WO2005007627A1

WO2005007627A1 - Phenylpyridine derivative, intermediate therefor, and herbicide containing the same as active ingredient

Info

Publication number: WO2005007627A1
Application number: PCT/JP2004/010560
Authority: WO
Inventors: Eiji Takizawa; Shuji Kumata; Takahiro Kiyokawa
Original assignee: Nihon Nohyaku Co., Ltd.
Priority date: 2003-07-18
Filing date: 2004-07-16
Publication date: 2005-01-27

Abstract

A phenylpyridine compound represented by the general formula (I): (I) (wherein R1 represents hydrogen, etc. and R2 represents hydrogen, etc., provided that R1 and R2 in combination can form a 4- to 8-membered ring containing X (shown later), carbon, nitrogen, oxygen, or sulfur; R3's may be the same or different and each represents hydrogen, etc., provided that two R3's in combination can form a 3- to 6-membered ring containing carbon, nitrogen, oxygen, or sulfur; R4's may be the same or different and each represents halogeno, etc.; R5's may be the same or different and each represents halogeno, etc., provided that two adjacent R5's can be bonded to each other to form -OCF2O-, etc.; X represents -C(=O)-, -C(=S)-, or -SOq- (wherein q is 1 or 2); t is an integer of 0 to 2; m is an integer of 0 to 3; n is an integer of 1 to 5; and p is 0 or 1) or a salt of the compound; and a herbicide containing any of these as an active ingredient.

Description

TECHNICAL FIELD Phenylpyridine derivatives, intermediates thereof and herbicides containing the same as an active ingredient

The present invention relates to a novel phenyl-pyridine or a salt thereof and a herbicide containing the same as an active ingredient and a method for using the same. Background art

Heretofore, it has been known that certain pyridine derivatives have a herbicidal activity and a plant growth regulating action (for example, Patent Document EP-A-0 595 340, International Publication No. 98) / 0 4 5 5 0 pamphlet, European Patent Application Publication No. 0 9 5 5 2 9 2 specification, International Publication No. 0/0 7 5 1 1 1 pamphlet, International Publication No. 0 1/0 0 5 8

See No. 0 pamphlet and International Publication No. 9/28 3 011 pamphlet. ). In addition, it has been shown that a phenoxypyridylmethylamine derivative exhibits a removing activity (for example, see WO 03/0000697 pamphlet). It is known to be useful as an intermediate (eg, J. Med.

See Chem., 34, 72-5-736 (1991). ). However, the present invention has not known a pyridine compound in which a benzene ring and a pyridine ring are directly bonded at a specific position and its herbicidal activity. Disclosure of the invention

A stable food supply is essential to address the food crisis associated with the world population growth expected in the near future. Stable food supply requires economic and efficient killing and control of weeds that hinder cultivation and harvesting. New herbicides and plant growth regulators are the solution. Development is becoming increasingly important.

An object of the present invention is to provide a novel herbicide having both high safety against crops and excellent herbicidal activity against weeds in order to respond to such social demands.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a group of compounds having a novel phenylpyridin skeleton has excellent herbicidal activity to solve the above problems. Reached.

That is, the present invention provides the following general formula (I):

(Wherein, R ¹ is a hydrogen atom, a CC ₈ alkyl group, a halo Ci-C ₈ alkyl group, a C2-C ₈ alkenyl group, a C ₂ -C ₈ alkynyl group, a Ci-Cs alkoxy group, a halo Ci-C ₈ alkoxy, Ci-C ₈ § alkylamino group, phenyl group, the same or different and a halogen atom, Xia amino group, two collected by filtration group, hydroxyl group, amino group, SH group, Ci-Cs alkyl group, a halo

Cl-Cs alkyl group, C2- C6 alkenyl group, Nono b C2-C6 alkenyl group, C ₂ -C ₆ § Rukiniru group, Nono b C2-Cs alkynyl, Ci-Cs alkoxy group, a halo CrC ₆ § alkoxy group , CRCS alkylthio group, halo C Cs alkylthio group, C ₂ -C ₆ § Lucenethiol group, / C2-CsCalkeninolethio group, CvCe T-Lucinolesulfinyl group, Halo CrCs Nolequinoles noreinole group, CrCeT Norequils norehoninole group, Halo CrCs Nolechlore carbonyl group Ha port CrCs Arukirukarubo - group, phenylpropyl group, CRCE Aruko key aryloxycarbonyl group, rather mono C Cs Arukirua Mi amino group or identical young selected from good di Ci'C ₆ Arukirua Mi amino group Te different dates that 1-5 substituents replacement Hue radicals having, full: Le Cl-C ₈ alkyl group, which may be the same or different, halogen atoms, Xia amino group, two collected by filtration group, a hydroxyl group, a Mi amino group, SH group, CrC ₆ Al kill group, a halo Cl- C6 alkyl group, C2- C6 alkenyl group, a halo C2- C6 alkenyl Le group, C2- C6 alkynyl group, a halo C2- C6 alkynyl group CrCs alkoxy group, a halo CrC ₆ alkoxy group, CrC ₆ alkylthio group, a halo CrCs alkylthio group, C2. C6 alkenylthio group, a halo C2- C6 alkenylthio group, Cl @ - C6 alkyl Angeles Le full I el group, C b CrCs quinolenos fluorinole group, CrCs alkynole sulphonyl group, H-type CrCs alkynole sulphonyl group, CrCs alkynolecanoleponyl group, nodro CrCs sanolecyl caneboninole group, phenyl carbinole group, Ci ₆ Aruko alkoxycarbonyl group, mono-Ci-Cs Arukirua Mi amino group or the same young and rather is substituted phenyl having from 1 to 5 substituents selected from a good-di Ci-C ₆ Arukirua Mi amino group or different on the ring ci-C ₈ alkyl group, Fuweniruamino group, may be made the same or different, Nono androgenic atom, Xia amino group, two collected by filtration group, a hydroxyl group, A Mi amino group,

SH group, CC ₆ alkyl group, halo Ci-C ₆ alkyl group, C ₂ -C ₆ alkenyl group, halo C2-C6 alkenyl group, C2-C6 alkynyl group, halo C2-C6 alkyl group,

CrC ₆ alkoxy group, halo CrC ₆ alkoxy group, Ci-C ₆ alkylthio group, C port CRCS Arukiruchio group, C2- C6 Aruke two thio groups, halo C2- C6 Arukeniru Chiomoto, CRCS Arukirusurufu I group, halo CRCS Arukirusurufu Carboxyl group, CrCs anolequinolenosolephonyl group, halo Ci-Ce alkylsulfonyl group, C Cs alkyl carbonyl group, halo CrCs alkyl carbonyl group, phenyl carbonyl rebonyl group, CrCs alkoxycarbonyl group, mono CrCs Arukirua Mi amino group or a substituted Fueniruami amino group having 1 to 5 substituents the same young and rather is selected from a good di CrC ₆ Arukirua Mi amino group or different on the ring, phenoxy group or identical Wakashi Ku is different may be a halogen atom, Xia amino group, two collected by filtration group, hydroxyl group, A Mi amino group, SH group, CRCS alkyl group, a halo CRCS alkyl group, C ₂ -C . ₆ alkenyl group, halo C ₂ -C ₆ alkenyl group, C2- C6 alkynyl group, a halo C2- C6 alkyl - le group, CRCS alkoxy group, a halo CRCS alkoxy, Ci-C ₆ Al Kiruchio group, C port C Ce Arukiruchio group, C2-C ₆ alkenylthio group, C b C ₂ -C ₆ Aruke two thio groups, Ci-Cs Arukirusu Norefu I group, C b C Cs Al Kirusu Norefu I group, Ci-Cs Anorekirusu Noreho Ninore group C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C And a substituted phenoxy group having 1 to 5 substituents on the ring selected from the group consisting of a di group and a di-CrC ₆ alkylamino group which may be the same or different. R ² is a hydrogen atom, CrCs alkyl group, C ₂ -C ₈ alkenyl group, C ₂ -C ₈ alkynyl group, C Cs alkoxy CrCs alkyl group, cyano C Cs alkyl group, C Cs alkyl carbonyl group, halo Ci-Cs An alkylcarbo group, a C2-C8 alkenylcarbonyl group, a Cssalkylsulfonyl group or a haloCssalkylsulfonyl group. Further, R ¹ and R ² can be combined to form a 4- to 8-membered ring containing X (X is shown below), a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.

R ³ may be the same or different and represents a hydrogen atom, a cyano group or a CrCs alkyl group, Also, two R3s can combine to form a ^{3- to} 6-membered ring containing a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. R ⁴ may be the same or different and include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxy group, a pentafluorosulfanyl group (--SF ₅ ), a CrC ₈ alkyl group, a halo Ci-C ₈ alkyl group, C ₂ -C ₈ alkenyl, C ₂ - C ₈ alkynyl group, Ci-Cs alkoxy group, a halo CRCS alkoxy group, Ci-Cs alkoxy carbo - le group, CRCS alkylthio group, CRCS alkylsulfinyl group, Ci'Cs Al Kirusuruho - showing the Le group, CRCS Arukiruamino group or the same or different and may di CI- C ₈ alkylamino group. R ⁵ may be the same or different, halogen atom, dC ₈ alkyl group, halo Cl-Cs alkyl group, C2-C8 alkenyl group, halo C2-C8 alkenyl group,

C ₂ -C ₈ alkynyl group, halo C ₂ -C ₈ alkynyl group, d-Cs alkoxy group, halo CrC ₈ alkoxy group, CrCs alkoxy CrCs alkyl group, halo C Cs alkoxy Ci-C ₈ alkyl group, CrC ₈ Alkoxy CrCs alkoxy group, nodro CrCs alkoxy CrCs alkoxy group, Ci-Cs alkylsulfonylamino group, halo CrCs alkylsulfo-amino group, Ci-Cs alkylthio group, halo C Cs alkylthio group, CrCs alkylsulfuryl group, Halo Ci-Cs alkylsulfinyl group, CrCs alkylsulfonyl group, halo CrCsanoloxysulfonyl group, CrCs alkylcarbonyl group, CrCs alkoxycarbonyl group, CCs alkylcarbonyloxy group, Haguchi CrCs alkylcarbonyloxy group, hydroxyl group , Formyl, cyano, nitro, trimethylsilyl, pentafluorosulfanyl ( SF ₅ ) or —C (R ⁶ ) = NOR ⁷ (wherein R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom, a Ci′C ₅ alkyl group or a halo Ci—Cs alkyl group. ) a group represented by also, two adjacent R ⁵ are together a connexion Jifuruoromechi Renjiokishi group together (one OCF ₂ 0_), Te trouble O b ethylenedioxy O alkoxy group (an OCF ₂ CF ₂ 0- ), _c X one C (= O) one can show a Mechirenjiokishi group or Echirenjiokishi group, - C (= S) in one or one SO q _ (wherein, q is 1 or 2 in the shown to). Shows the group represented. t represents an integer of 0 to 2, m represents an integer of 0 to 3, n represents an integer of 1 to 5, and p represents 0 or 1. The present invention relates to phenylviridines or salts thereof, a herbicide containing them as an active ingredient, and a method of using the same. Further, the present invention relates to an intermediate represented by the following general formula (II)

(II)

(In the formula, R ² is a hydrogen atom, a Ci-Cs alkyl group, a C ₂ -C ₈ alkenyl group, a C Cs alkynyl group, a CrC ₈ alkoxy C Cs alkyl group, a cyano CrC ₈ alkyl group, a CrCs alkyl group. R ³ may be the same or different, and may represent a hydrogen atom, a cyano group, or a d, a CrCs alkylcarbonyl group, a C Cs alkenylcarbonyl group, a C Cs alkylsulfonyl group, or a halo Ci-Cs alkylsulfonyl group. indicates -Cs alkyl group, also, two R ³ together such connexion carbon atom, a nitrogen atom, may form a 3-6 membered ring containing an oxygen atom or a sulfur atom. R ⁴ are the same or different may be a halogen atom, Shiano group, a nitro group, a hydroxyl group, a carboxyl group, penta full O b sulfur sulfonyl group (one SF _5), Ci-Cs alkyl group, a halo CrCs alkyl group, C2-C8 alkenyl, C2-Cs alkynyl Group, Ci-Cs alkoxy group Halo Ci'Cs alkoxy group, CrCs alkoxycarbonyl group, Ci-Cs alkylthio group, C Cs alkylsulfinyl group, Ci-Cs alkylsulfonyl group, Ci-Cs alkylamino group or di-Ci-Cs alkylamino which may be the same or different Base Indicates. R ⁵ may be the same or different, halogen atom, Ci'Cs alkyl group, halo

CRCS alkyl group, C2-C8 alkenyl, halo C2-C8 alkenyl, C2-C8 alkynyl, halo C2-C8 alkynyl group, CRCS alkoxy, halo Ci-Cs alkoxy group, Cr C ₈ alkoxy CRCS alkyl group, a halo ci-Cs alkoxy Ci-Cs alkyl group, CRCS alkoxy Ci'Cs alkoxy, halo Ci-Cs alkoxy CRCS alkoxy, CrC ₈ alkyl Le sulfonyl § amino group, halo Ci-Cs alkylsulfonyl § amino group, CRCS alkylthio O Group, halo CrCs alkylthio group, Ci-Cs alkylsulfinyl group, halo CrCs alkynolenorefininole group, CrCs anorekylsnolehoninole group, no-open CrCs anolequinolenoslehoninole group, Ci-Cs alkylcarbonyl group, CrCs alkoxycarbonyl group, C Cs alkyl carbonyloxy group, halo C Cs alkyl carbonyloxy group, hydroxyl group, formyl group, A cyano group, a nitro group, a trimethylsilyl group, a pentafluorosulfanyl group (—SF ₅ ) or —C (R ⁶ ) = NOR ⁷ (where R ⁶ and R ⁷ may be the same or different, and hydrogen atom, a Ci-C ₅ alkyl group or a halo Ci-C ₅ alkyl group.) a group represented by also, two adjacent R ⁵ a together with one another connexion difluorenylamino O b methylenedioxy O key sheet group (_OC F ₂ 0-), tetrafurfuryl O b ethylenedioxy O alkoxy group (an OC F2C F2O -), can exhibit Mechirenjiokishi group or Echirenjiokishi group. t represents an integer of 0 to 2, m represents an integer of 0 to 3, n represents an integer of 1 to 5, and p represents 0 or 1. The present invention also relates to a phenylpyridylalkylamine represented by the formula or a salt thereof. The invention's effect

According to the present invention, it is possible to obtain a herbicide exhibiting a high herbicidal effect and exhibiting sufficient safety for important crops and a useful compound used therefor. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

In the definition of the furubilidines represented by the general formula (I) or salts thereof of the present invention, the “halogen atom” represents a chlorine atom, a bromine atom, an iodine atom or a fluorine atom. The “CrC ₈ alkyl group” refers to a linear or branched or alicyclic alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, Normal propyl group, isopropyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butylinole group, cyclopropylmethyl group, normal pentyl group , A neopentyl group, a normal hexyl group, a cyclohexanol group, a 1,2,2-trimethylpropyl group, a 2-methylcyclopentyl group, and an n-octyl group. "Halo d-Cs alkyl group" refers to a straight-chain having 1 to 8 carbon atoms, which may be the same or different, and a branched chain having 3 to 8 carbon atoms. Or an alicyclic alkyl group, for example, chloromethyl group, 2-chloroethyl group, 2-phenololenothinole group, 2,2-dibutanoletinole group, 2,2,2-trifurenole Loetinole, 2,2,2-trichloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetra Fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-methyl-2,2,2-trifluoronorethyl group, 2,2,2-trifluoro-11- (trifluoromethyl) Chinole) ethinole group, 1-methyl-1,2,3,3,3-pentafluoropropynole group, 3-chloropropyl group, 3-propyl Mopropyl group, 4-chlorobutyl group, 4,4,4_ trifluoropropyl group, 5,5,5-triphenylenopentyl group, 6,6,6_ triphenylenohexyl group, 7-phnolehexyl group Group, 8-chlorooctinole group, 2, 2-diphnolecyclocyclopropyl And a (2,2-difluorocyclopropyl) methyl group, a 2,2-dichlorocyclopropyl group, a (2,2-dichlorocyclopropyl) methyl group, a perfluorooctyl group, and the like. “C ₂ -C ₈ alkenyl group” refers to a linear or branched C ₃ -C ₈ alkenyl group having 2 to 8 carbon atoms, for example, a vinyl group, Aryl group, 2-butenyl group, 2-methyl-2-propenyl group, 1-methyl-2-propidinole group, 1-methyl-2-butenyl group, 2-methylinyl 2-butenyl, 2-pentenyl group, 2-— Examples include a hexeninole group and a 2-cyclohexenyl group.

And "C ₂ -C ₈ alkynyl group", the number of carbon atoms 2-8 straight-chain, shows an alkynyl group having a carbon number 5-8 or a branched-chain or alicyclic, for example, propargyl group, Examples thereof include a 2-butynyl group, a 1-methyl-2-propynyl group, and a 2-cyclohexyl group.

“CrC ₈ alkoxy group” refers to a straight-chain alkoxy group having 1 to 8 carbon atoms or a branched or alicyclic alkoxy group having 3 to 8 carbon atoms, such as a methoxy group and an ethoxy group. Group, normal propoxy group, isopropoxy group, cyclopropoxy group, normal leptoxy group, secondary butoxy group, tertiary butoxy group, normal pen tinoleoxy group, isopentinoleoxy group, neopentinoleoxy group, cyclopentinoleo Examples include a xy group, a normal hexynoleoxy group, and a normanoleoctyloxy group.

“Halo Ci-C ₈ alkoxy group” refers to a straight-chain alkoxy group having 1 to 8 carbon atoms and a branched chain having 3 to 8 carbon atoms substituted by one or more halogen atoms which may be the same or different. Alicyclic or alicyclic alkoxy group, for example, chloromethoxy group, fluoromethyoxy group, triflorenomethoxy group, 2-chloroethoxy group, 2-furonoethoxy group, 2,2-difluoroethoxy group, 2,2 , 2-Trifluoroethoxy, 2,2,2_Trichloroethoxy, 3_Propoxy, 3—Promopropoxy, 3,3,3—Trifluoropropoxy, 2,2,3 1,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2-difluorocyclopropoxy group, 2,2-dichlorocyclopropoxy group, 1 —Methyl-2,2,2— Trif Oroethoxy group, 2,2,2-Trifrenole mouth _ 1- (Triphnorelomethinole) Ethoxy group, 1 —Methyl-1,2,2,3,3,3 —Pentafluoropropoxy group, 3 —Chloro Mouth Propoxy, 3 bromopropoxy, 4-chlorobutoxy, 4,4,4-trifluorobutoxy, 5,5,5-Trifluoropentyloxy, 6,6,6-Trifluorohexyloxy And the like.

When these groups show a part as “CrC ₈ alkyl”, “halo C-wide Cs alkyl”, etc., they also have the same meaning as the above “FCrCs alkyl group”, “halo C-wide C ₈ alkyl group” and the like. Further, “d-C ₅ ”, “d-C ₆ ”, etc. indicate the range of carbon number, such as 1 to 5 and 1 to 6 carbon atoms.

In the phenyl pyridines represented by the general formula (I), R ¹ is preferably a Cr Cs alkyl group, a halo Ci-Cs alkyl group, a C2-Cs alkenyl group, a halo C2-Cs alkenyl group or the same group. Having at least one substituent selected from a halogen atom, a CrC ₆ alkyl group, a halo CrCs alkyl group, a dC ₆ alkoxy group, a halo Ci-C ₆ alkoxy group, a cyano group, or a nitro group. A phenyl group, more preferably a CrCs alkyl group, a halo Ci-C ₅ alkyl group or a halogen atom, a halo CC ₅ alkyl group or a halo Ci-C ₅ alkoxy group which may be the same or different. It is a fuel group having one or more substituents selected.

R ² is preferably a hydrogen atom, a Ci'Cs alkyl group, a Ci-C ₈ alkoxy CrC ₈ alkyl group, a cyano CrCs alkyl group, a C Cs alkenyl group, a C2-Cs alkynyl group, a Ci-Cs alkyl carbonyl group And halo Ci-Cs alkyl carbonyl or C2-C8 alkenyl carbonyl, more preferably hydrogen, Ci-C ₈ alkyl or CrC ₈ alkyl carbonyl. R ³ is preferably a hydrogen atom or a C Cs alkyl group.

R ⁴ is preferably a CrCs alkyl group, a halo CrC ₈ alkyl group, a C ₂ -C ₈ alkenyl group, a halo C2-C8 alkenyl group, a C2.C8 alkynyl group, a nodro C2-C8 alkynyl group, a CrC8 alkoxy group, a haguchi CRCS alkoxy group, penta full O b sulfur - Le group (one SF _6), CRCS alkylthio group, Ci-Cs alkylsulfinyl group, C Cs alkylsulfonyl group, mono Ci-C ₈ alkyl amino or di-CrC ₈ alkylamino a group, still good Mashiku is, CrC ₅ alkyl group, a halo CrC ₅ alkyl group, Ci-C ₅ alkoxy group or halo d-Cs alkoxy group, the substitution position of R ⁴ is preferably a pyridine ring 4-position .

R ⁵ is preferably a CrC ₈ alkyl group, a halo CC ₈ alkyl group, a CrC ₈ alkoxy Ci-Cs alkyl group, a nodro CrCs alkoxy CrC ₈ alkyl group, a C ₂ -C ₈ alkyl group, a halo C ₂ -C ₈ alkenyl group, C ₂ -C ₈ alkynyl group, Nono b C ₂ -C ₈ alkynyl group, CRCS alkoxy group, halo Ci-Cs alkoxy group, Ci-Cs alkoxy Ci-Cs alkoxy group, halo Ci-Cs alkoxy CRCS alkoxy group, penta full O b sulfur sulfonyl group (- SF _5), trimethylsilyl group, Ci-C ₈ Ashiruokishi group, Nono b Ci-C ₈ Ashiruokishi group, CrC ₈ § Le kill sulfonyl § amino group, a halo CrCs alkylsulfonyl § amino group, C Cs alkyl Rukarubo - group, a CrC ₈ alkoxycarbonyl group, more preferably halo Ci-C ₈ alkyl group, Nono b C Cs alkoxy Ci-C ₈ alkyl group, a halo CrC ₈ alkoxy group or Jifuruorome Renjiokishi a group (-0 C FsO-).

X is preferably _c (= o) a group represented by one, t is preferably 1, m is preferably 1, n is preferably 1 or 2, and p is Preferably it is 0.

Examples of the salts of the phenylpyridines represented by the general formula (I) include acetates, propionates, butyrates, oxalates, adipates, dodecanediates, laurates, and stearate salts. Carboxylate such as trifluoroacetate, fumarate, maleate, benzoate, phthalate; methanesulfonate, 1,3-propanedisulfonate, p-toluenesulfonate, dodecyl Snorrephonates of benzenesulfonate; inorganic salts such as hydrochloride, sulfate, nitrate, carbonate and the like are exemplified.

The phenylviridines of the present invention represented by the general formula (I) are novel compounds and can be produced, for example, according to the following production methods 1 to 8. Production method 1. Production by reaction of acid halides or anhydrides with amines

^Rl

(IV)

(In the formula, R ¹ R ² , R ³ , R ⁴ , R ⁵ , X, t, m, n, and p are the same as described above, and Y represents a halogen atom.)

An acid halide represented by the general formula (III) or an acid anhydride represented by the general formula (IV) and a phenylpyridylalkylamine represented by the general formula (II) are mixed with an inert solvent and a base. By reacting in the presence or absence of a compound represented by the general formula (I) of the present invention. Phenylpyridines can be produced.

The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; acetone, methyl ethyl ketone, and methyl iso- Ketones such as butyl ketone; Halogenated hydrocarbons such as formaldehyde and dichloromethane; water; Esters such as methyl acetate, ethyl acetate; ethers such as getyl ether, tetrahydrofuran, and dioxane; Examples include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and pyridine. These inert solvents can be used alone or as a mixture of two or more. .

Examples of the base that can be used in this reaction include alkaline metal hydrides such as sodium hydride; alkaline metal hydroxides such as sodium hydroxide and hydroxyladium; sodium carbonate, carbonated carbonate and the like. Metal carbonates; inorganic salts; organic bases such as pyridine, DBU, triethylamine, etc .; and the amount of acid bases represented by the general formula (III) or the general formula (III) The reaction may be carried out by appropriately selecting an equimolar amount to an excess molar amount with respect to the acid anhydride represented by IV).

Since this reaction is an equimolar reaction, acid halides represented by the general formula (III) or acid anhydrides represented by the general formula (IV) and phenylpyridylalkyl represented by the general formula (II) are used. Equimolar amounts of luamines may be used, but any of the reactants may be used in excess, and preferably, the acid halides represented by the general formula (III) or the general formula (IV) It is preferable to use an excess of acid anhydrides.

The reaction may be carried out at a temperature in the range of 150 ° C. to the boiling point of the inert solvent used, and preferably in the range of 0 ° C. to 80 ° C. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

After the reaction, in order to isolate the objective substance, phenylubilidines represented by the general formula (I) of the present invention, when a solvent soluble in water is used, the solvent is distilled off under reduced pressure, And then extracted with water-insoluble aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chlorophonolem and dichloromethane; esters such as ethyl acetate; washed with saturated saline; It may be dried with a desiccant such as sodium or anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added to the reaction mixture, and the mixture is separated.The organic layer is washed with saturated saline, dried over a drying agent such as anhydrous sodium sulfate, anhydrous magnesium sulfate, and the like. The solvent may be distilled off. If necessary, the residue obtained after distilling off the solvent can be purified by recrystallization, suspension washing, column chromatography, etc. Production method 2. Production by reaction of isocyanates or isothiocyanates with amines

(Wherein, R ² , R ³ , R ⁴ , R ⁵ , t, m, n and p are as defined above, and R ⁸ is an optionally substituted alkyl group or an optionally substituted phenyl group. Z is an oxygen atom or sulfur Indicates a yellow atom. )

—The isocyanates or isothiocyanates represented by the general formula (V) and the phenylpyridylalkylamines represented by the general formula (II) in the presence or absence of an inert solvent and a base. By reacting, phenylpyridines of the present invention represented by the general formula (1-1) can be produced.

This reaction may be performed in the same manner as in Production Method 1. Production method 3. Production by reaction of carboxylic acids and amines

(Wherein, I ¹ , R ² , R ³ , R ⁴ , R ⁵ , t, m, n and p are the same as described above.)

The carboxylic acid represented by the general formula (VI) is reacted with a phenylpyridylalkylamine represented by the general formula (II) in the presence or absence of an inert solvent, a base, and a condensing agent, whereby the general formula of the present invention is obtained. The phenylviridines represented by (I) can be produced.

Examples of the condensing agent that can be used in this reaction include carbonyldiimidazole, dicyclohexylcarbodiimide, 2-chloro-1-methylpyridinium iodide, and the amount used is generally represented by the formula (VI). The reaction may be appropriately selected in the range of equimolar to excess molar with respect to the carboxylic acid.

Since this reaction is an equimolar reaction, the carboxylic acid represented by the general formula (VI) and the phenylpyridylalkylamine represented by the general formula (II) may be used in equimolar amounts. The agent can be used in excess.

The inert solvent, base, reaction temperature, reaction time and isolation method that can be used in this reaction may be the same as those in Production method 1. Production method 4. Production by reaction of carbonyl compound with oxyamines

(Wherein, I ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , X, t, m and p are the same as described above.) A carbonyl compound represented by the general formula (I-3) The oxoamines represented by the formula (VII) or the acid addition salts thereof are reacted in the presence or absence of an inert solvent and a base to give a compound represented by the general formula (1-4) of the present invention. Phenyluridines can be produced. The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction. For example, alcohols such as methanol, ethanol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene Water; halogenated hydrocarbons such as dichloromethane and the like; water; esters such as methyl acetate and ethyl acetate; ethers such as getyl ether, tetrahydrofuran and dioxane; acetonitrile, N, N-dimethylform Examples thereof include polar solvents such as amide, N-methylpyrrolidone, dimethylsulfoxide, and pyridine. These inert solvents can be used alone or in combination of two or more.

The base that can be used in this reaction may be the same as in Production method 1.

Since this reaction is an equimolar reaction, the carbonyl compound represented by the general formula (1_3) and the oxyamines represented by the general formula (VII) may be used in equimolar amounts. It can be used in excess, and it is preferred to use an excess of the oxamines represented by the general formula (VII).

The reaction temperature may be appropriately set in the range of 150 ° C. to the boiling point of the inert solvent to be used, and preferably in the range of room temperature to 80 ° C. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

After the reaction, the objective substance, phenylubilidines represented by the general formula (I-14) of the present invention, can be isolated in the same manner as in Production method 1. Production method 5 Production by cross-coupling reaction

(VIII) (IX) (I)

(Wherein, I ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, t, m, n and p are the same as above, and W is a chlorine atom, a bromine atom, an iodine atom, a methylsulfonyloxy group And a leaving group such as p-tolylsulfonyloxy group and trif-norelomethylsulfonyloxy group.)) The pyridines represented by the general formula (VIII) and the phenylboronic acids represented by the general formula (IX) By reacting in the presence or absence of a base and a transition metal catalyst in the presence or absence of a ligand or an inert solvent, the phenylpyridines represented by the general formula (I) of the present invention can be produced.

The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction. For example, alcohols such as methanol, ethanol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; getyl ether, tetrahydrofuran and dioxane; Ethers; polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine and the like; and these inert solvents may be used alone or in combination of two or more. Can be used in combination.

Examples of the base that can be used in the present reaction include alkali metal hydrides such as sodium hydride; sodium hydroxide, alkali metal hydroxides such as a hydroxide hydroxide, and sodium carbonate. Alkali metal carbonates such as lime and carbon dioxide; inorganic salts such as fluorinated lime; amines such as pyridine and triethylamine;

The reaction may be carried out by appropriately selecting the molar amount of the phenylboronic acid represented by the formula (IX) in an equimolar to excess molar amount, and preferably 2 times the molar amount.

Examples of transition metal catalysts usable in this reaction include palladium compounds such as palladium carbon, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tris (dibenzylacetone) palladium. Bis (triphenylphosphine) nickel oxide lid and tetrakis

(Triphenylphosphine) Nickel compounds such as nickel and the like can be mentioned, and the amount of use thereof is appropriately in the range of 0.001 times to equimolar to the pyridines represented by the general formula (VIII). The reaction may be carried out selectively, and it is preferable to use 0.001 to 0.2 times mol.

Examples of the ligand that can be used in this reaction include phosphine ligands such as triphenylphosphine, tritolylphosphine, and tri-t-butylphosphine. The molar ratio may be appropriately selected within the range of 5 to 100 moles, and is preferably in the range of 1 to 10 moles. Also, the reaction can be performed without using a ligand.

Since this reaction is an equimolar reaction, the pyridines represented by the general formula (VIII) and the phenylboronic acids represented by the general formula (IX) may be used in equimolar amounts. It is also possible to use, and it is preferred to use an excess of the phenylpoic acid represented by the general formula (IX).

The reaction temperature may be appropriately set in the range of 150 ° C. to the boiling point of the inert solvent to be used, and is preferably in the range of room temperature to 120 ° C. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

After the reaction, the desired product, phenylubilizine represented by the general formula (I) of the present invention, can be isolated in the same manner as in Production method 1. Production method 6. Production of furubilidines by hydrogen atom substitution reaction on nitrogen atom

(1-5) (X) (I)

(Wherein, R ¹ , R ² , R ³ , R \ R ⁵ , X, W, t, m, n and p are the same as described above.) The amines represented by the general formula (1 _ 5) and the general formula By reacting the compound represented by (X) with or without an inert solvent and a base, the compound represented by the general formula

The phenylviridines represented by (I) can be produced.

This reaction may be performed in the same manner as in Production Method 1. Production method 7. Production of pyridines by oxidation reaction

(1-6) (1-7)

(Wherein, RR ² , R ³ , R ⁴ , R ⁵ , X, t, m and n are the same as above.)

The pyridine-N-oxide represented by the general formula (1-7) is obtained by reacting the phenylubilidines represented by the general formula (I-16) with an oxidizing agent in the presence or absence of an inert solvent. Can be manufactured.

The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction. For example, aromatic hydrocarbons such as benzene, toluene, and xylene; acetone, methyl ethyl ketone, and methyl isobutyl Ketones such as ketones; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; organic acids such as formic acid, acetic acid and trifluoroacetic acid; acetonitrile, N, N-dimethylformamid And inert solvents such as N-methylpyrrolidone. These inert solvents can be used alone or in combination of two or more. Examples of the oxidizing agent that can be used in this reaction include m-chlorobenzoic acid, hydrogen peroxide, and peracetic acid.

Since this reaction is an equimolar reaction, it is sufficient to use the phenylaviridines represented by the general formula (1-6) and the oxidizing agent in equimolar amounts, but any of the reactants can be used in excess. Preferably, an oxidizing agent is used in excess.

The reaction may be carried out at a temperature in the range of from 150 ° C. to the boiling point of the inert solvent to be used, preferably from 0 ° C. to 25 ° C. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

After the reaction, the target product, pyridine-N-oxide represented by the general formula (1-7), can be isolated in the same manner as in Production method 1. Production Method 8. Production of Furubiridines Salts

(I) (1-8)

(Wherein, RR \ R ³ , R ⁴ , R ⁵ , X, t, m, n and p are the same as above, and A represents an acid.)

An acid addition salt represented by the general formula (I-18) is produced by reacting a phenylpyridine represented by the general formula (I) with an acid in the presence or absence of an inert solvent. be able to.

Organic acids and inorganic acids can be used in this reaction.As the organic acids, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecandioic acid, lauric acid, stearic acid, trifluoroacetic acid, Carboxylic acids such as fumaric acid, maleic acid, benzoic acid, and phthalic acid; sulfonic acids such as methanesulfonic acid, 1,3-propanedisulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; Can be. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid. The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; acetone, methyl ethyl ketone, and methyl iso- Ketones such as butyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as ethyl acetate and methyl acetate; tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N— Examples include polar solvents such as methylpyrrolidone and dimethylsulfoxide.

Since this reaction is an equimolar reaction, the phenylpyridines and the acids represented by the general formula (I) may be used in equimolar amounts, but any of the reactants may be used in excess, and the acids are preferably used. Should be used in excess.

The reaction temperature may be appropriately set in the range of 150 ° C. to the boiling point of the inert solvent to be used, and is preferably in the range of 0 ° C. to 25 ° C. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

After the reaction, in order to isolate an acid addition salt of a phenylviridine represented by the general formula (1-8) as a target product, the solvent may be distilled off under reduced pressure, and the precipitated crystal may be filtered off. Although it may be a pure product as it is, if necessary, it can be purified by washing with the above-mentioned inert solvent.

The amines represented by the general formula (II), which are intermediates, are described in WO 03/00000697 pamphlet, Japanese Patent Application Laid-Open No. 2002-36631 or J. Med. m., 1991, 3, 91, 3, 4, 7, 25—7, 36, but can also be produced by the following intermediate production method. Intermediate production method 1. Production of phenylcyanopyridines by reduction reaction

(Wherein, R ⁴ , R ⁵ , m, and n are the same as described above.)

A phenylpyridylalkylamine represented by the general formula (II-1) is produced by reducing a phenylcyanoviridine represented by the general formula (XI) in the presence or absence of an inert solvent. can do.

This reaction is carried out according to a method described in a known document (for example, see the Chemical Society of Japan, “New Experimental Chemistry Course”, Vol. 20, p. 279, 197, Maruzen Co., Ltd.). Preferred reduction methods include, for example, a method using a metal hydride such as sodium borohydride or lithium aluminum hydride as a reducing agent, a method of contacting a metal catalyst with hydrogen. Hydrogenation and the like can be mentioned.

When a metal hydride is used as a reducing agent, this reaction is a stoichiometric reaction, and therefore, the general formula (XI) may be used in a stoichiometric amount, but it is preferable to use an excess of the metal hydride. . The reaction may be carried out at a temperature in the range of 100 ° C. to the boiling point of the inert solvent, preferably in the range of 180 ° C. to room temperature. The reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from several minutes to 48 hours.

In the case of catalytic hydrogenation with a metal catalyst and hydrogen, examples of the metal catalyst include Raney nickel, palladium carbon, and platinum oxide.

The reaction may be carried out at any temperature within the range of room temperature to the boiling point of the inert solvent to be used, preferably from room temperature to 50 ° C. The hydrogen pressure may be appropriately set in the range of normal pressure to 100 kgfcm ² , and preferably in the range of normal pressure to 1 OK gf_ / cm ² . The reaction time varies depending on the scale of the reaction, temperature and pressure, but ranges from several minutes to 48 hours. Further, as described in the above-mentioned literature, additives such as acids and bases can be added for the purpose of improving the reaction rate and suppressing by-products.

The solvent is not particularly limited as long as it does not directly participate in the reaction. Examples thereof include alcohols such as methanol, ethanol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene; and acetone and methyle. Ketones such as methyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide And polar solvents such as N-methylpyrrolidone, dimethylsulfoxide and pyridine. These inert solvents can be used alone or in combination of two or more.

After the reaction, in order to isolate the objective phenylpyridylalkylamine represented by the general formula (II-11), the remaining metal hydride is treated, or the metal catalyst is filtered, and then the pressure is reduced. The solvent may be distilled off. It may be pure enough as it is, but if necessary, it can be purified by means such as distillation or column chromatography. Intermediate production method 2. Production by reduction of oximes

(In the formula, R ³ , R ⁴ , R ^! M and n are the same as described above, and R ⁹ represents a hydrogen atom or a —C ₆ alkyl group.)

A phenylpyridylalkylamine represented by the general formula (II-2) can be produced by reducing an oxime represented by the general formula (XII) in the presence or absence of an inert solvent. .

This reaction may be performed in the same manner as in Intermediate Production Method 1.

The oximes represented by the general formula (XII) as a raw material can be produced according to Production method 4. Intermediate production method 3 Production of salts of phenylpyridylalkylamines

(II) (Π-3)

(Wherein, R ² , R ³ , R ⁴ , R ⁵ , t, m, n and p are the same as above, and A represents an acid.)

That is, a phenylpyridylalkylamine represented by the general formula (II-12) is reacted by reacting a phenylpyridylalkylamine represented by the general formula (II) with an acid in the presence or absence of an inert solvent. Salts of amines can be produced.

This reaction may be performed in the same manner as in Production Method 8. Intermediate production method 4. Production of cyanopyridines

Some of the cyanopyridines represented by the general formula (XI) are novel compounds and can be produced by the following method.

(ΧΙΠ) (IX) (XI)

(Wherein, R ⁴ , R ⁵ , W, m, n and p are the same as above.)

Reaction of pyridines represented by the general formula (XIII) with phenylboronic acids represented by the general formula (IX) in the presence of a base and a transition metal catalyst, in the presence or absence of a ligand or an inert solvent By doing so, cyanopyridines represented by the general formula (XI) can be produced.

This reaction may be performed in the same manner as in Production Method 5.

Pyridines represented by the general formula (XIII), which are intermediates, are disclosed in JP-A-60-187564 according to the method described in Tetrahedron, 41, 4941 (19985). Can be manufactured. Intermediate manufacturing method 5.

The pyridines represented by the general formula (VIII), which are intermediates in the production method 5, can be produced by the following method.

R ⁸ NCZ

(V)

(VIII-1)

(Wherein, R ¹ R ² , R ³ , R ⁴ , R ⁸ , X, Y, W, Z, t, m, n, and p are as defined above.)

The acid halides represented by the general formula (III) or the acid anhydrides represented by the general formula (VI) and the amines represented by the general formula (XIV) are reacted in the presence of an inert solvent and a base or By reacting in the absence of pyridine, pyridines represented by the general formula (VIII) can be produced.

In addition, reacting the isocyanate represented by the general formula (V) or the isothiocyanate represented by the general formula (XIV) with the amamine represented by the general formula (XIV) in the presence or absence of an inert solvent and a base. Thus, pyridines represented by the general formula (VIII-1) can be produced.

This reaction may be performed in the same manner as in Production Method 1 or 2. The compounds of the present invention and intermediates thereof which can be produced by the above-mentioned production method are shown in Tables 1 to 6, but the present invention is not limited thereto. In the table,

Γη -J indicates noremal, “i−” indicates iso, “c-1” indicates cyclo, “t-1” indicates tertiary, and “1” indicates unsubstituted. In addition, “*” added to the compound No. indicates that it is a hydrochloride.

General formula (I_9)

Table 1

Table 2 (continued)

Compound R ¹ XR ^z R ³ (R ⁴ ) m (R ⁶ ) n P Melting point (.c)

N o. Ai is o nD / 23 ° C

2-50 * c-C ₃ H ₅ CO HH ― 3-OCF ₃₀ 175-177

2-51 c-C ₃ CO HH ― 3-OCF3 1 125-126

2-52 c-C ₃ CO cC ₃ HgC0 H ― 3-0CF ₃ 0 100 -102

2-53 c-C ₃ CO HH ― 3-C1 0 120-121

2-54 c-C ₃ H ₅ CO HH ― 3- N0 ₂ 0 142-144

2-55 c- C ₃ H ₅ CO CH ₃ C0 H ― 3-OCF3 0 83-84

2-56 i ^_ C ₃ H ₇ CO HH 3-CH ₃ 3-OCF3 0 125-127

2 57 c-CgH ₅ CO HH 3-CH ₃ 3-OCF30

2-58 i "C ₃ H ₇ CO HH -CH3 3-OCF3 0 78-79

2-59 c-C ₃ H ₅ CO HH 4-CH3 3-OCF3 0 128-130 i-C ₃ H ₇ CO HH 5-CH3 3-OCF3 0 81-83

2-61 cC ₃ H ₅ CO HH 5-CH3 3-OCFg 0 117-119

2-62 c-C ₃ H ₅ CO CH ₃₀ CH ₂ H ― 3-OCF3 0 1.5295

2-63 CH ₃ CO HH 4-CH ₃ 3-OCF3 0 122-123

2-64 CO H H -CH3 3-OCF3 0 85-87

2-65 nC ₃ H ₇ CO HH 4-CH3 3-OCF3 0 76-78

2-66 t-C ₄ U ₉ CO HH -CH3 3-OCF3 0 79-81

2-67 C1 ₂ CH CO HH 4-CH ₃ 3-OCF3 0 132-133

2-68 c-C ₃ ¾ CO HH ― 2-F-6-CF3 0 171 1-173

1 c-C ₃ ¾ CO HH ― 2, 3- 0CF ₂ 0-0 173-175

2-70 CH ₃ CO HH 4- CH ₃ 3-CF ₃ 0

2-71 CO H H 4-CH3 3-CF3 0 126-127

2-72 nC ₃ H ₇ CO HH -CH3 3-CF3 0 105-106

2-73 i ~ C ₃ H ₇ CO HH 4-CH3 3-CF3 0 115-116

2-74 cC ₃ ¾ CO HH -CH3 3-CF3 0 171-173

2-75 t-C ₄ H ₉ CO HH -CH3 3-CF3 0 59-60

2-76 C1 ₂ CH CO HH 4-CH3 3-CF3 0 139-141

. N Combination Table 2 (continued)

Compound R ¹ XR ² R ³ (R ⁴ ) m (R ⁵ ) n P Melting point ΓΟ

^! N tto. Ai is o ο nD / 23. C

2-104 tC ₄ Hg CO HH 4-CH3 2, 3-0CF ₂ 0- 0 112-113

2-105 -C3H5 CO HH 4-CH3 3 -CN 0 199-200 c_C 3 CO HH 4-CH3 3-F 0 128-130 c - C 3 H 5 CO HH 4-CH3 3- CI 0 136-138

2-108 cC ₃ H ₅ CO HH -CH3 2-OCFj 0 90-91

-CgHj CO HH 3-CH3 4-0CF ₃ 0 164-166

_{_{2-110 cC 3 H s CO HH 4}} -CH3 4-OCF3 0 155-156

2-111 c-C ₃ H ₅ CO HH 5-CHg 4-OCF3 0 161-163

2-112 C ₂ H ₅ CO HH 4-C ₂ ¾ 3-OCFg 0 87-88

2-113 i ~ C ₃ H ₇ CO HH 4-C ₂ H ₅ 3-0CF ₃ 0 98-99

2-114 c-C ₃ H ₅ CO HH 4-C ₂ H ₅ 3-OCF3 0 131-132

_{2-115 CO HH 4-C 2 H} 5 3-OCFg 0 89-91

2-116 i ~ C ₃ H ₇ CO HH 4-0C ₃ H ₇ -i 3-OCF3 0 112-113

2-117 -C3H5 CO HH 4-0C ₃ H 3-OCF3 0 131-132

2-118 c- C ₃ H ₅ CO HH 4-OH 3-OCFg 0 185-186

2-119 c_C ₃ CO HH 4-0CH ₂ CF ₃ 3-OCF3 0 140-141

2-120 c-C ₃ H ₅ CO H C¾ ― 3-OCF3 0 111-113

2-121 cC ₃ H ₅ CO HH 4- CI 3-OCFg 0 167-169

2-122 c-C ₃ CO HH 4-SCH3 3-OCF3 0 151-152 cC ₃ H ₅ CO HH -CH3 3, 4-0CH ₂ 0- 0 177-179

2-124 cC ₃ H ₅ CO HH -CH3 3-SCH3 0 127-128

_{_{2-125 c - C 3 H 5 CO}} HH 4-CH3 3-S0 2 CH 3 0 162-163

_{2-126 cC 3 ¾ CO HH -CH3 3} -SOCH3 0 131-132 cC 3 H 5 CO HH 4-C0 2 C 2 H 5 3-OCFg 0 102-104

2-128 cC ₃ H ₅ CO HH 4-S0 ₂ CH ₃ 3-OCF3 0 167-169

2-129 cC ₃ H ₅ CO HH 4-SOCH3 3-OCF3 0 120-122

2-130 i ~ C ₃ H ₇ CO HH -CF3 3-OCFg 0 129-131 0 Table 2 (continued)

Compound R ¹ XR ² R ³ (R ⁴ ) m ( ⁵ ) n P Melting point (° c)

N o. Or nD / 23 ° C

2-131 c-C ₃ H ₅ CO HH 4-CF _a 3-OCFg 0 162-163

2-132 l-CH ₃ -cC ₃ H ₄ CO HH 4-CH ₃ 3-0CF ₃ 0 61-63

2-133 2-C -c— C ₃ H ₄ CO HH 4-CH3 3-OCF, 0 103-105

2-134 (C¾) ₃ C-CH (CH ₃ ) CO HH -CH3 3-OCF3 0 103-105

2-135 4-FC ₆ H ₄ CO HH 4-CH3 3-OCF3 0 114-115

2-136 2, 4-FC ₆ H ₃ CO HH -CH3 3-OCF3 0 118-119

2-137 iC ₃ H ₇ NH CO HH -CH3 3-0CF ₃ 0 152-153

2-138 nC ₃ H ₇ NH cs HH -CH3 3-OCFg 0 72-74

2-139 c-C ₃ ¾ CO HH 4-C0 ₂ H 3-OCF3 0 191-193

2-140 c-C ₃ ¾ CO HH 4-CN 3-OCF3 0 173-175

General formula (I — 1 1)

Table 3

General formula (Π_ 4)

General formula (II 5

Disassembly) disassembly)

General formula (XI)

When the phenylpyridines represented by the general formula (I) of the present invention or salts thereof are used as herbicides, it is preferable to formulate them in a convenient form according to the conventional method for pesticide formulations. General. That is, the furubilidines represented by the general formula (I) or salts thereof of the present invention are mixed with a suitable inert carrier or, if necessary, together with a scavenger in an appropriate ratio. Dissolving, separating, suspending, mixing, impregnating, adsorbing or adhering to the appropriate dosage form, for example, suspension, milk suspension, emulsion, solution, wettable powder, granule, powder, tablet, diambo, The preparation may be used in a pack or the like.

The inert carrier that can be used in the present invention may be either a solid or a liquid. Examples of the material that can be a solid carrier include plant powders (eg, soybean flour, cereal flour, wood flour, bark flour) , Saw powder, tobacco stem powder, flour shell powder, bran, cellulose powder, residue after extraction of plant extracts, etc.), synthetic polymers such as pulverized synthetic resins, clays (eg kaolin, bentonite, acid clay, etc.) ), Talcs (for example, talc, pyrophyllite, etc.), silicas (for example, diatomaceous earth, silica sand, mica, and white carbon (a synthetic high-dispersion silicic acid also known as hydrous fine silicon or hydrous silicic acid, containing calcium silicate as a main component depending on the product) )}, Activated carbon, natural minerals (eg, powder, pumice, calcined diatomaceous earth, attapulgite zeolites, etc.), calcined silica Soil, crushed brick, fly ash, sand, plastic carrier, etc. (for example, polyethylene, polypropylene, polychlorinated vinylidene, etc.), inorganic mineral powders such as calcium carbonate, calcium phosphate, etc., ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea And fertilizers such as salt and salt, compost, etc., which are used alone or in the form of a mixture of two or more.

The material that can be a liquid carrier is selected from those which have a solvent function per se, and those which can disperse the active ingredient compound with the aid of a scavenger even without a solvent function. As examples, the following carriers can be exemplified, but these may be used alone or in the form of a mixture of two or more, and include, for example, water, alcohols (for example, methanolic ethanol, ethanolanol, isopropynoleanolecanol, ptanoyl, etc.). , Ethylene glycol glycol, etc.), ketones (eg, acetone, methylethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolp, dipropyl ether, tetrapropyl) Drofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.) , Aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, carbon tetrachloride, etc.), esters (eg, ethynole acetate, Disopinolephthalate, dibutylphthalate, dioctinolephthalate, etc.), amides (eg, dimethylformamide, getylformamide, dimethylacetamide, etc.), nitriles (eg, acetonitrile, etc.), dimethylsulfoxides, etc. Can be mentioned.

Examples of other scavengers include the following typical scavengers.These scavengers are used depending on the purpose, and may be used alone or in combination of two or more scavengers. In some cases, however, it is possible to use no adjuvant at all. Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and Z or wetting the active ingredient compounds, such as polyoxyethylene alkyl ethers, polyoxyethylene alkynolearyl ethers, polyoxyethylene higher fatty acid esters , Polyoxyethylene resin acid ester, polyoxyethylene sonorebitan monooleate, polyoxyethylene sonorebitan monooleate, alkylaryl sulfonate, naphthalenesulfonic acid condensate, ligunesulfonic acid salt, higher alcohol sulfate, etc. Surfactants can be exemplified.

In addition, for the purpose of stabilizing the dispersion of the active ingredient compound, and adhering or binding, the following auxiliary agents may be used. For example, casein, gelatin, starch, methylseed Auxiliary agents such as leulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, and lignin sulfonate can also be used. The following scavengers can be used to improve the flowability of the solid product. For example, scavengers such as wax, stearate and alkyl phosphate can be used. As a peptizer for suspending products, for example, an auxiliary agent such as a naphthalenesulfonic acid condensate or a condensed phosphate may be used. As the antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.

The compounding ratio of the active ingredient compound can be adjusted as required and is not particularly limited. The lower limit is about 0.001 weight. The range from about / ₀ to the upper limit is about 90% by weight. For example, the lower limit for powder or granules is 0.01 weight. / ₀ is preferable, more preferably about 0.1% by weight, and the upper limit is 50% by weight. / ₀ is preferred, more preferably 10 weight. / ₀ , and the lower limit for emulsion, wettable powder, wettable powder, etc. is 0.01 weight. / ₀ is preferred, more preferably 0.1 weight. / ₀ , and the upper limit is preferably about 90% by weight, more preferably about 60% by weight.

In the case where the preparation of the present invention represented by the general formula (I) containing n-birubiridines or a salt thereof is diluted with water and applied, the adhesive property and the spreadability are improved, and the herbicidal effect is improved. In order to increase the content, an auxiliary agent such as a spreading agent may be added to the spray liquid. Surfactants (the above-mentioned nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants), paraffin, polyacetic acid, and the like are used as adjuvants such as spreading agents. Examples include vinyl, polyacrylate, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, crop oil (mineral oil, animal and vegetable oil, etc.), and liquid fertilizer. If necessary, two or more of these scavengers may be used simultaneously. The amount of the auxiliary agent used, such as a spreading agent, varies depending on the type, but usually, it is appropriate to add 0.01 to 5% by weight to the spray liquid. Depending on the type of scavenger, it can be added in advance as a component in the drug product.

The application rate of the herbicide containing the furubilidines represented by the general formula (I) or a salt thereof represented by the general formula (I) of the present invention as an active ingredient depends on the structure of the compound, the target weed, the treatment time, the treatment method, and the properties of the soil. The amount of the active ingredient per hectare is usually in the range of 2 to 2000 g, preferably 5 to 100 g, although it depends on the conditions.

As the weeds targeted by the herbicide of the present invention, in the field, for example, Shiroza, Akaza, Inutade, Hartade, Inuvu, Aobu, Hakobe, Hotokenoza, Ichibi, Onamomi, Malva Asagao, Chosen Asagao, Seiyokarashina Examples include broad-leaved weeds such as crabs, violets, and kosendandasa, and narrow-leaved weeds such as mehishiba, ohishiba, inubie and enocologusa. In paddy fields, for example, broad-leaved weeds such as Kikasidasa, Azena, Konagi, Apnomome, Mizohakobe, Heramodaka, Omoda power, Perica, etc., narrow leaf weeds such as Tainubiye, Tamagayari, Inuhotari, Mizugayaya.

The herbicide of the present invention can control the above-mentioned weeds in upland fields and paddy fields by any of soil treatment, foliage treatment and flooding treatment. In addition, the herbicide of the present invention can be used for any of soil treatment and foliage treatment on cultivated crops including crops having improved genetic characteristics such as corn, wheat, rye, rice, soybean and the like and imparted with drug resistance and the like. Has little effect and can be used as a selective herbicide in the cultivation of these crops.

The herbicide of the present invention can be applied in combination with other pesticides such as insecticides, fungicides, plant growth regulators, and fertilizers used in the same field. It can also be mixed with other herbicides to stabilize the herbicidal effect. When the phenolyl pyridine represented by the general formula (I) of the present invention or a salt thereof and another herbicide are mixed and applied, each of them is applied. May be mixed at the time of application, or may be applied as a preparation containing both in advance. Examples of the herbicides that can be suitably mixed and applied for the above purpose include the following.

Glyphosate and its salts, glyphosinate and its salts, bialaphos and its salts, organophosphorus herbicides such as baptamiphos, alophos, bensulide, sulfarate, gallate, trialate, EPTC, petitate, esprocalp, thiobencalp (benthiocarp) , Molinate, Isoporinate, Dimepirate, Pilipticarp, Fenmedifam, Chlorprofam, Ashram, etc., Carbamate herbicides, Diperon, Linuron, Fluomeron, Diphenoxuron, Daimlon, Isoprolon, Isoperon, Teptiurone, Metaplatin Urea herbicides such as tobenzuron and chlorotoluron, metazachlor, arlacrol, ptakuronore, pretilacronole, and asetoclono , Metracuronole, teninolecuronore, dietatil, dimethenamide, propanil, diflufenican, mefenacet, flufenacet, amides such as promotide, isoxaben (benzamizole), amide herbicides, trifluralin, benzflurarine, prozamine Dinitroaniline-based herbicides such as butralin and pendimethalin,

2,4-D and its derivatives, 2,4,5-T and its derivatives, MCPA and its derivatives, dicloprop and its derivatives, mecoprop and its derivatives, MCPB and its derivatives, dicampa and its derivatives, 3,6-TBA and its derivatives, quinclorac and its derivatives, quinmelac and its derivatives, cloviralide and its derivatives, picloram and its derivatives, triclopyr and its derivatives, fluroxypyr and its derivatives, benazoline and its derivatives, Carboxylic acid herbicides such as diclohop and its derivatives, fluazifop and its derivatives, haloxyfop and its derivatives, fenoxaprop and its derivatives, quizalofop and its derivatives, clodinahop and its derivatives, cyhalofop and its derivatives, promoxinil and its derivatives Phenolic herbicides, such as derivatives of Ioxur and its derivatives, dinoterb and its derivatives, aroxydim and its salts, sethoxydim, cycloxydim, tralcoxidim, butroxydim, cletodim, tepraloxydim, sulcotrione, mesotrione, benzovicine Hexandione herbicide such as sick mouth,

Diphenyl ether herbicides such as chronorenitrofen, chrometoxini ニ, oxyfnoreonolefen, bifenox, asifnoleorphen and its salts, fluoroglycofen, lactofen, homesaphen, acronifen, etc. Amidosulfuron, Chlorimronechinore, Snorrehomeron Mechinore, Primis / Refron, Bensnoreflonmethinolle, Ethoxnorefron, Cycrosnorrefamron, Chronoresnoreflon, Methosnoreflonmechinore, Triveneurome , Trias noreflon, Synos noreflone, ethame tosnoleflon methinole, trifnoresnoleflon methinole, prosnoleflon, tifensnole fronmethinole, pyrazosulfroneethyl, halosulfuron methyl, Sulfonylurea herbicides such as Razasnoreflon, Limusnoreflon, Nicosnorefron, Funorepinolesnorrefron and its salts, Imazos noreflon, Snorefosnoreflon, Eodosnoreflon, Tritosnoreflon, Mesosnoreflon, etc. , Paraquat, diquat, etc., biviridinum herbicides, pyrazolate, virazoxifen, benzophenap, etc., pyrazole herbicides, simazine, atrazine, cyanazine, simetrine, dimetamethrin, triazifram, metrifudine, etc., triazine herbicides, etc. Imidazolinone herbicides such as imazamethavens, imazapyr and its salts, imazaquin and its salts, imazethapyr and its salts, imazamox and its salts, etc.

Other herbicides include indanophane, fluridone, full mouth chloridone, fururu tumon, nonolefnorelazone, cafence tronorole, fentrazamide, and snorrefent Razone, carfentrazone etil, pentoxazone, oxaxiazone, oxazia argyl, pyraflufenethil, isoppropazonole, flupoxum, kuguchi mazon, isoxaflu'tol, isoxachlortol, dichopinore, thiazopyr, piraziopac And its salts, pyriminobac-methyl, bispyribac and its salts, promacinoles, tarpacinoles, renasinole, funorepropasinoles, oxadiclomehon, simmethillin, chronorephthalimim, funolemicrolacpentinoles, funolemioxazine, Sinidonechinore, azafuezin, fluthiacet-methyl, funoremelam, methoslam, clorans ramethinole, benfresate, etofumeset, bentazone, pyracloninole, befurputami , Picolinafen, florasulam, propoxy force Rubazon, full force Luba Zon and its salts, Shinidonechiru, Pinokisaben and the like. Examples Hereinafter, the present invention will be described more specifically with reference to Examples, Formulation Examples, and Test Examples, but the present invention is not limited thereto unless it exceeds the gist thereof. Example 1. Production of N- [6- (3-trifluoromethoxyphenyl) 1-2-pyridyl] methylcyclopropanecarboxylic acid amide (Compound No. 2-3)

6- (3-Trifluoromethoxyphenyl) -1-pyridylmethylamine (0.3 g, 1.1 mmol), triethylamine (0.5 ml, 3.6 mmol) and toluene (20 ml) After the mixture was cooled to 0 to 4 ° C, a solution of cyclopropanecarboyl chloride (0.12 g, 1.1 mmol) in toluene (5 ml) was added, and the mixture was stirred for 30 minutes. Water (20 ml) was added to the reaction mixture, extracted with ethyl acetate, washed with dilute hydrochloric acid, water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the precipitated crystals were washed with hexane to obtain 0.31 g of the desired product.

Yield: 84%

Physical properties: Melting point 126-127 ° C Example 2. N- {6- [3- (1-Methoxyiminoethyl) phenyl] -12-pyridyl} methylcyclopropanecarboxylic acid amide (Compound N o. 2-3 6) Manufacturing

N— [6- (3-acetylphenyl) 1-2-pyridyl] methylcyclopropane rubonic acid amide (0.30 g, 1.0 mmol), methoxyamine hydrochloride (0.40 g, A mixture of 4.8 mmol), potassium carbonate (0.50 g, 3.6 mmol), ethanol (5 ml) and water (5 ml) was stirred at 60 ° C for 30 minutes. After evaporating the solvent under reduced pressure, water was added, extracted with ethyl acetate, washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crystals were washed with hexane to obtain 0.27 g of the desired product.

Yield: 84%

Physical properties: Melting point 1 1 1 1 1 1 8 ° C Example 3 of N- [6- (3-cyanophenyl) -12-pyridyl] methylcyclopropanecarboxylic acid amide (Compound No. 2-12) Manufacture

Under a nitrogen stream, N- (6-chloro-1-pyridyl) methylcyclopropanecarboxylic acid amide (0.30 g, 1.4 mmol), 3-cyanophenylboronic acid (0.25 g) , 1.7 mmol), 2M aqueous sodium carbonate solution (2.0 ml, 4.0 mmol), toluene (2.0 ml), dioxane (1.0 ml) and water (1.0 ml). After the temperature was raised to 70 ° C, tetrakis (triphenylphosphine) palladium (0. (10 g, 0.087 mmol), and the mixture was stirred under heating and reflux for 3 hours. Water (20 ml) was added to the reaction mixture, extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography, and the obtained crystals were washed with hexane to obtain 0.25 g of the desired product.

Yield: 64%

Physical properties: melting point 16 1 to 16 3 ° C Example 4.6 Preparation of 6- (3-trifluoromethoxyphenyl) _2-pyridylmethylamine (compound No. 5-5)

2-cyano-6- (3-trifluoromethoxyphenol) pyridine (12.5 g, 47.3 mimol), 10% palladium on carbon (2.47 g, 2.32 mimol) A mixture of concentrated hydrochloric acid (12.4 ml) and ethanol (250 ml) was stirred at room temperature under a hydrogen pressure of 5.0 kgf Zcm ² for 4 hours. After adding 28% sodium methoxide methanol solution to make it basic, the catalyst was filtered off and the solvent was distilled off under reduced pressure. Water (100 ml) was added to the residue, extracted with ethyl acetate, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 9.23 g of the desired product. Yield: 73%

Physical properties: Boiling point 137-138 ° C Zl. 0 mmHg Example 5.6 Production of 6- (4-trifluoromethoxyphenyl) -12-pyridylmethylamine hydrochloride (Compound No. 5-2)

Concentrated hydrochloric acid (6 ml) was added to a solution of 6- (4_ trifluoromethoxyphenyl) 1-2-pyridylmethylamine (9.25 g, 34.5 mmol) in methanol (50 ml), and the mixture was stirred at room temperature for 2 hours. did. The solvent was distilled off under reduced pressure, and the crystals were washed with methanol to obtain 9.35 g of the desired product.

Yield: 90%

Physical properties: melting point 205-5207C (decomposition) Example 6.2 Production of 2-cyano-6- (3-trifluoromethoxyphenyl) pyridine (compound No. 6-6)

Under a stream of nitrogen, 2-cyclo-1-6-anopyridine (8.4 g, 61 mmol), 3-trifluoromethoxyphenolenoboronic acid (15.0 g, 73 mmol), tonolenene (120 ml) ) And a 2M aqueous solution of sodium carbonate (60 ml, 120 mmol). After the temperature was raised to C, tetrakis (triphenylphosphine) palladium (3.5 g, 3.0 mmol) was added, and the mixture was stirred under heating and reflux for 3 hours. Water (200 ml) was added, extracted with ethyl acetate, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 13.1 g of the desired product.

Yield: 81%

Physical properties: melting point: 48-49 ° C. The representative preparation examples and test examples of the present invention are shown below, but the present invention is not limited thereto. In the preparation examples, “parts” means “parts by weight”. Formulation Example 1.

Compound of the present invention

N-methylpyrrolidone

Polyoxyethylene noninolephenyl ether

Mixture with alkylene sulfonic acid canolesum 0 parts

The above are uniformly mixed and dissolved to form an emulsion. Formulation example 2.

Compound of the present invention

Clay powder

Diatomaceous earth powder

The above is uniformly mixed and pulverized to obtain a powder. Formulation example 3.

5 parts of the compound of the present invention

90 parts mixed powder of bentonite and clay

5 parts calcium lignin sulfonate

The above components are mixed uniformly, kneaded by adding an appropriate amount of water, granulated, and dried to obtain granules, Formulation Example 4.

Compound of the present invention 20 parts

Kolin and synthetic high dispersion silicic acid 7 11 817 5 parts

Polyethylene xylene ethylenephenyl ether and ο ο ο 325

5 parts mixture with calcium alkylbenzenesulfonate

The above is uniformly mixed and pulverized to obtain a wettable powder. Test Example 1. Test of herbicidal effect on paddy field weeds before emergence

Fill a plastic pot of 75 cm ² with soil (clay loam), sow seeds of paddy field weed, Inohotarii, and cover with 75 cm ³ of soil mixed with eel, azaena and Mizohakobe. It was submerged at a depth of 5 cm. On the next day, a predetermined effective dose (gZha) of a drug containing the compound of the present invention as an active ingredient prepared according to Formulation Examples 1 to 4 was diluted with water and dropped on the water surface. Then, the plants were grown in a greenhouse, and the herbicidal effect was investigated 28 days after the treatment.

Judgment criteria for weeding effect

0 · · • 0% herbicidal effect

1--• 1% to 39% herbicidal effect

2 · · • 40% to 69% herbicidal effect

3 · · • 70% to 89% herbicidal effect

4... 90% or more herbicidal effect

The results are shown in Table 7. In addition, "one" in the table indicates unrated. 7 tables

1 1 thing ヌホセナナ

N o. (G / ha)

2-1 1000 1 0 0 4

2-2 1000 4 3 4 4

2-3 1000 4 4 4 4

2-4 1000 11--

2-5 1000 ― ― ― ―

2-6 1000 ― ― one ―

2-7 1000 0 0 1 4

2-8 1000 2 1 4 2

2-9 1000 2.1.4 4 4

2-10 1000 4 3 4 4

2-11 1000 0 0 0 1

2- 12 1000 0 1 3 4

2-13 1000 0 0 0 1

2-14 1000 0 0 2 4

1000 ― ― ― ―

2-16 1000 1 1 ― 1

2-17 1000 ― ―

2-18 1000 1 1 4 4

2-19 1000 2 1 4 4

2-20 1000 0 0 2 4

2-21 1000 1 0 2 4

2-22 1000 1 2 4 4

2-23 1000 1 1 4 4

2-24 1000 2 4 4 4

2-25 1000 ― One ― ―

2-26 1000 0 0 3 0

2-27 1000

2-28 1000

2-29 1000 Table 7 (continued)

Compounds Infuse Firefly, Nakonaki, Misohako

N o. (G / ha)

2-30 1000 3 1 1 4

2-31 1000 ― ― ― ―

1000 1 1 4 4

2-33 1000 1 ― ― ―

2-34 1000 ― ― ― ―

2-35 1000 ― ― ― ―

2-36 1000 1 0 4 4

1000 ― ― ― ―

1000 One---

2-40 1000 1 1 4 4 -41 1000 ― ― ―

1000 1 0 2 4

1000 ― ― ― -44 1000 ― One ― One

1000 ― ― ― ―

2-46 1000 2 2 4 4

2-47 1000 ― ― ― ―

2-48 1000 ― ― ― ―

2-49 1000 1 4 4 4

2-50 1000 5 4 4 4

2-51 1000 0 0 2 2

2-52 1000 ― ― ― ―

2-53 1000 2 2 4 4

2-54 1000 0 0 2 1

2-55 1000 2 3 4 4

2-56 1000

2-57 1000

2-58 1000 4 4 4 4

2-59 1000 4 4 4 4

Table 7 (continued)

、, Chemical

Thing a¾ ri inu small gu / lei; τ Τ:

Go to T Ί コ. Ο ο.

2-88 1000 4 4 4 4

2-89 1000 4 4 4 4

2-90 1000 3 4 4 4

2-91 1000 4 4 4 4

2-92 1000 4 4 4 4

2-93 1000 4 4 4 4

2-94 1000 4 4 4 4

2-95 1000 4 4 4 4

2-96 1000 3 4 4 4

2-97 1000 4 4 4 4

2-98 1000 4 4 4 4

2-99 1000 4 4 4 4

2-100 1000 4 4 4 4

2-101 1000 4 4 4 4

2-102 1000 4 4 4 4

2-103 1000 2 4 4 4

2-104 1000 4 4 4 4

2-105 1000 4 4 4 4

2-106 1000 4 4 4 4

2-107 1000 4 4 4 4

2-108 1000 4 4 4 4

2-109 1000 ― ― ― ―

2-110 1000 ― One ― ―

2-111 1000 ― ― ―

2-112 1000 1 4 4 4

2-113 1000 4 4 4 4

2-114 1000 .4 4 4 4

2-115 1000 4 4 4 4 Table 7 (continued)

Test Example 2. Herbicidal effect test on paddy field weeds after emergence.

7 5 was filled with soil in a plastic pot cm ² (clay loam), a paddy weed I Nubie, and sown Inuhotarui, Azena, after cover soil in soil 7 5 cm ³ was mixed seeds Elatine triandra Schk, It was submerged at a depth of 5 cm and grown in a greenhouse. At the time of the single leaf stage of the test plant, a drug containing the compound of the present invention as an active ingredient was treated as a drug solution having a predetermined effective dose (gZha). Then, the plants were grown in a greenhouse, the herbicidal effect was examined 28 days after the treatment, and the herbicidal effect was evaluated according to the criteria of Test Example 1. The results are shown in Table 8. In addition, "one" in the table indicates unrated. 8 tables

Ih compound ivj

N o. (G / ha)

2-1 1000 0 1 0 4

2-2 1000 3 4 1 4

2-3 1000 4 4 4 4

2-4 1000 ― ― ― ―

2-5 1000 ― ― ― ―

2-6 1000 ― ― ―

2-7 1000 0 1 0 4

2-8 1000 1 2 0 1

2-9 1000 2 1 0 4

2-10 1000 3 4 2 4

2-11 1000 0 0 0 4

2-12 1000 2 1 0 4

2-13 1000 0 1 0 1

1000 0 0 0 4

2-15 1000 ― ― ―

2-16 1000 ― ― ― ―

2-17 1000 ― ― ― ―

2-18 1000 0 0 0 4

2-19 1000 1 1 0 4

2-20 1000 1 1 0 4

2-21 1000 1 1 0 4

2-22 1000 1 0 0 4

2-23 1000 1 0 0 4

2-24 1000 2 2 4 4

2-25 1000 ― ― ― ―

2-26 1000 0 0 0 4

2-27 1000

2-28 1000

2-29 1000 Table 8 (continued)

I'd like to make a compound, Inuhi ', Einuhotariase, Namiso, Hako,

N o. (G / ha)

2-30 1000 0 0 0 3

2-31 1000 ― ― ― ―

2-32 1000 0 0 0 4

2-33 1000 1 ― ― ―

2-34 1000 ― ― ―

2-35 1000 ― ―

2-36 1000 0 0 3

2-37 1000 ― ― ―

2-38 1000 ― ― ― ―

1000 One---

2-40 1000 1 1 1 4

2-41 1000 ― ― ― ―

2-42 1000 0 0 0 4

2-43 1000 1 ― ― ―

2-44 1000 ― One

2-45 1000 ― ― ― ―

2-46 1000 2 1 1 4

2-47 1000 One-

2-48 1000 ― ― ― ―

2-49 1000 2 1 2 4

2-50 1000 3 3 2 4

2-51 1000 0 0 0 4

2-52 1000 ― ― ― ―

2-53 1000 2 1 1 4

2-54 1000 0 0 1 4

2-55 1000 3 2 2 4

2-56 1000

1000

2-58 1000 4 4 4 4 Table 8 (continued)

H 物 g 物 g g g ο g (g / ha)

2-59 1000 4 4 4 4

2-60 1000 One-One-

2-61 1000 1 0 0 4

2-62 1000 ― ― ― ―

2-63 1000 4 3 2 4

2-64 1000 4 4 4 4

2-65 1000 4 4 4 4

2-66 1000 4 4 4 4

2-67 1000 2 1 4 4

2-68 1000 ― ― ― ―

2-69 1000 4 2 3 4

2-70 1000 4 3 2 4

2-71 1000 4 2 2 4

2-72 1000 3 3 2 4

2-73 1000 4 4 4 4

2-74 1000 4 4 4 4

2-75 1000 4 4 4 4

2-76 1000 1 1 4 4

2-77 1000 ― ― ― ―

2-78 1000 4 4 4 4

2-79 1000 4 4 4 4

2-80 1000 4 4 4 4

2-81 1000 4 4 4 4

2-82 1000 4 4 4 4

2-83 1000 4 4 4 4

2-84 1000

2-85 1000

2-86 1000 2 1 2 4

2-87 1000 4 4 4 Table 8 (continued)

Goods Ryo Gena Miso, to Hako, No. (g / ha)

2-88 1000 ― 4 4 4

2-89 1000 ― 4 4 4

2-90 1000 ― 4 4 4

2-91 1000 4 3 4 4

2-92 1000 4 4 4 4

2-93 1000 3 4 4 4

2-94 1000 4 4 4 4

2-95 1000 4 4 4 4

2-96 1000 3 3 4 4

2-97 1000 ― 4 4 4

2-98 1000 ― 4 4 4

2-99 1000 4 4 4

2-100 1000 4 4 4

2-101 1000 4 4 4

2-102 1000 4 4 4 4

2-103 1000 4 4 4 4

2-104 1000 4 4 4 4

2-105 1000 4 4 4 4

2-106 1000 4 4 4 4

2-107 1000 4 4 4 4

2-108 1000 4 4 4 4

2-109 1000 ― ― ― ―

2-110 1000 ― ― ― ―

2-111 1000 ― ― ― ―

2-112 1000 4 4 4 4

2-113 1000 4 4 4 4

2-114 1000 4 4 4 4

2-115 1000 4 4 4 4

2-116 1000 1 1 2 4 Table 8 (continued:

Test example 3: Upland foliage treatment test

Field soil of dilapidated clay loam was filled in a resin vat with an area of 200 cm ² , and after fertilization, violets, chickweeds, yaemdara, pink locusts and wheat were sown and covered uniformly. Thereafter, cultivation management was continued in a greenhouse, and when the growing leaf age of the test weed reached the 1.02.0 leaf stage, the emulsion containing the compound of the present invention obtained in Formulation Example 1 as an active ingredient was diluted with water. The mixture was adjusted, and a predetermined amount was uniformly sprayed with a small power pressurizer so that the active ingredient had a predetermined dose (gZha). After that, cultivation management was continued in the greenhouse, and the herbicidal effect and phytotoxicity were investigated on the second day after the chemical treatment.

The herbicidal effect and phytotoxicity were evaluated by calculating the herbicidal rate or phytotoxicity using the following formula. Was evaluated according to the criteria of Weeding rate or phytotoxicity rate (%) = (1 aboveground live weight of weeds in one treated area) Aboveground fresh weight of weeds in untreated area XI 0 0 Criteria for herbicidal effect or phytotoxicity Weeding rate or phytotoxicity rate ( %)

0 0-20

1 2 0〜5 0

2 5 1-7 0

3 7 1 ~ 9 0

4 9 1 to 9 9

5 1 0 0

Table 9 shows the results.

Table 9

Test example 4: Upland soil treatment test

A field of 20 octn ² resin vat was filled with field soil of dilapidated clay loam, and after fertilization, violets, chickweeds, wild locusts, horned scallops and wheat were sowed and covered uniformly. . The wettable powder containing the compound of the present invention obtained in Formulation Example 4 as an active ingredient is diluted with water and adjusted, and a predetermined amount of the active ingredient is adjusted to a predetermined dose (g / ha) with a small power pressurized sprayer on the soil surface. Was sprayed uniformly. After that, cultivation management was continued in the greenhouse, and on the 21st day after the chemical treatment, the herbicidal effect and chemical damage were investigated. Herbicidal effects and phytotoxicity were evaluated according to the same criteria as in Test Example 3. The results are shown in Table 10. Table 10

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on July 18, 2003 (Japanese Patent Application No. 2003-277112), the contents of which are incorporated herein by reference. All references cited herein are incorporated in their entirety. Industrial applicability

According to the present invention, it is possible to obtain a herbicide exhibiting a high herbicidal effect and exhibiting sufficient safety for important crops and a useful compound used therefor.

Claims

The scope of the claims

General (/,

_ 1

\ /)

(Wherein, R ¹ is a hydrogen atom, a Ci-Cs alkyl group, a halo CrC ₈ alkyl group, a CrCs alkenyl group, a C ₂ -C ₈ alkynyl group, a Ci'Cs alkoxy group, a halo CC ₈ alkoxy group, a d-Cs § alkylamino group, phenyl group, which may be identical or different, Nono b Gen atoms, Xia amino group, two collected by filtration group, a hydroxyl group, A Mi amino group, SH group, CRCS alkyl group, halo Ci-C ₆ alkyl group, C ₂ -C ₆ alkenyl group, halo C2-C6 alkenyl group, C Cs alkynyl group, halo C ₂ -C ₆ alkynyl group, Ci-Cs alkoxy group, halo Ci-C ₆ alkoxy group, CC ₆ alkylthio group , halo Ci'C ₆ alkylthio group, c ₂ -c ₆ § Norekeniruchio group, Nono b C2- C6 § Honoré en Honoré Chio group, CrCeT Norekinoresu Honoré off I two Norre group, c b CrCeT Norekinoresu Norefu I two Honoré group, CrCeT Nolequinores Norejo Ninole group, Halo C Csalkylsulfo Le group, C Cs § Le kills carbonyl group, C port CrCs alkyl force Noreboniru group, phenylpropyl group, C Cs alkoxycarbonyl key aryloxycarbonyl group, mono Ci-C ₆ Arukirua Mi Roh rather to group or same young Te different dates Substituted phenyl group having 1 to 5 substituents selected from good di-CrC ₆ alkylamino groups, phenyl CrC ₈ alkyl group, which may be the same or different, halogen atom, cyano group, nitrite b group, a hydroxyl group, A Mi amino group, SH group, CrC ₆ Al kill group, a halo CrCs alkyl group, C2-C ₆ alkenyl group, a halo C2- C6 alkenyl Le group, C ₂ 'C ₆ alkynyl group, a halo C ₂ -C ₆ alkynyl group, CrC ₆ alkoxy group, halo Ci-Cs alkoxy group, C Cs alkylthio group, halo C Cs alkyl thio group, C ₂ -C ₆ alkenylthio group, halo C ₂ -C ₆ alkenylthio group, C Cs alkynoles B CrCs Anorekinoresu Norefu I two Honoré group, CrCeT Norekiru scan Noreho Ninore group, C b CrCeT "Norekinoresu Noreho Ninore group, CrCeT Rukiruka Rubo group, Nono b CrCs alkylene Honoré Kano repo group, phenylpropyl group, Cr C ₆ alkoxycarbonyl alkoxycarbonyl group, mono- CrCeT Rukirua Mi amino group or a substituted phenyl C Cs alkyl group having 1 to 5 substituents on the ring which is rather to the same young selected from good di- Ci-C ₆ Arukirua Mi amino group or different A phenylamino group, which may be the same or different, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group,

SH groups, Ci-Co alkyl group, halo Ci-C ₆ alkyl group, C2- C6 alkenyl group, Nono b C2- C6 alkenyl group, C ₂ -C ₆ alkyl group, Nono b C2- C6 alkynyl group, dC ₆ Alkoxy group, halo CrC ₆ Alkoxy group, Ci'Cs alkylthio group, Ha CrCs alkylthio group, Cs-Csalkenylthio group, halo C2-C6 Alkylthio group, CrCeT Nolequinoreles enole group, Ha B CrCs-anolequinoles phenol group, CrCs acrekylsnolefonyl group, halo Ci-Cs anolequinoles phenol group, Ci-Csalkyl carbonyl group, halo CrCsalkyl carbonyl group, phenylcarbonyl group, CrCs alkoxycarbonyl group, mono C Cs Arukirua Mi amino group or the same young and rather the substituent Fuweniruamino group having 1 to 5 substituents selected from a good di CrC ₆ Arukirua Mi amino group or different on the ring, Enoxy group or Same or different connexion is good, a halogen atom, Xia amino group, two collected by filtration group, hydroxyl group, A Mi amino group, SH group, Ci-Cs alkyl group, a halo CrCs alkyl group, C ₂ -C ₆ alkenyl group, Halo Cs-Cs alkenyl group, C ₂ -Cs alkynyl group, nodro C Cs alkynyl group, CC ₆ alkoxy group, halo CrCs alkoxy group, CrCs alkylthio group, halo Cl-C ₆ alkylthio group, C2-C6 alkenyl Thio group, halo

C2-C6 alkenylthio group, CCs alkylsulfinyl group, halo Ci-Cs alkylsulfinyl group, CrCsalkynolenolesulfonyl group, nitroCi-Csanorecynolesulfonyl group, Ci-Csanolekylcarbol group, halo C Cs Arukirukanorebo group, phenylpropyl group, Ci-Cs alkoxycarbonyl group, mono-dC ₆ 7 Rukirua Mi amino group or identical Wakashi Ku is selected from a good-di d-Cs Arukiru § Mi amino group or different Represents a substituted phenoxy group having 1 to 5 substituents on a ring. R ² is a hydrogen atom, a CrCs alkyl group, a C ₂ -C ₈ alkenyl group, a C ₂ -C ₈ alkynyl group, a CrCs alkoxy CrCs alkyl group, a cyano CrCs alkyl group, a Ci-Cs alkyl carbonyl group, a nodro CrCs alkyl carbonyl A C ₂ -C ₈ alkenylcarbonyl group, a Ci-Cs alkylsulfonyl group or a haloCrCs alkylsulfonyl group. Further, R ¹ and R ² can be combined to form a 4- to 8-membered ring containing X (X is shown below), a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. R ³ may be the same or different, represent a hydrogen atom, Shiano group or Ci-C ₈ alkyl group, and two R ³ includes a carbon atom together, a nitrogen atom, an oxygen atom or a sulfur atom A 3- to 6-membered ring can be formed. R ⁴ may be the same or different, and include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxy group, a pentafluorosulfanyl group (—SF ₅ ), a CrCs alkyl group, a nitrogen-containing Ci-Cs alkyl group, and a C ₂ alkyl group. -C ₈ alkenyl, C Cs alkynyl, CC ₈ alkoxy, halo CrCs alkoxy, CrCs alkoxycarbonyl, Ci-Cs alkylthio, Ci-Cs alkylsulfinyl, Ci-Cs alkylsulfonyl, CrCs alkylami And a di-Ci-C ₈ alkylamino group which may be the same or different. R ⁵ may be the same or different, and include a halogen atom, a Ci-Cs alkyl group, a halo CrCs alkyl group,

C2-C8 alkenyl, halo C2-C8 alkenyl, C2-C8 alkynyl, halo C ₂ -C ₈ al Kiniru group, Cl-C8 alkoxy group, a halo Cl'Cs alkoxy, Cl-C8 alkoxy Cl-C8 alkyl Group, halo Ci-Cs alkoxy C Cs alkyl group, CrCs alkoxy C Cs alkoxy group, halo Ci-Cs alkoxy C Cs alkoxy group, CrCs alkylsulfonylamino group, halo Ci-Cs alkylsulfonylamino group, Ci- Cs alkylthio group, halo Ci-C ₈ alkylthio group, Ci-Cs alkyl sulfide El group, halo CRCS alkylsulfinyl group, CRCS alkylsulfonyl group, a halo CRCS alkylsulfonyl group, C Cs alkyl ylcarbonyl group, CRCS alkoxycarbonyl group, CRCS alkylcarbonyl O alkoxy group, halo CrC ₈ alkylcarbonyl O alkoxy group, a hydroxyl group, a formyl group, Shiano group, nitro group, Torimechinoreshi Group, in penta full O b Sulfur sulfonyl group (one SF ₅₎ or one C (R ⁶⁾ = NOR7 (wherein, R6 and R7 may be the same or different, a hydrogen atom, Cr

Shows the C ₅ alkyl group or a halo Ci-Cs alkyl group. ) A group represented by Also, R ⁵ in which two adjacent such with one another connexion difluorenylamino O b methylenedioxy O alkoxy group (an OCF ₂ 0 -), tetrafurfuryl O b ethylenedioxy O dimethylvinylsiloxy groups ( _{_{- OCF 2 CF 2 0 -)}} , can exhibit Mechirenjio alkoxy group or Echirenjiokishi group. X represents a group represented by one C (= θ) one, -C (= S) — or one SO q — (wherein q represents 1 or 2). t represents an integer of 0 to 2, m represents an integer of 0 to 3, n represents an integer of 1 to 5, and p represents 0 or 1. The phenylviridines represented by the formula: or salts thereof.

2. R ¹ is a hydrogen atom, a CC ₈ alkyl group, a non-CrCs alkyl group, a C ₂ -C ₈ alkenyl group, a CrC ₈ alkoxy group, a Ci-Cs alkylamino group, a phenyl group or A substituted phenyl group substituted with 1 to 5 substituents selected from a halogen atom or a C Cs alkyl group, wherein R ² is a hydrogen atom, a CC ₈ alkyl group, a Ci'Cs alkoxy Ci-Cs alkyl group Or a CrC ₈ alkylcarbonyl group, R ³ may be the same or different, a hydrogen atom or a Ci-C ₈ alkyl group, R ⁴ may be the same or different, a halogen atom, a cyano group, a hydroxyl group, carboxy group, CC ₈ alkyl group, CRCS an alkoxy group, a halo Ci'Cs alkoxy group, Ci-Cs alkoxycarbonyl group, a CRCS alkylthio O group, Ci-Cs alkyl sulfide El group or CRCS alkylsulfonyl group, R ⁵ May be the same or different, CrC ₈ alkyl group, halo Ci-C ₈ alkyl group, d-Cs alkoxy group, halo CrC ₈ alkoxy group, Ci-Cs alkoxy CC ₈ alkoxy group, Ci-C ₈ alkylthio group, CrCs Al Rusurufieru group, CRCS alkylsulfonyl - le group, CI- Cs alkylcarbonyl group, a formyl group, a nitro group, Shiano group, a hydroxyl group, trimethyl silyl ^{group, -C (R 6) = NO} R 7 ( wherein, R ⁶ and R ^{group 7} are represented by the same.) to claim 1, wherein, Mechirenjiokishi group, difluoromethyl O b methylenedioxy O alkoxy group (an OCF ₂ 0 I) or tetrafluoropropoxy O b ethylenedioxy O alkoxy group (an OCF ₂ CF ₂ 2. The phenylpyridine or a salt thereof according to claim 1, which is 0_).

3. The phenylviridine or a salt thereof according to any one of claims 1 and 2, wherein m is 1.

4. The pyridine or a salt thereof according to any one of claims 1 to 3, wherein R ¹ is a CrCs alkyl group.

5. The method according to any one of claims 1 to 4, wherein R ⁵ may be the same or different, and is a halo Ci-C ₅ alkyl group, a halo Ci-C ₅ alkoxy group, or a difluoromethylenedioxy group (_OCF ₂₀ 0_). Or the phenylviridines or salts thereof according to item 1.

6. A herbicide containing the fluorpyridine compound or the salt thereof according to any one of claims 1 to 5 as an active ingredient.

7. A method for using a herbicide, which comprises applying an effective amount of the herbicide according to claim 6 to a soil or a plant.

8. —General formula (Π)

(Wherein, R ² is a hydrogen atom, a Ci-Cs alkyl group, a C ₂ -C ₈ alkenyl group, a C2-C8 alkynyl group, a Ci-C ₈ alkoxy Ci-C ₈ alkyl group, a cyano CrCs alkyl group, a CC ₈ alkyl R ³ is the same or different, and represents a hydrogen atom, a cyano group, a carbonyl group, a halo C Cs alkylcarbonyl group, a Cs-Cs alkenylcarbonyl group, a CrCs alkylsulfonyl group, or a halo Ci-Cs alkylsulfonyl group. It represents a group or a Ci-C ₈ alkyl group, and, the two R ³ together such connexion carbon atom, a nitrogen atom, may form a 3-6 membered ring containing an oxygen atom or a sulfur atom. R ⁴ is Same or different, halogen atom, cyano group A nitro group, a hydroxyl group, a carboxyl group, penta full O b Sulfur sulfonyl group _{(_ SF 5), Ci-} C 8 alkyl group, halo C Cs alkyl group, CC ₈ alkenyl, C ₂ -C ₈ alkyl group, CI- Cs alkoxy group, halo CrCs alkoxy group, Ci-Cs alkoxycarbonyl group, Ci-

Cs alkylthio group, Ci-Cs alkylsulfinyl group, Ci-Cs alkylsulfonyl group,

A Ci-C ₈ alkylamino group or a di-CrC ₈ alkylamino group which may be the same or different. R ⁵ may be the same or different, halogen atom, Ci-Cs alkyl group, halo

Cl'Cs alkyl group, C2-C8 Aruke - group, halo C2-C8 alkenyl, C2-C8 alkynyl, Nono b C ₂ -C8 alkynyl group, CRCS alkoxy, halo Ci-Cs alkoxy group, CI- C ₈ Alkoxy CrCs alkyl group, Nodro Ci-Cs alkoxy CrCs alkyl group, CrCs alkoxy CrC ₈ alkoxy group, halo Ci-C ₈ alkoxy CrC ₈ alkoxy group, CrCe alkylsulfonylamino group, Haguchi Ci-Cs alkylsulfonyl Amino groups, CRCS alkylthio O group, Nono b CRCS alkylthio group, CRCS alkylsulfinyl group, halo CrC ₈ Al keno less Honoré alkylsulfinyl group, Ci-Cs alkylsulfonyl group, halo Ci-Cs alkylsulfonyl group, Ci-Cs alkyl Carbonyl group, CrCs alkoxycarbonyl group, Ci-Cs alkyl carbonyloxy group, halo CrCs alkyl carbonyloxy group, hydroxyl group, formyl group, cyano group Nitro group, trimethylsilyl group, penta full O b Sulfur sulfonyl group (- SF ₅₎ or ^{- C (R 6) = NOR} 7 ( wherein, R ⁶ and R ⁷ are rather good be the same or different, a hydrogen atom, CI- C ₅ alkyl a group or halo d-Cs alkyl group.) a group represented by also, two adjacent R ⁵ connexion difluorenylamino situations with each other O b methylenedioxy O key sheet group (an OCF ₂ 0—), a tetrafluoroethylenedioxy group (one CF ₂ C FsO one), a methylenedioxy group or an ethylenedioxy group. t represents an integer of 0 to 2, πι represents an integer of 0 to 3, 11 represents an integer of 1 to 5, and p represents 0 or 1. ) Ferbililidylalkylamines or salts thereof represented by the formula:

9. R ² is hydrogen atom, CrCs alkyl group, Ci'Cs alkoxy Ci'Cs alkyl group or Ci-C ₈ alkylcarbonyl group, R ³ may be the same or different, hydrogen atom or Ci-C ₈ alkyl R ⁴ may be the same or different; halogen atom, cyano group, hydroxyl group, carboxy group, CrC ₈ alkyl group, CrC ₈ alkoxy group, halo CC ₈ alkoxy group, Ci-Cs alkoxycarbonyl group, Ci -Cs alkylthio group, Ci-Cs alkyl sulfinyl group or C Cs alkyl sulfonyl group, R ⁵ may be the same or different, Ci-C ₈ alkyl group, halo CrC ₈ alkyl group, Ci-C ₈ alkoxy group , halo CrC ₈ alkoxy group, CrC ₈ alkoxy C Cs alkoxy group, CRCS alkylthio group, C Cs Al Kirusurufiniru group, Ci-Cs alkylsulfonyl group, CRCS alkylcarbonyl group, a formyl group, a nitro group Shiano group, a hydroxyl group, a trimethylsilyl ^{group, - C (R 6) =} NOR 7 (. Wherein, R ⁶ and R ⁷ are the same in the range 8 claims) group represented by Mechirenjio alkoxy group, difluoromethyl O b methylenedioxy Okishi group (- OCF ₂ 0 -) or Tetorafuruoroe Chirenjiokishi group _{_{(- OC F 2 CF 2 0-}} ) Fuenirupiri Jill alkyl § Min compound and its salts according to claim 8, wherein a.