DD298728A5 - FUNGICIDE EFFECTIVE AGENT - 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 * and / or trans-dimethylmorpholinio-alkyl-aryl ketone salts of the general formula I or a mixture of these salts with their positional isomers * and / or trans-dimethylmorpholinio-alkyl aryl ketone salts of the general formula II Meaning of R1, R2, R3, n and X is given in the description. Formulas (I) and (II) {fungicidal agents; * and * fungal pathogens; combating; Agriculture; Horticulture}

Description

η Ibis 3 and

Χ ^θ mean the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or formulation excipients.

2. A method for controlling fungi, characterized in that means according to claim 1 are allowed to act on fungi or the objects to be protected against fungal attack.

3. Use of agents according to claim 1, characterized in that they are used to combat fungi.

Field of application of the invention

The invention relates to novel N-alkyl ^ .S-cis- and / or trans-dimethylmorpholinio-alkyl aryl ketone salts or a mixture of these salts with their positionally isomeric N-alkyl-2,5-cis- and / or trans-dimethylmorpholinio- alkyl aryl ketone salts and their use as fungicides in agriculture and horticulture.

Characteristic of the known state of the art 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 aralkyl substituents are fungicidally active (DE-PS 1167 588, Angewandte Chemie 7711965],

Pp. 327-333).

Furthermore, agents are known which substituted N-benzyl or alkoxymethyl-2,6-dimethylmorpholinium salts as active ingredients Fight against fungal pests (DD-PS 134037, DD-PS 134474, DD-PS 140403). However, the effect of the compounds mentioned is in certain areas of indication, especially at low levels Application rates and concentrations, not always fully satisfactory. Another disadvantage is that the plant compatibility

Of these compounds is in many cases not sufficient.

Object of the invention

The object of the invention is the development of new compounds with improved fungicidal activity and a process for their preparation, and fungicidal agents containing such compounds, and the use of such fungicidally active agents in agriculture and horticulture.

Explanation of the essence of the invention

The invention is based on the object, new N-alkyl-2,6-cis and / or trans-dimethylmorpholinio-alkyl-aryl ketone salts or a mixture of these salts with their positionally isomeric N-alkyl-2,5-cis- and / or fungicidal compositions containing trans-dimethylmorphollnio-alkyl-aryl ketone salts with good activity and broad spectrum of activity and to provide the highest possible plant biocompatibility.

To achieve this object, fungicidally active agents are proposed, which are characterized in that they are N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-aryl ketone salts of the general formula I or a mixture of these salts as active ingredients with their positionally isomeric N-alkyl-2,5-cis- and / or transdimethylmorpholinio-alkyl-aryl ketone salts of the general formula II,

H, 0

"Η ¹

H "C

^ 2 ₃ 3

© R ¹

(CH ₂ J-CO

(I)

(II)

in which

R ¹ straight-chain or branched alkyl having 8 to 18 C atoms,

R ² and R ^J, independently of one another, are identical or different, are hydrogen, straight-chain or branched alkyl having 1 to

4 C atoms, halogen or nitro, η Ibis 3 and X ^{e denote} the anion of a non-phytotoxic acid,

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

The compounds according to the invention can be prepared in four different geometric structures as N-alkyl-2,6-cis- or trans-dimethylmorpholinio-alkyl-aryl ketone salts or N-alkyl-2,5-cis- or trans-dimethylmorpholinio-alkyl-arylketori Salts or as mixtures of these isomers. In the compositions according to the invention, both the isomer mixture, as obtained in the synthesis, and the individual isomers can be used.

Surprisingly, it has been found that the compounds of the formulas I and II have a good fungicidal activity and a broad spectrum of activity and are particularly suitable for controlling phytopathogenic fungi on crop plants and vegetable stocks. The active compounds show good plant compatibility in the amounts required for controlling plant diseases.

Furthermore, it has been found that the compounds of the general formulas I and II are obtained by reacting N-alkyl-2,6-cis- and / or trans-dimethylmorpholine or a mixture of these compounds with at least 15% by weight of N-alkyl -2,5-cis- and / or transdimethylmorpholinu (according to DD PS 140412) of the formula III

H, 0

NO

(III)

NO

(IV) ^GH 3

in which R ^{1 has} the meaning given in the general formulas I and II, with a compound of the formula V,

2

(V)

wherein R ² , R ³ and η have the meaning given in the general formulas I and II and X is halogen, or alternatively reacts 2,6-cis- and / or trans-Dimethylmorpholino-alkyl-aryl ketones or a mixture of these compounds at least 15% by mass of 2,5-cis- and / or trans-dimethylmorpholino-alkyl-aryl ketones of the formulas VI and VII,

H,

-CCH ₂ ) -CO

(VII)

in which R ² , R ³ and η have the meaning given in the general formulas I and II with a compound of the formula VIII

R'-X (VIII)

wherein R ^{1 has} the meaning given in the general formulas I and II and X is halogen reacted.

Compounds of formulas III and IV are z. N-decyl, n-dodecyl, Cio-Cu-alkyl, n-tridecyl, iso-tridecyl, 1,5,9-trimethyldecyl,

n-hexadecyl or n-octadecyl-2,6- and 2,5-cis- and / or transdimethylmorpholine.

Compounds of the formula V are, for example, 2-bromoacetophenone, 2-bromo-4'-chloroacetophenone,

2,2 ', 4'-trichloroacetophenone, 2-bromo-4'-methylacetophenone, 2-bromo-4'-nitroacetophenone, 3-chloropropiophenone or 4-chlorobutyrophenone.

Compounds of formulas VI and VIII are e.g. 2,6- and 2,5-cis- and / or trans-dimethylmorphollno-methyl phenyl ketone,

methyl-chloro-phenyl-ketone, methyl-dichloro-phenyl-ketone, -methyl-4-metbyl-phenyl-ketone, -methyl-4-nitrophenyl-ketone, -ethyl-phenyl-ketone or -propyl-phenyl ketone.

Alkyl halides of the formula VIII are, for example, n-octyl bromide, n-decyl chloride, n-dodecyl chloride, n-tridecyl chloride, iso- Tridecyl chloride, 1,5,9-trimethyldecyl chloride, n-hexadecylbromide or n-octadecylbromide. The conversion to the active compounds of the formulas I and II are optionally in the presence of a solvent or Diluent at a temperature in the range between 10 and 18O ⁰ C, preferably between 30 and 15 ° C performed. The starting materials of the formulas III and IV or the formulas VI and VII are in stoichiometric amounts with a Compound of formula V or of formula VIII or preferably with an excess of 10 to 100% of a compound of Formula V or Formula VIII beyond the stoichiometric amount, based on the starting materials of the formulas III and IV

or the formulas Vl and VII implemented.

As preferred solvents and 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, propranols, butanols or hexanols; Nitriles such as acetonitrile; Esters, such as methyl acetate

or N-methyl-pyrrolidone; Dimethyl sulfoxide or water or mixtures of these solvents can be used.

The isolation of the active compounds of the general formulas I and II from reaction mixtures is not absolutely necessary since they

can be used without further purification operation for the production of fungicidally effective preparations.

The active compounds of the general formulas I and II have a good activity against microorganisms and can

Accordingly, be used to combat fungal pathogens in agriculture and horticulture use.

With the active substances occurring on plants or parts of plants undesirable fungi can be combated. The active ingredients

of the formulas I and II are also suitable as mordants for the treatment of seeds and plant cuttings for protection

Fungal infections and can be used against occurring in the soil phytopathogenic fungi. The fungicidal compositions according to the invention are useful for controlling economically important pathogenic fungi, such as

for example, Erysiphe, Botrytis, Phytophthora, Pythium, Fusarium, Mucor, Alternaria species, and the like. suitable.

Furthermore, the f unicidal agents also provide good activity against wood-discoloring and wood-destroying fungi, such. B. Pullaria pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum. Furthermore, the active compounds of the general formulas I and II show good activity against molds, such as. Penicillium, Fusarium or Aspergillus species that spoil high-moisture agricultural products or Processing products of agricultural products during storage or intermediate storage. Such

to be treated products include z. Apples, oranges, tangerines, lemons, grapefruits, peanuts, cereals and

Cereal products or legumes and meal. The active ingredients are, in addition to their broad spectrum of fungicidal activity, also different from phytopathogenic bacteria,

such as Xanthomonas or Erwinia species. -

Some agents also show an action against human pathogenic fungi, such. B. Trichophyten and Candida species. The inventive compositions are also suitable for controlling resistant strains of fungal pathogens against

known fungicidal active ingredients show resistance symptoms. "*

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, foams, pastes, soluble powders, granules, natural and active substances impregnated with active substance

Synthetic substances, ultra-fine encapsulations in polymeric materials and in coating compositions for seeds as well as ULV-KaIt- and

Warm mist formulations. The preparation of these formulations can be carried out in a known manner, for. B. by mixing or grinding the active ingredients

of the general formulas I and II with solvents and / or excipients, if appropriate using surface-active moieties, 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 prepared in the form of their formulations or by further dilution thereof Application forms in a conventional manner, for. By casting, dipping, spraying, spraying, atomizing, injecting, silting, Spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting, applied

become.

In the treatment of parts of plants, the drug concentrations in the use forms in a larger Range can be varied. They are generally between 0.001 and 1 wt .-%, preferably between 0.01 and 0.5 Ma .-%. The Drug application rates depend on the specific application and are generally between 0.1 and 3kg Active ingredient per hectare. In seed treatment, in general, amounts of active ingredient are from 0.0001 to 50 g per kilogram of seed, preferably

0.01 to 10g, needed.

For the preservation or post-harvest treatment of agricultural or processed products

agricultural products amount to the required amounts of active ingredient 0.01 to 100 g per kilogram of material to be treated, preferably 0.1 to 50 g.

In the treatment of soil, drug concentrations are from 0.0C01 to 0.1 mass%, preferably from 0.001 to 0.05 mass%,

required at the place of action.

The inventive method for controlling fungi is characterized in that fungicidally active agents with

the active compounds of the general formulas I and II on fungi or the objects to be protected against fungal attack in more effective

Allowing the amount to work. Dio active ingredients of the general forms! I and II may be in the formulations or in the different forms of application

with other known active substances, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides,

Growth regulators, plant nutrients and soil conditioners are mixed and applied. In

In many cases when mixing with fungicides, a widening of the fungicidal activity spectrum is obtained. At a

Number of mixtures of the fungicidally active agents according to the invention with known fungicides also occur synergistically Effects, 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 illustrate the invention further, but without limiting it and the effect of

Invention, compounds of general formula I to prove.

Ausführungsbelsptele The following examples illustrate the preparation of the compounds of the invention. The starting compounds for the preparation of the compounds according to the invention are known or can be prepared per se

known methods are produced.

example 1 N-iso-tridecyl-e-cis- and / or trans-dimethylmorpholinio-methyl phenyl ketone bromide

30 g of N-iso-tridecyl-2,6-cis and / or trans-dimethylmorpholine and 19.9 g of 2-bromoacetophenone are dissolved in 100 ml of acetonitrile 48

Heated to reflux. It is cooled and the solvent is distilled off in vacuo. The product is made with rijHexan

conducted. Concentration in vacuo gives 41.4 g of a light brown resin (Compound No. 3).

Example 2

2- (N- (Citj-Cu) alkyl-2,6-cis and / or trans and N- (CKR-C ₁₄₎ -alkyl-2,6-cis and / or trans-dimethylmorpholino] - ethyl phenyl chloride

30 g of N- (CITj-C14) -alkyl-2,6-cis- and / or trans-dimethylmorpholine with at least 15% by weight of N- (Cio-C14) ~ AIM'2,5-cis- and / or trans- dimethylrnorpholine and 16.9 g of 3-chloropropiophenone are heated to reflux in 100 ml of acetonitrile for 48 hours.

Then allowed to cool and the solvent is distilled off in vacuo. The residue is directed with η-hexane. To Concentration in vacuo gives 30.5 g of a yellow resin (compound no. 9). In a corresponding manner, the compounds of the general formula I and II listed below are prepared which are described in

usually yellow to brown viscous oils or hearts. They are in polar solvents, such as. For example, alcohols, acetone,

Dimethylformamide and dimethyl sulfoxide readily soluble and are characterized by their IR spectra.

Table 1: N-Alkyl ^ .ö-cis and / or trans-dimethylmorpholinioalkyl-aryl ketone salts or a mixture of these salts with their positionally isomers N-alkyl ^ .ö cis and / or trans-dimethylmorpholinio-alkyl-aryl ketone -Salt

^N \ Γ /

\ / ^N (CH _o) -V -C0

H, C

2 ' η

XCH ₂ ) -CO · - //

(I)

(ID

Verb. R ' R ² R ³ η X characteristic c = c (aromatic) No. IR spectra (film) C = O 1590 [cm " ¹ ] 1595 1 n-C "H, 7 H H 1 br 1695 1595 2 "-C ₁₂ H ₂₆ H H 1 br 1695 1595 3 ISO-Ci ₃ H ₂₇ H H 1 br 1690 1590 4 C ₁₀ -C 4 alkyl H H 1 br 1690 1585 5 ISO-C ₁₃ H ₂₇ 4-CI H 1 br 1690 1600 6 ISO-C ₁₃ H ₂₇ 2-CI 4-CI 1 Cl 1710 1595 7 ISo-C ₁₃ H ₂₇ 4-NO ₂ H 1 br 1690 1595 8th ISo-C ₁₃ H ₂₇ H H 2 Cl 1680 1600 9 Co-Ci ₄ -AIM H H 2 Cl 1680 10 ISO-C ₁₃ H ₂₇ H H 3 Cl 1685

The compounds of the general formulas I and II can, for. B. in the form of the following preparations are used:

I. Example

Solution concentrates: 80 parts by weight of compound 3 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 7 are mixed with 2.5 parts by weight of epoxidized vegetable oil, 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

Spray powder: 40 parts by weight of compound 1 are mixed well with 5 parts by weight of the sodium salt of a lignosulfonate from a sulfite liquor, 1 part by weight of sodium salt of di-iso-butylnaphthalene-sulfonic acid and 54 parts by weight of silica gel and ground in a corresponding mill. A spray powder is obtained which can be diluted with water to give suspensions of any desired concentration.

IV. Example

Granules: 5 parts by weight of compound 1 are mixed with 0.25 parts by weight of chlorohydrin and dissolved with β parts by weight of acetone. Thereafter, 3.5 parts by weight of polyethylene glycol and 0.25 parts by weight of cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

Example A Wheaty mildew test (Erysiphe graminis / wheat) Potted-grown wheat plants of the "Alcedo" variety are doused with active ingredient preparations at the onset stage

sprayed, which are prepared from 1 part by weight of active compound, 100 parts by weight of acetone and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired active ingredient concentration. After the drying of the

Spritzbelages the plants are dusted with conidia (spores) of wheat powdery mildew (Erysiphe graminis var. Tritici). Subsequently, the test plants 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 ⁰ C and 75 to 80% relative humidity in the

Greenhouse set up. After 5 days, the powdery mildew of the wheat plants is determined. The efficiency of the funds is from ABBOTT

calculated. From the experiments it is apparent that, for example, the compounds Nos. 5 to 10 when using a

Drug concentration of 100 mg χ Γ ¹ a better effect (efficiencies 95 to 100%). show as the known fungicide Tridemorph (efficiency 93%). Example B Grain egg test (Puccinio recondita / wheat) Wheat plants of the variety "Alcedo" grown under greenhouse conditions are in the single leaf stage (age: 7 days)

sprayed with drug solution consisting of 1 part by weight of active ingredient, 100 parts by weight of acetone and 0.25 parts by weight

Alkylarylpolyglykolether be prepared and diluted with water to the desired drug concentration. After the spray coating has dried on, the plants are inoculated with a spore suspension under TWEEN 20 addition. The Spore material is obtained from wheat plants infected with Puccinia recondite.). The inoculation closes

the incubation, which takes place in a humid chamber (100% humidity) for 24 h. Subsequently, the plants are in the

Greenhouse set up. After 10 days the Rostbefali the wheat plants is determined. The efficiency of the funds will become ABBOTT

calculated. From the experiments it is apparent that the compound No. 7 shows an efficiency of 86% when using a Wirkst -ffkonzentration of 250 mg χ I " ¹ .

Examples Botrytis test (Botrytis cineioa / field bean (Vicia faba) leaffed) Cut-off leaflets of field bean plants (Vicia faba) of the variety "Fribo" in a four-leaf stage

are immersed briefly in active compound preparations which consist of 1 part by weight of active compound, 100 parts by weight of acetone and 0.25

Parts by weight of alkylaryl polyglycol ether prepared and diluted with water to the desired drug concentration

become. After the spray coating has dried on, the leaves are inoculated with a conidia suspension of Botrytis cinerea, which is obtained by washing away 12 to 16-day old fungal cultures on malt agar medium (2% malt). The

Field bean leaflets are grown in an incubation booth in trays at a temperature of 22 ° C and 90 br, 100% more relative Humidity kept. After 2 days, the Botrytis infestation of field bean leaflet is determined. The infections were counted

and multiplied by a factor for the strength of infection (rating scale from 1 = no infestation to 5 = very severe infestation). The resulting value was given in% infection and from this in relation to the unhampered control of the

Efficiency calculated. The results of the experiments showed that the compounds Nos. 3 and 5, when used in a drug concentration of

500mg κ Γ 'achieve a better effect (efficiency of 89 or 100%) than the known active ingredient dicloran (2,6-dichloro-4-nitraniline) (efficiency 65%).

Claims (1)

1. fungicidally active agents, characterized in that they as active ingredients N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-aryl ketone salts of the general formula I or a mixture of these salts with their positionally isomeric N-alkyl -2,5-cis- and / or trans-dimethylmorpholinio-alkylaryl ketone salts of the general formula II (D (II) in which R ^{1 is} straight or branched alkyl having 8 to 18 C atoms, R ² and R ³ independently of one another or different hydrogen, straight-chain or branched alkyl having 1 to 4 C atoms, halogen or nitro, ^J