WO1996022285A1 - Derives de 1,2,4-triazine, procede pour leur production, et herbicide les contenant comme principe actif - Google Patents

Derives de 1,2,4-triazine, procede pour leur production, et herbicide les contenant comme principe actif Download PDF

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Publication number
WO1996022285A1
WO1996022285A1 PCT/JP1996/000077 JP9600077W WO9622285A1 WO 1996022285 A1 WO1996022285 A1 WO 1996022285A1 JP 9600077 W JP9600077 W JP 9600077W WO 9622285 A1 WO9622285 A1 WO 9622285A1
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group
carbon atoms
methyl
solution
atom
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PCT/JP1996/000077
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English (en)
Japanese (ja)
Inventor
Kenji Hirai
Koiti Shikakura
Tomoyuki Yano
Chikako Ishikawa
Sadayuki Ugai
Osamu Yamada
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Sagami Chemical Research Center
Kaken Pharmaceutical Co., Ltd.
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Priority to AU44586/96A priority Critical patent/AU4458696A/en
Publication of WO1996022285A1 publication Critical patent/WO1996022285A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
    • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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
    • C07D253/075—Two hetero atoms, in positions 3 and 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines

Definitions

  • the present invention relates to novel 1,2,4-triazine derivatives having high selectivity for crops and strong herbicidal activity against weeds, a method for producing them, and a herbicide containing them as an active ingredient.
  • 1,2,4-triazine derivative having a substituted phenyl group at the 4-position a compound described in European Patent Publication EP0438717-A2 is known, but a 2-position of a phenyl ring on a nitrogen atom is known.
  • X 1 represents a halogen atom.
  • X 2 represents a halogen atom.
  • X 3 is an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, and an alkynyl having 3 to 6 carbon atoms. Represents a cycloalkyloxy group having 10 to 10 carbon atoms or an aralkyloxy group having 7 to 8 carbon atoms, R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a carbon number.
  • Y represents an oxygen atom or a sulfur atom.
  • the 1,2,4-triazine derivative shown has excellent performance as a herbicide.
  • the present invention provides a compound represented by the following general formula (2)
  • R ′ has the same meaning as described above.
  • R z is a hydrogen atom, having 1 to 6 carbon atoms. Alkyl group, C3-8 alkenyl group, C3-6 alkynyl group or carbon number? ⁇ 8 aralkyl groups. ), And reacting with a ribonate ester represented by the general formula (4)
  • the present invention provides a compound represented by the general formula (lb) (lb) by oxidizing the compound represented by the general formula (la).
  • the present invention provides a method for producing a 1,2,4-triazine derivative which is a compound of the present invention. is there.
  • the present invention provides a method for producing a 1,2,4-triazine derivative represented by the formula:
  • X 1 represents a halogen atom.
  • X 2 represents a halogen atom.
  • X 3 is an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, and an alkynyl having 3 to 6 carbon atoms.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a 3 to 8 carbon atoms.
  • An alkenyl group of 3 to 6 carbon atoms, an alkynyl group of 3 to 6 carbon atoms Represents a cycloalkyl group having up to 8 or an aralkyl group having 7 to 8 carbon atoms.
  • Y represents an oxygen atom or a sulfur atom.
  • the present invention provides a herbicide containing a 1,2,4-triazine derivative represented by the formula (1) as an active ingredient.
  • the alkyl group having 1 to 12 carbon atoms represented by R 1 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples include a pentyl group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, and a dodecyl group.
  • alkyl groups may be substituted with a halogen atom or the like.
  • halogen atom or the like.
  • Specific examples include a trichloromethyl group and a trifluoromethyl group.
  • Examples of the alkenyl group having 3 to 8 carbon atoms represented by R ′ include 1-methylvinyl group, 1-methyl-1-propenyl group, 1-ethyl-1-propenyl group, 1-methyl-1 -Butenyl group, 1-ethyl-1-butenyl group, 1-propyl-1-butenyl group and the like.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R ′ include a cyclopropyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, and a 3-methylcyclopentyl group. Examples thereof include a methylcyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the cycloalkenyl group having 3 to 8 carbon atoms represented by R 1 include a 1-cyclobutenyl group, a 1-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 3-methyl-1-cyclopentenyl group, -Cyclohexenyl group, Examples thereof include a 2-methyl-recyclohexenyl group, a 3-methyl-1-cyclohexenyl group, a 4-methyl-1-cyclohexenyl group, a tricycloheptenyl group, and a 1-cyclooctenyl group. .
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a cyclopropylmethyl group, a pentyl group, and a neopentyl group.
  • alkyl groups may be substituted with a halogen atom, an alkoxy group having 2 to 7 carbon atoms, a cyano group, an acyl group having 2 to 7 carbon atoms, or the like.
  • Examples of the aralkyl groups of Nos. 8 to 8 include benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, and 2,5-dimethyl Benzyl group, 2,6-dimethylbenzyl group, 3,4-dimethylbenzyl group, 3,5-dimethylbenzyl group, 3,6-dimethylbenzyl group, 2-ethylbenzyl group, 3-ethylbenzyl group, 4-ethylbenzyl group , 2- (trifluoromethyl) benzyl group, 3- (trifluoromethyl) benzyl group, 4- (trifluoromethyl) benzyl group, 2,4-bis (trifluoromethyl) benzyl group, 2-methoxy Benzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2,3-dimethoxybenzyl, 2,
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R 3 include a cyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group, a 3-methylcyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, Examples thereof include a 3-methylcyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the alkenyl group having 3 to 8 carbon atoms represented by R 3 include an aryl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 2-pentenyl group, a 3-pentenyl group, and a 4-pentenyl group.
  • 2,4-pentagenenyl 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2,4-hexenyl, 2,5-hexenyl, 3 , 5-hexadenyl, 1-methyl-2-propenyl, 1-ethyl-2-propenyl, methallyl, crotyl, 1-methyl-2-butenyl, 2-methyl-2- Butenyl group, 3-methyl-2-butenyl group, trimethyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, trimethyl-2-pentenyl group, 2- Methyl-2-pentenyl group, 3-methyl-2-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-4-pentenyl group, 1-methyl-2-hexenyl group 2-methyl-2-hexenyl group, 3-methyl-2-hexenyl group, 4-methyl-2-hexenyl group, 4-methyl
  • alkenyl groups may be substituted with a halogen atom or the like.
  • alkenyl group substituted with a halogen atom examples include 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-chloro-2-butenyl, and 3-chloro- 2-butenyl, 4-chloro-2-butenyl, 3-chloro-3-butenyl, 4-chloro-3-butenyl, 3-chloro-2-pentenyl, 3-chloro- 3-pentenyl group, 2-chloro-2-hexene 3-, 2-chloro-2-hexenyl, 2-bromo-2-propenyl, 3-bromo-2-propenyl, 3,3-difluoro-2-propenyl, 2 , 3, 3-trifluoro-2-propenyl group and the like.
  • These alkenyl groups may be any of a cis-form, a trans-form and a
  • Examples of the alkynyl group having 3 to 6 carbon atoms represented by R 3 include a propargyl group, a 1-methyl-2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 2-pentynyl group, a 3-pentynyl group, and a 2-pentynyl group.
  • Examples include a hexynyl group and a 3-hexynyl group.
  • alkynyl groups may be substituted with a halogen atom or the like.
  • alkynyl group substituted with a halogen atom include a 3-bromo-2-propynyl group, a 4-bromo-2-butynyl group, a 4-bromo-3-butynyl group, and a 3-odo-2-propynyl group. , 4-odo-3-butynyl group, 5-odo-4-pentynyl group, 6-odo-5-hexynyl group and the like.
  • halogen atom represented by X 1 or X 2 examples include a fluorine atom, a bromine atom and a chlorine atom.
  • alkenyl groups may be any of a cis-form, a trans-form or a lance mixture under cis-no.
  • Puroparu Giruokishi group as Arukiniruokishi group having 3 to 6 carbon atoms represented by X 3, Bok-methyl-2-propynyl O alkoxy group, 2-Petit two Ruoki shea group, 3-Puchiniruokishi group, 2-Penchiniruokishi group, 3 -Pentynyloxy group, 2-hexynyloxy group, 3-hexynyloxy group and the like.
  • Cyclo propyl O alkoxy groups cycloalkyl O alkoxy group having 3 to 10 carbon atoms represented by X 3, 2-methylcyclopropyl O alkoxy group, a cycloalkyl Buchiruokishi group, cyclopentyloxy Ruo alkoxy group, 2-methylcyclopentyl Ruokishi group , 3-methylcyclopentyloxy, cyclohexyloxy, 2-methylcyclohexyloxy, 3-methylcyclohexyl Examples thereof include a oxy group, a 4-methylcyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
  • alkyl group having 1 to 6 carbon atoms represented by R 2 a methyl group, an ethyl group, a propyl group, an isopropyl group
  • examples thereof include a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group.
  • Examples of the alkenyl group having 3 to 8 carbon atoms represented by R 2 include an aryl group, a 1-butenyl group, a 1-pentenyl group, a trihexenyl group, a triheptenyl group,
  • Examples thereof include a 1-octenyl group and the like.
  • Examples of the alkynyl group having 3 to 6 carbon atoms represented by R 2 include a propargyl group, a 1-butynyl group, a 1-pentynyl group, and a trihexynyl group.
  • the number of carbon atoms represented by R 2 As the aralkyl group of ⁇ 8, a benzyl group,
  • Examples thereof include a 2-methylbenzyl group, a 3-methylbenzyl group, and a 4-methylbenzyl group.
  • examples of the leaving group represented by A include a halogen atom such as an iodine atom, a bromine atom, and a chlorine atom, or methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, and nitrogen. Sulfonates such as toluene sulphonate can be exemplified.
  • a method for producing the compound of the present invention will be described.
  • the 1,2,4-triazine derivative of the present invention can be produced according to the following synthesis route.
  • step-1 a condensation reaction of the thiosemicarbazide derivative (2) with a commercially available or synthesized a-ketocarboxylic acid ester (3.) according to the method described in JP-A-6-220027 is carried out, and the compound represented by the general formula (4)
  • step-1 a condensation reaction of the thiosemicarbazide derivative (2) with a commercially available or synthesized a-ketocarboxylic acid ester (3.) according to the method described in JP-A-6-220027 is carried out, and the compound represented by the general formula (4)
  • This is a step of obtaining a 2- (1-thiosemiforce rubazizono) acetic acid ester represented by the following formula:
  • the thiosemicarbazide derivative represented by the general formula (2) can be synthesized by treating a corresponding aniline derivative with thiophosgene to give an isothiocyanate, and then reacting with hydrazine.
  • the aniline derivative can be synthesized by converting the aniline derivative into dithiocarbamate using carbon disulfide and then reacting with hydrazine (see Reference Examples 1 to 3 below).
  • This reaction can be carried out in a solvent, and any solvent may be used as long as it does not hinder the progress of this reaction.
  • solvent examples include halogenated carbons such as dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, and the like.
  • Aromatic hydrocarbons such as xylene and benzene, fatty acids such as acetic acid and propionic acid, alcohols such as methanol, ethanol and propyl alcohol, ether, tetrahydrofuran and 1,4-dioxane Ethers such as xane and dimethyloxetane, ⁇ , ⁇ -dimethylformamide, dimethylsulfoxide, water and the like can be used, and these solvents can be used as a mixture.
  • the 2- (1-thiosemiforce rubazizono) acetic acid ester represented by 4) can be produced.
  • This 2- (1-thiosemi force rubazizono) acetic acid ester (4) can be used in the next step without isolation.
  • step-2 the cyclization reaction of 2- (thiosemi-forced rubazizono) acetic acid ester (4) in an organic solvent in the presence of a base or an acid is carried out to give 1,2, This is a step of producing a 4-triazine derivative.
  • Solvents that can be used in this reaction are not limited as long as they do not hinder the progress of this reaction.
  • dichloromethane, chloroform, carbon halides such as carbon tetrachloride, benzene, toluene, xylene, and benzene
  • Aromatic hydrocarbons alcohols such as methanol, ethanol, and propyl alcohol
  • ethers such as ether, tetrahydrofuran, 1,4-dioxane, and dimethyloxetane
  • ketones such as acetone, methylethylketone, and cyclohexanone
  • ⁇ -dimethylformamide, dimethylsulfoxide and the like can be used, and these solvents can be used as a mixture.
  • an inorganic base or an organic base can be used as the base that can be used in this reaction.
  • the inorganic base include potassium carbonate, sodium carbonate, sodium methoxide, sodium methoxide, and potassium permeate.
  • organic bases such as triethylamine, diisopropylethylamine, triptylamine, N-methylmorpholine, pyridine, picoline, lutidine, ⁇ , ⁇ -dimethylaniline, 4-t-butyl-N, N- Dimethylaniline and the like can be exemplified.
  • the amount of the base to be used is selected from the range of 0.1 to 10 equivalents based on 2- (1-thiosemicarbazizono) acetic acid ester (4).
  • An organic acid or an inorganic acid can be used as the acid that can be used in this reaction.
  • the organic acid include sulfonic acid, propionic acid, metal sulfonic acid, trifluorometal sulfonic acid, benzene sulfonic acid, and para toluene sulfonic acid.
  • the acid include inorganic acids, such as hydrochloric acid and sulfuric acid.
  • the amount of the acid to be used is selected from the range of 0.1 equivalent to the amount of the solvent with respect to 2- (thiosemi force rubazizono) acetic acid ester (4).
  • the 1,2,4-triazine derivative (la) that can be produced in this way is shown as having a structure in which the mercapto group at the 3-position is tautomeric to a thiocarbonyl group, but is chemically chemically modified. It is thought to exist as an equilibrium mixture with the carbonyl form, and the compounds of the present invention include these tautomers.
  • step 1 the 1,2,4-triazine derivative (la) is oxidized in the presence of a base in a mixed solvent of alcohol and water using an oxidizing agent to oxidize the thioxo group at the 3-position of the triazine ring.
  • This is a process for producing a 1,2,4-triazine derivative represented by the formula (lb) and having an oxo group at the 3-position of the triazine ring.
  • the alcohol solvent that can be used in this reaction may be any solvent as long as it does not inhibit the progress of this reaction, and methanol, ethanol, propanol, and the like can be used.
  • the mixing ratio of the alcohol solvent and water is selected from the range of the alcohol solvent / water ratio of 1/10 to 10/1.
  • sodium hydroxide sodium hydroxide, potassium hydroxide and the like can be used.
  • the amount of the base to be used is selected from the range of 0.1 to 10 equivalents based on the 3-thioxo-1,2,4-triazine derivative (la).
  • the oxidizing agent that can be used in this reaction it is preferable to use hydrogen peroxide in terms of a good yield.
  • step 4 the 1,2,4-triazine derivative (lb) is reacted with the compound represented by the general formula (5) in an organic solvent in the presence of a base, and R 2 is added onto the nitrogen atom at the 2-position.
  • R 2 is added onto the nitrogen atom at the 2-position.
  • three groups are introduced to produce a 1,2,4-triazine derivative (lc).
  • an inorganic base or an organic base can be used as the base that can be used in this reaction.
  • the inorganic base include potassium carbonate, sodium carbonate, sodium methoxide, sodium methoxide, and potassium permeate.
  • Organic bases such as 1-butoxide, sodium hydride, sodium amide, potassium amide and the like, for example, triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, Examples include pyridine, picoline, lutidine, N, N-dimethylaniline, 4t-butyl- ⁇ , ⁇ -dimethylaniline and the like.
  • the solvent that can be used in this reaction may be any solvent that does not hinder the progress of this reaction.
  • examples include halogenated carbons such as dichloromethane, chloroform, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethers such as ether, tetrahydrofuran, 1,4-dioxane, and dimethoxetane, ⁇ , ⁇ -dimethylformamide, ⁇ -methylpyrrolidone, Dimethyl sulfoxide and the like can be used, and these solvents can be used alone or as a mixture.
  • a halogen atom such as an iodine atom, a bromine atom, a chlorine atom or the like, or methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, para Sulfonates such as toluenesulfonate
  • sulfonates include acetonyl mesylate, acetonyl tosylate, aryl mesylate, arynoletosylate, amyl mesylate, amyl tosylate, benzyl mesylate, benzyl tosylate, 2-benzyl benzyl mesylate, 2-benzyl benzyl tosylate, and 3-benzyl benzyl tosylate.
  • Benzyloxybenzyl mesylate 3-benzyloxy Benzyl tosylate, 4-benzyloxybenzyl mesylate, 4-benzyloxybenzyl tosylate, 4-benzyloxy-2-butenyl mesylate, 4-benzyloxy-2-butenyl tosylate, 2-benzyloxy Xicetyl mesylate, 2-benzyloxysheltyl tosylate, 3-benzyloxypropyl mesylate, 2-benzyloxypropyl tosylate, 2-biphenylmethyl mesylate, 2-biphenylmethyl tosylate, 4-biphenyl Nylmethyl mesylate, 4-biphenylmethyl tosylate, 3,5-bis (trifluoromethyl) benzyl mesylate, 3,5-bis (trifluoromethyl) benzyl tosylate, 2-bromobenzyl mesylate, 2-bromobenzyl tosylate,
  • Examples thereof include 2-pentyl mesylate and 2-pentyl citrate. As described above, some of these sulfonates are commercially available and can be easily obtained. It can be easily produced by reacting.
  • the amount of the compound represented by the general formula (5) is 1,2,4-triazine derivative It is preferable to use 1.0 to 50 equivalents to (lb) in terms of good yield.
  • the amount of the base used is not particularly limited in the case of an organic base, and is 1.0 to 2.5 equivalents in terms of metal for an inorganic base, based on the 1,2,4-triazine derivative (lb). Is preferred in terms of good yield.
  • IRCKBr disk, cm- 1 3390, 2970, 1730, 1680. 1600, 1500, 1440, 1410, 13 80, 1300, 1260, 1200.
  • IRCneat, cnr 1 3560, 3390, 3080.3020, 2960, 2870, 2440, 1730, 1680, 1600, 1500, 1440, 1410, 1380, 1280, 1260, 1200, 1140, 1090, 1030.
  • IR (neat, cm “ 1 ): 2960, 1730, 1680, 1610, 1500, 1440, 1410, 1380, 1310, 1260, 1200, 1040.
  • IRCKBr disk, cnr 1 2960, 1760, 1730, 1680, 1610, 1500, 1440, 1410, 13 10, 1200, 1020.
  • IRCKBr disk, cnr 3250, 2940, 1730, 1670, 1500, 1440, 1400, 1230, 12 00.
  • the desiccant was separated, and the filtrate was concentrated to obtain a crude product.
  • Acetic acid 40 mL was added to the crude product, and the mixture was stirred under reflux with heating for 5 hours. After completion of the reaction, the reaction solution was poured into ice water (100L) and extracted with dimethyl ether (100 mL x 2). The organic layers were combined, washed with saturated chloride Na Bok potassium solution, ⁇ the c desiccant and dried over anhydrous magnesium sulfate to give the crude product by concentrating the Ura liquid.
  • reaction solution was extracted with getyl ether (100 mL ⁇ 3).
  • the organic layers were combined and washed with a saturated aqueous sodium chloride solution (50 mL).
  • the organic layer was dried with anhydrous magnesium sulfate. After separating the desiccant, the solvent was distilled off from the solution under reduced pressure.
  • reaction solution was extracted with Jetil ether (100 mL ⁇ 3). The organic layers were combined and washed with a saturated aqueous sodium chloride solution (50 mL). The organic layer was dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off from the solution under reduced pressure.
  • IRCKBr disk, cm- 1 3330, 2360, 1700, 1610, 1500, 1380, 1260, 1190.
  • IRC Br disk cm—3240, 2970, 1740, 1680, 1600, 1500, 1440, 1400, 12 40, 1200.
  • IRCneat, cnr ' 3140, 3070, 2960, 2250, 2130, 2040, 1710, 1610, 1500, 1450, 1420, 1400, 1380, 1330, 1270, 1200, 1060, 1030.
  • IRCKBr disk, cnr 3270, 2940, 1680, 1610, 1490, 1410, 1260, 1190, 1 050, 1020.
  • reaction mixture was cooled to room temperature, poured into ice water (50 niL), and extracted with getyl ether (100 mL ⁇ 3). The organic layers were combined and washed with water (50fflL x 5). The organic layer was dried over anhydrous magnesium sulfate, and after removing the desiccant, the solvent was distilled off under reduced pressure from the rapa solution. The obtained solid is washed with hexane and dried to give 4- (4-chloro-2-fluoro-5- (1-methyl-2-propynyl) oxyphenyl) -6-isopropyl-3-. A yellowish white solid (6.23 g, yield 94.8) of thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-5-one was obtained.
  • the pH of the solution was adjusted to 1 by dropwise addition of concentrated hydrochloric acid to the reaction solution at room temperature.
  • the reaction mixture was cooled to room temperature, poured into ice water (50 mL), and extracted with getyl ether (100 mL ⁇ 3). The organic layers were combined and washed with water (50 mL ⁇ 5). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and then the solvent was distilled off from the solution under reduced pressure.
  • the desiccant was filtered off, and the crude solution was concentrated to obtain a crude product.
  • Acetic acid 40 mL was added to this crude product, and the mixture was stirred for 5 hours under reflux with heating. After completion of the reaction, the reaction solution was poured into ice water (100 mL) and extracted with getyl ether (100 mL ⁇ 2). The organic layers were combined, washed with saturated chloride Na Bok Riumu solution, ⁇ the c desiccant and dried over anhydrous magnesium sulfate to give the crude product by concentrating the 3 ⁇ 4 solution.
  • the crude product was obtained by concentrating the solvent, and the crude product was washed with getyl ether hexane and dried to obtain 6-i-butyl-4- (4 -Black mouth-5-cyclopentyloxy-2-fluorophenyl) -3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-5-one yellow solid (3. 80 g, yield 95.53 ⁇ 4) was obtained.
  • reaction solution was extracted with getyl ether (100 mL ⁇ 3).
  • the organic layers were combined and washed with a saturated aqueous sodium chloride solution (50 mL).
  • the organic layer was dried with anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off from the solution under reduced pressure.
  • IRCKBr disk cm—3240, 2960, 1740, 1680, ⁇ 610, 1500, 1440, 1400, 12 00.
  • IRCKBr disk, cnr 3270, 2970, 1670, 1610, 1530, 1490, 1410, 1260, ⁇ 90.
  • IRCKBr disk, cm- 1 3310, 3290, 3040, 2950, 2870, 2540, 1700, 1680, 16 10, 1540, 1190, 1140, 1050, 1020.
  • reaction solution was extracted with ethyl ether (100 mL ⁇ 3). Combine the organic layers and add sat. Washed with aqueous lithium solution (50 mL). The organic layer was dried with anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off from the filtrate under reduced pressure.
  • reaction solution was extracted with ethyl ether (100 mL ⁇ 3). The organic layers were combined and washed with a saturated aqueous solution of sodium chloride (50 mL). The organic layer was dried over anhydrous magnesium sulfate. After separating the desiccant, the solvent was distilled off from the mixture under reduced pressure. C The resulting product was purified by silica gel chromatography (developing solution: hexane and ethyl acetate -5: 1).
  • IRC Br disk, cm- 1 3230, 2960, 1740. 1680, 1480, 1430, 1360, 1260, 1 220, 1200.
  • IRCKBr disk, cm- 1 3240, 3130, 2960, 1740, 1670, 1600, 1500, 1440, 14 00, 1240, 1200.
  • IRCKBr disk, cnr 3260, 3170, 2960, 1630, 1600, 1530, 1470, 1410, 12 60, 1180.
  • IRCKBr disk, cm ' 1 3380, 3200, 2970, 2680, 1610, 1540, 1500, 1420, 13 40, 1240.
  • the compound of the present invention thus obtained is excellent as a herbicide as described above. It has excellent performance.
  • the compound of the present invention can be used as it is, but in general, one or more adjuvants can be mixed and used as a herbicide.
  • various carriers, extenders, solvents, surfactants, stabilizers, etc. are blended and formulated in the usual manner, for example, into wettable powders, emulsions, powders, granules, flowables, etc. It is preferable to use it.
  • Examples of the solvent which is one of the auxiliary agents in the herbicide containing the compound of the present invention as an active ingredient include water, alcohols, ketones, ethers, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, and the like. Suitable are acid amides, esters, nitriles and the like, and one or a mixture of two or more of these are used.
  • a surfactant may be used as a spreading agent, a dispersant, an emulsifier, or a penetrant.
  • the surfactant include a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. These surfactants are utilized as one type or a mixture of two or more types depending on the application.
  • Preferable methods of using the herbicide containing the compound of the present invention as an active ingredient include soil treatment, water surface treatment, foliage treatment, and the like. Particularly superior effects are obtained by application from the time before germination of the control weeds to the time of germination. be able to.
  • Herbicides containing the compound of the present invention as an active ingredient include other active ingredients which do not inhibit the herbicidal activity of the present active ingredient, such as other herbicides, insecticides, fungicides, plant growth regulators and the like. Can be mixed or used together It is.
  • Manufacturing example-3 (granules)
  • a 1 / 10,000 are pot is filled with paddy soil, and after shaving, seeds of radish, tamagayalli, firefly, pine tree, and other annual broadleaf weeds are sown, and 2.5-leaf rice (cultivar: Koshihikari) was transplanted and kept in flooded state.
  • the present invention prepared according to the formulation example one day later The wettable powder or emulsion of the compound was diluted and processed to a predetermined dose per are. Fifteen days after the treatment, the herbicidal effect on the test weeds and the phytotoxicity on the rice were investigated using the criteria shown in Table 5, and the results are shown in Table 7. Table 7 Effect of pre-soil treatment on paddy soil
  • test compound No. is indicated by the compound number in Tables 1 to 4, the test compound A indicates chloronitrophen in Table 6, and the test compound B indicates acifluorfurun in Table 6.
  • the 1,2,4-triazine derivative of the present invention can be used for various weeds which are problematic in soil treatment and foliage treatment in upland fields, for example, broadleaf weeds such as Shiroza, Aobu, Ichibi and Yaegura, and grasses such as Nobie and Mehishiba. Miscellaneous It has an excellent herbicidal effect even on low-dose treatment of grass, and does not show any phytotoxicity which is a problem for major crops such as corn and wheat.
  • the compound of the present invention can be used for various weeds which are problematic in paddy fields, for example, grass weeds such as sand flies, broadleaf weeds such as azena, kikasigusa, and mizochobe, paddy field weeds such as fireflies and pine trees. It has an excellent herbicidal effect even at low doses, and has very little phytotoxicity to transplanted rice.
  • the high selectivity of the compound of the present invention for crops is completely unexpected from conventional 1,2,4-triazine derivatives, and this characteristic is clearly attributable to halogen atoms at the 2- and 4-positions on the phenyl ring. It is also obtained by introducing an alkoxy group, an alkenyloxy group, an alkynyloxy group, a cycloalkyloxy group, or an aryloxy group at the 5-position.
  • the present invention provides novel 1,2,4-triazine derivatives having high selectivity for crops and strong herbicidal activity against weeds, and further provides an industrial production method for these compounds. I do.

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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)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des dérivés de 1,2,4-triazine représentés par la formule générale (1) et possédant d'excellents effets comme principe actif efficace d'un herbicide, ainsi qu'un procédé pour leur production. Dans ladite formule, X1 représente halogéno; X2 représente halogéno; X3 représente alcoxy C¿1-12?, alcényloxy C3-6, alcynyloxy C3-6, cycloalkyloxy C3-10 ou bien aralkyloxy C7-8; R?1¿ représente hydrogène, alkyle C¿1-12?, alcényle C3-8, cycloalkyle C3-8, cycloalcényle C3-8 ou bien phényle, R?3¿ représente hydrogène, alkyle C¿1-12?, alcényle C3-8, alcynyle C3-6, cycloalkyle C3-8 ou bien aralkyle C7-8; et Y représente oxygène ou soufre. Ces composés peuvent être produits par réaction d'un 4-(2,4-dihalogéno-5-alcoxyphényl)thiosemi-carbazide avec un α-céto-ester et ils exercent un excellent effet herbicide dans les traitements des terres en milieu sec et des terres de rizières ainsi que dans les traitements du feuillage.
PCT/JP1996/000077 1995-01-20 1996-01-19 Derives de 1,2,4-triazine, procede pour leur production, et herbicide les contenant comme principe actif WO1996022285A1 (fr)

Priority Applications (1)

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AU44586/96A AU4458696A (en) 1995-01-20 1996-01-19 1,2,4-triazine derivatives, process for producing the same, and herbicide comprising the same as active ingredient

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JP733395 1995-01-20
JP7/7333 1995-01-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0869123A2 (fr) * 1997-03-31 1998-10-07 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
WO2008056257A2 (fr) * 2006-11-10 2008-05-15 Addex Pharma S.A Nouveaux dérivés de triazinedione en tant que modulateurs du récepteur gaba-b
US10081608B2 (en) 2010-06-29 2018-09-25 Fmc Corporation 6-acyl-1,2,4-triazine-3,5-dione derivative and herbicides

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EP0438717A2 (fr) * 1990-01-26 1991-07-31 Bayer Ag 1,2,4-Triazine-3,5-diones trisubstitués et intermédiaires
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WO1986000072A1 (fr) * 1984-06-12 1986-01-03 Fmc Corporation 2-aryl-1,2,4-triazine-3,5(2h,4h)-diones herbicides et leurs analogues sulfures
US5298502A (en) * 1988-12-12 1994-03-29 Fmc Corporation Method and composition for photodynamic treatment and detection of tumors
EP0438717A2 (fr) * 1990-01-26 1991-07-31 Bayer Ag 1,2,4-Triazine-3,5-diones trisubstitués et intermédiaires

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CHEMICAL ABSTRACTS, Abstract No. 116:117114, (1992), LU ZHONGE; XU TIANLIN; SHI XIAODONG, "Synthesis of 4, 6-Disubstituted 5-Thioxo-1,2,4-triazin-3-one from Benzothio Formanilide"; & CHIN. CHEM. LETT., 1991, 2(7), 525-526 (English). *
CHEMICAL ABSTRACTS, Abstract No. 117:111576, (1992), LU ZHONGE; SUN DAQING; XU TIANLIN; WAN JUN; XU LECUN; CHEM KEQIAN, "New Heterocycle Forming Reactions of Acyl Thioformanilides"; & ORG. PREP. PROCED. INT., 1992, 24(3), 358-362 (English). *
CHEMICAL ABSTRACTS, Abstract No. 98:179331, (1983), EL-BAHAIE, SAID A; BADAWY MOHAMED A.; ABDEL-HADY, SAYED A.; IBRAHIM YEHIA A., "Rearrangement and Alkylation of Some 1,2,4-Triazine Derivatives"; & HETEROCYCLES, 1983, 20(1), 51-54 (English). *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0869123A2 (fr) * 1997-03-31 1998-10-07 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
EP0869123A3 (fr) * 1997-03-31 2002-01-02 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
AU2007319000B2 (en) * 2006-11-10 2013-05-23 Addex Pharma S.A Novel triazinedione derivatives as GABA-B receptor modulators
WO2008056257A3 (fr) * 2006-11-10 2008-07-17 Addex Pharmaceuticals Sa Nouveaux dérivés de triazinedione en tant que modulateurs du récepteur gaba-b
JP2010509312A (ja) * 2006-11-10 2010-03-25 アデックス ファーマ ソシエテ アノニム Ｇａｂａｂ受容体調節因子としての新規トリアジンジオン誘導体
US8344138B2 (en) 2006-11-10 2013-01-01 Addex Pharma S.A. Triazinedione derivatives as GABAB receptor modulators
WO2008056257A2 (fr) * 2006-11-10 2008-05-15 Addex Pharma S.A Nouveaux dérivés de triazinedione en tant que modulateurs du récepteur gaba-b
AU2007319000B8 (en) * 2006-11-10 2013-09-12 Addex Pharma S.A Novel triazinedione derivatives as GABA-B receptor modulators
AU2007319000A8 (en) * 2006-11-10 2013-09-12 Addex Pharma S.A Novel triazinedione derivatives as GABA-B receptor modulators
EP2662366A1 (fr) * 2006-11-10 2013-11-13 ADDEX Pharma S.A. Derivés de triazindion comme modulateurs de récepteur GABA-B
US8779129B2 (en) 2006-11-10 2014-07-15 Addex Pharma S.A. Triazinedione derivatives as GABAB receptor modulators
EA020132B1 (ru) * 2006-11-10 2014-08-29 Аддекс Фарма С.А Новые производные триазиндиона в качестве модуляторов рецептора гамк
NO344044B1 (no) * 2006-11-10 2019-08-19 Addex Pharma Sa Nye triazindionderivater som GABA-B-reseptormodulatorer
US10081608B2 (en) 2010-06-29 2018-09-25 Fmc Corporation 6-acyl-1,2,4-triazine-3,5-dione derivative and herbicides

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