JPS6059919B2 - Novel 0,0-diaryl-1-acyloxy-2,2,2-trichloroethylphosphonate and fungicide composition containing the same as a main component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chemicals used to cure diseases of agricultural crops, and more particularly to novel organophosphorus compounds with fungicidal activity.

Organophosphorus fungicides are currently mainly used for Piricularia oryzae and Pellicularia sasaki.
(A.F. GranOv and N.
N. MelnikOvl“゜UspekhiKhim1
1-1973, 42, 9, 1681)
.

Fungicides are found in various types of organophosphorus compounds, including derivatives of phosphoric and phosphonic acids, phosphine and phosphonium salts, tetracoordinate phosphorus acids, and tetracoordinate phosphorus acids. Acid salts, tetracoordinated phosphorus acid esters, phosphoric acid amides. There is.

A bactericidal therapeutic compound known in the art for curing cutaneous mycoses is O.
0-dimethyl-1-acetoxy 2,2,2-trichloroethylphosphonate (chloracetophos),
very similar to the novel compounds of the present invention (USSR Inventor's Certificate No. 280768, BulletinOf
inventoryOnll97O, NO. 2 &. P. (see section).

Generally known organophosphorus fungicides have low effectiveness against many infectants of plant diseases.

In particular, it is less effective at killing Aspergillus fungi, which causes very dangerous diseases of grains and other crops. In order to successfully control Aspergillus in grains grown on large tracts of land, highly effective fungicides that are suitable for effective application methods such as ultra-small volume spraying (USVS) are needed. Dithiocarbamic acid derivatives, specifically zinc ethylene bisdithiocarbamate (Zineb), exhibit high activity against Aspergillus diseases of cereals.

However, these fungicides are not suitable for application by the USVS method. Moreover, these substances are not storage stable and are harmful to humans and from an environmental protection point of view (
1. Ch0ir1kaA. , MOsinskiS. Pr
．． Inst. pnem. Organ. , 1971, 3,
269;2. Ivan0va-Chemishansk
aja66GigienaiSanit3ria″19
71, NO. ll, 95;3, E. A. AntOnOv
ichetal. 6℃Igienai Sanitari
a-1972, NO. 9, 25). An essential drawback of dithiocarbamate fungicides is their limited application form. That is, these fungicides are only effective for prophylaxis (only before the onset of the disease syndrome). Therefore, these applications are only effective if a reliable prediction of disease progression can be obtained. Because of the deficiencies of dithiocarbamate fungicides, attempts have been made to find suitable substitutes for them (Gibney L., Chem. and
Eng. News. l975sS3sNO. 2 turtles 1 miser).

High bactericidal activity against diseases caused by Aspergillus oryzae is an inherent property of nickel salts or mixtures of nickel salts and ethylene bisdithiocarbamic acid derivatives (JOrles R.J.
,E. Afrie. Agric. and FORESTJ.
, 1961, 26, NO. 4, 210Hardis0n
J. R. , PhytOPathOlOgyll963,
Seki, NO. 2, 209). However, the use of nickel-containing fungicides has been banned since said compounds have harmful effects on the human body and the environment (J. HOrsef
all, PresentationOnbMICOngr'
EssOnPlantPrOtectiOnlMOSC
(See OWll9). There was a theory that ammonium salts of sulfoanilic acid, such as anilate, killed aspergillus fungi on grains and other plants (Soviet inventor's certificate No. 178236).
No., 1964; BulletinOfinVentlO
rlSll96eIsNO. 2, 138).

However, these compounds are toxic to plants and have low efficacy. Fungicides found to be effective in killing Aspergillus include 1,4-dioxide 2,3-dihydro 6-methyl-5-phenylcarbamoyl 1●4-
Oxatin (hydroxycarboxin, vegetable wax)
There is a C4 Systemie Furlgicides 5
′、6′■R″PubllshjngHOusell6
75, P. 2O9).

However, the use of these fungicides to treat aspergillus diseases in cereals is not economically viable in most cases due to the high cost of the compounds. The object of the present invention is a novel, readily available, inexpensive and harmless organophosphorus fungicide for humans and the environment, having a broad spectrum of action,
It is particularly effective in treating diseases caused by Aspergillus on grains, and [
Disinfectants are provided that are suitable for application by a variety of methods, including the JSVS method.

This purpose is based on the formula (wherein R is c1-Cr alkyl or phenyl,
and and n are each 1
or 2)
-Acyloxy-2●2●2-trichloroethylphosphonate, a novel organophosphorus compound.

It has been found that said compounds have fungicidal properties and can be successfully used as fungicides.

In accordance with the present invention, the fungicidal composition comprises the 0,0-diaryl-1-acyloxy-2●2,2-trichloroethylphosphonate and its carrier. Compounds according to the present invention have the corresponding O.0-diaryl-1-
Produced by acylating hydroxy-2,2,2-trichloroethylphosphonate with a carboxylic acid or its anhydride; ).
Departure 0・0-Diaryl-1-Hydroxy-2●2●2
-Trichloroethylphosphonate is the following (1), (Ii
) and (III). (1) By reacting triarylphosphite, phosphorus trichloride, and chloral hydrate (or chloral and water).

(Ii) by reacting a mixture of the reaction product of 2 moles of the corresponding phenol with 1 mole of phosphorus trichloride with chloral hydrate (or chloral and water).

(Iiii) By reacting the corresponding phenol, phosphorus trichloride and chloral hydrate.

In the formulas (1), (Ii) and (Ji), X. ．． Y.
．． m. ．． n is as described above.

The reaction can be carried out in the presence or absence of an inert organic solvent.

The resulting O-0-diaryl, -1-hydroxy-2.
Since 2,2-trichloroethylphosphonate (or mixture thereof) is produced substantially pure, it can be used for acylation without separation. In the synthesis of 0●0-diaryl-1-hydroxy-2●2-trichloroethylphosphonate, acetic anhydride was used as the acylating agent and O.0-diaryl-1-hydroxy-2●2●2-trichloroethyl was synthesized in the absence of a solvent. It is desirable to carry out the reaction without separation of the phosphonate intermediate.

This embodiment is characterized by technical simplicity, starting materials (
These include the availability of phosphorus trichloride, acetic anhydride and chloral hydrate or chloral and water), high yields of the desired compound, and no waste water or manufacturing waste.
The compounds of the present invention include storage-stable viscous oils or low-melting crystalline products and are soluble in common organic solvents such as aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ketones. .

Based on the compound, this makes it possible to obtain a preliminary form suitable for application by the USVS method (ultra-small volume spraying) and to form the required stock of the composition. With regard to its fungicidal properties with respect to Aspergillus diseases of cereals, the compounds of the present invention, in particular O-0-diphenyl-1-acetoxy 2●2●2-trichloroethylphosphonate, which is a very common representative example of the present invention, are effective against zineb and hydroxyl. Superior to prior art antimycotic fungicide compositions such as Carboxin.

The fungicidal preparation containing O.0-diphenyl-1-acetoxy2●2●2-trichloroethylphosphonate as the active principle is hereinafter referred to as "゜APHOS'3. In the treatment of plants, large-volume spraying method and Or 8e1
AphOs is used in both the 3■S method at a speed of
), it is possible to virtually completely protect the grain from Aspergillus even if the degree of infection is severe and it is possible to increase the grain yield to 24 c1 ha. The essential advantage of the fungicides according to the invention used to treat diseases caused by Aspergillus oryzae is that they are effective not only for the prevention of diseases, but also for the treatment of already infected plants. The fungicides according to the invention exhibit high effectiveness under a variety of agro-climatic conditions, such as frequent heavy rains, where conventional fungicides such as zineb and hydroxycarboxins are less effective.

One of the advantages of the fungicide according to the invention, in particular Afuos, is that
It maintains bactericidal properties for a longer period of time than Zineb.

This makes it possible to reduce the number of treatments. A considerable increase in the yield of winter wheat is possible even with only one preventive spray treatment with Afuos under conditions of increasingly severe diseases caused by stem rot in the surrounding plants. The compounds of the invention are not toxic to plants even when applied at effective or substantially high doses (concentrations).

Therefore, Afuos does not reduce the yield of wheat, and even when the dosage (concentration) is increased eightfold, the quality (germination, growth, etc.) is not adversely affected. The compounds of the present invention can also be used for rice Piriculariosis (Piricularia oryzae, PiriculariOsis), grape downy mildew (PiriculariOsis)
PlasmOparaviti
cOIa), SeptOriOsis
) i.e. white leaf stain of pear (Septria pyricola, S.
eptOriapiricOla), apple spot (Fujicladium dendriticum, FUSiCIadiLl)
Phytoph
thOrainfestans) has high bactericidal properties.

That is, in terms of effectiveness in suppressing the spores of Pyricularia oryzae, Afuos is about 4 times more effective than Kitacin (0.O-diethyl-S-benzylthiophosphate), which is commonly used for the treatment of Pyricularia oryzae. Unlike Kitacin and other organophosphorus fungicides (Kitacin, Inesine, QuinOsar e) used against rice pyriculariosis, O-0-diaryl-1-acyloxy- 2●2●
2-Trichloroethylphosphonate has no unpleasant odor. The fungicide according to the invention has low acute or chronic toxicity to warm-blooded animals.

That is, the acute toxicity of Afuos to white mice after oral administration is approximately 3500 m9/Kg of live weight. The compounds according to the invention rapidly degrade in the biosphere and become non-toxic and harmless to the environment.

Compositions according to the invention are prepared by intimately admixing the active ingredient and a suitable carrier. The active principal ingredients according to the invention are used in customary preliminary forms, such as emulsifiable concentrates (for large or small volume spraying), or in the form of solutions in organic solvents. The concentration of the active principle in the preliminary form varies within the range of 10 to 80% by weight. Alcohol, benzene, xylene, toluene, dimethyl sulfodide, aliphatic hydrocarbons, etc. can be used as the solvent, but the solvent must be substantially odorless, non-phytotoxic, and inert to the active principle. and must not be easily flammable.

Examples are given below for understanding of the invention.

Examples 1 and 2 are examples of the preparation of the compounds of the present invention, and Examples 3 to 15 demonstrate the bactericidal properties of the compounds of the present invention. Example 1 Preparation of 0-0-diphenyl-1-acetoxy 2,2,2-trichloroethylphosphonate (1) b Method A ~-1 The title compound is prepared using the starting material prepared by the above method (III) .

A mixture consisting of 0.1 mol of phosphorus trichloride, 0.2 mol of phenol, 0.1 mol of chloral hydrate and 20 ml of benzene is heated under reflux until the liberation of chloral hydrate from the reaction mixture has ceased (1 to 3 hours). Heat and 10-1
It was left to stand for 2 hours to crystallize.

The crystals you obtained? Separated by filtration and dried to a melting point of 116
-119C diphenyl-1-hydroxy-2,2,2
-trichloroethylphosphonate was obtained. Yield is 89%
It was hot. The melting point of the product after recrystallization from benzene was 125-126°C. Actual value (%) Cl27.
5l; P7.72, C, 4Hl.

Cl3O4P theoretical value (%): Cl27.88; P&12
15ml of benzene and diphenyl-1-hydroxy-2.
2● To a solution of 0.3 mol of 2-trichloroethylphosphonate at a temperature of 20-25° C. with stirring is added 0.06 mol of acetic anhydride containing 1 mol % of sulfuric acid and the mixture is heated at 65 to 7 CfC for 3 to 4 hours. It was heated at a temperature of .

The solvent as well as the resulting acetic acid and excess acetic anhydride are removed by distillation at a temperature of 100 to 12 degrees Hg (10-20 degrees Hg),
The residue was dissolved in 50 mt benzene and washed with water and 2% sodium bicarbonate.

The organic layer was dried using magnesium sulfate and the solvent was removed under vacuum. The residue was a colorless oily diphenyl-1-acetoxy 2●2●2-trichloroethylphosphonate which soon crystallized. The yield was 81% and the melting point of the product was 49-50°C. The compound was distilled (1-2 parts Hg) at a temperature of 195 to 1 part C. nBa0=
1.548;d? =1.387 Actual value (%): C45.
2l; H3.44; Cl24.66: P7
．． 6O: Cl6Hl4Cl3O5P Theoretical value (%): C4
5.26; H3.34; Cl25. lO;
The following absorption bands were observed in the P7.3l IR spectrum.

(νC7l-1): C=0 (1.770); phenyl ring (1.590; 1.480; 950-960; 690)
; P=0 (1.290); CCl3 (840) No absorption band of OH group characteristic of starting diphenyl-1-hydroxy-2●2●2-trichloroethylphosphonate was observed.

NMR-spectrum (carbon tetrachloride): δCH32+0.
5n1. d. (singlet) δ.

H6. l5±0.05n1. d. (Doublet); Jp-H
l2±0.2Hz; δC6H57.2±0.05n1.
d. The mass spectrum of the compound has a peak of molecular ion (M+) m/E422, 424.426 (three chlorine atoms) and fragment ion m/E33l, Tamaba 5 (M-C6H4-CH3), 287, 289, 291
(M-C6H4-CH3-CO2)269, 271(M
-CH2OOCl-CClCHOl (one chlorine atom), 2
It has a peak of 34 (M-CH2COClCCl2CHO).

A-2 The title compound is prepared using a starting material prepared by a modification of method (Ii) above.

A 1.5e three-necked flask was charged with 3 moles of phenol, 1.5 moles of chloral hydrate, and 250 ml of anhydrous benzene (or chloroform, carbon tetrachloride, dichloroethane).

To the thus obtained suspension was added 1.5 mol of phosphorus trichloride while stirring the mixture at 40-50° C. At that time, a violent reaction occurred and hydrogen chloride was generated. After intimately mixing the reagents, the reaction mixture is heated under reflux with stirring until substantially all hydrogen chloride is liberated (3-4 hours), then 3 moles of acetic anhydride are added and heating under reflux is continued. The reaction was completed (3-4 hours, control by thin layer chromatography method). The solvent, the resulting acetic acid and excess acetic anhydride were dissolved in 1
Distillation (10-2i) at a temperature of 00 to 120 DEG C. gave the crude product as a residue. The yield was approximately 100%5. To purify the resulting product, chlorobenzene (or chloroform, carbon tetrachloride, dichloroethane) 350
ml of 2% sodium bicarbonate solution (twice: 350 ml for each wash) and water (twice: 350 ml for each wash).
Washed with m1).

Separate the organic layer, remove the solvent, and reduce the residue from 100 to 1
On applying a vacuum of 1-5 mHg at a temperature of 30C, the product was obtained in the form of a colorless oil. The product is n 0 = 1.5
48:d? )=1.390; R, O. 64 (benzene-
Heptane-acetone (3:3:1) solvent system); upon storage for 1-2 days, the compound crystallizes and its melting point is 48
It was -500C. Yield was 76-80%. A portion of the compound was completely distilled at a temperature of 197-1 part DEG C. under a vacuum of 1-2 degrees Hg, Nr = 1.584; d = 1.390. Actual value (%) C45.68;
H3.4l; Cl24.88; P7.42A-3 The title compound is prepared using the starting material prepared by method (Ii) above.

In a flask equipped with a stirrer and a reflux condenser, 2 moles of phenol and 1 mole of phosphorus trichloride are intimately mixed at a temperature of 20 to 40 °C, and the temperature of the mixture is slowly increased to 100 °C.
Raised to -12CfC.

The reaction mixture was cooled to 20-50°C and 1 mol of chloral hydrate was added dropwise to it. The mixture is heated to a temperature of 40 to 100°C to 110°C, after which 1.2 mol of acetic anhydride is added to it and heating is continued to 90°C to 110°C.
Continue at 10° C. to achieve complete acetylation (1 to 3 hours). The reaction mixture was heated at a temperature of 80 to 130°C for 2
A vacuum of 0-1 TnHg gave a colorless or slightly colored oily commercial product as a residue. This is n 0 = 1.5
49-1.550, crystallized within 1-2 days and had a melting point of 50-M°C. The yield was 95-97%. ~-4 The title compound is prepared using the starting material prepared by method (Ii) above.

A mixture of 0.6 mol of phenol and 0.3 mol of phosphorus trichloride is stirred for three times at a temperature of 20 to 30°C, then the temperature of the mixture is raised to 110°C for 1 hour, and at this temperature the mixture is Further 0. Stir for hours.

The reaction mixture was cooled to 20-30 DEG C. and 0.3 mol of chloral and 0.3 mol of water were added simultaneously at this temperature with stirring. The mixture was heated at a temperature of 90 to 100 °C for 40-5 minutes, then 0.3 acetic anhydride was added.
6 mol was added thereto and heating was continued at a temperature of 90-110°C to complete the acetylation (1 to 3 hours). The reaction mixture was placed under a vacuum of 20-1 mHg at a temperature of 80 DEG to 130 DEG C., yielding the product as a colorless oil with n=1.549 as a residue. This is 1-
It crystallized within two days and had a melting point of 50-52'C.
The yield was 93%. Method B In 20 ml of chloroform, 0.03 mol of O-0-diphenyl-1-hydroxy-2●2●2-trichloroethylphosphonate, the starting material obtained in Method A-1, and 0.045 mol of acetic acid were suspended. 0.07 mol of chlorosulfonic acid was added to the suspension while stirring at a temperature of 25 to 35°C.

The reaction mixture was shaken 3 times and then added 2 times with water with further stirring.
5ml was added slowly. Separate the organic phase and add water (
Three times: 25 ml for each wash, 2% of sodium bicarbonate
The solution (25ml) was washed again with water and dried over sodium sulfate. The solvent was removed in vacuo to give a residue of product with n=1.548. It crystallized within 2-3 days and had a melting point of 49-5. Yield is 8
It was 6%. Example 2 Preparation of a mixture of 0●O-ditri-1-acetoxy 2,2,2-trichloroethylphosphonate.

The title compound is prepared according to method (11) above using the starting material prepared by a modification of A-3 or A-4.

A mixture of 0.5 mol of tricresol (crude mixture of ortho-, meta- and para-cresol) and 0.25 mol of phosphorus trichloride is added at a temperature in the range of 20 to 30°C for 0.5 mol. Stirred for an hour and then raised the temperature to 110-120C within 1 hour.

The reaction mixture was further diluted with 0. Hold under these conditions for 20
Cool to a temperature between
5 moles were added. It is further heated at a temperature of 100 to 110°C until the generation of hydrogen chloride stops, and then acetic anhydride is added.
．． 3 moles were added and heating continued to complete the acetylation. The reaction mixture was heated at 80 to 130°C, 20-1
TIr! Under vacuum of 1 tHg, the yield was 10 as a residue.
A mixture of 0%, slightly colored oily compounds was obtained. This is n
Blue 0 = 1.5315; d White 0 = 1.3262.
Actual value (%): C47.6l:H4. O9; Cl23.
32; P6.73Cl8Hl8Cl3O5
P theoretical value (%): C47.86; H4. O2; Cl23
．． 55; P6.86 Other compounds listed in Table 1 below were prepared under similar conditions.

Example 3 Fungicidal activity of O.0-diaryl-1-acetoxy 2●2●2-trichloroethylphosphonate against wheat stem fungus under greenhouse conditions.

Puccinia graminis (Puccinia gr'Ami)
Wheat grown for 10-12 days was sprayed with an emulsion of the test compound three days before inoculation with pedicelium nisospores. The working suspension is prepared by mixing the compound and Towin 20 in a 1:1 ratio, dissolving the mixture in an organic solvent (alcohol, acetone, xylene), and diluting the resulting concentrate with a theoretical amount of water. did. The bactericidal properties of the compounds were determined by measuring the reduction in the number of Aspergillus pustules compared to the control 8-10 days after inoculation. Control plants were sprayed with emulsions of solvent and surfactant at corresponding concentrations. The reproducibility of the experiment was seen in six pots, each containing five plants. The test results are listed in Table 2 below.

Zineb and chloroacetophos were used as control fungicides. Table 2 also lists data demonstrating the toxicity of the test compounds to warm-blooded animals. Example 4 0.0-diaryleum 1-acetoxy 2●2●2- against stem rot fungus of wheat in the fields
Efficacy of Trichloroethyl Phosphonate The effectiveness of the compound was investigated in the Moscow region on sowing of a spring wheat variety, KrasrlOzemaja, which is susceptible to the attack of the stem fungus (Paxenia graminis f. Tritici).

The seeds were sown in May and germinated on May 17th.

Plant leaf formation phase (stage 6 according to the Feeks scale)
) to create an infection background. The size of the pot used in the experiment was 1.5 d, and the reproducibility was good twice. Plants were present in pairs in comparison with reference and control. The test compounds were used in the form of an aqueous emulsion prepared from a concentrate containing the active principle, solvent and surfactant.

The emulsion is 700 to 800 e1y by hydraulic spraying means.
was applied on the plants at a rate of . The test compound and the reference fungicide were used at a dose of Kglha calculated with respect to the active principle. The fungicide was sprayed on the plants three times. The first time was on the day of the appearance of urticarial pustules on the inoculated plants, the second and third times were 15 and 12 days later, respectively.
I measured the damage to the plants twice. The first time was done nine days after the first spray and the second time two weeks after the third spray. Measured using the James scale. unfavorable seasonal conditions (heavy rain, heat or lack of sunlight);
Therefore, the maturation stage (11, 3) was delayed by almost a month than usual.

A very damaged plant, dried out due to a disease caused by Aspergillus oryzae, was harvested from a pot. The test results are shown in Table 3. From Table 3,
According to the present invention, O-0-diaryl-1-acyloxy-2●2●2-trichloroethylphosphonates have fungicidal properties and most of these compounds are conventionally used with respect to the degree of disease control and their influence on grain yield. The fungicide was found to be superior to Zineb. Example 5 Effectiveness of Afuos KE formulation (50% emulsion concentrate of Afuos) against wheat rot mold in fields The composition of the formulation was as follows (% by weight) Active ingredients
50 solvent (xylene)
46 surfactant (oxyfuos)
4Afuo vs. 5 is a clear light yellow liquid with a density of 1.07 at a temperature of 20°C and a viscosity of 3.5° at 20°C.
It was 6CPS.

The physical properties of the compounds are shown in Table 4 below.

StriifOrmi (Paccinia graminis F. tritici) or Striiformis (P. striifOrmi)
Ahuos KE formulations were tested against artificial paranoia under various agro-climatic conditions for sowing spring and winter wheat susceptible to s).

7 A test of this formulation against natural infection with P. triticina was carried out. An infection background in the inoculum was created by inoculating the inoculum with naspores of Aspergillus at the stage of plant leaf formation (phases 5-6). The initial infection produced pustules of more than 10 m in length per plant. The test pots were 5 or 25 pots, and were reproducible 6 or 7 times, respectively.

The locations of similar pots were random. The Ahuose formulation was used as an aqueous emulsion and sprayed onto plants using a hydraulic sprayer.

The working liquid application rate was 600elha.

The first spray was made on the day the first pustules appeared on the inoculated plants, and the second and third sprays were carried out 7 to 10 days apart. Zineb wettable powder (80%) and hydroxycarboxy wettable powder (75%) were used as reference compounds at the same application rate.

The effectiveness of the fungicide was measured by the degree of plant damage and grain yield.

The obtained results showed that the Afuo Gengo formulation was more effective in suppressing Aspergillus for sowing grains than conventional fungicides such as hydroxycarboxin and zineb.

The test results are listed in Table 1-5 and Table 6. Example 6 Afos (USVS method) against wheat fungus in fields
40%) formulation efficacy.

The composition of the formulation was as follows (wt%): 0.0-diphenyl-1-acetoxy 2.2.2-trichloroethylphosphonate (main active ingredient)
40 dilution solvent
57 Auxiliary Substances - GOudrOn
Three formulations contained a homogeneous dark brown liquid with a slightly peculiar odor.

The physical parameters of the formulation are listed in Table 7 below. US
Tests on Afuos preparations using the VS method were carried out in areas with different agro-climatic conditions using F. tritici or P. striformis.
The ultra-small volume spraying (USVS) method was used to sow spring and winter wheat, which is susceptible to damage from P. ifOrmis).

The parasitic background in the seed material was created by inoculating it with naspores of Aspergillus aspergillus.

Initial infection level was 10 or more pus spores per plant. The size of the test pots was 50 or 100 d, the reproducibility of the test was 3 and 5 times, respectively, and the pot positions were random.

Disc-fan sprayer T
It was applied on the plants by urbairTOT.

The application rate of the formulation was 7.5 fl ha. The first spray was made on the day the first diaspores appeared on the inoculated plants, and the second and third sprays were made 7 to 10 days apart. Zineb (80% wettable powder) was used as a reference fungicide, which was applied on the plants in the form of an aqueous suspension.

In this case, a hydraulic sprayer was used, and the application rate of the working liquid was 600.
It was 1 ha. The effectiveness of fungicides was measured by the degree of plant damage and grain yield.

The test results are listed in Table 8 below. According to the obtained results,
Afuos formulations applied onto plants by ultra-small volume spraying (USVS) have been found to be very effective compositions for controlling Aspergillus and Aspergillus aureus on sowing of wheat.

When applied three times at a rate of 7.5'1 ha, the Afuos formulation applied by the USVS method was shown to be substantially more effective in suppressing Aspergillus than Zineb 7, and said application resulted in significant yield loss. Promised to be less.

Example 7 The effectiveness of Afuosu Xiang preparation and Zineb against Aspergillus oryzae in wheat was compared by spraying them at different spray intervals (Krasnada region, 1977).

Plants at the leaf formation stage (phase 7 according to the Feeks scale) were infected with resuscitated diaspores of Aspergillus xanthus (10 m
91d).

The test pots (2d) were sprayed with an emulsion of Afota (G) and each spray area was 3k91 ha, calculated as the active ingredient.
A suspension of Zineb was sprayed at an application rate of 60,011 ha per active liquid. The results obtained show that when the spray interval is long and the number of treatments is the same (trials 3 and 4), the efficacy of Afuos is relatively high, whereas the efficacy of Zineb is reduced to practically zero. Yields of pots treated with Afuos were definitely higher compared to pots treated with Zineb. Example 8 Efficacy of Afuos KE preparation against stem fungus of winter wheat in a single spray of prophylactic treatment (Moscow region, 19
77) Leaf formation stage (phase 8 according to the Feeks scale)
) were sprayed with Afuos at a dose of 600'1 ha of application rate of 3k91ha1 active liquid, calculated as active ingredient.

At this point, no stem fungus was observed in the test pot, but in the surrounding seedlings, the degree of damage was approximately 1 pustules/1 stem (
stomach). 1%). After some time had passed, stem fungus spread all over the test pot from the surrounding seedlings. However, the degree of damage of protected plants was substantially lower than that of unprotected plants. The weight of 100 grains obtained from protected pots was 29.7 g, and that from unprotected pots was 24.0 y. Example 9 Effect of various doses of Ahuos on the yield of wheat plants and grains (evaluation of phytotoxicity) No phytotoxicity was observed in the tests of the Ahuos KE formulation for fungicidal properties.

In order to determine the effect of the formulation on plant productivity and crop quality, uninfected sows of spring-sown wheat were treated with Afuose Xiang at doses of 3, 6, 12 and 24 k91 ha calculated as active product. The aqueous emulsion was sprayed three times.

The size of the test pots was 3j1′, the reproducibility of the test was 6 times and similar pots were randomly located (Latin square).

The first spray is done at the time of leaf formation, the second and third are 1
I went every 0 days. As a control, another study was carried out in which pots were sprayed with Zineb based on the active principle at a dose of 3k91ha every 5 days. To determine toxicity to plants, a 5-point method was used (0, no phytotoxicity; 4, complete death of plants). The test results are shown in Table 10 below. Table 10 shows that Afuos KE causes leaf changes only when applied at a dosage of 24k91 ha.

However, it was also found that the grain yield and grain quality were not adversely affected. Furthermore, even when Afuos was used during the plant growth period, there was no adverse effect on the quality of the seeds during sowing. The germination energy and vigor after storing the grain for one year were 98.5 and 99.5%, respectively. Example 10 Grape bacteria (Plasmoparaviticola)
Effectiveness of Afosho preparation against humid subtropical regions (A
The test was carried out at dzharskaja ASSR).

Spray 6 times within the time limit determined from the Mueller scale.
I went around. Zineb (80% wettable powder) was used as a reference compound. The percentage of disease progression is determined by the formula: R=ΣR已卯 (where Σ, p... sum of the frequencies of points; n... number of leaves and fruits evaluated c...・Determined according to the highest point of the scale used).

The test results are listed in Table 11 below.

Example 11 Peach leaf stain caused by Septoria (Septria pyricola)
Effectiveness of Afuo vs. C formulation against humid subtropical regions (A
The test was carried out at dzharskaja ASSR).

Spraying was carried out three times at 15-16 day intervals. Zineb was used as a reference formulation. The percentage of disease control is calculated using the formula: X=02
It was determined according to Ekito 10 (in the formula K...degree of damage to control plants b...plant damage in various tests).

The test results are listed in Table 12 below.

Example 12 Efficacy of the Ahuos Xiang preparation against apple apple spot in the Krasnada region.

Simirenkorerle prone to apple spots
A test was conducted by cutting a branch from an apple tree of the T variety.

Branches with 8-12 day old leaves were placed in a container with KnOp solution and kept there until the end of the experiment.

Experiments were conducted using a 0.1% emulsion of Afuos.

Care was taken to ensure that the emulsion was evenly distributed over the upper and lower surfaces of the leaves. One day after treatment with a fungicide, Enturiaina equilis (Enturiaina equilis) appears on the apple branches.
an aqueous spore suspension (500,000 spores in 1 ml of suspension) was sprayed. Conidia collected from damaged apple leaves in an orchard were used. The infected plants were placed in a humid chamber and incubated at a temperature of 20°C for 2 hours.
It was held for 4 hours.

At the end of this period, the plants were removed from the humid chinbar and left at the same temperature. The relative humidity within the premises was less than 76%. The first signs of spotting are 8-1 under these conditions.
0 It was seen after the fire. Measurement of spot damage was performed using a 6-point method.

I noticed damage to the four upper leaves.

Reproducibility of the test was seen in three branches. Under the above conditions, Ahuos completely protected the apple trees from spotting, while Zineb reduced the severity of the damage by 97% compared to the control.

Example 13 Toxicity of Ahuos on spores of Pyricularia oryzae P. For growth, spores of A. oryzae were introduced into a drop of aqueous acetone solution of Afuos in the presence of the emulsifier Towin-80, the concentration of which was gradually reduced from 50 to 0.05 WL911.

After 2 hours, the number of spores that germinated and the number of spores that did not germinate were measured using a microscope.

300 spores were considered in each test. Test reproducibility 13 times. The afuos concentration was measured when 50% of the spores were dead.

Kitashichi at the same concentration was used as a reference compound.

An aqueous-acetone emulsion of Towin-80 at the highest tested concentration was used as an unprotected control. As shown by the results obtained, Afuos was superior in bactericidal activity to Kitacin by about 5@. The test results are listed in Table 13 below.

Example 14 Efficacy of the Afuosu preparation against Phytophthora phytophthora (Phytophthora infestans) A test was carried out by treating tubers damaged by Phytophthora.

The tubers were treated with a 1% water column emulsion of the formulation to thoroughly moisten them and kept in a humid chamber at a temperature of 18° C. for 14 days.
The sporulation ability was then measured. Tetramethylthiuram disulfide (TMTH) at the same concentration as the reference compound
was used.

Similar tubers not treated with fungicides were used as controls. Tests showed that no sporulation was observed in the tubers treated with the Afuos formulation.

Individual molecular sporophores were seen in the TMTD test, but sporulation was very intense in the control. Example 15 Toxicity of 0-0-diaryl-1-acyloxy-2.2.2-trichloroethylphosphonate to warm-blooded animals Toxicity (LD,O) was determined by oral administration of the compound on male and female white mice.

A portion of the test compound was mixed with Emulsion Twin-20 and diluted with distilled water to the desired working concentration. The formulation was administered directly into the stomach of the test animal 2-3 hours after feeding using a metal probe and syringe. The study was conducted at several different doses, with 6 animals for each dose.

The animals were then observed for 2 weeks. The test results are shown in Tables 2 and 12.

Claims (1)

[Scope of Claims] A novel O.O-diaryl-1-acyloxy-2.2.2-trichloroethylphosphonate represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R is a C_1-C_8-alkyl group or a phenyl group, and X and Y may be the same or different from each other, and each is a hydrogen atom, C_1-C_8-alkyl group, phenyl group or halogen, or in combination form a member of the benzene ring, and
m and n are each 1-2. A disinfectant composition containing O.O-diaryl-1-acyloxy-2.2.2-trichloroethylphosphonate represented by the following formula as an active ingredient and also a carrier thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼In the above formula, R is a C_1-C_8-alkyl group or a phenyl group, and X and Y may be the same or different from each other, and each represents a hydrogen atom, C_1-C_8-alkyl group, phenyl group or halide, or
Together, they form a member of a benzene ring, and m and n are each from 1 to 2. 3. The disinfectant composition according to claim 2, wherein the active ingredient is contained in an amount of 10 to 80% by weight. 4. The disinfectant composition according to claim 2, wherein the active ingredient is O.O-diphenyl-1-acetoxy-2.2.2-trichloroethylphosphonate.