JPS6241229B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula () [In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different, and 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], agricultural and horticultural disease control agents containing these compounds as active ingredients, and The present invention relates to methods for producing these compounds. 1,2-benzisothiazolin-3-one 1,
Since it was discovered that 1-dioxide derivatives 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. Among them, 3-allyloxy-1,2-benziisothiazole and 1,1-dioxide are in practical use as excellent anti-rotation agents (Japanese Patent Publication No. 45-38080 and Japanese Patent Publication No. 49-49). Publication No. 37247). As a result of further studies on new derivatives of this family of compounds, the present inventors have discovered that they have unexpectedly excellent anti-potato root blight and anti-leaf blight effects, as well as a compound that also has a control effect on vegetable diseases. A compound represented by the above general formula () (hereinafter referred to as "the compound of the present invention") was obtained. In other words, this new type is effective against two of the three major rice diseases, 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 to obtain a drug that has a wide range of uses and a high degree of safety that have never been seen before. 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, R ₁ and R ₂ are the same as above] and the following general formula () A salt of a compound represented by the formula [where n and It is synthesized by reacting the hydroxyl group of the compound in the presence of a reactive derivative. This reaction formula is shown below. [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 to use the compound represented by the general formula () as an anhydrous alkali metal salt, alkaline earth metal salt, or tertiary amine salt in advance as shown in Formula 1. After adding it to the reaction solution in the form of the free acid shown, a suitable base as a salt-forming reagent such as a tertiary amine such as triethylamine or an inorganic base such as alkali carbonate or alkali bicarbonate is added to the reaction solution. A method of forming salt can also be used. Next, examples of reactive derivatives of the hydroxyl group of the oxygen acid used in this reaction include phosphorus trichloride, phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, phosphorus pentabromide, and phosphate ester halogens. Nido, phosphite halogenide, phosphonic acid halogenide, phosphinate halogenide, thionyl chloride, sulfuryl chloride, thionyl bromide, sulfuryl bromide,
Phosgene, trichloromethyl chloroformate,
Chlorosulfonic acid, esters of chlorosulfonic acid, trimethylchlorosilane, dimethyldichlorosilane, trichloromethylsilane, organic sulfonic acid chloride, organic sulfinic acid chloride, organic sulfenic acid chloride, chloroformic acid ester, carboxylic acid chloride, etc. As acid halides of oxygen acids, carboxylic acid anhydrides, acid anhydrides of strong acids such as sulfuric anhydride, active esters of strong acids such as dialkyl sulfuric acid, and mixed acid anhydrides that can be formed with various organic acids and inorganic acids. Examples include, but are not limited to, mixed acid anhydrides formed between carboxylic acid and sulfonic acid, sulfuric acid, or carbonic acid. The reactive derivatives of these acids react with the compound represented by the general formula () in the presence of a salt of the compound represented by the general formula () to form the following general formula [formula] [where Y is the dissociative property of the above oxygen acid] A highly reactive cation represented by the residue excluding the hydrogen atom is generated, which reacts with the compound of the general formula (), and finally the compound represented by the general formula () is produced as a stable target compound. It is thought that it is generated. The above reactive derivatives of oxygen acids are usually used in an amount of equivalent to 2 equivalents based on the strong acid generated when the reactive derivatives of the above acids are completely hydrolyzed, relative to the salt of the compound of general formula (). is common. Note that a base may be appropriately added in order to neutralize the strong acid produced by the reaction so that the reaction with the compound of general formula () proceeds smoothly. In addition to the above-mentioned organic solvents, any organic solvent that does not participate in the reaction and can dissolve the raw material compounds and products relatively well can be conveniently used in this reaction. 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 reaction,
Either the solvent is distilled off and water is added to precipitate the crude product, or the inorganic salt is separated by dissolving it in an organic solvent, and the solvent is distilled off to obtain a crude product. A purified product can be obtained by recrystallizing from. EXAMPLES Next, specific synthesis examples of the compounds of the present invention are shown in Examples, but the present invention is not limited thereto. Example 1 2-{2'-[(dimethylaminomethyleneamino)
Sulfonyl]benzoyl}-1,2-benzisothiazolin-3-one Production of 1,1-dioxide Add 4.2 g of anhydrous saccharin sodium and 6.5 ml of dimethylformamide to 22 ml of dichloromethane.
The mixture was cooled to 0.degree. C. and 1.19 g of thionyl chloride was added thereto while stirring. After raising the temperature to room temperature in about 1 hour, the mixture was stirred at room temperature for 1 hour. After distilling off dichloromethane, add 100 ml of ice water to the residue, stir, filter the precipitated crystals, wash with water, and dry to obtain 3.64 g (86.4 g) of white crystals with a decomposition point of 169-173°C.
%) was obtained. This was recrystallized from acetone to obtain crystals (acicular) having a decomposition point of 183-185°C. NMR spectrum (DMSO- _d6 -TSP) δ: 8.54
~7.69 (9H, m, aromatic ring and methine proton); 3.12 (3H, s, _-CH3 ; 2.90 (3H, s,
-CH ₃ ) IR spectrum (Nujol) cm ^-1 (However, only the main absorption bands other than Nujol between 3500 and 1400 and 1000 and 600 cm ^-1 are listed. The range 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 ⁺ =421 detected Elemental analysis value C ₁₇ H ₁₅ N ₃ O ₆ S ₂ (421.45): Calculated value
C48.45%, H3.59%, N9.97%, S15.21% Analysis value
C48.31%, H3.60%, N9.83%, S15.18% Example 2 Add 10.25 g of anhydrous saccharin sodium and 25 ml of dimethylformamide to 25 ml of dichloromethane.
Add 2.55 g of phosphorus oxychloride to this while stirring at 15°C.
added. Thereafter, by the same operation as in Example 1
10.1 g of white crystals were obtained. This material is IR and
Comparison of NMR spectra showed complete agreement with the compound obtained in Example 1. Example 3 Add 2.05 g of anhydrous saccharin sodium and 3 ml of dimethylformamide to 10 ml of dichloromethane, cool to -40°C, and add 1.65 ml of 30% phosgene in carbon tetrachloride solution (W/V%) (5 mmol of phosgene) to this while stirring. ) was added. Hereinafter, Example 1
The same operation as above was carried out to obtain 1.76 g (83.5%) of white crystals. Comparison of NMR and IR spectra of this product showed complete agreement with the compound obtained in Example 1. Example 4 Add 4.1 g of anhydrous saccharin sodium and 8 ml of dimethylformamide to 8 ml of dichloromethane, and add -30
Cool to ℃ and add 915 mg of phosphorus trichloride to this while stirring.
added. Thereafter, the same procedure as in Example 1 was carried out to obtain 3.65 g (86.7%) of white crystals. Comparison of the IR and NMR spectra of this product showed complete agreement with the compound obtained in Example 1. Example 5 Add 2.05 g of anhydrous saccharin sodium and 6 ml of dimethylformamide to 5 ml of dichloromethane, and -
Cool to 50℃ and add 416 phosphorus pentoxide to this while stirring.
After that, the same procedure as in Example 1 was carried out to obtain 3.15 g (74.7%) of white crystals. This product is IR and
Comparison of NMR spectra showed complete agreement with the compound obtained in Example 1. Example 6 2-{2′-[(diethylaminomethyleneamino)
sulfonyl]benzoyl}-1,2-benzisothiazolin-3-one Production of 1,1-dioxide 4.2 g of anhydrous saccharin sodium was dissolved in 12 ml of diethylformamide, cooled to -40°C, and 1.18 g of thionyl chloride was added with stirring. Thereafter, 4.0 g (89.3%) of white crystals having a decomposition point of 186 to 187 DEG C. were obtained by the same operation as in Example 1. This product was recrystallized from acetone to obtain a pure product with a decomposition point of 194-195°C. NMR (DMSO- _d6 -TSP) δ: 8.47-7.67
(9H, m, aromatic ring and methine proton);
3.36 (2H, q, J=7Hz, _-CH2 - _CH3 ); 3.43
(2H, q, J=7dl, _-CH2 - _CH3 ); 1.18
(3H, t, J=7Hz, -CH ₂ -CH ₃ ); 1.02
(3H, t, J=7Hz, _-CH2 - _CH3 ). IR spectrum (Nujol): 3100, 1765, 1712,
1628, 957, 884, 816, 792, 773, 754, 738,
716, 676, 648, 606 Elemental analysis value C ₁₉ H ₁₉ N ₃ O ₆ S ₂ (449.50): Calculated value C50.77%, H4.26%, N9.35% Analysis value C49.02%, H4.12 %, N8.90% Example 7 2-{4'-chloro-2'-[(dimethylaminomethyleneamino)sulfonyl]benzoyl}-6-
Chlor-1,2-benzisothiazoline-3-
Production of 1,1-dioxide Add 2.39 g of 6-chlorosacchulin (melting point 216-218°C) and 1.01 g of triethylamine to 12 ml of dimethylformamide, cool to -50°C, add 0.6 g of thionyl chloride with stirring, and then Example 1
The white precipitate obtained in the same manner as above was filtered, washed with cold methanol and dried to obtain 1.92 g of white crystals with a decomposition point of 198-199°C. This was recrystallized from acetone to obtain crystals with a decomposition point of 201-202°C. NMR spectrum (DMSO- _d6 -TSP) δ: 8.80
~7.63 (7H, m, aromatic ring and methine proton); 3.12 (3H, s, _-CH3 ); 2.90 (3H,
s, _-CH3 ) IR spectrum (Nujol) cm ^-1 : 3100, 3070,
1758, 1712, 1632, 1589, 1432, 912, 860,
832, 764, 732, 674, 616 Elemental analysis value C ₁₇ H ₁₃ N ₃ O ₆ S ₂ Cl ₂ (490.33): Calculated value C41.64%, H2.67%, N8.57% Analysis value C41.64% , H2.57%, N8.59% Example 8 2-{4'-chloro-2'-[(diethylaminomethyleneamino)sulfonyl]benzoyl}-6-
Chlor-1,2-benzisothiazoline-3-
Production of 1,1-dioxide 2.39 g of 6-chlorosacchulin and 1.01 g of triethylamine were added to a mixture of 10 ml of dichloromethane and 10 ml of diethylformamide, and the mixture was cooled to -40°C.
Add 0.6 g of thionyl chloride to this while stirring, and after raising the temperature to room temperature in about 1 hour,
Stirred at room temperature for an hour. After distilling off dichloromethane,
Add 80 ml of ice water, decant the precipitated gum, add 30 ml of methanol to this gum, and stir to gradually form a homogeneous slurry. This is filtered, washed with cold methanol, dried and has a decomposition point of 195.
1.64 g of white crystals with a temperature of ~197°C were obtained. When this is further purified by recrystallization from acetone, the decomposition point
It showed 199-202℃. NMR spectrum (DMSO- _d6 -TSP) δ: 8.80
~7.63 (7H, m, aromatic ring proton and methine proton); 3.49 (2H, q, J = 7Hz, -C
H ₂ −CH ₃ ); 3.38 (2H, q, J=7Hz, −CH ₂
-CH ₃ ); 1.20 (3H, t, -CH ₂ -CH ₃ ); 1.04
(3H, t, _-CH2 - _CH3 ) IR spectrum (Nujol) cm ^-1 : 3084, 1760,
1715, 1621, 1588, 1451, 991, 959, 935,
889, 854, 832, 775, 765, 745, 729, 675,
615 Elemental analysis value C ₁₉ H ₁₇ N ₃ O ₆ S ₂ Cl ₂ (518.38): Calculated value C44.02%, H3.30%, N8.11% Analysis value C43.75%, H2.97%, N7. 88% Example 9 2-{2'-[(N-methyl-N-phenylaminomethyleneamino)sulfonyl]benzoyl}-
1,2-benzisothiazolin-3-one 1,
Production of 1-dioxide 4.2 g of anhydrous saccharin sodium was added to a mixture of 8 ml of dichloromethane and 8 ml of N-formyl-N-methylaniline, cooled to -40°C, and 1.3 g of thionyl chloride was added while stirring. After raising the temperature to room temperature in about 1 hour, the mixture was stirred at room temperature for 3 hours. After washing the oily substance obtained by distilling off dichloromethane with water, methanol was added and stirred, which crystallized.
3.1 Dried white crystals with decomposition point 188-190℃
I got g. When this was recrystallized from acetone, it showed a decomposition point of 208-210°C. NMR spectrum (DMSO- _d6 -TSP) δ: 8.33
~7.40 (14H, m, aromatic ring and methine proton); 3.39 (3H, s, _-CH3 ) IR spectrum (Nujol) cm ^-1 : 3080, 1766,
1718, 1700, 1607, 1580, 1499, 1417, 897,
817, 779, 746, 715, 705, 694, 672, 653,
634 Elemental analysis C ₂₂ H ₁₇ N ₃ O ₆ S ₂ (483.51): Calculated values C54.65%, H3.54%, N8.69% Analytical values C53.42%, H3.43%, N8.47% Implemented Example 10 2-{4'-chloro-2'-[(N-methyl-N-phenylaminomethyleneamino)sulfonyl]benzoyl}-6-chloro-1,2-benzisothiazolin-3-one 1,1- Dioxide production Add 2.1 g of 6-chlorosaccharin and 880 mg of triethylamine to a mixture of 5 ml of dichloromethane and 3 ml of N-formyl-N-methylaniline, and add -40
Cool to ℃ and add thionyl chloride to this with stirring.
After adding 572 mg of the mixture and raising the temperature to room temperature over about 1 hour, the mixture was stirred at room temperature for 2 hours. Hereinafter, Example 9
By the same operation as above, 1.28 g of white crystals having a decomposition point of 194-196°C was obtained. When this was recrystallized from acetone, it showed a decomposition point of 204-207°C. NMR spectrum (DMSO- _d6 -TSP) δ: 8.78
~7.38 (12H, m, aromatic ring and methine proton); 3.38 (3H, s, _-CH3 ) IR spectrum (Nujol) cm ^-1 : 3100, 1770,
1711, 1607, 1577, 1498, 901, 859, 834,
776, 765, 725, 698, 678, 665, 638, 602 Elemental analysis value C ₂₂ H ₁₅ N ₃ O _{6 S 2} Cl ₂ (552.39): Calculated value C47.84%, H2.74%, N7.61% Analysis values C47.58%, H2.63%, N7.65% Example 11 2-{4′-nitro-2′-[(dimethylaminomethyleneamino)sulfonyl]benzoyl}-6-
Nitro-1,2-benzisothiazoline-3-
Preparation of 1,1-dioxide 6-nitrosactucarin (melting point 204
1.14 g (~205°C) and 505 mg of triethylamine were added, and the mixture was cooled to -30°C. To this was added 300 mg of thionyl chloride while stirring. The temperature was raised to 0° C. in about 1 hour, and then stirred at room temperature for 5 hours. When dichloromethane was distilled off and 50 ml of ice water was added, white crystals precipitated, which were filtered, thoroughly washed with water, and dried to yield 910 mg of slightly pale yellow crystals. When this was recrystallized from acetone, slightly pale yellow crystals were obtained with a decomposition point of 206-208°C. NMR spectrum (DMSO- _d6 -TSP) δ: 9.45
~7.70 (7H, m, aromatic ring and methine proton); 3.14 (3H, s, _-CH3 ); 2.91 (3H,
s, _-CH3 ) IR spectrum (Nujol) cm ^-1 : 3110, 1763,
1709, 1635, 1536, 1429, 922, 893, 856,
807, 742, 732, 669, 661, 613 Elemental analysis value C ₁₇ H ₁₃ N ₅ O ₁₀ S ₂ (511.45) Calculated value C39.92%, H2.56%, N13.69% Analysis value C40.16%, H2.58%, N14.14% 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, R ₁ , R ₂ , X, and n in the table correspond to the above-mentioned general formula (), and the compound numbers of the present invention are also referred to in the following formulation examples and test examples. [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,
Add auxiliary agents such as spreading agents as necessary, or mix various liquid or solid carriers using methods commonly used in agricultural chemical manufacturing.
If necessary, add auxiliary agents such as wetting agents, spreading agents, dispersants, emulsifiers, and fixing agents, and prepare wettable powders, solutions, emulsions,
It can be used in the form of preparations such as 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 or vegetable oils and surfactants, etc. Solid carriers such as clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, calcium bicarbonate, etc. are used. Additives and active ingredients may vary within wide limits. When used as a liquid agent, the appropriate concentration in 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 present invention in an amount of 0.1 kg to 10 kg per 10 are. The pest control agent of the present invention is a known fungicide,
It can be mixed with insecticides, herbicides, plant growth regulators, or general fertilizers. Next, a formulation example in which the 1,2-benzisothiazolin-3-one 1,1-dioxide derivative of the present invention is used as an agricultural and horticultural fungicide will be shown.
The present invention is not limited to this. 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. 7 3 Parts Calcium Stearate 1 Silicic Anhydride Powder 1 Clay 48 Talc 47 A powder composition prepared by mixing and pulverizing 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 blight control test (water surface application) 8 parts of the compound of the present invention shown in Table 1, clay 89
1 part and 3 parts of carboxymethyl cellulose were pulverized and mixed, an appropriate amount of water was added, kneaded, and dried to prepare an 8% granule composition 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. Ten days after the application of the granules, inoculation of the rice bacterial leaf blight was carried out by single needle inoculation of 10 ⁸ cells/ml of the bacterial solution. On the 10th day after inoculation, the lesion length was measured on a total of 50 inoculated leaves in 3 pots in each area, 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 lesion length in sprayed area/average lesion length in non-sprayed area) x 100 The test results are shown in Table 2. [Table] Test Example 2 Rice bacterial leaf blight control test (spraying application) A 3% powder composition prepared by grinding and mixing 3 parts of the compounds shown in Table 1 and 97 parts of talc was tested for each of the compounds of the present invention. Prepared. The rice I tried was
The plants were cultivated in 1/5000 are pots, and the above-mentioned powders were sprayed in predetermined amounts 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 will be carried out on the 10th day after vaccination.
The lesion length was measured for a total of 50 inoculated pot leaves, and the control value was calculated using the formula in Test Example 1, and chemical damage was also observed and investigated at the same time. The test results are shown in Table 3. [Table] 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, and dried to form a 10% granule. Samples were prepared for each test compound of the invention.
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 sprayed and inoculated, and the plants were left standing in a humid room at 24°C overnight to infect the plants, and then transported into a greenhouse to induce disease. The investigation was conducted 7 days after vaccination and the number of lesions was counted.
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 (foliar spraying) Using rice seedlings at the 4-leaf stage grown in 8 resin pots with a diameter of 6.5 cm, the compounds shown in Table 1 were dissolved and diluted to the specified concentration. Adjust the chemical solution, spray 35ml per 3 pots with a spray gun, and air dry.
They were placed in a humid chamber at 24°C, uniformly inoculated with a spore suspension of blast fungus, kept in the 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] [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 plots were divided into three sections with each section having an area of 10 ^m2, and the number of plants planted was 25 per section. 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 begins 7 days after the first appearance of soft rot disease.
A total of 390 sprays were applied per 10 ares three times every week. Disease onset and phytotoxicity surveys were carried out 14 days after the final spraying, and the number of plants with water-soaked, softened leaves on the lower outer leaves was counted, and the control value was calculated using the formula ^* below, and phytotoxicity was also observed and investigated at the same time. The test results are shown in Table 6. [Table] 〓 Number of strains with common disease 〓
**A commercial product containing 84.1% basic copper chloride (50.0% as copper) was used as a control drug.

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different, and 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, R ₁ and R ₂ represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different, and 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] as an active ingredient. . 3 General formula () [In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different] 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,
which may be the same or different from each other] in the presence of a reactive derivative in the hydroxyl group of an oxyacid, according to the following general formula: () [In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different, and 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.