WO2018184579A1 - Composé de triazole et son utilisation en agriculture - Google Patents

Composé de triazole et son utilisation en agriculture Download PDF

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Publication number
WO2018184579A1
WO2018184579A1 PCT/CN2018/081979 CN2018081979W WO2018184579A1 WO 2018184579 A1 WO2018184579 A1 WO 2018184579A1 CN 2018081979 W CN2018081979 W CN 2018081979W WO 2018184579 A1 WO2018184579 A1 WO 2018184579A1
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WIPO (PCT)
Prior art keywords
alkyl
halo
substituted
alkenyl
alkynyl
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PCT/CN2018/081979
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English (en)
Inventor
Yitao LI
Jian Lin
Wenqiang YAO
Junxing XU
Yang Wu
Xinshuo LIU
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Dongguan Hec Tech R&D Co., Ltd.
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Application filed by Dongguan Hec Tech R&D Co., Ltd. filed Critical Dongguan Hec Tech R&D Co., Ltd.
Priority to EP18781838.0A priority Critical patent/EP3606910A4/fr
Publication of WO2018184579A1 publication Critical patent/WO2018184579A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention provides a novel triazole compound and a preparation method thereof, a composition containing the compound and their use in agriculture.
  • the present invention provides a novel triazole compound having fungicidal activity.
  • the invention provides a novel fungicidal compound having an excellent controlling effect on plant diseases, a fungicidal composition and formulation containing the fungicidal compound, and use thereof.
  • a compound having Formula (A) or a stereoisomer, an N-oxide or a salt thereof is provided herein.
  • each of R 1 and R 2 is independently H, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo substituted arylalkyl or heteroarylalkyl; or R 1 and R 2 , together with the N atom to which they are attached, form a heterocyclyl or heteroaryl group;
  • heterocyclyl or heteroaryl group formed from R 1 and R 2 , together with the N atom to which they are attached is optionally substituted with one or more R 12 ;
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl or haloaryl;
  • w 0, 1 or 2;
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl or cycloalkyl;
  • x 0, 1, 2, 3, 4, 5 or 6;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R z is C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-8 cycloalkyl, 3-12 membered heterocyclyl, C 6-10 aryl or C 1-9 heteroaryl;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy;
  • R 7 is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy or unsubstituted or substituted naphthyloxy.
  • provided herein is a compound having Formula (I) or a stereoisomer, an N-oxide or a salt thereof,
  • each of R 1 and R 2 is independently H, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo substituted arylalkyl or heteroarylalkyl; or R 1 and R 2 , together with the N atom to which they are attached, form a heterocyclyl or heteroaryl group;
  • heterocyclyl or heteroaryl group formed from R 1 and R 2 , together with the N atom to which they are attached is optionally substituted with one or more R 12 ;
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl or haloaryl;
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl or cycloalkyl;
  • x 0, 1, 2, 3, 4, 5 or 6;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene ring or naphthalene ring; and wherein the benzene ring or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R z is C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-8 cycloalkyl, 3-12 membered heterocyclyl, C 6-10 aryl or C 1-9 heteroaryl;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy;
  • R 7 is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy or unsubstituted or substituted naphthyloxy.
  • each of R 1 and R 2 is independently H, C 1-6 alkyl, C 1-6 alkoxy-C 1-6 -alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 2-10 heterocyclyl, C 6-10 aryl, C 1-9 heteroaryl, C 3-8 cycloalkyl-C 1-6 -alkyl, C 2-10 heterocyclyl-C 1-6 -alkyl, C 6-10 aryl-C 1-6 -alkyl, halo substituted C 6-10 aryl-C 1-6 -alkyl or C 1-9 heteroaryl-C 1-6 -alkyl; or R 1 and R 2 , together with the N atom to which they are attached, form a 3-8 membered heterocyclyl or C 1-9 heteroaryl group;
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 6-10 aryl or halo C 6-10 aryl ;
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl or C 3-8 cycloalkyl;
  • x 0, 1, 2, 3, 4, 5 or 6;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-6 cycloalkyl, 3-8 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl;
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R z is C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 3-6 cycloalkyl, 3-8 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylamino, halo C 1-6 alkyl or halo C 1-6 alkoxy;
  • R 7 is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy or unsubstituted or substituted naphthyloxy.
  • each of R 1 and R 2 is independently H, C 1-4 alkyl, C 1-3 alkoxy-C 1-3 -alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 2-6 heterocyclyl, C 6-10 aryl, C 1-5 heteroaryl, C 3-6 cycloalkyl-C 1-4 -alkyl, C 2-6 heterocyclyl-C 1-4 -alkyl, C 6-10 aryl-C 1-4 -alkyl, halo substituted C 6-10 aryl-C 1-4 -alkyl or C 1-5 heteroaryl-C 1-4 -alkyl; or R 1 and R 2 , together with the N atom to which they are attached, form the following sub-structures:
  • each of p 1 and p 2 is independently 0, 1, or 2;
  • q 0, 1 or 2;
  • each X 2 , X 3 , X 4 and X 5 is independently N or CH;
  • sub-structure (i) , (ii) , (iii) or (iv) is optionally substituted with one or more R 12 .
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 6-10 aryl or halo C 6-10 aryl.
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, -CH 3 , -CHF 2 , -CH 2 F, -CH 2 CH 3 , -CH 2 CH 2 F, -CH 2 CHF 2 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -C (CH 3 ) 3 , phenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl;
  • each R 5 , R 6 , R 7 , R 8 , R 9 , R c , R d , R m , R n , R y1 , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ; and wherein R 10 is as defined herein;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, C 1-4 alkylamino, halo C 1-4 alkyl or halo C 1-4 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, halo, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylamino, halo C 1-6 alkyl or halo C 1-6 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, halo, cyano, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, C 1-4 alkylamino, halo C 1-4 alkyl or halo C 1-4 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, F, Cl, Br, I, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, t-butyl, vinyl, propenyl, allyl, ethynyl, propinyl, propargyl, methoxy, ethoxy, isopropoxy, t-butoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, dimethylamino or diethylamino.
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl or C 3-6 cycloalkyl;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein.
  • R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein.
  • composition comprising the compound disclosed herein.
  • the composition further comprises an agrochemically acceptable surfactant and carrier.
  • provided herein is use of the compound or composition disclosed herein for controlling plant diseases.
  • the plant disease is caused by plant pathogenic fungi.
  • provided herein is a method of controlling plant diseases by using the compound or composition disclosed herein.
  • provided herein is the compound or composition disclosed herein for use in controlling plant diseases.
  • provided herein is use of the compound or composition disclosed herein in the manufacture of a fungicide.
  • the compound of Formula (A) or (I) can exist in different stereoisomeric or optical isomeric or tautomeric forms. All such isomers and tautomers and mixtures thereof with various proportions, and isotopic forms such as a compound containing deuterium are included within the scope of the invention.
  • Isotopically enriched compounds have structures depicted by the formulas given herein except that one or more atoms are replaced by an atom having a selected atomic mass or mass number.
  • isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 O, 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl, 125 I, respectively.
  • Any asymmetric atom (e.g., carbon or the like) of the compound (s) disclosed herein can be present in racemic or enantiomerically enriched, for example the (R) -, (S) -or (R, S) -configuration.
  • grammatical articles “a” , “an” and “the” are intended to include “at least one” or “one or more” unless otherwise indicated herein or clearly contradicted by the context.
  • the articles are used herein to refer to one or more than one (i.e. at least one) of the grammatical objects of the article.
  • a component means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used in an implementation of the described embodiments.
  • Stereoisomers refers to compounds which have identical chemical constitution, but differ with regard to the arrangement of the atoms or groups in space. Stereoisomers include enantiomer, diastereomers, conformer (rotamer) , geometric (cis/trans) isomer, atropisomer, etc.
  • Enantiomers refers to two stereoisomers of a compound which are non-superimposable mirror images of one another.
  • Diastereomer refers to a stereoisomer with two or more centers of chirality and whose molecules are not mirror images of one another. Diastereomers have different physical properties, e.g. melting points, boling points, spectral properties or biological activities. Mixture of diastereomers may separate under high resolution analytical procedures such as electrophoresis and chromatography such as HPLC.
  • optically active compounds Many organic compounds exist in optically active forms, i.e., they have the ability to rotate the plane of plane-polarized light.
  • the prefixes D and L, or R and S are used to denote the absolute configuration of the molecule about its chiral center (s) .
  • the prefixes d and l or (+) and (-) are employed to designate the sign of rotation of plane-polarized light by the compound, with (-) or l meaning that the compound is levorotatory.
  • a compound prefixed with (+) or d is dextrorotatory.
  • a specific stereoisomer may be referred to as an enantiomer, and a mixture of such stereoisomers is called an enantiomeric mixture.
  • a 50: 50 mixture of enantiomers is referred to as a racemic mixture or a racemate, which may occur where there has been no stereoselection or stereospecificity in a chemical reaction or process.
  • any asymmetric atom (e.g., carbon or the like) of the compound (s) disclosed herein can be present in racemic or enantiomerically enriched, for example the (R) -, (S) -or (R, S) -configuration.
  • each asymmetric atom has at least 50 %enantiomeric excess, at least 60 %enantiomeric excess, at least 70 %enantiomeric excess, at least 80 %enantiomeric excess, at least 90 %enantiomeric excess, at least 95 %enantiomeric excess, or at least 99 %enantiomeric excess in the (R) -or (S) -configuration.
  • the compounds can be present in the form of one of the possible stereoisomers or as mixtures thereof, such as racemates and diastereoisomer mixtures, depending on the number of asymmetric carbon atoms.
  • Optically active (R) -and (S) -isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be E or Z configuration. If the compound contains a disubstituted cycloalkyl, the cycloalkyl substituent may have a cis-or trans-configuration.
  • Any resulting mixtures of stereoisomers can be separated on the basis of the physicochemical differences of the constituents, into the pure or substantially pure geometric isomers, enantiomers, diastereomers, for example, by chromatography and/or fractional crystallization.
  • racemates of final products or intermediates can be resolved into the optical antipodes by methods known to those skilled in the art, e.g., by separation of the diastereomeric salts thereof.
  • Racemic products can also be resolved by chiral chromatography, e.g., high performance liquid chromatography (HPLC) using a chiral adsorbent.
  • HPLC high performance liquid chromatography
  • enantiomer may be obtained by asymmetric synthesis.
  • compounds disclosed herein may optionally be substituted with one or more substituents, such as are illustrated generally below, or as exemplified by particular classes, subclasses, and species of the invention.
  • substituents such as are illustrated generally below, or as exemplified by particular classes, subclasses, and species of the invention.
  • the phrase “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” .
  • substituted refers to the replacement of one or more hydrogen radicals in a given structure with the radical of a specified substituent.
  • an optionally substituted group may have a substituent at each substitutable position of the group.
  • substituent When more than one position in a given structure can be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at each position. Specifically, one example of “one or more” refers to one, two, three, four, five, six, seven, eight, nine or ten.
  • substituents of compounds disclosed herein include, but are not limited to, deuterium (D or H 2 ) , F, Cl, Br, I, cyano, hydroxy, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-
  • substituents of compounds disclosed herein are disclosed in groups or in ranges. It is specifically intended that the invention include each and every individual subcombination of the members of such groups and ranges.
  • the term “C 1 -C 6 alkyl” or “C 1-6 alkyl” is specifically intended to individually disclose methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl.
  • alkyl refers to a saturated linear or branched-chain monovalent hydrocarbon group of 1-20 carbon atoms, wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise stated, the alkyl group contains 1-20 carbon atoms. In some embodiments, the alkyl group contains 1-12 carbon atoms. In some embodiments, the alkyl group contains 1-8 carbon atoms. In other embodiments, the alkyl group contains 1-6 carbon atoms. In still other embodiments, the alkyl group contains 1-4 carbon atoms. In yet other embodiments, the alkyl group contains 1-3 carbon atoms.
  • alkyl group examples include methyl (Me, -CH 3 ) , ethyl (Et, -CH 2 CH 3 ) , n-propyl (n-Pr, -CH 2 CH 2 CH 3 ) , isopropyl (i-Pr, -CH (CH 3 ) 2 ) , n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ) , i-butyl (i-Bu, -CH 2 CH (CH 3 ) 2 ) , s-butyl (s-Bu, -CH (CH 3 ) CH 2 CH 3 ) , t-butyl (t-Bu, -C (CH 3 ) 3 ) , n-pentyl (-CH 2 CH 2 CH 2 CH 3 ) , 2-pentyl (-CH (CH 3 ) CH 2 CH 2 CH 3 ) , 3-pentyl (-CH (CH 2 CH 3 ) ) , n
  • alkylene refers to a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms. Unless otherwise stated, the alkylene group contains 1-12 carbon atoms. In some embodiments, the alkylene group contains 1-8 carbon atoms. In other embodiments, the alkylene group contains 1-6 carbon atoms. In still other embodiments, the alkylene group contains 1-4 carbon atoms. In yet other embodiments, the alkylene group contains 1-3 carbon atoms. In yet other embodiments, the alkylene group contains 1-2 carbon atoms.
  • Some non-limiting examples of such group include methylene (-CH 2 -) , ethylene (-CH 2 CH 2 -) , propylene (-CH 2 CH 2 CH 2 -) , -CH (CH 3 ) CH 2 -, -C (CH 3 ) 2 -, -CH 2 CH 2 CH (CH 3 ) -, -CH 2 CH 2 C (CH 3 ) 2 -, and the like.
  • alkenyl refers to a linear or branched-chain monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least one site of unsaturation, i.e., a carbon-carbon, sp 2 double bond, wherein the alkenyl radical may be optionally substituted independently with one or more substituents described herein, and includes radicals having “cis” and “trans” orientations, or alternatively, “E” and “Z” orientations.
  • the alkenyl contains 2 to 8 carbon atoms.
  • the alkenyl contains 2 to 6 carbon atoms.
  • the alkenyl contains 2 to 4 carbon atoms.
  • alkynyl refers to a linear or branched chain monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least one carbon-carbon, sp triple bond.
  • alkoxy refers to an alkyl group, as previously defined, attached to the parent molecular moiety via an oxygen atom.
  • alkoxy group include methoxy (MeO, -OCH 3 ) , ethoxy (EtO, -OCH 2 CH 3 ) , 1-propoxy (n-PrO, n-propoxy, -OCH 2 CH 2 CH 3 ) , 2-propoxy (i-PrO, i-propoxy, -OCH (CH 3 ) 2 ) , and so on.
  • alkylthio refers to an alkyl group, as previously defined, attached to the parent molecular moiety via a sulphur atom. Wherein the alkyl group is as defined herein. Some non-limiting examples of the alkylthio group include -SCH 3 , -SCH 2 CH 3 , -SCH 2 CH 2 CH 3 , -SCH (CH 3 ) 2 , and so on.
  • cycloalkyl refers to a monovalent or multivalent saturated ring having 3 to 12 carbon atoms as a monocyclic, bicyclic, or tricyclic ring system. In some embodiments, the cycloalkyl group contains 3 to 10 carbon atoms. In other embodiments, the cycloalkyl group contains 3 to 8 carbon atoms. In still other embodiments, the cycloalkyl group contains 3 to 6 carbon atoms.
  • the cycloalkyl radical is optionally substituted with one or more substituents described herein.
  • Some examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclohendecyl and cyclododecyl, etc.
  • the ring sulfur atom can be optionally oxygenized to S-oxide and the ring nitrogen atom can be optionally oxygenized to N-oxide.
  • heterocyclyl examples include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g. 2-pyrrolidinyl) , 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxolanyl, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl) , morpholinyl, thiomorpholinyl, 1-oxothiomorpholinyl,
  • heterocyclyl wherein the ring sulfur atom is oxidized is sulfolanyl, 1, 1-dioxo-thiomorpholinyl. And wherein the carbocyclyl group is optionally substituted with one or more substituents described herein.
  • 3-12 membered heterocyclyl typically describes the number of ring atoms of a molecule.
  • piperidinyl is an example of a 6 membered heterocyclyl group.
  • unsaturated refers to a moiety having one or more units of unsaturation.
  • heteroatom refers to one or more of oxygen, sulfur, nitrogen, phosphorus and silicon, including any oxidized form of nitrogen, sulfur, and phosphorus; the quaternized form of any basic nitrogen; or a substitutable nitrogen of a heterocyclic ring, for example, N (as in 3, 4-dihydro-2H-pyrrolyl) , NH (as in pyrrolidinyl) or NR (as in N-substituted pyrrolidinyl) .
  • halogen refers to fluorine (F) , chlorine (Cl) , bromine (Br) or iodine (I) .
  • aryl refers to monocyclic, bicyclic and tricyclic carbocyclic ring systems having a total of six to fourteen ring members, or six to twelve ring members, or six to ten ring members, wherein at least one ring in the system is aromatic, wherein each ring in the system contains 3 to 7 ring members and that has a single point or multipoint of attachment to the rest of the molecule.
  • aryl and “aromatic ring” can be used interchangeably herein. Examples of the aryl group would include phenyl, naphthyl, and anthryl.
  • the aryl radical is optionally substituted with one or more substituents described herein.
  • heteroaryl refers to monocyclic, bicyclic and tricyclic carbocyclic ring systems having a total of five to twelve ring members, or five to ten ring members, or five to six ring members, wherein at least one ring in the system is aromatic, and in which at least one ring member is selected from heteroatom, and wherein each ring in the system contains 5 to 7 ring members and that has a single point or multipoint of attachment to the rest of the molecule.
  • heteroaryl and “heteroaromatic ring” or “heteroaromatic compound” can be used interchangeably herein.
  • the heteroaryl group is optionally substituted with one or more substituents disclosed herein.
  • a 5-10 membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.
  • heteroaryl ring examples include 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl) , 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl) , triazolyl (e.g., 2-triazolyl and 5-triazolyl) , 2-thienyl, 3-
  • Salts of the compound disclosed herein include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium, and aminium (ammonium) cations of the formula N + (R 19 R 20 R 21 R 22 ) , wherein each R 19 , R 20 , R 21 and R 22 is independently selected from H, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl.
  • Salts of the compound having Formula (I) can be prepared by treatment of the compound having Formula (I) with a metal hydroxide, such as sodium hydroxide, or with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
  • a metal hydroxide such as sodium hydroxide
  • an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
  • acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
  • organic and inorganic acids for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly
  • the invention provides a novel fungicidal compound having an excellent controlling effect on plant diseases, a fungicidal composition and formulation containing the fungicidal compound, and use thereof.
  • a compound having Formula (A) or a stereoisomer, an N-oxide or a salt thereof is provided herein.
  • each of R 1 and R 2 is independently H, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo substituted arylalkyl or heteroarylalkyl; or R 1 and R 2 , together with the N atom to which they are attached, form a heterocyclyl or heteroaryl group;
  • heterocyclyl or heteroaryl group formed from R 1 and R 2 , together with the N atom to which they are attached is optionally substituted with one or more R 12 ;
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl or haloaryl;
  • w is 0 , 1 or 2;
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl or cycloalkyl;
  • x 0, 1, 2, 3, 4, 5 or 6;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R z is C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-8 cycloalkyl, 3-12 membered heterocyclyl, C 6-10 aryl or C 1-9 heteroaryl;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy;
  • R 7 is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy or unsubstituted or substituted naphthyloxy.
  • provided herein is a compound having Formula (I) or a stereoisomer, an N-oxide or a salt thereof,
  • each of R 1 and R 2 is independently H, alkyl, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, halo substituted arylalkyl or heteroarylalkyl; or R 1 and R 2 , together with the N atom to which they are attached, form a heterocyclyl or heteroaryl group;
  • heterocyclyl or heteroaryl group formed from R 1 and R 2 , together with the N atom to which they are attached is optionally substituted with one or more R 12 ;
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl or haloaryl;
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl or cycloalkyl;
  • x 0, 1, 2, 3, 4, 5 or 6;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R z is C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-8 cycloalkyl, 3-12 membered heterocyclyl, C 6-10 aryl or C 1-9 heteroaryl;
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy;
  • R 7 is not unsubstituted or substituted phenoxy, unsubstituted or substituted pyridyloxy or unsubstituted or substituted naphthyloxy.
  • each of R 1 and R 2 is independently H, C 1-6 alkyl, C 1-6 alkoxy-C 1-6 -alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 2-10 heterocyclyl, C 6-10 aryl, C 1-9 heteroaryl, C 3-8 cycloalkyl-C 1-6 -alkyl, C 2-10 heterocyclyl-C 1-6 -alkyl, C 6-10 aryl-C 1-6 -alkyl, halo substituted C 6-10 aryl-C 1-6 -alkyl or C 1-9 heteroaryl-C 1-6 -alkyl; or R 1 and R 2 , together with the N atom to which they are attached, form 3-8 membered heterocyclyl or C 1-9 heteroaryl;
  • R 12 is as defined herein.
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 6-10 aryl or halo C 6-10 aryl.
  • R 14 is as defined herein.
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl or C 3-8 cycloalkyl;
  • x is 0, 1, 2, 3, 4, 5 or 6.
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • R c , R d , R m , R n , R p , R q , R 15 , R 16 , R 17 , R 18 , R x and R y are as defined herein.
  • R y1 is as defined herein.
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halo C 1-6 alkyl, halo C 2-6 alkenyl, halo C 2-6 alkynyl, C 3-6 cycloalkyl, 3-8 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl.
  • each R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , R c , R d , R m , R n , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R 10 is as defined herein.
  • R z is as defined herein.
  • R z is C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 3-6 cycloalkyl, 3-8 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl.
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylamino, halo C 1-6 alkyl or halo C 1-6 alkoxy.
  • each of R 1 and R 2 is independently H, C 1-4 alkyl, C 1-3 alkoxy-C 1-3 -alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 2-6 heterocyclyl, C 6-10 aryl, C 1-5 heteroaryl, C 3-6 cycloalkyl-C 1-4 -alkyl, C 2-6 heterocyclyl-C 1-4 -alkyl, C 6-10 aryl-C 1-4 -alkyl, halo substituted C 6-10 aryl-C 1-4 -alkyl or C 1-5 heteroaryl-C 1-4 -alkyl; or R 1 and R 2 , together with the N atom to which they are attached, form the following sub-structures:
  • each of p 1 and p 2 is independently 0, 1 or 2;
  • q 0, 1 or 2;
  • each X 2 , X 3 , X 4 and X 5 is independently N or CH;
  • sub-structure (i) , (ii) , (iii) or (iv) is optionally substituted with one or more R 12 ;
  • R 12 is as defined herein.
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 6-10 aryl or halo C 6-10 aryl.
  • R 3 is H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, -CH 3 , -CHF 2 , -CH 2 F, -CH 2 CH 3 , -CH 2 CH 2 F, -CH 2 CHF 2 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -C (CH 3 ) 3 , phenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.
  • R 14 is as defined herein.
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl or C 3-6 cycloalkyl.
  • R c , R d , R m , R n , R p , R q , R x and R y are as defined herein.
  • R y1 is as defined herein.
  • each of R c , R d , R m , R n , R y1 , R x and R y is independently H, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6-10 aryl or C 1-5 heteroaryl.
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 15 ;
  • R 15 is as defined herein.
  • R 6 and R 7 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 16 ;
  • R 16 is as defined herein.
  • R 7 and R 8 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 17 ;
  • R 17 is as defined herein.
  • R 8 and R 9 together with the carbon atoms to which they are attached, optionally form a benzene or naphthalene ring; and wherein the benzene or naphthalene ring is optionally substituted with one, two, three, four, five, six, seven, eight or nine R 18 ;
  • R 18 is as defined herein.
  • each R 5 , R 6 , R 7 , R 8 , R 9 , R c , R d , R m , R n , R y1 , R x and R y is optionally substituted with one, two, three, four, five or six R 10 ;
  • R 10 is as defined herein.
  • each R 15 , R 16 , R 17 and R 18 is independently H, halogen, cyano, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, C 1-4 alkylamino, halo C 1-4 alkyl or halo C 1-4 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, halo, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylamino, halo C 1-6 alkyl or halo C 1-6 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, halo, cyano, nitro, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy, C 1-4 alkylamino, halo C 1-4 alkyl or halo C 1-4 alkoxy.
  • each R 5 , R 7 , R 8 , R 9 , R 15a , R 15b , R 15c , R 15d , R 16a , R 16b , R 16c , R 16d , R 16e , R 16f , R 18a , R 18b , R 18c and R 18d is independently H, F, Cl, Br, I, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, t-butyl, vinyl, propenyl, allyl, ethynyl, propinyl, propargyl, methoxy, ethoxy, isopropoxy, t-butoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, dimethylamino or diethylamino.
  • each R a and R b is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl or C 3-6 cycloalkyl;
  • provided herein is a compound having Formula (Ia) or a stereoisomer, an N-oxide or a salt thereof,
  • each R 5 , R 6 , R 7 , R 8 and R 9 is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, alkyl, haloalkyl, alkenyl, alkoxy or haloalkoxy;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene ring; and wherein the benzene ring is optionally substituted with one, two, three or four substituents selected from F, Cl, Br, I, cyano, nitro, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, haloalkyl or haloalkoxy.
  • each R 5 , R 6 , R 7 , R 8 and R 9 is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 2-6 alkenyl, C 1-6 alkoxy or halo C 1-6 alkoxy;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene ring; and wherein the benzene ring is optionally substituted with one, two, three or four substituents selected from F, Cl, Br, I, cyano, nitro, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkylamino, halo C 1-6 alkyl or halo C 1-6 alkoxy.
  • each R 5 , R 6 , R 7 , R 8 and R 9 is independently H, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 2-4 alkenyl, C 1-4 alkoxy or halo C 1-4 alkoxy;
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene ring; and wherein the benzene ring is optionally substituted with one, two, three or four substituents selected from F, Cl, Br, I, cyano, nitro, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkylamino, halo C 1-4 alkyl or halo C 1-4 alkoxy.
  • R 5 and R 6 together with the carbon atoms to which they are attached, optionally form a benzene ring; and wherein the benzene ring is optionally substituted with one, two, three or four substituents selected from F, Cl, Br, I, cyano, nitro, -CH 3 , -CF 3 , -OCH 3 or -OCF 3 .
  • provided herein is a compound having one of the following structures or a stereoisomer, an N-oxide or a salt thereof,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein.
  • R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein.
  • composition comprising the compound disclosed herein. Unless otherwise indicated, all tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors or prodrugs of the compounds of Formula (A) , (I) or (Ia) disclosed herein are within the scope of the present invention.
  • composition disclosed herein further comprises an agrochemically acceptable surfactant and carrier.
  • provided herein is use of the compound or the composition disclosed herein for controlling plant diseases; specifically for use as a fungicide.
  • the plant disease is caused by plant pathogenic fungi.
  • the compound of the invention can generally be used as an active ingredient of fungicides in a composition, i.e. formulation, usually including an agrochemically acceptable surfactant and carrier.
  • the above surfactant may be any common surfactant in the field of pesticide formulation, the optimization disclosed herein is one or more of emulsifier, dispersant and wetting agent.
  • the carrier may be any common carrier in the field of pesticide formulation, including any silicate, carbonate, sulfate, oxide, phosphate, plant carrier, synthetic carrier.
  • silica kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
  • the above emulsifier may be any common emulsifier in the field of pesticide formulation, specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, triphenylethylphenol polyoxyethylene ether phosphate, polyoxyethy fatty alcohol ether, alkyl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene polyoxypropylene ether, fatty amines, ethylene oxide adduct of fatty amide, polyoxyethylene fatty acid ester, ethylene oxide adduct of rosin acid, polyol fatty acid ester and ethylene oxide adduct thereof, styrenyl phenyl polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether, hydroxy terminated polyoxyethylene polyoxypropylene ether, styrenyl phenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
  • the above dispersant may be any common emulsifier in the field of pesticide formulation, specifically, the dispersant may be one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonated formaldehyde condensates sodium salt, rosin segmented polyoxyethylene ether polyoxypropylene sulfonates, hydroxy terminated polyoxyethylene polyoxypropylene ether segmented copolymer, triphenylethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt.
  • the above wetting agent may be any common wetting agent in the field of pesticide formulation, specifically, the dispersant may be one or more of lauryl sodium sulfate, sec-alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate, alkyl phenol resin polyoxyethylene ether sulfate.
  • the fungicide composition disclosed herein may also contain any common auxiliary for formulation in the field of pesticide formulation, specifically, the auxiliary for formulation may be one or more of solvent, cosolvent, thickener, antifreeze, capsule wall material, protective agent, defoamer, disintegrating agent, stabilizer, preservative and binder.
  • the auxiliary for formulation may be one or more of solvent, cosolvent, thickener, antifreeze, capsule wall material, protective agent, defoamer, disintegrating agent, stabilizer, preservative and binder.
  • the above solvent may be any common solvent in the field of pesticide formulation, specifically, the solvent may be one or more of organic solvent, plant oil, mineral oil, solvent oil and water.
  • the organic solvent includes one or more of N-methyl pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethyl decyl amide, N, N-dimethyl formamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, heptane, octane, methanol, isopropanol, butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
  • the plant oil includes one or more of methylated plant oil, pine oleoresin-based plant oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine nut oil.
  • the mineral oil includes one or more of liquid-wax, engine oil, kerosene and lubricant.
  • the above solvent may be used as a cosolvent.
  • the above antifreeze may be any common antifreeze in the field of pesticide formulation, the optimization disclosed herein is one or more of glycol, propanediol, glycerol and urea.
  • the above thickener may be any common thickener in the field of pesticide formulation, specifically, the thickener may be one or more xanthan gum, polyvinyl alcohol, polyallyl alcohol, polyethylene glycol, silica, diatomaceous earth, kaolin, clay, sodium alginate, aluminum silicate magnesium silicate, sodium aluminosilicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium and organobentonite.
  • the thickener may be one or more xanthan gum, polyvinyl alcohol, polyallyl alcohol, polyethylene glycol, silica, diatomaceous earth, kaolin, clay, sodium alginate, aluminum silicate magnesium silicate, sodium aluminosilicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium and organobentonite.
  • the above capsule wall material may be any common capsule wall material in the field of pesticide formulation, the optimization disclosed herein is one or more of polyurethane, polyurea and urea formaldehyde resin.
  • the above protective agent may be any common protective agent in the field of pesticide formulation, the optimization disclosed herein is one or more of polyvinyl alcohol and/or polyethylene glycol.
  • the above defoamer may be any common defoamer in the field of pesticide formulation, the optimization disclosed herein is one or more of organo-siloxane, tributyl phosphate and silicone.
  • the above stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.
  • the above preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzothiazoline-3-one (BIT for short) , isothiazolinone and potassium sorbate.
  • the present invention also provides a formulation prepared from the above fungicide composition, the form of the formulation is missible oil, aqueous emulsion, microemulsion, soluble liquid agent, aqueous suspension, suspoemulsion, ultra low volume sprays, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, granules, solid micro capsule, effervescent tablets, effervescent granules, water floating dispersible granules or seed dressing agent.
  • the above formulations all may be prepared by the common methods in this field.
  • a preparation method of the above missible oil may include, for example, mixing every active component, solvent, cosolvent and emulsifier to form a homogeneous transparent oil phase, i.e. missible oil may be obtained.
  • a preparation method of the above aqueous emulsion may include, for example, mixing active component (s) , emulsifier (s) , cosolvent (s) and solvent (s) to form a homogeneous oil phase; mixing water, thickener (s) and antifreeze (s) , etc. to form a homogeneous water phase; adding the water phase into the oil phase (or adding the oil phase into the water phase) under high speed shearing to form a aqueous emulsion with good dispersivity.
  • a preparation method of the above microemulsion may include, for example, mixing active component (s) , emulsifier (s) and solvent (s) to form a homogeneous oil phase. Adding water gradually with stirring to form a homogeneous transparent microemulsion.
  • a preparation method of the above aqueous/oil suspension may include, for example, grinding active component (s) , sufactant (s) , and the like adjuvant (s) in a sand grinding kettle with water or oil as medium to a certain particle size and filtering; adding measured thickener (s) to the grinded mother liquor, sheating to homogeneous dispersion; obtaining oil suspension or aqueous suspension.
  • a preparation method of the above water dispersible granules or soluble granules may include, for example, mixing every active component, dispersant, wetting agent, carrier, etc. homogeneously; shredding to a certain particle size through airflow; adding water and kneading; prilling in a granulator; and then drying to get water dispersible granules or soluble granules.
  • a preparation method of the above wettable powder or soluble powder may include, for example, mixing every active component, adjuvant and other carrier, and the like fillers thoroughly, shredding by using a super micro mill.
  • the fungicide composition disclosed herein may be provided in a form of a finished product, i.e. every components in the composition had been mixed; also may be in a form of a separate preparation, and mixing them in a container before using, diluting with water selectively according to the required concentration of the active component.
  • the compounds of this invention are useful as plant diseases controlling agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by plant fungal pathogens, the method comprises applying an effective amount of a compound of the invention or a fungicide composition containing the compound to plants to be protected or parts thereof, or to plant seeds to be protectedd.
  • the compounds and/or compositions of this invention can control diseases caused by a broad spectrum of plant fungal pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici, Pythium diseases such as Pythium aphanidermatum, and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica) , Pseudoperonospora spp.
  • Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici
  • Pythium diseases such as Pythium aphanidermatum
  • diseases in the Peronosporaceae family
  • Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres, anthracnose diseases such as Glomerella or Colletotrichum spp.
  • Puccinia spp. such as Colletotrichum graminicola and Colletotrichum orbiculare
  • Basidiomycetes including rust diseases caused by Puccinia spp.
  • Puccinia recondita Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis
  • Hemileia vastatrix and Phakopsora pachyrhizi other pathogens including Rhizoctonia spp.
  • compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • the use method of the fungicide composition disclosed herein is simple, which comprises applying the composition to crops or places for crops growth before or after germination of plant diseases by common methods, such as mix soil, spray, jet, pour, etc, the application amount is determined according to climatic conditions or crop states, in general, 10-5000 g per mu is applied, and which is diluted to 10-400 mg/L when applying, preferably, which is diluted to 100-300 mg/L.
  • the diluter is preferably water.
  • Fungicidal effect of the fungicide composition disclosed herein typically relates to extraneous factors such as climate, but the influence of climate can be reduced by using suitable formulation.
  • composition disclosed herein can be used mixing with other compounds having fungicidal, insecticidal, or herbicidal properties, also can be used mixing with nematocides, acaricides, protective agents, herbicide safeners, growth regulator, plant nutrients, or soil conditioners.
  • the preparation of the compounds of the present invention is represented by the following scheme. Unless otherwise mentioned, the compounds disclosed herein may be prepared by methods described herein. The raw materials, reagents, etc. used in the preparation of the compounds disclosed herein can be commercially purchased, or prepared according to the common methods in the field. In the present invention, if the chemical name of the compound doesn’t match the corresponding structure, the compound is characterized by the corresponding structure.
  • Compound of Formula (I) can be prepared by the procedure illustrated in scheme 1, and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein; Y is Cl, Br or I.
  • Oxidizing reaction of compound (a) and chlorine at a certain temperature (e.g. -10 °C to 10°C) under a condition of an acid (e.g. hydrochloric acid, dilute sulfuric acid, acetic acid, etc. ) can give compound (b) ; nucleophilic substitution reaction of compound (c) and R 4 -NH 2 at a certain temperature (e.g.
  • compound (d) condensation reaction of compound (b) and compound (d) at a certain temperature (e.g. -10 °C to 40 °C) under a condition of a base (e.g. pyridine, triethylamine, potassium carbonate, etc. ) can give compound (e) ; condensation reaction of compound (e) and R 1 R 2 N-SO 2 Cl at a certain temperature (e.g. -10 °C to 40 °C) under a condition of a base (e.g. pyridine, triethylamine, potassium carbonate, etc. ) can give compound (I) .
  • a base e.g. sodium hydroxide, sodium hydride, potassium carbonate, etc.
  • Compound of Formula (I) can be prepared by the procedure illustrated in scheme 2, and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein; Y is Cl, Br or I.
  • Oxidative coupling reaction of compound (a) and acyl chloride e.g. benzene sulfonyl chloride, p-toluene sulfonyl chloride
  • a certain temperature e.g. -10 °C to 40 °C
  • a base e.g. pyridine, triethylamine, potassium carbonate, etc.
  • compound (f) condensation reaction of compound (f) and R 1 R 2 N-SO 2 Cl at a certain temperature (e.g. -10 °C to 40 °C) under a condition of a base (e.g. pyridine, triethylamine, potassium carbonate, etc. ) can give compound (g) ; oxidation reaction of compound (g) and chlorine at a certain temperature (e.g. -10 °C to 10 °C) under a condition of an acid (e.g. hydrochloric acid, dilute sulfuric acid, acetic acid, etc. ) can give compound (h) ; condensation reaction of compound (h) and NH 2 -R 4 at a certain temperature (e.g.
  • compound (i) -10 °C to 40 °C) under a condition of a base (e.g. pyridine, triethylamine, potassium carbonate, etc. ) can give compound (i) ; nucleophilic substitution reaction of compound (i) and compound (c) at a certain temperature (e.g. -10 °C to 40 °C) under a condition of a base (e.g. sodium hydroxide, sodium hydride, potassium carbonate, etc. ) can give compound (I) .
  • a base e.g. pyridine, triethylamine, potassium carbonate, etc.
  • Compound of Formula (I) can be prepared by the procedure illustrated in scheme 3, and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b and x are as defined herein.
  • Condensation reaction of compound (h) and compound (d) at a certain temperature (e.g. -10 °C to 40 °C) under a condition of a base (e.g. pyridine, triethylamine, potassium carbonate, etc. ) can give compound (I) .
  • Formylthiosemicarbazide (12 g, 0.1 mol) was added to a 250 mL single neck flask, and then water (130 mL) and sodium carbonate (21.2 g, 0.25 mol) were added. The mixture was heated to 100 °C and reated for 4 hours, and then cooled to room temperature slowly. The reaction mixture was adjusted with dilute hydrochloric acid to pH 4-5. The resulting mixture was stirred at -10 °C slowly to crystallize, and then filtered. The solid was dried to give a white solid (5.6 g, yield was 55%) .
  • 1, 2, 4-Triazole-3-thiol (3 g, 0.03 mol) was dissolved in a hydrochloric acid solution (2 mol/L, 50 mL) .
  • the solution was cooled to 0 °C and mixed homogeneously, and chlorine was then bubbled (30 g, over a period of one hour) , a white solid precipitated out gradually.
  • nitrogen was used to purge superfluous chlorine out at 0 °C.
  • the resulting mixture was filtered, and the solid was dried to give a white solid (3.2 g, yield was 75%) .
  • 5-p-Fluorophenyl-1, 2, 4-triazole-3-thiol (3.9 g, 0.02 mol) was dissolved in a mixed hydrochloric acid (2 mol/L, 80 mL) and methanol (10 mL) solution. The solution was cooled to 0 °C and mixed homogeneously, and chlorine was then bubbled (30 g, over a period of one hour) . After stopping chlorine bubbling, nitrogen was used to purge superfluous chlorine out at 0 °C. The resulting mixture was extracted with dichloromethane (100 mL ⁇ 3) , and the combined organic layers were dried over magnesium sulfate and concentrated to give a brown oil (2.25 g, yield was 43.1%) .
  • the intermediate compounds listed in table 1 can be obtained according to the similar methods of example G by replacing benzyl chloride to corresponding raw materials.
  • the intermediate compounds listed in table 2 can be obtained according to the similar methods of example H by using corresponding raw materials under certain conditions.
  • reaction mixture was transferred to a separatory funnel and allowed to stand until it was separated into layers, the organic layer was washed with water (30 mL) 3 times and the solvent was removed by evaporating on a rotary evaporator under vacuum. A white powder was obtained (47.23 g, yield was 86.2%) .
  • the intermediate compounds listed in table 3 can be obtained according to the similar methods of example M by using corresponding raw materials.
  • the intermediate compounds listed in table 4 can be obtained according to the similar methods of example O by using corresponding raw materials and conditions.
  • the intermediate compounds listed in table 5 can be obtained according to the similar methods of example P by using corresponding raw materials and conditions.
  • the intermediate compounds listed in table 6 can be obtained according to the similar methods of example Q by using corresponding raw materials and conditions.
  • N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28 g, 1 mmol) in dry tetrahydrofuran (8 mL) was stirred at 0 °C under N 2 , and then sodium hydride (60%, 60 mg, 1.5 mmol, 3 batches) was added in portions. After the addition, the mixture was further stirred at 0 °C for 30 minutes and then warmed to room temperature, N, N-dimethylamino sulfonyl chloride (0.286 g, 2 mmol) was added dropwise slowly.
  • N-cyclopropyl-N- (4-fluorobenzyl) -1H-1, 2, 4-triazole-3-sulfonamide 0.296 g, 1.0 mmol
  • potassium carbonate 0.28 g, 2.0 mmol
  • DMF 10 mL
  • N, N-dimethylamino sulfonyl chloride 0.215 g, 1.5 mmol
  • the mixture was stirred at 25 °C for 8 hours and quenched with water (20 mL) .
  • the resulting mixture was extracted with ethyl acetate (15 mL ⁇ 3) .
  • N-cyclopropyl-5- (difluoromethyl) -N- (4-fluorobenzyl) -1H-1, 2, 4-triazole-3-sulfonamide 0.346 g, 1.0 mmol
  • potassium carbonate 0.28 g, 2.0 mmol
  • DMF 10 mL
  • N, N-dimethylamino sulfonyl chloride 0.215 g, 1.5 mmol
  • the mixture was stirred at 25 °C for 8 hours and quenched with water (20 mL) .
  • the resulting mixture was extracted with ethyl acetate (15 mL ⁇ 3) .
  • N-cyclopropyl-N- (4-fluorobenzyl) -5- (4-fluorophenyl) -1H-1, 2, 4-triazole-3-sulfonamide 0.390 g, 1.0 mmol
  • potassium carbonate 0.28 g, 2.0 mmol
  • DMF 10 mL
  • N, N-dimethylamino sulfonyl chloride 0.215 g, 1.5 mmol
  • the test targets Rhizoctonia Solani, Botrytis cinerea, Pseudoperonospora cubensis, Sphaerotheca Fuliginea.
  • Treating process the compound was dissolved in DMF to make 1%EC.
  • the fungicidal activities of the compounds of the invention were evaluated at a dose of 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm and 6.25 ppm against the four test targets by adopting a pot culture method.
  • Plotted cucumber seedlings in one leaf period (removing the growing point) with consistent growth were selected.
  • the selected Plotted cucumber seedlings were air-dried naturally, and after 24 h, Pseudoperonospora cubensis were inoculated to the treated cucumber seedlings by spraying a sporangia suspension (2 ⁇ 10 5 to 3 ⁇ 10 5 cells/ml) , the sporangia suspension was prepared from sporangium obtained by washing down from the back of fresh cucumber leaves with cucumber downy mildew using a dipping distilled water brush. The inoculation was carried out by spraying uniformly on the cucumber seedlings with a sprayer (pressure is 0.1 MPa) .
  • the inoculated test materials were moved to a climatic chamber, the relative humidity was maintained at 100%, the temperature was at about 21 °C. After 24 h, moisture inducement was performed under the temperature of about 21 °C and the relative humidity of about 95%. After 5 days, an investigation on gradation was carried out on a morbidity case of the blank control group, the control effect was calculated according to the disease index.
  • Cucumber seedlings in one leaf period (removing the growing point) with consistent growth were selected.
  • spray treatment with the formulation, which were dried in the shade for 24 h.
  • Conidia of fresh powdery mildew fungus on cucumber leaves were washed drown, and filtered through double-layer gauze and then prepared to a suspension at a concentration of 1 ⁇ 10 5 cells/mL, the inoculation was carried out by spraying.
  • the inoculated test materials were moved to a climatic chamber, the relative humidity was maintained between 60%and 70%, and the temperature was maintained between 21 °C and 23 °C. After about 10 days, an investigation on gradation was carried out on a morbidity case of the blank control group, the control effect was calculated according to the disease index.
  • a leaf inoculation method was adopted. Cucumber seedlings in two leaf period with consistent growth were selected. After spraying the selected cucumber seedlings with the formulation and air drying, mycelial piece obtained from the cultures of fungus was inoculated to the leaves of the cucumber seedlings. The inoculated cucumber seedlings was cultivated at a certain moisture and at 24-26 °C in dark for 24 hours and in natural light for about 3 days. After complete morbidity of the control group, the scab diameter of every inoculation point was metered by using a caliper, and the control effect was calculated.
  • Corn seedlings in two leaf and one bud period with consistent growth were selected. After 24 h of spray treatment with the formulation and air drying, mycelial piece obtained from the cultures of fungus was inoculated to the leaves of the selected corn seedlings. The inoculated corn seedlings was cultivated at a certain moisture and at 25-26°C in dark for 24 hours and in natural light for about 3 days. After complete morbidity of the control group, the scab diameter of every inoculation point was metered by using a caliper, and the control effect was calculated.
  • Table A the control effects of the compounds of the invention at 200 ppm on cucumber downy mildew
  • Example Control effect (%) 1 100 8 100 9 100 10 100 11 100 12 100 13 100 14 100 15 100 16 100 17 100 21 100 24 100 27 100 38 100 40 100 42 100 43 100 44 100 57 98 60 100 62 100 64 100 65 100 67 100 68 100 69 100 71 100 74 100 75 100 76 100 77 100 81 100 91 98
  • Table B the control effects of the compounds of the invention at 100 ppm on cucumber downy mildew
  • results listed in tables A and B indicated that the compounds of the invention have an obvious control effect at various concentrations on cucumber downy mildew, especially at 6.25 ppm, the compounds of the invention, for example, example 9, example 12, example 13, example 14, example 17, example 31 and example 132, have a control effect on cucumber downy mildew more than 40%.
  • results listed in tables C and E indicated that the compounds of the invention have a better control effect on cucumber downy mildew than that of prior art.
  • the compounds of the invention have an obvious control effect on Rhizoctonia solani, Botrytis cinerea and Sphaerotheca fuliginea at 200 ppm, the control effect is more than 30%.
  • the process of test of inhibition rates to the first well in the first line of a 96 well plate was added a given amount of the test medicinal liquid, and then it was serially diluted in required multiple to the 8 th well, the density of the pathogens of cucumber brown spot in the logarithmic growth were measured by a microscopic count method, the pathogens were diluted to a concentration of 10 7 to 10 8 CFU/mL with a culture solution; the pathogen solution was added into the 96 well plate, and 100 ⁇ L was added per well, the 9 th and 10 th wells were used as controls.
  • inhibition rate (%) (1-sample OD value /control OD value) x 100%. The results were listed in table F.
  • the broaden research of the compounds of the invention found that these compound have prominent control effects on potato late blight, wheat root rot and soybean root rot.
  • the compound of the invention have certain control effects on cucumber brown spot, wheat scab, corn curvularia leaf spot, rape sclerotinia stem rot, cotton fusarium wilt, apple ring rot, apple leaf spot, citrus scab, anthracnose of grape, peach brown rot, peanut spot disease, watermelon wilt, mango rot were test by the same method.
  • the compounds of the invention are high safety to crops and fruit trees such as rice, cucumber, wheat, potato, corn, soybean, rape, cotton, apple, citrus, grape, peach, peanut, watermelon, mango and so on, there is no evident injury at the concentration in the range from 1 ppm to 200 ppm.

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Abstract

La présente invention concerne un composé de triazole et son utilisation en agriculture. En particulier, la présente invention concerne un composé de triazole de formule (A) et son procédé de préparation, une composition et une formulation contenant ces composés et leur utilisation en tant que fongicides ; dans la formule R 1, R 2, R 3, w, R 4, R 5, R 6, R 7, R 8, R 9, R a, R b et x sont tels que définis dans la description.
PCT/CN2018/081979 2017-04-05 2018-04-04 Composé de triazole et son utilisation en agriculture WO2018184579A1 (fr)

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CN113429356A (zh) * 2020-03-23 2021-09-24 东莞市东阳光农药研发有限公司 三唑磺酰胺类衍生物及其在农业中应用
CN113929665A (zh) * 2020-06-29 2022-01-14 东莞市东阳光农药研发有限公司 芳香基取代的三唑磺酰胺衍生物及其制备方法和应用
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WO2021012264A1 (fr) * 2019-07-25 2021-01-28 东莞市东阳光农药研发有限公司 Dérivé de triazole sulfonamide, son procédé de préparation et son utilisation
CN112442018B (zh) * 2019-08-27 2024-02-02 东莞市东阳光农药研发有限公司 三唑-1,3-二磺酰胺衍生物及其在农业中的应用
CN112624988B (zh) * 2019-09-24 2024-01-16 东莞市东阳光农药研发有限公司 一种新的三氮唑化合物及其在农业中的应用
WO2021243480A1 (fr) * 2020-05-30 2021-12-09 东莞市东阳光农药研发有限公司 Dérivé de triazole sulfonamide, son procédé de préparation et ses utilisations
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