JPH0450299B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, X represents a halogen atom or a methyl group, Y represents an oxygen or sulfur atom, R ¹ represents a difluoromethyl group or a 2,2,2-trifluoroethyl group, and R ² represents a C ₃ to C ₈ alkyl group, _C3 ~
_C8 alkenyl group, _C3 - _C8 alkynyl group, _C4 - _C6
C ₁ - substituted with a cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted aralkyl group or halogen atom, C ₁ - _{C 4} alkoxy group, nitro group or C ₃ - C ₅ cycloalkyl group
_C4 alkyl group, _C3 - _C4 alkenyl group or _C3
~ _C4 alkynyl group. ] The present invention relates to an N-phenyl carbamate compound represented by the following and an agricultural and horticultural fungicide characterized by containing the same as an active ingredient. In the general formula [ ^] , examples of _{the halogen} atom represented by , n-
Butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 2,2
-dimethylpropyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-ethyl-1-methylpropyl, 1-methylhexyl, 1
-Methylheptyl group, etc., and _C3 - _C8 alkenyl groups include allyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-
2-propenyl, 1-methyl-3-butenyl, 3
-Methyl-2-butenyl, 1-ethyl-2-propenyl, 1-propyl-2-propenyl, 1-butyl-2-propenyl, 1-pentyl-2-propenyl groups, etc. as _C3 to _C8 alkynyl groups teeth,
propargyl, 2-butynyl, 3-butynyl, 1
-Methylpropynyl, 1,1-dimethylpropynyl, 1-ethylpropynyl, 1-propylpropynyl, 1-butylpropynyl, 1-pentylpropynyl groups, etc., and _C4 to _C6 cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, etc. Substituted or unsubstituted phenyl groups include phenyl, 2-methylphenyl, 3-methylphenyl groups, etc. Substituted or unsubstituted aralkyl groups include benzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chloro benzil,
2-fluorobenzyl, 3-fluorobenzyl,
4-fluorobenzyl, 2-bromobenzyl, 3
-bromobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-trifluoromethylbenzyl,
3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 4-tert-butylbenzyl, 2,3-dichlorobenzyl, 2,4-dichlorobenzyl, 2,5-dichlorobenzyl, 2,6
-dichlorobenzyl, 3,4-dichlorobenzyl, 3,5-dichlorobenzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5
-dimethylbenzyl, 2,6-dimethylbenzyl, 3,4-dimethylbenzyl, 3,5-dimethylbenzyl, α-methylbenzyl, α-ethylbenzyl, α-ethynylbenzyl, phenethyl, 4
-Chlorophenethyl, α-phenylbenzyl, furfuryl, cinnamyl group, etc. are halogen atoms,
_C1 - _C4 alkoxy group, nitro group or C3 _{- C5}
Examples of the _C1 - _C4 alkyl group, _C3 - _C4 alkenyl group or _C3 - _C4 alkynyl group substituted with a cycloalkyl group include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2, 2-trichloroethyl, 3-chloropropyl, 1-fluoromethyl-2-fluoroethyl, 1-chloromethyl-2-chloroethyl, 1-bromomethyl-2-
Bromoethyl, 2,3-dichloropropyl, 4-
Chloro-2-butenyl, 4-bromo-2-butenyl, 4-chloro-2-butynyl, 4-bromo-2
-butynyl, 1-methyl-2-methoxyethyl,
1-methyl-2-ethoxyethyl, 1-methyl-
2-butoxyethyl, 1-methoxymethyl-2-
Chloroethyl, 4-methoxy-2-butenyl, 4
-methoxy-2-butynyl, 2-nitrobutyl,
2-Methyl-2-nitropropyl, cyclopropylmethyl, 1-cyclopropylethyl, 1-cyclobutylethyl, 1-cyclobentylethyl, 1
-cyclopropylpropyl group, etc. The N-phenyl carbamate compounds represented by the general formula [] include Pyricularia oryzae of rice, Pseudoperonospora cubenisis of cucumber, Phytophthora infestans, and brown spot of Japanese cabbage. (Cercospora arachidicola), Venturia inaequalis on apples, Rhizoctonia solani on rice, Pythium aphanidermatum on cucumbers, Fusarium cxysporum f.sp. raphani on Japanese radish
It is characterized by its high effectiveness in controlling insects such as Many synthetic organic compounds with antibacterial properties have been discovered and developed as agricultural fungicides, making a great contribution to the stable supply of agricultural products. However, it is also true that there are many problems that should be further improved, such as insufficient control effect, occurrence of drug-resistant bacteria, and environmental pollution. The present inventors took the above points into consideration and as a result of repeated studies on various synthetic organic compounds, the above N-
We have discovered that phenyl carbamate compounds exhibit excellent disease control effects. In particular, it has not only a preventive effect but also a therapeutic effect, and shows a stable control effect even when actually used in the field. As a result of further studies on these N-phenyl carbamate compounds, some of them were found to be benomyl [methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate], fuberidazole [2-(2-furyl)benz imidazole], thiabendazole [2-(4-thiazolyl)benzimidazole], carbendazim [methylbenzimidazol-2-yl carbamate], thiophanatomethyl [1,2-bis(3-methoxycarbonyl-2-thioureido)benzene] ], thiophanate [1,2-bis(3-ethoxycarbonyl-2-thioureido)
Benzene] and other drug-resistant bacteria that are resistant to benzimidazole/thiophanate fungicides,
Brocimidone [N-(3',5'-dichlorophenyl)
-1,2-dimethylcyclopropane-1,2-dicarboximide], iprodione [3-(3',
5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione], vinclozolin [3-(3',5'-dichlorophenyl)
-5-methyl-5-vinyloxazolidine-2,
4-dione], serinal [ethyl (R,S)-3
-(3',5'-dichlorophenyl)-5-methyl-
It has been additionally discovered that it exhibits a strong selective bactericidal effect against drug-resistant bacteria that are resistant to cyclic imide fungicides such as 2,4-dioxoxazolidine-5-carboxylate]. Therefore, the compounds of the present invention are also extremely useful as agents for controlling drug-resistant bacteria. In actual fields where drug-resistant bacteria usually occur, there are cases where the majority of the bacteria are drug-resistant, and cases where resistant and susceptible bacteria coexist. Therefore, any of the above-mentioned N-phenyl carbamate compounds may be used alone, or benzimidazole
It may be used in combination with either a thiophanate fungicide or a cyclic imide fungicide, or in combination. In particular, when drug-susceptible bacteria and resistant bacteria are mixed together, one or more of the aforementioned N-phenyl carbamate fungicides and benzimidazole/thiophanate fungicides or cyclic When used in combination with one or more imide fungicides, a significantly high disease control effect was observed. Therefore, the agricultural and horticultural fungicidal composition according to the present invention,
It has high practical value as a fungicide that exhibits excellent pest control effects in any field. The compound of the present invention [ ] is a new compound, and can be produced, for example, by the following method. (a) General formula [] [In the formula, X and R ¹ have the same meanings as above. ] Aniline derivatives represented by and general formula [ ] [In the formula, Y and R ² have the same meanings as above. ] A manufacturing method of reacting with a chloroformic acid ester represented by: This reaction involves benzene, toluene, xylene,
Diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate,
The reaction is carried out in an organic solvent such as pyridine, dimethylformamide, or a mixture thereof, and can be carried out in high yield by using a dehydrochlorination agent such as pyridine, triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, etc. can. The reaction is cooled or heated (0 to
(150°C), the process can be completed instantly to 10 hours, and the desired product can be obtained in good yield. The aniline derivative represented by the general formula [] in production method (a) is the general formula [] [In the formula, X and R ¹ have the same meanings as above. ] Obtained by the reduction reaction of a nitrobenzene derivative represented by This nitrobenzene derivative is described, for example, in the literature J.
Org.Chem., 25 2009 (1960) and Unexamined Japanese Patent Publication No. 1987-
It can be easily obtained according to the method described in Publication No. 36467. (b) General formula [] [In the formula, X and R ¹ have the same meanings as above. ] A phenyl isocyanate dielectric substance represented by the general formula [] R ² YH [] [wherein Y and R ² have the same meanings as above. ] A manufacturing method of reacting with an alcohol or thiol represented by: This reaction can be carried out without solvent or with benzene, toluene,
The reaction can be carried out in an organic solvent such as xylene, diethyl ether, tetrahydrofuran, dioxane, dimethylformamide, chloroform, carbon tetrachloride, etc. without a catalyst or with a catalyst such as pyridine, triethylamine, diethylaniline, etc. The reaction is cooled or heated as necessary (0-50°)
By doing this, the process can be completed instantly to 10 hours, and the desired product can be obtained in good yield. The phenyl isocyanate derivative represented by the general formula [] can be obtained by reacting the aniline derivative represented by the general formula [] with phosgene. The present invention will be explained in more detail with reference to Examples. Example 1 Synthesis of 1-ethyl-2-propynyl N-(3-chloro-4-difluoromethoxyphenyl)carbamate (according to method (a)) 3-chloro-4-difluoromethoxyaniline
1.95g and diethylaniline 1.5g toluene
The solution was dissolved in 50 ml, and 1.45 g of 1-ethyl-2-propynyl chloroformate was added dropwise over 5 minutes under ice cooling. After stirring at room temperature for about 10 hours, the mixture was poured into ice water and extracted with ether. After washing with water and drying over magnesium sulfate, the solvent was distilled off to obtain 2.95 g of an oily substance. This product was purified by silica gel column chromatography using a mixed solvent of hexane and acetone.
-ethyl-2-propynyl N-(3-chloro-
2.76 g of white crystals of 4-difluoromethoxyphenyl) carbamate were obtained. (Yield 90.9%) Melting point 36
~36.5℃ Elemental analysis value C(%) H(%) N(%) Cl(%) Calculated value 51.41 3.98 4.61 11.67 (as C ₁₃ H ₁₂ ClF ₂ NO ₃ ) Actual value 51.67 4.02 4.55 11.53 Example 2 2, Synthesis of 4-dichlorobenzyl N-(3-chloro-4-difluoromethoxyphenyl)carbamate (according to method (b)) 1 g of triethylamine and 1.8 g of 2,4-dichlorobenzyl alcohol were dissolved in 100 ml of ethyl acetate. 2.2 g of 3-chloro-4-difluoromethoxyphenyl isocyanate was added dropwise. After stirring at room temperature for about 6 hours, the mixture was poured into ice water and extracted with ether. After washing with water and drying over magnesium sulfate, the solvent was distilled off to obtain 3.8 g of crude crystals. This product was purified by silica gel column chromatography using a mixed solvent of hexane and acetone, and white crystals of 2,4-dichlorobenzyl N-(3-chloro-4-difluoromethoxyphenyl) carbamate were obtained.
3.2g was obtained. (Yield 80.7%) Melting point 68-69℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 45.42 2.54 3.53 26.82 (as C ₁₅ H ₁₀ Cl ₃ F ₂ NO ₃ ) Actual measurement Value 45.38 2.60 3.55
26.79 Next, examples of the compounds of the present invention represented by the general formula [] obtained in the same manner as in Examples 1 and 2 are as follows, but the compounds of the present invention are not limited to these. Note that the compound numbers shown here are commonly used in the following formulation examples and test examples.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] When actually applying the compound of the present invention obtained in this way, it can be used in pure form without adding other ingredients, or it can be mixed with a carrier to make it easier to use as a fungicide. and commonly used forms such as powders, wettable powders, oils, emulsions,
It can be used as tablets, granules, microgranules, aerosols, flowables, etc. Furthermore, when one or more of the N-phenyl carbamate compounds according to the present invention and one or more of the aforementioned benzimidazole thiophanate fungicides or cyclic imide fungicides are used in combination, these It can be mixed with a carrier at a mixing ratio of 1:0.1 to 10 by weight, formulated into the above-mentioned form, and applied. The formulations generally contain from 1.0 to 95.0% by weight of active compound (including mixed ingredients), preferably
Contains 2.0 to 80.0%, usually 2 to 10 ares
An application amount of 100g is appropriate. Furthermore, the concentration used is preferably in the range of 0.005% to 0.5%, but the amount and concentration used depend on the dosage form, application time, method, location,
Since it varies depending on the target disease, target crop, etc., there is no problem in increasing or decreasing the amount without being limited to the above range. Test examples and formulation examples are shown below, and compound numbers 1 to 116 indicate the compounds listed in Table 1, and A to J indicate the following compounds.

【table】

[Table] Test Example 1 Rice blast control effect A 90 ml plastic pot was filled with rice soil, and rice (variety: Kinki No. 33) was sown. This was grown in a greenhouse, and a water-diluted solution of the test compound in the form of an emulsion was sprayed on the foliage of the seedlings at the 3-leaf stage until the droplets sufficiently adhered to the leaf surface. After the chemical solution was air-dried, a spore suspension of rice blast disease (Pyricularia oryzae) was spray inoculated. After this was left at 28°C and humid conditions for 3 days, the disease state was observed. The disease severity was calculated by the following method. That is, the lesions were classified into indexes of 0, 0.5, 1, 2, and 4 according to the degree of appearance of lesions on the examined leaves, and the degree of disease severity was calculated using the following formula. (Infection index) (Infection status) 0...No bacterial flora or lesions observed on the leaf surface. 0.5: Bacterial flora or lesions are observed on the leaf surface in less than 5% of the leaf area. 1...Bacterial flora or lesions are observed on the leaf surface in less than 20% of the leaf area. 2...Bacterial flora or lesions are observed on less than 50% of the leaf area. 4...Bacterial flora or lesions are observed on the leaf surface over 50% of the leaf area. Disease severity (%) = Σ (infection fingerprint) × (number of leaves) / (number of investigated leaves) × 4 × 100 Subsequently, the control value was calculated from the following formula. Control value (%) = 100−
(Incidence in compound treated area) / (Incidence in non-treated area) x 10
0 As a result, as shown in Table 2, the compound of the present invention showed excellent pest control value.

【table】

【table】

【table】

[Table] Note (1) Commercial fungicide test example 2. Effect on controlling downy mildew of cucumber A plastic pot was filled with sandy loam, and two cucumbers (variety: Sagami Hanshiro) were sown per pot. This was cultivated in a greenhouse for 14 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion was sprayed on the foliage of the seedlings so that the chemical solution was sufficiently attached to the leaf surface. Downy mildew fungus (Pseudoperonospora cubensis) on young seedlings after air-drying the chemical solution
A suspension of conidia was inoculated by spraying. This at 20℃
The plants were left under humid conditions for 3 days, and then cultivated for 3 days under fluorescent lamp illumination at 20°C to induce disease, and then the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1. As shown in Table 3, the results showed that the compound of the present invention had an excellent pesticidal effect.

【table】

[Table] Note (1) Commercial fungicide test example 3 Powdery mildew control effect on cucumbers A 90 ml plastic pot was filled with sandy loam, and cucumbers (variety: Sagami Hanshiro) were sown. This was cultivated in a greenhouse for 8 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed onto the foliage of the seedlings until the droplets sufficiently adhered to the leaf surface. After the chemical solution was air-dried, the seedlings were spray-inoculated with a conidial suspension of a chemical-resistant or sensitive cucumber powdery mildew fungus (Sphaerotheca fuliginea). The plants were placed in a greenhouse and cultivated for 10 days to develop the disease, and then the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1. As a result, as shown in Table 4, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria, but did not show any control effect when inoculated with drug-susceptible bacteria. On the other hand, none of the commercially available fungicides, benomyl, thiophanate methyl, and carbendazim, showed any control effect when inoculated with drug-resistant bacteria, but showed excellent control effects when inoculated with drug-susceptible bacteria. Compounds with similar chemical structures and commercially available herbicides with similar chemical structures used for comparison showed almost no control effect when inoculated with any of the bacteria.

【table】

[Table] Test Example 4 Control effect on gray mold disease of cucumbers A 90 ml plastic pot was filled with sandy loam, and cucumbers (variety: Sagami Hanshiro) were sown. This was cultivated at room temperature for 8 days to obtain cucumbers with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed onto the foliage of the seedlings until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, young seedlings are infected with chemical-resistant or susceptible botrytis fungus (Botrytis).
cinerea) was pasted on the leaf surface and inoculated. This was left under humid conditions at 20°C for 3 days to develop the disease, and then the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1. As a result, as shown in Table 5, the compounds of the present invention showed excellent control effects when inoculated with drug-resistant bacteria, and conversely, the commercially available fungicides benomyl and thiophanate methyl showed excellent control effects when inoculated with drug-susceptible bacteria. It was shown to be effective.

【table】

[Table] Test example 5 Powdery mildew control effect on cucumber Fill a 90ml plastic pot with sandy loam,
Kiyu cucumber (variety: Sagami Hanpaku) was sown. This was cultivated in a greenhouse for 8 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed onto the foliage of the seedlings until the droplets sufficiently adhered to the leaf surface. After the chemical solution was air-dried, the seedlings were spray inoculated with a conidial suspension obtained by mixing drug-resistant and susceptible bacteria of Sphaerotheca fuliginea. This at room temperature
After cultivation for 10 days and disease onset, the disease state was observed. The method for investigating the onset of the disease and the calculation of the control value are shown in Test Example 1.
I did the same thing. As a result, as shown in Table 6, by applying a mixture of any of the N-phenyl carbamate compounds according to the present invention and any of the benzimidazole/thiophanate fungicides, it was found that the control effect was clearly higher than that of each single agent. was recognized.

【table】

【table】

[Table] Test Example 6 Tomato gray mold control effect A 90 ml plastic pot was filled with sandy loam, and tomatoes (variety: Fukuju No. 2) were sown. This was cultivated at room temperature for 4 weeks to obtain tomato seedlings at the 4-leaf stage. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed on the leaves until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, Botrytis
A conidial suspension obtained by mixing drug-resistant and susceptible bacteria of C. cinerea was inoculated by spraying. After leaving it under humid conditions at 20°C for 5 days, the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1. As a result, as shown in Table 7, by applying a mixture of any of the N-phenyl carbamate compounds according to the present invention and any of the cyclic imide fungicides, it was found that the pest control effect was clearly higher than that of each single agent application. was recognized.

【table】

【table】

[Table] Formulation Example 1 Powder By thoroughly mixing 2 parts of compound (51), 88 parts of clay, and 10 parts of talc, a powder with a base ingredient content of 2% can be obtained. Formulation example 2 Wettable powder: If 30 parts of compound (22), 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of wetting agent (sodium lauryl sulfate) and 2 parts of dispersing agent (calcium lignin sulfonate) are thoroughly ground and mixed, the main ingredient will be contained. Obtain a hydrating agent with a volume of 30%. Formulation example 3 Wettable powder By thoroughly grinding and mixing 50 parts of compound (57), 45 parts of diatomaceous earth, 2.5 parts of a wetting agent (calcium alkylbenzenesulfonate) and 2.5 parts of a dispersing agent (calcium ligninsulfonate), the base ingredient content can be reduced to 50%. Obtain a hydrating powder. Formulation Example 4 Emulsion 10 parts of compound (30), 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether) are mixed to obtain an emulsion with a base agent content of 10%. Formulation Example 5 Powder 1 part of Compound (27), 1 part of Compound (E), 88 parts of clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder with a base ingredient content of 2%. Formulation example 6 Wettable powder 20 parts of compound (76), 30 parts of compound (A), 40 parts of powdered sucrose
By thoroughly grinding and mixing 5 parts of white carbon, 3 parts of a wetting agent (sodium lauryl sulfate), and 2 parts of a dispersing agent (calcium lignin sulfonate), a wettable powder with a base ingredient content of 50% is obtained. Formulation example 7 Wettable powder Compound (111) 30 parts, Compound (F) 20 parts, Diatomaceous earth 45 parts,
By thoroughly grinding and mixing 2.5 parts of a wetting agent (calcium alkylbenzenesulfonate) and 2.5 parts of a dispersing agent (calcium ligninsulfonate), a wettable powder with a base ingredient content of 50% is obtained. Formulation example 8 Wettable powder Compound (93) 50 parts, Compound (G) 25 parts, Diatomaceous earth 18 parts,
By thoroughly grinding and mixing 3.5 parts of a wetting agent (calcium alkylbenzenesulfonate) and 3.5 parts of a dispersing agent (calcium ligninsulfonate), a wettable powder with a base ingredient content of 75% is obtained.

Claims (1)

[Claims] 1. General formula [In the formula, X represents a halogen atom or a methyl group, Y represents an oxygen atom or a sulfur atom, R ¹ represents a difluoromethyl group or a 2,2,2-trifluoroethyl group, and R ² represents a C ₃ - _C8 alkyl group,
_C3 - _C8 alkenyl group, _C3 - _C8 alkynyl group, _C4
~ _C6 cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted aralkyl group, _C3 - _C4 alkynyl group substituted with a halogen atom,
Substituted with halogen atoms, _C1 - _C4 alkoxy groups, nitro groups or _C3 - _C5 cycloalkyl groups
Indicates a _C1 - _C4 alkyl group. ] An N-phenyl carbamate compound represented by: 2 General formula [In the formula, X represents a halogen atom or a methyl group, Y represents an oxygen atom or a sulfur atom, R ¹ represents a difluoromethyl group or a 2,2,2-trifluoroethyl group, and R ² represents a C ₃ - _C8 alkyl group,
_C3 - _C8 alkenyl group, _C3 - _C8 alkynyl group, _C4
~ _C6 cycloalkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted aralkyl group, _C3 - _C4 alkynyl group substituted with a halogen atom,
Substituted with halogen atoms, _C1 - _C4 alkoxy groups, nitro groups or _C3 - _C5 cycloalkyl groups
Indicates a _C1 - _C4 alkyl group. ] An agricultural and horticultural fungicide characterized by containing an N-phenyl carbamate compound represented by the following as an active ingredient.