JP2003313169A - 4,4-difluoro-3-butenyl compound and insecticidal miticide for agricultural and horticultural use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new substance useful as an insecticidal miticide for agricultural and horticultural use having high safety to mammals, and an insecticidal miticide for agricultural and horticultural use containing the new substance as an active component. <P>SOLUTION: The new substance is a 4,4-difluoro-3-butenyl compound expressed by formula (1) (Q is a heterocyclic group containing at least one nitrogen atom and optionally having substituents and bonded on the nitrogen atom; Q is not phthalimide group). The insecticidal miticide for agricultural and horticultural use contains the compound as an active component. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pest control agent,
New 4,4 useful especially as insecticides and acaricides for agriculture and horticulture
The present invention relates to a difluoro-3-butenyl compound and an agricultural / horticultural insecticide / acaricide composition containing the compound as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION As a compound having a 4,4-difluoro-3-butenyl group, US Pat. No. 5,081,287, WO
92/15555, WO 94/06777, WO 9
4/06782, WO 94/04727, WO 95
/ 19352, WO 95/24403, GB 228
7465, WO 97/08130, WO 98/40
352, JP H11-140063, WO 99/5.
2874, WO 99/52882, JP H12-3
09580 describes compounds having insecticidal, acaricidal or nematicidal activity. However, the compound of the present invention in which a 4,4-difluoro-3-butenyl group is directly substituted on the nitrogen atom of a heterocyclic group having at least one nitrogen atom is not disclosed.

[0003]

[Problems to be Solved by the Invention] As insecticides and acaricides have been used for many years, pests have acquired resistance and it has become difficult to control them, and development of new insecticides and acaricides is expected. There is. An object of the present invention is to provide a novel substance which is highly safe for mammals and is effective as an agricultural and horticultural insecticide and acaricide, and an agricultural and horticultural insecticide and acaricide having the novel substance as an active ingredient. Especially.

[0004]

The present invention relates to a 4,4-difluoro-3-butenyl compound represented by the formula (1).
Further, the present invention relates to an agricultural / horticultural insecticide / acaricide composition containing the 4,4-difluoro-3-butenyl compound represented by the formula (1) as an active ingredient.

[0005]

[Chemical 3] [In the formula, Q may have a substituent, at least 1
A heterocyclic group having two nitrogen atoms is shown attached at the nitrogen atom. However, Q = phthalimide group is excluded. ]

The present inventors have conducted extensive research to create a novel pest control agent, and as a result, 4,4-difluoro- which is a novel compound not described in the literature and represented by the formula (1) of the present invention. The inventors have found that the 3-butenyl compound exhibits excellent effects at low doses against harmful insects in various agricultural fields, particularly spider mites, and completed the present invention. The above WO
92/15555 describes a compound having Q = phthalimido group on page 10 as an intermediate for producing a fluoroalkenyl compound.
The pm, mortality rate was Nami mites (0%), green leafhoppers (0%), and green peach aphids (0%), which had no insecticidal / miticidal activity.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the heterocyclic group Q having at least one nitrogen atom according to claim 1 is, for example, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolinyl, thiazolidinyl, isothiazolinyl, Pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, dihydropyridyl, tetrahydropyridyl, piperidyl, oxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl, dihydrooxazinyl. , Thiamorpholino, dihydropyridazinyl, tetrahydropyridazinyl, hexahydropyrida Nyl, oxadiazinyl, dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiadinyl, dihydrothiadiadinyl, tetrahydrothiadiazinyl, dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl, dihydropyrazinyl, tetrahydropyrazinyl, piperazinyl, Dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, dihydrotetrazinyl, indolyl, indolinyl, isoindolyl, indazolyl, dihydroquinazolyl, tetrahydroquinazolyl, carbazolyl, benzoxazolinyl, benzisoxazolin Nyl, benzisothiazolinyl, benzimidazolyl, indazolinyl, dihydroquinolinyl, tetrahydroquinolinyl, dihydroisoquinolinyl Tetrahydroisoquinolinyl, pyridoindolyl, dihydrobenzoxazinyl, dihydrocinnolinyl, tetrahydrocinnolyl, dihydrophthalazinyl, tetrahydrophthalazinyl, dihydroquinoxalinyl, tetrahydroquinoxalinyl, purinyl, dihydro Examples thereof include benzotriazinyl, dihydrobenzotetrazinyl, phenothiazinyl and the like. These heterocyclic groups may include those having an oxo form or a thioketone form at any substitutable position, and these heterocyclic groups may have an appropriate substituent at any substitutable position. Good. For more details,
For example, the following can be illustrated. In the present invention, the above heterocyclic group Q having at least one nitrogen atom
For example, the following can be exemplified.

[0008]

[Chemical 4]

[Wherein R¹, R^Two, R^Three, R^Four, And R
⁵Are the same or different and are hydrogen atom, C_{1 -4}An alkyl group,
C_3-8Cycloalkyl group, C_1-4A haloalkyl group,
C_{1- Four}Alkylthio group, C_1-4Alkoxy Carboni
Group, phenyl group, benzyl group and heterocyclic group. Also
Halogen atom, C_1-4Alkyl group, C_1-4Halo al
Kill group, C_1-4Alkoxy group, C_1-4Halo arcoki
Shi group, C_1-4Alkylthio group, C_1-4Alkylsul
Finyl group, C_1-4Alkylsulfonyl group, nitro
Group, cyano group, amino group, formyl group, C_1-4Acyl
Group, carboxyl group, C_1-4Alkoxy carbonyl
Base, C_1-4Alkylaminocarbonyl group, phenoxy
Group, phenyl group, group R⁶-OCONH-, group R⁷-CO
NH-, group -C (R⁸) = NOR⁹, Group -C (R¹⁰)
(OR¹¹) (OR¹²A group selected from the group
Represents a phenyl group, a benzyl group or a heterocyclic group. R⁶
And R ⁷Is C_1-4Indicates an alkyl group. R⁸, R⁹as well as
R¹⁰Is a hydrogen atom or C_1-4Indicates an alkyl group. R
¹¹And R¹²Is C_1-4Alkyl group, but together
May form a ring. X is an oxygen atom or a sulfur atom
Indicates. ]

The heterocyclic group represented by R ^{1 to} R ⁵ includes
For example, pyrrolyl, furanyl, thienyl, pyrazolyl,
Isoxazolyl, isothiazolyl, imidazolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, oxazinyl,
Thiazinyl, oxadiazinyl, thiadiadinyl, triazinyl, tetrazinyl, indolyl, isoindolyl, benzofuranyl, benzothiophenyl, indazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, Examples thereof include quinazolinyl and quinoxalinyl.

Specific examples of the respective groups shown in the present specification include the following. The C _1-4 alkyl group refers to a linear or branched alkyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- Butyl group, ter
Examples thereof include t-butyl group. The C _3-8 cycloalkyl group is, for example, a cyclopropyl group, a cyclopentyl group,
Examples thereof include cyclohexyl group and cyclooctyl group.
The C _1-4 haloalkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, which is substituted by one or more halogen atoms which may be the same or different, and examples thereof include a fluoromethyl group and a chloro group. Methyl group, bromomethyl group,
Iodomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group,
1-fluoroethyl group, 1-fluoropropyl group, 2-
Examples thereof include a chloropropyl group, a 3-fluoropropyl group, a 3-chloropropyl group, a 1-fluorobutyl group, a 1-chlorobutyl group and a 4-fluorobutyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the C _1-4 alkoxy group, a linear or branched alkoxy group having 1 to 4 carbon atoms is shown, for example, a methoxy group, an ethoxy group,
Examples thereof include an isopropoxy group and a tert-butoxy group. The C _1-4 haloalkoxy group represents a linear or branched alkoxy group having 1 to 4 carbon atoms, which is substituted with one or more halogen atoms which may be the same or different, and includes, for example, a difluoromethoxy group, Trifluoromethoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethyl group,
Examples thereof include a 1,2-dibromoethoxy group.

The C _1-4 alkylthio group has 1 to 1 carbon atoms.
4 represents a linear or branched alkylthio group, and examples thereof include a methylthio group and an ethylthio group. C _1-4
The alkylsulfinyl group refers to a linear or branched alkylsulfenyl group having 1 to 4 carbon atoms, for example, methylsulfinyl group, isopropylsulfinyl group, n-
Hexylsulfinyl group and the like can be mentioned. The C _1-4 alkylsulfonyl group refers to a linear or branched alkylsulfonyl group having 1 to 4 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and an isopropylsulfonyl group.

The C _1-4 acyl group is a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a pivaloyl group. Examples of the C _1-4 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group and a tert-butoxycarbonyl group. The C _1-4 alkylaminocarbonyl group is, for example, a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-butylaminocarbonyl group or the like. Represented by the formula (1) in which these heterocyclic groups are bonded 4,
The 4-difluoro-3-butenyl compound is specifically a compound represented by the following formulas (I) to (XIII).

[0015]

[Chemical 5]

4,4 represented by the formula (1) of the present invention
A typical method for producing a -difluoro-3-butenyl compound will be described, but the present invention is not limited thereto. For example, the 1,3-thiazolin-2- (thi) one compound represented by the formula (I) of the present invention is produced by the method represented by the following reaction formula.

[0017]

[Chemical 6] [Wherein R ¹ , R ² and X are the same as defined above. Y represents a leaving group. ]

According to the reaction formula-1, the 1,3-thiazolin-2- (thio) one compound represented by the formula (2) is added to the formula (3) in the absence of a solvent or an inert solvent in the presence of a base. The 1,3-thiazoline-2-of the present invention represented by the formula (I) by reacting with a difluorobutenyl compound represented by
A (thi) one compound can be produced.

As the solvent used in this reaction, a solvent inert to the reaction can be used. For example, hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform and carbon tetrachloride, ethyl acetate and acetic acid. Esters such as methyl, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, dimethyl sulfoxide and the like And the like, and a mixed solvent of two or more kinds thereof, a mixed solvent of one or more kinds of these and water, and the like can be used. The amount of these solvents used is represented by the formula (2): 1,3-thiazoline-2-
(Thi) one compound 1 to 500 parts by weight, preferably 10 to 100 parts by weight, relative to 1 part by weight.

Examples of the base used in this reaction include alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, inorganic bases such as metal hydrides such as sodium hydride and calcium hydrogen, triethylamine, pyridine 1,8-diazabicyclo [5.4.
[0] Organic bases such as undecene, n-butyllithium and lithium diisopropylamide are used. These bases may be used alone or in combination of two or more.
When an organic base such as pyridine or triethylamine is used as the base, these may be used as they are as the solvent. The amount of these bases to be used is usually 0.1 to 100 equivalents, preferably 0.5 to 5 equivalents based on the 1,3-thiazolin-2- (thio) one compound represented by the formula (2). Good.

In this reaction, if necessary, a quaternary ammonium salt such as tetrabutylammonium bromide or benzyltriethylammonium chloride, or a phase transfer catalyst such as crown ethers can be used. They can be used alone or in combination of two or more. The amount of these catalysts used is usually 0.0001 to 10 equivalents, preferably 0.001 to 1,3-thiazolin-2- (thio) one compound represented by the formula (2).
It may be 1 equivalent.

1,3-thiazoline-2-of the formula (2)
The (thi) one compound and the difluorobutenyl compound of the formula (3) may be used in any proportions, but preferably, the latter is used in an amount of 0.
It should be 5 molar equivalents or more, preferably 0.8 to 1.5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, 1, represented by the formula (2),
Depending on the type of the 3-thiazolin-2- (thi) one compound, an isomer in which the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group is substituted with the difluorobutenyl compound of the formula (3) may be by-produced. It can be easily isolated by a separation means such as column chromatography.

In the difluorobutenyl compound represented by the formula (3), examples of the leaving group represented by Y include halogen atoms such as chlorine atom, bromine atom and iodine atom, alkyl sulfonate group and aryl sulfonate group. Can be mentioned. The difluorobutenyl compound represented by the formula (3) can be produced, for example, according to the method described in WO94 / 04727 or a known method.

The 1,3-thiazolin-2- (thi) one compound represented by the formula (2), which is the starting material of this reaction, is a compound of the Journal of Organic Chemistry.
alof Organic Chemistry), 5
7 , 1053 (1992) or a known method.

[0026]

[Chemical 7] [In the formula, R ¹ and R ² are the same as defined above. ]

According to the reaction formula-2, 1,3-thiazoline-2-represented by the formula (Ia) obtained by the reaction formula-1 is obtained.
The 1,3-thiazoline-2-one represented by the formula (Ib) is obtained by reacting the on compound with a thionating reagent in a suitable solvent.
A thione compound can be produced.

As the solvent used in this reaction, a solvent inert to the reaction can be used. For example, hydrocarbons such as hexane, cyclohexane and heptane, aromatic compounds such as benzene, chlorobenzene, toluene and xylene. Hydrocarbons, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform and carbon tetrachloride, esters such as ethyl acetate and methyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, acetonitrile, propionitrile, etc. Examples thereof include nitriles, alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, and sulfoxides such as dimethylsulfoxide, and a mixed solvent of two or more thereof. , One of these It can be used a mixed solvent of two or more of water. The amount of the solvent used may be 0.1 to 500 parts by weight, preferably 10 to 100 parts by weight, relative to 1 part by weight of the 1,3-thiazolin-2-one compound represented by the formula (Ia).

The thionation reagent used in this reaction is
Lawesson's reagent, boron sulfide, phosphorus pentasulfide, hydrogen sulfide and the like can be mentioned. In this reaction, 1,3-represented by the formula (Ia)
The thiazolin-2-one compound and the thionation reagent can be used in arbitrary ratios, but it is preferable that the latter is 0.1 to 5 mol per 1 mol of the former. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

The 4,5-dihydropyrazol-5- (thi) one compound represented by the formula (II) can be produced, for example, by the following reaction formula-3, but it is not limited to these methods.

[0031]

[Chemical 8] [Wherein R ¹ , R ² , R ³ and Y are the same as defined above. ]

The 4,5-dihydropyrazol-5-one compound represented by the formula (5), which is a starting material for the 4,5-dihydropyrazol-5- (thi) one compound represented by the formula (II), is a Of Organic Chemistry (Journal of Organic Chemi
reaction of β-ketoesters (4) obtained by the Reformatsky reaction of benzoic acid esters and bromoacetic acid esters with hydrazine hydrate as described in (1), 56 , 2587 (1991). Is obtained by A 4,5-dihydropyrazol-5-one compound (5) is reacted with a difluorobutenyl compound represented by the formula (3) in the presence of a base in the absence of a solvent or an inert solvent to give a compound of the formula (IIa) It is possible to obtain the 4,5-dihydropyrazol-5-one compound of the present invention represented by The solvent used in this reaction, the base, the amount thereof used, and the phase transfer catalyst used as necessary can be the same as those in Reaction formula-1. The 4,5-dihydropyrazol-5-one compound represented by the formula (5) and the difluorobutenyl compound represented by the formula (3) can be used in arbitrary proportions, but preferably the former 1 The latter is used in an amount of 0.5 molar equivalents or more, preferably 0.8 to 1.
It is preferable to use 5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

The compound (IIb) of the present invention is the compound (IIb of the present invention.
thionation of the carbonyl group of a)
n). Regarding the thionating reagent used in this reaction, the solvent, and the amount used, the reaction formula-
It can be the same as 2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

For example, the pyrazole compound represented by the formula (III) of the present invention is produced by the method represented by the following reaction formula.

[0035]

[Chemical 9] [Wherein R ¹ , R ² , R ³ and Y are the same as defined above. ]

According to reaction formula-4, the pyrazole compound represented by the formula (6) is reacted with the difluorobutenyl compound represented by the formula (3) in the absence of a solvent or an inert solvent in the presence of a base. Thus, the pyrazole compound of the present invention represented by the formula (III) can be produced.

The solvent used in this reaction, the base, the amount used thereof, and the phase transfer catalyst used as necessary can be the same as those in the reaction formula-1.

The pyrazole compound of the formula (6) and the difluorobutenyl compound of the formula (3) may be used in any proportions, but preferably, the latter is 0.1 mol equivalent to the latter. 5 molar equivalents or more, preferably 0.1.
It is preferable to set it to 8 to 1.5 molar equivalents. This reaction is -20 ℃
To the boiling temperature of the solvent used, and the reaction is generally completed in about 0.1 to 24 hours.

In this reaction, isomers having different substitution positions of the difluorobutenyl compound depending on the kind of the pyrazole compound represented by the formula (6) [the present compound (IIIa)]
May occur as a by-product, but can be easily isolated by a separation means such as column chromatography. The pyrazole compound represented by the formula (6), which is the starting material of this reaction, is an Australian Journal of Chemistry (Australian Journal of Chemistry).
Chemistry), 36 , 135 (1983) or a known method.

The 1,2,4-trizole derivative represented by the formula (IV) can be produced, for example, by the following reaction formula-5, but it is not limited to these methods.

[0041]

[Chemical 10] [Wherein R ¹ , R ² and Y are the same as defined above. ]

By reacting a 1,2,4-triazole compound represented by the formula (7) with a difluorobutenyl compound represented by the formula (3) in the presence of a base in the absence of a solvent or an inert solvent. The present invention represented by the formula (IV) 1, 2, 4-
A triazole compound can be obtained. The solvent used in this reaction, the base, the amount thereof used, and the phase transfer catalyst used as necessary can be the same as those in Reaction formula-1.

The 1,2,4-triazole compound of the formula (7) and the difluorobutenyl compound of the formula (3) may be used in arbitrary proportions, but preferably in the former 1 molar equivalent. On the other hand, the latter is 0.5 molar equivalent or more,
It is preferably 0.8 to 1.5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, the compound (IVa) of the present invention, which is an isomer having a different substitution position of the difluorobutenyl compound, may be produced, but it should be easily isolated by a separation means such as column chromatography. You can The 1,2,4-triazole compound (7) represented by the formula (7), which is a raw material of the 1,2,4-triazole derivative represented by the formula (IV), is a European patent (EP213).
718) or the Journal of Chemical Society (Journalof Chemical Soci)
ety), 518 (1961) or the like or a known method.

The 1,2,4-triazolin-5- (thio) one compound represented by the formula (V) of the present invention is produced by the method represented by the following reaction formula.

[0046]

[Chemical 11] [Wherein R ¹ , R ² , X and Y are the same as defined above. ]

According to Reaction formula-6, the 1,2,4-triazolin-5- (thio) one compound represented by the formula (8) can be prepared by reacting the compound represented by the formula (8) in the presence of a base in a solvent-free or inert solvent. By reacting with the difluorobutenyl compound represented by 3), the 1,2,4-triazoline-5- (thio) one compound of the present invention represented by the formula (V) can be produced.

The solvent used in this reaction, the base, the amount used thereof, and the phase transfer catalyst used as necessary can be the same as those in the reaction formula-1.

1,2,4-triazoline-5 of the formula (8)
The (thi) one compound and the difluorobutenyl compound of the formula (3) may be used in any proportions, but preferably, the latter is used in an amount of 0.
It should be 5 molar equivalents or more, preferably 0.8 to 1.5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, 1, represented by the formula (V),
Depending on the type of 2,4-triazolin-5- (thio) one compound, an isomer in which the difluorobutenyl compound of the formula (3) is substituted for the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group may be by-produced. However, it can be easily isolated by a separation means such as column chromatography. The 1,2,4-triazoline-5- (thi) one compound represented by the formula (8), which is the starting material of this reaction, is synthesized by Synthesis, 912 (1987) and Journal of Heterocyclic Chemistry.
Chemistry) 26 , 1723 (1989) or a known method.

In the formula (8), X in the 1,2,4-triazoline-5- (thio) one compound is an oxygen atom and the substituent R ¹ on the triazole ring is a trifluoromethyl group. 1,2,4-triazolin-5-one compound represented by 8a), or 1,2 represented by the formula (8b) in which X is a sulfur atom and the substituent R ¹ on the triazole ring is a trifluoromethyl group. The 4,4-triazoline-5-thione compound can also be produced by the reaction shown in the following Reaction scheme-7.

[0052]

[Chemical 12] [In the formula, R ² is the same as above. Z represents a halogen atom. ]

According to the reaction formula-7, the amino compound represented by the formula (9) is reacted with trifluoroacetic acid in the presence of triphenylphosphine and a base in carbon tetrahalide to prepare the compound represented by the formula (10). The trifluoroacetamidoyl halide compound represented by the formula (1) is produced, and then the hydrazine is reacted in the absence of a solvent or in a suitable solvent to produce the trifluoroacetamido razone compound represented by the formula (11). The obtained trifluoroacetamido razone compound represented by the formula (11) is reacted with at least one selected from the group consisting of phosgene and a phosgene equivalent in a suitable solvent to obtain the compound represented by the formula (8a). 3
-Trifluoromethyl-1,2,4-triazoline-5-
On compounds can be prepared. In addition, by reacting the obtained trifluoroacetamidorazone compound represented by the formula (11) with thiophosgene in a suitable solvent, 3-trifluoromethyl-1,2, represented by the formula (8b),
4-Triazoline-5-thione compounds can be prepared.

As the amino compound represented by the formula (9), commercially available compounds or known compounds can be used. Regarding the reaction for producing the trifluoroacetimidoyl halide compounds represented by the formulas (9) to (10), Journal of Organic Chemistry (Journal)
of Organic Chemistry) 53 ,
32 (1993) or a known method. Regarding the reaction for producing the trifluoroacetimidoyl halide compound represented by the formula (10) from the amino compound represented by the formula (9), the tetrahalogenated hydrocarbon used is, for example, carbon tetrachloride,
Examples thereof include carbon tetrabromide.

The amount of tetrahalogenated hydrocarbon used is
It is usually 1 to 10 with respect to the amino compound represented by the formula (9).
It may be 0 equivalent, preferably 2 to 20 equivalents, and can also serve as a solvent. As the triphenylphosphine used in this reaction, a commercially available product can be used, and the amount used is usually 1.5 with respect to the amino compound represented by the formula (9).
It may be 10 to 10 equivalents, preferably 2 to 5 equivalents.

As the base used in this reaction, for example, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, 4-N, N-diethylaminopyridine, 1,
Known organic bases such as 8-diazabicyclo [5.4.0] -7-undecene can be mentioned, and two or more of them may be used in combination. The amount of these bases used is usually 0.8 to 10 equivalents, preferably 1 to 2 equivalents relative to the amino compound represented by the formula (9). The trifluoroacetic acid used in this reaction may be a commercially available product, and the amount used is usually 0.3 to 2 with respect to the amino compound represented by the formula (9).
It may be equivalent, preferably 0.5 to 1.5 equivalent. This reaction is generally carried out at -20 to 190 ° C, preferably 0 to 80 ° C, and the reaction time is not particularly limited, but is generally 0.5.
It will be completed in about 24 hours.

In the reaction for producing the trifluoroacetamido razone compound represented by the formula (11) from the trifluoroacetimidoyl halide compound represented by the formula (10), anhydrous hydrazine and hydrazine 1 are used as hydrazine. Examples thereof include hydrates, hydrazine hydrochloride, hydrazine hydrobromide, hydrazine sulfate, and hydrazine carbonate. Among them, hydrazine monohydrate is preferable from the viewpoint of safety and reaction convenience. The concentration of hydrazine monohydrate is not particularly limited, but 60 to 100% (w / w) product can be preferably used. A commercial item can be used for these hydrazines. The amount of hydrazine used in this reaction is usually 1-10 equivalents, preferably 2-5 equivalents, relative to the trifluoroacetimidoyl halide compound represented by the formula (10). Although hydrogen halide is produced in this reaction, it may be trapped with an excess amount of hydrazine. A hydrazine salt such as hydrazine hydrochloride is preferably neutralized with a base before use.

When a solvent is used in this reaction, an inert solvent is preferable as the solvent, for example, hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, and chlorination. Methylene, dichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, ethyl acetate, esters such as methyl acetate, diethyl ether, tetrahydrofuran, ethers such as dioxane, acetonitrile, nitriles such as propionitrile, methanol, Alcohols such as ethanol and isopropyl alcohol,
Examples thereof include amides such as N, N-dimethylformamide and N, N-diethylformamide, sulfoxides such as dimethylsulfoxide, water and the like. A mixed solvent of two or more kinds of these, one kind or two or more kinds thereof A mixed solvent of water and water can be used. The amount of the solvent used is represented by the formula (10)
The amount may be 0.5 to 100 parts by weight, preferably 1 to 30 parts by weight, relative to 1 part by weight of the trifluoroacetimidoyl halide compound represented by.

This reaction is usually carried out at -20 ° C to about the boiling point of the solvent used, preferably 0 to 30 ° C, and the reaction time is not particularly limited, but it is generally completed in about 0.5 to 24 hours. A 3-trifluoromethyl-1,2,4-triazolin-5-one compound represented by the following formula (8a) or a 3-trifluoromethyl-1,2 compound represented by the following formula (8b) When used in the production reaction of a 1,4-triazoline-5-thione compound, the compound represented by the formula (1
The trifluoroacetamido-lazone compound represented by 1) can be used as it is without isolating and purifying it or after washing the reaction solution with water.

In the reaction for producing the 3-trifluoromethyl-1,2,4-triazolin-5-one compound represented by the formula (8a) from the trifluoroacetamidorazone compound represented by the formula (11), The phosgene equivalent is a compound capable of causing a reaction equivalent to that of phosgene such as trichloromethyl chloroformate and triphosgene. In this reaction, it is preferable to use these phosgene equivalents rather than phosgene because of safety and ease of handling.

In this reaction, the amount of phosgene and / or phosgene equivalent used is usually 0.5 to 2 equivalents, preferably 0.7 to 1 equivalent to the trifluoroacetamido razone compound represented by the formula (11). It should be 0.5 equivalent.

The solvent used in this reaction is preferably an inert solvent, for example, hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene, methylene chloride and dichloroethane. , Halogenated hydrocarbons such as chloroform and carbon tetrachloride, esters such as ethyl acetate and methyl acetate, diethyl ether, tetrahydrofuran,
Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol and isopropyl alcohol, amides such as N, N-dimethylformamide and N, N-diethylformamide, and sulfoxides such as dimethyl sulfoxide. Examples thereof include water and the like, and a mixed solvent of two or more kinds of these, a mixed solvent of one or more kinds of these and water, and the like can be used.

The amount of the solvent used may be 0.5 to 100 parts by weight, preferably 1 to 30 parts by weight, based on 1 part by weight of the trifluoroacetamidorazone compound represented by the formula (11). This reaction is generally carried out at -70 ° C to about the boiling point of the solvent used, preferably 0 to 30 ° C, and the reaction time is not particularly limited, but it is generally completed in about 0.5 to 24 hours.

In the reaction for producing the 3-trifluoromethyl-1,2,4-triazoline-5-thione compound represented by the formula (8b) from the trifluoroacetamidorazone compound represented by the formula (11), From the trifluoroacetamidorazone compound represented by the formula (11), 3-trifluoromethyl-1,2,4 represented by the formula (8a)
The type and amount of the solvent used, the reaction temperature, and the reaction time may be the same, except that thiophosgene is used instead of phosgene or a phosgene equivalent in the reaction for producing the triazolin-5-one compound. The amount of thiophosgene used is usually 0.5 to 2 equivalents relative to the trifluoroacetamidorazone compound represented by the formula (11),
Preferably, it should be 0.7 to 1.5 equivalents.

Further, according to the present invention represented by the formula (V), 1, 2,
The 1,2,4-triazoline-5-thione compound represented by the formula (Vb) in which X of the 4-triazolin-5- (thio) one compound is a sulfur atom is the present invention represented by the formula (V). The 1,2,4-triazolin-5- (thi) one compound of formula (Va) in which X is an oxygen atom is represented by the following reaction formula: It can be manufactured by a method.

[0066]

[Chemical 13]

A thionating reagent used in this reaction, a solvent,
The amounts of them used can be the same as those in reaction formula-2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

Hereinafter, 1,3 represented by the formula (VI) of the present invention,
A typical method for producing a 4-oxadiazoline-5- (thio) one compound will be described, but the present invention is not limited thereto. 1,3 represented by the formula (VI) of the present invention,
The 4-oxadiazolin-5- (thio) one compound is produced by the method represented by the following reaction formula.

[0069]

[Chemical 14] [In the formula, R ¹ , X and Y are the same as defined above. ]

According to Reaction formula-9, the 1,3,4-oxadiazolin-5- (thio) one compound represented by the formula (12) is added in the presence of a base in a solvent-free or inert solvent. Producing the 1,3,4-oxadiazolin-5- (thio) one compound of the present invention represented by formula (VI) by reacting with the difluorobutenyl compound represented by formula (3). You can

The solvent used in this reaction, the base, the amount used thereof, and the phase transfer catalyst used as necessary can be the same as those in the reaction formula-1.

The 1,3,4-oxadiazolin-5- (thi) one compound of the formula (12) and the difluorobutenyl compound of the formula (3) can be used in arbitrary proportions. However, it is preferable that the amount of the latter is 0.5 molar equivalent or more, preferably 0.8 to 1.5 molar equivalents, relative to the former 1 molar equivalent. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and
Generally, it is completed in about 0.1 to 24 hours.

In this reaction, depending on the kind of the 1,3,4-oxadiazolin-5- (thi) one compound represented by the formula (12), the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group may be replaced by the formula. Although the isomer in which the difluorobutenyl compound of (3) is substituted may be produced as a by-product, it can be easily isolated by a separation means such as column chromatography. The 1,3,4-oxadiazolin-5- (thi) one compound represented by the formula (12), which is the starting material of this reaction, is a Journal of Heterocyclic Chemistry (Journal of Heterocycle).
ic Chemistry), 32 , 123 (199)
5) and the method described in JP-A-9-157259 or a known method.

In addition, 1,3 of the present invention represented by the formula (VI)
The 1,3,4-oxadiazolin-5-thione compound represented by the formula (VIb) in which X of the 4-oxadiazolin-5- (thio) one compound is a sulfur atom is represented by the formula (VI). 1,2,3,4-oxadiazolin-5- (thi) one compound of the present invention represented by the formula (VIa) wherein X is an oxygen atom,
It can be produced from a 4-triazolin-5-one compound by a method represented by the following reaction formula.

[0075]

[Chemical 15] [In the formula, R ¹ is the same as defined above. ]

A thionation reagent used in this reaction, a solvent,
The amounts of them used can be the same as those in reaction formula-2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

Hereinafter, 1, represented by the formula (VII) of the present invention,
A typical method for producing a 3,4-thiadiazolin-2- (thio) one compound will be described, but the present invention is not limited thereto. For example, the 1,3,4-thiadiazolin-2- (thi) one compound represented by the formula (VII) of the present invention is produced by the method represented by the following reaction formula.

[0078]

[Chemical 16] [In the formula, R ¹ , X and Y are the same as defined above. ]

According to Reaction formula-11, the 1,3,4-thiadiazolin-2- (thio) one compound represented by the formula (13) can be prepared in the presence of a base in the absence of solvent or an inert solvent in the presence of a base ( By reacting with the difluorobutenyl compound represented by 3), the 1,3,4-thiadiazolin-2- (thio) one compound of the present invention represented by the formula (VII) can be produced.

The solvent used in this reaction, the base, the amounts thereof used, and the phase transfer catalyst used as necessary can be the same as those in the reaction formula-1.

1,3,4-thiadiazoline of the formula (13)
The 2- (thi) one compound and the difluorobutenyl compound of the formula (3) can be used in arbitrary proportions, but preferably 0.5 mole equivalent of the latter with respect to 1 mole equivalent of the former. As described above, it is preferably 0.8 to 1.5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, depending on the kind of the 1,3,4-thiadiazolin-2- (thi) one compound represented by the formula (13), the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group may be replaced by the formula (3 The isomer in which the difluorobutenyl compound is substituted may occur as a by-product, but it can be easily isolated by a separation means such as column chromatography. The 1,3,4-thiadiazolin-2- (thi) one compound represented by the formula (13), which is the starting material of this reaction, is a compound of Journal of Heterocyclic Chemistry.
Chemistry), 31 , 1439 (1994).
It can be manufactured according to the method described in 1 above or a known method.

Further, 1, represented by the formula (VII) of the present invention,
The 1,3,4-thiadiazolin-2-thione compound represented by the formula (VIIb) in which X of the 3,4-thiadiazoline-2- (thio) one compound is a sulfur atom is the compound represented by the formula (VII) of the present invention.
A 1,3,4-thiadiazolin-2- (thi) one compound represented by the formula (VIIa) in which X is an oxygen atom,
It can be produced from a 3,4-thiadiazolin-2-one compound by a method represented by the following reaction formula.

[0084]

[Chemical 17] [In the formula, R ¹ is the same as above. ]

A thionation reagent used in this reaction, a solvent,
The amounts of them used can be the same as those in reaction formula-2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

The typical method for producing the tetrazolinone compound of the present invention represented by the formula (VIII) will be described below, but the present invention is not limited thereto. For example, the tetrazolinone compound of the present invention represented by the formula (VIII) is produced by the method represented by the following reaction formula.

[0087]

[Chemical 18] [In the formula, R ¹ and Y are the same as defined above. ]

According to Reaction Scheme-13, the tetrazolin-5-one compound represented by Formula (14) is treated with or without a base in the presence of a base in the absence of solvent or an inert solvent. By reacting with a compound of formula (VIII
The tetrazolin-5-one compound of the present invention represented by a) can be produced. The solvent used in this reaction, the base, the amount thereof used, and the phase transfer catalyst used as necessary can be the same as those in Reaction formula-1.

Tetrazoline-5 represented by the formula (14)
The on-compound and the difluorobutenyl compound of the formula (3) may be used in arbitrary proportions, but preferably the former is 1 molar equivalent and the latter is 0.5 molar equivalent or more, preferably 0 molar equivalent. It is good to set it as 0.8-1.5 molar equivalent. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally 0.
It will be completed in about 1 to 24 hours.

Further, the tetrazoline-5-thione compound of the present invention represented by the formula (VIIIb) can be prepared from the tetrazolin-5-one compound of the present invention represented by the formula (VIIIa) by a method represented by the following reaction formula. It can be manufactured.

[0091]

[Chemical 19] [In the formula, R ¹ is the same as above. ]

A thionation reagent used in this reaction, a solvent,
The amounts of them used can be the same as those in reaction formula-2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours. The tetrazolin-5-one compound represented by the formula (14), which is a raw material of the tetrazolin-5-one compound represented by the formula (VIIIa) of the present invention, can be prepared by the method described in Journal of Organic Chemistry (Journal).
of Organic Chemistry) 45 ,
According to the method described in 5130 (1980), it can be produced from an isocyanate and trimethylsilane azide.

The typical method for producing the tetrazole compound of the present invention represented by the formulas (IX) and (X) will be described below, but the present invention is not limited thereto. The tetrazole compounds represented by the formulas (IX) and (X) can be produced, for example, according to the following reaction formula-13, but are not limited to these methods.

[0094]

[Chemical 20] [Wherein R ¹ and Y are the same as defined above. ]

According to Reaction formula-15, the tetrazole represented by the formula (15) is reacted with the difluorobutenyl compound represented by the formula (3) in the presence of a base in the absence of solvent or an inert solvent. As a result, the tetrazole compound of the present invention represented by the formulas (IX) and (X) can be obtained as a mixture. The solvent used in this reaction, the base, the amount thereof used, and the phase transfer catalyst used as necessary can be the same as those in Reaction formula-1. Formula (15)
The tetrazole compound represented by the formula (1) and the difluorobutenyl compound of the formula (3) may be used in any proportions, but preferably the latter is 0.5 molar equivalent or more with respect to the former 1 molar equivalent. , Preferably 0.8-1.
It is preferable to use 5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours. The tetrazole compounds of the present invention represented by the formulas (IX) and (X) obtained as a mixture by this reaction can be separated by silica gel chromatography, and each can be obtained as a pure compound. Formulas (IX) and (X)
The tetrazole compound represented by the formula (15) as a raw material of the tetrazole compound of the present invention represented by
urnal of the American Chem
ical Society) 80 , 3908 (195)
By the method described in 8), it can be produced from the reaction of nitriles represented by R ¹ —CN with sodium azide.

The typical method for producing the pyridazine-3 (2H)-(thio) one compound of the present invention represented by the formula (XI) will be explained below, but the present invention is not limited thereto. . For example, the pyridazine-3 (2H)-(thi) one compound of the present invention represented by the formula (XI) is produced by the method represented by the following reaction formula.

[0097]

[Chemical 21] [In the formula, R ¹ , R ² , R ³ , X and Y are the same as defined above. ]

According to Reaction formula-16, the pyridazine-3 (2H)-(thio) one compound represented by the formula (16) is reacted with the formula (3) in the absence of a solvent or an inert solvent in the presence of a base. The pyridazine-3 (2 of the present invention represented by the formula (XI) is reacted with a difluorobutenyl compound represented by the formula (XI).
H)-(thio) one compounds can be prepared.

The solvent used in this reaction, the base, the amounts thereof used, and the phase transfer catalyst used as necessary can be the same as those in the reaction formula-1.

Pyridazine-3 (2H)-of formula (16)
The (thi) one compound and the difluorobutenyl compound of the formula (3) can be used at any ratios, but preferably the former is 1 molar equivalent and the latter is 0.
It should be 5 molar equivalents or more, preferably 0.8 to 1.5 molar equivalents. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, depending on the kind of the pyridazine-3 (2H)-(thio) one compound represented by the formula (16), the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group is replaced with the difluoro group of the formula (3). An isomer substituted with a butenyl compound may be produced as a by-product, but can be easily isolated by a separation means such as column chromatography. The pyridazine-3 (2H)-(thio) one compound represented by the formula (16), which is the starting material of this reaction, is described in Journal.
Of Medicinal Chemistry (Journal
of Medicinal Chemistry), 4
4 , 2707 (2001) or a known method.

Further, the pyridazine-3 (2H)-represented by the formula (XIb) in which X of the pyridazine-3 (2H)-(thi) one compound represented by the formula (XI) of the present invention is a sulfur atom. The thione compound is a pyridazin-3 (2H) -one represented by the formula (XIa) in which X of the pyridazine-3 (2H)-(thio) one compound represented by the formula (XI) of the present invention is an oxygen atom. It can be produced from a compound by a method represented by the following reaction formula.

[0103]

[Chemical formula 22] [Wherein R ¹ , R ² and R ³ are the same as defined above. ]

According to Reaction formula-17, the above Reaction formula-14
The pyridazine-3 (2 represented by the formula (XIa) obtained in
H) -one compound is reacted with a thionation reagent in a suitable solvent to form pyridazine-3 (2) represented by the formula (XIb).
H) -Thion compounds can be prepared. The thionating reagent, solvent, and their amounts used in this reaction can be the same as those in Reaction Scheme-2. This reaction is-
It can be carried out in a temperature range from 20 ° C. to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

6H of the present invention represented by the formula (XII) below
A typical method for producing a -1,3,4-oxadiazin-5- (thio) one compound will be described, but the present invention is not limited thereto. For example, 6H-1,3,4-oxadiazine-5- (hi) of the present invention represented by the formula (XII)
The on compound is produced by the method represented by the following reaction formula.

[0106]

[Chemical formula 23] [Wherein, R ¹ , R ² , R ³ , X and Y are the same as defined above. ]

According to Reaction formula-18, the 6H-1,3,4-oxadiazin-5- (thio) one compound represented by the formula (17) can be prepared in the presence of a base in a solvent-free or inert solvent. The 6H- of the present invention represented by the formula (XII) is obtained by reacting with the difluorobutenyl compound represented by the formula (3).
The 1,3,4-oxadiazin-5- (thi) one compound can be prepared.

The solvent used in this reaction, the base, the amounts thereof used, and the phase transfer catalyst used as necessary may be the same as those in Reaction formula-1.

The 6H-1,3,4-oxadiazin-5- (thio) one compound of the formula (17) and the difluorobutenyl compound of the formula (3) can be used in arbitrary proportions. However, preferably, with respect to the former 1 molar equivalent,
It is preferable that the latter is 0.5 molar equivalent or more, preferably 0.8 to 1.5 molar equivalent. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

In this reaction, 6 represented by the formula (17)
Depending on the type of the H-1,3,4-oxadiazin-5- (thi) one compound, an isomer in which the difluorobutenyl compound of the formula (17) is substituted for the oxygen atom of the carbonyl group or the sulfur atom of the thiocarbonyl group is a side effect. Although it may occur, it can be easily isolated by a separation means such as column chromatography.

The 6H-1,3,4-oxadiazin-5- (thi) one compound represented by the formula (17), which is the starting material of this reaction, is the Journal of Medicinal Chromium.
), 1157 (1993) and U.S. Pat. No. 4,508,718 or a known method.

Further, 6H-1,3, represented by the formula (XII),
The 6H-1,3,4-oxadiazine-5-thione compound represented by the formula (XIIb) in which X of the 4-oxadiazine-5- (thio) one compound is a sulfur atom has a formula (X is an oxygen atom). It can also be produced from the 6H-1,3,4-oxadiazin-5-one compound represented by XIIa) by the reaction shown in the following Reaction scheme-19.

[0113]

[Chemical formula 24] [Wherein R ¹ , R ² and R ³ are the same as defined above. ]

A thionating reagent used in this reaction, a solvent,
The amounts of them used can be the same as those in reaction formula-2. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is completed in about 0.1 to 40 hours.

[0115]

[Chemical 25] [In the Formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, X and Y are the same as the above. ]

According to Reaction formula-20, the 3H-quinazolin-4- (thio) one compound represented by the formula (18) is represented by the formula (3) in the absence of a solvent or an inert solvent in the presence of a base. By reacting with a difluorobutenyl compound
The 3H-quinazoline-4-of the present invention represented by the formula (XIII)
A (thi) one compound can be produced.

The solvent used in this reaction, the base, the amounts thereof used, and the phase transfer catalyst used as the case requires may be the same as those in the reaction formula-1. Expression (1
The 3H-quinazolin-4- (thi) one compound of 8) and the difluorobutenyl compound of the formula (3) can be used in arbitrary proportions, but preferably, the former 1 molar equivalent, It is preferable that the latter is 0.5 molar equivalent or more, preferably 0.8 to 1.5 molar equivalent. This reaction can be carried out in the temperature range from -20 ° C to the boiling temperature of the solvent used, and is generally completed in about 0.1 to 24 hours.

The 3H-quinazolin-4- (thio) one compound represented by the formula (18), which is the starting material of this reaction, may be commercially available, or may be heterocycles, 11 , 139 (19
It can be manufactured according to the method described in 78) or a known method.

Each compound obtained by each of the above reactions can be easily isolated from the reaction mixture by a conventional separation means, for example, a conventional isolation and purification means such as an organic solvent extraction method, a chromatography method and a recrystallization method. It can be purified.

The 4,4-difluoro-3-butenyl compound represented by the formula (1) of the present invention exhibits desired efficacy against various pests in a low dose. Examples of the pests include pests in various agricultural and horticultural fields such as mites, hemiptera, thrips, and diptera shown below.

Examples of mites include spider mites, spider mites, citrus spider mites, apple spider mites, kanzawa mites, citrus rust mites, and the like. The hemiptera include, for example, planthoppers such as brown leafhoppers, leafhoppers such as leafhoppers, leafhoppers such as leafhoppers, whiteflies such as whiteflies whitefly, tobacco whitefly, and insecticides such as Aphis gossypii, Pseudococcidae, etc. , Aphids such as nashigumbai, aphids such as peach peach aphid, green aphid, aphid aphid, and cotton aphid. Examples of Thysanoptera include, but not limited to, Thrips palmi Thrips, Thrips palmi Thrips, Thrips palmi Thrips, and the like. Examples of Diptera include, for example, Pleurotus littoralis.

Further, 4,4 represented by the formula (1) of the present invention
The -difluoro-3-butenyl compound is effective not only for the above-mentioned various pests in the fields of agriculture and horticulture but also for exterminating various sanitary pests such as house flies and mosquitoes. The 4,4-difluoro-3-butenyl compound represented by the formula (1) of the present invention is safe for mammals in spite of having extremely strong insecticidal and acaricidal activity against the above-mentioned harmful insects. It has the excellent property of high.

When the compound of the present invention is used as an insecticidal or acaricidal agent, it may be used as it is without adding other components, but it is usually mixed with various carriers such as liquid, solid and gas, Further, if necessary, a surfactant or other auxiliary agent for formulation is added to the emulsion, wettable powder, dry flowable agent, flowable agent, water solvent, granule, fine granule, granule, powder, coating agent, spray. Formulations, aerosol formulations, microcapsule formulations, fumigation formulations, fumigation formulations and the like can be formulated and used in various formulation forms. In these preparations, the content of the compound of the present invention as an active ingredient can be appropriately selected from a wide range depending on various conditions such as the form of the preparation and the place of use, but is usually about 0.01 to 95% by weight, preferably 0. .1
It may be about 50% by weight.

Solid carriers used for preparing these preparations include, for example, kaolin clay, diatomaceous earth, bentonite, fubasami clay, acid clay, activated clay, zeolites, clays, clay such as attapargas clay, talc, ceramics. , Celite, quartz, sulfur, activated carbon, silica carbonate, hydrated silica, white carbon, calcium carbonate, titanium dioxide, vermiculite, perlite, inorganic minerals such as pumice, water-soluble salts such as potassium chloride, ammonium sulfate, sodium sulfate, wood powder , Corn cobs, walnut husks, powdered cellulose, starch, dextrin, saccharides and other plant-derived carriers, chemical fertilizers and other fine powders, granules and the like.

Examples of the liquid carrier include water, alcohols such as ethanol and cyclohexanol, polyhydric alcohols such as ethylene glycol and diethylene glycol, derivatives of polyhydric alcohols such as propylene glycol ether, acetone, methyl ethyl ketone and cyclohexanone. Ketones, hexane, cyclohexane,
Hydrocarbons such as kerosene, light oil, normal paraffin, machine oil, benzene, toluene, xylene, naphthalene, C
₉ Aromatic hydrocarbons such as alkylbenzene and alkylnaphthalene, esters such as ethyl acetate, butyl acetate and coconut oil fatty acid methyl ester, nitriles such as acetonitrile and isobutyronitrile, diisopropyl ether,
Ethers such as dioxane, acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-alkylpyrrolidone, halogenated hydrocarbons such as dichloromethane, trichloroethane, carbon tetrachloride, dimethyl sulfoxide, soybean oil , Vegetable oils such as cottonseed oil, coconut oil, and rapeseed oil. The gaseous carrier is generally used as a propellant, and examples thereof include butane gas, liquefied petroleum gas, dimethyl ether, carbon dioxide gas and the like.

Specific examples of the surfactant include, for example, sorbitan fatty acid ester as a nonionic surfactant,
Sugar ester type such as polyoxyethylene sorbitan fatty acid ester, fatty acid ester type such as polyoxyethylene fatty acid ester, vegetable oil type such as polyoxyethylene castor oil, alcohol type such as polyoxyethylene alkyl ether , Polyoxyethylene alkyl (C _8-12 ) phenyl ether / formalin condensate, etc., alkylphenol type, polyoxyethylene / polyoxypropylene block polymer, etc. polyoxyethylene / polyoxypropylene block polymer type, phenylphenyl Polyaromatic ring type such as ether, anionic surfactants include alkylbenzene sulfonate, alkyl sulfosuccinate, sulfonate type such as allyl sulfonate, alkyl sulfate, Ones sulfate type such as polyoxyethylene alkyl sulfates include lignin sulfite and the like.

Examples of the auxiliaries for the formulation include, for example, a sticking agent,
Examples thereof include dispersants, thickeners, preservatives, antifreezing agents, stabilizers and adjuvants. Examples of fixing agents and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacryl). Acids, etc.) and the like. Examples of the thickener include xanthan gum, water-soluble polymer compounds such as carboxymethyl cellulose, high-purity bentonite, and white carbon. Examples of the preservatives include sodium benzoate and parahydroxybenzoic acid ester. Examples of the antifreezing agent include ethylene glycol and diethylene glycol. Examples of the stabilizer include PAP (isopropyl acid phosphate), B
HT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactant,
Examples thereof include fatty acids and their esters. Examples of the adjuvant include vegetable oil such as soybean oil and corn oil, machine oil, glycerin, polyethylene glycol and the like.

These formulations may be colored with organic or inorganic dyes. The preparation thus obtained can be used as it is or diluted with water or the like. However, granules, powders and the like are usually used as they are without being diluted. When an emulsion, wettable powder, flowable agent, etc. is diluted with water before use, the concentration of the active ingredient is usually 0.000.
1 to 100% by weight, preferably 0.001 to 10% by weight
It should be about.

Further, the compounds of the present invention are other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators,
You may formulate by mixing with a synergist (for example, piperonyl butoxide), a soil conditioner, etc. beforehand. Alternatively, the formulation of the present invention and each of the above agents may be used together when used.

When the compound of the present invention is used as an insecticidal or acaricidal agent, its application rate is not particularly limited,
It is appropriately selected from a wide range according to various conditions such as application method, application time, application place, type of applied crop, pests to be controlled, type of mites, etc., but usually 0.1 g per 100 m ²
It is 1000 g, preferably 10 to 500 g. Also,
When the emulsion, wettable powder, flowable agent, etc. are diluted with water, the application concentration is usually 1 ppm to 1000 pp.
m, preferably 10 to 500 ppm, and granules, powders, etc. are applied as they are without any dilution.

[0131]

EXAMPLES Production examples of raw materials for producing the compound of the present invention are described below.
The present invention will be further clarified with reference to formulation examples and test examples, but the present invention is not limited thereto. In the following, simply "parts" means "parts by weight".

Production Example 1 Synthesis of 4- (2,4-dichlorophenyl) -3- (4,4-difluoro-3-butenyl) -1,3-thiazolin-2-one (Compound No. I-7) 2 ', 4'-Dichloroacetophenone 1.0 g (5.3
mmol) and methoxycarbonylsulfenyl chloride 0.67 g (5.3 mmol) and chloroform 20 m
1 was stirred at 30 ° C. for 24 hours. After concentration under reduced pressure, the obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (8/1) to give 2- (methoxycarbonyl) sulfenyl-
2 ', 4'-Dichloroacetophenone was obtained as a pale yellow oil. Yield: 620 mg Yield: 42.0% NMR (300 MHz, CDCl ₃ , δppm):
7.56 (d, 1H), 7.46 (d, 1H), 7.35
(Dd, 1H), 4.26 (s, 2H), 3.82 (s,
3H)

2- (methoxycarbonyl) sulfenyl-2 ', 4'-dichloroacetophenone 0.30 g
(1.08 mmol) and ammonium acetate 0.9 g (1
0.8 mmol) was suspended in 20 ml of acetic acid and stirred at 80 ° C. for 2 hours. The mixture was cooled to room temperature, added dropwise to 200 ml of ice water, and then extracted 3 times with 30 ml of ethyl acetate. The obtained ethyl acetate solution was washed with 50 ml of a saturated aqueous sodium hydrogen carbonate solution and then with 30 ml of a saturated saline solution. Anhydrous magnesium sulfate was added to the obtained ethyl acetate solution, which was dehydrated and dried, filtered off, and concentrated under reduced pressure. The obtained residue was washed with n-hexane to give 4-
(2,4-dichlorophenyl) -1,3-thiazoline-2
-One was obtained as a beige solid. Yield: 0.13 g Yield: 49.1% NMR (300MHz, DMSO -d 6, δppm):
11.4 (brs, 1H), 7.48 (d, 1H),
7.43 (d, 1H), 7.32 (dd, 1H), 6.3
5 (s, 1H)

4- (2,4-dichlorophenyl) -1,3
-Thiazolin-2-one 130 mg (0.53 mmo
l) and 4-bromo-1,1-difluoro-1-butene
90 mg (0.53 mmol) and potassium carbonate 110
mg (0.8 mmol) was suspended in 30 ml of acetonitrile, and heated to reflux overnight. After returning to room temperature, acetonitrile was removed under reduced pressure, the obtained residue was suspended in 30 ml of water, and then extracted with 10 ml of ethyl acetate three times. The resulting ethyl acetate solution was dehydrated and dried over anhydrous magnesium sulfate,
It was dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (6/1) as a developing solvent to give 4-
(2,4-Dichlorophenyl) -3- (4,4-difluoro-3-butenyl) -1,3-thiazolin-2-one was obtained as an orange oil. Yield: 61.5 mg Yield: 34.6%

Production Example 2 3- (4,4-Difluoro-3-butenyl) -4-phenyl-1,3-thiazoline-2-thione (Compound No .:
Synthesis of I-3) In Production Example 1, 2 ′, 4′-dichloroacetophenone was replaced with acetophenone, and then the same reaction was performed.
-(4,4-Difluoro-3-butenyl) -4-phenyl-1,3-thiazolin-2-one (Compound number: I-
2) was obtained as a beige solid. Overall yield: 21.6% 3- (4,4-difluoro-3-butenyl) -obtained
4-phenyl-1,3-thiazolin-2-one 0.68
g (2.55 mmol) and Lawson's reagent 0.52 g
(1.29 mmol) was suspended in 20 ml of toluene,
The mixture was heated under reflux for 4 hours. After returning to room temperature, it was filtered to remove insolubles, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent (4/1) of hexane and ethyl acetate, 3- (4,4-
Difluoro-3-butenyl) -4-phenyl-1,3-
Thiazoline-2-thione was obtained as an orange oil. Yield: 0.03 g Yield: 4.2%

Production Example 3 Synthesis example of 4- (3-aminophenyl) -3- (4,4-difluoro-3-butenyl) -1,3-thiazolin-2-one (Compound No. I-21) In 1, the 2 ', 4'-dichloroacetophenone was replaced with the 3'-nitroacetophenone, and the same reaction was performed below to give 3- (4,4-difluoro-3-butenyl).
-4- (3-Nitrophenyl) -1,3-thiazoline-
2-one (Compound No. I-20) was obtained as a yellow oil. Total yield: 3.53% Reduced iron 0.5 g (8.0 mmol) in 5% acetic acid aqueous solution
Suspend in 12 ml and stir at 75-80 ° C while
(4,4-Difluoro-3-butenyl) -4- (3-nitrophenyl) -1,3-thiazolin-2-one 0.5
A solution prepared by dissolving g (1.6 mmol) in 36 ml of a mixed solution of acetic acid and ethyl acetate (1/1) was added dropwise over 30 minutes, and then stirred for 30 minutes. The reaction solution was filtered through Celite, 100 ml of water was added to the obtained reaction solution, and the mixture was extracted 3 times with 20 ml of ethyl acetate. The obtained ethyl acetate solution was washed with 50 ml of a saturated aqueous sodium hydrogen carbonate solution, washed with water, dehydrated and dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (2/1) to give 4- (3-aminophenyl) -3- (4,4).
-Difluoro-3-butenyl) -1,3-thiazoline-
2-one was obtained as a beige solid. Yield: 0.29 g Yield: 64.2%

Production Example 4 4- (3-acetylaminophenyl) -3- (4,4-
Difluoro-3-butenyl) -1,3-thiazoline-2
Synthesis of 4-one (Compound No. I-22) 4- (3-aminophenyl) -3-obtained in Production Example 3
(4,4-Difluoro-3-butenyl) -1,3-thiazolin-2-one 0.145 g (0.514 mmol) was dissolved in tetrahydrofuran 20 ml to give pyridine.
0.05 ml was added. Acetyl chloride 0.04 ml (0.514 mmol) with stirring and cooling to 0 ° C.
5 ml of tetrahydrofuran solution of was added dropwise over 10 minutes. The reaction solution was stirred at room temperature for 1 hour, dried under reduced pressure, and the obtained residue was suspended in 50 ml of water and extracted 3 times with 15 ml of ethyl acetate. After washing with water, dehydration and drying with anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the mixture was dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (1/1) to give 4- (3-acetylaminophenyl) -3- (4,4-difluoro-). 3-
Butenyl) -1,3-thiazolin-2-one was obtained as an orange oil. Yield: 0.165 g Yield: 100%

Production Example 5 4- (3-ethoxycarbonylaminophenyl) -3-
Synthesis of (4,4-difluoro-3-butenyl) -1,3-thiazolin-2-one (Compound No. I-23) 4- (3-aminophenyl) -3-obtained in Production Example 3
(4,4-Difluoro-3-butenyl) -1,3-thiazolin-2-one 0.145 g (0.514 mmol)
Is dissolved in 20 ml of tetrahydrofuran and pyridine is added.
0.05 ml was added. Cool to 0 ° C. and stir, with stirring, ethyl chloroformate (0.05 ml, 0.514 mm).
a solution of 5 ml of tetrahydrofuran) in 10 minutes. The reaction solution was stirred at room temperature for 1 hour, dried under reduced pressure, and the obtained residue was suspended in 50 ml of water and extracted 3 times with 15 ml of ethyl acetate. After washing with water, dehydration and drying with anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the mixture was dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (1/1) to give 4- (3-ethoxycarbonylaminophenyl) -3- (4,4-difluoro). -3-Butenyl) -1,3-thiazoline-2-
The on was obtained as a beige solid. Yield: 0.18g Yield: 100%

Production Example 6 3- (4,4-difluoro-3-butenyl) -4- {4
Synthesis of-(methylsulfinyl) phenyl} -1,3-thiazolin-2-one (Compound No. I-12) In Production Example 1, 2 ', 4'-dichloroacetophenone was replaced with 4'-methylthioacetophenone, The following reaction was performed in the same manner to give 3- (4,4-difluoro-3-butenyl) -4- (4-methylthiophenyl) -1,3-thiazolin-2-one (Compound No. I-11) as a yellow oil. Got with. Overall yield: 4.91% 3- (4,4-difluoro-3-butenyl) -obtained
4- (4-Methylthiophenyl) -1,3-thiazolin-2-one 0.32 g (1.02 mmol) was dissolved in 30 ml of chloroform, and 80% metachloroperbenzoic acid 0.22 g (1 0.02 mmol) was added. The reaction solution was stirred at room temperature for 2 hours and then washed successively with 20 ml of saturated aqueous sodium carbonate solution and 20 ml of water. After washing with water, dehydration and drying with anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the mixture was dried under reduced pressure. Three
-(4,4-Difluoro-3-butenyl) -4- {4-
(Methylsulfinyl) phenyl} -1,3-thiazolin-2-one was obtained as an orange oil. Yield: 0.19 g Yield: 54.5%

Production Example 7 3- (4,4-difluoro-3-butenyl) -4- {4
Synthesis of-(methylsulfonyl) phenyl} -1,3-thiazolin-2-one (Compound No. I-13) 3- (4,4-difluoro-3-butenyl) -4- (4
-Methylthiophenyl) -1,3-thiazolin-2-one (Compound No. I-11) 0.15 g (0.48 mm)
ol) was dissolved in 30 ml of chloroform, and 0.31 g of 80% metachloroperbenzoic acid (1.
44 mmol) was added. The reaction solution was stirred at room temperature for 4 hours, then saturated aqueous sodium carbonate solution (20 ml) and water 2
It was washed successively with 0 ml. After washing with water, dehydration and drying with anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the mixture was dried under reduced pressure. 3- (4,4-difluoro-3-butenyl) -4- {4- (methylsulfonyl) phenyl}-
1,3-thiazolin-2-one was obtained as a pale yellow viscous liquid. Yield: 0.04 g Yield: 24.2%

Production Example 8 1- (4,4-Difluoro-3-butenyl) -4,4-dimethyl-3-phenyl-4,5-dihydropyrazole-
Synthesis of 5-one (Compound No. II-1) Ethyl α-benzoylisobutyrate 1.8 g (8.0 mmo)
l) and hydrazine monohydrate 1.2 g (24.0 mmo)
and 1) were heated to reflux in 5 ml of ethanol for 18 hours. The reaction solution was concentrated under reduced pressure, and the obtained crude product was washed successively with methanol, water, ether and hexane and dried under reduced pressure to give 4,4-dimethyl-3-phenyl-4, white solid. 5-Dihydropyrazol-5-one was obtained. Yield: 0.88 g Yield: 58% NMR (300 MHz, CDCl ₃ , δppm): 8.
93 (brs, 1H), 7.7-7.8 (m, 2H),
7.4-7.5 (m, 3H), 1.53 (s, 6H)

4,4-dimethyl-3-phenyl-4,5-
Dihydropyrazol-5-one 0.56 g (3.0 mm
ol), 4-bromo-1,1-difluoro-1-butene 0.51 g (3.0 mmol) and potassium carbonate 0.5.
50 g (3.6 mmol) of acetonitrile 10 ml
And heated to reflux overnight. After returning to room temperature, the solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give 1- (4,4-difluoro-3-butenyl) -4,4-dimethyl-3-phenyl as colorless oil. 4,5-Dihydropyrazol-5-one was obtained. Yield: 0.48g Yield: 57%

Production Example 9 Ethyl 1- (4,4-difluoro-3-butenyl)-
3-Phenylpyrazole-5-carboxylate (Compound No. III-7) and ethyl 1- (4,4-difluoro-3-butenyl) -5-phenylpyrazole-3-carboxylate (Compound No. III) -37) Synthetic Sodium hydride (60% oil suspension) 3.3 g suspended in a solution of toluene 30 ml, while stirring, acetophenone 10 g (83.2 mmol) and diethyl.
A mixed solution of 12.2 g (83.2 mmol) of oxalate was added dropwise so that the internal temperature of the reaction solution was kept at 10 ° C or lower. After completion of dropping, the mixture was stirred at room temperature for 2 hours. It was cooled to 0 ° C. and neutralized with a dilute aqueous hydrochloric acid solution. After washing the reaction solution with water,
Drying under reduced pressure gave ethyl 2-benzoylpyruvate as a brown oil. Yield: 15.4 g Yield: 82.6% NMR (300 MHz, CDCl ₃ , δppm): 1
5.35 (brs, 1H), 8.10-7.95 (m, 2
H), 7.70-7.45 (m, 3H), 7.20-7.1
0 (m, 1H), 4.40 (q, 2H), 1.42 (t,
3H)

100% (w / w) hydrazine hydrate 3.4 ml (70.0 mmol) ethanol 40
2 ml of the solution was cooled to 0 ° C. and the ethyl obtained in the above reaction 2
-Benzoyl pyruvate 15.1 g (68.6 mmo)
A solution of 1) in 20 ml of ethanol was added dropwise over 1.5 hours. After stirring at room temperature for 3 hours, the mixture was dried under reduced pressure, and the obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (2/1) to prepare ethyl 3-phenyl. Pyrazole
The 5-carboxylate was obtained as a yellow solid. Yield: 6.39 g Yield: 43.1% NMR (300 MHz, CDCl ₃ , δppm): 1
2.0-10.0 (brs, 1H), 7.80-7.72
(M, 2H), 7.50-7.30 (m, 3H), 7.1
0 (s, 1H), 4.38 (q, 2H), 1.38 (t,
3H)

0.5 g (2.31 mmo) of ethyl 3-phenylpyrazole-5-carboxylate obtained above
l) and 4-bromo-1,1-difluoro-1-butene
0.4 g (2.31 mmol) and potassium carbonate 0.48
g (3.5 mmol) was suspended in 30 ml of acetonitrile and refluxed under heating overnight. After returning to room temperature, acetonitrile was removed under reduced pressure, the obtained residue was suspended in 30 ml of water, and then extracted with 10 ml of ethyl acetate three times. The obtained ethyl acetate solution was dehydrated and dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (3/1) to obtain the target compound ethyl 1
-(4,4-Difluoro-3-butenyl) -3-phenylpyrazole-5-carboxylate was obtained as a colorless oil. At the same time ethyl 1- (4,4-difluoro-3
-Butenyl) -5-phenylpyrazole-3-carboxylate was also obtained as a yellow oil. Ethyl 1- (4,
4-Difluoro-3-butenyl) -3-phenylpyrazole-5-carboxylate (Compound No. III-7) Yield: 570 mg Yield: 80.5% Ethyl 1- (4,4-difluoro-3-butenyl) −
5-Phenylpyrazole-3-carboxylate (Compound No. III-37) Yield: 50 mg Yield: 7.06%

Production Example 10 Ethyl 1- (4,4-difluoro-3-butenyl)-
Synthesis of 3- (3-aminophenyl) pyrazole-5-carboxylate (Compound No. III-30) In Production Example 9, acetophenone was replaced with 3′-nitroacetophenone, and the same reaction was performed below to obtain ethyl 1
-(4,4-Difluoro-3-butenyl) -3- (3-
Nitrophenyl) pyrazole-5-carboxylate (Compound No. III-29) was obtained as a white solid. Total yield: 71.2% Obtained ethyl 1- (4,4-difluoro-3-butenyl) -3- (3-nitrophenyl) pyrazole-5-
Carboxylate was used as a starting material and the same procedure as in Production Example 3 was carried out to obtain a brown oil. Yield: 100%

Production Example 11 Ethyl 1- (4,4-difluoro-3-butenyl)-
3- (3-acetylaminophenyl) pyrazole-5-
Synthesis of carboxylate (Compound No. III-31) Ethyl 1- (4,4-difluoro-obtained in Production Example 10
Production Example 4 using 3-butenyl) -3- (3-aminophenyl) pyrazole-5-carboxylate as a starting material
Was carried out in the same manner as above to obtain a white solid. Yield: 83.0%

Production Example 12 Ethyl 1- (4,4-difluoro-3-butenyl)-
3- (3-methoxycarbonylaminophenyl) pyrazole-5-carboxylate (Compound number: III-3
2) Synthesis of ethyl 1- (4,4-difluoro-) obtained in Production Example 10
3-butenyl) -3- (3-aminophenyl) pyrazo-
Le-5-carboxylate 0.33 g (1.03 mmo
l) was dissolved in 10 ml of tetrahydrofuran, and 0.1 ml of pyridine was added while stirring at 0 ° C. Further 0
Methyl chloroformate 0.08 with stirring at ℃
ml (1.03 mmol) of tetrahydrofuran 5m
1 of solution was added dropwise over 10 minutes. The reaction solution was stirred at room temperature for 1 hour and then dried under reduced pressure, and the resulting residue was washed with water (1).
It was suspended in 0 ml and extracted 3 times with 15 ml of ethyl acetate. After washing with water, dehydration and drying with anhydrous magnesium sulfate, magnesium sulfate was removed by filtration, and the mixture was dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (2/1) as a developing solvent, and ethyl 1- (4,4-difluoro-3-butenyl) -3- (3 -Methoxycarbonylaminophenyl) pyrazole-5-carboxylate was obtained as a beige solid. Yield: 0.37 g Yield: 95.0%

Production Example 13 Ethyl 1- (4,4-difluoro-3-butenyl)-
3- (4-methylsulfinylphenyl) pyrazole-
Synthesis of 5-carboxylate (Compound No. III-14) In Production Example 9, acetophenone was replaced with 4′-methylthioacetophenone, and the reaction was performed in the same manner as described below to obtain ethyl 1- (4,4-difluoro-3-butenyl). -3-
(4-Methylthiophenyl) pyrazole-5-carboxylate (Compound No. III-13) was obtained as a colorless oil. At the same time, ethyl 1- (4,4-difluoro-3-
Butenyl) -5- (4-methylthiophenyl) pyrazole-3-carboxylate (Compound number: III-43)
Was obtained as an orange viscous liquid. Ethyl 1- (4,4-difluoro-3-butenyl)-
3- (4-Methylthiophenyl) pyrazole-5-carboxylate (Compound No. III-13) Yield: 53.0% Ethyl 1- (4,4-difluoro-3-butenyl)-
5- (4-Methylthiophenyl) pyrazole-3-carboxylate (Compound No. III-43) Yield: 29.8% Ethyl 1- (4,4-difluoro-3-butenyl) -3- ( 4-methylthiophenyl) pyrazole-
Using 5-carboxylate as a starting material, the reaction was carried out in the same manner as in Production Example 6 to obtain a light pink solid. Yield: 92.
5%

Production Example 14 Ethyl 1- (4,4-difluoro-3-butenyl)-
3- (4-methylsulfonylphenyl) pyrazole-
Synthesis of 5-carboxylate (Compound No. III-15) Ethyl 1- (4,4-difluoro-3-butenyl)-
Using 3- (4-methylthiophenyl) pyrazole-5-carboxylate (Compound No. III-13) as a starting material, a reaction was performed in the same manner as in Production Example 7 to obtain a white solid. Yield: 92.0%

Production Example 15 1- (4,4-Difluoro-3-butenyl) -5-methyl-3- (trifluoromethyl) pyrazole (Compound No. III-4) and 1- (4,4-difluoro-3) Synthesis of -butenyl) -3-methyl-5- (trifluoromethyl) pyrazole (Compound No. III-36) Hydrazine hydrate 1.12 ml (23.2 mmo)
1) and ethanol (30 ml) with stirring at 0 ° C while stirring 1,1,1-trifluoro-2,4-pentanedione (3.5 g, 22.7 mmol) in ethanol (10 m).
1 solution was added dropwise over 1.5 hours. 1 at room temperature
After time, it was dried under reduced pressure to obtain 5-methyl-3- (trifluoromethyl) pyrazole as a white solid. Yield: 3.67 g Yield: 96.1% NMR (300 MHz, CDCl ₃ , δppm): 1
0.0-8.0 (brs, 1H), 6.33 (s, 1
H), 2.36 (s, 3H)

0.4 g (2.4 mmol) of 5-methyl-3- (trifluoromethyl) pyrazole obtained in the above reaction
And 4-bromo-1,1-difluoro-1-butene 0.4
1 g (2.4 mmol) and 0.5 g of potassium carbonate (3.
6 mmol) was suspended in 30 ml of acetonitrile, and refluxed by heating overnight. After returning to room temperature, acetonitrile was removed under reduced pressure, the obtained residue was suspended in 30 ml of water, and then extracted with 10 ml of ethyl acetate three times. The obtained ethyl acetate solution was dehydrated and dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The obtained residue was purified by silica gel column chromatography using a developing solvent as a mixed solvent of hexane and ethyl acetate (3/1) to obtain 1- (4,4-difluoro-3-butenyl) -5-of the target compound. Methyl-3- (trifluoromethyl) pyrazole was obtained as a pale yellow oil. In addition, 1- (4,4-difluoro-3-butenyl) -3-
Methyl-5- (trifluoromethyl) pyrazole was obtained as a pale yellow oil. 1- (4,4-difluoro-3-butenyl) -5-methyl-3- (trifluoromethyl) pyrazole (Compound No. III-4) Yield: 3.2 mg Yield: 0.52% 1- (4 , 4-Difluoro-3-butenyl) -3-methyl-5- (trifluoromethyl) pyrazole (Compound No. III-36) Yield: 0.29 g Yield: 47.2%

Production Example 16 1- (4,4-Difluoro-3-butenyl) -5-methylthio-3-phenyl-1,2,4-triazole (Compound No. IV-1) and 2- (4,4) -Difluoro-3
-Butenyl) -3-methylthio-5-phenyl-1,2,
Synthesis of 4-triazole (Compound No. IV-2) thiosemicarbazide 5.0 g (55.0 mmol), sodium hydroxide 2.2 g (55.0 mmol), water
To a mixture of 9.2 ml and dioxane 10 ml, 57.1 g (51.0 mmol) of benzoyl chloride was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes and the solid was collected by filtration. 4.5 g (112.5 m) of sodium hydroxide was added to the filtrate.
mol) and 19 ml of water were added, and the mixture was heated to 90 ° C.
It was stirred for 1 hour. After cooling to room temperature, 20 ml of concentrated hydrochloric acid was added to the reaction solution. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to give yellow crude crystalline 5-mercapto-3-phenyl-1,2,4-triazole 12.7.
g was obtained. 5-mercapto-3-phenyl-1,2,4-
Triazole 12.7 g, methyl iodide 7.2 g (5
(1.0 mmol) was heated under reflux in 20 ml of ethanol for 4 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure and poured into ice water. After neutralizing with a saturated aqueous sodium hydrogen carbonate solution, 50 ml of ethyl acetate was extracted twice. The combined ethyl acetate extracts were washed with saturated saline,
After further drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was washed with hexane to give white solid 5-methylthio-3-phenyl-1,2,4-triazole. Yield: 5.1 g Yield: 52% NMR (300 MHz, DMSO-d ₆ , δppm):
7.9-8.0 (m, 2H), 7.4-7.5 (m, 3
H), 2.68 (s, 3H)

5-methylthio-3-phenyl-1,2,4
-Triazole 0.62 g (3.0 mmol), 4-bromo-1,1-difluoro-1-butene 0.51 g
(3.0 mmol) and 0.50 g of potassium carbonate (3.
6 mmol) was added to 10 ml of acetonitrile, and the mixture was heated under reflux overnight. After returning to room temperature, the solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give the desired 1- (4,4-difluoro-3-butenyl) -5-methylthio-3-phenyl-1, 2,4-triazole and 2- (4,4-difluoro-3-butenyl) -3-methylthio-5-phenyl-1,2,4-triazole were obtained. 1- (4,4-difluoro-3-butenyl) -5-methylthio-3-phenyl-1,2,4-triazole (Compound No. IV-1) Yield: 0.62 g Yield: 73% 2- ( 4,4-Difluoro-3-butenyl) -3-methylthio-5-phenyl-1,2,4-triazole (Compound No. IV-2) Yield: 0.14 g Yield: 17%

Production Example 17 3- (3-Bromophenyl) -1- (4,4-difluoro-3-butenyl) -4-methyl-1,2,4-triazolin-5-one (Compound No. V- 35) Synthesis of ethyl 3-bromobenzoate 11.3 g (49.5 mmo)
l) and 100% (w / w) hydrazine monohydrate 7 ml
(144 mmol) was heated to reflux for 30 minutes with stirring.
After cooling to room temperature (25 ° C.), the produced solid substance was collected by filtration, washed with water, and dried under reduced pressure to obtain 3-bromobenzoylhydrazine as a white solid. Yield: 9.9 g Yield: 86.7% NMR (300 MHz, DMSO-d ₆ , δppm):
9.89 (brs, 1H), 7.99 (dd, 1H),
7.81 (dd, 1H), 7.70 (dd, 1H), 7.
43 (dd, 1H), 4.53 (brs, 2H)

3-Bromobenzoylhydrazine 0.5
Tetrahydrofuran 20m in g (2.33mmol)
0.11 ml (2.33 mmol) of methylisocyanate was added with stirring at room temperature (25 ° C.). After stirring at room temperature (25 ° C) for 2 hours, 20 ml of diethyl ether was added, and the precipitated solid substance was collected by filtration to obtain 1- (3-bromobenzoyl) -4-methylsemicarbazide as a white solid. Yield: 0.6 g Yield: 94.8% NMR (300MHz, DMSO -d 6, δppm):
10.2 (brs, 1H), 8.09 (brs, 1
H), 7.93-7.86 (m, 2H), 7.75-7.6
5 (m, 1H), 7.48-7.40 (m, 1H), 6.
55-6.40 (brs, 1H), 3.34 (d, 3H)

0.5% (1.92 mmol) of 1- (3-bromobenzoyl) -4-methylsemicarbazide was added to 5%.
(W / w) Sodium hydroxide aqueous solution was added to 20 ml, and the mixture was heated under reflux overnight (12 hours). After cooling to room temperature (25 ° C.), the reaction solution was adjusted to acidic (pH 1) with a 10% (w / w) aqueous hydrochloric acid solution, the precipitated solid was filtered off, washed with water, and dried under reduced pressure to 3 -(3-Bromophenyl) -4-methyl-1,2,4-triazolin-5-one was obtained as a white solid. Yield: 0.2 g Yield: 43% NMR (300 MHz, DMSO-d ₆ , δppm):
12.1-12.0 (brs, 1H), 7.87 (d,
1H), 7.80-7.70 (m, 2H), 7.53 (d
d, 1H), 3.24 (s, 3H)

3- (3-Bromophenyl) -4-methyl-1,2,4-triazolin-5-one 0.5 g (1.8
4 mmol), 4-bromo-1,1-difluoro-1-
Butene 0.33 g (1.93 mmol) and potassium carbonate 0.35 g (2.8 mmol) were added to acetonitrile 20
The mixture was added to ml and heated to reflux overnight (12 hours). Room temperature (2
(5 ° C) and then concentrated under reduced pressure, leaving 20 ml of water in the residue.
Was added, and the mixture was extracted 3 times with 7 ml of ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to give the desired 3- (3-bromophenyl) -1- (4,4).
-Difluoro-3-butenyl) -4-methyl-1,2,4
-Triazolin-5-one was obtained as a pale yellow oil. Yield: 0.18g Yield: 28%

Production Example 18 1- (4,4-Difluoro-3-butenyl) -4-phenyl-3- (trifluoromethyl) -1,2,4-triazolin-5-one (Compound No. V-3 ) Of triphenylphosphine 262g (0.999mo)
150 ml of carbon tetrachloride was added to l), cooled to 0 ° C,
38.0 g (0.333 mol) of trifluoroacetic acid was slowly added. Then triethylamine 40.5g
(0.400 mol) was added, and the mixture was stirred under ice-cooling for 20 minutes, then added with aniline (37.3 g, 0.400 mol) and carbon tetrachloride (150 ml), and heated under reflux for 3 hours. After cooling, the mixture was concentrated under reduced pressure, the residue was suction filtered to remove the precipitate, and washed with n-hexane. The filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane) to give a colorless oily substance.
1-aza-2-chloro-3,3,3-trifluoro-1-
Phenyl-1-propene was obtained. Yield: 40.7 g Yield: 59.0% NMR (300 MHz, CDCl ₃ , δppm):
7.44 (d, 2H), 7.30 (t, 1H), 7.10
(D, 2H)

1-aza-2-chloro-3,3, obtained above
3-trifluoro-1-phenyl-1-propene 10.
0 g (0.048 mol) of tetrahydrofuran 10
It was dissolved in 0 ml and 100% (W / W) hydrazine monohydrate (7.21 g, 0.144 mol) was gradually added under cooling to 0 ° C., and the mixture was stirred at room temperature for 1 hour. Water for reaction 50
ml and 50 ml of ethyl acetate were added for liquid separation. The organic layer was washed 3 times with 50 ml of saturated saline and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure, and the obtained concentrated residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1: 3) to give 1-aza-3 as a colorless oil. There was obtained 3,3,3-trifluoro-1-phenyl-1-propen-2-ylhydrazine. Yield: 9.69 g Yield: 99.0% NMR (300 MHz, CDCl ₃ , δppm):
7.28-7.39 (m, 2H), 6.98 (t, 1
H), 6.67 (d, 2H), 5.52 (brs, 3H)

1-aza-3,3,3-trifluoro-1-
Phenyl-1-propen-2-ylhydrazine 1.0
tetrahydrofuran solution of g (0.005 mol) 3
0.73 g (0.0025 mo) of triphosgene in 0 ml.
1) was added, and the mixture was stirred at room temperature for 3 hours. Water in the reaction solution 2
0 ml and 20 ml of ethyl acetate were added for liquid separation. The organic layer was washed 3 times with 20 ml of saturated saline and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure, and the precipitated solid was suction filtered and washed 3 times with 10 ml of n-hexane to give 4-phenyl-3- (trifluoromethyl) -1,2,4-triazoline as a white solid. -5-one was obtained. Yield: 1.02 g Yield: 90% NMR (300 MHz, CDCl ₃ , δppm): 1
0.75 (s, 1H), 7.60-7.51 (m, 3
H), 7.32-7.42 (m, 2H)

4-phenyl-3- (trifluoromethyl) -1,2,4-triazolin-5-one 0.46 g
(2.0 mmol), 4-bromo-1,1-difluoro-
0.34 g (2.0 mmol) of 1-butene and 0.42 g (3.01 mmol) of potassium carbonate were added to 20 ml of acetonitrile, and the mixture was heated under reflux overnight (12 hours). After returning to room temperature (25 ° C), concentrate under reduced pressure, and add water to the residue.
0 ml was added, and the mixture was extracted 3 times with 7 ml of ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue is subjected to silica gel column chromatography (hexane: ethyl acetate = 1: 1).
The desired 1- (4,4-difluoro-3-butenyl) -4-phenyl-3- (trifluoromethyl)
-1,2,4-triazolin-5-one was obtained as a yellow oil. Yield: 0.18g Yield: 28%

Production Example 19 3- (3-Aminophenyl) -1- (4,4-difluoro-3-butenyl) -4-methyl-1,2,4-triazolin-5-one (Compound No. V- 41) In Production Example 17, ethyl 3-bromobenzoate was added to 3-
Instead of ethyl nitrobenzoate, the following reaction was performed in the same manner as described above, and 3- (3-nitrophenyl) -1- (4,4-difluoro-3-butenyl) -4-methyl-1,2,4-triazoline-5 was obtained. -One (Compound number: V-40) was obtained as a yellow oil. Total yield: 25.3% Obtained 3- (3-nitrophenyl) -1- (4,4-
Difluoro-3-butenyl) -4-methyl-1,2,4-
It was obtained in the same manner as in Production Example 3 from triazolin-5-one to obtain a yellow oil. Yield: 100%

Production Example 20 3- (3-acetaminophenyl) -1- (4,4-difluoro-3-butenyl) -4-methyl-1,2,4-triazolin-5-one (Compound No. V -42) 3- (3-Aminophenyl) -1 produced in Production Example 19
It was obtained in the same manner as in Production Example 4 from-(4,4-difluoro-3-butenyl) -4-methyl-1,2,4-triazolin-5-one to obtain a milky white solid. Yield: 59%

Production Example 21 1- (4,4-difluoro-3-butenyl) -4-methyl-3- {2- (methylsulfonyl) phenyl}-
1,2,4-triazolin-5-one (Compound number: V-
45) In Production Example 17, ethyl 3-bromobenzoate was added to 2-
1- (4,4-difluoro-3-butenyl) -4-, instead of methylthiobenzoate, was reacted in the same manner as described below.
Methyl-3- (2-methylthiophenyl) -1,2,4-
Triazolin-5-one (Compound No. V-44) was obtained as a colorless oil. Total yield: 29.7% Obtained 1- (4,4-difluoro-3-butenyl)-
4-methyl-3- (2-methylthiophenyl) -1,2,
It was obtained in the same manner as in Production Example 7 from 4-triazolin-5-one to obtain a colorless oil. Yield: 58%

Production Example 22 5- (3,5-Dichlorophenyl) -3- (4,4-difluoro-3-butenyl) -1,3,4-oxadiazolin-2-one (Compound No. VI-15) ) Synthesis of 3,5-dichlorobenzoic acid (25 g, 131 mol), concentrated sulfuric acid (15 ml) and ethanol (150 ml) were mixed and heated under reflux for 24 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure. 200 ml of water was added to the concentrated solution, and the mixture was extracted 3 times with 40 ml of ethyl acetate. The obtained ethyl acetate solution was washed successively with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried over anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, and the obtained solution was concentrated under reduced pressure. Ethyl 3,5-dichlorobenzoate was obtained as a colorless oil. Yield: 27.0 g Yield: 94.2% NMR (300 MHz, CDCl ₃ , δppm):
7.91 (d, 2H), 7.54 (d, 1H), 4.39
(Q, 2H), 1.40 (t, 3H)

Ethyl 3,5-dichlorobenzoate
A mixed solution of 27.0 g (123 mmol) and 100% hydrazine hydrate (30 ml) was heated under reflux for 1 hour.
After cooling to room temperature, the purified white solid was filtered, washed with water, and dried under reduced pressure to obtain 3,5-dichlorobenzoylhydrazine as a white solid. Yield: 25.0 g Yield: 100% NMR (300 MHz, DMSO-d ₆ , δppm):
10.07 (brs, 1H), 7.89 (d, 2H),
7.85 (d, 1H), 4.65 (brs, 2H)

3,5-dichlorobenzoylhydrazine
2.2 g (9.95 mmol) and triethylamine 2.
Suspend 7 ml in 70 ml tetrahydrofuran and
Cooled to. 1,1'-carbonyldiimidazole 3.
After adding 8 g (23.4 mmol), the mixture was stirred at room temperature for 12 hours. After concentration under reduced pressure, the obtained residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/1) to give 5- (3,5-dichlorophenyl) -1,3,4-oxaxane. Diazolin-2-one was obtained as a white solid. Yield: 2.05 g _{Yield: 97.4% NMR (300MHz, CDCl} 3 + DMSO-d 6,
δppm): 12.63 (brs, 1H), 7.68
(D, 2H), 7.65 (d, 1H)

5- (3,5-dichlorophenyl) -1,
0.3 g of 3,4-oxadiazolin-2-one (1.30
mmol), 4-bromo-1,1-difluoro-1-butene 0.22 g (1.30 mmol) and potassium carbonate
0.3 g (2.1 mmol) of acetonitrile 20 ml
And was heated to reflux overnight (12 hours). Room temperature (25
C.), concentrated under reduced pressure, 20 ml of water was added to the residue, and the mixture was extracted 3 times with 7 ml of ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1),
Target 5- (3,5-dichlorophenyl) -3- (4,4
-Difluoro-3-butenyl) -1,3,4-osadiazolin-2-one was obtained as a white solid. Yield: 0.15g Yield: 37.1%

Production Example 23 5- (3-aminophenyl) -3- (4,4-difluoro-3-butenyl) -1,3,4-oxadiazoline-2
-ON (Compound No. VI-30) In Production Example 22, 3,5-dichlorobenzoic acid was added to 3-.
Instead of nitrobenzoic acid, the same reaction as described below is carried out.
(4,4-Difluoro-3-butenyl) -5- (3-nitrophenyl) -1,3,4-oxadiazolin-2-one (Compound No. VI-29) was obtained as a pale yellow solid. Overall yield: 48.7% 3- (4,4-difluoro-3-butenyl) -obtained
It was obtained in the same manner as in Production Example 3 from 5- (3-nitrophenyl) -1,3,4-oxadiazolin-2-one to obtain a white solid. Yield: 59.0%

Production Example 24 5- {3- (acetamino) phenyl} -3- (4,4)
-Difluoro-3-butenyl) -1,3,4-oxadiazolin-2-one (Compound No. VI-31) Production Example 23
5- (3-aminophenyl) -3- (4,4) prepared in
It was obtained as a white solid by the same procedure as in Production Example 4 from -difluoro-3-butenyl) -1,3,4-oxadiazolin-2-one. Yield: 83.0%

Production Example 25 3- (4,4-difluoro-3-butenyl) -5- {3
-(Ethoxycarbonylamino) phenyl} -1,3,4
-Oxadiazolin-2-one (Compound number: VI-3
2) 5- (3-aminophenyl) -3 produced in Production Example 23
-(4,4-Difluoro-3-butenyl) -1,3,4-
It was obtained in the same manner as in Production Example 5 from oxadiazolin-2-one to obtain a white solid. Yield: 59.0%

Production Example 26 3- (4,4-difluoro-3-butenyl) -5- {2
-(Methylsulfonyl) phenyl} -1,3,4-oxadiazolin-2-one (Compound No. VI-35) In Production Example 22, 3,5-dichlorobenzoic acid was replaced with 2-.
Replace with methylthiobenzoic acid and react in the same manner as below. 3
-(4,4-Difluoro-3-butenyl) -5- (2-
Methylthiophenyl) -1,3,4-oxadiazoline-
2-one (Compound No. VI-34) was obtained as a white solid. Total yield: 84.6% Obtained 3- (4,4-difluoro-3-butenyl)-
It was obtained in the same manner as in Production Example 7 from 5- (2-methylthiophenyl) -1,3,4-oxadiazolin-2-one to obtain a white solid. Yield: 100%

Production Example 27 3- (4,4-difluoro-3-butenyl) -5- (3
-Chlorophenyl) -1,3,4-thiadiazoline-2-
Synthesis of ON (Compound No. VII-10) A mixed solution of 15 g of 3-chlorobenzoic acid, 15 ml of concentrated sulfuric acid and 150 ml of ethanol was heated under reflux for 24 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure. To the concentrated solution was added 200 ml of water, and the mixture was mixed with 40 ml of ethyl acetate to 3 times.
Extracted twice. The obtained ethyl acetate solution was washed successively with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried over anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, and the obtained solution was concentrated under reduced pressure. Ethyl 3-chlorobenzoate was obtained as a colorless oil. Yield: 17.6 g Yield: 84.6% NMR (300 MHz, CDCl ₃ , δppm):
8.02 (dd, 1H), 7.93 (dd, 1H), 7.
51 (dd, 1H), 7.38 (dd, 1H), 4.39
(Q, 2H), 1.40 (t, 3H)

Ethyl 3-chlorobenzoate 17.
A mixed solution of 6 g (95.4 mmol) and 100 ml of hydrazine hydrate (20 ml) was heated under reflux for 1 hour. After cooling to room temperature, the produced white solid was filtered and washed with water,
After drying under reduced pressure, 3-chlorobenzoylhydrazine was obtained as a white solid. Yield: 14.0 g Yield: 86.1% NMR (300MHz, DMSO -d 6, δppm):
10.12 (brs, 1H), 8.06 (dd, 1)
H), 7.99 (dd, 1H), 7.81 (dd, 1
H), 7.71 (dd, 1H), 4.76 (brs, 2)
H)

3-Chlorobenzoylhydrazine 2.0
g (11.7 mmol) and 2.7 g (35.1 mmol) of ammonium thiocyanate in ethanol 220
It was suspended in ml and 5 ml of concentrated hydrochloric acid was added. 22 with stirring
After heating under reflux for an hour, the temperature was returned to room temperature, and the mixture was concentrated under reduced pressure. After adding 60 ml of water, the solid matter was collected by filtration and washed with water. Drying under reduced pressure gave 1- (3-chlorobenzoyl) -thiosemicarbazide as a white solid. Yield: 0.63 g Yield: 23.4% NMR (300MHz, DMSO -d 6, δppm):
10.32 (brs, 1H), 9.19 (brs, 1
H), 7.80-7.30 (m, 6H)

While stirring 10 ml of concentrated sulfuric acid at room temperature, 1
-(3-chlorobenzoyl) -thiosemicarbazide
0.63 g (2.75 mmol) was added. 1 reaction solution
After stirring at 100 ° C. for an hour, it was poured into 100 ml of ice water. The solid is filtered off and recrystallized from ethanol to give 2-
Amino-5- (3-chlorophenyl) -1,3,4-thiadiazole was obtained as a white solid. Yield: 0.38 g Yield: 65.5% NMR (300MHz, DMSO -d 6, δppm):
8.00-7.55 (m, 4H), 4.60 (brs,
2H),

While stirring 8 ml of concentrated sulfuric acid at room temperature, 2-
Amino-5- (3-chlorophenyl) -1,3,4-thiadiazole 0.39 g (1.70 mmol) was added.
While maintaining the reaction solution at 10-15 ° C, 2 ml of an aqueous solution of 0.53 g (7.63 mmol) of sodium nitrite was added dropwise over 15 minutes. After the dropping, the mixture was stirred at room temperature for 30 minutes, and then 6 ml of 50% (w / w) acetic acid aqueous solution was added.
After stirring at room temperature for 24 hours, the reaction solution was poured into 50 ml of ice water, the formed solid matter was collected by filtration, washed with water, recrystallized from methanol, stirred with, and then poured into 100 ml of ice water. The solid is filtered off and recrystallized from methanol to give 5-
(3-chlorophenyl) -1,3,4-thiadiazoline-
2-one was obtained as a yellow solid. Yield: 0.25 g Yield: 69.4% NMR (300MHz, DMSO -d 6, δppm):
14-13 (brs, 1H), 8.1-7.5 (m, 4
H)

5- (3-chlorophenyl) -1,3,4-
Thiadiazolin-2-one 0.25g (1.2mmo
l), 4-bromo-1,1-difluoro-1-butene
0.21 g (1.23 mmol) and potassium carbonate 0.2.
23 g (1.76 mmol) of acetonitrile 20 m
It was suspended in 1 and heated to reflux overnight (12 hours). Room temperature (2
(5 ° C) and then concentrated under reduced pressure, leaving 20 ml of water in the residue.
Was added, and the mixture was extracted 3 times with 7 ml of ethyl acetate. The obtained ethyl acetate solution was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to give the desired 3- (4,4-difluoro-3-butenyl).
-5- (3-Chlorophenyl) -1,3,4-thiadiazolin-2-one was obtained as a yellow solid. Yield: 0.09 g Yield: 25.2%

Production Example 28 4- (4,4-difluoro-3-butenyl) -1-phenyl-5 (4H) -tetrazolinone (Compound No. VIII
-1) Synthesis Phenylisocyanate 1.2 g (10.0 mmol)
And trimethylsilyl azide 2.3 g (20.0 mmo
The mixture of l) was heated to reflux for 12 hours. After cooling to room temperature, the reaction mixture was poured into ice water. The aqueous layer was extracted twice with 30 ml of ethyl acetate. The combined ethyl acetate extracts were washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. By recrystallizing the obtained residue from ethyl acetate-hexane, 1-
Phenyl-5 (4H) -tetrazolinone was obtained. Yield: 1.4 g Yield: 86% NMR (300 MHz, CDCl ₃ , δppm): 1
4.2 (brs, 1H), 7.8-7.9 (m, 2H),
7.3-7.6 (m, 3H)

1-Phenyl-5 (4H) -tetrazolinone 0.48 g (3.0 mmol), 4-bromo-1,1
-Difluoro-1-butene 0.51 g (3.0 mmo
1) and 0.50 g (3.6 mmol) of potassium carbonate were added to 10 ml of acetonitrile, and the mixture was heated under reflux overnight.
After returning to room temperature, the solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give 4- (4,4-difluoro-3-butenyl) -1 as a colorless oil.
-Phenyl-5 (4H) -tetrazolinone was obtained. Yield: 0.50 g Yield: 66%

Production Example 29 5- (4-chlorophenyl) -1- (4,4-difluoro-3-butenyl)-(1H) -tetrazole (Compound No. IX-4) and 5- (4-chlorophenyl)- Two
-(4,4-Difluoro-3-butenyl)-(2H)-
Synthesis of tetrazole (Compound No. X-3) 4-chlorobenzonitrile 2.1 g (15.0 mmo)
l), sodium azide 2.9 g (45.0 mmol),
A mixture of 2.4 g (45.0 mmol) of ammonium chloride and 20 ml of dimethylformamide was added at 100 ° C. for 1 hour.
Stir for 2 hours. After cooling to room temperature, the reaction mixture was poured into ice water and the aqueous layer was acidified with dilute hydrochloric acid. The precipitated solid was collected by filtration and dried under reduced pressure to give a white solid
(4-Chlorophenyl)-(1H) -tetrazole was obtained. Yield: 2.4 g Yield: 88% NMR (300 MHz, DMSO-d ₆ , δppm):
8.07 (d, 2H), 7.51 (d, 2H)

5- (4-chlorophenyl)-(1H)-
Tetrazole 0.54 g (3.0 mmol), 4-bromo-1,1-difluoro-1-butene 0.51 g (3.5.
0 mmol) and potassium carbonate 0.50 g (3.6 mm)
ol) was added to 10 ml of acetonitrile, and the mixture was heated under reflux overnight. After returning to room temperature, the solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give the desired 5- (4-chlorophenyl) -1- (4,4).
-Difluoro-3-butenyl)-(1H) -tetrazole and 5- (4-chlorophenyl) -2- (4,4-
Difluoro-3-butenyl)-(2H) -tetrazole was obtained. 5- (4-chlorophenyl) -1- (4,4-difluoro-3-butenyl)-(1H) -tetrazole (Compound No. IX-4) Yield: 0.64 g Yield: 79% 5- (4- Chlorophenyl) -2- (4,4-difluoro-3-butenyl)-(2H) -tetrazole (Compound No. X-3) Yield: 0.05 g Yield: 6%

Production Example 30 Synthesis of 6- (4-chlorophenyl) -1- (4,4-difluoro-3-butenyl) -pyridazin-3 (2H) -one (Compound No. XI-9) 4'-chloro Acetophenone 5.0 g (32 mmo
1) and 20 ml of 40% aqueous glyoxylic acid solution were heated to reflux with stirring for 4 hours. The mixture was cooled to 0 ° C. in an ice bath, and while cooling, 50 ml of 25% aqueous ammonia was added little by little. 100 ml of ether was added, and the organic layer and the aqueous layer were separated with a separating funnel. 25% ammonia water in the organic layer 50
Extract with ml and combine the aqueous layers with 100 ml of ether.
Washed with. 20 ml of hydrazine monohydrate was added to the aqueous layer, and the mixture was heated under reflux overnight. The resulting crystals were filtered with suction and dried under reduced pressure to give 6- (4-chlorophenyl) -pyridazine-
3 (2H) -one was obtained as white crystals. Yield: 4.2 g Yield: 63% NMR (300 MHz, CDCl ₃ , δppm):
10.90 (brs, 1H), 7.8-7.7 (m, 3
H), 7.46 (dd, 2H), 7.07 (d, 1H)

6- (4-chlorophenyl) -pyridazin-3 (2H) -one 0.61 g (2.9 mmol), 4-
Bromo-1,1-difluoro-1-butene 0.50 g
(2.9 mmol) and potassium carbonate 0.45 g (3.
(2 mmol) was added to 20 ml of acetonitrile, and the mixture was heated under reflux overnight. After filtration through Celite, the mixture was concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 1: 2) to give the desired 6-
(4-chlorophenyl) -1- (4,4-difluoro-
3-Butenyl) -pyridazin-3 (2H) -one was obtained as a pale yellow oil. Yield: 0.69g Yield: 79%

Production Example 31 2- (3,5-Dichlorophenyl) -4- (4,4-difluoro-3-butenyl) -6H-1,3,4-oxadiazin-5-one (Compound No. XII-10) ) Synthesis of 3,5-dichlorobenzoylhydrazine 1.56 g
(7.61 mmol) of tetrahydrofuran 30 ml
Suspended in 0.75 ml (9.13 mmol) of pyridine
Was added and cooled to 0 ° C. A solution of 0.61 ml (7.61 mmol) of 2-chloroacetyl chloride in 5 ml of tetrahydrofuran was added dropwise with stirring over 10 minutes. After stirring at room temperature for 1.5 hours, the mixture was concentrated under reduced pressure, 50 ml of water was added to the obtained residue, and then 15 ml of ethyl acetate was added.
It was extracted 3 times with. The obtained ethyl acetate solution was dried over magnesium sulfate, removed by filtration, and dried under reduced pressure. The obtained solid was washed with hexane to obtain N-{(3,5-dichlorophenyl) carbonylamino} -2-chloroethanamide as a white solid. Yield: 2.14 g Yield: 100% NMR (300 MHz, DMSO-d ₆ , δpp
m): 10.8 (brs, 1H), 10.5 (brs,
1H), 7.95 (d, 2H), 7.75 (d, 1H),
4.18 (s, 2H)

N-{(3,5-dichlorophenyl) carbonylamino} -2-chloroethanamide 2.30 g
(8.85 mmol) and potassium carbonate 3.42 g (2
(6.5 mmol) was suspended in 3.5 ml of acetonitrile, and the mixture was heated under reflux for 12 hours with stirring. After returning the reaction solution to room temperature, it was concentrated under reduced pressure, and the resulting residue was mixed with 50 ml of water.
After the addition of, the mixture was extracted 3 times with 15 ml of diethyl ether. The obtained diethyl ether solution was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and dried under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 2/1) to give 2- (3,5-dichlorophenyl) -4H, 6H-1,3,4 as a white solid. -Oxadiazine-5-
Got on. Yield: 0.41 g Yield: 20.5% NMR (300 MHz, DMSO-d ₆ + CDCl
₃ , δppm): 11.2-11.0 (brs, 1)
H), 7.88 (dd, 2H), 7.45 (d, 1H),
4.74 (s, 2H)

2- (3,5-dichlorophenyl) -4H,
6H-1,3,4-oxadiazin-5-one 0.3 g
Anhydrous of (1.22 mmol) and 4-bromo-1,1-difluoro-1-butene 0.23 g (1.35 mmol)
It was dissolved in 20 ml of N, N-dimethylformamide.
While stirring at room temperature (25 ° C), sodium hydride (60
% Oil suspension) 0.03 g (1.25 mmol) was added. After stirring as it is at room temperature for 12 hours, ice water 20
Poured to 0 ml. The resulting solution is diethyl ether 2
After extraction with 0 ml three times, the obtained diethyl ether solution was washed successively with water and saturated saline, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was removed by filtration and the mixture was dried under reduced pressure. The obtained residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate =
2/1) to give 2- (3,5 as a pale yellow solid.
-Dichlorophenyl) -4- (4,4-difluoro-3)
-Butenyl) -6H-1,3,4-oxadiazine-5-
Got on. Yield: 0.13 g Yield: 31.7%

Production Example 32 2- (3-Aminophenyl) -4- (4,4-difluoro-3-butenyl) -6H-1,3,4-oxadiazin-5-one (Compound No. XII-31) In Production Example 31, 3,5-dichlorobenzoylhydrazine was replaced with 3-nitrobenzoylhydrazine, and the following reaction was performed in the same manner to give 4- (4,4-difluoro-3-butenyl) -2- (3-nitrophenyl). -6H-1,3,
4-oxadiazin-5-one (Compound number: XII-3
0) was obtained as a pale yellow solid. Overall yield: 5.74% 4- (4,4-difluoro-3-butenyl) -obtained
2- (3-Nitrophenyl) -6H-1,3,4-oxadiazin-5-one was obtained in the same manner as in Production Example 3 to obtain a beige solid. Yield: 100%

Production Example 33 5- {3- (acetamino) phenyl} -4- (4,4)
-Difluoro-3-butenyl) -6H-1,3,4-oxadiazin-5-one (Compound No. XII-32) 2- (3-aminophenyl) -4 obtained in Production Example 32
-(4,4-difluoro-3-butenyl) -6H-1,
It was obtained in the same manner as in Production Example 4 from 3,4-oxadiazin-5-one to obtain a white solid. Yield: 86.5%

Production Example 34 4- (4,4-difluoro-3-butenyl) -2- {4
-(Methylsulfinyl) phenyl} -6H-1,3,4
-Oxadiazin-5-one (Compound number: XII-1
4) In Production Example 31, 3,5-dichlorobenzoylhydrazine was replaced with 4-methylthiobenzoylhydrazine, and the same reaction was performed below to give 4- (4,4-difluoro-).
3-butenyl) -2- (4-methylthiophenyl) -6
H-1,3,4-oxadiazin-5-one (Compound No. XII-13) was obtained as a pale yellow oil. Overall yield: 6.23% Obtained 4- (4,4-difluoro-3-butenyl)-
2- (4-Methylthiophenyl) -6H-1,3,4-oxadiazin-5-one was obtained in the same manner as in Production Example 6 to obtain a white solid. Yield: 63.4%

Production Example 35 4- (4,4-difluoro-3-butenyl) -2- {4
-(Methylsulfonyl) phenyl} -6H-1,3,4
-Oxadiazin-5-one (Compound number: XII-1
5) 4- (4,4-difluoro-3-butenyl) -2- (4
-Methylthiophenyl) -6H-1,3,4-oxadiazin-5-one (Compound No. XII-13) was obtained in the same manner as in Production Example 7 to obtain a white solid. Yield: 63.4%

Production Example 36 3- (4,4-Difluoro-3-butenyl) -2-methylthio-3H-quinazolin-4-one (Compound No .:
XIII-1) 2-Methylthio-3H-quinazolin-4-one 0.51
g (2.6 mmol), 4-bromo-1,1-difluoro-1-butene 0.53 g (3.1 mmol) and potassium carbonate 0.43 g (3.1 mmol) were added to 10 ml of acetonitrile, and the mixture was heated under reflux overnight. . After returning to room temperature, the solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue is purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give the desired 3-
(4,4-Difluoro-3-butenyl) -2-methylthio-3H-quinazolin-4-one was obtained as a white solid. Yield: 0.16 g Yield: 22%

The compounds of the present invention shown in Tables 1 to 21 below were produced according to the method of any of the above Production Examples. In the table, Me: methyl group, Et: ethyl group, Pr: n-propyl group, iPr: isopropyl group, cPr: cyclopropyl group, tBu: tert-butyl group, cHex: cyclohexyl group, Ph: phenyl group, Py: Indicates a pyridyl group. Each compound obtained in each reaction is a conventional separation means, for example, an organic solvent extraction method, a chromatography method,
It can be easily isolated and purified from the reaction mixture by a conventional isolation and purification means such as a recrystallization method. Physical properties and the like of the obtained compound of the present invention are shown in Tables 22 to 54 below.
In addition, ¹ H-NMR spectrum shows tetramethylsilane (T
MS) was used as a reference substance.

[0195]

[Table 1]

[0196]

[Table 2]

[0197]

[Table 3]

[0198]

[Table 4]

[0199]

[Table 5]

[0200]

[Table 6]

[0201]

[Table 7]

[0202]

[Table 8]

[0203]

[Table 9]

[0204]

[Table 10]

[0205]

[Table 11]

[0206]

[Table 12]

[0207]

[Table 13]

[0208]

[Table 14]

[0209]

[Table 15]

[0210]

[Table 16]

[0211]

[Table 17]

[0212]

[Table 18]

[0213]

[Table 19]

[0214]

[Table 20]

[0215]

[Table 21]

[0216]

[Table 22]

[0217]

[Table 23]

[0218]

[Table 24]

[0219]

[Table 25]

[0220]

[Table 26]

[0221]

[Table 27]

[0222]

[Table 28]

[0223]

[Table 29]

[0224]

[Table 30]

[0225]

[Table 31]

[0226]

[Table 32]

[0227]

[Table 33]

[0228]

[Table 34]

[0229]

[Table 35]

[0230]

[Table 36]

[0231]

[Table 37]

[0232]

[Table 38]

[0233]

[Table 39]

[0234]

[Table 40]

[0235]

[Table 41]

[0236]

[Table 42]

[0237]

[Table 43]

[0238]

[Table 44]

[0239]

[Table 45]

[0240]

[Table 46]

[0241]

[Table 47]

[0242]

[Table 48]

[0243]

[Table 49]

[0244]

[Table 50]

[0245]

[Table 51]

[0246]

[Table 52]

[0247]

[Table 53]

[0248]

[Table 54]

Formulation examples are shown below. Formulation Example 1 (Emulsion) 10 parts by weight of each of the compounds of the present invention were dissolved in 45 parts by weight of Solvesso 150 and 35 parts by weight of N-methylpyrrolidone, and an emulsifier (trade name: Solpol 3005) was added thereto.
X, manufactured by Toho Kagaku Co., Ltd.) and mixed with stirring to obtain 10% emulsion of each.

Formulation Example 2 (Wettable powder) 20 parts by weight of each of the compounds of the present invention, 2 parts by weight of sodium lauryl sulfate, 4 parts by weight of sodium lignin sulfonate, 20 parts by weight of synthetic hydrous silicon oxide fine powder and 54 parts by weight of clay. Was added to the mixture and mixed with stirring with a mixer to obtain a 20% wettable powder.

Production Example 3 (Granule) To 5 parts by weight of each of the compounds of the present invention, 2 parts by weight of sodium dodecylbenzenesulfonate, 10 parts by weight of bentonite and 83 parts by weight of clay were added and sufficiently stirred and mixed.
An appropriate amount of water was added, and the mixture was further stirred, granulated with a granulator, and dried under ventilation to obtain 5% granules.

Production Example 4 (Dust) 1 part by weight of each of the compounds of the present invention was dissolved in an appropriate amount of acetone, and 5 parts by weight of synthetic hydrous silicon oxide fine powder and PAP were added to the solution.
0.3 part by weight of (acidic isopropyl phosphate) and 93.7 parts by weight of clay were added, and the mixture was stirred and mixed with a juice mixer to remove acetone by evaporation to obtain a 1% powder.

Formulation Example 5 (flowable agent) 20 parts by weight of each of the compounds of the present invention and 1.5 parts by weight of sorbitan trioleate were mixed with 28.5 parts by weight of an aqueous solution containing 2 parts by weight of polyvinyl alcohol, and then mixed in a sand grinder. After pulverization (particle size: 3 microns or less), an aqueous solution containing xanthan gum (0.05 parts by weight) and aluminum magnesium silicate (0.1 parts by weight) 4
0 parts by weight, 10 parts by weight of propylene glycol were further added, and mixed by stirring to obtain a 20% suspension in water.

Next, it is shown by way of test examples that the compound of the present invention is useful as an active ingredient of insecticides and acaricides.
The compounds of the present invention are shown by the compound numbers shown in Table 1.

Test Example 1 Insecticidal test against spider mites A non-woven fabric (4.5 x 5.5 cm) was dripped into the cup through a notch made in the lid of the plastic cup, tap water was put into the cup, and the lid was covered. Bean beans leaf pieces (about 3.5 cm x 4.5 cm) are placed on a non-woven fabric that has been sufficiently absorbed with water, and then leaf beans pieces that have been parasitic on Nami mites (about 20 individuals) are placed on it, and placed in a thermostatic chamber at 25 ± 2 ° C and a humidity of 40%. I let it stand. Next, an aqueous solution (100 ppm) of Solpol 355 (manufactured by Toho Kagaku) was added to a methanol solution of the compound of the present invention to prepare a chemical solution (200 ppm) of the compound of the present invention.
Next, after spraying this chemical solution, it was air-dried and kept in a thermostatic chamber (25 ±
The sample was allowed to stand still at 2 ° C. and a humidity of 50%), and two days after the treatment, the mortality rate of Nami mites was investigated.

As a result, the following compounds showed 100% acaricidal activity against spider mites. II-1, II-2, II-3, II-4, II-5, II-6, II
-7, II-9, II-10, II-11, II-12, II-1
3, II-14, II-16, II-17, II-18, II-1
9, II-20, II-21, II-24, II-25, II-3
1, II-32, II-33, II-35, III-11, III-24, III-41, III-45, V-4, V-6, V-7, V-8, V-11, V-1
2, V-13, V-14, V-15, V-17, V-1
9, V-20, V-21, V-22, V-24, V-2
5, V-26, V-27, V-35, V-36, V-3
8, V-39, V-40, V-41, V-43, V-4
7, V-48, V-49, V-50, V-51, V-5
2, V-53, V-54, V-55, V-56, V-5
7, V-58, VI-4, VI-5, VI-7, VI-8, VI-9, VI-10,
VI-11, VI-12, VI-13, VI-14, VI-15,
VI-16, VI-17, VI-19, VI-21, VI-22,
VI-25, VI-26, VI-27, VI-28, VI-29,
VI-33, VI-34, VI-35, VII-10, VIII-3, VIII-14, VIII-21, IX-6, IX-10, IX-12, IX-16, IX-21, IX
-22, XI-6, XI-8, XI-9, XI-13, XI-15, XI-1
8, XI-24, XI-26, XI-27, XII-1, XII-2, XII-4, XII-5, XII-6, XII-
7, XII-9, XII-10, XII-11, XII-12, XII
-13, XII-14, XII-16, XII-18, XII-2
2, XII-23, XII-24, XII-26, XII-27, XI
I-28, XII-30, XII-31, XII-34, XII-3
5, XII-36, XII-37, XII-42, XII-43, XI
I-44, XII-45, XII-46, XII-47

Test Example 2 Insecticidal test pot against green leafhopper (3 × 4 × 4 cm) 2.5 ml of the chemical solution of the compound of the present invention described in Test Example 1 in rice planted (concentration: 200 pp
m) was dropped on the soil surface. After the drug solution penetrates the soil,
Release 2nd instar larvae of the leafhopper leafhopper (about 7 individuals / cup) from the hole on the top with an acrylic cup, close the hole with absorbent cotton, and leave it in a temperature-controlled room (25 ± 2 ° C, humidity 50%). The mortality rate of leafhoppers was investigated day after day. As a result, the following compounds against the leafhopper leafhopper,
It showed 100% insecticidal activity. I-2, I-3, I-4, I-5, I-7, I-8, I
-9, I-10, I-11, I-12, I-13, I-
14, I-15, I-16, I-19, I-20, I-
22, I-24, II-1, II-4, II-5, II-6, II-10, II-1
3, II-14, II-18, II-21, II-28, II-2
9, II-32, V-1, V-2, V-4, V-10, V-11, V-1
2, V-15, V-18, V-21, V-22, V-2
5, V-29, V-33, V-36, V-37, V-3
9, VI-2, VI-4, VI-5, VI-7, VI-8, VI-9, VI
-11, VI-12, VI-13, VI-21, VI-27, VI
-30, VI-34, VI-35, VIII-10, VIII-13, VIII-26, XII-2, XII-4, XII-5, XII-9, XII-10, XII
-25, XII-26, XII-27, XII-28, XII-47

Test Example 3 Insecticidal test against green peach aphid A non-woven fabric (4.5 × 5.5 cm) was dropped into a plastic cup through a notch formed in the lid, tap water was put into the cup, and the lid was closed. Leaf piece of cabbage second leaf (2 cm
X 3 cm) and cover it with an acrylic cup for 25 ± 2
It was left to stand in a constant temperature room at a temperature of 40 ° C. and a humidity of 40%. The next day, the chemical solution (200 ppm) described in Test Example 1 was sprayed, air-dried, and allowed to stand in a thermostatic chamber (25 ± 2 ° C, humidity 50%) for 3 days to examine the mortality rate of the green peach aphid. As a result, the following compounds showed 100% insecticidal activity against the green peach aphid. I-1, I-2, I-3, I-4, I-5, I-6, I
-8, I-9, I-10, I-11, I-12, I-1
3, I-14, I-15, I-16, I-17, I-1
9, I-20, I-21, I-22, I-23, II-16, II-21, II-32, XII-9, XII-11, XII-12, XII-13, XII-1
6, XII-23, XII-24, XII-25, XII-27, XI
I-28, XII-31, XII-35, XII-37, XII-3
8, XII-39, XII-40, XII-41, XII-42, XI
I-43, XII-44, XII-46, XII-47

[0259]

INDUSTRIAL APPLICABILITY According to the present invention, a novel substance which is highly safe against mammals and is effective as an insecticide for agricultural and horticultural use and an acaricide, and an insecticide for agricultural and horticultural use containing the novel substance as an active ingredient An acaricide can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A01N 43/653 A01N 43/653 A Q 43/713 43/713 43/78 43/78 F 43/824 43 / 88 43/88 47/20 Z 47/20 C07D 231/20 Z C07D 231/20 237/04 237/04 237/14 237/14 239/95 239/95 249/08 535 249/08 535 249/12 504 249/12 504 506 506 509 509 509 511 511 257/04 A 257/04 E G 271/10 271/10 273/04 273/04 277/36 277/36 401/04 285/13 405/10 401/04 413/10 405/10 417/04 413/10 A01N 43/82 101E 417/04 C07D 285/12 C (72) Inventor Yasuhiro Endo 615 Satoura-cho, Satoura-cho, Naruto-shi, Tokushima Otsuka Chemical Co., Ltd. Naruto Laboratory (72 ) Inventor Yasuhiro Sasama 615 Satoura, Satoura-cho, Naruto City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Naruto Study (72) Inventor Naoki Ishii 615 Satoura, Satoura-cho, Naruto City, Tokushima Prefecture F-term (reference) in Naruto Laboratory, Otsuka Chemical Co., Ltd. (reference) 4C033 AD01 AD02 AD09 AD17 4C036 AD16 AD18 AD19 AD20 AD21 AD22 AD24 AD27 4C056 AA01 AB02 AC07 AD01 AE03 AF04 4C063 AA01 BB01 BB06 CC22 CC28 CC41 CC47 CC67 CC81 DD11 DD22 DD59 EE03 4H011 AC01 AC04 BA01 BB09 BB10 BB13 BC01 BC03 BC05 BC07 BC08 BC09 BC17 BC18 BC19 BC20 DA02 DA15 DA16 DC01 DC05 DC06 DC08 DH02 DH10 DH14

Claims (17)

[Claims] 1. A 4,4-difluoro-3-butenyl compound represented by the formula (1). [Chemical 1] [In the formula, Q may have a substituent, at least 1
A heterocyclic group having two nitrogen atoms is shown attached at the nitrogen atom. However, Q = phthalimide group is excluded. ] 2. A heterocyclic group group in which Q is represented by Q1 to Q13.
4,4-diflu of claim 1, which is one selected from
Oro-3-butenyl compound. [Chemical 2] [Where R¹, R^Two, R^Three, R^Four, And R⁵Are the same or
Differently hydrogen atom, C_{1 -4}Alkyl group, C_1-4Shiku
Lower alkyl group, C_1-4Haloalkyl group, C_{1- Four}Al
Kirthio group, C_1-4Alkoxycarbonyl group, phenyl
Group, benzyl group and heterocyclic group. Also halogen source
Child, C_1-4Alkyl group, C_1-4Haloalkyl group, C
_1-4Alkoxy group, C_1-4Haloalkoxy group, C
_1-4Alkylthio group, C_1-4Alkylsulfinyl
Base, C_1-4Alkylsulfonyl group, nitro group, sia
Group, amino group, formyl group, C_1-4Acyl group, cal
Boxyl group, C_1-4Alkoxycarbonyl group, C
_1-4Alkylaminocarbonyl group, phenoxy group,
Phenyl group, R group⁶-OCONH-, group R⁷-CONH
-, Group --C (R⁸) = NOR⁹, Group -C (R¹⁰) (O
R¹¹) (OR¹²A group selected from the group
A phenyl group, a benzyl group or a heterocyclic group is shown. R⁶as well as
R ⁷Is C_1-4Indicates an alkyl group. R⁸, R⁹And R
¹⁰Is a hydrogen atom or C_1-4Indicates an alkyl group. R¹¹
And R¹²Is C_1-4Shows an alkyl group, but together
To form a ring. X represents an oxygen atom or a sulfur atom
You ] 3. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q1). 4. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q2). 5. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q3). 6. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q4). 7. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q5). 8. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q6). 9. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q7). 10. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q8). 11. The 4,4-difluoro-3-butenyl compound according to claim 1, wherein Q is represented by formula (Q9). 12. The method according to claim 1, wherein Q is represented by formula (Q10).
The 4,4-difluoro-3-butenyl compound described. 13. The method according to claim 1, wherein Q is represented by formula (Q11).
The 4,4-difluoro-3-butenyl compound described. 14. The method according to claim 1, wherein Q is represented by formula (Q12).
The 4,4-difluoro-3-butenyl compound described. 15. The method according to claim 1, wherein Q is represented by formula (Q13).
The 4,4-difluoro-3-butenyl compound described. 16. An insecticidal and acaricidal composition for agricultural and horticultural use, which comprises the compound according to claim 1. 17. An insecticidal and acaricidal composition for agricultural and horticultural use, which comprises the compound according to claim 2.