WO1999025700A1 - Derives de triazole, leurs intermediaires de production, leurs procedes de production et herbicides contenant les derives en tant que principe actif - Google Patents

Derives de triazole, leurs intermediaires de production, leurs procedes de production et herbicides contenant les derives en tant que principe actif Download PDF

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Publication number
WO1999025700A1
WO1999025700A1 PCT/JP1998/004890 JP9804890W WO9925700A1 WO 1999025700 A1 WO1999025700 A1 WO 1999025700A1 JP 9804890 W JP9804890 W JP 9804890W WO 9925700 A1 WO9925700 A1 WO 9925700A1
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Prior art keywords
group
carbon atoms
reaction
triazol
methyl
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PCT/JP1998/004890
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English (en)
Japanese (ja)
Inventor
Tomoyuki Yano
Tomoko Yoshii
Kazuhisa Ikemoto
Kenji Hirai
Ryuta Ohno
Takuya Ueda
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Sagami Chemical Research Center
Kaken Pharmaceutical Co., Ltd.
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Application filed by Sagami Chemical Research Center, Kaken Pharmaceutical Co., Ltd. filed Critical Sagami Chemical Research Center
Priority to AU96502/98A priority Critical patent/AU9650298A/en
Publication of WO1999025700A1 publication Critical patent/WO1999025700A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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

  • Triazole derivatives intermediates for their production, methods for their production, and herbicides containing them as active ingredients
  • the present invention relates to novel triazole derivatives, intermediates for producing the same, methods for producing them, and herbicides containing them as active ingredients.
  • triazole derivatives having a herbicidal activity at the 1-position having a rubamoyl group for example, Japan Kokai Tokkyo Koho JP 57/148606, Japan Kokai Tokkyo Koho JP 59/39880, EP 422369 (Japan Kokai Tokkyo Koho JP 03 / Compounds described in Japanese Patent No. 99066), Japan Kokai Tokkyo Koho JP 05/140124 (Chemical Abstracts 119: 271169) and Japan Kokai Tokkyo Koho JP 05/194432 (Chemical Abstracts 119: 175893) are known.
  • the triazole derivatives described in these patent specifications have inferior herbicidal effects on weeds as shown in the test examples below, or those with strong activity have low safety on crops. It is not always a satisfactory compound.
  • a triazole in which the sulfur atom at the 3-position of the triazole ring is substituted by an alkyl group having a cyano group or an alkoxycarbonyl group at the 1-position.
  • a carbamoyltriazole derivative having insecticidal activity is known as an approximate compound of the compound of the present invention (US Pat. No. 3,308,131), but there is no description about a compound having a sulfur atom oxidized. Disclosure of the invention
  • the present invention provides a novel triazole derivative having excellent herbicidal activity and high crop selectivity, a method for producing the same, and a herbicide containing these derivatives as an active ingredient.
  • the present inventors have conducted intensive studies for a herbicide having excellent herbicidal activity and crop selectivity.
  • the triazole derivative of the present invention represented by the following general formula (1) causes harm to crops.
  • the present invention has been found to have excellent herbicidal activity without application at a low dose, and to have a simple production method for these.
  • the present invention provides a compound represented by the general formula (1):
  • R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, halogen
  • R 3 represents a cyano group or C00R Represents 1 and R 7 is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, optionally substituted by a halogen
  • R 5 each independently represents an Ararukiru group with carbon number ⁇ 11, hydrogen atom, a substituted optionally alkyl group of good 1 to 12 carbon atoms, the optionally substituted number 3 of 8 carbon Charcoal optionally substituted by cycloalkyl group or halogen atom
  • ⁇ and R 5 may be combined with the bonded carbon atom to form an optionally substituted ring.
  • R 4 or R 5 may be combined with an atomic group bonded together with R 7 to form an optionally substituted ring.
  • n represents an integer of 0 to 2. However, when n is 0 and R 3 is a cyano group or R 7 is C00R 7 which is an alkyl group having 1 to 12 carbon atoms, and R 5 cannot be hydrogen atoms at the same time. ),
  • a production intermediate represented by general formula (2)
  • R s represents a hydrogen atom or a group represented by R s C0
  • R 9 represents a chlorine atom, and has 1 to 1 carbon atoms.
  • 6 represents an alkyloxy group or a phenyloxy group which may be substituted.
  • X represents the same meaning as described above.
  • X represents a chlorine atom, an alkyloxy group having 1 to 6 carbon atoms, or a phenoxy group which may be substituted.
  • the present invention relates to a method for producing a triazole derivative represented by the formula:
  • a triazole derivative represented by R 6 (wherein R 3 , R ⁇ R 5 and R s have the same meanings as described above);
  • ir is an alkyl group having 1 to i2 carbon atoms which may be substituted, a cycloalkyl group having 3 to 8 carbon atoms which may be substituted, or a carbon atom which may be substituted with a halogen atom having 3 to 8 carbon atoms.
  • 12 alkenyl groups, an alkynyl group having 3 to 6 carbon atoms which may be substituted by a halogen atom, D also represents an aralkyl group having 7 to 11 carbon atoms or a phenyl group which may be substituted.
  • R 1 ′ R 3 R ⁇ R 5 and R 6 have the same meanings as described above.
  • the present invention also relates to a method for producing a triazolyl derivative represented by the formula:
  • R 4 , R ⁇ R 5 and n represent the same meaning as described above, and R is an optionally substituted alkyl group having 1 to 12 carbon atoms, and an optionally substituted 3 to 8 carbon atoms.
  • a cycloalkyl group, an alkenyl group having 3 to 12 carbon atoms which may be substituted by a halogen atom, or an alkenyl group having 7 to 11 carbon atoms which may be substituted represents an aralkyl group.
  • R ie represents Karubamo I le group represented by hydrogen or RHCO, R 1 and R 2 are as defined above. However, when Ri is a hydrogen atom, n is 0.
  • Ri is a hydrogen atom
  • n is 0.
  • R 4 R ⁇ R s R 7 ′ and n represent the same meaning as described above. However, when R 1 ′′ is a hydrogen atom, n is 0.) It relates to a method of manufacturing.
  • R 2 > NR 4
  • R 5 ′ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and a carbon atom optionally substituted with a halogen atom.
  • R 2 , R 3 , R ⁇ R 3 ′, R s and m have the same meanings as described above).
  • the present invention relates to a herbicide comprising a triazole derivative represented by the following formula: BEST MODE FOR CARRYING OUT THE INVENTION
  • the alkyl group having 1 to 12 carbon atoms represented by R 1 , R 2 , R ⁇ R ⁇ V, R 7 and R 7 ′ may be linear or branched.
  • alkyl groups include a halogen atom, a cycloalkyl group having 3 to 8 carbon atoms, a cyano group, a nitro group, an alkylthio group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. May be substituted by one or more of a carbonyl group, an acyl group having 1 to 6 carbon atoms, and more specifically, a 2-chloroethyl group, a 3-chloropropyl group, a 3-fluoropropyl group, and a cycloalkyl group.
  • R ⁇ R 1 Examples of the cycloalkyl group ', R 2, R ⁇ R ⁇ R 5', R 7 and R 7 carbon atoms 3 represented by '1-8, cyclopropyl group, cyclobutyl group, shea Kuropenchiru group, Examples thereof include a cyclohexyl group and a cyclooctyl group. Further, these cycloalkyl groups may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a cyano group, or the like.
  • R ⁇ R :, R 2, R ⁇ R ⁇ R, the number 3-12 carbons represented by R 'and R 7' ⁇ Q
  • the alkenyl group may be linear, branched or cyclic, or may be displaced, and may be a 1-propenyl group, an aryl group, a 2-methyl-2-propenyl group, a 2-butenyl group. , 3-butenyl, 2-pentenyl, 3-pentenyl, 1-cyclopentenyl, 2-hexenyl, 3-hexenyl, 1-cyclohexenyl, 2-heptenyl, tricyclooctenyl And the like.
  • alkenyl groups may be substituted with a halogen atom or the like, for example, a 2-chloro-2-propenyl group, a 3-chloro-2-propenyl group, a 4-chloro-2-butenyl group. And the like.
  • the alkynyl group having 3 to 6 carbon atoms represented by RR 1 ′, R 2 , R ⁇ R 5 and R 5 ′ may be linear or branched, and may be a propargyl group, 1 Examples thereof include -butyn-3-yl group, 3-methyl-1-butyn-3-yl group, 2-butynyl group, 2-pentynyl group, and 3-pentynyl group.
  • alkynyl groups may be substituted with a halogen atom or the like, for example, 3-fluoro-2-propynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, -Bromo-2-butynyl group, 4-bromo-3-butynyl group and the like.
  • R ', R 1' as the Ararukiru groups R 2, R ⁇ R ⁇ R 5 ', carbon atoms represented by R 1 and R 7 7 to 11, benzyl group, 1-Fuweniruechiru group, 2-phenylene Examples thereof include a rutile group, a 1-phenylpropyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.
  • a halogen atom an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, and an alkyloxycarbonyl having 1 to 6 carbon atoms It may be substituted one or more times with a group, carboxy group, cyano group, nitro group and the like.
  • R ⁇ R 1, R ⁇ IT and ⁇ substituted by a substituent on Fuweniru ring which may Fuweniru group optionally halogen atom represented, ⁇ alkyl group having 1 to 12 carbon atoms, the number 1-6 carbons Haloalkyl group, alkyl having 1 to 6 carbon atoms ⁇ ⁇
  • Examples thereof include an alkoxy group, an alkyloxycarbonyl group having 1 to 6 carbon atoms, a carboxy group, a cyano group, and a nitro group.
  • the alkyl groups on these alkyloxycarbonyl groups include a halogen atom, a cycloalkyl group having 3 to 8 carbon atoms, a cyano group, a nitro group, an alkylthio group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. May be substituted by one or more of an alkyloxy group of 1 to 6 carbon atoms, an alkyloxycarbonyl group of 1 to 6 carbon atoms, and an acyl group of 1 to 6 carbon atoms.
  • Examples of the halogen atom represented by R s include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a pentyl group. it can.
  • Examples thereof include an oxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and a pentyloxy group.
  • the substituent on the phenyl ring of the optionally substituted phenoxy group represented by R & is a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkyl group having 1 to 6 carbon atoms. Examples thereof include an alkyloxy group, an alkyloxycarbonyl group having 1 to 6 carbon atoms, a carboxy group, a cyano group, and a nitro group.
  • heterocyclic group formed integrally with the nitrogen atom to which R 1 and R 2 are bonded examples include a piperidino group, a piperazino group, a morpholino group, a pyrrolidino group, and the like.
  • One or more alkyl groups such as 1 to 6 may be substituted.
  • Examples of the ring formed integrally with the carbon atom to which R 4 and R 5 are bonded include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like. These include a halogen atom and a carbon atom having 1 carbon atom. It may be substituted with one or more alkyl groups such as 6 to 6.
  • an a-ptyrolactone ring As the ring formed integrally with the atomic group in which R 5 is bonded together with R 7 , an a-ptyrolactone ring, an a-pa'relolactone ring, a p-a-lactolactone ring, etc. should be exemplified. These may be substituted one or more times with a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the like.
  • a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, or a methanesulfonyloxy group or a trifluoromethanesulfonyloxy group
  • the alkyloxy group having 1 to 6 carbon atoms represented by X includes methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy.
  • a tert-butyloxy group, a pentyloxy group and the like examples include a halogen atom, an alkyl group having 1 to 12 carbon atoms, Examples thereof include a haloalkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, a carboxy group, a cyano group, and a nitro group.
  • the triazole derivative of the present invention can be produced, for example, by the following production method.
  • Production method 1 is 3-mercapto-1,2,4-triazole.
  • the derivative (4) is reacted with the compound (3) to produce the triazole derivative (2a) of the present invention, and then the triazole derivative (2a) is reacted with the tribasyl compound (5).
  • Step 1 consists of a 3-mercapto-1,2,4-triazole derivative (4) and a compound
  • the reaction must be carried out in the presence of a base
  • usable bases include triethylamine, tributylamine, and N-methylmorpholine.
  • Organic amines such as phosphorus, pyridine and dimethylaniline, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium bicarbonate, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydride and sodium amide
  • An example of the metal base can be exemplified.
  • the amount of the base to be used is not particularly limited, but it is preferable to use the base in an amount equal to or more than that of the reaction substrate in terms of good yield.
  • the reaction is preferably carried out in a solvent, and any solvent that does not harm the reaction can be used.
  • solvent examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene, methyl ether, and the like.
  • Ether solvents such as tetrahydrofuran, dioxane, 1,2-dimethoxetane (DME), halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc., ketones such as acetone and methylethylketone, and acetonitrile , Nitriles such as propionitrile, esters such as ethyl acetate and ethyl propionate, amides such as N, N-dimethylformamide (MF), N-methylpyrrolidone, dimethyl sulfoxide (DMS0); Water or a mixed solvent thereof can be used.
  • DME 1,2-dimethoxetane
  • halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc.
  • ketones such as acetone and methylethylketone
  • acetonitrile Nitriles such as propionitrile
  • the reaction temperature varies depending on the base used, and is selected from the range of -10 to 150 ° C. It is preferable to carry out the reaction in the range of around 0 ° C to the reflux temperature of the reaction mixture in terms of good yield.
  • the reaction After the completion of the reaction, if necessary, it can be purified by column chromatography or the like, if necessary, to obtain the desired product by a normal extraction operation. Further, the triazole derivative (2a) can be used as it is in the next step 12 without isolation.
  • the compound (3) in which R 3 is an ester is obtained by reacting a 2-halocarboxylic acid chloride derivative with an alcohol, or forming a hydroxyl group of a 2-hydroxycarboxylic acid derivative into a halogen atom or an alkane.
  • 15 can be produced by converting to an arenesulfonyloxy group according to a conventional method.
  • the 2-hydroxycarboxylic acid derivative serving as a raw material can be produced by a method of hydrolyzing a cyano group of a cyanohydrin derivative obtained by reacting a carbonyl compound with cyanuric acid or a method of alcoholysis.
  • the / 3, ⁇ -unsaturated -hydroxycarboxylic acid derivative contained in the raw material 2-hydroxycarboxylic acid derivative can be obtained by the method described in EP 153692 (Japan Kokai Tokkyo Koho JP 60/179147) or the method described therein.
  • the 2-hydroxycarboxylic acid derivative can also be produced by reducing the double bond of this ⁇ , ⁇ -unsaturated-hydroxy-carboxylic acid derivative. Can be manufactured.
  • Step 12 is a step of reacting the triazole derivative (2a) with the carbamoyl compound (5) in the presence of a base to produce the triazole derivative (la) of the present invention.
  • the reaction must be carried out in the presence of a base
  • usable bases include organic amines such as triethylamine, triptylamine, N-methylmorpholine, pyridine and dimethylaniline, potassium carbonate, and sodium carbonate. , Hydrogen bicarbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, sodium hydride, sodium amide, and the like.
  • the amount of the base used is not particularly limited, but it is preferable to use the base in an amount equal to or more than that of the reaction substrate in terms of a good yield.
  • the reaction is preferably performed in a solvent, and any solvent that does not harm the reaction can be used.
  • a solvent for example, benzene, toluene, xylene, ,
  • Aromatic hydrocarbon solvents such as benzene, etc., ether solvents such as dimethyl ether, tetrahydrofuran, dioxane, DME, etc., halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc.
  • Ketones such as tilethyl ketone; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate and ethyl propionate; amides such as DMF and N-methylpyrrolidone; DMS0; water; or a mixture thereof.
  • Solvents can be exemplified.
  • the reaction temperature varies depending on the base used, and is selected from the range of -10 to 150 ° C. However, it is preferable to carry out the reaction in the range from around 0 ° C to the reflux temperature of the reaction mixture, since the yield is good. preferable.
  • the desired product can be obtained by a usual extraction operation. If necessary, purification can be performed by column chromatography or the like.
  • the rubamoyl compound (5) used in the step 2 can be easily produced by reacting a commercially available amine corresponding to a part of the corresponding amine with phosgene or a phosgene equivalent according to a conventional method.
  • the production method 2 comprises a triazole derivative (2a), an acylating agent (6) To produce the triazole derivative (2b) of the present invention, and then reacting this with an amine (7) to obtain the triazole derivative of the present invention.
  • 2 shows a method for producing the body (la).
  • Step-3 is a step of reacting the triazole derivative (2a) with the acylating agent (6) to produce the triazole derivative (2b) of the present invention.
  • acylating agent (6) used in this reaction examples include phosgene, phosgene equivalents, and haloformates. Although some haloformate esters are commercially available, they can be easily produced by reacting the corresponding alcohol with phosgene or a phosgene equivalent according to a conventional method.
  • the reaction between the triazole derivative (2a) and phosgene or a phosgene equivalent is preferably performed in an organic solvent, and any solvent that does not harm the reaction can be used.
  • organic solvent any solvent that does not harm the reaction can be used.
  • benzene, toluene, xylene examples thereof include aromatic hydrocarbon solvents such as benzene and ethyl ester, esters such as ethyl acetate and ethyl propionate, and mixed solvents thereof.
  • the reaction temperature is selected from the range of ⁇ 10 to 150 ° C., but it is preferable to carry out the reaction in the range of 0 ° C. to the reflux temperature of the reaction mixture from the viewpoint of good yield.
  • a force product capable of obtaining the desired product by a usual isolation operation can be used in the next step without isolation.
  • the reaction of the triazole derivative (2a) with the haloformates be carried out in the presence of a base.
  • bases include triethylamine, tributylamine, N-methylmorpholine and pyridine.
  • Organic amines such as dimethylaniline, sodium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, sodium hydroxide, sodium hydride, sodium hydroxide, etc.
  • a group can be exemplified.
  • the amount of the base used is not particularly limited, but it is preferable to use the base in an amount equal to or more than the amount of the reaction substrate in terms of good yield.
  • the reaction is preferably carried out in an organic solvent.
  • Any solvent can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene, ether solvents such as dimethyl ether, tetrahydrofuran, dioxane, and DME, dichloromethane, and the like.
  • Halogen solvents such as carbon form, carbon tetrachloride, etc., ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, esters such as ethyl acetate and ethyl propionate, DMF, N
  • Examples include amides such as -methylpyrrolidone, DMS0, or a mixed solvent thereof.
  • the reaction temperature varies depending on the base to be used and is selected from the range of -10 to 150 ° C. It is preferable to carry out the reaction in the range of around 0 ° C to the reflux temperature of the reaction mixture from the viewpoint of good yield.
  • the product can be purified by a column chromatography or the like, if necessary, by an ordinary extraction operation.
  • the product can be used in the next step without isolation.
  • Step 14 is a step in which the triazole derivative (2b) is reacted with the amine (7) in the presence of a base to produce the triazole derivative (la) of the present invention. It is essential that the reaction is carried out in the presence of a base, and usable base groups include triethylamine, triptylamine, N-methylmorpholine, pyridine, dimethylaniline, 1,8-diazabicyclo.4.0] ⁇ Organic amines such as ndecene-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane, potassium carbonate, Examples thereof include alkali metal bases such as sodium carbonate, sodium bicarbonate, sodium bicarbonate, sodium hydroxide, sodium hydroxide, sodium hydride, and sodium amide.
  • base groups include triethylamine, triptylamine, N-methylmorpholine, pyridine, dimethylaniline,
  • the amount of the base to be used is not particularly limited, but it is preferable to use the base in an amount equal to or more than that of the reaction substrate in terms of good yield.
  • the reaction is preferably carried out in an organic solvent, and any solvent that does not harm the reaction can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene, Ether solvents such as mono-ter, tetrahydrofuran, dioxane, DME, etc .
  • halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc .
  • ketones such as acetone and methyl ethyl ketone
  • acetonitrile propionitrile etc.
  • examples thereof include nitriles, esters such as ethyl acetate and ethyl propionate, amides such as DMF and N-methylpyrrolidone, DMS0, and a mixed solvent
  • the reaction temperature varies depending on the base used, and is selected from the range of -10 to 150 ° C. However, it is preferable to carry out the reaction in the range from around 0 ° C to the reflux temperature of the reaction mixture, since the yield is good. preferable.
  • the product can be purified by column chromatography or the like, if necessary, to obtain the desired product by a normal extraction operation.
  • Production method 13 is a method for producing a triazole derivative (lb) of the present invention by reacting a triazole derivative (2a) with an isocyanate (8).
  • the reaction is preferably performed in an organic solvent, and any solvent that does not harm the reaction can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene Ether solvents such as tyl ether, tetrahydrofuran, dioxane, DME, etc.
  • Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc., ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitol, and esters such as ethyl acetate and ethyl propionate.
  • ketones such as acetone and methyl ethyl ketone
  • nitriles such as acetonitrile and propionitol
  • esters such as ethyl acetate and ethyl propionate.
  • Examples include amides such as DMF and N-methylpyrrolidone, DMS0, and a mixed solvent thereof.
  • the reaction it is not necessary to add a base because the triazole derivative (2a) itself as a raw material acts as a base, but triethylamine, tributylamine, N-methylmorpholine, pyridine, dimethylaniline and the like can be used.
  • Bases such as organic amines, potassium carbonate, sodium carbonate, hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium hydroxide, hydroxide hydroxide, alkali metal bases such as sodium hydride, sodium amide
  • the amount of the base used is not particularly limited, and it is preferable to use 0.01 to 2.0 equivalents, preferably 0.1 to 0.5 equivalents, based on the reaction substrate in terms of good yield.
  • the reaction temperature is selected from the range of ⁇ 10 to 150 ° C., but it is preferable to carry out the reaction in the range from around 0 ° C. to the reflux temperature of the reaction mixture from the viewpoint of good yield.
  • the desired product can be obtained by a usual extraction operation, but if necessary, it can be purified by column chromatography or the like.
  • Production method 4 involves oxidizing the sulfur atom of the triazole derivative (la). Is a step of producing the triazole derivative (lc) of the present invention.
  • Oxidation can be carried out using an oxidizing agent.
  • oxidizing agents that can be used include hydrogen peroxide, m-chloroperbenzoic acid, potassium permanganate, sodium metaperiodate, sodium hypochlorite, and oxidation. Osmium and the like can be exemplified.
  • the reaction is preferably performed in a solvent, for example, an aromatic solvent such as benzene, toluene, xylene, and benzene, an aliphatic hydrocarbon solvent such as hexane, pentane, and heptane; dichloromethane; A halogen solvent such as carbon chloride, an alcohol solvent such as methanol and ethanol, a carboxylic acid such as acetic acid and propionic acid, water, or a mixed solvent thereof can be used.
  • a solvent for example, an aromatic solvent such as benzene, toluene, xylene, and benzene, an aliphatic hydrocarbon solvent such as hexane, pentane, and heptane; dichloromethane; A halogen solvent such as carbon chloride, an alcohol solvent such as methanol and ethanol, a carboxylic acid such as acetic acid and propionic acid, water, or a mixed solvent thereof can be used.
  • the reaction temperature varies depending on the oxidizing agent used, and is selected from the range of -10 to 150 ° C. Performing the reaction in the range of around 0 ° C to the reflux temperature of the reaction mixture provides a good yield. Is preferred.
  • R 7 ′ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 3 to 12 carbon atoms. Represents an alkenyl group or an aralkyl group having 7 to 11 carbon atoms, ° represents a hydrogen atom or a radical group represented by R CO, and R 1 and R 2 have the same meanings as described above, provided that R 1 When "is a hydrogen atom, n is 0.)
  • the production method-5 includes a method for producing the triazole derivative (le) of the present invention by hydrolyzing an ester bond of the triazole derivative (Id), and a method for preparing a carboxylic acid of the triazole derivative (le) by a desired method.
  • the triazole derivative (1a), (lb) or (lc) of the present invention is a triazole derivative wherein R 3 is C00R 7 ′, or 3 shows a method for producing a triazole derivative in which R s is a hydrogen atom and R 3 is C00R 1 ′ in the triazole derivative (2) of the present invention.
  • Step 7 by hydrolyzing the ester bonds of the triazole derivative (Id), are known various methods for hydrolysis of c ester is a step for preparing a triazole Ichiru derivative (le) of the present invention
  • any method that does not harm other functional groups of the raw material substrate can be used in this step.
  • hydrolysis is carried out using an aqueous alkaline solution-specifically, sodium hydroxide, hydroxide hydroxide, sodium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, etc.
  • An aqueous solution of a genus base can be exemplified.
  • the reaction can be carried out in an organic solvent, for example, a solvent capable of forming a homogeneous solution with water, such as methanol, ethanol, propyl alcohol, butyl alcohol, tetrahydrofuran, dioxane, acetonitrile, or a mixed solvent thereof. can do.
  • a solvent capable of forming a homogeneous solution with water such as methanol, ethanol, propyl alcohol, butyl alcohol, tetrahydrofuran, dioxane, acetonitrile, or a mixed solvent thereof. can do.
  • the reaction temperature is selected from the range of 0 to 100 ° C., but it is preferable to carry out the reaction in the range of room temperature to the reflux temperature of the reaction mixture in terms of good yield.
  • Step-8 is a step of producing a triazole derivative (Id) by esterifying the carboxylic acid of the triazole derivative (le) with an alcohol (9).
  • a general method used for esterification of carboxylic acid such as a method of reacting a carboxylic acid with an alcohol in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid (Protection).
  • an acid catalyst such as sulfuric acid or p-toluenesulfonic acid
  • ive Groups in Organic synthesis TW Greene, John Wiley & Sons, 1981; Protective Groups in Organic Synthesis, Second Edition, T. Greene and PGM Wuts, John Wiley & Sons, 1991.
  • the desired ester (Id) can be produced.
  • the carboxylic acid (le) is converted to an acid chloride using a chlorinating agent such as thionyl chloride and then reacted with an alcohol (9), or an alcohol (9) is reacted with a thionyl chloride.
  • a chlorinating agent such as thionyl chloride
  • an alcohol (9) is reacted with a thionyl chloride.
  • the method of reacting the reactive species prepared by the above reaction with carboxylic acid (le) is preferred in that the desired product can be obtained in a simple and high yield.
  • Step-9 is a process in which a triazole derivative (If) and an alkylating agent are used. (10) is reacted in the presence of a base to produce a triazole derivative (lg) of the present invention.
  • the reaction must be carried out in the presence of a base
  • usable bases include organic amines such as triethylamine, triptylamine, N-methylmorpholine, and pyridine; lithium carbonate, sodium carbonate, and acetic acid.
  • examples thereof include alkali metal bases such as sodium, potassium acetate, sodium hydride, and sodium amide, and organic metal bases such as lithium diisopropylamide, among which sodium hydride, sodium amide, and lithium diisopropylamide.
  • a base such as chloride
  • the amount of the base used is not particularly limited, but it is preferable to use the base in an amount equal to or more than that of the reaction substrate in terms of good yield.
  • the reaction is preferably performed in an organic solvent, and any solvent that does not harm the reaction can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzene
  • examples include ether solvents such as tyl ether, tetrahydrofuran, dioxane, and DME, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, etc., amides such as MF and -methylpyrrolidone, and DMS0 or a mixture thereof. Can be shown.
  • the reaction temperature varies depending on the base used, and is selected from the range of -100 ° C to 150 ° C. Is preferred in terms of good yield.
  • the alkylating agent (10) used in this step is partially commercially available Can be produced by converting the hydroxyl group of the corresponding alcohol derivative into a halogen atom or an alkane or arenesulfonyloxy group according to a conventional method.
  • Example Example-1
  • Example 1 except that (1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) ethyl thioacetate (1-methoxycarbonyl) ethyl (0.081 g, 0.235 mmol) was used as a raw material. By carrying out the reaction in the same manner as in 3, a colorless and transparent oily product of (1-methoxyethyl) -1-sulfonylacetic acid (1-methoxycarbonyl) ethyl is obtained. (0.050 g, 56.5%). ⁇ -NMRCCDCl.
  • Example 1 except that methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) thio] propionate (0.859 g, 3.0 mmol) was used as a raw material. By carrying out the reaction in the same manner as in 3, a colorless transparent oil (0.880 g, 91.2%) of methyl 2- [ ⁇ -getylcarbamoyl-1H-1,24-triazol-3-yl) sulfonyl] propionate is obtained. Obtained.
  • Example 1 except that methyl 2-[(l-dimethylcarbamoyl-1H-1,2,4-triazol-3-yl) thio] propionate (0.388 g, 1.5 mmol) was used as a raw material. The reaction was carried out in the same manner as described above to obtain a colorless transparent oily substance of methyl 2-[(tridimethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfinyl] propionate (0.280 g, 68.1% ).
  • the raw material is 2-[(1-morpholinocarbon-1H-1 2 4-triazole-3- L) thio] propionate (0.601 g, 2.0 mmol) was used to carry out the reaction in the same manner as in Example 13 to give 2-[(trimorpholinocarbonyl - ⁇ -1,2,4- A colorless transparent oil (0.660 g, 99.3%) of methyl triazol-3-yl) sulfonyl] propionate was obtained.
  • Example 13 Same as Example 13 except that (1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) benzyl thioacetate (4.53 g, 13.Ommol) was used as a raw material. To give a white solid (4.39 g, 88.7%) of benzyl (1-getylcarbamoyl-1H-1,24-triazol-3-yl) sulfonylacetate.
  • Example 3 except that (1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) thioacetic acid (2-methoxethyl) (1.63 g, 5.16 mmol) was used as a raw material. By carrying out the reaction in the same manner as described above, a colorless and transparent oily substance (1.51 g) of (1-methylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonylacetate (2-methoxethyl) was obtained. , 83.9%).
  • the raw material is 2-[(l-Jetylcarbamoyl-1H-1,2,4-triazol-3-yl) thio] -2- (1-methylcyclopropyl-1-yl) ethyl acetate (0.400 g, 1.08 mmol), and the reaction was carried out in the same manner as in Example 3 to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazolyl-3-yl). ) Sulfonyl] -2- (1-methylcyclopropyl-1-yl) colorless transparent oil (0.469 g, 94.1%) of ethyl acetate was obtained.
  • Hydrogenated sodium (0.40 g, 10.0 ol) was placed in a two-necked eggplant flask (25 m) at 0 ° C in an argon atmosphere at 3 ° -mercapto-1,2,4-triazole (1.1 Olg, 9.99 ol). After stirring for 30 minutes at 0 ° C, dimethyl chloroformate (1.27mL, 9.95mmol) was added, and the temperature was gradually raised from 0 ° C to room temperature.
  • reaction solution was added to 1N hydrochloric acid (15 mL), extracted with ethyl acetate (15 mL ⁇ 3), and the organic layers were combined, washed with a saturated aqueous sodium chloride solution (15 mL), and dried over anhydrous water.
  • the desiccant was separated by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product, which was subjected to silica gel column chromatography (Co-gel C-200, ethyl acetate: ethyl acetate).
  • Example 3 By the same reaction procedure as in 36, 2-[(1H-1,2,4-triazol-3-yl) thio] -4-propylmethylpentanoate (0.750 g, 2.91 bandages 0 1 ) And dimethylcarbamoyl chloride (0.281 mL, 3.06 mmol) to give 2-[(1-dimethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) thio] -4- A colorless and transparent oily product of isopropyl methyl penisonate (0.903 g, 94.5%) was obtained.
  • the raw material is 2-[(1-diisopropylpropyl-lvamoyl-1H-1,2,4-triazol-3-yl) thio] -4-methylpentylisopropyl (0.500 g, 1.30 mmol)
  • the reaction was carried out in the same manner as in Example 13 except that was used, to give 2-[(tolisopropyl-caproluvamoyl-1H-1,2,4-triazol-3-yl) sulfonyl]-
  • a colorless transparent oily product of isopropyl 4-methylpentanoate (0.337 g, 61.5%) was obtained.
  • the raw material is 2-[ ⁇ 1- (N-methyl-N-phenylcarbamoyl) -1H-1,24-triazol-3-yl ⁇ thio] -4-propylmethylpentanoate (0.297 g, 0.76 imol) except that the reaction was carried out in the same manner as in Example 3 to give 2- (N-methyl-N-phenylcarbamoyl) -1H-1,2,4-triazo-1-yl.
  • a colorless transparent oil (0.317 g, 98.7%) of [l-3-yl ⁇ sulfonyl] -4-methylpenisobutanoate was obtained.
  • the raw material is 2- [U- (N- (1-phenylethyl) capsulebamoyl) -lH-l, 2,4-triazol-3-yl ⁇ thio] isopropyl -4-methylpentanoate (0.196g , 2- (U- (N- (1-phenylethyl) ylrubamoyl) -1H-1,2,4-triazoyl) by performing the reaction in the same manner as in Example 3 except that A colorless, transparent oil (0.107 g, 50.8%) of [l-3-yl ⁇ sulfonyl] -4-methylpenisobutanoate was obtained.
  • the raw material is 2-[ ⁇ (N-cyclohexylcarbamoyl) -1H-1,2,4-triazo-l-3-yl) thio] -4-isopropylmethylpentanoate (0.50 g, 1.31 mmol)
  • the reaction was carried out in the same manner as in Example 13 except for using 2-( ⁇ 1- (N-cyclohexylcarbamoyl) -1H-1,2,4-triazolyl-3-yl).
  • a colorless and transparent oily product of [sulfonyl] -4-methylpenoisobutyrate (0.202 g, 37.2%) was obtained.
  • reaction solution was poured into 1N hydrochloric acid (150 mL), and extracted with ethyl acetate (150 mL ⁇ 2).
  • the organic layer was washed with a saturated saline solution (150 mL), and then dried and dried over anhydrous sodium sulfate.
  • the drying agent was removed by filtration, and the filtrate was concentrated under reduced pressure.
  • the raw material is 2-[ ⁇ 1- (N-cyclohexyl-N-ethylcarbamoyl) -1H-1,2,4-triazol-3-yl ⁇ thio] -4-isobutyl isobutyl benzoate (0.400 g, 0.97 mmol) except that 2- [U- (N-cyclohexyl-N-ethylcarbamoyl) -1H-1, There was obtained a colorless transparent oil (0.393 g, 91.8%) of 2,4-triazol-3-yl) sulfonyl] -4-methylpentisobutyl citrate.
  • 'H-NMR (CDC1 3, TMS, ppm): ⁇ 0.
  • Example 1 By a reaction operation similar to that of 87, 2-[(1-chlorocarbonyl-1H-1,2,4-triazoI-3-yl) thio] -4-methylpentyne 2-((topyrrolidinocarbonyl-1H-1,2,4-triazol-3-yl) is reacted with pyrrolidine (0.74 g, 10.4 bandol). ) Thio] -4-iso-methylpentanoate as a colorless transparent oil (0.21 g, 11.4%) was obtained.
  • the raw material was methyl 2-[(tridecylcarbamoyl-1H-1,2,4-triazol-3-yl) thio] -2- (2,4-dichloromethyl) acetate (0.300 g, 0.72 g).
  • the reaction was carried out in the same manner as in Example 3 except that ol (ol) was used to give 2-[(todiethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl]
  • a white solid (0.240 g, 74.2%) of methyl 2- (2,4-dichlorophenyl) acetate was obtained.
  • Example 1 By the same reaction procedure as in 36, methyl 2-[(1H-1,2,4-triazol-3-yl) thio] -2- (2,4-dichlorophenyl) acetate (0.300 g, 0.94 mmol) and morpholinocarbonyl chloride (0.14 mL, 1.20 mmol) are reacted to give 2-[(1-morpholinocarbonyl-1H-1,2,4-triazol-3-yl) thio]- Methyl 2- (2,4-dichlorophenyl) acetate (0.340 g,
  • the raw material was methyl 2-[(1-morpholinocarbonyl-1H-1,2,4-triazol-3-ynole) thio] -2- (2,4-dichlorophenyl) acetate (0.340 g, 0.81 mmol). Except for using, the reaction was carried out in the same manner as in Example 3 to give 2-[(1-morpholinocarbonyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2 -A white solid (0.343 g, 94.2%) of methyl (2,4-dichlorophenyl) acetate was obtained.
  • Example 2 By the same reaction procedure as 36, methyl 2-[(1H-1,2,4-triazol-3-yl) thio] -2- (4-methylphenyl) acetate (0.380 g, 1.44 bandage) 0 1) is reacted with getylcarbamoyl chloride (0.20 mL, 1.58 mmol) to give 2-[(trimethylcarbamoyl-1H-1,2,4-triazol-3-yl) thio. [O] -Methyl 2- (4-methylphenyl) acetate was obtained as a yellow oil (0.512 g, 98.1%). 'H-NMR (CDC1 3, TMS, ppm): ⁇ ⁇ .25 (.
  • the raw material used was methyl 2- [ ⁇ -getylcarbamoyl-1 ⁇ -1,2,4-triazo-1-yl-3-yl) thio] -2- (4-methylphenyl) acetate (0.512 g, 1,41 mmol). Except for the above, the reaction was carried out in the same manner as in Example 3 to give 2-[(1-ethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2- (4- A white solid (0.460 g 82.7%) of methyl phenylacetate was obtained.
  • Example 3 except that 2-[(tridecylcarbamoyl-1H-1,2,4-triazol-3-yl) thio] -2-phenylacetate (0.460 g, 1.66 mmol) was used as a raw material. By carrying out the reaction in the same manner as described above, a white solid of propyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2-phenylacetate (0.430 g, 83.7%).
  • Example 1 By the same reaction procedure as in 116, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propyl (0.83 lg, 2.50 mmol) ) With isopropyl iodide (0.25 mL, 2.51 bandol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -3 A colorless transparent oily substance of propyl methylbutanoate (0.347 g, 37.1%) was obtained.
  • Example 1-1 By the same reaction operation as in 116, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.608 g, 2. OOmmol) and butyl iodide (0.23mL, 2.02 ol) and react with 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl ] A colorless transparent oily product of methyl hexanoate (0.500 g, 69.4%) was obtained.
  • Example 1 By the same reaction procedure as in 116, 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] ethyl ester (0.796 g, 2.50 bandages) ol) and isobutyl iodide (0.290 mL, 2.52 ol) to give 2-[(trimethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl]-4- A colorless transparent oily substance of methyl ethylpentanoate (0.305 g, 32.6%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] isopropyl acetate (0.997 g, 3. OOmmol) and isobutyl iodide (0.350 mL, 3.04 butylol) were reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl. ]-A yellow oily substance of isopropyl 4-methylpenanoate (0.435 g, 37.3%) was obtained.
  • Example 1 By the same reaction operation as in 116, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] isobutyl acetate (1.04 g, 3.00 g) Ol) and isobutyl iodide (0.350 mL, 3.04 mmol) to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] Yellow oil of isobutyl 4-methylpentanoate (0.541 g, 4 n
  • Example 1 By a reaction operation similar to that of 16, sec-butyl 2-[(1-methylethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] acetate (0. 866 g, 2.50 mmol) and isobutyl iodide (0.32 mL, 2.78 mmol) were reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazoIl-3- A colorless transparent oil (0.625 g, 62.1%) of sec-butyl 4-methylpentanoate) was obtained. 'H-NMRCCDCl s, TMS, pm): ⁇ 0.88 and O.
  • Example 1 By a reaction operation similar to that of 16, t-butyl 2-[(trimethylcarbamoyl-1H-1 2,4-triazol-3-yl) sulfonyl] acetate (1.04 g, 3. OOmmol) and isobutyl iodide (0.35mL 3.04mmol) to react with 2--2-[(tridecylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl]- A colorless transparent oily product of t-butyl 4-methylpentanoate (0.594 g, 49.2%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, pentyl 2-[(1-getylcarbamoyl-1H-124-triazolyl-3-yl) sulfonyl] acetate (1.08 g, 3.000 mmol) With isobutyl iodide (0.350 mL, 3.04 mmol) to give 2-[(trimethylcarbamoyl-1H-1,24-triazol-3-yl) sulfonyl] -4-methylpentenoic acid Pentyl yellow oil (0.695g, 55.6% ).
  • Example 1- [2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetic acid (2-methoxyethyl) (0.871 g, 2.50 mmol) and isobutyl iodide (0.29 mL, 2 ⁇ 521) to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3- [Yl] sulfonyl] -4-methylpentanoic acid (2-methoxethyl) as a colorless transparent oil (0.411 g, 53.8%).
  • Example 1 By a reaction operation similar to that of 16, a 2-[(1-getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] aryl (0.702 g, 2.12 01) and isobutyl iodide (0.30 mL, 2.61 mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] -A colorless transparent oily product of acrylyl 4-methylpenanoate (0.281 g, 34.3%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, a mixture of 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] benzyl (0.95 lg, 2 ⁇ 50 mmol) and isobutyl iodide (0.29 mL, 2.52 mmol) are reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl]- Benzyl 4-methylpentanoate as a colorless transparent oil (0.689 g, 63.1%).
  • Example 1 By the same reaction operation as in 116, methyl 2-[(trimethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.913 g, 3.000 mmol) ) And 3-bromopentane (0.380 mL, 3.06 bandol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -3 A colorless and transparent oily product of methyl-ethylpentenoate (0.056 g, 5.0%) was obtained.
  • Example 1 By the same reaction operation as in 116, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] acetate (0.913 g, 3. OOmmol) and (s)-(+)-1-bromo-2-methylbutane (0.375 mL, 3.04 bandages 1) to react with 2-[(1-Jetylcarbamoyl-1H-1,2,4 -Triazo-l-3-yl) sulfonyl] -4-methylhexanoate was obtained as a colorless transparent oil (0.308 g, 27.4%).
  • ⁇ -NMRCCDCl ,, TMS, ppm): (50.87 and 0.88 (total 3H, each t, J 7.6Hz), 0.90 and 0.91 (total 3H, each d ⁇ U ⁇ 3
  • Example 1 By the same reaction operation as in 116, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.913 g, 3 OOmmol) and cyclopentylmethyl tosylate (0.93g, 3.66mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl A colorless, transparent oil (0.102 g, 8.80%) of methyl 3-pentyl pentyl propionate was obtained.
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] isopropyl acetate (0.997 g, 3 ⁇ OO mmol) and cyclopentylmethyl tosylate (0.93 g, 3.66 mmol) to give 2-[(togetylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl A colorless transparent oil (0.062 g, 4.99%) of isopropyl-3-cyclopentylpropionate was obtained.
  • Example 1 By the same reaction operation as in 116, 2-[(trimethylcarbamoyl-1H-1,2,4-triazo-1-yl-3-sulfonyl) sulfonyl] isopropyl acetate (0.997 g, 3.00 ol) ) And bromomethylcyclohexane (0.42 mL, 3.04 ol) to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazo-l-3-yl) sulfo A colorless, transparent oil (0.102 g, 7.93%) of [isopropyl] -3-cyclohexylpropionate was obtained. !
  • Example 1 By a reaction operation similar to that of 16, a mixture of methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.913 g, 3 ⁇ The reaction between 00 ol) and 2-chloroethylmethyl sulfide (0.300 mL, 3.0 OO mmol) was carried out to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazo-1-yl). A colorless transparent oil (0.415 g, 36.5%) of methyl 3--3-yl) sulfonyl] -4-methylthiobutanoate was obtained.
  • Example 1 By the same reaction operation as in 16, (1-Jetylcarbamoy The reaction between methyl 1H-1,2,4-triazol-3-yl) sulfonylacetate (0.761 g, 2 • 50 mmol) and 4-bromobutyronitrile (0.25 mL, 2.52 mmol) is carried out. A colorless, transparent oil (0.35 g, 37.7%) of methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] -5-cyanopentanoate Obtained.
  • Example 1 By a reaction operation similar to that of 16-methyl, 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] methyl acetate (0.913 g, 3.000 mmol ) With cyclopropylmethyl bromide (0.300 mL, 3.09 butylol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl]- A colorless, transparent oil of methyl 3-cyclopropylpropionate (0.591 g, 55.0%) was obtained.
  • Example 1 By the same reaction procedure as in 116, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazo-1-yl) sulfonyl] ethyl (0.96 g, 3. Ommol) and cyclopentyl bromide (0.33 mL, 3.1 mmol) to give 2-[(togetylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl. ]-Colorless and transparent oil of 2-cyclopentyl acetate (0.056 g,
  • Example 1 By the same reaction procedure as in 116, 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] isopropyl acetate (1.00 g, 3.0 liters) ol) and cyclopentyl bromide (0.35 mL, 3.26 mmol) The reaction was carried out to give a colorless, transparent oily substance of 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2-cyclopentylacetate (0.100 g , 8.32%).
  • Example 1-1 By the same reaction operation as in 116, 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] isobutyl acetate (1.04 g, 3 • OO mmol) and cyclopentyl bromide (0.38 mL, 3.54 mmol) were reacted to obtain 2-[(tridecylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfo. A colorless, transparent oil (isobutyl) -2-yl-2-pentylacetate (0.109 g, 8.76%) was obtained.
  • Example 1 By a reaction operation similar to that of 116, t-butyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (1.04 g, 3. OOmmol) is reacted with cyclopentyl bromide (0.38mL, 3.54 bandol) to give 2-[(1-Jetylcarbamoyl-1H-1,2,4-triazol-3-yl) Sulfonyl] -t-butyl 2-cyclopentylacetate was obtained as a colorless transparent oil (0.083 g, 6.67%).
  • ⁇ - NMR (CDC1 3, TMS , ppm): ⁇ ⁇ .32 (6H, t, J 7.
  • Example 1 By the same reaction operation as in 116, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetonitrile (1.50 g, 5.53 bandits) ol) and cyclopentyl bromide (1.09 g, 7.19 mmol) 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2-cyclopentylacetonitrile as an orange oil (0.341 g, 20.4% ). !
  • Example 1 By a reaction operation similar to that of 16-, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.913 g, 3. OOmmol) and 3-methylcyclopentyl iodide (0.882g, 4.20mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) A colorless transparent oil (0.132 g, 11.4%) of methyl sulfonyl] -2- (3-methylcyclopentyl) acetate was obtained.
  • Example 1 By a reaction operation similar to that of 16, a mixture of methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] acetate (0.761 g, 2.50 MIO1 ) And ⁇ -phenethyl bromide (0.35 mL, 2.56 mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -A colorless transparent oily product of methyl 4-phenylbutanoate (0.576 g, 56.4%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propyl acetate (0.83 lg, 2.50 minol) ) And polyphenylbromide (0.35 mL, 256 mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -Colorless transparent oily substance of propyl 3-phenylbutanoate (0.63 Og, 57.7%). : H-NMR (CDC1 3, TS, ppm): ⁇ 50.68 and 0.99 (tota
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] isopropyl acetate (0.831 g, 2.50 mmol) ) And 3-phenethyl bromide (0.35 mL, 2.56 mmol) to give 2-[(1-Gethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] -A colorless transparent oily product of isopropyl 3-phenylbutanoate (0.568 g, 52.0%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(trimethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.913 g, 3. Ommol ) And 1- (2-trifluoromethylphenyl) ethyl iodide (1,08 g, 3.55 mmol) to give 2-[(1-getylcarbamoyl-1H-1,2,4- A white solid (0.102 g, 7.14%) of methyl triazole-3-yl) sulfonyl] -3- (2-trifluoromethylphenyl) butanoate was obtained. mp: 150.5 ⁇ 151.3 ° C;
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.761 g, 2.50 imnol ) And benzyl chloride (0.29 mL, 2.52 mmol) were reacted to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazoyl-3-yl) sulfonyl] -3 A colorless transparent oily substance of methyl-phenylpropionate (0.840 g, 84.8%) was obtained. !
  • Example 1 By a reaction operation similar to that of 16, a mixture of methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.761 g, 2.50 bandages) was obtained. ol) and 4-fluorobenzyl chloride (0.32 mL, 2.57 mmol) to give 2-[(Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) A colorless transparent oil (0.540 g, 52.4%) of methyl sulfonyl] -3- (4-fluorophenyl) propionate was obtained.
  • Example 1 By the same reaction operation as in 116, 2-[(t Reaction of Methyl 1H-1, 2,4-Triazol-3-yl) sulfonyl] acetate (0.913g, 3.OOmmol) with 2- (bromomethyl) naphthalene (0.664g, 3.OOmmol) To a colorless, transparent oily product of methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -3- (2-naphthyl) propionate ( 0.536 g, 40.2%).
  • Example 1 By a reaction operation similar to that of 16, a mixture of methyl 2-[(1-acetylethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] acetate (1.22 g, 4. OO mmol) and 1-phenylpropyl iodide (1.20 g, 4.57 mmol) to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) A colorless transparent oil (0.536 g, 30.4%) of methyl sulfonyl] -3-phenylpenate was obtained.
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] ethyl (0.955 g, 3.00 g) Ol) and 1-phenylpropyl iodide (0.865 g, 3.30 IMO1) were reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl). Sulfonyl]-colorless transparent oil of ethyl 3-phenylpentanoate (0.
  • Example 1 By a reaction operation similar to that of 16, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propyl acetate (0.998 g, 3. OO mmol) and 1-phenylpropyl iodide (0.950 g, 3.62 mmol) are reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) A colorless transparent oily product of propyl sulfonyl] -3-fluoropentanoate (0.581 g, 41.5%) was obtained. ! H-NMR (CDC1 3, TMS, ppm): 50.64 ⁇ 0.72 an 1 g
  • Example 1 By the same reaction operation as in 116, 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] isopropyl acetate (0.998 g, 3. OOmmol) and -trifluoropropyl iodide (0.865g, 3.30mmol) to give 2-[(trimethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl A colorless, transparent oil of isopropyl 3-phenylpentanoate (0.578 g, 41.3%) was obtained.
  • Example 1 By the same reaction operation as in 116, 2-[(t Reaction of methyl yl-1H-1,2,4-triazolyl-3-yl) sulfonyl] acetate (0.612 g, 2. Olmmol) with aryl bromide (0.175 mL, 2.02 mmol) Colorless transparent oil of methyl 2-, ([tetethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -4-pentenoate (0.210 g, 30.5%) I got
  • Example 1 By a reaction operation similar to that of 116, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] acetate (0.761 g, 2 50 marl ol) and 3-chloro-2--2-methyl-1-propene (0.25 mL, 2.53 mmol) to give 2-[(1-Jetylcarbamoyl-1H-1,2,4 -Triazol-3-yl) sulfonyl] -4-methyl-4-pentenoate was obtained as a colorless transparent oil (0.664 g, 74.1%).
  • Example 1 By the same reaction operation as in 116, methyl (1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonylacetate (0.761 g, 2 • 50 mmol) was obtained. ) And methyl bromoacetate (0.24 mL, 2.53 mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] -A white solid of methyl 3-methoxycarbonylpropionate (0.340 g, 36.1%) was obtained. mp:.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[[alpha] -ethylmethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propionate (0.637 g, After reacting 2.00 ol ol) with iodide chill (0.20 mL, 2.46 marl ol), 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3 -Yl) sulfonyl]-methyl 2-methylbutanoate as a white solid (0.280 g, 40.4%) was obtained.
  • Example 1 By the same reaction procedure as in 116, methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propionate (0.796 g, 2.50 2-((1-Jetylcarbamoyl-1H-1,2,4-triazol-3-ynole) sulfonyl] was reacted with butyl bromide (0.32 mL, 2.98 mmol). A colorless, clear oily product of methyl 2--2-methylhexanoate (0.329 g, 35.1%) was obtained.
  • Example 1 2-[(1-Jetylcarbamo Reaction of methyl -1H-1,2,4-triazole-3-yl) sulfonyl] propionate (0.796 g, 2.50 mmol) and isobutyl iodide (0.29 mL, 2.52 mmol) Colorless and transparent oily substance of methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2,4-dimethylpentenoate (0.628 g , 67.1%).
  • Example 1 By a reaction operation similar to that of 16, meth-2-one [0.7-g of 2-[(1-Getylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] propionate , 2.50 mmol) and benzyl chloride (0.330 mL, 2.60 mmol) were reacted to give 2-[(1-Jetylcarbamoyl-1H-1,2,4-triazol-3-yl). A white solid of methyl [sulfonyl] -2-methyl-3-phenylpropionate (0.709 g, 69.4%) was obtained.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(1-ethylethylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propionate (0.800 g, 2.5111111101) and 2,4-dimethylbenzyl chloride (0.37111 2.53 dragonol) were reacted to give 2-[(1-Jetylcarbamoyl-1H-1,2,4-triazole-3- [Yl] sulfonyl] -2-methyl-3- (2,4-dimethylphenyl) colorless transparent oil (0.810 g, 73.9%) of methyl propionate was obtained.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propionate (0.797 g, 2.50 iMol) and 4- 1-butylbenzyl chloride (0.46 mL, 2.50 mmol) were reacted to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazole-3- A white solid (0.950 g, 81.8%) of methyl [yl] sulfonyl] -2-methyl-3- (4-t-butylphenyl) propionate was obtained.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(1-getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] propionate (0.797 g, 2.50 mmol) ) And aryl bromide (0.22 mL, 2.54 bandol) to give 2-[(1-getylcarbamoyl-1H-1,2,4-triazolyl-3-inole) sulfonyl]- A white solid of methyl 2-methyl-4-pentenoate (0.836 g, 93.3%) was obtained. mp: 60, 0 ⁇ 61.0 ° C; MR (CDC1 3, TMS, ppm): 61.32 (.
  • Example 1 By a reaction operation similar to that of 16, methyl 2-[(trimethylcarbamoyl-1H-1,2,4-triazolyl-3-yl) sulfonyl] butanoate (0.832 g 2.50 mmol ) And propyl bromide (0.28 mL, 3.08 mmol) to give 2-[(1-Getylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfonyl] -2- A colorless transparent oily product of methyl ethylpentanoate (0.242 g, 25.8%) was obtained.
  • Example 1-1 By the same reaction procedure as in 116, methyl 2-[(1-ethylethylcarbamoyl-1H-1 2,4-triazol-3-yl) sulfonyl] butanoate (0.832 g, 2.50 mmol) and butyl bromide (0.32 mL, 2.98 mmol) to give 2-[(1-Jetylcarbamoyl-1H-1,2,4-triazol-3-yl) sulfur A colorless and transparent oily product of methyl [ruphonyl] -2-ethylhexanoate (0.229 g, 23.6%) was obtained.
  • reaction solution was added to 1N-hydrochloric acid (15 mL), and extracted with getyl ether (15 mL ⁇ 3 times). The organic layers were combined, washed with a saturated aqueous solution of sodium chloride (10 mL), and dried over anhydrous magnesium sulfate. The drying agent was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product.
  • reaction solution was added to 1N-hydrochloric acid (15 mL) and extracted with getyl ether (8 mL ⁇ 3). Combine the organic layers and wash with saturated aqueous sodium chloride solution (10) And dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the filtrate was concentrated under reduced pressure to obtain a crude product.
  • Me methyl; Et: ethyl; Pr: propyl; i-Pr: isopropyl; Bu: butyl; i-Bu: isobutyl; sec-Bu: secondary monobutyl; t-Bu: tertiary butyl

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Abstract

L'invention concerne des dérivés de triazole représentés par la formule générale (I), leurs procédés de production, leurs intermédiaires de production et des herbicides contenant les dérivés en tant que principe actif. Les herbicides présentent d'excellentes activités herbicides à petites doses et n'abîment que très peu les cultures.
PCT/JP1998/004890 1997-11-14 1998-10-29 Derives de triazole, leurs intermediaires de production, leurs procedes de production et herbicides contenant les derives en tant que principe actif WO1999025700A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019045085A1 (fr) * 2017-08-31 2019-03-07 北興化学工業株式会社 Dérivés de 1-(carbamoyle n,n-disubstitué) 4-(sulfonyle substitué)triazolin-5-one, dérivés de 4-(carbamoyle n,n-disubstitué) 1-(sulfonyle substitué)triazolin-5-one, et herbicide les contenant en tant que principe actif
CN113527224A (zh) * 2020-04-21 2021-10-22 宁夏苏融达化工有限公司 噻唑类衍生物及其在农业中的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308131A (en) * 1962-12-06 1967-03-07 Du Pont Tertiary carbamyl triazoles
WO1992002512A1 (fr) * 1990-08-03 1992-02-20 Chugai Seiyaku Kabushiki Kaisha Compose de triazole
JPH05194432A (ja) * 1992-01-21 1993-08-03 Hokko Chem Ind Co Ltd トリアゾール誘導体および除草剤
JPH05320158A (ja) * 1992-05-22 1993-12-03 Kumiai Chem Ind Co Ltd アルカン酸誘導体及びこれを含む除草剤
EP0654468A1 (fr) * 1993-11-23 1995-05-24 Bayer Ag Carbamoyl-triazoles substitués, leur utilisation comme herbicides, et intermédiailes triazoliques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308131A (en) * 1962-12-06 1967-03-07 Du Pont Tertiary carbamyl triazoles
WO1992002512A1 (fr) * 1990-08-03 1992-02-20 Chugai Seiyaku Kabushiki Kaisha Compose de triazole
JPH05194432A (ja) * 1992-01-21 1993-08-03 Hokko Chem Ind Co Ltd トリアゾール誘導体および除草剤
JPH05320158A (ja) * 1992-05-22 1993-12-03 Kumiai Chem Ind Co Ltd アルカン酸誘導体及びこれを含む除草剤
EP0654468A1 (fr) * 1993-11-23 1995-05-24 Bayer Ag Carbamoyl-triazoles substitués, leur utilisation comme herbicides, et intermédiailes triazoliques

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019045085A1 (fr) * 2017-08-31 2019-03-07 北興化学工業株式会社 Dérivés de 1-(carbamoyle n,n-disubstitué) 4-(sulfonyle substitué)triazolin-5-one, dérivés de 4-(carbamoyle n,n-disubstitué) 1-(sulfonyle substitué)triazolin-5-one, et herbicide les contenant en tant que principe actif
JPWO2019045085A1 (ja) * 2017-08-31 2020-12-17 北興化学工業株式会社 １−（ｎ，ｎ−ジ置換カルバモイル）４−（置換スルホニル）トリアゾリン−５−オン誘導体、４−（ｎ，ｎ−ジ置換カルバモイル）１−（置換スルホニル）トリアゾリン−５−オン誘導体、およびそれらを有効成分として含有する除草剤
US11076595B2 (en) 2017-08-31 2021-08-03 Hokko Chemical Industry Co., Ltd. 1-(n,n-disubstituted carbamoyl) 4-(substituted sulfonyl)triazolin-5-one derivative, 4-(n,n-disubstituted carbamoyl) 1-(substituted sulfonyl)triazolin-5-one derivative, and herbicide containing said derivative as active ingredient
AU2018325894B2 (en) * 2017-08-31 2022-08-04 Hokko Chemical Industry Co., Ltd. 1-(N,N-disubstituted carbamoyl) 4-(substituted sulfonyl)triazolin-5-one derivatives, 4-(N,N-disubstituted carbamoyl) 1-(substituted sulfonyl)triazolin-5-one derivatives, and herbicide containing same as active ingredient
JP7366746B2 (ja) 2017-08-31 2023-10-23 北興化学工業株式会社 １－（ｎ，ｎ－ジ置換カルバモイル）４－（置換スルホニル）トリアゾリン－５－オン誘導体、４－（ｎ，ｎ－ジ置換カルバモイル）１－（置換スルホニル）トリアゾリン－５－オン誘導体、およびそれらを有効成分として含有する除草剤
CN113527224A (zh) * 2020-04-21 2021-10-22 宁夏苏融达化工有限公司 噻唑类衍生物及其在农业中的应用

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