JPS6241228B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () [In the formula, A] represents a ring-constituting residue of a nitrogen-containing saturated 5- or 6-membered heterocycle containing at least one nitrogen in the ring, n represents the number of substituted X (an integer of 1 to 4),
X represents each of hydrogen, halogen, and nitro groups, and may be the same or different from each other]; agricultural and horticultural disease control agents containing these as active ingredients; and the general The present invention relates to a method for producing a compound represented by formula (). 1,2-benzisothiazolin-3-one 1,
Since it was discovered that derivatives of 1-oxide are useful as control agents for agricultural and horticultural diseases, and are particularly effective against rice blast, many related derivatives have been synthesized and tested. Typical examples of these are Publication No. 38080 of 1973 and Publication of Special Publication No. 49 of 1973.
Publication No. 37247 etc. can be mentioned. As a result of further research into new derivatives of this family of compounds, the present inventors have discovered a novel compound with the general formula A compound represented by () (hereinafter referred to as "compound of the present invention") was achieved. In other words, it is commonly effective against two of the three major diseases of rice, rice blast, leaf blight, and sheath blight, and is also effective against Chinese cabbage soft rot, which is an important disease of vegetables. The present invention has been completed as a new type of drug with unprecedented wide application and high safety. Hereinafter, the manufacturing method, application method, formulation examples, medicinal efficacy, etc. of the compound of the present invention will be explained in detail in order. The compound of the present invention has the following general formula () [In the formula, A is the same as above] An N-formyl nitrogen-containing heterocyclic compound;
The following general formula () [In the formula, n and Obtained by reaction.

[Table] This reaction is generally carried out in an organic solvent or using the general formula ()
The reaction is carried out using an excess amount of the compound shown as a solvent. It is convenient for the compound represented by the general formula () to be used in advance as an anhydrous alkali metal salt, alkaline earth metal salt, or tertiary amine salt, as shown in Formula 1. After adding it to the reaction solution in the form of the free acid shown by It is also possible to use a method in which the salt is formed by Next, examples of reactive derivatives of the hydroxyl group of the oxygen acid used in this reaction include phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, and phosphorus pentachloride. phosphorus chloride, phosphate ester halogenide, phosphite ester halogenide, phosphonic acid halogenide, phosphinate halogenide,
Thionyl chloride, sulfuryl chloride, thionyl bromide,
Sulfuryl bromide, phosgene, trichloromethyl chloroformate, chlorsulfonic acid, chlorosulfonic acid ester, trimethylchlorosilane, dimethyldichlorosilane, trichloromethylsilane,
Acid halogenides of various acids, strong acid anhydrides, sulfonic anhydrides, etc.
Mixed acid anhydrides that can be formed between dialkyl sulfuric acid, various organic acids and inorganic acids, such as mixed acid anhydrides that can be formed between carboxylic acids and sulfonic acids, sulfuric acid, or carbonic acid, various active esters, etc. These include, but are not limited to. These active derivatives of oxygen acids react with the compound represented by the general formula () in the reaction of formula 1 above to form the general formula

A formiminium cation, which is extremely reactive toward nucleophiles, is formed in the intermediate, and this is expressed by the general formula ().
Finally, the general formula () is obtained by reacting with the salt of the compound of
The mechanism for producing the stable compound of the present invention shown in is considered as one of the possible reaction mechanisms. The above reactive derivatives of oxyacids are usually used in an amount of equivalent to 2 equivalents based on the strong acid generated when the above reactive derivatives are hydrolyzed, based on the salt of the compound of general formula (). is common. Incidentally, a base may be appropriately added in order to neutralize the strong acid generated by the reaction and to allow the reaction with the saccharin salt to proceed smoothly. As the organic solvent used in this reaction, in addition to those mentioned above, any organic solvent that does not participate in the reaction and can dissolve the raw materials or products relatively well can be conveniently used. For example, dichloromethane, chloroform, carbon tetrachloride, acetone, benzene, toluene, ethyl ether, isopropyl ether, acetonitrile, tetrahydrofuran, dioxane, etc. can be used. Reaction temperature is -50℃~100℃, preferably -15℃
The reaction is usually carried out at ~30°C and the reaction time is from several tens of minutes to over ten hours. After the reaction, the target product can be easily isolated by conventional methods. For example, after the solvent is distilled off, water is added to precipitate the crude product, or the inorganic salt is separated by dissolving it in an organic solvent, the solvent is distilled off to obtain a crude product, and this is dissolved in an appropriate organic solvent. A purified product can be obtained by recrystallization. EXAMPLES Next, examples of synthesizing the compounds of the present invention will be more specifically shown in Examples, but the present invention is not limited thereto. Example 1 2-{2'-[(morpholinomethyleneamino)sulfonyl]benzoyl}-1,2-benzisothiazolin-3-one Production of 1,1-dioxide 3 ml of N-formylmorpholine and anhydrous saccharin sodium in 10 ml of dichloromethane 2.05 g was added, and the mixture was cooled to -30° C., and while stirring, 1.65 ml of a 30% phosgene in carbon tetrachloride solution (W/V%) (corresponding to about 5 mmol as phosgene) was added. Approximately 1
After raising the temperature to room temperature for an hour, stirring was continued at room temperature for 2 hours. After the solvent was distilled off under reduced pressure, water was added to the remaining oil and stirring was continued under ice cooling to crystallize the oil. This was filtered, thoroughly washed with water, and dried to obtain 1.70 g of white crystals (yield: 73.4%).
Decomposition point 160-169℃. The crude crystals were recrystallized from acetone to obtain white needle-like crystals with a decomposition point of 173-175°C. NMR spectrum (DMSO- _d6 -TSP) δ:
8.55-7.65 (9H, m, aromatic ring and methine proton); 3.575 (broad s); 3.52 (s) (total 8H,

[Formula] ) IR spectrum (Nujol) cm ^-1 (3500 to 1400
and only the main absorption bands other than Nujol between 1000 and 600 cm ^-1 are listed. Information between 1400 and 1000 cm ^-1 is omitted due to complexity. The same applies to the following compounds. ): 3100, 1766, 1706, 1626, 947, 881,
862, 804, 779, 749, 715, 672, 652, 639,
600 Mass spectrum: molecular ion peak M ⁺ =463 was detected. Elemental analysis value C ₁₉ H ₁₇ N ₃ O ₇ S ₂ (463.49) Calculated value C 49.24%, H 3.70%,
N 9.07%, S 13.83% Analysis value C 49.42%, H 3.75%,
N 8.79%, S 13.70% Example 2 6 ml of N-formylmorpholine and 4.2 g of anhydrous saccharin sodium were added to 20 ml of dichloromethane, cooled to -40°C, and 1.2 g of thionyl chloride was added thereto while stirring. A similar operation yielded 3.54 g of white crystals (yield 76.4%).
The IR and NMR spectra of this product matched those of the compound obtained in Example 1. Example 3 N-formylmorpholine in 50 ml of dichloromethane
11.5 g and 20.5 g of anhydrous saccharin sodium were added, and the mixture was cooled to 3°C. When 5.2 g of phosphorus oxychloride was added thereto while stirring, the internal temperature rose to 6°C. Thereafter, the mixture was stirred at room temperature for 2 hours, and the same procedure as in Example 1 was performed to obtain 13.17 g (56.8%) of white crystals. The IR and NMR spectra of this substance completely matched those of the compound obtained in Example 1. Example 4 6 ml of N-formylmorpholine, 3.66 g of anhydrous saccharin and 2.02 g of triethylamine were added to 20 ml of dichloromethane, cooled to -20°C, and 1.81 g of phosphorus tribromide was added thereto while stirring, and the following was carried out in Example 1.
In the same manner as above, 2.6 g (56.1%) of white crystals were obtained. The IR and NMR spectra of this substance matched those of the compound obtained in Example 1. Example 5 Preparation of 2-{4'-chloro-2'-[(morpholinomethyleneamino)sulfonyl]benzoyl}-6-chloro-1,2-benzisothiazolin-3-one 1,1-dioxide Add N to 10 ml of dichloromethane -Formylmorpholine
Add 10 ml, 2.39 g of 6-chlorosaccharin and 1.01 g of triethylamine, cool to -40°C, add 0.6 g of thionyl chloride to this with stirring, and add about 1 g of thionyl chloride.
The temperature was raised to 0° C. over an hour, and the mixture was stirred at room temperature for 3 hours. Dichloromethane is distilled off and the remaining oil is poured with ice water.
The white crystals precipitated by adding 80 ml were washed with methanol and dried to obtain 1.25 g of white crystals. Decomposition point 201-203℃. Recrystallize from acetone to reach decomposition point
White crystals with a temperature of 206-208°C were obtained. NMR spectrum (DMSO-d6-TSP) δ:
8.80-7.63 (7H, m, aromatic ring and methine proton); 3.64 (broad s) and 3.57 (s) (total
8H,

[Formula] ): IR spectrum (Nujol) cm ^-1 : 3100, 1764,
1709, 1624, 1589, 949, 882, 864, 838,
800, 762, 727, 676, 667, 640, 604 Elemental analysis value C ₁₉ H ₁₅ N ₃ O ₇ S ₂ Cl (533.37) Calculated value C 42.79%, H 2.83%, N 7.88% Analysis value C 42.98%, H 2.76%, N 7.93% Example 6 2-{4'-nitro-2'[(morpholinomethyleneamino)sulfonyl]benzoyl}-6-nitro-1,2-benzisothiazolin-3-one 1,1-dioxide Production: Add 300 mg of 6-nitrosactucarin (melting point 204-205°C), 1 ml of N-formylmorpholine and 135 mg of triethylamine to 3 ml of dichloromethane to give -30
Cool to ℃ and add thionyl chloride to this with stirring.
After adding 79 mg, the same procedure as in Example 1 was carried out to obtain 241 mg of pale yellow crystals having a decomposition point of 129 to 132°C.
This was recrystallized from acetone, with a decomposition point of 139-140℃.
Crystals showing the following were obtained. NMR spectrum (DMSO−d6−TST) δ: 8.88
~8.07 (7H, m, aromatic ring and methine proton); 3.70 ~ 3.28 (8H, m,

[Formula] ) IR spectrum (Nujol) cm ^-1 : 3075, 1739,
1613, 1538, 1440, 913, 892, 862, 811,
781, 739, 718, 669, 662, 634, Elemental analysis value C ₁₉ H ₁₅ N ₅ O ₁₁ S ₂ (553.49) Calculated value C 41.23%, H 2.73%, N 12.65% Analysis value C 41.54%, H 3.40 %, N 12.58% 1,2-benzisothiazolin-3-one 1,1 of the present invention synthesized by the above production method
Specific examples and physical properties of -dioxide derivatives are shown in Table 1, but the present invention is not limited thereto.
In addition, in the table

[Formula]

[Table] 1,2-benzisothiazoline-3- of the present invention
On 1,1-dioxide derivatives exhibit antibacterial activity against a wide range of pathogens of agricultural and horticultural crops, and have particularly excellent control effects against rice blight, rice blast, Chinese cabbage soft rot, and the like. In order to use the compound of the present invention as an agricultural and horticultural fungicide, the compound of the present invention may be used as it is or in water,
Dilute with solid powder or other suitable carrier,
If necessary, auxiliary agents such as a spreading agent may be added, or various liquid or solid carriers may be mixed using a method commonly used in agricultural chemical manufacturing, and if necessary, a wetting agent or a spreading agent may be added. By adding auxiliary agents such as dispersants, emulsifiers, and fixing agents, it can be used in the form of formulations such as wettable powders, solutions, emulsions, powders, and granules. In producing these preparations, the liquid carrier used is one that serves as a solvent for the compound of the present invention or one that can be dispersed or dissolved with the aid of an auxiliary agent. For example, kerosene, dioxane, acetone, dimethyl sulfoxide, animal and vegetable oils, and surfactants, and solid carriers such as clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, calcium bicarbonate, and the like are used. Additives and active ingredients may vary within wide limits. When used as a liquid, the appropriate concentration in the liquid is 10 ppm to 500 ppm, and when used as a powder or granule, it is desirable to contain the compound of the present invention in the range of 1% to 20%. It is preferable to apply the compound of the invention in an amount of 0.1 kg to 10 kg per 10 are. Furthermore, the pesticidal agent of the present invention can be used in combination with known bactericides, insecticides, herbicides, plant growth regulators, or general fertilizers. Next, the 1,2-benzisothiazoline of the present invention
Examples of formulations in which 3-one 1,1-dioxide derivatives are used as agricultural and horticultural fungicides are shown, but the present invention is not limited thereto. Formulation Example 1 Granule Compound of the Invention No. 1 8 parts by weight Clay 89 Carboxymethyl cellulose 3 The above ingredients are mixed, an appropriate amount of water is added, kneaded, and then dried to obtain a granule composition. Sprinkle 3 kg per 10 are. Formulation example 2 Wettable powder Compound No. 2 of the present invention 20 parts by weight Clay 10 Diatomaceous earth 65 Lignin sulfonic acid 3 Polyoxyethylene alkyl allyl ether
2. Prepared by uniformly mixing and pulverizing the above component substances,
Make a hydrating powder composition and use it at a specified concentration per 10 ares.
Spray 100-150 times. Formulation Example 3 Powder Invention Compound No. 3 3 Parts Calcium Stearate 1 Silicic Anhydride Powder 1 Clay 48 Talc 47 A powder composition prepared by grinding and mixing the above is sprinkled at 4 kg per 10 ares. Next, the excellent efficacy of the compound of the present invention as an agricultural and horticultural disease control agent will be demonstrated through test examples. Test Example 1 Rice leaf blight control test (water surface application) 8 parts of the compounds shown in Table 1, 89 parts of clay, and 3 parts of carboxymethyl cellulose were pulverized and mixed, an appropriate amount of water was added, kneaded and molded, and dried 8% Granule compositions were prepared for each test compound of the present invention. The rice used in the test was grown in a 1/5000-area pot, and a predetermined amount of each of the above granules was applied to the soil surface inside the pot just before heading. Granule application for inoculation of rice leaf blight fungus
Ten days later, 10 ⁸ bacteria/ml was inoculated by single needle injection. In the investigation, the lesion length was measured on a total of 50 inoculated leaves in 3 pots in each district on the 10th day after inoculation, the control value was calculated using the following formula, and chemical damage was also observed and investigated at the same time. Control value (%) = (1 - average lesion length in sprayed area/average lesion length in non-sprayed area) x 100 The test results are shown in Table 2.

[Table] Commercially available products were used.
Test Example 2 Rice leaf blight control test (spraying application) A 3% powder composition prepared by pulverizing and mixing 3 parts of the compound shown in Table 1 and 97 parts of talc was prepared for each test compound of the present invention. The rice I tried was
The plants were cultivated in 1/5000 are pots, and a predetermined amount of each of the above-mentioned powders was applied just before heading. Inoculation of rice bacterial leaf blight was carried out by single needle inoculation at 10 ⁸ bacteria/ml on the day of chemical application. The survey was conducted on the 10th day after inoculation by measuring the inoculated leaves in 3 pots in each district.
The lesion length was measured for 50 plants, the control value was calculated using the formula in Test Example 1, and the chemical damage was also observed and investigated at the same time. The test results are shown in Table 3.

【table】

[Table] *A commercially available product containing 6% nickel dimethyldithiocarbamate was used as the control drug.
Test Example 3 Rice blast control test 10 parts of the compound shown in Table 1, 87 parts of clay, and 3 parts of carboxymethyl cellulose were pulverized and mixed, an appropriate amount of water was added, kneaded, molded, and dried to form a 10% granule composition. A test sample of the compound of the present invention was prepared.
The rice used in the test was grown in a 1/5000-area pot, and at the 6-leaf stage, a predetermined amount of each of the above granules was applied to the soil surface inside the pot. One week after application, a spore suspension of the rice blast fungus was uniformly inoculated by spraying, and the plants were allowed to stand overnight in a humid room at 24°C to infect the plants, and then transported to a greenhouse to induce disease. The investigation was carried out 7 days after inoculation, and the number of lesions was counted, and the control value was calculated using the following formula, and chemical damage was also observed and investigated at the same time. Control value (%) = (1 - average number of lesions in sprayed area/average number of lesions in non-sprayed area) x 100 The test results are shown in Table 4.

[Table] was used.
Test example 4 Rice blast control test (spraying on foliage) Eight seedlings were grown in a resin pot with a diameter of 6.5 cm.
Using rice seedlings in the leaf stage, prepare a chemical solution by dissolving and diluting the compounds shown in Table 1 to the specified concentration, spraying 35 ml per 3 pots with a spray gun, and after air-drying for 24 hours.
The plants were placed in a humid chamber at ℃, uniformly inoculated with a spore suspension of blast fungus, kept in a humid chamber overnight, and then transferred to an artificial climate chamber to induce disease. Seven days after inoculation, the number of diseased lesions was counted, and the control value was calculated using the formula in Test Example 3. The test results are shown in Table 5.

[Table]
Test Example 5 Chinese cabbage soft rot control test A susceptible Chinese cabbage variety (Matsushima No. 1) was directly sown and prepared in a field where Chinese cabbage soft rot was common. The test plot was divided into 3 sections with each section having an area of 10 ^m2 , and the number of plants planted was 1 section.
The number of stocks was set at 25. A chemical solution having a predetermined concentration was prepared by dissolving the compound shown in Table 1 in a small amount of an organic solvent and suspending it in water. Chemical spraying is the first sign of soft rot disease7
3 times every other week from 1 day later, total 390 per 10 ares
Spread. Disease onset and drug damage surveys were conducted 14 days after the final spraying.
Plants with water-soaked, softened outer lower leaves were counted, and the control value was calculated using the formula * below, and chemical damage was also observed and investigated at the same time. The test results are shown in Table 6.

【table】

[Table] 〓 Number of strains with common disease 〓
** The control drug used was a commercially available product containing basic copper chloride, 84.1% (50.0% as copper).

Claims (1)

[Claims] 1 Formula () [In the formula, A] represents a ring-constituting residue of a nitrogen-containing saturated 5- or 6-membered heterocycle containing at least one nitrogen in the ring, n represents the number of substituted X (an integer of 1 to 4),
X represents a hydrogen, halogen, or nitro group, and may be the same or different. 2 formula () [In the formula, A] represents a ring-constituting residue of a nitrogen-containing saturated 5- or 6-membered heterocycle containing at least one nitrogen in the ring, n represents the number of substituted X (an integer of 1 to 4),
X represents each of hydrogen, halogen, and nitro groups, and may be the same or different.] An agricultural and horticultural disease control agent characterized by containing a compound represented by the following as an active ingredient. 3 General formula () [In the formula, A〓 represents a ring-constituting residue of a nitrogen-containing saturated 5- or 6-membered heterocycle containing at least one nitrogen in the ring] and the following general formula () [In the formula, n represents the number of substituted X (an integer of 1 to 4), X represents hydrogen, halogen, or nitro group,
The following general formula () is characterized by reacting a salt of a compound represented by [In the formula, A] represents a ring-constituting residue of a nitrogen-containing saturated 5- or 6-membered heterocycle containing at least one nitrogen in the ring, n represents the number of substituted X (an integer of 1 to 4),
X represents a hydrogen, halogen, or nitro group, and may be the same or different.