JPS6133191A - Fungicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fungicides based on thiophosphites, thiophosphite monoesters and their salts.

These esters may be referred to as thiophosphonic acid monoesters 0 (alkyl, aryl, etc.), but hereinafter referred to as thiophosphonic acid monoalkyl (aryl, etc.) in this specification. The present invention further relates to methods for preparing some of these compounds that have not been described in the literature.

In particular, the present invention provides compositions suitable for use in controlling parasitic fungi on plants, containing as active substance at least one thiophosphite having one of the following general formulas: Pertains to.

and [wherein R is a hydrogen atom; 8 (preferably 1 to 5) alkenyl groups, halogenalkenyl groups, alkynyl groups, halogenalkynyl groups, alkoxyalkyl groups, alkenoxyalkyl groups, or cyclohexyl groups, aryl groups, substituted aryl groups (preferably phenyl and Substituted phenyl), aralkyl group,! Substituted aralkyl group (preferably phenylalkyl)
, or a heterocyclic group (
preferably a tetrahydrofurfuryl group), M is a hydrogen atom,
Inorganic or organic cations (ammonium, 1 to 4 carbon atoms)
ammonium or cyclohexyl group substituted with 1 to 4 alkyl groups or hydroxyalkyl groups, ammonium polysubstituted with phenyl groups, or optionally nitrogen belonging to a heterocycle having 5 to 6 atoms, copper, zinc, manganese , a metal cation of an alkali metal, alkaline earth metal or heavier metal such as iron, nickel, aluminum), n is an integer equal to the valence of M. Particularly preferred compounds are those in which R is an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 2 to 5 carbon atoms whose main chain is a β-hydroxyethyl group or an α-hydroxyzolobyl group, and M is a hydrogen atom. or a compound represented by a general formula in which a metal cation of an alkali metal or an alkaline earth metal, or a polysubstituted or unsubstituted ammonium group or pyridinium group is represented by 1 to 4 methyl or ethyl groups.

Some of these compounds, such as ammonium and potassium thiophosphite, ethyl and butyl thiophosphite, and their sodium salts (C,A,.

48 volume, 324 3e) is publicly known.

However, many compounds are new. Furthermore, there is no literature indicating the use of known compounds as fungicides.

The compounds of the present invention in salt form can be expressed in three tautomeric formulas.

or or Following conventional practice, 2B will be used from now on.

However, both compounds of formula A and formula C are included within the scope of the present invention.

Generally, compounds of the invention may be prepared by hydrolysis or saponification of secondary thiophosphites.

When the secondary thiophosphite is a cyclic 9x7 ter, a hydroxyalkyl thiophosphite within the range of formula (■) is formed in the first step, and then hydrolysis is continued according to the reaction formula below to produce a thiophosphite of formula I. Salt is produced.

Sodium dithiophosphite was produced by this method. This is a novel process insofar as it relates to the production of metal thiophosphite salts.

2-thio-2H94-methyl-1,3,2-:, 'oxaphosphorane 479 in 640 cc of 1N NaOH solution
Add while stirring. Stirring is then continued for 2 hours. Since the product is water soluble, water is removed by vacuum distillation. The precipitate is washed with acetone and then dried to yield a white solid with a sulfur odor and 90% water of crystallization.

Yield: 63% Melting point: >300°C I (Analysis percentage of POtSNa*: % HNa P-8 Reference calculation value 1.65 29.5 19.9 2
0.48 Measured value 2.48 29.36 19.
8 20.55 White powder calcium thiophosphite HPO2S2-Ca2+ was produced in the same manner.

Yield: 68% Melting point: )300C HPOtSCa, 2HzO analysis percentage: %
HCa P S calculation value 3
．． 24 22.28 18.05 18.58 Measured value 3.46 22.23 17.69 1
8.21 Barium thiophosphite was produced in the same manner.

Barium hydroxide in NaOH, water 400 - 107
A suspension of I was used. After stirring for 2 hours, the resulting precipitate is washed with a small amount of ice water and acetone.

When dried, a white powder product is obtained which is sparingly soluble in water.

Yield: 82% Melting point: >300°C Analytical percentage of HPO2S Ba, 2H20
HBaPS calculated value 1.85
51.1 11.52 11.88 Measured value
2.26 50.75 11.47 11.80
This barium salt may be used for the preparation of new metal thiophosphite salts by a fold conversion reaction.

Partial hydrolysis or saponification of 2-thio-2H-1,3,2-dioxaphosphorane or dioxaphosphorinane derivatives according to the reaction formula below results in 2-hydroxyethyl thiophosphite and 3-hydroxypropyl thiophosphite, respectively. is generated.

r*=0.1 Yields are good and often quantifiable.

Magnesium 3-hydroxypropylthiophosphite was produced by this method.

A suspension of 6.91 g of 2-thio-2H-1,3,2-dioxaphospholinane and calcined magnesia II in 100 g of water is stirred for 2 hours. Allow the reactants to completely dissolve. Evaporation to dryness gives 8.5 g of a white hygroscopic powder.

Yield:=XOO% Analysis percentage of Cs HeMg0sPS:% CHM
g P S Calculated value 21.54 4.7'l 7.27 1
8.55 19.14 Measured value 21,60 5.0
9 7.18 18.29 18.99 Confirm the structure using a nuclear magnetic resonance (NMR) spectrophotometer. NV1
Using a 4-deformation apparatus with a magnetic field equal to 60 me/s and using deuterium-containing methanol as the solvent and hexamethylene disiloxane (HMDS) as the reference.
Use. The letter J indicates the coupling constant in cycles per second, and δ indicates the shift in ppm.

J: 590 c/s - H δ near, 90 ppm Other metal compounds were prepared in a similar manner using various cyclic derivatives and/or saponifying bases. The formulas, yields, properties and analytical percentages of these compounds are shown in the following table.

Using ammonia or substituted or unsubstituted primary, tertiary or tertiary amines, 2-
Ammonium hydroxyethylthiophosphite or ammonium 3-hydroxypropylthiophosphite may be produced.

In this way diethylammonium 2,2-dimethyl-3-hydroxypropylthiophosphite was produced.

CHs S 29 water and 4 diethylamine in 5 Qcc of acetonitrile
2-thio-g in 50 cc of acetonitrile.
2H-5,5-dimethyl-1,3,2-dioxaphosphorinane is rapidly introduced into a solution of 8.3 g at room temperature. After heating under reflux for 1 hour, the acetonitrile is evaporated under reduced pressure. Obtain a colorless oil.

Yield: =XOO% 20.

n D -1,500 Analysis percentage of GH24NO3: % CHNFS Calculated value 42.02 9.34 5.45 1
2.06 12.45 Measured value 41.99 9.20
5.30 11.98 12.40 NMR structure
Confirm with a spectrophotometer.

J: 574 c/s - H δ: 7.93 ppm Other substituted or unsubstituted ammonium salts were prepared in a similar manner using various cyclic derivatives and/or nitrogen bases.

The formulas, yields, physical properties, analytical percentages and, where possible, their NMR properties of these compounds are given in the following table.

A salt of a thiophosphite monoester was prepared using a known method (see Houben-Veil, 7Osphere Pindungen, p. 82, C.A., 483243 (1954)) according to the reaction formula below. O may be prepared by partial hydrolysis or saponification of the corresponding ester. Sodium ethylthiophosphite was prepared by this method.

10% Na in 7.7 g of diethyl thiophosphite dissolved in a mixture of 20 cc of ethanol and 100 cc of water.
Add 20 cc of OH aqueous solution with stirring. Continue stirring the mixture for 1 hour to react. After evaporation of the solvent, a gray product crystallizes out. Dissolve this in a small amount of acetone,
Salting out by adding petroleum ether@The precipitate is filtered and then dried in vacuo to give a white powder.

Yield: 60°C Melting point: 100°C Analysis percentage of C2H6Na0□PS: % CHNa P Calculated value 16.2 4.05 15.5 20.90 Measured value 16.2 4.16 15.5 20°95NM
Confirm the structure from the R result.

J: 574C/S -H δ: 7.96 ppm Diethylammonium isozolopylthiophosphite was produced in the same manner.

■ S'() Diisozolopyl thiophosphite 9.1f and diethylamine 5
(excess amount) and 1 t of water are dissolved in 80 cc of acetonitrile. Heat under reflux for 5 hours and evaporate the solvent under reduced pressure to yield a colorless oil 10.5F. On cooling it crystallizes to give an extremely hygroscopic white solid.

Yield: 100% Analysis percentage of C7H2oNO2PS: % CHNPS Calculated value 39.44 8.39 6.57 14.55
15.02 Measured value 39.49 8.96 6.73
14.55 15.06 Confirm the structure from the NMR results.

J: 5700/S-H δ: 7.91 ppm Other metal salts and other ammonium salts were prepared using various diesters and/or bases in a similar manner to the two examples in Tsumugi. The formulas, yields, physical properties, analytical percentages, and NMR results of these salts where available are shown in the following table.

It was found from the Examples described below that this series of compounds has excellent bactericidal properties. These examples demonstrate the efficacy of the following compounds.

In the Examples, "completely protected, suppressed or inhibited" means that 95 or more of the leaf surfaces were protected, that is, fungi were inhibited or inhibited, and "sufficiently protected" meant that the surface of the leaves was protected or inhibited. 80-9
This means that 5% is protected.

1 Sodium thiophosphite 2 Calcium thiophosphite 3 Barium thiophosphite 4 Sodium 1-methyl-2-hydroxyethylthiophosphite 5 Sodium 2-methyl-2-hydroxyethylthiophosphite 6 1-Methyl-2-hydroxyethyl Calcium thiophosphite 7 2-Methyl-2-hydroxyethylcalcium thiophosphite 8 Calcium 1-methyl-2-methyl-2-hydroxyethylthiophosphite 9 1-Methyl-2-methyl-2- and droxyethylthio Magnesium phosphite 10 Calcium 3-hydroxypropylthiophosphite 11 Magnesium 3-hydroxypropylthiophosphite 12 2.2-Dimethyl-3-hydroxypropylthiophosphite Sodium 13 2.2-Dimethyl-3-hydroxypropylthiophosphite Calcium 14 Magnesium 2.2-dimethyl-3-hydroxypropylthiophosphite 15 Ammonium 2-hydroxyethylthiophosphite 16 Ammonium 1-Mesol-2-hydroxyethylthiophosphite 17 Ammonium 2-methyl-2-hydroxyethylthiophosphite 18 1-Methyl-2-methyl-2-hydroxyethylthiophosphite ammonium 19 1-methyl-2-hydro5xyethylthiophosphite 20 diethylammonium 2-methyl-2-hydroxyethylthiophosphite 21 3-hydroxyzolo Ammonium birthiophosphite 22 Diethylammonium 3-hydroxypropylthiophosphite 23 2.2-Dimethyl-3-hydroxyzoropyrthiophosphite ammonium 24 2.2-Dimethyl-3-hydroxyzoropylthiophosphite diethylammonium 25 2 .2-Dimethyl-3-hydroxypropylthiophosphite pyridinium 26 Sodium ethylthiophosphite 27 Calcium ethylthiophosphite 28 Barium ethylthiophosphite 29 Magnesium ethylthiophosphite 30 Sodium isopropylthiophosphite 31 Calcium isopropylthiophosphite 32 Ammonium ethylthiophosphite 33 Diethylammonium ethylthiophosphite 34 Diethylammonium isopropylthiophosphite 35 Calcium n-propylthiophosphite Example
1. In vitro test The effect of the compound of the present invention on the following fungi is tested.

- Colletotrichum urinarium collecttotr
ichum1agenarlurrl+ This belongs to the Ascomycota family and is the cause of melon char blight.

- Biricularia oryzae piricularia o
ryzae.

It belongs to the Deuteromycota family and is the cause of rice blast disease.

Each test was conducted in the following steps.

Inject 5 cc of agar medium MALT-AGAR-MERCK into a test tube. Close the test tube and sterilize it. Next, medium t
Maintain molten state at -60°C. Then active substance 1100
Inject into the medium the necessary amount of acetone solution to achieve the desired dose, maintaining a ratio of 50 cc per pp.

The test tube is shaken and then left to cool until the contents solidify.

Next day, 100.000 spores/cc gold-containing spore suspension 0
．． Inject 5 cc with a syringe or inoculate a test tube with a mycelial explant 8 cm in diameter. Next, place the test tube in the dark at 26°C.
The test results are examined 9 days after inoculation.

Under these conditions, complete inhibition of fungi was found.

-For Colletotrichum lagenarium Compounds 9,12
．． 27.29, 33.35 at a dose of 200 ppm Compounds 8.18, 21.31 at a dose of 100 ppm Compound 6.7.15 at a dose of 50 ppm - For Pyricularia oryzae Compounds 2 and 19 were used at a dose of 50 ppm Then, fungi can be completely suppressed.

Example 2 Test Tomato fungi belong to a family of algal fungi that parasitize the leaves of growing tomatoes.

Approximately 608th tomato plant (Marmande plant) is completely sprayed with an acetone solution of the active substance or an aqueous suspension solution of an irrigation agent.

The suspension aqueous solution of the irrigation agent has the following composition (weight composition) - Active substance to be tested 20% - Deflocculant (calcium lignosulfate) 5% - Moisture ff
1l (sodium alkylarylsulfonate)
1% - filler (aluminum silicate) 7
A 4% aquarium is diluted to contain the desired amount of the active substance to be tested.

Each test is repeated twice.

After 48 hours, the leaves are cut and coated with 9 coats of wet paper covering the bottom of the Petri dish. Then spores so, oo.

A sheet of paper impregnated with the spore/e.g. gold-containing suspension is then left to stand for 8 days, maintaining the test temperature at 16 °C, and on the 8th day, the surface area attacked by the fungi is coated with the active substance. The results are tested in comparison to control plants treated with the non-containing composition.

Under these conditions, compound Ken 34 was administered at a dose of 2t/! When used, fungi are completely inhibited.

Example 3 It belongs to the family of Basidiomycetes that parasitize legumes.

An acetone solution or an aqueous suspension of a test substance having the same composition as in Example 2 is sprayed with a spray gun onto the back side of a leaf of approximately 108th potted legume (type Contender).

After 48 hours, the undersides of the leaves are sprayed with an aqueous spore suspension containing approximately go, ooo spores/cc. Next, place the flower pot at a temperature of 2.
Incubate in an incubator at 0°C and 100% relative humidity for 48 hours.

Approximately 10 days after fungal spraying, the results are examined in comparison to control plants. Control plants will be at least about 75% eroded.

Under these conditions, compound A34 completely protects legumes at a dose of 29/1.

Example 4 a) Preventive treatment A suspension aqueous solution of an irrigation agent having the following composition (weight composition) is sprayed with a spray gun on the underside of the leaves of a potted grape plant (Gyame species).

- Tested active substance 20% - peptizer (calcium lignosulfate) 5% - wetting agent (
Sodium alkylaryl sulfonate) 1%-
Filler (aluminum silicate) 74% Aqueous solution is diluted to prepare an aqueous suspension containing the desired dose of the active substance to be tested. Each test is repeated three times.

After 48 hours, fungal spores appeared on the underside of the leaves.

Plants are mixed with bacteria by spraying an aqueous suspension containing units/cc.

Next, the flowerpot was placed in medium II at a temperature of 20°C and a relative humidity of 100%.
Let stand in a container for 48 hours.

Plants are inspected 9 days after inoculation.

Under these conditions, at a dose of 0.5 t/l, compounds A1-3.8-11.18-21 and 24-31 completely protected the plants, while A4-6, 16.17 and 33 Protect plants well. Compound AI for dose 1 f/l
2.14.15.22.23 and 32 sufficiently protect the plants.

Furthermore, it was found that none of the tested compounds showed any signs of phytotoxicity.

b) Treatment after bacterial contamination The order of the above-mentioned treatment a) is changed, and the plants are first contaminated with bacteria and then treated with the active substance to be tested.

Observe the plants 10 days after inoculation.

Under these conditions, at a dose of 1t/It, compound 16.
17.19 and 20 have been found to completely inhibit the growth of mildew on grape plants.

The tested grape beads (Gyame variety) are sprayed with 40 cc f of a solution of the active substance to be tested at 0.5 f/ml'. After 2 days, the grapes are mixed with bacteria using a suspended aqueous solution containing C. spores/CC. Next, the grapes are heated indoors at a room temperature of 20°C and a relative humidity of 100% for 48 hours. After about 9 days, the degree of erosion is observed in comparison to non-eroded control plants sprayed with 40 cc of distilled water.

Under these conditions, compounds A1-34 were found to be absorbed through the roots at 0.5 t/) and fully protect grape leaves against downy mildew. This indicates that the effects of these compounds on It is a clear indication of systemicity.

Example 5 Five plots of a test tobacco plant (PH10) field were treated on June 15th for each tobacco plant.
160t/l maneb 80%, 300t/1 respectively
of sodium ethylthiophosphite 50%, magnesium ethylthiophosphite 50% of 300 f/l. One plot is left untreated as a control plot.

After 48 hours, the plants are artificially mixed with a fungus (Peronospora tabacina) and then steamed for one time. The treatment is repeated once a week.

On August 12th, measure the number of mold spots per plot and examine the results. The results are shown in the table below.

In other tests, the two compounds of the invention were found to be active in therapeutic treatments against the fungi and to have systemic effects.

Example 6 Testing on Avocado Plants Young plants of avocado (Persea indica species) were treated with Phytophthora cinnamomi phytophthoracin.
Namo i ft planted in the infiltrated soil, then 3
Spray the soil with a solution containing W/1 ammonium ethylthiophosphite. Some plants were left untreated as control plants (.

Under these conditions, the roots of the control plants are completely wiped out after 20 days, while 86 roots of the treated plants are found to be healthy. .

Example 7 Testing on pineapple plants Young plants of pineapple were treated with Phytophthora
After 8 hours, it is sprayed with a 0.5 f/) calcium ethylthiophosphite solution. After 30 days, the fungus is completely suppressed on the treated plants, while the control plants are infested.

Example 8 Ten strawberry plants (Silprise des Arts species) were immersed in an aqueous solution containing 0.2% calcium isozolopyrthiophosphite for 1 hour, dried, and then grown on June 14th.
The plants are planted in soil artificially mixed with P. actorum bacteria.

The plants are sprayed with the solution immediately after transplanting and every 8 days until July 18th. This is a total amount of active substances used per plant of 0. ! It's equivalent to M'J.

Control plants are soaked in water and sprayed with water.

Under these conditions, the Ichiza plants were completely protected when observed on July 14, while 76% of the control plants had died.

Example 9 On July 27th, a green pepper plant (Yorowan f type), which was cultivated in a test for green pepper plants, was infected with Phytophthora capsikii Phytop.
The plants are transplanted into flowerpots in soil artificially contaminated with hthora capsici bacteria. Immediately after transplant and until July 18th 8
The plants are sprayed every day with an aqueous solution containing calcium 1-methyl-2-hydroxyethylthiophosphite. This reduces the total amount of active substance used per treated plant to 0.5.
Make it 9.

Control plants are sprayed with water.

Under these conditions, when observed at the end of August, 10 plants were healthy, but the control plants were wiped out by the 25th day of the month.

All of the above examples clearly demonstrate the remarkable bactericidal activity of the compounds of the present invention against various fungi belonging to the Ascomycota, Basidiomycota, Deuteromycota, and Phycomycota series, and in particular, against the growth of grape-parasitic fungi. It exhibits a systemic anti-mildew effect that is exerted to prevent and control the spread of the disease and further prevent further epidemics.

However, it has been found that the compounds of the present invention are extremely effective against other types of parasitic fungi. These fungi include, for example, Guignardiabidvrellii, which parasitizes grapes.
, Pseudobelonospora humulisperma PhytoP
hthora megas erma, phytophthora
Phytophthora drech
sterl and other Phytophthora n that parasitize plants growing in temperate or tropical climates, especially crocodiles, bell peppers, onions, chili peppers, tomatoes, beans, ornamental plants, pineapple, dice, citrus, cacao, palms, gums, etc.
Ph7tOphthOra Sp-.

Therefore, the compound of the present invention reduces the percentage of fungal diseases caused by algae and fungi.
It is particularly suitable for use in the preventive or curative treatment of diseases caused by Ascomycetes, Basidiomycetes and Deuteromycetes on the above-mentioned plants.

These compounds were combined with other fungicidal phosphorus derivatives with anti-mildew properties, including 2-hydroxy-1,3゜2-dioxaphosphorane, β-hydroxyethyl phosphite, phosphonic acid diesters, phosphorus compounds, amino phosphites, 2-
Hydroxy-1,3゜2-dioxaphosphorinane, γ-
It has also been found that it may be mixed with hydroxypropyl phosphite, phosphorus-based trialkylimides, 2H-2-thio-1,3,2-dioxaphosphorane and phospholinane. These compounds are disclosed in U.S. Pat.
No. 3-37994, No. 73-43081, 73-4
No. 5627.

No. 71-08995, No. 74-10988, 74-
No. 13246.

74-34529, 74-34530 and 75-
This is the purpose of No. 04394.

The dosage of the compounds of the invention can vary widely depending on the strength of the fungi and the weather conditions. Generally, the optimal active substance dose is between 0.01 and 5 F/no.

In actual use, the compounds of the present invention are rarely used as they are. In many cases, said compound, in addition to the active substance of the invention, forms part of the medicament, which usually consists of a support and/or a surfactant. means a substance, organic or non-organic, natural or synthetic, which is combined with the active substance in order to facilitate its application to the seeds or soil or its transport or handling. The support is solid (clay, natural or synthetic silicate, resin, wax, solid fertilizer)
It may be a fluid (water, alcohol, ketone, petroleum fraction, chlorinated hydrocarbon, liquid ibis gas).

Surfactants may be ionic or nonionic emulsifiers, dispersants or wetting agents. Suitable surfactants are, for example, polyacrylates, ligninsulfonates, fatty alcohols, fatty acids or condensates of fatty amines with ethylene oxide.

The compounds of the present invention may be prepared in the form of aqueous solutions, soluble powders, dustable powders, granules, solutions, concentrated emulsions, emulsions, concentrated suspensions, and aerosols.

Usually prepared wettable powders contain from 20 to 951 parts by weight of the active substance, and in addition to the solid support, usually contain 0 to 5% by weight of a wetting agent and 3 to 10% by weight of a dispersing agent. and
If necessary, one or more stabilizers and/or other additives such as penetrants, adhesives or anti-caking agents, colorants, etc.
Contains ~10 weight rice cakes. An example of the composition of an irrigation agent is shown below.

- Active substances 50% - Calcium lignosulfate (peptizer) 5% - Anionic wetting agent 1% - Anti-caking silica
5%-kaolin (filler)
A 39% water-soluble powder may be prepared by mixing 20-95% by weight of active substance, O-10% anti-caking filler and 0-1% wetting agent. The remaining components consist of water-soluble fillers, primarily salts.

An example of the composition of the water-soluble powder is shown below.

- Active substance 70% - Anionic wetting agent 0.5% - Anticaking silica 5% - Sodium sulfate (soluble filler) 24.5% Aqueous dispersions and emulsions, e.g. Compositions obtained by dilution with water are also within the scope of the present invention. These emulsions may be water-in-oil or oil-in-water and may have a thick consistency similar to mayonnaise.

The compositions according to the invention may contain other ingredients such as film-protecting colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants, and may also contain agrochemicals, in particular acaricidal or insecticidal It may also contain other known active substances having properties.

Claims (4)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 is a hydroxyalkyl group with 1 to 8 carbon atoms, M' is a hydrogen atom or an inorganic or organic cation, n' is M' is an integer equal to the valence of the compound. (2) The compound according to claim 1, wherein R' is a substituted or unsubstituted 2-hydroxyethyl group or 3-hydroxypropyl group. (3) The compound according to claim 1 or 2, wherein M' is an alkali metal or alkaline earth metal cation. (4) The compound according to any one of claims 1 to 3, which comprises hydrolyzing or saponifying a substituted or unsubstituted 2-thio-1,3,2-dioxaphosphorane or phosphorinane. Manufacturing method.