JPS6040429B2 - Satucalin derivatives and agricultural and horticultural fungicides containing satsucalin derivatives as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula (where X represents a hydrogen atom, a halogen atom or a lower alkyl group, and R represents an ethyl group or an isopropyl group).

) and an agricultural and horticultural fungicide containing the same as an active ingredient. The general formula (1
), the halogen atom includes chlorine, bromine or iodine, preferably a chlorine atom.

Examples of the lower alkyl group include straight or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl or isopropyl, with methyl being preferred. Examples of the novel saccharin derivatives of this invention include the following.

(1} 2-(2,6-diethylphenyl)-1,2-benzisothiazol-3(2H)-one 1,1-dioxide [2] 2-(2,6-diethylphenyl)-5-chloro 1,2-penzisothiazol-3(2H)-one 1,1-dioxide {3'2-(2,6-diethylphenyl)-6-chloro1,2-benzisothiazol-3(2H)-one 1
・1-dioxide (4} 2-(2,6-diethylphenyl)-5-methyl-1,2-benzisothiazol-3(pan)-one 1
・1-dioxide (5-2-(2,6-diisopropylphenyl)-1
・2-Benzisothiazole-3(2H)-one 1.1
-Dioxide As shown in the following formula, the novel compound (1) according to the present invention is an anthranilic acid derivative represented by the formula (0), for example, 0rg. Syn. Coil. Vol. 0, 5
80 (1943) to obtain a diosalicylic acid derivative, and then the diosalicylic acid derivative was prepared according to the method described in Shigeru et al. 61, 1308 (1928)
and FannacoEd. Sci. 231075 (1
968) (method A), or the 0-sulfobenzoic anhydride derivative (
m) with 2,6-dialkyl-substituted aniline (W) and heating the resulting sulfamomoylbenzoic acid derivative in the presence of a dehydrating agent such as oxychloride.

(Method B). A method B method (In the formula, X and R represent the same rhombus as described above.

) The method for producing the novel saccharin derivative (1) of the present invention will be explained in more detail with reference to Examples.

Example 1 2-(2,6-diethylphenyl)-1,2-benzisothiazole-3(spot)-one 1,1-dioxide■
Dissolve 50 parts of sodium sulfide in 60 parts of boiling water, add 6.5 parts of powdered sulfur to the reddish brown solution, and add a solution of 8 parts of sodium hydroxide dissolved in 20 parts of water.
Cool to 2°C, add 27.5 ml of anthranilic acid, 40 ml of concentrated hydrochloric acid, 100 ml of water, and 1 ml of sodium nitrite.
A diazonium solution prepared by dropping the diazonium solution over 15 minutes at 5℃ or below on the 3.8th night was dropped at 0-6℃ over about 50 minutes, and after the dropping was completed, the vessel was returned to room temperature and lit for 2 hours. .

(During this period, a small amount of ether was added from time to time to suppress foaming.) The reaction mixture was then filtered to remove sulfur, and the dark brown furnace liquor was made acidic by adding 36 g of concentrated hydrochloric acid. The slurry-like wet precipitate is suspended in 200 parts of water, dissolved by adding 20 parts of anhydrous sodium carbide, and then the insoluble matter is separated by furnace. Add concentrated hydrochloric acid to the furnace solution to adjust the pH to 3-4, filter it through the furnace, wash with about 1 sleeve of water, and dry over pentoxide to obtain a melting point of 2.
27.8 g of dithiosalicylic acid was obtained in the form of a yellow-white fine powder having a molecular weight of 80 to 295 mm (decomposed). ■ Add 5 parts of thionyl chloride to 1.5 parts of dithiosalicylic acid, stir at 70°C for 1 hour, distill off the thionyl chloride, and add 25 parts of thionyl chloride to 1.5 parts of dithiosalicylic acid. A solution of 1.5 parts of 2,6-diethylaniline and 1.0 parts of triethanolamine dissolved in 5 parts of benzene was added dropwise to the ice-cooled glass over 5 minutes, and after the dropwise addition was completed, The mixture was heated under reflux for 30 minutes.

After cooling, the reaction mixture was washed with hydrochloric acid for 20 minutes, then with water (50 minutes x 2), and the washing liquid was washed with benzene (10W' x 2
), the extract was combined with the benzene layer, dried over anhydrous sodium sulfate, and the solvent was removed to obtain a yellow-brown clay oil. This includes 20% of benzene and 4% of thionyl chloride.
After heating and refluxing for 3 hours, benzene and thionyl chloride were distilled off, and the brown oily residual sugar was extracted with 15% acetic acid. The mixture was dissolved in 35% hydrogen oxide solution 7 times a week, and stirred at room temperature for 30 minutes and then heated at 10,000 for 2 hours. After cooling, 40 g of water was added to the reaction mixture and filtered, the reddish-brown wet crystals were dissolved in 50 benzene, dried over a small amount of silica gel and anhydrous sodium sulfate, filtered again, and the benzene was removed from the furnace liquid. This gave 1.2 yen of yellowish white crystals. This product was recrystallized from ethanol to obtain the desired compound in the form of colorless needles having a melting point of 213-21,500. (Yield 31.
7%) Elemental analysis value (%) C, 7th, calculated value as 7N03 C, 64.74; day, 5.43; N, 4.44;
S, 10.17 experimental value C, 46.8 days, 5.32
:N, 4.31:S, 10.19 Infrared absorption spectrum (
Nuiol) Skin-1: 1735 (>C=○), 1595
(C=C), 1350, 1310, 1185 (>S02
) Nuclear magnetic resonance spectrum (CDC13) 6ppm: 1.
20 (thin, triple line, J=8.0HZ, -CH2CH3)
2.71 (4 days, quartet, J=8.0 days 2, 1CH2)
7.20-8.28 (7 days, multiplet) ■ of Example 1 above
The following compound was produced according to the method of .

2,2-dithio-5,5-dichlorosalicylic acid, decomposition point 31000 2,2'-dithio-4,4'-dichlorosalicylic acid, decomposition point 311-31〆0 2,2-dithio-5,5'-dimethylsalicylic acid , decomposition point 270-27500 The following compound was produced according to the method (2) of Example 1 above.

2-(2,6-diisopropylphenyl)-1,2-penzisothiazol-3(ga)-one 1,1-dioxide, melting point 256-25800 ■ 0-Sulfobenzoic anhydride 1.85 After heating and refluxing under 50% xylene (Nakataka Azusa), 1.50% of 2,6-jethylaniline was added and the mixture was heated and refluxed for 1 hour.

After cooling, the solvent was distilled off from the reaction mixture to obtain a colorless crystalline residue of 3.40%, which was reconsolidated with methanol-benzene at a ratio of 1:10 to give a decomposition point of 215-2203°.
A colorless prismatic crystal of 0-(2,6-diethylphenylsulfamoyl)benzoic acid having the following formula was obtained. Elemental analysis value (%) C, 7th, calculated value as state 04S C, 61.
24; day, 5.74; N, 4.20; S, 9.62 experimental value C, 61.21: day, 5.75; N, 4.17; S
, 9.95 infrared absorption spectrum (Nuiol) skin-1:
3300 (NH), 1600 (>C=○), 1290,
1155 (>S02) nuclear magnetic resonance spectrum (D6-D
MSO) 6PPm: 1.10 (Mother's Day, Triple Line, J: 8.
0 days 2, 1CH2CH3) 2.70 (4 days, quartet, J
=8.0HZ, one CH2) 7.03 to 8.17 (secondary H,
Multiplet, Arom. H x 70NH) 11.00 (IH,
Singlet, COOH) 0.10 ml of (2,6-diethylphenylsulfamoyl)benzoic acid and 0.5 ml of phosphoryl chloride were heated at ambient temperature of 110 qo for 2 hours.

After cooling, the reaction mixture was poured into 25 ml of ice water, and 25 ml of benzene was added.
Extract by adding
After washing with water and drying with anhydrous sodium sulfate, the solvent was removed from the extract to obtain 0.09 g of yellowish brown powder (yield: 9
4.7%). When this product is recrystallized from ethanol, a colorless powder having a melting point of 213 to 215 qo is obtained. The target compound in the form of rhythm crystals was obtained. Example 2 2-(2,6-diethylphenyl)-6-chloro1.
2-penzisothiazol-3 (2H)-otho1,1-
Dioxide (1) 0.58 of 212-dithio-4-chlorosalicylic acid and 2 of thionyl chloride were added, and the mixture was heated under reflux for 1.5 hours. After stirring, thionyl chloride was distilled off from the reaction mixture.

The dark brown crystalline residue was dissolved in 20% of benzene, and a mixed solution of 0.92% of 2,6-diethylaniline and 5% of benzene was added dropwise over about 1 minute under ice cooling, and the solution was dissolved at room temperature. 1
After heating for 8 minutes and then 10 minutes at 6,000 ℃, the solvent was distilled off, and the residue was suspended in 10 methanol and filtered.
After washing with methanol (2 x 3) and drying, 2.2 is a colorless powder with a melting point of 290-310 qo (decomposition).
-dithio-4,4-dichlorobis(2''-purdiethylbenzanilide) 0.67% was obtained (yield: 57.
8%) Infrared absorption spectrum (Nuicl) arc-1:32
00 (NH), 1640 (C=○) ■ 2,2-dithio-4,4-dichlorobis(2'',6''-diethylbenzanilide) 0.64 hours, with 15' of benzene and 2 units of thionyl chloride After heating the mixture under reflux for 1 hour, the solvent was removed, thionyl chloride, 2' was added, and the mixture was heated for 2 hours.

After cooling, thionyl chloride was distilled off from the reaction mixture, and the residue (brown oil) was dissolved in 30 volumes of benzene and washed with 5% aqueous sodium hydrogen carbonate solution and then with water (10 times [3 times]). After vertically drying with anhydrous sodium sulfate and removing the solvent, a brown oily product of 2-(2,6-jethylphenyl)-16-chloro-1,2-benzisothiazol-3(2H)-one was obtained. 63 evenings were obtained. A portion was recrystallized from isopropyl ether to obtain yellowish brown prismatic crystals having a melting point of 163-165oo. Infrared absorption spectrum (Nu
iol) Kay-1: 1660 (C=0), 1600 (C=
C) ■ 2-(2,6-diethylphenyl)-6-chloro1,2-penzisothiazo-3(ga)-one o
．． After dissolving 6M in acetic acid 5', 35% hydrogen oxide 2
．． 5 was added and heated under reflux for 2 hours.

After cooling, the solution was distilled off from the reaction mixture, and the residue was dissolved in benzene 2
After dissolving in 5' of 5% sodium hydrogen carbonate aqueous solution (
After washing with water (10 parts x 3) and drying over anhydrous sodium sulfate, the solvent was removed from the solution to obtain a yellow oil with a weight of 0.48 cm. This material was dissolved in a small amount of benzene and subjected to silica gel column chromatography.
Elution was carried out with benzene, the eluate was collected, and the solvent was removed from the eluate to obtain 0.31 g of the objective compound as a glassy solid having a melting point of 48-500C. (Yield 47.0%). Infrared absorption spectrum (liquid film) arc-1: 1745 (C=○), 1600 (C=C), 1350,
1290, 1185 (>S02) magnetic resonance spectrum (
CDC13) 6ppm: 1.18 (thin, triple line, J=8
．． 0HZ) 2.67 (4 days, quartet, J=8.0HZ)
7.13 to 8.15 (Square, multiplet) The following compounds were produced according to the method (2) of Example 2 above.

2,2-dithiobis-(2″·6″-diethylbenzanilide), decomposition point 293-295pm, slightly brown powder crystals 2
・2-dithiobis-(2″/6″-diisopropylbenzanilide), decomposition point 306-310q○, slightly brown powder crystals 2,2-dithio-5,6-dichlorobis(2″/6″-diisopropylbenzanilide)
"-diethylbenzanilide), decomposition point 305-306
0○, pale brown powder crystals 2,2-dithio-5,5-dimethylbis(2'',6''-diethylbenzanilide), decomposition point 283-285 qo, slightly brown crystals Following the method of Example 2 (2) above. of compounds were produced.

2-(2,6-diethylphenyl)-1,2-benzisothiazol-3(2H)-one, melting point 116-117
0, colorless needle crystals 2-(2,6-diisopropylphenyl)-1,2-benzisothiazol-3(2H)-one, melting point 165-167o0, yellow crystals 2-(2,6-diethylphenyl) 15-Kuroro 1・
2-penzisothiazol-3(2H)-one, melting point 1
56-158C○, yellow columnar crystals 2-(2,6-diethylphenyl)-5-methyl-1.
2-penzisothiazol-3(pan)-one, melting point 12
0 to 123 oo, light brown crystals The following compound was produced according to the method (2) of Example 2 above.

2-(2,6-diethylphenyl)-5-chloro-1.
2-Benzisothiazol-3(2H)-one 1,1-dioxide, melting point 220-22100, colorless needle crystals Example 3 2-(2,6-diethylphenyl)-5-methyl-1.
2-Benzisothiazol-3(pan)-one 1,1-dioxide 2-(2,6-diethylphenyl)-5-methyl-1.
After dissolving 2.05 ml of 2-penzisothiazol-3(spot)-one in 1 ml of acetic acid, 5 ml of 35% hydrogen peroxide solution was added, stirred at room temperature for 10 minutes, and then heated under reflux for 2 hours. .

After cooling on ice, the reaction mixture was filtered, and the residue was polished on furnace paper with water (5x5) and dried to give 1.80 kg of colorless crystals with a melting point of 194-197q0. Combine the furnace liquid and washing liquid,
Extract with 30 parts of benzene and 10 parts of water, and add the extract to 1 part of water.
After polishing at 0.0° C. and drying over anhydrous sodium sulfate, the solvent was removed from the solution to obtain a yellow viscous oil of 0.20° C. The mixture was combined with the previously obtained colorless crystals, subjected to silica gel column chromatography, dissolved with benzene, the eluate was collected, and the solvent was distilled off from the eluate to obtain 1.75 mm of colorless powder. This product is recrystallized from ethanol with a melting point of 200~
1.65 g of the target compound in the form of colorless needles having a temperature of 202° C. was obtained. (Yield 72.7%) Elemental analysis value % C, 8 days, calculated value as Bu03S C, 65.63; 5.81: N,
4.25: S, 9.73 experimental value C, 65.34: day,
5.70 N, 4.24:S, 9.73 Infrared absorption spectrum (Nuiol) arc-1:1730 (C=○), 16
00 (C=C), 1350, 1305, 1185 (>S
02) Nuclear magnetic resonance spectrum (CDC13) 6ppm:
1.17 (spot, triple line, J=8.0HZ,) 2.67 (
4 days, quartet, J = 8.0HZ,) 2.55 (chihito, singlet) 7.13 to 7.95 (thin, multiplet,) Also, benzene-acetone (10:1) mixture Elute with a solution, collect the eluate, and distill off the solvent from the eluate to obtain a colorless powder of 0.209
was gotten.

This product was recrystallized from ethanol with a melting point of 170-17
0.18 g of 2-(2,6-jethylphenyl)-5-methyl-1,2-benzisothiazol-3(pan)-one 1-oxide was obtained as colorless columnar crystals having a molecular weight of 300. Elemental analysis value (%) C. 8th, Calculated value as Bu02S C,
68.98; Sun, 6.11, N, 4.47:S, 10.
23 Experimental value C, 67.51; Sun, 5.86: N, 4.
36;S, 9.98 infrared absorption spectrum (Nuiol
) Skin-1: 1720 (C=0), 1605 (C=C),
1120 (S→〇) nuclear magnetic resonance spectrum (CDC13
) 6ppm: 1.13 (Chichi, Mie Line, J=8.0HZ
) 1.18 (milk day, three solid line, J=8.0HZ) 2.50
(Group, 5 lanes, J = 8.0 days 2) 2.53 (Thin, single line) 2.67 (However, 5 lanes, J = 8.0 HZ) 7.13~7
．． 93 (thin, multiple lines) The following compound was produced according to the method of Example 3 above.

2-(2,6-diethylphenyl)-1,2-penzisothiazol-3(pan)-one 1-oxide, melting point 16
0 to 161°C, colorless prismatic crystals 2-(2,6-diisopropylphenyl)-1,2-penzisothiazole-3(2H)-one 1-oxide,
The novel saccharin derivative (1) of the present invention is useful as a fungicide for agriculture and horticulture.

Traditionally, organic chemicals and antibiotics have been widely used to treat rice sheath blight, and pentachloronitrobenzene (hereinafter abbreviated as PCNB) to treat damping off, but these are not necessarily safe for livestock, fish, shellfish, and crops. No, no.

For example, organic antibacterial agents have a strong bactericidal effect, but have chronic toxicity to humans and animals, and are harmful to rice yields. Antibiotics have low toxicity but lack residual efficacy, and PCNB also requires control of seedlings. However, there are problems such as growth problems, and there is a strong desire for the development of new and improved drugs.

The present inventors have demonstrated that the compound having the general formula (1) has excellent control effects against various plant diseases, and has particularly shown excellent efficacy and residual efficacy in controlling sheath blight, which is a major disease of rice. It was also found that the toxicity of this method against livestock, fish, and shellfish was extremely low, and no chemical damage was observed to the target crops or other crops.

When the compound of the present invention is used as a fungicide for agriculture and horticulture, it is usually applied directly or mixed with a carrier and, if necessary, other adjuvants, to form an agrochemical formulation.
It is prepared and used in the form of formulations, such as powders, coarse powders, granules, wettable powders, emulsions, and aqueous solutions. Suitable solid carriers include inorganic materials such as clay, talc, clay, kaolin, bentonite, clay, calcium carbonate, diatoms, silicic anhydride, and synthetic calcium silicates.

Suitable carriers include aliphatic hydrocarbons such as ligroin, kerosene, and key oil; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; chlorinated hydrocarbons such as chloroform and dichloroethane; Examples include alcohols such as propanol and n-butanol, ketones such as acetone, methylethiketone, and cyclohexanoso, and amine derivatives such as ethanolamine and dimethylformamide. In addition, various nonionic and ionic surfactants are used to improve the properties of formulations or enhance their biological effects, as well as polymeric compounds such as sodium alginate, carboxymethylcellulose, methylcellulose, and vorivinyl alcohol, as well as sulfite bran liquid. You may add auxiliary agents such as.

It is preferable that other fungicides are added to the above-mentioned preparation of the present invention in order to spread the bactericidal spectrum, and in some cases, a synergistic effect can be expected.

Examples of such other fungicides include, for example, methyl 1-(butylcarbamoyl)-2-penzimidazole car/dimate; methyl benzimidazole-2-car/dimate; 1,2-bis(5-methoxy carbonyl)-2-thiouridobenzene; 3-hydroxy-5-methylinxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid; 0,0-diisopropyl-S-benzyl phosphorothioate; PCN
B; Kasugamycin: Blasticidin S; 4, 5, 6
- Bactericidal agents such as 7-tetrachlorophthalide may be mentioned, but are not limited to these. Furthermore, it can be used in combination with other insecticides, acaricides, herbicides, plant growth regulators, nematicides, bactericides, fertilizers, etc., if necessary. The above formulation is used by spraying 1 to 1,000 doses, preferably 5 to 200 doses of the active ingredient per 10 ares on the leaves of crops, or by rinsing the soil or applying it in water.

Next, examples of formulations of the agricultural and horticultural fungicides of the present invention will be given.

In the text, all parts simply refer to parts by weight. Formulation Example 1 Powder Compound No. 1 3 parts, talc 47 parts Clay 47
1 part and 3 parts of white carbon are uniformly mixed in a mixer and ground in a hammer mill to obtain a powder.

Formulation example 2 Wettable powder Compound No. 2 Compound 5 Ikarito, White carbon 5 parts,
5 parts of Solbol AC-249 (trade name, Toho Kagaku Co., Ltd.) and 4 parts of clay are uniformly mixed in a mixer and ground in a hammer mill to obtain a wettable powder.

Formulation Example 3 Granules 5 parts of Compound No. 3, 20 parts of bentonite, 1 part of calcium lignin sulfonate and 74 parts of clay were mixed, an appropriate amount of water was added and kneaded, and after granulation using a screw extrusion type granulator. Granules are obtained by drying and sizing.

Next, a test example showing the effect of the compound of the present invention as an agricultural and horticultural fungicide will be given.

The test drug was manufactured according to Formulation Example 2, and a wettable powder containing 50% of the compound of the present invention was used. Test Example 1 Rice Monge Disease Control Test Rice seedlings at the 4th to 5th leaf stage (variety: Kogane Nishiki) were sprayed with 300 and 10 pm test chemicals in 3 pots and 30 on a desk, and left at room temperature for 2 hours. After that, in advance, Pelli
4 to 5 oat grains cultured with C. arasasakii) were placed near the stalks of rice plants and transferred to a temperature of 25 to 270 °C, and 10 days after inoculation, the degree of disease onset was investigated by the height of lesion formation (skin). .

The results are shown in Table 1. Table 1 Test Example 2 Cucumber seedling damping-off control test Seedling damping-off fungus (Rhiz
octoniasolam) into the soil, put this soil in a pot with a diameter of 12 skins, sow 20 cucumbers (variety: Sagami Hanjiro), and then add 500 and 250 ppm supply reagent solution from above to the pot in 3 batches. I rinsed at the same rate as before.

After keeping 25 pots at a temperature of ○ for two weeks, the number of seedlings (plants) affected by seedling damping-off was investigated. One ward has three lotuses, and the total value is shown in Table 2.

Table 2

Claims (1)

[Claims] 1 Has a general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a hydrogen atom, a halogen atom, or a lower alkyl group, and R_1 represents an ethyl group or an isopropyl group.) Satucalin derivative. 2 The active ingredient is a saccharin derivative having the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. An agricultural and horticultural fungicide.