JPS61246193A - Phosphinylsemicarbazide, agricultural and horticultural fungicide comprising same as active ingredient and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 and R2 are 1-4C alkyl; X is O or S; Y and Z are H, halogen, lower alkyl, lower alkoxy, nitro or trifluoromethyl). EXAMPLE:1-Phenyl-4-(dimethoxyphosphinyl)-semicarbazide. USE:An agricultural and horticultural fungicide. PREPARATION:A phosphinyl isocyanate (e.g., diethoxyphosphinyl isocyanate) shown by the formula II is reacted with a phenylhydrazine (e.g., phenylhydrazine, etc.) shown by the formula III in the presence (absence) of a solvent such as THF, etc., preferably at 10-80 deg.C.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to novel phosphinyl semicarbazides, agricultural and horticultural fungicides containing the same as active ingredients, and a manufacturing method. (I) (in the formula, % R1sRl each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, Y,
Z independently represents a hydrogen atom, a halogen atom, a lower furkyl fi, a lower alkoxy group, a trifluoromethyl group, and phosphinyl semicarbazides represented by This invention relates to a horticultural fungicide and a method for producing the compound.

(Prior art) A large number of pesticides are used to control crop diseases in the cultivation of agricultural crops, but due to insufficient control efficacy or the emergence of drug-resistant bacteria, the drugs are no longer effective. The use of some plants has been restricted, some have caused phytotoxicity and contamination of plants, and some have been highly toxic to humans, livestock, and fish.
There are many disinfectants that are not necessarily satisfactory.

(Problems to be Solved by the Invention) Therefore, there is a strong demand for a drug that is free from the above-mentioned drawbacks and can be used safely.

(Means for Solving the Problems) The present inventors conducted research on a large number of compounds with the above drawbacks in mind, and as a result, the group of compounds represented by the general formula (I) have been found to be effective against various plant diseases. The present invention has been completed and a new agricultural and horticultural fungicide has been provided.

The fungicide of the present invention exhibits a control effect against a wide range of plant diseases, and has particularly excellent efficacy against rice blast, citrus black spot, cucumber botrytis, and rice sheath blight.

Compounds similar to the present invention include 1-(phenyl)-
In 4-(jethoxyphosphinyl)-thiosemicarbazide, J. Med. Chem., 11 (5)
.

p1075-7 and U.S. Patent No. 5,992.3'7
No. 3 describes its synthesis method and its effectiveness as an antibacterial agent, and also describes 1-(phenyl)-4
-(dipropoxyphosphinothioyl)-thiosemicarbazide, Phosphorus 5ulfur
.

13(31, P371-BK) A method for its synthesis has been described. However, nothing is known about the synthesis method and bactericidal activity of the compounds of the present invention.

Furthermore, the compound of the present invention has superior bactericidal activity compared to the above-mentioned known compounds.

The compounds of the present invention will be explained in more detail. The compounds of the present invention are phosphinyl semicarbazides represented by the general formula (I), and examples of the compounds of the present invention included in the general formula (I) include the following.

1-Pheny/I/-4-(dimethoxyphosphinyl)-
Semicarbazide 1-(2/-chlorophenyl)-4-(jethoxyphosphinyl)-semicarbazide 1-(2/, 4/-dichlorophenyl)-4-(dimethoxyphosphinothioyl)-semicarbazide 1-(
3'-)IJ fluoromethyl-47-chlorophenyl)-
4-(di-n-propoxyphosphine/'f-oil)-
Semicarbazide 1-(4'-ethylphenyl)-4-(diis.

-propoxyphosphinyl)-semicarbazide 1 +
(4/-methoxyphenyl)-4-(di-n-butylphosphinyl)-semicarbazide 1-(4/-nitrophenyl)-4-(di is.

-butylphosphinothioyl)-semicarbazide 1-
(5/-70 lophenyl)-4-(methoxyethoxyphosphinyl)-semicarbazide 1- (4/-, bromophenyl)-4-(dimethoxyphosphinyl)-semicarbacito 1- (5/, 5/ -dichlorophenyl)-4-(
Dicotoxyphosphinothioyl)-semicarbazide 1-
(2/-Chloro-4'-nitrophenyl)-4-(jethoxyphosphinyl)-semicarbazide The compound of the present invention has the general formula (wherein % R1pR2 are each independently an alkyl group having 1 to 4 carbon atoms, phosphinyl isocyanates represented by the general formula (wherein Y and Z are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group); , representing a trifluoromethyl group) in the presence or absence of a solvent.

As the solvent, it is preferable to use a solvent that is inert to phosphinyl isocyanates, and it is not preferable to use a solvent that has a -class amino group, a secondary amino group, or a hydroxyl group. Preferred solvents include aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, ether solvents, tertiary amine solvents represented by pyridine, and aprotic polar solvents represented by DMF-+DMSO. and so on. Further, in order to accelerate the reaction rate, it is also possible to add a small amount of a tertiary amine such as pyridine or triethylamine, or a polar solvent such as DMF. The reaction can be carried out at a temperature of -10 to 150C, preferably at a temperature of 10 to 80C.

Phosphinyl incyanates tfi, Zh, 0bshch represented by the general formula (2) are raw materials of the present invention.

Khim, 56(8), 1455-7 (1966)
It can be manufactured by the method described in . The other raw material, the phenylhydrazines represented by the general formula (IID), can be obtained by the general production method described in Shin Jikken Kagaku Koza Volume 14-1 (Maruzen), etc.

(Example) Hereinafter, the method for producing the compound of the present invention will be explained in more detail by giving a synthesis example.

Example 1 Synthesis of 1-7enyl-4-(jethoxyphosphinyl)-semicarbazide (Compound 1)
150 f was dissolved in THF 11 and jetoxyphosphinyl incyanate 250 was dissolved under stirring at 15-20 p.
f was added dropwise over 30 minutes. After stirring at room temperature for 4 hours, the reaction solution was concentrated under reduced pressure to obtain 4009 crude crystals of 1-phenyl-4-(jethoxyphosphinyl)-semicarbazide. The crude crystals were recrystallized with a mixed solvent of toluene and ethanol to obtain white crystals 3705' of the desired product.

Dissolve this in heavy chloroform and use PM manufactured by JEOL Ltd.
H'-NMR from X-60 type NMRffilJ regular machine
When measured, ・61.5 Ppm (Tri, 6H
), ij 4,1 yp(pent, 4FI'), δ0
．． A spectrum of 5 to 8.4 p% (Mix, 8H) was shown. In addition, the melting point of this crystal is 145C, and the melting point of this crystal is 145C.
? The Rf value was 0.17 when a Shikagel plate (A57251) manufactured by Co., Ltd. was used and 90 volume t% of toluene and 10 volume t% of isopropanol were used as developing solutions.

Hereinafter, the compounds shown in Table 1 were synthesized in the same manner as in Example 1. 71 *) The Rf value is measured using a silica gel plate (A5
729) was used, and the developing solution was 9° volume t% toluene and 1 volume ingropanol. Table 2 below
．． The same applies to 5.4.

Example 2 Synthesis of 1-(4'-methoxyphenyl)-4-(di-n-butoxyphosphinyl) semicarbazide (compound 23)
After dissolving in 0- and adding sodium cyanate 651,
The mixture was reacted at 80°C for 6 hours to synthesize di-n-butoxyphosphinyl isocyanate. Di-n-butoxyphosphinyl incyanate was isolated and cooled to room temperature for 4 hours.
-Methoxyphenylhydrazine15. Added B f.

Then, stir at room temperature for 2 hours to make sure. After the reaction is complete, acetonitrile is distilled off under reduced pressure, the concentrate is poured into 1 t of water, and then extracted with 500 g of ethyl acetate. The ethyl acetate layer was washed with 1/100 normal hydrochloric acid 500 times and further washed with water. The ethyl acetate layer was dehydrated with anhydrous sodium sulfate and then concentrated to dryness to obtain a concentrate of 52f. This concentrate was separated by column chromatography using a t-column filled with silica gel and toluene as a solvent, and a white 1-(4'-methoxyphenyl 1-4-(di-n
-butoxyphosphinyl) semicarbazide crystals9. !
I got 1M'l.

This product was converted into Hl + NM by the same method as in Example 1.
When R was measured, δ0.95 to 1.8 (Mix,
14H), δ3.7 PP (Sing, 5H)
, δ4.0pP (Tetra, 4H), δ6.7~1
3.3 ppm (Mix, 7 H) (7) Show the spectrum.

The melting point of NX was 121C, and the Rf measured by TLC was 0, 26 when measured under the same conditions as in Example 1.

The compounds shown in Table 2 were synthesized in the same manner as in Example 2.

Table 2 Example 3 1-(sl,41-dichlorophenyl)-4-(jetoxyphosphinothioyl)semicarno<shi)" (
Synthesis of compound 27) s, 4-) Chlorphenylhydrazine salt e Salt 14ay was suspended in DMF 500- and under stirring at 40-45c.
Triethylamine 66? was added, and furthermore, jetoxyphosphonotioyl isocyanate 1152 was added dropwise over 10 minutes. Furthermore, after reacting for 1 hour at 60°C, it was cooled and poured into 3 tons of water with stirring. After stirring for 5 hours, yellow crude crystals of the target substance precipitated. The crude crystals of 1832 of the target substance were obtained by separating, washing with water, and drying. By recrystallizing with a mixed solvent of toluene and ethanol, 1551 white crystals of the desired product were obtained.

This product was subjected to Hl-NMR analysis in the same manner as in Example 1.
I measured δ1.3 pIpm (Tri,
6H), δ5.8-4.5 jps (MiXI 4H3
, δ6.5-8.4 (Mix.

6H) spectrum is shown. Mayu's melting point is 155C, and the TLC Rf measured under the same conditions as Example 1 is 0.
．． It was 39.

The compounds shown in Table 3 were synthesized in the same manner as in Example 3.

Table 3 The compounds shown in Table 4 were synthesized in the same manner as in Example 1.

The fungicide of the present invention can be used as a pure active ingredient, and can also be used as an agricultural chemical in a form that can be used in general formulations, such as irrigation agents, granules, powders, emulsions, It can also be used in the form of an aqueous solvent, aerosol, or the like. As additives and carriers, when a solid agent is intended, vegetable powders such as soybean flour and wheat flour, and fine mineral powders such as diatomaceous earth, apatite, gypsum, talc, pyrophyllite, and clay are used. If you are aiming for a liquid dosage form,
Kerosene, mineral oil, petroleum, naphtha, xylene,
Cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone,
Use water etc. as a solvent.

In these preparations, a surfactant may be added if necessary to obtain a uniform and stable form. The hydratactic powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the powders and granules are used as they are by spraying them on plants.

Next, some examples of the composition of the present invention will be shown, but the additives and their addition ratios should not be limited to these examples and can be varied over a wide range.

Example 4 Wettable powder compound 40 parts Diatom ±
53 parts Higher alcohol sulfate 4 parts Alkylnaphthalene sulfonic acid
By uniformly mixing 3 parts or more and pulverizing it finely, an aquarium containing 40% of the active ingredient can be obtained.

Example 5 Emulsion compound 30 parts xylene
33 parts dimethylformamide
By mixing and dissolving 30 parts or more of 7 parts or more of polyoxyethylene alkyl allyl ether, an emulsion containing 50% of the active ingredient is obtained.

Example 6 Dust compound 10 parts Merck
89 parts polyoxyethylene alkyl allyl ether If 1 part or more is mixed uniformly and finely ground, a powder containing 10% of the active ingredient is obtained.

Although it goes without saying that the compound of the present invention is sufficiently effective alone, it is insufficiently or weakly effective against pests and diseases other than those shown in the examples below, so various fungicides may be used to compensate for this. It can also be used in combination with one or more types of insecticides, insecticides, and acaricides.

Representative examples of fungicides, insecticides, and acaricides that can be used in combination with the compounds of the present invention are shown below.

[Fungicides]: Cabtan, TMTD, Zineb, Maneb, Mancozeb, TPN, 7en7ram, Flavax°,
Arietch, glothiocarp, triadimefon, triadimenol, polyoxin, tridemolk, metaxanine, fluoroxyl, triforin, imbrothiolane, probenazole, plastocydi/-85 kasugamycin, validamycin, PCNB, iprodione, vinclozolin, procimide/, benomyl, thiophanate methyl, basic copper chloride , basic copper sulfate, triphenyltin hydroxide, chinomethionate, propamocarb, pinapacryl [insecticide, acaricide]: BOPE, chlorbenzilate,
Chlorzolobyrate, Furoclonol, Phenine Bromorate, Kelsen, Zipton, Chlor 7 Enamidine,
Amitrus, B P P SJ' PPS.

Benzomate, cyhexatin, distanoxane, polynactin, thioquinox, CPCBS, tetradifo/,
Tetrasul, cycloplate, kayasite, kayahope, polysulfide lime, 3-n-dodecyl-1,4-su7toquinon-2-yl acetate, fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, vamidethion, 7E/toate, dimethoate , formothion, malan/, dibuterex, thiometone, phosmet, menazone, dichlorphos, acephate, EPBP
.

Dialifor, Methyl Parathion, Oxydimedone Methyl, Nithion, Aldicarb, Proboxur, Permethrin/, Cypermethrin, Decamethrin, 7 Embererate, Fenpropathrin, Pyrethrin, Allethrin, Tetramethrin, Resmethrin/, Halthri/, Dimethrin, Propathrin, Brothrin , 5-phenoxybenzyl-2, i-dichloro-1-(4-ethoxyphenyl)-1-cyclopropanecarboxylate, α-cyano-3-phenoxybe/zyl-2,2-dichloro-1
-(4-ethoxyphenyl)-1-cyclopropanecarboxylate), (R8)-α-cyano-3-phenoxybenzyl (R8)-2-(4-trichloromethoxyphenyl)-3-methylbutyrate, ( R8)-α-cyano-3-phenoxybenzyl (R8)-2-(2-chloro-4-trichloromethylanilino)-3-methylbutyrate, machine oil.

(Effects of the Invention) Next, the bactericidal activity of the compound of the present invention will be explained in detail with reference to test examples.

Test Example 1 Rice blast control test Rice seedlings (variety Nijukoku) that had reached the four-leaf stage after sowing 20 seeds in a 12-diameter flat pot were treated with a diluted solution of a test compound at a predetermined concentration.
．． The spore suspension was sprayed at a rate of 50 spores per pot at a pressure of 5 kP/cm". The spore suspension was placed in an air-dry bag and microscopy*20a magnification to obtain a spore suspension of approximately 50 spores per field of view.
icularia oryzae) was precultured in an oatmill medium at 27C for 14 days, and the obtained spores were used.] Each pot was inoculated by spraying. Keep moist for 2 days after implantation.
Afterwards, they are kept in a glass greenhouse.

10 days after inoculation, conduct an investigation according to the disease severity shown below, and calculate the disease severity.

Number of lesions per leaf: 01 to 34 to 1111 or more applicable leaves
The a b c d results are shown in Table 5.

Table 5 *Control compound (11=known compound-1-phenyl-4-
(Jetoxyphosphinothioyl) thiosemicarno (cyto** Control compound (2) - Commercial drug Rabside = 4.5
．． 6.7-Tetrachlorophthalide Test Example 2 Rice sheath blight control test 1 / Rice at the earing stage grown in Wagnerbot at 5000 a (variety: Hare, 2 plants per pot).

1 share! ] A diluted solution of the test compound at a predetermined concentration was sprayed at a pressure of 0.5 kg/d at a rate of 50 ml per pot. After air-drying this, the rice sheath blight fungus (Pe1f 1cularias) was cultured in a rice straw medium at 27C for 4 days.
asakii) was inserted into the stem at a position of 10 Iyr1 above the ground and inoculated, and after being kept under humid conditions for 5 days, it was cultivated in a glass room. 11 days after inoculation, the following disease onset was investigated and the disease severity was calculated.

Table 6 shows the results of lesion length (crll) of 01 to 34 to 1011 or more corresponding number of stems (trees) ab c d.

Table 6 × Control compound (1) = Known compound = 1-phenyl-4-
(Jetoxyphosphinothioyl)thiosemicarbazide and PSA synthetic medium 18- were mixed and placed in a Petri dish at a predetermined compound concentration (10
A flat medium of 0PP1) was prepared. After transferring 5 m of the following test bacteria to a flat medium and culturing at 27'C for 48 hours, the presence or absence of bacterial growth was examined.

Test bacteria and preculture Preculture temperature: 27G in both cases Survey category The results are shown in Table 7.

Table 7

Claims (3)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents an oxygen atom or a sulfur atom. ,Y
, Z each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group. ) Phosphinyl semicarpazides. (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents an oxygen atom or a sulfur atom. ,Y
, Z each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group. ) An agricultural and horticultural fungicide characterized by containing a phosphinyl semicarpazide as an active ingredient. (3) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_1 and R_2 each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents an oxygen atom or a sulfur atom. .)
Phosphyl isocyanates represented by the general formula (
III) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, Y and Z each independently represent a hydrogen atom, a halogen atom,
Represents a lower alkyl group, lower alkoxy group, nitro group, or trifluoromethyl group. ) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 each independently have a carbon number of 1 to 4 alkyl group, X represents an oxygen atom or a sulfur atom, Y
, Z each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, or a trifluoromethyl group. ) A method for producing phosphinyl semicarpazides.