DD278269A1 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal agents that can be used to combat fungal pathogens in agriculture and horticulture. The fungicidal compositions contain as active ingredients N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-carboxylic acid nitrile salts of the general formula I in which R 1 is alkyl having 6 to 20 C atoms, R 2 is alkylene having 1 to 6 C atoms and X represent the anion of an acid. Formula (I)

Description

Field of application of the invention

The invention relates to novel N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-carboxylic acid nitrile salts and their use as fungicides in agriculture and horticulture.

Characteristic of the known technical solutions

It is known to use N-alkylmorpholines and their salts and their molecular and addition compounds as fungicides (DE-PS 1164152, DE-PS 1173722, DE-PS 2461 513).

It is also known that quaternary ammonium compounds of long-chain N-alkyl-2,6-dimethylmorpholinen with lower alkyl, alkenyl, alkoxyalkyl or Ara.Kyl substituents are fungicidally effective (DE-PS 1167588; Angewandte Chemie 77 [19651,

Furthermore, agents are known which contain substituted N-benzyl or alkoxymetnyl-2,6-dimethylmorpholinium salts as active substances for controlling fungal pathogens (DD-PS 134037, DD-PS 134474, DD-PS 140403).

It is also known that salts of morpholino-carboxylic acid esters with long-chain alkanesulfonic or alkanecarboxylic acids have fungicidal properties (DD-PS 201 371).

However, the action of the compounds mentioned is not always completely satisfactory in certain indication areas, in particular at low application rates and concentrations. In addition, they show a rather high selectivity against certain types of fungal pathogens, which greatly limits the broad use of these agents. A further disadvantage is that the plant compatibility of these compounds is not sufficient in many cases.

Object of the invention

The aim of the invention is the development of new compounds with improved fungicidal activity and a process for their preparation and of fungicidal compositions containing such compounds, and the use of such fungicides in agriculture and horticulture.

Explanation of the essence of the invention

The invention has for its object to provide novel N-alkyl-2,6-cis urd / or trans-dimethylmorpholinio-carbonitrile salt-containing fungicidal compositions having good activity and broad spectrum of activity and the highest possible plant compatibility.

To solve this problem, fungicidal agents are proposed, which are characterized in that they contain at least one N-alkyl-2,6-cis- and / or trans-dimethylnorpholinio-carbonitrile salt of the general formula I,

I ₃ C

M ₃ V. \ i ² -CEN

in the

R ¹ straight-chain or branched alkyl having 6 to 20 C atoms,

R ² straight-chain or branched alkylene having 1 to 6 carbon atoms and

Χ ^Θ the anion tiner does not mean pytotoxic acid,

in addition to the usual solvents, carriers and / or formulation auxiliaries.

The compounds according to the invention can be present in two different geometric structures as N-alkyl-2,6-cis-dimethylmorpholinio-carbonitrile salt or N-alkyl-2,6-trans-dimethylmorpholinio-carbonitrile salt or as mixtures of these two isomers.

Surprisingly, it has been found that the N-alkyl-2,6-cis- and / or trans-dimethylmorpholiniocarbonsäurenitril salts of the general formula I have a good fungicidal activity and a broad spectrum of activity and in particular for controlling Pnytopalhogenen fungi on crop plants and plant Stock goods are suitable.

The active ingredients show a gule compatibility with the plant required for the control of plant diseases.

Furthermore, it has been found that the N-alkyl-2,6-cis- and / or transdimethylmorphoHnio-carbonitrile salts of the general formula I are obtained by reacting an N-alkyl-2,6-cis- and / or transdimethylmorpholin of the formula II

(II)

wherein R 'has the meaning given in the general formula I, with a compound of the formula III,

XR ² -C = N (III)

in which R ^{2 has} the meaning given in general formula I and un 1 X represents halogen,

or alternatively a 2,6-cis- and / or trans-dimethylmorpholino-carboxylic acid of the formula IV,

(IV)

wherein R ^{2 has} the meaning given in the general formula I, with a compound of the formula V,

R'-X (V)

wherein R 'has the meaning given in the general formula I and X is halogen reacted.

N-alkyl-2,6-cis- and / or trans-dimethylmorpholines of formula II are e.g. n-decyl, n-dodecyl, n-tridecyl, iso-tridecyl, 1,5,9-trimethyldecido, n-hexadecyl or n-didecyl-2,6-cis- and / or trans- dimethylmorpholine.

Halo-carboxylic acid nitriles of the formula III are, for example, chloroacetonitrile, 2-bromopropionitrile, 3-chloropropionitrile, 2-bromobutyronitrile, 2-bromo-isobutyronitrile, 4-chlorobutyronitrile, 2-bromovaleononitrile, 5-bromovaleronitrile, 2-bromo-capronitrile, 6-bromocapronitrile or 7 -Bromönanthsäurenitril.

2,6-cis- and / or trans-dimethylmorpholinio-carbonitriles of the formula OV are z. B. 2,6-cis and / or trans-dimethylmorpholino-acetonitrile, 2- (2,6-cis- and / or trans-dimethylmorpholino) -propionitrile, 3- (2,6-cis- and / or trans-Dimethylmorpholino ) propionitrile, 3- (2,6-cis and / or trans ⁿ .inethylmorpholino) propionitrile, 2- (2,6-cis and / or trans-dimethylmorpholino) butyronitrile, 4- (2,6 -cis- and / or tranv-dimethylmorpholino) -butyronitrile, 5- (2,6-cis- and / or trans-dimethylmorpholino) -valeronitrile, 2- (2,6-cis- and / or trans-dimethylmorpholinol-capronitrile, 6- (2,6-cis- and / or trans-dimethylmorpholino) -capronitrile or 7- (2,6-cis- and / or trans-Dimethylmorpholino) önanthsäurenittil.

Alkyl halides of the formula V are, for example, n-octyl bromide, n-decyl chloride, n-dodecyl chloride, n-tridecyl chloride, isotridecyl chloride, 1,5,9-trimethyldecyl chloride, hexadecyl bromide or didecyl bromide.

The conversion to ( 's compounds of the formula I is given ^ Il in the presence of a solvent or diluent at a temperature in the range between 10 and 180 ° C, preferably between 30 and 15O ⁰ C.,. Or the starting materials of the formula Il of formula IV are in stoichiometric amounts with a Vc: bond of formula III or the formula V or preferably with an excess of 10 to 100% of a compound of formula III or

of the formula V beyond the stoichiometric amount, based on the starting materials of the formula II or the formula IV reacted.

As preferred solvents or diluents, for example, aliphatic or aromatic, optionally halogenated hydrocarbons, such as n-pentane, cyclohexane, benzene, toluene, chlorobenzene, chloroform or methylene chloride; aliphatic ketones, such as acetone, methyl ethyl ketone or cyclohexanone; Ethers, such as diethyl ether, tetrahydrofuran or dioxane; Alcohols, such as methanol, ethanol, propanols, butanols or hexanols; Nitriles, such as acetonitrile; Esters, such as methyl acetate; Amides, such as dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone; Dimothylsulfoxid or water or mixtures of these solvents can be used.

The isolation of the compounds of the general formula I according to the invention from the reaction mixtures is not absolutely necessary, since they can also be used without further purification to prepare fungicidal preparations.

The active compounds of the general formula I according to the invention have good activity against microorganisms and can accordingly be used for combating fungal pathogens in agriculture and horticulture. With the active substances occurring on plants or parts of plants undesirable fungi can be combated. The active compounds of general formula I are also suitable as mordants for the treatment of seed and plant cuttings for protection against fungal infections and can be used against occurring in the soil phytopathogenic fungi.

The active compounds according to the invention are suitable for controlling economically important pathogenic fungi, such as, for example, Erysiphe, Botrytis, Phytophthora, Phythium, Fusarium, Mucor, Alternaria species and the like.

Furthermore, the active ingredients also provide good activity against wood-discoloring and wood-destroying fungi, such as e.g.

Pu'lana pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum.

Fernör show the active compounds of general formula I according to the invention a good activity against molds, such as. B.

Penicillium, Fusarium or Aspergillus Aids which cause spoilage of high moisture agricultural products or processed agricultural products during storage or intermediate storage.

For such to be treated P ^r oducts include. As apples, oranges, tangerines, lemons, grapefruit, peanuts, cereals and cereal products or pulses and meal.

The active compounds according to the invention, in addition to their broad fungicidal spectrum of vigor, are also different against phytopathogenic bacteria, such as, for example, Xanthomonas or Erwinia arias.

Some agents also show an action against human pathogenic fungi, such. P Trichophyte and Candida species.

The active compounds of the invention are also suitable for controlling resistant oinmme fungal pathogens that show resistance to known fungicidal agents.

The active compounds according to the invention can be converted into the customary formulations. i, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, natural and synthetic substances impregnated with active substance, superfine encapsulation in polymeric substances and in seed coatings, and ULV caustic and heat-fog formulations.

The preparation of these formulations can be carried out in a known manner, for. Example, by mixing or grinding the active compounds of the general formula I according to the invention with solvents and / or carriers, optionally with the use of surfactants, such as emulsifiers and / or dispersants.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by mass.

The active compounds may be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution in a customary manner, e.g. By casting, dipping, spraying, spraying, atomizing, injecting, silting, spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 0.001 and 1 wt .-%, preferably between 0.01 andO, 5Ma .-%. The drug application rates depend on the specific application and are generally between 0.1 and 3 kg of active ingredient per hectare.

In seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are needed.

For preservation or post-harvest treatment of agricultural products or processing products of agricultural products, the required amounts of active ingredient 0.01 to 100 g per kilogram of material to be treated, preferably 0.1 to 50g.

In the treatment of the soil, drug concentrations of 0.0001 to 0.1% by weight, preferably from 0.001 to 0.05% by weight, are required at the site of action.

The method according to the invention for controlling fungi is characterized in that fungicidal agents with the active ingredients of the general formula I according to the invention are allowed to act on fungi or the objects to be protected against fungal attack in an effective amount.

The active compounds according to the invention can be mixed and applied in the formulations or in the various application forms with other known active compounds such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, growth regulators, plant nutrients and soil conditioners. In many cases, a mixture of fungicides results in a broadening of the fungicidal activity spectrum. In a number of mixtures of the active compounds according to the invention with known fungicides also synergistic effects occur, wherein the fungicidal activity of the combination product is greater than that of the added effectiveness of the individual components.

The following examples are intended to further illustrate the invention without, however, limiting it and demonstrating the effect of the compounds of general formula I according to the invention.

embodiments

The following examples illustrate the preparation of the compounds of the invention.

example 1

N-iso-tridecyl-e-cis- and / or trans-dimethylmorpholinio-acetonitrile chloride 30 g of N-isotridecyl-cis- and / or tris-dimethylmorpholine and 8.3 g of chloroacetonitrile are refluxed in 100 ml of acetonitrile for 30 hours , It is cooled and the solvent is distilled off in vacuo. The product is directed with η-hexane.

Concentration in vacuo gives 25.8 g of a light brown viscous oil (compound no. C).

IR spectrum (film): C ^ N absorption 2295 cm '.

Boispiel 2

S-fN-iso-tridecyl ^ .G-cis and / or trans-dimethylmorpholiniol-propionitrile chloride 16.8 g of 3- (2,6-cis- and / or trans-dimethylmorpholino) -propionitrile and 22 g of iso-tridecyl chloride ( Mixture of various C 1 -C 4 -alkyl chlorides containing 60 to 70% n-tridecyl chloride) in 100 ml of acetonitrile are refluxed for 24 hours.

After cooling, the solvent is distilled off in vacuo. The product is dissolved in a little acetone and treated with n-hexane until complete precipitation as an oily phase. Concentration in vacuo gives 23.1 g of a yellowish resin (compound no. 10).

IR spectrum (film): C = N absorption 230Ou (TT ¹ .

In a similar manner, the following compounds of general formula I are prepared, which are usually yellow to brown viscous oils or resins, in polar solvents, such as. As alcohols, acetone, dimethylformamide and dimethyl sulfoxide, are readily soluble and characterized by IR spectra.

The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared by processes known per se.

(I)

No. R ' R ² X 1 n-octyl CH ₂ Cl 2 n-decyl CH ₂ Cl 3 n-dodecyl CH ₂ ci 4 n-tridecyl CH ₂ Cl 5 1,5,9-trimethyldecyl CH ₂ Cl 6 iso-tridecyl CH ₂ Cl 7 n-hexadecyl CH ₂ Cl 8th n-didecyl CH ₂ Cl 9 iso-tridecyl CH (CH ₃ ) br 10 iso-tridecyl (CH ₂ J ₂ Cl 11 iso-tridecyl CH (C ₂ H ₆ ) br 12 iso-tridecyl (CH ₂ I ₃ ci 13 iso-tridecyl CH (C ₃ H ₇ ) br 14 iso-tridecyl (CH ₂ J ₄ br 15 iso-tridecyl CH (C ₄ H ₉ ) br 16 iso-tridecyl (CH ₃ J ₅ br 17 iso-tridecyl (CH ₂ I ₆ br

The compounds of the general formula I according to the invention can be used, for example, in the form of the following preparations:

I.Beispiel

Solution concentrates: 80 parts by weight of compound 6 are mixed with 20 parts by weight of N-methyl-2-pyrrolidone. A solution is obtained which is suitable for use in the form of very small drops.

II. Example

Emulsifiable concentrates: 25 parts by weight of compound 10 are mixed with 2.5 parts by weight of epoxidized vegetable oils, 10 parts by weight of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts by weight of dimethylformamide and 57.5 parts by weight of xylene. From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

III. example

Granules: 5 parts by weight of compound 12 are mixed with 0.25 part by weight of epichlorohydrin and dissolved with 6 parts by weight of acetone. Thereafter, 3.5 parts by weight of polyethylene glycol and 0.25 parts by weight Cctylpolyglykolether be added. The resulting solution is sprayed on kaolin. Then the acetone was evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

The following examples are intended to illustrate the invention further, but without limiting it and to demonstrate the effect of the compounds of general formula I:

Example A

Mycelial growth test

The fungicidal activity of the agent against the test fungi is in a conventional manner as inhibition of radial mycelial growth on malt agar medium (2% malt) determined in Petri dishes of 9cm in diameter at a Inkubationsternperatur of 25 ⁰ C. The active ingredients are dissolved in dimethylformamide, diluted with water and so added to the liquid agar that the desired drug concentration is achieved in the nutrient medium. The DMF content does not exceed 0.5% by volume. After cooling, the plates are inoculated. The evaluation takes place depending on the growth rate of the fungi, if the controls without the addition of active ingredient are interspersed to 70 to 90% of the shell diameter. For evaluation, the percentage growth inhibition of the active compounds compared to the controls without added active ingredient is calculated (Table A).

Table A: Growth inhibition of fungi in the mycelium growth test

Connection no. Wirkstoffkonz. Growth inhibition in percent Phytophthora 6 Botrytis cactorum • 10 cinerea 100 mg χ Γ ¹ 16 10mg χ I ' 100 87 100 91 100 88

Example B

Wheaty mildew test (Erysiphe graminis / wheat)

Wheat plants of the cultivar "Alcedo" grown in pots are sprayed wet with active ingredient preparations prepared from 1 part by weight of active compound, 100 parts by weight of acetone and 0.25 part by weight of alkylaryl polyglycol ether and diluted with water to the desired active substance concentration. After the spray coating has dried on, the plants are pollinated with conidia (spores) of the wheat powdery mildew (Erysiphe graminis car. Tritici).

Subsequently, the test plants are set up for a period of 2 to 3 hours at 90 to 100% relative humidity in an incubation cabin and then at temperatures between 20 and 22 ° C and 75 to 80% relative humidity in the greenhouse.

The experiments show that, for example, the compounds Nos. 6 and 10 when using a drug concentration of 100mg χ Γ 'a better effect (efficiencies 95 and 100%) show than the known fungicide Saprol (N, N-bis (1 -Formamido-2,2,2-trichloroethyl) -piperazine (efficiency 85%).

Claims (3)

1. Fungicidal agent, characterized in that it comprises at least one N-alkyl-2,6-cis- and / or transdimethylmorpholinio-carbonitrile salt of the general formula I, ο _; v- xw _(|) Il C Ιχ ¹ "- Γ - \ in the R ^{1 is} straight-chain or branched alkyl having 6 to 20 C atoms, R ^{2 is} straight-chain or branched alkylene having 1 to 6 C atoms and Χ ^{θ is} the anion of a non-phytotoxic acid, the usual solvents, carriers and / or formulation auxiliaries. 2. A method for controlling fungi, characterized in that means according to item 1 is allowed to act on fungi or the objects to be protected against fungal attack. 3. Use of agents according to item 1, characterized in that they are used to combat fungi.