate

Compound 39 20.0%

Blend of oil-soluble sulfonate and polyoxyethylene ether 10.0%

Isophorone 70.0%

The compounds of the present invention are useful as control agents for plant diseases. The present invention therefore also includes a method for controlling plant diseases caused by fungal plant pathogens, which comprises applying to the plant or plant part to be protected, or to the plant or plant part to be protected, an effective amount of a compound of the present invention or a fungicidal composition containing said compound. Protected plant seeds or seedlings. The compounds and compositions of the present invention provide control of plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes classes. They are effective in controlling a broad spectrum of plant diseases, especially foliar pathogens of ornamental, vegetable, pasture, cereal and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronosporatabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Altemaria brassicae ), Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea ), Moniliniafructicola, Pyricularia oryzae, Podosphaeraleucotricha, Venturia inaequalis, Erysiphegraminis, Uncinula necatur, Pucciniarecondita, Wheat stem rust Puccinia graminis, Hemileiavastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerothecafuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthoramegasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Powdery mildew (Erysiphe polygoni), Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and others closely related to these pathogens genus and species.

The compounds of the present invention also have broad-spectrum inhibitory activity against aquatic and terrestrial arthropods (the term "arthropod" includes insects, mites and nematodes) that feed on leaves, fruits, stems or roots. Animals are pests of agricultural crops, forestry, greenhouse crops, ornamental plants, growing and storage of nursery crops and storage of food and fiber products, and livestock, household, 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. However, all compounds of the present invention show inhibitory activity against the following pests: Lepidoptera eggs, larvae and adults; Coleoptera eggs, leaf-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults; Eggs, larvae and adults of the orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the orders Acarina; eggs, larvae and adults of the orders Thysanoptera, Orthoptera and Dermatoptera; eggs, larvae and adults of the orders Diptera; nematodes Eggs, larvae and adults. The compounds of the present invention are also effective against pests of the orders Hymenoptera, Isoptera, Fleas, Blattellas, Thysanoptera and Rodentia, and pests belonging to the phylum Arachnida and Flatworms. In particular, the compounds of the present invention are effective against eleven-star melon leaf beetle (Diabrotica undecimpunctata howardi), six-spot leafhopper (Mascrosteles fascifrons), cotton boll weevil (Anthonomus grandis), two-spot spider mite (Tetranychusurticae), grass armyworm (Spodoptera frugiperda) , Aphis fabae, Myzus persica, Aphis gossypii, Diuraphisnoxia, Sitobion avenae, Heliothisvirescens, American rice weevil Lissorhoptrus oryzophilus, Oulemaoryzae, Sogatella furcifera, Nephotettix cincticeps, Nilaparvatalugens, Laodelphax striatellus, Chilo suppressalis), Cnaphalocrocis medinalis, Scotinophara lurida, Oebalus pugnax, Leptocorisa chinensia, Cletus puntiger and green bug ( Nezara viridula) has inhibitory activity. These compounds are active against mites and have shown ovicidal, larvicidal and chemical sterilant activity against certain families such as Tetranychus two-spotted spider mite, red spider mite, red spider mite, red spider mite, Pacific red spider mite, Turkestan spider mite Mites, Byrobiarubrioculus, Panonychus apple, Panonychus citrus, Hornbeam oriental spider mite, Walnut Tetranychus spp., Eotetranychus six-spotted, Oriental Tetranychus longma, Eotetranychus banksi, Grass small clawed mite, Tetranychidae Including Brachylus liutii, Brachycarpus purpura, Brachycarpus californica, Brachyphys ovale, Eriophyidae includes Phyllocoptruta oleivora, Orange gall mite, Peach silvery gall mite, Pear leaf rust mite and Eriophyes mangiferae. For a detailed description of pests see WO90/10623 and WO92/00673.

The compounds of the present invention can also be combined with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemical sterilization agents, semiochemical repellents, attractants , pheromones, food additives or other bioactive compounds are mixed to form multi-ingredient insecticides to produce broad-spectrum agricultural protection. Examples of agricultural protective agents formulated with the compounds of the present invention are: insecticides such as abamectin, acephate, acetophos, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlorpyrifos-methyl, fluorine Cypermethrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, s-fenvalerate, fenoxycarb , Fenfenthrin, Fenvalerate, Fipronil, Flucyvalerate, Fluvalinate, Tefenthion, Imidacloprid, Isofenphos, Malathion, Metaldehyde, Methylamine Phosphorus, methomyl, methomyl, methoprene, methoxychlor, 7-chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4-(tri Fluoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-methyl carboxylate (DPX-JW062), monocrotophos, Dioxacarb, parathion, methyl parathion, permethrin, phorate, phosthion, imophos, phosphamide, pirimicarb, profenofos, rotenone, thioprofos, insect Hydrazide, tefluthrin, terbufos, dimechlor, thiodicarb, perbromethrin, trichlorfon, and triflumuron, fungicides such as azoxystrobin (ICIA5504), benomyl, blasticide Su-s, tribasic coppersulfate, furfurazole, captafate, captan, carbendazim, chloroneb, chlorothalonil, acetone, copper salt, cymoxanil, cyproconazole, pyrimidine Cyprodinil (CGA219417), pyridoxone, clonamide, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, difenfofos, epoxiconazole (BAS480F), chlorine Phenyridinol, carbazole, seed dressing, fenpropidin, fenpropimorph, fluazinam, fluoroquinazole, flusilazole, fluoramide, fuconazole, folpet, aluminum triethphosphate, furaxyl, Hexaconazole, Conconazole, Isofridan, Iprodione, Daobenling, Kasugamycin, kresoxim-methyl (BAS490F), Mancozeb, Maneb, Rustamine, Metalaxyl, Leaf Conazole, 7-benzothiazole thiocarbamate S-methyl ester (CGA245704), 5-methyl-5-(4-phenoxyphenyl)-3-phenylamino-2,4-oxazolidinedi Ketone (DPX-JE874), myclobutanil, ferric ammonium carboxylate (iron carboxylate), oxadaxyl, penconazole, pentocuron, allylbenzothiazole, prochloraz, propiconazole, pyridoxine , pyroquinone, sulfonic yellow powder, tebuconazole, tetraflumezole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, fafenazole, validamycin and Vinclozolin, nematocides such as aldoxycarb and fenamiphos, fungicides such as streptomycin, acaricides such as amitraz, acetidine, ethyl acetate fofol, tricyclotin, dicofol, dienochlor, quinacarid ether, fenbutatin, fenpropathrin, fenpyroxifen, hexythiazox, propyzafen, pyridaben and tebufenpyrad, and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus and Insect pathogens, viruses and fungi.

Combination with other fungicides or arthropodicides with a similar spectrum of control but a different mode of action is particularly beneficial in combating resistance in some cases.

For better control of plant diseases caused by fungal phytopathogens (such as lower usage rates or wider phytopathogen control spectrum) or resistance to drug resistance, it is preferred that the compounds of the present invention be combined with cyproconazole, pyrimidine Fungicide mixture of cyprodinil (CGA219417), epoxiconazole (BAS480F), fenpropidin, fenpropimorph, flusilazole and tebuconazole. Particularly preferred mixtures (compounds in Compound No. Reference Index Tables A-C) are selected from the group consisting of: Compound 9 and cyproconazole, Compound 9 and cyprodinil (CGA219417), Compound 9 and epoxiconazole (BAS480F), Compound 9 and fenoxazole Pyridine, compound 9 and fenpropimorph, compound 9 and flusilazole, compound 9 and tebuconazole, compound 12 and cyproconazole, compound 12 and cyprodinil (CGA219417), compound 12 and epoxiconazole (BAS480F), compound 12 and fenpropidin, compound 12 and fenpropimorph, compound 12 and flusilazole, compound 12 and tebuconazole, compound 39 and cyproconazole, compound 39 and cyprodinil (CGA219417), compound 39 and epoxiconazole (BAS480F) , compound 39 and fenpropidin, compound 39 and fenpropimorph, compound 39 and flusilazole, compound 39 and tebuconazole, compound 45 and cyproconazole, compound 45 and cyprodinil (CGA219417), compound 4 and epoxiconazole (BAS480F), compound 45 and fenpropidin, compound 45 and fenpropimorph, compound 45 and flusilazole, compound 45 and tebuconazole, compound 53 and cyproconazole, compound 53 and cyprodinil (CGA219417), compound 53 and epoxiconazole (BAS480F), compound 53 and fenpropidin, compound 53 and fenpropimorph, compound 53 and flusilazole, compound 53 and tebuconazole, compound 54 and cyproconazole, compound 54 and cyprodinil (CGA219417 ), compound 54 and epoxiconazole (BAS480F), compound 54 and fenpropidin, compound 54 and fenpropimimorph, compound 54 and flusilazole, compound 54 and tebuconazole, compound 103 and cyproconazole, compound 103 and azuridine Amine (CGA219417), compound 103 and epoxiconazole (BAS480F), compound 103 and fenpropidin, compound 103 and fenpropimorph, compound 103 and flusilazole, compound 103 and tebuconazole.

Plant diseases are usually controlled by applying an effective amount of the compounds of the present invention to the plant parts to be protected, such as roots, stems, leaves, fruits, seeds, tubers or bulbs, before or after infection, or to the parts of the plants to be protected. growing environment (soil or sand). The compounds can also be applied to the seeds to protect the seeds and seedlings.

For the control of plant diseases, the rate at which these compounds are used is influenced by many environmental factors and should be determined according to the actual situation of use. Foliage is generally protected when treated at less than 1 g/ha (hectare) to 5000 g/ha of active ingredient. Seeds and seedlings are usually protected when treated at a rate of 0.1-10 g per kg of seed.

Achieved by applying an effective amount of one or more compounds of the present invention to the environment of the pest, including agricultural and/or non-agricultural foci of infection, to the area to be protected, or directly to the pest to be controlled Purposes of controlling arthropod pests and protecting agricultural, horticultural and special crops. Thus, the present invention also includes a method of controlling arthropod and nematode pests inhabiting leaves and soil and protecting agricultural and/or non-agricultural crops, which method comprises administering an effective amount of one or more compounds of the present invention, or containing at least A composition of such compounds is applied to the environment of the pest, including agricultural and/or non-agricultural foci of infection, to the area to be protected, or directly to the pest to be controlled. The preferred method of use is spraying. Alternatively, granular forms of these compounds can be applied to plant foliage or to the soil. Other methods of application include direct and residual spraying, aerial spraying, seed coating, microencapsulation, whole plant inhalation, poison baits, eartags, group drugs, aerosols, fumigants, aerosols, powders, and others . The compounds may also be incorporated into baits ingested by arthropods or placed in trapping devices such as traps and the like.

For the control of arthropod pests, the compounds of the present invention may be applied in their pure form, but are most commonly used in the form of compounds containing one or more compounds together with suitable carriers, diluents, and surfactants, and possibly food ( Depending on the use considered) Mixed preparations. Preferred methods of application include spraying an aqueous dispersion of the compound or a solution in a refined oil. Compositions with spray oils, spray oil concentrates, distribution adhesives, adjuvants, other solvents and synergists such as metal piperonyl butoxide often increase the potency of the compounds.

The rate of use 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, season, host crop or animal, feeding behaviour, mating behaviour, ambient humidity , temperature, etc. Normally, an application rate of about 0.01-2 kg of active ingredient per hectare is sufficient to control pests in agroecosystems, but as little as 0.001 kg/ha may be sufficient or as much as 8 kg/ha may still be required. For non-agricultural use, effective use rates range from about 1.0-50 mg/square meter, but as little as 0.1 mg/square meter is sufficient or as much as 150 mg/square meter is still required.

The following tests demonstrate the control effect of the compounds of the present invention on specific pathogens and arthropod pests. For assays on arthropod pests, "control effect" means inhibition of arthropod development (including mortality), which results in a marked reduction in feeding. However, the protection against the control of pathogenic and arthropod pests afforded by the compounds of the present invention is not limited to these species. See Index Tables A-C for compound descriptions. The following abbreviations are used in the following index tables: t = tertiary, c = ring, Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl, MeO and OMe = methoxy, EtO = ethoxy group, PhO=phenoxy, PhS=phenylthio, CN=cyano, NO2=nitro, Me3Si=trimethylsilyl and CHO=formyl. The abbreviation "dec" means that the compound decomposes at the melting point. The abbreviation "Ex" stands for "Example" followed by a number indicating the Example in which the compound was prepared.

化合物号       Y             Z           mp(℃)1Ex.18         CH₂ON=C(Me)  4-HO-Ph     油**对¹HNMR参考索引表Cindex table A

Compound No. Y Z mp(°C)1Ex.18 CH ₂ ON=C(Me) 4-HO-Ph Oil** Pair ¹ HNMR Reference Index Table C

化合物号  X       R^3a        Y             Z                               mp(℃)2         MeO     H           CH₂S         3-(MeOC(=NH))-6-               190(分解)index table B

Compound No. X R ^3a Y Z mp(℃)2 MeO H CH ₂ S 3-(MeOC(=NH))-6- 190(decomposition)

(MeC(=O))-2-pyridyl3 MeO H CH ₂ S 3-CN-6-(MeC(=O))-2-pyridyl 105-1104 MeO H CH ₂ S 3-CN-6- (MeC(OMe) ₂ )-2-pyridine 190(decomposition)

Base 5 Cl H CH ₂ S 3-CN-6-(MeC(=O))-2-pyridyl 143-1486 Cl H CH ₂ S 3-CN-6-(CH ₃ C(OMe) ₂ )-2 -pyr117-123

7EX.11 Cl H O 3-HO-PH 135-1388Ex.12 meo H o 3-HO-PH 153-1559ex.3 meo H o 3- (1,3-benzopyrum intervioxyxyne - 168-169

5-yl)-1,2,4-thiadiazol-5-yl 10 MeO HO 2-NH ₂ -3-(2-Me-PhO)-Ph 72-7511Ex.4 MeO HO 5-(1-adamant Alkyl)-1,3,4-oxadiazole *

-2-yl12Ex.21 MeO H CH ₂ ON=C(Me) 3-(CF ₃ CH ₂ CH ₂ SiMe ₂ )-Ph oil*13 MeO H CH ₂ ON=C(Me) 3-(4-Me ₃ Si-PhCH ₂ O)-Ph oil*14 Cl H CH ₂ 3,5-DiMe-4-(2-pyrimidinyl-S)- 154-156

1H-Pyrazol-1-yl Compound No. X R ^3a Y Z mp(°C)15 Cl H CH ₂ ON=C(Me) 3-(4-Me ₃ Si-PhCH ₂ O)-Ph Oil*16 MeO HO 3- (PhCH ₂ O)-Ph 98-10017 MeO HO 3-(c-Hexyl-O)-Ph Oil*18 MeO H CH ₂ ON=C(Me) 4-(PhCH ₂ OC(=O))-2- Pyridyl 130-13219 MeO HO 3-NH ₂ -6-Cl-2-pyridyl 163-16620 MeO HO 3-PhS-Ph Oil*21 MeO HO 3-(4-Cl-PhCH ₂ O)-Ph Oil* 22 MeO HO 3-(2,4-diCl-PhCH ₂ O)-Ph oil*23 MeO HO 3-(2-CF ₃ -PhCH ₂ O)-Ph oil*24 MeO H O 3-(4-CF ₃ -PhCH ₂ O)-Ph Oil*25 MeO HO 3-(2,5-DiMe-PhCH ₂ O)-Ph Oil*26 MeO HO 3-(2,6-DiF-PhCH ₂ O)-Ph Oil *27 MeO HO 3-(3-MeO-PhCH ₂ O)-Ph 128-13128 MeO HO 3-(4-F-PhCH ₂ O)-Ph oil*29 MeO H CH ₂ ON=C(Me) 4- (Me ₃ Si-C≡C)-2-pyridyl oil*30 MeO HO 3-(2-Me-PhCH ₂ O)-Ph 104-10531 MeO HO 3-(3-Me-PhCH ₂ O)-Ph Oil*32 MeO HO 3-(4-Me-PhCH ₂ O)-Ph Oil*33 MeO HO 3-(2-CN-PhCH ₂ O)-Ph 97-9834 MeO HO 3-(2-NO ₂ -PhCH ₂ O)-Ph 135-13635 MeO HO 3-(3,5-DiF-PhCH ₂ O)-Ph Oil*36 MeO HO 3-(2-F-PhCH ₂ O)-Ph Oil*37 MeO H O 3 -(3-F-PhCH ₂ O)-Ph Oil*38 MeO H O 3-(3-CF ₃ -PhCH ₂ O)-Ph Oil*39Ex.13 MeO H O 3-(2-Cl-PhCH ₂ O)- Ph 112-11440 MeO HO 3-(3-Cl-PhCH ₂ O)-Ph oil*41 MeO HO 3-(3,5-diCl-PhCH ₂ O)-Ph oil*42 MeO HO 3-(2- Pyridyl-CH ₂ O)-Ph oil*43 MeO HO 3-(4-pyridyl-CH ₂ O)-Ph oil*Compound No. X R ^3a Y Z mp(℃)44 MeO HO 3-(3,3-di F-2-MeO-1-cyclobutene- oil*

1-yl)-1,2,4-thiadiazol-5-yl 45Ex.2 MeO H O O 3-[1-(4-Cl-Ph)-cyclopropyl]-1,2,4- 123- 124

                                                                                                                                                                                                                                        , 

Azol-5-yl 47Ex.10 MeO HO 3-((EtO) ₂ CH)-1,2,4-thiadiazole-*

5-yl48 MeO H O O 3-(1,2,3,4-tetrahydro-1-naphthyl-O)-Ph Oil*49 MeO H O O 4-Cl-5-CHO-2-thiadiazole 8 9 -10150 MeO 6-Me O 3-(2-F-PhS)-Ph Oil*51 MeO H O O 3-(4-F-Ph-C ≡ C) -1,2,4- Diazole

                                                                                                                                 , 

Azol-5-yl 53Ex.20 MeO H CH ₂ ON=C(Me) 3-((CF ₃ ) ₃ Ge)-Ph oil*54Ex.14 MeO 6-Me O 3-[1-(4-Cl- Ph)-cyclopropyl]-1,2,4- 119-121

                                                                                                               ,

MEO diezo-5-base 56 meo 6-me o 3- (1-pH-cyclopen) -1,2,4-噻 噻 唑-138-141

                                                                                                                                 , 

MeO 5-yl 58 MeO HO 3-(2-Cl-4-F-PhCH ₂ O)-Ph oil*59 MeO HO 3-(2,5-diF-PhCH ₂ O)-Ph 83-8660 MeO HO 3-(2,3-diF-PhCH ₂ O)-Ph oil*61 MeO HO 3-(3,5-DiCl-PhOCH ₂ )-Ph oil*Compound No. X R ^3a Y Z mp(℃)62 MeO H O 3-(4-thiomorpholinyl-CH ₂ )-Ph oil*63 MeO HO 3-(2-naphthyl-CH ₂ )-1,2,4-thiadiazole-*

5-yl 64 MeO HO 4-Cl-5-C(O)NH ₂ -2-thiadiazole solid*65 MeO HO 3-(t-BuC(=O)O)-1,2,4-thiadiazole Azole-137-138

5-yl 66Ex.5 MeO HO 3-(2-Cl-PhCH ₂ O)-1,2,4-thiadiazole 107-1 08

-5-yl67Ex.19 MeO HO 3-(CF ₃ S(O) ₂ O)-Ph oil*68 MeO H CH ₂ ON=C(Me) 3-(PhCH ₂ O)-Ph oil*69 MeO H O 4-(3-CF ₃ -Ph)-5-CO ₂ H-2-thiazole 204-

Base 205 (Decomposition)70 MeO H CH ₂ ON=C(Me) 3-(HC≡CCH ₂ O)-Ph Oil*71Ex.17 MeO H CH ₂ ON=C(Me) 3-(t-BuOC(= O)CH ₂ O)-Ph Oil*72 MeO HO 3-[3,5-(CF ₃ S(O) ₂ O) ₂ -Ph]- *

1,2,4-Thiadiazol-5-yl73 MeO H CH ₂ ON=C(Me) 3-(MeOC(=O)CH ₂ O)-Ph oil*74 MeO HO 3-((EtO) ₂ CHC≡C)-Ph oil*75 MeO HO 4-(3,5-diCF ₃ -Ph)-5-CHO-2- solid*

Thiazolyl 76 MeO HO 3-((EtO) ₂ CHC≡C)-1,2,4-thiadi 55-58

Azol-5-yl 77 MeO HO 3-((t-BuO) ₂ CHC≡C)-1,2,4-thia 115-116

Oxadiazol-5-yl 78Ex.9 MeO HO 3-(CF ₃ S(O) ₂ O)-1,2,4-thiadiazole-*

5-yl79 MeO HO 3-(2,5-DiCl-PhS(O) ₂ O)-1,2,4-*

Thiadiazol-5-yl80 MeO HO 3-(4-Br-PhS(O) ₂ O)-1,2,4-thia*

Oxadiazol-5-yl Compound No. X R ^3a Y Z mp(°C)81 MeO H O 3-(Me ₂ C(OH)C≡C)-Ph 165-16782 MeO H O 3-((t-BuO) ₂ CHC≡C )-Ph oil*83 MeO HO 3-(Me ₂ C(OH)C≡C)-1,2,4-thiophene oil*

                                                               

7-yl)-1,2,4-thiadiazol-5-yl85 MeO HO 3-(Ph ₂ C(Me))-1,2,4-thiadiazol- solid*

5-yl86 MeO HO 3-(4-Br-Ph-C(Me) ₂ )-1,2,4-thia Solid*

Oxadiazol-5-yl87 MeO HO 3-(2-naphthyl-C(Me) ₂ )-1,2,4-thia Solid*

Oxadiazol-5-yl88 MeO HO 3-(3,5-diF-Ph-C(Me) ₂ )-1,2,4-*

Thiadiazol-5-yl89MeOHO 3-(3,5-diCF ₃ -Ph-C(Me) ₂ )-*

1,2,4-Thiadiazol-5-yl90 MeO HO 3-(3-CF ₃ -Ph-C(Me) ₂ )-1,2,4-Thiadiol*

Oxadiazol-5-yl91Ex.6 MeO HO 3-(Me ₂ C(CN))-1,2,4-thiadiazole-5- solid*

Group 92 MeO HO 3-(3-Cl-Ph-C(Me) ₂ )-1,2,4-thiabis*

Azol-5-yl93 MeO HO 3-(3-MeO-Ph-C(Me) ₂ )-1,2,4-thiol oil*

Oxadiazol-5-yl94 MeO HO 3-(4-Cl-Ph-C(Me) ₂ )-1,2,4-thiadiol*

Azol-5-yl95 MeO 6-Me O 6-(1H-indazol-1-yl)-4-pyrimidine 175-17996Ex.7 MeO H O 3-(PhCH ₂ O)-1,2,4-thiadi Azole-5-*

Base 97Ex.8 MeO HO 3-HO-1,2,4-Thiadiazol-5-yl Oil*Compound No. X R ^3a Y Z mp(°C)98Ex.15 Cl H CH ₂ ON=C(Me) 3-HO -Ph oil*99Ex.16 MeO H CH ₂ ON=C(Me) 3-HO-Ph oil*100 MeO HO 3-(4-Cl-PhOC(Me) ₂ )-1,2,4-thiophene*

Oxadiazol-5-yl 101 MeO 6-Me O 3-(Me ₃ SiC≡C)-1,2,4-thiadiazole-5-*

Base 102 MeO HO 3-(Me ₃ SiC≡C)-1,2,4-thiadiazole-5-*

Base 103 MeO HO 3-(Me ₃ SiC≡C)-Ph *104 MeO HO 6-(2-Cl-PhCH ₂ O)-4-pyrimidinyl 133-135105 MeO 6-Me O 6-(2-Cl- PhCH ₂ O)-4-pyrimidinyl 135-137106 MeO 6-Me O 6-(3,5-diF-PhCH ₂ O)-4-pyrimidinyl oil*107 MeO 6-Me O 6-(2,3 -DiF-PhCH ₂ O)-4-pyrimidinyl oil*108 MeO HO 6-(2,4-diF-PhCH ₂ O)-4-pyrimidinyl oil*109 MeO HO 6-(2,3-di F-PhCH ₂ O)-4-pyrimidinyl oil*110 MeO HO 6-(2-Cl-PhCH ₂ CH ₂ O)-4-pyrimidine oil*

Base 111 MeO 6-Me O 6-(2-Cl-PhCH ₂ CH ₂ O)-4-pyrimidine Oil*

Base 112 MeO HO 6-(4-Me-PhCH ₂ O)-4-pyrimidinyl oil*113 MeO 6-Me O 6-(4-Me-PhCH ₂ O)-4-pyrimidinyl oil*114 MeO HO 6 -(2,4-DiCl-PhOCH ₂ CH ₂ O)-4-Oil*

Pyrimidinyl 115 MeO 6-MeO 6-(2,4-DiCl-PhOCH ₂ CH ₂ O)-4-Oil*

Pyrimidinyl 116 MeO HO 6-(3,5-diCF ₃ -PhCH ₂ O)-4-pyrimidine Oil*

Base 117 MeO 6-Me O 6-(3,5-diCF ₃ -PhCH ₂ O)-4-pyrimidine 141-143

Compound No. X R ^3a Y Z mp(°C)118 MeO H O 6-(3-CF ₃ -PhCH ₂ CH ₂ O)-4-pyrimidine Oil*

Base 119 MeO 6-Me O 6-(3-CF ₃ -PhCH ₂ CH ₂ O)-4-pyrimidine Oil*

Base 120 MeO HO 6-(1-naphthyl-CH ₂ CH ₂ O)-4-pyrimidine Oil*

Base 121 MeO 6-MeO 6-(1-naphthyl-CH ₂ CH ₂ O)-4-pyrimidine Oil*

Base 122 MeO H O 6-(4-pyridyl CH ₂ O)-4-pyrimidinyl oil*123 MeO 6-Me O 6-(4-pyridyl CH ₂ O)-4-pyrimidinyl oil*124 MeO H O 6 -(MeOCH ₂ CH ₂ O)-4-pyrimidinyl oil*125 MeO 6-Me O 6-(MeOCH ₂ CH ₂ O)-4-pyrimidinyl oil*126 MeO 6-Me O 6-(2-Me- PhCH ₂ O)-4-pyrimidinyl oil*127 MeO 6-Me O 6-(3-Cl-PhCH ₂ S)-4-pyrimidinyl oil*

*See ¹ HNMR data in Index Table C

index table C

Compound No. ¹ HNMR data (CDCl ₃ solution, unless otherwise indicated) ^a 1 δ7.52 (d, 1H), 7.42 (m, 2H), 7.32 (m, 2H), 6.72 (m, 3H), 594 ( AB q,2H),3.94(d,3H),3.44(d,3H),2.16(d,3H).11δ7.8(d,1H),7.5(t,1H),7.42(m,2H), 3.86(s,3H),3.44(s,3H),2.1(brs,3H),2.04(brm,6H),1.79(brm,6H).12 δ7.7(s,1H),7.6(m,2H ),7.4-7.5(m,3H),7.4(t,1H),7.2(d,21H),5.2-5.3(q,2H),3.882(s,3H),3.401(s,3H),2.201( s,3H),2.0(m,2H),1.0(m,2H),0.32(s,5.5H).13 δ7.6(m,3H),7.4(m,4H),7.2(d,1H) ,6.9(d,1H),5.2(q,2H),5.061(s,2H),3.868(s,3H),3.405(s,3H),2.174(s,3H),0.271(s,7H). 15 δ7.5-7.6(m,5H),7.4(t,3H),7.226(s,2H),7.15(d,1H),69(d,1H),5.1-5.3(q,2H),5.058 (s,2H),3.463(s,3H),2.156(s,3H),0.271(s,9H).17 δ1.2-1.4(m,3H),1.4-1.6(m,2H),1.7- 1.8(m,3H),1.9-2.0(m,2H),3.39(s,3H),3.86(s,3H),4.2(m,1H),6.5-6.6(m,2H),6.65(m, 1H),7.0(m,1H),7.2(m,2H),7.3-7.4(m,2H).20 δ3.38(s,3H),3.80(s,3H),6.8-6.9(m,1H ),6.9-7.1(m,2H),7.2-7.4(m,10H).21 δ3.38(s,3H),3.85(s,3H),4.99(s,2H),6.6(m,2H) ,6.7(m,H),7.0(m,1H),7.2(m,2H),7.3-7.4(m,6H).22 δ3.38(s,3H),3.85(s,3H),5.08( s,2H),6.65(m,2H),6.75(m,1H),7.0(m,1H),7.2-7.3(m,3H),7.3-7.4(m,3H),7.50(m,1H) .23 δ3.38(s,3H),3.84(s,3H),5.23(s,2H),6.6-6.75(m,3H),7.0(m,1H),7.2(m,2H),7.3- 7.5(m,3H),7.6(m,1H),7.7(m,2H).24 δ3.37(s,3H),3.85(s,3H),5.08(s,2H),6.6-6.7(m ,2H). 6.7 (m, 1H), 7.0(m,1H),7.2-7.3(m,2H),7.3-7.4(m,2H),7.52(d,J=8.1Hz,2H),7.62( d,J=8.2Hz,2H)25 δ2.31(s,3H),2.32(s,3H),3.39(s,3H),3.85(s,3H),5.30(s,2H),6.6(m ,2H),6.68(m,1H),6.75(m,1H),7.0-7.1(m,3H),7.2(m,3H),7.35-7.40(m,2H).26 δ3.38(s, 3H),3.84(s,3H),5.07(s,2H),6.6-6.7(m,2H),6.75(m,1H),6.9(m,2H),7.05(m,1H),7.2-7.3 (m,2H),7.3-7.4(m,3H).28 δ3.38(s,3H),3.85(s,3H),4.97(s,2H),6.6-6.7(m,2H),6.75( m,1H),7.0-7.1(m,3H),7.2-7.3(m,2H),7.3-7.4(m,4H).29 δ8.50(d,1H),7.80(s,1H),7.60 (d,1H),7.50-7.40(m,2H),7.28-7.24(m,2H),5.3(dd,2H),3.90(s,3H),3.43(s,3H),2.27(s,3H ),0.27(s,9H).31 δ2.36(s,3H),3.38(s,3H),3.84(s,3H),4.97(s,2H),6.6-6.7(m,2H),6.75 (m,1H),7.0(m,1H),7.1-7.3(m,6H),7.3-7.4(m,2H).32 δ2.35(s,3H),3.38(s,3H),3.84( s,3H),4.97(s,2H),6.6-6.7(m,2H),6.75(m,H),7.0(m,1H),7.2-7.25(m,4H),7.3-7.4(m, 4H).33 δ3.38(s,3H),3.86(s,3H),5.21(s,2H),6.6-6.7(m,2H). 6.7 (m, 1H), 6.75(m,1H), 7.0-7.1(m,1H),7.2-7.3(m,2H),7.35-7.50(m,3H),7.6-7.8(m,2H),35 δ3.37(s,3H),3.86(s,3H ),5.00(s,2H),6.6-6.8(m,4H),6.9-7.0(m,3H),7.2-7.3(m,2H),7.3-7.4(m,2H).36 δ3.38( s,3H),3.84(s,3H),5.08(s,2H),6.6-6.7(m,2H),6.75(m,1H),7.0-7.25(m,5H), 7.3-7.4(m, 3H),7.48(m,1H).37 δ3.38(s,3H),3.85(s,3H),5.01(s,2H),6.6-6.7(m,2H),6.75(m,1H), ,7.0(m,2H),7.1-7.3(m,4H),7.3-7.4(m,3H).38 δ3.38(s,3H),3.85(s,3H),5.06(s,2H), 6.6-6.7(m.2H),6.75(m,1H),7.0(m,1H),7.2-7.3(m,2H),7.3-7.4(m,2H),7.5(m,1H),7.6( m,2H),7.67(m,1H).40 δ3.38(s,3H),3.85(s,3H),4.99(s,2H),6.6(m,2H),6.7(m,1H), 7.0(m,1H),7.2-7.4(m,8H).41 δ3.38(s,3H),3.86(s,3H),4.96(s,2H),6.6-6.7(m,3H),7.0 (m,1H),7.2-7.3(m,5H),7.3-7.4(m,3H).42 δ3.38(s,3H),3.84(s,3H),5.16(s,2H),6.6( m,1H),6.7(s,1H),6.75(m,1H),7.0(m,1H),7.2-7.3(m,3H),7.35(m,2H),7.5(m,1H),7.70 (m,1H),8.6(m,1H).43 δ3.37(s,3H),3.86(s,3H),5.04(s,2H),6.6-6.65(m,2H),6.70(m, 1H),7.0(m,1H),7.2-7.3(m,2H),7.3-7.4(m,4H-),8.6(dd,J=1.5,4.5Hz,2H).44 δ7.54(m, 2H),7.46(m,2H),4.06(s,3H),3.83(s,3H),3.39(s,3H),3.02(m,2H).46 δ7.53(m,2H),7.45( m,2H),7.36(m,3H),3.81(s,3H),3.41(s,3H),1.65(m,2H),1.35(m,2H).47 δ7.6-7.4(m,4H ),5.53(s,1H),3.81(s,3H),3.8-3.65(m,4H),3.40(s,3H),1.23(t,6H).48 δ1.8(m,1H),2.0 (m,2H),2.1(m,1H),2.7-2.9(m,2H),3.38(s,3H),3.85(s,3H),5.35(s,1H),6.6(m,1H), 6.7(m,1H),6.8(m,1H),7.0(m,1H),7.15-7.3(m,5H),7.3-7.4(m,3H).50 δ2.26(s,3H),3.39 (s,3H),3.81(s,3H),6.8(m,2H),6.93(t,J=1.8Hz,1H),6.98(d,J=7.7Hz,1H),7.05-7.11(m, 3H),7.2-7.4(m,4H).51 δ7.6-7.55(m,4H),7.5(m,4H),7.1(t,2H),3.84(s,3H),3.40(s,3H ).52 δ8.65(d,1H),7.7(m,1H),7.65-7.5(m,3H),7.5-7.4(m,2H),7.3(m,1H),3.84(s,3H) ,3.40(s,3H).53 δ7.941(s,1H),7.7(d,1H),7.55(m,2H),7.4-7.5(m,2H),7.4-7.5(m,2H), 7.1(t,2H),5.2-5.4(q,2H),3.889(s,3H),3.413(s,3H),2.152(s,3H).57 δ7.44(m,2H),7.32(m ,4H),7.09(d,J=2.6Hz,1H),6.91(dd,J=8.8,2.6Hz,1H),3.81(s,6H),3.40(s,3H),1.65(m,2H) ,1.35(m,2H).58 δ3.38(s,3H),3.85(s,3H),5.09(s,2H),6.6-6.7(m,2H),6.7-6.8(m,1H), 6.9-7.1(m,2H),7.2-7.3(m,2H),7.3-7.4(m,4H).59 δ3.38(s,3H),3.85(s,3H),5.06(s,2H) ,6.6-6.8(m,3H),6.95-7.05(m,4H),7.2-7.3(m,2H),7.3-7.4(m,2H).60 δ3.38(s,3H),3.85(s ,3H),5.09(s,2H),6.6-6.8(m,3H),7.0(m,1H),7.1(m,2H),7.2-7.3(m,3H),7.3-7.4(m,2H ).61 δ3.37(s,3H),3.85(s,3H),4.99(s,2.H),6.81(m,2H),7.0(m,3H),7.05(m,1H),7.1 -7.2(m,2H),7.3-7.4(m,3H).62 δ2.60-2.75(m.8H),3.38(s,3H),3.48(s,2H),3.88(s,3H), 6.85-7.00(m,3H),7.07(d,J=7.7Hz,1H),7.15-7.30(m,2H),7.36(dd,J=1.6,7.7Hz,2H).63 δ7.79(m ,4H),7.55-7.4(m,7H),4.28(s,2H),3.68(s,3H),3.37(s,3H).64 δ7.55(m,2H),7.45(m,2H) ,3.87(s,3H),3.40(s,3H).67 δ7.42(m,3H),7.3(m,1H),7.04(m,3H),6.96(t,1H),3.83(s, 3H),3.38(m,3H).68 δ7.6(m,1H),7.4(m,7H),7.24(m,4H),6.86(d,4H),5.23(s,2H),5.08( q,2H),3.89(s,3H),3.37(s,3H),2.23(s,3H).70 δ7.6(m,1H),7.46(m,2H),7.24(m,2H), 6.88(m,4H),5.08(q,2H),4.785(q,2H),3.92(s,3H),3.39(s,3H),2.48(t,1H),2.23(s,3H).71 δ7.6(m,1H),7.45(m,2H),7.23(m,4H),6.87(m,1H),5.09(AB q,2H),4.63(s,2H),3.91(s,3H ),3.39(s,3H),2.28(s,3H),1.48(s,9H).72 δ8.16(s,2H),7.60(m,2H),7.51(m,2H),7.31(m ,1H),3.84(s,3H),3.38(s,3H).73 δ7.61(m,1H),7.45(m,2H),7.23(m,4H),6,88(m,1H) ,5.075(m,2H),4.745(s,2H),3.915(s,3H),3.77(s,3H),3.39(s,3H),2.28(s,3H).74 δ7.37(m, 2H),7.25(m,3H),7.11(s,1H),6.99(m,2H),5.46(s,1H),3.83(s,3H),3.79(m,2H),3.64(m,2H ),3.38(s,3H),1.26(t,3H).75 δ9.9(s,1H),8.15(s,2H),8.0(s,1H),7.6(m,2H),7.5(m ,2H),3.9(s,3H),3.4(s,3H)78 δ7.6-7.4(m,4H),3.84(s,3H),3.41(s,3H).79 δ8.06(s, 1H),7.6-7.4(m,6H),3.82(s,3H),3.40(s,3H).80 δ7.88(d,2H), 7.7-7.3(m,6H), 3.81(s,3H ), 3.40 (s,3H).82 δ7.36(d,2H),7.21(m,3H),7.08(s,1H),6.97(d,2H),5.61(s,1H),3.84(s ,3H),3.38(s,3H),1.35(s,18H).83 δ7.55(m,2H),7.46(m,2H),3.84(s,3H),3.40(s,3H),2.18 (s,1H),1.60(s,6H).85 δ7.55-7.40(m,4H),7.29(m,3H),7.25-7.20(m,7H),3.62(s,3H),3.39( s,3H),2.18(s,3H).86 δ7.52(m,2H),7.42(m,4H),7.22(d,2H),3.69(s,3H),3.38(s,3H), 1.75(s,6H).87 δ7.79(m,4H),7.50-7.40(m,7H),3.62(s,3H),3.35(s,3H),1.88(s,6H).88 δ7. 53(m,2H),7.46(m,2H),6.85(m,2H),6.65(m,1H),3.72(s,3H),3.38(s,3H),1.75(s,6H).89 δ7.80(s,2H),7.74(s,1H),7.50(m,2H),7.45(m,2H),3.71(s,3H),3.38(s,3H),1.83(s,6H) .90 δ7.60(s,1H),7.51-7.41(m,7H),3.66(s,3H),3.38(s,3H),1.80(s,6H).91 δ7.57(m,2H) ,7.48(m,2H),3.83(s,3H),3.40(s,3H),1.77(s,6H).92 δ7.50-7.40(m,4H),7.30-7.20(m,4H), 3.67(s,3H),3.38(s,3H),1.76(s,6H).93 δ7.53(m,2H),7.45(m,2H),7.21(m,1H),6.89(m,2H ),6.75(d,1H),3.77(s,3H), 3.64 (s,3H), 3.38 (s,3H), 1.77 (s,6H).94 δ7.51(m,2H),7.45(m ,3H),7.26(m,3H),3.68(s,3H),3.38(s,3H),1.76(s,6H).96 δ7.6-7.3(m,9H),5.37(s,2H) ,3.79(s,3H),3.40(s,3H).97 δ7.3-7.1(m,4H),3.98(s,1H),3.89(s,3H),3.41(s,3H).98 δ8 .09(brs,1H),7.62(d,1H),7.51(m,2H),7.22(m,4H),6.9(d,1H),5.08(q,2H),3.44(s,3H), 2.25(m,4H).99 δ7.6(dd,1H),7.45(m,2H),7.25(m,3H),7.19(m,2H),6.85(dd,1H),5.08(AB q, 2H),3.92(s,2H),3.39(s,3H),2.24(s,3H).100 δ7.49(m,2H),7.45(m,2H),7.15(d,1H),6.68( d,1H),3.80(s,3H),3.37(s,3H),1.75(s,6H).101 δ7.42(m,H),7.30(m,2H),3.82(s,3H), 3.40(s,3H),2.29(s,3H),0.25(s,9H).102 δ7.54(m,2H),7.46(m,2H),3.83(s,3H),3.39(s,3H ),0.25(s,9H).103 δ7.36(m,2H),7.22(m,2H),7.09(s,1H),6.98(d.,2H),3.84(s,3H),3.39( s,3H),0.25(s,9H).106 δ8.44(s,1H),7.43(m,2H),7.22(m,1H),7.11(m,1H),6.86(m,2H), 6.22(d,1H),5.43(s,2H),3.78(s,3H),3.33(s,3H),2.27(s,3H).107 δ8.44(s,1H),7.39(m,1H ),7.16(m,5H),6.24(s,1H),5.5(s,2H-),3.78(s,3H),3.33(s,3H),2.27(s,3H).108 δ8.45( m,1H),7.39 (m,5H), 6.86 (m,2H), 6.26 (m,1H),5.44(s,2H),3.77(s,3H),3.33(s,3H).109 δ8. 44(s,1H),7.32(m,7H),6.27(m,1H),5.51(s,2H),3.77(s,3H),3.33(s,3H).110 δ8.4(d,1H ),7.35(m,8H),6.2(d,1H),4.58(t,2H),3.77(s,3H),3.33(s,3H),3.2(t,2H).111 δ8.4(d ,1H),7.25(m,7H),6.17(d,1H),4.57(t,2H),3.78(s,3H),3.34(s,3H),3.21(t,2H),2.27(s, 3H).112 δ8.43(d,1H),7.41(m,6H),7.19(d,2H),6.24(m,1H),5.38(s,2H),3.76(s,3H),3.33( s,3H),2.36(s,3H).113 δ8.43(d,1H),7.35(m,3H),7.2(m,3H),7.09(m,1H),6.21(d,1H), 5.37(AB q,2H),3.76(s,3H),3.33(s,3H),2.35(s,3H),2.27(s,3H).114 δ8.42(s,1H),7.4(m, 5H),7.19(m,H),6.89(d,1H),6.27(s,1H),4.76(t,2H),4.34(1,2H),3.79(s,3H),3.34(s,3H ).115 δ8.42(d, 1H),7.38(m,4H),7.17(m,1H),6.89(d,1H), 6.24(s,1H),4.75(t,2H), 4.33(t ,2H),3.79(s3H),3.34(s,3H), 2.27(s,3H).116 δ8.43(s,1H),7.87(m,3H),7.41(m,4H),6.34(AB q,2H),3.78(s,3H),3.33(s,3H).118 δ8.41(s,1H),7.4(m,8H),6.19(s,1H),4.58(t,2H), 3.77(s,3H),3.33(s,3H),3.13(t,2H).119 δ8.4(s,1H),7.44(m,5H),7.2(d,1H),7.09(d,1H ), 6.17(s,1H),4.57(t,2H),3.77(s,3H),3.33(s,3H),3.13(t,2H),2.27S,3H).120 δ8.42(d, 1H),8.14(m,1H),7.85(d,1H),7.77,(m,1H),7.47(m,6H),7.32(m,2H),6.2(d,1H),4.68(m, 2H),3.76(s,3H),3.54(t,2H), 3.33(s,3H).121 δ8.42(d,1H),8.15(d,1H),7.85(d,1H),7.75, (m,1H),7.48(m,2H),7.38(m,3H),7.22(m,1H),7.09(d,1H),6.18(s,1H),4.68(m,2H),3.77( s,3H),3.54(t,2H),3.33(s,3H),2.27(s,3H).122 δ8.7(d,1H),8.59(m,1H),8.44(s,1H), 7.77,(m,1H),7.41(m,5H),6.27(d,1H),5.45(s,2H),3.78(s,3H),3.33(s,3H).123 δ8.7(s, 1H),8.59(d,1H),8.43(d,1H),7.77,(m,1H),7.32(m,3H),7.11(m,1H),6.24(m,1H),5.44(s, 2H),3.78(s,3H),3.33(s,3H),2.27(s,1H).124 δ8.4(d,1H),7.4(m,4H),6.27(d,1H),4.52( m,2H),3.78(s,3H),3.72(m,2H),3.42(s,3H),3.33(s,3H).125 δ8.4(s,1H),7.38(t,1H), 7.2(d,1H),7.1(d,1H),6.22(d,1H),4.5(m,2H),3.78(s,3H),3.7(m,2H),3.42(s,3H),3.35 (s,3H),2.27(s,3H).126 δ8.45(d,1H),7.39(m,2H),7.23(m,4H),7.11(d,1H),6.22(d,1H) ,5.41(AB q,2H),3.77(s,3H),3.33(s,3H),2.38(s,3H),2.27(s,3H).127 δ8.59(d,1H),7.52(m ,1H),7.38(m,2H),7.22(m,3H),7.09(m,1H),6.68(d,1H),4.57(AB q,2H),3.75(s,3H),3.32(s ,3H),2.04(s,3H).

a ¹ HNMR data are expressed in ppm downfield from tetramethylsilane. Coupling is expressed as: (s)-singlet, (d)-doublet, (t)-triplet, (q)-tetramodal, (m)-multimodal, (AB q)-AB quadruplet, (dd) - double bimodal, (brs) - broad unimodal and (brm) - broad multimodal.

Biological Examples of the Invention

In an amount corresponding to 3% of the final volume; the test compound was first dissolved in acetone and then suspended in purified water containing 250 ppm of surfactant ^Trem_014 (polyol ester) at a concentration of 200 ppm. The resulting test suspensions were then used in Tests AF. 200 ppm of these test suspensions were sprayed at the test point of run-off of the test plants at a rate corresponding to 500 g/ha.

Test A

The test suspension was sprayed on the test sites of wheat seedlings. The next day wheat seedlings were inoculated with spore powder of Erysiphe graminis f.sp. tritici (causative agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which the degree of disease was determined.

Test B

The test suspension was sprayed on the test sites of wheat seedlings. The next day, the spore suspension of Puccinis recondita (the pathogen of wheat leaf stitch) was inoculated into wheat seedlings, incubated in a fully saturated environment at 20°C for 24 hours, and then moved to a growth room at 20°C Incubate for 6 days, after which the extent of disease is determined.

Test C

The test suspension was sprayed on the test sites of rice seedlings. The next day, the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causative agent of rice blast), incubated in a saturated environment at 27°C for 24 hours, and then moved to a growth chamber at 30°C for 5 days, after which the degree of disease was determined.

Test D

The test suspensions were sprayed on the test sites of potato seedlings. The next day, seedlings were inoculated with a spore suspension of Phytophthora infestans (the causative agent of potato and tomato late blight) and incubated in a saturated environment at 20°C for 24 hours, then moved to a growth chamber at 20°C for incubation 5 days, after which the extent of disease was determined.

Test E

The test suspension was sprayed onto the test sites of grape seedlings. The next day, the spore suspension of Plasmopara viticola (the pathogen of grape downy mildew) was inoculated on the seedlings, incubated in a saturated environment at 20°C for 24 hours, and then moved to a growth chamber at 20°C for incubation for 6 days, and then incubated in a saturated environment at 20°C for 24 hours, after which the degree of disease was determined.

Test F

The test suspension was sprayed onto the test sites of cucumber seedlings. Seedlings were inoculated the following day with a spore suspension of Botrytis cinerea (causative of gray mold disease in various crops), incubated in a saturated environment at 20°C for 48 hours, and then moved to a growth chamber at 20°C Incubate for 5 days, after which the extent of disease is determined.

The results of Tests A-F are listed in Table A. In this table, a rating of 100 indicates 100% disease control, while a rating of 0 indicates no disease control (relative to the control group). A dash (-) indicates no test results. ND indicates that disease control could not be determined due to phytotoxicity.

Table A Compound No. Test A Test B Test C Test D Test E Test F1 75 85 0 0 0 ^a 02 21 ^b 37 ^b 0 ^b - 7 ^b -3 0 0 0 21 5 ^b 684 0 24 0 21 5 ^b 685 0 85 0 21 16 ^b 446 60 24 0 21 7 ^b 47 0 0 0 0 - 268 0 0 0 0 - 329 99 100 74 96 94 ^a 010 85 85 32 22 28 ^a 3911 94 99 0 92 67 ^a 3912 63 127 3 0 ^a 6413 92 97 91 31 28 ^a 3814 0 0 0 53 - 015 86 85 0 3 - 016 99 100 91 93 92 ^a 017 100 100 91 64 72 ^a 018 89 94 0 84 46 ^a 1 719 0 0 2 0 0 ⁰ 2 100 53 96 87 ^A 4621 99 90 100 94 ^A 9722 99 100 78 100 ^A 8723 99 100 ^{78 A} 7724 97 78 92 51 ^A 025 99 100 9626 99 100 ^A 6027 97 100 60 61 88 ^a 3128 98 100 90 75 71 ^a 3129 89 100 74 47 15 ^a 0 30 99 100 86 96 72 ^a 031 99 100 86 59 75 ^a 132 32 ^c 84 ^a 38 ^b 84 ^b 93 ^a -920 98 75 ^A 4334 75 100 86 96 100 ^A 8135 99 99 92 96 ^A 136 100 100 96 100 ^A 8137 99 94 84 95 ^A 4338 100 100 74 55 ^A 139 97 83 ^B 100 ^A 040 99 100 74 99999 67 ^a 4341 98 100 78 61 99 ^a 7742 63 85 0 82 47 ^a 7743 0 67 0 54 10 ^a 044 99 ^d 99 d 78 ^d ND 12 ^{a 87 d} 45 77 100 73 ND 100 ^a 046 ^b 100 949 a 105 0 ⁹ 047 38 26 28 32 16 ^A 048 97 97 97 91 100 ^A 3149 68 0 83-050 93 100 45 ^A 051 100 73 99 35 ^A 5552 95 85 51 73 11 ^A 225 84 100 ^A 2254 999999 100 97 ND 100 ^A 055 73 99 53 65 100 ^A 056 99 100 94 ND 100 ^A 057 96 100 53 0 100 ^{A 058 100 94- 100 A 059} 97 79 42 ^A 060 98 77 ^A 4261 26 85 0 79 55 ^a 4262 0 99 32 79 12 ^a 063 98 100 32 ND 99 ^a 064 0 0 0 22 - 065 28 68 0 0 0 ^a 066 99 100 86 0 85 ^a 067 100 100 91 65 24 27 ^a 8 3568 59 ^a 6969 62 0 0 0 - 070 91 99 32 74 43 ^a 8271 60 99 53 17 73 ^a 072 91 93 32 0 - 073 57 94 0 23 38 ^a 074 100 100 53 - 72 ^a 075 949 - 69 ^a 9 20 ^a 97 ^d 0 ^d 0 ^d 0 ^a 0 ^d 77 21 ^a 99 6 0 82 ^a 078 11 ^a 86 35 0 19 ^a 079 30 ^a 97 91 0 0 ^a 080 0 ^a 97 64 0 6 ^a 081 30 97 0 0 - 082 99 100 74 62 - 083 0 66 0 0 6 ^a 084 94 99 86 58 ^e 93 ^a 085 83 93 32 0 71 ^a 086 96 100 74 100 ^f 100 ^a 087 94 100 74 15 100 ^a 1908 ^f 86 ^a 089 98 97 53 100 ^f 18 ^a 090 97 100 32 39 ^e - 091 58 99 0 100 ^e 12 ^a 092 31 100 53 92 ^g 96 ^a 093 85 100 32 73 ^e 87 ^a 094 92 ^a 98 ^a 0 ^a - 99 ^a -95 99 100 97 85 ^E 100 ^A 0101 98 97 86 74-91102 86 ⁶⁷ 57-91103 100 86 85-0104 100 74 100 ^F 96 ^A 0105 100 74 100 ^F 1006 100 ^F 97 ^A 0107 100 100 73 100 ^F 3 ^A 0108 97 97 74 82 ^E 97 ^A 0109 99 53 90 64 ^A 49110 86 97 53 22 ^A 1111 97 99 86 90 52 99 99 52 50 ^A 0113 100 94 455554555 45 ⁴⁵ 45 45 45 45 45 45 45 45 100 ^a 0114 100 100 99 75 11 ^a 0115 99 100 99 99 79 ^a 0116 98 100 94 94 64 ^a 0117 98 100 86 94 84 ^a 20118 83 100 86 51 50 ^a 0119 83 100 94 90 86 ^a 0120 90 100 53 68 76 ^a 0121 99 99 97 100 ^e 99 ^a 0122 78 94 0 19 11 ^a 0123 87 97 0 61 4 ^a 0124 78 86 0 0 2 ^a 0125 95 99 0 19 4 ^a 0126 100 100 97 100 ^f 274 ^a 9 7 47 ^a 94

^a Compound was tested at 10ppm (equivalent to 25/ha)

^b compound was tested at 40ppm (equivalent to 100g/ha)

^c compound was tested at 2ppm (equivalent to 5g/ha)

^d Compounds were tested at 100ppm (equivalent to 250g/ha)

^e 20% burns plants

^f 100% burnt plants

^g 50% burnt plants

Test G

Eleven-star melon leaf beetle

Test units were prepared, each consisting of a 230-ml (8 oz) plastic cup filled with a 6.5- ^cm2 (1 square inch) wheatgerm food plug. A solution of each test compound in a 75:25 acetone-distilled water solvent was sprayed into the pan and cup. Spraying was accomplished by passing the pans and cups on a conveyor belt under flat blast hydraulic nozzles discharging at 207 kPa (30 p.si) at a spray rate of 0.138 kg active ingredient per hectare (approximately 0.13 pounds per acre). After the sprayed cups had dried, 5 second instar larvae of Diabrotica undecimpunctatahowardi were placed in each cup. The cups were conditioned for 48 hours at 27°C and 50% relative humidity, after which mortality readings were taken. The same units were read again at 6-8 days to calculate delayed toxicity. Among the compounds tested, the following compounds produced a control effect level of not less than 80%: 44, 50, 54, 55, 56, 115 and 126.

Test H

Inhibition of aphid exposure test

Individual nasturtium leaves were infested with 10-15 aphids (various forms and growth stages of the sugar beet aphid (Aphis fabae)) and the undersides of the leaves were sprayed (upward facing) as described for Test G. The leaves were then placed in 0.94-cm (3/8 inch) diameter vials containing 4 ml of sucrose solution (approximately 1.4 g per liter) and covered with a clean 29-ml (1 oz) plastic cup to prevent Aphids escape as they fall from leaves. The test units were conditioned for 48 hours at 27°C and 50% relative humidity, after which time mortality readings were taken. Among the compounds tested, the following compounds produced a mortality level not lower than 80%: 5.

Test I

two-spotted spider mite

The underside of kidney bean leaves was infested with 25-30 adult mites (Tetranychus urticae), with an area of approximately 6.5 cm ² (1 square inch) per leaf infected, and the test compound was dissolved in a solvent of 75:25 acetone-distilled water. The solution is sprayed through hydraulic nozzles onto the upturned undersides of leaves. Spraying was accomplished by passing the foliage on a conveyor belt directly under flat blast hydraulic nozzles discharging at 207 kPa (30 p.si) at a spray rate of 0.138 kg active ingredient per hectare (approximately 0.13 lbs. per acre). The leaf squares were placed backside up on a square of damp cotton cloth in a Petri dish with the leaf periphery pressed against the cotton sheet with tweezers so that mites could not escape onto the untreated leaf surface. The test units were conditioned for 48 hours at 27°C and 50% relative humidity, after which time mortality readings were taken. Among the compounds tested, the following produced a mortality level of not less than 80%: 12, 13, 45, 54, 86, 88, 89, 90, 111, 113, 114, 115, 116, 117, 118, 119 and 126.

The same units were left for an additional 5 days and read out for larval and ovicidal lethality and/or developmental effects. Among the compounds tested, the following produced an activity level of not less than 80%: 63.

Test J

Inhibition of contact activity in leafhopper nymphs

Seedlings of three kinds of rice (Oryza sativa) at the 1.5-leaf developmental stage and about 10-cm tall were transplanted into 14-ml (0.5 oz) plastic cups containing Kumiai Brown artificial soil. Then 7ml of distilled water was added to the cup. Test compounds were prepared by first dissolving the test compounds in acetone, then adding water to give a final test concentration of 75:25 (acetone-water). Four plastic cups (each in duplicate) were then placed on the spray chamber turntable. 50 ml of the compound solution was sprayed on the cup for 45 seconds through an air-mist nozzle at a pressure of 2.0 kg/cm ² . During the 45-second spraying period, the turntable completes 7.5 revolutions. After compound application, the treated cups were left to dry in a ventilated cabinet for about 2 hours. After drying, the cups were placed in conical test units and the soil surface was covered with 2-3 mm of quartz sand. 8-10 third instar green leafhopper (Nephotettix cincticeps) nymphs were moved into the test unit using an aspirator. The test units were placed in an environment of 27°C and 65% relative humidity. Live and dead nymphs were counted at 24 and 48 hours post infection. Insects that cannot move are classified as dead. Among the compounds tested, the following compounds produced a mortality level of not less than 80% at 48 hours: 12 and 54 when applied at a rate corresponding to 0.05 kg per hectare.

Test K

Two-spotted spider mite larva (Tetranychus urticae)

The compound solution was prepared by dissolving the test compound in a minimum amount of acetone and then adding water with a wetting agent until the compound concentration was 50 ppm. The test solution (equivalent to 28 g/ha) was sprayed with a rotary disc sprayer onto the test sites of two-week-old red kidney bean plants infested with eggs of the two-spotted spider mite. The plants were kept at 25°C and 50% relative humidity. Among the compounds tested, the following compounds produced not less than 80% larvicidal/ovicidal activity after 7 days of spraying: 54 and 89.

Claims (11)

1. the compound of Xuan Zi formula I, the upper applicable Yan of its N-Yang compound and agricultural,E Xuan Zi wherein: ⅰ) optional You R³,R ⁴The Yi of Zhong or R³And R⁴1 of both replacements, the 2-phenylene; ⅱ) naphthalene nucleus, prerequisite are when G and Y are connected on same ring, and Ze G and Y are connected in the Xiang adjacent member of this ring, and described naphthalene nucleus is chosen You R wantonly³,R ⁴The Yi of Zhong or R³And R⁴Both replace; And III) ring body Xi, the monocycle of Xuan Zi 5-12 Yuan and the dicyclo aromatic heterocycle system that condenses, each Za ring body Xi contains Za Yuan of 1-6 independent Xuan Zi nitrogen, Yang and sulphur, prerequisite is that each Za ring body Xi contains many 4 nitrogen-atoms of Zhi, many 2 Yang Yuan of Zhi and many 2 sulphur atoms of Zhi, each bicyclic system that condenses is optional contains Yi non-aromatic ring, this non-aromatic ring is optional comprise Yi or two Q Zuo Wei ring the member and optional comprise individual or two the independent Xuan Zi C of Yi (=O) and S (O)₂Ring members, prerequisite is that G is connected on aromatic ring, and when G and Y are connected on same ring, Ze G and Y are connected in the Xiang adjacent member of this ring, each aromatic heterocycle system is chosen You R wantonly³,R ⁴The Yi of Zhong or R³And R⁴Both replace; A Wei O, S, N, NR⁵Or CR¹⁴ G Wei C or N, prerequisite is when G Wei C, Ze A Wei O, S or NR⁵And (floating) the two keys that float are connected on G; And when G Wei N, Ze A Wei N or CR¹⁴And two keys that should float are connected on A; W Wei O, S, NH, N (C₁-C ₆Alkyl) or NO (C₁-C ₆Alkyl); X is OR¹、S(O) _mR ¹Or halogen; R¹Wei C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, C₂-C ₄Alkyl oxycarbonyl base or C₂-C ₄Alkoxyl Tang base; R²Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, C₂-C ₄Alkyl oxycarbonyl base, C₂-C ₄Alkoxyl Tang is basic, Qiang is basic, C₁-C ₂Alkoxyl or acetoxyl group; R³And R⁴Basic, the C of independent Wei halogen, cyano group, Xiao base, Qiang separately₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₁-C ₆Alkoxyl, C₁-C ₆Halogenated alkoxy, C₂-C ₆Alkenyloxy, C₂- C ₆Chain oxy-acetylene, C₁-C ₆Alkylthio group, C₁-C ₆Alkyl sulfinyl, C₁-C ₆Alkyl sulfonyl base, formoxyl, C₂-C ₆Alkyl oxycarbonyl base, C₂-C ₆Alkoxyl Tang base; NH₂C(O)、(C ₁-C ₄Alkyl) NHC (O), (C₁-C ₄Alkyl)₂NC(O)、Si(R ²⁵) ₃、Ge(R ²⁵) ₃、(R ²⁵) ₃Si-C ≡ C-, or phenyl, phenylacetylene base, benzoyl or phenyl sulfonyl, each You R⁸Replace and optional You Yi or a plurality of R¹⁰Replace; Or as E Wei 1,2-phenylene and R³And R⁴Be connected in Xiang neighbour's Yuan when upper, R³And R⁴Can Yi playing Zuo is C₃-C ₅Alkylene base, C₃-C ₅Halo alkylene base, C₃-C ₅Alkenylene or C₃-C ₅The halo alkenylene, each optional You 1-2 C₁-C ₃Alkyl replaces; R⁵Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, C₂-C ₄Alkyl oxycarbonyl base or C₂-C ₄Alkoxyl Tang base; Y Wei-O-,-S (O)_n-、-NR ¹⁵-、-C(=O)-、-CH(OR ¹⁵)-、-CHR ⁶-、-CHR ⁶CHR ⁶-、 -CR ⁶=CR ⁶-、-C≡C-、-CHR ¹⁵O-、-OCHR ¹⁵-、-CHR ¹⁵S(O) _n-、-S(O) _nCHR ¹⁵、 -CHR ¹⁵O-N=C(R ⁷)-、-(R ⁷)C=N-OCH(R ¹⁵)-、-C(R-)=N-O-、-O-N=C(R ⁷)-、 -CHR ¹⁵OC(=O)N(R ¹⁵)-、-CHR ¹⁵OC(=S)N(R ¹⁵)-、-CHR ¹⁵OC(=O)O-、 -CHR ¹⁵OC(=S)O-、-CHR ¹⁵OC(=O)S-、-CHR ¹⁵OC(=S)S-、 -CHR ¹⁵SC(=O)N(R ¹⁵)-、-CHR ¹⁵SC(=S)N(R ¹⁵)-、-CHR ¹⁵SC(=O)O-、 -CHR ¹⁵SC(=S)O-、-CHR ¹⁵SC(=O)S-、-CHR ¹⁵SC(=S)S-、 -CHR ¹⁵SC(=NR ¹⁵)S-、-CHR ¹⁵N(R ¹⁵)C(=O)N(R ¹⁵)-、-CHR ¹⁵O- N(R ¹⁵)C(=O)N(R ¹⁵)-、-CHR ¹⁵O-N(R ¹⁵)C(=S)N(R ¹⁵)-、 -CHR ¹⁵O-N=C(R ⁷)NR ¹⁵-、-CHR ¹⁵O-N=C(R ⁷)OCH ₂-、-CHR ¹⁵O-N=C(R ⁷)-N=N-、 -CHR ¹⁵O-N=C(R ⁷)-C(=O)-、-CHR ¹⁵O-N=C(R ⁷)-C(=N-A ²-Z ¹-)-A ¹-、 -CHR ¹⁵O-N=C(R ⁷)-C(R ⁷)=N-A ²-A ³-、-CHR ¹⁵O-N=C(-C(R ⁷)=N-A ²-Z ¹)-、 -CHR ¹⁵O-N=C(R ⁷)-CH ₂O-、-CHR ¹⁵O-N=C(R ⁷)-CH ₂S-、 -O-CH ₂CH ₂O-N=C(R ⁷)-、-CHR ¹⁵O-C(R ¹⁵)=C(R ⁷)-、-CHR ¹⁵O-C(R ⁷)=N-、 -CHR ¹⁵S-C(R ⁷)=N-、-C(R ⁷)=N-NR ¹⁵-、-CH=N-N=C(R ⁷)-、 -CHR ¹⁵N(R ¹⁵)-N=C(R ⁷)-、-CHR ¹⁵N(COCH ₃)-N=C(R ⁷)-、-OC(=S)NR ¹⁵C(=O)-、 -CHR ⁶-C(=W ¹)-A ¹-、-CHR ⁶CHR ⁶-C(=W ¹)-A ¹-、-CR ⁶=CR ⁶-C(=W ¹)-A ¹-、 -C≡C-C(=W ¹)-A ¹-、-N=CR ⁶-C(=W ¹)-A ¹-, or Wei Zhi, connect key, and the directionality of Y key is defined as: the part that is connected on this key Zuo side is connected in E, and this key You side partly is connected in Z; Z¹Wei H or-A³-Z ²-； W ¹Wei O or S; A¹Wei O, S, NR¹⁵Or Zhi connects key; A²Wei O, NR¹⁵Or Zhi connects key; A³Wei-C (=O)-,-S (O)₂-or Zhi connect key; Z²Xuan Zi: ⅰ) C₁-C ₁₀Alkyl, C₂-C ₁₀Alkenyl and C₂-C ₁₀Alkynyl group, each optional You Yi or a plurality of R¹⁰Replace; ⅱ) C₃-C ₈Cycloalkyl, C₃-C ₈Cycloalkenyl group and phenyl, each optional You Yi or a plurality of R¹⁰Replace; ⅲ) ring body Xi, monocycle, the dicyclo that condenses of Xuan Zi 3-14 Yuan and the three ring non-aromatic heterocyclic systems that condense, the monocycle of Yi and 5-14 Yuan, the dicyclo that condenses and the three cyclophane Zu Za ring body Xi that condense, each Za ring body Xi contains Za Yuan of 1-6 independent Xuan Zi nitrogen, Yang and sulphur, prerequisite is that each Za ring body Xi contains many 4 nitrogen-atoms of Zhi, many 2 Yang Yuan of Zhi and many 2 sulphur atoms of Zhi, each non-aromatic or aromatic heterocycle system optional You Yi or a plurality of R¹⁰Replace; ⅳ) polycyclic system, the dicyclo that Xuan Zi 8-14 Yuan condenses and the three-ring system that condenses, Zhe Xie system Wei aromatics carbocyclic ring system, non-aromatic carbocyclic ring system, or contain the ring body Xi of Yi or two non-aromatic rings, each non-aromatic ring comprise Yi or two Zuo Wei member's the Q of ring and Yi or two independent Xuan Zi C (=O) and S (O)₂Ring members, take and any Zuo as remaining ring of aromatics carbocyclic ring, each polycyclic system optional You Yi or a plurality of R¹⁰Replace; And v) optional You Yi or a plurality of R¹⁰The adamantyl (adamantyl) that replaces; Each R⁶Independent Wei H, 1-2CH₃、C ₂-C ₃Alkyl, C₁-C ₃Alkoxyl, C₃-C ₆Cycloalkyl, formamido group, C₂-C ₄Alkyl-carbonyl-amino, C₂-C ₄Alkoxyl Tang base is amino, NH₂C(O)NH、(C ₁-C ₃Alkyl) NHC (O) NH, (C₁-C ₃Alkyl)₂NC(O)NH、 N(C ₁-C ₃Alkyl)₂, piperidyl, Lin Ji, 1-2 halogen, cyano group or Xiao base; Each R⁷Independent Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₁-C ₆Alkoxyl, C₁-C ₆Halogenated alkoxy, C₁-C ₆Alkylthio group, C₁-C ₆Alkyl sulfinyl, C₁-C ₆Alkyl sulfonyl base, C₁-C ₆Alkyl halide sulfenyl, C₁-C ₆Haloalkyl sulfinyl, C₁-C ₆Halogenated alkyl sulfonyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, C₂-C ₄Alkyl oxycarbonyl base, C₂-C ₄Alkoxyl Tang base, halogen, cyano group, Xiao base, Qiang are basic, amino, NH (C₁-C ₆Alkyl), N (C₁-C ₆Alkyl)₂Or Lin Ji; Z Xuan Zi: ⅰ) C₃-C ₈Cycloalkyl, C₃-C ₈Cycloalkenyl group and phenyl, each You R⁹Replace and optional You Yi or a plurality of R¹⁰Replace; ⅱ) ring body Xi, monocycle, the dicyclo that condenses of Xuan Zi 3-14 Yuan and the three ring non-aromatic heterocyclic systems that condense, the monocycle of Yi and 5-14 Yuan, the dicyclo that condenses and the three cyclophane Zu Za ring body Xi that condense, each Za ring body Xi contains Za Yuan of 1-6 independence Xuan Zi nitrogen, Yang and sulphur, prerequisite is that each Za ring body Xi contains many 4 nitrogen-atoms of Zhi, many 2 Yang Yuan of Zhi and many 2 sulphur atoms of Zhi, each non-aromatic or aromatic heterocycle system You R⁹Replace and optional You Yi or a plurality of R¹⁰Replace; ⅲ) polycyclic system, the dicyclo that Xuan Zi 8-14 Yuan condenses and the three-ring system that condenses, Zhe Xie system Wei aromatics carbocyclic ring system, non-aromatic carbocyclic ring system, or contain the ring body Xi of Yi or two non-aromatic rings, each non-aromatic ring comprise Yi or two Zuo Wei member's the Q of ring and Yi or two independent Xuan Zi C (=O) and S (O)₂Ring members, take and any Zuo as remaining ring of aromatics carbocyclic ring, each polycyclic system You R⁹Replace and optional You Yi or a plurality of R¹⁰Replace; And ⅳ) You R⁹Replace and optional You Yi or a plurality of R¹⁰The adamantyl that replaces; Each Q independence Xuan Zi-CHR¹³-、-NR ¹³-,-O-and-S (O)_p-； R ⁸Wei H, 1-2 halogen, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₁-C ₆Alkoxyl, C₁-C ₆Halogenated alkoxy, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₁-C ₆Alkylthio group, C₁-C ₆Alkyl halide sulfenyl, C₁-C ₆Alkyl sulfinyl, C₁-C ₆Alkyl sulfonyl base, C₃-C ₆Cycloalkyl, C₂-C ₆Alkenyloxy, CO₂(C ₁-C ₆Alkyl), NH (C₁- C ₆Alkyl), N (C₁-C ₆Alkyl)₂, cyano group, Xiao base, SiR¹⁹R ²⁰R ²¹Or GeR¹⁹R ²⁰R ²¹； R ⁹2-3 C of Wei You₁-C ₃The C that alkoxyl replaces₁-C ₆Alkyl, a You Yi Qiang base or 1-3 C₁-C ₄The C that alkoxyl replaces₂-C ₄Alkynyl group, C₂-C ₆Halo alkynyl group, few 1-4 the halogen of Yi Xuan Zi of You Zhi, a 1-2 C₁-C ₃Alkyl, a 1-2 C₁-C ₃An alkoxyl and Yi Z³The C that replaces of member₃-C ₆Cycloalkyl, C₃-C ₆Cycloalkenyl group or C₃-C ₆Cycloalkyloxy, few 1-2 the halogen of Yi Xuan Zi of each optional You Zhi, a 1-2 C₁-C ₃Alkyl, a 1-2 C₁-C ₃An alkoxyl and Yi Z³The member replace, adamantyl, C₂-C ₆Alkoxyl alkyl, C₂-C ₆Alkylthio alkyl, C₂-C ₆Cyano group alkyl, C₃-C ₆Alkoxy alkenyl, C₇-C ₁₀THP trtrahydropyranyl Yang base alkynyl group, You cyano group, C (=O) OR²⁶Or C (=O) N (R²⁶) ₂The C that replaces₁-C ₃Alkoxyl, C₃-C ₆Halogenated alkenyl oxy, C₃-C ₆Alkynyl group Yang base, C₃-C ₆Halo alkynyl group Yang base, C₂-C ₆Alkoxyl alkoxyl, C₅-C ₉Trialkyl silylation alkoxyl alkoxyl, C₂-C ₆Alkylthio group alkoxyl, You cyano group, C (=O) OR²⁶Or C (=O) N (R²⁶) ₂The C that replaces₁-C ₃Alkylthio group, C₁-C ₆Haloalkyl sulfinyl, C₁-C ₆Halogenated alkyl sulfonyl, C₃-C ₆Alkenyl thio, C₃-C ₆Halo alkenyl thio, C₃-C ₆Sulfur-based chain acetylene, C₃-C ₆Halo sulfur-based chain acetylene, C₂-C ₆Alkoxyl alkylthio group, C₂-C ₆Alkylthio group alkylthio group, sulfo-cyanato-, Qiang base, Qiu are basic, amino, N (R²⁶)(R ²⁸)、SiR ²²R ²³R ²⁴、GeR ²²R ²³R ²⁴、(R ²⁵) ₃Si-C≡C-、 OSi(R ²⁵) ₃、OGe(R ²⁵) ₃、C(=O)R ²⁹、C(=S)R ²⁶、C(=O)OR ³⁰、 C(=S)OR ²⁶、C(=O)SR ²⁶、C(=S)SR ²⁶、C(=O)N(R ²⁶) ₂、 C(=S)N(R ²⁶) ₂、C(=NR ²⁶)O(R ²⁷)、OC(=O)R ²⁶、OC(=S)R ²⁶、 SC(=O)R ²⁶、SC(=S)R ²⁶、N(R ²⁶)C(=O)R ²⁶、N(R ²⁶)C(=S)R ²⁶、 OC(=O)OR ²⁷、OC(=O)SR ²⁷、OC(=O)N(R ²⁶) ₂、SC(=O)OR ²⁷、 SC(=O)SR ²⁷、S(O) ₂OR ²⁶、S(O) ₂N(R ²⁶) ₂、OS(O) ₂R ²⁷Or N (R²⁶)S(O) ₂R ²⁷ Or R⁹Wei benzyloxy, benzyloxy methyl, phenylacetylene base, phenoxy group methyl, thiophenyl, phenyl sulfonyl, benzylthio, Bi Ding ylmethyl, Bi Ding ylmethoxy, Bi Ding base Yang ylmethyl, Bi Ding ethyl-acetylene base, Bi Ding sulfenyl, thienyl methyl, thiophenic sulfur base, Fu Nan ylmethyl, Fu Nan base Yang base, furansulfenyl, Mi Ding ylmethyl or Mi Ding sulfenyl, choose You R on each Zai aromatic ring wantonly¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; Or R⁹Wei You 1-2 phenyl, Nai base, phenoxy group, benzyloxy, Bi Ding base, Mi Ding base, thienyl or the Fu Nan base C that replaces₂-C ₆Alkyl or C₂-C ₆Alkoxyl, each aromatic ring is chosen You R wantonly¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; Or R⁹Wei-A⁴-Z ⁴ Each R¹⁰Independent Wei halogen, optional by 1-3 C₁-C ₃The C that alkoxyl replaces₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, C₂-C ₆Alkoxyl alkyl, C₂-C ₆Alkylthio alkyl, C₂-C ₆Cyano group alkyl, C₃-C ₆Alkoxyl alkynyl, C₇-C ₁₀THP trtrahydropyranyl Yang base alkynyl group, benzyloxy methyl, C₁-C ₄Alkoxyl, C₁-C ₄Halogenated alkoxy, C₃-C ₆Alkenyl oxy, C₃-C ₆Halogenated alkenyl oxy, C₃-C ₆Alkynyl group Yang base, C₃-C ₆Halo alkynyl group Yang base, C₃-C ₆Cycloalkyloxy, C₃-C ₆Alkoxyl alkoxyl, C₅-C ₉Trialkyl silylation alkoxyl alkoxyl, C₂-C ₆Alkylthio group alkoxyl, C₁-C ₄Alkylthio group, C₁-C ₄Alkyl halide sulfenyl, C₁-C ₄Alkyl sulfinyl, C₁-C ₄Haloalkyl sulfinyl, C₁-C ₄Alkyl sulfonyl base, C₁-C ₄Halogenated alkyl sulfonyl, C₃-C ₆Alkenyl thio, C₃-C ₆Halo alkenyl thio, C₃-C ₆Sulfur-based chain acetylene, C₃-C ₆Halo sulfur-based chain acetylene, C₂-C ₆Alkoxyl alkylthio group, C₂-C ₆Alkylthio group alkylthio group, Xiao base, cyano group, sulfo-cyanato-, Qiang base, Qiu are basic, N (R²⁶) ₂、 SF ₅、Si(R ²⁵) ₃、Ge(R ²⁵) ₃、(R ²⁵) ₃Si-C≡C-、OSi(R ²⁵) ₃、OGe(R ²⁵) ₃、 C(R ¹⁸)=NOR ¹⁷、C(=O)R ²⁶、C(=S)R ²⁶、C(=O)OR ²⁶、C(=S)OR ²⁶、 C(=O)SR ²⁶、C(=S)SR ²⁶、C(=O)N(R ²⁶) ₂、C(=S)N(R ²⁶) ₂、 C(=NR ²⁶)OR ²⁷、OC(=O)R ²⁶、OC(=S)R ²⁶、SC(=O)R ²⁶、SC(=S)R ²⁶、 N(R ²⁶)C(=O)R ²⁶、N(R ²⁶)C(=S)R ²⁶、OC(=O)OR ²⁷、OC(=O)SR ²⁷、 OC(=O)N(R ²⁶) ₂、SC(=O)OR ²⁷、SC(=O)SR ²⁷、S(O) ₂OR ²⁶、 S(O) ₂N(R ²⁶) ₂、OS(O) ₂R ²⁷、N(R ²⁶)S(O) ₂R ²⁷ Or phenyl, Bian base or phenoxy group, optional You R on each Zai phenyl ring¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; Or as Y and Yi R¹⁰Adjacent Yuan of Xiang and the Y that are connected on Z are CHR¹⁵O-N=C(R ⁷)-、 -O-N=C(R ⁷)-、-O-CH ₂CH ₂O-N=C(R ⁷)-、-CHR ¹⁵O-C(R ¹⁵)=C(R ⁷)-、 CH=N-N=C(R ⁷)-、-CHR ¹⁵N(R ¹⁵)-N=C(R ⁷)-or-CHR¹⁵N(COCH ₃)-N=C(R ⁷)-time, Ze R⁷Be connected the adjacent R that connects of Xiang¹⁰Can Yi rise into-(CH₂) _r-J-, so J also is connected on Z; J Wei-CH₂-、-CH ₂CH ₂-、-OCH ₂-、-CH ₂O-、-SCH ₂-、-CH ₂S-、-N(R ¹⁶)CH ₂-or-CH₂N(R ¹⁶), each CH of described J₂Group is chosen a You 1-2 CH wantonly₃Replace; Z³the Wei phenyl, the Nai base, 1H-Bi coughs up base, Fu Nan base, thienyl, the 1H-pyrazolyl, 1H-Mi Zuo base, isoxazolyl, oxazolyl, Yi Sai Zuo base, Sai Zuo base, 1H-1, 2, the 3-triazolyl, 2H-1, 2, the 3-triazolyl, 1H-1, 2, the 4-triazolyl, 4H-1, 2, the 4-triazolyl, 1, 2, the 3-oxadiazolyl, 1, 2, the 4-oxadiazolyl, 1, 2, the 5-oxadiazolyl, 1, 3, the 4-oxadiazolyl, 1, 2, 3-Sai di azoly, 1, 2, 4-Sai di azoly, 1, 2, 5-Sai di azoly, 1, 3, 4-Sai di azoly, the 1H-tetrazole radical, the 2H-tetrazole radical, Bi Ding base, pyridazinyl, Mi Ding base, pyrazinyl, 1, 3, the 5-triazine radical, 1, 2, 4-triazine radical or 1, 2, 4, 5-tetrazine base, each optional You R¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; R⁴Wei O, S, Zhi chain or Zhi chain C₁-C ₆The alkylene base, or Zhi connects key; Z⁴Xuan Zi: ⅰ) 1H-Bi coughs up base, the 1H-pyrazolyl, 1H-Mi Zuo base, isoxazolyl, oxazolyl, Yi Sai Zuo base, Sai Zuo base, 1H-1, 2, the 3-triazolyl, 2H-1, 2, the 3-triazolyl, 1H-1, 2, the 4-triazolyl, 4H-1, 2, the 4-triazolyl, 1, 2, the 3-oxadiazolyl, 1, 2, the 4-oxadiazolyl, 1, 2, the 5-oxadiazolyl, 1, 3, the 4-oxadiazolyl, 1, 2, 3-Sai di azoly, 1, 2, 4-Sai di azoly, 1, 2, 5-Sai di azoly, 1, 3, 4-Sai di azoly, the 1H-tetrazole radical, the 2H-tetrazole radical, pyridazinyl, pyrazinyl, 1, 3, the 5-triazine radical, 1, 2, 4-triazine radical and 1, 2, 4, 5-tetrazine base, each optional You R¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; ⅱ) ring body Xi, monocycle, the dicyclo that condenses of Xuan Zi 3-14 Yuan and the three ring non-aromatic heterocyclic systems that condense, the dicyclo that condenses of Yi and 8-14 Yuan and the three cyclophane Zu Za ring body Xi that condense, each Za ring body Xi contains Za Yuan of 1-6 independence Xuan Zi nitrogen, Yang and sulphur, prerequisite is that each Za ring body Xi contains many 4 nitrogen-atoms of Zhi, many 2 Yang Yuan of Zhi and many 2 sulphur atoms of Zhi, each non-aromatic or optional You R of aromatic heterocycle system¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; And ⅲ) polycyclic system, the dicyclo that Xuan Zi 8-14 Yuan condenses and the three-ring system that condenses, Zhe Xie system Wei aromatics carbocyclic ring system, non-aromatic carbocyclic ring system, or contain the ring body Xi of Yi or two non-aromatic rings, each non-aromatic ring comprise Yi or two Zuo Wei member's the Q of ring and Yi or two independent Xuan Zi C (=O) and S (O)₂Ring members, take and any Zuo as remaining ring of aromatics carbocyclic ring, each polycyclic system is chosen R wantonly¹¹,R ¹²The Yi of Zhong or R¹¹And R¹²Both replace; Each R¹¹With each R¹²Independent Wei 1-2 halogen, C₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₂-C ₆Alkoxyl alkyl, C₂-C ₆Alkylthio alkyl, C₃-C ₆Oxyalkyl chain alkynyl, C₇-C ₁₀THP trtrahydropyranyl Yang base alkynyl group, benzyloxy methyl, C₁-C ₄Alkoxyl, C₁-C ₄Halogenated alkoxy, C₃-C ₆Alkenyl oxy, C₃-C ₆Halogenated alkenyl oxy, C₃-C ₆Alkynyl group Yang base, C₃-C ₆Halo alkynyl group Yang base, C₂-C ₆Alkoxyl alkoxyl, C₅-C ₉Trialkyl silylation alkoxyl alkoxyl, C₂-C ₆Alkylthio group alkoxyl, C₁-C ₄Alkylthio group, C₁-C ₄Alkyl halide sulfenyl, C₁-C ₄Alkyl sulfinyl, C₁-C ₄Haloalkyl sulfinyl, C₁-C ₄Alkyl sulfonyl base, C₁-C ₄Halogenated alkyl sulfonyl, C₃-C ₆Alkenyl thio, C₃-C ₆Halo alkenyl thio, C₂-C ₆Alkylthio group alkylthio group, Xiao base, cyano group, sulfo-cyanato-, Qiang base, Qiu are basic, N (R²⁶) ₂、 SF ₅、Si(R ²⁵) ₃、Ge(R ²⁵) ₃、(R ²⁵) ₃Si-C≡C-、OSi(R ²⁵) ₃、OGe(R ²⁵) ₃、 C(=O)R ²⁶、C(=S)R ²⁶、C(=O)OR ²⁶、C(=S)OR ²⁶、C(=O)SR ²⁶、 C(=S)SR ²⁶、C(=O)N(R ²⁶) ₂、C(=S)N(R ²⁶) ₂、OC(=O)R ²⁶、 OC(=S)R ²⁶、SC(=O)R ²⁶、SC(=S)R ²⁶、N(R ²⁶)C(=O)R ²⁶、 N(R ²⁶)C(=S)R ²⁶、OC(=O)OR ²⁷、OC(=O)SR ²⁷、OC(=O)N(R ²⁶) ₂、 SC(=O)OR ²⁷、SC(=O)SR ²⁷、S(O) ₂OR ²⁶、S(O) ₂N(R ²⁶) ₂、OS(O) ₂R ²⁷Or N (R²⁶)S(O) ₂R ²⁷ Or phenyl, phenoxy group, Bian base, benzyloxy, phenyl sulfonyl, phenylacetylene base or Bi Ding ethyl-acetylene base, optional You 1-2 independent Xuan Zi halogen, C on each Zai aromatic ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The group of halogenated alkoxy, Xiao base and cyano group replaces; Each R¹³Independent Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, or optional You halogen, C₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The phenyl that halogenated alkoxy, Xiao base or cyano group replace; R¹⁴Wei H, halogen, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂- C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group or C₃-C ₆Cycloalkyl; Each R¹⁵Independent Wei H, C₁-C ₃Alkyl, C₃-C ₆Cycloalkyl, perhaps Wei phenyl or Bian base, optional You halogen, C on each Zai phenyl ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄Halogenated alkoxy, Xiao base or cyano group replace; Or as Y Wei-CHR¹⁵N(R ¹⁵)C(=O)N(R ¹⁵)-time, two R that are connected on described group nitrogen-atoms¹⁵Can play Zuo Wei-(CH by Yi₂) _s-; Or as Y Wei-CHR¹⁵O-N=C(R ⁷)NR ¹⁵-time, R⁷R with the connection of Xiang being connected¹⁵Can play Zuo Wei-CH by Yi₂-(CH ₂) _s-、-O-(CH ₂) _s-、-S-(CH ₂) _s-or-N (C₁-C ₃Alkyl)-(CH₂) _s-, and the directionality of described key is defined as: the part that is connected on this key Zuo side is connected in carbon, and this key You side partly is connected in nitrogen; R¹⁶、R ¹⁷And R¹⁸Independent Wei H, C separately₁-C ₃Alkyl, C₃-C ₆Cycloalkyl, or optional You halogen, C₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The phenyl that halogenated alkoxy, Xiao base or cyano group replace; R¹⁹、R ²⁰、R ²¹、R ²²And R²³Independent Wei C separately₁-C ₆Alkyl, C₁-C ₄Haloalkyl, C₂-C ₆Alkenyl, C₁-C ₄Alkoxyl or phenyl; R²⁴Wei C₁-C ₄Haloalkyl; Each R²⁵Independent Wei C₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₂-C ₄Alkenyl, C₁-C ₄Alkoxyl or phenyl; Each R²⁶Independent Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, or phenyl or Bian base, optional You 1-2 independent Xuan Zi halogen, C on each Zai phenyl ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The group of halogenated alkoxy, Xiao base and cyano group replaces; Each R²⁷Independent Wei C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, or phenyl or Bian base, optional You 1-2 independent Xuan Zi halogen, C on each Zai phenyl ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The group of halogenated alkoxy, Xiao base and cyano group replaces; Each R²⁸Independent Wei C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, or phenyl or Bian base, optional You 1-2 independent Xuan Zi halogen, C on each Zai phenyl ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The group of halogenated alkoxy, Xiao base and cyano group replaces; R²⁹Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂-C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, or choose You 1-2 independent Xuan Zi halogen, C on the Zai phenyl ring wantonly₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The Bian base that the group of halogenated alkoxy, Xiao base and cyano group replaces; R³⁰Wei H, C₁-C ₆Haloalkyl, C₂-C ₆Alkenyl, C₂-C ₆Halogenated alkenyl, C₂- C ₆Alkynyl group, C₂-C ₆Halo alkynyl group, C₃-C ₆Cycloalkyl, or phenyl or Bian base, optional You 1-2 independent Xuan Zi halogen, C on each Zai phenyl ring₁-C ₄Alkyl, C₁-C ₄Haloalkyl, C₁-C ₄Alkoxyl, C₁-C ₄The group of halogenated alkoxy, Xiao base and cyano group replaces; M, n and p be independent Wei 0,1 or 2 separately; R Wei 0 or 1; With s Wei 2 or 3; Prerequisite is as Y Wei-CH (OR¹⁵)-、-CHR ⁶-、-CHR ⁶CHR ⁶-、-CR ⁶=CR ⁶-、-C≡C-、 -CHR ¹⁵O-、-OCHR ¹⁵-、-S(O) _nCHR ¹⁵-、-(R ⁷)C=N-OCH(R ¹⁵)-、 -CHR ¹⁵O-N=C(R ⁷)-CH ₂O-、-CHR ¹⁵O-C(R ¹⁵)=C(R ⁷)-、-CHR ⁶-C(=W ¹)-A ¹-、-CHR ⁶CHR ⁶-C(=W ¹)-A ¹、-CR ⁶=CR ⁶-C(=W ¹)-A ¹-or-C ≡ C-C (=W¹)-A ¹In-time, Ze Z is not phenyl, Fu Nan base, thienyl, Bi Ding base and Mi Ding base.

2. the compound of claim 1 wherein: E Xuan Zi 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-and 2,3-Nai, two bases; 1H-Bi coughs up-1,2-, 2,3-and 3,4-, two bases; 2,3-and 3,4-Fu Nan, two bases; 2,3-and 3,4-Sai fen, two bases; 1H-Bi Zuo-1,5-, 3,4-and 4,5-, two bases; 1H-Mi Zuo-1,2-, 4,5-and 1,5-, two bases; 3,4-and 4,5-isoxazole, two bases; 4,5-oxazole, two bases; 3,4-and 4,5-Yi Sai Zuo, two bases; 4,5-Sai Zuo, two bases; 1H-1,2,3-triazole-1,5-and-4,5-two bases; 2H-1,2,3-triazoles-4,5-two bases; 1H-1,2,4-triazole-1,5-two bases; 4H-1,2,4-triazole-3,4-two bases; 1,2,3-oxadiazole-4,5-two bases; 1,2,5-oxadiazole-3,4-two bases; 1,2,3-Sai diazole-4,5-two bases; 1,2,5-Sai diazole-3,4-two bases; 1H-tetrazolium-1,5-two bases; 2,3-and 3,4-Bi Ding, two bases; 3,4-and 4,5-Da Qin, two bases; 4,5-Mi Ding, two bases; 2,3-Bi Qin, two bases; 1,2,3-triazine-4,5-two bases; 1,2,4-triazine-5,6-two bases; 1H-Yin Duo-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-2,3-, 4,5-, 5,6-and 6,7-, two bases; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6-and 6,7-benzofuran, two bases; Benzo [b] Sai fen-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6-and 6,7-, two bases; 1H-Yin Zuo-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6-and 6,7-, two bases; 1H-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6-and 6,7-, two bases; 1,2-benzoisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6-and 6,7-, two bases; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6-and 6,7-benzoxazole, two bases; 1,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6-and 6,7-, two bases; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6-and 6,7-benzothiazole, two bases; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7-and 7,8-Kui Lin, two bases; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7-and 7,8-Yi Kui woods, two bases; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7-and 7,8-cinnoline, two bases; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7-and 7,8-phthalazines, two bases; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7-and 7,8-Kui Zuo Lin, two bases; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7-and 7,8-Kui Wo Lin, two bases; 1,8-Nai Ding-2,5-, 2,6-, 2,7-, 3,5-, 3,6-, 4,5-, 2,3-and 3,4-, two bases; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-pteridine two bases; Pyrazolo [5,1-b] Sai Zuo-2,6-, 2,7-, 3,6-, 3,7-, 2,3-and 6,7-, two bases; Sai Zuo is [2,3-C]-1,2 also, 4-triazole-2,5-, 2,6-, 5,6-two bases; 2-Yang generation-1,3-benzo dioxole-4,5-and 5,6--, two-Ji; 1,3-dioxy generation-1H-Yi Yin Duo-2,4-, 2,5-, 4,5-and 5,6-, two bases; 2-Yang generation-2H-1-benzofuran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7-and 7,8-, two bases; [1,2,4] triazols [1,5-a] Bi Ding-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7-and 7,8-, two bases; 3,4-dihydro-2,4-dioxy generation-2H-1,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-, 5,6-, 6,7-and 7,8-, two bases; 2,3-dihydro-2-Yang generation-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6-and 6,7-benzofuran, two bases; Thieno [3,2-d] Sai Zuo-2,5-, 2,6-and 5,6-, two bases; 5,6,7,8-tetrahydrochysene-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-and 3,4-Kui Lin, two bases; 2,3-dihydro-1,1,3-trioxy--1,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6-and 6,7--, two-Ji; 1,3-benzo dioxole-2,4-, 2,5-, 4,5-and 5,6-, two bases; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6-and 6,7-benzofuran, two bases; 2,3-dihydro-1,4-benzo dioxa Ying (benzodioxin)-2,5-, 2,6-, 2,7-, 2,8-, 5,6-and 6,7-, two bases; And 5,6,7,8-tetrahydrochysene-4H-encircles [b] Sai fen-2 in heptan, 4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-and 2,3-, two bases; Each aromatic ring system is chosen You R wantonly³,R ⁴The Yi of Zhong or R³And R⁴Both replace; W is O; R¹Wei C₁-C ₃Alkyl or C₁-C ₃Haloalkyl; R²Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl or C₃-C ₆Cycloalkyl; R³And R⁴Independent Wei halogen, cyano group, Xiao base, C separately₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₁-C ₆Alkoxyl, C₁-C ₆Halogenated alkoxy, C₁-C ₆Alkylthio group, C₁-C ₆Alkyl sulfonyl base, C₂-C ₆Alkyl oxycarbonyl base, C₂-C ₆Alkoxyl Tang base, (C₁-C ₄Alkyl) NHC (O), (C₁-C ₄Alkyl)₂NC (O), benzoyl or phenyl sulfonyl; Y Wei-O-,-S (O) n-,-NR¹⁵-、-C(=O)-、-CH(OR ¹⁵)-、-CH ₂-、-CH ₂CH ₂-、 -CH=CH-、-C≡C-、-CH ₂O-、-OCH ₂-、-CH ₂S(O) _n-、-S(O) _nCH ₂-、 -CH ₂O-N=C(R ⁷)-、-(R ⁷)C=N-OCH(R ¹⁵)-、-C(R ⁷)=N-O-or Wei Zhi, connect key; R⁷Wei H, C₁-C ₆Alkyl, C₁-C ₆Haloalkyl, C₁-C ₆Alkoxyl, C₁-C ₆Alkylthio group, C₂-C ₆Alkenyl, C₂-C ₆Alkynyl group, C₃-C ₆Cycloalkyl, halogen or cyano group; Or as Y and Yi R¹⁰Adjacent Yuan of Xiang and the Y that are connected on Z are CH₂O-N=C(R ⁷)-, Ze R⁷Be connected the adjacent R that connects of Xiang¹⁰Can Yi rise into-(CH₂) _r-J-, so J also is connected on Z; Z Xuan Zi C₃-C ₈cycloalkyl, phenyl, the Nai base, the En base, phenanthryl, 1H-Bi coughs up base, Fu Nan base, thienyl, the 1H-pyrazolyl, 1H-Mi Zuo base, isoxazolyl, oxazolyl, Yi Sai Zuo base, Sai Zuo base, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1,2, the 4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-Sai di azoly, 1,2,4-Sai di azoly, 1,2,5-Sai di azoly, 1,3,4-Sai di azoly, the 1H-tetrazole radical, the 2H-tetrazole radical, Bi Ding base, pyridazinyl, Mi Ding base, pyrazinyl, the 1,3,5-triazines base, 1,2,4-triazine radical, 1,2,4,5-tetrazine base, 1H-Yin Duo base, benzofuranyl, benzo [b] thienyl, the 1H-indazolyl, the 1H-benzimidazolyl, Ben Bing Evil Zuo base, benzothiazolyl, quinolyl, isoquinolyl, the cinnoline base, phthalazinyl, quinazolyl, quinoxalinyl, 1,8-Nai Ding base, pteridyl, 2,3-dihydro-1H-Yin base, 1,2,3,4-tetralyl, 6,7,8,9-tetrahydrochysene-5H-benzocyclohepta thiazolinyl, 5,6,7,8,9,10-hexahydrobenzene and cyclo-octene base, 2,3-dihydro-3-Yang is for benzofuranyl, 1,3-dihydro-1-Yang is for the Yi benzofuranyl, 2,3-dihydro-2-Yang is for benzofuranyl, 3,4-dihydro-4-Yang generation-2H-1-benzopyranyl, 3,4-dihydro-1-Yang generation-1H-2-benzopyranyl, 3,4-dihydro-3-Yang generation-1H-2-benzopyranyl, 3,4-dihydro-2-Yang generation-2H-1-benzopyranyl, 4-Yang generation-4H-1-benzopyranyl, 2-Yang generation-2H-1-benzopyranyl, 2,3,4,5-tetrahydrochysene-5-Yang generation-1-benzo oxa-Ying in heptan base (benzoxepinyl), 2,3,4,5-tetrahydrochysene-2-Yang generation-1-benzo oxa-Ying in heptan base, 2,3-dihydro-1,3-dioxy generation-1H-Yi Yin Duo base, 1,2,3,4-tetrahydrochysene-1, the 3-dioxy is for Yi Kui beautiful jade base, 3,4--dihydro-2,4-dioxy generation-2H-1,3-benzoxazinyl, 2-Yang generation-1,3-benzo dioxole base, 2,3-dihydro-1,1,3-trioxy--1,2-benzisothiazole base, the 9H-fluorenyl, Azulene base and Sai Zuo be [2,3-c]-1,2 also, 4-triazolyl, each group You R⁹Replace and optional You Yi or a plurality of R¹⁰Replace; And R¹⁵Wei H, C₁-C ₃Alkyl or C₃-C ₆Cycloalkyl.

3. the compound of claim 2 wherein: E is selected from group 1, the 2-phenylene; 1,6-, 1,7-, 1,2-and 2,3-naphthalene two bases; 2,3-and 3,4-furans two bases; 2,3-and 3,4-thiophene two bases; 2,3-and 3,4-pyridine two bases; 4,5-pyrimidine two bases; 2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6-and 6,7-cumarone two bases; Benzo [b] thiophene-2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6-and 6,7-two bases; Each aromatic ring system is optional by R ³, R ⁴In one or R ³And R ⁴Both replace; Z is selected from phenyl, naphthyl, 2-thiazolyl, 1,2,4-oxadiazole base, 1,3, and 4-oxadiazole base, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, pyridyl and pyrimidyl, each group is by R ⁹Replacement is also optional by one or more R ¹⁰Replace; R ⁷Be H, C ₁-C ₆Alkyl, C ₁-C ₆Haloalkyl, C ₁-C ₆Alkoxyl group, C ₁-C ₆Alkylthio, C ₂-C ₆Alkenyl, C ₂-C ₆Alkynyl group, cyclopropyl, halogen or cyano group; R ⁹Serving as reasons, at least one is selected from 1-2 halogen, a 1-2 C ₁-C ₃Alkyl, a 1-2 C ₁-C ₃Alkoxyl group and a Z ³The C that replaces of member ₃-C ₆Cycloalkyl is chosen wantonly and is selected from 1-2 halogen, a 1-2 C by at least one ₁-C ₃Alkyl, a 1-2 C ₁-C ₃Alkoxyl group and a Z ³The C that replaces of member ₃-C ₆Cycloalkyloxy, C ₁-C ₆Haloalkyl sulfinyl, C ₁-C ₆Halogenated alkyl sulfonyl, sulfo-cyanato-, SiR ²²R ²³R ²⁴, GeR ²²R ²³R ²⁴, (R ²⁵) ₃Si-C ≡ C-, C (=O) R ²⁹, C (=O) OR ³⁰, S (O) ₂OR ²⁶, S (O) ₂N (R ²⁶) ₂Or OS (O) ₂R ²⁷, or R ⁹Be benzyloxy, phenylacetylene base, phenoxymethyl, thiophenyl, phenyl sulfonyl, benzylthio-, pyridyl methoxyl group, pyridyl oxygen ylmethyl, pyridyl ethynyl or furyl oxygen base, each is optional by R on aromatic ring ¹¹, R ¹²In one or R ¹¹And R ¹²Both replace; Or R ⁹Be the C that replaces by 1-2 phenyl, naphthyl, phenoxy group, benzyloxy, pyridyl, pyrimidyl, thienyl or furyl ₂-C ₆Alkyl or C ₂-C ₆Alkoxyl group, each aromatic ring is optional by R ¹¹, R ¹²In one or R ¹¹And R ¹²Both replace; Or R ⁹For-A ⁴-Z ⁴Each R ¹⁰Independent is halogen, C ₁-C ₄Haloalkyl, C ₂-C ₆Alkynyl group, nitro, cyano group, Si (R ²⁵) ₃Or (R ²⁵) ₃Si-C ≡ C-; Or as Y and a R ¹⁰The adjacent atom and the Y that are connected on the Z are-CH ₂O-N=C (R ⁷)-time, R then ⁷With the described adjacent R that is connected ¹⁰Can be together-(CH ₂) _r-J-, so J also is connected on the Z; J is-CH ₂-or-CH ₂CH ₂-; Z ³Be phenyl, furyl, thienyl or pyridyl, each is optional by R ¹¹, R ¹²In one or R ¹¹And R ¹²Both replace; A ⁴Be direct key; Z ⁴For choosing wantonly by R ¹¹, R ¹²In one or R ¹¹And R ¹²1 of both replacements, 3-benzo dioxolyl; And r is 1.

4. the compound of claim 3 wherein: E is selected from group 1, the 2-phenylene; 2,3-and 3,4-thiophene two bases and 2,3-and 3,4-pyridine two bases; Each aromatic ring system is optional by R ³, R ⁴In one or R ³And R ⁴Both replace; A is O or N; X is OR ¹R ¹Be C ₁-C ₃Alkyl; R ²Be H or C ₁-C ₂Alkyl; Y is-O-,-S (O) n-,-NR ¹⁵-,-C (=O)-,-CH (OR ¹⁵)-,-CH ₂-,-CH ₂CH ₂-,-CH=CH-,-C ≡ C-,-CH ₂O-,-OCH ₂-,-CH ₂S (O) _n-,-S (O) _nCH ₂-,-CH ₂O-N=C (R ⁷)-,-(R ⁷) C=N-OCH (R ¹⁵)-,-CH ₂OC (=O) NH-,-CH ₂S-C (R ⁷)=N-or be direct key; Z is selected from phenyl, 2-thiazolyl, 1,2,4-thiadiazolyl group, pyridyl and pyrimidyl, and each group is by R ⁹Replacement and optional by one or more R ¹⁰Replace; R ⁷Be H, C ₁-C ₃Alkyl, C ₁-C ₃Haloalkyl, C ₁-C ₃Alkoxyl group, C ₁-C ₃Alkylthio or cyclopropyl; And R ¹⁵Be H, C ₁-C ₃Alkyl or cyclopropyl.

5. the compound of claim 4 wherein: R ¹Be methyl; R ²Be methyl; Y is-O-,-CH ₂O-,-CH ₂O-N=C (R ⁷)-or-(R ⁷) C=N-OCH (R ¹⁵)-; R ⁹For by a Z ³The C that replaces ₃-C ₆Cycloalkyl, C ₃-C ₆Cycloalkyloxy, SiR ²²R ²³R ²⁴, GeR ²²R ²³R ²⁴, (R ²⁵) ₃Si-C ≡ C-, S (O) ₂OR ²⁶, S (O) ₂N (R ²⁶) ₂Or OS (O) ₂R ²⁷, or R ⁹Be benzyloxy or pyridyl methoxyl group, each is optional by R on aromatic ring ¹¹, R ¹²In one or R ¹¹And R ¹²Both replace, or R ⁹Be the C that replaces by phenyl ₂-C ₆Alkyl, described phenyl is optional by R ¹¹, R ¹²In one or R ¹¹And R ¹²Both replace, or R ⁹For-A ⁴-Z ⁴Each R ¹⁰Independent is halogen, C ₁-C ₄Haloalkyl, C ₂-C ₆Alkynyl group or Si (R ²⁵) ₃And Z ³For choosing wantonly by R ¹¹, R ¹²In one or R ¹¹And R ¹²The phenyl that both replace.

6. the compound of claim 5 is wherein: Y is-O-or-CH ₂O-N=C (R ⁷)-; And R ⁹For by a Z ³The C that replaces ₃-C ₆Cycloalkyl, C ₃-C ₆Cycloalkyloxy, SiR ²²R ²³R ²⁴, GeR ²²R ²³R ²⁴Or (R ²⁵) ₃Si-C ≡ C-, or R ⁹For optional by R on aromatic ring ¹¹, R ¹²In one or R ¹¹And R ¹²The benzyloxy that both replace, or R ⁹For-A ⁴-Z ⁴

7. be selected from the compound of following claim 6: 4-[2-[[3-(1,3-benzo dioxole-5-yl)-1,2,4-thiadiazoles-5-yl] oxygen] phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone; 4-[2-[[[[1-[3-[dimethyl (3,3, the 3-trifluoro propyl) silyl] phenyl] ethylidene] amino] oxygen] methyl] phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone; The 4-[2-[3-[(2-chlorophenyl) methoxyl group] phenoxy group] phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone; 4-[2-[[3-[1-(4-chlorophenyl) cyclopropyl]-1,2,4-thiadiazoles-5-yl] oxygen] phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone; 4-[2-[[3-[1-(4-chlorophenyl) cyclopropyl]-1,2,4-thiadiazoles-5-yl] oxygen]-the 6-aminomethyl phenyl]-2,4-dihydro-5-methoxyl group-2-methyl-3H-1,2,4-triazole-3-ketone; 2,4-dihydro-5-methoxyl group-2-methyl-4-[2-[[[[1-[3-[three (trifluoromethyl) germyl] phenyl] ethylidene] amino] oxygen] methyl] phenyl]-3H-1,2,4-triazole-3-ketone; And 2,4-dihydro-5-methoxyl group-2-methyl-4-[2-[3-[2-(TMS) ethynyl] phenoxy group] phenyl]-3H-1,2,4-triazole-3-ketone.

8. comprise the compound of claim 1 of fungicidal significant quantity and the fungicide composition of at least a tensio-active agent, solid diluent or liquid diluent.

9. the method for the plant disease that caused by fungal plant pathogen of control, this method comprise compound administration with the claim 1 of fungicidal significant quantity in this plant or plant part, or are applied to plant seed or rice shoot.

10. comprise the compound of claim 1 of Arthropodicidal significant quantity and the Arthropodicidal dompositions of at least a tensio-active agent, solid diluent or liquid diluent.

11. control arthropodan method, this method comprises that the compound with the claim 1 of Arthropodicidal significant quantity contacts with described arthropods or their environment.