JPS60215692A - Intermolecular salt of phosphonic acid for protecting crops from fungal diseases - 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 an inner salt of phosphonic acid, a method for producing the same, and its use in the agricultural field.

In the literature (French Patent No. 2,254,276),
As an active substance, the general formula (where R is an optionally substituted alkyl, alkenyl or alkynyl, aryl or heterocyclic group;
Disinfectant compositions are described containing derivatives of phosphonic acids with M being an ammonium or metal cation.

However, the present applicant has discovered a phosphonic compound of general formula (1) which has not been reported in the literature and is the main feature of the present invention.

Here, R is H or C, Nc, alkyl, R1 and R2
are the same or different from each other, H, C3-C4 alkyl (when R=H), C1-C12 alkyl (U=Ct
~C, when alkyl χ), C8~C, alkenyl or alkynyl (when R = H), C5~CI2 alkenyl or alkynyl (when l = c, ~C, alkyl), alkyl and alkoxy fractions carbon atom 1~
alkoxyalkyl having 12 atoms, aryl especially phenyl (when R=C, NC, alkyl), or aralkyl, or R1 and R1 taken together with the N atom, a non-aromatic group having 5 to 6 atoms; forming a heterocyclic group, which group optionally contains, in addition to said N atom, a heteroatom selected from the group consisting of 0, N and S, and also optionally a C1-C4 alkyl or a carbon in the alkyl moiety. optionally said second heteroatom N has the formula BS
and R4 are the same or different, and H't c
, ~C4 alkyl or phenyl.

Note that the heterocyclic group is preferably pyrrolidine, piperidine, morpholine, thiomorpholine, or piperazine.

The compounds of formula (I) have the property of protecting crops from fungal diseases and can therefore be used in the agricultural field.

Another subject of the invention are compositions containing compounds of formula (1) as active substances.

A further subject of the invention is a synthetic method for obtaining compounds of formula (1).

For the subject matter or purpose of Sen, please see the explanations and "examples" below.
It will be clear to those skilled in the art.

A compound having the formula (1) of R=C, ~C, alkyl is
Dialkyl phosphoric acid preferably dimethyl phosphite or diethyl phosphite and 2-hydroxyalkylamine are combined with the following formula (where R, R', R'', R'' and R4 are the same meanings as defined above). It is prepared by reacting according to

This reaction involves contacting the two reagents in an inert solvent and heating the resulting solution to a temperature in the 150-190"C range for 1-6 hours to remove the alcohol that forms while producing the product of organic synthesis. The separation, purification, and
This is carried out by separating the desired product from the solvent by extraction and crystallization techniques.

Inert solvents useful in the synthetic process of the present invention are selected from the classes of non-polar solvents and non-pritic polar solvents. Some examples of non-polar solvents are helobenzene, especially 1,2-dichlorobenzene, xylene, decalin and tetralin.

Some examples of non-flotic polar solvents are dimethylformamide and acetonitrile.

More particularly, according to a preferred method of the invention, stoichiometrically equal amounts of dialkyl phosphate and 2-hydroxyalkylamine are reacted in 1,2-dichlorobenzene for 1 to 5 hours. , while the solution is heated to reflux.

Afterwards, the lower alcohol is distilled off from the reaction environment. As soon as all the alcohol has been removed, the ionic compound is isolated by cooling and removing the reaction solvent. The product to be obtained can ultimately be e.g.
It is purified by treatment with a polar solvent such as acetonitrile and separated from the solvent by evaporation or decantation.

Examples of compounds made according to the process detailed in Method B in Example 1 below are shown in Table 1.

A compound having the formula (1) with R==H, dialkyl phosphite preferably dimethyl phosphite or G diethyl phosphite and a 2-hydroxyalkylamine in at least stoichiometric amounts. It is prepared by reacting in the presence of water and under heating according to the following formula, where R'', R2, R'' and R'+ have the same meaning as defined above.

This reaction involves bringing the reagents into contact with each other in a polar or non-polar solvent, heating the resulting solution to a temperature in the range 140-180°C, and removing the formed methyl or ethyl alcohol from the reaction environment. It is carried out by doing.

The solvent utilized in the synthesis process of the present invention is, for example, t
A non-polar solvent such as 2-dichlorobenzene or e.g.
It is selected from the class of protic polar solvents such as methanol or a mixture of methanol and methanol.

Depending on the 2-hydroxyalkylamine used, it may be advisable to use different types of solvents.

More specifically, if the reaction is carried out in a non-polar solvent, stoichiometrically equal amounts of the dialkyl phosphite, 2-
The hydroxyalkylamine and water are reacted in 1+2-dichlorobenzene for 0.5 to 5 hours, during which time the mixture is heated to reflux. The temperature of the mixture is then reduced to 170-1
By gradually raising the temperature to 80°C, the lower alcohol is distilled off from the reaction environment. As soon as all the alcohol has been removed, it is cooled to separate the ionic compounds from the non-polar solvent.

The product thus obtained is purified by heat treatment with lower alcohols (methanol, ethanol, impropatol). After such final processing, the compound is generally in crystalline solid form.

Examples of compounds prepared according to the process detailed in Method C in Example 2 below are shown in Table 2.

If the reaction is carried out in a protic polar solvent, it is combined with stoichiometrically equal amounts of dialkyl phosphite and 2-
This is accomplished by contacting the hydroxyalkylamine in the presence of a solvent mixture consisting of water and methanol. While heating the solution, the methanol solvent and the lower alcohol (methanol or ethanol) formed during the reaction are distilled off from the reaction environment.

Subsequently, the reaction mixture is introduced into a rotary evaporator under reduced pressure, while the temperature is gradually increased to 140-160°C.

The residues obtained under these conditions are lower alcohols (
It is purified by heat treatment with methanol, ethanol, impropatur).

Examples of compounds prepared according to the above method detailed in Example 2 below are shown in Table 1.

The compounds of general formula (1) have the property of protecting crops from diseases induced by fungi. In fact, when applied to the foliar surface of crops (e.g. tomatoes and grapes), this compound is
Phytophthora infestans, especially Phytophthora infestans.
FI) and Plasmopara vitifula (Plasmop
To render mature crops harmless to infectious diseases caused by pathogens such as Ara viticola).

Such an application, called prophylactic application, makes it possible to achieve a protective effect that lasts for at least 7 days from treatment to pathogenic strain infection of the crop.

On the other hand, a protective effect is provided even when treating plants that are still infected with pathogenic strains. Application in such cases lies in the systematic
) Due to its properties, it has a healing effect.

Surprisingly, the Applicant has discovered that this type of treatment
It has been found that the compounds of the invention are highly effective when implemented in the treatment of grape crops in which the epidemic caused by Plasmopara vitifura is still ongoing. This effect is completely unexpected since a control compound representing a previously known phosphite (AlSette) does not show any activity when applied under the same conditions (see Table 18). It is.

"Strain characteristic J means that the compound enters the crop through its leaves or roots, moves to the vascular system, and is used to immunize or treat areas that are not directly infected but are attacked by infectious diseases. It refers to a complex property that allows one to act.

The use of active compositions containing one or more compounds of formula (I) as active substances is often expedient for practical use in agriculture.

Such compositions can be applied to any part of the crop, such as, for example, the leaves, stems, branches and roots, or to the seeds before sowing or to the soil around the crop. The compositions used may be in the form of dry powders, wettable powders, emulsifiable concentrates, slurries or pastes, granules, solutions, suspensions, etc. The choice of composition type will depend on the application. The compositions are prepared in conventional manner, for example, by dissolving or diluting the active substance in the presence of a melt and/or a solid diluent, optionally a surfactant. As a solid diluent or carrier, silica, kaolin, bentonite,
Talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, cast, clay, synthetic silicates, attapulgite, sepiolite can be used. Liquid diluents include, in addition to water, aromatics (penzole, quidyrol or alkylpenzole mixtures), chloroaromatics (chlorbenzole), paraffins (petroleum distillates), alcohols (methanol, propatool, butanol), amines. , amide (dimethylformamide).

Ketones (cyclohexanone, acetophenone, isophorone, ethyl amyl ketone), esters (isobutyl acetate) can be used. As surfactants, alkyl sulfates, sodium salts, calcium salts, or triester cotanolamide salts of alkyl sulfuric acids, alkyl sulfonic acids, or alkylaryl sulfonic acids, polyethoxylated alkylphenols, fatty alcohol condensates with ethylene oxide, polyoxyethylated fatty acids, sorbitol Polyoxyethylated esters, polyoxyethylated fats, lignin sulfonates can be used. The compositions may also contain special additives, such as adhesion promoters such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, for specific purposes. If desired, other compatible active substances such as fungicides, herbicides, plant growth regulators, insecticides and fertilizers can also be added to the compositions forming the subject of the invention.

The concentration of active substance in the composition can vary over a wide range depending on the active compound, the culture, the pathogen, the environmental conditions and the type of formulation used. When using an emulsifiable concentrate, it is diluted to a concentration of active substance ranging from 0.1 to 5 g/1 part aqueous emulsion.

The following examples are provided to illustrate the invention.

Example 1 Method for producing 2-()limethylammonium)ethyl phosphite inner salt (compound 1) A N,N-dimethylformamide 50gLt, dimethyl phosphite 22F and 2-dimethylaminoethanol 17
．． 8 I! The solution prepared by dissolving was heated under reflux for 6 hours. The reaction mixture was then concentrated by atmospheric distillation to remove the formed methanol and about 2 Qm of solvent.

The mixture was then evaporated in a rotary evaporator at a residual pressure of 15 Torr and the bath temperature was raised to 80°C.

The obtained residue was treated with 100 ml of acetonitrile under vigorous stirring to obtain a solid. This was separated by filtration and dried in a vacuum dryer. 24 g of product was obtained. The compound appeared as a white hygroscopic solid.

mp 208-210℃ (decomposition) IR (nujol) 2350cya-', '125
0cm-', 1060cmu plate C, H, 4No, P
: Calculation: C! 15.93%, H8,44%, H8,38%
, PlB, 50% Actual measurement: C34,6B%, H945%, H8,35%, P
lB, 00% Method B 1.2-Dichlorobenzene 50- to dimethyl phosphite 2
2 g and 2-dimethylaminoethanol 17,8 g
The solution prepared by dissolving was heated under reflux for 5 hours. Thereafter, the methanol formed during the reaction was removed from the mixture by atmospheric distillation.

The resulting semi-solid phase was then separated from the overlying liquid phase and treated with acetonitrile 100- under vigorous stirring to obtain a crystalline solid. The solid was then separated by filtration and dried in a vacuum dryer. 22.5 g of product was obtained as a white hygroscopic solid.

mp 208-210"C (disassembly) IR (nujol) ν233Qcnr', 1230
C"", 1060Cf+r' analysis C, H,, No,
P: Calculation: C35, 93%, H8, 44%, H8, 38%,
p IEL50% Actual measurement: C54, 95%, H933%, H8, 20%, P
18.10% Example 2 Method C A solution consisting of 12.2.9 g of 2-aminoethanol and 5.6 g of water was added to a solution of 22 g of dimethyl phosphite in 1,2-dichlorobenzene (50 tn/) under strong stirring at room temperature. It was added gradually. After the addition was complete, the mixture was refluxed for 30 minutes, and then the methanol formed during the reaction was slowly distilled off until the temperature was 170° C. and humid.

The mixture is then cooled and the solvent separated from the insoluble oil phase by decantation followed by methanol 5011
The mixture was refluxed for 1 hour with 1 t of water.

In this way, a satisfactory solid was obtained. This was separated by filtration and dried in a reduced F+ dryer. The compound obtained was 14.79 and was a white solid.

mp 198~20D"C (Nujoru) ν2340, 1220, 1070C 1 Analysis C, H, NO, P: Calculation: C19, 20%, H6, 45%, N11.20%
, P24.7% Actual measurement: C19.99%, H640%, N 1α68%,
P241% Method D A solution consisting of 12.2 g of 2-aminoethanol, 25 methanol and 25 flt of water was dissolved in methanol (so<
)-dimethyl phosphite 22 dissolved in water (2sv) mixture
F! The mixture was lubricated with oil at room temperature under vigorous stirring.

After the addition was complete, the solution was heated to slowly distill off the methanol from the reaction environment. The reaction mixture was then transferred to a rotary evaporator and gradually heated under reduced pressure (15 torr) until a temperature of about 140"C was reached.

Heating was continued under these conditions to make the residue permanent.

A white solid residue of 251i+ was thus obtained. This was stirred and refluxed with 50% of ethanol. A white solid was separated from the cooled ethanol suspension by filtration and, after drying, 22.6 g of solid product was obtained.

-mp 198-200℃ (decomposition) -Lee (Nushor) ν2340, 1220, 1070
CF1 analysis C, H8No3P: Actual measurement: C19, 31%, H6, 45%, N10.85%
, P24.6% Examples 3-14 The therapeutic and preventive activities of the compounds of the invention against grape downy mildew (powdery mildew) and tomato blight (insect infestation) infections were determined according to Method Q below.

Treatment activity: Grape grains of the grape crop Dolcetto grown stingily in a conditioned environment at 25° C. and 60% relative humidity were sprayed with an aqueous suspension of Plasmopara biticola conidia (200,000 conidia/cc).

After 24 hours of residence in a moisture-saturated environment at 21°C, both sides of the leaves were treated with the test compound in aqueous acetone (acetone 20%).
v/v) solution.

After the incubation period (7 days), the degree of infection was reduced to 100
Visual evaluation was performed according to a rating scale from (healthy crop) to 0 (completely infected crop).

- Preventive activity Doleetto, a grape crop grown in an environment conditioned at 25°C and 60% relative humidity, is
Treatment was by spraying a solution of the test compound in aqueous acetone (acetone 20% v/v).

Seven days after this treatment, the undersides of the leaves were sprayed with an aqueous suspension of Plasmopara biticola conidia (200,000 conidia/CC). After 24 hours of residence in a moisture-saturated environment at 21°C, the grape crops were incubated at 21°C and 70% relative humidity for 7 hours.
Incubated for days.

The degree of infection was evaluated according to a rating scale from 100 (healthy crop) to 0 (completely contaminated crop).

- Therapeutic activity An aqueous suspension of Phytophthora infestans conidia (200,
000 conidia/cc).

After 24 hours of residence in a moisture-saturated environment, both sides of the leaves were treated with the test compound in aqueous acetone (acetone 20% v/v): m
treated with liquid.

After the incubation period (7 days), the degree of infection was reduced to 100
Visual evaluation was performed according to a rating scale from (healthy crop) to 0 (completely infected crop).

Leaves of a marginally grown tomato crop Marmande, conditioned at 26° C. and 160% relative humidity, were sprayed with a solution of the test compound in aqueous acetone (acetone 20% v/v). After 7 days, the crop leaves were contaminated by spraying the underside of the leaves with an aqueous suspension of Phytophthora infestans conidia (200,000 conidia/cc). After 24 hours of residence in a moisture-saturated environment at 21°C, the crops were transferred to a separate environment conditioned at 16°C and 70% relative humidity and incubated for 4 days.

After this period, the degree of infection was evaluated according to a rating scale of 100 (healthy crop) to 0 (fully infected crop).

Compound number 1.2.3.4.6.7.17.18 in Table I
．． 19 and 2o and Compound Nos. 21, 22 and 24 of Table ■ at various doses are shown in Table H below in comparison with compound Al1ette ■ having the formula % Formula %:

Claims (1)

[Claims] 1. General formula (1) R is H or C1-C2 alkyl, R1 and R2
are the same or different from each other, HN C3-C4 alkyl (when R=lH), C1-C1, alkyl (R=
C1-C, when alkyl), C8-CIl alkenyl or alkynyl (when R=H), C3-Cat alkenyl or alkynyl (when R=C, ~C, alkyl), fractional dicarbon of alkyl and alkoxy alkoxyalkyl-aryl having 1 to 12 atoms, especially fenyA/(when R=C, ~Cx furkyl), or aralkyl, or R and R2 taken together with the N atom have 5 to 6 atoms; and optionally, in addition to the N atoms, oS
containing a heteroatom selected from the group consisting of N and S and also optionally substituted with C1-C4 alkyl or alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety, optionally said second heteroatom N
but the formulas R3 and R4 are the same or different, and H
SC, ~represents a C-th alkyl or phenyl group] Compound 0 2. R is methyl, ethyl or H, R2 is methyl, ethyl or H, R is enyl, H or tert-butyl, RB is H or ethyl, R4 is H1 methyl or & is maphenyl,
A compound according to claim 1. &R is methyl, ethyl or H, R1 and R2 together with the N atom form a heterocyclic group selected from the group consisting of morpholine and piperidine, R3 is H and R4 is H or & A compound according to claim 1, which is methyl. 4. The compound according to claim 1 having the formula: 5. The compound according to claim 1 having the formula: 6. A compound according to claim 1 having formula 6. 1. A compound according to claim 1 having formula 1. 8. A compound according to claim 1 having the formula. 9 A compound according to claim 1 having the formula. 10. A compound according to claim 1 having the formula. The compound according to claim 1 having the formula 11. The compound according to claim 1 having the formula 12. The compound according to claim 1 having the formula 15. The compound according to claim 1 having the formula 15. 15. The compound according to claim 1, having the formula %. 15. The compound according to claim 1, having the formula %. 16. The compound according to claim 1, having the formula %. A compound according to claim 1 having the formula 17. A compound according to claim 1 having the formula 18. A compound according to claim 1 having the formula 19. A compound having the formula 20. 21. The compound according to claim 1 having the formula. 22. The compound according to claim 1 having the formula. 25. The compound according to claim 1 having the formula. 24. The compound according to claim 1 having the formula. 25. The compound according to claim 1 having the formula (1), wherein R is C, -yC, alkyl. In producing the compound described in
A process consisting in reacting stoichiometric amounts of a dialkyl phosphite and a 2-hydro p-xyalkylamine in an inert solvent at the solvent reflux temperature according to the following formula R2. 26. In producing the compound according to claim 1, in which R in formula (1) is H, chemical ftm amounts of dialkyl phosphite, 2-hydroxyalkylamine, and water are mixed with polar or A method consisting of reacting in a non-polar solvent under heat according to the following formula. 2Z In the eradication of infectious diseases caused by fungi on useful crops, the claimed scope of the invention provides for the application of effective amounts on crops, seeds or surrounding soil when the infectious diseases caused by fungi are expected or are still in progress. A method for eradicating infectious diseases, which comprises spraying the compound according to item 1 as it is or in the form of an appropriate composition. 28. The infectious disease is caused by the fungus Phytophthora infestans (
Phytophthora 1nfestans)
and Plasmopara biticola
Claim 27 by Viticola)
Methods for eradicating infectious diseases as described in section. 29. Compositions comprising one or more compounds according to claim 1 as active substances, a solid or liquid carrier, and other additives as optional ingredients.