JPH10182579A - Carboxylic acid ester derivative, production thereof and production of pyridazine-3-one derivative using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as an intermediate compound for a pyridazine-3-one derivative having an excellent hermicide activity. SOLUTION: This carboxylic acid ester derivative is a compound expressed by formula I [R is a 1-6C alkyl; R<2> , R<3> are each H or a 1-3C alkyl; Q is a (substituted) phenyl]. The compound of the formula I is obtained by reacting e.g. a hydrazone compound expressed by formula II with a malonic acid monoester derivative expressed by formula III in a secondary amine (a cyclic amine such as piperidine, morpholine and pyrrolidine or a dialkylamine such as diethylamine and isopropylamine) and pyridine and/or quinoline, preferably at 6-100 deg.C for 1-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a carboxylic ester derivative, a method for producing the same, and pyridazine-3 using the same.
A method for producing an -one derivative.

[Problems to be Solved by the Invention] Formula 8

Embedded image Have excellent herbicidal activity, and it has been desired to develop an advantageous production method of these pyridazin-3-one derivatives.

Means for Solving the Problems The present inventors have conducted intensive studies to find an advantageous method for producing the pyridazin-3-one derivative.

Embedded image [Wherein, R represents a C1-C6 alkyl group, R ² represents a hydrogen atom or a C1-C3 alkyl group, R ³ represents a hydrogen atom or a C1-C3 alkyl group, Q is optionally substituted Represents a phenyl group. The carboxylic acid ester derivative represented by the above formula is a pyridazine-
The present invention was found to be an important intermediate because it can be led to a 3-one derivative or the like, and the present invention has been accomplished. That is, the present invention relates to a compound represented by the general formula (hereinafter, referred to as the present compound), a method for producing the compound of the present invention, and a compound represented by the general formula:

Embedded image [Wherein, Q, R ² and R ³ represent the same meaning as described above. And a method for producing a pyridazin-3-one derivative represented by the formula: Here, the optionally substituted phenyl group represented by Q includes, for example, Q-1, Q-2, Q-3, Q-4 or Q-5 groups represented by the following general formula (11). can give.

Embedded image[Wherein, X represents a hydrogen atom or a halogen atom, and Y represents
Halogen, nitro, cyano or trifluoro
Z represents a methyl group¹And Z^TwoIs an oxygen atom or
Represents a sulfur atom; n represents 0 or 1;^FourIs hydrogen
An atom or a C1-C3 alkyl group,^FiveIs C1-
C6 alkyl group, C1-C6 haloalkyl group, (C3-
C8 cycloalkyl) C1-C6 alkyl group, C3-C
6 alkenyl group, C3-C6 haloalkenyl group, C3-
C6 alkynyl group, C3-C6 haloalkynyl group, shea
C1-C6 alkyl group, (C1-C4 alkoxy) C
1-C4 alkyl group, (C1-C3 alkoxy) (C1
-C3 alkoxy) C1-C3 alkyl group, carboxy
C1-C6 alkyl group, (C1-C6 alkoxy) carb
Bonyl C1-C6 alkyl group, {(C1-C4 alkoxy)
B) C1-C4 alkoxy @ carbonyl C1-C6 al
Kill group, (C3-C8 cycloalkoxy) carbonyl C
1-C6 alkyl group, -CH_TwoCON (R¹²) R¹³Group,
-CH_TwoCOON (R¹²) R¹³Group, -CH (C1-C4
Alkyl) CON (R¹²) R¹³Group, -CH (C1-C4
Alkyl) COON (R¹²) R¹³Group (where R¹²And
And R¹³Are each independently a hydrogen atom, a C1-C6 alkyl
Group, C3-C8 cycloalkyl group, C1-C6 haloa
Alkyl group, C3-C6 alkenyl group, C3-C6 alkyl
Nyl group, cyano C1-C6 alkyl group, (C1-C4
Alkoxy) C1-C4 alkyl group, (C1-C4 alkyl)
Ruthio) C1-C4 alkyl group, carboxy C1-C6
Alkyl group, (C1-C6 alkoxy) carbonyl C1
-C6 alkyl group, (C3-C8 cycloalkoxy) ca
Rubonyl C1-C6 alkyl group, (C1-C6 alkyl
Ru) carbonyloxy C2-C6 alkyl group, (C1-
C6 alkyl) carbonylamino C2-C6 alkyl
Group, hydroxy C2-C6 alkyl group, substituted
A benzyl group, an optionally substituted phenyl group,
Or {(C1-C4 alkoxy) C1-C4 alkyl}
Represents a carbonyl C1-C6 alkyl;
¹²And R ¹³And trimethylene, tetramethylene, pentame
Tylene, ethyleneoxyethylene or ethylenethioe
Represents styrene. ), (C1-C4 alkylthio) C1-
C4 alkyl group or hydroxy C1-C6 alkyl group
And R⁶Is a C1-C6 alkyl group, a C1-C6 halo
Alkyl group, cyano group, carboxyl group, hydroxy C
1-C6 alkyl group, (C1-C6 alkoxy) C1-
C6 alkyl group, (C1-C6 alkoxy) (C1-C
6 alkoxy) C1-C6 alkyl group, (C1-C6
Alkyl) carbonyloxy C1-C6 alkyl group, (C
1-C6 haloalkyl) carbonyloxy C1-C6
Alkyl group or (C1-C6 alkoxy) carbonyl group
And R⁷Represents a hydrogen atom or a C1-C6 alkyl group
Represents, R⁸Is a C1-C6 alkyl group, a C1-C6 haloa
Alkyl group, hydroxy C1-C6 alkyl group, (C1-
(C4 alkoxy) C1-C4 alkyl group, (C1-C3
Alkoxy) (C1-C3 alkoxy) C1-C3Al
A kill group, (C1-C6 alkyl) carbonyloxy C1
-C6 alkyl group, (C1-C6 haloalkyl) carbo
Nil C1-C6 alkyl group, carboxy group, carboxy
C1-C6 alkyl group, (C1-C8 alkoxy) cal
Bonyl group, (C1-C6 haloalkoxy) carbonyl
Group, (C3-C10 cycloalkoxy) carbonyl group,
(C3-C8 alkenyloxy) carbonyl group, (C3
—C8 alkynyloxy) carbonyl group, (C1-C6)
Alkyl) aminocarbonyl group, di (C1-C6 alkyl)
Ru) aminocarbonyl group, (C1-C6 alkyl) amido
A noncarbonyloxy C1-C6 alkyl group or di (C
1-C6 alkyl) aminocarbonyloxy C1-C6
B represents a hydrogen atom, a halogen atom,
Toro, cyano, chlorosulfonyl, OR¹Group, S
R¹Group, SO_TwoOR^{twenty one}Group, COOR^{twenty two}Group, CR^{twenty three}= CR^{twenty four}
COOR^{twenty five}Group or CH_TwoCHWCOOR^{twenty five}Represents a group
You. {Where W is hydrogen atom, chlorine atom or bromine atom
Represents a child, R¹Is a hydrogen atom, a C1-C6 alkyl group, C
1-C6 haloalkyl group, C3-C8 cycloalkyl
Group, benzyl group, C3-C6 alkenyl group, C3-C6
Haloalkenyl group, C3-C6 alkynyl group, C3-C
6 haloalkynyl group, cyano C1-C6 alkyl group,
(C1-C4 alkoxy) C1-C4 alkyl, (C
1-C4 alkylthio) C1-C4 alkyl group, carbo
Xy C1-C6 alkyl group, (C1-C8 alkoxy)
Carbonyl C1-C6 alkyl group, (C1-C6 haloa
Alkoxy) carbonyl C1-C6 alkyl group, ｛(C1
—C4 alkoxy) C1-C4 alkoxy @ carbonyl
C1-C6 alkyl group, (C3-C8 cycloalkoxy
(C) carbonyl C1-C6 alkyl group, (C3-C8
Chloroalkyl) (C1-C6 alkoxycarbonyl) C
1-C6 alkyl group, -CH_TwoCOON (R¹²) R
¹³Group, -CH (C1-C4 alkyl) COON (R¹²)
R¹³Group, -CH_TwoCON (R¹²) R¹³Group, -CH (C1
—C4 alkyl) CON (R¹²) R¹³Group (where R¹²
And R¹³Has the same meaning as described above. ), (C2-C6 Al
(Cenyl) oxycarbonyl C1-C6 alkyl group, (C
3-C6 haloalkenyl) oxycarbonyl C1-C6
Alkyl group, (C3-C6 alkynyl) oxycarbonyl
C1-C6 alkyl group, (C3-C6 haloalkini)
L) oxycarbonyl C1-C6 alkyl group, (C1-
C6 alkylthio) carbonyl C1-C6 alkyl group,
(C1-C6 haloalkylthio) carbonyl C1-C6
Alkyl group, (C3-C6 alkenylthio) carbonyl
C1-C6 alkyl group, (C3-C6 haloalkenylthio)
E) carbonyl C1-C6 alkyl group, (C3-C6
Rukinylthio) carbonyl C1-C6 alkyl group, (C
3-C6 haloalkynylthio) carbonyl C1-C6
Alkyl group, (C3-C8 cycloalkylthio) carboni
C1-C6 alkyl group, (C3-C8 cyclohaloal
(Cithio) carbonyl C1-C6 alkyl group, ((C3
-C8 cycloalkyl) C1-C6 alkylthio) cal
Bonyl C1-C6 alkyl group, di (C1-C6 alkyl
C) C = NO carbonyl C1-C6 alkyl group, (substituted
Optionally substituted benzylthio) carbonyl C1-C6
Alkyl group, (optionally substituted phenylthio) ca
Rubornyl C1-C6 alkyl group, hydroxy (C2-C
6 alkoxy) carbonyl C1-C6 alkyl group, (C
1-C6 alkyl) carbonyloxy (C2-C6 alkyl
(Coxy) carbonyl C1-C6 alkyl group, (C1-C
6-alkyl) carbonylamino (C2-C6 alkoxy)
B) a carbonyl C1-C6 alkyl group, ｛(C1-C6
Alkoxy) carbonyl C1-C6 alkyl @ oxyca
Rubonyl C1-C6 alkyl group, hydroxy C1-C6
Alkyl group, C1-C6 alkoxycarbonyl group, C1
-C6 haloalkoxycarbonyl group, C3-C8 cyclo
Alkoxycarbonyl group, C3-C6 alkenyloxy
Carbonyl group, benzyloxycarbonyl group, C1-C
6 alkylcarbonyl groups, optionally substituted benzyl
Roxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted phenoxycarbonyl C1-C6 alkyl
Group, optionally substituted furyloxycarbonyl C1
-C6 alkyl group, optionally substituted furyl C1-
A C6 alkyloxycarbonyl C1-C6 alkyl group,
Optionally substituted thienyloxycarbonyl C1-
C6 alkyl group, optionally substituted thienyl (C1
-C6 alkyl) oxycarbonyl C1-C6 alkyl
Group, optionally substituted pyrrolyloxycarbonyl C
1-C6 alkyl group, optionally substituted pyrrolyl
Xy (C1-C6 alkyl) oxycarbonyl C1-C
6-alkyl group, imidazoyl oxo which may be substituted
Cicarbonyl C1-C6 alkyl group, even when substituted
Good imidazoyl (C1-C6 alkyl) oxycarbo
Nyl C1-C6 alkyl group, optionally substituted pyra
Zoyloxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted pyrazoyl (C1-C6 alkyl) oxo
Cicarbonyl C1-C6 alkyl group, even when substituted
Good thiazoyloxycarbonyl C1-C6 alkyl
Group, optionally substituted thiazoyl (C1-C6 alkyl
Kill) oxycarbonyl C1-C6 alkyl group, substituted
Oxazoyloxycarbonyl C1-C optionally
6 alkyl groups, optionally substituted oxazoyl (C
1-C6 alkyl) oxycarbonyl C1-C6 alkyl
Group, optionally substituted isothiazoyloxycarbyl
A bonyl C1-C6 alkyl group, an optionally substituted
Sothiazoyl (C1-C6 alkyl) oxycarbonyl
C1-C6 alkyl group, optionally substituted isoxa
Zoyloxycarbonyl C1-C6 alkyl group, substituted
Isoxazoyl (C1-C6 alkyl) optionally
Oxycarbonyl C1-C6 alkyl group, substituted
Pyridyloxycarbonyl C1-C6 alkyl
Group, optionally substituted pyridyl (C1-C6 alkyl
G) an oxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted pyrazinyloxycarbonyl C1-C6
Alkyl group, optionally substituted pyrazinyl (C1-C
6 alkyl) oxycarbonyl C1-C6 alkyl group,
Optionally substituted pyrimidinyloxycarbonyl C
1-C6 alkyl group, optionally substituted pyrimidini
(C1-C6 alkyl) oxycarbonyl C1-C6
Alkyl group, optionally substituted pyridazinyloxy
Carbonyl C1-C6 alkyl group, which may be substituted
Pyridazinyl (C1-C6 alkyl) oxycarboni
C1-C6 alkyl group, optionally substituted India
Lysinyloxycarbonyl C1-C6 alkyl group, substituted
Indolidinyl (C1-C6 alkyl)
G) an oxycarbonyl C1-C6 alkyl group, substituted
Indolyloxycarbonyl C1-C6
Alkyl group, optionally substituted indolyl (C1-C
6 alkyl) oxycarbonyl C1-C6 alkyl group,
Optionally substituted indazolyloxycarbonyl C
1-C6 alkyl group, optionally substituted indazoly
(C1-C6 alkyl) oxycarbonyl C1-C6
Alkyl group, quinolyloxycarb optionally substituted
A bonyl C1-C6 alkyl group, an optionally substituted
Noryl (C1-C6 alkyl) oxycarbonyl C1-
C6 alkyl group, optionally substituted isoquinolylo
An oxycarbonyl C1-C6 alkyl group, or substituted
Optionally substituted isoquinolyl (C1-C6 alkyl) oxo
Represents a C 1 -C 6 alkyl group or a general formula
Formula 12

Embedded image {Wherein, R ¹⁴ represents a C1-C5 alkyl group, R ¹⁵ represents a hydrogen atom, a hydroxyl group or a group represented by —O—COR ¹⁶ (R ¹⁶ represents a C1-C6 alkyl group, a C1-C6 haloalkyl group , A C3-C6 alkenyl group, a C3-C8 cycloalkyl group, an optionally substituted phenyl group, an optionally substituted benzyl group, or a C1-C6 alkoxy group.) } Or a group represented by the general formula

Embedded image Wherein R ¹⁷ is a hydrogen atom, a halogen atom or C1-C
6 represents an alkyl group, and R ¹⁸ represents a C3-C8 cycloalkyl group, a benzyl group, a C2-C8 having an epoxy group on a carbon chain.
10 alkyl groups, (C3-C8 cycloalkyl) C1-
C6 alkyl group, (C3-C8 cycloalkyl) C2-
A C6 alkenyl group wherein the same carbon atom is OR ¹⁹ and OR
C1-C6 alkyl group substituted with ^20, the same C2-C6 alkenyl group in which the carbon atom is substituted with OR ¹⁹ and OR ^20, C1-C6 alkyl group in which the same carbon atom is substituted with SR ¹⁹ and SR ²⁰ , the same C2-C6 alkenyl group in which the carbon atom is substituted with SR ¹⁹ and SR ²⁰ (wherein each of R ¹⁹ and R ²⁰ are independently C1-C6 alkyl group, or represents a C1-C6 haloalkyl radical, R ¹⁹ and R ²⁰ may be ethylene optionally substituted with a halogen atom, trimethylene optionally substituted with a halogen atom, tetramethylene optionally substituted with a halogen atom, optionally substituted with a halogen atom Pentamethylene or ethyleneoxyethylene which may be substituted with a halogen atom.), A carboxy C2-C6 alkenyl group, (C1-C8 alkyl Carboxylate) carbonyl C2-C6 alkenyl group, (C1-C8 haloalkoxy) carbonyl C2-C6 alkenyl group, {(C1-C4 alkoxy)
Represents a C1-C4 alkoxy @ carbonyl C2-C6 alkenyl group or a (C3-C8 cycloalkoxy) carbonyl C2-C6 alkenyl group. R ²¹ represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6
R ²² represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a benzyl group, a C3-C6 alkenyl group, a C3-C6 alkenyl group, −
C6 haloalkenyl group, C3-C6 alkynyl group, C3
-C6 haloalkynyl group, cyano C1-C6 alkyl group, (C1-C4 alkoxy) C1-C4 alkyl group,
(C1-C4 alkylthio) C1-C4 alkyl group, carboxy C1-C6 alkyl group, (C1-C8 alkoxy) carbonyl C1-C6 alkyl group, (C1-C6 haloalkoxy) carbonyl C1-C6 alkyl group,
{(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C1-C6 alkyl group, (C3-C8 cycloalkoxy) carbonyl C1-C6 alkyl group, (C1-
C6 alkyl) carbonyl C1-C6 alkyl group, (C
1-C6 haloalkyl) carbonyl C1-C6 alkyl group, {(C1-C4 alkoxy) C1-C4 alkyl} carbonyl C1-C6 alkyl group, (C3-C8 cycloalkyl) carbonyl C1-C6 alkyl group, -CH ₂ C
OON (R ²⁶⁾ R ²⁷ group, -CH (C1-C4 alkyl)
COON (R ²⁶⁾ R ^{27 _{group, -CH 2 CON (R 26)}} R 27
Group, -CH (C1-C4 alkyl) CON (R ²⁶⁾ R ²⁷
Groups (where R ²⁶ and R ²⁷ are each independently a hydrogen atom,
C1-C6 alkyl group, C1-C6 haloalkyl group, C
3-C6 alkenyl group, C3-C6 alkynyl group, cyano C1-C6 alkyl group, (C1-C4 alkoxy) C
1-C4 alkyl group, (C1-C4 alkylthio) C1
-C4 alkyl group, carboxy C1-C6 alkyl group,
(C1-C6 alkoxy) carbonyl C1-C6 alkyl group, (C3-C8 cycloalkoxy) carbonyl C1
-C6 alkyl group or ｛(C1-C4 alkoxy)
C1-C4 alkyl} carbonyl C1-C6 or represents alkyl, or tetramethylene between R ²⁶ and R ^27, represent a pentamethylene or ethyleneoxyethylene. ), {(C1-C6 alkoxy) carbonyl C1-
C6 alkyl} oxycarbonyl represents a C1-C6 alkyl group or a hydroxy C1-C6 alkyl group,
²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or a C1-C6 alkyl group, and R ²⁵ represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group or Represents a C3-C6 alkenyl group. }]

[0002]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the present invention, the halogen atoms represented by X and Y are a fluorine atom, a chlorine atom,
A bromine atom or an iodine atom, and C1 represented by R
The -C6 alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like, R ²
And a C1-C3 alkyl group represented by R ³ includes:
Methyl group, ethyl group and the like, C1 represented by R ¹
-C6 alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t
-Butyl group (where "t" represents [tertiary]:
The same), an amyl group, an isoamyl group, a t-amyl group, and the like. Examples of the C1-C6 haloalkyl group include a 2-chloroethyl group, a 2-bromoethyl group, a 2,2,2-trifluoroethyl group, and the like. , C3-C8 cycloalkyl groups include a cyclopropyl group, a cyclobutyl group,
A cyclopentyl group and a cyclohexyl group;
Examples of the 3-C6 alkenyl group include an allyl group, a 1-methyl-2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, and a 2-methyl-3-butenyl group. Examples of the C3-C6 haloalkenyl group include a 2-chloro-2-propenyl group and a 3,3-dichloro-2-propenyl group. Examples of the C3-C6 alkynyl group include a propargyl group and 1- Methyl-2
-Propynyl group, 2-butynyl group, 1,1-dimethyl-
A 2-propynyl group and the like; a C3-C6 haloalkynyl group and the like; a 3-bromopropargyl group and the like; a cyano C1-C6 alkynyl group and the like; a cyanomethyl group and the like; a C1-C4 alkoxy C1- C4
Examples of the alkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. Examples of the (C1-C4 alkylthio) C1-C4 alkyl group include a methylthiomethyl group and a methylthioethyl group. And carboxy C1-C6 alkyl groups include carboxymethyl group, 1-carboxyethyl group, 2
-Carboxyethyl group and the like, and (C1-C8 alkoxy) carbonyl C1-C6 alkyl group includes methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, butoxycarbonylmethyl group, Isobutoxycarbonylmethyl group, t-butoxycarbonylmethyl group, amyloxycarbonylmethyl group, isoamyloxycarbonylmethyl group, t-amyloxycarbonylmethyl group, 1-methoxycarbonylethyl group, 1-
Ethoxycarbonylethyl group, 1-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group,
1-butoxycarbonylethyl group, 1-isobutoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, 1-amyloxycarbonylethyl group, 1-isoamyloxycarbonylethyl group, 1-t-butoxycarbonylethyl group, 1 -Amyloxycarbonylethyl group, 1-isoamyloxycarbonylethyl group, 1-t
-Amyloxycarbonylethyl group and the like;
{(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C1-C6 alkyl groups include methoxymethoxycarbonylmethyl, methoxyethoxycarbonylmethyl, 1-methoxyethoxycarbonylethyl, and the like. Examples of the alkoxy) carbonyl C1-C6 alkyl group include a cyclobutyloxycarbonylmethyl group, a cyclopentyloxycarbonylmethyl group, a cyclohexyloxycarbonylmethyl group,
A 1-cyclobutyloxycarbonylethyl group, a 1-cyclopentyloxycarbonylethyl group, a 1-cyclohexyloxycarbonylethyl group, and the like;
Examples of the 6 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an isopropoxycarbonyl group, an isobutoxycarbonyl group, a t-butoxycarbonyl group, and the like, and a C1-C6 haloalkoxycarbonyl group. Examples thereof include a 2,2,2-trichloroethylcarbonyl group, and examples of the C3-C8 cycloalkoxycarbonyl group include a cyclopropyloxycarbonyl group and a cyclobutyloxycarbonyl group.
Examples of the 3-C6 alkenyloxycarbonyl group include an allyloxycarbonyl group and the like, and {(C1-C6 alkoxy) carbonyl C1-C6 alkyl} oxycarbonyl C1-C6 alkyl group includes a (methoxycarbonyl) methoxycarbonylmethyl group , (Ethoxycarbonyl) methoxycarbonylmethyl group and the like.
The C1-C6 alkyl group represented by ¹² and R ^13, a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, as the C1-C3 alkyl group represented by R ^4, such as methyl group and the like , C1- represented by R ⁵
Examples of the C6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a butyl group, and an isoamyl group. As the C1-C6 haloalkyl group, a 2-chloroethyl group, a 2-bromoethyl group, −
A chlorobutyl group, a 3-bromobutyl group, a difluoromethyl group and the like, and (C3-C8 cycloalkyl) C1
Examples of the -C6 alkyl group include a cyclopentylmethyl group, and examples of the C3-C6 alkenyl group include an allyl group, a 1-methyl-2-propenyl group, a 3-butenyl group,
Examples thereof include a 2-butenyl group, a 3-methyl-2-butenyl group, and a 2-methyl-3-butenyl group. Examples of the C3-C6 haloalkenyl group include a 2-chloro-2-propenyl group,
3,3-dichloro-2-propenyl group and the like;
As the 3-C6 alkynyl group, a propargyl group, 1-
A methyl-2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 1,1-dimethyl-2-propynyl group, and the like; and a C3-C6 haloalkynyl group includes 3-yo-
De-2-propynyl group, 3-bromo-2-propynyl group and the like. Examples of the cyano C1-C6 alkyl group include:
And a C1-C4 alkoxy C group.
Examples of the 1-C4 alkyl group include a methoxymethyl group,
Examples of the carboxy C1-C6 alkyl group include a carboxymethyl group, a 1-carboxyethyl group, and a 2-carboxyethyl group, and a (C1-C6 alkoxy) carbonyl C1- Examples of the C6 alkyl group include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, a butoxycarbonylmethyl group, an isobutoxycarbonylmethyl group, a t-butoxycarbonylmethyl group, and an amyloxycarbonylmethyl group. An isoamyloxycarbonylmethyl group, a t-amyloxycarbonylmethyl group,
1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-propoxycarbonylethyl group, 1
-Isopropoxycarbonylethyl group, 1-butoxycarbonylethyl group, 1-isobutoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, 1-amyloxycarbonylethyl group, 1-isoamyloxycarbonylethyl group, 1-t -Butoxycarbonylethyl group and the like, and {(C1-C4 alkoxy) C1-C4
Examples of the alkoxy @ carbonyl C1-C6 alkyl group include a methoxyethoxycarbonylmethyl group, a 1-methoxymethoxycarbonylethyl group, and the like.
As a C8 cycloalkoxy) carbonyl C1-C6 alkyl group, a cyclobutyloxycarbonylmethyl group,
A cyclopentyloxycarbonylmethyl group, a cyclohexyloxycarbonylmethyl group, a 1-cyclobutyloxycarbonylethyl group, a 1-cyclopentyloxycarbonylethyl group, a 1-cyclohexyloxycarbonylethyl group, and the like; and the hydroxy C1-C6 alkyl group includes hydroxy. Methyl group, hydroxyethyl group,
A hydroxypropyl group and the like, represented by R ⁶ ;
Examples of the C1-C6 alkyl group include a methyl group and an ethyl group. Examples of the C1-C6 haloalkyl group include a bromomethyl group, a dibromomethyl group, a tribromomethyl group,
Bromoethyl group, chloromethyl group, dichloromethyl group,
Trichloromethyl group and the like, and hydroxy C1-C
Examples of the 6 alkyl group include a hydroxymethyl group, and examples of the (C1-C6 alkoxy) C1-C6 alkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and an isopropoxymethyl group.
{(C1-C6 alkoxy) C1-C6 alkoxy} C1
Examples of the -C6 alkyl group include a methoxymethoxymethyl group, a methoxyethoxymethyl group, and an ethoxymethoxymethyl group. Examples of the (C1-C6 alkyl) carbonyloxy C1-C6 alkyl group include an acetyloxymethyl group and an ethylcarbonyloxy group. A methyl group, an isopropylcarbonyloxymethyl group and the like, and (C1-
C6 haloalkyl) carbonyloxy C1-C6 alkyl group includes a trifluoroacetyloxymethyl group,
A chloroacetyloxymethyl group, a trichloroacetyloxymethyl group and the like, and (C1-C6 alkoxy)
Examples of the carbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, isopropoxycarbonyl group, isobutoxycarbonyl group, such as isoamyl oxycarbonyl group and the like, represented by R ⁷ C
Examples of the 1-C6 alkyl group include a methyl group.
^The C1-C6 alkyl group represented by ⁸ includes a methyl group, an ethyl group, and the like, the C1-C6 haloalkyl group includes a chloromethyl group, a bromomethyl group, and the like, and the hydroxyloxy C1-C6 alkyl group includes a hydroxy group. And a C1-C4 alkoxy C1- group.
Examples of the C4 alkyl group include a methoxymethyl group, an ethoxymethyl group, an isopropoxymethyl group, a butoxymethyl group,
Isobutoxymethyl group and the like, and (C1-C3 alkoxy) (C1-C3 alkoxy) C1-C3 alkyl group include a methoxymethoxymethyl group, a methoxyethoxymethyl group, an ethoxymethoxymethyl group, and the like.
Examples of the (C1-C6 alkyl) carbonyloxy C1-C6 alkyl group include an acetyloxymethyl group, an ethylcarbonyloxymethyl group, and an isopropylcarbonyloxymethyl group. Examples of the (C1-C6 haloalkyl) carbonyl C1-C6 alkyl group include: 2-chloroethylcarbonyloxymethyl group and the like; carboxy C1-C6 alkyl group include carboxymethyl group; and (C1-C8 alkoxy) carbonyl group include methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group. Butoxycarbonyl group, amyloxycarbonyl group, isopropoxycarbonyl group, isobutoxycarbonyl group, isoamyloxycarbonyl group, etc., and (C1-C6 haloalkoxy) carbonyl group is 2 Chloroethoxy carbonyl group, 2-
Bromoethoxycarbonyl group, 3-chlorobutoxycarbonyl group, 1-chloro-2-propoxycarbonyl group,
1,3-dichloro-2-propoxycarbonyl group, 2,
A 2-dichloroethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, a 2,2,2-tribromoethoxycarbonyl group and the like, and (C3-C10 Examples of the (cycloalkoxy) carbonyl group include a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, and a cyclohexyloxycarbonyl group.
Examples of the —C8 alkenyloxy) carbonyl group include an allyloxycarbonyl group, a 3-butenyloxycarbonyl group, and a 1-methyl-2-propenyloxycarbonyl group. Examples of the (C3-C8 alkynyloxy) carbonyl group include propargyloxy. A carbonyl group, a 3-butynyloxycarbonyl group, a 1-methyl-2-propynyloxycarbonyl group, and the like. Examples of the (C1-C6 alkyl) aminocarbonyl group include a methylaminocarbonyl group, an ethylaminocarbonyl group, and a propylaminocarbonyl group. And the di (C1-C6 alkyl) aminocarbonyl group includes a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group and the like, and a (C1-C6 alkyl) amino group.
Examples of the aminocarbonyloxy C1-C6 alkyl group include a methylaminocarbonyloxymethyl group, an ethylaminocarbonyloxymethyl group, and a propylaminocarbonyloxymethyl group, and a di (C1-C6 alkyl) aminocarbonyloxy C1-C6 alkyl group. Examples thereof include a dimethylaminocarbonyloxymethyl group and a diethylaminocarbonyloxymethyl group. R
Examples of the C1-C6 alkyl group represented by ²² include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a butyl group, a t-butyl group, an amyl group, an isoamyl group, and a t-amyl group. Examples of the C1-C6 haloalkyl group include a 2-chloroethyl group, a 2-bromoethyl group and a 2,2,2-trifluoroethyl group, and examples of the C3-C8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl. And C3-C6 alkenyl groups such as allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-cyclohexyl. A methyl-3-butenyl group and the like;
Examples of the C6 haloalkenyl group include a 2-chloro-2-propenyl group and a 3,3-dichloro-2-propenyl group, and examples of the C3-C6 alkynyl group include a propargyl group and a 1-methyl-2-propynyl group. , 2-butynyl group and the like, and as the C3-C6 haloalkynyl group,
3-bromopropargyl group and the like, and cyano C1-
Examples of the C6 alkyl group include a cyanoethyl group. Examples of the (C1-C4 alkoxy) C1-C4 alkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, and the like.
Examples of the (C4 alkylthio) C1-C4 alkyl group include a methylthioethyl group and the like, and carboxy C1-C6
Examples of the alkyl group include a carboxymethyl group, a 1-carboxyethyl group, a 2-carboxyethyl group, and the like.
Examples of the (C1-C8 alkoxy) carbonyl C1-C6 alkyl group include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a propoxycarbonylmethyl group,
Isopropoxycarbonylmethyl group, butoxycarbonylmethyl group, isobutoxycarbonylmethyl group, t-butoxycarbonylmethyl group, amyloxycarbonylmethyl group, isoamyloxycarbonylmethyl group, t-amyloxycarbonylmethyl group, 1-methoxycarbonylethyl group 1-ethoxycarbonylethyl group, 1-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-butoxycarbonylethyl group, 1
-Isobutoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, 1-amyloxycarbonylethyl group, 1-isoamyloxycarbonylethyl group, 1-
t-butoxycarbonylethyl group, 1-amyloxycarbonylethyl group, 1-isoamyloxycarbonylethyl group, 1-t-amyloxycarbonylethyl group and the like, and {(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl Examples of the C1-C6 alkyl group include a methoxymethoxycarbonylmethyl group, a methoxyethoxycarbonylmethyl group, and a 1-methoxyethoxycarbonylethyl group. Examples of the (C3-C8 cycloalkoxy) carbonyl C1-C6 alkyl group include cyclobutyl Oxycarbonylmethyl group, cyclopentyloxycarbonylmethyl group, cyclohexyloxycarbonylmethyl group, 1-cyclobutyloxycarbonylethyl group, 1-cyclopentyloxycarbonylethyl group, 1
-Cyclohexyloxycarbonylethyl group and the like. Examples of the C1-C6 alkyl group represented by R ²³ and R ²⁴ include a methyl group and the like, examples of the halogen atom include chlorine atom and bromine atom, and examples of the C1-C6 alkyl group represented by R ²⁵ include , Methyl group, ethyl group,
Propyl group, isopropyl group, isobutyl group, butyl group, t-butyl group, amyl group, isoamyl group, t-amyl group and the like. As the C1-C6 haloalkyl group, 2-chloroethyl group, 2-bromoethyl group, 2,
2,2-trifluoroethyl group and the like, and C3-C
Examples of the cycloalkyl group 8 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the C3-C6 alkenyl group include an allyl group, a 1-methyl-2-propenyl group, and a 3-butenyl group. , 2-butenyl group, 3-methyl-2-butenyl group, 2
-Methyl-3-butenyl group and the like. The C1-C6 alkyl group represented by R ²⁶ and R ^27, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. The compound of the present invention has several isomers derived from a double bond, optical isomers and diastereomers derived from an asymmetric carbon, and the compound of the present invention includes these isomers and mixtures thereof. included.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention has the general formula

Embedded image [Wherein Q and R ³ represent the same meaning as described above. And a hydrazone compound represented by the general formula

Embedded image [Wherein, R and R ² represent the same meaning as described above. And a malonic acid monoester derivative represented by the formula [1] in the presence of a base. The reaction conditions for this reaction (hereinafter referred to as step 1 of the present invention) include the following step 1 of the present invention.
-1 or the conditions shown in Step 1-2 of the present invention.

I) Step 1-1 of the Present Invention A hydrazone compound represented by the following general formula:
A method of reacting a malonic acid monoester derivative represented by the following formula 15 in the presence of a secondary amine and one or more of pyridine and quinoline:
The reaction is carried out in pyridine and / or quinoline, and the reaction temperature is usually in the range of 40 to 140 ° C., preferably 6 to 140 ° C.
0-100 ° C. The range of the reaction time is from instant to 24 hours, preferably from 1 to 5 hours. The amount of the reagent used for the reaction is 1 to 10 mol of the malonic acid monoester derivative represented by the formula 15 and 0 mol of the secondary amine per 1 mol of the hydrazone compound represented by the formula 14 0.1 to 5 mol, preferably 0.8 to 2 mol, more preferably 1 to 2 mol. As secondary amines,
Cyclic amines such as piperidine, morpholine and pyrrolidine; and dialkylamines such as diethylamine and diisopropylamine. In this reaction, hexane, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
1,1-trichloroethane, chlorobenzene, halogenated hydrocarbons such as dichlorobenzene, diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethers such as methyl-t-butyl ether, acetonitrile, Nitriles such as isobutyronitrile; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, propanol, butanol and isopropanol; acid amides such as N, N-dimethylformamide; dimethylsulfoxide and sulfolane It is also possible to use sulfur compounds or mixtures thereof.

II) Step 1-2 of the Present Invention A hydrazone compound represented by the general formula:
A method of reacting a malonic acid monoester derivative represented by Chemical formula 15 in the presence of a base such as an organic base such as a dialkylaniline derivative or a tertiary amine The reaction is carried out without a solvent or in a solvent. The temperature range is usually 20 to 2
00 ° C, preferably 40 to 150 ° C. The range of the reaction time is usually from instant to 72 hours. The amount of the reagent used for the reaction is determined by the amount of the hydrazone compound 1 represented by the general formula (14).
The amount of the malonic acid monoester derivative represented by the general formula is usually 1 to 10 mol, preferably 1 to 2 mol, and the amount of the base is represented by the general formula:
Is usually 1 mol to a large excess, preferably 1 to 10 mol, per 1 mol of the malonic acid monoester derivative represented by the formula (1). As the base, N, N-dimethylaniline, N, N
-Dialkylaniline derivatives such as diethylaniline, triethylamine, diisopropylethylamine, tri-
n-propylamine, tri-n-butylamine, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.
0] Organic bases such as tertiary amines such as undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,4-diazabicyclo [2.2.2] octane And preferred are trialkylamines such as triethylamine, diisopropylethylamine, tri-n-propylamine and tri-n-butylamine. As the solvent, hexane, heptane, ligroin,
Hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,
Halogenated hydrocarbons such as 1,1-trichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, etc. Ethers, nitrogen-containing aromatic compounds such as pyridine and quinoline, acid amides such as N, N-dimethylformamide, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile and isobutyronitrile, methanol, ethanol, propanol and butanol
And alcohols such as isopropanol, water, and mixtures thereof. After completion of the reaction, the reaction solution is concentrated as it is, or the reaction solution is poured into an aqueous solution of a mineral acid such as hydrochloric acid or dilute sulfuric acid, and extracted with an organic solvent. The organic layer is dried and concentrated. The compound of the present invention can be obtained by performing post-treatments such as, and, if necessary, purifying it by operations such as recrystallization and column chromatography. The compound of the present invention is usually obtained as a mixture of diastereomers,
Can be used as a raw material for the next reaction without being separated, and if necessary, can be subjected to a further precise separation operation such as chromatography, and then subjected to the next reaction. is there.

The above general formula used in the production method
Can be produced by hydrolyzing the corresponding malonic acid diester in the presence of a base. The reaction is usually carried out in a solvent, the reaction temperature is usually from 0 to 110 ° C, the reaction time is usually from an instant to 72 hours, and the amount of the base used for the reaction is malonic acid as a raw material. The ratio of 1 mole to 1 mole of diester is a theoretical amount, and it is preferable to use 1 mole. As the base, for example, inorganic bases such as sodium hydroxide and potassium hydroxide can be used. As the solvent used for the reaction, hexane, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, diisopropyl ether, 1, Ethers such as 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and methyl tert-butyl ether; alcohols such as methanol, ethanol, ethylene glycol and isopropanol; Water or a mixture thereof is exemplified. After completion of the reaction, post-treatments such as pouring the reaction solution into an aqueous solution of a mineral acid such as hydrochloric acid or dilute sulfuric acid, extracting the same with an organic solvent, drying and concentrating the organic layer, and the like are necessary. Then, purification by an operation such as recrystallization or column chromatography can give the malonic acid monoester derivative represented by the general formula (15).

A hydrazone compound represented by the following general formula:

Embedded image wherein CF ₃ C (＝ O) CV ₂ R ³ wherein R ³ has the same meaning as described above, and V represents an iodine atom, a bromine atom or a chlorine atom. Is reacted with water in the presence of a base to give a compound of the general formula

A carbonyl compound represented by CF ₃ C (＝ O) C (＝ O) R ³ [wherein R ³ has the same meaning as described above], a hydrate thereof, or an acetal derivative Derivation (hereinafter referred to as reaction 1), and then this and general formula 18

Embedded image Q-NHNH ₂ [wherein, Q is as defined above. (Hereinafter referred to as reaction 2). The above reaction 1 is usually performed in a solvent, and the reaction temperature is usually in the range of 0 to 100.
The reaction time is usually from instant to 72 hours, and the amount of the reagent used for the reaction is such that the amount of water and the base is 2 moles per mole of the compound represented by the general formula (16). Although it is a stoichiometric amount, an excess amount can be used if necessary. As the base, both an organic base and an inorganic base can be used, and examples thereof include sodium acetate and potassium acetate. In addition, the carbonyl compound represented by the general formula (17) can be produced in the presence of water or an alcohol.
The reaction can be carried out as a hydrate or an acetal derivative.

The above reaction 2 is usually carried out in a solvent, the reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is in the range of
Typically, from instant to 72 hours. The theoretical amount of the reagent to be subjected to the reaction is a ratio of 1 mol of the hydrazine derivative represented by the general formula (1) to 1 mol of the compound represented by the general formula (1) used in the reaction 1. If necessary, an excess amount of the compound represented by the general formula (16) can be used. The hydrazine derivative can also be used as a salt such as a hydrochloride or a sulfate. The solvents used in Reaction 1 and Reaction 2 include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether;
Aromatic hydrocarbons such as benzene, toluene and xylene,
Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, diethyl ether, diisopropyl ether,
Ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and methyl-t-butyl ether; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and isobutyronitrile; Methanol, ethanol, ethylene glycol,
Examples thereof include alcohols such as isopropanol, water, and mixtures thereof. After the reaction is completed,
After adding water as necessary, the resulting crystals are collected by filtration or
Alternatively, the desired product can be isolated by performing ordinary post-treatments such as extraction with an organic solvent and concentration, and then, if necessary, further purifying the mixture by operations such as chromatography and recrystallization.

A hydrazine derivative represented by the following general formula:

Embedded image Q-NH ₂ [wherein, Q is as defined above. The aniline derivative represented by the formula [1] is diazotized with nitrous acid, sodium nitrite or the like under acidic conditions, and then reduced with stannous chloride or the like. (For example, see Organic Synthetic Collective Volume 1, p442.) The aniline derivative represented by the general formula
US Patent Specification US Pat. No. 4,670,046, US Pat.
0,695, USP 4,709,049, USP 4,6
40,707, USP 4,720,297, USP 5,
169,431 and JP-A-63-156787, or can be produced according to the method described therein.

In the hydrazone compound represented by the general formula (14), the compound in which R ³ is a hydrogen atom can also be produced from the aniline derivative represented by the general formula (19) in accordance with the following scheme (20).

Embedded image [Wherein, Q represents the same meaning as described above, and R ²⁸ represents C1-C6
Represents an alkyl group. ] The reaction of each step is as follows, for example. (1) Step of producing compound [II] from compound [I] Compound [II] is prepared by reacting compound [I] with nitrite such as sodium nitrite and potassium nitrite in water under acidic conditions. After forming a diazonium salt, the diazonium salt is represented by the general formula

Embedded image CF ₃ C (＝ O) CH ₂ C (＝ O) OR ²⁸ wherein Q and R ²⁸ have the same meaning as described above. To a compound represented by the formula (T) in the presence of a base such as sodium acetate and pyridine (T
(See etrahedron, Vol. 35, p2013 (1979)) (2) Step of producing compound [III] from compound [II] Compound [III] usually hydrolyzes compound [II] in a solvent in the presence of a base. It can be manufactured by the following. The range of the reaction temperature is usually from 0 to 100 ° C, and the range of the reaction time is usually from an instant to 24 hours. The theoretical amount of the reagent used for the reaction is 1 mole of the base with respect to 1 mole of the compound [II], but can be changed as required. Examples of the base include inorganic bases such as sodium hydroxide, lithium hydroxide, lithium hydroxide monohydrate, barium hydroxide, and potassium hydroxide. Hexane, heptane, ligroin,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, chlorobenzene,
Halogenated hydrocarbons such as dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, and methanol And alcohols such as ethanol, ethanol, ethylene glycol and isopropanol, water and the like, and mixtures thereof. (3) Step of producing compound [IV] from compound [III] Compound [IV] is obtained by heating compound [III] in a solvent,
It can be produced by decarboxylation. The temperature range of the reaction is usually 50 to 200 ° C., and the reaction time range is usually instantaneous to 72 hours. Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, chloroform, carbon tetrachloride, and 1,2-dichloroethane. , Chlorobenzene, halogenated hydrocarbons such as dichlorobenzene, etc., ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether , Acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone; acid amides such as N, N-dimethylformamide; triethylamine, diisopropylethylamine; N, N-dimethylaniline;
Tertiary amines such as N-diethylaniline and N-methylmorpholine; nitrogen-containing aromatic compounds such as pyridine and picoline; sulfur compounds such as dimethylsulfoxide and sulfolane; fatty acids such as formic acid, acetic acid and propionic acid;
, Ethanol, ethylene glycol, isopropanol
And alcohols such as water, water and the like, and mixtures thereof. In this reaction, a metal such as copper can be used as a catalyst, if necessary. After completion of the reaction, the reaction solution is collected by filtration, or subjected to ordinary post-treatment such as extraction with an organic solvent and concentration, and, if necessary, further purified by an operation such as chromatography and recrystallization. The desired product can be isolated. The compound [I
V], Q represents Q-1, B represents OR ¹ or SR ¹ , and R ¹ represents a carboxy C1-C6 alkyl group. In compound [II], B represents OR ¹ or SR ¹ and R ¹ is (C1-C8
It can also be produced via a compound representing an (alkoxy) carbonyl C1-C6 alkyl group, by hydrolysis and decarboxylation.

Next, the compounds of the present invention obtained by such a production method are shown in (Table 1) to (Table 21), and the hydrazone compound represented by the general formula (14) and the general formula used in the reaction step 1 of the present invention. The malonic acid monoester derivatives represented by Chemical Formula 15 were prepared as shown in Table 22 and Table 2, respectively.
Although illustrated in 3), the present invention is not limited to these. In each table, c means cyclo, i means iso, and E
t represents an ethyl group, and Bu represents a butyl group. General formula 22

Embedded image A compound represented by the formula:

[0012]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

Formula 23

Embedded image Compound represented by

[Table 18]

[0014]

[Table 19]

[Table 20]

[0015]

[Table 21]

A hydrazone compound represented by the general formula:

[Table 22] Malonic acid monoester derivative represented by the general formula:

[Table 23]

Next, the step of producing the pyridazin-3-one derivative represented by the general formula (10) from the compound of the present invention (hereinafter, referred to as step 2 of the present invention) will be described. In the step 2 of the present invention, the reaction can be performed under the following conditions.

1) Step 2-1 of the present invention The compound of the present invention is added with 1,8-diazabicyclo [5.
4.0] By reacting with an organic base such as undec-7-ene, the pyridazine-
A 3-one derivative can be produced. The amount of the base to be used is a catalytic amount to a large excess amount, preferably 1 mol to an excess amount, per 1 mol of the compound of the present invention. The range of the reaction temperature varies depending on the base used, but is usually from 30 to 250.
° C. The range of reaction time is from instant to 240 hours. The reaction is usually performed in a solvent or without solvent, and as a solvent used for the reaction, hexane, heptane, octane, aliphatic hydrocarbons such as ligroin, benzene,
Aromatic hydrocarbons such as toluene, ethylbenzene, xylene and mesitylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene,
Halogenated hydrocarbons such as dichlorobenzene and trichlorobenzene, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl-t
Ethers such as -butyl ether; ketones such as methyl isobutyl ketone and cyclohexanone; acid amides such as N, N-dimethylformamide; and mixtures thereof. After completion of the reaction, the reaction solution may be directly subjected to a concentration operation, or the reaction solution may be poured into water,
After extraction with an organic solvent, the organic layer is subjected to post-treatment operations such as drying and concentration, and if necessary, purified by recrystallization, column chromatography or the like to obtain the pyridazine-3 represented by the general formula (10). An -one derivative can be obtained.

3) Step 2-2 of the Present Invention The compound of the present invention can be reacted with a sulfonic acid to produce a pyridazin-3-one derivative represented by the general formula (10). Examples of the sulfonic acid used in the reaction include p-toluenesulfonic acid and benzenesulfonic acid. The amount of the sulfonic acid used is from a catalytic amount to a large excess amount, preferably from 1 mol to an excess amount, per 1 mol of the compound of the present invention. The reaction temperature range is usually from 30 to 250 ° C. The range of reaction time is from instant to 240 hours. The reaction is usually performed in a solvent,
As the solvent used for the reaction, hexane, heptane,
Aliphatic hydrocarbons such as octane and ligroin, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and mesitylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, etc. Halogenated hydrocarbons, ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and methyl tert-butyl ether, ketones such as methyl isobutyl ketone and cyclohexanone, and mixtures thereof And the like. After completion of the reaction, the reaction solution is subjected to a concentration operation as it is, or a post-treatment operation such as pouring the reaction solution into water, extracting with an organic solvent, drying and concentrating the organic layer is performed, if necessary. For example, a pyridazin-3-one derivative represented by the general formula (10) can be obtained by purification by an operation such as recrystallization and column chromatography.

In the step 2 of the present invention, depending on the conditions, a pyridazin-3-one ring is formed,
In some cases, a pyridazin-3-one derivative in which the substituent on the benzene ring has been converted may be obtained.

Some of the compounds that can be produced by the step 2 of the present invention are shown in Table 24. General formula 24

Embedded image A compound represented by the formula:

[Table 24]

Pyridazine-3 represented by the general formula:
The -one derivative has an excellent herbicidal effect, and has a herbicidal effect on various weeds which are the following problems in foliage treatment and soil treatment in a field. Polygonum convolvulus (Polygonum convolvulus)
ygonum lapathiolium), Polygonu
m pensylvanicum), harade (Polygonum persicaria),
Rumex crispus, Rumex crispus, Rumex crispus
x obtusifolius), knotweed (Polygonum cuspidatum) Papilionidae Weed Papilio (Portulaca oleracea) Papilionidae weed Chickweed (Stellaria media) Apolaceae weed Shiroza (Chenopodium album), Butterfly (Kochia scopari)
a) Amaranthus retroflexus, Amaranthus hybridus, Brassica weed Wild radish, Raphanus raphanistrum, Sinapis arvensis, Capsella bursa
-Pastoris) Legume weeds Sesbania exaltata, Cassia obtusifolia, Florida Vega Weed (Des
modium tortuosum), white clover (Trifoliumrepens) Malvaceae weed, Abutilon theophrasti, American sika deer (S
ida spinosa) Violaceae Weeds Field Panji- (Viola arvensis), Wild Panji- (Viola tricolor) Rubiaceae Weeds Yaemugra (Galium aparine) Convolvulaceae Weeds (Ipomo
ea hederacea var integriuscula)
oea lacunosa), Convolvulus arvens
is) Lamiaceae Weeds, Lamium purpureum,
(mium amplexicaule) Solanaceae weed White Datura (Datura stramonium), Solanum nigrum (Solanum nigrum) Scrophulariaceae weed (Lepidoptera persica), Veronica persica,
eronica hederaefolia) Asteraceae weed, Xanthium pensylvanicum, wild sunflower (Hel
ianthus annuus), dog chamomile (Matricaria perforat
a or inodora), common marigold (Chrysanthemum)
segetum), Orofagi (Matricaria matricarioide)
s), Ragweed (Ambrosia artemisiifolia), Oobtaxa (Ambrosia trifida), Eugeron ca
nadensis), Artemisia princeps, Artemisia princeps, Solidago altissima (Echinochloa crus-galli), Enokorogosa (Se
taria viridis), Achinoekorogosa (Setaria faber
i), crabgrass (Digitaria sanguinalis), crabgrass (Eleu
sine indica), Poa annua, Blackgrass (Alopecurus myosuroides), Oats (Avena)
fatua), sorghum sorghum (Sorghum halepense), barley (Agropyron repens), and Umanohashiki (Bromus tect)
orum), Cynodon dactylon, Panicum dichotomiflorum, Texas Panicum
cum texanum), shark cane (Sorghum vulgare), astragalidae weed, communisina (Commelina communis), astragalus weed, Equisetum arvense, Cyperus iria, Cyperus iria, Cyperus rot.
undus) and yellowtail sedge (Cyperus esculentus) The pyridazin-3-one derivative represented by the general formula (10) effectively eliminates various weeds that are problematic in non-tillage cultivation of soybean, corn, wheat and the like. be able to.

The pyridazin-3-one derivative represented by the general formula (10) has a herbicidal effect on various weeds which are the following problems in flooding treatment of paddy fields. Grass weeds Raspberry (Echinochloa oryzicola) Scrophulariaceae weed Azena (Lindernia procumbens) Berberidaceae weed, Rotala indica, Ammannia m
ultiflora) Dipterocarpaceae Weedweed (Elatine triandra) Cyperaceae Weeds Cyperus difformis, Firefly (Scirpus
juncoides), pine flies (Eleocharis acicularis), Cyperus serotinus, and black-tailed oysters (Eleochari)
s kuroguwai) Watermelon Weed Konagi (Monochoria vaginalis) Omodaka Weed Urikawa (Sagittaria pygmaea), Omodaka (Sagittaria)
trifolia), Spiderfish (Alisma canaliculatum) Himeboshi family weed Hirumeshiro (Potamogeton distinctus) Apiaceae weed Seri (Oenanthe javanica) It can control a wide range of weeds that occur in forested lands or waterways, canals or other non-agricultural lands. Further, the pyridazin-3-one derivative represented by the general formula 10 has a herbicidal effect on aquatic weeds such as water hyacinth (Eichhornia crassipes) generated in waterways and canals. Further, the pyridazin-3-one derivative represented by the general formula (10) is obtained from corn (Zea may
s), wheat (Triticum aestivum), barley (Hordeum vu
lgare), rice (Oryza sativa), sorghum (Sorghum bicol)
or), soybean (Glycine max), cotton (Gossypium spp.), sugar beet (Beta vulgaris), peanuts (Arachis hypogae)
a), sunflower (Helianthus annuus), rape (Brassica n
apus), horticultural crops such as flowers and vegetables, and transplanted paddy rice.

Pyridazine-3 represented by the general formula:
When the -one derivative is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other pharmaceutical auxiliaries to form an emulsion, a wettable powder, a suspension, a granule,
It is used in the form of a concentrated emulsion, wettable powder, etc. These preparations contain a pyridazin-3-one derivative represented by the general formula (10) as an active ingredient in a weight ratio of 0.001 to 8%.
0%, preferably 0.005 to 70%. As a solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, mineral fine powder such as calcite, organic fine powder such as walnut shell powder, and water-soluble organic fine powder such as urea Fine powders of inorganic salts such as ammonium sulfate and the like, and fine powders of synthetic silicon hydrate. Examples of the liquid carrier include aromatic hydrocarbons such as alkylbenzene such as methylnaphthalene, phenylxylylethane, and xylene; isopropanol; Alcohols such as ethylene glycol and 2-ethoxyethanol;
Esters such as dialkyl phthalate, ketones such as acetone, cyclohexanone and isophorone, mineral oils such as machine oil, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone , Water and the like.
Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ethers.
Anionic surfactant such as telluric acid ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester And the like. Other pharmaceutical auxiliaries include ligninsulfonate, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl isopropyl phosphate) and the like.

Pyridazine-3 represented by the following general formula:
The -one derivative is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of the weed. Examples of the soil treatment include soil surface treatment and soil admixture treatment. Examples of foliage treatment include a treatment from above a plant body and a local treatment for treating only weeds so as not to adhere to crops. When the pyridazin-3-one derivative represented by the general formula (10) is used as an active ingredient of a herbicide, the amount of treatment depends on weather conditions, formulation form, treatment time, treatment method, soil conditions, target crops, target weeds, and the like. May vary, but usually 0.01 g to 10,000 per hectare
g, preferably 1 g to 8000 g. Emulsions, wettable powders, suspensions, concentrated emulsions, wettable powders and the like are usually prepared in an amount of 10 to 1000 liters per hectare (if necessary). The treatment is carried out by diluting with water (to which an auxiliary agent such as a spreading agent is added), and the granules and certain suspending agents are usually treated without any dilution. Here, as an auxiliary agent used as needed, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate (Crop oil conce
ntrate), vegetable oils such as soybean oil, corn oil, cottonseed oil and sunflower oil.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. 1) Production Example of the Compound of the Present Invention (Step 1 of the Present Invention) Production Example 1-1 At room temperature under a nitrogen stream, 3,3,3-trifluoro-2-
Oxopropanal 1- (4-chloro-2-fluoro-5-isopropoxyphenylhydrazone) 0.285
g was dissolved in 1.7 ml of pyridine. To this solution, 0.086 ml of piperidine and 0.149 g of methylmalonic acid monoethyl ester were added, and the mixture was heated to 90 ° C. and stirred for 2 hours. After returning the reaction solution to room temperature, it was concentrated under reduced pressure and diluted with 100 ml of diethyl ether. The diluted solution is twice with 20 ml of a 3N aqueous hydrochloric acid solution and 30 ml of a saturated aqueous sodium bicarbonate solution.
After washing once with ml, drying with magnesium sulfate and filtration,
Concentration under reduced pressure gave a crude product. The crude product thus obtained was subjected to column chromatography to obtain 0.224 g of the present compound (1-217) as a mixture of the following two isomers. Isomer ¹¹ H-NMR [300 MHz, CDCl ₃ , TMS] δ
(Ppm); 1.25 (3H, t), 1.31 (3H,
d), 1.37 (3H, d), 1.38 (3H, d),
3.24 (1H, q), 4.16 (2H, q), 4.4
9 (1H, m), 4.68 (1H, s), 7.02 (1
H, d), 7.05 (1H, d), 7.48 (1H, b
rs), 8.26 (1H, brs) isomer 2 ¹ H-NMR [300 MHz, CDCl ₃ , TMS] δ
(Ppm); 1.26 (3H, t), 1.36 (9H,
d), 3.20 (1H, q), 4.20 (2H, m),
4.47 (1H, m), 4.84 (1H, s), 6.9
8 (1H, d), 7.04 (1H, d), 7.20 (1
H, brs), 8.06 (1H, brs)

Production Example 1-2 3,3,3-Trifluoro-2-oxopropanal
5.0 g of 1- (4-chloro-2-fluoro-5-isopropoxyphenylhydrazone) was dissolved in 20 g of toluene, 2.46 g of methylmalonic acid monoethyl ester and 3.1 g of triethylamine were added, and the mixture was heated under reflux for 8 hours. Reacted. After completion of the reaction, the reaction solution was returned to room temperature, poured into water and extracted with toluene. The organic layer was washed sequentially with diluted hydrochloric acid and water, dried, and concentrated. The resulting residue was subjected to column chromatography to give the compound of the present invention (1-21)
7) 3.6 g were obtained.

Production Example 1-3 3,3,3-trifluoro-2-oxopropanal
5.0 g of 1- (4-chloro-2-fluoro-5-isopropoxyphenylhydrazone) was added to 1,4-dioxane 2
0 g of methyl malonic acid monoethyl ester.
46 g and 2.51 g of sodium acetate were added and reacted under heating and reflux for 24 hours. After completion of the reaction, the reaction solution was returned to room temperature, poured into water and extracted with toluene. The organic layer is
The extract was washed successively with dilute hydrochloric acid and water, dried, and concentrated. The resulting residue was subjected to column chromatography to obtain 3.95 g of the present compound (1-217).

Production Example 1-4 3,3,3-trifluoro-2-oxopropanal
5.0 g of 1- (4-chloro-2-fluoro-5-isopropoxyphenylhydrazone) was added to 1,4-dioxane 2
0 g of methyl malonic acid monoethyl ester.
46 g and 4.22 g of potassium carbonate were added, and the mixture was heated to reflux for 6 hours.
Allowed to react for hours. After completion of the reaction, the reaction solution was returned to room temperature, poured into water and extracted with toluene. The organic layer was washed sequentially with diluted hydrochloric acid and water, dried, and concentrated. The resulting residue was subjected to column chromatography to obtain 1.24 g of the present compound (1-217).

2) Preparation Example of the Pyridazin-3-one Derivative from the Compound of the Present Invention (Step 2 of the Present Invention) Preparation Example 2-1 0.224 g of the compound of the present invention (1-217) was added to 2.0 ml of toluene under a nitrogen stream. After dissolution, 0.189 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred under heating and reflux for 3 hours. After returning the reaction solution to room temperature, it was diluted with 100 ml of diethyl ether. This diluted solution was washed once with 30 ml of a saturated aqueous solution of sodium bicarbonate and once with 30 ml of saturated saline, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product thus obtained was subjected to column chromatography to give 2- (2-fluoro-4
0.126 g of -chloro-5-isopropoxyphenyl) -4-methyl-5-trifluoromethylpyridazin-3-one (compound 5-2) was obtained. ¹ H-NMR (300 MHz, CDCl ₃ , TMS) δ
(Ppm): 1.38 (6H, d, J = 6.3 Hz),
2.43 (3H, q, J = 2.0 Hz), 4.47 (1
H, m), 6.99 (1H, d, J = 5.0 Hz),
7.29 (1H, d, J = 9.5 Hz), 8.00 (1
H, s)

Production Example 2-2 1.0 g of the compound (1-217) of the present invention was added to xylene 5.0.
g, and 0.35 g of 1,8-diazabicyclo [5.4.0] undec-7-ene was added and reacted under heating and reflux for 2 hours. After completion of the reaction, the reaction solution was returned to room temperature, poured into water and extracted with toluene. The organic layer was washed with water, dried and concentrated. The resulting residue was subjected to column chromatography to give 2- (2-fluoro-4-chloro-5-isopropoxyphenyl) -4-methyl-5-
Trifluoromethylpyridazin-3-one (compound 5-
2) 0.22 g was obtained.

Next, a method for synthesizing the starting compounds used in the step 1 of the present invention will be described in reference examples. Reference Example 1 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water
Was added to 1,1-dibromo-3,
6.6 g (24.3 mmol) of 3,3-trifluoroacetone was added and reacted at 70 ° C. for 20 minutes. Next, the reaction solution was allowed to cool to room temperature, and then 2-fluoro-4-chloro-5-
5.8 g of isopropoxyphenylhydrazine (21.5 mmo
A solution of l) dissolved in about 20 ml of diethyl ether was added, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed once with 10 ml of a saturated saline solution, dried over anhydrous magnesium sulfate, and diethyl ether was distilled off to obtain 3,3,3-trifluoro-2-oxo-propanal 1. 6.5 g (20.0 mmol) of-(4-chloro-2-fluoro-5-isopropoxyphenylhydrazone) (compound 3-3) was obtained. ¹ H-NMR [250 MHz, CDCl ₃ , TMS, δ (ppm)] 1.39
(6H, d, J = 6.0Hz), 4.38−4.52 (1H, m), 7.15 (1H, d, J
= 10.5Hz), 7.22 (1H, d, J = 7.3Hz), 7.43 (1H, q, J = 1.7H)
z), 9.18 (1H, brs)

Reference Example 2 Production method based on the following scheme 25

Embedded image Ethyl 4,4,4-trifluoroacetoacetate 20.1 g
And a solution of 25 g of sodium acetate in 150 ml of water were added to a solution of diazonium hydrochloride derived from compound [I-1] (20.3 g of 4-chloro-2-fluoro-5-isopropoxyaniline, 20 ml of concentrated hydrochloric acid, (Prepared from 20 ml and 7.3 g of sodium nitrite) were added dropwise at a temperature of 10 ° C or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and the resulting crystals were collected by filtration, washed with water, and dried to obtain 34 g of the compound [II-1] in the scheme 16 as crystals. (Yield: 85%) 15.9 g of the compound [II-1] obtained in the above reaction and 1.7 g of lithium hydroxide monohydrate were added to 30 ml of 1,4-dioxane and 3 ml of water, and the mixture was heated under reflux for 6 hours. did. The reaction solution was poured into ice water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, and the organic layer was dried and concentrated. The residue was washed with hexane to obtain 11.3 g of a compound [III-1].
(Yield 76.3%) 7.4 g of the compound [III-1] obtained in the above reaction was dissolved in 42 ml of N, N-dimethylformamide, and
The temperature of the reaction solution was raised to 0 ° C. and kept as it was for 30 minutes. Thereafter, the mixture was cooled to room temperature, the reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, dried over anhydrous magnesium sulfate, and concentrated to obtain 5.9 g of (Compound 3-3: Compound [IV-1] in Scheme 25). (Yield 90%)

Reference Example 3 Preparation of malonic acid monoester compound 20.0 g of methyl malonic acid diethyl ester was added to 30 g of water.
And ethanol in a mixed solution of 30 g.
9.6 g of an aqueous NaOH solution was added dropwise, and the mixture was vigorously stirred at room temperature for 7 hours. After the reaction is completed, 35% hydrochloric acid is added to the reaction solution at pH
And concentrated under reduced pressure. 80 g of water was added to the obtained residue, and extracted with 40 g (× 2) of ethyl acetate. The organic layers were combined and concentrated under reduced pressure.
-Hexane 100g was added, the precipitated crystals were filtered off,
The filtrate was concentrated under reduced pressure to obtain 16.1 g of methylmalonic acid monoethyl ester. ¹ H-NMR [250 MHz, CDCl ₃ , TMS] δ (pp
m): 1.29 (3H, t, J = 7.1 Hz), 1.44 (3H, d, J = 7.3 Hz), 3.
48 (1H, q, J = 7.3 Hz), 4.22 (2H, q, J = 7.1 Hz), 10-13 (1
H, brs)

Next, formulation examples are shown. The compounds are indicated by the compound numbers described in the above (Table 24). Parts are parts by weight. Formulation Example 1 50 parts of each of the compounds 5-1 to 5-9, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 10 parts of each of Compounds 5-1 to 5-9, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of cyclohexanone are mixed well and each emulsion is prepared. Get. Formulation Example 3 2 parts of each of compounds 5-1 to 5-9, synthetic hydrous silicon oxide 2
Parts, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 64 parts of kaolin clay are crushed and mixed well,
After adding water and kneading well, the mixture is granulated and dried to obtain each granule. Formulation Example 4 25 parts of each of the compounds 5-1 to 5-9, 50 parts of a 10% aqueous solution of polyvinyl alcohol and 25 parts of water are mixed, and wet-pulverized until the average particle diameter becomes 5 μm or less. To obtain a suspension.

Next, a test example shows that the pyridazin-3-one derivative represented by the general formula (10) is useful as an active ingredient of a herbicide. Evaluation of herbicidal efficacy and phytotoxicity
When the germination or growth of the test plants (weeds and crops) at the time of the survey is not or has little difference compared to that of the untreated plants, it is set to "0". "5" is what is suppressed to
And divided into six stages of 0 to 5, 0, 1, 2, 3,
Shown at 4 and 5. Evaluations of herbicidal efficacy “4” and “5” indicate excellent herbicidal efficacy, and evaluations of “3” or less indicate insufficient herbicidal efficacy.

Test Example 1 Upland field foliage treatment test A cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm was filled with soil, sowed with Malva American morning glory and strawberry, and grown in a greenhouse for 19 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 1000 liters per hectare, and the whole was sprayed from above the plant with a sprayer. Processed. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was examined. The results are shown in (Table 25).

[Table 25]

Test Example 2 Upland Soil Surface Treatment Test A cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm was filled with soil, and seeds of Malva American morning glory and ibis were sown. A test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 1,000 liters per hectare, and the whole surface of the soil was uniformly treated with a sprayer. After the treatment, the plants were bred in a greenhouse for 19 days and their herbicidal efficacy was examined. The results are shown in (Table 26).

[Table 26]

Test Example 3 Paddy Field Flooding Treatment Test Cylindrical plastic pots having a diameter of 9 cm and a depth of 11 cm were filled with soil, and seedlings were sowed. After being submerged into paddy fields, they were grown in a greenhouse. Seven days later, the test compound was made into an emulsion in accordance with Formulation Example 2, a predetermined amount of the emulsion was diluted with water, and 50 liters per hectare were treated on the water surface. After the treatment, the plants were grown in a greenhouse for 19 days, and the herbicidal efficacy was examined. The results are shown in (Table 27).

[Table 27]

According to the present invention, the pyridazin-3-one derivative represented by the general formula (10) can be easily produced.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C07D 237/14 C07D 237/14

Claims (13)

[Claims] 1. A compound represented by the general formula: [Wherein, R represents a C1-C6 alkyl group, R ² represents a hydrogen atom or a C1-C3 alkyl group, R ³ represents a hydrogen atom or a C1-C3 alkyl group, Q is optionally substituted Represents a phenyl group. ] A carboxylic acid ester derivative represented by the formula: 2. In the above general formula 1, Q is a general formula
Chemical formula 2 Chemical formula 2[Wherein, X represents a hydrogen atom or a halogen atom, and Y represents
Halogen, nitro, cyano or trifluoro
Z represents a methyl group¹And Z^TwoIs an oxygen atom or
Represents a sulfur atom; n represents 0 or 1;^FourIs hydrogen
An atom or a C1-C3 alkyl group,^FiveIs C1-
C6 alkyl group, C1-C6 haloalkyl group, (C3-
C8 cycloalkyl) C1-C6 alkyl group, C3-C
6 alkenyl group, C3-C6 haloalkenyl group, C3-
C6 alkynyl group, C3-C6 haloalkynyl group, shea
C1-C6 alkyl group, (C1-C4 alkoxy) C
1-C4 alkyl group, (C1-C3 alkoxy) (C1
-C3 alkoxy) C1-C3 alkyl group, carboxy
C1-C6 alkyl group, (C1-C6 alkoxy) carb
Bonyl C1-C6 alkyl group, {(C1-C4 alkoxy)
B) C1-C4 alkoxy @ carbonyl C1-C6 al
Kill group, (C3-C8 cycloalkoxy) carbonyl C
1-C6 alkyl group, -CH_TwoCON (R¹²) R¹³Group,
-CH_TwoCOON (R¹²) R¹³Group, -CH (C1-C4
Alkyl) CON (R¹²) R¹³Group, -CH (C1-C4
Alkyl) COON (R¹²) R¹³Group (where R¹²And
And R¹³Are each independently a hydrogen atom, a C1-C6 alkyl
Group, C3-C8 cycloalkyl group, C1-C6 haloa
Alkyl group, C3-C6 alkenyl group, C3-C6 alkyl
Nyl group, cyano C1-C6 alkyl group, (C1-C4
Alkoxy) C1-C4 alkyl group, (C1-C4 alkyl)
Ruthio) C1-C4 alkyl group, carboxy C1-C6
Alkyl group, (C1-C6 alkoxy) carbonyl C1
-C6 alkyl group, (C3-C8 cycloalkoxy) ca
Rubonyl C1-C6 alkyl group, (C1-C6 alkyl
Ru) carbonyloxy C2-C6 alkyl group, (C1-
C6 alkyl) carbonylamino C2-C6 alkyl
Group, hydroxy C2-C6 alkyl group, substituted
A benzyl group, an optionally substituted phenyl group,
Or {(C1-C4 alkoxy) C1-C4 alkyl}
Represents a carbonyl C1-C6 alkyl;
¹²And R ¹³And trimethylene, tetramethylene, pentame
Tylene, ethyleneoxyethylene or ethylenethioe
Represents styrene. ), (C1-C4 alkylthio) C1-
C4 alkyl group or hydroxy C1-C6 alkyl group
And R⁶Is a C1-C6 alkyl group, a C1-C6 halo
Alkyl group, cyano group, carboxyl group, hydroxy C
1-C6 alkyl group, (C1-C6 alkoxy) C1-
C6 alkyl group, (C1-C6 alkoxy) (C1-C
6 alkoxy) C1-C6 alkyl group, (C1-C6
Alkyl) carbonyloxy C1-C6 alkyl group, (C
1-C6 haloalkyl) carbonyloxy C1-C6
Alkyl group or (C1-C6 alkoxy) carbonyl group
And R⁷Represents a hydrogen atom or a C1-C6 alkyl group
Represents, R⁸Is a C1-C6 alkyl group, a C1-C6 haloa
Alkyl group, hydroxy C1-C6 alkyl group, (C1-
(C4 alkoxy) C1-C4 alkyl group, (C1-C3
Alkoxy) (C1-C3 alkoxy) C1-C3Al
A kill group, (C1-C6 alkyl) carbonyloxy C1
-C6 alkyl group, (C1-C6 haloalkyl) carbo
Nil C1-C6 alkyl group, carboxy group, carboxy
C1-C6 alkyl group, (C1-C8 alkoxy) cal
Bonyl group, (C1-C6 haloalkoxy) carbonyl
Group, (C3-C10 cycloalkoxy) carbonyl group,
(C3-C8 alkenyloxy) carbonyl group, (C3
—C8 alkynyloxy) carbonyl group, (C1-C6)
Alkyl) aminocarbonyl group, di (C1-C6 alkyl)
Ru) aminocarbonyl group, (C1-C6 alkyl) amido
A noncarbonyloxy C1-C6 alkyl group or di (C
1-C6 alkyl) aminocarbonyloxy C1-C6
B represents a hydrogen atom, a halogen atom,
Toro, cyano, chlorosulfonyl, OR¹Group, S
R¹Group, SO_TwoOR^{twenty one}Group, COOR^{twenty two}Group, CR^{twenty three}= CR^{twenty four}
COOR^{twenty five}Group or CH_TwoCHWCOOR^{twenty five}Represents a group
You. {Where W is hydrogen atom, chlorine atom or bromine atom
Represents a child, R¹Is a hydrogen atom, a C1-C6 alkyl group, C
1-C6 haloalkyl group, C3-C8 cycloalkyl
Group, benzyl group, C3-C6 alkenyl group, C3-C6
Haloalkenyl group, C3-C6 alkynyl group, C3-C
6 haloalkynyl group, cyano C1-C6 alkyl group,
(C1-C4 alkoxy) C1-C4 alkyl, (C
1-C4 alkylthio) C1-C4 alkyl group, carbo
Xy C1-C6 alkyl group, (C1-C8 alkoxy)
Carbonyl C1-C6 alkyl group, (C1-C6 haloa
Alkoxy) carbonyl C1-C6 alkyl group, ｛(C1
—C4 alkoxy) C1-C4 alkoxy @ carbonyl
C1-C6 alkyl group, (C3-C8 cycloalkoxy
(C) carbonyl C1-C6 alkyl group, (C3-C8
Chloroalkyl) (C1-C6 alkoxycarbonyl) C
1-C6 alkyl group, -CH_TwoCOON (R¹²) R
¹³Group, -CH (C1-C4 alkyl) COON (R¹²)
R¹³Group, -CH_TwoCON (R¹²) R¹³Group, -CH (C1
—C4 alkyl) CON (R¹²) R¹³Group (where R¹²
And R¹³Has the same meaning as described above. ), (C2-C6 Al
(Cenyl) oxycarbonyl C1-C6 alkyl group, (C
3-C6 haloalkenyl) oxycarbonyl C1-C6
Alkyl group, (C3-C6 alkynyl) oxycarbonyl
C1-C6 alkyl group, (C3-C6 haloalkini)
L) oxycarbonyl C1-C6 alkyl group, (C1-
C6 alkylthio) carbonyl C1-C6 alkyl group,
(C1-C6 haloalkylthio) carbonyl C1-C6
Alkyl group, (C3-C6 alkenylthio) carbonyl
C1-C6 alkyl group, (C3-C6 haloalkenylthio)
E) carbonyl C1-C6 alkyl group, (C3-C6
Rukinylthio) carbonyl C1-C6 alkyl group, (C
3-C6 haloalkynylthio) carbonyl C1-C6
Alkyl group, (C3-C8 cycloalkylthio) carboni
C1-C6 alkyl group, (C3-C8 cyclohaloal
(Cithio) carbonyl C1-C6 alkyl group, ((C3
-C8 cycloalkyl) C1-C6 alkylthio) cal
Bonyl C1-C6 alkyl group, di (C1-C6 alkyl
C) C = NO carbonyl C1-C6 alkyl group, (substituted
Optionally substituted benzylthio) carbonyl C1-C6
Alkyl group, (optionally substituted phenylthio) ca
Rubornyl C1-C6 alkyl group, hydroxy (C2-C
6 alkoxy) carbonyl C1-C6 alkyl group, (C
1-C6 alkyl) carbonyloxy (C2-C6 alkyl
(Coxy) carbonyl C1-C6 alkyl group, (C1-C
6-alkyl) carbonylamino (C2-C6 alkoxy)
B) a carbonyl C1-C6 alkyl group, ｛(C1-C6
Alkoxy) carbonyl C1-C6 alkyl @ oxyca
Rubonyl C1-C6 alkyl group, hydroxy C1-C6
Alkyl group, C1-C6 alkoxycarbonyl group, C1
-C6 haloalkoxycarbonyl group, C3-C8 cyclo
Alkoxycarbonyl group, C3-C6 alkenyloxy
Carbonyl group, benzyloxycarbonyl group, C1-C
6 alkylcarbonyl groups, optionally substituted benzyl
Roxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted phenoxycarbonyl C1-C6 alkyl
Group, optionally substituted furyloxycarbonyl C1
-C6 alkyl group, optionally substituted furyl C1-
A C6 alkyloxycarbonyl C1-C6 alkyl group,
Optionally substituted thienyloxycarbonyl C1-
C6 alkyl group, optionally substituted thienyl (C1
-C6 alkyl) oxycarbonyl C1-C6 alkyl
Group, optionally substituted pyrrolyloxycarbonyl C
1-C6 alkyl group, optionally substituted pyrrolyl
Xy (C1-C6 alkyl) oxycarbonyl C1-C
6-alkyl group, imidazoyl oxo which may be substituted
Cicarbonyl C1-C6 alkyl group, even when substituted
Good imidazoyl (C1-C6 alkyl) oxycarbo
Nyl C1-C6 alkyl group, optionally substituted pyra
Zoyloxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted pyrazoyl (C1-C6 alkyl) oxo
Cicarbonyl C1-C6 alkyl group, even when substituted
Good thiazoyloxycarbonyl C1-C6 alkyl
Group, optionally substituted thiazoyl (C1-C6 alkyl
Kill) oxycarbonyl C1-C6 alkyl group, substituted
Oxazoyloxycarbonyl C1-C optionally
6 alkyl groups, optionally substituted oxazoyl (C
1-C6 alkyl) oxycarbonyl C1-C6 alkyl
Group, optionally substituted isothiazoyloxycarbyl
A bonyl C1-C6 alkyl group, an optionally substituted
Sothiazoyl (C1-C6 alkyl) oxycarbonyl
C1-C6 alkyl group, optionally substituted isoxa
Zoyloxycarbonyl C1-C6 alkyl group, substituted
Isoxazoyl (C1-C6 alkyl) optionally
Oxycarbonyl C1-C6 alkyl group, substituted
Pyridyloxycarbonyl C1-C6 alkyl
Group, optionally substituted pyridyl (C1-C6 alkyl
G) an oxycarbonyl C1-C6 alkyl group, substituted
Optionally substituted pyrazinyloxycarbonyl C1-C6
Alkyl group, optionally substituted pyrazinyl (C1-C
6 alkyl) oxycarbonyl C1-C6 alkyl group,
Optionally substituted pyrimidinyloxycarbonyl C
1-C6 alkyl group, optionally substituted pyrimidini
(C1-C6 alkyl) oxycarbonyl C1-C6
Alkyl group, optionally substituted pyridazinyloxy
Carbonyl C1-C6 alkyl group, which may be substituted
Pyridazinyl (C1-C6 alkyl) oxycarboni
C1-C6 alkyl group, optionally substituted India
Lysinyloxycarbonyl C1-C6 alkyl group, substituted
Indolidinyl (C1-C6 alkyl)
G) an oxycarbonyl C1-C6 alkyl group, substituted
Indolyloxycarbonyl C1-C6
Alkyl group, optionally substituted indolyl (C1-C
6 alkyl) oxycarbonyl C1-C6 alkyl group,
Optionally substituted indazolyloxycarbonyl C
1-C6 alkyl group, optionally substituted indazoly
(C1-C6 alkyl) oxycarbonyl C1-C6
Alkyl group, quinolyloxycarb optionally substituted
A bonyl C1-C6 alkyl group, an optionally substituted
Noryl (C1-C6 alkyl) oxycarbonyl C1-
C6 alkyl group, optionally substituted isoquinolylo
An oxycarbonyl C1-C6 alkyl group, or substituted
Optionally substituted isoquinolyl (C1-C6 alkyl) oxo
Represents a C 1 -C 6 alkyl group or a general formula
Chemical formula 3 Chemical formula 3{Where R¹⁴Represents a C1-C5 alkyl group;^FifteenIs water
A hydrogen atom, a hydroxyl group or -O-COR¹⁶Represented by
Group (R¹⁶Is a C1-C6 alkyl group, a C1-C6 halo
Alkyl group, C3-C6 alkenyl group, C3-C8 cycle
Loalkyl group, optionally substituted phenyl group, substituted
A benzyl group or a C1-C6 alcohol
Represents a xy group. ). } Represents a group represented by
Or the general formula:<Where R¹⁷Is a hydrogen atom, a halogen atom or C1-C
6 represents an alkyl group;¹⁸Is C3-C8 cycloalkyl
C2 -C having a group, a benzyl group and an epoxy group on the carbon chain
10 alkyl groups, (C3-C8 cycloalkyl) C1-
C6 alkyl group, (C3-C8 cycloalkyl) C2-
C6 alkenyl group, the same carbon atom is OR¹⁹And OR
²⁰A C1-C6 alkyl group substituted with the same carbon atom
Is OR¹⁹And OR²⁰C2-C6 alkenyl substituted with
Group, the same carbon atom is SR¹⁹And SR²⁰Is replaced by
C1-C6 alkyl group, the same carbon atom is SR¹⁹And
And SR²⁰A C2-C6 alkenyl group (here
And R¹⁹And R²⁰Are each independently a C1-C6 alkyl
A C1-C6 haloalkyl group, or R¹⁹And R²⁰When
And ethylene and ha which may be substituted with a halogen atom.
Trimethylene, halo optionally substituted with a logen atom
Tetramethylene, halo optionally substituted with a gen atom
Pentamethylene which may be substituted with a gen atom or
Ethyleneoxy optionally substituted by halogen atoms
Represents styrene. ), Carboxy C2-C6 alkenyl
Group, (C1-C8 alkoxy) carbonyl C2-C6
Lucenyl group, (C1-C8 haloalkoxy) carbonyl
C2-C6 alkenyl group, ｛(C1-C4 alkoxy)
C1-C4 alkoxy @ carbonyl C2-C6 alkenyl
Or (C3-C8 cycloalkoxy) carbo
Represents a C2-C6 alkenyl group. >
Represents, R^{twenty one}Is a C1-C6 alkyl group, a C1-C6 haloa
Alkyl group, C3-C8 cycloalkyl group, C3-C6
Lucenyl group, C3-C6 haloalkenyl group, C3-C6
Alkynyl group, C3-C6 haloalkynyl group or ben
Represents a zyl group, R^{twenty two}Is a hydrogen atom, C1-C6 alkyl
Group, C1-C6 haloalkyl group, C3-C8 cycloal
Kill group, benzyl group, C3-C6 alkenyl group, C3-
C6 haloalkenyl group, C3-C6 alkynyl group, C3
-C6 haloalkynyl group, cyano C1-C6 alkyl
Groups, (C1-C4 alkoxy) C1-C4 alkyl groups,
A (C1-C4 alkylthio) C1-C4 alkyl group,
Ruboxy C1-C6 alkyl group, (C1-C8 alkoxy
B) a carbonyl C1-C6 alkyl group;
Loalkoxy) carbonyl C1-C6 alkyl group,
{(C1-C4 alkoxy) C1-C4 alkoxy}
Rubonyl C1-C6 alkyl group, (C3-C8 cycloa
(Ruoxy) carbonyl C1-C6 alkyl group, (C1-
C6 alkyl) carbonyl C1-C6 alkyl group, (C
1-C6 haloalkyl) carbonyl C1-C6 alkyl
Group, {(C1-C4 alkoxy) C1-C4 alkyl}
Rubonyl C1-C6 alkyl group, (C3-C8 cycloa
Alkyl) carbonyl C1-C6 alkyl group, -CH_TwoC
OON (R²⁶) R²⁷Group, -CH (C1-C4 alkyl)
COON (R²⁶) R²⁷Group, -CH_TwoCON (R²⁶) R²⁷
Group, -CH (C1-C4 alkyl) CON (R²⁶) R²⁷
Group (where R²⁶And R²⁷Are each independently a hydrogen atom,
C1-C6 alkyl group, C1-C6 haloalkyl group, C
3-C6 alkenyl group, C3-C6 alkynyl group, shea
C1-C6 alkyl group, (C1-C4 alkoxy) C
1-C4 alkyl group, (C1-C4 alkylthio) C1
-C4 alkyl group, carboxy C1-C6 alkyl group,
(C1-C6 alkoxy) carbonyl C1-C6 alkyl
Group, (C3-C8 cycloalkoxy) carbonyl C1
-C6 alkyl group or ｛(C1-C4 alkoxy)
C1-C4 alkyl｝ carbonyl C1-C6 alkyl
Represents or R²⁶And R²⁷With tetramethylene, pe
Tamethylene or ethyleneoxyethylene
You. ), {(C1-C6 alkoxy) carbonyl C1-
C6 alkyl} oxycarbonyl C1-C6 alkyl
Or a hydroxy C1-C6 alkyl group;
^{twenty three}And R^{twenty four}Are each independently a hydrogen atom, a halogen
A C 1 -C 6 alkyl group;^{twenty five}Is hydrogen
Atom, C1-C6 alkyl group, C1-C6 haloalkyl
A C3-C8 cycloalkyl group or a C3-C6 alkyl group
Represents a phenyl group. }], Q-1, Q-2, Q-
The carboxyl according to claim 1, which is 3, Q-4 or Q-5.
Acid ester derivatives. 3. The carboxylate derivative according to claim 2, wherein Q is Q-1. 4. The carboxylic ester derivative according to claim 3, wherein B is a hydrogen atom, an OR ¹ group or an SR ¹ group (R ¹
Has the same meaning as in claim 2. A) a carboxylate derivative. 5. The carboxylic ester derivative according to claim 3, wherein Y is a halogen atom, B is a hydrogen atom,
1-C6 alkoxycarbonyl group, OR ¹ group or SR ¹
Wherein R ¹ is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a benzyl group, a C3-C6 alkenyl group,
C3-C6 haloalkenyl group, C3-C6 alkynyl group, C3-C6 haloalkynyl group, cyano C1-C6 alkyl group, (C1-C4 alkoxy) C1-C4 alkyl group, (C1-C4 alkylthio) C1-C4 alkyl group A carboxy C1-C6 alkyl group, a (C1-C8 alkoxy) carbonyl C1-C6 alkyl group, (C1-
C6 haloalkoxy) carbonyl C1-C6 alkyl group, {(C1-C4 alkoxy) C1-C4 alkoxy} carbonyl C1-C6 alkyl group, (C3-C8 cycloalkoxy) carbonyl C1-C6 alkyl group, C
1-C6 alkoxycarbonyl group, C1-C6 haloalkoxycarbonyl group, C3-C8 cycloalkoxycarbonyl group, C3-C6 alkenyloxycarbonyl group,
A carboxylate derivative which is a benzyloxycarbonyl group or a C1-C6 alkylcarbonyl group. 6. The carboxylic ester derivative according to claim 3, wherein Y is a halogen atom, B is an OR ¹ group or an SR ¹ group, wherein R ¹ is a hydrogen atom or A carboxylate derivative which is a C1-C6 alkyl group. 7. The carboxylate derivative according to claim 5, wherein B is OR ¹ . 8. The carboxylate derivative according to claim 6, wherein B is OR ¹ . 9. The method according to claim 1, wherein R is a methyl group or an ethyl group.
9. The carboxylic ester derivative according to 7 or 8. 10. A compound represented by the general formula: [Wherein Q and R ³ represent the same meaning as in claim 1]. And a hydrazone compound represented by the general formula: Wherein R and R ² have the same meaning as in claim 1. A method for producing a carboxylic acid ester derivative represented by the general formula 1 characterized by reacting a malonic acid monoester derivative represented by the formula [1] in the presence of a base. 11. The method according to claim 11, wherein the base is sodium acetate, potassium carbonate,
1,8-diazabicyclo [5.4.0] undec-7
The method according to claim 10, which is -ene or triethylamine. 12. A compound represented by the general formula (7), wherein a sulfonic acid is allowed to act on the carboxylic ester derivative represented by the general formula (1). Wherein Q, R ² and R ³ have the same meaning as in claim 1. A method for producing a pyridazin-3-one derivative represented by the formula: 13. A carboxylate derivative represented by the general formula 1 is converted to 1,8-diazabicyclo [5.4.0].
Characterized by acting Undec-7-ene,
A method for producing a pyridazin-3-one derivative represented by the general formula (7).