DD263685A1 - FUNGICIDAL AGENT WITH ADDITIONAL PLANT GROWTH REGULATORY EFFECT - Google Patents

Abstract

The invention relates to novel N-alkyl-2,6-dimethylmorpholino-carboxylic acid ester salts of the general formula I, to a process for their preparation and to their use as fungicides for combating fungal pathogens in agriculture and horticulture. In addition, the agents according to the invention have plant growth-regulating properties. The meaning of R1, R2, R3, Z and X can be taken from the description.

Description

-1-

The invention relates to novel N-alkyl-2 _/ 6-cie and / or trans-dimethylmorpholinio-carboxylic acid ester salts and their use as fungicidal agents in agriculture and horticulture with additional plant growth regulating properties.

Ch.ar.ak.t.e.r.ls.tiX ^ cle.c. _b.eJca.gqt.e.n. , T.e.Qh.qi.a.cJie.n. Jiö.a.u.gg.e.n.

It is known to use N-alkylmorpholines and their salts as well as their Mo ^ addition and addition compounds as fungicides (DE-PS 1 164 152, DE-PS 1 173 722, DE-PS 24 61 513). 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 effective (DE-PS 1 167 588, Angewandte Chemie 77 (1965), p 327-333 ). Furthermore, agents are known which contain substituted N-benzyl or alkoxymethyl-2,6-dimethylmorpholinium salts as active ingredients for controlling fungal pathogens (DD-PS 134 037, DD-PS 134 474, DD-PS 140 403). It is also known that salts of morpholinocarboxylic acid esters with long-chain alkanesulfonic or alkanecarboxylic acids have fungicidal properties (DD-PS 201 371).

Furthermore, it is already known, 2,3-dihydro-6-methyl-5-phenylcarbamoyl, 4-oxathiin-4,4-dioxide (oxycarboxine), N, N ¹ -bis (1-formamido-2,2,2- trichloroethyl) -piperazine (triforine) or zinc ethylene-bis-dithiocarbamate (zineb) as active ingredients in fungicidal plant disease control agents (The Pesticide Manual, British Crop Protection Council, Uondon, 1979). 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.

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: .. Ejit charge

The aim of the invention is the development of new compounds with improved fungicidal activity and additional growth-regulating properties and a process for their preparation / and fungicidal compositions containing such compounds, as well as the use of such fungicides in agriculture and horticulture. »

, d.e.8, Jteacas. .flex, ..E.r, £ i.adu.Q.g

The invention has for its object to provide new N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-carboxylic acid ester salt-containing fungicidal agent with good efficacy and broad spectrum of activity and the highest possible plant tolerance and additional plant growth-regulating properties.

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-dimethylmorpholinio-carboxylic acid salt of the general formula I,

H ₃ C

0 N ^ X (I)

in the

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

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

R is straight-chain or branched alkyl having 1 to 20 C atoms, a straight-chain or branched alkyl having 1 to 4 substituted by halogen, hydroxyl, alkoxy having 1 to 4 C atoms, dialkylamino having 2 to 16 C atoms, nitro and / or cyano 6 C atoms,

an optionally halogen-substituted alkenyl having 2 to 6 C atoms, alkynyl having 3 to 6 C atoms,

Cycloalkyl having 3 to 12 carbon atoms / wherein the cycloalkyl radical may optionally be substituted by one or more alkyl radicals having 1 to 7 carbon atoms, cycloalkylalkyl having 4 to 10 carbon atoms, aryl which is mono- or polysubstituted by identical or different straight-chain or branched Alkyl with 1 bia 6 C atoms, alkoxy having 1 to 4 carbon atoms, aryl-lower-alkyl having 7 to 12 carbon atoms, acyl having 1 to 4 carbon atoms, halogen, aryl, nitro and / or cyano substituted may be aryl-lower-alkyl having 7 to 12 C-atoms, which is mono- or polysubstituted by identical or different straight-chain or branched alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen, haloalkyl with 1 to 4 C atoms, nitro and / or cyano may be substituted,

Z oxygen or sulfur and X is the anion of a non-phytotoxic acid,

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

The compounds of the invention may exist in two different geometric structures as N-alkyl ^ cis-dimethylniorpholinio-carboxylic acid ester salt or N-alkyl ^ ö trans-dimethylniorpholinio-carboxylic acid ester salt or as mixtures of these two isomers.

Surprisingly, it has been found that the N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-carboxylic acid ester salts of the general formula I according to the invention have a strong fungicidal activity and a broad activity spectrum and, in particular, 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. In addition, the compounds according to the invention, with their growth-regulating properties, can positively influence crop plants in the desired manner.

Furthermore, it has been found that the N-alkyl-2/6-cis- and / or tranedimethylmorpholinio-carboxylic acid ester salts of the general formula I are obtained by reacting an N-alkyl-2 _/ 6-cie and / or transdimethylmorpholine of the formula II

H ₃ C-

NR ¹ (II)

H ₃ C

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

X - R ² - CO - Z - R ³ (III)

2 3

wherein R, R and Z have the meaning given in the general formula I and X is halogen reacted

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

N - R ² - CO - Z - R ³ (IV)

H ₃ C

2 3

in which R, R and Z have the meaning given in general formula I, with a compound of Fornel V,

R ¹ - X (V)

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

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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-trimethyldecyl, n-pentadecyl or n-didecyl-2,6-cis- and / or trans-dimethylmorpholine ,

Halocarboxylic esters of the formula III are, for example, chloroacetic acid C 1 -C 4 -alkyl esters, chloroacetic acid 4-chlorobutyl ester _/ 4-hydroxychloroacetate, 2-ethoxyethyl chloroacetate, chloroacetic acid cyanoethyl ester, chloroacetic acid 2-nitroethyl ester, cyclohexyl chloroacetate, 2 Methyl bromo-propionate, 2-bromopropionic allyl ester, 2-bromopropionic acid naphthyl ester, phenyl chloroacetate, thiol-chloroacetic acid phenyl-2-bromobutyric acid ethyl ester _/ 2-bromoboronic acid benzyl ester, chloroacetic acid 4-chlorophenyl ester, 4-tert-butylphenyl chloroacetate, chloroacetic acid S ^ dichlorophenyl ester, chloroacetic acid 2 _/ 6-dimethylphenyl ester _/ chloroacetic acid 2 _/ 6-dibromo-4-nitrophenyl ester, chloroacetic acid 2 _/ 6-dibro ^ n-4-cyanophenyl ester, chloroacetic acid-2, o-dichlorobenzylescer, chloro-4-cyanobenzyl ester , Chloroacetic acid 4-nitrophenyl ester or the chloro

3 acetate anion if R is absent.

2,6-cis- and / or trans-dimethylmorpholino-carboxylic acid esters of the formula IV are, for example, 2,6-cis- and / or trans-dimethylmorpholinoacetic acid C ₁ -CpQ-alkyl ester, -acetic acid phenyl ester, -thiol-acetic acid-phenyl ester, - acetic acid 4-chlorophenyl ester, acetic acid-4-nitrophenylestur, acetic acid-S ^ -dichlorphenylester, acetic _{acid-2/6-dibromo-4-cyanophenyl /} acetic acid benzyl ester, acetic acid 2,6-dichlorobenzyl ester, -2- propionate,

3 -2-Butyric acid methyl ester or acetate, if R does not exist

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

The conversion to the novel compounds of formula I are optionally carried out in the presence of a Uösungs- or diluent at a temperature ranging between 10 and 180 ⁰ C, preferably between 30 and 150 ⁰ C. The starting materials of the formula II or of the formula IV are reacted in stoichiometric amounts with a compound of the formula III or of the formula V or preferably with an excess of from 10 to 100% of a compound of the formula III or of the formula V on the stoichiometric amount, relative to the starting materials of the formula II or, the research ^v mel IV is 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; Dimethyl sulfoxide or water or mixtures of these!. Solvents are 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 operation for the production of fungicidal preparations.

The active compounds of the general formula I according to the invention have a strong 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 the 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. In addition, the active ingredients in their application influence the growth processes of crops in a positive way.

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The active compounds according to the invention are particularly suitable for preventing and curing plant diseases / caused by fungi, e.g. Erysiphe graminis (powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Erysiphe polygon! (Dohnenmehltau), Podosphaera leucotricha (apple powdery mildew), Sphaerotheca pannosa (rose mildew), Uncinula necator (vineyard powdery mildew); Rust diseases, such as those of the genera Puccinia, Uromyces or Hemileia, in particular Puccinia graminis (cereal black rust), Puccinia coronata (oat crown rust), Puccinia sorghi (corn rust), Puccinia recondita (cereal 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 to tea; Phytophthora infestans on potatoes and tomatoes; Alternaria solani on tomatoes. Furthermore, various of these agents are also differentially effective against phytopathogenic fungi, such as e.g. Ustilago avenae (flare), Ophiobolus graminis (cereal foot disease), Septoria nodorum (cereal leaf and tuberola), Venturia inaequulis (apple scab) and various specis of the genera Rhizoctonia, Tilletia, Helminthosporium, Peronospora, Pythiurn or Mucor.

Particularly interesting are the active compounds according to the invention for combating a variety of fungal diseases on various crops or their seeds, especially wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, bananas, sugarcane, fruit, ornamentals in horticulture, vegetables like cucumbers, beans or cucurbits.

In addition, the active compounds according to the invention, with their plant-growth-regulating properties, can positively influence the development of crop plants in the desired manner. The effects of the compounds are essentially dependent on the time of application, based on the stage of development of the seed or of the plants, on the amounts of active substance applied to the plants or their surroundings and on the mode of administration.

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Furthermore, the active ingredients also provide good activity against wood-discoloring and wood-destroying fungi, such as e.g. Pullaria pullulans, Apsergillus niger, Polystictus versicolor or Chaetomium globosum.

Furthermore, the active compounds of the general formula I according to the invention exhibit a good activity against molds, such as, for example, Penicillium, Fusarium or Aspergillus species that cause spoilage of high moisture agricultural products or processed agricultural products during storage or storage. Such products to be treated include e.g. Apples, oranges, mandarins, lemons, grapefruits, peanuts, cereals and cereal products or pulses and meal.

Active ingredients according to the invention are, in addition to their broad spectrum of fungicidal activity, also different in activity against phytopathogenic bacteria, such as, for example, Xanthomonas or Erwinia species.

Some of the active ingredients also show activity against human pathogenic fungi, e.g. Trichophyte and Candida species.

A part of the active compounds of the general formula I is characterized not only by the protective effect but also by a systmic effect development. Thus, they are absorbed both via the root and the leaves and transported in the plant tissue or fed via the seed to the aerial parts of the plant.

The active compounds according to the invention are furthermore suitable for controlling resistant strains of fungal pathogens which are resistant to known fungicidal active compounds, such as e.g. Active substances from the group of dicarboximidide fungicides, such as, for example, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine (vinclozoline) or 5-methyl-

(Myclozoline); Active substances from the group of the benzimidazole or thjophanate fungicides, such as, for example, methyl l- (n-butylcarbamoyl) -benzimidazol-2-ylcarbamate (benomyl), benzimidazol-2-yl-carbamic acid methyl ester (carbaldehyde) or l, 2 Bis- (3-ethoxycarbonyl-2-thioureido) -benzene (thiophanate); Active ingredients from the

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Group of the azole fungicides, such as l- (4-chlorophenoxy-3,3-dimcthyl-l- (lH-l _{/ 2/4-triazol-l-yl)} -butan-2-one (triadimefon) or l- / 2 '- (2'',4''-Dichlorphenyl) -2 "- (propenyloxy) -ethyl / -l, 3-imidazol (imazalil); agents from the group of aromatic hydrocarbons containing fungicides such as _2/5 Dichloro-1, 4-dimethoxybenzene (chloroneb) or 2,6-oichloro-4-nitroaniline (diclorane); active substances belonging to the group of acylalanine fungicides, such as DLJ-N- (2,6-dimethylphenyl) - N- (2'-methoxyacetyl) -alanine methyl ester (metalaxyl) or DL'-N-, (2, δα ime-1-phenyl) -N- (2-furoyl) -alan-in-myrole (furalaxyl) or Active substances from the group of pyrimidine fungicides, such as, for example, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrinidine (dimethirimol) or 2-chlorophenyl-4-chlorophenyl-pyrimidin-5-yl-methanol (fenarimol) , Show resistance symptoms.

The anions X ~ listed in the general formula I of the active compounds according to the invention are not decisive for the fungicidal action.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, natural-impregnated synthetic substances, superfine encapsulations in polymeric substances and in enveloping compositions Seeds and UL'V cold and hot side formulations. The preparation of these formulations can be carried out in a known manner, e.g. by mixing or grinding the active compounds of the general formula I according to the invention with solvents and / or carriers, if appropriate using surface-active agents, such as emulsifiers and / or dispersants. As liquid solvents, it is possible to use aromatics such as toluene, xylene or alkylnaphthalenes; chlorier'.e aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions; Alcohols, such as butanols or glycols, and their esters and ethers; Ketones, such as acetone, methyl ethyl ketone,

Methyl isobutyl ketone or cyclohexanone; strong polar solvents such as water, dimethylformamide or dimethyl sulfoxide can be used. Likewise, liquefied solvents which are gaseous under normal conditions, such as e.g. Aerosol propellants, such as halogenated hydrocarbons, propane, butane, nitrogen and carbon dioxide are used.

As solid carriers are e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as high-silica, per se silica, alumina and silicates. As solid carriers for granules, e.g. crushed and fractionated ground natural minerals such as calcite, marble, pumice, dolomite and synthetic granules of inorganic or organic flours and granules of organic materials such as sawdust, cellulose powder, bark and nutshell flour are used. As emulsifying agents, e.g. nonionic and anionic emulsifiers, such as alkali, alkaline earth or ammonium salts of L-igninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acid, alkylarylsulfonates, fonates, alkyl sulfates, alkylsulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthaleneculfonic acid, L-auryl ether sulfate, fatty alcohol sulfates, fatty acid alkali metal salts and alkaline earth metal salts, Salts of sulfated MexadecanoJe, lleptdecanole or Octadecanole, salts of sulfated Fettalkoholglykolethern, Konaensationsprodukte of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalenes and naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octyl phenol ether, AlkylphenolpoIyglykolether, tributyl phenyl polyglycolether, alkylaryl polyether alcohols, iso Tridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, L'auryl alcohol polyglycol ether acetal and sorbitol esters.

Suitable dispersants are for example L'ignin-Suifitablaugen and methylcellulose into consideration.

Adhesives such as carboxymethyl cellulose, natural and synthetic latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulations. As further additives, dyes and trace nutrients in the

Formulations of the active ingredients may be included.

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

The method according to the invention for controlling fungi is characterized in that fungicidal agents with the active compounds of the general formula I according to the invention can be acted upon by 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. Fungicides which can be combined with the active compounds according to the invention, without restricting the possible combinations, are, for example:

Sulfur,

Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zincin im. thyldi thiocarbamate, manganese ethylene bisdithiocarbamate, Mö.igan-ZtnJcethylenediamine bis-dithiocarbamate and zinc ethylenebisdithiocarbamate,

Tetramethyl thiuram sulfides,

Ammonium complex of zinc (N, N-ethylene-bis-dithiocarbamate) and iM, N'-polyethylene-bis (thiocarbamoyl) -disulfide, ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate ) and N, N'-propylene-bis- (thiocarbamoyl) -disulfide,

N-trichloromethylthio-tetrahydrophthalimide. N-trichloromethylthio-phthalimide,

2 "3685

N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide,

_{4/6-dinitro-2-} (l-methylheptyl) -phenylcrotonat, _{4/6 DinitΓo-2-sec-butylphenyl-3/3-dimethylacΓylat, 4/6-dinitro-2-sel} <.- bύtylphenyl isopropyl carbonate _/

Methyl (n-butylcarbamoyl) -benzimidazol-2-yl-carbarn-acid, ethyleneglycate-2-y- ^1- carboxylate, 2- (fur-2-yl) -benzimidazole,

2- (thiazol-4-yl) -benzimidazole,

1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, l _/ 2-bis (3-ethoxycarbonyl-2-thioureido) -benzene _/ 2 _/ 3-dihydro-6-methyl-5-phenylcarbamoyl l _/ 4-oxathiin, 2,3-dihydro-6-inethyl ~ 5-phenylcarbamoyl-l, _{4-oxathiin-4/4-dioxide /}

Tetrachloro-ioophthalsäuredinitril,

2,3-dichloro-l _/ 4-naphthoquinone,

2,3-dicyano-l _/ 4-dithioanthraquinone,

N-tridecyl-2/6-dimethylmorpholine or its salts, iSI-C ₁₀ -C ₁₄ -alkyl-2 _/ 5 and / or 2, 0-dimethylmorpholine, 1-cyclododecyl-2,6-dimethylmorphol in or its salts , N- / 3-p-tert-butylphenyl) -2-methyl-propyl / -2,6-cis-dimethylmorpholine or its salts

IN, N ¹ -bis- _{(l-formamido-2/2/2-trichloroethyl)} -piperazine N- _{(l-formamido-2/2/2-trichloroethyl)} -3 _/ 4 dichloroaniline N- (l-formamido 2 _/ 2 _/ 2-trichloroethyl) -morpholine

5-butyl-2-ethylamino-4 "-hydroxy-6-methylpyrimidine 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine

2-Dichlorophenyl-phenyl-pyrimidine-G-yl-methanol 2-chlorophenyl-4-chloropheny1-pyrimidin-5-yl-methanol Bis- (4-unophenyl) -pyridin-3-yl-methanol

5-Methyl-5-vinyl-3- (3,5-chloro-phosphoryl) -1,3-oxazole-idine-2,4-dione 5-methyl-5-methoxymethyl-3- (3,5-dichlorophenyl) - l, 3--oxazol] idin-2,4-dione

3- (3,5-dichlorophenyl) -IM-isopropyl-2,4-dioxo-imidazolidin-l-carboxamide

N-iS / S-DichlorphenyO-l ^ -dimethylcyclopropan-l ^ -dicarboximid

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1- (4-chlorophenoxy) -3 _/ 3-di-ethyl-1- (1 _/ 2 _/ 4-l- (4-chlorophenoxy) -3 _/ 3-dimethyl-1- (l _/ 2,4-triazole-1 -yl) -butan-2-ol 1- / 2- (2,4-dichlorophenyl) -2- (propenyloxy) -ethyl] - imidazole 1- / 1S-propyl-N- (2,4,6-trichlorophenoxy ) -ethyl-carbanidyl / -imidazole L- / 2- (2,4-dichlorophenyl) -4-ethyl-1,3-dicxolan-2-yl-methyl / 1H-1,2,4-triazole

l- / 2- (2,4-dichlorophenyl) 4-n-propy1-1,3-dioxolan-2-yl-methy1 / -1H-1,2,4-triazole

1- (2 _/ 4-dichlorophenyl) -2- (1 _/ 2 _/ 4-triazol-1-yl) -4 _/ 4-dimethyl-1-pentan-3-one

2 _/ 5-dichloro-1, 4-dimethoxybenzene

2 _/ 6-dichloro-4-nitroaniline

diphenyl

2-Mcthyl-benzoic acid anilide

2-O-benzoic acid anil id

2 _/ 5-Diniethyl-furan-3-carboxylic acid anilide 2 _/ 4 _/ 5-trimethyl-furan-3-carboxylic acid anilide N-cyclohexyl-N-methoxy ^^ - dimethyl-furan-S-carboxamide 3 - / 3- (3 _/ 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl-glutarimide N-diclilorobutylthio-N ', N'-dimethyl-i-m-phenyl-sulfuric acid diamide

DL-iM- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester DL-N- (2 _/ 6-dimethylphenyl) -IM- (2-furoyl) -alanine-niethylester i -In-cliloracetyl-DL-2-aminobutyrolactone (2,6-Diniethylphenyl) - \

2 _/ 4-diclilor-6- (2-chloroanilino) -s-triazine, 0,0-diethyl-phthalimido-phosphonothioal; 5-Anilino-l- (bis (dimethylamino) -phosphinyl) -3-phenyl-l _/ 2 _/ 4-triazole 0,0-Diethy1-S-benzyl-thioI phosphoric acid ester 2-thio-l _/ 3-clithLo ( 4 _/ 5-b) -quinoxaline)

4- (2-Clilorplienyl hydrazone) -3-ethyl-5-isoxysilone pyridine-2-thiol-1-oxide

8-llydroxycliinol in or its salts

4-dimethylanilinophenyl diazo-sulfonic acid sodium salt 5-nitro-isopropylthiacid di-isopropylose ter

2-cyano-N- (ethyl-1-aminocarbonyl) -2- (methoxyimino) -acetamide 2-ladeptadecyl-2-iiiiidazole in-acetate Oodecyl-cjuariidine acetate

2 ί 3 * 8 5

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

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a broad range. They are generally between Ο, ΟυΟΙ and 1 mass%, preferably between 0.5 and 0.001% by mass. The drug application rates depend on the specific application and are generally between 0.1 and 3 kg of active ingredient or more per hectare.

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

For the preservation or post-harvest treatment of agricultural products or processing products of agricultural products, the required Wirkstoffinengen cheated 0.01 to 100 g per kilogram of material to be treated, preferably 0.1 to 50 g. In the treatment of the soil, drug concentrations of 0.0001 to 0.1% by mass, preferably 0.001 to 0.05% by mass, are required at the site of action.

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.

killed

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Alia f.ü.h.rmn.gab.e. Lap, ie Le.

The following examples illustrate the preparation of the invention compounds.

Beisgiel_l

N-isotridecyl ^ / ö-cis / trans-methyl acetate dimethylmorpholinio chloride

30 g of N-iso-tridecyl-2,6-cis / trans-dimethylmorpholine and 10.9 g of methyl chloroacetate are heated to reflux with addition of a catalytic amount of sodium iodide in 100 ml of acetonitrile for 20 hours. It is cooled and the solvent is distilled off in vacuo. The product is directed with η-hexane. After concentration in vacuo, 38 g of a yellow-brown viscous oil (Compound No. 5) IR spectrum (film): C = O absorption 1740 cm ".

Beisp_iel_2

N-iso-tridecyl ^ S-cis / trans-dimethylmorpholinio-acetic acid S ^ - dichlorophenyl ester chloride

30 g of N-isotridecyl-2, G-cis / trans -dimethylmorpholine and 24 g of chloroacetic acid-3,4-dichlorophenyl ester are heated in 100 ml of n-butenol with the addition of a catalytic amount of sodium iodide for 16 hours to reflux. It is cooled and the solvent is distilled off in vacuo. The remaining product is dissolved in a little diethyl ether and mixed with η-hexane until complete precipitation as an oily phase. After concentration in vacuo, 48 g of a dark brown resin (Compound No. 55) are obtained. IR spectrum (film): C = O absorption 1740 cm ^-1

C = C absorption (aromatic) 1590 cm "

Example 3

2- (N-iso-tridecyl-2 _/ G-cis / trans-dimethylmorpholinio) -propionic acid methyl ester chloride

20 g of 2- (2 _/ 6-cis / trans-dimethylmorphol ino) -propionaiiremethylester and 22 g of iso-tridecyl chloride (mixture of different C ^ -C ^

- 16 -

chloride containing 60 to 70% n-tridecyl chloride) in 100 ml of dimethylformamide are refluxed for 10 hours. After cooling, the!. Solvent is distilled off in vacuo. The product is dissolved in a little acetone and η-hexane is added until complete precipitation as an oily phase. Concentration in vacuo gives 19 g of a light brown resin (compound no. 8) IR spectrum (film): C = O absorption 1735 cm

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 e.g. Alcohols, acetone, dimethylformamide and dimethyl sulfoxide, are well soluble and have the characteristic absorption band of the carbonyl group in the IR spectrum. 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.

- 17 -

^ -, R ¹ '3'

R ² - CO - Z - R ³

^RJ

1 n-decyl CH ₂ 0 methyl Cl 2 n-dodecyl CH ₂ 0 methyl Cl 3 n-tridecyl CH ₂ 0 methyl Cl 4 1,5,9-trimethyl-decyl CH ₂ 0 methyl Cl 5 iso-tridecyl CH ₂ 0 methyl Cl 6 n-pentodecyl CH ₂ 0 methyl br 7 n-didecyl CH ₂ 0 methyl br 8th iso-tridecyl CH (CH ₃ ) 0 methyl Cl 9 iso-tridecyl CH (CpH.) 0 methyl Mr ' IO iso-tridecyl C (CHg) ₂ 0 methyl br 11 iso-tridecyl C (C ₂ H ₅ ) ₂ 0 methyl br 12 iso-tridecyl CH (C ₅ H ₁₁ ) 0 methyl br 13 iso-tridecyl (CH ₂ ) 3 0 methyl Cl 14 iso-tridecyl CH ₂ 0 n-butyl Cl 15 iso-tridecyl CH ₂ S n-butyl Cl 16 iso-tridecyl CH ₂ 0 2-ethylhexyl Cl 17 iso-tridecyl CII ₂ 0 n-dodecyl ci 18 iso-tridecyl CH ₂ 0 iso-octadecyl Cl 19 iso-tridecyl CH ₂ 0 4-hydroxybutyl Cl 20 iso-tridecyl CH ₂ 0 2-ethoxyethyl Cl 21 iso-tridecyl CH ₂ 0 4-chlorobutyl Cl 22 iso-tridecyl CH ₂ 0 2,2,2-trichloroethyl Cl 23 iso-tridecyl CH " 0 2-nitroethyl Cl

2636S5

R ¹ - 18 - Z R ³ X No. iso-tridecyl R ² 0 2-cyanoethyl Cl 24 iso-tridecyl Chg 0 cyclopentyl Cl 25 iso "ridecyl , CH ₂ S cyclohexyl Cl 26 iso-tridecyl iso-tridecyl Chg 0 0 2,6-dimethylcyclohexylcyclodckyl Cl Cl 27 28 iso-tridecyl CH ₂ CH ₂ 0 cyclododecyl Cl 29 iso-tridecyl Chg 0 5- (2-ethylcyclohexyl) pentyl Cl 30 iso-tridecyl Chg 0 eyelododecylmethyl Cl 31 iso-tridecyl Chg 0 allyl Cl 32 iso-tridecyl Chg 0 crotyl Cl 33 iso-trideoyl CH ₂ 0 propargyl Cl 34 iso-tridecyl Chg 0 phenyl Cl 35 iso-tridecyl Chg S phenyl Cl 36 iso-tridecyl CH ₂ 0 1-naphthyl Cl 37 iso-tridecyl Chg 0 4-biphenyl Cl 38 iso-tridecyl Chg 0 2-chlorophenyl Cl 39 iso-tridecyl Chg 0 3-bromophenyl Cl 40 iso-tridecyl Chg 0 4-chlorophenyl Cl 41 iso-tridecyl Chg 0 4-sec-butylphenyl Cl 42 iso-tridecyl CH ₂ 0 4-tert-butylphenyl Cl 43 iso-tridecyl CH ₂ 0 2-methoxy-phenyl Cl 44 iso-tridecyl Chg 0 4-methoxyphenyl Cl 45 iso-tridecyl CH ₂ 0 4-propionylphenyl Cl 46 iso-tridecyl CH ₂ 0 4-benzylphenyl Cl 47 iso-tridecyl Chg 0 2-nitrophenyl Cl 48 iso-tridecyl CH ₂ 0 4-nitrophenyl Cl 49 iso-tridecyl Chg 0 4-cyar.ophenyl Cl 50 iso-tridecyl Chg 0 2,3-dichlorpheny1 Cl 51 iso-tridecyl Chg 0 2,4-dibromophenyl Cl 52 iso-tridecyl CH ₂ 0 2,5-dichlorophenyl Cl 53 iso-tridecyl Chg 0 2.6-dichlorophenyl Cl 54 iso-tridecyl Chg 0 3,4-Dichlorophenyl Cl 55 iso-tridecyl Chg 0 3.5 dicnlorphenyl Cl 56 CH ₉

- 19 -

263 * 85

R ^v

57 iso-tridecyl CH ₂ 58 Isotridecyl CH ₂ 59 iso-tridecyl CH ₂ 60 iso-tridecyl CH ₂ 61 iso-tridecyl CH ₂ 62 iso-tridecyl CH ₂ 33 iso-tridecyl CH ₂ 64 iso-tridecyl CH ₂ 65 iso-tridecyl CH ₂ 66 iso-tridecyl CH ₂ 67 iso-tridecyl Chg 68 iso-tridecyl Chg 69 iso-tridecyl Chg 70 iso-tridecyl Chg 71 iso-tridecyl Chg 72 iso-tridecyl Chg 73 iso-tridecyl Chg 74 iso-tridecyl Chg 75 iso-tridecyl Chg 76 iso-tridecyl Cup 77 iso-tridecyl Chg 78 iso-tridecyl Chg 79 iso-tridecyl Chg 80 iso-tridecyl CKg 81 iso-tridecyl CH ₂ -CO-O

0 2,6-dimethy1phenyl Cl 0 3,4-dimethylphenyl Cl 0 2,3-dimethoxyphenyl Cl 0 2-chloro-4-nitrophenyl Cl 0 2,4,6-tribromophenyl Cl 0 2,3,5-trichlorophenyl Cl 0 2,3,6-trimethylphenyl Cl 0 2,6-dibromo-4-nitro-phenyl Cl 0 2,6-dibnom4 "cyano-phenyl Cl 0 2,4-dichloro-O-methyl-phenyl Cl 0 benzyl Cl S benzyl Cl 0 4-chlorobenzyl Cl 0 4-bromobenzyl Cl 0 4-methylbcnzyl Cl 0 4-tert-butylbenzyl Cl 0 3-methoxybenzyl Cl 0 4-nitrobenzyl Cl 0 4-cyanobenzyl Cl 0 2,4-dichlorobenzyl ci 0 2,6-you lorbenzyl Cl 0 2,3,4-trichlorobenzyl Cl 0 2,3,6-trichlorobenzyl Cl 0 3-phenylpropyl Cl unavailable

- 20 -

6 3 6 8

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

Solution concentrates: 80 parts by weight of compound 5 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.

Concentrates which may be emulsified: 25 parts by weight of compound 55 are mixed with 2.5 parts by weight of epoxidized vegetable oil per part by weight of an alkylaryl ether / fatty alcohol polyglycol ether mixture containing 5 parts by weight of dimethylformamide and 57.5 parts by weight of emulsion Concentration to be made ·

Injection powder: 40 parts by weight of compound 65 are mixed well with 5 parts by weight of the sodium salt of a Lügninsulfonsäure from a sulfite liquor, 1 part by weight of sodium salt of diisobutylnaphthalenecarboxylic acid and 54 parts by weight of silica gel and ground in an appropriate mill. A spray powder is obtained which can be diluted with water to give suspensions of any desired concentration.

Dusts: 5 parts 55 parts by weight are intimately mixed and ground with 95 parts by weight of finely divided kaolin. The dusts can be dusted in this form for use.

V. and A.iap-i.e-L

Granules: 5 parts by weight of compound 57 are mixed with 0.25 parts 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 Uösurig thus obtained is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

- 21 -

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

Beisßiel_A

Mycelium growth., - Test

The fungicidal activity of the agent against the test fungi is prepared conventionally ice inhibition of the radial mycelial growth on MaTzagar Agar (2% malt) determined in Petri dishes of 9 cm in diameter at an incubation temperature of 25 ⁰ C. The active ingredients verden to 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 is carried out depending on the growth rate of the fungi, when the controls without the addition of active ingredient are interspersed with 70 to 90% of the shell diameter. The percentage growth inhibition of the active substances is calculated (Table A).

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

Growth inhibition in percent

Botrytis cinerea Phytophthora cactorum Connection no. Drug-10 pg / ml -, kOJlZ ... 50 μg / ml Oxycarboxine (known) 20 50 5 88 85 8th 91 48 9 92 51 14 89 100 16 79 100 24 91 35 78 67 41 86 100 49 84 60 55 97 100

- 22 -

Continuation Table A

Connection N ^r

Growth inhibition in percent

Botrytis Phytophthora cinerea cactorum

Active ingredient - 10 pg / ml 50 pg / ml .kariz ....

57 64 65 81

94 92 95 78

100 100 100

Beisp_iel_B

Barley mildew test (Erysiphe graminis / barley)

In tubes with sand barley plants of the variety "Astacus" in the single-leaf stage are dewy sprayed with active ingredient preparations prepared from 1 part by weight of active ingredient, 100 parts by weight of dimethylformamide and 0.25 parts by weight of alkylaryl and diluted with water to the desired active ingredient concentration. After the spray coating has dried on, the plants are pollinated with conidia of barley powdery mildew (Erysiphe graminis var. Hordei). Subsequently, the test plants for a period of 2 to 3 hours at 90 to 100% relative humidity in an incubation and then at temperatures between 20 and 22 ⁰ C and 75 to 80 % rel. humidity in the greenhouse. After 7 days, the powdery mildew of barley plants is determined. The grading values obtained according to STEPHAN (Arch. Phytopath., PfI. Schutz 14 (1978), 163-175) are converted into the level of infestation according to KRÜGER (Nachr.-Bl. Pflanzenschutz DDR 1381, 145-147). This results in the efficiency according to ABBOTT accordingly

". , , / _V x degree of infestation control degree of infestation variant _inn efficiency (%) = BwnTtgWYölTFFoTI ¥ * ^X

The results are shown in Table B.

- 23 -

Table B: Effect against Erysiphe graminis on barley. Active substance concentration: 10 mg / l

Connection No. Efficiency in percent

N-methyl-N-tridecyl-2 _/ 6-dimethyl

morpholine methosulfate

(known from DE-PS 11 67 588) 82nd

Triforine (known) 86 *

5 88

8 82

9 87 14 93 24 97 35 94 55 88 65 90

Beisp_iel_C

Wheaty mildew test (Erysiphe graminis / wheat)

Wheat plants of the "Alcedo" variety grown in pots are sprayed wet with active ingredient preparations in the single-leaf stage / which are prepared from 1 part by weight of active compound, 100 parts by weight of dimethylformamide 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 oidia (spores) of wheat powdery mildew (Erysiphe graminis var. 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 ⁰ C and 75 to 80% relative humidity in the greenhouse.

After 5 days, the powdery mildew of the wheat plants is determined. The efficiency of the means is calculated by the method described in Example B.

 The results are shown in Table C.

- 24 -

Table C: Effect against Erysiphe graminis on wheat. Active substance concentration: 100 mg / l

Connection Nn. Efficiency in percent

N-methyl-N-tridecyl-2,6-dimethyl-57

morpholinium methosulfate

(known from DE-PS H 67 588)

5 88

Cucumber mildew test (mixed culture of Erysiphe cichoracearum and

Sphaerotheca fuliginea / cucumber)

Cucumber plants of the cultivar "Eva" grown in pots are inoculated in the four-leaf stage with a conidia suspension of a mixed culture of Erysiphe cichoracearum and Sphaerotheca fuligenea

After 4 days, the plants are dewatered sprayed with Wirkstoffbreitht, which are prepared from 1 part by weight of active compound, 100 parts by weight of dimethylformamide 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, the plants are placed in the greenhouse at a temperature of 20 ^° C. and 70 to 80% relative humidity.

After 6 or 9 days, the powdery mildew of cucumber plants is determined. The rating values obtained according to BOL ¹ LlE (Nachrichtbl. Dt. Pflanzenschutzdienst 16 (1964), 92-94) are converted into the degree of infestation according to KRÜGER and from this into the efficiency according to ABBOTT

 The results are shown in Table D.

- 25 -

Table D: Action against Erysiphe cichoracearum and Sphaerotheca fuliginea (mixed culture) on cucumbers Concentration of active ingredient: 500 mg / l

Connection No. Efficiency in percent

Days after the middle application

6 _λ "9

Tridemcrph (known) 100 88

5 100 100

Deisgiel_E

Grain egg test (Puccinia recondita / wheat)

Wheat plants of the variety "Alcedo" grown in pots are cut back to the height of 12 cm in the two-leaf stage. The secondary leaf of the plants is removed. Thereafter, the wheat plants are sprayed with active compound preparations prepared from 20 parts by weight of active ingredient, 10 parts by weight of polyoxyethylene sorbitan monstearate (Tween 60), 5 parts by weight of polypropylene glycol, 25 parts by weight of cyclohexanone and 40 parts by weight of toluene and diluted with water to the desired active ingredient concentration. After the spray coating has dried on, the plants are inoculated with spores of the wheat brown rust (Puccinia recondita), which are applied as a suspension in water with Tween 60 additive. The test plants are then incubated for a period of 24 hours in a steam-saturated incubation cabin and thereafter placed at temperatures of 20 to 22 ⁰ C and at 70 to 80% relative humidity in the greenhouse.

After 10 days, the rust attack of the wheat plants is determined. The efficiency of the means is calculated according to the method described in Example B.

- ²⁶ - 2 * 36 * 85

The results are listed in Table E.

Table E: Action against Puccinia recondita on wheat. Active substance concentration: 500 mg / l

Connection No. Efficiency in percent

Triforine (known) 85

5 95

Beisgiel_F

Botrytis test, (Botrytis cinerea / Field bean (Vicia faba) leafflatter)

Cut-leaved leaflets of potted bean plants (Vicia faba) of the variety "Fribo" in four-bladed stdium are coated with active compound preparations prepared from 1 part by weight of active compound, 100 parts by weight of dimethylformamide and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired active ingredient concentration. After the spray coating has dried on, the leaves are inoculated with a conidia suspension of Botrytis cinerea, which is obtained by washing off 12-day-old fungal cultures on malt agar nutritive medium (2 % malt). The broadleaf leaflets are kept in an incubation booth in trays at a temperature of 22 ⁰ C and 90 to 100 % relative humidity. After 4 days, the Botrytis infestation of field bean leaflet is determined. The percentage of attack on the entire leaf area is converted into the efficiency of the means according to ABBOTT. The results are shown in Table F.

Table F: Action against Botrytis cinerea on field bean (Vicia faba) leaf drop Drug concentration: 100 mg / l

Connection No. Efficiency in percent

Tridemorph (known) 42

5 45

14 68

55 48

. ". 2 m 85

Beisgiel_G

Plant Growth Regulation Test

Cucumber plants of the variety "Eva" are used in pots in humus soil, which is sufficiently supplied with nutrients, up to a stature height of 9 cm in the greenhouse. 10 plants are used per variant. The cucumber plow ^. are sprayed with active compound preparations prepared from 1 part by weight of active compound, 100 parts by weight of dimethylformamide and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired active ingredient concentration.

After a growth time of 14 days after the medium application, initial measurements are made on the treated plants and the untreated control plants

 The results are shown in Table G.

Table G: Effect on the growth of cucumber plants in foliar treatment. Active ingredient concentration: 1000 mg / l

Compound No. Plant height

Untreated Control 23 100

5 15,6 68

Claims (4)

1. Fungicidal agent with additional plant growth-regulating action, characterized in that it comprises at least one N-alkyl-2,6-cis and / or trans-dimethylmorpholinio-carboxylic acid ester salt of the general formula I, ) ' R ² - CO - Z - R ³ H ₃ C in the R is straight-chain or branched alkyl having 6 to 20 C atoms, 2
R is straight-chain or branched alkylene having 1 to 6 C atoms, 3
R is straight-chain or branched alkyl having 1 to 20 C atoms, a straight-chain or branched alkyl having 1 to 4 substituted by halogen, hydroxyl, alkoxy having 1 to 4 C atoms, dialkylamino having 2 to 16 C atoms, nitro and / or cyano 6 C atoms, an optionally halogen-substituted alkenyl having 2 to 6 C atoms, alkynyl having 3 to 6 C atoms, cycloalkyl having 3 to 12 carbon atoms, where the cycloalkyl radical is optionally substituted by one or more alkyl radicals having 1 to 7 C atoms Atoms, cycloalkylalkyl may have 4 to 10 C atoms, aryl which is mono- or polysubstituted, identically or differently, by straight-chain or branched alkyl having 1 to 6 C atoms, alkoxy having 1 to 4 C atoms, aryl-lower Alkyl with 7 to 12 carbon atoms, acyl having 1 to 4 carbon atoms, halogen, aryl, nitro and / or cyano may be substituted, aryl-lower-alkyl having 7 to 12 carbon atoms, which is mono- or polysubstituted, identical or differently by straight-chain or branched alkyl having 1 to 6 C atom en, alkoxy having 1 to 4 carbon atoms, halogen, halogenoalkyl having 1 to 4 carbon atoms, nitro and / or cyano may be substituted, Z is oxygen or sulfur and X ~ denote the anion of a non-phytotoxic acid, or R and X are not present in addition to the customary solvents, excipients and / or formulation auxiliaries. - 29 - 2. A method for controlling fungi, characterized in that means according to item 1 on fungi or to protect against fungal attack on objects act. 3. Use of agents according to item 1, characterized in that they are used to combat fungi. 4. Use of the means according to item 1, characterized in that they are used to regulate plant growth. "