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WO1994013665A1 - Composes a base d'amides cycliques, procede de production et compositions herbicides les contenant - Google Patents

Composes a base d'amides cycliques, procede de production et compositions herbicides les contenant Download PDF

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Publication number
WO1994013665A1
WO1994013665A1 PCT/JP1993/001815 JP9301815W WO9413665A1 WO 1994013665 A1 WO1994013665 A1 WO 1994013665A1 JP 9301815 W JP9301815 W JP 9301815W WO 9413665 A1 WO9413665 A1 WO 9413665A1
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WIPO (PCT)
Prior art keywords
substituted
methyl
group
halogen atom
phenyl
Prior art date
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PCT/JP1993/001815
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English (en)
Inventor
Masahiko Ikeguchi
Keiichiro Ito
Masahiko Sawaki
Yasuo Morishima
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Ishihara Sangyo Kaisha Ltd.
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Filing date
Publication date
Application filed by Ishihara Sangyo Kaisha Ltd. filed Critical Ishihara Sangyo Kaisha Ltd.
Priority to BR9307666A priority Critical patent/BR9307666A/pt
Priority to EP94903001A priority patent/EP0690857A1/fr
Priority to AU57144/94A priority patent/AU5714494A/en
Priority to KR1019950702422A priority patent/KR950704306A/ko
Publication of WO1994013665A1 publication Critical patent/WO1994013665A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to cyclic amide compounds of the formula (I) given hereinafter, a process for their production, their use as herbicides, and intermediates useful for their production, herbicidal compositions comprising the cyclic amide compounds and other herbicidaUy active components, and a herbicidal method which comprises applying such herbicidal compositions to plants.
  • Japanese Unexamined Patent Publication No. 89485/1992 discloses cyclic amide derivatives having herbicidal activities, but such derivatives are different in the chemical structure from the compounds of the present invention represented by the formula (I) given hereinafter.
  • the present invention provides a cyclic amide compound of the formula (I):
  • R 1 is a phenyl group which may be substituted
  • R 2 is a hydrogen atom or an alkyl group which may be
  • D is an oxygen atom, a sulfur atom or -N(R 4 )-, wherein R 4 is an alkyl group.
  • the present invention further provides a process for producing such a cyclic amide compound, herbicidal compositions containing it, herbicidal methods of applying such herbicidal compositions and an intermediate useful for its production.
  • the substituent for the phenyl group which may be substituted, for R 1 may, for example, be a halogen atom; an alkyl group which may be substituted by a halogen atom; an alkoxy group which may be substituted by a halogen atom; an alkylthio group which may be substituted by a halogen atom or an alkylsulfonyl group which may be substituted by a halogen
  • R 3 may, for example, be a halogen atom; an alkyl group which may be substituted by a halogen atom; an alkoxy group which may be substituted by a halogen atom; an alkylthio group which may be substituted by a halogen atom; an alkylsulfonyl group which may be substituted by a halogen atom; an aryl group which may be substituted by a halogen atom or a halogenoalkyl group; a heteroaryl group which may be substituted by a halogen atom or a halogenoalkyl group; an aryloxy group which may be substituted by a halogen atom or a halogenoalkyl group; or a heteroaryloxy group which may be substituted by a halogen atom or a halogenoalkyl group.
  • the above aryl group or aryl moiety may, for example, be a phenyl group or a naphthyl group
  • the above heteroaryl group or heteroaryl moiety may, for example, be a pyridyl group, a pyrrole group, a thienyl group or a furyl group.
  • the number of such substituents may be one or more, and in the case of a plurality of substituents, such substituents may be the same or different.
  • furan-2-yl includes, for example, furan-2-yl, furan-3- yl, thiophen-2-yl, thiophen-3-yl, l-methylpyrrol-2-yl and
  • ⁇ includes, for example,
  • isothiazol-3-yl includes, for example, isothiazol-3-yl, isoxazol-3-yl, l-methylpyrazol-3-yl, isothiazol-4-yl, isoxazol-4-yl, l-methylpyrazol-4-yl, isothiazol-5-yl.
  • isoxazol-5-yl and l-methylpyrazol-5-yl includes, for example, benzofuran-2-yl, benzofuran-3-yl, benzothiophen-2-yl, benzothiophen-3-yl, l-methyl-indol-2-
  • N fOj includes, for example, benzisothiazol-3-yl, benzisoxazol-3-yl and 1- methyl-benzopyrazol-3-yl.
  • R 1 , R 2 , R 3 and R 4 in the formula (I) may, for example, be a C ⁇ _ 8 , preferably C 1 _ ⁇ , linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group or an octyl group.
  • the halogen atom for R 1 , R 2 or R 3 or the halogen atom as a substituent may be fluorine, chlorine, bromine or iodine.
  • the number of halogen atoms as substituents may be one or more, and in the case of a plurality of such substituted halogen atoms, they may be the same or different.
  • R 1 is preferably a phenyl group.
  • R 2 is preferably an alkyl group which may be substituted by a halogen atom, more preferably an unsubstituted alkyl group.
  • R 3 is preferably ⁇ ⁇ ⁇ which may be substituted.
  • R la is a phenyl group which may be substituted by a substituent selected from the group consisting of a halogen atom, a C ⁇ _ 4 alkyl group, a halogen-substituted ⁇ _ alkyl group and a C 1 _ 4 alkoxy group
  • R 2a is a C** ⁇ alkyl group which may be substituted by a halogen atom
  • R 3a is a furan-2-yl group, a furan-3-yl group, a thiophen-2-yl group, a thiophen-3-yl group, a 1- methylpyrrol-2-yl group, a l-methylpyrrol-3-yl group, a thiazol-2-yl group, a thiazol-4-yl group, a thiazol-5-yl group, an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl
  • R lb is a phenyl group which may be substituted by a substituent selected from the group consisting of a halogen atom, a C ⁇ _ ⁇ alkyl group, a halogen-substituted C 1 _ 4 alkyl group and a C 1 _ 4 alkoxy group
  • R 2b is a C 1 _ 4 alkyl group which may be substituted by a halogen atom
  • R 3b is a benzothiazol-2-yl group, a benzoxazol-2-yl group or a l-methylbenzimidazol-2-yl group, provided that these substituents may be substituted by from 1 to 4 substituents selected from the group consisting of a halogen atom, a C ⁇ _ alkyl group, a halogen-substituted C 1 _ alkyl group and a C 1 _ 4 alkoxy group.
  • R lc is a phenyl group which may be substituted by a substituent selected from the group consisting of a halogen atom, a C ⁇ _ ⁇ alkyl group, a halogen-substituted C 1 _ 4 alkyl group and a C* ⁇ alkoxy group
  • R 2c is a C 1 _ 4 alkyl group which may be substituted by a halogen atom
  • R 3c is a benzothiazol-2-yl group, which may be substituted by from 1 to 4 substituents selected from the group consisting of a halogen atom, a C 1 _ 4 alkyl group, a halogen-substituted C 1 _ 4 alkyl group and a C ⁇ _ alkoxy group.
  • cyclic amide compounds of the formula (I) the following compounds are most preferred.
  • the compound of the formula (I) can be prepared, for example, by a process represented by the following reaction (A) .
  • R 1 , R 2 and R 3 are as defined above, and each of R 8 and R 9 is an alkyl group.
  • the reaction (A) is usually carried out in the presence of a solvent.
  • the solvent may, for example, be an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; a cyclic or non-cyclic aliphatic hydrocarbon such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane or cyclohexane; an ether such as dioxane or tetrahydrofuran; an ester such as methyl acetate or ethyl acetate; or an aprotic polar solvent such as dimethylsulfoxide, sulforane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone or pyridine.
  • the reaction (A) is carried out under heating, and the reaction temperature is usually from 30 to 300°C, preferably from 50 to 200°C.
  • the reaction time is usually from 0.01 to 100 hours, preferably from 0.01 to 20 hours.
  • the compound of the formula (II) is a known compound or can readily be produced by known methods disclosed in e.g. Japanese Unexamined Patent Publications No. 89485/1992 and No. 172485/1984, Chem. Pharm. Bull., vol. 31, No. 6, 1896-1901 (1983), and ditto, vol. 32, No. 10, 3848-3856 (1984).
  • the compound of the formula (III) can be produced, for example, from R 3 -CN or a nitrile compound of the formula (VII).
  • the compound of the formula (III) can be obtained by introducing a methylene group to the amino group of the compound of the formula (IV).
  • methylene-introducing reactions commonly used in this field can widely be employed.
  • a method of using formalin or paraformaldehyde may be mentioned.
  • the compound of the formula (IV) may be synthesized from R 3 -CN by means of a Grignard reagent or other reagents commonly used in this field, or may be prepared by converting a carbonylamide compound of the formula (V) to an amino compound by a Hofmann rearrangement reaction.
  • a suitable method commonly used in this field can be employed for the Hofmann rearrangement reaction.
  • Such a Hofmann rearrangement reaction may be conducted, for example, by treatment in the presence of an alkali- hypohalite.
  • the carbonylamide compound of the formula (V) can be obtained by hydrolyzing the nitrile group of the compound of the formula (VI). This hydrolysis may be carried out by a method commonly used in this field. For example, treatment with an acid, alkali or peroxide in the presence of water, may be mentioned, and reagents as described hereinafter may be employed for this purpose.
  • the nitrile compound of the formula (VI) can be prepared by introducing a methyl group to the methylene group adjacent to the nitrile group of the compound of the formula (VII).
  • a suitable method commonly used in this field may be employed.
  • a methyl halide may be reacted in the presence of a strong alkali.
  • a methyl halide may be reacted in the presence of an alkali metal compound.
  • the compound of the formula (III) can be produced by a method as represented by the following reaction (B).
  • this compound of the formula (III) may exist in an equilibrium state with its trimer.
  • R 3 is as defined above, M is a sodium atom or a potassium atom, and X is chlorine, bromine or iodine, provided that R 3 in the formula R 3 -CN does not include a group substituted by a bromine atom or an iodine atom.
  • R 3a is as defined above.
  • D is -N(R 4 ) -, wherein R 4 is an alkyl group:
  • R 5 is a hydrogen atom; a halogen atom; an alkyl group which may be substituted by a halogen atom; an alkoxy group which may be substituted by a halogen atom; an alkylthio group which may be substituted by a halogen atom; an alkylsulfonyl group which may be substituted by a halogen atom; an aryl group which may be substituted by a halogen atom or a halogenoalkyl group; a heteroaryl group which may be substituted by a halogen atom or a halogenoalkyl group; an aryloxy group which may be substituted by a halogen atom or a halogenoalkyl group; or a heteroaryloxy group which may be substituted by a halogen atom or a halogenoalkyl group, Y is a hydrogen atom; a halogen atom; an alkyl group which may be substituted by
  • the plurality of R 5 may be the same or different.
  • NBS represents N-bromosuccinimide
  • NCS represents N- chlorosuccinimide.
  • R 3 is which may be substituted, the compounds of the formulas (VII) to (III) can be produced by reacting a hetero ring-forming reagent commonly used in this field, such as a nitrile compound, with the compound of the formula:
  • the compound of the formula (VII) can be produced by using CNCH 2 CN or CNCH 2 COOH as the hetero ring-forming reagent under the conditions commonly known in this field.
  • the compound of the formula (VI) can be prepared by a method represented by the reaction (G) or (H)
  • the compound of the formula (V-l) can be prepared by a method represented by the reaction (I).
  • the compound of the formula (IV) can be prepared by a method represented by the reaction (J) .
  • the solvent or the inert solvent to be used in the above reactions (B) to (K) may suitably be selected from aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; cyclic and non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as diethyl ether, dioxane and tetrahydrofuran; nitriles such as acetonitrile, propionitrile and acrylonitrile; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as dimethylsulfoxide, sulforane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and pyridine; ketones such as acetone and methyl eth
  • the base may suitably be selected from carbonates such as potassium carbonate and sodium carbonate; hydrogen carbonates such as potassium hydrogencarbonate and sodium hydrogencarbonate; metal hydroxides such as potassium hydroxide and sodium hydroxide; tertiary amines such as triethylamine; and pyridines such as pyridine and 4- dimethylaminopyridine.
  • the inert gas may suitably be selected from such gases as argon, helium and nitrogen.
  • N,N'-dicyclohexylcarbodiimide may, for example, be mentioned.
  • the catalyst may, for example, be 2,2'-azobisisobutyronitrile, metachloroperbenzoic acid or light.
  • the acid may, for example, be formic acid, hydrochloric acid, hydrobromic acid or sulfuric acid.
  • the alkali may, for example, be potassium hydroxide, sodium hydroxide or sodium metal.
  • the peroxide may, for example, be hydrogen peroxide.
  • the reducing agent for the nitro group in the reaction (K) may, for example, be tin chloride, sodium sulfide (Na 2 S, Na 2 S 2 , Na 2 S ⁇ ), sodium hydrosulfide (NaSH), sodium dithionite (Na 2 S 2 0 4 ), ammonium sulfide ((NH 4 ) 2 S) or hydrazine in addition to those described in the above reaction scheme.
  • platinum dioxide, Raney nickel, palladium-carbon, rhodium, iron, copper or a hydrogen- transfer catalyst may, for example, be used for the reaction with hydrogen, ammonium formate, alcohol, cyclohexene, formic acid, triethylammonium formate or ammonium chloride.
  • Gramineous weeds include Echinochloa such as barnyardgrass (Echinochloa oryzicola) or cockspur grass (Panicum crus-qalli) , Brachiaria such as alexandergrass (Brachiaria plantaqinea) or paragrass (Panicum purpurascen) , and eptochloa such as sprangletop (Leptochloa chinensis) or red sprangletop (Leptochloa panicea) .
  • Echinochloa such as barnyardgrass (Echinochloa oryzicola) or cockspur grass (Panicum crus-qalli)
  • Brachiaria such as alexandergrass (Brachiaria plantaqinea) or paragrass (Panicum purpurascen)
  • eptochloa such as sprangletop (Leptochloa chinensis) or red sprangletop (Leptochloa
  • Cyperaceae such as Japanese bulrush (Scirpus juncoides) , flatsedge (Cyperus serotinus) , small-flower umbrellaplant (Cyperus difformis) , slender spikerush (Eleocharis acicularis) , and water chestnut (Eleocharis kuroquwai) , alismataceae such as Japanese ribbon wapato (Saqittaria pyqmaea) , arrow-head (Saqittaria trifolia) , and narrowleaf waterplantain (Alisma canaliculatum) , pontederiaceae such as monochoria (Monochoria vaqinalis) and monochoria species (Monochoria korsa
  • Cyperaceae such as Japanese bulrush (Scirpus juncoides) , flatsedge (Cyperus serotinus) , small-flower umbrellaplant (Cyperus difformis)
  • R la , R 2a and R 3a are as defined above, are capable of controlling noxious weeds especially in a paddy rice field, e.g. gramineous weeds such as barnyardgrass, selectively at a low dose without giving any phytotoxicity to rice plants, and they are excellent in the persistency of the herbicidal effects as compared with conventional herbicides, whereby constant herbicidal effects can be expected over a long period of time.
  • R l , R 2b and R 3b are as defined above, are capable of controlling noxious weeds especially in a paddy rice field, e.g. gramineous weeds such as barnyardgrass, selectively at a low dose without giving any phytotoxicity to rice plants, and they are excellent in the persistency of the herbicidal effects as compared with conventional herbicides, whereby constant herbicidal effects can be expected over a long period of time.
  • compounds of the formula (I) still typical compounds of the formula:
  • R lc , R 2c and R 3c are as defined above, are capable of controlling noxious weeds especially in a paddy rice field, e.g. gramineous weeds such as barnyardgrass, selectively at a low dose without giving any phytotoxicity to rice plants, and they are excellent in the persistency of the herbicidal effects as compared with conventional herbicides, whereby constant herbicidal effects can be expected over a long period of time.
  • a herbicidal composition containing the compound of the present invention may be applied to various places including not only paddy fields but also upland fields and non-agricultural fields such as forests, farm roads, open grounds and factory sites. Further, the manner of application may suitably be selected from soil treatments and foliage treatments.
  • the compound of the present invention is usually mixed with various agricultural adjuvants and formulated into various formulations such as granules, water dispersible granules, wettable powders, aqueous suspensions, oil suspensions, aqueous solutions, emulsifiable concentrates, tablets or capsules. It can be formulated into any formulations konwn in this field so long as the object of the present invention is satisfied.
  • Such agricultural adjuvants include solid carriers such as diatomaceous earth, hydrated lime, calcium carbonate, talc, white carbon, kaoline, bentonite, jeaklite, clay, and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, and alcohol; spreaders and surfactants such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium lignin sulfonate, polyoxyethylene alkylaryl ether sulfate, polyoxyethylene glycol alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkylaryl ether, an ester of polyoxyethylene aliphatic acid, and an ester of polyoxyethylene sorbit
  • Such adjuvants may be selected from those known in this field so long as the object of the present invention is satisfied. Further, other conventional adjuvants such as bulking agents, thickeners, anti- settling agents, anti-freezing agents, dispersion stabilizers, phytotoxicity-reducing agents, and antifungus agents may be used.
  • the weight ratio of the compound of the present invention to the agricultural adjuvants is usually from 0.1:99.9 to 90:10, preferably from 0.2:99.8 to 80:20.
  • the dose of the herbicidal composition of the present invention can not generally be defined, since it may vary depending upon the weather condition, the soil condition, the type of the formulation, the types of the weeds to be controlled, the season for the application, etc.
  • the compound of the present invention would be applied in an amount of from 0.1 to 40 g/a, preferably from 0.5 to 20 g/a.
  • the herbicidal compositions of the present invention may be used in admixture with or in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents.
  • Said other agricultural chemicals include, for example, herbicides, fungicides, antibiotics, plant hormones and insecticides. In such a case, they may exhibit even better effects or activities.
  • the compounds of the present invention are used in admixture with or in combination with one or more other herbicidaUy active components as will be described hereinafter, synergistic effects may be obtained.
  • the ratio of the compound of the present invention to such other herbicidaUy active component can not generally be defined, since it varies depending upon the weather condition, the soil condition, the type of the formulation, the season for the application, the manner of the application, etc.
  • at least one such other herbicidaUy active component may be incorporated usually in an amount of from 0.01 to 100 parts by weight, preferably from 0.02 to 60 parts by weight, per part by weight of the compound of the present invention.
  • the total dose of all the active ingredients is usually from 0.2 to 100 g/a, preferably from 0.5 to 50 g/a.
  • pyrazole compounds such as 2-[4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5- yloxy]acetophenone (common name: pyrazoxyfen) , 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-pyrazolyl-p- toluenesulfonate (common name: pyrazolate), and
  • urea compounds such as l-( ⁇ , ⁇ _ ⁇ dimethylbenzyl)-3-(p-tolyl)urea (common name: daimuron), and
  • R la , R 2a and R 3a are as defined above, are expected to provide more excellent effects and activities when used in admixture with or in combination with one or more other herbicidal components as mentioned above, whereby they pave a way to control noxious weeds grown in a paddy field, selectively at a low dose without giving any phytotoxicity to rice plants, and constant herbicidal effects are expected to be obtained over a long period of time.
  • R lb , R 2b and R 3b are as defined above, are expected to provide more excellent effects and activities when used in admixture with or in combination with one or more other herbicidal components as mentioned above, whereby they pave a way to control noxious weeds grown in a paddy field, selectively at a low dose without giving any phytotoxicity to rice plants, and constant herbicidal effects are expected to be obtained over a long period of time.
  • R lc , R 2c and R 3c are as defined above, are expected to provide more excellent effects and activities when used in admixture with or in combination with one or more other herbicidal components as mentioned above, such as a diphenyl ether compound, a heterocyclic compound, an anilide compound, a carbamate compound, a phenoxy alkanoic acid compound, a sulfonylurea compound, a pyrazole compound, a benzylamide compound, a urea compound, a triazine compound, a phenoxy compound and other compounds, whereby they pave a way to control noxious weeds grown in a paddy field, selectively at a low dose without giving any phytotoxicity to rice plants, and constant herbicidal effects are expected to be obtained over a long period of time.
  • herbicidal components such as a diphenyl ether compound, a heterocyclic compound, an anilide compound, a carbamate compound, a phen
  • hydrochloric acid was dropwise added to the reaction product at a temperature of from -10 to +20°C to adjust the pH to 1. Then, toluene was added thereto, and the mixture was back-extracted with dilute hydrochloric acid (10%). 5 Ammonia was dropwise added to the obtained aqueous layer at a temperature of from -10 to +20°C to adjust the pH to 14. The mixture was extracted with methylene chloride and washed with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate, and the 0 solvent was distilled off under reduced pressure to obtain 870 mg of oily l-(benzothiazol-2-yl)-l- methylethylamine.
  • reaction product was put into ice water and extracted with ethyl ether.
  • the extract was washed with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate, and then ethyl ether was distilled off at a temperature of not higher than 40°C to obtain 73.8 g of oily brown 2-chloro-5-chloromethylthiophene.
  • ethyl ether was distilled off at a temperature of not higher than 40°C to obtain 73.8 g of oily brown 2-chloro-5-chloromethylthiophene.
  • 2-chloro-5-chloromethylthiophene obtained in the above Step (1), 39.5 g of sodium cyanide, 100 m£ of acetone and 100 ⁇ n? of water were mixed, and the mixture was reacted at about 60°C for 5.5 hours with stirring.
  • reaction product was poured into ice water and extracted with ethyl acetate.
  • the extract was washed with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the residue was purified by column chromatography (developing solvent: toluene) to obtain 11.2 g oily brown 2-(5-chlorothiophen- 2-yl)-2-methylpropionitrile.
  • reaction product was cooled to room temperature and extracted with ethyl acetate.
  • the extract was washed a few times with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate, and then the solvent was distilled off.
  • reaction product was adjusted to pH 1 with hydrochloric acid and washed with toluene.
  • Aqueous ammonia was added to the aqueous layer to make it alkaline and then extracted with methylene chloride.
  • the extract was washed with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 1.6 g of oily l-(5-chlorothiophen-2-yl)-l-methylethylamine.
  • reaction mixture was cooled to room temperature. Then, the solvent was distilled off, and the residue was purified by column chromatography (developing solvent: methylene chloride) to obtain 500 mg of the desired product as white crystals having a melting point of from 160 to 162°C.
  • the mixture was reacted at room temperature overnight and then gradually poured into ice water.
  • the reaction product was alkalized with aqueous ammonia and then extracted with ethyl acetate.
  • the extract was washed with a sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 5.57 g of 2-methyl-2-(2- pyridyl)propionamide (melting point: 99 - 100°C) as white crystals.
  • reaction product was subjected to cerite filtration, and then water was added thereto.
  • the mixture was extracted with methyl chloride, and the extract was washed with water and then dried over anhydrous sodium sulfate.
  • the solvent was distilled off, and the residue was purified by column chromatography (developing solvent: methylene chloride) to obtain 16.3 g of 7-chlorobenzothiazol-2- ylacetonitrile as yellow crystals having a melting point of from 112 to 113°C.
  • 16.3 g of 7-chlorobenzothiazol-2-ylacetonitrile obtained in the above Step (2) was suspended in 200 ⁇ ⁇ £ of dry tetrahydrofuran.
  • This suspension was dropwise added to 6.87 g of sodium hydride (60%) in an inert gas atmosphere. The mixture was reacted at 60°C for one hour and then cooled to -10°C. Then, 11.7 rcn? of iodomethane was added thereto at a temperature of not higher than 10°C, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the reaction product was put into ice water and extracted with ethyl acetate. The extract was washed with a sodium chloride aqueous solution and dried over anhydrous sodium sulfate.
  • reaction mixture was cooled to room temperature and extracted with methylene chloride.
  • the extract was washed with water and then dried over anhydrous sodium sulfate.
  • Paddy field soil was put into a l/10,000are pot, and seeds of barnyardgrass (Echinochloa crusqalli) and Japanese bulrush (Scirpus juncoides) were sown and slightly covered with soil. Then, the pot was left to stand still in a greenhouse in a state where the irrigated water depth was from 0.5 to 1 cm, and two days later, tubers of Japanese ribbon wapato (Saqittaria pyqmaea) were planted. Into a separate l/10,000are pot, soil was put in the same manner, then irrigated, paddled and levelled, and next day, rice seedlings grown to a 2 leaf state were transplanted at a rate of 2 seedlings per pot.
  • the irrigated water depth was maintained at a level of from 3 to 4 cm, and when barnyardgrass and Japanese bulrush reached a 0.5 leaf stage, Japanese ribbon wapato reached to a primary leaf stage and rice reached four days old after transplantation, an aqueous diluted solution of a wettable powder having the compound of the present invention formulated in accordance with a usual formulation method, was uniformly dropwise applied by a pipette so that the dose of the active ingredient would be at a predetermined level.
  • SH Japanese bulrush (Scirpus juncoides)
  • Paddy field soil was put into a l/10,000are pot, and seeds of barnyardgrass (Echinochloa crusqalli) were sown and slightly covered with the soil. Then, the pot was left to stand in a greenhouse in such a state that the irrigated water depth was from 0.5 to 1 cm. When its leaf stage reached a 2 leaf stage, the irrigated water depth was changed to from 3 to 4 cm, and an aqueous diluted solution of a wettable powder having the compound of the present invention formulated in accordance with a conventional formulation method, was uniformly dropwise applied by a pipette, so that the dose of the active ingredient would be at a predetermined level.
  • barnyardgrass Echinochloa crusqalli

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyrrole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

L'invention concerne un composé à base d'amide de formule (I): où R1 représente un groupe phényle qui peut être substitué, R2 représente un atome d'hydrogène ou un groupe alkyle qui peut être substitué par un atome d'halogène, et R3 est (a) qui peut être substitué, (b) qui peut être substitué, (c) qui peut être substitué, (d) qui peut être substitué, (e) qui peut être substitué, (f) qui peut être substitué ou (g) qui peut être substitué, où D représente un atome d'oxygène, un atome de soufre ou -N(R4)-, où R4 représente un groupe alkyle, un procédé permettant de produire un tel composé, une composition herbicide contenant un tel composé en tant qu'ingrédient actif, un procédé herbicide et un intermédiaire dans la production d'un tel composé. Ce composé à base d'amide cyclique inventé est utile comme ingrédient herbicide actif qui permet de tuer sélectivement des mauvaises herbes sans présenter de phytotoxicité à l'encontre des plantes cultivées.
PCT/JP1993/001815 1992-12-15 1993-12-15 Composes a base d'amides cycliques, procede de production et compositions herbicides les contenant WO1994013665A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9307666A BR9307666A (pt) 1992-12-15 1993-12-15 Compostos c¡clicos de amida processo para sua produ-Æo e composi-{es herbicidas que cont-m esses compostos
EP94903001A EP0690857A1 (fr) 1992-12-15 1993-12-15 Composes a base d'amides cycliques, procede de production et compositions herbicides les contenant
AU57144/94A AU5714494A (en) 1992-12-15 1993-12-15 Cyclic amide compounds, process for their production and herbicidal compositions containing them
KR1019950702422A KR950704306A (ko) 1992-12-15 1993-12-15 시클릭 아미드 화합물, 이의 제조 방법 및 이를 함유하는 제초제 조성물(Cyclic Amide Compounds, Process for their Production and Herbicidal Compositions Containing them)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4/361733 1992-12-15
JP36173392 1992-12-15

Publications (1)

Publication Number Publication Date
WO1994013665A1 true WO1994013665A1 (fr) 1994-06-23

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PCT/JP1993/001815 WO1994013665A1 (fr) 1992-12-15 1993-12-15 Composes a base d'amides cycliques, procede de production et compositions herbicides les contenant

Country Status (8)

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EP (1) EP0690857A1 (fr)
KR (1) KR950704306A (fr)
CN (1) CN1038682C (fr)
AU (1) AU5714494A (fr)
BR (1) BR9307666A (fr)
MX (1) MX9307874A (fr)
TW (1) TW253885B (fr)
WO (1) WO1994013665A1 (fr)

Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO1996011906A1 (fr) * 1994-10-17 1996-04-25 Novartis Ag Procede de preparation de 3-aminobenzonitriles substitues
WO1997021688A1 (fr) * 1995-12-11 1997-06-19 Rhone-Poulenc Agriculture Ltd. Derives de 1,3-oxazin-4-one en tant qu'herbicides
FR2765872A1 (fr) * 1997-06-10 1999-01-15 Rhone Poulenc Agriculture Herbicides
US9173887B2 (en) 2010-12-22 2015-11-03 Abbvie Inc. Hepatitis C inhibitors and uses thereof
AU2010311466B2 (en) * 2009-10-28 2016-03-03 Dompe' Farmaceutici S.P.A. 2-aryl-propionamide derivatives useful as bradykinin receptor antagonists and pharmaceutical compositions containing them
EP3676260A4 (fr) * 2017-08-31 2021-06-02 Ahammune Biosciences Private Limited Nouveaux composés de thiophène, procédé de synthèse et d'utilisation de ceux-ci
WO2022009863A1 (fr) * 2020-07-07 2022-01-13 大日本住友製薬株式会社 Dérivé de benzisoxazole
JP2023102778A (ja) * 2022-01-12 2023-07-25 住友ファーマ株式会社 ベンゾイソキサゾール誘導体を含有する医薬組成物

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JPS59172485A (ja) * 1983-03-18 1984-09-29 Tetsuzo Kato ２，２−ジメチル−１，３−ジオキシン−４−オン誘導体の製造法
EP0372586A2 (fr) * 1988-12-09 1990-06-13 Kumiai Chemical Industry Co., Ltd. Dérivés d'amides cycliques et herbicides
JPH0489485A (ja) * 1990-07-30 1992-03-23 Daicel Chem Ind Ltd １，３―オキサジン―４―オン誘導体とその製造方法及び植物成長抑制剤
WO1993015064A1 (fr) * 1992-01-30 1993-08-05 Mitsubishi Petrochemical Co., Ltd. Derive de 1,3-oxazin-4-one, herbicide contenant ce derive et nouvel intermediaire pour la production dudit derive
JPH05201811A (ja) * 1992-01-29 1993-08-10 Daicel Chem Ind Ltd ２，３−ジヒドロ−４ｈ−１，３−オキサジン−４−オン誘導体系除草剤

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US4138243A (en) * 1976-08-12 1979-02-06 Ciba-Geigy Corporation Novel heterocyclic compounds
US4220655A (en) * 1976-08-12 1980-09-02 Ciba-Geigy Corporation Pesticidal 5-oxo-2,5 dihydropyrrole
JPS59172485A (ja) * 1983-03-18 1984-09-29 Tetsuzo Kato ２，２−ジメチル−１，３−ジオキシン−４−オン誘導体の製造法
EP0372586A2 (fr) * 1988-12-09 1990-06-13 Kumiai Chemical Industry Co., Ltd. Dérivés d'amides cycliques et herbicides
JPH0489485A (ja) * 1990-07-30 1992-03-23 Daicel Chem Ind Ltd １，３―オキサジン―４―オン誘導体とその製造方法及び植物成長抑制剤
JPH05201811A (ja) * 1992-01-29 1993-08-10 Daicel Chem Ind Ltd ２，３−ジヒドロ−４ｈ−１，３−オキサジン−４−オン誘導体系除草剤
WO1993015064A1 (fr) * 1992-01-30 1993-08-05 Mitsubishi Petrochemical Co., Ltd. Derive de 1,3-oxazin-4-one, herbicide contenant ce derive et nouvel intermediaire pour la production dudit derive

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU695287B2 (en) * 1994-10-17 1998-08-13 Novartis Ag Process for the preparation of substituted 3-aminobnzonitriles
WO1996011906A1 (fr) * 1994-10-17 1996-04-25 Novartis Ag Procede de preparation de 3-aminobenzonitriles substitues
US6046135A (en) * 1995-12-11 2000-04-04 Rhone-Poulenc Agriculture Ltd 1,3-oxazin-4-one derivatives as herbicides
WO1997021688A1 (fr) * 1995-12-11 1997-06-19 Rhone-Poulenc Agriculture Ltd. Derives de 1,3-oxazin-4-one en tant qu'herbicides
ES2151820A1 (es) * 1997-06-10 2001-01-01 Mitsubishi Chem Corp Herbicidas a base de derivados de 1,3-oxazin-4-ona, composiciones que los contienen y procedimiento para su preparacion.
US6159902A (en) * 1997-06-10 2000-12-12 Mitsubishi Chemical Corporation Herbicides
FR2765872A1 (fr) * 1997-06-10 1999-01-15 Rhone Poulenc Agriculture Herbicides
AU2010311466B2 (en) * 2009-10-28 2016-03-03 Dompe' Farmaceutici S.P.A. 2-aryl-propionamide derivatives useful as bradykinin receptor antagonists and pharmaceutical compositions containing them
US9173887B2 (en) 2010-12-22 2015-11-03 Abbvie Inc. Hepatitis C inhibitors and uses thereof
US9453007B2 (en) 2010-12-22 2016-09-27 Abbvie Inc. Hepatitis C inhibitors and uses thereof
US9567355B2 (en) 2010-12-22 2017-02-14 Abbvie Inc. Hepatitis C inhibitors and uses thereof
EP3676260A4 (fr) * 2017-08-31 2021-06-02 Ahammune Biosciences Private Limited Nouveaux composés de thiophène, procédé de synthèse et d'utilisation de ceux-ci
WO2022009863A1 (fr) * 2020-07-07 2022-01-13 大日本住友製薬株式会社 Dérivé de benzisoxazole
JPWO2022009863A1 (fr) * 2020-07-07 2022-01-13
JP2023102778A (ja) * 2022-01-12 2023-07-25 住友ファーマ株式会社 ベンゾイソキサゾール誘導体を含有する医薬組成物

Also Published As

Publication number Publication date
MX9307874A (es) 1994-07-29
EP0690857A1 (fr) 1996-01-10
KR950704306A (ko) 1995-11-17
BR9307666A (pt) 1999-08-24
CN1091133A (zh) 1994-08-24
CN1038682C (zh) 1998-06-10
TW253885B (fr) 1995-08-11
AU5714494A (en) 1994-07-04

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