JPH0468308B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (However, in the formula, R ₁ and R ₂ may be the same or different, and include an alkyl group having 1 to 5 carbon atoms; a cycloalkyl group; a lower alkenyl group; a lower alkynyl group; an alkoxyalkyl group having 1 to 5 carbon atoms. ; an alkoxyalkoxyalkyl group having 3 to 6 carbon atoms; a benzyl group optionally substituted with a halogen atom; and a group

[Formula] and R ₁ and R ₂ together represent a group.

[Formula] (R ₃ is a hydrogen atom; lower alkyl group; cycloalkyl group; lower alkoxy group; alkoxyalkyl group having 2 to 4 carbon atoms; phenyl group; 1 to 3 halogen atoms, lower alkyl group, lower alkoxy Group; phenyl group substituted with lower haloalkoxy group and methylenedioxy group;
Represents a naphthyl group and a pyridyl group. ). The present invention relates to ketene S,S-acetals represented by ) and to agricultural and horticultural fungicides containing the compounds as active ingredients. As a result of repeated research in search of new and useful compounds, the present inventors found that ketene S,S-acetals represented by the general formula () are new compounds that have not been described in literature, and that they are effective against various plant diseases. The present invention was completed by discovering that this compound exhibits excellent effects in the following manner. The compound represented by the general formula () of the present invention is
For example, it can be synthesized by the method shown below. (However, in the formula, R ₁ , R ₂ , R ₃ have the same meanings as above, and X represents a halogen atom.) That is, 2-(1,2,
Adding carbon disulfide to 4-triazol-1-yl) acetonitrile in the presence of a base and a suitable solvent to obtain an intermediate represented by the compound ()',
This intermediate is isolated without isolation or as a salt, and then a halide represented by the general formula () is reacted with the intermediate represented by the compound ()' in an equimolar amount, and further the intermediate represented by the general formula () is reacted with the intermediate represented by the compound ()'. Ketene S,S-acetals represented by the general formula () can be obtained by reacting with halides represented by the formula (). In addition, when R ₁ and R ₂ are the same in the general formula (), the corresponding halide may be reacted in a proportion of twice or more per mole of the intermediate represented by the compound ()'. It is also possible to obtain ketene S,S-acetals represented by the general formula (). In addition, when R ₁ and R ₂ in the general formula () are combined to form a ring, the compound represented by the compound ()' is used in an equal mole or more proportion to 1 mole of the intermediate represented by the compound ()'. The dihalides represented can be reacted to obtain ketene S,S-acetals represented by the general formula (). The solvent that can be used in this reaction may be any solvent as long as it does not inhibit the progress of this reaction, and examples include alcohols such as methanol, ethanol, and isopropanol; dimethyl sulfoxide, dimethylformamide, hexamethylene phosphoramide, and water. can. These solvents can be used alone or in combination. Bases that can be used in this reaction include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, etc. These can be used as solids or dissolved in solutions. It can also be used. The reaction temperature is preferably selected from the range of 0 to 100°C, but it is particularly preferable to carry out the reaction around room temperature. The reaction time is preferably selected appropriately from the range of 0.5 to 24 hours. The amount of base used is 2-
(1,2,4-triazol-1-yl) may be selected from the range of 1 to 4 times the mole per mole of acetonitrile. After completion of the reaction, the reaction solution may be treated in a conventional manner, for example, extracted and separated with a suitable solvent, and further purified by recrystallization or chromatography. Ketene S,S-acetals represented by the general formula () are often obtained as a mixture of Z and E geometric isomers. In many cases, a mixture of the Z-isomer and the E-isomer can be separated into their respective geometric isomers by appropriate separation means, such as recrystallization or chromatography. The present invention includes all geometric isomers, ie, E-form and Z-form, as well as mixtures thereof in arbitrary proportions. Representative examples of compounds represented by the general formula () are shown in Tables 1 and 2 below, but the present invention is not limited thereto. General formula (-1)

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[Table] General formula (-2)

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[Table] Table 3 below lists NMR spectrum data for each compound that is a viscous oil.

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[Table] Synthesis examples of the present invention are listed below. Synthesis Example 13,3-bismethylthio-2-(1,2,
Synthesis of 4-triazol-1-yl)acrylonitrile (compound number 1) 2-(1,2,4-triazol-1-yl)
Acetonitrile 1.1g (0.01mol), carbon disulfide 0.8
(0.01 mol) and 40 ml of dimethyl sulfoxide, 1.4 g of potassium hydroxide powder was added, and the mixture was stirred at room temperature for 1 hour. Then methyl iodide
3.0 g (0.02 mol) was added dropwise, and the reaction was further carried out with stirring for 2 hours. After the reaction was completed, 30 ml of water was added to the reaction solution, the target product was extracted with ethyl acetate, the organic layer was washed with water and dried, the solvent was distilled off, and the remaining oil was purified by silica gel chromatography to obtain an oil 1.3. g
I got it. Physical properties: n ^19.5 _D 1.6280 Yield 63.2% NMRCDCl ₃ TMS (ppm) 2.33 (S, 3H, -CH ₃ ), 2.65 (S, 3H, -CH ₃ ) 8.01, 8.27 (1H each, triazole ring) Synthesis example 23-ethylthio-3-n-butylthio-
2-(1,2,4-triazol-1-yl)
Synthesis of Acetonitrile (Compounds No. 2 and No. 5) A mixture of 0.5 g (4.6 mmol) of 2-(1,2,4-triazol-1-yl)acetonitrile, 0.4 g (5.3 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide. potassium hydroxide powder
0.65 g was added and stirred at room temperature for 1 hour. Next, 0.6 g (4.4 mmol) of n-butyl bromide was added dropwise, and after 30 minutes, 0.7 g of ethyl iodide was added.
(4.5 mmol) was added and the reaction was carried out for 1 hour.
After the reaction was completed, 20 ml of water was added to the reaction solution, the target product was extracted with ethyl acetate, the organic layer was washed with water and dried, the solvent was distilled off, and the remaining oil was separated and purified using silica gel chromatography. 0.24g of each isomer of isomer and Z-isomer as oil and
Obtained 0.2g. Physical property value; E body n ^20.5 _D 1.5812,
Yield 19.3% (Compound No. 5) Z form n ^20.5 _D
1.5825, yield 23.7% (compound number 2) NMR δCDCl ₃ TMS (mm) E form 1.18 (t, 3H, -CH ₃ ), 1.33 (;, 3H, -
CH ₃ ), 1.30 to 1.90 (m, 4H, −CH ₂ CH ₂ −),
2.78 (t, 2H, −CH ₂ S−), 3.13 (t, 2H, −
CH ₂ S), 7.96, 8.31 (1H each, triazole ring) Z-form 1.38 (t, 3H, -CH ₃ ) 1.52 (t, 3H, -
CH ₃ ), 1.42 to 1.80 (m, 4H, −CH ₂ CH−),
2.73 (t, 2H, −CH ₂ S−), 4.11 (t, 2H, −
-CH ₂ S-), 7.83, 8.11 (each 1H, triazole ring) Synthesis Example 32-(4-ethyl-1,3-dithiolane-2-ylidene)-2-(1,2,4-triazole-1- Synthesis of acetonitrile (Compound No. 20) 2-(1,2,4-triazol-1-yl)
Add potassium hydroxide powder to a mixed solution of 0.6 g (5.6 mmol) of acetonitrile, 0.4 g (5.3 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide while stirring.
0.8 g (12 mmol) was added, and the reaction was carried out at room temperature for 1 hour. Then 1,2-dibromobutane
1.3 g (6.0 mmol) was added dropwise with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 20 ml of water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and dried.
The solution was distilled off, and the residue was purified by silica gel chromatography to obtain 0.9 g of an oil. Physical properties n ^16.5 _D 1.6263 Yield 75% NMR δCDCl ₃ TMS (ppm) 0.80-1.30 (m, 3H, -CH ₃ ), 1.52-2.10 (m,
2H, −CH ₂ −), 3.20 to 3.85 (m, 2H, −CH ₂ )
3.90~4.30 (m, 1H, -CH-), 8.05, 8.29 (each
1H, triazole ring) Synthesis Example 42-Synthesis of (4-phenyl-1,3-dithiolane-2-ylidene)-2-(1,2,4-triazol-1-yl)acetonitrile (Compound No. 28) 2- (1,2,4-triazol-1-yl)
Add potassium hydroxide powder to a mixed solution of 0.6 g (5.6 mmol) of acetonitrile, 0.4 g (5.3 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide while stirring.
0.8 g (12 mmol) was added and the reaction was carried out at room temperature for 1 hour. Thereafter, 1.6 g (6.1 mmol) of 1-phenyl-1,2-dibromoethane was added dropwise with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 20 ml of water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and dried. The solvent was distilled off, and the residue was purified by silica gel chromatography to obtain 0.35 g of an oily substance. Yield 24% NMR δCDCl ₃ TMS (ppm) 3.73, 3.80 (each d, 2H, -CH ₂ -), 5.22, 5.31
(each t, 1H, -CH-,), 7.45 (m, 5H, phenyl ring), 8.10, 8.35 (each 1H, triazole ring) Synthesis example 52-[4-(4-fluorophenyl)-1,
3-dithiolane-2-ylidene]-2-(1,
2,4-triazol-1-yl)acetonitrile (compound number 34) 2-(1,2,4-triazol-1-yl)
Add potassium hydroxide powder to a mixed solution of 0.6 g (5.6 mmol) of acetonitrile, 0.4 g (5.3 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide while stirring.
0.8 g (12 mmol) was added, and the reaction was carried out at room temperature for 1 hour. Thereafter, 1.7 g (6.0 mmol) of 1-(4-fluorophenyl)-1,2-dibromoethane was added dropwise with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 20 ml of water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and dried. The solvent was distilled off, and the residue was purified by silica gel chromatography to obtain 0.2 g of an oil. Physical properties n ^20.5 _D 1.6232 Yield 15.9% NMR δCDCl ₄ TMS (ppm) 3.81 (d, 2H, -CH ₂ -), 5.29 (t, 1H, -
CH-), 6.90-7.60 (m, 4H, phenyl ring),
8.02, 8.32 (1H each, triazole ring) Synthesis Example 62-[4-(2-difluoromethoxyphenyl)1,3-dithiolane-2-ylidene]-2
-Synthesis of (1,2,4-triazol-1-yl)acetonitrile (compound number 39) 2-(1,2,4-triazol-1-yl)
Add potassium hydroxide powder to a mixed solution of 0.7 g (6.5 mmol) of acetonitrile, 0.5 g (6.6 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide while stirring.
0.9 g (13.7 mmol) was added, and the reaction was carried out at room temperature for 1 hour. Then, 2.2 g of 1-(2-difluoromethoxyphenyl)-1,2-dibromoethane
(6.4 mmol) was added dropwise with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 20 ml of water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and dried. The solvent was distilled off, and the residue was purified by silica gel chromatography to obtain 0.29 g of crystalline material. Physical properties Melting point, 78.2℃ Yield 12.7% NMR δCDCl ₃ TMS 3.82 (d, 2H, -CH ₂ -), 5.31 (t, 1H, -
CH−), 6.62 (t, 1H, −CHF ₂ −), 7.10~
7.90 (m, 4H, phenyl ring) 8.05, 8.32 (each
1H, triazole ring) Synthesis Example 72-[4-(2,4-dichlorophenyl)
-1,3-dithiolane-2-ylidene]-2-
Synthesis of (1,2,4-triazol-1-yl)acetonitrile (Compound No. 42 and No. 43) 2-(1,2,4-triazol-1-yl)
Add potassium hydroxide powder to a mixed solution of 0.7 g (6.5 mmol) of acetonitrile, 0.5 g (6.6 mmol) of carbon disulfide, and 25 ml of dimethyl sulfoxide while stirring.
0.9 g (13.7 mmol) was added, and the reaction was carried out at room temperature for 1 hour. Thereafter, 2.3 g (6.9 g) of 1-(2,4-dichlorophenyl)-1,2-dibromoethane
mmol) was added dropwise with stirring, and the reaction was carried out for 2 hours. After the reaction was completed, 20 ml of water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and dried. The solvent was distilled off, and the residue was purified by silica gel chromatography to obtain 0.55 g of E form and 0.10 g of Z form as oils. E form (compound number 42) viscous oil yield 23.9% Z form (compound number 43)
Viscous oil Yield 4.2% NMR δCDCl ₃ TMS (ppm) E form 3.44-4.07 (m, 2H, -CH ₂ -), 5.66
(dd, 1H, -CH-), 7.17-7.68 (m, 3H, phenyl ring), 8.03, 8.31 (each 1H, triazole ring) Z-form 3.50-4.15 (m, 2H, -CH ₂ -), 5.56
(dd, 1H, -CH-), 7.10-7.60 (m, 3H, phenyl ring) 7.99, 8.29 (each 1H, triazole ring) If these oils are left alone, compound number 42
Compound No. 43 was obtained as crystals with a melting point of 160-162°C, and compound No. 43 was obtained as crystals with a melting point of 141-142°C. The compounds of the present invention are useful as agricultural and horticultural fungicides. For example, rice blast disease (Piricularia oryzae);
Powdery mildew of barley and wheat (Erysiphe graminis)
and powdery mildew of cucumbers (Sphaerotheca
fulginea), apple powdery mildew (Podosphaera
Powdery mildew on various host plants such as P. leucotricha and Powdery mildew of grapes (Uncinula necator);
vecondita); oat crown rust (Puccinia
coronate) and other host plant rusts; tomato gray late blight (Phytophthora capsici) and other host plant blights; cucumber gray mold and other diseases, and lawn rust (Puccinia spp.) brown patch (Rhizoctonia solani) It is extremely effective in controlling and controlling diseases such as Kuhr). The compounds of the present invention are also useful as plant growth regulators, for example, to prevent lodging of paddy rice and wheat, and to suppress the growth of grass. When the compound of the present invention is used as an agricultural and horticultural fungicide as an active ingredient,
It is prepared into a dosage form convenient for use. For example, it is prepared by mixing with adjuvants in the form of powders, granules, fine granules, wettable powders, emulsions, oils, aerosols, flow dusts, smoking agents, transpiration agents, tablets, etc., and is used for vegetables, flowers, and specialty crops. It can be applied to the leaves of fruit trees, trees, etc., either as is or diluted with an appropriate amount of water. In the present invention, the amount of the active ingredient to be applied depends on the type of compound,
The amount of the active ingredient can be selected from the range of 5 to 500 g per 10 ares, although it does not necessarily vary depending on the subject, method of use, etc. The agent of the present invention can also be used in a mixed composition or in combination with agricultural chemicals, fertilizers, plant nutrients, etc. that can be used in the same way when the agent is applied. For example, when an agricultural and horticultural fungicide containing the compound of the present invention as an active ingredient is used to control a disease, it can be mixed with a control agent for other pests that occur at the same time as the disease outbreak to create a multipurpose control agent. You can also do that. Test examples and formulation examples of the present invention are listed below, but the present invention is not limited thereto. Test Example 1: Treatment effect test for barley powdery mildew Powdery mildew fungus (Erysiphe
graminis F.sp.hordei), and one day later, a drug containing the compound of the present invention as an active ingredient was diluted to a predetermined concentration and sprayed on a turntable using a spray gun. After spraying, they were stored in a greenhouse at 25°C, and 7 days after inoculation, the control effects of each were investigated in comparison with the untreated plot. Judgment is based on the following criteria. 4: Control value 100-95% 3: 94-80% 2: 79-60% 1: 59-0% The results are shown in Table 4.

[Table] Test Example 2: Rice sesame leaf blight control test A chemical solution adjusted to a specified concentration was applied to rice at the 5-leaf stage (variety: Nipponbare, 10 plants planted) in clay pots (diameter 9 cm) using a spray gun. After one day, a spore suspension of Cochliobolus myabeanus was spray inoculated. After being left in a humid room for 20 hours, the plants were transferred to a greenhouse, and 6 days after inoculation, the number of diseases on each leaf was investigated and the control value was calculated. The effectiveness was evaluated using the same criteria as in Test Example 1 (three consecutive trials in one section). The results are shown in Table 5.

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[Table] Test Example 3: Rice blast disease control effect Rice planted in clay pots with a diameter of 9 cm (variety: Nipponbare,
At the 5th leaf stage, 10 plants were planted), a chemical solution prepared at a predetermined concentration containing the compound of the present invention as an active ingredient was sufficiently sprayed with a spray gun, and one day after the spraying, a spore suspension of rice blast fungus (Pyricularia oryzae) was prepared. was inoculated by spraying. After being placed in a humid room for 20 hours, it was transferred to a greenhouse, and 6 days after inoculation, the number of lesions was investigated, compared with the untreated area, the control value was calculated, and the effectiveness was evaluated using the same criteria as Test Example 1. The results are shown in Table 6.

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[Table] Test Example 4: Soybean purpura control test A chemical solution of a prescribed concentration was sufficiently sprayed on soybeans at the first compound leaf stage (variety: Tamanishiki), and one day later, conidia of Cerkospora kikuchii were spray-inoculated. did. One week after inoculation, the degree of disease onset was compared with that of the untreated plot, the respective control values were calculated, and the effectiveness was determined using the same criteria as Test Example 1. The results are shown in Table 7.

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[Table] Test Example 5: Test for controlling cucumber vine split disease by seed disinfection Fusarium oxysporum f.Sp.
cucumerinum) were immersed in a chemical solution of a predetermined concentration for 20 hours, placed on a selective medium for Fusarium (Komada medium), and after one week, the growth status of the bacterial flora around the seeds on the medium was investigated. , the control value was calculated in comparison with no treatment, and the effectiveness was determined using the same criteria as in Test Example 1. The results are shown in Table 8.

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[Table] Formulation example 1: Wettable powder Compound No. 1 50 parts Diatomaceous earth/clay mixture 45 parts Polyoxyethylene nonyl phenyl ether 5 parts Mix and grind the above uniformly to make a wettable powder. Formulation Example 2: Emulsion Compound No. 26 20 parts Tetrahydrofuran 20 parts Xylene 45 parts Mixture of polyoxyethylene nonyl phenyl ether and alkylbenzene sulfonate 15 parts Mix and dissolve the above ingredients uniformly to obtain an emulsion. Prescription 3: Powder Compound No. 39 4 parts Mixture of diatomaceous earth, clay, and talc 95 parts Calcium stearate 1 part Mix and grind the above uniformly to form a powder. Formulation Example 4: Granules Compound No. 8 3 parts Bentonite-clay mixture 92 parts Calcium ligninsulfonate 5 parts Mix and grind the above ingredients uniformly, add an appropriate amount of water, knead well, and granulate to obtain granules.

Claims (1)

[Claims] 1 General formula () (However, in the formula, R ₁ and R ₂ may be the same or different, and include an alkyl group having 1 to 5 carbon atoms; a cycloalkyl group; a lower alkenyl group; a lower alkynyl group; an alkoxyalkyl group having 2 to 5 carbon atoms. ; an alkoxyalkoxyalkyl group having 3 to 6 carbon atoms; a benzyl group optionally substituted with a halogen atom; and a group [formula], and R ₁ and R ₂ together represent a group [formula] (R ₃ is a hydrogen atom; lower alkyl group; cycloalkyl group; lower alkoxy group; alkoxyalkyl group having 2 to 4 carbon atoms; phenyl group; 1 to 3 halogen atoms; lower alkyl group; lower alkoxy group; lower haloalkoxy phenyl group substituted with a group and a methylenedioxy group;
Represents a naphthyl group and a pyridyl group. ). ) Ketene S,S-acetals represented by 2 General formula () (However, in the formula, R ₁ and R ₂ may be the same or different, and include an alkyl group having 1 to 5 carbon atoms; a cycloalkyl group; a lower alkenyl group; a lower alkynyl group; an alkoxyalkyl group having 2 to 5 carbon atoms. ; an alkoxyalkoxyalkyl group having 3 to 6 carbon atoms; a benzyl group optionally substituted with a halogen atom; and a group [formula], and R ₁ and R ₂ together represent a group [formula] (R ₃ is a hydrogen atom; lower alkyl group; cycloalkyl group; lower alkoxy group; alkoxyalkyl group having 2 to 4 carbon atoms; phenyl group; 1 to 3 halogen atoms, lower alkyl group, lower alkoxy group; lower haloalkoxy phenyl group substituted with a group and a methylenedioxy group;
Represents a naphthyl group and a pyridyl group. ). An agricultural and horticultural fungicide characterized by containing ketene S,S-acetals represented by ) as an active ingredient.