WO2000010984A1 - Derives de triazolinone et compositions herbicides - Google Patents

Derives de triazolinone et compositions herbicides Download PDF

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WO2000010984A1
WO2000010984A1 PCT/JP1999/004457 JP9904457W WO0010984A1 WO 2000010984 A1 WO2000010984 A1 WO 2000010984A1 JP 9904457 W JP9904457 W JP 9904457W WO 0010984 A1 WO0010984 A1 WO 0010984A1
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group
general formula
derivative
substituted
formula
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PCT/JP1999/004457
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Japanese (ja)
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WO2000010984A9 (fr
Inventor
Ken Morita
Toshiharu Ohno
Tsunehiro Kido
Kazuo Hirayama
Hiroyuki Okita
Yoshihisa Watanabe
Masahide Onoe
Kenji Takatsuji
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Hokko Chemical Industry Co., Ltd.
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Priority claimed from JP24773898A external-priority patent/JP3732014B2/ja
Priority claimed from JP25458998A external-priority patent/JP3837242B2/ja
Priority claimed from JP25455398A external-priority patent/JP3837241B2/ja
Application filed by Hokko Chemical Industry Co., Ltd. filed Critical Hokko Chemical Industry Co., Ltd.
Priority to AU53017/99A priority Critical patent/AU5301799A/en
Publication of WO2000010984A1 publication Critical patent/WO2000010984A1/fr
Publication of WO2000010984A9 publication Critical patent/WO2000010984A9/fr

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    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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

Definitions

  • the present invention relates to a novel triazolinone derivative useful as a herbicide, and also relates to a herbicide composition containing the derivative as an active ingredient.
  • Japanese Patent Application Laid-Open No. 64-29368 describes that a compound represented by the following general formula (A) is useful as a herbicide.
  • X and Y represent an oxygen atom or a sulfur atom, represents a hydrogen atom
  • R 2 represents an optionally substituted fuunyl group, an aralkyl group, etc.
  • R 3 and R 4 represent a hydrogen atom, an alkyl Group or aryl group which may be substituted).
  • Patent Publication No. 3-17836 discloses that a compound represented by the following general formula (B) is useful as a herbicide.
  • R is a-(: 4 alkyl group, benzyl group, cyclohexyl group or substituted phenyl group
  • R 2 is the same or different and is a C 7 cycloalkyl group, phenyl group or substituted phenyl group. And or R and R 2 together are a methyl-substituted morpholino group).
  • X represents a C ⁇ C ⁇ alkyl group
  • n represents 1, 2, 3 or 4
  • R 2 represents 0 ⁇ to (: a 6 alkyl group, a C 2 to C 4 alkenyl group, a C 2 2 -C 6 alkynyl group, C 3 -C 8 consequent Roaruki group, by Ri optionally substituted ⁇ aryl group or if indicate carded a by Ri halogen substituted or unsubstituted Ararukiru group when, or with R 2 may be optionally substituted with the nitrogen atom to which they are attached).
  • JP-A-9-183770 discloses the following general formula (D) It is described that the compound represented by is useful as a herbicide.
  • R 3 represents a 6-membered heterocyclic group consisting of 2 or 3 nitrogen atoms and 4 or 3 carbon atoms, and the group may be a nitrogen atom, a C . 1 -C 4 7 Norekinore group, ⁇ -alkoxy, C ⁇ alkylthio, di (( ⁇ - (-.
  • R 2 is alkyl each independently group, an alkenyl group, consequent Roaruki Honoré group, Nono b alkyl group, c b Anorekeniru group, an alkynyl group, or by Ri is substituted when or whether show also good Fuyu two Le radical and R 2 are they are attached Form a 5- or 6-membered heterocyclic ring with the nitrogen atom which is present, which may be benzo-fused and, optionally, one or more alkyl groups May be substituted with a group).
  • JP-A-8-81459 describes that a compound represented by the following general formula (E) is useful as a herbicide.
  • R 2 are each an alkyl group, Nono Roarukiru group, a cycloalkyl group, an Anorekeniru group, Nono Roaruke two Honoré group, an alkynyl group, or an optionally substituted Fuyuniru group, or R 2 is Together with the nitrogen atom to which they are attached, they form a 5- or 6-membered heterocycle, which may be benzo-fused and, optionally, one or more.
  • (: 4 may be substituted with an alkyl group, represents a nitro, norrogen, anorecynole group, a noroanolequinolene group, an anorecoxy group, a haloalkoxy group, an alkylthio group or a phenoxy group; Represents 0, 1, 2 or 3, and when n represents 2 or 3, R 3 may be the same or different.
  • JP-A-8-99975 describes that a compound represented by the following general formula (F) is useful as a herbicide.
  • R 2 are each independently an alkyl group, a halogenoquinolene group, a cycloanolequinolene group, an anorecheninole group, Alkenyl group, an alkynyl group, an alkoxy group, or an optionally substituted Fuyu two group, or with R 2 is and 5-membered or 6-membered heterocyclic ring Shikimoto together with the nitrogen atom to which R 2 is attached forming a heterocyclic ring - 4 alkyl group may be substituted by Ri optionally in case, R 3 is nitrogen, oxygen or consists heteroatom and carbon selected in arbitrary from Iou 5-membered heterocyclic And the heterocyclic ring may be arbitrarily substituted by a substituent selected from a halogen atom, a phenyl group, a halogen-substituted fuunyl group, a benzyl group and the like).
  • JP-A-10-81675 states that oen, a compound represented by the following general formula (G) is a useful N as a herbicide.
  • the N, 0, and a hetero atom from the Ri group consisting by S 1 which optionally Ru is selected to three of, by Ri halogen and or _ 4 alkyl may also be 5-membered substituted with if or showing a terrorist cyclic group to the, or Okishiran - 2-I le, click Rolle optionally substituted pyridyl or even - 4 alkyl - S (0) m - indicates, 0 m in here, 1 or 2 indicates whether or C 3 6 alicyclic hydrocarbon group shown, be replaced Ri by the case R 2 and R 3 are each independently 6 Al kill C 3 _ 7 consequent opening alkyl or R 4 represents hydrogen or a methyl group, and n represents 0 or 1.
  • the present inventors have described in the specification of PCT application, PCT / JP98 / 00803 (filed on February 26, 1998) (published as WO 98/38176 in September 3, 1998) Disclosed that they succeeded in synthesizing a large number
  • halogen atom a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a cyano group, a nitro group, a methylthio group, a methylsnorefinyl group, a methylsulfonyl group, and a phenoxy group.
  • n is 0 or an integer of 1 to 5).
  • R 3 is a hydrogen atom or a methyl group, and k represents an integer of 1 to 2), which is an unsubstituted or substituted benzyl group or a phenethyl group; Further, a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, and R 2 is a lower alkyl group, a lower cycloalkyl group or a formula
  • Y may be the same or different; halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, or cyano group
  • a benzyl group which may be substituted with a halogen atom on the benzene ring of a benzene or unsubstituted phenyl group, which is an unsubstituted or substituted phenyl group represented by the formula: Unsubstituted or substituted pyridyl group represented by a hydrogen atom or a chlorine atom).] 1-substituted-4-hydroxylvamoyl-1,2,4, -trizole-5- On derivatives.
  • An object of the present invention is to provide a novel triazolinone derivative which replaces these known herbicidal compounds, and to provide a herbicidal composition containing the same as an active ingredient. And there.
  • the present inventors have synthesized a large number of novel triazolinone derivatives to achieve the above object, and studied the herbicidal effect of the derivatives.
  • the novel triazolinone derivative represented by the following general formula (I) is excellent in use at a low dose without causing harm to crops such as rice, soybean, corn, and wheat.
  • the present invention has been completed based on these findings.
  • R 2 represents a lower alkyl group, a lower cycloalkyl group or a substituted phenyl group represented by the following formula (wherein , M is 0
  • Y may be the same or different, and may be a halogen atom, a lower alkyl group, A lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a cyano group), and (i) R 3 represents a lower cycloalkyl group, a lower alkenyl group or a linear or branched alkyl group ( The straight or branched chain C 8 alkyl group is a halogen atom, a lower alkoxy group, a lower cycloalkyl group, a trifluoromethyl group, a phenoxy group, a tetrahydrovinylyl group, a trimethylsilyl group.
  • R 3 comprises 1 or 2 nitrogen atoms and 5 or 4 carbon atoms as ring members 6 Membered heterocyclic group (the 6-membered heterocyclic group is optionally selected from one, two or more substituents selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group)
  • R 3 is a group represented by the formula R 3x- (CH 2 ) n-wherein R 3x is (a) arbitrarily selected from nitrogen, oxygen or Represents a 5-membered unsaturated heterocyclic group containing one, two or three heteroatoms and carbon atoms as ring-forming atoms, or R 3x represents (b) a nitrogen atom and a carbon atom A 6-membered unsaturated heterocyclic group which is contained as a ring-forming atom, wherein the 5- or 6-membered unsaturated heterocyclic group is a halogen atom,
  • the formula group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom, and when R 3x is a 5-membered unsaturated heterocyclic group, n represents 0 or 1, and R 3x When n is a 6-membered unsaturated heterocyclic group, n represents 1).]
  • the first novel triazolinone derivative of the general formula (I) is characterized in that the 2-position of the 1,2,4-triazol-3-one ring has a lower cycloalkyl group, a lower alkenyl group, A lower alkyl group which may be substituted, or a 6-membered heterocyclic group having 1 or 2 nitrogen atoms and 5 or 4 carbon atoms as ring members, or a formula R 3x- (CH 2 ) n- (wherein n is 0 or 1, and R 3x is one, two or three heteroatoms and carbon atoms arbitrarily selected from nitrogen, oxygen or iodine as ring-forming atoms.
  • R 3x represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms. And its 4-position is substituted with a ⁇ , ⁇ -disubstituted carbamoyl group. It is intended to.
  • I ⁇ R ⁇ 5-membered heterocyclic ring represented by the above general formula (I) (R 3x ) or a lower alkyl group referred to in the definition of a 6-membered heterocyclic ring (R 3 , R 3x ) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl.
  • the alkyl group referred to in the definition of R 3 in the general formula (I) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butynole, isobutyl, s-butynole, t-butyl , N-pentyl, isopentinole, 2-methinolebutinole, neopentinole, n-hexinole, n-heptinole, n-octinole, 4-methinolle pentinole, 3-methinopentenole, 2-methinopentenole, 3, methinolepentinole — Dimethylbutyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylinobutylene, 1-ethylinobutylinole, 1-methyl-1-ethylpropyl, 1-methyl-2-ethylinopropyl, 2-
  • lower alkenyl group used in the definition of R 2 and represented by the general formula (I) 5 includes, for example, vinyl, 1-propininole, 2-propininole, 1-methinole 2-Pro-Peninole, 2-Methinole 2-Pl-Peninole, 2-Echinole 1 2-Pro-Peninole, 2-buteninole, 1-Methinole 2-buteninole, 2-Methinole 1-buteninole, 1-Ethyl- 2 carbons, such as 2-buteninole, 3-buteninole, 2-10 pentinole, 3-pentennole, 4-pentennole, 2-hexenyl, 3-hexenyl or 4-hexenyl group Means up to 6 linear or branched alkenyl groups.
  • alkynyl group referred to in the definition of in general formula (I) for example, 2-propynyl, 1-methynole-2-propynyl, 2-butyninole, 1-methinole 2-butyninole, 1-ethyl-2-butyninole, 3-butyninole, 2-methinole-3-butyninole.
  • the lower alkylcarbonyl group referred to in the definition of R 3 in the general formula (I) includes, for example, acetyl, propionyl, n -butylyl, isobutylyl, bivaloyl or valeryl group.
  • cycloalkyl group referred to in the definition of R 2 and R 3 in the general formula (I) for example, cyclopropyl, cyclobutynole, cyclopentinole, cyclohexynole, 2-methynoresic
  • a branched alkyl group having 3 to 7 carbon atoms, such as propyl mouth, 2-methylcyclopentyl or 2-methylhexyl, may have a branched chain.
  • halogen atom referred to in the definition of Y and R 3 in the general formula (I) means each atom of chlorine, bromine, fluorine or iodine.
  • Examples of the lower haloalkyl group in the definition of the heterocyclic ring of Y and R 3 , and R 3x in the general formula (I) include, for example, trif norenolomethine, chloronomethine, bromomethinole, and dichloronole.
  • Mechinore diphnoleolomethinole, trichloronoremethinole, 2-chloronorechinole, 2-bromechinore, 1,1-diphnoleolochinole, 2,2,2-trifluoreneole, 3-octanepropiryl Or a lower alkyl group in which the above-mentioned lower alkyl group such as 3-iodopropyl group is substituted by a halogen atom such as chlorine, bromine, fluorine or iodine.
  • a halogen atom such as chlorine, bromine, fluorine or iodine.
  • R 3 and heterocyclic ring (R 3 , R 3x ) in the general formula (I) for example, methoxy, ethoxy, n-propoxy, isopropoxy, n- Butoxy s-butoxy, t-butoxy, n-pentinoleoxy, isopene It means a straight or branched lower alkoxy group having 1 to 6 carbon atoms, such as a tiloxy or n-hexyloxy group.
  • the lower haloalkoxy group referred to in the definition of Y in the general formula (e) includes, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, and the like. Means 6 haloalkoxy groups.
  • the lower alkylcarbonyl group referred to in the definition of R 3 in the general formula (I) includes, for example, acetyl, propionyl, n -butylyl, isobutylyl, bivaloyl or valeryl group. It means a linear or branched lower phenol group having 1 to 6 carbon atoms.
  • the triazolinone derivative of the first invention is a triazolinone derivative in the case where in the general formula (I) is a lower alkyl group and R 2 is a mono- or di-ha-substituted phenyl group. It is preferably a conductor, and in particular, a triazolinone derivative in the case where in formula (I) is a isopropyl group and R 2 is a mono- or di-fluoro-substituted phenyl group. Is preferred.
  • triazolinone derivative of the general formula (I) of the first present invention has the following general formulas (la) to (6) as its preferred embodiments (1) to (6). If).
  • R la represents an isopropyl group
  • R 2a represents a 4-fluorophenyl group
  • R 3a represents an isopropyl group, a 2,2,2-trifluoroethyl group or a phenoxypropyl group.
  • R lb represents an isopropyl group
  • R 2b represents a 4-fluorophenyl group or a 2,4-difluorophenyl group
  • R 3b represents a cyclopentynole group, a cyclohexynole group, or a 5- Hexenyl group, isopropynole group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, n-octyl group, 6-cyclopentyl pentynole group, 2,2-diethoxytyl group, cyclo Hexinolemethyl group, 2,2,2-triphenylolenoethyl group, phenoxethyl group, phenoxypropyl group, tetrahydropyran-2-ynolemethyl group, trimethylsilylmethyl group, ethoxycarbonylmethyl group, Represents rubamoinolemethyl group, phenacyl
  • R lc represents a straight-chain alkyl group
  • R 2c represents a straight-chain alkyl group which is the same as or different from R lc
  • R 3c represents a 2,2,2-trifluoroethyl group; phenoxethyl; Or a fuynoxypropyl group).
  • R ld represents an isopropyl group
  • R 2d represents a 4-fluorophenyl group or a 2,4-difluorophenyl group
  • R 3d represents a chlorine atom, a bromine atom, a lower alkyl group, a lower alkyl group.
  • 2-, 3- or 4-pyridyl group, 2-pyrazidyl group, 2-pyrazidyl group, 2-pyridyl group Represents a 6-membered heterocyclic group which is a -pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group, a 3-pyridazinyl group or a 4-pyridazinyl group.
  • R le is an isopropyl group or an ethyl group
  • R 2e is an ethyl group, a 4-fluorophenyl group or a 2,4-difluorophenyl group
  • R 3e is nitrogen, oxygen or thiol group.
  • the 5-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom, and n represents 0 or 1.) Triazolinone derivative.
  • R lf is an isopropyl group, and R ? F is 4-fluoro.
  • R 3f is a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as a ring-constituting atom; Unsaturated heterocyclic groups are optionally mono-, di- or tri-substituted by halogen, lower alkyl, lower alkoxy, lower haloalkyl, phenyl, norophenyl or lower alkoxycarbonyl groups.
  • the 6-membered unsaturated heterocyclic group may be benzo-condensed with a benzene ring which may be substituted with a halogen atom, and the triazolinone derivative represented by the formula: .
  • R 3b is a 2,2,2-trif-lenorethynole group.
  • R le is an isopropyl group, preferably R 2e 4-fluorophenyl group or 2,4-difluorophenyl group, and R 3e is 5
  • the membered unsaturated heterocyclic groups are represented by the following formulas (i) to (viii)
  • Et al is, in derivatives of the general formula (the If), a R lf harm Sopu port propyl group, R 2f is 4 - fluorophenyl group or a 2, 4 - a difluorophenyl group, R 3f force s click port openings Preference is given to pyridinole, dichloropyridyl, fluoropyridyl, difluoropyridyl or benzopyridyl.
  • a preferred specific example of the derivative of the general formula (la) is 2-phenoxypropynole-4- (N-2,4-diphnoleophane feninole-N-isopropynole) 2,4—triazonole—3—on or 2- (2,2,2-triphnolerotechnole) -4— (N-2,4-diphnoleolophenynole-N—sopropinole) Moinole-1,2,4-triazole-3-one or 2-sopropynole-4- (N-2,4-diphnoleolophenyno-N-sopropinole) — 1, 2, 4-triazonole — 3-on.
  • a preferred specific example of the derivative of the general formula (lb) is 2- (2-pentinole) -14- (N-2,4-diphenoleon) N-isopropynole) 1, 2, 4—triazonole 3—on or 2 — ((1,3—dioxolan-2—inole) methinole) 4-1 (N—2,4-diphnoleolophenyl-N-isopro) Pinore) Canolenoc Moinore-1,2,4—Triazol-3-one or 2-phenoxixetinole-4- (N—2,4-difunoleo Mouth Feninole N-isop Mouth Pill) Canolebamoinole — 1, 2, 4 -triazole — 3 -one or 2 — (2,2,2 triphenylenole) — 4- (N— 4 -funoleo ⁇ Sopro pinole) It is 1,2,4 -triazole-3-one.
  • a preferred specific example of the derivative of the general formula (Ic) is 2-phenoxetinole — 4— (N, N-Jetinole) (1,2,4-triazole) 3-On or 2- (2,2,2-trifone) 1 4-— ⁇ , ⁇ -Jetinoleka 1,2,4—Triazole -3-On or 2 -Phenoxypro pinole-4- ⁇ , ⁇ -Jetinoleka ⁇ ⁇ ⁇ 1 1, 2, 4 ⁇ 3 — — — ⁇ ⁇ 3.
  • a preferred specific example of the derivative of the general formula (Ie) is 4- (N-2,4-diphnoleopene feninole-N-isopropynole) Chinole 1,2,3-thiaziazono 1-5-yl) methinole) — 1,2,4-triazonole —3—one or 4— (N—2,4—diphnoreolo feninole— N-i sopro pinole) canoleno ku moinore-2-(2-quinoline olenometh) oe — 1,2,4-triazonoleone 3-—one or 4- (N—2,4-diphneolelopheninole) -N-Isopropinole) Canoleno Moi-nore-2-((2-Cheninole) methinole) One 1,2,4-triazol-3-one.
  • a preferred specific example of the derivative of the general formula (If) is 4- (N-4-fluoropheninole-N-isopropynole) canolebamoy. Pyrinole) methinole) — 1,2,4—triazol-3-one or 4--2,4-diphnoreolo-fueno-no-N-isopro-pinore) ⁇ Mouth mouth pyrazinole) methyl)-1,2,4 -triazonole-3-one.
  • Other preferred specific examples of the derivatives of the above general formulas (la) to (If) are shown in Table 2 below.
  • the present invention relates to a herbicidal composition containing a triazolinone derivative as an active ingredient.
  • composition preferably contains a derivative in which, in the above general formula (I), is a lower alkyl group and R 2 is a mono- or di-ha-substituted phenyl group.
  • the derivative of the general formula (I) contained in the herbicidal composition according to the second present invention as an active ingredient is preferably a derivative of the following general formulas (Ia) to (If). OCN is better.
  • R lc , R 2c and R 3c have the same meanings as defined above], respectively.
  • R ld , R 2d and R 3d have the same meanings as defined above.
  • R le , R 2e and R 3e each have the same meaning as defined above, and n represents 0 or 1].
  • R lf , R 2f and R 3f each have the same meaning as defined above].
  • Me is a methyl group
  • Et is an ethyl group
  • Pr is a propyl group
  • Bu is a butyl group
  • Pentyl is a pentynole group
  • Hexyl is a hexyl group
  • Allyl is an arinole group
  • Propargyl is Prono means zero- reginole group.
  • Iso-Pr is isopropyl group
  • n-Pr is n-propynole group
  • iso-Bu is isobutynole group
  • n-Bu is n-butynole group
  • cyclo-Pentyl is cyclopentinole group
  • cyclo-Hexyl Represents a cyclohexyl group.
  • A can be produced by three methods: O, the first method (A), the second method (B), or the third method (C) described below.
  • the first method Oen (A) comprises a first step (a) and a second step (b) represented by the following reaction formula.
  • the first method (A) consists of two steps (a) and (b), as described above.
  • a 1,2,4-triazol-3-one represented by the formula (11) is reacted with a carbamoyl oxalate represented by the general formula (III), A triazolinone derivative represented by the formula (IV) is obtained.
  • the second step (b) comprises reacting the compound represented by the general formula (IV) obtained in the first step with the compound represented by the general formula (V).
  • the compound of the general formula (I) can be produced.
  • R 3 represents a lower cycloalkyl group, a lower alkenyl group, or an alkyl group (the alkyl group may be a straight or branched chain; Atom, lower alkoxy group, lower cycloalkyl group, trifluoromethyl group, phenoxy group, tetrahydrovinylyl group, trimethylsilyl group, ethoxycarbonyl group, aminocarbonyl group, benzoyl group And optionally substituted by a substituent selected from the group consisting of a lower alkylcarbonyl group and a dioxolanyl group).
  • R 3 is a group R 3x - (CH 2) n - If the R 3x are nitrogen, oxygen or hetero atoms, carbon atoms and the ring atoms of Iou atom to Ru chosen any Represents a 5-membered unsaturated heterocyclic group containing as a substituent, or R 3x represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms. Is shown.
  • the 5- or 6-membered unsaturated heterocyclic group may be a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a phenyl group substituted with a halogen atom, or a lower alkoxycarbonyl group.
  • the unsaturated heterocyclic group may be optionally substituted, and the unsaturated heterocyclic group may be benzo-fused with a benzene ring which may be substituted with a halogen atom.
  • n represents 0 or 1 when R 3 x is a 5-membered unsaturated heterocyclic group, and represents 1 when R 3 x is a 6-membered unsaturated heterocyclic group.
  • R 2 have the same meaning as described above.
  • X in the compounds of the above general formulas (V) and (V ') represents a halogen atom such as a chlorine atom, a bromine atom and an iodine atom.
  • X in the compound of the above general formula (V ′) represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.
  • a 1,2,4-triazol-3-one represented by the formula (II) is added to a carbamoyl alcohol represented by the general formula (III) in the presence of a solvent. This can be achieved by mixing and reacting the rides with the dehydrochlorinating agent.
  • dehydrochlorinating agents used in the reaction of the first step (a) include organic tertiary amines such as triethylamine, tributylamine, getylisopropylamine, 4-dimethylaminopyridine or pyridine.
  • the amount of the above base is represented by the general formula
  • organic solvent used in the reaction examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic alcohols such as methyl alcohol, ethyl alcohol and tert-butyl alcohol, and acetate.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic alcohols such as methyl alcohol, ethyl alcohol and tert-butyl alcohol
  • Nitrils such as ril or propionitol
  • esters such as ethyl acetate or ethyl propionate
  • ethers such as ethynoleate ether or tetrahydrofuran, acetate or methyl ethyl ketone, etc.
  • Ketones or pyridine can be used, or a mixed solvent thereof can also be used.
  • it is tertiary monobutyl alcohol or acetone.
  • the reaction in the first step (a) is usually carried out at a reaction temperature of from room temperature to 150 ° C, preferably from 20 to 80 ° C.
  • the reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.
  • the compound of the general formula (IV) obtained in the first step (a) is collected from the reaction solution by usual post-treatment. For example, it can be obtained by adding an extraction solvent such as toluene and water to the reaction solution, washing with water, and distilling off the solvent.
  • the obtained compound of the general formula (IV) can be purified, if necessary, by an operation such as column chromatography or recrystallization.
  • the reaction in the second step (b) of the first method (A) is carried out in the presence of a solvent in the presence of a solvent in the presence of a 1,2,4-triazole- represented by the general formula (IV) obtained in the first step (a). This is achieved by mixing and reacting the 3-one derivative with halides represented by the general formulas (V) and (V ') and a dehydrochlorinating agent.
  • a base for example, triethylamine, triptinoleamine, getylisopropylamine, 4-dimethylaminopropyl Organic tertiary amines such as gin and pyridine ⁇
  • Al-metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tertiary laboxide
  • Alkali metal carbonates such as sodium and sodium carbonate, potassium carbonate, alkali metal hydroxides such as sodium hydroxide and sodium hydroxide, sodium hydride
  • hydrogenated alkali metals such as potassium hydride, but preferably potassium carbonate.
  • solvents used in the reaction include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, aliphatic alcohols such as methyl alcohol, ethanol alcohol, tertiary alcohol, alcohol alcohols such as alcohol.
  • Nitrils such as tonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, ethers such as getyl ether, tetrahydrofuran, and acetone Ketones such as ton, methylethyl ketone, amides such as ⁇ , ⁇ -dimethyl honoleamide, ⁇ , ⁇ -dimethyl acetoamide, pyridine, or the like; or These mixed solvents can also be used. Preferably it is acetonitril and ⁇ , ⁇ -dimethylformamide.
  • the reaction in the second step (b) is usually carried out at a reaction temperature of from room temperature to 150 ° C, and preferably the reaction temperature is 20 to 80 ° C.
  • the reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.
  • the compound of the general formula (I), which is the target reaction product produced in the second step (b), is collected from the obtained reaction solution by usual post-treatment.
  • it can be obtained by adding an extraction solvent such as toluene and water to a reaction mixture, washing with water, and distilling off the solvent.
  • the obtained target product can be purified by an operation such as column chromatography or recrystallization, if necessary.
  • the compound of the general formula (IX) obtained in the third step is added to the compound represented by the general formula (III) together with a dehydrochloride, together with a dehydrochlorinating agent.
  • the compound of the general formula (I) of the present invention is obtained.
  • R 3 is a lower consequent opening alkyl group, a lower alkenyl group or ( ⁇ ⁇ C 8 alkyl group, the C ⁇ Cs alkyl groups are branched A halogen atom, a lower alkoxy group, a lower cycloanolealkyl group, a trifluoromethyl group, a phenoxy group, a tetrahydrovinylyl group, a trimethylsilyl group, an ethoxycarbonyl group, a carbamoyl group, It may be arbitrarily substituted by a substituent selected from the group consisting of a benzoyl group, a lower alkylcarbonyl group and a dioxolaninole group ( in the above reaction formula, and R 2 has the same meaning as described above. Have.
  • first step (c), the second step (d) and the third step (e) of the second method (B) are carried out according to the method described in JP-T-Hei 7-503253, The compound represented by (IX) is obtained.
  • the above-mentioned first steps (to (e) are carried out in one reaction vessel, and the above-mentioned intermediate formulas (VII) and (VII) are carried out without isolation.
  • the solvent tertiary butyl alcohol which is anhydrous or contains water is used.
  • the amount of tertiary butyl alcohol used and the ratio of tertiary butyl alcohol water must be such that the reactants are at least partially solubilized.
  • the reaction of steps (c) to (e) is carried out in a solvent containing about 50 g to 2000 g of tert-butyl alcohol per hydrazine represented by the above general formula (VI). Will be implemented.
  • the weight of water that initially forms the reaction solvent is less than the weight of tertiary butyl alcohol in the reaction solvent.
  • the solvent containing tertiary butyl alcohol used in the reaction system is tertiary butyl alcohol Z water in a weight ratio of 955 to 70 to 30.
  • the reaction between the hydrazine represented by the general formula (VI) and formaldehyde is carried out in a temperature range of -10 ° C to 60 ° C. Preferably it is 0 ° C to 30 ° C.
  • formaldehyde is used in an equimolar amount or a 20% excess relative to the hydrazine represented by the general formula (VI).
  • a 1% to 10% molar excess of formaldehyde is used.
  • the reaction time varies depending on the reaction substrate. The reaction is usually completed in 5 to 30 minutes.
  • the hydrazone represented by the general formula (VII) is reacted with a sodium cyanate and a proton source in a solvent containing the above tert-butyl alcohol to react with the general formula. It forms triazolidinones represented by (VI 11).
  • This reaction can be run from -10 ° C to 60 ° C for 1 hour Complete in 24 hours. It is preferably completed at a temperature of 0 ° C to 35 ° C for 2 to 5 hours.
  • the amount of sodium cyanate can be used in equimolar to 20% excess. Preferably a 5% to 10% molar excess is used.
  • the source of protons is any organic acid such as acetic acid, propionic acid or butyric acid. Preferably it is acetic acid.
  • the amount of organic acid used can be up to 20% excess of the sodium cyanate used in the reaction. Preferably, use an excess of 5% or less acetic acid.
  • the third step (e) comprises oxidizing the triazolidinone represented by the general formula (VIII) using sodium hypochlorite in a solvent containing the above tert-butyl alcohol. Can be achieved.
  • the reaction is performed at 0 ° C to 60 ° C. Preferably it is 10 ° C to 40 ° C.
  • the reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 2 to 24 hours.
  • the sodium hypochlorite used is usually used in the form of an aqueous solution, and its concentration is preferably 5% to 15%.
  • the amount of sodium hypochlorite used can be up to a 40% molar excess. Preferably an excess of up to 10% is used.
  • the triazolinones represented by the general formula (IX) are subjected to a usual post-treatment from the obtained reaction solution. Collected. For example, from the reaction solution, tertiary butyl alcohol as a solvent Water and water are concentrated under reduced pressure, and the resulting residue is extracted with an extraction solvent such as ethyl acetate and water, extracted, washed with water, and then the solvent is distilled off.
  • the obtained compound represented by the general formula (IX) can be purified, if necessary, by an operation such as column chromatography, recrystallization, or re-extraction using an aqueous alkaline solution.
  • the compound of the formula (IX) is reacted with a carbamoyl lip of the formula (III) in the presence of a dehydrochlorinating agent.
  • a dehydrochlorinating agent used in this reaction include organic tertiary amines such as triethylamine, triptylamine or getylisopropylamine, 4-dimethylaminopyridine and pyridine.
  • Alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium tertiary oxide, alkali metal carbonates, such as sodium or potassium carbonate, Alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, and hydrogenated alkali metals such as sodium hydride or potassium hydride can be mentioned.
  • the preferred dehydrochlorinating agent is carbon dioxide lime.
  • potassium carbonate it is preferable to use about one equivalent of the above base per equivalent of the compound represented by the general formula (IX).
  • Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene, xylene, and methyl alcohol.
  • Fatty alcohols such as cornole, ethnoleanole cornole, tertiary butylinoleanorecole, etc., nitriles such as acetonitrile, propionitrile, ethyl acetate and ethyl propionate Esters, such as acetyl ether, tetrahydrofuran, etc., ketones, such as acetone, methylethylketone, ⁇ , ⁇ -dimethylformamide, ,, ⁇ -dimethylacetamide, etc.
  • Amides or pyridine can be used, or a mixed solvent thereof can be used. Preferably it is an acetate nitrile.
  • the reaction temperature of the above fourth step (f) is usually from room temperature to 150 ° C, preferably from 20 to 80 ° C.
  • the reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.
  • the compound of the general formula (I), which is the target reaction product obtained in the fourth step (f), is collected from the obtained reaction solution by usual post-treatment.
  • it can be obtained by adding an extraction solvent such as toluene and water to the reaction mixture, extracting the mixture, and then distilling off the solvent from the extract.
  • the obtained target product (I) can be purified by an operation such as column chromatography / recrystallization if necessary.
  • the third method (C) involves three steps as described in the following reaction formula when the target compound of the general formula (I) and R 3 is R 3x- (CH 2 ) n- . Consists of
  • the third step (i) is achieved by mixing the triazolinones represented by the general formula (XII) with the sorbamoyls represented by the general formula (III) and the dehydrochlorinating agent,
  • the compound of the above general formula (D), which is the compound of the present invention, is obtained.
  • R 3x is a 5-membered unsaturated compound containing a heteroatom and a carbon atom as ring-forming atoms arbitrarily selected from nitrogen, oxygen or iodine atom.
  • R 3x represents a cyclic group, or R 3x represents a 6-membered unsaturated heterocyclic group containing a nitrogen atom and a carbon atom as ring-forming atoms.
  • the 5- or 6-membered unsaturated heterocyclic group may be optionally substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a phenyl group, a phenyl group substituted with a halogen atom, or a lower alkoxycarbonyl group. It may be substituted, and the unsaturated heterocyclic group may be benzo-fused with a benzene ring which may be substituted with a halogen atom.
  • n represents 0 or 1 when R 3x is a 5-membered unsaturated heterocyclic group, and represents 1 when R 3x is a 6-membered unsaturated heterocyclic group.
  • R 2 have the same meaning as described above (hereinafter the same).
  • reaction solvent used in the first step (g) in the third method (C) water or a 1N aqueous hydrochloric acid solution is used.
  • the reaction solvent is preferably water.
  • the hydrazines (X) are in the free form, use 1N aqueous hydrochloric acid as the reaction solvent and use an amount sufficient to neutralize the hydrazines, but an excess is preferable. Is between 10% and 50%. Glyoxylic acid used in this reaction is usually used in the form of an aqueous solution.
  • the concentration of the aqueous solution of glyoxylic acid can be used as long as it can be obtained industrially, but is preferably 40%. Further, the amount of glycoxylic acid used in the reaction is 1 equivalent to 1.5 equivalents, preferably 1 equivalent.
  • the reaction is usually carried out at a reaction temperature of 0 ° C to 50 ° C, and preferably the reaction temperature is 0 ° C to 20 ° C.
  • the reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 10 minutes to 1 hour.
  • the compound of the general formula (XI) which is a reaction product produced in the first step (g), precipitates in the form of a powder from the obtained reaction solution, and is collected by filtration.
  • the collected reaction target product (XI) does not usually need to be purified, but can be used in the next step (h) only by removing water by drying as it is.
  • the solvent used in the reaction of the second step (h) of the third method (C) for example, aromatic hydrocarbons such as benzene, toluene, and xylene can be used, but preferably toluene is used. is there.
  • the diphenyl azide phosphorinole and triethylamine used in the reaction can be used in a molar excess of 10% with respect to the compound of the general formula (XI) to be reacted, but are preferably used in equimolar amounts.
  • the reaction is usually performed at 80 ° C to 150 ° C, and preferably the reaction temperature is 100 ° C to 120 ° C.
  • the reaction time varies depending on the reaction substrate and reaction temperature, but is usually completed in 30 minutes to 3 hours.
  • the compound of the general formula (XII), which is a reaction product produced in the second step (h), is collected from the obtained reaction solution by a usual post-treatment.
  • a 2N aqueous solution of sodium hydroxide is added to the reaction mixture to extract it with alkali, and the alkaline extract is neutralized with concentrated hydrochloric acid to obtain a powder or oil.
  • Precipitates If precipitated as a powder, it can be isolated by filtration. If it precipitates as an oil, it can be separated using an extraction solvent such as toluene or ethyl acetate.
  • the obtained product (XII) can be purified, if necessary, by an operation such as column chromatography or recrystallization.
  • the compound of formula (XII) is reacted with the compound of formula (III) in the presence of a dehydrochlorinating agent.
  • a dehydrochlorinating agent used in this reaction, a base, Organic tertiary amines such as triethylamine, triptylamine, getylisopropylamine, 4-dimethylaminopyridine, pyridine, sodium methoxide Alkali metal alkoxides, such as sodium ethoxide, potassium tertiary oxide, alkali metal carbonates, such as sodium carbonate and potassium carbonate, water Alkali metal hydroxides such as sodium oxide and potassium hydroxide; and alkali metal hydrides such as sodium hydride and potassium hydride.
  • it is preferably calcium carbonate.
  • the amount of the above base is preferably about 1 equivalent to the compound of the formula (III) when using carbon dioxide lime.
  • Examples of the solvent used in the reaction in the third step (i) include aromatic hydrocarbons such as benzene, toluene, and xylene, methionoleanol, ethanol alcohol, and tert-butyl alcohol. Fatty alcohols, acetonitril, nitriles such as propionitol, esters such as ethyl acetate and ethyl propionate, ethylenol, Athenoles such as tetrahydrofuran, ketones such as acetone and methylethylketone, amides such as ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ , ⁇ -dimethylinoacetamide Similar pyridine can be used, or a mixed solvent thereof can also be used.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • methionoleanol such as benzene, toluene, and x
  • the reaction in the third step (i) is usually carried out at a reaction temperature of from room temperature to 150 ° C, and preferably the reaction temperature is 20 to 8 Q ° C.
  • the reaction time varies depending on the reaction temperature and the reaction substrate, but is usually completed in 30 minutes to 24 hours.
  • the compound of the general formula (I), which is the target reaction product obtained in the third step (i), is collected from the obtained reaction solution by a usual post-treatment.
  • it can be obtained by adding an extraction solvent such as toluene and water to a reaction mixture, extracting the mixture, and then distilling the solvent from the extract.
  • the obtained target product (I) can be purified by an operation such as column chromatography or recrystallization, if necessary.
  • the 1,2,4-triazol-3-one of the formula (II), which is a starting material used in the first method (A), is a known compound, and is, for example, a chemical compound. Chemiste Berichte, Vol. 98, pp. 3025-3033 (1965), and The Journal of Organic Chemistry, Vol. 47, pp. 474-482, The Journal of Organic Chemistry. 1982), which is easily synthesized according to the method described in Reference Production Example 1 below.
  • carbamoyl alcohols of the general formula (III) used as reactants in the above methods (A) and (B) are organic compounds. It is well known in the field of chemistry, but is easily synthesized according to the method described in, for example, Chemische Berichte, vol. 88, p. 301 (1955).
  • halides represented by the general formulas (V) and (V ') used in the first method ( ⁇ ) are well known in the field of organic chemistry. It is easily synthesized according to the method described in Organic Syntheses Collective Volume I, p. 435 (1941).
  • herbicidal composition according to the second aspect of the present invention will be specifically described.
  • Aichibi As for broadleaf weeds, Aichibi (Abut i lor ⁇ .
  • Examples of useful cultivated plants or crops of the family Cereals in the field to which the compound of the present invention can be applied include Hordeine (Oryza), Sugarcane (Saccharum), and Wheat.
  • Broad leaf crops include peanuts (Arach i ⁇ ), sugar beet (Beta), oilseed rape (Brassir), and soybean (Glyc.ine.) There are poeta (Gossy i urn) and tomato (Lycope rsi con).
  • the triazolinonone derivative of the general formula (I) of the first invention is formulated in the form of a composition in which the triazolinone derivative is combined with a carrier as an active ingredient. Is performed.
  • the active ingredient that is, the compound of the general formula (I) of the active ingredient
  • the active ingredient is used as a carrier or diluent, an additive, and an auxiliary agent. At least one of them is mixed by a known method and is usually used as an agricultural chemical, for example, granules, fine granules, wettable powders, wettable powders, emulsions, aqueous solvents, flowables, tablets , Powders, microforces, pastes and the like.
  • Pesticides such as fungicides, insecticides, herbicides, herbicides, safeners, plant growth regulators, fertilizers, and soil conditioners. And can be.
  • other pesticides such as fungicides, insecticides, herbicides, herbicides, safeners, plant growth regulators, fertilizers, and soil conditioners.
  • fungicides insecticides, herbicides, herbicides, safeners, plant growth regulators, fertilizers, and soil conditioners.
  • other pesticides such as fungicides, insecticides, herbicides, herbicides, safeners, plant growth regulators, fertilizers, and soil conditioners.
  • fungicides such as fungicides, insecticides, herbicides, herbicides, safeners, plant growth regulators, fertilizers, and soil conditioners.
  • any solid or liquid carrier can be used as long as it is a carrier generally used for agricultural chemical formulations.
  • the carrier is not limited to a specific one.
  • these solid carriers include mineral powders (kaolin, bentonite, cres, montmorillonite, talc, diatomaceous earth, mica, birch mullite, quartz, calcium carbonate, linnite, Carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable powders (soy flour, flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin) ), Alumina, silicates, saccharide polymers, highly dispersible carboxylic acids, waxes and the like.
  • liquid carrier examples include water, alcohols (methinoleanol / norethone, n-propynoleanol / northone, isopropinoleanol / butanol, butanol / ethylene glycol, benzyl alcohol, etc.), and aromatics.
  • alcohols metalhinoleanol / norethone, n-propynoleanol / northone, isopropinoleanol / butanol, butanol / ethylene glycol, benzyl alcohol, etc.
  • aromatics aromatics.
  • Hydrocarbons toluene, benzene, xylene, ethylbenzene, methyl naphthalene, etc.
  • ethers ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.
  • ketones acetone, methyl ethyl ketone, Cyclohexanone, methyl isobutyl ketone, isophorone, etc.
  • esters ethyl acetate, butyl acetate, Ethylene glycol acetate, amyl acetate, etc.
  • acid amides dimethyl formamide, dimethyl acetate, etc.
  • nitriles acetonitrile, propionitrile, acryl
  • sulfoxides dimethyl sulfoxide, etc.
  • alcohol ethers ethylene glycol monomethyl ether ether, ethylene glycol monoethyl ether, etc.
  • surfactants When formulated into emulsions, wettable powders, flowables, etc., various surfactants are added to the composition for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, etc. You.
  • surfactants include nonionic surfactants (eg, polyoxyethylene alkyl ether, polyoxyethylene olenoquinolester, and polyoxyethylene sonolevitan alkyl ester), and anionic surfactants.
  • Activators such as anolequinolebenzene snorrephonate, anolequinolenes olenosuccinate, alkynolesulfate, polyoxyethylene olenoalkyl alkyl sulfate, and arylsolenoate
  • Cationic surfactants alkylamines (raurilamin, stearyl trimethylammonium chloride, etc.), polyoxyethylene alkylamines), amphoteric surfactants [Carboxylic acid (betaine type), sulfuric acid But not limited to only those exemplified.
  • auxiliary agents such as polyvinyl alcohol (PVA), canoleboximetinose renorelose (CMC), arabian rubber, polyvinyl acetate, sodium alginate, gelatin, and tragacanth rubber can be used.
  • PVA polyvinyl alcohol
  • CMC canoleboximetinose renorelose
  • arabian rubber polyvinyl acetate
  • sodium alginate sodium alginate
  • gelatin gelatin
  • tragacanth rubber acanth rubber
  • the compound of the present invention represented by the general formula (I) is used in an amount of 0.001% to 95% (% by weight; the same applies hereinafter), preferably, in producing each of the above-mentioned preparations. It can be formulated so as to contain 0.01% to 75%.
  • the herbicidal composition is in the form of granules, 0.01% to 10%, in the case of wettable powders, flowables, solutions, and emulsions, 1 to 75%, powders, driftless powders, In the case of fine powder, it can be contained in the range of 0.01% to 5%.
  • Formulations prepared in this way for example, in the case of granules and flowables, can be used as they are on the soil surface, in soil or in water in the range of about 0.3 g to 300 g per 10 ares as the equivalent of the active ingredient. Sprinkle it.
  • wettable powders, emulsions, and the like they may be diluted with water or a suitable solvent, and the resulting diluted chemical solution may be applied as an active ingredient in a range of about 0.3 g to 300 g per 10 ares.
  • the resulting reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter product name ⁇ Kiriyama funnel '' to remove insolubles, and 200 ml of water in a 500 ml separating funnel was removed. Opened inside. Extract twice with 80 ml of toluene at one time, and separate 160 ml of the combined toluene extract into 500 ml The mixture was washed with 100 ml of water and dried with 50 g of anhydrous sodium sulfate for 10 minutes.
  • the sodium sulfate used for this drying was filtered under reduced pressure using an aspirator, using a Nutsche type 6-cm diameter product name “Kiriyama funnel”, and the solvent of the filtrate was used using an aspirator.
  • the residue was distilled off under reduced pressure to obtain 1.25 g of a crude product.
  • Each extraction was performed twice with 80 ml of toluene, and 160 ml of the combined toluene layer was placed in a separating funnel having a capacity of 500 ml, washed with 100 ml of water, and dried with 50 g of anhydrous sodium sulfate for 10 minutes.
  • the sodium sulfate used for this drying was filtered under reduced pressure using an aspirator using a Nutsche type 6-cm diameter product name “Kiriyama funnel”, and the solvent of the filtrate was removed under reduced pressure using an aspirator. And 0.94 g of a crude product was obtained.
  • the resulting reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel” to remove insolubles, and the filtrate solvent was filtered using an aspirator.
  • the solvent was distilled off under reduced pressure.
  • the obtained residue was transferred to a separating funnel having a capacity of 50 ml of toluene and 20 ml of water for extraction, and the toluene layer was dried with 20 g of anhydrous sodium sulfate for 30 minutes.
  • the sodium sulfate used for the drying was filtered under reduced pressure by aspirator using a Nutsche type “Kiriyama funnel” with a trade name of 6 cm in diameter to remove insolubles.
  • the solvent of the filtrate was distilled off under reduced pressure using an aspirator to obtain a crude product l.Og.
  • Tertiary butyl alcohol was distilled off from the reaction mixture under reduced pressure using an acrylic. Then, the residue was dissolved in 300 ml of ethyl acetate, transferred to a 500 ml separating funnel, and washed with 100 ml of water. The organic layer was dried with anhydrous sodium sulfate (80 g) for 1 hour. The reaction product was dissolved in toluene and extracted with a 2N sodium hydroxide solution. The sodium sulfate used for this drying was filtered under reduced pressure using an aspirator using a Nutsche type 9 cm diameter trade name “Kiriyama funnel”. The solvent was distilled off from the filtrate under reduced pressure using an aspirator.
  • the resulting reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche 6 cm diameter trade name “Kiriyama funnel” to remove insolubles.
  • the solvent was distilled off from the filtrate under reduced pressure using an aspirator and concentrated. Dissolve the residue in 30 ml of a mixture of toluene and ethyl acetate (1: 1 V / V), And washed with 20 ml of water.
  • the aqueous layer was further extracted with 30 ml of a mixture of toluene and ethyl acetate (1: 1 v / V).
  • the organic layers were combined and dried with 30 g of anhydrous sodium sulfate for 20 minutes.
  • reaction mixture was filtered under reduced pressure using an aspirator using a Nutsche type 4 cm diameter trade name “Kiriyama funnel” to remove insolubles.
  • the solvent was distilled off from the filtrate under reduced pressure using an aspirator to obtain 1.3 g of a crude product.
  • silica gel Merolek, trade name: silica gel 60H
  • the reaction mixture was cooled to 20 ° C., and the precipitated white crystals were subjected to suction filtration under reduced pressure using an aspirator using a Nutsche type 9.5 cm diameter trade name “Kiriyama funnel”.
  • the obtained white crystalline 1,2,4-triazol-3-one was washed with 100 ml of ethyl alcohol and air-dried. Yield 52.2 g (91% yield, mp 235-237 ° C) 0
  • the precipitated pale yellow powder was suction-filtered and washed with water, and the pale yellow powder was dried in a desiccator under reduced pressure.
  • a total of 23 g of this pale yellow powder is suspended in 220 ml of toluene, 11.6 g of triethylamine is added, and 26 g of diphenylphosphine azide is added dropwise. For 1 hour.
  • 450 ml of a 2N aqueous sodium hydroxide solution was added to the mixture under ice water to extract.
  • 95 g of 35% hydrochloric acid was gradually added to the aqueous aqueous layer obtained as an extract to make it acidic.
  • the precipitated crystals were filtered and washed with water.
  • Compound No. is as shown in Table 2 above, and “parts” in the examples all mean parts by weight.
  • Compound No.1 1 part Calcium lignin sulfonate 1 part Laurenol resulfate 1 part Bentonite 30 parts Talc 67 parts Add 15 parts of water to the above components, knead with a kneader, and extrude Granulated with a granulator. This is dried in a fluidized drier to obtain granules containing 1% of active ingredient.
  • Ester sodium salt 2.0 parts Polyoxyethylene rennoyl ether 2.0 parts propylene glycol 5.0 parts Antifoam 0.5 parts
  • the components of 70.5 parts or more of water are uniformly mixed and pulverized with a wet ball mill to obtain a flowable agent containing 20% of active components.
  • Compound No. 6 15 parts White carbon 15 parts Lignin sulphonic acid canolesum 3 parts Polyoxyethylene nonylphenyl ether 2 parts Diatomaceous earth 5 parts Clay 60 parts % Wettable powder.
  • herbicides using the compound of the general formula (I) according to the present invention can be formulated as herbicide compositions in various dosage forms according to the above-mentioned formulation examples.
  • Test Example 1 Test for herbicidal effect on red snapper (pretreatment)
  • Herbicidal effect (%) [1- (a / b)) x 100 [where a represents the dry weight (g) of the weed in the treated plot, and b represents the dry weight (g) of the weed in the untreated plot. Represents].
  • a wettable powder containing the following comparative compounds 8, 0, £,?, And 6 was prepared according to Example 15, and the test was carried out in the same manner. The results are also shown in Table 3.
  • the comparative compound A used has the following formula (a)
  • Comparative compound B has the following formula (b)
  • Comparative compound F has the following formula (f)
  • Comparative compound G is represented by the following formula (g) (g) (Described in W098 / 38176)
  • Test Example 2 Test for herbicidal effect on Japanese millet (growth treatment)
  • a hydrating agent containing comparative compounds A, B, C, D, E, F, and G as comparative drugs was prepared according to Example 15, and tested similarly. The results are shown in Table 4 (Compound No. is the compound No. shown in Table 2. The same applies hereinafter).
  • Test Example 3 Test on herbicidal effect on paddy field weeds (Azena, Konagi, Firefly)
  • rice seedlings of 2.5 leaves stage product type: Nipponbare
  • rice seedlings of 2.5 leaves stage product type: Nipponbare
  • Subsequent management was performed in a glass greenhouse.
  • the wettable powder prepared according to Example 15 was diluted with water, and the water diluent was used. A predetermined amount of the liquid was dropped. Twenty-eight days after the chemical treatment, the phytotoxicity of rice was investigated and the results are shown in Table 6.
  • the phytotoxicity to paddy rice was investigated based on the following evaluation indicators.
  • a wettable powder containing the above comparative compound, 8, 0, £,?, 6 was prepared according to Example 15, and the test was carried out similarly. Table 6 shows the results.
  • Test Example 5 Test of herbicidal effect on field weeds and test of chemical injury 1) Test of herbicide effect on field weeds
  • Field soil (alluvial loam) is packed in a pot made of 1 / 10,000 ares, and seeds (5 soybeans, 5 corns, 5 sugar beets, 10 rapeseed, 10 rape seeds) of each crop 5 grains, 10 grains of wheat and 10 grains of wheat) were sowed in separate pots, and the surface layer was lightly pressed.
  • seeds soybeans, 5 corns, 5 sugar beets, 10 rapeseed, 10 rape seeds of each crop 5 grains, 10 grains of wheat and 10 grains of wheat
  • the surface layer was lightly pressed.
  • the emulsion prepared according to Example 16 was diluted with water, and the diluted water solution was sprayed on the soil surface at a rate of 100 liters per 10 liters. When the active ingredient application rate was converted, it was equivalent to 50 g per 10 ares.
  • Comparative compound A 60 70 50 60 60 2 2 1 2 1 3 2
  • Comparative compound B 60 50 60 60 60 2 1 2 2 2 2 2 2
  • Comparative compound F 60 60 70 60 60 2 1 1 2 2 2 2 2
  • novel herbicidal triazolinonone derivative of the general formula (E) according to the present invention can selectively control various weeds in paddy fields and fields at a low application rate and has low phytotoxicity to crops, so that it can be selectively used. Excellent herbicidal activity. Therefore, the novel compounds of the general formula (e) according to the present invention are extremely useful as selective herbicides.

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  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des dérivés de triazolinone représentés par la formule générale (I) (dans laquelle R1 représente alkyle inférieur, alkényle inférieur, alkynyle inférieur, ou cylcoalkyle inférieur; R2 désigne alkyle inférieur, cycloalkyle inférieur, ou phényle substitué; et R3 symbolise cylcoalkyle inférieur, alkényle inférieur, alkyle C1-C8, un groupe hétérocyclique à cinq ou six chaînons, ou similaire). Les dérivés 2-substitués-4-(N,N-disubstitués carbamoyl)-1,2,4-triazol-3-one de formule générale (I) exercent d'excellents effets herbicides sur diverses plantes nuisibles, sans pour autant causer de dommages chimiques majeurs aux plantes de grande culture.
PCT/JP1999/004457 1998-08-19 1999-08-19 Derives de triazolinone et compositions herbicides WO2000010984A1 (fr)

Priority Applications (1)

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AU53017/99A AU5301799A (en) 1998-08-19 1999-08-19 Triazolinone derivatives and herbicide compositions

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP10/247738 1998-08-19
JP24773898A JP3732014B2 (ja) 1998-08-19 1998-08-19 ６員複素環置換トリアゾリノン誘導体及び除草剤
JP25458998A JP3837242B2 (ja) 1998-08-25 1998-08-25 トリアゾリノン誘導体および除草剤
JP25455398A JP3837241B2 (ja) 1998-08-25 1998-08-25 トリアゾリノン誘導体および除草剤
JP10/254589 1998-08-25
JP10/254553 1998-08-25

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WO2000010984A9 WO2000010984A9 (fr) 2000-08-17

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Publication number Priority date Publication date Assignee Title
WO2004048346A1 (fr) * 2002-11-28 2004-06-10 Hokko Chemical Industry Co., Ltd. Procede de production d'un derive de 4-carbamoyl-1,2,4-triazol-5-one substitue a la position 1
WO2006067139A1 (fr) * 2004-12-21 2006-06-29 Janssen Pharmaceutica N.V. Derives de triazolone, tetrazolone et imidazolone utilises comme antagonistes des recepteurs alpha2c-adrenergiques
CN114591294A (zh) * 2022-03-21 2022-06-07 中国农业大学 含有氯吡啶亚甲基的三唑酮类化合物及其制备方法与应用

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JPS50117775A (fr) * 1974-03-06 1975-09-16
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WO1998038176A1 (fr) * 1997-02-26 1998-09-03 Hokko Chemical Industry Co., Ltd. Derives de 4-carbamoyl-1,2,4-triazol-5-one substitue en 1 utilises en tant qu'herbicide

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JPS50117775A (fr) * 1974-03-06 1975-09-16
EP0202929A2 (fr) * 1985-05-23 1986-11-26 UNIROYAL CHEMICAL COMPANY, Inc. Tetrazolinones substitués
JPH08311048A (ja) * 1995-03-13 1996-11-26 Nippon Bayeragrochem Kk テトラゾリノン類及びその水田用除草剤としての利用
WO1998038176A1 (fr) * 1997-02-26 1998-09-03 Hokko Chemical Industry Co., Ltd. Derives de 4-carbamoyl-1,2,4-triazol-5-one substitue en 1 utilises en tant qu'herbicide

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048346A1 (fr) * 2002-11-28 2004-06-10 Hokko Chemical Industry Co., Ltd. Procede de production d'un derive de 4-carbamoyl-1,2,4-triazol-5-one substitue a la position 1
WO2006067139A1 (fr) * 2004-12-21 2006-06-29 Janssen Pharmaceutica N.V. Derives de triazolone, tetrazolone et imidazolone utilises comme antagonistes des recepteurs alpha2c-adrenergiques
JP2008524312A (ja) * 2004-12-21 2008-07-10 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ アルファ−２ｃアドレノレセプターアンタゴニストとしての使用のためのトリアゾロン、テトラゾロン及びイミダゾロン誘導体
EA011514B1 (ru) * 2004-12-21 2009-04-28 Янссен Фармацевтика Н.В. Производные триазолона, тетразолона и имидазолона для применения в качестве антагонистов альфа-2с-адренорецептора
CN114591294A (zh) * 2022-03-21 2022-06-07 中国农业大学 含有氯吡啶亚甲基的三唑酮类化合物及其制备方法与应用
CN114591294B (zh) * 2022-03-21 2023-09-29 中国农业大学 含有氯吡啶亚甲基的三唑酮类化合物及其制备方法与应用

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