JPH0465829B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, X and Y are the same or different and represent a halogen atom, a lower alkenyl group, a lower cyanoalkenyl group, a lower alkyl group, a lower alkoxyl group, or a cyano group, or a halogen atom,
It represents a lower alkyl group which may be substituted with a hydroxyl group or a cyano group, or the general formula -
CH ₂ CR ³ , −COOR ³ , −CH(OR ³ ) ₂ ,

[In the formula, R ² represents the same meaning as above, and W represents a halogen atom. ]

A production method that involves reacting with the compound shown in This reaction is generally carried out in an organic solvent such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide, or a mixture thereof; This can be carried out by using a dehydrohalogenating agent such as sodium oxide, potassium hydroxide, or sodium hydride, or, if necessary, a catalyst such as tetrabutylammonium bromide. The reaction may be carried out by cooling or heating (from 0°C to
150℃), it can be completed within 12 hours,
The target product can be obtained in good yield. Furthermore, in the case where R ² in the general formula [] represents a group represented by the general formula -COR ⁶ (herein, R ⁶ represents the same meaning as above), the compound of the present invention can be prepared by, for example, the following method. can also be manufactured. Production method (b) N-phenyl carbamate compound represented by the above general formula [] and the general formula [] (R ⁶ CO) ₂ O [] [wherein R ⁶ represents the same meaning as above. ] A manufacturing method of reacting with an acid anhydride represented by: This reaction is generally carried out in an organic solvent such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide or a mixture thereof;
High yields can be achieved by using deoxidizing agents such as triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, and sodium hydride, and if necessary, catalysts such as concentrated sulfuric acid and tetrabutylammonium bromide. can. The reaction can be completed within 12 hours by cooling or heating (0° to 150°C) as necessary, and the desired product can be obtained in good yield. Furthermore, the compound of the present invention can also be produced, for example, by the following method. Manufacturing method (c) General formula [] [In the formula, X, Y, Z and R ² have the same meanings as above. ] Aniline derivatives shown by the general formula [ ] A production method that involves reacting with the compound shown in This reaction is generally carried out in an organic solvent such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide or a mixture thereof;
High yields can be achieved by using a dehydrochlorination agent such as triethylamine, diethylaniline, sodium hydroxide, potassium hydroxide, or the like. The reaction is cooled or heated (0 to 150℃) as necessary.
°C), the reaction can be completed within 12 hours and the desired product can be obtained in good yield. Note that the N-phenyl carbamate compound represented by the general formula [ ], which is the raw material in manufacturing methods (a) and (b), and the aniline derivative represented by the general formula [], which is the raw material in manufacturing method (c), are patented in Europe. It is obtained by a method similar to the method described in Publication No. 0063905. Next, a manufacturing example will be shown. Production example 1 Isopropyl N-acetyl-N-(3-chloro-4-ethoxy5-methoxymethylphenyl)
Production of carbamate [according to production method (b)] Isopropyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)carbamate
3.02 g was dissolved in 50 ml of acetic anhydride, 2 drops of concentrated sulfuric acid were added, and the mixture was heated under reflux for 30 minutes. After the reaction was completed, the reaction mixture was poured into ice water and extracted with ether. The solvent was washed with aqueous sodium bicarbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of hexane and acetone to obtain isopropyl N-acetyl-N-
2.71 g of (3-chloro-4-ethoxy-5-methoxymethylphenyl)carbamate was obtained. (yield
67%) n ²⁶ _D 1.4954 Production example 2 Isopropyl N-benzoyl-N-(3,4
-Diethoxy-5-methylphenyl)carbamate [according to production method (a)] Isopropyl N-(3,4-diethoxy-5
-Methylphenyl)carbamate (2.81 g) was dissolved in 50 ml of dimethylformamide, and 0.5 g of sodium hydride (50%) was added therein. Mixture at 60℃
After heating for 15 minutes, 1.41 g of benzoyl chloride was added and further heated for 30 minutes. After the reaction was completed, the reaction mixture was poured into ice water and extracted with ether. The solvent was washed with aqueous sodium bicarbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of hexane and acetone to obtain isopropyl N-benzoyl-N-(3,4-diethoxy-5-methylphenyl)carbamate 3.35
I got g. (Yield 87%) n ²⁶ _D 1.5313 Production example 3 Production of isopropyl N-benzoyl-N-(3-chloro-4-ethoxy-5-methoxymethylphenyl) carbamate [according to production method (c)] N-(3 3.2 g of -chloro-4-ethoxy-5-methoxymethyl)benzamide was dissolved in 50 ml of dimethylformamide, and 0.5 g of sodium hydride (50%) was added therein. After the mixture was heated at 60° C. for 15 minutes, 1.23 g of isopropyl chloroformate was added and heated for an additional 30 minutes. After the reaction was completed, the reaction mixture was poured into ice water and extracted with ether. The solvent was washed with aqueous sodium bicarbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of hexane and acetone to obtain isopropyl N-benzoyl-N-(3-chloro-4-ethoxy-5
-methoxymethylphenyl)carbamate 3.37g
I got it. (Yield 83%) n ²⁶ _D 1.5307 Production example 4 Isopropyl N-methyl-N-(3-chloro-4-ethoxy-5-methoxymethylphenyl)
Production of carbamate [according to production method (a)] N-(3-chloro-4-ethoxy-5-methoxymethylphenyl) carbamate 2.0 g tetrahydrofuran 30 ml, potassium hydroxide powder 0.56 g and tetra-n-butylammonium bromide
1.88 g of methyl iodide was added to 0.5 g of the mixture at 25°C with stirring. After further stirring at the same temperature for 1.5 hours, the mixture was heated and refluxed for 3 hours, and then cooled to room temperature.
The reaction mixture was poured into water and extracted with toluene. The solvent was washed with dilute hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and tetrahydrofuran to obtain isopropyl N-methyl N-(3-chloro-4-ethoxy-5-methoxymethylphenyl). ) 2.01 g of carbamate was obtained. (Yield 96%) n ²⁵ _D
1.5104 Production Example 5 Production of isopropyl N-ethoxycarbonylmethyl-N-(3,4-diethoxy-5-methylphenyl)carbamate [according to production method (a)] Isopropyl N-(3,4-diethoxy-5
-methylphenyl)carbamate 2.0 g, tetrahydrofuran 30 ml, potassium hydroxide powder 0.60 g and tetra-n-butylammonium bromide
Bromoacetic acid ethyl ester 2.38 to 0.50g mixture
g was added with stirring at 25°C. Furthermore, at the same temperature 2
After stirring for an hour, the mixture was heated and refluxed for 5 hours, and then cooled to room temperature. The reaction mixture was poured into water and extracted with toluene. The solvent was washed with dilute hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure,
The obtained residue was purified by silica gel column chromatography using a mixed solvent of toluene and tetrahydrofuran to obtain isopropyl N-ethoxycarbonylmethyl-N-(3,4-diethoxy-5
-methylphenyl)carbamate 2.40 g were obtained.
Yield 92%) n ²⁶ _D 1.4921 Production example 6 Isopropyl N-propargyl-N-(3,
Production of 4-diethoxy-5-methylphenyl) carbamate [according to production method (c)] Toluene solution of 2.0 g of N-propargyl-N-(3,4-diethoxy-5-methyl)aniline 30
1.37 g of isopropyl chloroformate and 1.66 g of N,N-diethylaniline were added to the solution at 25° C. with stirring. After further stirring at the same temperature for 2 hours, the mixture was heated and refluxed for 2 hours, and then cooled to room temperature. The reaction mixture was poured into water and extracted with toluene. The solvent was washed with dilute hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of toluene and tetrahydrofuran to obtain isopropyl N-propargyl-N-(3,4-diethoxy-
2.63 g of 5-methylphenyl)carbamate were obtained. (Yield 96%) n ²⁶ _D 1.5032 Examples of the compounds of the present invention represented by the general formula [] are as follows, but the compounds of the present invention are not limited to these.

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[Table] Next, reference test examples are given to further clarify the usefulness of the compound of the present invention as a fungicide for agricultural and horticultural purposes.
The commercially available fungicides of the control compounds are shown by the common names in Table 2.

[Table] Reference test example 1 Powdery mildew control effect of cucumber Powdery mildew control effect A 90 ml plastic pot was filled with sandy loam, and cucumber (variety: Sagami Hanshiro) was sown. This was cultivated at room temperature for 8 days to obtain cucumber seedlings with expanded cotyledons. The seedlings were sprayed with a water-diluted solution of an emulsion of the compound of the present invention and a hydrating powder of a control compound described below until a sufficient amount of droplets adhered to the leaf surface. After air-drying the seedlings, the seedlings were spray-inoculated with a conidial suspension of a drug-resistant or susceptible cucumber powdery mildew fungus (Sphaerotheca fuliginea). After cultivating this in a greenhouse for 10 days to develop the disease, the disease state was observed. The disease severity was calculated by the following method. That is, depending on the appearance of lesions on the investigated leaves, 0,
The disease was classified into indexes of 0.5, 1, 2, and 4, and the disease severity was calculated using the following formula. (Infection index) (Infection status) 0...No fungal growth or lesions observed on the leaf surface. 0.5: Bacterial flora or lesions are observed on the leaf surface on 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 {(Sickness index) x (Number of leaves)}/(Number of inspected leaves) x 4 x 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 100 As a result, as shown in Table 3, the compound of the present invention showed an excellent control effect when inoculated with drug-resistant bacteria. However, when inoculated with drug-susceptible bacteria, no control effect was shown. 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.

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[Table] Reference test example 2 Sugar beet brown spot control effect Fill a 90ml plastic pot with sandy loam and add sugar beet (variety: Detroit Dark Red)
was sown. After 20 days of cultivation in a greenhouse, the resulting seedlings were sprayed with a water-diluted solution of an emulsion of the compound of the present invention described below and a hydrating powder of a control compound until the droplets sufficiently adhered to the leaf surface. Chemical resistant or susceptible sugar beet brown spot fungus (Cercospora
beticola) was inoculated by spraying with a conidial suspension. After cultivating the plants in a greenhouse for 10 days under humid conditions by covering them with a vinyl cover, the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Reference Test Example 1. As shown in Table 4, similar to the results of Reference Test Example 1, the compounds of the present invention exhibited excellent control effects when inoculated with drug-resistant bacteria; Carbendazim showed excellent control effects when inoculated with drug-susceptible bacteria.

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[Table] Reference test example 3 Pear scab control effect A 90 ml plastic pot was filled with mixed soil of peat moss and sandy loam, and seeds collected from pear fruit (variety: Chojuro) were sown. This was cultivated in a greenhouse for 20 days, and a water diluted solution of an emulsion of the compound of the present invention described below and a hydrating powder of the control compound described below was sprayed on 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 Venturia nashicola, which is either resistant or susceptible to the drug. 3 under humid conditions at 20°C.
The plants were then cultivated for 20 days under fluorescent lighting at 20°C to develop the disease. The disease onset investigation method and control value calculation were the same as in Reference 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.

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[Table] Reference test example 4 Control effect on gray mold disease of cucumber A 90 ml plastic pot was filled with sandy loam, and cucumber (variety: Sagami Hanshiro) was sown. This was cultivated in a greenhouse for 8 days to obtain cucumbers with expanded cotyledons. To these young seedlings, 10 ml of a water diluted solution of an emulsion of the present compound and a hydrating powder of the control compound described below was applied per pot and sprayed on the foliage. After the chemical solution was air-dried, the young seedlings were inoculated with bacterial colony cuttings (5 mm in diameter) of chemically resistant or sensitive Botrytis cinerea by pasting them on the leaves. This was left under humid conditions at 20°C for 3 days to develop the disease, and then the state of disease onset was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Reference Test Example 1. As a result, as shown in Table 6, 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.

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Claims (1)

[Claims] 1. General formula [Wherein, X and Y are the same or different and represent a halogen atom, a lower alkenyl group, a lower alkynyl group, a lower alkoxyl group, a lower alkyl group, or a substituent represented by the general formula -CH ₂ OR ³ (here, R ³ represents a lower alkyl group). Z represents a fluorine atom or a substituent represented by the general formula -OR ⁵ (where R ⁵ represents a lower alkenyl group or a lower alkynyl group, or is substituted with a halogen atom, a lower alkoxyl group, or a lower cycloalkyl group) represents a lower alkyl group which may be A represents an oxygen atom or a sulfur atom. R ¹ represents a halogen atom or a lower alkyl group which may be substituted with a lower alkoxy group.
R ² represents a cyano group, lower alkyl group, lower alkenyl group, or lower alkynyl group, or represents a lower alkyl group substituted with a cyano group, lower alkoxycarbonyl group, or lower cycloalkyl group, or represents an aralkyl group. or the general formula -COR ⁶ (wherein R ⁶ represents a lower alkyl group, a lower cycloalkyl group, or a lower alkyl group substituted with a phenoxy group, a phenyl group, or an aralkyl group). ]
-Phenyl carbamate compounds.