KR820000505B1 - Process for the preparation of dichloromaleic acid diamidees - Google Patents

Abstract

Fungicidal title compds.[I; R = substituted C1-8 aliphatic radical(e.g.; Me, Et, CH2CH2N(Me)C6H5, 4-FC6H4, CH2C(CH3):CH2, CH2C:CH) were prepd. by reaction of dichloromaleic acid halide(II; X = halogen) and amine(III). Thus, 10.0 g II (X = Cl) was reacted with 45 ml 25% III(R = Et) followed by filtration to give 8.7 g I(m.p.; 154-155oC, yield; 81%).

Description

[Name of invention]

Method for preparing dichloromaleic acid diamide derivative

Detailed description of the invention

The present invention relates to a process for the preparation of new dichloromaleic acid diamide derivatives useful as fungicides.

It has already been published that N- (p-fluoroophenyl) -2,3-dichloro maltide has a very good action against citrus melanoma (see German Publication 2,156,967 and US Patent Specification 3,734,927). However, the range of action of the compounds mentioned is not completely satisfactory when sprayed in small quantities. Zinc ethylene-1,2bis-dithio carbamate is also commonly known for a long time as a standard preparation having bactericidal action.

mpfungssmittel”“chemistry of plant protection agents and agents for combating pests”), Springer-Verlag, Berlim/Heidelberg/New Your(1970), 2 page 65).(R.wegier, “chemie der pflanzenschutz und schadlingsbek

mpfungssmittel ”“ chemistry of plant protection agents and agents for combating pests ”), Springer-Verlag, Berlim / Heidelberg / New Your (1970), 2 page 65).

Moreover, it has been known for a relatively long time that acylation of aniline with dichloromaleic acid dichloride results in the formation of mixed products (J.prak.chemie 130,255 (1931)). As recently known, dichloro maleic acid dichloride is present in the lacto (cyclic) form as tetrachloro-5H-furan-2-one, but the lactodal acid chloride of dicarboxylic acid contains the complete lacto idal ring in reaction with the nucleophilic reagent. Products can be obtained mainly (Chem. Ber. 104, 3,378 (1971). Ring-opened derivatives are obtained (Chem. Ber. 109, 1,163 (1976)). Thus, J. prakt. Chem 130,255 (1931)), the mixed product is described as acylating aniline with dichloromaleic acid dichloride, respectively, and C ₁₆ H is a yellow product having a melting point of 170 ° C. and a white product having a melting point of 193 ° C. ₁₂ Cl ₂ has the same empirical formula of the N ₂ O _2. symmetrical dichloro maleic acid bisphenyl already draw-described white product produced only (melting point 193 ℃) is dichloro maleic acid chloride is first treated with aluminum chloride Possible only when eoteul and it will be described the conversion of a galactosidase to yidalhyeong stranded symmetrical.

The previously described dichloro maleic acid bis-phenylamide has been described as having no biological action (J. Prak. Chem. 130,255 (1931)).

The present invention provides dichloromaleic acid diamide derivatives of the following general formula (I) as new compounds.

In the above general formula

R represents an optionally substituted aliphatic radical of up to 8 carbon atoms, a tetrachloro radical of 3 to 6 carbon atoms or a substituted phenyl radical.

They have strong bactericidal properties.

R represents a straight or branched saturated or unsaturated aliphatic radical of up to 6 carbon atoms or the aliphatic radical represents a halogen atom, cyano, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, phenyl, phenoxine, 5 or The heterocyclic group and the hydrogen atom containing a six-membered ring may each optionally take one or more selected from substitutable amino groups of alkyl or phenylloim up to 4 carbon atoms, and the heterocyclic group may be an oxygen atom or a sulfur atom. And one or more heteroatoms selected from nitrogen atoms, which may be saturated or unsaturated (e.g., buryl groups, pyranyl groups (derives of pyrans) and hydrogenated and partially hydrogenated derivatives thereof) ] A cycloalkyl group of 5 or 6 carbon atoms; alkyl, alkenyl, alkynyl, alkoxy and alkylio (in each case Phenyl, phenoxy, halogen, nitro, cyano, halogenomethyl (e.g. trifluoromethyl), halogenoethyl, trifluoromethoxy, trifluorotomethylio, thiocyanate, carboxyl Preference is given to phenyl consisting of one or more substituents each independently selected from alkoxycarbonyl groups and acetylamino groups of up to 4 carbon atoms in the group and alkyl moiety.

The present invention provides a method for preparing dichloromaleic acid diamide derivative of general formula (I) by reacting dichloro maleic acid halide of general formula (II) with an amine of general formula (III) in the presence of a diluent and an acid binder. do.

In the above general formula

X represents halogen, in particular chlorine is preferred

R is as described above.

Finally, the reaction process for producing only the modified symmetric compound of formula (I) (even when the compound of formula (II) is used as a starting material) is carried out by first adding the amine of formula (III) to the reaction vessel first. It can be easily obtained by adding dichloro maleic acid halide (formula II).

Surprisingly, the dichloromaleic acid diamide derivatives of general formula (I) according to the invention exhibit significantly stronger bactericidal activity than compounds known in the art. The material according to the invention represents an advance in technology.

Furthermore, it is surprising that the formation of a single product of general formula (I) is achieved in a simple manner by means of continuous hooks according to the invention. The omission of the process of treating dichloromaleic acid halides with the required aluminum chloride or other Lewis acids according to previous knowledge represents a simplification of the technique.

When tetrachloro-5H-furan-2-silver (“dichloromaleic acid dichloride”) and ethylamine are used as starting materials, the reaction process can be expressed as follows.

Dichloromaleic acid halides of formula (II) can be prepared by well-known methods, such as the halogenation of dichloromaleic anhydride in the presence of a catalyst such as iron salt using a halogen such as phosphorus pentachloride, phosgene or thionyl chloride or chlorine. Can be.

The amine of general formula (III) is a compound which can be obtained by a well-known method, and can be obtained normally in an organic chemistry laboratory. [Tetrahydropyran-2-yl] -methylamine, also called, for example, 2-aminomethyl-tetrahydropyran, is obtained by hydrogenating 2-cyano-tetrahydropyran with, for example, lithium alanic acid or hydrogen under pressure. (See Beilstein 18, E 3/4, 7, 045). On the other hand, 2-aminomethyl-2,4-dihydropyran can be prepared by hydrogenating 2-formyl-3,4-dihydropyran under high pressure in the presence of ammonia.

The amines can of course also be used in the form of acid addition products such as hydrochlorides or hydrobromide or in the form of adducts with fumaric acid, organic acids mentioned here as examples.

Diluents used in the reaction according to the invention are all conventional polar solvents. Water is preferably used and alcohols such as methanol, ethanol or propanol as well as ketones such as acetone are used. Mixtures of other solvents can also be used, for example mixtures consisting of water and water soluble solvents.

Conventional acid binders (bases), in particular inorganic acid binders such as alkali metal hydroxides and alkali metal carbonates (eg sodium hydroxide, potassium carbonate) can be used as auxiliary. If the reaction is carried out in an organic solvent, a tertiary amine such as triethylamine or pyridine is preferably used.

The amines of formula (III) used as starting materials are preferred because they can be used in excess and can be applied simultaneously as reactants and acid binders.

The reaction temperature can vary within a substantial range.

In general, half silver is carried out at -5 ° to + 150 ° C, with + 10 ° to 50 ° C being preferred.

In the preparation according to the invention it is preferred to use 2 moles of amine of formula (III) and at least 2 moles of acid binder for the molar sugar of dichloro maleic acid halide of formula (II), as already mentioned, separately It is possible to use an excess of the amine of general formula (III) instead of the acid binder, in the latter case at least 4 moles of amine per mole of dichloromaleic acid dihalide are required. The mixture is carried out in a conventional manner, for example by filtering off and drying the final product precipitated from water.

The active compounds according to the invention exhibit potent toxin action. They do not harm crop plants at the concentrations required for fungal treatment. For this reason they are suitable for use as a plant protection agent in fungal treatment. Mycotoxins are used as plant protection agents in the treatment of fungal pathogens, fungal steels, pathogenic fungi, junctional fungi, streptococci, basidiomycetes and insecure fungi.

The active compounds according to the present invention have a broad spectrum action and can be used not only for parasitic fungi that develop on the ground or on plants through the soil, but also for pathogens in seeds.

In addition, they show particularly good activity against tomato's brown and nymph disease (Phytophthora infestans) and Pyricularia oryzae bacteria causing disease in rice.

In the cultivation of cereals, it has excellent activity against grain rust (Puccinia recondila), wheat sorghum (Tilletia caries) and barley streaks (Helminthosporium gramineum). Have

As plant protection agents, the compounds according to the invention can be used for soil treatment, seed treatment and ground treatment of plants.

The active compounds are solvents, emulsions, water-soluble powders, suspensions, powders, powders, foaming agents, pastes, water-soluble powders, granules, aerosols, suspension-emulsion concentrates, seed treatment powders, natural and synthetic substances mixed with active compounds, and polymeric substances. It can be converted to conventional formulations such as ULV cold mist and warm mist formulations, as well as formulations using combustion devices such as microcapsules, seed coating compositions and fumigation cartridges, fumigation cans and fumigation coils.

These formulations can be prepared by known methods by mixing with the active compound optionally using diluents or carriers in the liquid or liquefied gaseous or solid phase and surfactants such as emulsifiers and / or suspending agents and / or foaming agents. When water is used as the extender, for example, an organic solvent is used as a cosolvent.

Liquid solvent diluents or carriers, especially solvents, include aromatic hydrocarbons such as xylene, toluene or alkyl naphthalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffin (for example mineral oil fraction); Alcohols such as aliphatic or cycloaliphatic hydrocarbons, butanol or glycol as well as ethers and esters thereof, ketones such as acetone, methylethylketone, methylisobutylketone or cyclohexanone, or strong such as dimethylformamide and dimethyl sulfoxide Polar solvents as well as water are mainly suitable.

Liquefied gaseous diluents or carriers refer to liquids which become gases at room temperature and atmospheric pressure, for example aerosol sprays such as butane, propane, nitrogen and carbon dioxide, as well as halogenated hydrocarbons.

Solid carriers include natural minerals such as kaolin, clay, talc, clay, quartz, etapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silicic acid, alumina and silicate. Solid carriers for granules include crushed and protected natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic wheat and granules of organic substances such as sawdust, coconut shells, corn foil and tobacco bags. This is used.

As emulsifiers and / or foaming agents, polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohols (eg alkylarylpolyglycol ethers), alkylsulfonates, alkylsulfates, arylsulfonates as well as albumin hydrolysates are used. . Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinylacetate) and carboxymethylcellulose in the form of powders, granules or lattice may be used in the formulation.

Colorants, for example inorganic dyes such as iron oxide, titanium oxide and procian blue and organic dyes such as azalyl dyes, azo dyes or metal phthalocyanine dyes and traces such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc The element can be used.

In general, the formulation contains 0.1 to 95% by weight, preferably 0.5 to 90% by weight of the active compound.

The compounds according to the invention are present in the formulation as mixtures with other active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, algal repellents, growth factors, plant nutrients and soil structure improving agents.

The active compound may be used as a dosage form immediately or in a further diluted form, such as solution, emulsion, suspension, powder, paste and granule. They can be used in conventional methods such as by watering, spraying, spraying, powdering, dispersing, drying, misting, moisting, slurrying or by incorporation.

Especially when used as foliar fungicides and foliar bacteria, the concentration of active compound in the form of use can vary within substantial ranges. Generally 0.5 to 0.0005% by weight, preferably 0.2 to 0.001% by weight.

In the seed treatment, the amount of the active compound is 0.01 to 50 g, preferably 0.5 to 5 g per kilogram of seed.

The amount of active compound in the soil treatment is 1 to 1,000 g per cubic meter of soil, preferably 10 to 200 g.

In addition to bactericidal activity, the compound according to the present invention, when applied in an appropriate amount and concentration, acts as a plant growth regulator.

The present invention provides bactericidal compositions containing the compounds of the present invention as active ingredients in a mixture with a solid or liquefied gas diluent or carrier or with a liquid diluent or carrier containing a surfactant.

The present invention provides a method for the treatment of fungi characterized by application to a fungus or its habitat in the form of a composition containing the compound of the invention as an active ingredient, alone or in admixture with a diluent or carrier.

The invention also provides for the protection of crops from damage by fungi by applying the compounds of the invention, alone or in admixture with a carrier or diluent, to the cultivated area immediately before and during growth.

It is shown that the present invention improves the conventional feeding method of harvested crops.

The bactericidal activity of the compounds of the invention is illustrated by the following biological test examples.

In these examples the compounds according to the invention are the same as the numbers of the corresponding preparation examples (given in parentheses) as seen later in this specification.

EXAMPLE

The amount of active compound required for the desired active compound concentration in the nutrient medium is mixed with the solvent mixture described above. The concentrate is mixed thoroughly with the liquid nutrient medium cooled to 42 ° C. in the above ratio and poured into a 9 cm diameter Petri dish. Control plate media without preparations are also made.

When the nutrient medium is cooled and solidified, the plate is inoculated with the following species and cultured at about 21 ° C.

Evaluation is performed after 4 to 10 days depending on the growth rate of the organism. The evaluation is carried out by comparing the growth of the organism on the treated nutrient medium to the growth on the control nutrient medium.

The following specific values are used in the assessment of organism growth:

1: no growth

Strong growth inhibition up to 3

Moderate Growth Inhibition to 5

Until 7: slight growth

9; Same growth as untreated control

Evaluation of the test is for example compounds (1), (6), (7), (15), (14), (2), (3), (8) and (11) Thiorum (Sclerotinia sclerotiorum), Fusarium nivale, Cletotrichum coffeanum, Rhizoctonia Solani, Verticillium alboatatum, Pycurilaria Pyricularia Oryzae, Helminthosporium gramineum, Mycosphaerella musicola, phytophthora cactorum, and Pelicularia sasaki It has been shown to have a superior action than that of the compound of the prior art.

Example B

The amount of active compound required for the desired active compound concentration in the irrigation liquid is mixed with the solvent and dispersant in the amounts described above and the concentrate is diluted with the above amount of water.

Spray about 14 days old rice until it has been soaked with water. The plants are placed in a greenhouse at 22-24 ° C. and relative humidity of about 70% until dry. Pyracularia Orissa is inoculated with them in an aqueous suspension of 100,000 to 200,000 spores / ml and boxed at 24 to 24 ° C. and 100% relative humidity.

Five days after inoculation, infections on all leaves that were present at the time of inoculation were not treated but were measured as a percentage of inoculated control plants.

The evaluation is expressed as a number from 1 to 9. 1 indicates 100% action, 3 indicates excellent action, 5 indicates normal action, and 9 indicates no action.

Example C

The amount of active compound required for the active compound of the desired concentration in the spray solution is mixed with the solvent of the above-mentioned amount and the concentrate is diluted with the above-mentioned amount of water containing the above-mentioned additives.

Spray the spray solution until it is soaked in a young tomato plant with 2-4 leaves. The plants are placed in a greenhouse for 24 hours at 20 ° C. and 70% relative humidity. Tomato plants are inoculated with a water soluble suspension of phytophthora mfestans.

The plants are placed in a moist chamber at a relative humidity of 100% and a temperature of 18 to 20 ° C.

After 5 days the infection of tomato plants is measured. Assessment data is translated into percent infection. 0% means no infection and 100% means that the plant is totally infected.

Evaluation of the test indicates that compounds (6), (15), (2), (10), (8), (16), (17) and (11) have a superior action than known conventional compounds. .

Production Example

Example 1

10.0 g (45.1 mmol) of tetrachloro-5-furan-2-one (dichloromaleic acid dichloride) are added to 45 ml of 25% strength ethylamine solution with global stirring at room temperature. The precipitated product is filtered and dried. 8.7 g of dichloromaleic acid bis-diethylamide having a melting point of 154 to 155 캜 are obtained. The yield was 81% of theory.

Example 2

22.2 g (0.1 mole) of dichloromaleic acid dichloride is slowly added to a mixture of 20.2 g (0.2 mole) of triethylamine and 19.4 g (0.2 mole) of pullulylamine in 200 ml of acetone with global stirring at room temperature. . The reaction mixture is poured into 100 ml of water and the precipitated product is filtered off and dried. 29.0 g of dichloromaleic acid bis-furfurylamide at a melting point of 149 DEG C were obtained, and the yield was 85% of theory.

Example 3

160 g of 10% strength sodium hydroxide solution is added to 40.1 g (0.4 mol) of 2-chloro ethylamine hydrochloride dissolved in 150 ml of water and 22.2 g (0.1 mol) of dichloromaleic acid dichloride are added slowly at room temperature. The precipitated product is filtered off and dried. 19.7 g of dichloromaleic acid bis- (2-chloroethyl) -amide having a melting point of 107 to 110 ° C was obtained and the yield was 64% of theory.

Compounds of formula (I) wherein R is as shown below were prepared analogously to the above examples.

Claims (1)

A process for preparing dichloromaleic acid diamide derivative of general formula (I), wherein the dichloromaleic acid halide of general formula (II) is reacted with an amine of general formula (III) in the presence of a diluent and an acid binder.

Wherein R represents optionally substituted aliphatic radicals up to 8 carbon atoms, cycloalkyl radicals of 3 to 6 carbon atoms or substituted phenyl radicals and X represents halogen.