WO1997047626A1 - Derives d'hydantoine bicycliques, produits intermediaires destines a leur fabrication, procede de preparation de ces derives et herbicides les contenant en qualite d'ingredient actif - Google Patents

Derives d'hydantoine bicycliques, produits intermediaires destines a leur fabrication, procede de preparation de ces derives et herbicides les contenant en qualite d'ingredient actif Download PDF

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Publication number
WO1997047626A1
WO1997047626A1 PCT/JP1997/002046 JP9702046W WO9747626A1 WO 1997047626 A1 WO1997047626 A1 WO 1997047626A1 JP 9702046 W JP9702046 W JP 9702046W WO 9747626 A1 WO9747626 A1 WO 9747626A1
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group
carbon atoms
atom
formula
alkyl group
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PCT/JP1997/002046
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English (en)
Japanese (ja)
Inventor
Kenji Hirai
Tomoyuki Yano
Natsuko Okano
Kazuhisa Ikemoto
Tomoko Yoshii
Sadayuki Ugai
Osamu Yamada
Takuya Ueda
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Sagami Chemical Research Center
Karen Pharmaceutical Co., Ltd.
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Priority to AU31069/97A priority Critical patent/AU3106997A/en
Publication of WO1997047626A1 publication Critical patent/WO1997047626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to a novel bicyclic hydantoin derivative, an intermediate for producing the same, a method for producing them, and a herbicide containing the derivative as an active ingredient.
  • bicyclic hydantoin derivatives having a substituted aryl group on the 3-position nitrogen atom have herbicidal activity (for example, EP-0070389 A, DE 3643748 A, 4-243866), and there is no report on the synthesis of a derivative having a double bond at the bridgehead of a bicyclic hydantoin derivative as represented by the general formula (1) of the present invention. Disclosure of the invention
  • the present inventors have conducted intensive studies in search of an excellent herbicide.
  • the bicyclic hydantoin derivative represented by the following general formula (1) of the present invention which has never been known before, exhibits excellent herbicidal activity.
  • the present invention has been found, and further, these simple manufacturing methods have been found, and the present invention has been completed. That is, the present invention provides a compound represented by the general formula (1)
  • X 1 represents a hydrogen atom or a halogen atom
  • X 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxycarbonylmethyloxy group having 1 to 6 carbon atoms, or a carbon atom having 1 to 1 carbon atoms.
  • 6 represents an alkoxycarbylmethylthio group.
  • X 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a nitro group, an amino group, a hydroxyl group or YR 1; 1 ′ ′ represents an alkyl group having 1 to 12 carbon atoms; Cycloalkyl group, alkenyl group having 2 to 12 carbon atoms, alkynyl group having 2 to 12 carbon atoms, aralkyl group having 7 to 11 carbon atoms, alkoxycarbonyl group having 1 to 12 carbon atoms or carbon number 7 to 11 represents an aralkyloxy group.
  • Y represents an oxygen atom or a sulfur atom. Or a general formula (3)
  • X 1 represents a hydrogen atom or a halogen atom
  • Z represents an oxygen atom or a sulfur atom
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
  • the present invention relates to a bicyclic hydantoin derivative represented by the formula:
  • X ′ represents a hydrogen atom or a halogen atom
  • X 2 ′ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms
  • X 3 ′ represents a halogen atom or a 1 to 8 carbon atom.
  • Y represents an oxygen atom or a sulfur atom.
  • the present invention relates to a method for producing a bicyclic hydantoin derivative represented by
  • R '"-L (Wherein, is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms or a carbon atom having 7 to 12 carbon atoms.
  • L represents an aralkyl group and L represents a leaving group.
  • R 2 ′ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
  • L represents a leaving group.
  • the present invention also provides an intermediate for producing these bicyclic hydantoin derivatives, which is represented by the following general formula (5):
  • the present invention relates to a method for producing a thiomorpholine carboxylic acid derivative represented by the formula:
  • the present invention relates to a herbicide containing, as an active ingredient, a bicyclic hydantoin derivative represented by the formula: BEST MODE FOR CARRYING OUT THE INVENTION
  • examples of the halogen atom represented by X 1 , X 2 , X 2 , X 3 and X 3 ′ include a fluorine atom, a chlorine atom and a bromine atom.
  • the alkyl group having 1 to 8 carbon atoms represented by X 2 , X 2 ′, X 3 and X 3 ′ may be linear or branched, and may be a methyl group, an ethyl group, a propyl group. Groups, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and the like.
  • alkyl groups may be substituted with a halogen atom or the like, and specific examples thereof include a trifluoromethyl group, a difluoromethyl group, a 2-chloroethyl group, a 2,2,2-trifluoroethyl group, and a 3-chloropropyl group. And a 3-fluoropropyl group.
  • R ⁇ R The alkyl group of from 1 to 1 2 carbon atoms which is represented by '", R 2 and R 2', may be straight chain or branched, a methyl group, Echiru group, propyl Group, isopropyl, butyl, isobutyl, se-butyl, tert-butyl, pentyl, neopentyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pendecyl group, dodecyl group and the like.
  • alkyl groups may be substituted with a halogen atom, an alkoxy group, a carboxy group, an alkoxycarbonyl group, an acyl group, a cyano group, or the like, and more specifically, a trifluoromethyl group, Difluoromethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, 3-chloropropyl group, 3fluoropropyl group, methoxymethyl group, ethoxyquinmethyl group, carboxymethyl group, methoxycarbonylmethyl group, Ethoxycarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, butoxycarbonylmethyl group, pentyloxycarbonylmethyl group, hexyloxycarbonylmethyl group, octyloxycarbonylmethyl group, 2-methoxycarbonylethyl Group, acetonyl group, 1 Examples thereof include an acetylethy
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R 1 and R "include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like.
  • the alkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • the alkenyl group having 2 to 12 carbon atoms represented by R, R ′ ′′, R 2 and R 2 may be linear or branched, and may be an ethenyl group or a methallyl group. , 1-propynyl group, acrylyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 2 hexenyl group, and 3-hexenyl group.
  • the group may be substituted with a halogen atom or the like, and examples thereof include a 2-chloro-2-propenyl group, a 3-chloro-2-propenyl group, and a 4-chloro-2-butenyl group. Can be.
  • the alkynyl group having 2 to 12 carbon atoms represented by R 2 and R 2 ' may be linear or branched, and may be an ethynyl group, a propargyl group, a 1-methyl group.
  • Propargyl group, 1.1-dimethyl Examples thereof include a propargyl group, a 2-pentynyl group, a 3-pentynyl group, a 2-pentynyl group, and a 3-pentynyl group.
  • a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbon group having 1 to 6 carbon atoms may be mentioned on the aromatic ring of these aralkyl groups. Or a carboxy group, a hydroxyl group, a substituted or unsubstituted amino group, a cyano group, a nitro group, or the like.
  • Examples of the alkoxycarbonyl group having 1 to 12 carbon atoms represented by R 1 and R 1 ′ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group. Group, hexyloxycarbonyl group, octyloxycarbonyl group and the like.
  • R ', R 1' The Ararukiruoki aryloxycarbonyl group having a carbon number of ⁇ 1 1 represented by and R 1 ", benzyl O alkoxycarbonyl group, 4-methylbenzyl O alkoxycarbonyl group, 4 main Bok alkoxybenzylacetic O carboxymethyl Examples thereof include a carbonyl group, a 3-fluorobenzyloxycarbonyl group, and a 2-naphthylmethyl carbonyl group.
  • the alkyl group having 1 to 6 carbon atoms represented by R 3 may be linear or branched, and may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec A butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like can be exemplified.
  • An alkane such as a toluenesulfonyloxy group or an arenesulfonyloxy group can be exemplified.
  • dehydro (thio) morpholinecarboxylic acid derivative refers to a derivative of the general formula (5) in which X is an oxygen atom.
  • An oral morpholine carboxylic acid derivative and a dehydrothiomorpholine carboxylic acid derivative in which X is a sulfur atom are used as generic terms.
  • (thio) morpholine carboxylic acid derivative is a generic term for a morpholine carboxylic acid derivative and a thiomorpholine carboxylic acid derivative.
  • the arylisocyanate derivative represented by the general formula (4) which is a raw material for producing the bicyclic hydantoin derivative represented by the general formula (1), which is a compound of the present invention, is partially commercially available. It can be easily produced by reacting the corresponding aniline derivative with phosgene or a phosgene equivalent according to a conventional method.
  • the corresponding aniline derivative can be produced, for example, by the method described in EP-04241559A, EP-0496347A, or WO94 / 06753.
  • the dehydro (thio) morpholine carboxylic acid derivative represented by the general formula (5) is obtained by an addition ring-opening reaction between an N-benzyloxycarbonylaziridine-2-carboxylic acid derivative and 2-chloroethanol.
  • the N-benzyloxycarbonyl 0- (2-chloroethyl) serine derivative obtained by deprotecting the protecting group of the amino group and then carrying out a cyclization reaction in the presence of a base. It can be produced by reacting a (thio) morpholine carboxylic acid derivative represented by the formula (17) with an N-halogenating agent, followed by the action of a base, and elimination of hydrogen halide.
  • dehydro (thio) morpholinecarboxylic acid derivatives are in an equilibrium state between the 2,3-dehydro form and the 3,4-dehydro form, and the individual isomers and mixtures thereof are also included in the present invention. Included.
  • This reaction is preferably carried out in an organic solvent, for example, aromatic solvents such as benzene, toluene, xylene, and benzene, aliphatic hydrocarbon solvents such as hexane, pentane, and heptane; Ether solvents such as drofuran, dioxane, 1,2-dimethoxyethane, etc., halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, etc., alcohol solvents such as methanol and ethanol, or a mixed solvent thereof Can be used.
  • aromatic solvents such as benzene, toluene, xylene, and benzene
  • aliphatic hydrocarbon solvents such as hexane, pentane, and heptane
  • Ether solvents such as drofuran, dioxane, 1,2-dimethoxyethane, etc.
  • halogen solvents such as m
  • N halogenating agent examples include tert-butyl hypochlorite, N-chloro succinic acid imid, N-bromosuccinic acid imid and the like.
  • Bases that can be used as a hydrogen halide trapping agent include, for example, triethylamine, triptylamin, methylmorpholine, pyridine, dimethylaniline, 1,5-diazabicyclo [5.4.0] indene-5-ene, Examples include organic amines such as 1,4-diazabicyclo [2.2.2] octane, alkali metal bases such as sodium hydride and sodium amide, and metal alcoholates such as sodium methoxide and sodium ethoxide. be able to.
  • the reaction temperature for both the N-halogenation reaction and the dehydrogenation hydrogenation reaction is selected from the range of -30 to 150 ° C, but the reaction is carried out at around 0 ° C at the reflux temperature of the reaction mixture. Is preferred in terms of good yield.
  • the bicyclic hydantoin derivative of the present invention can be produced, for example, by the following production method.
  • the production method 11 is characterized in that the aryl isocyanate derivative (4) and dehydro (thio) morpholy
  • a method for producing the bicyclic hydantoin derivative (6) of the present invention by a cycloaddition reaction with a dicarboxylic acid derivative (5) will be described.
  • the production process of the bicyclic hydantoin derivative (6) is as follows. First, as shown in Production method 11, the amino group of the dehydro (thio) morpholinecarboxylic acid derivative (5) is added to the isocyanate group. After the formation of urea intermediate (18) ( ⁇ .-present-1), the amide nitrogen and ester are cyclized in the molecule to form bicyclic This gives the hydantoin derivative (6).
  • the urea intermediate (18) can be isolated, but the cyclization reaction from this to the bicyclic hydantoin derivative (6) (Step 1) has a high reaction rate. The desired product can be obtained in a one-step reaction without isolation.
  • Steps 1 and 2 are preferably performed in the presence of a base because the reaction rate is high and the yield is good.
  • a base since the dehydro (thio) morpholinecarbonic acid derivative itself is a base, it is not necessarily used. Not necessary.
  • bases that can be used include organic amines such as triethylamine, triptylamin, N-methylmorpholine, pyridine, and dimethylaniline, carbon dioxide, sodium carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, and the like.
  • alkali metal bases such as sodium hydride and sodium amide.
  • the amount of the base used There is no particular limitation on the amount of the base used, 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.
  • Solvents that can be used include, for example, aromatic solvents such as benzene, toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; getyl ether; tetrahydrofuran; Ether solvents such as dioxane and 1,2-dimethoxetane, halogen solvents such as methylene chloride, chloroform, and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; acetonitrile and propionitrile; Examples thereof include nitriles, esters such as ethyl acetate and ethyl propionate, amides such as N, dimethylformamide and N-methylpyrrolidone, and a mixed solvent thereof.
  • aromatic solvents such as benzene, toluene, xylene, and benzene
  • the reaction temperature is selected from the range of 130 to 150 ° C., but it is preferable to carry out the reaction at about 0 ° C. at the reflux temperature of the reaction mixture in terms of good yield.
  • the desired product can be obtained by a usual extraction operation, but if necessary, it can be purified by column chromatography.
  • the aryl isocyanate (4) to be used as a raw material in Step 11 is a known compound, for example, according to the method described in EP-0241559A, JP-A-1-203306 or JP-A-5-17427. Can be manufactured.
  • R 4 represents an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 11 carbon atoms
  • 5 represents an aralkyl group having 7 to 11 carbon atoms.
  • X 3 ′ is an alkoxycarbonyloxy group or an aralkyloxycarbonyl group.
  • a hydroxy-protecting group such as a hydroxy group, which can be deprotected by hydrolysis, such as a bicyclic hydantoin derivative (7), or X 3 ′ is deprotected by hydrogenolysis such as an aralkyloxy group.
  • a bicyclic hydantoin derivative (7 "), which is a hydroxyl-protecting group, as a raw material and deprotecting (Steps 1 and 4)
  • a bicyclic hydantoin derivative (5) in which the phenyl ring at the 5-position is a hydroxyl group (8)
  • an alkylating agent (9) in the presence of a base to produce the bicyclic hydantoin derivative (10) of the present invention.
  • Step-3 is to selectively hydrolyze an alkoxycarbonyloxy group or an aralkyloxycarboxyloxy group at the 5-position of the phenyl ring of the bicyclic hydantoin derivative (7,) to obtain a bicyclic hydantoin derivative ( This is the process for manufacturing 8).
  • the hydrolysis reaction for deprotection proceeds easily under either acidic or basic conditions.
  • Acids that can be used include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and bases such as inorganic bases such as potassium hydroxide, sodium hydroxide, carbonate carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Metal alcoholates such as trimethymethoxide and sodium methoxide can be exemplified.
  • the amount of the acid and the base used is not particularly limited, but it is preferable to use the same amount or more based on the reaction substrate because the reaction rate is high and the yield is good.
  • the reaction usually employs a solvent, and any solvent that does not harm the reaction can be used.
  • solvent any solvent that does not harm the reaction can be used.
  • examples include methanol, ethanol, propanol, butanol, toluene, benzene, tetrahydrofuran, and acetonitrile.
  • Tril, dioxane or water, and a mixed solvent thereof can be exemplified.
  • the reaction temperature is selected from the range of 110 to 150 ° C., but it is preferable to carry out the reaction at around room temperature to the reflux temperature of the reaction mixture.
  • the desired product can be obtained by ordinary isolation procedures. If necessary, the product can be purified by column chromatography.
  • Step-4 is a step for producing a bicyclic hydantoin derivative (8) by selectively hydrogenating and decomposing an aralkyloxy group at the 5-position of the phenyl ring of the bicyclic hydantoin derivative (7 ").
  • the hydrogenation decomposition reaction of the aralkyl group can be performed under any reaction conditions as long as it does not harm the other functional groups present.However, the reaction between the hydrogen donor and the metal catalyst converts hydrogen. It is preferable to carry out the reaction by a method in which it is generated in the reaction system in terms of good yield.
  • a hydrogen donor formic acid, ammonium formate, cyclohexene, cyclohexadiene, etc. can be used.
  • Platinum black, palladium carbon, palladium hydroxide, palladium oxide, platinum black, platinum carbon, platinum oxide and the like can be exemplified.
  • the reaction is preferably performed in an organic solvent, and any solvent that does not harm the reaction can be used.
  • examples include methanol, ethanol, benzene, toluene, xylene, and a mixed solvent thereof. it can.
  • the reaction temperature is selected from the range of -10 to 150, but it is preferable to carry out the reaction at about 0 ° C at the reflux temperature of the reaction mixture.
  • the desired product can be obtained by a usual isolation operation, but if necessary, it can be purified by column chromatography or recrystallization.
  • step-5 the bicyclic hydantoin derivative (8), which can be produced by step-13 or step-14, is reacted with an alkylating agent represented by the general formula (9) in the presence of a base.
  • This is a step of producing the bicyclic hydantoin derivative (10) of the present invention.
  • a base It is essential that the reaction is carried out in the presence of a base.
  • bases include organic amines such as triethylamine, tributylamine, N-methylmorpholine, pyridine and dimethylaniline, lithium carbonate, and the like.
  • alkali metal bases such as sodium carbonate, sodium bicarbonate, sodium bicarbonate, sodium hydride, and sodium amide.
  • the amount of the base to be used is not particularly limited, but it is preferable to use the base in an equivalent amount or more based on 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 are useful.
  • Ether-based solvents such as ter, tetrahydrofuran, dioxane, 1,2-dimethoxetane, halogen-based solvents such as methylene chloride, chloroform, carbon tetrachloride, etc., ketones such as acetone and methylethylketone, acetate nitrile, propio Nitriles such as nitrile, ethyl acetate, Examples thereof include esters such as ethyl propionate, amides such as N.N-dimethylformamide and N-methylpyrrolidone, and mixed solvents thereof.
  • reaction proceeds even at room temperature, the reaction is completed in a short time by carrying out the heating, and the desired product can be obtained in good yield.Therefore, the reaction is carried out under heating at about 50 to 150 ° C. Is preferred.
  • the product can be purified by a column chromatography, if necessary, by a force capable of obtaining the desired product by a normal isolation operation.
  • Production method 13 is a method for preparing the bicyclic hydantoin derivative (1) of the present invention, wherein X 2 Is a fluorine atom, and X 3 is a nitro group.
  • the bicyclic hydantoin derivative (11) is used as a starting material, and the bicyclic hydantoin derivative of the present invention Via the hydantoin derivative (13), the two-nitro group is selectively reduced and simultaneously converted into a bicyclic hydantoin derivative (14) by an intramolecular cyclization reaction, and finally the 4-position of the benzo (thio) oxazine ring
  • This is a method for producing the bicyclic hydantoin derivative (16) of the present invention by alkylating a nitrogen atom.
  • step 16 the bicyclic hydantoin derivative (11) is reacted with a glycolic acid or thioglycolic acid derivative (12) in the presence of a base to select an active fluorine atom f adjacent to the ditro group.
  • a base to select an active fluorine atom f adjacent to the ditro group.
  • this is a step of producing a bicyclic hydantoin derivative (13) having a thio group.
  • glycolic acid or thioglycolic acid derivative (12) as a reaction reagent is commercially available, but an ester can be easily produced by esterifying glycolic acid or thioglycolic acid according to a conventional method.
  • the reaction is preferably carried out in the presence of a base because the reaction rate is high and the yield is good.
  • a base examples include organic compounds such as triethylamine, tributylamine, methylmorpholine, pyridine and dimethylaniline.
  • alkali metals such as amines, carbon dioxide, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydride and sodium amide. It is preferable to use the base in an amount of 1 equivalent or more based on the reaction substrate from the viewpoint of good yield.
  • Solvents that can be used include, for example, aromatic solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; getyl ether; tetrahydrofuran , Dioxane, ether solvents such as 1,2-dimethoxetane, halogen solvents such as methylene chloride, chloroform and carbon tetrachloride, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitol Examples thereof include nitriles such as ril, esters such as ethyl acetate and ethyl propionate, amides such as N, N dimethylformamide and N-methylpyrrolidone, and a mixed solvent thereof. .
  • the reaction temperature is selected from the range of 0 to 150 ° C., but it is preferable to carry out the reaction at room temperature to the reflux temperature of the reaction mixture in terms of good yield.
  • Step-17 is carried out by selectively reducing the two-position group at the 5-position of the phenyl ring of the bicyclic hydantoin derivative (13), which can be produced by the method of Step-6, to an amino group. This is a step of condensing with an ester of the formula (1) to form a benzo (thio) oxazinone ring.
  • this step it is necessary to selectively reduce the nitro group to the amino group without impairing the carbonyl group ⁇ double bond in the molecule, and use reduced iron as the reducing agent. Is preferred. It is preferable to use an excess amount of reduced iron with respect to the substrate in order to complete the reaction, and the reaction is usually performed using 10 to 50 equivalents.
  • the reaction needs to be performed in a solvent, and a carboxylic acid solvent such as acetic acid or propionic acid can be usually used. It can also be carried out in a mixed solvent with an acetate such as methyl acetate / ethyl acetate.
  • the reaction temperature is selected from the range of room temperature to 150, but it is preferable to carry out the reaction at the reflux temperature of an acetic acid / ethyl acetate mixed solvent system in that the reaction is quick and the yield is good.
  • the desired product can be obtained by ordinary isolation procedures. If necessary, the product can be purified by column chromatography.
  • Step-17 comprises reacting the bicyclic hydantoin derivative (14), which can be produced by step-6, with an alkylating agent represented by the general formula (15) in the presence of a base, This is a step of producing a sex hydantoin derivative (16).
  • the reaction must be carried out in the presence of a base.
  • bases include organic amines such as triethylamine, triptylamine, N-methylmorpholine, pyridine and dimethylaniline, potassium carbonate, and carbonate.
  • alkali metal bases such as sodium, potassium bicarbonate, sodium bicarbonate, sodium hydride, sodium amide, and the like.
  • the amount of the base to be used is not particularly limited, but the yield is good when the reaction is carried out using an equivalent amount or more based on the reaction substrate. It is preferred in that respect.
  • 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 are useful.
  • Ether solvents such as ter, tetrahydrofuran, dioxane, 1,2-dimethyloxetane, etc .; halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, etc .; ketones such as acetone and methyl ethyl ketone; acetonitrile And nitriles such as propionitrile and the like, esters such as ethyl acetate and ethyl propionate, amides such as N, N-dimethylformamide and N-methylpyrrolidone, or a mixed solvent thereof. be able to.
  • reaction proceeds even at room temperature, the reaction is completed in a short time by carrying out the heating, and the desired product can be obtained in good yield.Therefore, the reaction is carried out under heating at about 50 to 150 ° C. Is preferred.
  • the desired product can be obtained by a usual isolation operation. If necessary, the product can be purified by column chromatography.
  • the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited thereto.
  • Methyl 2,3-dehydromorpholine-3-carboxylate (0.53 g, 3.70 mmol) in toluene (14 mL of solution) was added to a solution of 4-chloro-2-fluoro-5-methoxyphenylisocyanate (0 mL). 79 g, 3.92 MIO1) and a solution of triethylamine (0.23 mL, 1.7 mmol) in toluene (6 mL) were added dropwise with stirring under ice-cooling, and the mixture was stirred for 30 minutes. The reaction solution was stirred at room temperature for 12 hours. Thereafter, the mixture was further stirred for 5 hours at 80 ° C.
  • Methyl 2,3-dehydromorpholine-3-carboxylate (0.26 g, 1.82 mmol) in toluene (7 mU, 5- (butyne 3-yloxy) -4-chloro-2-fluorophenylisocyanate (0.36 g, A solution of 1.50 mmol) and triethylamine (0.1 mL, 0.8 mmol) in toluene (3 mL) was added dropwise with stirring under ice-cooling, and the mixture was stirred for 30 minutes at 0 ° C. After stirring the reaction solution at room temperature for 48 hours, The mixture was further stirred for 7 hours at 80 ° C.
  • Methyl 2,3-dehydromorpholin-3-carboxylate (1.78 g, 12.4 mmol) in toluene (35 m) was added to 4-chloro-2-fluoro-5-methoxycarboxycarbonyloxyphenylisocyanate (3.0 g, 12.2 mmol).
  • 4-chloro-2-fluoro-5-methoxycarboxycarbonyloxyphenylisocyanate 3.0 g, 12.2 mmol.
  • triethylamine 0.7 mL, 5 mmol in toluene (15 m in water) were added dropwise with stirring under ice-cooling, and the mixture was stirred for 30 min at 0 ° C.
  • Methyl 2,3-dehydromorpholine-3-carboxylate (3.18g, 22.2mmo) in toluene (70mU solution, 2,4-difluoro-5-to-two-port phenyl isocyanate (4.0g, 20.20g) Omol) in toluene (30 m
  • triethylamine (1.39 niL, 10 mmol) was added, and the mixture was stirred at 0 ° C for 30 minutes. Thereafter, the reaction mixture was stirred at room temperature for 3 hours and further at 80 ° C for 7 hours.
  • the aqueous layer was extracted with ethyl acetate (50 mL ⁇ 3), the organic layer was washed with a saturated aqueous sodium chloride solution (300 mL), dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure.
  • reaction solution was filtered through celite, water (50 mL) was added to the filtrate, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (10 mL ⁇ 2). The organic layers were combined, and a saturated aqueous solution of sodium hydrogencarbonate (20 mL ⁇ 4) and a saturated aqueous solution of sodium chloride (washed with 20 m and dried over anhydrous magnesium sulfate.
  • the compound of the present invention when used as a herbicide, it can be used as it is, but in general, one or several adjuvants can be mixed and used as a herbicide.
  • various carriers, extenders, solvents, surfactants, stabilizers, and the like are blended and formulated into a formulation such as a hydrating agent, an emulsion, a powder, a granule, a flowable and the like by a conventional method. It is preferred to use
  • 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, Suitable are acid amides, esters, nitriles and the like, and one or a mixture of two or more of these are used.
  • fillers examples include clays such as clay or bentonite, talcs such as talc and phyllite, mineral powders such as diatomaceous earth and oxides such as white carbon, and vegetable powders such as soybean powder and CMC. Etc. 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 preferred effects are obtained by application from the time before germination to the time of germination of the control weeds.
  • Herbicides containing the compound of the present invention as an active ingredient include other active ingredients that do not inhibit the herbicidal activity of the present active ingredient, such as other herbicides, insecticides, fungicides, plant growth regulators, and the like. Mixed use or combined use is also possible.
  • Emulsion was obtained by uniformly mixing 20 parts of the compound of the present invention, 35 parts of xylene, 40 parts of hexagon hexanone, and 5 parts of Solbol 90OA (manufactured by Toho Chemical).
  • Formulation Example 1 (Wetting powder)
  • Test Example-1 (Effect on paddy weeds)
  • a pot of 1 / 10,000 is filled with paddy soil, and after shaving, seeds of Tainubie, Tamagayari, Konagi, Firefly, Matsubai, and other first-year broadleaf weeds are sown. (Variety: Koshi Hikari) was transplanted and kept in port water. One day later, a wettable powder or an emulsion of the compound of the present invention prepared according to Formulation Examples 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 in accordance with the criteria shown in Table 19, and the results are shown in Table 20. Table-20 Effect of soil treatment before weed emergence by paddy soil
  • a field soil was filled into a 10xl0citi 2 ⁇ 5cm deep bat, and seeds of linubi, mexishba, aobu, shiroza and corn were sown and covered with 0.5cm of soil.
  • the wettable powder or emulsion of the present compound prepared according to the formulation example was diluted and uniformly spread on the covering soil so as to have a predetermined dose per are.
  • the herbicidal effect on the test weeds and the phytotoxicity on corn were investigated in accordance with the criteria shown in Table 19, and the results are shown in Table 21.
  • the field soil was filled in a back Bok area 10Xl0cm 2 depth 5Cra, this Inubi E, Ichibi, after grown to sown Aobyu and Chenopodium album 15 days, the present invention prepared according to Formulation Example foliage of a plant
  • the hydrate or emulsion of the compound was diluted, adjusted to a predetermined concentration, added with a spreading agent, and sprayed with 20 liters of water per are.
  • the herbicidal effect on the test weeds was investigated in accordance with the criteria shown in Table 19, and the results are shown in Table 22. Table-22 Effects of foliage treatment
  • the bicyclic hydantoin derivative of the present invention has excellent herbicidal activity against a wide variety of weeds, and can be used as an effective active ingredient of a herbicide. These derivatives are easily produced by the production method of the present invention.
  • the herbicide of the present invention can be used as an agricultural and horticultural herbicide for paddy fields or field effects.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Cette invention concerne de nouveaux dérivés d'hydantoïne bicycliques qui possèdent une excellente action herbicide. Cette invention concerne également un procédé de préparation de ces dérivés, ainsi que des herbicides les contenant en qualité d'ingrédient actif. Ces dérivés d'hydantoïne bicycliques, qui correspondent à la formule générale (1), peuvent être obtenus en faisant réagir, par exemple, un dérivé d'isocyanate aryle correspondant à la formule générale (4) avec un dérivé d'acide déhydro(thio)morpholinecarboaxylique correspondant à la formule générale (5).
PCT/JP1997/002046 1996-06-14 1997-06-13 Derives d'hydantoine bicycliques, produits intermediaires destines a leur fabrication, procede de preparation de ces derives et herbicides les contenant en qualite d'ingredient actif WO1997047626A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31069/97A AU3106997A (en) 1996-06-14 1997-06-13 Bicyclic hydantoin derivatives, intermediates for the preparation thereof, process for the preparation of them, and herbicides containing the same as active ingredient

Applications Claiming Priority (2)

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JP8/154563 1996-06-14
JP15456396 1996-06-14

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WO1997047626A1 true WO1997047626A1 (fr) 1997-12-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008227A2 (fr) * 2000-07-21 2002-01-31 Lion Bioscience Ag Derives d'hydantoine bicycliques et bibliotheques combinatoires de ces derniers
WO2012041789A1 (fr) 2010-10-01 2012-04-05 Basf Se Benzoxazinones herbicides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092606A1 (fr) * 2001-05-15 2002-11-21 Takeda Chemical Industries, Ltd. Derives d'imidazolidine fusionnes, leur procede de preparation et d'utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179276A (en) * 1977-02-01 1979-12-18 E. I. Du Pont De Nemours And Company Novel imidazothiazine-1,3 (2H)-diones
EP0070389A2 (fr) * 1981-06-16 1983-01-26 Sumitomo Chemical Company, Limited 2-(2-Fluoro-4-halophényl-5-substitué)hydantoines, leur préparation et application
DE3827221A1 (de) * 1988-08-11 1990-02-15 Bayer Ag Substituierte n-phenyl-stickstoff- bzw. stickstoff-schwefel-heterocyclen, verfahren sowie entsprechende heterocyclische phenolderivate, phenyliso(thio)cyanate und -carbamate als zwischenprodukte zu ihrer herstellung, ihre verwendung in herbiziden und pflanzenwuchsregulierenden mitteln
WO1996020195A1 (fr) * 1994-12-27 1996-07-04 Sagami Chemical Research Center Derives d'hydantoine, procede de production et herbicides les incluant comme ingredients actifs

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179276A (en) * 1977-02-01 1979-12-18 E. I. Du Pont De Nemours And Company Novel imidazothiazine-1,3 (2H)-diones
EP0070389A2 (fr) * 1981-06-16 1983-01-26 Sumitomo Chemical Company, Limited 2-(2-Fluoro-4-halophényl-5-substitué)hydantoines, leur préparation et application
DE3827221A1 (de) * 1988-08-11 1990-02-15 Bayer Ag Substituierte n-phenyl-stickstoff- bzw. stickstoff-schwefel-heterocyclen, verfahren sowie entsprechende heterocyclische phenolderivate, phenyliso(thio)cyanate und -carbamate als zwischenprodukte zu ihrer herstellung, ihre verwendung in herbiziden und pflanzenwuchsregulierenden mitteln
WO1996020195A1 (fr) * 1994-12-27 1996-07-04 Sagami Chemical Research Center Derives d'hydantoine, procede de production et herbicides les incluant comme ingredients actifs

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* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 59, No. 5, 2 September 1963, SILVANO ROSSI et al., "Dihydro-1,4-Thiazines"; & GAZZ. CHIM. ITAL., 92, p. 1367-1378, (1962). *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008227A2 (fr) * 2000-07-21 2002-01-31 Lion Bioscience Ag Derives d'hydantoine bicycliques et bibliotheques combinatoires de ces derniers
WO2002008227A3 (fr) * 2000-07-21 2002-08-29 Lion Bioscience Ag Derives d'hydantoine bicycliques et bibliotheques combinatoires de ces derniers
WO2012041789A1 (fr) 2010-10-01 2012-04-05 Basf Se Benzoxazinones herbicides

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