DE4115433A1 - N-Alkyl-2,6-di:methylmorpholinio-azolyl:alkane salts - useful as fungicides for treatment of plants, seeds or stored goods - Google Patents

Abstract

N-alkyl-2,6-dimethylmorpholinio -azolylalkane salts of formula (I), and mixts. of (I) with positionally isomeric N-alkyl-2,5-dimethyl morpholino-azolylalkane salts (II). R = 8-16C alkyl; Az = 1,2,4-triazol-1-yl or imidazol-1-yl; n = 1-6; X- = an anion of a non-phytotoxic salt. R = i-C13H27 or n-C12H25; X = Cl or Br. USE - (I) are active against microorganisms and are esp. useful as fungicides, e.g., against Erysiphe graminis or Puccinia recondita. Compsns. contg. (I) or (I) in combination with at least 15wt.% of (II) are useful. Dosage is 0.01-50 (esp. 0.1 to 10)g/kg for seed treatment, 0.01-20 (esp. 0.1-10)g/kg for harvested or stored goods, or 0.2-2 kg/ha for treatment of plants.

Description

The present invention relates to new N-alkyl-dimethylmorpholinioazolylalkane Salts, their preparation and their use as fungicides.

Morpholine fungicides have been used in practical applications for some time Plant protection found (DE 11 64 152, DD 1 40 412). Most recently N-alkyl-dimethylmorpholinium compounds have become common with time good fungicidal activity known (DD 2 63 686, DD 2 63 685, DD 2 63 687). However, the effects of these substances are specific Indications are not always entirely satisfactory.

There were new N-alkyl-2,6-dimethylmorpholinio-azolylalkane salts of general formula I and a mixture of these salts with their positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane Salt,

in the
R straight-chain or branched alkyl with 8-16 C atoms,
Az 1,2,4-triazol-1-yl or imidazol-1-yl,
n 1 to 6 and
X⊖ is the anion of a non-phytotoxic acid,
found.

The compounds according to the invention can have four different geometrical shapes Structures as N-alkyl-2,6-cis-dimethylmorpholinio- azolylalkane salts, N-alkyl-2,6-trans-dimethylmorpholinio-azolylalkane Salts, N-alkyl-2,5-cis-dimethylmorpholinio-azolylalkane salts  and / or N-alkyl-2,5-trans-dimethylmorpholinio-azolylalkane salts are available. For the fungicidal application, both the mixture of isomers, as is the case with the synthesis, as well as the separate ones Use isomers.

It was also found that the N-alkyl-2,6-dimethylmorpholinio- azolylalkane salts of the formula I and a mixture of these salts with their positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane Get salt if you

• a) N-alkyl-2,6-cis and / or trans-dimethylmorpholines or a mixture of these compounds with at least 15% by mass of N-alkyl-2,5-cis and / or trans-dimethylmorpholines of the general formula II in which R has the meaning given in the formula I, with a compound of the general formula III, X- (CH₂) _n -Az (III) in the
  X represents halogen and
  Az and n have the meaning given in the formula I,
  in the presence of a solvent or diluent or
• b) 2,6-cis and / or trans-dimethylmorpholine-azolylalkanes or a mixture of these compounds with at least 15% by mass of 2,5-cis and / or trans-dimethylmorpholine-azolylalkanes of the general formula IV, in the Az and n have the meaning given in the formula I, with an alkyl halide of the general formula V, RX (V) in the
  R has the meaning given in formula I and
  X stands for halogen
  in the presence of a solvent.

N-alkyl-2,5- or 2,6-dimethylmorpholines of the formula II are, for. B. n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, or pentadecyl-2,6-dimethylmorpholine.

Alkyl halides of the formula V are, for example, n-octyl chloride, n-dodecyl chloride, n-tridecyl chloride, iso-tridecyl chloride, n- Tetradecyl bromide or pentadecyl bromide.

Finally, it was found that the new N-alkyl-2,6-dimethylmorpholinio- azolylalkane salts and a mixture of these salts with at least 15% by mass of their positionally isomeric N-alkyl-2,5-dimethylmorpholinio- azolylalkane salts have a strong fungicidal activity and have a broad spectrum of activity and as active ingredients of fungicidal agents for combating phytopathogenic fungi Cultivated plants and vegetable stocks are suitable. In the required The use concentration of the invention Fungicides are well tolerated by plants.

The substances according to the invention are surprisingly distinguished due to a better fungicidal effect than tridemorph and aldimorph from which known active substances of chemically similar constitution and have the same direction of action. The substances according to the invention thus represent a valuable addition to the technology.  

The reactions to the substances of formula I are in general in the presence of a solvent or diluent at one temperature in the range between 10 and 180 ° C, preferably between 30 and 150 ° C carried out. The starting materials of formula II or of the formula IV are in stoichiometric amounts with a compound of formula III or formula V or preferably with a 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 formula II or formula IV implemented. Examples of preferred solvents or diluents are 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; Dimethyl sulfoxide or water or mixtures of these solvents can be used.

The isolation of the substances of the general formula I from the reaction mixtures is not strictly necessary as it is without further Cleaning operation for the production of fungicidal preparations can be used.

The active compounds according to the invention have a strong activity against microorganisms and can therefore be used to combat fungal pathogens in agriculture and horticulture Find use. They can be used on plants or parts of plants occurring unwanted fungi are controlled. The fungicides are suitable also as a mordant for the treatment of seeds and plant cuttings for the protection of fungal infections and can be used against Soil phytopathogenic fungi can be used.

The substances according to the invention are particularly suitable for prevention and curing plant diseases caused by fungi be such. B. Erysiphe graminis (powdery mildew), Erysiphe cichoracearum (cucumber mildew), Erysiphe polygoni (bean mildew),  Podosphaera leucotricha (powdery mildew), Sphaerotheca pannosa (Powdery mildew), Uncinula necator (powdery mildew); Rust diseases, such as those of the genera Puccinia, Uromyces or Hemileia, in particular Puccinia graminis (black grain), Puccinia coronata (Oat crown grate), Puccinia sorghi (corn grate), Puccinia recondita (Grain brown rust), Uromyces fabae (bush bean rust), Hemileia vastatrix (coffee rust); Botrytis cinerea on vines and strawberries; Monilia fructigena on apples; Plasmopara viticola on vines; Mycosphaerella musicola on bananas; Corticum salmonicolor on Hevea; Ganoderma pseudoferreum on Hevea; Exobasidium vexans on tea. Furthermore, various of these agents have different effects against phytopathogenic fungi, such as. B. Ustilago avenae (flying fire), Ophiobolus graminis (cereal foot diseases), Septoria nodorum (Grain leaf and husk tan), Venturia inaequalis (apple scab) as well as other fungal pathogens, such as Rhizoctonia, Tilletia, Helminthosporium, Alternaria, Mucor, Sclerotinia, Fusacrium, Pseudocercosporella and Cladosporium.

The active compounds according to the invention are particularly interesting for fighting a variety of fungal diseases on different Cultivated plants or their seeds, in particular wheat, rye, Barley, oats, rice, corn, cotton, soy, coffee, bananas, Sugar cane, fruit, ornamental plants in horticulture, vegetables, such as cucumber, Beans or squash.

Furthermore, the substances also have a good activity against wood-discoloring and wood-destroying mushrooms, such as B. Pullaria pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum.

Furthermore, the active compounds according to the invention show good activity against mold, such as B. Penicillium, Fusarium or Aspergillus Species that spoil from high moisture agricultural products or processed agricultural products Products in storage or temporary storage cause. Products to be treated in this way include e.g. B. apples, oranges, mandarins, lemons, grapefruits, Peanuts, cereals and cereal products or legumes and  - grist.

Some of the active ingredients of the general formula I stand out in addition to the protective effect through systemic development out. So they are both about the root and about the leaves are picked up and in the plant tissue or over the seeds fed to the aerial parts of the plant.

The substances according to the invention are also suitable for combating resistant strains of fungal pathogens against known Fungicides such as B. Active substances from the group of dicarboximide Fungicides such as 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) - 2,4-dioxo-1,3-oxazolidine (vinclozolin); Active substances from the group the benzimidazole fungicides, such as 1- (n-butyl- carbamoyl) -benzimidazol-2-yl-carbamic acid methyl ester (benomyl); Active ingredients from the group of azole fungicides, such as 1- (4-chlorophenoxy-3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butane 2-on (triadi phone); Active ingredients from the aromatic group Fungicides containing hydrocarbons, such as 2,5-dichloro-1,4-dimethoxybenzene (Chloroneb); Active substances from the Group of pyrimidine fungicides, such as 5-butyl-2- dimethylamino-4-hydroxy-6-methyl-pyrimidine (dimethirimol) resistance symptoms demonstrate.

The anions listed in the general formula I of the active ingredients X⊖ do not affect phytotoxic acids, e.g. hydrochloric acid, Hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, Propionic acid, oxalic acid, n-dodecylsulfonic acid and n-dodecylphenylsulfonic acid. They are for fungicidal effectiveness however not decisive.

The active ingredients can be converted into the usual formulations such as solutions, emulsions, suspensions, foams, pastes Granules, natural and synthetic impregnated with active ingredient Fabrics, ultra-fine encapsulations in polymeric fabrics and in coating compositions for seeds as well as ULV cold and warm mist formulations.

These formulations can be prepared in a known manner take place, e.g. B. by mixing or grinding the active ingredients  of general formula I with common solvents and / or carriers, optionally using surfactants Agents such as emulsifiers and / or dispersants.

In the formulations, adhesives, such as carboxymethyl cellulose, natural and synthetic latex-shaped polymers, such as Gum arabic, polyvinyl alcohol and polyvinyl acetate are used will. Dyes and trace nutrients can be used as additional additives be contained in the formulations of the active ingredients. The formulations generally contain between 1 and 95 % By mass of active ingredient, preferably between 5 and 90% by mass. The method according to the invention for combating fungi is characterized in that fungicidal agents with the invention Active ingredients of general formula I on mushrooms or the items to be protected from fungal attack in an effective amount can act.

The active ingredients can be in the formulations or in the various Forms of use with other conventional active ingredients, such as Fungicides, bactericides, insecticides, acaricides, nematicides, Herbicides, growth regulators, plant nutrients and soil conditioners are mixed and applied. In many cases you get when mixing with fungicides a broadening of the fungicidal spectrum of activity. At a Number of mixtures of the substances according to the invention with known ones Fungicides also have synergistic effects, with the fungicides Effectiveness of the combination product is greater than that the additive effectiveness of the individual components.

The fungicidal compositions can be used as such or in the form of them application forms prepared by further dilution in the usual way Way, e.g. B. by pouring, dipping, spraying, spraying, atomizing, Inject, muddy, spread, pickle or incrustate be applied.  

When treating parts of plants, the drug concentrations can varied in the application forms in a larger area will. They are generally between 0.001 and 1 mass%, preferably between 0.01 and 0.5 mass%. The active ingredient application rates depend on the specific application and are generally between 0.2 and 2 kg of active ingredient per hectare.

When treating seeds, amounts of active ingredient are generally used from 0.01 to 50 g per kilogram of seed, preferably 0.1 to 10 g needed.

For conservation or post-harvest treatment of agricultural Products or processed products of agricultural products the required amounts of active ingredient are 0.01 to 20 g each Kilogram of material to be treated, preferably 0.1 to 10 g.

In the treatment of the soil active ingredient concentrations of 0.0001 to 0.1% by mass, preferably from 0.001 to 0.05% by mass, required at the place of action.

The following examples are intended to explain the invention further, without however restricting them and the effect of the invention Evidence of fungicides.  

Manufacturing examples

The following examples illustrate the preparation of the invention Connections and their precursors.

The starting compounds for the synthesis of the substances according to the invention are known or can be produced by known processes.

Representation of the α-halogen-ω- (azol-1-yl) alkanes of the formula III Preparation of 1-bromo-3- (1,2,4-triazol-1-yl) propane (intermediate) for connection number 4

A mixture of 6.9 g is added to 60.6 g (0.3 mol) of 1,3-dibromopropane (0.1 mol) 1,2,4-triazole and 6.9 g (0.05 mol) potassium carbonate in 75 ml of acetone were added dropwise and the mixture was stirred at room temperature for 5 hours. The precipitated inorganic residue is filtered off and the solvent stripped in vacuo. The remaining syrupy mass is taken in a mixture of 100 ml of methylene chloride and 100 ml Water, separates the organic phase, washes twice with water and dries over sodium sulfate. After distilling off the Methylene chloride in vacuo remain 11.8 g (0.06 mol) of 1-bromo-3- (1,2,4- triazol-1-yl) propane as a viscous brownish mass (62% of theory).

Example 1 Preparation of 1- (N-iso-tridecyl-2,6-dimethylmorpholinio) -3- (1,2,4- triazol-1-yl) propane bromide (Compound # 4)

To 14.9 g (0.05 mol) of N-iso-tridecyl-2,6-dimethylmorpholine and 9.5 g (0.05 mol) 1-bromo-3- (1,2,4-triazol-1-yl) propane are dissolved in 60 ml a mixture of dimethylformamide / toluene (1: 1) dissolved and after Add a catalytic amount of potassium iodide for 30 hours at 100 ° C heated. After cooling, the mixture is filtered and the solvent mixture distilled off in vacuo. The remaining oily residue will extracted several times with n-hexane. Eventually the solvent residues completely removed in vacuo. 13.6 g (0.028 mol) remain of a yellow-brown viscous resin (Verb. No. 4) (56% of theory).  

The compounds of the general Manufacture formula I, the yellow to brown viscous oils or resins represent. They are in polar solvents, like alcohols, Ketones, dimethylformamide and dimethyl sulfoxide are readily soluble and are characterized by their IR spectra.

Examples are given in Table 1.

Table 1

N-alkyl-2,6-dimethylmorpholinio-azolylalkane salts

The compounds of general formula I can, for. B. in the form of the following Formulations are used:

Example I

Solution concentrates: 60 parts by weight of compound 10 are mixed with 40 parts by weight of N-methyl-2-pyrrolidone. It will be a solution obtained, which is suitable for use in the form of tiny drops.  

Example II

Emulsifiable concentrates: 10 parts by weight of compound 4 are with 15 parts by weight of polyoxyethylene sorbitan monolaurate, 60 parts by weight Dimethylformamide and 15 parts by weight of xylene mixed. This concentrate can be diluted with water to make emulsions any desired concentration.

Example III

Granules: 5 parts by weight of compound 5 with 0.25 parts by weight Epichlorohydrin mixed and with 6 parts by weight of acetone solved. Then 3.5 parts by weight of polyethylene glycol and 0.25 Parts by weight of cetyl polyglycol ether were added. The so obtained Solution is sprayed onto kaolin. Then the acetone evaporated in vacuo. A microgranulate is obtained which in this form can be used.

The following examples are intended to demonstrate the fungicidal activity of the invention Explain substances without restricting them.

Examples of use Example A Effect of N-alkyl-dimethylmorpholinio-azolylalkane salts after protective application in the host-parasite combination Barley - Erysiphe graminis

"Vogelsanger Gold" barley plants grown in pots are in the single-leaf stage (age: 7 days) with an active ingredient solution (10 EC) sprayed with dew. After the active ingredient coating has dried on the plants are inoculated by dusting them with barley powdery mildew. Then the plants are kept at 90- 100% relative humidity in and after an incubation cabin set up in the greenhouse.

After a clear course of infection (7 days) the mildew infestation becomes of the barley plants and from this the efficiency according to ABBOTT calculated.  

Example B Effect of N-alkyl-dimethylmorpholinio-azolylalkane salts after curative application in the host-parasite combination Wheat - Erysiphe graminis

Wheat plants of the "Alcedo" variety are grown in pots in the one-leaf stage with conidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici) pollinated. Then be the test plants for a period of 2 to 3 hours 90 to 100% relative humidity in an incubation cabin and then set up in the greenhouse. Two days after that The plants are inoculated with an active ingredient solution (10 EC) sprayed with dew and returned to the greenhouse. After 5 days, the mildew infestation of the wheat plants is determined and the efficiency is calculated according to ABBOTT.  

Example C Effect of N-alkyl-dimethylmorpholinio-azolylalkane salts after protective Use in the host-parasite combination Wheat - Puccinia recondita

Wheat plants of the variety grown under greenhouse conditions "Alcedo" are in the single-leaf stage with an active ingredient solution (10 EC) sprayed with dew. After the spray coating has dried on, the Plants inoculated with a spore suspension with the addition of Tween 20. The spore material is derived from wheat plants with Puccinia recondita are infected. The inoculation follows Incubation in a humidity chamber (approx. 100% humidity) for 24 h. Then the plants in the greenhouse set up. After 10 days the wheat plants become rusty determined and the efficiency calculated according to ABBOTT.

Claims (7)

1. N-alkyl-2,6-dimethylmorpholinio-azolylalkane salts of the general formula I and a mixture of these salts with their positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane salts, in which
R for straight-chain or branched alkyl having 8-16 carbon atoms,
Az for 1,2,4-triazol-1-yl or imidazol-1-yl and
n 1-6 stands and
X⊖ is the anion of a non-phytotoxic acid. 2. N-alkyl-2,6-dimethylmorpholinio-azolylalkane salts of the formula I and a mixture of these salts with their positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane salts,
in which
R for i-C₁₃H₂₇ or n-C₁₂H₂₅,
Az for 1,2,4-triazol-1-yl or imidazol-1-yl and
n stands for 1-6 and
X⊖ means chloride or bromide. 3. Process for the preparation of N-alkyl-2,6-dimethylmorpholinio-azolylalkane salts of the formula I and a mixture of these salts with their positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane salts, characterized in that

• a) N-alkyl-2,6-cis and / or trans-dimethylmorpholines or a mixture of these compounds with at least 15% by mass of N-alkyl 2,5-cis and / or trans-dimethylmorpholines of the general formula II in which R has the meaning given in the formula I, with a compound of the general formula III, X- (CH₂) _n -Az (III) in the
  X represents halogen and
  Az and n have the meaning given in the formula I,
  in the presence of a solvent or diluent or
• b) 2,6-cis and / or trans-dimethylmorpholine-azolylalkanes or a mixture of these compounds with at least 15% by mass of 2,5-cis and / or trans-dimethylmorpholine-azolylalkanes of the general formula IV, in the Az and n have the meaning given in the formula I, with an alkyl halide of the general formula V, RX (V) in the
  R has the meaning given in formula I and
  X stands for halogen
  in the presence of a solvent.

4. Fungicidal agents, characterized by a content of at least an N-alkyl-2,6-dimethylmorpholinio-azolylalkane salt of the formula I or a mixture of this salt with at least 15% by mass of its positionally isomeric N-alkyl-2,5-dimethylmorpholinio-azolylalkane Salt.   5. Use of N-alkyl-dimethylmorpholinio-azolylalkane salts of Formula I to combat fungal attack on plant materials or stocks. 6. A method for combating phytopathogenic fungi, characterized in that that N-alkyl-dimethylmorpholinio-azolylalkane Salts of formula I act on mushrooms or their habitat leaves. 7. A process for the preparation of fungicidal compositions, characterized in that that N-alkyl-dimethylmorpholinio-azolylalkane Salts of the formula I with customary auxiliaries or carriers mixed.