+

WO1997013765A1 - Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif - Google Patents

Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif Download PDF

Info

Publication number
WO1997013765A1
WO1997013765A1 PCT/JP1996/002934 JP9602934W WO9713765A1 WO 1997013765 A1 WO1997013765 A1 WO 1997013765A1 JP 9602934 W JP9602934 W JP 9602934W WO 9713765 A1 WO9713765 A1 WO 9713765A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl group
general formula
cyano
integer
Prior art date
Application number
PCT/JP1996/002934
Other languages
English (en)
Japanese (ja)
Inventor
Yoriyuki Takashima
Misako Yoshikawa
Original Assignee
Idemitsu Kosan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to AU72272/96A priority Critical patent/AU7227296A/en
Publication of WO1997013765A1 publication Critical patent/WO1997013765A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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

Definitions

  • the present invention relates to a novel 2-cyano 1,3-dione derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.
  • the triazine herbicide atrazine and the acid anilide herbicide alaclor and metolachlor have been mainly used as soil treatment agents, but these herbicides are used in high doses. It causes environmental problems such as groundwater pollution.
  • no-tillage cultivation is a method of cultivating crops without cultivating the field, which is in contrast to normal tillage cultivation.
  • cultivation of the fields (cultivation) and the release of fertile topsoil due to rainwater, etc. is a major problem in agriculture and can be a kind of desertification. There is also.
  • no-tillage cultivation there is no problem of runoff of topsoil, but without cultivation, the soil is solidified, chemicals are less likely to penetrate into the soil, and the effectiveness of soil treatment is reduced.
  • Representative compounds of the 2-cyano 1,3-dione derivatives described in the above publication include the following compound B.
  • Compound B as a compound having a thiochroman ring and having herbicidal activity, a compound in which a thiochroman ring and a virazol ring are bonded is already known as a virazole derivative (International Publication WO 93/113, filed on International Patent Application). Publication No. 18031).
  • the primary object of the present invention is to provide a 2-cyano 1,3-dione derivative having a ring.
  • a second object of the present invention is to provide a method for producing the 2-cyano 1,3-dione derivative.
  • a third object of the present invention is to provide a herbicide containing the 2-cyano 1,3-dione derivative as an active ingredient. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, a novel 2-cyano 1,3-dione derivative in which a thiochroman ring is bonded to a 2-cyano-1,3-dione structure has been obtained.
  • the present inventors have found that they have an excellent herbicidal activity capable of selectively controlling a wide range of field weeds such as grasses and broadleaf weeds without causing phytotoxicity to corn, and completed the present invention.
  • the first object of the present invention is to
  • R 1 is a Ci-C 6 alkyl group, a C 3 -C 6 cycloalkyl group, or one (CH 2 ) q -0R 6 (where q is an integer of 1 or 2, and R 6 is an alkyl Is a group)
  • R 2 to R 5 are each independently a hydrogen atom, or a C 1 to C 4 alkyl group
  • X is an alkyl group
  • n represents the number of substituents X, and is an integer of 0, 1 or 2
  • n is an integer of 0, 1 or 2
  • R 7 and R 8 are each independently a hydrogen atom, a Cj-C 4 alkyl group, or an alkoxy group, and R 7 and / or R 8 are a C! -C 4 alkyl group or C,
  • the carbon atom in the substituent may be substituted by 1 to 9 halogen atoms, and when the carbon number is C 2 to C 4 , an unsaturated bond it may form a; and R 7 and R 8 are both ⁇ 4 alkyl or ( ⁇ To ( 4 In the case of an alkoxy group, the carbon atoms in both substituents may be bonded to each other to form a 3- to 7-membered ring;
  • R 9 is an oxygen atom, a sulfur atom, or a CiC alkoxyimino group, and when R 9 is a C alkoxyimino group, the carbon atoms in the substituent are substituted with 1 to 9 halogen atoms. If the number of carbon atoms is from C 2 to C 4 , an unsaturated bond may be formed. ).
  • a 2-gamma 1,3-dione derivative (hereinafter, may be referred to as "2-cyano 1,3-dione derivative (I)"), which is the first gist of the present invention represented by the following formula:
  • 1 is a Ci Ce alkyl group, a C 3 -C 6 cycloalkyl group, or — (CH 2 ) q —OR 6 (where q is an integer of 1 or 2, and R 6 is an alkyl group There is)
  • R 2 to R 5 are each independently a hydrogen atom, or a ( ⁇ to ( ⁇ alkyl group,
  • X is ( ⁇ ⁇ ( 4 alkyl group
  • n represents the number of substituents X, and is an integer of 0, 1 or 2
  • n is an integer of 0, 1 or 2
  • R 71 and R 81 are each independently a hydrogen atom or a C! CA alkyl group. ]
  • 2-cyano-1,3-dione derivative hereinafter sometimes referred to as "2-cyano-1,3-dione derivative (Ia-1)"
  • R 1 is -0; 6 alkyl group, C 3 -C 6 cycloalkyl group, or 1 (CH 2 ) q — OR 6 (where q is an integer of 1 or 2 and R 6 is a CC 4 alkyl group)
  • R Z R 5 are each independently a hydrogen atom or ⁇ 4 alkyl group
  • X is a C 1 C 4 alkyl group
  • n represents the number of substituents X, and is an integer of 0 or 1;
  • n is an integer of 0 1 or 2;
  • R 72 and R 82 are each independently a hydrogen atom or a C, C 4 alkoxy group, and when R 72 and / or R 8 ′ 2 is a ⁇ to ⁇ 4 alkoxy group, the carbon in the substituent
  • the elemental atom may be substituted by 19 halogen atoms, and may have an unsaturated bond if the carbon number is C 2 C 4 .
  • a 2-cyano 1,3-dione derivative (hereinafter sometimes referred to as “2-cyano 1,3-dione derivative (Ia-2)”) which is a third aspect of the present invention represented by the general formula: (Lb)
  • R 2 R 5 are each independently a hydrogen atom or a CC 4 alkyl group
  • X is a C t C 4 alkyl group
  • n represents the number of substituents X, and is an integer of 0 or 1;
  • n is an integer of 0 1 or 2;
  • R 1 D is a C, -C 4 alkyl group, and the carbon atom in the substituent may be substituted by 19 halogen atoms. If the number of carbon atoms is C 2 C 4 , an unsaturated bond May be formed. ]
  • the present invention is a fourth aspect of the present invention represented by a 2-cyano 13-dione derivative (hereinafter sometimes referred to as a “2-cyano 13-dione derivative (lb)”). Achieved by The second object of the present invention is to
  • R 1 is a group represented by: (: 6 alkyl group, C 3 -C 6 cycloalkyl group, or one (CH 2 ) q —OR 0, wherein q is an integer of 1 or 2, and R 6 is , ⁇ C 4 alkyl group)
  • R 2 to R 5 are each independently a hydrogen atom, or a C 1 to C 4 alkyl group
  • X is an alkyl group
  • n represents the number of substituents X, and is an integer of 0, 1 or 2
  • n is an integer of 0, 1 or 2
  • Z is the base ⁇ or
  • R 7 and R 8 are each independently a hydrogen atom, an alkyl group, or a C! CA alkoxy group, and when R 7 and / or R 8 is a ⁇ ⁇ 4 alkyl group or a 4 alkoxy group, Has a carbon atom in the substituent which may be substituted by 1 to 9 halogen atoms, and may have an unsaturated bond if the carbon number is from C 2 to C 4 ;
  • R 7 and R 8 are both a Ct C alkyl group or a C! C alkoxy group, the carbon atoms in both substituents may be bonded to each other to form a 3- to 7-membered ring ;
  • R 9 is an oxygen atom, a sulfur atom, or a C, to C 4 alkoxyimino group, and when R 9 is a C, to C 4 alkoxyimino group, the carbon atom in the substituent is 1 to 9 Pieces of c May be substituted by a halogen atom, and may have an unsaturated bond if the number of carbon atoms is c 2 to c 4 . ). ] -Reacting the isoxazole derivative represented by the formula with a base, characterized by the general formula (I)
  • Herbicides hereinafter sometimes referred to as “herbicides of the present invention”).
  • the 2-cyano 1,3-dione derivative of the present invention has the general formula (I)
  • R 1 is a C ⁇ Cs alkyl group, a C 3 -C 6 cycloalkyl group, or one (CH q- 0R 6 ).
  • the Ci ⁇ C 6 alkyl group such as methyl group, Echiru group, Purobiru group, butyl group, pentyl group, hexyl group and the like to, Purobiru group, butyl group, pentyl
  • the hexyl and hexyl groups may be straight-chain or branched.
  • C 3 -C 6 cycloalkyl group, for example Shikuropuro Examples include a bil group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and a cyclopropyl group is preferable.
  • R 1 is (CH 2 ).
  • q represents an integer of 1 or 2
  • R 6 represents a C! To C 4 alkyl group
  • the C and C 4 alkyl groups include those exemplified in X below.
  • Preferred one (CH 2 ) q —OR 6 groups include, for example, one CH 2 ⁇ CH 3 group.
  • X is a C ⁇ C alkyl group, ( ⁇ The ⁇ 4 alkyl groups such as methyl group, Echiru group, Purobiru group, and butyl group, Purobiru group and butyl groups have branches be of straight-chain X is preferably a methyl group.
  • n represents the number of substituents X, and is an RCN integer of 0, 1 or 2.
  • m represents the number of substituents X, and is an RCN integer of 0, 1 or 2.
  • a plurality of Xs may be the same or different.
  • m is 1 or 2.
  • the substituent X is preferably substituted at the 5-position and / or 8-position of the thiochroman ring, particularly at the 5-position or at both the 5- and 8-positions.
  • R 2 , R 3 , and R ⁇ R 5 are each independently a hydrogen atom or a C, to C 4 alkyl group, and examples of the C, to C 4 alkyl group include those exemplified for X above. Preferably it is a hydrogen atom or a methyl group.
  • n the number of oxygen atoms bonded to the sulfur atom, and is an integer of 0, 1 or 2.
  • n 0, sulfide
  • n 1, sulfoxide
  • n 2, sulfone.
  • n 2 (sulfone).
  • R 7 and R 8 in the above formula (a) are each independently a hydrogen atom, ( ⁇ to ( 4 alkyl group, Or a C, -C 4 alkoxy group.
  • alkyl group include those exemplified for X above.
  • R 7 and Z or R 8 are a C, to C 4 alkyl group, 1 to 9 of the hydrogen atoms in the carbon chain may be arbitrarily substituted with a halogen atom.
  • -CH 2 F group one CHF 2 group, one CF 3 group, -CH 2 C 1 radical, one CC1 3 group, - CH 2 B r groups, one CH 2 I group, one CH 2 CH 2 F groups, - CH 2 CF 3 group, one CF 2 CH 3 group, - CF 2 CHF 2 group, one C 2 F 5 group, one CH 2 CH 2 C 1 radical, -CH 2 CC 1 3 group one CC 1 2 CH 3 groups, 1 C 2 C 15 groups,-CF (CH 3 ) 2 groups, 1 CH (CF 3 ) CH 3 groups, 1 CH (CF 3 ) 2 groups, 1 CC 1 (CH 3 ) 2 group, one CH (CC 1 3) 2 group, one CH 2 CH 2 CH 2 F group, -CH 2 CH 2 CF 3 group, one a C 3 F 7 group,.
  • R 7 and / or R 8 are C 2 ⁇ .
  • adjacent carbon atoms in the substituent may form a double bond or a triple bond.
  • R 7 and R 8 are each independently an alkyl group, any carbon atom in R 7 and any carbon atom in R 8 are bonded to each other to form a 3- to 7-membered ring. Can also be formed. Specific examples include
  • Examples of the C! C ⁇ alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • the alkyl chain in the propoxy group and the butoxy group may be linear or branched.
  • R 7 and / or R 8 is a C, C 4 alkoxy group, 19 of the hydrogen atoms in the carbon chain may be substituted by a halogen atom.
  • OCF 3 group one OCCl 3 group one OCH 2 CH 2 F group, one 0CH 2 CH 2 C1 groups, one OCH 2 CH 2 B r group, -OCHzC H 2 I group, one OCH 2 CF 3 group, over 0 11 2 ((1 3 group, - OCF (CH 3) 2 group, one CH (CF 3) CH 3 group one OCH (CF 3) 2 group, one OCH (CC 1 3) 2 group, ten CH 2 CH 2 CH 2 F group, one OCH 2 CH 2 CF 3 group, one 0 CH 2 CF 2 CF 3 group, 10 Mr.
  • H 2 CH 2 CH 2 C1 groups one OCH 2 CH 2 CH 2 CH 2 F group, One OCH 2 CH 2 CH 2 CH 2 C 1 group, one OCH (CH 3 ) CH 2 CH 2 C 1 group, —OCH (CF 3 ) C 2 H 5 group, preferably one OCH 2 CH 2 F group, one 0CH 2 CH 2 C1 groups, one OC H 2 CF 3 group, one OCF (CH 3) 2 group, one OCH (CF 3) CH 3 group is an OCH (CF 3) 2 group, more preferably - OCH 2 CH 2 F group.
  • R 7 and / or R 8 is a C 2 C 4 alkoxy group
  • adjacent carbon atoms in the substituent may form a double bond or a main heavy bond.
  • one OCH 2 CH CH 2 group, —OCH 2 C ⁇ CH group.
  • R 7 and R 8 are each independently a Ct C 4 alkoxy group, any carbon atom in R 7 and any carbon atom in R 8 are bonded to each other, A member ring can be formed. Specific examples include CH 3 CH 3 CH 3 CH 3 c H : ⁇ . %; ° c 3 ⁇ 4T ⁇ ° CH3 . . .
  • 0 is 0 .
  • R 9 is an oxygen atom, a sulfur atom, or a C! Ca alkoximino group, and ( ⁇ to ( ⁇ as the alkoxyino group, a methoxyimino group, an ethoxyimino group, a propoxyimino group,
  • the alkyl chain in the propoxyimino group and the butoxyimino group may be linear or branched.
  • R 9 is ( ⁇ to (: 4 alkoxyimino group
  • a NOCH 2 CH 2 F group
  • a NOCH 2 CH 2 C 1
  • a NOCH 2 CF 3
  • a NOCF (CH 3 ) 2 group
  • a NOCH (CF 3 ) CH 3 group
  • Is the NOCH 2 CH 2 F group.
  • R 9 is a C 2 -C 4 alkoxyimino group
  • adjacent carbon atoms in the substituent may form a double bond or a triple bond.
  • NOCH CH 2 group
  • NOC (CH 3) CH 2 group
  • NOCH C (CH 3 ) 2 group
  • ⁇ CH 2 CH CH 2 group
  • NU Ji H 2 C (CH 3) CH 2 group
  • the 2-cyano 1,3-dione derivative according to the second aspect of the present invention has the general formula (la-1)
  • R 71 and R 81 are each independently hydrogen atom or ( ⁇ - (4 alkyl group, and specific examples of the ⁇ 0 4 alkyl group, in the group Z in formula (I) This is as described in detail in the description of R 7 and R 8.
  • the third gist of the present invention a 2-cyano 1,3-dione derivative, is represented by the general formula (la-2)
  • R 72 and R 82 are each independently a hydrogen atom or a 4 alkoxy group.
  • Specific examples of the C] to C 4 alkoxy groups include R 7 and R 7 in the group Z in the general formula (I). it is as described in the description of R 8.
  • the 4-cyano 1,3-dione derivative which is the fourth gist of the present invention has a general formula (lb)
  • R 1 is a substituted group May be substituted by 1 to 9 halogen atoms, and may form an unsaturated bond if the number of atoms is C 2 or more Specific examples of R 1Q in this case Is the same as described in detail in the description of R 9 in the group Z in the general formula (I).
  • the 2-cyano 1,3-dione derivative represented by the general formula (I) can take the following three types of structures due to tautomerism, but the 2-cyano 1,3-dione derivative of the present invention Contains all these isomeric structures.
  • the dione derivative is an acidic substance and can be easily converted to a salt by treating with a base.
  • This salt is also included in the 2-cyano 1,3-dione derivative of the present invention.
  • the base is not particularly limited as long as it is known, and examples thereof include organic bases such as amines and anilines and inorganic bases such as sodium compounds.
  • the amines include monoalkylamine, dialkylamine, and trialkylamine.
  • Alkyl group in ⁇ Rukiruamin compound is usually C, ⁇ 4 alkyl group.
  • anilines include aniline, monoalkyl aniline, and dialkyl aniline.
  • Examples of the sodium compound include sodium hydroxide and sodium carbonate, and examples of the potassium compound include potassium hydroxide and potassium carbonate.
  • each asymmetric carbon exists depending on the type of the substituents R 2 , R 3 , R 4 and R 5 , and various isomers may exist.
  • the 2-cyano 1,3-dione derivative of the present invention includes all isomers and mixtures thereof.
  • the 2-cyano 1,3-dione derivative represented by the formula (1) has an asymmetric carbon depending on the type of the substituents R 7 and R 8 , and may have various isomers. Since cyano 1,3-dione derivatives include all isomers and their mixtures ⁇ .
  • ⁇ is a group (b)
  • R 9 is a ( ⁇ -( 4 alkoxyimino group, a 2-cyano 1,3-dione derivative (when Z is a group (bl) ), That is, the general formula (lb)
  • the 2-cyano 13-dione derivative of the present invention can be produced by the following reaction.
  • Ar is a group
  • R 2 R 3 RR 5 X mn and Z in Ar are as defined in the general formula (I).
  • the 2-isocyanol 13-dione derivative is obtained by reacting the isoxazole derivative as a starting material represented by the formula (XXX) with a base and cleaving the isoxazole ring. (I) can be produced.
  • Examples of the base that can be used in the method of the present invention include organic bases such as triethylamine and pyridine, alkoxides such as sodium ethoxide, alkali metals such as sodium and potassium, and alkali metals such as calcium and magnesium. Earth metal.
  • organic bases such as triethylamine and pyridine
  • alkoxides such as sodium ethoxide
  • alkali metals such as sodium and potassium
  • alkali metals such as calcium and magnesium. Earth metal.
  • the amount of the base used is not particularly limited, but may be in the range of 0.1 to 5 normal equivalents relative to the isoxazole derivative (XXX).
  • the reaction solvent that can be used in the method of the present invention is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbon solvents such as dichloromethane and dichloroethane
  • aromatic solvents such as benzene, toluene, and xylene
  • hydrocarbon solvent a chain or cyclic ether solvent such as dimethyl ether, dioxane, and tetrahydrofuran.
  • the reaction temperature may be in the range of o ° C to the reflux temperature of the solvent used.
  • the desired product is isolated from the reaction solution according to a conventional method and, if necessary, purified to obtain the desired 2-cyano 1,3-dione derivative (I).
  • the isoxazole derivative represented by the formula (XXX), which is a starting material in the method of the present invention, can be produced by the method described in International Publication WO96 / 25441'3. It can be produced by the reaction shown in the following formula.
  • R 1 is as defined in general formula (I), and Ar is as defined above.
  • the dimethylaminomethylidene derivative represented by the formula (II) is reacted with a hydrochloride of hydroxyamine in a solvent such as ethanol or acetonitrile at a temperature ranging from room temperature to the reflux temperature of the solvent to be used to form a compound of the general formula (XXX) ))) Can be produced.
  • a solvent such as ethanol or acetonitrile
  • the thus-prepared isoxazole derivative (XXX) is distilled off according to a conventional method, the solvent is distilled off, the residue is dissolved in a solvent such as methylene chloride, and the obtained solution is washed with water.
  • the compound (dimethylaminomethylidene derivative) represented by the general formula ( ⁇ ) can be produced by a known method, for example, by the following steps.
  • the acid halide compound represented by the general formula (IV) is produced by reacting the carboxylic acid represented by the general formula (III) with a halogenating agent such as, for example, thionyl chloride, oxalyl chloride and phosphorus oxychloride. can do.
  • a halogenating agent such as, for example, thionyl chloride, oxalyl chloride and phosphorus oxychloride. can do.
  • the compound represented by the general formula (V) is obtained by converting the acid halide compound represented by the general formula (IV) into a base such as sodium methoxide, magnesium ethoxide, etc. It can be produced by reacting with a diketone compound of the general formula (VI) in an inert solvent such as trahydrofuran or getyl ether at a temperature ranging from room temperature to the reflux temperature of the solvent used.
  • the diketone compound of the general formula (VI) can be produced, for example, by the method described in JP-A-3-118374.
  • the diketone intermediate represented by the general formula (VII) is produced by decarboxylation of the compound represented by the general formula (V) using an acid catalyst such as 4-toluenesulfonic acid.
  • decarboxylation is described in, for example, Japanese Patent Application Laid-Open No. 3-1183874).
  • the compound of the general formula (II) can be prepared by reacting the diketone intermediate of the general formula (VII) in an inert solvent such as hexane at a temperature ranging from room temperature to the reflux temperature of the solvent used, for example, dimethylformate. It can be produced by reacting with amide acetal such as amide dimethyl acetal. Also, amide acetal such as dimethylformamide dimethyl acetal can be used in combination as a solvent. The obtained compound (II) can be used for the synthesis of isoxazole derivative (XXX) without purification.
  • an inert solvent such as hexane
  • the method for producing the carboxylic acid (IIIa-1) for producing the 2-cyano-1,3-dione derivative (Ia-1) of the present invention comprises: Although it is described in detail in W095 / 04504, an example of the production method is shown below.
  • X 1 represents X or a halogen atom
  • L represents a halogen atom or a 100H group.
  • the thiophenol represented by the general formula (XVI) as a starting material can be produced by a known method (for example, “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds III”). 170 Page 4 8 ⁇ Chapter 1 Thiols f. Synthetic Method via Dithiocarbonate ”Maruzen Co., Ltd., issued on February 20, 1986).
  • the thiochroman derivative represented by the general formula (XVII) can be produced by either the method (a) or the method (b). Hereinafter, each step will be described.
  • the thiochroman derivative represented by the general formula (XVII) can be obtained by converting thiophenol (XVI) and an arylhalide represented by the general formula (XVIII) in an inert solvent such as acetone, dimethyl ether, dimethylformamide, etc. O In the presence of bases such as sodium hydroxide, water, oxidizing lime, anhydrous sodium carbonate, and triethylamine.
  • a sulfide derivative represented by the general formula (XIX) is obtained, and this sulfide derivative is further converted to polyphosphoric acid, sulfuric acid, phosphorus pentoxide or an ion exchange resin (for example, Manufactured by reacting in the presence of Amberlyst TM.
  • ion exchange resin for example, Manufactured by reacting in the presence of Amberlyst TM.
  • : 3 is limited to a hydrogen atom.
  • the thiochroman derivative represented by the general formula (XVII) is composed of thiophenol (XVI) and an aryl represented by the general formula (XVIII) It can be produced by condensing an alcohol with an acid catalyst such as formic acid, etc.
  • the catalyst may be used in combination with formic acid as a solvent, but a separate solvent may be used.
  • the reaction temperature can be appropriately selected from the range of room temperature to the reflux temperature of the solvent, in which case R 3 is limited to a hydrogen atom.
  • the thiochroman derivative represented by the general formula (XVII) can be produced by condensing a thiophenol represented by the general formula (XVI) and an alcohol represented by the general formula (XX) using an acid catalyst such as formic acid. It can.
  • an acid catalyst such as formic acid.
  • Formic acid as a catalyst can be used also as a solvent, but a solvent may be used separately.
  • the solvent used is not particularly limited as long as it is a solvent inert to the reaction.
  • the reaction temperature can be appropriately selected from the range of room temperature to the reflux temperature of the solvent.
  • the thiochroman derivative represented by the general formula (XXI) is obtained by adding a compound represented by the general formula (XVII) to a solvent such as methylene chloride, chloroform, carbon tetrachloride, or the like. It can be produced by reacting with a halogenating reagent such as bromine, sulfuryl chloride or chlorine at a temperature in the range of c to the reduction temperature of the solvent.
  • a solvent such as methylene chloride, chloroform, carbon tetrachloride, or the like. It can be produced by reacting with a halogenating reagent such as bromine, sulfuryl chloride or chlorine at a temperature in the range of c to the reduction temperature of the solvent.
  • the compound represented by the general formula (XXII) is obtained by adding the thiochroman derivative represented by the general formula (XXI) to an ether-based compound such as tetrahydrofuran or getyl ether in the presence of iodine, methyl iodide, or butyl bromide. In a solvent, it is reacted with magnesium at a temperature ranging from o ° c to the reflux temperature of the solvent to form a Grignard reagent.
  • (C 0 2) can be prepared by reacting the.
  • the carboxylic acid represented by the general formula (IIIa-1) is a sulfide compound represented by the following general formula (II), for example, hydrogen peroxide, peracetic acid, sodium periodate, m-chloroperbenzoic acid
  • a sulfide compound represented by the following general formula (II) for example, hydrogen peroxide, peracetic acid, sodium periodate, m-chloroperbenzoic acid
  • the carboxylic acid (IIIa-l H ) in which the substituent X is not bonded to the 8-position of the thiochroman ring is an 8-chloro-thiochroman derivative (IIIa -l cl ) in a solvent such as 60% aqueous ethanol using zinc powder for reduction.
  • a base such as sodium hydroxide or lithium hydroxide
  • R 7 is a to ( 4 alkoxy group)
  • R 8 is a hydrogen atom.
  • a carboxylic acid (Ilia) for producing a compound that is an atom is produced according to the following reaction scheme.
  • R 2 , R 3 , R 4 , R 5 , R 6 , X, m, n and R 72 are as defined in the above general formula (la-2), and Ha 1 is a halogen atom, an atom Is shown.
  • R 2 , R 3 , R ⁇ R 5 , R 10 , X, m and n are as defined in the above general formula (lb), and Ha 1 represents a halogen atom.
  • the above method for producing carboxylic acid (Illb) is described in detail in W094 / 1431.
  • the herbicide according to the sixth aspect of the present invention contains the 2-cyano 1,3-dione derivative of the present invention represented by the formula (I) as an essential component. It can be mixed with liquid carriers or solid carriers such as mineral fine powders and formulated into wettable powders, emulsions, powders, granules and the like. A surfactant may be added to impart spreadability or the like.
  • the application rate of the 2-cyano 1,3-dione derivative of the present invention should be appropriately selected depending on the type of weeds to be controlled, the season, and the like. However, in soil treatment, it is usually 10 to 4,000 Og / ha. It is preferably 100 to 2,000 g / ha, and for foliage treatment, it is usually 10 to 4,000 g / ha, preferably 100 to 2,000 g / ha.
  • the herbicide of the present invention When used in the form of a wettable powder, it is usually 10 to 55% by weight of the 2-cyano-1,3-dione derivative of the present invention, 40 to 88% by weight of a solid carrier and a surfactant.
  • a composition may be prepared by blending at a ratio of 2 to 5% by weight and used.
  • the 2-cyano 1,3-dione derivative of the present invention When used in the form of a-agent, the 2-cyano 1,3-dione derivative of the present invention is usually 20 to 50% by weight, the solvent is 35 to 75% by weight, and the surfactant is 5 to 15% by weight. It may be prepared by mixing at a ratio of%.
  • Examples of the fine powder of the mineral substance include diatomaceous earth, oxides such as slaked lime, phosphates such as apatite, sulfates such as Secco, and the like. Examples include talc, pie mouth ferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silicates such as calcium stone powder.
  • Organic solvents are used as the solvent. Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene, chlorinated hydrocarbons such as 0-chlorotoluene, trichloroethane, and trichloroethylene, and cyclohexanol.
  • Alcohols such as dimethyl alcohol, amyl alcohol, and ethylene glycol; ketones, such as isophorone, cyclohexanone, cyclohexenyl-cyclohexanone; ethers, such as butyl sesolve, dimethyl ether, methylethyl ether; isopropyl acetate, and benzyl acetate And esters such as methyl fluorate, amides such as dimethylformamide, and mixtures thereof.
  • ketones such as isophorone, cyclohexanone, cyclohexenyl-cyclohexanone
  • ethers such as butyl sesolve, dimethyl ether, methylethyl ether
  • isopropyl acetate isopropyl acetate
  • esters such as methyl fluorate, amides such as dimethylformamide, and mixtures thereof.
  • any of an anionic type, a nonionic type, a cationic type and a zwitterionic type (amino acid, bayone, etc.) can be used.
  • the herbicide of the present invention can contain other herbicidal active ingredients as needed, together with the 2-cyano 1,3-dione derivative represented by the general formula (I) as an active ingredient.
  • herbicidally active ingredients include conventionally known herbicides such as phenoxy, diphenyl ether, triazine, urea, carbamate, thiocarbamate, acid anilide and pyrazole. , Phosphoric acid, sulfonyl urea, oxadiazone, etc., among these herbicides. It can be selected as needed.
  • the herbicide of the present invention can be mixed with an insecticide, a fungicide, a plant growth regulator, a fertilizer, and the like, if necessary.
  • an insecticide a fungicide, a plant growth regulator, a fertilizer, and the like.
  • Table 1 below shows the structural formulas of the compounds obtained in the above (2-1) to (2-13).
  • Table 2 below shows the structural formulas and NMR data of the compounds obtained in (3-1) to (3-13) above.
  • Table 3 below shows the structural formulas of the compounds obtained in (4-1) to (4-13) above.
  • the compounds obtained in (4-1) to (4-13) above were used without purification for the synthesis of isoxazole derivatives (XXX) (Production Reference Examples (5-1) to (5-13)).
  • XXX isoxazole derivatives
  • talc trade name: di-cryt
  • alkylaryl sulfonic acid trade name: Neoberex, manufactured by Kao Atlas Co., Ltd.
  • Anionic surfactant mixture trade name: Solpol 800A, manufactured by Toho Chemical Industry Co., Ltd. 1.5 parts by weight was uniformly ground and mixed to obtain a carrier for a hydrating agent.
  • the ratio of the residual weight of the untreated area minus (the residual weight of the treated area / the residual weight of the untreated area) XI 00 was determined.
  • a.i. active ingredient From the results in Table 9, it was confirmed that the herbicide of the present invention does not cause harm to corn and can selectively control a wide range of field weeds at a low dose.
  • a novel 2-cyano 1-3-dione derivative which has no harm to useful crops such as corn and can selectively control a wide range of field weeds such as grasses and broadleaf weeds at a low dose.
  • a herbicide containing this as an active ingredient was provided.

Landscapes

  • 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)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention porte sur des dérivés de 2-cyano-1,3-dione de formule générale (I), sur leur procédé de fabrication et sur des herbicides dont ils constituent le principe actif. Dans la formule (I), R1 représente alkyle C¿1-6?, cycloalkyle C3-6 ou -(CH2)q-OR?6¿ (q valant 1 ou 2 et R6 étant alkyle C¿1-4?); R?2 à R5¿ représentant chacun indépendamment H ou alkyle C¿1-4?; X représente alkyle C1-4; m et n valent chacun indépendamment 0, 1 ou 2); et Z représente (a) ou (b) où R?7 et R8¿ représentant chacun indépendamment H, alkyle C¿1-4? ou alcoxy C1-4, ou R?7 et R8¿ peuvent être liés l'un à l'autre pour former un cycle à 3- à 7- éléments; et R9 représente O, S ou alcoxyimino C¿1-4?.
PCT/JP1996/002934 1995-10-09 1996-10-09 Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif WO1997013765A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72272/96A AU7227296A (en) 1995-10-09 1996-10-09 2-cyano-1,3-dione derivatives and herbicides containing the same as active ingredient

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP26133195 1995-10-09
JP7/261331 1995-10-09

Publications (1)

Publication Number Publication Date
WO1997013765A1 true WO1997013765A1 (fr) 1997-04-17

Family

ID=17360337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/002934 WO1997013765A1 (fr) 1995-10-09 1996-10-09 Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif

Country Status (2)

Country Link
AU (1) AU7227296A (fr)
WO (1) WO1997013765A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
WO2000014087A1 (fr) * 1998-09-04 2000-03-16 Aventis Cropscience Gmbh Derives de benzoyl, leur procede de production et leur utilisation comme herbicides et regulateurs de croissance des plantes
JP2002518416A (ja) * 1998-06-23 2002-06-25 アベンティス・クロップサイエンス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 除草剤と毒性緩和剤の結合

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04312565A (ja) * 1991-01-25 1992-11-04 Rhone Poulenc Agriculture Ltd 除草剤
JPH054960A (ja) * 1991-01-25 1993-01-14 Rhone Poulenc Agriculture Ltd 新規な除草剤
JPH06503953A (ja) * 1990-12-20 1994-05-12 ゼネカ・リミテッド Ｄｎａ、ｄｎａ構造体、細胞及びこれらから誘導した植物
JPH06329620A (ja) * 1993-05-18 1994-11-29 Rhone Poulenc Agriculture Ltd 新規除草剤
JPH0770039A (ja) * 1993-05-18 1995-03-14 Rhone Poulenc Agriculture Ltd 除草剤
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06503953A (ja) * 1990-12-20 1994-05-12 ゼネカ・リミテッド Ｄｎａ、ｄｎａ構造体、細胞及びこれらから誘導した植物
JPH04312565A (ja) * 1991-01-25 1992-11-04 Rhone Poulenc Agriculture Ltd 除草剤
JPH054960A (ja) * 1991-01-25 1993-01-14 Rhone Poulenc Agriculture Ltd 新規な除草剤
JPH06329620A (ja) * 1993-05-18 1994-11-29 Rhone Poulenc Agriculture Ltd 新規除草剤
JPH0770039A (ja) * 1993-05-18 1995-03-14 Rhone Poulenc Agriculture Ltd 除草剤
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
JP2002518416A (ja) * 1998-06-23 2002-06-25 アベンティス・クロップサイエンス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 除草剤と毒性緩和剤の結合
JP4653307B2 (ja) * 1998-06-23 2011-03-16 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 除草剤と毒性緩和剤の結合
WO2000014087A1 (fr) * 1998-09-04 2000-03-16 Aventis Cropscience Gmbh Derives de benzoyl, leur procede de production et leur utilisation comme herbicides et regulateurs de croissance des plantes
US6297196B1 (en) 1998-09-04 2001-10-02 Hoechst Schering Agrevo Gmbh Benzoyl derivatives, process for their preparation and their use as herbicides and plant growth regulators
RU2223271C2 (ru) * 1998-09-04 2004-02-10 Авентис Кропсайенс Гмбх Бензоилпроизводные соединения и гербицидное средство на их основе

Also Published As

Publication number Publication date
AU7227296A (en) 1997-04-30

Similar Documents

Publication Publication Date Title
JP3008398B2 (ja) 置換ベンゼン誘導体
RU2133747C1 (ru) Производные пиразола или их соли, гербицид, их содержащий, и производные ароматической карбоновой кислоты или их соли
JP3245421B2 (ja) シクロヘキサンジオン誘導体
JPH03163063A (ja) ３―置換フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
JP2005314407A (ja) 新規なハロアルキルスルホンアニリド誘導体、除草剤及びその使用方法並びにその中間体
JP2704655B2 (ja) ３一置換フェニルピラゾール誘導体又はその塩類及び除草剤
JPH0564952B2 (fr)
JPH08217777A (ja) ２−ピラゾリン−５−オン誘導体及びその中間体並びに除草剤
JP3029545B2 (ja) トリアジン誘導体
US4008067A (en) Oxacyclohexane derivatives
JP2905982B2 (ja) 複素環含有フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
KR19980702235A (ko) 이속사졸 유도체
WO1997013765A1 (fr) Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif
JPH06271562A (ja) シクロヘキサンジオン誘導体および除草剤
JP2887701B2 (ja) ３−置換フェニルピラゾール誘導体又はその塩類及びその用途
JPH06321932A (ja) シクロヘキサンジオン誘導体および除草剤
KR950003497B1 (ko) 제초성 시클로헥산-1,3-디온 유도체와 그 제조방법
JPH1059929A (ja) シクロヘキサンジオン誘導体および除草剤組成物
JPH0768220B2 (ja) 新規ピラゾ−ル誘導体、その製造法およびそれらを含有する農園芸用殺菌剤
JPS62201855A (ja) カルボキサミド類、その製法及び農業用殺菌剤
JP2943778B2 (ja) 置換ベンゼン誘導体
JPH0826914A (ja) トリケトン誘導体
JPH11236376A (ja) 新規ベンゾイルピラゾール化合物および除草剤
JPS59163363A (ja) シクロヘキセノン誘導体、製造方法及び選択的除草剤
WO1999033820A1 (fr) Derives de la tricetone

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AU BB BG BR CA CN CZ EE FI GE HU IS JP KG KR LK LR LT LV MD MG MK MN MX NO NZ PL RO SG SI SK TR TT UA US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载