KR20010014410A - 3-(Substituted phenyl)-4-halopyridazine derivatives, pesticides containing the same as the active ingredient, and intermediates thereof - Google Patents

Abstract

The present invention provides novel 3-substituted phenyl-4-halopyridazine derivatives useful as pesticides, in particular herbicides.

Description

3-substituted phenyl-4-halopyridazine derivatives, pesticides containing the same as the active ingredient, and intermediates according to the present invention.

Conventionally, many herbicides have been used in the cultivation of important crops such as barley, corn, soybeans, and rice. Desired herbicide conditions include high herbicidal effect, low herbicidal spectrum, adequate reactivity, and sufficient safety for crops. It is the present situation that we cannot say that we are satisfied enough.

On the other hand, 4-chloro-3-phenyl-6,7-dihydro-5H-cyclopenta [c] pyridazine or 4-chloro-3-phenyl-5,6 which is 3-substituted phenyl-4-halopyridazines A method for synthesizing, 7,8-tetrahydrocinnoline is described in Tetrahedron Letters, 37, 1351 (1996), but this document describes 4-chloro-3-phenyl-6,7-dihydro. No mention is made of the fact that -5H-cyclopenta [c] pyridazine or 4-chloro-3-phenyl-5,6,7,8-tetrahydrocinnoline has herbicidal activity. In addition, the compound which has a substituent in the phenyl group of the 3-position of a pyridazine ring and a cinnoline ring is not described at all.

Synthesis and herbicidal activity of 3-substituted phenylpyridazines are also described in US Pat. Nos. 5,623,072 and 5,616,789. However, in this document, the substituent of the phenyl group at the 3-position of the pyridazine ring is characterized by having a hydrogen atom, a nitro group or an amino group at the 4-position, such as a hydrogen atom at the 2-position, a haloalkyl at the 3-position, and the 3 of the pyridazine ring. The herbicidal activity of the compound having a halogen or cyano group at the 4 position in the phenyl group at the position is not described at all.

The present invention provides novel 3-substituted phenyl-4-halopyridazine derivatives and pesticides having the same as active ingredients, particularly pesticides effective as herbicides.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined the synthesis | combination of the 3-substituted phenyl-4-halopyridazine derivatives, and its herbicidal activity in order to solve the problem with the herbicide mentioned above, The phenyl group of the 3-position of a pyridazine ring The 3-substituted phenyl-4-halopyridazine derivative having a halogen or cyano group at position 4 of the present invention not only has high herbicidal effect but also shows sufficient safety against several important crops, thus completing the present invention. .

That is, the gist of the present invention lies in the 3-substituted phenyl-4-halopyridazine derivatives of the formula (I) and pesticides, in particular herbicides, comprising the active ingredient thereof.

In Formula I above,

X is a halogen atom,

Y is a hydrogen atom or a halogen atom,

Z is a halogen atom or a cyano group,

n and m are each independently 0 or 1,

R ¹ is an alkyl group or a haloalkyl group of C ₁ -C ₆ a hydrogen atom, a halogen atom, a C ₁ -C _6,

R ² is a hydrogen atom or an alkyl group of C ₁ -C ₆ , or a ring of -KLM- with R ¹ , wherein K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , oxygen atom, sulfur atom or C ₁ A nitrogen atom substituted with an alkyl group of -C ₆ , L is CR ⁸ R ⁹ , an oxygen atom, a sulfur atom or a nitrogen atom substituted with an alkyl group of C ₁ -C ₆ , and M is a CR ¹⁰ R ¹¹ , an oxygen atom, a sulfur atom or A nitrogen atom substituted with a C ₁ -C ₆ alkyl group (wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or a C ₁ -C ₆ alkyl group) provided that K, L and M are oxygen atoms at the same time, Not a sulfur atom or a nitrogen atom substituted with a C ₁ -C ₆ alkyl group;

R ³ is a hydrogen atom, a nitro group or -QR ¹² {where Q is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or -NR ^13- (wherein R ¹³ is a hydrogen atom, an alkyl group of C ₁ -C ₆ , C ₂ -C ₆ alkenyl group, a halo-alkenyl group, an alkoxyalkyl group of C ₂ -C ₆ C ₂ -C ₆ alkynyl group, C ₁ -C ₆ haloalkyl group, C ₂ -C ₆ of, C ₂ -C ₆ of an acyl group, a alkoxycarbonyl group, phenyl group or phenyl C ₁ -C ₆ alkylsulfonyl group, a halo-C ₁ -C ₆ alkylsulfonyl group, C ₂ -C ₆ alkenyl sulfonyl group, C ₂ -C ₆ of the alkyl group substituted by a C ₁ -C _3), and, R ¹² is an alkynyl group of a hydrogen atom, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of, C ₃ -C ₈ a cycloalkyl group, a cycloalkyl group of C _4, C ₄ -C ₁₀ a (cycloalkyl) alkyl group, a cyclo alkenyl group of _{C 3 -C 8, C 1 -C} 10 alkyl group substituted with -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₃ -C ₈ halocycloalkyl group, C ₂ -C ₇ cyano Alkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₂ -C ₁₀ alkylthioalkyl group, C ₂ -C ₁₀ alkylsulfonylalkyl group, C ₂ -C ₆ acyl group, C ₃ -C ₆ oxoalkyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylsulfonyl group, C ₂ -C ₆ alkenylsulfonyl group, phenyl group, C ₁ -C ₃ alkyl group substituted with phenyl group, 3- to 6 Heterocyclic groups of a member (wherein the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms), three to six membered heterocyclic groups (wherein the rings contain one or two oxygen atoms, sulfur atoms and / or nitrogen atoms) C ₁ -C ₃ alkyl group substituted with Group or formula of (II) Group of (III), wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom, a sulfur atom or -NR ^16- , wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ a), and, R ¹⁵ is a hydrogen atom, an alkynyl group, a cycloalkyl group of C ₃ -C ₆ of the C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ of, C ₄ -C ₁₀ A cycloalkyl group substituted with an alkyl group of C, a cycloalkenyl group of C ₃ -C ₆ , a haloalkyl group of C ₁ -C ₆ , a haloalkenyl group of C ₂ -C ₆ , a halocycloalkyl group of C ₃ -C ₆ , C _2- C ₅ cyanoalkyl group, C ₂ -C ₆ alkoxyalkyl group, C ₂ -C ₆ alkylthioalkyl group, C ₂ -C ₆ alkylsulfonylalkyl group, C ₃ -C ₆ oxoalkyl group, C ₃ -C ₇ acyloxyalkyl group, C ₃ -C ₇ alkoxycarbonylalkyl group, phenyl group, C ₁ -C ₃ alkyl group substituted with phenyl group, 3- to 6-membered heterocyclic group (the ring is 1 or 2 oxygen atoms, sulfur atom And / or contains nitrogen atoms) or from 3 to An alkyl group of C ₁ -C ₃ substituted with a six-membered heterocyclic group (wherein the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms), and R ¹⁵ represents that W represents -NR ^16- Can form a 5 or 6 membered heterocyclic group containing 1 or 2 nitrogen atoms and / or 0 or 1 oxygen atom together with W], and R ¹² , R ¹³ or R ¹⁵ is a phenyl group, A C ₁ -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group (the ring contains one or two oxygen atoms, sulfur and / or nitrogen atoms) or a 3- to 6-membered heterocyclic group ( When the ring is a C ₁ -C ₃ alkyl group substituted with 1 or 2 oxygen atoms, sulfur atoms and / or nitrogen atoms), the phenyl group and heterocyclic group are 1 to 3 identical or different halogen atoms, C ₁ -C group with an alkyl group, a trifluoromethyl _4, an alkoxy group, an acyloxy group of C ₂ -C ₅ in the _{C 1 -C 4, C 1 -C} 4 Alkylthio group, the alkoxycarbonyl may be substituted}, of C ₁ -C ₄ alkylsulfonyl group, a nitro group, a cyano group or a C ₂ -C _5.

The present invention is explained in more detail below.

The 3-substituted phenyl-4-halopyridazine derivatives used as herbicides in the present invention are compounds of formula (I) above.

In Chemical Formula I,

As X, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mentioned, Among these, a chlorine atom is preferable.

Y is a hydrogen atom; Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mentioned, Among these, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is especially preferable.

As Z, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; Or cyano groups, of which chlorine atoms are preferred.

n and m are each independently 0 or 1, preferably m = 0, particularly preferably n = 0 and m = 0.

As R ¹ , a hydrogen atom; Halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Alkyl groups of C ₁ -C ₆ such as 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group and 1-ethyl-2-methylpropyl group;

Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2,2-pentafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bro Mother profile, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2,2,2-trifluoro- C ₁ -C such as 1-methylethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group The haloalkyl group of ₆ is mentioned, Among these, Preferably, they are a hydrogen atom, an alkyl group, or a haloalkyl group.

As R ^{2, a} hydrogen atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethyl propyl group, there may be mentioned an alkyl group of C ₁ -C _6, such as 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group.

In addition, R ¹ and R ² may be bonded to each other to form a ring of -KLM-. Wherein K is a group of CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ ; Oxygen atom; Sulfur atom; Or a nitrogen atom substituted with a C ₁ -C ₆ alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group, and L is a group of CR ⁸ R ⁹ ; Oxygen atom; Sulfur atom; Or a nitrogen atom substituted with a C ₁ -C ₆ alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group, and M is a group of CR ¹⁰ R ¹¹ ; Oxygen atom; Sulfur atom; Or a nitrogen atom substituted with a C ₁ -C ₆ alkyl group such as methyl group, ethyl group, propyl group, and isopropyl group.

The substituents R ⁴ to R ¹¹ are each independently a hydrogen atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethyl-propyl, and 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group alkyl of C ₁ -C _6, such as.

When R ¹ and R ² combine to form a ring of -KLM-, K is preferably a group of CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ ; Or an oxygen atom, L is a group of CR ⁸ R ⁹ or an oxygen atom, M is a group of CR ¹⁰ R ¹¹ or an oxygen atom, particularly preferably K is CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ It is a group of R <^7> , L is group of CR <^8> R <^9> , M is the case of forming the hydrocarbon group of 5 or 6 ring members which is CR <^10> R <^11> , More preferably, it is K, L, and M Each of these is a methylene group.

R ³ is a hydrogen atom, a nitro group or a group of —QR ¹² .

Q in -QR ¹² is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or a group of -NR ^13- , an oxygen atom or a group of -NR ¹³ -is preferable, and an oxygen atom is particularly preferable.

R ¹³ in —NR ¹³ — is a hydrogen atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3.8-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1, Alkyl groups of C ₁ -C ₆ such as 1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, and 1-ethyl-2-methylpropyl group;

Vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylallyl, 2-methylallyl, 1-pentenyl, 2-pente Neyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-2-butenyl group, 3- Methyl-3-butenyl, 1,1-dimethylallyl, 1-ethylallyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl C ₂ -C ₆ alkenyl groups such as 4-methyl-3-pentenyl, 1-propylallyl, and 1-ethyl-1-methylallyl;

Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentyn Neyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexyl alkynyl of C ₂ -C ₆ such as a group;

Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2,2-pentafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bro Mother profile, 2,2,3,3,8-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2,2,2-trifluoro- 1-methyl-ethyl group, a butyl group 4-fluoro, 4-chlorobutyl group, 4-bromo-butyl group, 2,2,3,3,4,4,4-heptafluoropropane, such as a butyl group C ₁ - Haloalkyl group of C ₆ ;

Haloalkenyl groups such as C ₂ -C ₆ such as 3,3-dichloroallyl group;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxy C ₂ -C ₆ alkoxyalkyl groups such as ethyl group, 3-methoxypropyl group, 4-methoxybutyl group and 5-methoxypentyl group;

Acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2,2-dimethylbutyryl, 2-ethylbutyryl, 2-methylvalrylyl, Acyl groups of C ₂ -C ₆ such as 3-methyl valeryl group and 4-methyl valeryl group;

Methyl sulfonyl group, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl, pentyl sulfonyl, alkylsulfonyl of hexyl sulfonyl group such as a C ₁ -C ₆ group;

C ₁ -C ₆ haloalkylsulfonyl groups such as trifluoromethylsulfonyl group;

Alkenyl sulfonyl group of the vinyl sulfonyl group, allyl sulfonyl group, such as C ₂ -C _6;

C ₂ -C ₆ alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropylcarbonyl group, butoxycarbonyl group and pentyloxycarbonyl group;

Phenyl groups such as phenyl group, 4-chlorophenyl group, 3-chlorophenyl group and 2-chlorophenyl group;

Or a C ₁ -C ₆ alkyl group substituted with a phenyl group such as a benzyl group or a phenethyl group,

Preferably a hydrogen atom, a C ₂ -C ₆ acyl group, an alkoxycarbonyl group of C ₁ -C ₆ alkylsulfonyl group or a C ₂ -C _6, particularly preferably an alkyl hydrogen atom, C ₁ -C ₆ Sulfonyl group or C ₂ -C ₆ alkoxycarbonyl group.

In QR ¹² , R ^{12 is a} hydrogen atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, C ₁ -C ₁₀ alkyl groups such as 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, heptyl group, octyl group and nonyl group;

Vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylallyl, 2-methylallyl, 1-pentenyl, 2-pente Neyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-2-butenyl group, 3- Methyl-3-butenyl, 1,1-dimethylallyl, 1-ethylallyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl C ₂ -C ₁₀ alkenyl groups such as 4-methyl-3-pentenyl, 1-propylallyl, 1-ethyl-1-methylallyl and geranyl;

Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentyn Neyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexyl alkynyl groups, such as C ₂ -C ₁₀ group;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo heptyl, cyclooctane group and the like cycloalkyl group of C ₃ -C _8;

1-methylcyclopropyl group, 2-methylcyclopropyl group, 1,2-dimethylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2- Ethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1,2,2,3-tetramethylcyclopropyl group, 1-methylcyclobutyl group, 2- Methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 1- Ethylcyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1,2-dimethylcyclopentyl group, 1 , 3-dimethylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 3,3-dimethylcyclopentyl group, 1- to Cyclopentyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 3,4-dimethyl Cycloalkyl groups substituted with C ₄ -C ₁₀ alkyl groups such as cyclohexyl, 4,3-dimethylcyclohexyl and 1-ethylcyclohexyl;

(Cyclopropyl) methyl group, (cyclobutyl) methyl group, (cyclopentyl) methyl group, (cyclohexyl) methyl group, (cycloheptyl) methyl group, (cyclooctyl) methyl group, (cyclopropyl) ethyl group, (cyclobutyl) ethyl group, (cyclo Pentyl) ethyl group, (cyclohexyl) ethyl group, (cycloheptyl) ethyl group, (cyclooctyl) ethyl group, (cyclopropyl) propyl group, (cyclobutyl) propyl group, (cyclopentyl) propyl group, (cyclohexyl) propyl group, C ₄ -C ₁₀ (cycloalkyl) alkyl groups such as (cycloheptyl) furol group;

C ₃ -C ₈ cycloalkenyl groups such as 2-cyclopropenyl group, 2-cyclobutenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group;

Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2,2-pentafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bro Mother profile, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2,2,2-trifluoro- C ₁ -C such as 1-methylethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group ₁₀ haloalkyl group;

C ₂ -C ₁₀ haloalkenyl groups such as 3,3-dichloroallyl group;

Halocycloalkyl groups such as C ₃ -C ₈ , such as 2,2-difluorocyclopentyl group;

Cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutyl group, 2-cyanobutyl group C ₂ -C ₇ cyanoalkyl groups such as 3-cyanobutyl group and 4-cyanobutyl group;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxy C ₂ -C ₁₀ alkoxyalkyl groups such as ethyl group, 3-methoxypropyl group, 4-methoxybutyl group and 5-methoxypentyl group;

Methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, isopropylthiomethyl group, butylthiomethyl group, 2- (methylthio) ethyl group, 2- (ethylthio) ethyl group, 2- (propylthio) ethyl group, 2- (isopropyl thio) ethyl, 2- (butylthio) ethyl group, 3- (methylthio) propyl, 4- (methylthio) butyl group, 5- (methylthio) pentanoic alkylthio group of C ₂ -C ₁₀ group such as;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, propylsulfonylmethyl group, isopropylsulfonylmethyl group, butylsulfonylmethyl group, 2- (methylsulfonyl) ethyl group, 2- (ethylsulfonyl) ethyl group, 2- (propylsulfonyl ) Ethyl group, 2- (isopropylsulfonyl) ethyl group, 2- (butylsulfonyl) ethyl group, 3- (methylsulfonyl) propyl group, 4- (methylsulfonyl) butyl group, 5- (methylsulfonyl) phen alkyl sulfonic the C ₂ -C ₁₀ group such as a sulfonyl group;

Acetyl, pyridionyl, butyryl, isobutyryl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2,2-dimethylbutyryl, 2-ethylbutyryl, 2-methylvalrylyl , 3-methyl-ballet group, an acyl group of C ₂ -C _6, such as 4-methyl-ballet group;

C ₃ -such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. An oxoalkyl group of C ₆ ;

Methyl sulfonyl group, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl, pentyl sulfonyl, alkylsulfonyl of hexyl sulfonyl group such as a C ₁ -C ₆ group;

C ₁ -C ₆ haloalkylsulfonyl groups such as trifluoromethylsulfonyl group;

Alkenyl sulfonyl group of the vinyl sulfonyl group, allyl sulfonyl group, such as C ₂ -C _6;

Phenyl groups such as phenyl group, 4-chlorophenyl group, 3-chlorophenyl group and 2-chlorophenyl group;

Or a C ₁ -C ₃ alkyl group substituted with a phenyl group such as a benzyl group or a phenethyl group;

2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-furyl group, 2-furyl group, 1-pyranyl group, 2-pyranyl group, 3-pyranyl group, 1-dihydrofuryl group, 2-dihydrofuryl group, 1-dihydropyranyl group, 2-dihydropyranyl group, 3-dihydropyranyl group, 1-tetrahydrofuryl group, 2-tetrahydrofuryl group, 1-tetrahydropyranyl group, 2 3- to 6-membered heterocyclic groups such as a tetrahydropyranyl group, 3-tetrahydropyranyl group, etc., wherein the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms;

3- to 6-membered heterocyclic groups such as 1-tetrahydromethyl group and 2-tetrahydromethyl group (the rings contain 1 or 2 oxygen atoms, sulfur atoms and / or nitrogen atoms)

An alkyl group of C ₁ -C ₃ substituted with;

Chemical formula, such as 1- (gamma) butyrolactone group and 2- (gamma) butyrolactone group Group or formula of (II) Group of (III);

In formula (III), R ^{14 represents a} hydrogen atom; Or a C ₁ -C ₄ alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, and W is an oxygen atom or a sulfur atom Or -NR ^16- .

R ¹⁶ of —NR ¹⁶ — is a hydrogen atom; Or a C ₁ -C ₄ alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group or tert-butyl group.

R ^{15 is} selected from a hydrogen atom; Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methyl Butyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Alkyl groups of C ₁ -C ₆ such as 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group and 1-ethyl-2-methylpropyl group;

Vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylallyl, 2-methylallyl, 1-pentenyl, 2-pente Neyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-2-butenyl group, 3- Methyl-3-butenyl, 1,1-dimethylallyl, 1-ethylallyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl C ₂ -C ₆ alkenyl groups such as 4-methyl-3-pentenyl, 1-propylallyl, and 1-ethyl-1-methylallyl;

Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentyn Neyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexyl alkynyl of C ₂ -C ₆ such as a group;

Cyclopropyl group, a cyclobutyl group, a cyclopentyl group of the cycloalkyl groups, cyclohexyl groups, etc. of C ₃ -C _6;

1-methylcyclopropyl group, 2-methylcyclopropyl group, 1,2-dimethylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2- Ethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1,2,2,3-tetramethylcyclopropyl group, 1-methylcyclobutyl group, 2- Methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 1- Ethylcyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1, 2-dimethylcyclopentyl group, 1 , 3-dimethylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 3,3-dimethylclopentyl group, 1-ethyl yarn Clopentyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 3,4-dimethyl Cycloalkyl groups substituted with C ₄ -C ₁₀ alkyl groups such as cyclohexyl, 4,3-dimethylcyclohexyl and 1-ethylcyclohexyl;

C ₃ -C ₆ cycloalkenyl groups such as 2-cyclopropenyl group, 2-cyclobutenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group;

Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2,2-pentafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bro Mother profile, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2,2,2-trifluoro- 1-methyl-ethyl group, a butyl group 4-fluoro, 4-chlorobutyl group, 4-bromo-butyl group, 2,2,3,3,4,4,4-heptafluoropropane, such as a butyl group C ₁ - Haloalkyl group of C ₆ ;

Haloalkenyl groups such as C ₂ -C ₆ such as 3,3-dichloroallyl group;

Halocycloalkyl groups such as C ₃ -C ₆ such as 2,2-difluorocyclopentyl group;

Cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutyl group, 2-cyanobutyl group C ₂ -C ₅ cyanoalkyl groups such as 3-cyanobutyl group and 4-cyanobutyl group;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxy C ₂ -C ₆ alkoxyalkyl groups such as ethyl group, 3-methoxypropyl group, 4-methoxybutyl group and 5-methoxypentyl group;

Methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, isopropylthiomethyl group, butylthiomethyl group, 2- (methylthio) ethyl group, 2- (methylthio) ethyl group, 2- (propylthio) ethyl group, 2- (isopropyl thio) ethyl, 2- (butylthio) ethyl group, 3- (methylthio) propyl, 4- (methylthio) butyl group, 5- (methylthio) pentanoic alkylthio group such as alkyl group of C ₂ -C _6;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, propylsulfonylmethyl group, isopropylsulfonylmethyl group, butylsulfonylmethyl group, 2- (methylsulfonyl) ethyl group, 2- (ethylsulfonyl) ethyl group, 2- (propylsulfonyl ) Ethyl group, 2- (isopropylsulfonyl) ethyl group, 2- (butylsulfonyl) ethyl group, 3- (methylsulfonyl) propyl group, 4- (methylsulfonyl) butyl group, 5- (methylsulfonyl) phen alkyl sulfonic group and the like of the C ₂ -C ₆ alkyl sulfonyl;

C ₃ -such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. An oxoalkyl group of C ₆ ;

2- (acetyloxy) ethyl group, 2- (propionyloxy) ethyl group, 2- (butyryloxy) ethyl group, 2- (isobutyryloxy) ethyl group, 2- (valeryloxy) ethyl group, 2- (isovalle Ryloxy) ethyl group, 2- (pivaloyloxy) ethyl group, 2- (acryloyloxy) ethyl group, 2- (propioyloxy) ethyl group, 2- (methacryloyloxy) ethyl group, 2- ( C ₃ -C ₇ acyloxyalkyl groups such as crotonoyloxy) ethyl group, 3- (acetyloxy) propyl group, 4- (acetyloxy) butyl group and 5- (acetyloxy) pentyl group;

Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, butoxycarbonylmethyl group, isobutoxycarbonylmethyl group, secondary-butoxycarbonylmethyl group, tertiary-part A methoxycarbonylmethyl group, a pentyloxycarbonylmethyl group, isopentyloxycarbonylmethyl group, hexyloxycarbonylmethyl group, 2- (methoxycarbonyl) ethyl group, 2- (ethoxycarbonyl) ethyl group, 2- (propoxycarbon) Yl) ethyl group, 2- (isopropoxycarbonyl) ethyl group, 2- (butoxycarbonyl) ethyl group, 2- (isobutoxycarbonyl) ethyl group, 2- (secondary-butoxycarbonyl) ethyl group, 2- (Tert-butoxycarbonyl) ethyl group, 2- (pentyloxycarbonyl) ethyl group, 2- (isopentyloxycarbonyl) ethyl group, 1- (methoxycarbonyl) ethyl group, 1- (ethoxycarbonyl) Ethyl group, 1- (propoxycarbonyl) ethyl group, 1- (isopropoxycarbonyl) ethyl group, 1- (butoxycarbonyl) ethyl group, 1- (isobutoxycarbonyl) ethyl group, 1- (secondary-part Methoxycarbonyl) ethyl group, 1- (tert-butoxide Cicarbonyl) ethyl group, 1- (pentyloxycarbonyl) ethyl group, 1- (isopentyloxycarbonyl) ethyl group, 3- (methoxycarbonyl) propyl group, 3- (ethoxycarbonyl) propyl group, 3- (Propoxycarbonyl) propyl group, 3- (isopropoxycarbonyl) propyl group, 3- (butoxycarbonyl) propyl group, 1- (methoxycarbonyl) propyl group, 1- (ethoxycarbonyl ) Propyl group, 1- (propoxycarbonyl) propyl group, 1- (isopropoxycarbonyl) propyl group, 1- (butoxycarbonyl) propyl group, 1- (methoxycarbonyl) -1-methyl Ethyl group, 1- (ethoxycarbonyl) -1-methylethyl group, 1-methyl-1- (propoxycarbonyl) ethyl group, 1- (isopropoxycarbonyl) -1-methylethyl group, 1- (butoxy Carbonyl) -1-methylethyl group, 4- (methoxycarbonyl) butyl group, 4- (ethoxycarbonyl) butyl group, 4- (propoxycarbonyl) butyl group, 3- (isopropoxycarbonyl C ₃ -C ₇ alkoxycarbonylalkyl groups such as) butyl group;

Phenyl group;

A substituted methyl group with a phenyl group, an ethyl group, a propyl group, an isopropyl group an alkyl group of C ₁ -C _3, and the like;

3- to 6-membered heterocyclic groups containing one or two oxygen atoms, sulfur atoms and / or nitrogen atoms;

Or C ₁ -C ₃ alkyl groups such as methyl, ethyl, propyl and isopropyl groups substituted with 3 to 6 membered heterocyclic groups containing one or two oxygen atoms, sulfur atoms and / or nitrogen atoms. have.

Examples of the 3- to 6-membered heterocyclic group containing one or two oxygen atoms, sulfur atoms and / or nitrogen atoms include an oxiranyl group, an oxetanyl group, a tetrahydrofuryl group, a furyl group, a thienyl group, a pyrrolyl group and a pyrrolidy Nyl group, oxazolyl group, thiazolyl group, imidazolyl group, isoxazolyl group, isothiazolyl group, pyrazolyl group, tetrahydropyranyl group, pyridyl group, piperidyl group, pyrimidinyl group, pyridazinyl group, A morpholinyl group and a piperadinyl group are mentioned, These may have a substituent.

In addition, R <^15> can form a ring with W, when W is -NR <^16> -. R ¹⁵ represents the formation of a heterocyclic group of 5 or 6 members, which contain the R ¹⁵ is 1 or 2 nitrogen atoms and / or zero or one oxygen atom with W when forming a W and the ring. 5- or 6-membered heterocyclic groups containing 1 or 2 nitrogen atoms and / or 0 or 1 oxygen atom are 1-pyrrolidinyl group, 1-pyrrolyl group, 2-isoxazolidinyl group, 1-pyrazolyl Group, 1-imidazolyl group, 1-piperidyl group, 4-morpholinyl group, perhydro-1,2-oxazin-2-yl group, 1-piperidinyl group, etc., and these have a substituent Can be.

The R ¹² , R ¹³ or R ¹⁵ is a phenyl group, a C ₁ -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group (the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms) Or a C ₁ -C ₃ alkyl group substituted with a 3 to 6 membered heterocyclic group (the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms), the phenyl group and the heterocyclic group May have a substituent. Specific examples of the substituent include one to three halogen atoms such as fluorine, chlorine, bromine and iodine atoms; C ₁ -C ₄ alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary-butyl group and tert-butyl group; Trifluoromethyl group; C ₁ -C ₄ alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary-butoxy and tert-butoxy groups; Acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, acryloyloxy group, propioloyloxy group, methacryloyloxy group, chloro an acyloxy group of C ₂ -C _5, such as the buttocks acryloyloxy group; Import-methylthiophene, ethyl come tea, tea come propyl, isopropyl come tea, thio-butyl, iso-butyl thio group, sec-butyl thio group, t-alkylthio-butyl thio group such as a C ₁ -C ₄ ; Methyl sulfonyl group, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl group, isobutyl-sulfonyl, sec-butyl sulfonyl group, t-butyl sulfonyl group such as alkylsulfonyl group of C ₁ -C ₄ ; Nitro group; Cyano group; Or C such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, secondary-butoxycarbonyl group, tert-butoxycarbonyl group _And alkoxycarbonyl groups of ₂ -C ₅ .

Of these, R ³ is preferably a hydrogen atom, a nitro group or -QR ¹² {wherein Q is an oxygen atom or -NR ^13- (wherein R ¹³ is a hydrogen atom, an acyl group of C ₂ -C ₆ , C _1- C is an alkylsulfonyl group or an alkoxy carbonyl group of C ₂ -C ₆ of _6), and, R ¹² is a hydrogen atom, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl of the group, a halo-cycloalkyl group of C ₃ -C ₈ cycloalkyl group, C ₃ -C ₈ cycloalkyl alkenyl, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₁₀ of the, C ₂ -C ₇ cyanoalkyl group, an alkyl group of C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, C ₁ a C ₁ -C ₆ substituted by alkylsulfonyl group, phenyl group -C ₆ of the, C ₁ -C substituted with 3- to 6-membered heterocyclic groups (wherein the rings contain 1 or 2 oxygen atoms), with 3 to 6-membered heterocyclic groups (where the rings contain 1 or 2 oxygen atoms) ₃ , alkyl group, chemical formula Group or formula of (II) Group of (III) wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom or -NR ^16- (wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ ) R ¹⁵ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ].

R ³ is particularly preferably a hydrogen atom, a nitro group or —QR ¹² {wherein Q is an oxygen atom or —NR ¹³ —, where R ¹³ is a hydrogen atom, an alkylsulfonyl group of C ₁ -C ₆ or C _2- an alkoxycarbonyl group of C _6), and, R ¹² is a hydrogen atom, an alkynyl group, a cycloalkyl group of C ₃ -C ₈ of the C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of the , C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, C ₁ An alkylsulfonyl group of -C ₆ , a C ₁ -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group (the ring contains one or two oxygen atoms), a 3- to 6-membered heterocyclic group Wherein the ring contains one or two oxygen atoms and is an alkyl group of C ₁ -C ₃ , a group of formula II or a group of formula III

More preferably R ³ is -QR ¹² [wherein Q is an oxygen atom, R ¹² is an alkynyl group of the alkenyl group, C ₂ -C ₁₀ alkyl group _{C 1 -C 10, C 2 -C} 10, C 3 -C ₈ cycloalkyl group, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ Substituted with an oxoalkyl group, a 3-6 membered heterocyclic group (wherein the ring contains one or two oxygen atoms), a 3-6 membered heterocyclic group (where the ring contains one or two oxygen atoms) C ₁ -C ₃ alkyl group or the above formula (II).

Further, as a combination of substituents, preferably R ¹ and R ² are bonded together to form a ring, and R ³ is a hydrogen atom, a nitro group or -QR ¹² {where Q is an oxygen atom or -NR ^13- (where R ¹³ is an alkoxycarbonyl group of a hydrogen atom, C ₁ -C ₆ alkylsulfonyl group or a C ₂ -C _6), and, R ¹² is an alkyl group of a hydrogen atom, C ₁ -C _10, alkenyl of C ₂ -C ₁₀ , Alkynyl group of C ₂ -C ₁₀ , cycloalkyl group of C ₃ -C ₈ , haloalkyl group of C ₁ -C ₁₀ , haloalkenyl group of C ₂ -C ₁₀ , cyanoalkyl group of C ₂ -C ₇ , C ₂ alkoxyalkyl group -C _10, C ₃ -C ₆ heterocyclic group of the oxo group, a C ₁ -C ₆ alkylsulfonyl group, a C ₁ -C ₃ alkyl group, a 3-to 6-substituted phenyl group in the (Current ring 1 Or a C ₁ -C ₃ alkyl group substituted with a three to six member heterocyclic group, the ring containing one or two oxygen atoms, containing two oxygen atoms, Group or formula of (II) Group of (III), wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom or -NR _16- (wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ) R ¹⁵ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ], and

Especially preferably, R ¹ and R ² are bonded together to form a carbocyclic ring and R ³ is -QR ¹² , wherein Q is an oxygen atom, R ¹² is an alkyl group of C ₁ -C ₁₀ , C ₂ -C ₁₀ Alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₃ -C ₈ cycloalkyl group, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, 3- to 6-membered heterocyclic group (the ring contains 1 or 2 oxygen atoms), 3- to 6-membered heterocyclic group Ring is a C ₁ -C ₃ alkyl group substituted with 1 or 2 oxygen atoms or a group represented by the above formula (II).

Among these, More preferably, Y is a halogen atom.

When the compound of the formula (I) contains a pyridazine ring moiety and a hydroxyl group or a nitrogen atom in the substituent R ³ , a salt may be formed at the moiety.

Specific examples thereof include alkali metal salts such as sodium salts, potassium salts, and calcium salts, or halogenated metal salts such as alkaline earth metal salts, hydrofluoric acid salts, hydrochlorides, hydrobromide salts, and iodide hydrochlorides; Inorganic acid salts such as nitrates, perchlorates, sulfates, and phosphates; Sulfonates such as methanesulfonic acid salts, trifluoromethanesulfonic acid salts, and p-toluenesulfonic acid salts.

In addition, compounds of formula V or formula V ′ are novel compounds as important intermediates for the synthesis of compounds of formula I of the present invention.

In the above formulas V and V ',

Y, Z, R ¹ , R ² and R ³ are as defined in claim 1 of the claims.

On the other hand, the compound of formula V and the compound of formula V 'are structural isomers and readily isomerize in the presence of an acid or an alkali. For example, when chlorination is carried out by a reagent such as phosphorus oxychloride, the reaction proceeds through the compound of formula (V), and when the base is alkylated such as sodium hydride, the reaction proceeds through the compound of formula (V ').

Next, the novel tri-substituted phenyl-4-halopyridazine, derivatives thereof and intermediates thereof of the present invention will be described. The compound of the present invention of formula (I) can be produced, for example, by any one of the following production methods (1) to (13).

Manufacturing method (1)

In the above scheme,

X, Y, Z, R ¹ and R ² are the same as defined above,

R ^{3 '} is an inert group which is not affected by the present reaction such as a hydrogen atom, a nitro group, an alkoxy group, an alkylthio group, a dialkylamino group and the synthesis of the following raw material [VII],

R <^17> is lower alkyl groups, such as a methyl group and an ethyl group.

The reaction is carried out in the presence of a base, in the absence of a solvent or in a solvent, at a temperature in the range of usually 0 to 200 ° C, preferably 50 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, base 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of compound [VIII] to 1 equivalent of compound [VII] .

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (methanol, ethanol, 2-propanol, etc.), organic acids (formic acid, acetic acid, etc.), water and these And mixtures thereof.

Bases used may include triethylamine, diisopropylethylamine, pyridine, picoline, N, N-diethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0]- Organic bases such as 7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride and potassium hydride And inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium acetate, potassium acetate, sodium fluoride and potassium fluoride.

Manufacturing method (2)

In the above scheme,

X, Y, Z, R ¹ and R ² are as defined above,

R ^{3 ″} is an inert group which is not affected by the present reaction of hydrogen atom, nitro group, alkoxy group, alkylthio group, dialkylamino group and the like and the synthesis of intermediate [V] shown below.

The reaction is usually carried out in the range of a temperature of 0 to 200 캜, preferably 10 to 100 캜 in the presence of a halogenating agent in the absence of a solvent or in a solvent. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, of halogenating agent relative to 1 equivalent of [V].

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene etc.), ethers (diethyl ether, tetrahydrofuran, dioxane etc.), mixtures thereof, etc. are mentioned. Examples of the halogenating agent to be used include phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, hydrogen chloride, phosphorus tribromide, hydrogen bromide, sulfatrifluoride diethylamine complex, tetrabutylammonium fluoride, hydrogen fluoride and the like.

Manufacturing Method (3)

In the above scheme,

X, Y, Z, R ¹ , R ² and Q are as defined above, except that R ¹² in [Ia] excludes a hydrogen atom.

The reaction is carried out in the absence of a solvent or in a solvent, in the presence of an acid, usually at a temperature in the range of -20 to 200 ° C, preferably 10 to 100 ° C. When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, Acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol, etc.), water, and mixtures thereof.

Examples of the acid used include acids such as formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and p-toluenesulfonic acid. In addition, [Ia] which is a raw material compound can be synthesized by the production method (1) or the production method (2). In [Ia], R ¹² is preferably an alkyl group, a cycloalkyl group, an acyl group or an alkoxyalkyl group.

When it is expected that R ¹² affects the cyclization reaction described in the above Preparation Method (1) as in Formula III, the compound obtained by the above Preparation Method (3) may be prepared by the following Preparation Method (4) or (5). By derivatization).

Manufacturing method (4)

In the above scheme,

X, Y, Z, R ¹ , R ² , R ¹² and Q are as defined above (where R ¹² excludes hydrogen atoms),

V is a halogen atom such as chlorine atom, bromine atom or iodine atom; Lower alkylsulfonyloxy groups such as methylsulfonyloxy group; Or arylsulfonyloxy groups such as p-toluenesulfonyloxy group.

The reaction is carried out in the presence of a base, in the absence of a solvent or in a solvent, at a temperature in the range of usually 0 to 200 ° C, preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, of R ¹² -V relative to 1 equivalent of [Ib]. .

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (methanol, ethanol, 2-propanol, etc.), organic acids (formic acid, acetic acid, etc.), water and these And mixtures thereof. Bases used include triethylamine, pyridine, picoline, N, N-diethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1 Organic bases such as, 5-diazabicyclo [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide And inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium fluoride and potassium fluoride.

Manufacturing Method (5)

In the above scheme,

X, Y, Z, R ¹ , R ² , R ¹² and Q are as defined above (where R ¹² excludes hydrogen atoms),

R <^18> is lower alkyl groups, such as a methyl group and an ethyl group.

The reaction is usually carried out at a temperature in the range of 0 to 100 ° C., preferably 0 to 50 ° C., in the presence of triphenylphosphine and azodicarboxylic acid dialkyl in the absence of a solvent or in a solvent. The amount of the compound used in the reaction typically [1b] 1 equivalent of R ¹² -OH is 1.0 to 3.0 equivalents per equivalent, preferably 1.0 to 1.5 equivalents, of triphenylphosphine is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 The equivalent, azodicarboxylic acid dialkyl is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetonitrile and the like) and mixtures thereof.

Manufacturing Method (6)

In the above scheme,

X, Y, Z, R ¹ and R ² are as defined above.

The reaction is carried out in the range of -10 to 150 캜, preferably 20 to 60 캜, in the absence of a solvent or in a solvent. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents of a nitrating agent relative to 1 equivalent of [Ic].

When using a solvent, a suitable solvent includes inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic acids (formic acid, acetic acid, etc.), organic anhydrides (acetic anhydride, etc.), and the like. Examples of the nitrating agent used include mixtures of inorganic acids (sulfuric acid, hydrochloric acid) with nitric acid or nitrates (sodium nitrate, potassium nitrate, etc.), nitric acid, nitronium tetrafluoroborate, nitronium trifluoromethanesulfonate, and the like. .

Manufacturing method (7)

In the above scheme,

X, Y, Z, R ¹ and R ² are as defined above.

The reduction reaction is usually performed at a temperature in the range of 50 to 100 ° C. in the absence of a solvent or in the presence of a metal or a metal compound and an acid. The amount of the metal or metal compound used is usually 1 to 20 equivalents, preferably 2 to 10 equivalents, relative to 1 equivalent of [Id]. The amount of acid used is usually 0.01 to 20 equivalents, preferably 0.01 to 10 equivalents, relative to 1 equivalent of [Id].

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetonitrile, and the like), organic acids (formic acid, acetic acid), water, and mixtures thereof. The amount of solvent used is usually 1 to 100 times, preferably 1 to 20 times the weight of [Id]. Examples of the metal or metal compound to be used include iron, zinc, tin, tin chloride (II) and the like. Examples of the acid used may include hydrochloric acid, sulfuric acid, acetic acid, and the like. In addition, the reaction uses sodium sulfide, sodium hydrosulfide, sodium dithionate, ammonium sulfide, hydrogen / metal catalyst (palladium-carbon, platinum-carbon, rhodium-alumina, platinum, Raney nickel, etc.) as a reducing agent. It is also possible.

Manufacturing Method (8)

In the above scheme,

X, Y, Z, R ¹ , R ² , R ¹² and R ¹³ are as defined above, except R ¹² excludes hydrogen atoms,

V is a halogen atom such as chlorine atom, bromine atom or iodine atom; Lower alkylsulfonyloxy groups such as methylsulfonyloxy group; Or arylsulfonyloxy groups such as p-toluenesulfonyloxy group.

The reaction is carried out in the presence of a base, in the absence of a solvent or in a solvent, at a temperature in the range of usually 0 to 200 ° C, preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, and 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, of R ¹³ -V to 1 equivalent of [If]. .

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (methanol, ethanol, 2-propanol, etc.), organic acids (formic acid, acetic acid, etc.), water and these And mixtures thereof. Bases used include triethylamine, pyridine, picoline, N, N-diethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1 Organic bases such as, 5-diazabicyclo [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide And inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium fluoride and potassium fluoride.

Manufacturing Method (9)

In the above scheme,

X, Y, R ¹ , R ² and R ³ are as defined above,

X 'is a halogen atom,

Met is a metal atom.

The reaction is carried out in a solvent-free or in a solvent, usually at a temperature of 0 to 250 캜, preferably 100 to 200 캜. The amount of the compound used for the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents of cyanolating agent (Met-CN) to 1 equivalent of [Ih].

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (methanol, ethanol, 2-propanol, etc.), organic acids (formic acid, acetic acid, etc.), water and these And mixtures thereof. Copper cyanide, potassium cyanide, sodium cyanide, etc. are mentioned as a cyanoating agent used.

Manufacturing Method (10)

In the above scheme,

X, Y, Z, R ¹ , R ² , R ³ , n and m are as defined above (where n + m> 0).

The reaction is usually carried out at a temperature in the range of 0 to 200 ° C., preferably 10 to 100 ° C., without or using a solvent, in the presence of an oxidant, in the presence or absence of a metal or metal complex. The amount of the compound used in the reaction is typically 1.0 to 3.0 equivalents, preferably 1.5 to 2.5 equivalents of oxidizing agent relative to 1 equivalent of [I], and 0.05 to 1.5 equivalents, preferably 0.1 to 0.1, when a metal or metal complex is required. 1.0 equivalent.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol, etc.) , Organic acids (formic acid, acetic acid, and the like), water, and mixtures thereof. Examples of the oxidizing agent used include m-chlorobenzoic acid, peracetic acid, hydrogen peroxide, tert-butyl hydroperoxide and the like. As a metal or metal complex used, a vanadium, molybdenum, a titanium tetraisopropoxide- diiso tartrate complex, etc. are mentioned.

Manufacturing Method (11)

In the above scheme,

X, Y, Z, R ¹ , R ² and R ³ are the same as defined above,

H-U is an acid which forms a salt with the compound of the present application, and specifically, hydrofluoric acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid; Inorganic acids such as nitric acid, perchloric acid, sulfuric acid, phosphoric acid; Sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid.

The reaction is carried out in the absence of a solvent or in a solvent, in the presence of H-U, at a temperature in the range of usually 0 to 200 ° C, preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of H-U, based on 1 equivalent of [I].

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), aprotic polar solvents (N , N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetonitrile and the like), alcohols (methanol, ethanol, 2-propanol and the like), water and mixtures thereof and the like.

Manufacturing Method (12)

In the above scheme,

X, Y, Z, R ¹ , R ² and R ³ are as defined above,

X 'is a halogen atom,

P is a -B (OH) ₂ or -Met'-X "(Here, the metal such as Met 'is magnesium, zinc, X" is a halogen atom).

The reaction is carried out at a temperature in the range of 0 to 200 ° C., preferably 10 to 100 ° C., with or without a solvent, in the presence or absence of a metal or metal complex. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, preferably 0.01 to 1.0 equivalents, preferably 0.05 to 0.5 equivalents of metal or metal complex, relative to 1 equivalent of [IX] to be.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, Acetonitrile), and mixtures thereof. In the case of using a metal or metal complex, suitable metals or metal complexes include metals such as nickel, iron, ruthenium, cobalt, rhodium, iridium, palladium, and platinum, tetrakis (triphenylphosphine) palladium, and tris (dibenzylidene). Acetone) dipalladium, dichlorobis (triphenylphosphine) palladium, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis (acetylacetonate) nickel, dichloro [1,1'-bis (di The above-mentioned metals such as phenylphosphino) ferrocene] palladium, or the chlorides and triphenylphosphines, tri (o-tolyl) phosphine, 1,2-bis (diphenylphosphino) ethane, And metal complexes formed with ligands such as 2-bis (diphenylphosphino) propane, 1,1'-bis (diphenylphosphino) ferrocene, dibenzylideneacetone, and acetylacetone.

Manufacturing Method (13)

In the above scheme,

X, Y, Z, R ¹ , R ² and R ³ are as defined above,

W is a halogen atom such as chlorine atom, bromine atom or iodine atom; Methylsulfonyloxy group; Lower alkylsulfonyloxy groups such as; Lower haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy group; Or arylsulfonyloxy groups such as p-toluenesulfonyloxy group.

The reaction is carried out at a temperature in the range of −50 to 200 ° C., preferably 0 to 100 ° C., with or without solvent, in the presence of a base, in the presence or absence of a metal or metal complex. The amount of the compound used in the reaction is usually 1.0-3.0 equivalents, preferably 1.0-1.5 equivalents, 1.0-3.0 equivalents, preferably 1.0-1.5 equivalents, metal or [XI] based on 1 equivalent of [XII] The metal complex is 0.01 to 1.0 equivalent, preferably 0.05 to 0.5 equivalent.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Dichlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, Acetonitrile), and mixtures thereof. Bases used include triethylamine, pyridine, picoline, N, N-diethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1 Organic bases such as, 5-diazabicyclo [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, butyllithium, secondary -Butyllithium, tert-butyllithium, phenyllithium, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, lithium diisopropylamide, tert-butoxy potassium, sodium hydroxide, potassium hydroxide, Inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium fluoride and potassium fluoride. Copper chloride, copper bromide, copper iodide, iron chloride, iron bromide, iron iodide, etc. are mentioned as a metal or metal complex used.

In addition, the raw material compound [VII] in the said manufacturing method (1) can be manufactured according to following Reaction Formula, for example.

In the above scheme,

X, Y, Z, R ³ and R ¹⁷ are as defined above.

In addition, in the said manufacturing method (2), raw material compound [V] can be manufactured according to following Reaction Formula, for example.

In the above scheme,

X, Y, Z, R ¹ , R ² and R ³ are as defined above,

V and W are the same or different halogen atoms such as chlorine, bromine and iodine atoms.

According to the structure of the compound of the present invention, isomers such as optical isomers and diastereomers exist, and the compounds of the present invention include all of them. When using the compound of this invention as a herbicide, each isomer separated according to a well-known method may be used independently, but can be used as a mixture of isomers.

When the compound of the present invention is used as a herbicide, the compound of the present invention (hereinafter, also referred to as "element") may be applied as it is, but generally, a suitable adjuvant may be used, such as a hydrating agent, a granule, an emulsion, a fluidizing agent, or the like. Use in form. As an adjuvant, For example, solid carriers, such as kaolin, bentonite, talc, diatomaceous earth, white carbon, starch; Water, alcohols (methanol, ethanol, propanol, butanol, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), ethers (diethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (Kerosine, kerosene, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (dichloroethane, carbon tetrachloride, trichlorobenzene, etc.), acid amides (dimethylformamide, etc.) Solvents such as esters (ethyl acetate, butyl acetate, fatty acid glycerin esters and the like), nitriles (acetonitrile and the like); Nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyldimethylbenzyl ammonium chloride, alkylpyridinium chloride, etc.), anionic surfactants (alkylbenzenesulfon Acid salts, lignin sulfonates, higher alcohol sulfates and the like), and surfactants such as amphoteric surfactants (alkyldimethylbetaine, dodecylaminoethylglycine, etc.). These solid carriers, solvents, surfactants, etc. are each used as one or more mixture as needed.

The dosage of the compound of the present invention varies depending on the conditions of the structure, the target weeds, the treatment time, the treatment method, the soil properties, etc., but the amount of the active ingredient per hectare is usually in the range of 2 to 2000 g, preferably 5 to 1000 g. Is suitable.

As a target weed of the compound of the present invention, in the field, for example, white hyacinth, hyacinth, perilla, perilla, perilla, green amaranth, chickweed, vast greens, mother-of-pearl, wild horse, wild morning glory, datura, wild mustard, rake, Western violets, weasel, hairy ferns, bees, king burrows, kelp, ragweed, and the like.

Moreover, in a rice paddy, a knotweed flower, a single flower, a watering cane, a back grass, a water sun, a taxi, a peeling, an egg shell, a snare, a peel, a tadpole, a beech, etc. are mentioned, for example. The compound of the present invention can control the weeds in any case of pre-germination soil treatment and growing foliage treatment. In addition, the compound of the present invention has little effect on cultivated crops such as corn, wheat, barley, rice and soybeans in any case of pre-germination soil treatment and growing foliage treatment, and can be used as a selective herbicide.

Herbicides containing the compound of the present invention as an active ingredient may be mixed with other pesticides used in the same field, such as insecticides, fungicides, plant growth regulators and fertilizers. It is also possible to stabilize the herbicidal effect by mixing with other herbicides. When the compound of this invention and another herbicide are mixed and applied, each formulation may be mixed at the time of application, but can be applied as a preparation containing both. As a herbicide which can be mixed and used suitably with the compound of this invention, the following are mentioned, for example.

Carbamate Herbicides:

2-chloroallyl diethyldithiocarbamate,

S-2,3-dichloroallyl diisopropylthiocarbamate,

S-2,2,3-trichloroallyl diisopropylthiocarbamate,

S-ethyl dipropylthiocarbamate,

S-ethyl diisobutylthiocarbamate,

S-benzyl 1,2-dimethylpropyl (ethyl) thiocarbamate,

S-4-chlorobenzyl diethylthiocarbamate,

S-ethyl perhydroazepine-1-thiocarboxylate,

S-isopropyl perhydroazepine-1-thiocarboxylate,

S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate,

0-3-tert-butylphenyl 6-methoxy-2-pyridyl (methyl) thiocarbamate,

3- (methoxycarbonylamino) phenyl 3'-methylphenylcarbamate,

Isopropyl 3'-chlorophenylcarbamate,

Methyl (4-aminophenylsulfonyl) carbamate and the like

Urea herbicides:

3- (3,4-dichlorophenyl) -1,1-dimethylurea,

3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea,

1,1-dimethyl-3- [3- (trifluoromethyl) phenyl] urea,

3- [4- (4-methoxyphenoxy) phenyl) -1,1-dimethylurea,

1- (1-methyl-1-phenylethyl) -3-p-tolylurea,

3- (4-isopropylphenyl) -1,1-dimethylurea,

3- (5-tert-butylisoxazol-3-yl) -1,1-dimethylurea,

1- (5-tert-butyl-1,3,4-thiadiazol-2-yl) -1,3-dimethylurea,

1- (benzothiazol-2-yl) -1,3-dimethylurea and the like

Amide herbicides:

2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide,

N- (butoxymethyl) -2-chloro-2 ', 6'-diethylacetanilide,

2-chloro-2 ', 6'-diethyl-N- (2-propoxyethyl) acetanilide,

2-chloro-N- (ethoxymethyl) -6'-ethylacet-o-tolimide,

2-chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) acet-o-tolimide,

2-chloro-N- (3-methoxy-2-tenyl) -2 ', 6'-dimethylacetanilide,

N- (chloroacetyl) -N- (2,6-diethylphenyl) glycineethyl ester,

2-chloro-N- (2,4-dimethyl-3-thienyl) -N- (2-methoxy-1-methylethyl) aceamide,

3 ', 4'-dichloropropionanilide,

2 ', 4'-difluoro-2- [3- (trifluoromethyl) phenoxy] nicotinanilide,

2- (1,3-benzothiazol-2-yloxy) -N-methylacetanilide,

2-bromo-N- (a, a-dimethylbenzyl) -3,3-dimethylbutylamide,

N- [3- (ethyl-1-methylpropyl) isoxazol-5-yl] -2,6-dimethoxybenzamide and the like

Dinitroaniline herbicides:

2,6-dinitro-N, N-dipropyl-4- (trifluoromethyl) aniline,

N-butyl-N-ethyl-2.6-dinitro-4- (trifluoromethyl) aniline,

2,6-dinitro-N ', N'-dipropyl-4- (trifluoromethyl) -m-phenylenediamine,

4- (dipropylamino) -3,5-dinitrobenzenesulfonamide,

N-tert-butyl-4-tert-butyl-2,6-dinitroaniline,

N- (1-ethylpropyl) -2,6-dinitro-3,4-xyldine and the like

Carboxylic Acid Herbicides:

(2,4-dichlorophenoxy) acetic acid and derivatives thereof,

(2,4,5-trichlorophenoxy) acetic acid and derivatives thereof,

(4-chloro-2-methylphenoxy) acetic acid and derivatives thereof,

2- (2,4-dichlorophenoxy) propionic acid and derivatives thereof,

4- (2,4-dichlorophenoxy) butyric acid and its derivatives,

2,3,6-trichlorobenzoic acid and derivatives thereof,

3,6-dichloro-2-methoxybenzoic acid and derivatives thereof,

3,7-dichloroquinoline-8-carboxylic acid,

7-chloro-3-methylquinoline-8-carboxylic acid,

3,6-dichloropyridine-2-carboxylic acid and salts thereof,

4-amino-3,5,6-trichloropyridine-2-carboxylic acid and salts thereof,

(3,5,6-trichloro-2-pyridyloxy) acetic acid and derivatives thereof,

(4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy) acetic acid and derivatives thereof,

(4-chloro-2-oxobenzothiazolin-3-yl) acetic acid and derivatives thereof,

2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid and derivatives thereof,

2- [4- [5- (trifluoromethyl) -2-pyridyloxy] phenoxy] propionic acid and derivatives thereof,

2- [4- [3-chloro-5- (trifluoromethyl) -2-pyridyloxy] phenoxy] propionic acid and derivatives thereof,

2- [4- (6-chloro-1,3-benzooxazol-2-yloxy) phenoxy] propionic acid and derivatives thereof,

2- [4- (6-chloroquinoxalin-2-yloxy) phenoxy] propionic acid and derivatives thereof,

2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionic acid and derivatives thereof, and the like

Phenolic Herbicides:

3,5-dibromo-4-hydroxybenzonitrile and salts thereof,

4-hydroxy-3,5-diiodobenzonitrile and salts thereof,

2-tert-butyl-4,6-dinitrophenol and salts thereof

Cyclohexanedione Herbicides:

Methyl 3- [1- (allyloxyimino) butyl] -4-hydroxy-6,6-dimethyl-2-oxo-3-cyclohexene-1-carboxylate and salts thereof,

2- [1- (ethoxyimino) butyl] -5- [2- (ethylthio) propyl] -3-hydroxy-2-cyclohexen-1-one,

2- [1- (ethoxyimino) butyl] -3-hydroxy-5- (thian-3-yl) -2-cyclohexen-1-one,

2- [1- (ethoxyimino) propyl] -3-hydroxy-5- (2,4,6-trimethylphenyl) -2-cyclohexen-1-one,

2- [1- (3-chloroallyloxyimino) propyl] -5- [2- (ethylthio) propyl] -3-hydroxy-2-cyclohexen-1-one,

2- [2-chloro-4- (methylsulfonyl) benzoyl] cyclohexane-1,3-dione, etc.

Diphenyl ether herbicides:

4-nitrophenyl 2,4,6-trichlorophenyl ether,

2- (2,4-dichlorophenoxy) -2-nitroanisole,

2-chloro-4- (trifluoromethyl) phenyl 3-ethoxy-4-nitrophenyl ether,

Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate,

5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid and salts thereof,

0- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoyl] ethyl glycolate,

Ethyl 0- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoyl] -DL-lactate,

5- [2-chloro-4- (trifluoromethyl) phenoxy] -N- (methylsulfonyl) -2-nitrobenzamide,

2-chloro-6-nitro-3-phenoxyaniline, etc.

Sulfonylurea herbicides:

Ethyl 2- (4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamoyl) benzoate,

Methyl 2- (4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) benzoate,

Methyl 2- [4,6-bis (difluoromethoxy) pyrimidin-2-ylcarbamoylsulfamoyl] benzoate,

Methyl 2- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoylmethyl) benzoate,

1- (2-chlorophenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea,

Methyl 2- (4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl) benzoate,

Methyl 2- [4-methoxy-6-methyl-1,3,5-triazin-2-yl (methyl) carbamoylsulfamoyl] benzoate,

1- [2- (2-chloroethoxy) phenylsulfonyl] -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea,

1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -3- [2- (2-methoxyethoxy) phenylsulfonyl] urea,

Methyl 2- [4-ethoxy-6- (methylamino) -1,3,5-triazin-2-ylcarbamoylsulfamoyl] benzoate,

Methyl 3- (4-methoxy-6-methyl-1,3,5-triazine-2-ylcarbamoylsulfamoyl) thiophene-2-carboxylate,

Ethyl 5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate,

Methyl 3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate,

1- (4,6-dimethoxypyrimidin-2-yl) -3- [3- (trifluoromethyl) -2-pyridylsulfonyl] urea,

1- (4,6-dimethoxypyrimidin-2-yl) -3- [3- (ethylsulfonyl) -2-pyridylsulfonyl] urea,

2- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -N, N-dimethylnicotinamino,

1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea,

1- [2- (cyclopropylcarbonyl) phenylsulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea,

1- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -3- [2- (3,3,3-trifluoropropyl) phenylsulfonyl] urea and the like

Bipyridinium-based herbicides:

1,1'-dimethyl-4,4'-bipyridinium dichloride,

1,1'-ethylene-2,2'-bipyridinium dibromide, etc.

Pyrazole herbicides:

4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl toluene-4-sulfonate,

2- [4- (2,4-dichlorobenzoyl) 1,3-dimethylpyrazol-5-yloxy] acetphenone,

2- [4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethylpyrazol-5-yloxy] -4'-methylacetphenone, etc.

Triazine Herbicides:

6-chloro-N ² , N ⁴ -diethyl-1,3,5-triazine-2,4-diamine,

6-chloro-N ² -ethyl-N ⁴ -isopropyl-1,3,5-triazine-2,4-diamine,

2- [4-chloro-6- (ethylamino) -1,3,5-triazin-2-ylamino] -2-methylpropionitrile,

N ² , N ⁴ -diethyl-6- (methylthio) -1,3,5-triazine-2,4-diamine,

N ^2- (1,2-dimethylpropyl) -N ⁴ -ethyl-6- (methylthio) -1,3,5-triazine-2,4-diamine,

4-amino-6-tert-butyl-3- (methylthio) -1,2,4-triazine-5 (4H) -one and the like

Imidazolinone herbicides:

Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -4 (5) -methylbenzoate,

2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid and salts thereof,

2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) quinoline-3-carboxylic acid and salts thereof,

5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid and salts thereof,

2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- (methoxymethyl) pyridine-3-carboxylic acid and salts thereof

Other herbicides:

1-methyl-3-phenyl-5- [3- (trifluoromethyl) phenyl] -4-pyridone,

3-chloro-4- (chloromethyl) -1- [3- (trifluoromethyl) phenyl] -2-pyrrolidinone,

5- (methylamino) -2-phenyl-4- [3- (trifluoromethyl) phenyl] furan-3 (2H) -one,

4-chloro-5- (methylamino) -2- [3- (trifluoromethyl) phenyl] pyrazine-3 (2H) -one,

N, N-diethyl-3- (2,4,6-trimethylphenylsulfonyl) -1H-1,2,4-triazole-1-carboxamide,

N- [2,4-dichloro-5- [4- (difluoromethyl) -4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl ] Phenyl] methanesulfonamide,

1- [4-chloro-3- (2,2,3,3,3-pentafluoropropoxymethyl) phenyl] -5-phenyl-1H-1,2,4-triazole-3-carboxamide ,

2- (chlorobenzyl) -4,4-dimethylisoxazolidin-3-one,

5-cyclopropyl-4- [2- (methylsulfonyl) -4- (trifluoromethyl) benzoyl] isoxazole,

5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazole-2 (3H) -one,

Ethyl [2-chloro-5- [4-chloro-5- (difluoromethoxy) -1-methylpyrazol-3-yl] -4-fluorophenoxy] acetate,

S, S'-dimethyl 2- (difluoromethyl) -4-isobutyl-6- (trifluoromethyl) pyridine-3,5-dicarbothioate,

Methyl 2- (difluoromethyl) -5- (4,5-dihydro-1,3-thiazol-2-yl) -4-isobutyl-6- (trifluoromethyl) pyridine-3-carboxyl Rate,

2-chloro-6- (4,6-dimethoxypyrimidin-2-ylthio) benzoic acid and salts thereof,

Methyl 2- (4,6-dimethoxypyrimidin-2-yloxy) -6- [1- (methoxyimino) ethyl] benzoate,

2,6-bis (4,6-dimethoxypyrimidin-2-yloxy) benzoic acid and salts thereof,

5-bromo-3-secondary-butyl-6-methylpyrimidine-2,4 (1H, 3H) -dione,

Tert-butyl-5-chloro-6-methylpyrimidine-2,4 (1H, 3H) -dione,

3-cyclohexyl-1,5,6,7-tetrahydrocyclopentapyrimidine-2,4 (3H) -dione,

Isopropyl 2-chloro-5- [1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl] benzoate,

1-methyl-4-isopropyl-2-[(2-methylphenyl) methoxy] -7-oxabicyclo [2.2.1] heptane,

N- (4-chlorophenyl) -3,4,5,6-tetrahydrophthalimide,

Pentyl [2-chloro-4-fluoro-5- (1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl) phenoxy] acetate,

2- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzooxazin-6-yl] -4,5,6,7 Tetrahydro-1H-isoindole-1,3 (2H) -dione,

N- (2,6-difluorophenyl) -5-methyl [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide,

N- (2,6-dichloro-3-methylphenyl) -5,7-dimethoxy [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide,

2,3-dihydro-3,3-dimethylbenzofuran-5-yl ethanesulfonate,

2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulfonate,

Methyl [[2-chloro-4-fluoro-5-[(tetrahydro-3-oxo-1H, 3H- [1,3,4] thiadiazolo [3,4a] pyridazine-1-ylidene) Amino] phenyl] thio] acetate,

2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethyl indan-1,3-dione and the like.

Example

Next, an Example is given and this invention is demonstrated further more concretely. However, this invention is not limited to the following Example, unless the summary is exceeded.

Reference Example 1

Ethyl 1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate

The mixture of 6.1 g of 4'-chloro-5 '-(cyclopentyloxy) -2'-fluoroacetophenone, 2.5 g of ethyl carbadate and 20 ml of toluene was heated under reflux for 10 hours, and the water was constantly Remove to system. After standing overnight, it is concentrated to give the crude product. Purification by column chromatography (developing solvent hexane: ethyl acetate / 7: 1) affords 4.2 g of the title compound. Physical properties and NMR spectral data are as follows.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.93 (1H, br), 7.22 (1H, d, J = 6.0 Hz), 7.10 (1H, d, J = 10.5 Hz), 4.84 (1H, m) , 4.32 (2H, q, J = 6.9 Hz), 2.22 (3H, s), 1.98-1.80 (4H, m), 1.75-1.59 (2H, m), 1.35 (3H, t, J = 6.9 Hz).

Reference Example 2

Ethyl 2,2,2-trichloro-1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate

A mixture of 1.8 g of ethyl 1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate, 2.4 g of N-chlorosuccinimide, and 30 ml of carbon tetrachloride obtained in Reference Example 1 Heated to reflux for 28 h. The precipitated crystals were separated by filtration at room temperature overnight and the crystals were washed with ethyl acetate. The filtrate obtained is concentrated to give 2.6 g of ethyl 2,2-dichloro-1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate. The mixture of crude product and 4.5 g of sulfyl chloride is stirred at 50 ° C. for 17 hours. Thereafter, the reaction solution is slowly added dropwise to the stirring ice water. The precipitated crystals were separated by filtration, dissolved in ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crystals obtained are filtered off, washed with hexane and dried to give 1.8 g of the title compound. Physical properties and NMR spectral data are as follows.

Melting point. 230.0-231.0 ℃

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.58 (1H, br), 7.32 (1H, d, J = 9.3 Hz), 6.94 (1H, d, J = 5.7 Hz), 4.75 (1H, m) 4.29 (2H, q, J = 6.9 Hz), 1.98-1.80 (4H, m), 1.75-1.59 (2H, m), 1.33 (3H, t, J = 6.9 Hz).

IR (KBr) ν (cm ⁻¹ ): 2965, 1630, 1490, 1450, 1402, 1341, 1190.

Reference Example 3

Ethyl 4-chloro-5-cyclopentyloxy-2-fluorophenylglyoxylate

Put a stirrer bar in a 100 ml four-necked flask and install the cooling tube and thermometer with a dial. A mixture of 0.49 g of metal magnesium, one piece of iodine and 2 ml of THF is stirred under a stream of nitrogen for 15 minutes until the color of iodine disappears to activate the magnesium. Here, a solution of THF 6 ml of 2.0 g of 1-bromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene and 0.1 ml of dibromoethane was kept slowly at an internal temperature of 35 ° C. or lower for 15 minutes. Dropping After completion of the dropwise addition, 2 ml of a solution of 0.1 ml of THF in 0.1 ml of dibromoethane was slowly added dropwise while maintaining the internal temperature at 35 ° C. or lower over 5 minutes to adjust the Grignard reagent.

Put a stirrer bar into a 2000 ml four-necked flask and install a cooling tube and a thermometer with jiru. A mixture of 30.0 grams of metal magnesium, about one minute of iodine and 150 ml of THF is stirred under a stream of nitrogen for 15 minutes until the color of iodine disappears to activate magnesium. The Grignard reagent adjusted first was added to the syringe and 220 ml of THF was added thereto, followed by 181.94 g of 1-bromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene and 10.8 ml of dibromoethane. The 180 ml solution is slowly added dropwise while maintaining the internal temperature at 30 to 36 ° C. over 2 hours. After completion of the dropwise addition, 15 ml of a THF solution of 2.7 ml of dibromoethane was slowly added dropwise while maintaining the internal temperature at 35 ° C or lower over 30 minutes.

Put a stirrer bar into a 3000 ml four-necked flask and install a cooling tube and a thermometer with jiru. A 800 ml solution of 184.0 g of diethyloxalate was added thereto and cooled to -30 ° C under a stream of nitrogen. The Grignard reagent adjusted first is dripped slowly over 1.5 hours, keeping below -30 degreeC. Furthermore, it heated up at -20 degreeC and stirred for 1 hour. Saturated aqueous ammonium chloride solution is slowly added to the reaction mixture to terminate the reaction, and the temperature is raised to room temperature. The reaction mixture is extracted with ethyl acetate and the organic phase is washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product obtained by distilling off unreacted diethyloxalate in the crude product at a bath temperature of 70 ° C. at 0.5 mmHg was purified by flash column chromatography (developing solvent hexane: ethyl acetate / 20: 1-15: 1) and titled 101.1 g of compound is obtained. Physical properties and NMR spectral data are as follows.

Melting Point 54.5-55.1 ℃

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.40 (1H, d, J = 6.0 Hz), 7.22 (1H, d, J = 10.2 Hz), 4.85 (1H, m), 4.43 (2H, q, J = 6.9 Hz), 1.98-1.80 (4H, m), 1.75-1.59 (2H, m), 1.40 (3H, t, J = 6.9 Hz).

Reference Example 4

4-Chloro-5-cyclopentyloxy-2-fluorophenylglyoxylic acid

A mechanical stirrer and thermometer are installed in a 2000 ml three-necked flask, and 40.00 g of sodium hydroxide and 500 ml of water are added to adjust the 2N aqueous sodium hydroxide solution. After cooling to room temperature, 109.8 g of ethyl 4-chloro-5-cyclopentyloxy-2-fluorophenylglyoxylate obtained in Reference Example 3 was slowly added and stirred for 1.5 hours. After completion of the reaction, 1000 ml of 1N aqueous hydrochloric acid solution was slowly added to make the reaction solution acidic. The reaction mixture was extracted three times with ether, and the organic phase obtained was washed twice with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to give 99.8 g of the title compound. Physical properties and NMR spectral data are as follows.

Melting Point 94.2-96.7 ℃

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.99 (1H, t, J = 7.8 Hz), 7.33 (1H, dd, J = 1.5, 8.4 Hz), 7.26 (1H, dd, J = 1.5, 9.9 Hz), 7.03 (1H, broad singlet).

IR (KBr) ν (cm ⁻¹ ): 2985, 1720, 1692, 1606, 1408, 1250, 1215, 1080, 990, 900, 861, 540.

Example 1

3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-4-hydroxy- [5H] -cyclopenta [c] pyridazine

A 1000 ml flask is equipped with a stirrer bar, a salt curl tube and an alkali trap. To this, 99.8 g of 4-chloro-5-cyclopentyloxy-2-fluorophenylglyoxylic acid obtained in Reference Example 4 and 122.0 ml of thionyl chloride were added thereto, and the mixture was stirred by heating at 60 ° C. for 2.5 hours. Thereafter, a distillation set is installed to raise the bath temperature to 110 ° C. to distill off unreacted thionyl chloride. Further 120 ml of benzene was added and distilled off with the remaining thionyl chloride, followed by drying under reduced pressure with a vacuum pump to obtain crude glyoxylic acid chloride.

A stirrer bar, salt curl tube and thermometer are installed in a 2000 ml four neck flask. 54.2 g of N- (1-cyclopenten-l-yl) -morpholine, 66.6 g of triethylamine, and 500 ml of methylene chloride were added thereto, followed by cooling to -5 DEG C under a nitrogen stream. The methylene chloride (200 mL) solution of the glyoxylic acid chloride adjusted first here is dripped slowly, maintaining solution temperature at 1 degrees C or less over 1 hour. Again, the reaction mixture is stirred at 1-10 ° C. for 1 hour. The reaction mixture was filtered to wash the residue (triethylamine hydrochloride) with 150 ml of methylene chloride. The filtrate was transferred to a 2000 ml flask, 19.8 g of hydrazine hydrate was added dropwise while 500 ml of 2-propanol was added and stirred, and the mixture was stirred at room temperature for 1 hour, and then left overnight. The reaction mixture is concentrated under reduced pressure and the residue is suspended with ethanol. The suspension solution is filtered, the residue is washed with ethanol and hexane and dried under reduced pressure to give 55.5 g of the title compound. The residue obtained by concentrating the filtrate under reduced pressure was once again suspended in ethanol, filtered in the same manner, washed, dried and further obtained 13.6 g of the title compound. Physical properties and NMR spectral data are as follows.

Melting point 300 ℃ or more

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.23 (1H, d, J = 6.3 Hz), 7.18 (1H, d, J = 9.6 Hz), 4.79 (1H, m), 3.05 (2H, t, J = 7.5 Hz), 2.96 (2H, t, J = 7.5 Hz), 2.17 (2H, qui, J = 7.5 Hz), 1.95-1.53 (8H, m).

IR (KBr) ν (cm ⁻¹ ): 3050, 2920, 1580, 1560, 1492, 1465, 1401, 1187.

Example 2

4-chloro-3- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

10 ml solution of 1.50 g of ethyl 2,2,2-trichloro-1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate obtained in Reference Example 2 0.42 g of triethylamine was slowly added dropwise to the mixture. 0.64 g of 1-morpholino-1-cyclopentene is added to the mixture and heated to reflux for 7 hours. After standing overnight, the mixture was extracted with ethyl acetate from the reaction mixture, washed sequentially with saturated aqueous ammonium chloride solution, saturated aqueous sodium bicarbonate and then with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane: ethyl acetate / 9: 1-3: 1) to afford 0.50 g of the title compound (Table 1, No. 18).

Example 3

4-chloro-3- (4-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

Methylene of 2.4 g of 4-chloro-3- (4-chloro-5-cyclopentyloxy-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine in 4 ml of 75% sulfuric acid 2 ml solution of chloride is slowly added dropwise. After stirring for 30 minutes at room temperature, the reaction mixture is added dropwise to crushed ice water and extracted with ethyl acetate. The aqueous layer is further neutralized with saturated sodium bicarbonate water and then extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is washed with a small amount of ethyl acetate and hexanes to give 1.68 g of the title compound (Table 1, No. 12) as crystals.

Example 4

Ethyl 2- [2-chloro-4-fluoro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) phenoxy] propionate

0.40 g of 4-chloro-3- (4-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine, 0.29 g of ethyl α-bromopropionate A mixture of 0.22 g of potassium carbonate and 5 ml of acetone was heated to reflux for 5 hours under stirring. The reaction solution was cooled to room temperature, saturated aqueous ammonia solution was added, and extracted with ethyl acetate. The organic phase is washed with saturated brine and dried over sodium sulfate. The crude product obtained by concentration under reduced pressure was purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to give 0.44 g of the title compound (Table 2, No. 54).

Example 5

4-chloro-3- [4-chloro-2-fluoro-5- (1-methyl-2-propynyloxy) phenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

0.61 g of 4-chloro-3- (4-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine and triphenylphosphine (TPP) 0.67 0.44 g of azodicarboxylic acid diethyl (DEAD) was slowly added dropwise to 5 ml of tetrahydrofuran solution of 0.21 g of 1-butene-3-ol. Then stir overnight at room temperature. The crude product obtained by concentration of the reaction solution under reduced pressure was purified by flash column chromatography (hexane-ethyl acetate / 3: 1), and the obtained crystals were washed with hot water to obtain 0.46 g of the title compound (Table 1, No. 24). To obtain.

Example 6

4-chloro-3- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

3- (4-Chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-4-hydroxy- [5H] -cyclopenta [c] pyridazine 1.45 obtained in Example 1. g and 3.00 g of toluene solution (10 ml) of phosphorus oxychloride are stirred at room temperature for 1 hour. The reaction mixture was added to ice-cold water (100 mL) and extracted with ethyl acetate. The organic phase obtained was washed with saturated sodium bicarbonate, saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product obtained is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 1.50 g of the title compound (Table 1, No. 18).

Example 7

4-bromo-3- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

3- (4-Chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-4-hydroxy- [5H] -cyclopenta [c] pyridazine 9.00 obtained in Example 1. g 30 ml solution of phosphorus tribromide is heated and stirred at 80 to 90 ° C. for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water, and extracted with chloroform. The organic layer obtained was washed with saturated sodium bicarbonate, followed by saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (developing solvent hexane: ethyl acetate / 3: 1-5: 2) to afford 3.00 g of the title compound.

Example 8

4-chloro-3- (4-chloro-5-nitro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

To 7.4 g of 4-chloro-3- (4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine, 35 ml of concentrated sulfuric acid was added and stirred while cooling to 7 ° C. To obtain a homogeneous system. An acid mixture (2.5 ml of concentrated sulfuric acid, 2.5 ml of 60% nitric acid) was slowly added dropwise to the mixture at 6 to 12 ° C for 10 minutes. The reaction mixture was developed in ice water (400 mL) and extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate and saturated brine in that order, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to give 5.12 g of the title compound (Table 1, No. 8).

Example 9

4-chloro-3- (5-amino-4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

A mixture of 6.0 g of iron, 6 ml of water and 1.5 ml of acetic acid is heated to reflux for 30 minutes. After cooling to room temperature add isopropanol (20 mL) and heat to 70 ° C. while 4-chloro-3- (4-chloro-2-fluoro-5-nitrophenyl) -6,7-dihydro-5H-cyclo 20 ml of a solution of 5.05 g of N-methylpyrrolidone (NMP) with penta [c] pyridazine are slowly added. Thereafter, the mixture was heated and stirred at 80 ° C. for 1.5 hours, cooled to room temperature, and an aqueous potassium carbonate solution (1.25 g of potassium carbonate and 10 ml of water) was added. The mixture is filtered through Celite and the residue is washed with ethyl acetate. The crude product obtained by concentrating the filtrate was extracted with ethyl acetate, and the organic layer was washed with saturated sodium bicarbonate and saturated brine in that order, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 4.59 g of the title compound (Table 1, No. 61).

Example 10

Ethyl N- [4-chloro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] carbamate

Pyridine solution of 1.50 g of 4-chloro-3- (5-amino-4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine and 0.57 g of ethyl chloroformate ( 15 ml) is stirred for 8 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed sequentially with 1N aqueous hydrochloric acid solution, saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 1.10 g of the title compound (Table 1, No. 63).

Example 11

Ethyl N- [4-chloro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] -N-propargylcarbamate

0.12 g of sodium hydride is washed with hexane and suspended in 5 ml of dimethylformamide after removing the oil. To the solution was added 10 g of ethyl N- [4-chloro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] carbamate. After stirring for 30 minutes at room temperature, 0.35 g of propargyl bromide was added and stirred for another 2 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with an aqueous saturated ammonium chloride solution, saturated sodium bicarbonate and saturated brine in that order, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 0.75 g of the title compound (Table 1, No. 68).

Example 12

N- [4-chloro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] propanesulfonamide

4-chloro-3- (5-amino-4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine 3.00 g, n-propanesulfonylchloride 2.10 g, pyridine 20 ml of 1.6 g methylene chloride solution is stirred for 7 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed sequentially with 1N aqueous hydrochloric acid solution, saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 2.95 g of the title compound (Table 1, No. 64).

Example 13

N- [5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -4-cyano-2-fluorophenyl] ethanesulfonamide

3.69 g of N- [4-bromo-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] ethanesulfonamide, cyanated 10 ml of 0.91 g of copper dimethylformamide solution was heated to reflux for 2.5 hours. After cooling to room temperature, an aqueous solution of iron chloride (3.5 g of FeCl ₃ , 4 ml of water) was added thereto, followed by further stirring at room temperature for 20 minutes. Water was added to the reaction mixture, followed by extraction three times with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 2: 1) to afford 0.32 g of the title compound (Table 1, No.86).

Example 14

4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-2-oxy- [5H] -cyclopenta [c] pyridazine

4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-1H-cyclopenta [c] pyridazine 1.12 g, m-chloroperbenzoic acid (mCPBA) 10 ml of 0.90 g chloroform solution is stirred at room temperature for 3 hours. 15 ml of saturated sodium bicarbonate water is added to terminate the reaction. The reaction mixture was extracted with ethyl acetate, and the organic layer obtained was washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product is purified by flash column chromatography (hexane-ethyl acetate / 1: 1) to afford 0.52 g of the title compound (Table 1, No.93).

Example 15

4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro- [5H] -cyclopenta [c] pyridazine hydrochloride

4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-1H-cyclopenta [c] pyridazine 0.60 g of a 5% hydrochloric acid methanol solution 2.00 g The solution is stirred for 3 hours at room temperature. The reaction mixture is concentrated under reduced pressure to filter the obtained crystals. The crystals are washed with hexane and dried to give 0.59 g (Table 1, No. 88).

The other compounds of Tables 1-5 can also be manufactured according to the method in any one of Examples 1-15. The structures of the obtained compounds are all confirmed by various spectra. Table 6 shows the physical and spectral data of the compounds described in Tables 1 to 5.

The following is a formulation example of the compound of the present invention. In addition, below "part" and "%" mean "weight part" and "weight%", respectively.

Formulation Example 1 Hydration

40 parts of the compound of the present invention shown in Tables 1 and 2, 20 parts of Cabrex # 80 (trade name, Shionogi Seiyaku Co., Ltd.), 35 parts of kaolin clay (trade name, Tsuchiya Kaolin Co., Ltd.), and a higher alcohol sulfate ester surfactant. After mixing 5 parts of sorbol 8070 (trade name, Tohogagaku Co., Ltd.), it is mixed and ground uniformly to obtain a hydrating agent containing 40% of the active ingredient.

Formulation Example 2 Emulsion

After dissolving 20 parts of the compounds of the present invention of the compounds described in Tables 1 to 5 in a mixed solvent consisting of 35 parts of xylene and 30 parts of N, N-dimethylformamide, sorbol 3005X (polyoxyethylene-based surfactant) was added thereto. 15 parts of Tohogagaku Co., Ltd. was added to obtain an emulsion containing 20% of the active ingredient.

Formulation Example 3 Fluidizing Agent

After mixing and dispersing 8 parts of ethylene glycol previously mixed with 30 parts of the compounds of the present invention shown in Tables 1 to 5, 5 parts of sorbol AC3020 (trade name, Tohogagaku Co.), 0.1 part of xanthan gum and 56.9 parts of water, This slurry-like mixture was wet pulverized with Dinomil (trade name, Synmal Enthaprise Co., Ltd.) to obtain a fluidizing agent containing 30% of the active ingredient.

Formulation Example 4 Granules

1 part of the compounds of the present invention shown in Tables 1 to 5, 43 parts of clay (manufactured by Nihon Talc Co., Ltd.), 55 parts of bentonite (manufactured by Toyoyo Yoko Co., Ltd.), and succinate-based surfactant eyrol CT-1 (trade name, Tohogagaku Corporation) ) 1 part is mixed, mixed and ground, and 20 parts of water is added to mix. Further, this was extruded from a hole having a diameter of 0.6 mm using an extrusion granulator, dried at 60 ° C. for 2 hours, and then cut into lengths of 1 to 2 mm to obtain granules containing 1% of the active ingredient.

The following is a test example of the compound of the present invention.

Test Example 1 Freshwater Soil Treatment Test

After filling and fertilizing non-impact loam into a pot made of a resin with an area of 200 cm 2, fertilize it by adding an appropriate amount of water, and then weed seeds of blood, spruce, knotweed and tadpoles within 0.5 cm from the soil surface. Mix. After that, water is obtained and a fresh water depth of 3.5 cm is maintained.

On the 5th day of weed sowing, the fluidizing agent containing the compound of the present invention obtained in Preparation Example 3 as an active ingredient was diluted and adjusted with water, and a predetermined amount was added dropwise to the fresh water surface so that the amount of the active ingredient used was 10 g per each.

After that, the cultivation management in the greenhouse is continued and the herbicidal effect is investigated 28 days after the treatment. The results are shown in Table 17 (compound numbers in Table 7 correspond to compound numbers in Tables 1 to 5). In addition, evaluation of the herbicidal effect is obtained by calculating the Y value by the equation (1) and expressed as a herbicidal effect coefficient according to the following criteria.

Test example 2 soil treatment test of the field soil

Filling the batter soil with volcanic ash in the batter with an area of 200 cm2, and fertilizing the soil, the soil surface was uniformly mixed with the weed seeds of bark, ragweed, white mallow (Japanese name) and large chickweed. The hydrous agent containing the compound of the present invention obtained in 1 as an active ingredient is diluted and adjusted with water, and a predetermined amount is uniformly sprayed onto the soil surface with a small power pressurized sprayer so that the amount of the active ingredient is 10 g per each are used.

After that, the cultivation management in the greenhouse is continued to investigate the herbicidal effect on the 28th day after the treatment. The results are shown in Table 8 (compound numbers in Table 8 correspond to compound numbers in Tables 1 to 5).

In addition, evaluation of the herbicidal effect is shown similarly to the criteria of Test Example 1.

Test Example 3 Field foliage treatment test

A batter made of a resin having an area of 200 cm 2 is filled with a field soil volcanic ash soil, and after application, sowing a western lampshade, round leaf morning glory, open cover, and gingiva grass is uniformly covered. After that, the cultivation management in the greenhouse is continued, and when the weed growth age of the weeds reaches 1.0 to 2.0 leaves, the amount of the active ingredient is adjusted by diluting and adjusting the hydrating agent containing the compound of the present invention obtained in Formulation Example 1 as the active ingredient. A predetermined amount is uniformly sprayed with a small power pressurized spray bottle so that it is 10 g per each ar. At 21 days after drug treatment, the herbicidal effect is investigated.

The results are shown in Table 9 (compound numbers in Table 9 correspond to compound numbers in Tables 1 to 5).

In addition, evaluation of the herbicidal effect is shown similarly to the criteria of Test Example 1.

The compound of the present invention exhibits high herbicidal effect with a small amount of use, has little problem such as weakness and is useful as a herbicide.

Claims (16)

3-substituted phenyl-4-halopyridazine derivatives of formula (I). In Formula I above, X is a halogen atom, Y is a hydrogen atom or a halogen atom, Z is a halogen atom or a cyano group, n and m are each independently 0 or 1, R ¹ is an alkyl group or a haloalkyl group of C ₁ -C ₆ a hydrogen atom, a halogen atom, a C ₁ -C _6, R ² is a hydrogen atom or an alkyl group of C ₁ -C ₆ , or a ring of -KLM- with R ¹ , wherein K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , oxygen atom, sulfur atom or C ₁ A nitrogen atom substituted with an alkyl group of -C ₆ , L is CR ⁸ R ⁹ , an oxygen atom, a sulfur atom or a nitrogen atom substituted with an alkyl group of C ₁ -C ₆ , and M is a CR ¹⁰ R ¹¹ , an oxygen atom, a sulfur atom or A nitrogen atom substituted with a C ₁ -C ₆ alkyl group (wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or a C ₁ -C ₆ alkyl group) provided that K, L and M are oxygen atoms at the same time, Not a sulfur atom or a nitrogen atom substituted with a C ₁ -C ₆ alkyl group; R ³ is a hydrogen atom, a nitro group or -QR ¹² {where Q is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or -NR ^13- (wherein R ¹³ is a hydrogen atom, an alkyl group of C ₁ -C ₆ , C ₂ -C ₆ alkenyl group, a halo-alkenyl group, an alkoxyalkyl group of C ₂ -C ₆ C ₂ -C ₆ alkynyl group, C ₁ -C ₆ haloalkyl group, C ₂ -C ₆ of, C ₂ -C ₆ of an acyl group, a alkoxycarbonyl group, phenyl group or phenyl C ₁ -C ₆ alkylsulfonyl group, a halo-C ₁ -C ₆ alkylsulfonyl group, C ₂ -C ₆ alkenyl sulfonyl group, C ₂ -C ₆ of the alkyl group substituted by a C ₁ -C _3), and, R ¹² is an alkynyl group of a hydrogen atom, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of, C ₃ -C ₈ a cycloalkyl group, a cycloalkyl group of C _4, C ₄ -C ₁₀ a (cycloalkyl) alkyl group, a cyclo alkenyl group of _{C 3 -C 8, C 1 -C} 10 alkyl group substituted with -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₃ -C ₈ halocycloalkyl group, C ₂ -C ₇ cyano Alkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₂ -C ₁₀ alkylthioalkyl group, C ₂ -C ₁₀ alkylsulfonylalkyl group, C ₂ -C ₆ acyl group, C ₃ -C ₆ oxoalkyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ haloalkylsulfonyl group, C ₂ -C ₆ alkenylsulfonyl group, phenyl group, C ₁ -C ₃ alkyl group substituted with phenyl group, 3- to 6 Heterocyclic groups of a member (wherein the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms), three to six membered heterocyclic groups (wherein the rings contain one or two oxygen atoms, sulfur atoms and / or nitrogen atoms) C ₁ -C ₃ alkyl group substituted with Group or formula of (II) Group of (III), wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom, a sulfur atom or -NR ^16- , wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ a), and, R ¹⁵ is a hydrogen atom, an alkynyl group, a cycloalkyl group of C ₃ -C ₆ of the C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ of, C ₄ -C ₁₀ A cycloalkyl group substituted with an alkyl group of C, a cycloalkenyl group of C ₃ -C ₆ , a haloalkyl group of C ₁ -C ₆ , a haloalkenyl group of C ₂ -C ₆ , a halocycloalkyl group of C ₃ -C ₆ , C _2- C ₅ cyanoalkyl group, C ₂ -C ₆ alkoxyalkyl group, C ₂ -C ₆ alkylthioalkyl group, C ₂ -C ₆ alkylsulfonylalkyl group, C ₃ -C ₆ oxoalkyl group, C ₃ -C ₇ acyloxyalkyl group, C ₃ -C ₇ alkoxycarbonylalkyl group, phenyl group, C ₁ -C ₃ alkyl group substituted with phenyl group, 3- to 6-membered heterocyclic group (the ring is 1 or 2 oxygen atoms, sulfur atom And / or contains nitrogen atoms) or from 3 to An alkyl group of C ₁ -C ₃ substituted with a six-membered heterocyclic group (wherein the ring contains one or two oxygen atoms, sulfur atoms and / or nitrogen atoms), and R ¹⁵ represents that W represents -NR ^16- Can form a 5 or 6 membered heterocyclic group containing 1 or 2 nitrogen atoms and / or 0 or 1 oxygen atom together with W], and R ¹² , R ¹³ or R ¹⁵ is a phenyl group, A C ₁ -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group (the ring contains one or two oxygen atoms, sulfur and / or nitrogen atoms) or a 3- to 6-membered heterocyclic group ( When the ring is a C ₁ -C ₃ alkyl group substituted with 1 or 2 oxygen atoms, sulfur atoms and / or nitrogen atoms), the phenyl group and heterocyclic group are 1 to 3 identical or different halogen atoms, C ₁ -C group with an alkyl group, a trifluoromethyl _4, an alkoxy group, an acyloxy group of C ₂ -C ₅ in the _{C 1 -C 4, C 1 -C} 4 Alkylthio group, the alkoxycarbonyl may be substituted}, of C ₁ -C ₄ alkylsulfonyl group, a nitro group, a cyano group or a C ₂ -C _5. The method of claim 1, wherein, R ¹ is a haloalkyl group of a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C _6, R ² is with a hydrogen atom, an alkyl group, or R ¹ a C ₁ -C ₆ - Ring of KLM-, wherein K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , an oxygen atom, a sulfur atom or a nitrogen atom substituted with an alkyl group of C ₁ -C ₆ , and L is CR ⁸ R ⁹ , oxygen Is a nitrogen atom substituted with an atom, a sulfur atom or an alkyl group of C ₁ -C ₆ , and M is a CR atom substituted with CR ¹⁰ R ¹¹ , an oxygen atom, a sulfur atom or an alkyl group of C ₁ -C ₆ (wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₆ ), provided that K, L and M are not oxygen atoms, sulfur atoms or nitrogen atoms substituted with C ₁ -C ₆ alkyl groups at the same time. 3-Substituted Phenyl-4-halopyridazine Derivatives of Formula (I). The compound of claim 1, wherein R ² is a ring of —KLM— with R ¹ , wherein K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ or an oxygen atom, and L is CR ⁸ R ⁹ or an oxygen atom. And M is CR ¹⁰ R ¹¹ or an oxygen atom (wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₆ ), provided that K, L and M are oxygen atoms at the same time 3-substituted phenyl-4-halopyridazine derivative of formula (I). 2. The carbon ring of claim 1, wherein R ² together with R ¹ is a carbon ring of —KLM—, wherein K is CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ , L is CR ⁸ R ⁹ , and M is CR ¹⁰ R ¹¹ , wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₆ . Chopped derivatives. The compound of claim 1, wherein R ³ is a hydrogen atom, a nitro group or —QR ¹² {wherein Q is an oxygen atom or —NR ¹³ —, where R ¹³ is a hydrogen atom, an acyl group of C ₂ -C ₆ , C ₁ alkylsulfonyl group, or a -C alkoxycarbonyl group of C ₂ -C ₆ of _6), and, R ¹² is a hydrogen atom, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of the Alkynyl group, C ₃ -C ₈ cycloalkyl group, C ₃ -C ₈ cycloalkenyl group, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₁₀ halocycloalkyl group , C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₃ alkyl group substituted with phenyl group , C ₁ -substituted with 3 to 6 membered heterocyclic groups (wherein the ring contains 1 or 2 oxygen atoms), with 3 to 6 membered heterocyclic groups (the ring contains 1 or 2 oxygen atoms) Alkyl group of C ₃ Group or formula of (II) Group of (III) wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom or -NR ^16- (wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ ) Wherein R ¹⁵ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ]. 3 -substituted phenyl-4-halopyridazine derivatives of formula (I). The compound of claim 1, wherein R ³ is a hydrogen atom, a nitro group or —QR ¹² {wherein Q is an oxygen atom or —NR ¹³ —, where R ¹³ is a hydrogen atom, an alkylsulfonyl group of C ₁ -C ₆ or C ₂ -C ₆ alkoxycarbonyl group), R ¹² is a hydrogen atom, C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₃ -C ₈ Cycloalkyl group, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₃ alkyl group substituted with a phenyl group, 3- to 6-membered heterocyclic group (the ring contains 1 or 2 oxygen atoms), 3- to 6-membered An alkyl group of C ₁ -C ₃ substituted with a heterocyclic group, wherein the ring contains one or two oxygen atoms, Group or formula of (II) Group of (III), wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom or -NR ^16- (where R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ ) Wherein R ¹⁵ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ]. 3 -substituted phenyl-4-halopyridazine derivatives of formula (I). The method of claim 1, wherein, R ³ is -QR ¹² [wherein, Q is an oxygen atom, R ¹² is an alkynyl group of the alkenyl group, C ₂ -C ₁₀ in C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ a, C ₃ -C ₈ cycloalkyl group, C ₁ -C ₁₀ haloalkyl group, C ₂ -C ₁₀ haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C _3- A C ₆ oxoalkyl group, a 3-6 membered heterocyclic group (the ring contains one or two oxygen atoms), a 3-6 membered heterocyclic group (the ring contains one or two oxygen atoms) Substituted C ₁ -C ₃ alkyl group or formula 3-substituted phenyl-4-halopyridazine derivative of formula (I). 2. The carbon ring of claim 1, wherein R ² together with R ¹ is a carbon ring of —KLM—, wherein K is CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ , L is CR ⁸ R ⁹ , and M is CR ¹⁰ R ¹¹ , wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₆ . R ³ is a hydrogen atom, a nitro group or -QR ¹² {wherein Q is an oxygen atom or -NR ^13- (wherein R ¹³ is a hydrogen atom, an alkylsulfonyl group of C ₁ -C ₆ or an alkoxy of C ₂ -C ₆ a carbonyl group), and, R ¹² is a hydrogen atom, an alkynyl group, a cycloalkyl group of C ₃ -C ₈ of the C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of, C ₁ - Haloalkyl group of C ₁₀ , haloalkenyl group of C ₂ -C ₁₀ , cyanoalkyl group of C ₂ -C ₇ , alkoxyalkyl group of C ₂ -C ₁₀ , oxoalkyl group of C ₃ -C ₆ , C ₁ -C ₆ Alkylsulfonyl group, C ₁ -C ₃ alkyl group substituted with phenyl group, 3- to 6-membered heterocyclic group (the ring contains 1 or 2 oxygen atoms), 3- to 6-membered heterocyclic group (wherein the ring is 1 Or a C ₁ -C ₃ alkyl group substituted with one of two oxygen atoms, Group or formula of (II) Group of (III) wherein R ¹⁴ is a hydrogen atom or an alkyl group of C ₁ -C ₄ , W is an oxygen atom or -NR ^16- (wherein R ¹⁶ is a hydrogen atom or an alkyl group of C ₁ -C ₄ ) Wherein R ¹⁵ is a hydrogen atom or an alkyl group of C ₁ -C ₆ ]. 3 -substituted phenyl-4-halopyridazine derivatives of formula (I). The compound of claim 1, wherein R ² is a ring of —KLM— with R ¹ , wherein K is CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ , L is CR ⁸ R ⁹ , and M is CR ^10. R ¹¹ (wherein the substituents R ⁴ to R ¹¹ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₆ ), and R ³ is —QR ¹² , wherein Q is an oxygen atom, and R ¹² is an alkyl group of C ₁ -C _10, C ₂ -C ₁₀ alkenyl group, an alkynyl group, a haloalkyl group of C ₃ -C ₈ cycloalkyl group, C ₁ -C ₁₀ of the _{C 2 -C 10, C 2 -C} 10 Haloalkenyl group, C ₂ -C ₇ cyanoalkyl group, C ₂ -C ₁₀ alkoxyalkyl group, C ₃ -C ₆ oxoalkyl group, 3- to 6-membered heterocyclic group (the ring being 1 or 2 oxygen atoms Or a C ₁ -C ₃ alkyl group substituted with a 3- to 6-membered heterocyclic group (wherein the ring contains 1 or 2 oxygen atoms) 3-substituted phenyl-4-halopyridazine derivative of formula (I). 10. The 3-substituted phenyl-4-halopyridazine derivative of formula I according to any one of claims 1 to 9, wherein Y is a halogen atom. 3-substituted phenyl-4-hydroxypyridazine derivatives of formula V or 3-substituted phenylpyridazin-4-one derivatives of formula V '. Formula V Formula V ' In the above formulas V and V ', Y, Z, R ¹ , R ² and R ³ are as defined in claim 1. 3-substituted phenyl-4-hydroxypyridazine derivatives of formula VI or 3-substituted phenylpyridazin-4-one derivatives of formula VI '. Formula VI Formula VI ' In the above formulas VI and VI ', k is 1 to 2, R ³ is a hydrogen atom, a nitro group or -QR ¹² where Q is an oxygen atom or -NR ^13- (wherein R ¹³ is a hydrogen atom, an alkylsulfonyl group of C ₁ -C ₆ or alkoxy of C ₂ -C ₆ a carbonyl group), and, R ¹² is a hydrogen atom, an alkynyl group, a cycloalkyl group of C ₃ -C ₈ of the C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ of, C ₁ - Haloalkyl group of C ₁₀ , haloalkenyl group of C ₂ -C ₁₀ , cyanoalkyl group of C ₂ -C ₇ , alkoxyalkyl group of C ₂ -C ₁₀ , oxoalkyl group of C ₃ -C ₆ , C ₁ -C ₆ An alkylsulfonyl group, a C ₁ -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group (wherein the ring contains 1 or 2 oxygen atoms) or a 3-6 membered heterocyclic group (wherein the ring is 1 Or a C ₁ -C ₃ alkyl group substituted with two oxygen atoms. 13. The 3-substituted phenyl-4-hydroxypyridazine derivative or the 3-substituted phenylpyridazin-4-one derivative according to claim 11 or 12, wherein Y is a halogen atom. A pesticide comprising the 3-substituted phenyl-4-halopyridazine derivative according to any one of claims 1 to 10 as an active ingredient. 15. The pesticide of claim 14, which is a herbicide. The pesticide of Claim 14 which is a herbicide for water use.