WO2001017969A1 - Derives ureides de l'acide 6-[phenoxy(substitue ou non substitue)]picolinique, procede de production associe et herbicides - Google Patents

Derives ureides de l'acide 6-[phenoxy(substitue ou non substitue)]picolinique, procede de production associe et herbicides Download PDF

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WO2001017969A1
WO2001017969A1 PCT/JP2000/006139 JP0006139W WO0117969A1 WO 2001017969 A1 WO2001017969 A1 WO 2001017969A1 JP 0006139 W JP0006139 W JP 0006139W WO 0117969 A1 WO0117969 A1 WO 0117969A1
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group
alkyl
atom
alkoxy
amino
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PCT/JP2000/006139
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English (en)
Japanese (ja)
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Yoichi Kanda
Hisashi Kanno
Kazuo Yoshida
Masato Arahira
Yuichi Kokaji
Tsutomu Sato
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Kureha Kagaku Kogyo Kabushiki Kaisha
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Priority to AU68757/00A priority Critical patent/AU6875700A/en
Priority to JP2001521716A priority patent/JP4626119B2/ja
Publication of WO2001017969A1 publication Critical patent/WO2001017969A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products

Definitions

  • the present invention relates to a herbicide comprising 6-[(substituted or unsubstituted) phenoxy] picolinic acid perylene derivative as an active ingredient; — [(Substituted or unsubstituted) phenoxy] picolinic acid perylene derivative.
  • Japanese Unexamined Patent Publication (Kokai) No. 4-290805 discloses a compound represented by the formula (A) and a specific example thereof, N- (dimethylamino) carbonyl-1 6- [3- (trifluoromethyl) phenoxy] _ 2 _ pyridinecarboxamidoca has been described.
  • the definition of the substituent is described by partially extracting the substituent which overlaps with the substituent of the compound of the formula (I) shown below.
  • X 1 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, a haloalkylthio group, an alkenylthio group or an alkynylthio group, Same or different substituents above
  • n represents an integer of 1 to 5. When m is 2 or more, X 1 may be the same or different.
  • Y 1 represents a halogen atom, an alkyl group or a haloalkyl group.
  • n shows the integer of 0-3.
  • Y 1 may be the same or different.
  • R 1 1 and R 2 1 are each independently a hydrogen atom or an alkyl group.
  • the present invention has been made in view of the above circumstances, and has as its object to show excellent selectivity between crops and weeds without causing phytotoxicity to subsequent crops such as rotation or double cropping, and
  • An object of the present invention is to provide a compound showing a certain herbicidal effect at a dose, a method for producing the compound, and a herbicide containing the compound.
  • the present inventors have conducted various studies on the relationship between chemical structure and herbicidal activity with the task of finding an industrially useful 6-[(substituted or unsubstituted) phenoxy] picolinic acid ureide derivative.
  • a new, yet unreported, 6-[(substituted or unsubstituted) phenoxy] picolinic acid ureide derivative of formula (I) has very high herbicidal activity with excellent selectivity and low dose.
  • the present invention has been found, and the present invention has been completed.
  • the first gist of the present invention resides in a herbicide containing a 6-[(substituted or unsubstituted) phenoxy] picolinic acid peridode derivative of the formula (I) as an active ingredient.
  • RR 2 is independently a hydrogen atom, C, -C 8 alkyl, C 2 -C 6 alkyl, [di (C ⁇ C ⁇ alkyl) amino] CC 4 alkyl, (C ⁇ C ⁇ alkoxy) C! C alkyl, (CC 4 haloalkoxy) C Alkyl, Hydroxyalkyl,
  • C! C ⁇ alkyl group, halogen atom, C i -C 4 alkoxy group and C ⁇ -alkylthio group are substituted with at least one of the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • R 1 and R 2 are both an alkyl group
  • R 1 and R 2 are combined with the nitrogen atom to which R 1 and R 2 are bonded, and R 1 and R 2 are directly bonded to form a ring, Or an oxygen atom, an amino group or A ring may be formed via the nitrogen atom of the alkylamino group.
  • m represents an integer of 0 to 5. When m is 2 or more, Xs may be the same or different.
  • Y is a halogen atom, ( ⁇ Ji alkyl groups, C -C 4 haloalkyl group, CC ⁇ alkoxy groups, C
  • Alkylamino group, ⁇ ⁇ (: ⁇ dialkylamino group or a C 7 -C 8 7 aralkyl (( ⁇ Ji showing a 4 alkyl) Amino group.
  • n shows the integer of 0-3.
  • Y may be the same or different.
  • Z represents an oxygen atom or a sulfur atom.
  • R 1 when R 1 is bonded to the nitrogen of the ureide by nitrogen, oxygen or sulfonyl, R 2 is selected from a hydrogen atom or a group bonded to the nitrogen of the ureide by carbon.
  • R 2 when R 1 is bonded to the nitrogen of the ureide by nitrogen, oxygen or sulfonyl, R 2 is selected from a hydrogen atom or a group bonded to the nitrogen of the ureide by carbon.
  • RRX, m, Y, ⁇ and ⁇ are defined by
  • R 1 and R 2 simultaneously represent a C 1 -C 8 alkyl group.
  • n represents an integer of 0 to 5.
  • Xs may be the same or different.
  • Y represents s , a halogen atom, a C i -C 4 alkyl group or a C -dialkyl group.
  • n represents an integer of 0 to 3. When n is 2 or more, Y may be the same or different.
  • a second gist of the present invention is to provide a 6-[(substituted or unsubstituted) phenoxy] picolinic acid isocyanate represented by the following chemical formula (II) and an amamine represented by the chemical formula (XXII): A 6-[(substituted or unsubstituted) phenoxy] picolinic acid ureide derivative of the chemical formula (I).
  • a third aspect of the present invention resides in a 6-[(substituted or unsubstituted) phenoxy] picolinic acid peridode derivative of the formula (I).
  • R ⁇ R 2, X, m, ⁇ illustrating the specific contents of ⁇ and Zeta.
  • R 1 and R 2 may be the same or different, and have the same definition. However, as the group represented R 1 is then, if R 1 is attached to the nitrogen of the Ulei de nitrogen, oxygen or sul Honiru, R 2 is attached to the nitrogen of Urei de hydrogen atom or a C Selected from the groups Desirable R 2 is a hydrogen atom or a C Cs alkyl group, more preferably a hydrogen atom or C 1 to C 4. It is an alkyl group.
  • R 2 is selected from a hydrogen atom or a group that is carbon-bonded to the nitrogen of the metal oxide.
  • Preferred R 2 is a hydrogen atom or a C 1 -C 8 alkyl group, more preferably a hydrogen atom or a C i -C 4 alkyl group, particularly preferably a hydrogen atom.
  • C! CA alkyl group, a halogen atom, C i ⁇ C 4 are substituted at least at one alkoxy group and C ⁇ Ji group consisting al Kiruchio group, a nitrogen atom, at least of the group consisting of an oxygen atom and a sulfur atom
  • R 1 for example, [di ( ⁇ , ⁇ ( 4 alkyl) amino] ( ⁇ ⁇ ( ⁇ alkyl Is [di (C ⁇ C ⁇ alkyl) amino] is C It means that it is bonded to an alkyl carbon atom.
  • the number substituted depends on the type of the group and the halogen atom.
  • the outer () or inner group is preferably 1-2, More preferably, one is bonded.
  • hydroxy, mercapto or cyano is preferably attached to one to two, more preferably one.
  • halogen is a chlorine atom, a bromine atom or an iodine atom, preferably one or two, more preferably one, is bonded.
  • the halogen is a fluorine atom
  • 1 to (the number of substitutable hydrogen atoms on a carbon atom), preferably [1 to (the number of substitutable hydrogen atoms on a carbon atom)] 1 to 2 bonds are doing.
  • (C ⁇ -C 4 alkylthio) C 2 -C 4 alkyl such as 2- (methylthio) ethyl, 2- (ethylthio) ethyl, 3- (methylthio) propyl, and 3- (ethylthio) propyl
  • Propargyl 1, 1-dimethyl-C 3 -C 6 alkynyl, such as propargyl, cyclopropyl, cyclobutyl, cyclopentyl, C 3 to C 8 cycloalkyl cyclohexyl like cyclohexane,
  • Halophenyls such as 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, and 2,4-difluorophenyl; (CC ⁇ alkyl) phenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl,
  • (C ⁇ -C 4 haloalkyl) phenyl such as 3-(trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl,
  • Phenyl-alkyl such as phenylmethyl, 1-phenylethyl, etc.
  • Halophenylamino such as (2-chlorophenyl) amino, (3-chlorophenyl) amino, (4-chlorophenyl) amino,
  • C alkoxy such as methoxy, ethoxy, propoxy, etc.
  • R 1 In the definition of R 1 , the following groups may be mentioned as heterocycles.
  • It contains at least one member of the group consisting of nitrogen, oxygen and sulfur, such as 1,2,4-dithiazole-5-thioxo-3-yl, and is a member of 5 to 6 members A heterocyclic group having oxo or thioxo bonded to a carbon atom;
  • a heterocyclic group
  • Benzochiazo one rule 2 I le such as 5-black port benzoxazol-2-I le, C ⁇ C ⁇ alkyl group, a halogen atom, C I ⁇ C 4 alkoxy and C, ⁇ 4 A 5- to 6-membered heterocyclic group which is substituted with at least one member of the group consisting of alkylthio groups and contains at least one member of the group consisting of nitrogen, oxygen and sulfur atoms and is condensed with a benzene ring .
  • R 1 and R 2 are both an alkyl group
  • R 1 and R 2 are combined with the nitrogen atom to which R 1 and R 2 are bonded, and R 1 and R 2 are directly bonded to form a ring
  • a ring may be formed via a nitrogen atom of an oxygen atom, an amino group or a C i -C 4 alkylamino group.
  • the following groups can be mentioned as examples when one NR 1 R 2 forming a ring is used as a group.
  • Propyleneimine-1-yl azetidine-11-yl, pyrrolidine-11-yl, piperidine-11-yl, 2-methylbiperidine-11-yl, 3-methylbiperidine-1-yl, etc.
  • a group in which R 1 and R 2 are directly bonded to form a ring A group that forms a ring by bonding 5 ′ to the oxygen atom of the hydroxyl group bonded to R 1 and R 2 , such as morpholine-4-yl and 2,6-dimethylmorpholine-4-yl;
  • the group forming these rings is preferably a 3- to 10-membered ring, particularly preferably a 3- to 6-membered ring.
  • C ⁇ ⁇ 4- fluoroalkyl group, trifluoromethyl group, alkyl group, methyl group, ethyl group, (1-methyl) ethyl group, etc.
  • Alkoxy groups include methoxy group, ethoxy group, (1-methyl) ethoxy ban, etc.
  • CiC haloalkoxy groups include trifluoromethoxy group, difluoromethoxy group, etc.
  • C alkylthio groups include methylthio group.
  • C to (: 4 haloalkylthio groups include trifluoromethylthio group, difluoromethylthio group, and the like; halogen atoms generally include fluorine, chlorine, Bromine and the like.
  • X is preferably a trifluoromethyl group, a methyl group, a methoxy group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, a difluoromethylthio group, chlorine, or bromine.
  • X is a trifluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, or a trifluoromethylthio group.
  • M of the present compound (I) is preferably an integer of 0 (meaning unsubstituted) to 3, and more preferably a compound in which m is 1 and X is bonded to the 3-position.
  • C 4 -alkyl groups include methyl group, ethyl group, (1-methyl) ethyl group, Propyl group, etc., C ⁇ - ⁇ , and as the alkyl group, trifluoromethyl group, etc.
  • Examples of the alkylthio group include a methylthio group, an ethylthio group, and (1
  • Ci ⁇ c 4 alkylamino group Mechiruamino group, Echiruamino group, isopropylamino group or the like, the alkyl amino group, Jimechiruamino group, Jechiruamino group, C 7 -C 8 7 aralkyl (C ⁇ C ⁇ alkyl) amino group.
  • the halogen atom usually include fluorine, chlorine, and bromine.
  • Preferred Y includes chlorine, methyl group and methoxy group.
  • n is 1-2 Power preferable,, n is Y is especially preferred power? of is bonded to the 4-position by 1.
  • C 6 H 5 of R 1 of compound (1-516) represents an unsubstituted benzene ring
  • 2—C 1—C 6 H 4 of R 1 of compound (1-517) is benzene.
  • R 1 of 3- F- C 6 H 4 of the compound (1-545) showed that the fluorine atom is substituted at the 3-position of the benzene ring
  • 2 of R 1 in compound (1-547) 4 1 F 2 —C 6 H 3 indicates that the fluorine atom is substituted at the 2-position and 4-position of the benzene ring, respectively.
  • Table 1992 24 also has the same meaning.
  • a solvent obtained by mixing one or more of the following solvents is used in the reaction step or the product separation step.
  • the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; aliphatic hydrocarbons such as pentane, hexane, heptane, and methylcyclohexane; methylene chloride, 1,2-dichloroethane, and tetraethylene Chlorinated hydrocarbons such as chloroethane, chloroform, carbon tetrachloride, and benzene; N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, etc. Amides; ethers such as getyl ether, dimethoxetane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane.
  • the reaction in the method for producing the above compound (I) of the present invention is advantageously performed in a solvent or a solvent mixture.
  • a solvent composition composed of solvents that do not form a uniform phase with each other can also be used. If the reaction mixture contains a heterogeneous solvent or a solvent or a substrate that is insoluble in the solvent, it is appropriate to add a phase transfer catalyst such as a conventional quaternary ammonium salt or crown ether. It is.
  • the base when the use of a base is preferred in the reaction step or the product separation step, one or more of the bases described below can be used in combination.
  • the base include organic amines such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, and the like.
  • the 6-[(substituted or unsubstituted) phenoxy] picolinic acid ureide derivative of the chemical formula (I) of the present invention is obtained by reacting the 6-[(substituted or unsubstituted) fuunoxy] picolinic acid isocyanate of the chemical formula (II) with the chemical formula ( XXII) by reacting with 0.7 to 1.5 moles of the amines.
  • the reaction solvent in the above production method is usually methylene chloride, 1,2-dichloroethane, Chlorinated hydrocarbons such as black form, ethers such as tetrahydrofuran and dioxane,
  • Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone are used.
  • methylene chloride, 1,2-dichloroethane, chloroform and tetrahydrofuranca are used.
  • the 6-[(substituted or unsubstituted) phenoxy] picolinic acid isocyanate of the above formula ( ⁇ ) and the amine ( ⁇ ) are preferably mixed in an organic solvent, and usually mixed at 0 to 50, preferably 0 to 50. Is reacted at a reaction temperature of 20 to 30 ° C.
  • the reaction time is generally 1 to 7 hours, preferably 3 to 4 hours. If necessary, 3 ⁇ 4 such as triethylamine may be used as a catalyst.
  • the following reaction formula 1 shows a step of synthesizing a compound (I) from a compound (II) and an amine (XXII).
  • ⁇ to ⁇ 4 alkylamino is a C 7 to C 8 ⁇ in the definition of ⁇ .
  • Aralkyl (C] -C 4 alkyl) benzyl, which is included in ⁇ Mi Roh ((Interview ⁇ Ji alkyl Le) Amino can the be induced de base Njiru by the decomposition pressure hydrogenation.
  • catalysts having an increased surface area such as platinum, palladium, nickel, etc., and their activities, and these metals are usually used as activated carbon, carbon, barium carbonate, alumina, etc. Is shown. Of these, palladium carbon, Raney nickel and the like can be preferably used.
  • reaction accelerator among the above-mentioned acids, hydrochloric acid, perchloric acid, acetic acid and the like can be preferably used. The reaction is carried out at room temperature to 40 ° C for 30 minutes to several days.
  • sulfur oxidation (c ⁇ c ⁇ alkylthio) ci ⁇ c 4 alkoxy, are able to induce (c! To c 4 alkylsulfonyl) c to c 4 alkoxy.
  • organic peroxides such as peracetic acid, perbenzoic acid, metaclo-perbenzoic acid, perphthalic acid, hydrogen peroxide, sodium hypochlorite, and chlorine are usually used.
  • peracetic acid hydrogen peroxide may be added to an acetic acid solution of an oxidizing substance to be generated and used in a reaction vessel.
  • reaction solvent an organic solvent which is inert and dissolves the oxidized substrate can be preferably used.
  • the reaction temperature is generally in the range of 0 to 100 ° C, preferably in the range of 0 to 70 ° C.
  • Reaction time is from a few minutes to a few days In oxidizing sulfur to sulfinyl, the use of a periodate such as sodium periodate allows the desired product to be obtained in good yield.
  • X m represents a substituent on the phenoxy ring, e.g., 3- CF 3 compound (II- 1) indicates that the Ca? Bonded to a carbon atom of Hue phenoxy ring on 3-position.
  • 2-Cl, 5-CF 3 of compound (II-33) has a C1 force bond to the 2-position carbon atom on the phenoxy ring, and CF 3 is bonded to the 5-position carbon atom on the phenoxy ring.
  • Oxalyl chloride is generally used in an amount of 0 to 1.5 mol, preferably 1.0 to L.2 mol, per mol of 6-[(substituted or unsubstituted) phenoxy] picolinic acid amide of the formula (III).
  • chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, and chloroform
  • ethers such as tetrahydrofuran and dioxane, preferably methylene chloride, 1,2-dichloroethane , Mouth form, tetrahydrofuran, more preferably 1,2-dichloroethane.
  • 6-[(Substituted or unsubstituted) phenoxy] picolinic acid amide (III) is obtained by converting 6-[(substituted or unsubstituted) phenoxy] picolinic acid (VI) with a chlorinating agent such as thionyl chloride.
  • a chlorinating agent such as thionyl chloride.
  • the reaction is carried out at a reaction temperature of 80 to 90 ° C. for a reaction time of usually 30 minutes to 6 hours, preferably 1.5 to 3 hours to give 6-[(substituted or unsubstituted) phenoxy] picolinic acid chloride.
  • the compound (III) can be produced by reacting at a temperature of preferably 20 to 25 ° C, usually for 30 minutes to 5 hours, preferably 1 to 2 hours.
  • the reaction solvent include chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, and preferably methylene chloride and 1,2-dichloromethane. Mouth ethane or the like can be used.
  • Y n represents a substituent on the pyridine ring.
  • 4- ⁇ CH 3 in the compound number ( ⁇ -1) is attached to the carbon atom at the 4-position on the pyridine ring.
  • X m represents a substituent on the phenoxy ring.
  • 3-CF 3 in compound (III-1) indicates that CF 3 is bonded to the 3-position carbon atom on the phenoxy ring.
  • Y n represents a substituent on the pyridine ring.
  • X m represents a substituent on the phenoxy ring.
  • 3-CF 3 in compound (IV-1) indicates that CF 3 is bonded to the 3-position carbon atom on the phenoxy ring.
  • compound (VIII) is reacted with (substituted or unsubstituted) phenol in a solvent under basic conditions.
  • the base include the following types.
  • Alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium;
  • Alkoxides of alkali metals such as sodium methoxide, sodium ethoxide, potassium t-butoxide;
  • Alkali metal hydrides such as sodium hydride and potassium hydride
  • Hydroxidizing hydration metal hydroxide such as sodium hydroxide
  • Carbonated lime metal carbonates such as sodium carbonate
  • Alkaline earth metal hydrides such as calcium hydride
  • Organometallic compounds of alkali metals such as methyllithium, ethyllithium, butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium;
  • Organic Grignard reagents such as methylmagnesium iodide, ethylmagnesium bromide, n-butylmagnesium bromide;
  • Organometallic compounds of alkali metals and organic copper compounds prepared from Grignard reagents and monovalent copper salts;
  • Alkali metal amides such as lithium diisopropyl amide
  • Triethylamine Triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] pendec-17-ene (abbreviated as DBU below), etc.
  • bases such as organic amines.
  • Preferred bases include alkali metal hydrides such as sodium hydride and potassium hydride. Can be exemplified.
  • the amount of the base to be used is generally 0.8 to: L0 mol, preferably 1 to 5 mol. (Substituted or unsubstituted)
  • the amount of the phenol is usually 0.8 to 15 times, preferably 1.2 to: L0 times the mol of the compound (VIII).
  • a catalyst such as copper halide may be added.
  • the amount of addition is usually 0.01 to: L0 mole, preferably 0 to!; 5 to 1 mole relative to compound (VIII).
  • the reaction temperature is generally in the range of 0 ° C to 200 ° C, preferably in the range of 60 ° C to 180 ° C. Reaction times are usually from hours to days.
  • the (substituted or unsubstituted) phenol a commercially available product or a compound that can be produced by existing technology can be used.
  • the following compounds can be exemplified.
  • the hydrolysis can be performed under both acidic and basic conditions.
  • an inorganic acid such as hydrochloric acid, hydrobromic acid or sulfuric acid is usually used as the catalyst.
  • water to which an organic acid such as acetic acid is added in addition to water that is usually used can be used.
  • an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base.
  • the solvent usually, a solvent to which alcohol or the like is added in addition to water can be used.
  • the hydrolysis temperature is usually in the range of 20 ° C to reflux point, preferably in the range of 50 ° C to reflux point. Reaction times range from minutes to days.
  • hydrolysis When hydrolysis is performed in a highly concentrated acid solution (for example, 35% hydrochloric acid or 90% sulfuric acid), the hydrolysis is performed at 70 to 150 °, preferably at 90 to 130 ° for 10 minutes to 2 hours. Preferably, it can be carried out by heating for 0.5 to 1 hour.
  • a highly concentrated acid solution for example, 35% hydrochloric acid or 90% sulfuric acid
  • X m represents a substituent on the phenoxy ring.
  • 3-CF 3 of the compound (VI-1) has a CF 3 force bond to the carbon atom at the 3-position on the phenoxy ring.
  • the compound (VI-1) has a CF 3 force bond to the carbon atom at the 3-position on the phenoxy ring.
  • Compound (VI-13) is synthesized from 2-cyclomouth pyridine N-oxide (XX) as follows.
  • the compound (XX) is reacted with dimethyl sulfate to synthesize 2-chloropyridinium monomethyl sulfate (XIX) having a methoxy group bonded to the nitrogen at position 1.
  • Compound (XVIII) can be phenoxylated to give 2-cyano-6- (3-trifluorophenoxy) pyridine (IX).
  • compound (VI-13) By hydrolyzing compound (IX) under acidic conditions, compound (VI-13) can be produced.
  • reaction scheme 7 shows a synthesis route for 2-cyano-14-methoxy-16-cyclopyridine of chemical formula (VIII-a), which is one of the starting compounds of compound (VI-1). o
  • methoxide as a nucleophile allows the preparation of 2-methoxy-4-methoxypyridine N-oxide (XI). This is reacted with dimethyl sulfate to form a substituted pyridinium monomethyl sulfate (X) in which a methoxy group is bonded to the nitrogen at position 1, It is then reacted with a cyanate such as sodium cyanide to form a cyano ion adduct. This adduct can be demethanolized to synthesize 2-chloro-6-cyano-4-methoxypyridin (VIII-a).
  • reaction for introducing a cyano group at the 2-position is also carried out by reacting compound CXXIII) with cyanotrimethylsilane and dimethylcarbamoyl chloride (usually simultaneously) instead of dimethyl sulfate and cyanate. I can do it.
  • reaction formula 12 shows the above-mentioned steps.
  • the following compounds can be exemplified as the nucleophilic reagent used in the above-mentioned nucleophilic substitution reaction of the 412-nitro group.
  • ⁇ ⁇ ⁇ such as CH 3 , OC 2 H 5 , OCH (CH 3 ) 2 ( ⁇ ⁇ ( ⁇ To introduce an alkoxy group, C i ⁇ C 4 like methyl alcohol, ethyl alcohol, 1-methylethyl alcohol Arcanol; ⁇ _CH 2 CH 2 F, to introduce a C i to C 4 haloalkoxy group such as OCH 2 CHF 2, ⁇ _CH 2 CF 3, OCH 2 CH 2 CF 3 is 2 full O b ethyl alcohol, 2 (Such as: 2,2-difluoroethyl alcohol, 2,2,2-trifluoroethyl alcohol, 3,3,3-trifluoropropyl alcohol;
  • nucleophilic substitution reaction of the 1,2-nitro group it is preferable to carry out the reaction in the presence of a basic compound that captures the conjugate acid of the leaving group.
  • the nucleophilic substitution reaction is carried out using these alcohols or thioalcohols and a basic compound, more preferably an alkali metal alkoxide or an alkali metal thioalkoxide.
  • the amount of the compound used in the nucleophilic substitution reaction is 0.8 to 1.2 equivalents of the nucleophile and 0.8 to 1.2 equivalents of the basic compound per mol of the substrate.
  • the reaction temperature is -10 to: 120 ° C, and the reaction time is 30 minutes to 5 days.
  • the solvent used in the reaction can be appropriately selected depending on the nucleophile used; alcohols such as methanol and ethanol; ketones such as acetone and methylethylketone; dimethylformamide; N, N-dimethyla Aprotic polar solvents such as cetamidodiacetonitrile; ethers such as ethyl ether, tetrahydrofuran and dioxane.
  • a C-(: 4- dialkylamine such as dimethylamine or methylethylamine is substituted with Can be used.
  • C 7 -C 8 aralkyl such as methyl (benzyl) amino group
  • C ⁇ CAalkyl such as methyl (benzyl) amino group
  • a C 7 -C 8 aralkyl (C C ⁇ alkyl) amines can be used.
  • a nucleophilic reagent may be used in an increased amount of 0.8 to 1.2 equivalents, which is usually used, to 1.6 to 2.4.
  • amines (XXII) will be described.
  • Compounds such as (unsubstituted or substituted) ammonia, (unsubstituted or substituted) hydroxylamine or (unsubstituted or substituted) hydrazine include amines (XXII) which are commercially available products and compounds that can be manufactured by existing technologies. Can be used.
  • R 1 one of R 2 is a compound of hydrogen atoms (hereinafter, for convenience, the first Amin and forth) in both the of RR 2 months? Not a hydrogen atom of ⁇ f Certainly (hereinafter, for convenience, the second Amine).
  • C i C g As alkylamines, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, 1-methylethylamine, 2-methylpropylamine, 3-methylbutylamine, 1,1-dimethyl Ethylamine;
  • alkylamines ethoxymethylamine, 2-methoxyethoxylamine, 2-ethoxyethoxylamine, 3-methoxypropylamine;
  • alkylamines include methylsulfonylmethylamine, 2_ (methylsulfonyl) ethylamine, 2- (ethylsulfonyl) ethylamine, 3- (methylsulfonyl) propylamine, and 3- (ethylsulfonyl) propylamine;
  • (C ⁇ -C 4 haloalkylsulfinyl) As C 2 -C 4 alkylamine, 2-[(2-fluoroethyl) sulfinyl] ethylamine, 2-[(2,2,2-trifluoroethyl) sulfinyl] ethylamine; As a haloalkylsulfonyl) C 2 -C 4 Arukiruami emissions, 2- [(2-Furuoroechiru) sulfonyl] Echiruamin, 2- [(2, 2, 2-tri-off Ruoroechiru) sulfonyl] Echiruamin;
  • anilines include 2-methylaniline, 3_methylaniline, 4-methylaniline, and 4-ethylaniline;
  • Methyl, hydrazine as C 1, to C 4 alkyl hydrazine
  • N, N-di (Ci C alkyl) hydrazine as N, N-dimethylhydrazine, N, N-getylhydrazine;
  • 2- fluoroethoxylamine as C 2 -C haloalkoxylamine;
  • (C ⁇ C alkoxy) C, -C 4 alkoxylamine as (ethoxy) methoxylamine;
  • C 1 -C 4 alkyl sulfonamides methyl sulfonamide, ethyl sulfonamide, 1-methylethyl sulfonamide;
  • Di (C i -C 4 alkyl) amines such as dimethylamine, getylamine, zipperamine, dibutylamine, N-ethylmethylamine;
  • N- (C alkyl) aniline N-ethylenaniline, N-methylaniline;
  • Examples of amines in which R 1 and R 2 are directly bonded to form a ring include propyleneimine, azetidine, pyrrolidine, piperidine, 2-methylbiperidine, and 3-methylbiperidine;
  • R 1 and R 2 form a ring via an oxygen atom, morpholine, 2, 6-1-dimethylmorpholine;
  • Amin to ⁇ Ji bonded via a nitrogen atom of the 4 alkylamino groups form a ring piperidines Rajin, N- Mechirubiperajin.
  • amines for example, the following compounds obtained by known methods can be used? I can do it.
  • N-substituted phthalimid ⁇ N-substituted amide obtained by the reaction of carboxamides such as phthalimid and benzamide with the following substituted halogenated, substituted dialkyl sulfate compounds, substituted sulfonic acid ester compounds, etc.
  • Primary amines obtained by removing protecting groups such as phthalic acid from the compounds;
  • the primary amine is reacted with a dicarboxylic anhydride such as phthalic anhydride or an acyl halide, and the amino-protected compound is subjected to various modification reactions according to existing technologies, for example, a halogen atom under basic conditions.
  • a dicarboxylic anhydride such as phthalic anhydride or an acyl halide
  • the amino-protected compound is subjected to various modification reactions according to existing technologies, for example, a halogen atom under basic conditions.
  • the C! ⁇ (4 Al force Nord and C, ⁇ C 4 alkyl A primary amine prepared by performing a nucleophilic substitution reaction with a thiol or the like or an oxidation reaction of a sulfur atom or the like and then performing a deprotection group;
  • substituted hydroxyamines are described in terms of methoxylamine, ethoxylamine, aryloxylamine, methoxylmethylamine, phenylmethoxylamine, N-methylhydroxylamine, N-phenylhydroxylamine, and the like.
  • Various 0-substituted, .N-substituted hydroxylamine compounds on the market are listed.
  • the removal of a compound formed by the reaction of an acyl-substituted compound such as N-hydroxyphthalimid ⁇ or benzohydroxamic acid with the following substituted halide, substituted dialkyl sulfate, substituted sulfonic ester, etc.
  • Substituted hydroxylamines can also be obtained by various existing techniques, such as by protecting groups.
  • substituted hydrazines examples include methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, 1,2-diethylhydrazine, 2-chlorophenylhydrazine, 3-chlorophenylhydrazine, and 4-chlorohydrazine.
  • R] amines (XXII), in the definition of R 2, (CC ⁇ alkylsulfinyl) C 2 -C 4 alkyl and (C ⁇ C ⁇ alkylsulfonyl) CC ⁇ alkyl, (C! ⁇ C 4 alkylthio) C 2 -C 4 alkyl can also be derived by utilizing an oxidation reaction of the sulfur. Similarly, sulfur oxidation (C ⁇ -C 4 haloalkylthio) C 2 -C 4 alkyl,
  • the oxidizing agent used for the sulfur oxidation of amines (XXII) or amines (XXII) protected with amines is usually an organic peroxide such as peracetic acid, perbenzoic acid, metabenzo-perbenzoic acid, or perphthalic acid. Oxides, hydrogen peroxide, sodium hypochlorite, chlorine, potassium permanganate, ruthenium oxide, osmium oxide, chromic acid, periodate, periodate and the like can be mentioned.
  • hydrogen peroxide can be added to an acetic acid solution of an oxidized substrate to be generated and used in a reaction vessel.
  • reaction solvent an organic solvent which is inert and dissolves the oxidized substrate can be preferably used.
  • the reaction temperature is generally in the range of 0 to 100 ° C, preferably in the range of 0 to 70 ° C.
  • the reaction time is on the order of minutes to days.
  • a periodate such as sodium periodate can be used to obtain the desired product in good yield.
  • the 6 _ [(substituted or unsubstituted) phenoxy] picolinic acid peridode derivative of the above formula (I) of the present invention exhibits a reliable herbicidal effect at a low dose and exhibits selectivity between crops and weeds. . Therefore, the herbicide of the present invention containing this compound as an active ingredient is useful for controlling dicotyledonous weeds and monocotyledonous weeds in important crops such as wheat, rice, corn and soybean before or after germination. Particularly suitable. It can also be used to control weeds in non-agricultural lands such as farmlands, paddy fields, orchards, and other non-agricultural lands such as grounds and plant sites.
  • Examples of dicotyledonous weeds that can be controlled by the herbicide of the present invention include Polygonaceae, Papilionidae, Akazaceae, Hyuaceae, Aoaceae, Brassicaceae, Akanaceae, Asteraceae, Sesame Family, and Sesame Family.
  • examples of monocotyledon weeds include Gramineae and Calagidaceae.
  • This compound (I) can be used as it is as a herbicide, but it is usually used in the form of powders, wettable powders, granules, emulsions and other forms together with formulation aids.
  • one or more compounds of the present invention (I) are usually contained in the preparation in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 70% by weight.
  • carriers, diluents, and surfactants used as formulation aids solid carriers include talc, kaolin, bentonite, diatomaceous earth, white carbon, and clay.
  • the liquid diluent include water, xylene, toluene, cyclobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, and alcohol.
  • emulsifiers usually include polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan monolaurate and the like.
  • Dispersant Examples thereof include lignin sulfonate and dibutyl naphthalene sulfonate.
  • the wetting agent generally include alkyl sulfonates and alkyl phenyl sulfonates.
  • the concentration of this compound (I) is usually in the range of 0.001 to 1.0%.
  • the amount of the present compound (I) to be used is usually 0.001 to: L0 kg, preferably 0.01 to 5 k per lha.
  • the concentration and amount used of these vary depending on the dosage form, time of use, method of use, place of use, target crop, and the like, so it is of course possible to increase or decrease the amount without being limited to the above range.
  • the present compound (I) can be used in combination with other active ingredients such as fungicides, insecticides, acaricides, herbicides and the like.
  • IRKBr cm— 1 2224, 1698, 1620, 1578, 1454, 1332, 1178, 1126.
  • the obtained crude product was suspended in 10 ml of dichloromethane, and isopropylamine (0.142 g, 1 6 X 1.5 mmol) in dichloromethane solution was added dropwise, and the mixture was stirred at room temperature for 2 hours, water was added to the reaction mixture, and the mixture was partitioned, and the organic layer was washed with water and anhydrous sodium sulfate. After drying and distilling off the solvent, the residue was purified by silica gel column chromatography to obtain the desired product having the following properties: white solid, mp 65-67 ° C, yield 0.23 g, yield 39.6%.
  • IR KBr cm -1 3388, 3336, 1716, 1690, 1612, 1550, 1498, 1434, 1332, 1218, 1186, 1136.
  • IRKBr cm -1 3376, 3344, 1712, 1614, 1488, 1332, 1306, 1218, 1188, 1142,
  • IRKBr cm -1 3488, 3348, 3200, 1732, 1706, 1614, 1458, 1374, 1330, 1220,
  • IRKBr cm -1 3380, 3344, 3084, 1720, 1614, 1578, 1542, 1494, 1428, 1362, 1328, 1282, 1220, 1170, 1126, 1094, 1068, 1044, 992, 882, 856, 812, 784 , 760, 702, 662, 600.
  • IRKBrcm— 1 3352, 3268, 1686, 1614, 1512, 1474, 1458, 1326, 1148, 1124.
  • 6- [3- (Trifluoromethyl) phenoxy] —4-methoxy-2-pyridinepyridine isocyanate (0.3 g, 0.887 mmo 1) was suspended in 10 ml of dichloromethane and cooled under water cooling. A 2-m1 dichloromethane solution of 4-cyclomouth benzylamine (0.156 g, 0.887 mm 01) was added dropwise. Then, the mixture was stirred at room temperature for 3 hours, and water and dichloromethane were added to the obtained reaction solution and partitioned.
  • IRKBr cm -1 3376, 3360, 1730, 1695, 1520, 1350, 1230, 1140.
  • Dimethyl sulfate (8.3 g, 0.070 X 1 m 0 1) was added dropwise to 4-methoxyethoxy N-oxide (11.lg, 0.070 mo 1). After stirring at room temperature to obtain a homogeneous solution, the mixture was continuously stirred overnight. After decanting and washing with Jettlether, it was dissolved in 70 ml of water. Under a nitrogen atmosphere, sodium hydrocyanic acid (8.3 g, 0.070 X 2.4 m 01) dissolved in 7 Om 1 of water was added dropwise at 110 ° C. in about 1 hour. After stirring for 2 hours, the precipitate was separated by filtration and washed with water.
  • 3-(Trifluoromethyl) phenol (3.74 g, 0.0178 X1.3 mo 1) was dissolved in about 20 ml of dimethylformamide, and sodium hydride [0.8 1 g (ca. 60% inmineraloil), 0.0 1 7 8 1.1 mo 1] and then 2-black 6-cyano 4-methoxypyridine (3.0 g, 0 0.178mo 1) and stirred at about 110 ° C for about 5 hours.
  • the reaction solution was partitioned with hexane-saturated aqueous sodium bicarbonate solution, and then washed with saturated saline.
  • reaction mixture was partitioned between ethyl acetate and 1N aqueous hydrochloric acid, and washed with saturated aqueous sodium hydrogen carbonate and saturated saline.
  • the organic layer was dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography (eluent: ethyl acetate Z hexane) to obtain the desired product having the following characteristics. Yield 0.88 g, 84% yield, solid, m.p. 150-151.
  • sodium cyanide (16 g, 0.0836 X3.9 mo1) was dissolved in 78 ml of water, and cooled to 17 ° C to 15 ° C under nitrogen.
  • the solution A prepared above was added dropwise thereto. After stirring at this temperature for 1.5 hours, the precipitated crystals were filtered, washed with water, and the solid was washed with a small amount of ethyl acetate to obtain a compound having the following properties. Yield 6.88 g, 54% yield, solid, mp96-97 ° C.
  • Keridonic acid 25 g, 0.123 m 01
  • 40% methylamine aqueous solution 500 m 1
  • the mixture was acidified with concentrated hydrochloric acid, and the precipitated solid was collected by filtration, washed with water and dried to obtain a compound having the following properties.
  • N-Methylkeridamic acid (XXI) 13 g, 0.066 mol was added to thionyl chloride (50 ml) containing a catalytic amount (using 35 mg) of N, N-dimethylformamide. The mixture was stirred at 901C for 1 hour and 30 minutes. Thereafter, thionyl chloride was completely distilled off, and the residue was added to 100 ml of methanol under cooling with water. After stirring for 2 hours, methanol was distilled off, and the residue was partitioned between ethyl acetate and water. The obtained organic layer was washed with a saturated saline solution and dried over anhydrous sodium sulfate.
  • 2-cyano 6- [3- (Trifluoromethyl) phenoxy] pyridine (3.00 g, 0. 1 mol) is suspended in about 15 ml of concentrated hydrochloric acid. Stirred for hours. After cooling, water was added to the reaction solution, and the mixture was partitioned with ethyl acetate / water. After washing with a saturated saline solution, the extract was dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography (eluent: ethyl acetate Z hexane) to obtain the desired product having the following characteristics. Yield 3.02g, 94% yield, solid, mp88-90 ° C.
  • DMSO-d6 deuterated chloroform
  • CDC deuterated chloroform

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des herbicides contenant en tant que principe actif des dérivés uréides de l'acide 6-[phénoxy(substitué ou non substitué)]picolinique, représentés par la formule générale (I). Ces herbicides possèdent un effet herbicide certain, même à petite dose, ainsi qu'une sélectivité entre récoltes et mauvaises herbes, et ils sont notamment conçus pour lutter contre les mauvaises herbes des familles dicotylédones ou monocotylédones qui poussent en même temps que des récoltes importantes telles que le froment, le riz, le maïs ou le soja, avant ou après germination de ces récoltes. Dans la formule, R1 et R2 représentent chacun alkyle, alcoxy, etc.; Z représente O ou S; X représente alkyle, alcoxy, etc.; Y représente haloalkyle, etc., m est choisi entre 0 et 5 et n entre 0 et 3.
PCT/JP2000/006139 1999-09-09 2000-09-08 Derives ureides de l'acide 6-[phenoxy(substitue ou non substitue)]picolinique, procede de production associe et herbicides WO2001017969A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU68757/00A AU6875700A (en) 1999-09-09 2000-09-08 6-[(substituted or unsubstituted)phenoxy]picolinic acid ureide derivatives, process for producing the same and herbicides
JP2001521716A JP4626119B2 (ja) 1999-09-09 2000-09-08 ６−［（置換または無置換）フェノキシ］ピコリン酸ウレイド誘導体、その製造方法及び除草剤

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JP11/255263 1999-09-09
JP25526399 1999-09-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63166865A (ja) * 1986-12-22 1988-07-11 バイエル・アクチエンゲゼルシヤフト 置換されたフエノキシピリジン類
JPH02178266A (ja) * 1988-12-27 1990-07-11 Chugai Pharmaceut Co Ltd ニコチン酸アニリド系化合物及び該化合物を含有する除草剤
EP0488474A1 (fr) * 1990-11-28 1992-06-03 Shell Internationale Researchmaatschappij B.V. Dérivés herbicides de carboxamide
EP0881217A1 (fr) * 1995-12-28 1998-12-02 Kureha Kagaku Kogyo Kabushiki Kaisha Procede de production de pyridinecarboxamides ou de thiocarboxamides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63166865A (ja) * 1986-12-22 1988-07-11 バイエル・アクチエンゲゼルシヤフト 置換されたフエノキシピリジン類
JPH02178266A (ja) * 1988-12-27 1990-07-11 Chugai Pharmaceut Co Ltd ニコチン酸アニリド系化合物及び該化合物を含有する除草剤
EP0488474A1 (fr) * 1990-11-28 1992-06-03 Shell Internationale Researchmaatschappij B.V. Dérivés herbicides de carboxamide
EP0881217A1 (fr) * 1995-12-28 1998-12-02 Kureha Kagaku Kogyo Kabushiki Kaisha Procede de production de pyridinecarboxamides ou de thiocarboxamides

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JP4626119B2 (ja) 2011-02-02

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