DD298727A5 - MICROBICIDE MEDIUM - Google Patents

Abstract

The invention relates to microbicidal agents which can be used to control pestilling microorganisms in agriculture and horticulture. The microbicidal agents contain as active ingredients a mixture of * and / or * with at least 15 * proportion of * and / or trans-dimethylmorpholinio-carboxylic acid-N-alkoxycarbonyl-alkyl) -anilide salts of the general formula I. The meaning of R1 to R6 and X can be found in the description. Formula (I) {microbicidal agent; Mixture of * and * microorganisms; combating; Agriculture; Horticulture}

Description

in the

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

R ² straight-chain or branched alkylene having 1 to 6 C atoms,

R ^{3 is} hydrogen or alkyl having 1 to 4C atoms,

R ^{4 is} hydrogen or alkyl having 1 to 4 C atoms,

R ⁵ and R ^{6 are} independently the same or different hydrogen, straight or

branched alkyl having 1 to 4 carbon atoms or halogen and X ^{9 is} the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or formulation excipients.

2. A method for controlling microorganisms, characterized in that means according to claim 1 to microorganisms or act before microorganisms or the microorganisms to be protected objects.

3. Use of agents according to claim 1, characterized in that they are used for controlling microorganisms.

Field of application of the invention

The invention relates to a mixture of N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkanecarboxylic acid N '- (alkoxycarbonylalkyl) -anilide salts and at least 15 wt .-% proportion of N-alkyl-2.5 cis and trans dimethylmorpholiniocarboxylic acid N'-lalkoxy-carbonyl-alkyD-anilide salts and its use as microbicides 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 (DD-PS 1164152, DE-PS 1173722, DE-PS 2461513).

Furthermore, salts of α-aminoacetanilides, which include the morpholine as the amine component, with lower alkyl, cyanoalkyl, alkenyl and alkynyl substituents as agents for influencing or regulating plant growth are mentioned (DE-PS 2657728 and DE-PS 2915250 ).

Furthermore, N-alkyl-2,6-dimethylmorpholinio-carboxamide salts are known as active ingredients in fungicidal agents with additional plant growth-regulating properties (DD-PS 263686). It is also known that morpholino

alkanecarboxylic acid N '- (alkoxyalkyl) -anilides and their salts as microbicides to use (DE-PS 2643477).

However, the effect of the compounds mentioned is not always satisfactory in certain indication areas. A further disadvantage is that the plant compatibility of these compounds is insufficient in many cases.

Object of the invention

The object of the invention is the development of novel compounds with improved microbicidal activity and a process for their preparation and of microbicidal compositions containing such compounds, as well as the use of such microbicides in agriculture and horticulture.

Explanation of the essence of the invention

The invention is based on the object, a mixture of N-alkyl-2,6-cis- and / or trans-dimethylmorpholinioalkancarbonsäur6-N '- (ilkoxycarbonyl-alkyl) -anilide salts and at least 15 wt .-% proportion of N-alkyl To provide -2,5-cis and / or transdimethylmorpholinio-alkanoic acid N '- (alkoxycarbonyl-alkyl) -anilide salts containing microbicidal agents with high activity and broad spectrum of activity and the highest possible plant tolerance. To solve this problem microbicidal agents are proposed which are characterized in that they contain a mixture of N-alkyl-2,6-cis and / or trans-dimethylmorpholinlo-alkanecarboxylic acid N'-lalkoxycarbonyl-alkyO-anilide salts and at least 15% by weight of N-alkyl-2,5-cis- and / or trans-dimethylmorpholinio-alkanecarboxylic acid-N'-lalkoxycarbonyl-alkyl) -anilide salts of the general formula I

^s r2_ CO-ii; j: ^(l)

^ CH- COOR *;

in the

R ¹ straight-chain or branched alkyl having 8 to 18 C atoms, R ² straight-chain or branched alkylene having 1 to 6 C atoms, R ^{3 is} hydrogen or alkyl having 1 to 4 C atoms, R ^{4 is} hydrogen or alkyl having 1 to 4 C atoms, R ⁶ and R ⁸ are each independently the same or different hydrogen, straight-chain or branched alkyl with 1 to

4 C atoms or halogen and

X ^{e is} the anion of a non-phytotoxic acid,

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

The compounds according to the invention can be mixed in four different geometric structures as N-alkyl-2,6-cisund / or transdimethylmorpholinioalkanecarboxylic acid-N'-lalkoxycarbonyl-alkyU-anilide salts or N-alkyl-2,5-cis and N-alkyl or trans-dimethylmorpholinio-alkanecarboxylic acid N'-lalkoxycarbonyl-alkyD-anilide salts.

Surprisingly, it has been found that the compounds of the general formula I have a strong microbicidal activity and a broad spectrum of action and are particularly suitable for controlling phytopathogenic fungi on crops and vegetable crops. The active compounds show good plant compatibility in the amounts required for controlling plant diseases.

It has furthermore been found that the compounds of general formula I are obtained by reacting a mixture of N-alkyl-2,6-cis- and / or trans-dimethylmorpholine and at least 15% by weight of N-alkyl. cis and / transdimethylmorpholine (according to DD-PS 140412) of the formula II,

H ₅ C

- R ¹

^R (II)

v- ₅

wherein R ¹ basitzt the meaning given in the general formula I. with a compound of formula III,

, 5

XR ² -CO-N "(I")

i ^s CH-COOR ⁴

wherein R ² to R ^e have the meaning given in the general formula I and X is halogen, or alternatively a mixture of 2,6-cis- and / or trans-dimethylmorpholino-alkanecarboxylic acid-N-lalkoxycarbonyl-alkyll-anilide and at least 15% by mass of 2,5-cis- and / or trans-dimethylmorpholino-alkanecarboxylic acid-N-lalkoxycarbonyl-alkyO-anilide of the formula IV,

Η ² - 00 .. ..

CB.

in which R ² to R ^{e have} the meaning given in the general formula I, with a compound of the formula V, R'-X (V)

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

Compounds of the formula II are z. For example, n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, 1,5,9-trimathyldecyl, n-hexadecyl or Octadecyl-2,6-cis- and / or trans-dimethylmorpholine. Haloalkanecarboxylic acid N-lalkoxycarbonyl-alkyll-anilides of the formula III are, for example, chloroacetic acid N- (methoxycarbonylmethyl) -anilide, chloroacetic acid N- (methoxycarbylmethyl) -4-chloroanilide, chloroacetic acid N- (methoxycarbonylmethyl) -2,6-dimethylanilide, chloroacetic acid N-d-methoxycarbonyl-ethyD-anilide, chloroacetic acid N- (1'-methoxycarbonyl-ethyl) -4-chloroanilide, chloroacetic acid N- (1'-methoxycarbonyl-ethyl) -2,6-dimethylanilide, 2- Bromopropionic acid N-d-methoxycarbonyl-ethyl-M-chloroanilide, 2-bromo-caproic acid N-d-methoxycarbonyl-ethyl) -4-

chloranilidoder

6-bromo-caproic acid-N-d '-methoxycarbonyl-ethyl) -4-chloroanilide, where appropriate used as a mixture of the enantiomeric forms.

Compounds of formula IV are e.g. 2,6- and 2,5-cis- and / or trans-dimethylmorpholino-acetic acid N-lmethoxycarbonyl-

methylo-anilide, acetic acid N-1-methoxycarbonyl-m-thylM-chloroanilide, -acetic acid N- (methoxycarbonyl) -methyl) -2,6-dimethylanilide, -acetic acid-N-1-methoxycarbonyl-methyl-SB-dichloroanilide, acetic acid-N - (i'-methoxycarbonyl-alkyl) -anilide, -acetic acid-N-d-methoxycarbonyl-ethyl) -chloranilide-acetic acid-N-d-methoxycarbonyl-ethyl-1-methyl-chloroanilide.-acetic acid-N- α-methoxycarbonyl-ethyl-1-yl-dimethylanilide, -2-propionic acid N- (1'-methoxycarbonyl-ethyl) -4-chloroanilide, ε-caproic acid N-d'-methoxycarbonyl-ethyl-1-chloroanilide or-e- caproic acid N-ti'-methoxycarbonyl-ethyl) ^ -chloroanilide. The compounds of formula IV, which may occur in optically active forms, are used as a racemic mixture.

Alkyl halides of the formula V are, for example, hexyl bromide, n-octyl bromide, 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 formol I are optionally 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 performed. The starting materials of the formula II or of the formula IV are used in stoichiometric amounts with a compound of the formula III or of the formula V or preferably with an excess of 10 to 100% of a compound of the formula III or of the formula V over the stoichiometric amount also, based on the starting materials of the formula II or the formula IV, implemented.

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

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 formula I from the reaction mixtures is not absolutely necessary since they too

can be used without further purification operation for the production of microbicidal preparations. ν

The active compounds of the general formula I have a good activity against microorganisms and can accordingly

to combat fungal pathogens in agriculture and horticulture. With the active substances occurring on plants or parts of plants undesirable fungi can be combated. The active ingredients of the general

Formula I are also suitable as seed dressers for the treatment of seeds and plant cuttings for protection against fungal infections

and can be used against phytopathogenic fungi occurring in the soil.

The microbicidal agents according to the invention are for controlling economically important pathogenic fungi, such as

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

Furthermore, the microbicidal agents also provide good activity against wood-discoloring and wood-destroying fungi, such as

e.g. Pullaria pullulans, Aspergillus niger, Polystictus versicolor or Chactomium globosum.

Furthermore, the active ingredients of general formula I show a good activity against molds, such as. Penicillium, Fusarium

or Asporglllus 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 microbicidal agents according to the invention are furthermore suitable for controlling resistant strains of fungal pathogens,

which show resistance to known fungicidal active ingredients.

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 fabrics, Founstverkapselungen in polymeric materials and in coating compositions for seeds and 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 formula I with solvents and / or carriers, optionally with the use of surface-active agents, 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 weight. The active compounds may be prepared as such, in the form of their formulations or by further dilution therefrom 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 Wirkstoffmongen 0.01 to 100g per kilogram of material to be treated, preferably 0.1 to 50g.

In the treatment of soil, drug concentrations are from 0.0001 to 0.1 mass%, preferably from 0.001 to 0.05 mass%,

required at the place of action.

The inventive method for controlling microorganisms is characterized in that microbicides Agent with the active compounds of the general formula I on microorganisms or to be protected against microorganism infestation Allow objects to act in an effective amount. The active compounds of the general formula I can be used in the formulations or in the various forms of application

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 microbicidal agents according to the invention with known fungicides also occur synergistic Effects on. 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 the effect of

prove compounds of general formula I according to the invention.

Ausführungsbelsplele 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- (C ₁₀ -C _{) 4} ) -alkyl-2,6-ci8 and / or trans and N- (C, trC, ₄ ) -alkyl-2,5-cis- and / or trans-dimethylmorpholino- acetic acid-N'-d'-methoxy-carbonyl-ethylM-chloroanilide chloride

6, OgN- (C ₁₀ -C 4) alkyl-2,6-cis and / or trans -methylmorpholine with at least 15% by mass of N- (C ₁ -C 14) -alkyl-2,5-cis and / or trans- dimethylmorpholine and 5.8 g of chloroacetic acid N-d-methoxycarbonyl-ethylM-chloroanilide are heated to reflux with addition of a catalytic amount of sodium iodide in 15 ml of n-propanol for 48 hours. Then allowed to cool and the solvent is distilled off in vacuo.

The residue is directed with hexane. The product is dissolved in a little acetone and mixed with η-hexane for complete deposition. The oily phase is separated and freed from solvent residues in vacuo. This gives 7.7 g of a tan resin (compound no.7). IR spectrum (film) / cm~V: 2925,2855,2630-2580,2480-2430,1745,1670,1605,1495,1465,1380, 1 250,1 215,1130,1 090,1 020,830

Example 2 N- (C _ia- Cu) -alkyl-2,6-cis- and / or trans- and N- (C ₁₀ -C 14 -alkyl ₎ B-Cls and / or trans-dimethylmorpholino-acetic acid NMmethoxycarbonyl-methylM-chloroanilide chloride

6.0 g of N- (C, Ir-Ci4) alkyl-2,6-cis- and / or trans-dimethylmorpholin with at least 15Ma .-% proportion of N- (Ci ₀ -C ₁₄ I -AlkVl ^ ₁ B-CiS - and / or trans-dimethylmorpholine and 5.5 g of chloroacetic acid-N-lmethoxycarbonyl-methylM-chloroanilide are dissolved in 20 ml of n-propanol and heated to reflux with the addition of a catalytic amount of sodium iodide for 36 hours

Cooling, the solvent is distilled off in vacuo. The residue is repeatedly directed with η-hexane. The product

is dissolved in a little acetone and η-hexane added until complete precipitation as an oily phase. Finally, the

Remains solvent residues in vacuo. There are obtained 6.9 g of a yellow resin (Compound No. 4). IR spectra (film) / cm "" '/: 2930, 2850, 2620, 2525, 2570, 2420, 1750, 1670, 1600, 1495, 1760, 1380, 1220, 10, 10, 10, 8, 80, 860

Table 1: N-Alkyl ^ .e-cis / trans-dimethylmorpholinio-alkane-carboxylic acid N'-lalkoxycarbonyl-alkyO-anilide salts with at least 15% by mass of N-alkyl-2,5-cis- and / or trans -dimethylmorpholino-carboxylic acid N'-CalkoxycarbonylalkyD anilide salts

\ .p "/ - R ⁶ ·?

CH-COOR ⁴

Verb. R ¹ R ² R ³ R ⁴ R ⁶ R ⁶ X 1 n-C "H, 7 CH ₂ CH ₃ CH ₃ 2-CH ₃ 6-CH ₃ br 2 C ₁ OC ₁₄ -AlkW CHj H CH ₃ H H Cl 3 nc ₁₂ Hj ₆ CHj H CH ₃ 4-CI H Cl 4 C ₀ -C ₁₄ alkyl CHj H CH ₃ 4-CI H Cl cn Co-C ₁₄ -AlkVl CHj CH ₃ CH ₃ H H Cl 6 NC, ₂ Hj5 CHj CH ₃ CH ₃ 4-CI H Cl 7 Cu-Cu-alky! CHj CH ₃ CH ₃ 4-CI H Cl 8th C ₁₀ -C ₁₄ alkyl CHj CH ₃ CH ₃ 3-CI 5-CI Cl 9 C ₁₀ -C ₁₄ alkyl CH, CH ₃ CH ₃ 2-CH ₃ 4-CI Cl 10 Co-Cu-alky! CHj CH ₃ CH ₃ 3-CI 4-CI Cl

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

!.Example

Solution concentrates: 80 parts by weight of compound 4 are mixed with 20 parts by weight of N-methyl-2-pyrrolidone. It will

obtained a solution that is suitable for use in the form of very small drops.

!!.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 with 5 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor, 1 part by weight Natriun. Salt of di-iso-butylnaphthalen-sulfonic acid and 54 parts by weight of silica gel well mixed and milled in an appropriate MOhIe. A spray powder is obtained which can be diluted with water to give suspensions of any desired concentration. _s

IV. Example

Granules: 5 parts by weight of compound 1 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 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 in the single-leaf stage with active compound preparations

besp'üht, cus 1 part by weight of active ingredient, 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. After the drying of the

Spraying the plants are dusted with conidia (spores) of the 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. 4 and 7 when using a

Active ingredient concentration of 100 mg χ Γ ^{1 shows} a better effect (83% or 100% efficiency than the known fungicide

Aldimorph.

Example B Botrytis test (Botrytis cinerea / Field Bean (Vicia faba) leaffed) Cut off leaf spring of field bean plants (Vicia faba) of the variety "Fribo" in the four-leaf stage

are briefly dipped in active ingredient 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 and diluted with water to the desired drug concentration. After the spray coating has dried on, the leaves are inoculated with a conidia suspension of Botrvtis cinerea, which is obtained by washing away 12 to 16-day-old fungal cultures on malt agar nutritive medium (2% malt). The

Field bean leaflets are in an incubation cabin in trays at a temperature of 22 ⁰ C and 90 to 100% 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

The resulting value was given in% infection and from this in relation to the untreated control of the

Efficiency calculated. The results of the experiments showed that compounds Nos. 4 and 7, when used in a drug concentration of

500 mg x I " ¹ achieve a better effect (efficiency of 67 or 77%) than the known active ingredient dicloran (2,6-dichloro-4-nitraniline) (efficiency 65%).

Claims (2)

1. Microbicidal agents, characterized in that they are a mixture of N-alkyl-2,6-cis- and / or
trans-dimethylmorpholinioalkancarbonsäure NMalkoxycarbonyl-alkyO-anilide salts and
at least 15% by weight of N-alkyl-2,5-cis- and / or trans-dimethylmorpholinioalkanecarboxylic acid NMA-alkoxycarbonyl-alkyl anilide salts of the general formula I ² -CO-N CH-COOR ⁴