JPH0219357A - Sulfonamide derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R is substituted pyrazolyl, (substituted) isoxazolyl, substituted isothiazolyl, etc.; R<1> is alkyl, phenyl, halogen- substituted alkyl, etc.] EXAMPLE:N-(5,5-Dichloro-4-pentenyl)-N-(1-ethylpyrazol-5-yl)metha-nesul fonamide. USE:An agricultural and horticultural fungicide showing excellent effects as a controller for blast of rice plants and also useful as a controller for sheath blight of rice plant, downy mildew of cucumber, powdery mildew of cucumber and KUROSUSU disease of KOMATSUNA (a kind of Chinese cabbage), characteristically having residual effects and rain resistance. PREPARATION:A sulfonamide derivative shown by formula II is reacted with a base such as NaOH or KOH to give an alkali metallic salt of sulfonamide derivative shown by formula III (M is alkali metal). Then this salt is reacted with 1,1,5-trichloro-1-pentene shown by formula IV to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (I!,!! Field of Application) The present invention relates to a novel sulfonamide derivative and an agricultural and horticultural fungicide containing the same as an active ingredient.

(Prior Art) It has been known that certain sulfonamide derivatives have bactericidal activity6, for example, Japanese Patent Publication No. 55-L
l Publication No. 643 Mei St describes N-3,3-dichloro(
J-2-propenyl (substituted) sulfonamide derivative is 1
4 III It is described as being useful as a fungicide for JX. However, the bactericidal activity of these known compounds was not necessarily satisfactory.

(To be solved by the invention) In order to develop more useful agricultural and horticultural fungicides, the present inventors synthesized various sulfonamide derivatives and investigated their fungicidal activity. pathogenic bacteria,
Especially rice weight 5! We have completed the present invention by discovering that this product has extremely excellent bactericidal activity against the disease rice blast.

(Means for solving the problem) The sulfonamide derivative of the present invention has a general formula of at least one of a benzyl group, a nitro group, a thiocyanato group, and an alkoxycarbonyl group, and a pyrazolyl group directly substituted with H.

isoxasilyl group which may be substituted with a halogen atom or a lower alkyl group, isothiazolyl J & which is directly substituted with a lower alkyl group, alkylthio Js, a phenyl group and at least one of alkoxycarbonyl, 1, and G. imidazolyl group, pyridyl group optionally substituted with a halogen atom or halogen monosubstituted alkyl group, pyrimidinyl group optionally substituted with a halogen atom, lower alkyl group or alkylthio group, quinolyl J1%, quinoxalinyl group, lower alkyl represents a pyrazinyl group or a phthalimidoyl group which may be substituted with a group, and R' is an alkyl group, a phenyl group, a halogen-substituted alkyl group, or am and R1 can also form a ring containing adjacent nitrogen atoms.

The compounds of the present invention represented by -homicide are exemplified in Tables 1, 2, and 3. In addition, the compound number will be referred to in the subsequent description.

1A [In the formula, R is a halogen atom, a lower alkyl group, or a phenyl group.

R’　　R” Table 1 continued 4.・,<So,C1l・ (CHa), Cl1=CCl.

1.13 The compound of the present invention can be produced, for example, by the method shown below.

(Production method 1) (In the formula, 1M represents an alkali metal atom, and R and R1 have the same meanings as above.) In ai1 method i, the sulfonamide derivative is first mixed with alcohol, acetone, dimethylformamide (DMr")
), dissolved in a solvent such as benzene, toluene, etc., and reacted with a base such as sodium hydroxide, potassium hydroxide, metallic sodium, sodium hydride, etc. 1. The reaction temperature is within the range of room temperature to the boiling point of the solvent used.

If the reaction is carried out for 1 to 5 hours, the alkali metal salt of the sulfonamide derivative can be obtained in high yield.Next, the metal salt of the sulfonamide derivative and 1.1.5-)-lichloro-1-pentene are combined. acetone, alcohol, benzene,
Toluene, DMF, dimethyl sulfoxide (DMSO)
The compound of the present invention can be produced by reacting in a solvent such as. The reaction time is 1 to 40 hours, but preferably the reaction is carried out at a temperature of 60 to 100°C for 4 to 20 hours.

('Fi construction θ, 2) "SO" (Go,), C1i: CCI, "Rx
-“80・”(CH,), CH=CC1° (in the formula,
represents a halogen atom, and M, R and R' are the same 5 as above.
In production method 2, first, the N (5* 5-dichloro-4-pentenyl) sulfonamide derivative is mixed with acetone,
alcohol.

Dissolve in a solvent such as benzene, toluene + DMSO + DMF.

Sodium hydroxide, potassium hydroxide, metallic sodium,
The reaction mixture with a base such as sodium hydride is m
It is within the range of the boiling point of the lu to ffl medium used, and the reaction is carried out for 1 to 5 hours.

^ Can you obtain an alkali metal salt of a sulfonamide derivative in a yield of ?

By reacting this with a halide of the heterocycle represented by RX without subjecting it to +rtm or separating it, the compound of the present invention can be obtained! It is possible to make 12 pieces.

The reaction time is 1 to 40 hours, preferably 4 to 20 hours at room temperature to 100°C.

Use an alkali metal salt of a sulfonamide derivative as the solvent for the reaction! You can use something similar to the one used when building +2.

(I2 production method 3) Salt A1 RNH (CH,) J (:H=CC1, + R'SO
, C1 → (wherein R and R' have the same meanings as above,
)12 In production method 3, N-(5,5-dichloro-4
- Pentenyl) amine derivative is dissolved in a solvent such as benzene, toluene, xylene, ether, etc., and sulfonyl chloride is added in the presence of a base such as dimethylaniline, triethylamine, pyridine, sodium carbonate, etc. The reaction temperature ranges from 0°C to the boiling point of the solvent used. The compound of the present invention can be produced by reacting for a reaction time of 1 to 10 hours. The preferred reaction temperature is 5° C. to normal μ, and one reaction time is 1 to 3 hours.

Next, production examples of the compounds of the present invention will be specifically explained.

Production example l N-(5,5-dichloro-4-pentenyl)-N-(1
-Synthesis of ethylpyrazol-5-yl)methanesulfonamide (compound l) 3-0g (0.0te mol) of N-(1-ethylpyrazol-5-yl)methanesulfonamide was dissolved in 40ml of DMF.
0.134 g of 60% sodium hydride dissolved in
(0,016 mol) was added slowly at room temperature. After stirring for 2 hours at room temperature, 2-6 g (0,010 mol) of 1,1,5-trichloro-]-pentene were added dropwise. After 4i lower,
After the completion of the reaction, stirring was continued for 4 hours at 80°C.

Pour the reaction solution into water, extract with ether, and wash the extract with water.

It was dried with liquid magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and the refractive index (
n; @) 1.5241 target (N1 color liquid) 2.4.
I got it.

Production example 2 N-(4-bromo-1-ethylpyrazol-5-yl)
Synthesis of -N-(5,5-dichloro-4-pentenyl)methanesulfonamide (compound 19) N-(4-bromo-1=ethylpyrazol-5-yl)
Meta'/X/Lz phonamide 2. G g (0.01 mol) was dissolved in 30 ml of DMF, and 0.39 g (0.01 mol) of 60% sodium hydride was gradually added at room temperature. After stirring at room temperature for 2 hours, 1.7 g (0.01 mol) of 5-trichloro-1-pentene was added dropwise.After the reaction was completed, stirring was continued at 80°C for 12 hours. 1. The reaction solution was poured into water and extracted with ether. The extract was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with rhohexane.
2.0 g of the target product (white powder) was obtained at 3°C.

! II Preparation Example 3 N-(4-chloro-1-ethylpyrazol-5-yl)
-N-(5,5-dichloro-4-pentenyl)N',
Synthesis of N'-dimethylsulfamide (compound 62)N
-(4-chloro-1-ethylpyrazol-5-yl)-
N',N'-dimethylsulfamide 2.1g (0
,008 mol) was dissolved in 30 ml of DMF, and 0.32 g (0.008 mol) of 60% sodium hydride was gradually added at room temperature. After stirring at room temperature for 2 hours, 1,1.5
After 0 dropwise addition of 1.4 g of -trichloro-1-pentene, stirring was continued at 90°C for 10 hours.

After the reaction was completed, one reaction solution was poured into water, ether was extracted, and the extract was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue W1 was purified by column chromatography to obtain the target product (
yellow viscous liquid) 2.2. I got it.

! 1 structure fs4 N-(5,5-dichloro-4-pentenyl)-N-(3
- Synthesis of methylisothiazol-5-yl)metalsulfonamide (compound 90) 1.2g (0,006 mol) of N-(3-methylisothiazol-5-yl)methanesulfonamide was dissolved in DMF2
Dissolve in 0 ml 60% sodium hydride 0.24
g (0,006 mol) were added slowly at room temperature. After stirring at room temperature for 2 hours, 1.1 g (0,006 mol) of 1,1.5-trichloro-1-pentene was added dropwise. 71N
After the completion of the reaction, stirring was continued for 10 hours at 90°C.After the completion of the reaction, the reaction solution was poured into water and extracted with ether.The extract was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure.

The residue was washed with n-hexane to obtain 0.70 g of the desired product (brown crystals) with a melting point of 58 to 61°C.

! +2 Example 5 N (ng 5-dichloro-4-pentenyl) -
Synthesis of N-(4-methylpyrimidin-2-yl)methanesulfonamide (Compound 96) 2.5 g (0,013 mol) of N-(4-methylpyrimidin-2-yl)methanesulfonamide was dissolved in DMF30
Go% sodium hydride O-53g dissolved in ml
(0,013 mol) was gradually added in chamber t1. 2 at room temperature
After stirring for an hour, 2.3 g (o, o la mol) of L, l, 5-trichlor-1-pentene was added dropwise. After 8 drops, the mixture was stirred at 80°C for 16 hours. After completion of the 0 reaction, 1 reaction solution 11. in water. extracted with ether, washed the extract with water,
It was dried with anhydrous magnesium sulfate. Remove the solvent under reduced pressure,
The residue was purified by Kara 15 chromatography, and the refractive index (
3.0 g of the desired product (pale yellow viscous liquid) of nV) l,5;186 was obtained.

! Reconstruction Example 6 N-(5,5-dichloro-4-pentenyl)-N-(5
- Synthesis of methylisoxazol-3-yl)chloromethanesulfonamide (compound 77) N-(5-methylisoxazol-3-yl)chloromethanesulfonamide 4.0 g (0,010 mol)
Dissolve and hydrogenate 60% in DMF 30m 1 i? 'J' 740.76g (0,019 mol) 'J! a
I added it gradually. After stirring for 2 hours at room temperature.

1.1.5-trichloro-4-pentene 3.3 g (
After 0 dropwise addition of 0,019 mol), the mixture was stirred at 80 to 90°C for 121 hours.

After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate.
The extract was washed with water and dried over anhydrous sodium sulfate. Ethyl #acid was distilled off using an evaporator, and the residue was purified using column chromatography to give a refractive index (ny) of 1-527.
3.4 g of the target product No. 1 (It color viscous compound) was obtained.

Production Example 7 N-(2-chloropyrimidin-4-yl)-N-(5,
Synthesis of 5=dichloro-4-pentenyl) methanesulfonamide (compound 99)
Dissolve in 50 mL 60% sodium hydride 0.6
g (o,ol 5 mol) was added slowly at room temperature. After stirring at room temperature for 1 hour, 3.0 g (0.02 mol) of 2゜4-dichloropyrimidine was added, and the mixture was stirred for 1 hour at room temperature.
After the completion of the reaction, the reaction solution was poured into water.

The extract was extracted with ether, washed with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the remaining liquid was purified by column chroma 1 to graphie, and the refractive index (n-p'')
4.0 g of the target product (pale yellow liquid) of l-5443 was obtained.

The horticultural fungicide of the compound of the present invention contains a sulfonamide derivative as an active ingredient.

Although the compounds of the present invention may be used as such, they are usually used as I[
! A surfactant, a dispersant, an adjuvant, and the like are mixed together and formulated into a powder, a wettable powder, an emulsion, a granule, or a granule according to a conventional method. Suitable 1n forms include, for example, talc,
Solid carriers such as bentonite, clay, kaolin, diatoms, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, etc., 2-propertool.

Examples of surfactants and dispersants include liquid carriers such as xylene, cyclohexanone, methylnaphthalene, and the like.

Dinaphthylmethane disulfonate, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate.

Examples include polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monoalkylate, and the like. Examples of the auxiliary agent include carboxymethyl cellulose. These preparations can be diluted to an appropriate degree and sprayed, or
1rm 1g.

The blending ratio of the active ingredient is selected as appropriate depending on the need, but in the case of powders and granules, it is 0.1 to 20% (ffi amount),
In the case of emulsions and wettable powders, 5 to 80% (spray amount) is appropriate.

The application amount of the am common fungicide of the present invention varies depending on the type of compound used, the tendency of occurrence of the target disease 1, the degree of damage, environmental conditions, the agent 1f1 used, etc., but it can be used as is, like powders and granules. In this case, the active ingredient is 0.1g to 5kg per 10 ares.

It is preferable to appropriately select from the range of 1g to Ikg.
Also, when used in liquid form such as 1L preparation and hydrating powder, 0
．． 1 p pm~10.0OOpptn, evening I or lO~3. It is preferable to appropriately select from the range of OOOppm.

Next, examples of the horticultural fungicide of the present invention will be specifically explained. In the following examples, % indicates the percentage of overlapping.

Example 1 Powder 2% of compound (1), ±5% of diatoms and 93% of clay were uniformly mixed and pulverized to obtain a powder.

Example 2 Wettable powders 50% of compound (2), 45% of diatomaceous earth, 2% of sodium dinaphthylmethane disulfone and 3% of sodium ligninsulfonate were uniformly mixed and ground to prepare a wettable powder.

Example 3 Emulsion An emulsion was prepared by uniformly dissolving 30% of emulsion compound (01), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate TS, and 35% of methylnaphthalene.

Example 4 Granule compound (77) 5%, sodium salt of lauryl alcohol fRW1 ester 2%, sodium lignin sulfonate 5%, carboxymethyl cellulose 2% and clay 8
Mix and grind 6% uniformly. 20 parts by weight of water were added to 80 parts by weight of this mixture, kneaded, processed into granules of 14 to 32 mesh using a press/fli type granulator, and then dried to form granules.

(Effects of the Invention) The horticultural fungicide of the present invention has better performance compared to the above-mentioned known compounds.

It is particularly effective as a control agent for blast disease, and is also effective as a control agent for rice sheath blight, cucumber downy mildew, cucumber powdery mildew, and Japanese mustard rot. For rice blast disease, stem 11111 [shows high activity not only by cloth but also by water th + application, does not cause chemical damage to crops, and has the characteristics of being excellent in residual effect and amphoteric resistance. There is.

Next, the agriculture of the present invention! i The effects of the fungicidal fungicide will be specifically explained using test examples.

Test Example 1 Rice blast disease preventive effect test 20 grains of paddy (variety: Aichi) were sown in self-made pots with a diameter of 90 m, and grown for 3 to 4 weeks in a &l room.

Fourth! A hydrating powder prepared according to Example 2 was diluted with water to an active ingredient concentration of 50 II P m, and 10 ml per L pot was sprayed on the rice seedlings developed by J. After air drying,
A spore suspension of the blast fungus was inoculated and placed in an M room at 25°C. Five days after inoculation, plots were placed and the control value was calculated according to the formula below.

The results are shown in Table 4.

As a comparative drug, the following compound described in Japanese Patent Publication No. 11643/1983 was used.

Comparative drug 1: N-(0-chlorophenyl)
-1! -(3゜3-dichloro-2-pentenyl)methanesulfonamide comparison drug 2: N-(3,4-dichlorophenyl)-N~(3,3-dichloro-2-pentenyl)methanesulfonamide comparison drug 3:N -(P-chlorophenyl)-N-(3
゜3-dichloro-2-pentenyl) methanesulfonamide comparative drug 4: N-(3,3-dichloro-2-
Pentenyl)-N-(0-methoxyphenyl)methanesulfonamide comparative drug 5: N-(3,3-dichloro-2-
pentenyl)-N-phenylmethanesulfonamide comparative drug (3: N-(3,3-dichloro-2-pentenyl)-N-(0-phenylphenyl)methanesulfonamide comparative chestnut j'FJ 7: N-(3 ,3-dichloro-2-pentenyl)-N-(0-tolyl)methanesulfonamide Comparative drug 8:N-(0-chlorophenyl)-N-(3
゜3-Dichloro-2-pentenyl) 2-probensulfonamide Test Example 2 #l Blast disease Pre-watering surface application effect test 1 (Rice seedlings (variety: Aichi M) were transplanted to a white porcelain surface of a 12 cm shuttle.

They were grown in a greenhouse for 3-4 weeks. When the 3rd to 4th liter of rice had developed, a hydrating agent prepared according to Example 2 was applied to the water surface so that the active ingredient was 1 -/lO are. Shi J
A suspension of rice blast fungus Breast 7-1111 was spray-inoculated into a 117-diameter plant, and the plant was placed in a greenhouse at 25°C.

After #511 contact, 13 spots were counted and the control value was calculated according to the calculation formula of Test Example 1.

The results are shown in Section 5A.

Test example 3 Rice sheath blight prevention effect test directly! Paddy rice seeds (variety Nikinanpu) on a 7 cm unglazed pottery
15 seeds each were inserted into the seedlings and grown in UV for 4 to 5 weeks. According to Example 2 for rice seedlings with the fifth leaf developed! 1lI
The wettable powder prepared in II was diluted with water to an active ingredient concentration of 500 ppm, and the mixture was applied to the body using a lomlfi cloth.

Sheath wilt #I21 cultured for 70 days on rice husk bran medium after air drying
The fungus was inoculated at the base of the plant, placed in a one-layer room (28°C), and after 50 days, the height of the lesion formed on the leaf sheath was measured, and the control value was calculated according to the following formula.

The results are shown in Table 6 according to the evaluation criteria below.

Evaluation criteria A class: Control value 90% or more B class: # Less than 80-90% C class:
# Less than 50% to less than 80% D class: # Less than 50% test example 4 Cucumber and disease prevention effect test D cs X
Cucumber seeds (variety:
12 seeds of each seed (Surikata Hanshiro) were sown and grown in the U room for 7 days.

A wettable powder prepared according to Example 2 was diluted with water to a cucumber seedling with developed cotyledons so that the active ingredient concentration was 500 ppm.

Sprayed 10ml per pot. After air-drying, a suspension of cucumber and disease vesicles Y-s was spray inoculated and placed in a greenhouse at 20-22°C. After inoculation 7 [1], the degree of disease onset was investigated according to the following criteria, and the degree of disease onset and control value were determined.

Classification! I! : Small: Medium: Human: Incidence level (%) = Incidence level: Less than 1/3 of the affected area where no disease is observed #1/3 to less than 273 # 273 or more (n'XO) + (n'Xl) + ( n”X2)+(n”X
3) x io.

na2 Number of violets with disease onset level "healthy" nl: Number of leaves with disease severity "small"n": Number of leaves with disease severity r width J n1: Number of leaves with disease severity r large J: n"+n"+n"+n ”The results are shown in Table 7 according to the evaluation JA standard below.

Fraud! i) & Semi-A class: Control value is 90% or more B class: # Less than 80-90% C class:
# Less than 50-80% D class: #5
Vinyl chloride with less than 0% IJ rs X D cs! ! ! Sow 12 Komatsuna seeds in a pot, l! ! It was grown indoors for 711 days. Komatsunayo + with expanded cotyledons? A hydrating agent prepared according to Example 2 was added to i with an active ingredient concentration of 500 p p
1 (diluted with water to 1, and sprayed 10ml per pot. After wind ft, a spore suspension of Brassicaceae black sooty fungus was spray inoculated and placed in the M room of aOt:. The number of lesions was counted and the average number of lesions per leaf was determined, and the control value was calculated using the formula below. Table 8 shows the results of evaluation according to the 21 value standard.

Evaluation J1 quasi-Δ class: Control value is 90% or more Class 8: # Less than 80-90% C class:
# Less than 50-80% D class: #5
Less than 0% test example 5 Komatsuna black soot disease preventive effect test test example 6
Cucumber powdery mildew prevention effect test 9 cs X 9 a
Twelve cucumber seeds (Product H1: Sagami Hanshiro) were sown on the vinyl chloride surface of the celluloid and grown in a colander for 7 days.

A wettable powder prepared by 3I according to Example 2 was diluted with water to an active ingredient concentration of 500 ppm, and 10 ml of the solution was sprayed on cucumber seedlings with cotyledons per pot. After air drying, the cucumber powdery mildew spores were removed at 25-30℃.
I put it in the layer chamber. Contact! The degree of disease onset in the entire pot was investigated using the following criteria for 110 diameter small pots.

1nnWt Onset 4: O: No onset 1: Less than 25% diseased area 2: 25-50% full JI# area 3:
Diseased area of 50 to less than 75% 4: The results of diseased area of 75% or more are shown in Table 9 in number of diseased m.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. an isoxazolyl group optionally substituted with a halogen atom or a lower alkyl group, an isothiazolyl group substituted with a lower alkyl group, an imidazolyl substituted with at least one of an alkylthio group, a phenyl group, and an alkoxycarbonyl group. group, a pyridyl group optionally substituted with a halogen atom or a halogen-substituted alkyl group,
A pyrimidinyl group, a quinolyl group, a quinoxalinyl group, which may be substituted with a halogen atom, a lower alkyl group or an alkylthio group, a pyrazinyl group or a phthalimidoyl group which may be substituted with a lower alkyl group, and R^1 is an alkyl group. , phenyl group, halogen-substituted alkyl group or group ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 and R^3 are the same or different and represent a hydrogen atom or a lower alkyl group, ^3 can also form a ring containing adjacent nitrogen atoms.) ] A sulfonamide derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. an isoxazolyl group optionally substituted with a halogen atom or a lower alkyl group, an isothiazolyl group substituted with a lower alkyl group, an imidazolyl substituted with at least one of an alkylthio group, a phenyl group, and an alkoxycarbonyl group. group, a pyridyl group optionally substituted with a halogen atom or a halogen-substituted alkyl group,
A pyrimidinyl group, a quinolyl group, a quinoxalinyl group, which may be substituted with a halogen atom, a lower alkyl group or an alkylthio group, a pyrazinyl group or a phthalimidoyl group which may be substituted with a lower alkyl group, and R^1 is an alkyl group. , phenyl group, halogen-substituted alkyl group or group ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 and R^3 are the same or different and represent a hydrogen atom or lower alkyl group, and R^2 and R ^3 can also form a ring containing adjacent nitrogen atoms.) ] An agricultural and horticultural fungicide containing a sulfonamide derivative represented by the following as an active ingredient.