JPH03215491A - Thiophosphinic amide derivatives and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I (R is lower alkyl, lower alkenyl, lower alkoxy-lower alkyl, cyano-lower alkyl, phenyl-lower alkyl, pyridyl-lower alkyl, benzimidazolyl-lower alkyl, etc.). EXAMPLE:N-(ethyldiphenylphosphoranylidene)-p,p-diphenylthiophosphinic amide. USE:A horticultural germicide. PREPARATION:An N-(diphenylphosphino)-p,p-diphenylthiophosphinic amide of formula II is subjected to a reaction with a halide of formula RX (X is halogen) in the presence of a base such as sodium hydride or triethylamine in an organic solvent such as toluene or DMF in general.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel thiophosphinic acid amide derivatives. Further details are shown in the general formula (r) below.
The present invention relates to a p, p, p', p'-tetraphenyl N-phosphoranylidene thiophosphinic acid amide derivative and an agricultural and horticultural fungicide containing the derivative as an active ingredient.

Therefore, the present invention is applicable to the chemical industry as well as the agricultural and horticultural fields.
It is particularly useful in the agricultural chemical manufacturing industry.

The only literature knowledge regarding phosphinic acid amide derivatives is in Chemical Berichte No. 1054 No. 8 No. 24
76 (1972), N-(methyldiphenylphosphoranylidene)-p,p-cyphenylphosphinic acid amide was obtained by the following route. However, represented by the general formula (I) below of the present invention,
p, p, p', p'-tetraphenyl N-phosphoranylidene thiophosphinic acid amide derivatives have not been described in any literature, and it is not known that they have any activity as agricultural or horticultural fungicides. (Clearly trying to solve the problem) Known N-(methyldiphenylphosphoranylidene)-p
, p-diphenylphosphinic acid amide shows no fungicidal activity for agricultural and horticultural purposes. On the other hand, there are important diseases such as downy mildew, late blight, powdery mildew, and rust on fruit trees, vegetables, and grains.
Various drugs have been used so far, but due to drug resistance problems, they can no longer be used, or their use has declined.
It is becoming limited. Therefore, in these fields, the emergence of new fungicides with different skeletons from conventional drugs has become a major issue, and the present invention aims to solve these problems. In order to achieve the above object, the present inventors synthesized a large number of compounds and conducted intensive studies on their usefulness.
As a result, we succeeded in synthesizing thiophosphinic acid amide derivatives represented by the following general formula (I), and these derivatives are new compounds that have not been described in literature, and moreover, l:
! It was found that it has high activity and safety as a horticultural fungicide.

Therefore, the first gist of the present invention is the following general formula (1) (wherein R is a lower alkyl group, a lower alkenyl group, a lower alkoxy lower alkyl group, a cyano lower alkyl group,
Phenyl lower alkyl group, lower alkoxycarbonyl lower alkyl group, aminocarbonyl lower alkyl group, lower alkylaminocarbonyl lower alkyl group, phenyl lower alkylaminocarbonyl lower alkyl group, phenyl aminocarbonyl lower alkyl group, bilicyl lower alkyl group, quinolyl lower Indicates an alkyl group or a penzimidazolyl lower alkyl group. However, the phenyl lower alkyl group may be substituted with either a halogen atom or a lower alkoxy group on the benzene ring. ) is a thiophosphinic acid amide derivative represented by The lower alkyl group and lower alkenyl group referred to herein may both be straight or branched. In addition, "lower" here refers to those having 1 to 6 carbon atoms. The second gist of the present invention is an agricultural and horticultural fungicide characterized by containing a thiophosphinic acid amide derivative represented by general formula (I) -L as an active ingredient. Next, specific examples of the compounds of the present invention represented by general formula (I) are shown in Table 1. In addition, compound degradation is also referred to in the following Examples and Test Examples.

Table 1 (Effects) - The compound of the present invention of general formula (I) is a new compound. This compound of general formula (I) acts as an active ingredient in agricultural and horticultural river fungicides. Example (Part 1) Method for producing the compound of the present invention The fold formation of the compound of general formula (1) according to the first embodiment of the present invention can be carried out by the method described below. That is, it can be produced by a method of reacting N-(diphenylphosphino)-p,p-diphenylthiophosphinic acid amide represented by formula (II) with halites represented by general formula (m).

(O)2-PNIIP-(@)2 10X-》
((II) (m) SIl (f) (In the formula, R is the same as above, and X represents halogen r-.) This condensation reaction is usually carried out in an organic solvent.The solvent that can be used is , hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as ethyl ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, acetone and methyl isobutyl ketone. These include ketones, alcohols such as methanol and ethanol, amides such as dimethylformamide and dimethylacetamide, and dimethylsulfoxide.Acid binders include inorganic substances such as sodium hydride, sodium amide, sodium hydroxide, and potassium carbonate. A base or an organic base such as triethylamine or pyridine can be used. The reaction proceeds at room temperature, but the reaction time can be shortened by heating up to the boiling point of the solvent. If binder salts are present, the desired product can be obtained by filtering them out and distilling off the solvent.Also, if water is mixed with benzene, toluene, tetrahydrofuran, chloroform, etc. The compound of the present invention can also be obtained by adding a solvent to the sample and distilling off the solvent.Production examples of the compound of the present invention are shown in Examples 5 to 2.

The compound of formula (II), which is a starting material, is a new compound or a known compound, which can be obtained by reacting sudiphenylphosphinoamine and anhydrous aluminum chloride in toluene, and then adding WL yellow powder. The production of the compound of formula (II), which can be carried out, is shown in the reference production example. Furthermore, the compound of formula (m) is a known compound. A mixture of 41.7 g of synthetic cyphenylphosphinosiphenylthiophosphinic acid amide, 15.6 g of ethyl iodide, 13.8 g of woodless potassium carbonate, and 250 m of acetonitrile was refluxed for 3 hours. After cooling, inorganic salts are filtered off,
When the filtrate is concentrated, the title compound appears as pale brown crystals.4
0.9g was obtained. When recrystallized with a mixed solvent of acetone-hexane, it becomes white crystals with a melting point of 129-131
”Showed C.

U To a mixture of 41.7 g of diphenylphosphinosiphenylthiophosphinic acid amide and 250 ml of detrahydrofuran, 4.0 g of sodium hydride (60% oily) was added, and then 12.7 g of Pensilkolite was added.
It was refluxed for 5 hours. After cooling, toluene and water were added and the organic layer was separated.

After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 45.1 g of the title compound as pale brown crystals.
Obtained. Recrystallization from ethyl acetate-hexane solvent gave white crystals with a melting point of 187-189°C.

Reference production example 38.5g of N-(cyphenylphosphino)1P his-cyphenylphosphinoamine and toluene
Anhydrous aluminum chloride in a mixture of 200mi 13.4
After adding g and stirring at room temperature for 3 hours, sulfur powder 3.2
g and stirred at room temperature for 2 hours. After the reaction was completed, the reaction mixture was poured into ice water, the liquid layer was added, and after further washing with water, the solvent was distilled off under reduced pressure to obtain 37.1 g of the title compound as a pale brown oil. When purified by silica gel column chromatography using a mixed solvent of hexane and ethyl citrate, it becomes a colorless oil.
It showed 1.4762. Example (Part 2) Method for producing a fungicide for agriculture and horticulture The second fungicide for agriculture and horticulture according to Part 1 of the present invention is prepared by formulating the compound of formula (I) above according to a conventional formulation and using it. I can do something. That is, the general formula (1
) with suitable carriers and adjuvants, such as surfactants, binders, stabilizers, etc., to produce permanent agents, emulsions, liquids, sol agents (flowable agents), oil agents, powders, DL agents, etc.
(Triftless type) It may be formulated as a powder, fine powder, coarse powder, etc. The content of the compound of the present invention in these preparations is 1 to 90% in the case of permanent formulations, emulsions, sol formulations, and oil formulations.
(wt%: hereinafter the same), in the case of powders, DL powders, fine powders, and coarse powders, it can be contained in the range of 0.5 to 5%, and in the case of powders, it can be contained in the range of 1 to 10%. ．． The method of using the agricultural and horticultural fungicide of the present invention is generally as follows. Namely, permanent agents, solutions, emulsions, and sol agents (
For flowable agents) and oil agents, add 500 to 20 with water.
Diluted by 00 times, the active ingredient is generally 1 to 10,000p.
The concentration of the solution is adjusted to pm. Mo and lO are per,
50 to 300 doses of this diluted solution, usually in the range of 100 to 200 doses, are sprayed on the foliage of the plant where the disease occurs.

In addition, liquids, emulsions, and sol agents (floorful agents) can be used as concentrated liquids without diluting with water, or diluted to within 10 times with water. agent, UL
V spraying agent), 50 to 3000 mJ per 10 are
It is dispersed using eagles or helicopters. In addition, powders, DL powders, fine granules, and coarse powders weigh 2 to 5 kg per 1O area (approximately 50 to 500 g as active ingredient), on the stalks of the disease-infested area of the plant, 1; on the soil surface, 1;
It is applied in the soil or on the water surface. A method for formulating the compound of the present invention represented by general formula (I) as an agricultural and horticultural fungicide is shown in Examples 3 to 6 below.

Example 3 LtQ Compound 2 parts of compound Nb2, PAP (physical property improver)
1 part and 97 parts of clay are uniformly mixed and ground to obtain a powder containing 2% of the active ingredient.

Song J Zi M4 L Danchu Compound 11kl7 20 parts of the compound, 3 parts of potassium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of white clay were uniformly mixed and pulverized to contain 20% of the active ingredient. Obtain Eiwaza. If 30 parts of compound 8012, 40 parts of methyl ethyl ketone and 30 parts of polyoxyethylene nonylphenyl ether are mixed and dissolved, the active ingredient will be 30%.
Obtain an emulsion containing Example 6 Z soil 1 Compound No. 8 compound 40 parts, lauryl sulfate 2 parts, alkylnaphthalene sodium sulfonate 2 parts, acetoxybrobyl cellulose 1 part and wood 55F
Mix 4 uniformly to obtain a sol containing 40% of the active ingredient. Effects of the Invention The novel compound of the present invention is useful as an agricultural and horticultural fungicide because it exhibits high control effects against downy mildew, late blight, powdery mildew, and rust, which are important diseases of fruit trees, vegetables, and grains. It is. Next, the usefulness and specific examples of the compound of the present invention represented by general formula (1) are shown in Test Examples 1 to 4. Example 4: Cucumber seedlings (variety: Sagami Hanjiro) in the second nesting stage were cultivated in soil in clay pots with a diameter of 9 cm in a disease-proof greenhouse and were prepared according to Example 4. 20 ml of diluted hydrating agent at a specified concentration per pot.
It was sprayed vertically. Then, with a damp brush, remove the cucumber and the diseased bacteria (Pseudo eronos oraC 11 b
The spores were scraped off from the infected leaves of Veronosvora cubensis and suspended in a 50 ppm aqueous solution of a spreading agent (polyoxyethylene alkyl ether). Then, the spore concentration is 5 x 106 spores (pieces/m sentence)
After the chemical spraying, a spore suspension of cucumber and disease bacteria was spray inoculated. And 20℃, humidity 100%
The cucumber plants were left standing in a humid room under the following conditions for 211 days to develop the disease. Six days after inoculation, the cucumber and lesion area ratio (%) per lIJ were investigated, and the control value (%) was calculated using the following formula.
was calculated. This test was conducted twice per 1 chemical solution concentration area, and the average control value (%) was determined, and the evaluation value was determined according to the criteria described in F.
In addition, chemical damage to cucumbers was investigated using the following criteria. The results are shown in Table 2.

In addition, the evaluation value of the bactericidal effect and the investigation index of drug damage were similarly used in Test Examples 2 to 4 below. l O O% 80 to less than 100% 60 to less than 80% 40 to less than 60% 20 to less than 40% less than 20% -1 - 5: Extremely low 4 = Worn 3; High 2; Slightly l: Slightly O: 1) The numbers in parentheses for non-sprayed plots indicate the average percentage of diseased area per leaf. Note 2) Comparative drug A. B used the following.

(Compound described in Chemical Berichte Vol. 105, No. 8, p. 2476 (1972)) CO The fifth violet of a tomato (Product 14 Futabako K) grown in a greenhouse in a vinyl pot with a diameter of 9 cm. A predetermined dilution of 7Ag1t and a hydrating powder was applied to stage seedlings according to Example 4.
We used an automatic spraying device to spray 30 meters per 3 bots. The day after the chemical treatment, tomato Phytophthora blight (Ph
yto hthorainfestans: Rinse the zoospore sacs of Phytophthora infestans (
(Adjust the zoospore concentration to 10'/ml)
The tomato nests were inoculated using a spray gun. After storing the seeds in a humid room at 20°C and 100% humidity for 5 days, the 1st to 4th true leaves were investigated for the percentage of tomato diseased disease area (%), the average diseased area percentage was determined, and the comparison with the non-sprayed area was calculated. The control value (%) was calculated.

This test was conducted in duplicate per 1 chemical solution concentration area, and the average control value (%) was calculated and converted into an evaluation value of bactericidal effect. Also,
The phytotoxicity of tomatoes was investigated using the same criteria as in Test Example 1. The results are shown in Table 3. xl00 Note 1) Comparative drugs A and B are the same compounds shown in Table 2. Note 2) The numbers in parentheses for unsprayed plots indicate the number of lesions per leaf. Confectionery Team J Barley Powdery Mildew A permanent agent prepared according to Example 4 in the 1% stage of barley (variety: Azuma Golden) cultivated on top in a clay pot with a diameter of 9 cm in a greenhouse. After spraying 10m of a chemical solution with a prescribed concentration per pot and leaving it overnight, a spore suspension of barley powdery mildew 11 (Erysiphe graminis) was inoculated by spraying. After 711 inoculations, the lesion area ratio (%) of barley powdery mildew was investigated, and the control value (%) was calculated using the following formula and converted into an evaluation value of bactericidal effect. In addition, the degree of drug damage to barley was investigated using Test Example 1 and the rotation standard, and the results are displayed. The results are shown in Table 4. ×100? 2) Comparative drug A is the same compound as shown in Table 2. In addition, the following Comparative Drug C was used. (Common name: Kinomethionate) f12) The numbers in parentheses ( ) in the non-sprayed area indicate the number of lesions per leaf. Test Example 4 Wheat rot disease control effect test Soil cultivation in a clay pot with a diameter of 9 cm in a greenhouse To the cultivated wheat seedlings (variety: Norin 6l13) at the first nest stage, a predetermined concentration diluted solution of a permanent agent prepared according to Example 4 was sprayed at 20mM per 3 pots. Wheat rot disease formed on wheat (Puccini)
a recondiLa: Puccinia reconcita)
Spores per field of view under a microscope with 150x magnification: F-
Suspend the spores in sterilized water to which 50 ppm of Tween 20 (trade name of Kao Soap's polyoxyethylene sorbitan monolaurate) has been added to a concentration of approximately 50 spores, and add the spore suspension to the confectionery to be treated. I was inoculated with Akigiri. After being kept in a greenhouse at 20°C and 100% humidity overnight, they were transferred to a greenhouse at 20°C to induce disease onset. After 10 days of inoculation, the number of summer spores developed per sweet was taken out, and the control value (
%) was calculated.

This test was conducted using three pots per chemical solution concentration area, and the average control value (%) was calculated and converted into an evaluation value of bactericidal effect. In addition, the degree of drug damage to wheat was investigated using Test Example 1 and the rotation standard, and the results are shown in Table 5. tFI) Comparative drug A is the same compound shown in Table 2. In addition, the following drug was used as comparative drug D. Comparison drug: DS I1 Note 2) The numbers in parentheses ( ) for non-sprayed plots indicate the disease IMa per leaf.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a lower alkyl group, a lower alkenyl group, a lower alkoxy lower alkyl group, a cyano lower alkyl group, a phenyl lower alkyl group, Lower alkoxycarbonyl lower alkyl group, aminocarbonyl lower alkyl group, lower alkylaminocarbonyl lower alkyl group, phenyl lower alkylaminocarbonyl lower alkyl group, phenylaminocarbonyl lower alkyl group, pyridyl lower alkyl group, quinolyl lower alkyl group or benzimidazolyl lower A thiophosphinic acid amide derivative represented by an alkyl group (wherein the phenyl lower alkyl group may be substituted with either a halogen atom or a lower alkoxy group on the benzene ring). 2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a lower alkyl group, a lower alkenyl group, a lower alkoxy lower alkyl group, a cyano lower alkyl group, a phenyl lower alkyl group, a lower alkoxycarbonyl lower alkyl group) , aminocarbonyl lower alkyl group, lower alkylaminocarbonyl lower alkyl group, phenyl lower alkylaminocarbonyl lower alkyl group, phenylaminocarbonyl lower alkyl group, pyridyl lower alkyl group, quinolyl lower alkyl group or benzimidazolyl lower alkyl group.However, , the phenyl lower alkyl group may be substituted with either a halogen atom or a lower alkoxy group on the benzene ring).