WO2000037460A1 - 5-azolylpyrimidine compounds, process for the preparation of the same, and germicides for agricultural and horticultural use - Google Patents

Abstract

5-Azolylpyrimidine compounds represented by general formula (1); a process for the preparation thereof; and germicides for agricultural and horticultural use, containing the same: formula (1) wherein R1 is SO¿mR?4, hydrogen, C¿1?-C20 alkoxy, or the like (where R?4 is C¿1-C6 alkyl or pyridyl and m is an integer of 0 to 2); R2 is halogeno, C¿1?-C6 alkoxy, C1-C6 haloalkoxy, phenoxy, or the like; R?3 is C¿1-C20 alkoxy, SOmR5, O-(CH¿2)n-R?6, hydrogen, C¿3?-C9 alkenyloxy, halogeno, C1-C6 haloalkoxy, C3-C9 alkynyloxy, or the like (where R?5 is C¿1-C6 alkyl and n is an integer of 1 to 4); and Y is CH or N.

Description

 Specification

5-Azolylpyrimidine compounds, their preparation and fungicides for agricultural and horticultural use

 The present invention relates to a novel 5-azolylpyrimidine compound useful as a fungicide for agricultural and horticultural use. Background art

 Compounds similar to the present invention include Gaodeng Xuexiao Huaxue Xuebao (1 995), 16 (11), 1 740—1743, and China-Chemical-Letter (Chin. Chem.). Lett.) (1 994), 5 (1), 31-34, describe 5-azolylpyrimidine derivatives.

 However, the 1-position of this derivative is fixed to an amino group and a thiol group, and no disclosure of a 5-azolylpyrimidine compound having a substituent introduced therein as in the present invention is found. Therefore, the 5-azolylpyrimidine compound of the present invention is a novel compound and has not been known to have a fungicidal activity for agricultural and horticultural purposes.

 An object of the present invention is to provide a novel 5-azolylpyrimidine compound, a method for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient. Disclosure of the invention

 The present inventors have conducted studies to solve the above problems, and as a result, have found that a novel 5-azolyl bilimidine compound has remarkable bactericidal activity for agricultural and horticultural use, and have completed the present invention.

 That is, the present invention is as follows.

式中、 R lは、 SO_mR⁴, 水素原子， ハロゲン原子， 炭素原子数 1 6個の ハロアルキル基， 炭素原子数 1 6個のハロアルコキシ基， 炭素原子数 3 6 個のシクロアルコキシ基， 炭素原子数 3 9個のアルケニルォキシ基， 炭素原 子数 3 9個のアルキニルォキシ基， 0-(CH₂)_n- R6， 炭素原子数 1 6個の アルキル基又は炭素原子数 1 20個のアルコキシ基を表し、 ここで、 R⁴は、 炭素原子数 1 6個のアルキル基又はピリジル基を表し； R⁶は、 置換基を有 してもよいフエニル基， フヱノキシ基， 炭素原子数 1 6個のアルコキシ基， S i(CH₃)₃, CN, NO ₂又は N (R 7) R8を表し； 1^ 7及び 8は、 水素 原子， 炭素原子数 1 6個のアルキル基を表し、 これらは同一であってもよ く ； mは、 0 2の整数を表し； nは、 1 4の整数を表し； R2は、 置換基 としてハロゲン原子， 炭素原子数 1 6個のアルキル基， 炭素原子数 1 6個 のアルコキシ基， 炭素原子数 1 6個のハロアルコキシ基， 炭素原子数 1 6 個のハロアルキル基， CNもしくは N0₂を有してもよいフエニル基， フエノ キシ基又はナフチル基を表し； R ³は、 炭素原子数 1 2 0個のアルコキシ基，The first invention has the following formula (1):

In the formula, R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 16 carbon atoms, a haloalkoxy group having 16 carbon atoms, a cycloalkoxy group having 36 carbon atoms, Alkenyloxy group having 39 carbon atoms, alkynyloxy group having 39 carbon atoms, 0- (CH ₂ ) _n -R6, alkyl group having 16 carbon atoms or carbon atom having 1 20 R ⁴ represents an alkyl group having 16 carbon atoms or a pyridyl group; R ⁶ represents a phenyl group, a phenoxy group, or a carbon atom which may have a substituent; 1 6 alkoxy group, a _{S i (CH 3) 3,} CN, NO 2 , or N (R 7) R8; 1 ^ 7 and 8 represent a hydrogen atom, C 1 6 alkyl group having a carbon atom M represents an integer of 02; n represents an integer of 14; R2 represents a halogen atom as a substituent, Atoms 1 6 alkyl group, C 1 6 alkoxy group having a carbon atom, a carbon atom number of 1 6 haloalkoxy group, C 1 6 haloalkyl group having a carbon atom may have a CN or N0 ₂ R ³ represents a phenyl group, a phenoxy group or a naphthyl group; R ³ is an alkoxy group having 120 carbon atoms;

S〇 _m R50- (CH ₂ ) _n -R6, hydrogen atom, alkenyloxy group with 39 carbon atoms, halogen atom, haloalkoxy group with 16 carbon atoms, 36 carbon atoms A cycloalkoxy group or an alkynyloxy group having 39 carbon atoms, wherein R ⁵ represents an alkyl group having 16 carbon atoms; R ⁶ has the same meaning as described above; Or N

The present invention relates to a 5-azolylpyrimidine compound represented by the formula:

 The second invention (synthesis method 1)

The following equation (2):

In the formula, R ² , 1 ^ ⁴ and \ are as defined above.

And a compound represented by

式中、 R 1は、 前記と同義である、 The following equation (3):

Wherein R 1 is as defined above,

In the above formula (1), R ³ is an alkoxy group having 1 to 20 carbon atoms, SO _m R ⁵ or 0- (CH ₂ ) _n -R ⁶ The present invention relates to a method for producing a 5-azolylpyrimidine compound represented by the formula:

 The third finding (synthesis method 2) is that

The following equation (4):

式中、 1^²及び¥は、 前記と同義である、

Wherein 1 ^ ² and ¥ are as defined above,

And reacting the compound represented by the formula (3) with the compound represented by the formula (3). A method for producing a 5-azolylpyrimidine compound represented by the formula (1), wherein R ³ is a hydrogen atom. Things.

 The fourth invention (synthesis method 3)

式中、 n' は、 0又は 1を表し； R 9は、 SO_mR4， 水素原子， ハロゲン原 子， 炭素原子数 1〜 6個のハロアルキル基， 炭素原子数 1〜 6個のハロアルコ キシ基， 炭素原子数 3〜 6個のシクロアルコキシ基， 炭素原子数 3〜 9個のァ ルケニルォキシ基， 炭素原子数 3〜 9個のアルキニルォキシ基， 0- (CH₂)_n -The following equation (5):

In the formula, n ′ represents 0 or 1; R 9 is SO _m R 4, a hydrogen atom, a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms. A cycloalkoxy group having 3 to 6 carbon atoms, an alkenyloxy group having 3 to 9 carbon atoms, an alkynyloxy group having 3 to 9 carbon atoms, 0- (CH ₂ ) _n-

R ⁶ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; R 2, R ⁵ and Y are as defined above,

And a compound represented by

The following equation (6):

R ¹⁰ in one XH (6) formula, X is S or 0; R ^{1 0} is a carbon atom number of 1-6 or a haloalkyl group, a cycloalkyl group having 3 to 6 carbon atoms, 3 carbon atoms Represents an alkenyl group of 9 to 9 carbon atoms, an alkynyl group of 3 to 9 carbon atoms,-(CH ₂ ) _n -R ⁶ or an alkyl group of 1 to 20 carbon atoms,

And a method for producing a 5-azolylpyrimidine compound represented by the formula (1), wherein R ³ is —XR 10. The fifth invention (Synthesis method 4)

The following equation (7):

In the formula, W represents a halogen atom; R ² , 1-9 and 丫 are as defined above. ,

Wherein the compound represented by the formula (6) is reacted with the compound represented by the formula (6), wherein R ³ represents —XR 10 in the formula (1). It concerns the manufacturing method.

 The sixth kakimaki relates to a fungicide for agricultural and horticultural use containing the 5-azolylpyrimidine compound represented by the above formula (1) as an active ingredient. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 The various substituents and the like represented by the above compounds are as follows.

 1)

R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cycloalkoxy having 3 to 6 carbon atoms. Group, alkenyloxy group having 3-9 carbon atoms, alkynyloxy group having 3-9 carbon atoms, 〇- (CH ₂ ) _n -R ⁶ , alkyl group having 1-6 carbon atoms, carbon atom number 1 to 20 alkoxy groups can be mentioned.

(1) In SO _m R4, m is an integer of 0 to 2; R 4 has 1 carbon atom

And up to 6 alkyl groups and pyridyl groups.

 Examples of the alkyl group include a linear or branched alkyl group; preferably an alkyl group having 1 to 4 carbon atoms; and more preferably an alkyl group having 1 to 3 carbon atoms. It is.

(2) Examples of the alkyl group having 1 to 6 carbon atoms include linear or branched ones; preferably 1 to 3 carbon atoms; and more preferably 1 to 3 carbon atoms; , it is CH _3.

(3) Examples of the alkoxy group having 1 to 20 carbon atoms include straight-chain or branched ones; preferably, the alkoxy group has 1 to 3 carbon atoms; Preferably, it is OCH ₃ , 〇C ₃ H ₇ — n, 〇C ₃ H ₇ -iso.

 (4) Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably, a chlorine atom and a fluorine atom.

(5) Examples of the haloalkyl group include straight-chain or branched ones; preferably, it has 1 to 6 carbon atoms; more preferably, CF 3.

(6)) Examples of the haloalkoxy group include linear or branched ones; preferably those having 1 to 6 carbon atoms; and more preferably OCH ₂ CF ₃ It is.

 (7) The cycloalkoxy group preferably has 3 to 6 carbon atoms; more preferably, cyclopropoxy.

 (8) Examples of the alkenyloxy group include linear or branched ones; preferably those having 3 to 9 carbon atoms; and more preferably Roxy.

 (9) Examples of the alkynyloxy group include linear or branched ones; preferably those having 3 to 9 carbon atoms; and more preferably propynyloxy.

(10) 0- (CH ₂ ) _n — In R ⁶ , n is an integer of 1 to 4; R 6 is a phenyl group which may have a substituent, a phenoxy group, a carbon atom number of 1 to 6 _{alkoxy, S i (CH 3) 3} , CN, N0 2, N (R 7) can be exemplified R 8.

 Examples of the substituent for the phenyl group and the phenoxy group include a halogen atom.o

 The position of substitution is not particularly limited; substitution at the 4-position is preferred.

 Examples of the substituted halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably, a chlorine atom and a fluorine atom.

 Alkoxy groups include linear or branched ones; preferably those having 1 to 4 carbon atoms; and more preferably those having 1 to 3 carbon atoms. belongs to.

In N (R 7) R ⁸ , 1 ^ ⁷ and 1 ^ ⁸ can be a hydrogen atom, a linear or branched alkyl group, preferably having 1 to 6 carbon atoms. And more preferably CH ₃ .

 (R2)

Examples of R ² include a phenyl group, a phenoxy group and a naphthyl group.

(1) Examples of the phenyl, phenoxy or naphthyl group include substituted or unsubstituted ones.

Examples of the substituent include a halogen atom, CN, NO ゥ, an alkyl group having 1 to 6 carbon atoms, Examples thereof include an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms.

 Examples of the halogen atom include a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; preferably, a chlorine atom. The position of the substitution is not particularly limited, but substitution at the 2-, Z- or 4-position is preferred.

Examples of the alkyl group having 1 to 6 carbon atoms include linear or branched ones; preferably 1 to 3 carbon atoms; and more preferably CH ₃ It is. The position of the substitution is not particularly limited, but substitution at the 4-position is preferable. Examples of the alkoxy group having 1 to 6 carbon atoms include linear or branched ones; preferably 1 to 3 carbon atoms; and more preferably OCH ₃ The position of the substitution is not particularly limited, but substitution at the 4-position is preferable. Examples of the haloalkyl group having 1 to 6 carbon atoms include linear or branched ones; preferably 1 to 3 carbon atoms; and more preferably CF ₃ It is. The substitution position is not particularly limited, but the 4-position substitution is preferred.

Examples of the haloalkoxy group having 1 to 6 carbon atoms include straight-chain or branched ones; preferably having 1 to 3 carbon atoms; more preferably Is OCF ₃ . The position of the substitution is not particularly limited, but substitution at the 4-position is preferable.

 (R3)

The R3, having 1 to 20 carbon atoms alkoxy _{groups, SO m R5, 0- (CH} 2) n - R 6, a hydrogen atom, 3-9 pieces of Arukeniruokishi group number of carbon atoms, a halogen atom, a carbon Examples include haloalkoxy groups having 1 to 6 atoms, cycloalkoxy groups having 3 to 6 carbon atoms, and alkynyloxy groups having 3 to 9 carbon atoms.

(1) Examples of the alkoxy group having 1 to 20 carbon atoms include a linear or branched alkoxy group; preferably, the alkoxy group has 1 to 6 carbon atoms; is favored _{properly, OCH 3, OC 2 H 5} , OC 3 H 7 -n, OC 4 H 9 - n, OC 6 H 1 3 - n, 〇_C 20 H 4 i - a n.

(2) In S_〇 _m R 5, m is an integer from 0 to 2; the R5, mention may be made 1-6 alkyl group carbon atoms.

Examples of the alkyl group include a linear or branched one; Has 1 to 4 carbon atoms; more preferably CH ₃ and C ₂ H ₅ . '

(3) In 〇- (CH ₂ ) _n -R 6, n is an integer of 1-4; R 6 is a phenyl group, a phenoxy group, an alkoxy group, S i (CH ₃ ) 3, CN, N〇 ₂ , N (R7) R8.

And n is preferably 2 when R ⁶ is a phenyl group, a phenoxy group, an alkoxy group, N 0 ₂ , N (R 7) R 8 and CN; and ₃ when S 6 is S i (CH ₃ ) 3. It is.

 Examples of the phenyl group and the phenoxy group include substituted and unsubstituted ones.

 Examples of the substituent include a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; preferably, a chlorine atom. The position of the substitution is not particularly limited, but substitution at the 4-position is preferable.

 Alkoxy groups include straight-chain or branched ones; preferably they have 1 to 4 carbon atoms; and more preferably 1 to 3 carbon atoms. belongs to.

In ^{N (R7) R 8, 1} ^ 7及Pi 1 ^ ⁸ is a hydrogen atom, a linear or can be given branched alkylene Le groups but, preferably, the number is 1-6 carbon atoms And more preferably CH ₃ .

(4) Examples of the alkenyloxy group having 3 to 9 carbon atoms include straight-chain or branched ones; preferably, the alkenyloxy group has 3 to 7 carbon atoms; _{preferably, OCH 2 CH = CH 2,} OCH (CH 3) a CH ₂ CH = CH _2.

 (5) Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably, a chlorine atom.

(6) Examples of haloalkoxy groups having 1 to 6 carbon atoms include straight-chain or branched alkoxy groups having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom as a substituent. But preferably has 1 to 4 carbon atoms; more preferably OCH ₂ CF ₃ .

(7) Examples of the alkynyloxy group having 3 to 9 carbon atoms include straight-chain or branched ones; preferably, the alkynyloxy group has 3 to 5 carbon atoms; Preferably, OCH ₂ C≡CH. (8) The cycloalkoxy group preferably has 3 to 6 carbon atoms; more preferably, cyclopropoxy. ·

 (Y)

 Examples of Y include CH and N.

 Examples of the compound (1) include compounds obtained by combining the above-mentioned various substituents. Preferred compounds from the viewpoint of drug efficacy are as follows.

(1) A compound wherein 1 ^ 1 is 50 ₁₁₁ 1 ^ 4, R 2 is a phenyl group, 1 ^ 3 is an alkoxy group having ₁ to ₁₂ carbon atoms, and Y is CH.

 For example, compounds 1, 30, and 37 in Table 1 below can be mentioned.

 (2) The compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is an alkoxy group having ι to ΐ 2 carbon atoms, and Y is CH.

 For example, compounds 5, 11, 16, 17, 20, 24, 27, 33, 35, 36, and 40 in Table 1 below can be mentioned.

(3) The compound wherein R 1 is an alkyl group having 1 to 6 carbon atoms, R 2 is a phenyl group, 1 ^ 3 is 30 ₁₁₁ 1 ^ 5, and Y is CH.

 For example, there can be mentioned Compound 8 in Table 1 below.

(4) R 1 is SO _m R ^4, R2 is a phenyl group, R3 is S_〇 _ra R 5,

Compounds wherein Y is CH.

 For example, compounds 10 and 25 in Table 1 below can be mentioned.

 (5) The compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is an alkoxy group having 1 to 12 carbon atoms, and Y is N.

For example, compounds 15, 29, 54, and 65 in Table 1 below can be mentioned ₍

(6) The compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is S0 _m R 5, and Y is CH.

 For example, compounds 19 and 44 in Table 1 below can be mentioned.

 (7) The compound wherein R 1 is an alkoxy group having 1 to 6 carbon atoms, R 2 is a phenyl group, 3 is an alkoxy group having 1 to 12 carbon atoms, and Y is CH.

 For example, compounds 26 and 31 in Table 1 below can be mentioned.

 (8) The compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is a hydrogen atom, and γ is CH.

For example, Compound 28 in Table 1 below can be mentioned. (9) The compound wherein 1 ^ 1 is 50 ₁₁₁ 1 ^ 4, R 2 is a phenyl group, R 3 is an alkoxy group having 1 to 12 carbon atoms, and Y is N.

 For example, compounds 43 and 62 in Table 1 below can be mentioned.

(10) 1 ^ 1 50 _∞ 1 ^ ⁴ Deari, R 2 is Fuweniru group, an R 3 force s hydrogen atoms, compounds wherein Y is CH.

 For example, compounds 45 and 49 in Table 1 below can be mentioned.

(11) A compound wherein R ¹ is an alkoxy group having 1 to 6 carbon atoms, R 2 is a phenyl group, R ³ is a hydrogen atom, and Y is CH.

 For example, there can be mentioned Compound 47 in Table 1 below.

 (12) A compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is an alkynyloxy group having 3 to 9 carbon atoms, and Y is CH.

 For example, Compound 52 in Table 1 below can be mentioned.

(13) The compound wherein R 1 is an alkoxy group having 1 to 6 carbon atoms, R 2 is a phenyl group, 1 ^ 3 is 50 ₁₁₁ 1 ^ 5, and Y is N.

 For example, compounds 56 and 66 in Table 1 below can be mentioned.

(14) a compound wherein R 1 is an alkoxy group having 1 to 6 carbon atoms, R 2 is a phenyl group, 1 ^ ³ is an alkoxy group having 1 to 12 carbon atoms, and Y is N .

 For example, compound 57 in Table 1 below can be mentioned.

(15) A compound wherein R ¹ is a hydrogen atom, R ² is a phenyl group, 1 ^ 3 is a haloalkoxy group having 1 to 6 carbon atoms, and Y is CH.

 For example, compound 58 in Table 1 below can be mentioned.

(16) The compound, wherein R ¹ is a hydrogen atom, R 2 is a phenyl group, R 3 is an alkenyloxy group having 3 to 9 carbon atoms, and Y is CH.

 For example, compound 59 in Table 1 below can be mentioned.

(1 7) R ¹ is a hydrogen atom, R 2 is a phenyl group, 1 ^ 3 is 50 ₁₁₁ 1 ^ 5,

Compounds wherein Y is N.

 For example, compounds 53 and 63 in Table 1 below can be mentioned.

 (18) A compound wherein R 1 is a hydrogen atom, R 2 is a phenyl group, R 3 is an alkynyloxy group having 3 to 9 carbon atoms, and Y is N.

 For example, there can be mentioned Compound 64 in Table 1 below.

(19) R 1 is S_〇 _m R ^4, R2 is a phenyl group, R3 is located at S_〇 _m R5 Compounds wherein Y is N.

 For example, compound 67 in Table 1 below can be mentioned.

 (Synthesis method of compound (1))

 The method for synthesizing the compound (1) of the present invention will be described in more detail.

 Preferred methods for producing compound (1) include the following two methods (Synthesis methods 5 and 5) in addition to Synthetic methods 1, 2, 3 and 4 described as the second, third, fourth and fifth kaki. 6) can be listed.

Synthesis method 5

The following equation (8):

式中、 R², R9及び Yは、 前記と同義である、

Wherein R ² , R 9 and Y are as defined above,

A method for producing a compound (7) represented by the above formula (7), comprising reacting the compound represented by the formula (1) with a halogenating agent without using a solvent or in the presence of a base.

Synthesis method 6

A method for producing a compound (8) represented by the above formula (8), comprising reacting the compound (7) with a hydroxide of an alkali metal in a solvent.

 The above synthesis methods 1 to 6 of the compound (1) of the present invention will be described in more detail.

 (Synthesis method 1)

 Synthesis method 1 is a method in which compound (1) is obtained by reacting compound (2) with compound (3) in a solvent in the presence of a base.

The type of the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, rigoin, hexane, chlorobenzene, dichlorobenzene, Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic hydrocarbons such as formaldehyde, dichloroethane, trichloroethylene; ethers such as getyl ether, tetrahydrofuran, dioxane, etc. Alcohols such as methanol, ethanol, ethylene glycol and the like; Aprotic polar solvents such as N, N-dimethylformamide, dimethylsulphoxide, N, N-dimethylimidazolidinone, N-methylpyrrolidone; and mixtures of the above solvents.

The amount of the solvent to be used, the compound (2) can be used as becomes 5-8 0% by weight; 1 0-7 0 weight _^0/0 are preferred.

 The reaction temperature is not particularly limited, but is in the range of from room temperature to the boiling point of the solvent used or less; 10 to L 10 ° C is preferable.

 The type of base is not particularly limited, and organic and inorganic bases, for example, organic bases such as triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, DBU; sodium methoxide, Alkali metal alkoxides such as potassium-t-butoxide; and inorganic bases such as hydroxides, hydrides, carbonates, and hydrogencarbonates of alkali metal and alkaline earth metal. it can.

 The amount of the base to be used is 1 to 5 moles relative to compound (2); preferably 2 to 3.5 moles.

 The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower;

 The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 7 hours. Compound (3) is used in an amount of 1.0 to 5 moles, preferably 1.0 to 3 moles, based on Compound (2).

 The compound (2) used in the present invention is produced according to the method described in Tetrahedron. Lett., 1973, 30 (372), p. 420. Can o

 As the compound (3), a commercially available product can be used.

 After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, recrystallization, various chromatography and other known means. And can be appropriately refined.

 (Synthesis method 2)

 Synthesis method 2 is a method of reacting compound (4) with compound (3) in a solvent in the presence of a base to obtain compound (1).

Examples of the solvent include ethers described in Synthesis Method 1, chlorinated or unaromatic aromatic, aliphatic, alicyclic hydrocarbons, alcohols, aprotic polar solvents, and And mixtures of the above-mentioned solvents.

 How much solvent is used in compound (4)? A force that can be used so as to be 5 to 80% by weight s; 10 to 70% by weight is preferable.

 The reaction temperature is not particularly limited, but is in the temperature range from room temperature to the boiling point of the solvent used or less; preferably from 10 to 110 "C.

 The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The compound (3) is used in an amount of 1.0 to 5 times the molar amount of the compound (4); the amount of the starting compound used is preferably 1.0 to 3 times the molar amount.

 Compound (4) can be produced by the method described in Journal of the American Chemical Society, 1980, Vol. 102, page 2838.

 After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration, and the like, and if necessary, known means such as recrystallization and various types of chromatography. And can be appropriately refined.

 (Synthesis method 3)

 Synthesis method 2 is a method in which compound (5) and compound (6) are reacted in a solvent in the presence of a base to obtain compound (1).

 Examples of the type of the solvent include the ethers described in Synthesis Method 1, chlorinated or unaromatic aromatic, aliphatic, alicyclic hydrocarbons, alcohols, aprotic polar solvents, and the above. Mixtures of solvents can be mentioned.

The amount of the solvent to be used, the compound (5) can be used in such a manner that 5 to 80 wt%; 1 0-70 weight _^0/0 are preferred.

 The reaction temperature is not particularly limited, but is in a temperature range from room temperature to the boiling point of the solvent used or lower; preferably from 10 to 110.

 The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The compound (3) is used in an amount of 1.0 to 10 times the amount of the compound (5); the amount of the starting compound used is preferably 1.0 to 8 times.

In the compound (5), the compound where n ′ = 0 can be produced by the method described in the synthesis method (1). The compound with n = 1 can be produced according to the method described in Journal of Chemical Society (C), 1967, p. 568. As the compound (6), a commercially available product can be used.

 After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration, and the like, and if necessary, known means such as recrystallization and various types of chromatography. And can be appropriately refined.

 (Synthesis method 4)

 Synthetic method 4 is a method of obtaining compound (1) by reacting compound (7) with compound (6) in a solvent in the presence of a base.

 Examples of the type of the solvent include those described in Synthesis Method 1 and water.

 The solvent can be used in such an amount that the compound (7) is 5-80% by weight; however, it is preferably 10-70% by weight.

 The type of base is not particularly limited, and organic and inorganic bases, for example, organic bases such as triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, DBU; sodium methoxide, Alkali metal alkoxides such as potassium-t-ptide and the like; inorganic bases such as hydroxides, hydrides, carbonates and hydrogencarbonates of alkali metal and alkaline earth metal can be mentioned. .

 The amount of the base to be used is 1 to 5 moles compared to Compound (7); preferably, it is 1.2 to 2.0 moles.

 The reaction temperature is not particularly limited, but is in the range of 100 ° C. to a temperature not higher than the boiling point of the solvent used; −80 to 〜10 ° C. is preferable.

 The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The amount of the starting compound used is 1.0 to 5 times the molar amount of the compound (6) relative to the compound (7); preferably 1.0 to 3 times the molar amount.

 Compound (7) can be produced by (Synthesis method 5).

 After completion of the reaction, the target compound (1) produced as described above is subjected to usual post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization, various chromatographic methods, and other known means. And can be appropriately refined.

 (Synthesis method 5)

 Synthesis method 5 is a method for obtaining compound (7) by reacting compound (8) with a halogenating agent in the absence of a solvent or in the presence of a base.

Examples of the halogenating agent include chlorinating agents such as oxychloride phosphorus, a mixture of oxychloride quinoline and pentachloroaniline, phosphorus oxybromide, and a mixture of phosphorus oxybromide and phosphorus tribromide. of Brominating agents can be mentioned.

 The amount of the halogenating agent to be used is about 10-fold the molar amount of compound (8)], but preferably about 1- to 2-fold the molar quantity.

 Examples of the type of the base include tertiary amines such as diisopropylethylamine, dimethylaniline and getylaniline.

 The amount of the base to be used is 1 to 10 moles relative to compound (8); preferably, it is 1.2 to 10 moles.

 The reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower; preferably from room temperature to 150 ° C.

 The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. Compound (8) can be produced by synthetic method (6).

 After completion of the reaction, the target compound (7) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, known means such as recrystallization and various types of chromatography. And can be appropriately refined.

 (Synthesis method 6)

The synthesis method (6) is a method for obtaining the compound (8) according to the synthesis method (5) by reacting the compound (7) with a hydroxide of an alkali metal in a solvent.

 Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide.

 The amount of the alkali metal hydroxide to be used is 1 to 10 moles relative to compound (7); preferably 1 to 3 moles.

 Examples of the type of the solvent include the solvent and water described in Synthesis Method 1, a mixture of these solvents, and the like.

 The amount of the solvent to be used may be such that the amount of the compound (7) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.

 The reaction temperature is not particularly limited, but is in the range of from 20 to the boiling point of the solvent to be used; it is preferably from 110 to 100 ° C.

The reaction time varies depending on the concentration and temperature described above; it is usually 1.6 to 5 hours. After completion of the reaction, the target compound (8) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, and filtration, and if necessary, recrystallization, various chromatography, and other known means. And can be appropriately refined. Examples of the compound (1) include compounds 1 to 71 shown in Table 1 below.

 Examples of the pathogenic bacteria for agricultural and horticultural use which are effective in controlling the compound (1) of the present invention include wheat rust, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, cucumber gray mold, cucumber and cucumber bacterium. , Rice blast fungus and tomato late blight fungus.

 The agricultural and horticultural fungicide of the present invention contains at least one compound (1) as an active ingredient.

Compound (1), depending also can force ⁵ ,, usually conventional methods can be used alone, carrier, interfacial active agents, dispersing agents, adjuvants, formulation and the like (e.g., powders, emulsions, microgranules, granules Agents, wettable powders, oily suspensions, aerosols and the like).

 Carriers include, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, bamboo silicate, bamboo silicate, bamboo sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatics Group hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.) , Esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), liquids such as water Carrier; air, nitrogen, Acid gas, gaseous carriers such as Freon (in this case, can be morphism mixed injection), and the like.

 Examples of surfactants and dispersants that can be used to improve the performance of this agent, such as adhesion to animals and plants, improved absorption, and dispersion, emulsification, and spreading of drugs, include, for example, alcohol sulfate esters, alkyls Sulfonates, ligninsulfonates, polyoxyethylene glycol ethers and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as adjuvants.

 In the production of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in an appropriate combination, respectively, according to the respective purposes.

When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50 in an emulsion. % For powders, usually 0.3 to 25% by weight, for wettable powders, usually 1 to 90% by weight 6, for granules, usually 0.5 to 5% by weight 96, for oils, usually 0.5 to 5% by weight, the aerosol is usually from 0.1 to 5 weight ^_0/0.

 These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them onto the foliage of plants, soil, or the surface of paddy fields, or directly applying them, depending on the purpose. Example

 Hereinafter, the present invention will be described specifically with reference to Examples. Note that these examples do not limit the scope of the present invention.

Example 1 (Synthesis of Compound (1))

 (1) Synthesis of (3,4-dichlorobenzoyl) triazolylketene dimethyldithioacetal

 In a solution of 3.6 g (9 Ommo 1) of 60% sodium hydride in DMF (40 ml), under stirring at 30 ° C, 3,4-dichlorophenacyltriazole 11 g (43 mmo 1) and disulfide A solution of 4.2 m 1 (7 Ommo 1) of carbon in DMF (40 m 1) was added dropwise over 30 minutes.

 After stirring at 120 ° C. for 1 hour, 5.6 ml (9 Ommo 1) of methyl iodide was added dropwise, and then water (100 ml) was added dropwise.

 The reaction solution was extracted twice with 30 ml of ethyl acetate, and the combined organic layers were washed with brine, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 11.5 g (yield: 75%) of (3,4-dichlorobenzyl) triazolylketene dimethyldithioacetal.

1 H-NMR (40 OH z , CDC 1 3)

 δ (p pm) 2.21, 2.44 (s, each 3H), 7.04-7.40 (m, 3H), 7.92 (s, 1H), 8.28 (s, 1H )

 (2) Synthesis of 4- (3,4-dichlorophenyl) -16-methylmercapto-15-triazolylpyrimidine (Compound 64)

(3,4-Dichlorobenzoyl) triazolylketene dimethyldithioacetal 3.2 g (8.9 mm 01) of t-butanol (30 m 1) solution was added to vinegar with stirring at room temperature. 2.08 g (2 Ommo 1) of formamidine acid and 4.14 g (3 Ommo 1) of potassium carbonate were added and stirred for 6 hours.

 After the completion of the reaction, 100 ml of water was extracted, extracted twice with 30 ml of ethyl acetate, and the combined organic layers were washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 4.8 g (93% yield) of 4- (3,4-dichlorophenyl) -16-methylmercapto-15-triazolylpyrimidine. I got

1 H-NMR (30 OMH z , CDC 1 3)

δ (p pm) 2.62 (s, 3 H), 7.15 (d, J = 8.3 Hz, 1 H), 7.22 (dd, J = 8.3, 1.95) Hz, 1 H), 7.39 (d, J = l. 95 Hz, 1 H), 8.04 (s, 1 H), 8.07 (s, 1 H), 9.10 ( (s, 1H) (3) Synthesis of 4- (3,4-dichlorophenyl) -1-6-methanesulfinyl-5-triazolylpyrimidine

 4 To a solution of 1.7 g (5 mmo 1) of methylene chloride (20 ml) in a solution of 1.7 g (5 mmo 1) of 1- (3,4-dichlorophenyl) -16-methylmercapto-15-triazolylbilimidine was stirred at 0 ° C with stirring.

A solution of 1.36 g (5.5 mmo 1) of 70% p-shiridani benzoic acid peroxidic acid in methylene chloride (2 Oml) was added dropwise.

After stirring at room temperature for 40 minutes, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 4- (3,4-dichlorophenyl) -16-methanesulfinyl-15-tria. 1.3 g (74% yield) of zolylpyrimidine were obtained. ¹ H-NMR (30 OMH z, CDC 13)

 8 (p pm) 3.12 (s, 3 H), 7.28 (d, J = 8.7 Hz, 1 H),

7.38 (dd, J = 8.3, 1.95 Hz, 1 H), 7.46 (d, J = 1.95 Hz, 1 H), 7.89 (s, 1 H) , 8.09 (s, 1H), 9.57 (s, 1H) (4) 4- (3,4-dichlorophenyl) 16- (2-propynyl) 15-triazolylpyrimidine (compound 65) Synthesis of

 4- (3,4-Dichloromethylphenyl) -1-6-methanesulfinyl-1-5-triazolylpyrimidine 0.6 g (1.7 mmo 1) in DMF (5 ml) solution was stirred at room temperature with vinyl alcohol 0. 17 g (3. Ommo 1) and 0.28 g (2 mMol) of potassium carbonate were added.

After stirring for 1 hour, calorie water 2 Om 1, extract twice with ethyl acetate 2 Om 1, and combine The organic layer was washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 4 — (3,4-dichlorophenyl) -16_ (2-propynyl) -15-triazolylpyrimidine 0.29 g (yield 49 %).

1 H-NMR (30 OMH z , CDC 1 3)

δ (p pm) 2.55 (t, J = 2.44 Hz, 3 H), 5.19 (d, J = 2.44 Hz, 2 H), 7.26-7.36 (m, 3H), 7.93 (s, 1H), 8.31 (s, 1H), 8.94 (s, 1H)

 (5) Synthesis of 4- (3,4-dichlorophenyl) -1-6-n-propoxy-15-triazolyl pyrimidine (Compound 66)

4- (3,4-Dichlorophenyl) -1-6-methanesulfinyl-1-5-triazolylpyrimidine 0.7 g (1.98 mm 01) in DMF (5 ml) solution was stirred at room temperature with _n -propanol 0 9 g (15 mmo 1) and 0.41 g (3 mmo 1) of potassium carbonate were calories.

 After stirring for 2 hours, 20 ml of water was extracted and extracted twice with 2 Oml of ethyl acetate. The combined organic layers were washed with a saturated diet, dried over sodium sulfate, and evaporated under reduced pressure.

 The resulting residue was purified by silica gel column chromatography to obtain 0.27 g of 4-1 (3,4-dichloromouth phenyl) -16-n-propoxy. 5-triazolylpyrimidine. 39%).

1 H-NMR (30 OMH z , CDC 1 3)

δ (p pm) 0.96 (t, J = 7.3 Hz, 3 H), 1.79 (m, 2 H), 4.48 (t, J = 6.6 Hz, 2H), 7 26—7.35 (m, 3H), 7.92 (s, 1H), 8.27 (s, 1H), 8.88 (s, 1H)

 (6) Synthesis of 4- (3,4-dichlorophenyl) -12-methylmercapto-16-methoxy-5-triazolylpyrimidine (compound 43)

 (3,4-Dichlorobenzoyl) triazolylketene Dimethyldithioacetal 1.3 g (4. Ommo 1) in methanol (15 ml) was stirred at room temperature with 0.61 g (8 Omm 01) and 1.5 g (8. Om mo 1) of 28% sodium methoxide were added, and the mixture was heated under reflux for 2 hours.

After cooling at room temperature, 20 ml of 0.2 N aqueous sodium hydroxide and 1 Om1 of ethyl acetate were added, and the aqueous phase was separated. Add 0.8 ml (13 mmo I) of methyl iodide, stir for 10 minutes at room temperature, extract twice with 30 ml of ethyl acetate, wash the combined organic layer with saturated saline, and add sulfuric acid. It was dried over sodium and evaporated under reduced pressure.

 The resulting residue was purified by silica gel column chromatography to give 4-g- (3,4-dichlorophenyl) -12-methylmercapto-16-methoxy-1-5-triazolylpyrimidine 0.1 g ( Yield 7%).

1 H-NMR (3 00MHz, CDC 1 3)

δ (p pm) 2.61 (s, 3 H), 4.07 (s, 3 H), 7.17 (d, J = 7.6 Hz, 1 H), 7.23 (d, 2 H), 7.34 (t, 1 H), 7.92 (s, 1 H), 8.13 (s, 1 H)

 (7) Synthesis of 4- (3,4-dichlorophenyl) -1,2,6-bis (methylmercapto) -15-imidazolylpyrimidine (Compound 25)

 Dissolve 0.6 g (15 mmo 1) of 60% sodium hydride in ethanol (10 ml), and dissolve (3,4-dichlorobenzyl) imidazolylketene dimethyldithioacetal 1.5 g (4. 2mmo 1) and 2.22 g (8.0 mmol) of methyl isothiourea sulfate were added, and the mixture was stirred at room temperature for 30 minutes, and then heated and refluxed for 3 hours.

 After cooling at room temperature, 100 ml of water was added, and the mixture was extracted twice with 50 ml of ethyl acetate. The combined organic layers were washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 0.64 g (yield 40%) of (3,4-dichlorophenyl) -1,2,6-bis (methylmercapto) -15-triazolylbilimidine. Obtained.

m.p. 1 28.0-1 29.5

^{1 H-NMR (27 OMH z} , CDC 1 3)

 8 (p pm) 2.58 (s, 3 H), 2.63 (s, 3 H), 6.82 (s, 1 H), 7.05 (d, J = l. 47 Hz , 1 H), 7.08 (s, 1 H), 7.18 (d, J = 2.20 Hz, 1 H), 7.2 1 (d, J = 2.20 Hz, 1 H) , 7.36 (t, 2H)

 (8) Synthesis of 4- (3,4-dichlorophenyl) -1,2,6-diethoxy-5-imidazolyl pyrimidine (Compound 26)

0.5 g (13 mmo 1) of 60% sodium hydride was dissolved in ethanol (10 ml), and (3,4-dichlorophenyl) -1,2,6-bis (methylmercapto) -15-tol was dissolved. 0.4 g (1. Ommo 1) of liazolylpyrimidine was added, and the mixture was heated under reflux for 2 hours. After cooling at room temperature, 5 Om 1 of water was extracted and extracted twice with 2 Om 1 of ethyl acetate. The combined organic layers were washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 0.2 g (yield 50%) of (3,4-dichlorophenyl) -1,2,6-bis (methylmercapto) -1,5-triazolyl bilimidine. Was.

m.p. 1 28.0-1 29.5

^{1 H-NMR (2 7 OMH} z, CDC 1 3)

 S (p pm) 1.37 (t, J = 7.3 Hz, 3 H), 1.45 (t, J = 7.3 Hz, 3 H), 4.46 (q, J = 7.3 Hz, 2 H), 4.52 (q, J = 7.3 Hz, 2 H), 6.75 (d, 1 H), 6.99 (s, 1 H), 7. 1 0—7.3 8 (m, 4 H)

 (9) Synthesis of 4- (3,4-dichlorophenyl) -12-methylmercapto-15-imidazolylpyrimidine (compound 45)

 A solution of 30.0 g (118 mm 01) of 3,4-dichlorophenacylimidazole in 17 g (14 Ommo 1) of DMF dimethyl acetal was stirred at 60 for 1 hour.

 After cooling, 100 ml of water was added, and the mixture was extracted twice with 30 ml of ethyl acetate.

 The combined organic layers were washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure. 37 g of the obtained 1- (2,4-dichlorophenyl) 1-2-imidazolyl-13- (N, N-dimethylamino) -2-propen-1-one was used in the next reaction without purification. .

 1- (2,4-dichlorophenyl) 1-2-imidazolyl-3- (N, N-dimethylamino) 1-2-propene-1-one 3.0 g (c a. 1 Ommo 1) of methanol (1 5ml) To the solution was added 1.52 g (2 Ommo 1) of thiourea and 2.76 g (2 Ommo 1) of potassium carbonate while stirring at room temperature, and the mixture was stirred at room temperature for 2 hours, and then 0.6 ml of methyl iodide was added. 1 (1 Ommo 1) was added, and the mixture was stirred at room temperature for 10 minutes.

 100 ml of water was added thereto, and the mixture was extracted twice with 50 ml of ethyl acetate. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

The resulting residue was purified by silica gel column chromatography to obtain (3,4-dichlorophenyl) -1,2,6-bis (methylmercapto) -1,5-imidazolyl bilimidine 2.2 g (yield 68%) I got mp 1 36.0-1 37.0 in

l H-NMR (3 00MHz, CDC 1 3)

δ (p pm) 2.62 (s, 3 H), 6.80 (t, J = 1.22 Hz, 1 H), 7.08 (t, J = 0.98 Hz, 1 H), 7.17 (d, J = 7.3 Hz, 1 H), 7.33 (dd, J = 8.1, 1.8 Hz, 1 H), 7.38 (s, 1 H) , 7.40 (d, J = 1.95 Hz, 1 H), 8.60 (s, 1 H)

 (10) Synthesis of 4- (3,4-dichlorophenyl) -6-chloro-5-imidazolylpyrimidine (Compound 51)

 4- (3,4-Dichlorophenyl) -6-methanesulfinyl-1-5-triazolyl pyrimidine 1.2 g (3.6 mm 01) was added to a 2N aqueous sodium hydroxide solution (5 ml), and 10 After stirring for 2 minutes, the mixture was neutralized with 2N hydrochloric acid.

 The reaction solution was extracted twice with 30 ml of ethyl acetate, and the combined organic layers were washed with brine, dried over sodium sulfate, and evaporated under reduced pressure.

 1.0 g of the obtained 4- (3,4-dichlorophenyl) -16-hydroxy-15-imidazolyl pyrimidine was used in the next reaction without purification.

 4- (3,4-dichlorophenyl) -1-6-hydroxy-5-imidazolylpyrimidine 1.0 g (c a.3.3 mmo 1) and diisopropylethylamine 3.87 g (3 Ommo 0.92 g (6. Ommo 1) of phosphorus oxychloride was added dropwise to a solution of 1) in toluene (1 Om 1), and the mixture was refluxed for 3 hours.

 Water 2 Om 1 was carefully added at first, and after cooling at room temperature, extraction was performed twice with 1 Om 1 of ethyl acetate. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and evaporated under reduced pressure.

 The obtained residue was purified by silica gel column chromatography to obtain 0.2 g of 4- (3,4-dichlorophenyl) -16-chloro-5-imidazolylpyrimidine (yield: 1796).

1 H-NMR (30 OMH z , CDC 1 3)

 S (p pm) 6.91 (s, J = 1.22 Hz, 1 H), 7.13—7.31 (m, 4 H), 7.43 (d, 1 H), 7 . 64 (s, 1 H), 9.15 (s, 1 H) (11) Synthesis of other compounds (1) in Table 1

Other compounds (1) in Table 1 were synthesized according to the methods (1) to (10) described above. Table 1 shows the compounds (1) synthesized as described above and their physical properties. Table 1

第 1表 (続き)

Table 1 (continued)

Conversion

Compound R ¹ _R 2 _R 3 Y Property

19 Η SCH ₃ CH pale yellow viscous liquid

20 Η OC ₆ H ₁₃ -n CH Light yellow viscous liquid

21 ^SCH 3 OCH ₃ CH ρ208 ~ 210¾:

22 ^SCH 3 OC ₁₄ H ₂₉ -n ^ m *

 CH yellow viscous liquid

2.3 SCH ^ OC ^ H -n

 ^ 6 13 CH yellow "囬

24 H Ov- ₁ 14 _{/ t} H «Z _Q yn CH White massive solid

25 SCH-, 1 SCH _¾ CH mp128 ~ 129.5

26 OCum _J H _< ;

 J CH yellow viscous liquid

27 H a OC yH,

 1 m 3 CH brown viscous liquid

28 H ^C '1 H CH Light yellow viscous liquid

29 H 0¾Η ₅ N Yellow viscous liquid

30 SCH

^0CH 3 CH mp 119 ~ 120

31 OCH ₃

^0CH 3 CH Light red viscous liquid

32 OC ₃ H ₇ -n OC, H "-n CH Light yellow viscous liquid

33 H ci-O- 0C H ₇ -n CH Light yellow viscous liquid

34 SCH ₃ ci-O- OC T H ₇ -n CH Orange viscous liquid

35 H ci--0CH ₃ CH Γη.ρ.ΐ71〜173Χ:

36 H ci--OC ₄ H ₉ -n CH Colorless viscous liquid Table 1 (continued)

(1)

Conversion

Compound R ¹ _R 2 _R 3 Y Property

χ J 1ι SCH 3 2 5

¾ JQO OCH ₃ SC

 2 5 tl tl 在 在 * Λ rl OCH CH m.D. 170 ~ 172 * C

4 AU (\ rl

4.1 SC つ_ς

 2 5 2 5 tl

OC H ₇ -iso OCH

43 SCH _¾

 3 OCH-3 I old days Λ tii yaro Λ parent ^ ¾ liquid sa

44 H SC

 2 H 5 t ^> Viscous liquid

45 SCH _¾ H CH mp137〜138 * C

46 SC, H.H CH m.p.l 37-138

47 OCH H CH m.p.151 ~ 151. ^ C

48 OC „H ₇ -iso H CH mp105.5 ~ 107.5

49 SOCH ₃ H CH mp183〜184 * G

50 H CH

51 H _Cl CI CH orange powdery solid

52 H, o CH Brown viscous liquid

53 H ^SC 2 ^H 5 N Light brown viscous liquid

54 H CI-Q7 OCH ₃ N light brown viscous liquid Table 1 (continued)

実施例 2 (製剤の調製）

Example 2 (Preparation of formulation)

 (1) Preparation of granules

 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoretsu powder (trade name; manufactured by Kao Corporation), and 2 parts by weight of sodium ligninsulfonate are uniformly mixed. Then, a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

 (2) Preparation of wettable powder

 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of White Ribon, 1.5 parts by weight of Neorex Powder (trade name; manufactured by Kao Corporation), and Demol (trade name: Kao Corporation) 0.5 parts by weight were uniformly mixed and then pulverized to obtain a wettable powder.

(3) Emulsion preparation

 To 20 parts by weight of the compound (1) and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.) was added, mixed uniformly, and dissolved to obtain an emulsion.

 (4) Preparation of powder

 Compound (1) was uniformly mixed with 5 parts by weight of powder, 50 parts by weight of talc, and 45 parts by weight of kaolin to obtain a powder.

Example 3 (Efficacy test)

 (1) Control efficacy test for rice blast (preventive effect)

 10 rice plants (variety: Nipponbare) were grown per pot in a plastic flowerpot with a diameter of 6 cm, and the compounds shown in Table 1 were prepared according to Example 2 in 1.5-leaf seedlings according to Example 2. ) Was diluted to 500 ppm with water containing a surfactant (0.01%), and 20 ml was sprayed per pot.

 After spraying, the plants were grown in a glass greenhouse until inoculation.

Day after the chemical spray, Pyricularia oryzae partial resistance spore suspension (3 X 1 0 ⁵ spores Roh m 1) was prepared, which was uniformly inoculated by spraying the plants.

 Four days after inoculation, the plants were cultivated in a moist chamber (dark for the first three days and under light for one day) at 25, and the degree of rice blast lesions on the leaves was examined.

 As a result, Compounds 1, 19, 20, 44, 53 and 58 showed 10% of the lesion area.

 (2) Efficacy test for prevention of wheat rust (prevention test)

10 wheat per pot in a 6 cm diameter plastic flowerpot (cultivar: Kobushiko) Wheat), and the wettable powder of the compound (1) described in Table 1 prepared according to Example 2 was added to the 1.5-leaf stage seedlings with a surfactant (0.01%). ) Was diluted to 500 ppm with water and sprayed at 20 ml per pot.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7 × 10 ⁴ spores Zm 1) of wheat leaf rust was uniformly spray-inoculated on the plants.

 After inoculation, they were grown for one week in a glass greenhouse, and the degree of wheat leaf rust spots on the first leaf was examined.

As a result, compound 1 9, 33, 35, 36, 44, 47, 52 ^force? Showed 1 0% or less lesion area.

 (3) Efficacy test for prevention of powdery mildew of wheat (prophylactic test)

 In a 6 cm diameter plastic flowerpot, 10 varieties of wheat (cultivar: chromium) were grown per pot, and the seedlings at the 1.5-leaf stage were prepared according to Example 2 according to Table 2. The wettable powder of the compound (1) was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed at 2 Om1 per pot.

 After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then conidiospores of powdery mildew of powdery mildew were collected from the diseased leaves, and sprinkled evenly over the plants sprayed with the drug to inoculate.

 After inoculation, the plants were grown in a glass greenhouse for 10 days, and the degree of the powdery mildew spot on the first leaf was examined.

 As a result, compound 5, 11 1, 15, 16, 19, 20, 26 to 31 1, 33, 35, 37, 40, 43, 44, 52 to 59, and 62 to 67 had a lesion area of 10%. The following is shown. (4) Control efficacy test for cucumber and disease (prevention test)

One cucumber (cultivar: Sagami Hanshiro) is grown per pot in a plastic flower pot with a diameter of 6 cm. The seedlings at the 5-leaf stage are prepared as described in Table 1 according to Example 2. The wettable powder of the compound (1) was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed at 20 ml per pot. After spraying, the cells were cultured in a glass greenhouse for 2 days. Then, cucumber and zoospores of the fungus were prepared from the diseased leaves.

After inoculation, the plants were kept in the dark at 20 ° C for 2 days, then grown in a glass greenhouse for 5 days, and the extent of the cucumber and the lesions appearing on the first leaf were examined.

As a result, the compound showed 8, 16 and 49 ^s and a lesion area of 10% or less. (5) Efficacy test (prevention test) for cucumber gray mold

Paper towels moistened with distilled water were spread in a plastic case (35 cm x 25 cm), and the cut leaves of Japanese cucumber (variety: Sagami Hanjiro) cotyledons were lined up. 5% sucrose on Kiyuuri cotyledons, 1% yeast extract solution Kiyuuri gray mold fungus spore suspension prepared by (1 0 ⁵ spores Zm 1) 5 0 dropwise mu I, paper de Isku (diameter thereon 7 mm).

 Next, 500 ppm of a compound (1) shown in Table 1 (containing 0.05% surfactant) was dropped 90 ° I onto the paper disc.

 The plastic case was closed, closed with vinyl tape, and kept in a constant temperature oven at 20 ° C for 4 days, and the degree of the fungus spots on the cotyledon that appeared on the cotyledon was examined.

 As a result, compounds 8, 10, 24, 25, 30, 40, 43, 45, 56, 62, and a lesion area of 1096 or less were shown. Industrial applicability

 The novel 5-azolyl pyrimidine compound of Honkiaki has an excellent agricultural and horticultural bactericidal effect.

Claims

1. The following equation (1) blue

Enclosure In the formula, R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, and a cycloalkyl having 3 to 6 carbon atoms. Alkoxy group, alkenyloxy group having 3 to 9 carbon atoms, alkynyloxy group having 3 to 9 carbon atoms, 0 to (CH ₂ ) _n -R ⁶ , alkyl having 1 to 6 carbon atoms A group or an alkoxy group having 1 to 20 carbon atoms, wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a pyridyl group; R ⁶ may have a substituent Represents a phenyl group, a phenoxy group, an alkoxy group having 1 to 6 carbon atoms, Si (CH ₃ ) ₃ , CN, NO ₂ or N (R7) R8; 1 ^ 7 and shaku 8 represent a hydrogen atom, a carbon atom represents an atomic number from 1 to 6 alkyl groups, they rather it may also be the same; m represents an integer of 0 to 2; is eta represents an integer of 1 to 4; R ² is substituted Examples of the group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, Represents a phenyl group, a phenoxy group or a naphthyl group which may have CN or Ν〇2; R ³ is an alkoxy group having 1 to 20 carbon atoms, SO _m R5, 0- (CH ₂ ) _n- R6, hydrogen atom, alkenyloxy group having 3 to 9 carbon atoms, halogen atom, haloalkoxy group having 1 to 6 carbon atoms, cycloalkoxy group having 3 to 6 carbon atoms or 3 to 9 carbon atoms R ⁵ represents an alkyl group having 1 to 6 carbon atoms; R ⁶ has the same meaning as described above; Y represents CH or N; A 5-azolylpyrimidine compound represented by the formula: 2. The following equation (2): (2)

In the formula, R ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or a carbon atom as a substituent. 1-6 pieces of haloalkyl groups, CN or N0 ₂ good off Eniru group which may have a represents a Fuwenokishi or naphthyl group; R ⁴ represents 1-6 alkyl group or a pyridyl group carbon atoms; γ represents CH or N; And a compound represented by The following equation (3):

(3) In the formula, R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, and a carbon atom having 3 to 6 carbon atoms. Cycloalkoxy groups, alkenyloxy groups having 3 to 9 carbon atoms, alkynyloxy groups having 3 to 9 carbon atoms, 0- (CH ₂ ) _n -R ⁶ , 1 to 6 carbon atoms Represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms, wherein R ⁴ represents an alkyl group or a pyridyl group having 1 to 6 carbon atoms; and R ⁶ represents a substituent. a phenyl group which may be, phenoxy group, the carbon atom number 1-6 alkoxy _{groups, S i (CH 3) 3} , CN, N0 2 or N represents R8 (R?); R7 and R8 are hydrogen atom, Represents an alkyl group having 1 to 6 carbon atoms, which may be the same; m represents an integer of 0 to 2; n represents an integer of 1 to 4; Characterized by reacting with the compound represented by The following equation (1 '):

In the formula, R 3 ′ represents an alkoxy group having 1 to 20 carbon atoms, SO _m R 5 or 0- (CH ₂ ) _n -R ⁶ , wherein R ⁵ represents 1 to 6 carbon atoms. Rl, R2, 6 and 丫 are as defined above, A method for producing a 5-azolylpyrimidine compound represented by the formula: 3. Next equation (4) (Four)

In the formula, R ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a carbon atom as a substituent. 1 to 6 haloalkyl groups, a phenyl group, a phenoxy group or a naphthyl group optionally having CN or NO ₂ ; Y is CH or N; The following equation (3):

In the formula, R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, and a cycloalkyl having 3 to 6 carbon atoms. Alkoxy group, alkenyloxy group having 3 to 9 carbon atoms, carbon atom Represents an alkynyloxy group having 3 to 9 carbon atoms, 0- (CH ₂ ) _n -R ⁶ , an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a pyridyl group; R ⁶ has the same meaning as described above; m represents an integer of 0 to 2; n is an integer of 1 to 4 Represents Characterized by reacting with the compound represented by The following formula (1 "):

Wherein R l, 1 ^ ² and ぴ are as defined above, A method for producing a 5-azolylpyrimidine compound represented by the formula: 4. Next equation (5 ')

In the formula, R ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a carbon atom as a substituent. 1-6 pieces of haloalkyl groups, CN or N0 ₂ good off Eniru group which may have a represents a Fuwenokishi or naphthyl group; R ⁵ represents a C 1 -C 6 alkyl group; Y is Represents CH or N; W, is a halogen atom or SO _n , Represents R5; n 'represents 0 or 1; is R ^5, represents an alkyl group having 1 to 6 carbon atoms; R9 is SO _m R ^4, a hydrogen atom, a halogen atom, 1 to carbon atoms 6 haloalkyl groups, 1 to 6 carbon atoms haloalkoxy groups, 3 to 3 carbon atoms 6 cycloalkoxy groups, alkenyloxy groups having 3 to 9 carbon atoms, alkynyloxy groups having 3 to 9 carbon atoms, 〇- (CH ₂ ) _n -R ⁶ , 1 to 6 carbon atoms R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a pyridyl group; R ⁶ represents a substituted or unsubstituted alkyl group or an alkoxy group having 1 to 20 carbon atoms; a phenyl group which may be, phenoxy group, the carbon atom number 1-6 alkoxy group, a S i (CH 3) 3, CN, N0 2 or N (R7) R8; R 7 and _R 8 are hydrogen Atom, carbon represents an alkyl group having 1 to 6 atoms, which may be the same, And a compound represented by The following equation (6): R ^10- one XH (6) In the formula, X represents S or 0; R 10 is a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 3 to 9 carbon atoms, charcoal Represents an alkynyl group having a prime number of 3 to 9,-(CH ₂ ) _n -R6 or an alkyl group having 1 to 20 carbon atoms; Characterized by reacting with the compound represented by The following equation (1 ",):

Wherein R l, R2, RIO, X and Y are as defined above, A method for producing a 5-azolylpyrimidine compound represented by the formula: 5. Among the compounds represented by the formula (5,), a compound wherein W is a halogen atom is represented by the following formula (8):

Wherein R2, 1 ^ ⁹ and ¥ have the same meanings as in claim 5; 6. The method for producing a 5-azolylpyrimidine compound according to claim 5, which is obtained by reacting the compound represented by the formula (I) with a halogenating agent in the absence of a solvent or in the presence of a base. 6. The following equation (1

In the formula, R 1 is SO _m R ⁴ , a hydrogen atom, a halogen atom, a haloalkyl group having 16 carbon atoms, a haloalkoxy group having 16 carbon atoms, a cycloalkoxy group having 36 carbon atoms, Alkenyloxy group having 39 carbon atoms, alkynyloxy group having 39 carbon atoms, 0- (CH ₂ ) _n -R ⁶ , alkyl group having 16 carbon atoms or carbon atom having 1 Represents 20 alkoxy groups, wherein R ⁴ represents an alkyl group having 16 carbon atoms or a pyridyl group; R ⁶ represents a phenyl group, a phenoxy group, or a carbon atom which may have a substituent; Represents an alkoxy group of 16 numbers, Si (CH ₃ ) ₃ CN, NO ₂ or N (R?) R8; 1 ^ 7 and 1 ^ 8 are a hydrogen atom, an alkyl group having 16 carbon atoms M represents an integer of 02; n represents an integer of 14; R ² represents a halogen atom as a substituent, Alkyl group with 16 atoms, 16 carbon atoms An alkoxy group, a haloalkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a phenyl group optionally having CN or N〇2, a phenoxy group or a naphthyl group; R ³ is a carbon atom number of from 1 to 20 alkoxy groups, S_〇 ^{_{m R 5, 0- (CH 2}} ) n -R 6, hydrogen atom, 3-9 pieces of Arukeniruo alkoxy group carbon atoms, a halogen atom, Haloalkoxy groups with 1 to 6 carbon atoms, carbon atoms Represents a cycloalkoxy group having 3 to 6 carbon atoms or an alkynyloxy group having 3 to 9 carbon atoms, wherein R ⁵ represents an alkyl group having 1 to 6 carbon atoms; and R ⁶ has the same meaning as described above. Y represents CH or N; A fungicide for agricultural and horticultural use containing a 5-azolylpyrimidine compound represented by the following formula: