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WO1999001436A1 - Derives de 3-(phenyle substitue)-4-halopyridazine, pesticides les contenant en tant qu'ingredients actifs et leurs intermediaires - Google Patents

Derives de 3-(phenyle substitue)-4-halopyridazine, pesticides les contenant en tant qu'ingredients actifs et leurs intermediaires Download PDF

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Publication number
WO1999001436A1
WO1999001436A1 PCT/JP1998/002941 JP9802941W WO9901436A1 WO 1999001436 A1 WO1999001436 A1 WO 1999001436A1 JP 9802941 W JP9802941 W JP 9802941W WO 9901436 A1 WO9901436 A1 WO 9901436A1
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group
atom
substituted
alkyl
alkyl group
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PCT/JP1998/002941
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English (en)
Japanese (ja)
Inventor
Masashi Kishida
Bunji Natsume
Masayuki Tomida
Osamu Ikeda
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Mitsubishi Chemical Corporation
The Japan Association For Advancement Of Phyto-Regulators
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Priority to AU79357/98A priority Critical patent/AU7935798A/en
Publication of WO1999001436A1 publication Critical patent/WO1999001436A1/fr

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Classifications

    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/08—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems

Definitions

  • the present invention resides in a novel 3-substituted phenyl-4,018-opening pyridazine derivative and an agricultural chemical containing the same as an active ingredient, and particularly provides an agricultural chemical effective as a herbicide.
  • Desirable herbicide conditions include a high herbicidal effect at low doses, a broad herbicidal spectrum, a moderate residual effect, and sufficient crop safety. Currently, many herbicides do not sufficiently meet these requirements.
  • 3-substituted phenyl-4-halopyridazines such as 4-chloro-3-phenyl-6,7-dihydro-5H-cyclopentyl [c] pyridazine and 4-chloro-3-phenylphenyl 5,
  • the method for synthesizing 6,7,8-tetrahydrocinnoline is described in Tetrarahedron Letters, 37, 1351 (1996).
  • 4-chloro-3-3-phenyl5,6,7,8-tetrahydrocinnoline has no mention of herbicidal activity .
  • the substituent of the phenyl group at the 3-position of the pyridazine ring is a hydrogen atom at the 2-position, Which has a hydrogen atom, a nitro group, or an amino group at the 4-position, and a herbicidal activity of a compound in which the phenyl group at the 3-position of the pyridazine ring has a halogen or cyano group at the 4-position. It has not been. Disclosure of the invention
  • the present inventors have conducted intensive studies on the synthesis and herbicidal activity of 3-substituted phenyl 4-halopyridazine derivatives in order to solve the above-mentioned problems of the herbicides.
  • the phenyl group at the 3-position of the pyridazine ring was obtained.
  • 3-substituted phenyl-4,18-opening pyridazine derivatives having a halogen or cyano group at the 4-position of the plant have not only high herbicidal activity but also sufficient safety for some important crops.
  • the present invention has been completed.
  • the gist of the present invention resides in a 3-substituted fuirin-4-halopyridazine derivative represented by the following general formula [I] and a pesticide containing the same as an active ingredient, particularly a herbicide.
  • ⁇ represents a halogen atom
  • ⁇ represents a hydrogen atom or a Hagen atom
  • ⁇ represents a Haguchigen atom or a cyano group
  • ⁇ and m each independently represent 0 or 1
  • R ′ represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group or a C, 1 C 6 haloalkyl group,
  • R 2 is a hydrogen atom, an alkyl group of C, C 6 , or R ′ —— K—L—M— (where I i, CR 4 R 5 , CR 4 R 5 CR 6 R 7 , an oxygen atom , A sulfur atom or a nitrogen atom substituted with a C, -Cs alkyl group, L is CR 8 R 9 , oxygen Atom, a sulfur atom or d - represents nitrogen atom substituted with an alkyl group of C 6, M represents a CR R 11 oxygen atom, a sulfur atom or C, the nitrogen atom substituted with an alkyl group having -C 6 (above Each of the substituents R 4 to shaku 11 independently represents a hydrogen atom or a d-C 6 alkyl group. However, K, L and ⁇ are not simultaneously oxygen atoms, sulfur atoms or nitrogen atoms substituted by C, -C 6 alkyl groups. ) To form a ring represented by
  • R 3 is a hydrogen atom, a nitro group or a QR 12 (wherein Q is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or —NR 13 — (wherein, R 13 is a hydrogen atom, C, -C 6 Alkyl group, C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, C -C haloalkyl group, C 2 -C haloalkenyl group, C 2 -C alkoxyalkyl group, c 2 - Ashiru group C 6 - alkylsulfonyl group c 6, - C haloalkylsulfonyl group, - ⁇ Luque sulfonyl sulfonyl Le group C 6, C 2 - alkoxycarbonyl group C 6, Fuweniru group or Fuweniru group replacement d-in -.
  • R '2 is -.. C, alkyl, C 2 alkenyl groups, C 2 -. alkynyl group , a cycloalkyl group c 3 -c 8, C 4 - .
  • C Shikuroa alkyl group substituted by an alkyl group c 4 -. the (cycloalkyl) alkyl group, Shikuroa alkenyl groups c 3 -c 8, C i - .
  • C Ha port alkyl group, C 2 -. C, haloalkenyl group,
  • C - halocycloalkyl group C a Shianoarukiru group of C 2 -C 7, C 2 - C,.
  • Alkylsulfonylalkyl group C 2 —C 6 acyl group, C 3 —C 6 oxoalkyl group, —C alkylsulfonyl group, Ct—Ce haloalkylsulfonyl group, C 2 —c 6 alkenyl sulfonyl group, Fuweniru groups, C substituted with Fuweniru group, an alkyl group of one C 3, 3- 6-membered Hajime Tamaki (said ring, 1 one two oxygen atoms, sulfur atoms and or nitrogen atom A C, -C 3 alkyl group substituted with a 3-6 membered heterocyclic group (the ring contains 1-2 oxygen, sulfur and Z or nitrogen atoms)
  • General formula [ ⁇ ] Or a group represented by the following general formula [m]
  • R represents a hydrogen atom or a C 4 alkyl group
  • W is an oxygen atom, a sulfur atom or —NR ′ 6 —
  • R ′ 6 is a hydrogen atom or a C 1, C 4 alkyl group
  • R 15 is a hydrogen atom, a C 1, —C 6 alkyl group, a C 2 —C 6 alkenyl group, a C 2 —C 6 alkynyl group, a C 3 —C 6 cycloalkyl group, .
  • C 4 one CI cycloalkyl group substituted with an alkyl group, C 3 - Shikuroa alkenyl group C 6, - haloalkyl group C 6, C 2 - haloalkenyl group C 6, c 3 - halo C 6 Cycloalkyl group, c 2 —c 5 cyanoalkyl group, c 2-
  • the ring contains 1-2 oxygen, sulfur and nitrogen or nitrogen atoms) or a 3- to 6-membered heterocyclic group (the ring consists of 12 oxygen atoms, sulfur atoms C substituted with you and containing Z or a nitrogen atom), - an alkyl group of C 3.
  • R ′ 5 is a 5- to 6-membered heterocyclic group containing 1 to 2 nitrogen atoms and / or 0 to 1 oxygen atom together with W when W represents —NR ′ 6 — May be formed. ) Represents a group represented by.
  • the same group or heterocyclic group may be 1 to 3 identical or different halogen atoms, C, —C 4 alkyl group, trifluoromethyl group, d—C Substituted with 4 alkoxy groups, C 2 -C 5 acyloxy groups, -C 4 alkylthio groups, C, 1 C 4 alkylsulfonyl groups, nitro groups, cyano groups or C 2 -C 5 alkoxycarbonyl groups You may. ).
  • the 3-substituted phenyl-4-halopyridazine derivative used as a herbicide is represented by the above general formula [I].
  • X includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, of which a chlorine atom is preferable.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, of which a chlorine atom is preferable.
  • Examples of Y include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Of these, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is particularly preferable.
  • Z examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and a cyano group, with a chlorine atom being preferred.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • a cyano group with a chlorine atom being preferred.
  • R 1 represents a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, or a halogen atom such as an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group; t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2_methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group Hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl,
  • Fluoromethyl chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1 , 1,2,2,2-pentanofluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl , 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 2,2,2-trifluoro-1-methyl C, -C 6 haloalkyl groups such as ruethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4, -heptafluorobutyl group And preferably a hydrogen atom, an al
  • R 2 represents a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl , 1_methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylbutyl Methyl pentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-methylbutyl group Echirubuchiru group, 1, 1, 2-trimethyl-propyl, 1 - Echiru - 1 - methylprop
  • R ′ and R 2 may combine to form a ring represented by 1 K 1 L 1 M—.
  • K is a group represented by CR 4 R 5 or CR 4 R 5 CR 6 R 7 ; an oxygen atom; a sulfur atom; or a C, 1 C 6 such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • L represents a nitrogen atom substituted by an alkyl group
  • L represents a group represented by CR 8 R 9 ; an oxygen atom; a sulfur atom; or a C, -C 6 alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • M is a group formula represented by CR ID R U; oxygen atom; a sulfur atom; or a methyl group, Echiru group, propyl groups, C or isopropyl group, an alkyl group having -C 6 Represents a nitrogen atom substituted with
  • Examples of the substituent R 4 to R U independently represent a hydrogen atom; a methyl group, E Ji group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, t- butyl group, a pentyl group , Isopentyl group, neopentyl group, t-pentyl group,
  • K is preferably a group represented by CR 4 R 5 or CR 4 R 5 CR 6 R 7 ; or an oxygen atom
  • L is a group or an oxygen atom represented by CR 8 R 9
  • M is a group or an oxygen atom represented by CR R ′ 1
  • K is CR 4 R 5 or CR 4 is a group represented by R 5 CR 6 R 7
  • a group L is represented by CR 8 R 9
  • ring members 5-6 hydrocarbon group is a group
  • M is represented by CR 1 ° R u
  • K, L and L are each a methylene group.
  • R 3 is a hydrogen atom, a nitro group or a group represented by QR 12 .
  • Q represents an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by —NR 13 —, and an oxygen atom or a group represented by —NR 13 — Preferred, particularly preferred is an oxygen atom.
  • R 13 in NR ' 3 — is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl , T-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl Group,
  • C 2 -C 6 alkenyl groups such as 3-pentenyl group, 1-propylaryl group, 1-ethyl-1-methylaryl group;
  • o-butyl group A C 6 haloalkyl group;
  • a C 2 -C 6 haloalkenyl group such as a 3,3-dichloroallyl group
  • Methoxymethyl, ethoxymethyl, propoxymethyl isopropoxymethyl, butoxymethyl, 2-methoxyxyl, 2-ethoxyquinethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl Group,
  • a C 2 -C 6 alkoxyalkyl group such as a 3-methoxypropyl group, a 4-methoxybutyl group, or a 5-methoxypentyl group;
  • C 2 -C 6 acyl group such as 4-methylvaleryl group
  • -Ce alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, and hexylsulfonyl;
  • Triflate Ruo B C such as methylsulfonyl group, haloalkylsulfonyl group -Ce; vinylsulfonyl groups, C 2 etc.
  • a C 2 -C alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropylcarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group;
  • an alkyl group of c 3 substituted with a phenyl group such as a benzyl group or a phenyl group.
  • R 12 is a hydrogen atom; a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, t- butyl group, pentyl group, isopentyl group, neopentyl group , T-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl Group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group , 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylprop
  • Ethynyl 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1_pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3 -C 2 -C alkynyl groups such as hexynyl, 4-hexynyl and 5-hexynyl;
  • a C 3 -C 8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group;
  • a C 2 -C 6 acyl group such as, 4-methylvaleryl group
  • C-C oxoalkyl groups such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. ;
  • a C, -C haloalkylsulfonyl group such as a trifluoromethylsulfonyl group
  • a C 2 -C e alkenylsulfonyl group such as a vinylsulfonyl group and an arylsulfonyl group
  • Phenyl groups such as phenyl group, 4-chlorophenyl group, 3-chlorophenyl group and 2-chlorophenyl group;
  • a 3- to 6-membered heterocyclic group such as a tetrahydrobilanyl group or a 3-tetrahydrobilanyl group (the ring contains 12 oxygen atoms, sulfur atoms and Z or nitrogen atoms);
  • R 14 is a hydrogen atom; or a methyl group, an ethyl group, And C 1 -C 4 alkyl groups such as benzyl, isopropyl, butyl, isobutyl, sec-butyl and tributyl, and W is represented by oxygen, sulfur or —NR 16 — Represents a group.
  • One NR 16 - as for R '6 is a hydrogen atom; or a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, a a t- butyl group and the like C ⁇ -C 4 It is an alkyl group.
  • the R '5 hydrogen atom; a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, Bok butyl group, a pentyl group, Isopenchi group, neopentyl group, t-pentyl group , 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2- Methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, A C, -C 6 alkyl group such as a 2-ethylbutyl group, a 1,
  • C 2 _Cs alkenyl groups such as 3-pentenyl group, 1-propylaryl group, 1-ethyl-1-methylaryl group and the like;
  • a C 3 -C 6 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group;
  • a C3-C6 cycloalkenyl group such as a 2-cyclopropenyl group, a 2-cyclobutenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 2-cyclohexenyl group, or a 3- cyclohexenyl group; Fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1 , 1,2,2,2-pentafluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 3-bromopropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoroprop
  • Cyanomethyl group 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutyl group,
  • a C 2 -C 5 cyanoalkyl group such as a 2-cyanobutyl group, a 3-cyanobutyl group or a 4-cyanobutyl group;
  • Methoxymethyl group, ethoxyquinmethyl group, propoxymethyl group isopropoxymethyl group, butoxymethyl group, 2-methoxethyl group, 2-ethoxyquinethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxyethyl group ,
  • a C 2 -C 6 alkoxyalkyl group such as a 3-methoxypropyl group, a 4-methoxybutyl group, or a 5-methoxypentyl group;
  • C 3 -Ce oxoalkyl groups such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. ;
  • a C, -C3 alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group substituted with a phenyl group;
  • Examples of the 3- to 6-membered heterocyclic group containing one or two oxygen atoms, sulfur atoms and / or nitrogen atoms include an oxylanyl group, an oxetanyl group, a tetrahydrofuryl group, a furyl group, a chenyl group, a pyrrolyl group, a pyrrolidinyl group, Oxazolyl, thiazolyl, imidazolyl, isooxazolyl, isothiazolyl, pyrazolyl Groups, tetrahydroviranyl group, pyridyl group, piperidyl group, pyrimidinyl group, pyridazinyl group, morpholinyl group, piperazinyl group, and these may have a substituent.
  • R 15 may form a ring together with W when W represents —NR 16 —. And if R 15 to form a W and ring, 5 R 15 contains 1 one two nitrogen atoms Contact preliminary or 0- 1 oxygen atoms with W - to form a 6-membered heterocyclic group Is shown.
  • 1-Pyrrolidinyl, 1-pyrrolyl, 2-isoxazolidinyl, 1-virazolyl are 5- to 6-membered heterocyclic groups containing one or two nitrogen atoms and zero or one oxygen atom.
  • R 12 , R ′ 3 or R 15 force phenyl group, C 1 -C 3 alkyl group substituted with a phenyl group, 3- to 6-membered heterocyclic group (the ring is composed of 12 oxygen atoms , Containing a sulfur atom and / or a nitrogen atom) or a 3- to 6-membered heterocyclic group containing 1 to 2 oxygen atoms, a sulfur atom and a Z or nitrogen atom
  • the phenyl group and the heterocyclic group may have a substituent.
  • substituents include 13 identical or different halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
  • t- butylthio group - alkylthio group C 4; methylsulfonyl group, C, -d alkylsulfonyl groups such as ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl; nitro; cyano; Or a C 2 -C 5 alkyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, etc. Coxycarbyl groups and the like.
  • R 3 is preferably a hydrogen atom, a nitro group or one QR ' 2 [wherein Q is an oxygen atom or one NR' 3 — (R ' 3 is a hydrogen atom, a C 2 -C 6 acryl group, ,
  • R 12 represents an alkylsulfonyl group of Ce or an alkoxycarbonyl group of C 2 -Ce), and R 12 is a hydrogen atom;
  • An alkyl group of C 2 —C .
  • Haguchi alkyl group, C 2 — C .
  • R 14 represents a hydrogen atom or a C, C 4 alkyl group
  • W is an oxygen atom or a NR 16 —
  • R ′ 6 is a hydrogen atom or C, -C 4 alkyl
  • R ′ 5 represents a hydrogen atom or a C, —C 6 alkyl group.
  • R 3 is a hydrogen atom, a nitro group or —QR 12 [wherein Q is an oxygen atom or —NR 13 — (R 13 is a hydrogen atom, d-Ce alkylsulfonyl group or C 2 -Ce alkoxy R ′ 2 is a hydrogen atom, C 1 -C, An alkyl group of C 2 —. An alkenyl group, C 2 . Alkynyl group, C 3 -C 8 cycloalkyl group, C, — C,. A C 2 -C 10 haloalkenyl group; a C 2 -CT cyanoalkyl group; C 2 .
  • R 3 is one QR 12 [wherein Q represents an oxygen atom, R 12 is —C ID alkyl group, C 2 —C ,. An alkenyl group, C 2 _C ,. Alkynyl group, a cycloalkyl group of C 3 -C 8 of, C! — C,. Haguchi alkyl group, C 2 — d. A haloalkenyl group; a C 2 -C 7 cyanoalkyl group; C 2 .
  • R ′ and R 2 are preferably bonded together to form a ring, and R 3 is a hydrogen atom, a nitro group or a QR 12 [wherein Q is an oxygen atom or a nitrogen atom.
  • NR 13 — (wherein, R 13 represents a hydrogen atom, C, a C 6 alkylsulfonyl group or a C 2 -C 6 alkoxycarbonyl group), and R ′ 2 represents a hydrogen atom, C , One C,.
  • R 14 represents a hydrogen atom or an alkyl group of C, —C 4
  • W is an oxygen atom or one NR 16 —
  • R 16 is a hydrogen atom or a d-C 4 alkyl group
  • R 15 represents a hydrogen atom or an alkyl group of C or -C 6 .
  • R ′ and R 2 are bonded together to form a carbocycle, and R 3 is —QR 12 (wherein Q represents an oxygen atom, and an alkyl group of R ′ d —C ,.
  • Q represents an oxygen atom
  • R ′ d —C an alkyl group of R ′ d —C ,.
  • Y is more preferably a halogen atom.
  • the compound represented by the above general formula [I] may form a salt at the pyridazine ring portion and, when the substituent R 3 contains a hydroxyl group or a nitrogen atom, the portion.
  • alkali metal salts such as sodium salt, potassium salt, or calcium salt, or alkaline earth metal salts, hydrofluoride, hydrochloride, hydrobromide, hydroiodide, etc.
  • Inorganic acid salts such as nitrates, perchlorates, sulfates and phosphates; sulfonates such as methanesulfonate, trifluoromethanesulfonate and P-toluenesulfonate Is mentioned.
  • the compound of the present invention represented by the general formula [I] can be produced, for example, by any one of the following production methods (1) and (13). Manufacturing method (1)
  • R 3' are water atom, a nitro group, an alkoxy group, an alkylthio group, this reaction and such dialkylamino groups It is an inert group that is not affected by the synthesis of the following raw materials [] .
  • R 17 represents a lower alkyl group such as a methyl group or an ethyl group.
  • the above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 50 to 100 ° C.
  • the amount of the compound to be used in the reaction is usually 1 to 1 equivalent of [VII], 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and 1.0 to 1.5 equivalents of base. 3.0 equivalents, preferably 1.0 to 1.5 equivalents o
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • Bases used include triethylamine, diisopropylethylamine, pyridine, picoline, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,01-7- ⁇ decene, 1, 5-diazabicyclo [4,3,0] -5-none
  • Organic bases such as 1,4-diazabicyclo [2,2,2] octane, sodium hydride, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and carbonate
  • Inorganic bases such as sodium hydrogen hydride, sodium bicarbonate, sodium acetate, potassium acetate, sodium fluoride, potassium fluoride and the like.
  • R 3 ′′ represents a hydrogen atom, a nitro group, an alkoxy group, an alkylthio group, a dialkylamino group, etc. It is an inert group that is not affected by the synthesis of the intermediate [V] shown below:)
  • the above reaction is carried out in the absence of a solvent or in a solvent, usually in the presence of a halogenating agent, usually from 0 to 200 ° C.
  • the reaction is preferably carried out at a temperature in the range of 10 to 100 ° C.
  • the amount of the compound used in the reaction is usually 1.0 to 3 with respect to 1 equivalent of [V]. 0.0 equivalents, preferably 1.5 to 2.0 equivalents.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Examples include form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers (eg, getyl ether, tetrahydrofuran, dioxane), and mixtures thereof.
  • the halogenating agents used include phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, hydrogen chloride, phosphorus tribromide, hydrogen bromide, sulfate trifluoride, getylamine complex, and tetrabutylammonium. Examples include mufluoride and hydrogen fluoride. Manufacturing method (3)
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, Chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (getyl ether, tetrahydrofuran, dioxane, etc.), non-protonic polar solvents (N, N-dimethylformamide, Examples include N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (eg, methanol, ethanol, 2-propanol), water, and
  • the starting material [Ia] can be synthesized by the above-mentioned production method (1) or (2).
  • [I a] in R '2 is an alkyl group, a cycloalkyl group, Ashiru group or an alkoxyalkyl group, and the like are preferable.
  • the compound obtained in the above production method (3) is prepared by the following production method. It can be produced by derivatization according to (4) or (5). Manufacturing method (4)
  • V is chlorine A halogen atom such as an atom, a bromine atom or an iodine atom; a lower alkylsulfonyloxy group such as a methylsulfonyloxy group; or an arylsulfonyloxy group such as a P-toluenesulfonyloxy group.
  • the above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 10 to 100 ° C.
  • the amount of the compound used in the reaction is usually to [I b] is 1 equivalent, R 12 -.
  • V is 1.0 to 3 0 equivalents, preferably 1! ) To 1.5 equivalents
  • the base is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • bases used include triethylamine, pyridine, picoline, N, N-ethylylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene.
  • Organic bases such as 1,5-diazabicyclo [4,3,0] -5-nonene and 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, lithium hydride, and hydroxide
  • Inorganic bases such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium acetate, potassium acetate, sodium fluoride, and lithium fluoride.
  • OH is from 1.0 to 3 0 equivalents, preferably 1.0 to 1.5 equivalents
  • the phenylphosphine is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents
  • the dialkyl azodialkyl arbonate is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents. .
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • the above reaction is carried out without solvent or in a solvent, usually at 110 to 150 ° C., preferably. Is carried out in a temperature range of 20 to 60 ° C.
  • the amount of compound used in the reaction is usually
  • the ditrophy agent is used in an amount of 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, based on 1 equivalent of [Ic].
  • suitable solvents include inorganic acids (such as sulfuric acid and hydrochloric acid), organic acids (such as formic acid and acetic acid), and organic anhydrides (such as acetic anhydride). Mixtures of inorganic acids (sulfuric acid, hydrochloric acid) and nitric acid or nitrate (sodium nitrate, potassium nitrate, etc.), nitric acid, nitrodimethyltetrafluoroborate And ditronium trifluoromethanesulfonate.
  • inorganic acids such as sulfuric acid and hydrochloric acid
  • organic acids such as formic acid and acetic acid
  • organic anhydrides such as acetic anhydride
  • the above reduction reaction is carried out in the absence of a solvent or in a solvent, usually in the presence of a metal or metal compound, and an acid. Is performed in a temperature range of 50 to 100 ° C. Used metal, or The amount of the metal compound is usually 1 to 20 equivalents, preferably 2 to 10 equivalents, based on 1 equivalent of [Id]. The amount of the acid used is usually from 0.01 to 20 equivalents, preferably from 0.01 to 10 equivalents, for 1 equivalent of [Id].
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • Examples of the metal or metal compound used include iron, zinc, tin, tin (II) chloride and the like.
  • Examples of the acid used include hydrochloric acid, sulfuric acid, and acetic acid.
  • sodium sulfide, sodium hydroxide sulfide, sodium dithionite, ammonium sulfide, hydrogen Z metal catalyst palladium-carbon, platinum-carbon, rhodium-alumina, platinum, Raney nickel
  • V is a chlorine atom Halogen atoms such as bromine atom and iodine atom; lower alkylsulfonyl groups such as methylsulfonyloxy group Roxy group; or arylsulfonyloxy group such as P-toluenesulfonyloxy group. )
  • the above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 10 to 100 ° C.
  • the amount of the compound used in the reaction is usually such that R 13 — V is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, relative to 1 equivalent of [If].
  • the base is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • bases used include triditylamine, pyridine, picoline, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene, 1,5-diazabicyclo [4,3,0] -Organic bases such as 5-nonene and 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, sodium hydroxide, hydrating power, and carbonic acid Inorganic bases such as sodium carbonate, sodium hydrogen carbonate, sodium hydrogencarbonate, sodium hydrogen carbonate, sodium acetate, sodium acetate, sodium fluoride, potassium fluoride, and the like. Manufacturing method (9)
  • the above reaction is carried out without a solvent or in a solvent, usually at a temperature of 0 to 250 ° C, preferably 100 to 200 ° C.
  • the amount of the compound used in the reaction is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents of the cyanating agent (Met-CN) per 1 equivalent of [Ih]. Is equivalent.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • the above reaction is carried out without solvent or in a solvent, in the presence of an oxidizing agent, in the presence or absence of a metal or a metal complex, ordinarily at 0 to 200 ° C., preferably at 10 to 100 ° C. Performed in a temperature range.
  • the amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.5 equivalents, relative to 1 equivalent of [I], and is preferably a metal or metal.
  • a complex is required, it is used in an amount of 0.05 to 1.5 equivalents, preferably 0.1 to 1.0 equivalent.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • c H—U is an acid that forms a salt with the compound of the present application, and specifically, Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid; inorganic acids such as nitric acid, perchloric acid, sulfuric acid, and phosphoric acid; methanesulfonic acid, trifluoromethanesulfone Acid, sulfonic acid such as p-toluenesulfonic acid.)
  • Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid
  • inorganic acids such as nitric acid, perchloric acid, sulfuric acid, and phosphoric acid
  • methanesulfonic acid trifluoromethanesulfone Acid
  • sulfonic acid such as p-toluenesulfonic acid.
  • the above reaction is carried out without solvent or in a solvent in the presence of H—U, usually at a temperature of 0 to 200 ° C., preferably 10 to 100 ° C.
  • the amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of H—U to 1 equivalent of [I].
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • X, Y, Z, R ′, R 2 , and R 3 are the same as defined above.
  • X ′ represents a halogen atom
  • P represents one B (OH) 2 or one Met′— X ⁇ (Me t 'represents a metal such as magnesium or zinc, and X ⁇ represents a halogen atom).
  • the above reaction is carried out in the absence or presence of a metal or metal complex in a solvent or in a solvent.
  • the reaction is carried out at a temperature of 0 to 200 ° C., preferably 10 to 100 ° C.
  • the amount of the compound used in the reaction is usually [IX] to 1 equivalent, [X] to 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents. It is 0.01 to 1 equivalent, preferably 0.05 to 5 equivalents.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • ethers eg, ethyl ether, tetrahydrofuran, dioxane
  • aprotic polar solvents N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetate nitrile, etc.
  • suitable metals or metal complexes include nickel, iron, ruthenium, cobalt, orifice, iridium, palladium, platinum, and other metals, and tetrakis (triphenylphosphine) palladium.
  • the aforementioned metals such as dimethyl, or chlorides of the aforementioned metals and triphenylphosphine, tri (0-tolyl) phosphine, 1,2-bis (diphenylphosphine) ethane, 1,2-bis (diphne)
  • metal complexes formed with ligands such as 1,1'-bis (diphenylphosphino) phenene, dibenzylideneacetone, and acetylacetone.
  • W is a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom; a methylsulfonyloxy group and the like.
  • the reaction is carried out in the absence or presence of a base, in the presence or absence of a metal or metal complex in the presence or absence of a solvent, at a temperature of 50 to 200 ° C, preferably 0 to 100 ° C. Done in a range.
  • the amount of the compound used in the reaction is usually [ ⁇ ] to 1 equivalent, [XI] to 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and base to 1.0 equivalent. 33.0 equivalents, preferably 1.0 05 equivalents, and the metal or metal complex is 0.01 11.0 equivalents, preferably 0.05 50.5 equivalents.
  • suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, quinylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform).
  • bases used include triethylamine, pyridine, picoline, N, N-ethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene, 1,5-diazabicyclo Organic bases such as [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, butyllithium, sec-butyllithium, t-butyl Lithium, phenyllithium, sodium methoxide, potassium methoxide, sodium ethkind, potassium ethoxide, lithium diisopropylamide, potassium t-butoxide, sodium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, hydrogen bicarbonate, sodium acetate, potassium acetate, sodium fluoride, Tsu and potassium of inorganic bases.
  • the starting compound [W] in the above-mentioned production method (1) can be produced, for example, according to the following reaction formula.
  • the starting compound [V] in the production method (2) can be produced, for example, according to the following reaction formula.
  • X, Y, Z, R 1 , R 2 , and R 3 are the same as defined above.
  • V and W are the same or different, and are halogen atoms such as chlorine, bromine, and iodine.
  • the compound of the present invention has isomers such as optical isomers and diastereomers depending on its structure, and the compound of the present invention includes all of these.
  • each isomer separated according to a known method may be used alone, or may be used as a mixture of isomers.
  • the compound of the present invention when used as a herbicide, the compound of the present invention (hereinafter sometimes referred to as “the drug substance”) may be applied as it is, but usually, an appropriate adjuvant, Used in the form of granules, emulsions, flowables, etc.
  • adjuvants include solid carriers such as kaolin, bentonite, talc, diatomaceous earth, white carbon, starch; water, alcohols (methanol, ethanol, propanol, butanol, ethylene glycol, etc.), ketones (acetone, Methylethyl ketone, cyclohexanone, etc.), ethers (eg, methyl ether, dioxane, cellosolves), aliphatic hydrocarbons (eg, kerosene, kerosene), aromatic hydrocarbons (eg, benzene, toluene, xylene) , Solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (dichloroethane, carbon tetrachloride, trichlorobenzene, etc.), acid amide Solvents (eg, dimethylformamide), esters (eg, ethyl acetate, butyl a
  • the application rate of the compound of the present invention varies depending on conditions such as the structure of the compound, the target weed, the treatment time, the treatment method, and the properties of the soil.
  • the amount of the active ingredient per hectare is 2 to 200,000. Grams, preferably in the range of 5 to 1000 grams, are suitable.
  • the target weeds of the compound of the present invention are, for example, in the field, for example, Shiroza, Akaza, Inutade, Hartade, Inoubu, Aobu, Hakobe, Hotokenoza, Ichibi, Ona Momi, Wild Asagao, Dwarf Asagao, Wild Karasina, Yaemada Usumire, Orosagigiku, Kosendangsa, Mehishiba, Ohishiba, Inubie, Enokorogusa and the like.
  • the compound of the present invention can control the above weeds both in the pre-emergence soil treatment and in the foliage treatment during the growing season.
  • the compound of the present invention has little effect on cultivated crops such as corn, wheat, barley, rice, soybean and the like in both pre-emergence soil treatment and growing foliage treatment, and is used as a selective herbicide. can do.
  • the herbicide containing the compound of the present invention as an active ingredient can be mixed and applied with other pesticides used in the same field, for example, insecticides, fungicides, plant growth regulators, and fertilizers. It is also possible to stabilize the herbicidal effect by mixing and applying other herbicides. It is possible.
  • the compound of the present invention and another herbicide are mixed and applied, the respective preparations may be mixed at the time of application, or may be applied as a preparation containing both in advance. Examples of the herbicides that can be suitably mixed and applied with the compound of the present invention include the following.
  • Triazine herbicides are Triazine herbicides:
  • a stirrer bar was placed in a lOOmL four-necked flask, and a gym-mouth condenser tube and a thermometer were installed.
  • a mixture of 0.49 g of metallic magnesium, a piece of iodine, and 2 mL of THF was stirred under a nitrogen stream for 15 minutes until the color of iodine disappeared to activate magnesium.
  • a solution of 2.0 g of tribromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene in 0.1 mL of dibromoethane in 6 mL of THF was heated to an internal temperature of 35 ° C or less over 15 minutes. It was dripped slowly while keeping.
  • a stirrer bar was placed in a 2000 mL four-necked flask, and a gym-mouth-one cooling tube and a thermometer were installed.
  • the Grignard reagent prepared above was added thereto by syringe, and after adding 220 mL of THF, 181.94 g of tribromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene, 181.94 g of dibromoethane, and 10.8 g of dibromoethane were added.
  • a stirrer bar was placed in a 3000 mL four-necked flask, and a gym-mouth-one cooling tube and a thermometer were installed. Thereto was added a solution of 184.0 g of getyl oxalate in 800 mL of ether, and the mixture was cooled to -30 ° C under a nitrogen stream. The Grignard reagent prepared above was slowly added dropwise over 1.5 hours while maintaining the temperature at -30 ° C or lower. The temperature was further raised to ⁇ 20 ° C., and the mixture was stirred for 1 hour. A saturated aqueous solution of ammonium chloride was slowly added to the reaction mixture to terminate the reaction, and the temperature was raised to room temperature.
  • a mechanical stirrer and a thermometer were installed in a 2000 mL three-necked flask, and 40.00 g of sodium hydroxide and 500 mL of water were added thereto to prepare a 2N aqueous sodium hydroxide solution. After cooling to room temperature, 109.8 g of ethyl 4-chloro-5-cyclopentyloxy-2-fluorophenylglycoxylate obtained in Reference Example 3 was slowly added, and the mixture was stirred for 1.5 hours. After completion of the reaction, slowly add 1000 mL of 1N hydrochloric acid aqueous solution. To make the reaction solution acidic.
  • a 100 mL flask was equipped with a stirrer bar, a salt tube and an alkali trap. Thereto, 99.8 g of 4-chloro-5-cyclopentyloxy-2-fluorophenyldalioxylic acid obtained in Reference Example 4 and 122.0 mL of thionyl chloride were added, and 2.5 at 60 ° C. The mixture was heated and stirred for hours. Thereafter, a distillation set was installed, and the bath temperature was raised to 110 ° C, and unreacted thionyl chloride was distilled off. Further, 120 mL of benzene was added and distilled off together with the remaining thionyl chloride, followed by drying under reduced pressure with a vacuum pump to obtain crude glyoxylic acid chloride.
  • a stirrer bar, a salt tube and a thermometer were installed in a 2000 mL four-necked flask. Then, 54.2 g of N- (1-cyclopentene-tolyl) -morpholine, 66.6 g of triethylamine and 500 mL of methylene chloride are added, and the mixture is cooled to -5 ° C under a nitrogen stream. Then, the previously prepared solution of glyoxylic acid chloride in methylene chloride (200 mL) was added for 1 hour. The solution was dripped slowly while keeping the temperature of the solution below rc. Further, the reaction mixture was stirred at 1-10 ° C for 1 hour.
  • the reaction mixture was filtered and the residue (triethylamine hydrochloride) was washed with 150 mL of methylene chloride.
  • the filtrate was transferred to a 2000 mL flask, 500 mL of 2-propanol was added, hydrazine hydrate 19.8 was added dropwise with stirring, the mixture was stirred at room temperature for 1 hour, and then left standing for one hour.
  • the reaction mixture was concentrated under reduced pressure, and the residue was suspended in ethanol.
  • the suspension was filtered, and the residue was washed with ethanol and hexane and dried under reduced pressure to obtain 55.5 g of the title compound.
  • the residue obtained by concentrating the filtrate under reduced pressure was suspended again in ethanol, filtered, washed and dried in the same manner to obtain 13.6 g of the title compound.
  • the physical property values and NMR spectrum data are as follows.
  • Example 8 -(4-Chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydroxyl-4-hydroxy- "5 ⁇ -cyclopenta [obtained in Example 1
  • the 30 mL solution of phosphorus tribromide was heated and stirred for 2 hours at 80-90 ° C. After the reaction was completed, it was cooled to room temperature, the reaction mixture was poured into ice water, and extracted with chloroform. The extract was washed with a saturated aqueous solution of sodium bicarbonate and then with a saturated saline solution, and dried over anhydrous sodium sulfate. After filtration, the mixture was concentrated. The crude product was purified by flash column chromatography (developing solvent hexane: ethyl acetate Z3: 1-5: 2) to obtain 3.00 g of the title compound.
  • the reaction mixture is poured into ice water (400 mL), extracted with ethyl acetate, and the obtained organic layer is washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated.
  • the crude product was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to obtain 5.12 g of the title compound (Table 1, No. 8).
  • Tables 1 to 5 can also be produced according to any of the methods of Examples 1 to 15. The structure of the obtained compound was confirmed by all various spectra.
  • Table 16 shows the physical properties of the compounds described in Tables 1 to 5 and spectral data.
  • Table 7 shows the results. (The compound No. in Table 7 corresponds to the compound No. in Tables 1 to 5 in Tables 1 to 5.) The herbicidal effect was evaluated using the above-ground live weight of weeds in the treatment plot.
  • Test example 2 Upland soil treatment test
  • a field of volcanic ash soil was filled in a resin bag with an area of 200 cm 2 , and after fertilization, the soil was uniformly mixed with the seeds of weeds such as crabgrass, enocologza, shiroza, and oota, and Formulation Example 1
  • the wettable powder containing the compound of the present invention as an active ingredient obtained by the above was diluted with water and adjusted to obtain a treatment amount of the active ingredient of 10 g per are with a small power pressurized sprayer. Was sprayed uniformly.

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Abstract

Nouveau dérivé de 3-(phényle substitué)-4-halopyridazine utile en tant que pesticide, notamment en tant qu'herbicides.
PCT/JP1998/002941 1997-07-01 1998-06-30 Derives de 3-(phenyle substitue)-4-halopyridazine, pesticides les contenant en tant qu'ingredients actifs et leurs intermediaires WO1999001436A1 (fr)

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AU79357/98A AU7935798A (en) 1997-07-01 1998-06-30 3-(substituted phenyl)-4-halopyridazine derivatives, pesticides containi ng the same as the active ingredient, and intermediates thereof

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JP9/175589 1997-07-01
JP17558997 1997-07-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999059983A1 (fr) * 1998-05-20 1999-11-25 Basf Aktiengesellschaft 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines substituees
CN107074779A (zh) * 2014-10-03 2017-08-18 住友化学株式会社 哒嗪化合物
WO2020215604A1 (fr) * 2019-04-22 2020-10-29 江苏清原农冠杂草防治有限公司 Composition herbicide comprenant un composé de trifluorométhylpyridazine et son application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56113767A (en) * 1980-02-14 1981-09-07 Mitsui Toatsu Chem Inc Phenylpyridazine derivative, its salt, and agricultural and gardening fungicide
DE4013734A1 (de) * 1990-04-28 1991-10-31 Agrolinz Agrarchemikalien Muen Herbizides mittel
JPH04221302A (ja) * 1990-04-05 1992-08-11 Agrolinz Agrarchemikalien Gmbh 除草剤組成物、雑草の防除方法および除草剤組成物の製造方法
JPH069574A (ja) * 1992-02-17 1994-01-18 Agrolinz Agrarchemikalien Gmbh 除草性ｎ−シアノピリダジノン

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56113767A (en) * 1980-02-14 1981-09-07 Mitsui Toatsu Chem Inc Phenylpyridazine derivative, its salt, and agricultural and gardening fungicide
JPH04221302A (ja) * 1990-04-05 1992-08-11 Agrolinz Agrarchemikalien Gmbh 除草剤組成物、雑草の防除方法および除草剤組成物の製造方法
DE4013734A1 (de) * 1990-04-28 1991-10-31 Agrolinz Agrarchemikalien Muen Herbizides mittel
JPH069574A (ja) * 1992-02-17 1994-01-18 Agrolinz Agrarchemikalien Gmbh 除草性ｎ−シアノピリダジノン

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999059983A1 (fr) * 1998-05-20 1999-11-25 Basf Aktiengesellschaft 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines substituees
CN107074779A (zh) * 2014-10-03 2017-08-18 住友化学株式会社 哒嗪化合物
CN107074779B (zh) * 2014-10-03 2020-05-01 住友化学株式会社 哒嗪化合物
WO2020215604A1 (fr) * 2019-04-22 2020-10-29 江苏清原农冠杂草防治有限公司 Composition herbicide comprenant un composé de trifluorométhylpyridazine et son application

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