JP3390200B2 - Silicon-containing azole compounds and fungicides - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silicon-containing azole compound having an excellent bactericidal action.

[0002]

2. Description of the Related Art Although various triazole and imidazole compounds having bactericidal activity and antifungal activity are known, a tertiary alcohol triazole compound having a partial structure of a tertiary alcohol is a silicon group. The following compounds having a are known.

That is, JP-A-61-257975 describes a silicon-containing triazole compound as a plant growth regulator together with many other compounds. However, what is specifically described is the 3-t of Example 11.
-Butyl-3-hydroxy-4- (1,2,4-triazol-1-yl) -1-trimethylsilyl-1-pentyne only. This compound has a t-butyl group in place of the optionally substituted phenyl group in the compound of the present invention, the compound of the present invention is an alkane derivative, whereas it is an alkyne derivative, and further has a silicon group. Differs from the compound of the present invention in that the carbon chain that binds to the triazole group is longer.

GB-A-2224278 also describes silicon-containing triazole compounds along with many other compounds. However, the specific description is
It is only 3- (2,4-dichlorophenyl) -3-hydroxy-4- (1,2,4-triazol-1-yl) -1-trimethylsilyl-1-butene of Example 4.
In this compound, the carbon chain connecting the silicon group and the triazole group is butene, whereas the compound of the present invention is propane, and therefore differs in length and unsaturation.

Pestic. Sci. 29 , 427-435 (1990) (J.-
F. Chollet et al.) As a fungicide, compound XX [4- (4-chlorophenyl) -4-hydroxy-
5- (1,2,4-triazol-1-yl) -3-trimethylsilyl-1-pentene] differs from the compound of the present invention in that it has a vinyl group as a substituent of the propane chain.

[0006]

The prior art compounds listed above are generally of low activity.

When the fungicidally active compound having an azole ring is actually used as a pesticide, it is desirable that the compound be active in a lower dose and be harmless. Recently, labor-saving control and safety for workers have been particularly demanded, but a compound having a permeation migration property is very advantageous in this respect. For example, the target disease can be effectively controlled by treating seeds of various crops with a drug or throwing the drug wrapped in a water-soluble film into a paddy field in rice cultivation.

Most of the compounds described in the above-mentioned prior art do not show osmotic migration activity at all, and they are not sufficiently effective in bactericidal activity. Said J.-F. Cho
The only one isomer of 4- (4-chlorophenyl) -4-hydroxy-5- (1,2,4-triazol-1-yl) -3-trimethylsilyl-1-pentene described in Llet et al. Although it has migration activity, its osmotic migration activity and bactericidal activity are significantly lower than those of the compounds of the present invention. Also, the other isomer of this compound shows no osmotic translocation activity.

In addition, J.-F. Chollet et al. Suggest that a compound having an unsaturated hydrocarbon group (particularly a compound having an allyl group) has the highest activity, but the compound of the present invention It does not have a saturated hydrocarbon group.

[0010]

Means for Solving the Problems As a result of years of intensive studies on the synthesis of a derivative having an azole heterocycle and its physiological activity, the present inventors have found that the structure is completely different from that of a known azole fungicide. The compound containing a novel silicon atom represented by the following formula (I) exhibits bactericidal activity, particularly an excellent control effect as an agricultural bactericide, and has little chemical damage.
The present invention has been completed by finding that it has a very high permeation migration property.

The present invention has the general formula (I)

[0012]

[Chemical 2]

[Wherein A is 1,2,4-triazole-
1-yl group or imidazol-1-yl group, n is 1, 2 or 3, and when n is 2 or 3, each X may be the same or different, and X is a hydrogen atom or halogen. Atom, phenyl group, same or different 1 to 3
Lower alkyl groups optionally substituted with halogen,
Or a lower alkoxy group which may be substituted with 1 to 3 halogens which are the same or different, and R represents a lower alkyl group having 2 to 6 carbon atoms] is a novel silicon-containing azole compound .

In the above formula, the "halogen atom" for X includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom.

In the above formula, "lower alkyl group" for X
As, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-
Butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, A straight chain having 1 to 6 carbon atoms such as 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethylbutyl. Or a branched chain alkyl group, preferably a linear or branched chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

In the above formula, the "lower alkyl group substituted by 1 to 3 halogens which are the same or different" in X is, for example, trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, dibromomethyl, fluoromethyl. , 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 2-bromoethyl, 2-chloroethyl, 2-fluoroethyl, 2,2-
Examples thereof include dibromoethyl, chloropropyl, trifluoropropyl, fluorobutyl, trichloropentyl, and trifluorohexyl, in which the above "lower alkyl group" is substituted with the same or different 1 to 3 halogen atoms. A straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms having 1 to 3 of the same halogen atom substituted is preferable, and a methyl group or ethyl group having a fluorine atom or chlorine atom is more preferable. It is a group having 1 to 3 substituents, most preferably a trifluoromethyl group.

In the above formula, the "lower alkoxy group" for X is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,
s-butoxy, t-butoxy, n-pentoxy, isopentoxy, 2-methylbutoxy, neopentoxy, 1-ethylpropoxy, n-hexyloxy, 4-
Methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-
Dimethyl butoxy, 2,2-dimethyl butoxy, 1,1
-Dimethylbutoxy, 1,2-dimethylbutoxy, 1,
3-dimethylbutoxy, 2,3-dimethylbutoxy, 2
-C1-C6 linear or branched alkoxy groups such as ethylbutoxy are preferable, and C1-C4 linear or branched alkoxy groups are more preferable. It is a methoxy group or an ethoxy group.

In the above formula, the "lower alkoxy group substituted by 1 to 3 halogens which are the same or different" in X is, for example, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy,
Dibromomethoxy, fluoromethoxy, 2,2,2-trichloroethoxy, 2,2,2-trifluoroethoxy, 2-bromoethoxy, 2-chloroethoxy, 2-fluoroethoxy, 2,2-dibromoethoxy, 3-chloro Examples include propoxy, trifluoropropoxy, fluorobutoxy, trichloropentoxy, trifluorohexyloxy, and the like, wherein the above “lower alkoxy group” is substituted with the same or different 1 to 3 halogen atoms. Preferred is a straight-chain or branched-chain alkoxy group having 1 to 3 carbon atoms substituted with 1 to 3 of the same halogen atom, and more preferred is a methoxy group or ethoxy group having a fluorine atom or chlorine atom. It is a group having 1 to 3 substituents, most preferably a trifluoromethoxy group.

In the above formula, "lower alkyl group" for R
As, for example, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, n-pentyl, isopentyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 1-methylpentyl,
3,3-dimethylbutyl, 1,3-dimethylbutyl, 1
-C2-C6 linear or branched alkyl groups such as ethylbutyl, preferably C2-C4.
A straight chain or branched chain alkyl group, and more preferably an ethyl group.

In the above general formula (I), A is preferably a 1,2,4-triazol-1-yl group.

In the above general formula (I), n is preferably 1 or 2, and more preferably 1.

In the above general formula (I), X is preferably a hydrogen atom or a halogen atom, more preferably a fluorine atom or a chlorine atom.

In the above general formula (I), the substitution position of X is preferably the 2-position, 4-position, or 2, -position of the benzene ring.
It is fourth, and more preferably fourth.

The silicon-containing azole compounds of the present invention are specifically shown in Table 1 below, but the present invention is not limited thereto.

In Table 1, Tri represents a 1,2,4-triazol-1-yl group, Imid represents an imidazol-1-yl group, and Ph represents a phenyl group.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

Of the above-exemplified compounds, preferably compound numbers 1, 2, 3, 4, 6, 9, 11, 12, 13, 1
4, 16, 17, 18, 19, 20, 32, 33, 3
4, 35, 36 and 37, more preferably compound numbers 1, 2, 3, 4, 6, 9, 11, 12, 1
Compounds 3, 14, 34 and 35, most preferably compounds Nos. 1, 2 and 3.

The compound of the present invention is produced by the production method shown in the following scheme.

[0034]

[Chemical 3]

(In the above formula, A, X, R and n have the same meanings as described above, and R'and R "represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms). explain in detail.

Step-1 is a step for producing an intermediate (IV) by adding a silyl compound (III) to a ketone (II), which is described in J. Organometallic. Chem., 368 1-18 (198).
It can be produced by the method described in 9). The ketone (II) can be produced according to the method described in JP-B-63-46075, and the silyl compound (III) is
It can be produced by the method described in Ann. Chim., 1 , 161 (1956).

Step-2 is a step for producing the compound (I) of the present invention by reducing the double bond of the intermediate (IV). Reaction is new experimental chemistry course 15, oxidation and reduction (II),
It can be produced according to the general catalytic hydrogenation method described on page 333 [edited by the Chemical Society of Japan, 1980].

The catalyst used in this reaction is not particularly limited as long as it does not inhibit the reaction, but is preferably 1%.
~ 20% palladium on carbon, more preferably 5% ~
10% palladium on carbon. In this case, the halogen on the benzene ring may be reduced and removed. Other catalysts can be used if it is desired to avoid it. Examples of such a catalyst include platinum oxide and the like.

The reaction is carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably methanol, ethanol or n-. Alcohols such as propanol, isopropanol, n-butanol; methyl acetate, ethyl acetate, propyl acetate, methyl propionate,
Mention may be made of fatty acid esters such as ethyl propionate.

The reaction is carried out at atmospheric pressure or under pressure, preferably atmospheric pressure to 5 atm. The reaction time varies depending mainly on the reaction temperature, the raw material compound and the type of solvent used, but is usually 30 minutes to 30 hours, and preferably 1 hour to 15 hours. Reaction temperature is usually -10 ° C to 50 ° C
And is preferably 10 ° C to 30 ° C.

The compound of the present invention is used as a fungicide for agriculture, and shows a therapeutic and prophylactic effect against plant diseases without damaging host plants.

That is, by using it as a spraying agent or a water surface application agent, it is possible to particularly strongly control rice blight and blast, which are important diseases in rice cultivation.

When used as a soil treatment or seed treatment agent, beet caused by Rhizoctonia,
Especially effective against seedling wilt of various crops such as cotton and cucumber,
It is possible to effectively control soil-borne diseases such as white silkworm diseases such as eggplants and cucumbers, and black blight of potatoes.

On the other hand, crops such as rice, tomato, potato, cotton, eggplant, cucumber and green beans are not affected by practical doses.

Further, it can be effectively used as a fungicide also in orchards, non-agricultural lands, forests and the like.

The compound of the present invention is mixed with a carrier and, if necessary, other auxiliary agents, and has a formulation form usually used as a bactericide, such as powder, coarse powder, fine granule, granule, wettable powder,
It is prepared and used as a flowable agent, emulsion, aqueous solution, water solvent, oil suspension agent, etc. Of course, a crude product can be used as an active ingredient.

The term "carrier" as used herein refers to a synthetic compound which is mixed with a fungicide in order to assist the accessibility of the active ingredient compound to the site to be treated and to facilitate the storage, transportation or handling of the active ingredient compound. Or, means a natural inorganic or organic substance.

Suitable solid carriers include clays represented by kaolinite group, montmorillonite group or attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime. , Apatite, zeolite,
Inorganic substances such as anhydrous silicic acid and synthetic calcium silicate; soybean flour,
Tobacco powder, walnut powder, wheat flour, wood powder, starch, crystalline cellulose, and other plant organic substances; coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum, dummal gum, etc. Examples thereof include synthetic or natural polymer compounds; waxes such as carnauba wax and beeswax; and urea.

Suitable liquid carriers include paraffin or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene; tetrachloride. Chlorinated hydrocarbons such as carbon, chloroform, trichloroethylene, monochlorobenzene and o-chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone, methyl ethyl ketone,
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclo Alcohols such as hexanol and benzyl alcohol; ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethylsulfoxide; and water.

Surfactants used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, etc. are nonionic, anionic, cationic. Both ionic and zwitterionic may be used, but usually nonionic and / or anionic ones are used.

Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; and polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol. Butyl naphthol, octyl naphthol, and other alkyl naphthols that have been polymerized with ethylene oxide; palmitic acid, stearic acid, oleic acid, and other higher fatty acids that have been polymerized with ethylene oxide; stearic acid, dilauryl phosphoric acid, etc. Or dialkyl phosphoric acid polymerized with ethylene oxide; amines such as dodecylamine and stearic acid amide polymerized with ethylene oxide; sorbitan, etc. Higher fatty acid esters of alcohols and those it is polymerized addition of ethylene oxide;
Examples thereof include those obtained by polymerizing addition of ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium laurin sulphate, oleyl alcohol sulphate amine salts; sulfosuccinic acid dioctyl ester sodium,
Examples thereof include alkyl sulfonates such as sodium 2-ethylhexene sulfonate, sodium isopropyl naphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and aryl sulfonates such as sodium dodecylbenzene sulfonate.

Further, the fungicide of the present invention includes casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like for the purpose of improving the properties of the preparation and enhancing the biological effect. A high molecular compound and other auxiliary agents can also be used together.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

Dusts usually contain, for example, 0.1 to 25% by weight of the active ingredient compound, and the balance is a solid carrier.

The wettable powder contains, for example, 1 to 80% by weight of the active ingredient compound, and the balance is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a thixotropic agent, a defoaming agent, etc. Is added.

Granules, for example, usually contain the active ingredient compound 1
˜35% by weight with the balance mostly solid support.

The fungicide of the present invention is mixed with other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. to expand the range of application. However, it is possible to save labor.

The amount to be treated varies depending on the weather conditions, formulation form, treatment time, treatment method, place, target disease, target crop, etc., but usually 0.1 as an active ingredient amount per are.
g to 100 g, preferably 5 to 40 g, and emulsions, wettable powders, suspending agents and the like are usually used in a predetermined amount of 1
1 liter to 10 liters of water per areal (if desired, a spreading agent such as a surfactant, polyoxyethylene resin acid, lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, paraffin) can be added. The granules and the like are usually used without being diluted.

[0059]

[Examples] Formulation examples, examples and test examples are shown below,
The present invention will be described in more detail. % Means% by weight and part means part by weight.

Example 1 2-Phenyl-1- (1,2,4-triazole-1-
Yl) -3-trimethylsilyl-2-pentanol (Compound No. 1B) 10% Palladium on 30.6 mg of palladium on 10 ml of ethanol in 4- (4-chlorophenyl) -4-hydroxy-
Among the isomers of 5- (1,2,4-triazol-1-yl) -3-trimethylsilyl-1-pentene, 67 mg (0.2 mmol) of a highly polar compound (isomer B of Reference Example 2) was added. , A Parr hydrogenation device, and shaken under a hydrogen atmosphere for 12 hours. After completion of the reaction, the catalyst was filtered off using Celite and the filtrate was concentrated. Preparative thin layer chromatography of the concentrate (developing solvent: ethyl acetate: n-hexane = 1: 1)
And purified to give 27.2 mg of the desired product.

Amorphous; 45% yield NMR (200MHz, CDCl ₃ ) δppm: 0.18 (9H, s), 0.65 (3H, t, J =
7.4Hz), 1.09 (1H, t, J = 4.9Hz), 1.42 (2H, dq, J = 4.9, 7.4H
z), 4.46 (1H, d, J = 3.7Hz), 4.65 (1H, d, J = 3.7Hz), 7.11 ~
7.27 (5H, m), 7.54 (1H, s), 7.76 (1H, s) MS (M / Z): 304 (M + 1), 288, 221, 188 Example 2 2- (4-chlorophenyl)- 1- (1,2,4-tri
Azol-1-yl) -3-trimethylsilyl-2-pe
Ntanol (Compound No. 2A) 4- (4-chlorophenyl) -4-hydroxy-5-
Among the isomers of (1,2,4-triazol-1-yl) -3-trimethylsilyl-1-pentene, 30 mg (0.089 mmol) of a low polarity compound (isomer A of Reference Example 2) was added to 10 ml of ethyl acetate. Dissolved in 9.0 mg of platinum oxide
(0.04 mmol) was added. After shaking with a Parr apparatus for 8 hours in a hydrogen atmosphere, platinum oxide was filtered off and the filtrate was concentrated. The obtained concentrate was purified by preparative thin layer chromatography (developing solvent: ethyl acetate: n-hexane = 1: 1) to obtain 23 mg of the target product 2A.

Melting point 108-111 ° C .; Yield 76% NMR (200MHz, CDCl ₃ ) δppm: -0.24 (9H, s), 1.14 (3H, t, J =
7.5Hz), 1.14 (1H, t, J = 4.7Hz), 1.64 ~ 2.05 (2H, m), 4.3
8 (1H, d, J = 13.6Hz), 4.68 (1H, d, J = 13.6Hz), 7.16 (4H, s),
7.45 (1H, s), 7.80 (1H, s) MS (M / Z): 338 (M + 1), 322, 255, 222 Example 3 2- (4-chlorophenyl) -1- (1,2, 4-tri
Azol-1-yl) -3-trimethylsilyl-2-pe
Ntanol (Compound No. 2B) Of the isomers of Example 2, the same treatment as in Example 2 was carried out except that a highly polar compound (isomer B of Reference Example 2) was used as a starting material, and the target product 2B was used as 26 Obtained 0.5 mg.

Oily substance; yield 78% NMR (200MHz, CDCl ₃ ) δppm: 0.19 (9H, s), 0.66 (3H, t, J =
7.4Hz), 1.05 (1H, t, J = 4.8Hz), 1.39 (2H, dq, J = 4.8, 7.4H
z), 4.44 (1H, d, J = 3.7Hz), 4.65 (1H, d, J = 3.7Hz), 7.20 (4
H, s), 7.63 (1H, s), 7.78 (1H, s) MS (M / Z): 338 (M + 1), 322, 255, 222 Example 4 2- (4-fluorophenyl) -1 -(1,2,4-to
Lyazol-1-yl) -3-trimethylsilyl-2-
Pentanol (Compound No. 3A) ethanol 10ml suspension of 10% palladium carbon 8.52mg, 4- (4- fluorophenyl) -4-hydroxy-5- (1,2,4-triazol-1-yl) -3
Of the isomers of -trimethylsilyl-1-pentene, 12.9 mg (0.04) of a low polarity substance (isomer A of Reference Example 1).
4) under a hydrogen atmosphere with a Parr hydrogenator.
Shake for hours. After completion of the reaction, the catalyst was filtered off using Celite and the filtrate was concentrated. Preparative thin layer chromatography of the concentrate (developing solvent: ethyl acetate: n-hexane = 1:
Purification in 1) yielded 12.2 mg of the target product 3A.

Melting point 104-106 ° C .; Yield 93% NMR (200 MHz, CDCl ₃ ) δppm: -0.25 (9H, s), 1.13 (1H, t, J =
4.8Hz), 1.14 (3H, t, J = 7.5Hz), 1.61 ~ 2.03 (2H, m), 4.3
8 (1H, d, J = 13.6Hz), 4.69 (1H, d, J = 13.6Hz), 6.89 (2H, dd,
J = 8.7, 8.7Hz), 7.18 (2H, dd, J = 5.2, 8.7Hz), 7.44 (1H,
s), 7.80 (1H, s) MS (M / Z): 322 (M + 1), 306, 239, 206 Example 5 2- (4-fluorophenyl) -1- (1,2,4-to)
Lyazol-1-yl) -3-trimethylsilyl-2-
Pentanol (Compound No. 3B) In the same manner as in Example 1, 4- (4-fluorophenyl)-
4-hydroxy-5- (1,2,4-triazole-1
Of the isomers of -yl) -3-trimethylsilyl-1-pentene, a highly polar substance (isomer B of Reference Example 1) was used to convert Compound 3B, which is the target isomer of Example 4, into 57
mg was obtained.

Amorphous; yield 88% NMR (200MHz, CDCl ₃ ) δppm: 0.18 (9H, s), 0.66 (3H, t, J =
7.5Hz), 1.05 (1H, t, J = 4.8Hz), 1.41 (2H, dq, J = 4.8, 7.5H
z), 4.44 (1H, d, J = 3.8Hz), 4.64 (1H, d, J = 3.8Hz), 6.91 (2
H, dd, J = 8.7,8.7Hz), 7.23 (2H, dd, J = 5.3, 8.7Hz), 7.62
(1H, s), 7.78 (1H, s) MS (M / Z): 322 (M + 1), 306, 239, 206 Reference Example 1 2- (4-fluorophenyl) -1- (1,2, 4-to
Lyazol-1-yl) -3-trimethylsilyl-4-
Penten-2-ol To 180 mg (6.7 mmol) of aluminum shavings was added 2 ml of dry ether, and the mixture was vigorously stirred. Mercury chloride 40
After adding mg and stirring for a while, a very small amount of trans-3-trimethylsilylallyl bromide was added to start the reaction. Then, a solution of trans-3-trimethylsilylallyl bromide (1.88 g, 9.9 mmol) in dry ether (5 ml) was added dropwise and the mixture was stirred. Heat to reflux for 5 hours,
After cooling, 2 ml of dry ether and 7 ml of dichloromethane were added. A solution of 2- (1,2,4-triazol-1-yl) -4'-fluoroacetophenone (616 mg, 3 mmol) in dichloromethane (8 ml) was added thereto, and the mixture was stirred for 1 hour. The reaction mixture was poured into ice water, an aqueous ammonium chloride solution was added, and the mixture was extracted with dichloromethane. The organic layer was washed twice with water, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated to give a residue, which was subjected to silica gel column chromatography (elution solvent ethyl acetate: n-hexane =).
1:10), and first the low polar substance (isomer A) was added to 1
8.1 mg (yield 3.5%) and then 208 mg (yield 51%) of a highly polar substance (isomer B) were obtained.

Isomer A (low polar substance) melting point 93 to 97 ° C .; Yield 3.5% NMR (200MHz, CDCl ₃ ) δppm: -0.26 (9H, s), 2.23 (1H, d, J)
= 10.6Hz), 4.22 (1H, d, J = 14.0Hz), 4.57 (1H, d, J = 14.0H
z), 5.07 (1H, dd, J = 1.8, 17.9Hz), 5.16 (1H, dd, J = 1.8, 1
0.6Hz), 6.19 (1H, ddd, J = 10.6, 10.6, 17.9Hz), 6.90 (2
H, dd, J = 8.8,8.8Hz), 7.19 (2H, dd, J = 3.7,8.8Hz), 7.41
(1H, s), 7.80 (1H, s) MS (M / Z): 320 (M + 1), 304, 237, 229 Isomer B (highly polar substance) Melting point 92-95 ° C; Yield 51% NMR (200MHz, CDCl ₃ ) δppm: -0.08 (9H, s), 2.09 (1H, d, J
= 11.3Hz), 4.52 (2H, s), 4.89 (1H, dd, J = 2.1, 16.8Hz), 5.
02 (1H, dd, J = 2.1, 10.1Hz), 5.65 (1H, ddd, J = 10.1, 11.3,
16.8Hz), 6.95 (2H, dd, J = 8.9, 8.9Hz), 7.29 (2H, dd, J =
5.2, 8.9Hz), 7.76 (1H, s), 7.83 (1H, s) MS (M / Z): 320 (M + 1), 304, 237, 229, 206 Reference Example 2 2- (4-chlorophenyl) -1- (1,2,4-tri
Azol-1-yl) -3-trimethylsilyl-4-pe
Nten-2-ol In the same manner as in Reference Example 1, isomer A (low polar substance) and isomer B (high polar substance) were obtained.

Isomer A (low polar substance) Melting point 134-135 ° C .; Yield 7.2% NMR (270 MHz, CDCl ₃ ) δppm: -0.25 (9H, s), 2.22 (1H, d, J)
= 10.5Hz), 4.21 (1H, d, J = 14.0Hz), 4.56 (1H, d, J = 14.0H
z), 5.07 (1H, dd, J = 1.7, 17.4Hz), 5.15 (1H, dd, J = 1.7, 1
0.5Hz), 6.18 (1H, ddd, J = 10.5, 10.5, 17.4Hz), 7.15 (2
H, d, J = 9.3Hz), 7.19 (2H, d, J = 9.3Hz), 7.41 (1H, s), 7.80
(1H, s) MS (M / Z): 336 (M + 1), 320, 253, 245 Isomer B (highly polar substance) Melting point 124-125 ° C; Yield 44.0% NMR (270MHz, CDCl ₃ ) δppm: -0.07 (9H, s), 2.09 (1H, d, J
= 11.6Hz), 4.51 (2H, s), 4.87 (1H, dd, J = 2.3, 16.9Hz), 5.
01 (1H, dd, J = 2.3, 10.5Hz), 5.62 (1H, ddd, J = 10.5, 11.6,
16.9Hz), 7.22 (2H, d, J = 8.6Hz), 7.27 (2H, d, J = 8.6Hz),
7.75 (1H, s), 7.82 (1H, s) MS (M / Z): 336 (M + 1), 320, 253, 245, 222 Formulation Example 1 (wettable powder) Compound No. 3B 80%, Sodium alkylnaphthalene sulfonate (2%), sodium lignin sulfonate (2%), synthetic amorphous silica (3%) and kaolinite (13%) were mixed, ground with a hammer mill and mixed again to obtain a wettable powder.

Formulation Example 2 (wettable powder) 25% of the compound No. 2B, 2.5% of sodium dodecylbenzene sulfonate, 2.5% of sodium lignin sulfonate, 55% of diatomaceous earth and 15% of synthetic amorphous silica are mixed and ground. As a wettable powder.

Formulation Example 3 (emulsion) Compound No. 3B, compound 15%, cyclohexanone 35
%, Polyoxyethylene nonyl phenyl ether 11
%, Calcium dodecylbenzene sulfonate 4% and methylnaphthalene 35% were uniformly dissolved to obtain an emulsion.

Formulation Example 4 (Emulsion) Compound No. 1B (15%), calcium dodecylbenzenesulfonate (25%) and a blend of nonionic surfactant (25%) and xylene (60%) were combined and stirred to dissolve the active ingredient. To give an emulsion.

Formulation Example 5 (granules) Compound No. 3B, compound 5%, sodium lauryl sulfate 2%, sodium lignin sulfonate 5%,
2% sodium carboxymethyl cellulose and 86% clay were uniformly mixed and ground. 20 parts of water was added to 100 parts of this mixture, and the mixture was kneaded.
It was processed into granules of 4 to 32 mesh and then dried to obtain granules.

Formulation Example 6 (Granule) 5% of the compound No. 2B, bentonite 30%, talc 62%, sodium lignin sulfonate 2% and sodium dodecylbenzene sulfonate 1% were uniformly mixed and ground. 20 parts of water was added to 100 parts of this mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and then dried to obtain granules.

Formulation Example 7 (Granule) 4% of the compound No. 1B, 30% of bentonite, 63% of clay, 1% of polyvinyl alcohol and 2% of sodium dodecylbenzene sulfonate were uniformly mixed and ground. 20 parts of water was added to 100 parts of this mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and then dried to obtain granules.

Formulation Example 8 (Granule) 4% of the compound No. 3B, bentonite 35%, talc 58.8%, sodium alkylnaphthalene sulfonate 2% and sodium dioctyl sulfosuccinate 0.2% were uniformly mixed, Crushed. This mixture 10
20 parts of water was added to 0 part of the mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion type granulator, and then dried to obtain granules.

Formulation Example 9 (Granule) 5% of the compound No. 1B, 1% of white carbon,
Sodium lignin sulfonate 5%, clay 84% and sodium carboxymethyl cellulose 5% were well pulverized and mixed, water was added and well kneaded, and then granulated and dried to obtain granules.

Formulation Example 10 (powder) 2% of compound No. 3B, 5% of diatomaceous earth and 9 of clay
3% was uniformly mixed and pulverized to obtain a powder.

Formulation Example 11 (Liquid formulation) A 10% compound of Compound No. 2B, 2% sodium dodecylbenzenesulfonate and 88% water were dissolved to prepare a liquid formulation.

Formulation Example 12 (Liquid) A compound of Compound No. 3B (30%) and dimethyl sulfoxide (70%) were combined and stirred to give a liquid.

Formulation Example 13 (Granule) Bentonite 30%, talc 64.5% and sodium dioctyl sulfosuccinate 0.5% were uniformly mixed. After adding 18 parts of water to 95 parts of the mixture and kneading, granulating using an extrusion-type granulator, drying, and then sieving 14 to 14
A 32 mesh granular carrier was obtained. To 95% of this granular carrier, 5% of the compound of Compound No. 1B was added and absorbed, and uniformly mixed to obtain granules.

Formulation Example 14 (Granule) Clay 86%, sodium dioctyl sulfosuccinate 0.5%, dextrin 7% and sodium carboxymethyl cellulose 1.5% were uniformly mixed. 14 parts of water was added to 95 parts of this mixture, and the mixture was kneaded, granulated using an extrusion type granulator, dried, and then sieved to obtain 14 to 32.
A granular carrier of mesh was obtained. To 95% of this granular carrier was added 5% of compound No. 2B, and the mixture was absorbed to obtain a granule.

Formulation Example 15 (Flowable) 1% of sodium dodecylbenzene sulfonate and 5% of a condensate of sodium naphthalene sulfonate were added to 41% of water.
Compound No. 3B, compound 30%, dissolved in 8%
Was suspended. The suspension was ground with a sand mill to an average particle size of 1.5 μm. Separately, xanthan gum 0.2% and magnesium aluminosilicate 2% were dissolved and dispersed in water 20% to prepare a liquid, which was added to the pulverized slurry and uniformly stirred to obtain a suspension type flowable.

Formulation Example 16 (Flowable) 5% of the compound No. 3B, 3.5% of polyoxyethylene nonylphenyl ether and 1.5% of calcium dodecylbenzene sulfonate were uniformly dissolved. This solution was added to 56.65% of water with stirring to emulsify,
A homogenizer was used to prepare a fine emulsion. Separately, xanthan gum (0.35%) and magnesium aluminosilicate (3%) were dissolved and dispersed in water (30%) to prepare a solution, which was mixed with the above emulsion and uniformly stirred to obtain an emulsion type flowable.

Formulation Example 17 (Granular wettable powder) Compound No. 2B 60%, sodium lignin sulfonate 15%, clay 17%, granular calcium carbonate 5% and sodium dodecylbenzene sulfonate 3%
Were mixed and ground using a jet mill. The crushed product was placed in a fluidized bed granulation dryer, granulated while spraying water and dried, and then a 32 to 100 mesh section was sieved to obtain a granular wettable powder.

Test Example 1 Rice blast control test (therapeutic effect) A rice blast fungus (Pyr) was added to a rice seedling at 4-5 leaf stage (variety: Kofu).
(Conicularia oryzae) was spray-inoculated with a conidia suspension. After inoculation, the rice seedlings were placed in a room at a temperature of 20-22 ° C and a relative humidity of 100% for 24 hours, and then a 10 ppm solution of the test compound was added to the solution.
Sprayed at a rate of 30 ml per pot. Subsequently, the rice seedlings were placed in the same room for 6 days to cause disease, and the control efficacy was investigated based on the number of lesions formed on the upper 2 leaves. The results are shown in Table 2.

The control efficacy was evaluated by visually observing the degree of disease of the test plant and observing the following criteria (the same applies to the following test examples).

5: No illness was observed at all. 4: 10% or less of the untreated group (the same applies to the case where the test compound is not tested) with the degree of disease onset. 3: The degree of disease is 10% or more and 30% or less of the untreated section. 2: The degree of disease is 30% or more and 50% or less of the untreated area. 1: The degree of disease is 50% or more and 70% or less of the untreated area. 0: The degree of disease was 70% or more of the untreated plot, showing no difference from the untreated plot.

Test Example 2 Control test for rice blight (protective effect) The test compound 1 was added to a rice seedling at 4-5 leaf stage (variety: Nipponbare).
The 00 ppm solution was sprayed at a rate of 30 ml per 3 pots.
Twenty-four hours after spraying the drug solution, Rhizoctonia s
(4-5) oat grains in which olani) were cultured were placed on the surface of rice seedlings and placed in a room at a temperature of 25-27 ° C and a relative humidity of 100% for 5 days to cause disease. The control efficacy was investigated based on the height of the lesion formed on the leaf sheath. The results are shown in Table 2.

Test Example 3 Controlling Rice Leaf Spot Disease (Therapeutic Effect) Oat grains pre-cultured with rice leaf spot fungus (Rhizoctonia solani) were placed at the edge of a 4-5 leaf stage rice seedling (variety: Nipponbare). Four
-5 seeds were placed and inoculated. After inoculating the bacteria, the rice seedlings are heated to 25-2
After being placed in a room at 7 ° C. and 100% relative humidity for 24 hours, a 10 ppm solution of the test compound was sprayed at a rate of 30 ml per 3 pots. Subsequently, the rice seedlings were placed in the same room for 5 days to cause disease, and the control efficacy was investigated based on the height of lesions formed on leaf sheaths. The results are shown in Table 2.

Test Example 4 Rice crest blight control test (water application) 3-4 leaf stage rice seedlings grown in a pot (variety: Nipponbare)
Was maintained in a submerged state with a water depth of 1 cm, and the test compound was applied to the pot so that the amount of the active ingredient was 100 g / 10a. After placing the rice seedlings in a glass greenhouse for 7 days, the rice seedling blight fungus (R
4-5 seeds of oats cultivated by culturing hizoctonia solani) were placed on the surface of rice seedlings and inoculated. After being placed in a room at a temperature of 25 to 27 ° C. and a relative humidity of 100% for 5 days to cause the disease, the control efficacy was investigated based on the height of lesions formed on the leaf sheath.
The results are shown in Table 2.

Test Example 5 Wheat leaf rust control test (therapeutic effect) Wheat seedlings at 1.5 leaf stage (variety: Norin 61) were inoculated by sprinkling with spores of wheat leaf rust (Puccinia recondita). After inoculation of the fungus, wheat seedlings were heated at a temperature of 20-22 ° C and a relative humidity of 1
After being placed in a 00% room for 24 hours, then at 15-20 ° C
2 days after the transfer to the glass greenhouse at 3 ppm, a 3 ppm solution of the test compound was sprayed at a rate of 30 ml per 3 pots. Subsequently, the wheat seedlings were placed in a glass greenhouse for 10 days to cause disease, and the control efficacy was investigated based on the area of lesions formed on the first leaves. The results are shown in Table 2. Test Example 6 Barley Powdery Mildew Control Test (Therapeutic Effect) Barley seedlings (cultivar: Akakami Riki) of 1 leaf stage were treated with barley powdery mildew.
(Erysiphe graminis f.sp.hordei) was sprinkled and inoculated. After inoculating the bacteria, the barley seedlings were placed in a glass greenhouse at a temperature of 15 to 20 ° C. for 24 hours, and then 3 ppm of the test compound
The solution was sprayed at a rate of 30 ml per 3 pots. continue,
Put barley seedlings in a glass greenhouse for 10 days to cause illness
The control efficacy was investigated based on the area of lesions formed on the leaves. The results are shown in Table 2.

The compounds used for comparison are as follows.

Comparative Compound 1 4- (4-chlorophenyl) -4-hydroxy-5-
(1,2,4-Triazol-1-yl) -3-trimethylsilyl-1-pentene (Pestic. Sci., 29 , 427-435
(1990) One optical isomer of compound XX described in (1990) Comparative compound 2 4- (4-chlorophenyl) -4-hydroxy-5-
(1,2,4-Triazol-1-yl) -3-trimethylsilyl-1-pentene (Pestic. Sci., 29 , 427-435
(1990) one optical isomer of compound XX described in (1990) -diastereomer of comparative compound 1) Comparative compound 3 3-t-butyl-3-hydroxy-4- (1,2,4-)
Triazol-1-yl) -1-trimethylsilyl-1
-Pentine (Isomer A described in Example 11 of JP-A-61-257975) Comparative compound 43- (2,4-dichlorophenyl) -3-hydroxy-
4- (1,2,4-triazol-1-yl) -1-trimethylsilyl-1-butyne (Pestic. Sci., 29 , 427-4
35 (1990) Compound II, and British Patent No. 2224278.
Intermediates described in Example 4 of the specification) Comparative compound 5 4- (4-chlorophenyl) -4-hydroxy-5-
(1,2,4-Triazol-1-yl) -1-trimethylsilyl-1-pentene (Pestic. Sci., 29 , 427-435
(1990) Compound XXIII) Comparative compound 6 3- (2,4-dichlorophenyl) -3-hydroxy-
4- (1,2,4-triazol-1-yl) -1-trimethylsilyl-1-butene (British Patent No. 222427)
Compound No. 13 described in Example 4 of No. 8)

[0093]

[Table 7]

Test Example 7 Antifungal test Agar medium (malt extract 2%, glucose 1%, peptone 0.3% and agar 2) was placed in a Petri dish having a diameter of 9 cm.
%) Was solidified and then pre-incubated with a flora disk (diameter about 4 mm) of the test bacteria inoculated to the center of the medium.

Three days after the inoculation of the bacteria, after the chemical treatment, a dry heat sterilized paper disk (diameter 8 mm, thickness 0.7 mm) was placed on the circumference about 1 cm away from the circumference of the grown bacteria,
After culturing at 5 ° C for 5 days, the efficacy was judged by the presence or absence of invasion of bacteria into the paper disc.

As the test bacteria, Aspergillus
Niger (Aspergillus niger) (hereinafter referred to as fungus A), Gliocladium virens (hereinafter referred to as fungus B) and Fusarium moniliforme (Fusar)
30 ml of an acetone solution prepared by adjusting the concentration of the compound of the present invention to 300 ppm was added to a paper disk as a sample.

The indications showing the antifungal effect are as follows.

+: No growth of bacteria is observed on the sample -: Growth of bacteria is observed on the sample The results are shown in Table 3.

Test Example 8 Wood preservative efficacy test A test was carried out in the same manner as the fungicidal test. However, as test bacteria, wood decay assay fungus Kawaritake (Coriolus versicolor) (hereinafter referred to as fungus D) and Tyromyces palustris (hereinafter, referred to as JIS-A-9201)
Both of them were used.

The results are shown in Table 3. The display method is
According to Test Example 7.

[0101]

[Table 8]

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasuhiko Kondo 1041 Yasu-cho, Yasu-gun, Shiga Sankyo Co., Ltd. (56) References JP-A-5-222060 (JP, A) JP-A-61-257975 (JP) , A) British Patent Application Publication 2224278 (GB, A) (58) Fields searched (Int.Cl. ⁷ , DB name) C07F 7/10 C07F 7/12 A01N 55/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the general formula (I): [In the formula, A represents a 1,2,4-triazol-1-yl group or an imidazol-1-yl group, and n is 1, 2 or 3
When n is 2 or 3, each X may be the same or different, and X may be substituted with a hydrogen atom, a halogen atom, a phenyl group, or the same or different 1 to 3 halogens. A preferred lower alkyl group or a lower alkoxy group which may be substituted with the same or different 1 to 3 halogens, and R represents a lower alkyl group having 2 to 6 carbon atoms]. 2. A bactericide containing the compound according to claim 1 as an active ingredient.