JP5425909B2 - Novel 4-heterocyclic substituted pyrimidine derivatives and agricultural and horticultural pest control agents containing them - Google Patents

Description

  The present invention relates to a novel 4-heterocyclic substituted pyrimidine derivative, a method for producing the same, and an agricultural and horticultural pest control agent containing the compound as an active ingredient.

  From Patent Documents 1 to 3, it is known that a compound in which a heterocycle is substituted at the 4-position of thienopyrimidine has pest control activity. However, it cannot be said that the pesticidal activity of these compounds is sufficient.

JP 52-68197 A Japanese Patent Application Laid-Open No. 4-216785 Special table 2008-517936

  In addition to the above, 4-heterocyclic substituted pyrimidines having pesticidal activity are disclosed, for example, in Patent Documents 4 to 17 below.

International Publication No. 94008975 European Patent No. 0407899 International Publication No. 010996314 International Publication No. 02068413 International Publication No. 02074753 International Publication No. 030439993 International Publication No.04103978 International Publication No. 05019207 International Publication No. 0507798 JP-A-2005-350353 JP 2006-1914 International Publication No. 07036477 International Publication No. 07083692 International Publication No. 07093527

  However, bacteria and pests that are resistant to existing pest control agents are not followed. Therefore, development of a novel pyrimidine compound that does not intersect with existing control agents and has excellent pest control activity is still required.

  As a result of repeated studies by the present applicants in order to achieve the above object, it has been found that a novel pyrimidine derivative represented by the following formula (1) exhibits an excellent pest control activity.

  That is, the present invention relates to a novel 4-heterocyclic substituted pyrimidine derivative represented by the following formula (1), a production method thereof, and an agricultural and horticultural pest control agent comprising the same as an active ingredient.

  The novel 4-heterocyclic substituted pyrimidine derivative of the present invention represented by the following formula (1) exhibits an excellent control effect against pests, particularly agricultural and horticultural pests.

  The details of the present invention are as follows.

The compound of the present invention is a 4-heterocyclic substituted pyrimidine derivative represented by the following formula (1).
In equation (1),
R ¹ and R ² are independently a hydrogen atom, a halogen atom, an amino group, a cyano group, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different and substituted with a halogen atom 1 to 13 A linear or branched haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, the same or Differently, it represents a straight-chain or branched haloalkoxy group having 1 to 6 carbon atoms, a straight-chain or branched alkenyloxy group having 2 to 6 carbon atoms, which is substituted with 1 to 13 halogen atoms. .

Alternatively, R ¹ and R ² may be combined to form a benzene ring or an aromatic heterocyclic ring, and the ring is a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms. A linear or branched haloalkyl group having 1 to 6 carbon atoms, which is the same or different and substituted with a halogen atom 1 to 13, a linear or branched alkoxy group having 1 to 6 carbon atoms, The linear or branched haloalkoxy groups having 1 to 6 carbon atoms which are the same or different and are substituted with halogen atoms 1 to 13 may be optionally substituted one or more.

R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a straight chain substituted with a halogen atom 1 to 13 Or a branched haloalkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, the same or different, and having 1 carbon atom substituted with a halogen atom 1 to 13 -6 haloalkoxy groups, cyano groups, and nitro groups.

Alternatively, R ³ and R ⁴ may be combined with the carbon atom to which they are bonded to form a carbonyl group.

n = 0 to 5
Q is a linear or branched alkyl group having 1 to 6 carbon atoms, and is the same or different and is a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 A linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched haloalkoxy group having 1 to 6 carbon atoms which is the same or different and is substituted with a halogen atom 1 to 13 A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkynyl group having 2 to 6 carbon atoms, the same or different, and substituted with a halogen atom 1 to 11 A linear or branched haloalkenyl group having 2 to 6 carbon atoms, a linear or branched alkenyloxy group having 2 to 6 carbon atoms, a linear or branched carbon atom having 2 to 6 carbon atoms Alkynyloxy groups, the same or different A linear or branched haloalkenyloxy group having 2 to 6 carbon atoms substituted with a halogen atom 1 to 11, (straight or branched alkyl having 1 to 6 carbon atoms) -CO -An acyl group represented by a group, (a linear or branched alkyl having 1 to 6 carbon atoms)-an acyloxy group represented by a -CO-O- group, or a linear or branched carbon atom having 1 to 6 alkyl) -alkoxycarbonyl group represented by —O—CO— group, linear or branched alkylthio group having 1 to 6 carbon atoms, the same or different, and directly substituted with halogen atoms 1 to 13 A linear or branched haloalkylthio group having 1 to 6 carbon atoms, an alkylsulfinyl group represented by (linear or branched alkyl having 1 to 6 carbon atoms) -SO- group (the same or different , Halogen atom 1 A linear or branched haloalkyl having 1 to 6 carbon atoms substituted with 13) -halo-sulfinyl group represented by -SO- group (a linear or branched alkyl having 1 to 6 carbon atoms) An alkylsulfonyl group represented by —SO ₂ — group (the same or different, linear or branched alkyl having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms) —SO ₂ — group A haloalkylsulfonyl group, a linear or branched dialkylamino group having 1 to 6 carbon atoms, (the same or different, the number of linear or branched carbon atoms substituted with 1 to 13 halogen atoms) 1-6 alkyl) -amino groups substituted by an alkylsulfonyl group represented by —SO ₂ — group, _two linear or branched alkyl groups having 1 to 6 carbon atoms are placed in the amino group. A carbonyl group substituted by a substituted dialkylamino group , a sulfonyl group substituted by a dialkylamino group in which a linear or branched alkyl group having 1 to 6 carbon atoms is substituted on the amino group , a halogen atom, a hydroxyl group , A cyano group, a nitro group, a phenyl group, a naphthyl group, and an aromatic heterocyclic group.

  When n is 2 or more, these substituents Q may be the same or different.

A represents a 5-membered ring structure represented by the formula (2).
In equation (2),
V represents an oxygen atom or a sulfur atom.

X is an oxygen atom, a sulfur atom, —CR ¹¹ R ¹² —, —NR ¹³ — (R ^{11 to} R ¹³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or, differently, a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms is shown.

R ⁵ and R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched group substituted with a halogen atom 1 to 13 1 to 6 carbon atom haloalkyl groups. Alternatively, R ⁵ and R ⁶ may be combined with the carbon atom to which they are bonded to form a carbonyl group.

R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with halogen atoms 1 to 13 6 represents a haloalkyl group.

Of the atoms constituting the ring, N _a represents a nitrogen atom bonded to the 4-position of the pyrimidine ring, and C _b is bonded to a carbon atom bonded to phenyl, R ³ , or R ^4. Carbon atom.

Or A shows the cyclic structure of the 6-membered ring represented by Formula (3).
In formula (3), W represents an oxygen atom or a sulfur atom.

Y is an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —NR ¹⁶ — (R ^{14 to} R ¹⁶ are independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or, differently, a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms is shown.

Z represents an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —S (O) —, —S (O) ₂ —, —NR ¹⁶ —.

  However, Y and Z are not oxygen atoms at the same time, and are not sulfur atoms at the same time.

R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched group substituted with a halogen atom 1 to 13 1 to 6 carbon atom haloalkyl groups.

R ¹⁰ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 6 represents a haloalkyl group.

Of the atoms constituting the ring, N _c represents a nitrogen atom bonded to the 4-position of the pyrimidine ring, and C _d bonded to a carbon atom bonded to phenyl, R ³ , or R ^4. Carbon atom.

Production method of the compound of the present invention The compound of the present invention represented by the formula (1) is a 4-halopyrimidine derivative represented by the formula (4) and the formula (5) or the formula (6) as shown below. It can be produced by reacting the represented heterocyclic ring in the presence of a base.
However, the union of (1a) and (1b) indicates (1).
(In the above formula, R ^{1 to} R ¹⁰ , Q, V, W, X, Y, Z, and n have the same meaning as described above, and L represents a halogen atom)

  A solvent is usually used for the above reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the above reaction, and acid amides such as N, N-dimethylformamide and N-methylpyrrolidone, ethers such as 1,4-dioxane and tetrahydrofuran, Examples thereof include aromatic hydrocarbons such as benzene and toluene.

  Examples of the base that can be used in the above reaction include sodium hydride, sodium methylate, sodium ethylate, and potassium tertiary butyrate.

  The amount of the reagent used for the reaction is usually about 1 to 1.5 for the heterocyclic ring represented by the formula (5) or the formula (6) with respect to 1 equivalent of the pyrimidine derivative represented by the formula (4). Equivalent, base is about 1-2 equivalents.

  In the above reaction step, the reaction temperature and reaction time are usually −80 ° C. to 50 ° C., 10 minutes to 24 hours. After completion of the reaction, it is obtained by subjecting it to normal treatment and purifying it by operations such as column chromatography and recrystallization as necessary.

  The 4-halopyrimidine derivative of the formula (4) is commercially available, or a part thereof can be synthesized by the methods described in Patent Documents 18 and 19, or the like.

  The heterocyclic ring of the formula (5) is commercially available, or a part thereof can be synthesized by the method described in Non-Patent Documents 1 and 2, Patent Document 20 or the like, or a method according to them.

  About the heterocyclic ring of Formula (6), the one part can be synthesize | combined by the method as described in a nonpatent literature 1, 3, 4, etc., or the method according to them.

Japanese Patent Application Laid-Open No. 2002-7762 JP 2002-275164 A JP 2007-254409 A

Journal of Organic Chemistry, Vol. 70, No. 14, (2005) 5725-5728 Synthetic Communications, 25 (4), 561-568 (1995) Synthetic Communications, 27 (10), 1777-1782 (1997) Bioorganic & Medicinal Chemistry Letters, 18 (2008) 4316-4320

  The novel 4-heterocyclic substituted pyrimidine according to the present invention exhibits excellent pest control activity. The range of the 4-heterocyclic substituted pyrimidine derivative of the compound of the present invention includes various salts (sodium salt, potassium salt, magnesium) of the derivative in addition to the 4-heterocyclic substituted pyrimidine derivative represented by the formula (1). Salts, calcium salts, aluminum salts, etc.), hydrates, solvates, and polymorphic substances are also encompassed by the present invention. Furthermore, all possible stereoisomers or optical isomers present in the compound of the present invention, and mixtures containing two or more kinds of isomers in any ratio are also included in the scope of the compound of the present invention.

  Hereinafter, although the detail of the structure of this invention compound (1) is demonstrated, it is not limited to the compound which has specific groups, such as group illustrated there.

The compound of the present invention is a pyrimidine derivative in which a heterocyclic ring is substituted at the 4-position as shown in the general formula (1). More specifically, it is a compound in which one of the nitrogen atoms constituting the heterocyclic ring is bonded to the 4-position of the pyrimidine, and has a substituent on the carbon atom constituting the heterocyclic ring adjacent to the nitrogen atom. A good phenylmethyl group or benzoyl group is bonded.
R ¹ and R ^{2 in} formula (1) are independently a hydrogen atom, a halogen atom, an amino group, a cyano group, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a halogen atom A linear or branched haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a linear or branched carbon atom having 1 to 6 carbon atoms substituted with 1 to 13 An alkoxy group, which is the same or different and represents a linear or branched haloalkoxy group having 1 to 6 carbon atoms and an alkenyloxy group having 2 to 6 carbon atoms substituted with 1 to 13 halogen atoms, Preferably, R ¹ is the same or different and is a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with halogen atoms 1 to 13 (for example, 1-fluoroethyl group, 1-chloroethyl group, 1-Brom A methyl group), R ² is a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom).

R ¹ and R ² may be combined to form a benzene ring or an aromatic heterocycle (eg, furan, thiophene, pyrrole, pyrazole, thiazole, pyrimidine), and a benzene ring or a thiophene ring is preferable. . The ring includes a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and the number of linear or branched carbon atoms substituted with 1 to 13 halogen atoms. 1 to 6 haloalkyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, the same or different, linear or branched carbon atoms 1 substituted with halogen atoms 1 to 13 To 6 haloalkoxy groups, and these substituents may be optionally substituted one or more, but may be unsubstituted or substituted with halogen (for example, fluorine atom, chlorine atom, bromine atom). preferable.

R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a straight chain substituted with a halogen atom 1 to 13 Or a branched haloalkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, the same or different, and having 1 carbon atom substituted with a halogen atom 1 to 13 6 to 6 haloalkoxy groups, cyano groups and nitro groups, preferably R ³ and R ⁴ are the same or different and are a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group).

n = 0 to 5
Q is a linear or branched alkyl group having 1 to 6 carbon atoms, and is the same or different and is a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 A linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched haloalkoxy group having 1 to 6 carbon atoms which is the same or different and is substituted with a halogen atom 1 to 13 A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkynyl group having 2 to 6 carbon atoms, the same or different, and substituted with 1 to 4 halogen atoms A linear or branched haloalkenyl group having 2 to 6 carbon atoms, a linear or branched alkenyloxy group having 2 to 6 carbon atoms, a linear or branched carbon atom having 2 to 6 carbon atoms Alkynyloxy groups, the same or different , A linear or branched haloalkenyloxy group substituted with 1 to 4 halogen atoms, (linear or branched alkyl having 1 to 6 carbon atoms) -CO- An acyl group represented by a group, (a linear or branched alkyl having 1 to 6 carbon atoms) -CO-O- group, an (acyloxy group represented by a linear or branched carbon atom having 1 to 6 carbon atoms) Alkyl) -O-CO- group, a linear or branched alkylthio group having 1 to 6 carbon atoms, the same or different, and a straight chain substituted with 1 to 13 halogen atoms Or a branched or branched haloalkylthio group having 1 to 6 carbon atoms, an alkylsulfinyl group represented by (a linear or branched alkyl having 1 to 6 carbon atoms) -SO- group (the same or different, Halogen atoms 1-1 A straight-chain or branched haloalkyl having 1 to 6 carbon atoms substituted with a haloalkylsulfinyl group represented by -SO- group, (a straight-chain or branched alkyl having 1 to 6 carbon atoms)- SO 2 _- alkylsulfonyl group represented by group, (identical or different, alkyl of has been being linear or branched 1 to 6 carbon atoms substituted by halogen atoms 1 to 13) -SO 2 _- represented by group A haloalkylsulfonyl group, a linear or branched dialkylamino group having 1 to 6 carbon atoms, (the same or different, a linear or branched carbon atom having 1 to 13 carbon atoms substituted by 1 to 13 halogen atoms) ˜6 alkyl) -amino group substituted by an alkylsulfonyl group represented by —SO ₂ — group, and _two linear or branched alkyl groups having 1 to 6 carbon atoms are substituted on the amino group. A carbonyl group substituted by a dialkylamino group , a sulfonyl group substituted by a dialkylamino group in which a linear or branched alkyl group having 1 to 6 carbon atoms is substituted on the amino group , a halogen atom, a hydroxyl group, A cyano group, a nitro group, a phenyl group, a naphthyl group, or an aromatic heterocyclic group, preferably a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group), an alkoxy group (for example, a methoxy group), a halogen atom ( For example, fluorine atom, chlorine atom), phenyl group, aromatic heterocyclic group.

  When n is 2 or more, these substituents Q may be the same or different.

Alternatively, R ³ and R ⁴ may be combined with the carbon atom to which they are bonded to form a carbonyl group.

  n = 0-5 is shown.

A in Formula (1) represents a 5-membered ring structure represented by Formula (2).
V represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

X is an oxygen atom, a sulfur atom, —CR ¹¹ R ¹² —, —NR ¹³ — (R ^{11 to} R ¹³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or a different, linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms, preferably an oxygen atom or —CR ¹¹ R ¹² — (for example, R ¹¹ and R ¹² are both hydrogen atoms).

R ⁵ and R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched group substituted with a halogen atom 1 to 13 Wherein R ⁵ and R ⁶ are both hydrogen atoms, R ⁵ and R ⁶ are both alkyl groups (for example, methyl group, ethyl group, isopropyl group), or R Either ⁵ or R ⁶ is a hydrogen atom, and the other is an alkyl group (for example, methyl group, ethyl group, isopropyl group). Alternatively, R ⁵ and R ⁶ may be combined with the carbon atom to which they are bonded to form a carbonyl group.

R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with halogen atoms 1 to 13 6 represents a haloalkyl group, preferably a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group).

Of the atoms constituting the ring, N _a represents a nitrogen atom bonded to the 4-position of the pyrimidine ring of formula (1), and C _b represents phenyl, R ³ , R ^{4 of} formula (1). A carbon atom bonded to a carbon atom bonded to is shown.

Alternatively, A in the formula (1) represents a 6-membered ring structure represented by the formula (3).
In formula (3), W represents an oxygen atom or a sulfur atom, preferably an oxygen atom.

Y is an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —NR ¹⁶ — (R ^{14 to} R ¹⁶ are independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms, preferably an oxygen atom or —CR ¹⁴ R ¹⁵ — (for example, R ¹⁴ and R ¹⁵ are both hydrogen atoms).

Z represents an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —S (O) —, —S (O) ₂ —, —NR ¹⁶ —, preferably an oxygen atom or —CR ¹⁴ R ¹⁵ — ( For example, R ¹⁴ and R ¹⁵ are both hydrogen atoms).

  However, Y and Z are not oxygen atoms at the same time, and are not sulfur atoms at the same time.

R ⁸ and R ⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched group substituted with a halogen atom 1 to 13 Wherein R ⁸ and R ⁹ are both hydrogen atoms, R ⁸ and R ⁹ are both alkyl (for example, methyl group, ethyl group, isopropyl group), or R ⁸ Alternatively, either one of R ⁹ is a hydrogen atom, and the other is an alkyl group (for example, a methyl group, an ethyl group, or an isopropyl group).

R ¹⁰ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 6 is a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group).

Also, among the atoms constituting the ring, _{N c} represents the 4-position and nitrogen atom linked to the pyrimidine ring of formula (1), also _{C d} is phenyl of formula ^(1), R 3, ^{R 4} A carbon atom bonded to a carbon atom bonded to is shown.

  In the present invention, the term “halogen” includes fluorine, chlorine, bromine and iodine.

  In the present invention, the term “halo” in “halo...” (For example, “haloalkyl”) includes fluorine, chlorine, bromine and iodine.

  In the present invention, the term “alkyl” represents a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. , Isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, or n-hexyl group.

  In the present invention, the term “alkenyl” refers to a linear or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include an ethenyl group and a propenyl group.

  In the present invention, the term “alkynyl” refers to a linear or branched alkynyl group having 2 to 6 carbon atoms, and examples thereof include an ethynyl group and a propynyl group.

  In the present invention, the term “haloalkyl” is the same or different and represents a linear or branched alkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms, such as a fluoromethyl group, Examples thereof include a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a dichloroethyl group, and a bromopropyl group.

  In the present invention, the term “cycloalkyl” refers to a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  In the present invention, the term “alkoxy” refers to an (alkyl) -O— group in which the alkyl portion has the above meaning, and examples thereof include a methoxy group, an ethoxy group, and an isopropoxy group.

  In the present invention, the term “haloalkoxy” refers to a (haloalkyl) -O— group in which the haloalkyl moiety has the above meaning, and examples thereof include a difluoromethoxy group, a trifluoromethoxy group, and a chloropropoxy group.

  In the present invention, the term “alkenyloxy” refers to an (alkenyl) -O— group in which the alkenyl moiety has the above meaning, and examples thereof include an ethenyloxy group, a propenyloxy group, and a butenyloxy group.

  In the present invention, the term “haloalkenyl” is the same or different and represents a linear or branched alkenyl group having 2 to 6 carbon atoms substituted with 1 to 4 halogen atoms. A tenenyl group, a trichloropropenyl group, etc. can be mentioned.

  In the present invention, the term “haloalkenyloxy” means a (haloalkenyloxy) -O— group in which the haloalkenyl moiety has the above-mentioned meaning, and examples thereof include a trifluoroethenyloxy group and a trichloropropenyloxy group. it can.

  In the present invention, the term “acyl” represents a group represented by (a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms) —CO— group, such as a methylcarbonyl group, Examples thereof include an ethylcarbonyl group and a propylcarbonyl group. In the present application, the aliphatic hydrocarbon group means alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl.

  In the present invention, the term “acyloxy” refers to a (linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms) —CO—O— group, for example, methylcarbonyloxy group, ethylcarbonyl An oxy group etc. can be mentioned.

  In the present invention, the term “alkoxycarbonyl” refers to an (alkoxy) -CO— group in which the alkoxy moiety has the above meaning, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

  In the present invention, the term “alkylthio” refers to an (alkyl) -S— group in which the alkyl moiety has the above meaning, and examples thereof include a methylthio group, an ethylthio group, and a propylthio group.

  In the present invention, the term “haloalkylthio” means a (haloalkyl) -S— group in which the haloalkyl moiety has the above meaning, and examples thereof include a chloroethylthio group and a trifluoroethylthio group.

  In the present invention, the term “alkylsulfinyl” refers to an (alkyl) -SO— group in which the alkyl portion has the above meaning, and examples thereof include a methylsulfinyl group and an ethylsulfinyl group.

  In the present invention, the term “haloalkylsulfinyl” refers to a (haloalkyl) -SO— group in which the haloalkyl moiety has the above meaning, and examples thereof include a trifluoromethylsulfinyl group.

In the present invention, the term “alkylsulfonyl” refers to an (alkyl) -SO ₂ — group in which the alkyl moiety has the above meaning, and examples thereof include a methylsulfonyl group.

In the present invention, the term “haloalkylsulfonyl” refers to a (haloalkyl) -SO ₂ — group in which the haloalkyl moiety has the above meaning, and examples thereof include a difluoromethylsulfonyl group and a trifluoromethylsulfonyl group.

In the present invention, the term “dialkylamino” refers to an (alkyl) ₂ —N— group in which the alkyl moiety has the above meaning, and examples thereof include a dimethylamino group and a diethylamino group.

In the present invention, the term “haloalkylsulfonylamino” refers to a (haloalkyl) -SO ₂ —NH— group in which the haloalkyl moiety has the above meaning, and examples thereof include a trifluoromethylsulfonylamino group.

  In the present invention, the term “dialkylaminocarbonyl” means a (dialkylamino) -CO— group in which the dialkylamino moiety has the above meaning, and examples thereof include a dimethylaminocarbonyl group and a diethylaminocarbonyl group.

In the present invention, the term “dialkylaminosulfonyl” means a (dialkylamino) -SO ₂ — group in which the dialkylamino moiety has the above meaning, and examples thereof include a dimethylaminosulfonyl group and a diethylaminosulfonyl group.

  In the present invention, the term “aromatic heterocycle” comprises 1 to 3 rings, and at least one or two or more atoms (hetero atoms) selected from a nitrogen atom, an oxygen atom and a sulfur atom as ring atoms. ) And a heterocyclic compound having (4n + 2) (n is 1, 2 or 3) π electrons in the ring. In the present invention, the term “aromatic heterocyclic group” means a group excluding a hydrogen atom on any ring atom (carbon atom or hetero atom) constituting the “aromatic heterocyclic ring”. Examples of such aromatic heterocyclic groups include furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, triazinyl and the like.

Application as agricultural and horticultural pest control agent The compound represented by the general formula (1) has a pest control action and can be used as an agricultural and horticultural pest control agent.

  In the present invention, “agricultural and horticultural pests” refers to all pests that cause harmful effects on vegetables, fruit trees, paddy rice, flower buds, and the like. The pests refer to plant diseases and storage diseases such as various agricultural and forestry and horticulture, as well as various agricultural and forestry and horticultural and storage pests, sanitary pests and nematodes.

  Specific examples of plant diseases for which the compounds of the present invention exhibit a controlling effect include the following.

Rice blast (Pyricularia oryzae), rice rot (Rhizoctonia solani), rice idiot (Gibberella fujikuroi), wheat powdery mildew (Erysiphe graminis f.sp.tritici), barley powdery mildew (Erysiphe graminis f.sp) hordei), wheat eye spot disease (Pseudocercosporella herpotrichoides), wheat black rust (puccinia graminis), wheat anthracnose (Colletotrichum graminicola), wheat leaf blight (Septoria tritici), potato epidemic (Phytophthora infestans), potato summer plague Alternaria solani), potato anthracnose (Colletotrichum atramentarium), potato black rot (Thanatephorus cucumeris), potato gray mold (Botrytis cinerea), azuki bean powder (Erysiphe pisi), azuki bean brown (Cercospora canescens) Nuclear disease (Sclerotinia sclerotiorum), azuki bean anthracnose (Colletotrichum phaseolorum), brown bean disease (Cercospora canescens), kidney bean sclerotia (Sclerotinia sclerotiorum), kidney bean Colletotrichum lindemuthianum, kidney bean gray mold (Botrytis cinerea), soybean anthracnose (Colletotrichum truncatum), soybean purpura (Cercospora kikuchii), soybean rust (Phakopsora pachyrhizi), konjac anthracnose (Gloeosporium conch) Diseases (Colletotrichum theae-sinensis), spinach brown spot (Cercospora beticola), spinach anthracnose (Colletotrichum spinaciae), spinach downy mildew (Peronospora effusa), cabbage black spot (Alternaria brassicae), cabbage black soot (olaternaria brassicic) ), Cabbage nuclear disease (Sclerotinia sclerotiorum), cabbage gray mold disease (Botrytis cinerea), komatsuna anthracnose disease (Colletotrichum higginsianum), Chinese cabbage fungus nuclear disease (Sclerotinia sclerotiorum), Chinese cabbage mold black spot disease (Alternaria brassicae, Alternaria brassicia) Black spot (Alternaria cucumerina), pumpkin gray mold (Botrytis cinerea), pumpkin downy mildew (Pseudoperonospora cubensis), Cucumber powdery mildew (Sphaerotheca fuliginea), cucumber plague (Phytophthora melonis), cucumber brown spot (Corynespora cassiicola), cucumber sclerotia (Sclerotinia sclerotiorum), cucumber black spot (Alternaria cucumerina), genus cucumber hum Cucumber vines (Fusarium oxysporum f.sp. And diseases (Pseudoperonospora cubensis), watermelon powdery mildew (Sphaerotheca fuliginea), watermelon plague (Phytophthora cryptogea), watermelon mycosis (Sclerotinia sclerotiorum), watermelon anthracnose (Colletotrichum orbiculare), watermelon mildew (Pseudoperonospora Brown spot disease (Corynespora cassiicola), Melon sclerotia (Sclerotinia sclerotiorum), Melon vine split disease (Fusarium oxysporum f.sp. melonis), Melon downy mildew (Pseudope) ronospora cubensis), Fusarium oxysporum, Sclerotinia sclerotiorum, Puccinia cnici-oleracei, Gloeosporium chrysanthemi, Gloeosporus carium disease, Carrot powdery mildew (Erysiphe heraclei), carrot fungus nuclear disease (Sclerotinia intermedia, Sclerotinia sclerotiorum), carrot black leaf blight (Alternaria dauci), carrot black spot (Alternaria radicina), red pepper pepper wilt (Fusarium oxysporum) Pepper powdery mildew (Oidiopsis sicula), red pepper, pepper sweet potato (Phytophthora capsici), red pepper pepper sclerotia (Sclerotinia sclerotiorum), red pepper, pepper anthracnose (Colletotrichum gloeosporioides) ), Tomato wilt (Fusarium oxysporum f.sp. lycopersici), tomato powdery mildew (Oidiopsis) sicula), tomato plague (Phytophthora infestans), tomato mycosis (Sclerotinia sclerotiorum), tomato gray mold (Botrytis cinerea), tomato leaf mold (Fulvia fulva), eggplant plague (Phytophthora infestans), eggplant brown spot (Thanatephorus) cucumeris), eggplant brown rot (Phytophthora capsici), eggplant mycosis (Sclerotinia sclerotiorum), eggplant brown spot (Alternaria solani), strawberry wilt (Fusarium oxysporum), strawberry wilt (Verticillium dahliae), strawberry powdery mildew (Sphaerotheca humuli), strawberry plague (Phytophthora nicotianae var. Parasitica), strawberry fruit rot (Pythium ultimum var. fragariae), strawberry anthracnose (Colletotrichum acutatum, Glomerella cingulata), strawberry gray mold (Botrytis cinerea), asparagus brown spot (Cercospora asparagi), asparagus stem blight (Phomopsis asparagi) Asparagus rust (Puccinia asparagi-lucidi), Asparagus anthracnose (Colletotrichum gloeosporioides), Asparagus gray mold (Botrytis cinerea), onion plague (Phytophthora nicotianae), onion yellow spot (Cladosporium allii-cepae), onion rot Disease (Fusarium oxysporum f.sp. cepae), onion fungus nuclear disease (Sclerotinia sclerotiorum), onion black spot blight (Septoria alliacea), onion black spot (Alternaria sp.), Onion rust (Puccinia allii), onion Sclerotinia allii, onion small rot (Botrytis squamosa), onion white plague (Phytophthora porri), onion anthracnose (Colletotrichum circinans), onion black spot (Alternaria sp.), Onion gray mold Disease (Botrytis cinerea), onion gray rot (Botrytis allii), onion leaf blight (Pleospora herbarum), onion downy mildew (Peronospora destructor), leek rust (Puccinia allii), leek white leaf blight (Botrytis b) yssoidea), leek plague (Phytophthora nicotianae), leek wilt (Fusarium oxysporum), leek black astringency (Mycosphaerella allicina), leek black leaf blight (Septria alliacea), leek black spot (Alternaria porri), leek small fungus nucleus Disease (Sclerotinia allii), leek rust (Puccinia allii), leek small rot rot (Botrytis squamosa), leek white plague (Phytophthora porri), leek anthracnose (Colletotrichum circinans), leek downy mildew (Peronospora destructor), Mango anthracnose (Colletotrichum gloeosporioides), oyster powdery mildew (Phyllactinia kakikola), oyster-contaminated fruit diseases (Colletotrichum ssp., Glomerella sp.), Oyster keratosis (Cercospora kakivora), oyster keratosis (Cercospora kaki) Oyster brown spot disease (Macrophoma kaki), Oyster black spot disease (Fusicladium levieri), Oyster black spot disease (Phomopsis kakivora), Oyster black spot disease (Pseudocercospora fuliginosa), Oyster leaf spot disease (Physalospora kaki), Oyster soot disease (Aureobasidium pullulans), Capnophaeum fuliginodes, Cladosporium herbarum, Microxyphium sp., Scorias communis, Tripospermum juglandis) Oyster soot spot (Zygophiala jamaicensis), Oyster anthracnose (Gloeosporium kaki), Oyster gray mold (Botrytis cinerea), Oyster leaf blight (Pestalotia diospyri), Oyster leaf anthracnose (Glomerella cingulata), oyster circle leaf defoliation (Mycosphaerella nawae), ume powdery mildew (Podosphaera tridactyla, Sphaerotheca pannosa), ume branch blight (Botryosphaeria dothidea), ume fungus nuclear disease (Sclerotinia sclerotiorum), ume black star disease (Cladospium carpium) , Plum white rust (Leucotelium pruni-persicae), ume white coat (Rosellinia necatrix), ume heart rot (Fusarium lateritium), ume stomata (Pseudocercospora circumscissa), plum scab (Sphaceloma pruni-domesticae), Japanese apricot anthracnose (Glomerella cingulata), Japanese apricot gray mold (Botrytis cinerea), Japanese apricot ash scab (Monilinia fructicola, Monilinia laxa), Japanese apricot leaf anthracnose (Glomerella mume), sugarcane sclerotia (Sclerotinia sclerotiorum), sugar beet Disease (Podosphaer a tridactyla), sweet scab (Rhizopus nigricans), sweet potato anthracnose (Glomerella cingulata), sweet scab (Botrytis cinerea), sweet scab (Monilinia fructicola), pear powdery mildew (Phyllactinia mali) Pear plague (Phytophthora cactorum, Phytophthora syringae), pear black scab (Venturia pirina), pear anthracnose (Colletotrichum gloeosporioides), pear scab (Gymnosporangium asiaticum), pear powdery mildew (Phyllactia , Phytophthora syringae), pear black spot disease (Venturia nashicola), pear black spot disease (Alternaria kikuchiana), pear soot spot disease (Leptothyrium pomi), pear anthracnose disease (Glomerella cingulata), pear gray mold disease (Botrytis cinerea), pear ash Star disease (Monilinia fructigena), pear leaf anthracnose (Colletotrichum gloeosporioides), pear ring rot (Physalospora piricola), peach leaf mold (Fusarium oxysporum, Gibberella zeae), peach udon Diseases (Podosphaera tridactyla, Sphaerotheca pannosa), peach sclerotia (Sclerotinia sclerotiorum), peach black mold (Rhizopus nigricans), peach black rot (Cladosporium carpophilum), peach white rust (Leucotelium pruni-persicae) Disease (Stenella sp.), Peach perforation disease (Pseudocercospora circumscissa, Phyllosticta persicae), peach anthracnose (Gloeosporium laeticolor), peach gray mold (Botrytis cinerea), peach ash star disease (Monilinia fructicola), peach homohomosis opsis sp.), apple scab (Gymnosporangium yamadae), apple powdery mildew (Podosphaera leucotricha), apple blight (Phytophthora cactorum, phytophthora cambivola, Phytophthora syringae), apple brown spot (Diplocarpon mali) Cristulariella moricola), apple black spot disease (Venturia inaequalis), apple soot spot disease (Zygophiala jamaicensis), apple anthracnose disease (Glomerella cingulata), apple gray mold disease (Botrytis cinerea), apple spotted leaf fall Disease (Alternaria mali), grape powdery mildew (Uncinula necator), grape shoot blight (Sclerotinia sclerotiorum), grape late rot (Glomerella cingulata), grape brown spot (Pseudocercospora vitis), grape brown leaf blight (Briosia ampelophaga), grape black rot (Elsinoe ampelina), grape black rot (Guignardia bidwellii), grape vine split (Phomopsis viticola), grape downy mildew (Plasmopara viticola), chestnut anthracnose (Glomerella cingulata), chestnut Soot disease (Capnodium salicinum), chestnut brown spot disease (Morenoella quercina), chestnut powdery mildew (Microsphaera alphitoides), chestnut leaf blight (Monochaetia monochaeta), citrus gray mold disease (Botrytis cinirea), citrus brown rot (Phytophthora citrophthora) ), Citrus black spot (Diaporthe citri), citrus yellow spot (Mycosphaerella citri, Mycosphaerella horii), citrus scab (Elsinoe fawcettii), citrus freckles (Mycosphaerella pinodes), citrus anthracnose (Colletotrichum gloeosp oides), citrus rust (Colletotrichum gloeosporioides), etc.

  Moreover, the following are mentioned as a specific example of the pest which this invention compound shows a control effect, for example.

  As the bugs of the stink bugs, there are planthoppers such as the brown planthopper (Laodelphax striatellus), the brown planthopper (Nilaparvata lugens) and the white-tailed planthopper (Sogatella furcifera). Leafhoppers such as Empoasca onukii and Nephotettix cincticeps. Aphids such as cotton aphids (Aphis gossypii), black pea aphids (Lipaphis erysimi), peach aphids (Myzus persicae). Stink bugs such as Trigonotylus tenuis and Riptortus clavatus. Whiteflies such as Grape Whiteflies (Aleurolobus taonabae), Silver Leaf Whiteflies (Bemisia argentifolii), Tobacco Whiteflies (Bemisia tabaci), and Whiteflies Whitefly (Trialeurodes vaporariorum). Whales such as citrus whale (Diaphorina citri). The scale insects such as the horn beetle (Ceroplastes ceriferus) and the scaleworm (Chloropulvinaria aurantii). Bamboo worms such as pear worm scale (Comstockaspis perniciosa), citrus spot worm (Pseudaonidia duplex), and Yenen scale (Unaspis yanonensis). Gumbai beetles such as Kikugunbai (Galeatus affinis).

  Lepidopterous insects include Adoxophyes orana, Adoxophyes honmai, Apple sincoy (Grapholita inopinata), Pear tiger moth (Grapholita molesta), Legumin squirrel (Leguminivora glycinivorella), mulberry ute Toads such as. Tutuga such as Chilo suppressalis, Cnaphalocrocis medinalis, Ephestia elutella, Glyphodes pyloalis, Parapediasia teterrella. Common moths such as Galleria mellonella. Butterflies such as Parrotara guttata. Agrotis ipsilon, Helicoverpa armigera, Mamestra brassicae, Ayayoto (Pseudaletia separata), Seiamito (Sesamia inferens), Spodoptera litura, Spodoptera litura, Spodoptera optura , Moths such as Helicoverpa spp. And Earias spp. Memushiga, such as Argyresthia conjugella. Sink moths such as peach sink squid (Carposina sasakii). White butterflies such as Pieris rapae. Hosoga species such as Caloptilia theivora, Appleoptia zachrysa, Phyllonorycter ringoniella, Spulerrina astaurota. Sink moths such as peach sink moth (Carposina niponensis). Chibiga such as Lomonetia clerkella. Hosoga species such as Phyllonorycter ringoniella. Stigmata such as mandarin orange (Phyllocnistis citrekka). Suga, such as Plutela xylostella. Kibaga such as pink ball worm (Pectinophora gossypiella).

  Examples of fly insect pests include Culex pipiens pallens, Culex tritaeniorhynchus, and Culex quinquefasciatus. Houseflies such as the housefly (Musca domestica) and the housefly (Muscina srabulans). Bumbleflies such as the fly fly (Delia platura) and the onion fly (Delia antique). Some fly flies such as soybean flies (Asphondylia yushimai). Fruit flies such as fruit flies (Bactrocera cucurbitae), fruit flies such as Bactrocera dorsalis, fruit flies, butterflies, fly flies, abs, sand flies, and leafhoppers such as Agromyza oryzae.

  Coleoptera insects include corn root worms such as Western corn root worm (Diabrotica virgifera virgifera) and Southern corn root worm (Diabrotica undecimpunctata). Scarabaeidae such as Anomala cuprea, Anomala rufocuprea, and Popillejaponica. Aphid such as tobacco beetle (Lasioderma serricorne). Weevil such as cotton weevil (Anthonomus gradis gradis), beetle weevil (Callosobruchuys chienensis), weevil (Lissorhoptrus oryzophilus), weevil (Listroderes costirostris), weevil (Sitophilus zeamais). Grub beetles such as Tenebrio molitor and Tribolium castaneum. Leaf beetles such as rice beetle (Oulema oryzae), leaf beetle (Aulacophora femoralis), leaf beetle (Phyllotreta striolata), and color beetle (Leptinotarsa decemlineata). Epilacunas such as Epilachna vigintioctopunctata. Nagashin worms, longhorn beetles, etc.

  Thrips such as Thrips palmi as thrips. Frankliniella occidentalis, etc. Silto slips such as Shiroto thrips dorsalis.

  Examples of bee pests include bees, ants, and wasps.

  Examples of cockroach insects include cockroaches and German cockroaches.

  Grasshopper pests include grasshoppers and vignetting.

  Examples of flea pests include human fleas.

  Examples of lice insects include beetles.

  Termite pests include termites.

  As the mite insect pests, spider mites (Tetranychus urticae), Kanzawa spider mites (Tetranychus kanzawai), citrus spider mites (Panonychus citri), apple spider mites (Panonychus ulmi), spider mites, etc. Fusid mites such as Acarops pelekassi and Aculus schlechtendali. Dust mites such as Polyphagotarsonemus latus. Tick such as tick (Haemaphysalis longicornis), tick (Haemaphysalis flava), Dermacentor taiwanicus, Ixodes ovatus, Ixodes persulcatus, Boophilus tick (Boophilus microplus) Mite, such as Tyrophagus putresxentiae. Leopard mites such as Dermatophagoides farinae and Dermatophagoides ptrenyssnus. Clawed ticks (Cheyletus eruditus), stag beetles (Cheyletus malaccensis), crested ticks (Cheyletus moorei), etc.

  The nematodes include Aphelenchoides ritzemabosi, Aphelenchus avenae, Pratylenchus coffeae, Pratylenchus fallax, Heterodera glycine, Heterodera (Globodera rostochiensis), Meloidogyne hapla, Meloidogyne incognita, Tylenchulus semipenetrans and the like.

  The compound according to the present invention is applied to a plant by spraying, spraying, applying, etc., or treating plant seeds, soil surrounding the plant or soil sowing seeds, paddy fields, hydroponics water as an active ingredient This can be done by processing. When used as a fungicide, the application can be done before or after the plant is infected with the pathogen. When used as an insecticide, application can be performed before or after the occurrence of pests.

  The active compound of the present invention can be used alone or as a preparation thereof, but it can be used as a bactericidal / fungicidal agent, bactericidal agent, acaricide, nematicide, insecticide, biological pesticide, herbicide, plant hormone agent , Plant growth regulators, synergists, attractants, repellents, pigments, fertilizers, etc., or mixtures of one or more selected from those active ingredients to control pests It can also be used as an agent. There, it can be expected that the action, pests to be controlled, expansion of the appropriate period of use, or reduction of dosage, synergistic effect, or prevention of development of resistance, etc. Shinogi, cooperative medicinal effects with joint ingredients are achieved.

Examples of co-components in the mixture are the following compounds:
Fungicide:
Azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, fluconazole, hexaconazole Hexaconazole, imibenconazole, metoconazole, microbutanil, penconazole, propiconazole, simeconazole, tebuconazole, triadmephone (triimon) Azimenol, triticonazole, imazalil, triflumizole, pefurazoate, prochloraz, fenarimol, fenhexamid, fenpropimod Off (fenpropimorph), Piperarin (piperalin), spiroxamine (spiroxamine), etc..
Iprodione, myclozolin, procymidone, vinclozolin, quinoxyfen, fludioxonil, etc.
Chlorothalonil, dithianon, captan, folpet, iminoctadine-albesilate, iminoctadine-triacetate, ferbam, nabam , Maneb, mancozeb, metiram, propineb, polycarbamate, thiuram, ziram, zineb, cupric oxide Cupric hydroxide, copper oxychloride, copper sulfate (anhydride), copper sulfate, sulfur, and the like.
Benomyl, carbendazim, dietofencarb, zoxamide, pencycuron, fluopicolide, etc.
Furametpyr, penthiopyrad, thifluzamide, boscalid, oxycarboxin, carboxyxin, fluopyram, flutolanil, mepronil, etc.
Azoxystrobin, picoxystrobin, kresoximmethyl, trifloxystrobin, orysastrobin, metinominostrobin, pyraclostrobin, famoxadone famoxadone), fenamidone, pyribencarb, etc.
Diflumetorim, cyazofamid, amisulbrom, meptyl dinocap, fluazinam, ferimzone, etc.
Iprobenfos, isoprothiolane, quintozene, propamocarb, prothicarb, dimethomorph, iprovalicarb, benthiavalicarb, mandipropamid, mandipropamid
Balidamycin, polyoxin B, etc.
Pyroquion, tricyclazole, carpropamid, diclocymet, fenoxanil, etc.
Acibenzolar-S-methyl, probenazole, isothianil, laminarin, etc.
Simoxanil, fosetyl-Al, triazoxide, metasulfocarb, flusulfamide, etc.
Ethaboxam, cyflufenamid, metrafenone, etc.
Cyprodinil, mepanipyrim, pyrimethanil, blastcidin-S, streptomycin, kasugamycin, etc.
Metalaxyl, metalaxyl-M, oxadixyl, bupirimate, hymexazol, oxolinic acid, etc.

Insecticides, acaricides, nematicides:
Aldicarb, benfuracarb, carbaryl, carbofuran, carbofuran, carbosulfan, fenobucarb, methiocarb, metomyl, oxamyl, thiodicarb ),etc.
Acephate, chlorpyrifos, diazinon, dimethoate, malathion, methamidophos, monocrotophos, parathion-methyl, profenofos , Terbufos, etc.
Endosulfan, ethiprole, fipronil, etc.
Bifenthrin, cypermethrin, esfenvalerate, etofenprox, lambda-cyhalothrin, tefluthrin, DDT (DDT), methoxychlor, etc. .
Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, etc.
Spinosyn, spinetoram, etc.
Abamectin, emamectin benzoate, milbemectin, etc.
Kinoprene, metoprene, phenoxycarb, pyriproxyfen, etc.
Methyl bromide, chloropicrin, etc.
Pymetrozine, flonicamid, etc.
Clofentezine, hexythiazox, etoxazole, etc.
Diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, etc.
Chlorfenapyr, etc.
Bensultap, cartap, thiocyclam, etc.
Chlorfluazuron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, proflumuron, proflumuron ),etc.
Cyromazine, chromafenozide, halofenozide, methoxyfenozide, tebufenozide, etc.
Amitraz, hydramethylnon, acequinocyl, etc.
Fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone, etc.
Indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, etc.
Aluminum phosphide, etc.
Chlorantranilprole, flubendiamide, etc.
Azadirachtin, benzoximate, bifenazate, chinomethionate, dicohol, pyridalyl, etc.

Herbicide:
Bensulfuron-methyl, azimsulfuron, cinosulfuron, cyclosulfamuron, pyrazosulfuron-ethyl, propyrisulfuron, flucetosulfuron (flucetosulfuron) ), Metazosulfuron, imazosulfuron, indanofan, cyhalofop-butyl, tenylchlor, esprocarb, etobenzanid, cefentrol, cafenprole , Dimethametryn, daimuron, bifenox, pyributicarb, pyriminobac-methyl, pretilachlor, bromobutide, benzofena p), benthiocarb, pentoxazone, fenoxasulfone, pyroxasulfone, benfuresate, mefenacet, fenoxaprop-P-ethyl ), Metamifop, phenmedipham, diclofop-methyl, desmedipham, ethofumesate, isoproturon, amidosulfuron, anilofos ), Benfuresate, penoxsulam, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, ethoxysulfuron, iodosulfuron, isoxadifen ( isoxadifen), horamsulfuron, Pyraclonil, mesosulfuron, diuron, neburon, dinoterb, carbetamide, carboxamide, bromoxynil, oxadiazon, dimefuron, difenfenan, diflufenican Aclonifen, benzofenap, topramezone, pyrasulfotole, oxaziclomefone, isoxaflutole, oxadiargyl, flurtamone, tribuinme ), Metabenzthiaazuron, tribufos, metamitron, methitron, ethiozin, flufenacet, sulcotrione, benzobicyclon, mesotrione , Tefyltrione, Fentrazamide, propoxycarbazone, flucarbazone, metosulam, amicarbazone, etc.
Glyphosate-isopropylamine, glyphosate-trimesium, glufosinate, bialaphos, butamifos, prosulfocarb, asuram, linuron (linuron), calcium peroxide, alachlor, pendimethalin, acifluorfen-sodium, lactofen, ioxynil, alloxydim, cetoxydim (sethoxydim), napropamide, pyrazolate, pyraflufen-ethyl, imazapyr, sulfentrazone, oxadiazon, paraquat, diquat , Simazine, atrazine, fluthiaset Le (fluthiacet-methyl), Gizarohoppu Ethyl (quizalofop-ethyl), bentazone (bentazone), triaziflam (triaziflam), etc.
Thidiazuron, mefenpyr, ethephon, cyclanilide, etc.

Biological pesticides:
Nuclear polyhedrosis virus (NPV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), etc.
Steinernema carpocapsae, Steinernema glaseri, Monocrosporium phymatophagum, Steinernema kushidaie, trans Paste, e
Agrobacterium radiobacter, Bacillus subtilis, Erwinia carotovora, Pseudomonas fluorescens, Talaromyces flavmacho dermatroder ),etc.
Bacillus thuringiensis, Beauveria brongniartii, Beauveria bassiana, Paecilomyces fumosoroseus, Verticillium lecanii, verticillium lecanii, camp ris est.
Onsatsume wasp (Encarsia formosa), Sakakuyaku bee (Eretmocerus eremicus), Scarlet hornet (Eretmocerus eremicus), Collared wasp (Aphidius colemani), Aphidoletes aphidimyza, Isaea ae Spotted bee (Dacnusa sibirica), dusty mite (Phytoseiulus persimilis), Amblyseius cucumeris, Amblyseius californicus, Orius strigicollis, etc.

Pheromone agents:
Codrelua ((E, E) -8,10-Dodecadien-1-ol), Dout Armilla B ((Z) -9-Tetradecen-1-ol), Tetradodecenyl acetate ((Z) -11-Tetradecenyl acetate), pyrimalua (14-Methyl-1-octadecene), peach flua ((Z) -13-Eicosen-10-one), etc.

Natural fungicides and natural insecticides:
Machine oils, Methylphenyl acetate, α-Pinene, Protein hydrolysate, (Z) -1-Tetradecen-1-ol, Turpentine ,etc.

As the form of the pharmaceutical preparation, powder, granule, powder, wettable powder, granule wettable powder, aqueous solvent, granular aqueous solvent, tablet, emulsion, liquid agent, oil agent, surf agent, flowable, emulsion, microemulsion, Examples include Suspoemulsion, Suspension, Microcapsule, Jumbo, Aerosol, ULV (Cold Mist, Warm Mist), Smoke, Fumigant, Paste, Coating Agent, Seed Coating Oil It is done. Such embodiments are suitable for improving the dispersibility and other properties of the active ingredient and, if desired, carriers such as at least one compound of the invention and a suitable solid carrier, liquid carrier, liquid gaseous carrier, etc. It can be produced by an ordinary method of mixing together with auxiliary agents (for example, surfactant, spreading agent, dispersant, stabilizer).

  Examples of solid carriers include plant materials (eg, crystalline cellulose, starch, wood flour, cork, coffee husk, etc.), fibrous materials, artificial plastic powder, inorganic mineral materials (eg, kaolin, bentonite, white clay, diatomaceous earth). , Synthetic hydrous silicon oxide, clay, acid clay, talc, vermulite, montmorillonite, pumice, sulfur powder, apatite, mica, sericite, quartz powder, activated carbon, calcium carbonate, etc.), polymer compound (polyvinyl chloride) , Petroleum resin, etc.), chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, ammonium chloride, calcium chloride, urea, etc.).

  Examples of liquid carriers and diluents include water, alcohols (methanol, ethanol, isopropanol, cyclohexanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), ethers (ethyl cellosolve, butyl cellosolve, dioxane, etc.) , Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (kerosene, paraffin, etc.), esters (isopropyl acetate, benzyl acetate, etc.), nitriles, amides (N, N -Dimethylformamide, dimethyl sulfoxide, etc.), halogenated hydrocarbons (chlorobenzene, trichloroethylene) and the like.

  Examples of the gaseous carrier, that is, the propellant, include carbon dioxide gas, butane gas, and fluorocarbon.

  Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and their polyoxyethylenates, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like. .

  Examples of other formulation adjuvants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid) And the like, PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol), Stabilizers such as vegetable oil, molasses, agar, mineral oil, fatty acid, fatty acid ester and the like can be mentioned.

In general, the formulation contains 0.1 to 95% by weight, preferably 1 to 80% by weight, of at least one compound of the general formula (1). These preparations can be treated alone, diluted, or sprayed, sprayed, applied, etc. on plants, or plant seeds, or the soil surrounding seeds or the seeds sowed in seeds, paddy fields, hydroponics Can be processed into water. When spraying, spraying and applying the compound according to the present invention to plants, it is usually used at a concentration of 50 to 5000 ppm, and when treated in the soil surrounding the plant or water of paddy fields, it is used in an amount of about 1 to 1000 g / ha. And when processing to the soil in which a seed is seed | inoculated, it is normally used in the quantity of 0.1-1 kg / m < ² >.

  The present invention will be described with reference to examples and test examples, but the present invention is not limited to these examples.

Synthetic production example of 4-heterocyclic substituted pyrimidine derivatives (R) -4-Benzyl-3- (thieno [2,3-d] pyrimidin-4-yl) oxazolidine-2-one (Compound 1)
(R) -4-Benzyloxazolidinone (0.50 g) was dissolved in N, N-dimethylformamide (10 ml), sodium hydride (0.14 g, oily, 60%) was added, and the mixture was stirred at room temperature for 5 minutes. Subsequently, 0.40 g of 4-chlorothieno [2,3-d] pyrimidine was added and stirred at room temperature for 5 hours. After completion of the reaction, 30 ml of water was added and extracted with 50 ml of ethyl acetate. The organic layer was washed with 50 ml of water and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to obtain (R) -4-benzyl-3- (thieno [2,3 -D] Pyrimidin-4-yl) oxazolidine-2-one 0.38 g was obtained.

  Compounds 2, 5, 9, 13, 17, 20 to 23, 26 to 35, 37 to 40, and 53 to 55 were prepared in the same manner as in Production Example 1, except that starting materials suitable for the respective compounds were selected. Was synthesized.

Production Example 2 (S) -5-Benzyl-1- (thieno [2,3-d] pyrimidin-4-yl) pyrrolidin-2-one (Compound 7)
A solution of 0.62 g of (S) -5-benzylpyrrolidin-2-one in N, N-dimethylformamide was cooled to 0 ° C., 0.39 g of potassium t-butoxy and 4-chlorothieno [2,3-d] pyrimidine 0 .40 g was added in order. The mixture was warmed to room temperature and stirred overnight. After completion of the reaction, 30 ml of water was added and extracted with 50 ml of ethyl acetate. The organic layer was washed with 50 ml of water and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to obtain (S) -5-benzyl-1- (thieno [2,3 -D] 0.17 g of pyrimidin-4-yl) pyrrolidin-2-one was obtained.

  Compound 8 was synthesized in the same manner as in Production Example 2, except that (R) -5-benzylpyrrolidin-2-one was used instead of (S) -5-benzylpyrrolidin-2-one.

Production Example 3.4 4- (Biphenyl-2-ylmethyl) -3-thieno [2,3-d] pyrimidin-4-yl) oxazolidine-2-one (Compound 46)
4- (2-bromobenzyl) -3- (thieno [2,3-d] pyrimidin-4-yl) oxazolidine-2-one (compound 33) 0.30 g, tetrakistriphenylphosphine palladium 0.089 g, phenylboron 0.14 g of acid, 5 ml of toluene, 1 ml of ethanol and 2 ml of 2N aqueous sodium carbonate solution were mixed and heated to reflux for 3 hours. After cooling to room temperature, 50 ml of ethyl acetate was added and insolubles were filtered off. The solution was washed with 50 ml of water, dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to give 4- (biphenyl-2-ylmethyl) -3-thieno [2, 3-d] pyrimidin-4-yl) oxazolidine-2-one 0.28 g was obtained.

  Compounds 47 to 51 were synthesized in the same manner by selecting starting materials suitable for each compound according to Preparation Example 3.

  As the starting materials used in Production Examples 1 and 2, commercially available reagents can be used, or they can be synthesized by known methods. The synthesis example is given below and explained in detail.

Production Example 4.4 4-Chloro-6- (1-fluoroethyl) -5-iodopyrimidine (Synthetic Intermediate of Compound 20)
The compound was synthesized according to the method described in JP-A No. 2000-7661 (Patent Document 18) or JP-A No. 2000-7661 (Patent Document 19).

Production Example 5 (S) -5-Benzylpyrrolidin-2-one (Synthesis intermediate of Compound 7)
Synthesized according to the method described in J. Org. Chem., Vol. 70, No. 14 (2005) 5725-5728 (Non-patent Document 1).

Step 5-1 (R) -1- (2,2-Dimethyl-4,6-dioxo-1,3-dioxane-5-yl) -1-oxo-3-phenylpropan-2-ylcarbamic acid t- 12.8 g of butyl (R) -2- (t-butoxycarbonylamino) -3-phenylpropanoic acid, 7.67 g of Meldrum's acid and 8.87 g of N, N-dimethylaminopyridine were dissolved in 200 ml of dichloromethane. The solution was cooled to 0 ° C., and 100 ml of a dichloromethane solution of 11.0 g of N, N-dicyclohexylcarbodiimide was added dropwise over 1 hour while stirring. The mixture was warmed to room temperature and stirred overnight. After filtering insoluble matter, the organic layer was washed with 100 ml of 5% aqueous sodium hydrogensulfate solution and dried over anhydrous magnesium sulfate. After filtration, the solution was concentrated to 200 ml and used as it was in the next reaction.

Step 5-2 (S) -1- (2,2-Dimethyl-4,6-dioxo-1,3-dioxane-5-yl) -3-phenylpropan-2-ylcarbamate t-butyl Step 5- (R) -1- (2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-yl) -1-oxo-3-phenylpropan-2-ylcarbamic acid synthesized in step 1 Acetic acid (30 ml) was added to butyl in dichloromethane (200 ml) and cooled to 0 ° C. After adding sodium borohydride 4.54g over 3 hours, it stirred at room temperature for 18 hours. After completion of the reaction, the organic layer was washed 3 times with 100 ml of water, and then twice with 100 ml of saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting solid was washed with ether to give (S) -1- (2,2-dimethyl-4,6-dioxo-1,3-dioxane-5 Yl) 11.6 g of t-butyl-3-phenylpropan-2-ylcarbamate was obtained.
δ = 1.36 (9H, s), 1.73 (3H, s), 1.77 (3H, s), 1.98-2.39 (2H, m), 2.85 (2H, d), 3.78-4.00 (1H, m), 4.00- 4.60 (2H, m), 6.92-7.51 (5H.m)

Step 5-3 (S) -2-Benzyl-5-oxopyrrolidine-1-carboxylate t-butyl (S) -1- (2,2-dimethyl-4,6-dioxo- synthesized in Step 5-2 8.70 g of t-butyl 1,3-dioxane-5-yl) -3-phenylpropan-2-ylcarbamate was mixed with 100 ml of toluene and heated to reflux for 5 hours. After cooling to room temperature, the solvent was distilled off to obtain 6.30 g of (S) -2-benzyl-5-oxopyrrolidine-1-carboxylate.
δ = 1.20-2.46 (4H, m), 1.58 (9H, s), 2.73 (1H, dd), 3.15 (1H, dd), 4.20-4.53 (1H, m), 6.96-7.59 (5H, m)

Step 5-4 (S) -5-Benzylpyrrolidin-2-one 6.00 g of t-butyl (S) -2-benzyl-5-oxopyrrolidine-1-carboxylate synthesized in Step 5-3 was added to 200 ml of dichloromethane. Dissolved. After the solution was cooled to 0 ° C., 3.4 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 4 hours. After slowly adding 100 ml of saturated aqueous sodium hydrogen carbonate solution and extracting with dichloromethane, the organic layer was washed with 200 ml of water and dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtration. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to obtain 2.17 g of (S) -5-benzylpyrrolidin-2-one. Obtained.
δ = 1.56-2.50 (4H, m), 2.50-3.12 (2H, m), 3.71-4.04 (1H, m), 5.76 (1H, bs), 6.90-7.60 (5H, m)
(R) -5-Benzylpyrrolidin-2-one (synthetic intermediate of compound 8) is (R) -2- (t-butoxycarbonylamino) according to the method described in Steps 5-1 to 5-4. The synthesis was performed in the same manner using (S) -2- (t-butoxycarbonylamino) -3-phenylpropanoic acid instead of -3-phenylpropanoic acid.

Production Example 6 (R) -4-Benzyl-1-methylimidazolidin-2-one (synthesis intermediate of compound 9)
The synthesis was performed with reference to the method described in JP-A-2007-254409 (Patent Document 20).

Step 6-1 (R) -1- (Methylamino) -1-oxo-3-phenylpropan-2-ylcarbamate t-butyl (R) -2- (t-butoxycarbonylamino) -3-phenylpropane Acid 22.4 g, triethylamine 42.7 g, methylamine hydrochloride 11.4 g, O-benzotriazolyl-N, N, N ′, N′-tetramethyluronium tetrafluoroborate (TBTU) 32.5 g in acetonitrile Dissolved in 400 ml and stirred overnight at room temperature. After the solvent was distilled off, water was added and the mixture was extracted with 200 ml of ethyl acetate. The organic layer was washed with 100 ml of 0.1N hydrochloric acid, and then washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 15.6 g of t-butyl (R) -1- (methylamino) -1-oxo-3-phenylpropan-2-ylcarbamate.
δ = 1.40 (9H, s), 2.72 (3H, d), 3.05 (2H, d), 4.27 (1H, q), 4.98 (1H, d), 5.68 (1H, bs), 6.91-7.54 (5H, m)

Step 6-2 (R) -2-Amino-N-methyl-3-phenylpropanoic acid amide (R) -1- (methylamino) -1-oxo-3-phenylpropane-2 synthesized in Step 6-1 -3.90 g of t-butyl carbamate was dissolved in 30 ml of tetrahydrofuran, and 20 ml of 4N hydrochloric acid was added. After stirring the solution at room temperature overnight, tetrahydrofuran was distilled off under reduced pressure. A 10% aqueous sodium hydroxide solution was added to adjust the pH to 9, followed by extraction with 150 ml of dichloroethane and drying with anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 2.52 g of (R) -2-amino-N-methyl-3-phenylpropanoic acid amide.
δ = 1.39 (2H, s), 2.67 (1H, dd), 2.82 (3H, d), 3.29 (1H, dd), 3.61 (1H, dd), 6.80-7.70 (6H, m)

Step 6-3 (R) —N ¹ -Methyl-3-phenylpropane-1,2-diamine In a nitrogen stream, 2.10 g of lithium aluminum hydride was suspended in 40 ml of anhydrous tetrahydrofuran and cooled to 0 ° C. . A solution of 1.97 g of (R) -2-amino-N-methyl-3-phenylpropanoic acid amide synthesized in step 6-2 in 40 ml of tetrahydrofuran was slowly added dropwise. The mixture was heated to reflux for 6 hours and cooled again to 0 ° C. The reaction is stopped by slowly adding 15% potassium hydroxide until the suspension turns white, the solid is filtered, the solvent is distilled off and (R) -N ¹ -methyl-3-phenylpropane-1, 1.27 g of 2-diamine was obtained.
δ = 1.30 (3H, bs), 2.11-2.91 (2H, m), 2.44 (3H, s), 2.91-3.28 (1H, m), 6.90-7.56 (5H, m)

Step 6-4 (R) -4-Benzyl-1-methylimidazolidin-2-one (R) -N ¹ -methyl-3-phenylpropane-1,2-diamine 4.75 g synthesized in Step 6-3 Was dissolved in chloroform (100 ml) and cooled to 0 ° C. To this solution, 3.00 g of triphosgene was added, followed by dropwise addition of 5.85 g of triethylamine. The mixture was stirred at room temperature for 2 hours and then washed successively with 100 ml of 0.1N hydrochloric acid aqueous solution and 100 ml of saturated brine. After drying with anhydrous magnesium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to give (R) -4-benzyl-1-methylimidazolidine-2- 2.72 g of on was obtained.
δ = 2.76 (3H, s), 2.81 (2H, d), 3.12 (1H, dd), 3.46 (1H, t), 3.62-4.05 (1H, m), 4.66 (1H, bs), 6.85-7.60 ( 5H, m)

Production Example 7.4 4- (2-Methylbenzyl) -3- (thieno [2,3-d] pyrimidin-4-yl) oxazolidine-2-one (Synthetic intermediate of Compound 21)
It was synthesized according to the method described in Synthetic Communications, 25 (4), 561-568 (1995) (Non-patent Document 2).

  The amino acid derivative used as a starting material is commercially available or can be synthesized based on the method described in Patent Document 21 and the like.

Special table hei 10-502511

Step 7-1 Methyl 2- (ethoxycarbonylamino) -3-ortho-tolylpropanoate 75 ml of methanol was cooled to 0 ° C., and 15 ml of acetyl chloride was slowly added dropwise. After stirring for 30 minutes, 7.31 g of 2-amino-3-orthotolylpropanoic acid hydrochloride was added and stirred overnight at room temperature. After distilling off the solvent, 120 ml of water and 60 ml of ethyl acetate were added, and 14.2 g of sodium bicarbonate was added little by little. To this mixture, 3.9 ml of ethyl chloroformate was slowly added dropwise, followed by stirring at room temperature for 1 hour. After dilution by adding 60 ml of ethyl acetate, the solution was partitioned into an organic layer and an aqueous layer. The organic layer was washed with 100 ml of water and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 6.10 g of methyl 2- (ethoxycarbonylamino) -3-ortho-tolylpropanoate.
δ = 1.19 (3H, t), 2.34 (3H, t), 3.06 (2H, t), 3.68 (3H, s), 4.06 (2H, q), 4.59 (1H, q), 5.10 (1H, d) , 6.85-7.28 (4H, m)

Step 7-2 Ethyl 1-hydroxy-3-ortho-tolylpropan-2-ylcarbamate 60.000 g of ethanol were added to 6.10 g of methyl 2- (ethoxycarbonylamino) -3-ortho-tolylpropanoate obtained in Step 7-1. 30 ml of tetrahydrofuran was added. 5.11 g of calcium chloride was added to this solution and cooled to 0 ° C. 3.48 g of sodium borohydride was added little by little and stirred overnight at room temperature. The reaction was stopped by slowly adding 100 ml of 1M aqueous citric acid solution, and the organic solvent was distilled off, followed by extraction with 100 ml of ethyl acetate and drying over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 5.30 g of ethyl 1-hydroxy-3-orthotolylpropan-2-ylcarbamate.
δ = 1.21 (3H, t), 2.36 (3H, s), 2.54 (1H, bs), 2.85 (2H, d), 3.49-3.82 (2H, m), 3.82-4.25 (1H, m), 4.08 ( 2H, q), 4.96 (1H, d), 7.13 (4H, bs)

Step 7-3 4- (2-Methylbenzyl) oxazolidine-2-one 5.30 g of ethyl 1-hydroxy-3-orthotolylpropan-2-ylcarbamate obtained in Step 7-2 was dissolved in 150 ml of toluene. 1.55 g of potassium carbonate was added. After refluxing for 19 hours, the solvent was distilled off and 150 ml of ethyl acetate was added. The organic layer was washed with 200 ml of water and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 4.00 g of 4- (2-methylbenzyl) oxazolidine-2-one.
δ = 2.31 (3H, s), 2.88 (2H, d), 3.80-4.25 (2H, m), 4.25-4.60 (1H, m), 5.41 (1H, bs), 6.78-7.42 (4H, m)

  Synthesis intermediates of compounds 22, 23, 26 to 35, 37 to 40, 52, and 53 were synthesized using raw materials having appropriate substituents according to the method described in Steps 7-1 to 7-3. .

Production Example 8 (R) -5-Benzylmorpholin-3-one (Synthesis intermediate of Compound 54)
Synthetic Communications, 27 (10), 1777-1782 (1997) (Non-patent Document 3) Biosynthesis & Medicinal Chemistry Letters, 18 (2008) 4316-4320 (Non-patent Document 4).

Step 8-1 (R) -2-Chloro-N- (1-hydroxy-3-phenylpropan-2-yl) acetamide 3.65 g of triethylamine was added to 100 ml of a dichloromethane solution of 4.55 g of (R) -phenylalaninol. And cooled to 0 ° C. Subsequently, 3.74 g of chloroacetyl chloride was added dropwise and stirred overnight at room temperature. The reaction solution was washed with 100 ml of water, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1), and the solvent was distilled off to give (R) -2-chloro-N- (1-hydroxy-3). -Phenylpropan-2-yl) acetamide 3.55 g was obtained.
δ = 2.35 (1H, t), 2.91 (2H, d), 3.42-3.80 (2H, m), 4.00 (2H, s), 4.01-4.40 (1H, m), 6.77 (1H, bs), 6.98- 7.49 (5H, m)

Step 8-2 (R) -5-Benzylmorpholin-3-one (R) -2-Chloro-N- (1-hydroxy-3-phenylpropan-2-yl) acetamide obtained in Step 8-1 53 g was dissolved in 75 ml of tetrahydrofuran and cooled to 0 ° C. 1.24 g of 60% sodium hydride was added and stirred overnight at room temperature. After completion of the reaction, 100 ml of ice water was added to the solution, followed by extraction with 200 ml of ethyl acetate, and then the organic layer was washed with 100 ml of water and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1) and the solvent was distilled off to obtain 1.35 g of (R) -5-benzylmorpholin-3-one. Obtained.
δ = 2.51-3.07 (2H, m), 3.40-4.20 (3H, m), 4.17 (2H, s), 6.01 (1H, bs), 7.02-7.50 (5H, m)
(S) -5-Benzylmorpholin-3-one (an intermediate for the synthesis of compound 55) is prepared according to the steps described in Steps 8-1 to 8-2, and (S) instead of (R) -phenylalaninol. -Synthesized using phenylalaninol.

  In addition, various salts (sodium salt, potassium salt, magnesium salt, calcium salt, aluminum salt, etc.), hydrate, solvate, and crystal polymorph of the derivative of the present invention synthesized above are obtained by using conventional means. Can be obtained. Furthermore, all possible stereoisomers or optical isomers present in the compound of the present invention can also be obtained by using a starting material having a suitable configuration in advance or using conventional means such as a well-known optical resolution method. .

The physical properties of the compounds synthesized above are shown in Table 1 (Table 1-1 to Table 1-3), and their ¹ H NMR spectral data are shown in Table 2 (Table 2-1 to Table 2-3). In the present specification, “Table 1” is a generic name (generic name) of Table 1-1 to Table 1-3, and “Table 2” is a generic name of Table 2-1 to Table 2-3 (generic name). Name). The ¹ H NMR spectrum data described in this specification is measured at 90 Hz using deuterated chloroform (CDCl ₃ ) as a solvent. Further, tetramethylsilane (TMS) is used as an internal standard, and the measured value is indicated by a δ value (ppm).

In Table ^{1-1~1-3, Me, Et, i Pr} , Bu, t Bu, Ph , respectively, represent methyl, ethyl, isopropyl, butyl, tertiary butyl, phenyl.

  Further, the configuration is based on the raw material, and rac. Indicates a racemate.

Formulation Example 1 Emulsion 10 parts of the compound of the present invention was dissolved in 45 parts of 1,2-dimethyl-4-ethylbenzene and 35 parts of 1-methyl-2-pyrrolidinone, and this was dissolved in Solpol 3005X (a surface activity manufactured by Toho Chemical Co., Ltd.). 10 parts of the product was added and stirred to obtain a 10% emulsion.

Formulation Example 2 Wetting Agent 10 parts of the compound of the present invention was added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of white carbon and 64 parts of clay. A wettable powder was obtained.

Formulation Example 3 Granules To 5 parts of the compound of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 2 parts of carboxymethylcellulose, 2 parts of sodium lauryl sulfate, 10 parts of bentonite and 79 parts of clay were added and mixed thoroughly. An appropriate amount of water was added and the mixture was further stirred, granulated with a granulator, and dried by ventilation to obtain a 5% granule.

Formulation Example 4 Powder 1 part of the present compound is dissolved in 2 parts of soybean oil, 5 parts of white carbon, 0.3 part of isopropyl phosphate (PAP) and 91.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer. A 1% powder was obtained.

Formulation Example 5 Flowable Agent 20 parts of the present compound and 20 parts of water containing 2 parts, 1 part and 0.2 part of polyoxyethylene alkyl ether, sodium dialkylsulfosuccinate and 1,2-benzisothiazolin-3-one, respectively. After mixing and wet pulverization using a dynomill, 60 parts of water containing 8 parts and 0.32 parts of propylene glycol and xanthan gum were mixed to obtain a 20% suspension in water.

Formulation Example 6 Granule wettable powder To 20 parts of the present compound, 2 parts of sodium lauryl sulfate, 3 parts of sodium alkylnaphthalene sulfonate, 5 parts of dextrin, 20 parts of white carbon and 50 parts of clay were added and mixed thoroughly. An appropriate amount of water was added, and the mixture was further stirred, granulated with a granulator, and dried by ventilation to obtain a 20% granular wettable powder.

Test Examples Test examples of the present compound as agricultural and horticultural fungicides will be described. In the following test examples, the following compound X described in Patent Document 1 was used as a comparative compound.

[Bactericidal efficacy test]
1) Control effect test against tomato plague The compound group shown in Tables 1-1 to 1-3 and a 10% wettable powder of Compound X (prepared according to Formulation Example 2) were prepared at 125 ppm, and pot planted tomato ( Variety; sugar lamp, 4.5 leaf stage) was sprayed with 15 ml per pot using a spray gun. One day later, a zoospore suspension (Phytophthora infestans) zoospore suspension (zoospore concentration 1.0 × 10 ⁴ cells / ml) was spray-inoculated, placed in a humid room condition at 21 ° C. for 1 day, and further placed in a greenhouse. After causing sufficient disease after 3 days, the degree of disease on each leaf was investigated, and the control value was calculated using the following formula.
Control value calculation; control value = {(untreated disease area ratio−treated drug disease area ratio) / untreated disease area ratio} × 100

  Compounds 1, 17, 20, 21, 26, 30, 34, 37, 38, 40, 41, 48, 49, 50, 51, 54 showed an effect with a control value of 60 or more, while compound X had a control value of 0. 0.0 and did not show an effective control effect.

2) Control effect test against cucumber downy mildew The compound group shown in Tables 1-1 to 1-3 and the 10% wettable powder of Compound X (prepared according to Formulation Example 2) were prepared to 125 ppm, and potted 15 ml per pot was sprayed onto cucumber (variety: Sagamihanjiro, 2.5 leaf stage) using a spray gun. One day later, a conidial suspension (conidia concentration 1.0 × 10 ⁴ / ml) of cucumber downy mildew (Pseudoperonospora cubensis) was spray-inoculated. After inoculation, leave for 1 day under wet room conditions at 21 ° C, and after 3 days in a greenhouse, cause sufficient disease. Compare the degree of disease of each leaf with the untreated group, and control effect as in Test Example 1) Judgment was made.

  While compounds 1,17,21,22,23,27,28,29,31,32,33,34,38,39,47,50,51,53,54 showed an effect with a control value of 60 or more, Compound X showed a control value of 0.0 and an effective control effect.

[Insecticidal efficacy test]
1) Efficacy test against cotton aphids Place a 3 cm diameter cucumber leaf on a moist sponge in a plastic cup, release 5 female female aphids (Aphis gossypii) females, leave them overnight, and then lay larvae Numbers were counted. The compound group described in Table 1-1 to Table 1-3, and 0.4 ml each of a chemical solution prepared by diluting 10% wettable powder of Compound X to 250 ppm were sprayed, and the number of dead insects was investigated two days later and the death The rate was calculated. A mortality rate of 95% or more was judged as A, 80% or more and less than 95% as B, and 60% or more and less than 80% as C. The results are shown in the table below.

In this study, the mortality from Compound X was 0%.

2) Efficacy test against adult female spider mite A piece of green beans with a diameter of 3 cm was placed on a moist sponge in a plastic cup, and 10 female adult female spider mite (Tetranychus urticae) were released. The compound group described in Table 1-1 to Table 1-3, and 0.4 ml each of a chemical solution prepared by diluting 10% wettable powder of Compound X to 250 ppm were sprayed, and the number of dead insects two days later was investigated to die. The rate was calculated. A mortality rate of 95% or more was judged as A, 80% or more and less than 95% as B, and 60% or more and less than 80% as C. The results are shown in the table below.

In this study, the mortality from Compound X was 0%.

3) Efficacy test on nymph spider eggs After placing 3 cm diameter kidney beans on a moist sponge in a plastic cup, 10 adult nymph mite (Tetranychus urticae) females were released and allowed to lay overnight at room temperature. The released adult female was removed. Spray the compound group described in Table 1-1 to Table 1-3 and 0.4 ml each of the chemical solution prepared by diluting 10% wettable powder of Compound X to 250 ppm, and investigate the number of unhatched eggs after 6 days. The egg kill rate was calculated. An egg killing rate of 95% or more was judged as A, 80% or more and less than 95% as B, and 60% or more and less than 80% as C. The results are shown in the table below.

In this test, the oocyte killing rate by Compound X was 0%.

  Since the novel compound of the present invention represented by the formula (1) exhibits an excellent control activity against pests such as pathogenic bacteria, insects and mites that particularly affect agricultural and horticultural plants, it is extremely useful as a new agricultural chemical.

Claims (6)

A 4-heterocyclic substituted pyrimidine derivative represented by the following formula (1).
In equation (1),
R ¹ and R ² are independently a hydrogen atom, a halogen atom, an amino group, a cyano group, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different and substituted with a halogen atom 1 to 13 A linear or branched haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, the same or Differently, it represents a linear or branched haloalkoxy group having 1 to 6 carbon atoms, a linear or branched alkenyloxy group having 2 to 6 carbon atoms, which is substituted with 1 to 13 halogen atoms. .
Alternatively, R ¹ and R ² may be combined to form a benzene ring or an aromatic heterocyclic ring, and the ring is a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms. A linear or branched haloalkyl group having 1 to 6 carbon atoms, which is the same or different and substituted with a halogen atom 1 to 13, a linear or branched alkoxy group having 1 to 6 carbon atoms, The linear or branched haloalkoxy groups having 1 to 6 carbon atoms which are the same or different and are substituted with halogen atoms 1 to 13 may be optionally substituted one or more.
R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a straight chain substituted with a halogen atom 1 to 13 Or a branched haloalkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, the same or different, and having 1 carbon atom substituted with a halogen atom 1 to 13 -6 haloalkoxy groups, cyano groups, and nitro groups.
Alternatively, R ³ and R ⁴ may be combined with the carbon atom to which they are bonded to form a carbonyl group.
n = 0 to 5
Q is a linear or branched alkyl group having 1 to 6 carbon atoms, and is the same or different and is a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 A linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched haloalkoxy group having 1 to 6 carbon atoms which is the same or different and is substituted with a halogen atom 1 to 13 A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkynyl group having 2 to 6 carbon atoms, the same or different, and substituted with a halogen atom 1 to 11 A linear or branched haloalkenyl group having 2 to 6 carbon atoms, a linear or branched alkenyloxy group having 2 to 6 carbon atoms, a linear or branched carbon atom having 2 to 6 carbon atoms Alkynyloxy groups, the same or different Te, straight-chain or branched halo alkenyloxy group having 2 to 6 carbon atoms are replaced by halogen atoms 1 to 11, (straight chain or branched alkyl having 1 to 6 carbon atoms) -CO -An acyl group represented by a group, ( linear or branched alkyl having 1 to 6 carbon atoms)-an acyloxy group represented by a -CO-O- group, (linear or branched carbon atoms having 1 to 6 alkyl) -alkoxycarbonyl group represented by —O—CO— group, linear or branched alkylthio group having 1 to 6 carbon atoms, the same or different, and directly substituted with halogen atoms 1 to 13 A linear or branched haloalkylthio group having 1 to 6 carbon atoms, an alkylsulfinyl group represented by (linear or branched alkyl having 1 to 6 carbon atoms) -SO- group (the same or different , Halogen atom 1 A haloalkylsulfinyl group represented by a straight-chain or branched haloalkyl having 1 to 6 carbon atoms and a —SO— group substituted with ˜13 (a straight-chain or branched alkyl having 1 to 6 carbon atoms); ) An alkylsulfonyl group represented by —SO ₂ — group (same or different, linear or branched alkyl having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms) —SO ₂ — group A linear or branched dialkylamino group having 1 to 6 carbon atoms, or a linear or branched carbon atom which is the same or different and is substituted with a halogen atom 1 to 13 number 1-6 alkyl) -SO 2 _- 2 pieces in alkylsulfonylamino group substituted by a group, a linear or branched alkyl group is an amino group having 1 to 6 carbon atoms represented by group Conversion carbonyl group substituted by a dialkylamino group, a linear or branched sulfonyl group substituted by a dialkylamino group in which the alkyl group has two substituents on the amino group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group , A cyano group, a nitro group, a phenyl group, a naphthyl group, and an aromatic heterocyclic group.
When n is 2 or more, these substituents Q may be the same or different.
A is shows the annular structure of 5-membered ring represented by the formula (2).
In equation (2),
V represents an oxygen atom or a sulfur atom.
X is an oxygen atom, a sulfur atom, —CR ¹¹ R ¹² —, —NR ¹³ — (R ^{11 to} R ¹³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or, differently, a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms is shown.
R ⁵ and R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched group substituted with a halogen atom 1 to 13 1 to 6 carbon atom haloalkyl groups. Alternatively, R ⁵ and R ⁶ may be combined with the carbon atom to which they are bonded to form a carbonyl group.
R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with halogen atoms 1 to 13 6 represents a haloalkyl group.
Of the atoms constituting the ring, N _a represents a nitrogen atom bonded to the 4-position of the pyrimidine ring, and C _b is bonded to a carbon atom bonded to phenyl, R ³ , or R ^4. Carbon atom.
Or A shows the cyclic structure of the 6-membered ring represented by Formula (3).
In formula (3), W represents an oxygen atom or a sulfur atom.
Y is an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —NR ¹⁶ — (R ^{14 to} R ¹⁶ are independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same Or, differently, a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms is shown.
Z represents an oxygen atom, a sulfur atom, —CR ¹⁴ R ¹⁵ —, —S (O) —, —S (O) ₂ —, —NR ¹⁶ —.
However, Y and Z are not oxygen atoms at the same time, and are not sulfur atoms at the same time.
R ⁸ and R ⁹ independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched haloalkyl group having 1 to 6 carbon atoms.
R ¹⁰ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, the same or different, and a linear or branched carbon atom having 1 to 6 carbon atoms substituted with a halogen atom 1 to 13 6 represents a haloalkyl group.
Of the atoms constituting the ring, N _c represents a nitrogen atom bonded to the 4-position of the pyrimidine ring, and C _d bonded to a carbon atom bonded to phenyl, R ³ , or R ^4. Carbon atom. The formula (1), wherein R ¹ is alkyl halide and R ² is halogen, or R ¹ and R ² are combined to form a benzene ring or a thiophene ring. Compound. In the formula (2), V is an oxygen atom, X is ^-CR 11 ^{R 12} - or is, or, V and X is an oxygen atom A compound according to claim 1 or 2. In formula (3), W and Y are oxygen atoms and Z is —CR ¹⁴ R ¹⁵ —, or W and Z are oxygen atoms and Y is —CR ¹⁴ R ¹⁵ —. The compound of any one of these. By reacting the 4-halopyrimidine derivative represented by the formula (4) with the heterocyclic ring represented by the formula (5) or the formula (6) in the presence of a base, the formula (1a) or the formula ( A method for producing a 4-heterocyclic substituted pyrimidine derivative represented by 1b). However, the union of the compound represented by Formula (1a) and the compound represented by Formula (1b) shows the compound represented by Formula (1).
(In the above formula, R ^{1 to} R ¹⁰ , Q, V, W, X, Y, Z, and n have the same meaning as described above, and L represents a halogen atom)   A pest control agent comprising one or more 4-heterocyclic substituted pyrimidine derivatives represented by formula (1) according to claim 1 as an active ingredient.