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WO2001079199A1 - Derives de l'acetylene et herbicides en contenant - Google Patents

Derives de l'acetylene et herbicides en contenant Download PDF

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Publication number
WO2001079199A1
WO2001079199A1 PCT/JP2001/003120 JP0103120W WO0179199A1 WO 2001079199 A1 WO2001079199 A1 WO 2001079199A1 JP 0103120 W JP0103120 W JP 0103120W WO 0179199 A1 WO0179199 A1 WO 0179199A1
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Prior art keywords
group
represented
sho
atom
formula
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PCT/JP2001/003120
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English (en)
Japanese (ja)
Inventor
Hiroshi Yamamoto
Kazuyoshi Koike
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Idemitsu Kosan Co., Ltd.
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Priority to AU2001246897A priority Critical patent/AU2001246897A1/en
Publication of WO2001079199A1 publication Critical patent/WO2001079199A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to a novel acetylene derivative and a herbicide using the same. More specifically, the present invention provides an acetylene derivative capable of controlling a wide range of field weeds at a low dose without causing phytotoxicity to field-cultivated crops such as corn, and an acetylene derivative containing the acetylene derivative as an active ingredient. It relates to herbicides. Background art
  • Herbicides are extremely important drugs for labor saving in weed control and for improving the productivity of agricultural and horticultural crops.Therefore, research and development of herbicides has been actively carried out for many years, and a wide variety of chemicals are currently in practical use. ing. Therefore, even today, the development of new drugs with even more excellent herbicidal properties, especially those that can control only the target weeds at low doses without causing phytotoxicity to cultivated crops, has been developed. It is desired.
  • Atrazine and the acid-based herbicides alaclor (a1 achlor) and metolachlor have been used, but atrazine has low activity against grass weeds. Conversely, it has low activity against broadleaf weeds. Therefore, it is currently difficult to control gramineous and broadleaf weeds at once with a single agent. In addition, these herbicides require high doses and are not preferred on environmental issues.
  • these chiochroman derivatives Compared with the 4-benzoyl derivative, these chiochroman derivatives have a high herbicidal activity 1 ", but are not sufficient. Furthermore, their safety against corn is also insufficient.
  • the present invention provides a novel compound capable of controlling a wide range of field weeds at a low dose without causing phytotoxicity to field cultivated crops such as corn under such circumstances, and a herbicide using the same. It is intended to provide an agent.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a pyrazole compound having a specific structure in which an acetylene group is introduced into the molecule can achieve the object.
  • the present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I):
  • X is an oxygen atom
  • z is an oxygen atom or formula
  • Z is not 1 SO 2 —.
  • Y is the expression When X is a group represented by the formula:
  • o 2 0 is not a group represented by 2.
  • X is an oxygen atom or a formula
  • R 1 is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted, the alkyl group may 6 chain have a halogen atom or c 3 to c s cyclic alkyl group or a C 2 -C 6 alkenyl group,, C 2 to c 6 Haroanorekeniru group, C 2 -C 6 Arukyuru group, Shiano group, a carboxyl group,
  • (C CA alkoxy) carbyl group tri (.- dialkyl) silyl group, C i Cs alkylthio group, C 6 -C 6 alkyl sulfier group, C 1 -C 6 alkyl sulfonyl group, substituted or unsubstituted phenylthio Group, substituted or unsubstituted phenylsulfuryl group, substituted or unsubstituted phenylsulfonyl group, C 1 -C 6 anolexoxy group, substituted or unsubstituted phenoxy group, substituted or unsubstituted phenyl group
  • R 2 is a hydrogen atom, a halogen atom, one or two oxygen atoms and no or sulfur May be interrupted by atom, also good Ci Cs chain optionally having a halogen atom Joa Kill group or C 3 -C 6 cyclic alkyl group or a C 2 -C 6 alkenyl group,, C 2 -C 6 Haloalkenyl group, C 2 -C 6 alkynyl group, cyano group, carboxyl group, (CC alkoxy) carbyl group, tri (C 1 -C 4 alkyl) silyl group, substituted or unsubstituted funil group, or substituted or unsubstituted A substituted 5- or 6-membered aromatic heterocyclic group, wherein the sulfur atom may be partially or completely oxidized by oxygen;
  • R 3 is a hydrogen atom, one or two oxygen atoms and Z or may be interrupted by a sulfur atom, also a halogen atom or may 6 chain alkyl group which may have a is c 3 to c 6 cyclic alkyl or c 2 to c 6 alkenyl group,, c 2 to c 6 Haroa alkenyl group, a C 2 -C 6 Arukyuru group, the sulfur atom may be partially or completely oxidized by oxygen.
  • R 4 may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.Ci-C 6 chain alkyl group, or C 2 -C 6 alkenyl group, C 2 -C 6 haloalkenyl group, a C 2 -C 6 alkynyl group, Shiano group, a carboxyl group or a - (Ji ⁇ . alkoxy) force Rupoeru group, the sulfur atom to the oxygen It may be partially or completely oxidized.
  • R 5 is a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, or optionally C i to C 6 chain which may have a halogen atom
  • Roarukokishiru group (Ci C alkoxy) carbonyl group, a mercapto group, C 1 -C 4 alkylthio O group, C ⁇ ⁇ 4 alkylsulfinyl group, Ji-Ji alkylsulfonyl group, C 2 -C 6 Arukeyuru group, C 2 -C 6 haloalkenyl group or C 2 -C 6 alkynyl group, and the sulfur atom contained in the above-mentioned C 6 -C 6 chain alkyl group or C 3 -C 6 cyclic alkyl group is partially or completely depleted by oxygen. It may be oxidized.
  • R 6 is a halogen atom, a nitro group, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, or optionally C ⁇ 6 chain alkyl group which may have a halogen atom or a C 3 to C 6 cyclic alkyl group, or carboxyl group, cyano group, thiocyano group, alkoxyl group, haloalkoxyl group, -C 4 alkoxy) carboxy group, a mercapto group, Ci C alkylthio group, -C 4 alkyl sulfide El group, C i ⁇ C 4 alkylsulfonyl group, C 2 ⁇ 6 Al Keeru group, ⁇ 2 ⁇ 6 haloalkenyl group, or a C 2 -C 6 alkynyl group, the
  • the sulfur atom contained in the C i -C 6 chain alkyl group or the C 3 -C 6 cyclic alkyl group may be partially or completely oxidized by oxygen.
  • Xi X 7 represents an oxygen atom or a sulfur atom, respectively.
  • R 7 and R 8 may be each independently interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and a Z or sulfur atom, and have a halogen atom.
  • a hydrogen atom which may be C ⁇ C 6 linear alkyl or C 3 ⁇ C 6 cycloalkyl group or a carboxyl group, Shiano group, Ci C alkoxyl group, Ci ⁇ C 3 ⁇ 4 Roh, Roarukokishiru group, (C 1 -C 4 Alkoxy) alcohol group, C 1 -C 4 alkynolethio group, alkylsulfiel group, C alkylsulfonyl group, formula
  • R 9 is a hydrogen atom, C Cs alkyl group, C Ce haloalkyl group, - shows the S0 2 R 39 - COR 39 or.
  • R 10 may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.
  • the sulfur atom contained in the alkyl group or C 3 -C 6 cyclic alkyl group is It may be partially or completely oxidized.
  • R 11 and R 12 are each independently a hydrogen atom, a nitro group, a carboxyl group, a cyano group, a di-alkyl group,.
  • ⁇ ⁇ represents a haloalkyl group, a (CC alkoxy) carbol group or COR 39 .
  • R 13 represents a hydrogen atom, a Ci Cs alkyl group, a Ci Ca haloalkyl group, or a substituted or unsubstituted phenyl group.
  • R 14 represents a hydrogen atom, a halogen atom, a C i C alkyl group or a haloalkynole group.
  • R 15 ⁇ R 23, R 26 and R 27 are each a hydrogen atom, a halogen atom, Ci C alkyl group or. ⁇ represents a mouth alkyl group.
  • R 24 and R 25 are each a hydrogen atom, a halogen atom, Ci Ca alkyl group, C i ⁇ C 4 haloalkyl group, an alkoxyl group, Ji ⁇ Ji ⁇ Roanorekokishi group, a carboxyl group, (C 1 -C 4 alkoxy) Karuponiru group, Ci ⁇ C 4 alkyl thio groups, C ⁇ 4 alkylsulfinyl groups, C ⁇ C 4 alkylsulfonyl - group, an amino group, a mono (Ci C alkyl) amino group or a di (Ci C alkyl) amino group Show.
  • R 28, 1 29 and 1 31 to 1 34 are each a hydrogen atom, a halogen atom, Ci C alkyl group or. ⁇ represents a mouth alkyl group.
  • R 35 ⁇ Pi R 36 are each independently a hydrogen atom, a halogen atom, Ci CT alkyl group, Ji-Ji, mouth alkyl group, C 1 -C 4 forces or R 3 5 illustrates an alkoxyl group, R 36 and The carbon atoms to which they are attached together form the formula
  • R 30 , R 37 , R 38 and R 40 each represent a hydrogen atom or an alkyl group.
  • R 39 represents a CiC alkyl group, ⁇ to ⁇ , a loalkynole group or a substituted or unsubstituted phenyl group.
  • n 0 or 1.
  • acetylene derivative represented by these is provided.
  • the present invention also provides a herbicide containing the acetylene derivative and / or a salt thereof as an active ingredient. Best mode for implementing efforts
  • the acetylene derivative of the present invention has the general formula (I)
  • X is an oxygen atom or a formula
  • Z is an oxygen atom, or the formula
  • Z represents an asymmetric group
  • the bond on the left is bonded to the benzene ring
  • the bond on the right is bonded to the Y moiety.
  • Z is not 1 SO 2 —.
  • Y is the expression Or —— C— N ⁇ when it is a group represented by
  • 0 is not a 2 0 2 in a group represented by.
  • R 36 The group represented by R 36 is shown.
  • R 1 is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted by, or optionally C i ⁇ C 6 chain alkyl group which may have a halogen atom or a C 3 ⁇ C 6 cycloalkyl group or a C 2 -C 6 alkenyl, - le group, C 2 to c 6 haloalkenyl group, or c 2 to c 6 alkyl group, Shiano group, a carboxyl group, (Ci C alkoxy ) Karuponiru group, tri (Ji-Ji alkyl) silyl group, C Ce alkylthio group, C 1 -C 6 alkyl sulfide El group, C 1 -C 6 alkyl Rusuruhoniru group, a substituted or unsubstituted phenylene group, a heteroarylthio group, a substituted or unsubstituted Hue Nils
  • the one where the sulfur atom is partially oxidized is a sulfoxide group (one so—), and the one where the sulfur atom is completely oxidized is a sulfone group (one so 2 —).
  • phenyl group When the above-mentioned phenyl group, phenylthio group, phenylsulfinyl group, phenylsulfonyl group, phenoxy group or aromatic heterocyclic group has a substituent, examples of the substituent include a halogen atom, a nitro group, Carboxyl group, cyano group,
  • C 4 alkyl group Ci-C, mouth alkyl group, Ci CA alkoxyl group, Ci C haloalkoxynole group, (.-dialkoxy) carboyl group, alkylthio group, CC AT norequils / refinyl group and C i-
  • One or two groups selected from the group consisting of C 4 alkynolesulfenol groups are preferred.
  • R 1 preferred are a hydrogen atom, a halogen atom, a C 6 -C 6 alkyl group which may be interrupted by one or two oxygen atoms and / or sulfur atoms, and C i Ce haloalkyl group or a C 3 -C 6 cycloalkyl group, more can be mentioned tri (Ci C alkyl) silyl group, a (Ji-Ji alkoxy) carbonyl group, and Fueeru group, as more preferable, a hydrogen atom, halogen And a CiC alkyl group. Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.
  • R 2 is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted by, also have good Ci Ce-chain alkyl group or a C 3 be ⁇ a halogen atom C 6 cyclic alkyl group, or C 2 -C 6 alkenyl group, C 2 -C 6 haloalkyl group, or C 2 -C 6 alkyl group, cyano group, carboxyl group, (C i C alkoxy) carboyl group, tri Alkyl) represents a silyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group, and the above sulfur atom is partially or completely substituted by oxygen.
  • substituent group When having the full sulfonyl group Ya aromatic heterocyclic group substituents, are in this substituent group include a halogen atom, a nitro group, a carboxyl group, Shiano group, C 1 -C 4 7 alkyl group, Ci Among C haloalkyl groups, alkoxyl groups, ⁇ - ⁇ haloalkoxyl groups, (C i C anoreoxy) carbonyl groups, Ci C alkylthio groups, CC alkylsulfiel groups and CC alkylsulfonyl groups One or two groups selected from the above can be preferably mentioned.
  • R 2 preferred are a hydrogen atom, one or two oxygen atoms and a C to C 6 alkyl group which may be interrupted by Z or a sulfur atom, and C 1 to C 6 haloalkyl group or a C 3 -C 6 cycloalkyl group, more a phenyl group can ani gel, hydrogen atom ⁇ Pi 0 1 ⁇ is as more preferable.
  • 4 Alkyl groups can be mentioned, and particularly preferred are a hydrogen atom and a methyl group.
  • R 3 may be interrupted by a hydrogen atom, one or two oxygen atoms and a hydrogen atom or a sulfur atom, and may have a halogen atom.
  • Ci Cs chain alkyl group or C 3 -C 6 ring Fushimi alkyl or C 2 -C 6 alkenyl group,, C 2 -C 6 Haroa alkenyl group, or c 2 to c 6 shows an alkynyl group
  • the sulfur atom is optionally be part partial or completely oxidized by oxygen Is also good.
  • R 3 preferred are a C 6 -C 6 alkyl group, a haloalkyl group and a C 3 -C 6 alkyl group which may be interrupted by a hydrogen atom, one or two oxygen atoms and / or a sulfur atom.
  • a C 6 cycloalkyl group can be mentioned, and more preferred are a hydrogen atom and 1 to 4 alkyl groups. Particularly preferred are a methyl group, an ethynole group and an isopropyl group. be able to.
  • R 4 may be interrupted by a hydrogen atom, one or two oxygen atoms and Z or sulfur atoms, and may have a halogen atom.
  • Ci-C 6 chain alkyl group, or C 2 -C 6 Aruke - group, C 2 -C 6 Haroaruke - group, c 2 to c 6 alkynyl group, a Shiano group forces Rupokishiru group or (Ci Ca alkoxy) carbonylation group, the sulfur atom It may be partially or completely oxidized by oxygen.
  • preferred are a hydrogen atom, one or two oxygen atoms, and a C 1 -C 6 alkyl group which may be interrupted by a Z or sulfur atom. 1 to.
  • Examples include a 6- haloalkyl group, a carboxyl group and a (C CA alkoxy) carboyl group. More preferred are a hydrogen atom and a C i C alkyl group, and particularly preferred are Represents a hydrogen atom or a methyl group.
  • R 5 is a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and C-C 6 chain alkyl group or c 3 -c 6 cyclic alkyl group which may be interrupted by a sulfur atom and may have a halogen atom, or a carboxyl group, a cyano group, a thiocyano group, ci C alkoxyl group, c to c, Roarukokishiru group, (Ci C alkoxy) carboxamide group, a mercapto group, alkylthio O group, C i ⁇ C 4 alkylsulfinyl group,. ⁇ . Alkylsulfonyl group, C 2
  • ⁇ C 6 Arukeyuru group ⁇ 2 ⁇ 6 Haroarukeniru group or ⁇ 2 to. 6 Arukiniru group indicates, the C ⁇ s chain alkyl or C 3 -C 6 sulfur atom in the cyclic alkyl group may be by connexion partially or completely oxidized to oxygen.
  • R 5 preferred are a halogen atom, an ethoxy group, a CiC 6 alkyl group optionally interrupted by one or two oxygen atoms and a sulfur or a sulfur atom, or ( ⁇ to Flip mouth alkyl group or C 3 -C 6 cycloalkyl group, more Shiano group, Ci C alkoxyl group, Ci ⁇ C 4 haloalkoxyl group, c 1 to c 4 alkylthio group, C i ⁇ C 4 alkylsulfinyl group and Alkylsulfo
  • a halogen atom a nitro group, C 1 -C 4 alkyl group, 0 1 ⁇ 4 Haroarukiru groups and ⁇ 1.
  • An alkylsulfonyl group can be mentioned, and a particularly preferable example is a halogen atom, a nitro group and an alkyl group, and a most preferable example is a chlorine atom, a methyl group and an ethyl group. it can.
  • R 6 is a halogen atom, a nitro group, one or two oxygen atoms and // or may be interrupted by a sulfur atom, also a halogen atom which may have a Ci Ce chain alkyl or C 3 A C 6 -cyclic alkyl group, or a carboxyl group, a cyano group, a thiocyano group, a C 1 -C 4 alkoxyl group. ⁇ ⁇ , lower alkoxyl group,
  • -C 4 alkoxy) carbonyl group a mercapto group, an alkylthio group, -C 4 alkyl sulfide El group, C I ⁇ C 4 alkylsulfonyl group, c 2 to c 6 an alkenyl group, C 2 -C 6 haloalkenyl group or a C It indicates 2 -C 6 alkynyl group, the C i Cs-chain alkyl group or a C 3 -C 6 sulfur atoms in the cyclic alkyl group may be by connexion partially or completely oxidized to oxygen.
  • R 6 preferred are a halogen atom, - Toromoto, C 1 -C 4 alkyl group, ⁇ 1 ⁇ 4 Haroarukiru Moto ⁇ Pi ⁇ 1 ⁇ 4 Arukirusuruho - be exemplified Le group And more preferred are a halogen atom, a nitro group and .
  • ⁇ alkyl group and particularly preferred are
  • alkyl group can be mentioned, and a most preferred example is a methyl group.
  • Each of ⁇ to 7 represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred.
  • 17 and 18 may each be independently interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and / or sulfur atoms, and have a halogen atom. May be C! A C 6 -chain alkyl group or a C 3 -C 6 cyclic alkyl group, or a carboxyl group, a cyano group, a Ci-C 4 alkoxyl group,
  • substituent group include a halogen atom, a nitro group, a carboxyl group, Shiano group, C 1 -C 4 7 alkyl group, Ci ⁇ C, mouth alkyl group, C alkoxyl group, Ci ⁇ C, mouth alkoxyl group, ((: -dialkoxy) carbonyl group, alkylthio group, C 1 -C 4 alkylsulfinyl group and alkylsulfol group Preferred are one or two groups selected.
  • R 7 and R 8 preferred are a C 6 -alkyl group which may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms.
  • alkylsulfide el groups C alkylsulfonyl Moto ⁇ Pi formula one OCOR 39, - OC0 2 R 37 , one O CONR 13 R 14, one ⁇ _CHR 37 CN, - OC HR 37 COR 39, - OCHR 37 C 0 2 R 38, can be a group represented by one OCHR 37 CONR 13 R 14, more preferred are A C Ce alkyl group, which may be interrupted by a hydrogen atom, one or two oxygen atoms and a sulfur atom, or a Ci C alkoxyl group; ⁇ .
  • R 9 is a hydrogen atom, a C Cs alkyl group, Or an alkyl group, — COR 39 or SO 2 R 39 .
  • R 9 preferred are a hydrogen atom and 1 to 6 alkyl groups, and more preferred are a hydrogen atom, a methyl group and an ethyl group.
  • R 1G may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.
  • the sulfur atom contained in the chain alkyl group or the C 3 -C 6 cyclic alkyl group may be partially or completely oxidized by oxygen.
  • R 1 like this.
  • a hydrogen atom, one or two oxygen atoms and a C to C 6 alkyl group or a C Cs haloalkyl group which may be interrupted by a Z or sulfur atom and also a C 2 to C S Arukeeru group, C 2 -C 6 Haroaru Kenyir group and C 2 -C can be mentioned alkynyl groups, as a more preferable, a hydrogen atom, ⁇ 1 ⁇ 4 Arukiru Moto ⁇ Pi ⁇ 1 ⁇ 4
  • a halalkyl group can be mentioned, and a particularly preferred example is a methyl group and an ethyl group.
  • R 11 and R 12 are each independently a hydrogen atom, a nitro group, a carboxyl group, shea Anomoto, Ci ⁇ C 4 alkyl group, Ji, ⁇ Ji haloalkyl group, (Ci ⁇ C 4 alkoxy) A carbyl group or 1 COR 39 is shown.
  • R 11 and R 12 preferred are a hydrogen atom
  • Alkyl groups, C to C, alkyl groups and (CiC alkoxy) carbonyl groups can be mentioned, and more preferred are a hydrogen atom and a CiC alkyl group.
  • R 13 represents a hydrogen atom, Ci Cs alkyl, Ci C port alkyl group or a substituted young properly unsubstituted phenylene Le group.
  • examples of the substituent include a halogen atom, a nitro group, a carboxyl group, a cyano group, a C 1 -C 4 alkyl group, a C 1 -C haloalkyl group, and a C i -C 4 alkoxyl group.
  • Haloalkoxyl group
  • C i ⁇ C 4 alkylthio group C 1 -C 4 alkyl Surufieru groups and C i ⁇ C 4 1 or the like preferably two groups selected from among alkyl sulfo Interview le radical Can be.
  • R 13 preferred are a hydrogen atom, a Ci Cs alkyl group, or a halogen atom, ⁇ 1- . 4 alkyl groups and 1 to. 4
  • a phenyl group which may be substituted with one or two groups selected from among alkoxyl groups can be mentioned, and more preferred are a hydrogen atom and 1 to 1 . 4 Alkyl groups can be mentioned.
  • R 14 represents a hydrogen atom, a halogen atom, an alkyl group or ⁇ to ⁇ , and an alkyl group.
  • Preferred examples of R 14 include a hydrogen atom and a CC alkyl group, and more preferred examples include a hydrogen atom and a methyl group.
  • R 15 to R 23 , R 26 and R 27 are each a hydrogen atom, a halogen atom,. ⁇ Alkyl group or ⁇ . And a mouth alkyl group. Among them, preferred are a hydrogen atom, a halogen atom and a CiCa alkyl group, and more preferred are a hydrogen atom, a chlorine atom and a methyl group.
  • R 24 ⁇ Pi R 25 are each a hydrogen atom, a halogen atom, Ci C alkyl groups, C ⁇ 4 Haroanorekinore group, Ci C Arukokishinore groups, C 1 -C 4 Haroanorekokishi group, a carboxyl group, (Ji ⁇ . Alkoxy ) Carbyl group, Archi A luthio group, CiC alkylsulfiel group, Ci- 4 alkylsulfonyl group, amino group, mono (CiCalkyl) amino group or di (CiCalkyl) amino group.
  • R 24 and R 25 preferred are a hydrogen atom, a halogen atom, a CCA alkyl group, a CiCa haloalkyl group and a to alkoxyl group, and more preferred are , A hydrogen atom, a chlorine atom, a methyl group and a methoxy group.
  • R 28 , R 29 and R 31 to R 34 each represent a hydrogen atom, a halogen atom, a Ci C alkyl group or a C 1 to C 2 alkyl group. Among them, preferred are a hydrogen atom and 1 to 4 alkyl groups, and more preferred are a hydrogen atom and a methyl group.
  • R 35 and R 36 each independently represent a hydrogen atom, a halogen atom, a CiCT alkyl group, an alkyl group, a force representing an alkoxy group, or R 35 , R 36, and a bond thereof.
  • R 35 and R 36 include a hydrogen atom, an alkyl group, a C i -C 4 alkoxyl group and R 35 , R 36 and the carbon atom to which they are bonded, formula
  • R 30 , R 37 , R 38 and R 4 each represent a hydrogen atom or a CiCa alkyl group. Among them, preferred are a hydrogen atom, a methyl group and an ethyl group.
  • R 39 represents a CiC alkyl group, di-, di-alkyl group, or substituted or unsubstituted fluorine group.
  • the substituent include a halogen atom, a nitro group, a force Rupokishiru group, Shiano group, ⁇ ⁇ c 4 Anorekiru group, C i ⁇ C 4 Haroarukinore group, ⁇ ⁇ .
  • Preferable examples are one or two groups selected from alkyl sulfol groups.
  • a C 4 haloalkyl group or a halogen atom is A C 4 haloalkyl group or a halogen atom.
  • Alkyl group and Examples include a phenyl group which may be substituted with one or two groups selected from alkoxyl groups, and more preferred examples include a CiC alkyl group.
  • C 6 alkyl groups include the formulas CH 2 X 8 CH 3 , CH 2 X 8 CH 2 CH 3 , CH 2 X 8 CH 2 CH 2 CH 3 , — CH 2 CH 2 X 8 CH 3 , -CH 2 CH 2 X 8 CH 2 CH 3 , — CH (CH 3 ) X 8 CH 2 CH 3 , -CH 2 X 8 CH (CH 3 ) 2 , CH 2 X 8 C (CH 3 ) 3 , -CH 2 X 8 CH (CH 2 CH 3 ) 2 , -CH 2 X 8 CH 2 CH 2 X 9 CH 3 , One CH 2 X 8 CH 2 CH 2 X 9 CH 2 CH 3 ,-CH 2 X A group represented by 8 CH 2 CH 2 X CH (CH 3
  • C is interrupted by one or two oxygen atoms and / or sulfur atoms and has a halogen atom.
  • c 1 to c 6 The Haroaruki Le group (chain), for example, one of the above-exemplified or two oxygen atoms ⁇ Pi Z Or one in which one or more hydrogen atoms of a 6- alkyl group (chain) interrupted by a sulfur atom is replaced by a halogen atom, specifically, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. be able to.
  • C 3 -C 6 cycloalkyl groups For example, the expression
  • X 8 and X 9 each represent an oxygen atom or a sulfur atom.
  • they are partially oxidized to sulfoxide (so) or completely oxidized to sulfon (so 2 ). You may.
  • n 0 or 1.
  • M is preferably 2
  • p and q are each preferably 0 or 1.
  • acetylene derivatives represented by the general formula (I) preferred are those represented by the general formula (Ia) (I-a)
  • X is
  • Such compounds include compounds represented by the general formula (Ib), the general formula (I-c), the general formula (I-d) or the general formula (I-e) Is the same as the previous statement. )
  • the salt when the compound can form a salt, the salt is also included in the acetylene derivative of the present invention.
  • INDUSTRIAL APPLICABILITY The acetylene derivative of the present invention does not cause phytotoxicity to field cultivated crops such as corn, has excellent herbicidal activity, and can control a wide range of field weeds at a low dose.
  • acetylene derivative for example, the compound represented by the general formula () wherein X 1 in the general formula (I) is an oxygen atom is represented by the following reaction formula:
  • Method A in which a pyrazole derivative of the general formula (II) is reacted with a hachigen compound of the general formula (III), and a pyrazole derivative of the general formula 1) is reacted with the general formula (IV).
  • Method B of reacting with alcohol.
  • a pyrazole derivative of the general formula (II) is reacted with a halogenic compound of the general formula (III) in an inert solvent in the presence of a hydrogen halide scavenger to obtain a compound of the general formula (III). 1 ′) is produced.
  • the halogen compound of the general formula (III) is added to one mole of the virazole derivative of the general formula (II). 'It is generally preferred to use 1 to 3 moles.
  • the hydrogen halide scavenger for example, bases such as sodium carbonate, potassium carbonate, triethylamine and pyridine are used.
  • These hydrogen halide scavengers are preferably used in an amount equal to or greater than the amount of the compound of the general formula ( ⁇ ), and the reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used.
  • the inert solvent include aromatic hydrocarbons such as benzene and toluene, ethers such as getyl ether, ketones such as methylethyl ketone, and halogenated hydrocarbons such as dichloromethane, chlorohonolem, and dichloroethane.
  • a pyrazolyl derivative of the general formula (II) is reacted with an alcohol of the general formula (IV) in an inert solvent in the presence of a dehydrating condensing agent such as azodicarboxylic acid diester or triphenylphosphine.
  • a dehydrating condensing agent such as azodicarboxylic acid diester or triphenylphosphine.
  • a compound represented by the general formula (1 ′) is produced.
  • the alcohol of the general formula (IV) is preferably used in a proportion of generally 1 to 2 mol per mol of the pyrazole derivative of the general formula (II).
  • the reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used.
  • the inert solvent examples include, for example, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl / leethenole, halogenated hydrocarbons such as dichloromethane, chloroform / lem, and dichloroethane.
  • the compound represented by the general formula (1 ′) is reacted with a Lawesson reagent in an inert solvent: Generally, it is preferable to use 1-2 equivalents of the Lawesson reagent with respect to the pyrazole derivative (1 ′).
  • the reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used. Examples of the solvent used for the reaction include aromatic hydrocarbons such as benzene and toluene, and ethers such as getyl ether and dimethoxetane.
  • the pyrazole derivative represented by the general formula (II) can be prepared by a known method (for example, WO93 / 18031, WO94 / 01431, WO95 / 4054, W096 / 25412, W095 / 13275,
  • WO96 / 30368 WO96 / 31507, W097 / 12885, WO97 / 19087, W097 / 42185, WO97 / 01550, WO97 / 03045, WO97 / 08164, W098 / 28291, WO97 / 30986, WO97 / 30993, WO98 / 12180, W098 / 12192, W098 / 49159, W098 / 35954, special (Kaihei 7-291970, JP-A-7-316149, USP5607898, USP5631210, USP5723411, USP5885936, DE4427996, DE4427997, DE19532312, etc.).
  • the herbicide of the present invention contains, as an active ingredient, the acetylene derivative of the present invention represented by the general formula (1) and Z or a salt thereof as an active ingredient.
  • these compounds are used as a liquid carrier such as a solvent or a mineral substance. It can be mixed with a solid carrier such as fine powder and formulated into wettable powders, emulsions, powders, granules, etc. for use.
  • Surfactants may be added to provide emulsification, dispersibility, spreadability, etc. during formulation.
  • the herbicide of the present invention is used in the form of a wettable powder, the acetylene derivative of the present invention and / or a salt thereof is usually added at a rate of 10 to 55% by weight.
  • the composition may be prepared by blending the solid carrier in an amount of 40 to 88% by weight and the surfactant in an amount of 2 to 5% by weight.
  • the acetylene derivative of the present invention and / or a salt thereof is usually 20 to 50% by weight, and the solid carrier is 35 to 75% by weight. /.
  • the composition may be prepared by mixing at a ratio of 15% by weight.
  • the acetylene derivative of the present invention and / or its salt are usually 1 to 15% by weight, 80 to 97% by weight of a solid carrier and 2 to 5% by weight of a surfactant.
  • the acetylene derivative of the present invention and / or a salt thereof is usually blended in a proportion of 1 to 15% by weight, a solid carrier in an amount of 80 to 97% by weight, and a surfactant in a proportion of 2 to 5% by weight.
  • the composition may be prepared by heating.
  • fine powder of a mineral substance is used as the solid carrier.
  • the fine powder of the mineral substance include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as Secco, talc, and the like. Pai-mouth ferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silicates such as kaite powder.
  • Organic solvents are used as the solvent.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • chlorinated hydrocarbons such as 0-chlorotoluene, trichloroethane and trichloroethylene
  • cyclohexanol Amanol alcohol, ethylene glycol / vinyl alcohol, etc., isophorone, cyclohexanone, cyclohexenyl-cyclohexanone, ketones, etc.
  • esters such as methyl phthalate, amides such as dimethylformamide, and mixtures thereof. Can be .
  • surfactant examples include aion type (fatty acid salt, alkyl sulfate, a / lex / madzenesulfonic acid, dianolex / resulfosuccinate, alkynolephosphate, salt of naphthalenesulfonic acid-formalin condensate, polyoxygen salt).
  • Ethylenealkyl sulfate, etc. Noon type (polyoxyethylene alkyl ether, polyoxyethylene alkyl phenylene ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. ), Cationic type or amphoteric type (amino acid, betaine, etc.) can be used.
  • the herbicide of the present invention may contain other herbicidal active ingredients, if necessary, together with the acetylene derivative represented by the general formula (I) and / or its salt as an active ingredient.
  • herbicidally active ingredients include conventionally known herbicides such as phenoxy, diphenyl ether, triazine, urea, carbamate, thiocarbamate, acid alide, acetylene, and phosphorus.
  • An acid type, a sulfonylurea type, an oxadiazone type and the like can be mentioned, and these can be appropriately selected and used from these herbicides.
  • the herbicide of the present invention can be mixed with an insecticide, a bactericide, a plant growth regulator, a fertilizer, and the like, if necessary.
  • the herbicide of the present invention can be used as a herbicide for upland fields in any of soil treatment, soil admixture treatment and foliage treatment.
  • field weeds Crolanaceae weeds represented by Solanum nigrum, Datura stramonium, etc., Almtilon theophrasti, and American stag beetle Malvaceae weeds such as (Sida spinosa), convolvulaceae weeds such as Ipomoea spps.
  • Amaranthaceae typified by Amaranthus lividus, etc.
  • Xanthium strumarium Ragweed (Ambrosia artemisiaefolia), Helianthus (Helianthus annus), lian Asteraceae represented by cicada (Cirsium arvense), nopolgum (Senecio vulgaris), and shrimp (Erigeron annus) (Compositae) Weed, cruciferae (Cruciferae) represented by weeds (Rorippa indica), wild ash (Sinapis arvensis), napsuna (Capsellaureabursa—pastoris), etc.
  • Polygonaceae Polygonaceae (Polygonaceae) weeds, Portulaca oleracea (Portulaca ole)
  • Scrophulariaceae represented by (Veronica persica), etc., and communis (CommeHna communis), etc.
  • weeds such as Graminaceous weeds, and Cyperus rot ndus, Cyper s esculentus, and the like.
  • the compound of the present invention can be used as a herbicide for paddy fields in any of soil treatment and foliage treatment under flooding.
  • paddy weeds include paddy weeds, such as Alisma canaliculatum, Sagittaria trifolia, and Sagittaria pygmaea.
  • Examples include Lythraceae weeds and Gramineae weeds such as Ecliinochloa crus-galli.
  • the effective application amount of the compound of the present invention for weeding can be determined in consideration of various conditions such as the form of the preparation, the application method, the type and amount of the weeds, and the growth condition. It is usually 0.001 to 3.0 kg / ha, preferably 0.01 to 0.31 ⁇ ⁇ / 11 &, and those skilled in the art can easily determine the effective amount for obtaining the required herbicidal effect.
  • Compounds 1-1 to 1-1188 are compounds represented by the general formula (1b), and the substituents 1 ⁇ to 16 of each compound have the structure shown in the row of the corresponding number in Table 1. Have.
  • Compound II—1 ⁇ ! I-1188 is a compound represented by the general formula ( ⁇ -c), and the substituents R 1 to R 6 of each compound have a structure shown in the row of the corresponding number in Table 1.
  • Compound III-1 to: [II-1188 is a compound represented by the general formula (_d), and the substituents R 1 to R 6 of each compound are shown in the row of the corresponding number in Table 1. It has a structure.
  • Compounds IV-1 to IV-1188 are compounds represented by the general formula (_e), and the substituents R 1 to R 6 of each compound have a structure shown in the row of the corresponding number in Table 1. .
  • Compounds V-1 to V-1188 are compounds represented by the general formula (1f), and the substituents 1 ⁇ to 16 of each compound have a structure shown in the row of the corresponding number in Table 1. . (I 'one f)
  • Compound VI- 1 ⁇ VI- 1188 is the substituent RR 6 compound of general formula a and each of the compounds represented by (one g) having the shown in the corresponding row of numbers structure in the first table.
  • Compounds VII-1 to VII-1188 are compounds represented by the general formula (1h), and the substituents R to 6 of each compound have a structure shown in the row of the corresponding number in Table 1. .
  • Compounds VIII-1 to VIII-1188 are compounds represented by the general formula (I′-i), and the substituents R i to R 6 of each compound are shown in the row of the corresponding number in Table 1. Having a structure.
  • Compounds IX—1 to IX—1188 are compounds represented by the general formula (I′—j), and the substituent R ⁇ to scale 6 of each compound is shown in the row of the corresponding number in Table 1. Having a structure.
  • Compounds X—1 to X—1188 are compounds represented by the general formula (I′—k), and the substituents R 1 to R 6 of each compound have the structure shown in the row of the corresponding number in Table 1. Having.
  • Compound XI-1 to: XI-1188 is a compound represented by the general formula (I ′ 11), and the substituent 6 of each compound has a structure shown in the row of the corresponding number in Table 1. . ( ⁇ 'ichi 1)
  • Compounds XII-1 to ⁇ -1188 are compounds represented by the general formula (I′-1 m), and the substituents R i to R 6 of each compound are shown in the row of the corresponding number in Table 1. Having a structure.
  • Compound XIII- 1 ⁇ - 1188 is Ri compound der represented by the general formula (I 'one eta), the substituents R to R 6 of each compound were shown in the row of numbers corresponding in the second table structure Having.
  • Et ethyl group
  • n-Pr n-propyl group
  • i-Pr isopropyl group
  • n-Bu n-butyl group
  • i-1 Bu isobutyl group
  • t-1 Bu tert-butyl group
  • Ph fuel group
  • TMS trimethylsilyl group.
  • Table 3 shows the NMR and IR spectrum data of typical compounds of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention porte sur des dérivés de l'acétylène de formule générale (I) et/ou leurs sels, et sur des herbicides en contenant. Les éléments R?1 à R6 X1¿, Y et Z de la formule sont chacun tels que définis dans la description. Lesdits dérivés et lesdits herbicides ne causent pas de dommages aux cultures de montagne tout en s'attaquant à une grande variété de mauvaises herbes de montagne, même à dosage faible.
PCT/JP2001/003120 2000-04-18 2001-04-11 Derives de l'acetylene et herbicides en contenant WO2001079199A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016001119A1 (fr) 2014-07-01 2016-01-07 Bayer Cropscience Aktiengesellschaft Associations de principes actifs insecticides et fongicides
CN108264484A (zh) * 2016-12-30 2018-07-10 浙江省化工研究院有限公司 一种带醚结构的取代的苯基酮类化合物、其制备方法及应用
WO2019007887A1 (fr) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Associations de principes actifs insecticides et fongicides
WO2019007888A1 (fr) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Associations de principes actifs insecticides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997023135A1 (fr) * 1995-12-25 1997-07-03 Idemitsu Kosan Co., Ltd. Composition herbicide
WO1999003856A1 (fr) * 1997-07-18 1999-01-28 Rhone-Poulenc Agriculture Limited Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997023135A1 (fr) * 1995-12-25 1997-07-03 Idemitsu Kosan Co., Ltd. Composition herbicide
WO1999003856A1 (fr) * 1997-07-18 1999-01-28 Rhone-Poulenc Agriculture Limited Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016001119A1 (fr) 2014-07-01 2016-01-07 Bayer Cropscience Aktiengesellschaft Associations de principes actifs insecticides et fongicides
CN108264484A (zh) * 2016-12-30 2018-07-10 浙江省化工研究院有限公司 一种带醚结构的取代的苯基酮类化合物、其制备方法及应用
WO2019007887A1 (fr) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Associations de principes actifs insecticides et fongicides
WO2019007888A1 (fr) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Associations de principes actifs insecticides

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AR028348A1 (es) 2003-05-07

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