DD263690A1 - FUNGICIDAL AGENT WITH ADDITIONAL PLANT GROWTH REGULATORY EFFECT - Google Patents

Abstract

The invention relates to a mixture of N-alkyl-2,6-dimethylmorpholinio-alkyl-phenyl ether salts and at least 15 wt .-% proportion of N-alkyl-2,5-dimethylmorpholinio-alkyl-phenyl ether salts of the general formula I and its use as a fungicidal agent for the control of fungal pests in agriculture and horticulture with additional plant growth regulating properties. The meaning of R1, R2, R3, R4, R5 and X can be taken from the description. Formula (I)

Description

Z63C90

The invention relates to a mixture of N-alkyl-2,6-cis and / or 'trans-dimethylmorpholinio-alkyl-phenyleth; r salts and at least

15% by weight of N-alkyl-S-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether salts and their use as fungicides in agriculture and horticulture with additional plant growth-regulating properties.

Clia.rakte.r.ia.t.lk, -the. .bek.a naLe.n .te chniaahca .L.ö.aunf) .ea

It is known to use N-alkylmorpholines urvd their salts and their molecular 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), Pp. 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 furthermore known that morpholinoalkylalkyl ethers, 4-alkylcyclohexyl ethers and 4-alkylaryl ethers have fungicidal properties (German Patent 1,190,724, Angewandte Chemie 77 (1965), pages 327-333, Angewandte Chemie 9Z (1980), p -181). Furthermore, it is already known 2,3-dihydro-6-methyl-5-phenylcarbamoyl-3,4-oxathiin-4,4-dioxide (oxycarboxine), N, N) 'iso- (1-formamido-2, 2 , 2-trichloroethyl) -piperazine (triforine) or zinc ethylene-bis-dithiocarbamate (zineb) as active ingredients in fungicidal agents used to control fungal plant diseases (The Pesticide Manual, British Crop Protection Council, London, 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 very high selectivity against certain types of fungal pathogens, whereby a wide application of these agents strong

_ ₂ . 265690

is restricted. A further disadvantage is that the PFlanzenverträglichkeit these compounds is not sufficient in many cases.

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 of fungicidal compositions containing such compounds, and the use of such fungicides in agriculture and horticulture.

_; of

The invention is based on the object, a mixture of N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether salts and at least 15 percent by weight of N-alkyl-2,5-cis- and / or To provide träns-dime thylmorpholinio-alkyl-phenyl ether-aspartic fungicidal compositions having 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 are a mixture of N-alkyl-2,6-cis and / or trans-diinethylmorphol inio-alkyl-phenyl ether salt and at least 15 percent by weight of N ~ alkyl -2,5-cis and / or transdimcthylmorpholinio-alkyl-phenyl ether salts of the general formula I,

in the

\\ ^x straight-chain or branched alkyl having 6 to 20 C atoms, R straight-chain or branched alkylene having 1 to 6 C atoms, R, R and R independently of one another the same or different

- 3 - Z & 1C90

Hydrogen / straight chain or branched alkyl having 1 to 6 C atoms, alkoxy having 1 to 4 C atoms, acyl having 1 to 4 C atoms, halogen, Halo.jenal.kyl having 1 to 4 C atoms, cycloalkyl with 3 up to 7 C-atoms, aryl-lower-alky1 with 7 to 12 C-atoms, aryl, nitro, cyano, thiocyanato, NHCO !? ¹ , COOR ¹ and / or CONR ¹ R "', wherein R ¹ and R ¹ ' independently of one another are pure hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms, aryl or aryl-ηieder-alkyl having 7 to 12 hydrocarbon atoms , and

X "mean the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or Formierungshilfsstopen included.

The compounds according to the invention can be mixed in four different geometric structures as N-alkyl-2,6-cis- and / or trans-dimethylmorpholiηio-alkyl-phenyl ether salts or N-alkyl-2,5-cis- and / or trans -dimethylmorpholinio-alkyl-phenyl ether salt.

Surprisingly, it has been found that the compounds of general formula I according to the invention have a strong fungicidal activity and a broad spectrum of action and are particularly suitable for controlling phytopathogenic fungi on crop plants and vegetable stocks. The active compounds show good plant tolerance in the effort required to combat 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 compounds of the general formula I according to the invention are obtained by reacting a mixture of N-alkyl-2,6-cis and / or trns-dimethylmorpholine and at least 15 percent by weight of N-alkyl-2,5-cis and / or trans-dimethylmorpholine (according to DD-PS 140 412) of the formula II,

7Λ) ^

QN - R ^J and 0 NR ³

H ₃ C

(N)

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

x - R ² - o -r "Sa-R ⁴ du)

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

or alternatively a mixture of 2,6-cis- and / or trans-dimethylinorpholino-alkyl-phenyl ethers and at least 15 percent by weight of 2,5-cis- and / or trans-dimethylmorpholino-alkyl-phenyl ethers of the formula IV,

0 N - R

- 0 - (/ ^ Λ and 0 N- R ² -0 - // -Λ ^ - (IV) \ \ J \

II ₃ C ₃

2 3 4 5 in which IC, R, R and R have the meaning given in the general formula I,

with a compound of formula V,

R ³ - X (V)

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

Compounds of the formula are e.g. n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, 1,5,9-triethyldecyl, n-pentadecyl or n-oidecyl-2,6- and 2,5-cis and / or trans-dimethylmorpholine.

Haloalkylphenyl ethers of the formula III are, for example, 2-bromoethylphenyl ether, 2-chloroethyl-4-tert-butylphenyl ether, 2-bromoethyl-4-nitrophenyl ether, 2-bromoethyl-4-cyanophenyl ether, 2-bromoethyl-2,6 dichlorophenyl ethers, 2-bromoethyl-3,4-dichlorophenyl ether,

2-bromoethyl-2,6-dichloro-4-cyanophenylether _/ 2-bromoethyl-3,5-dichloro-phenylether, 2-bromoethyl-4-benzylphenylether, 2-bromoethyl-4-acetamidophenylether, 3-bromopropylphenylether, 3 Bromopropyl 4-tert-butylphenyl ether, 3-bromopropyl-2,6-dimethylphenyl ether or 3-bromopropyl-2, G-dibromo-thiocyanotophenyl ether.

Compounds of formula IV are e.g. 1- (2,6- and 2,5-cis- and / or trans-dimethylmorpholine) ethyl phenyl ether, 4-cyano phenyl ether, 4-tert-butyl phenyl ether, 5-nitrophenyl ether, -3,4 dichlorophenyl ether, -2, 6-dichloro-cyano-phenyl ether, 3- (2,6- and 2,5-bis- and / or trans-dimethylinorpholino) -propyl-phenyl ether, 4-tert-butyl-phenyl-ethene, -3 , 5-dichlorophenyl ether, 2,6-dimethylphenyl ether or 2,6-dibromophenyl ether.

Alkyl halides of the formula V are, for example, n-decyl chloride, n-dodecyl chloride, n-tridecyl chloride, isotridecyl chloride, 3,5,9-trimethyldecyl chloride, pentadecyl bromide or oidecyl bromide.

690

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 100 ⁰ C, preferably between 30 and 150 ⁰ C. The starting materials of the formula II or the formal IV are in stoichiometric amounts with a compound of formula III or of formula V or preferably with an excess of 10 to 100% of a compound of formula III or of 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 Es3igsäuremethylester; 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 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.

The active substances according to the invention are particularly suitable for the prevention and curing of plant diseases caused by fungi, e.g. Erysiphe graniinis (cereal powdery mildew) / Erysiphe cichoracearum (cucumber powdery mildew), Erysiphe polygon! (Bean powdery mildew), Podosphaera ieucotricha (apple downy 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); Rctrytis 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 (flotation), Ophiobolus graminis (cereal foot disease), Septoria nodorum (cereal and spelled tusks), Venturia inaequalis (apple scab) and various species of the genera Rhizoctonia, Tilletia, Helminthosporium, Peronospora, Pythium 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 developmental periodicity of the seed or plants, on the amounts of active substance applied to the plants or their surroundings and on the mode of administration.

CBO

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 odqr 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 causing spoilage of high moisture agricultural products or processed agricultural products during storage or intermediate storage. Such products to be treated include e.g. Apples, oranges, tangerines, grapes, pomelos, peanuts, cereals and cereal products or pulses and meal.

The active compounds according to the invention, in addition to their broad spectrum of fungicidal activity, are also different against phytopathogenic bacteria, such as, for example, xanthomona: * 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 distinguished, in addition to the protective action, by a systenic action development. Thus, they are taken up via the root as well as the leaves and transp- ted 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 stray regars which are resistant to known fungicidal active compounds, such as e.g. Active substances from the group of dicarboximide fungicides, such as, for example, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine (vinclozolin) or 5-methyl-5 methoxymethyl-3- (3,5-dichlorophenyl) -1,3-oxazolidine-2,4-dione tMyclozoline); Active substances from the group of the benzimidazole or thiophanate fungicides, such as, for example, 1- (n-butylcarbamoyl) -benzimidazol-2-yl-carbamic acid methylstyrene (benoinyl), benzimidazol-2-yl-carbamic acid methyl ester (carbendazim) or 1,2-bis- (3-ethoxy-ccirbonyl-2-thoureido) -benzene (thiophanate); Active ingredients from the

Group of the azole fungicides, such as l- (4-chlorophenoxy-3,3-dimethyl-l- (lH-l _{/ 2/4-triazol-l-yl)} -butan-2-one (triadimefon) or 1- / 2 ¹ - (2 '', 4 '' -dichlorophenyO-2 ¹ - (propenyloxy) ethyl / -l, 3-imidazole (imazalil); active compounds from the group of aromatic hydrocarbons-containing fungicides, such as, for example, Dichloro-1, 4-dimethoxybenzene (chloroneb) or 2,6-dichloro-4-nitroaniline (dicloran); active substances from the group of acylalanine fungicides, such as DL'-N - (. 6-dimethylphenyl ) -N- (2'-methoxyacetyl-alanine methyl ester (metalaxyl) or DL ^! - \ '- (2, G-dimethylphenyl) -III- (2-furoyl) alanine methyl ester (Furalaxyl)) the group of pvrimidine fungicides, such as 5-ethyl-2-dimethylamino-4-hydroxy-G-methyl-pyrimidine (dirnethirimol) or 2-chlorophenyl-4-chlorophenyl-pyrimidin-5-yl-methanol 'fenarimol), resistance phenomena demonstrate.

The anions X.sup.- 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 and synthetic substances impregnated with active ingredient, ultra-fine encapsulations in polymeric substances and in filling compositions Seeds and UL ¹ V KaIt and Warmneber formulations. The preparation of these formulations can be carried out in a known manner, for example by mixing or grinding the active compounds of the general formula I according to the invention with solvents and / or excipients, if appropriate using surface-active agents, such as emulsifiers and / or dispersants. As liquid solvents, aromatics such as toluene, xylene or alkylnaphthalenes; chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions; Alcohols, wi * · butanols or glycols and their esters and ethers; Ketones, such as acetone, methyl ethyl ketone,

- ίο -

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

As solid carriers are e.g. natural Geoteinsmehlc, w.i <? Kaolins, clays, talc, chalk, quartz, montmorillonite or diatomaceous earth and synthetic minerals, such as finely divided silica, alumina and silicates in question. As solid carriers for granules, e.g. crushed and fractionated natural geoteine flours, 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 bark meal. 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, alkyl sulfates, alkylsulfonates, alkali metal and alkaline earth salts of dibutylnaphthalenesulfonic acid, Uaurylethersulfat, fatty alcohol sulfates, fatty alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols or octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated · Niiphtlialen and naphthalene derivatives with formaldehyde, condensation products of naphthalenes and naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octyl.phenolether, alkylphenol polyglycol ethers, tributyl phenylpolyglykolether, alkylarylpolyether, 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 sulfite blebone and methyl cellulose.

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

- Ii - ZCi C90

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 erfindungsgeinäßen method for controlling fungi is' characterized by that one acts fungicidal agents with the active compounds of general formula I according to the invention on * fungi or the objects to be protected against fungal attack in an effective amount> leaves.

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 chemical structure improvers. In many cases, a mixture of fungicides results in a broadening of the fungicidal spectrum of activity. In a number of mixtures of erf indungsgeinäßen active ingredients 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,

Dithiocarbamnes and their derivatives, such as ferridiaethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, manganese-Z int-et hyend i at in-bis-di-thiocarbamate and zinc thy lenbisdi thiocarbamate,

Tetramethyl thiuram sulfide,

Ammonium complex of zinc (N, N-ethylene-bis-dithioearbamate) and N, N ¹ -polyethylene-bis (thiocarbamoyl) -disulfide, ammonia complex of zinc (N, N'-propylene-bis) dithiocarbamate) and N, N'-propylene-bis-ctliiocarbamoyo-disulfide, N-tri-methylmethylthio-t.elrahydrophthalimide, N-trichloromethylthio-plithalimide,

iM- (l _/ l _/ 2 _/ 2-tetrachloroethylthio) -tetrahydrophthalitnide _/

4,6-dinitro-2- (1-methylheptyl) -phenylcrotonate _/ 4,6-dinitro-2-sec-butylphenyl-3 _/ 3-dimethylacrylate _/ 4,6-dinitro-2-sec-butylphenyi-isopropylcarbonate;

methyl (1- (n-butylcarbanoylo) benzimidazol-2-yl) -carbanoate _/ benzii] ethylazol-2-yl-carbinoleate methyl ester / 2- / fur-2-yl) -benzimidazole _y

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

1 .. 2-bis (3-niethoxycarbonyl-2 ~ thioiircido) -benzene _y 1,2-bis (3-ethoxycarbonyl-2-tbioureido) -benzene, _2/3-dihydro - 6-methyl-5- phenylcarbamoyl-l _/ 4-oxathiin, _2/3-6 DihydΓO ·· methyl-5-phenylcanbaπloyl-l _/ 4-oxathi ^ _{n-4/4-dioxide /}

Tetrachloro-isopi-thiourinitrile, 2,3-dichloro-l, 4-faphthoquinone, 2 _/ 3-dicyano-l _/ 4-dithioanthraquinone _/

iM-Tridecyl-2 _/ 6-dimethylmorpholine or its salts, i \ -G ^> ₁₀ -C ₁₄ -alkyl-2 _/ 5 and / or 2,6-di-ethylmorphol in N-cyclododecyl-2 _/ G-dimethylmorpliolin or its Salts, N- / 3-p-tert-butylphenyl) -2-methyl-propyl / -2, cis-dimethylmorpholine or its salts

N, N "-Dis- (l-ßbrmainido-2,2 _# 2-trichloroethyl) -pi; jerazin N- (l-formamido-2 _/ 2,2-trichloroethyl) -3 _/ 4-dichloroaniline i \ ^l - ( 1-forinamido-2 _/ 2 _/ 2-trichloroethyl) -morpholine

5-Biyl-2-ethylamirio-4-liy (Jro>: y-6-diethylpyri [i] idine 5-butyl-2-dimethylantinij-1-yl-hydroxy-G-ethyl-pyrimidine

2 _/ 4-dichlorophenyl-plienyl-pyriniidin-5-yl-methyl-2-chlorophenyl-4-chlorophenyl-pyridyl-5-yl-methanol Bis- (4-chlorophenyl) -pyridin-3-yl-methanol

5-methyl-1-5-vinyl-3 - (3,5-dichlorophenyl) -1,3-oxazole id in-2,4-dione

2,4-dione

3- (3,5-dichlorophenyl) -SISI-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide a hi id

i \ i_ (3 _{/ c} 5_Di hi _or phenyl) -l _/ 2 diinethylcyclopropan-l, 2-dicarboximide

IC) C90

-S, 3-dimethy1-1- (1,2 _/ 4-triazol-1-yl) -butan-2-ol 1- (2- (2,4-dichlorophenyl) -2- (propenyloxy) -ethyl) imidazole 1-ZN-propyl-N-cc ^, 6-trichlorophenoxy) -ethyl-carbamoyl / imidazo 1 l- / 2- (2,4-dichlorophenyl) -4-ethyl-l _/ 3-dioxolane -2-yl-niethyl / -lH-1,2,4-triazole

1- (2- (2,4-dichlorophenyl) -4-n-propyl) -1,3-dioxolan-2-ylmethyl- / 1H-1,2,4-triazole 1- (2,4-dichlorophenyl) - 2- (l _{/ 2;} 4-triazol-l-yl) -4 _/ 4 dimethylrpentan-3-one

2 _/ 5-dichloro-1, 4-dimethoxybenzene 2 _/ 6-dichloro-4-nitroaniline diphenyl

2-Methyl-benzoic acid ani1 id

2-iodo-benzoic acid anilide

2 _/ 5-Diiriethyl furan-3-carboxylic acid anilide

2 _/ 4,5-trimethyl-furan-3-carboxylic acid anilide N-cyclohexyl-1,2-di-methal-furan-3-carboxylic acid amid 3- / 3- (3 _/ 5- Dimethyl-2-oxycyclohexyl) -2-hydroxyethyL7-glutarimide N-di-chloro or fluoromethylthio-iST, N '-d ime-thy 1-N-phenyl-sulfuric acid ediamide

DL'-N- (2,6-dimethyl-plienyl) -N- (2'-Niethoxyacety-O-alanine-methyl ester DL'-N- (2,6-dimethyl-phenyl) -N- (2-furoyl) -alanine-methyl ester N- (2,6-D imidyl-1-phenyl) -N-chloro-acetyl-DL-2-aminobiityrolactone

2 _/ 4-Dichloro-6- (2-chloroanilino) -s-triazine O, 0-diethyl-phthaliniido-phosphonottiioate

5-amino-l ~ (bis (dimethylamino) -phosphinyl) -3-phenyl-l, 2,4-triazole 0,0-diethyl-S-benzyl-1-thiophosphoric acid ester 2-thio-l _/ 3-dith ±) - (4,5-b) -chinoxaiin)

4- (2-chlorophenylhydrazono) -β-ethyl-δ-isoxazolone pyridine-2-thiol -] - oxide

8-hydroxyquinoline or its salts

4-diene-1-aminophenyl diazo-sulfonic acid sodium salt 5-nitro-isophthalic diisopropyl ester

2-Cyano-N- (ethylamino-carbonyl) -2- (methoxy-imino) -acetamide 2-heptadecyl-2-imidazoline-acetate Dodecyl-guanidine-acetate

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, nebulizing, injecting, silting, spreading, dusts, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of plant parts, the drug concentrations in the forms of application can be varied over a wider range. They are generally between 0.0001 and 1 percent by mass, preferably between 0.5 and 0.001 percent 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.

The seed treatment generally requires amounts of active ingredient of 0.001 to 50 g or more per kilogram of seed, preferably 0.01 to 10 g.

For preservation or Nacherntebchandlung of agricultural products or processing products of agricultural products, the required amounts of active ingredient 0.01 to 100 g per kilogram of material to be treated, preferably 0.1 to 50 g. In the treatment of the soil are Wirkstoffkonzentrat ions of 0.0001 to 0.1 mass percent, preferably from 0.001 to 0.05 mass percent, required at the site of action.

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

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 per se or can be prepared by processes known per se.

Beisgiel_l

3- / N- (C ₁₀ -C ₁₄ ) -alkyl-2 _/ 6-cis- and / or trans- and N- (C ₁₀ -C ₁₄ ) -alkyl-2,5-cis- and / or trans -dimethylmorpholinio / propyl-2,6-dimethylphenyl bromide

15 g of N- (C ₁₀ -C ₁₄ ) -alkyl-2,6-cis- and / or trans- and at least mass percent of N- (C _{; 10} -C _; j ₄ ) -alkyl-2 _/ 5-cis- and / or transdimethylmorpholine and 12.2 g of 3-bromopropyl-2 _/ 6-dimethylphenyl ether in 50 ml of acetonitrile are heated under reflux with the addition of a catalytic amount of sodium iodide for 24 hours · After cooling, the solvent is distilled off in vacuo, it is taken in a little acetone and the solution is added until complete precipitation with η-hexane. The oily phase is separated off and freed of solvent residues in vacuo. This gives 21 g of a yellow-brown viscous oil (Compound No. 26) IR spectrum (film): cm " ¹ 2960, 2925, 2870, 2490, 1470, 1380, 1260,

1195, 1090, 1040

Beisgiele_2

2- / N- (C ₁₀ -C ₃₄ ) -alkyl-2,6-cis- and / or trans- and N- (C ₁₀ -C ₁₄ ) -alkyl-2,5-cis- and / or trans- dimethylmorpholinio _ / - ethyl-3,4-dichlorophenyl ether chloride

17 g of 2- (2,6-cis- and / or tranaKimethylmorpholino) -ethyl-3,4-dichlorophenyl ether and at least 15 percent by weight of 2- (2,5 cis- and / or trans-dimethylmorpholino) -ethyl-3,4 -dichlorophenyl ether and 11 g of iso-tridecyl chloride (mixture of various C ₃₁ -C alkyl halides containing 60 to 70% n-tridecyl chloride) in 50 ml of dimethylformamide are heated to reflux for 10 hours.

Z6J 690

The mixture is allowed to cool and the solvent is distilled off in vacuo. The remaining residue is dissolved in a little acetone and treated with n-hexane until complete precipitation as an oily phase. The product is separated off and freed of solvent residues in vacuo. This gives 19 g of a brown resinous product (Compound No. 25) IR spectrum (film): cm " ¹ 2950," 920, 2870, 2690, 2620, 2910, 1590,

3570, 1470, 1385, 1330, 1280, 1225, 1175,

1120, 1085, 1060, 1015

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, e.g. Alcohols, acetone, dimethylformamide and dimethyl sulfoxide, are well soluble, i © IR spectrum have the characteristic absorption bands.

Z63C9O

and

No. R ¹ R ² R ³ R ⁴ R ⁵ X

1 n-octyl (CH ₂ ) ₂ 2 -Cl 6-Cl II Br

2 n-dodecyl (CH ₂ ) ₃ 4-Cl 'HH Dr

3 n-tridecyl (Cll _o ) _? 4-Cl H Il Br

C.

4 1,5,9-tri- (Cll _o ) ₃ 4-Cl HH Br methyldecyl

5 isotridecyl (CH ₂ ) ₂ Il II Br

6 iso-tridecyl (CII ₂ ) ₂ 4-Cl HH Cl

7 iso-tridecyl (CH ₂ ) ₂ 3-FHH Br

8 iso-tridecyl (CH ₂ ) ₂ 4-tert-butyl H Il Cl

9 iso-tridecyl (CH _{2) 3} 4-tert-butyl Il Il Br .10 iso-tridecyl (CH _0)., 4-OCIL · Il H Br 1.1 iso-tridecyl (Cll _{o) 3} 3-CII ₃ Il Il Br

12 iso-tridecyl (Cl! ₀ ) ₀ 4-Co-CII ₃ HH Br

13 iso-tridecyl (CIU) ₉ 3-NH-CO-CILH H Br

14 iso-tridecyl (CH ₂ ) ₂ 3-CO-OC ₂ II ₅ II H Br

15 iso-tridecyl (CH ₀ ) ,, 3-CO-N (C II) II Il Br

16 iso-tridecyl (CH ₂ ) ₂ 4-NO ₂ H II Br

17 iso-tridecyl (CH _{O) 2} 4-CN Il Il Br 13 iso-tridecyl (CHg) ₂ 4-phenyl Il Il Cl

19 iso-tridecyl (CHg) ₂ 4-benzyl HH Cl

20 iso-tridecyl (CII ₂ ) ₂ 2-Br 4-Br H Br

21 iso-tridecyl (CH ₂ ) ₂ 2-Cl 3-Cl II Br

22 iso-tridecyl (CHg) ₃ 2-Cl 4-Cl II Br

23 iso-tridecyl (CH _n ), 2-Cl 5-Cl H Br

ZCJ 6 90

No. R ³ R ² R ³ R ⁴ R ⁵ X 24 iso-tridecyl (CH ₂ ) 2 2-Cl 6-Cl H br 25 iso-tridecyl (CH ₂ ) 2 3-Cl 4-Cl Il gl 26 iso-tridecyl (CH ₂ ) 3 2-CH ₃ 6-CIl ₃ Il Dr 27 iso-tridecyl (CH ₂ ) ₂ 3-CII ₃ 4-CH ₃ Il br 28 iso-tridecyl (CH ₂ ) ₂ 3-Cl 5-Cl H br 29 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-NO ₂ H br 30 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-Cl 6-Cl br 31 iso-tridecyl (CHg) ₂ 2-CII ₃ 3-CII ₃ G-CH ₃ br 32 iso-tridecyl (CH ₂ ) ₂ 2-CfI ₃ 4-Cl 6-CH ₃ br 33 iso-tridecyl (CH ₂ ) ₄ 2-Cl-I ₃ 4-Cl 6-CII ₃ br 34 iso-tridecyl (OH ₂ ) 2 2-Cl 4-CN East-C1 br 35 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-NO ₂ 6-Cl br 36 iso-tridecyl (CHp) ο Cm \ J 2-Dr 4-SCN 6-Br br 37 ⁿ " ^C 15 ^H 31 (CH ₂ ) ₂ 4-Cl H H br 38 P-CH ₁ (CH ₂ ) ₂ 4-Cl Il H br

- 19 - Ιί, ΠΒΟ

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.

Emulsifiable concentrates: 25 parts by weight of compound 24 are mixed with 2.5 parts by weight of epoxidized vegetable oil, 10 parts by weight of an alkylarylsulfonate / fatty alcohol polyglycoletheri 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 .. B.elsg ie.I

Spray powder: 40 parts by weight of compound 6 are mixed well with 5 parts by weight of the sodium salt of a Uigninsulfonsäure from a sulfite liquor, 1 part by weight of sodium salt of di-iso-butylnaphthalen-sulfonic 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 by weight of compound 25 are intimately mixed and ground with 95 parts by weight of finely divided kaolin. The dusts can be dusted in this form for use.

Granules: 5 parts by weight of compound 6 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 solution obtained in this way is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

- 20 - 163 <* 3O

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:

Beisgiele_A

Myzelwachsturns test

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

Table A: Growth inhibition of Botrytis cinerea in the mycelium growth test. Active substance concentration: 10 pg / ml

Compound No. Growth inhibition in percent

Oxycarboxine (known) 20

1 24

5 82

6 76 9 79

16 73

17 81

24 87

25 82

26 73 34 88

- ²¹ - ZCi

Beisgiel_D

Cereal Mildew Test (Erysiphe graminis / Barley Leaf Pieces)

Leaf pieces (length 4 cm) of barley plants of the "Astacus" variety are prepared together with a conidia suspension of Erysiphe graminis var. Hordei and active ingredient preparations / which are prepared from 1 part by weight of active ingredient and ίΟΟ parts by weight of dimethylformamide and diluted with water to the desired active substance concentration for 2 hours 20 ⁰ C shaken. Subsequently, the .Blattstücke 7 days in an incubation chamber in trays at temperatures of 20 to ?? ° C and maintained at 90 to 100% relative humidity. The efficacy is determined by calculating the percentage inhibition of infection from the reduction in the number of pustules compared to the controls without added active substance. The results are listed in Table B.

Table B: Action against Erysiphe graminis on barley blot pieces Effective concentration; 0.05 pg / ml

Compound No. Inhibition of infection in percent

Triforine (known) 35

5 100

6 100 17 100

24 91

25 100

26 100 34 75

Beisgiel_C

Phytophthora test (Phytophthora infestans / tomato leaf discs)

To perform the test, leaf disks are punched out of adult leaves of tomato plants of the "Tamina" variety. The zoospore suspension of Phytophthora infestans needed for inoculation is obtained by flushing fungal turf from tuber halves of susceptible potato varieties.

The active compound preparations are prepared from 1 part by weight of active compound and 100 parts by weight of dimethylformamide, which are diluted with water to the desired active substance concentration. The treatment of the tomato leaf pieces with the active ingredients and the inoculation are carried out simultaneously by adding the active compound preparation of the desired concentration to the zoospore suspension of Phytophthora infestans and, after shaking, pouring this mixture onto the leaf discs laid out in petri dishes. After 2 hours, the supernatant liquid is poured off. The dishes are kept in an incubation chamber at temperatures between 18 and 20 ⁰ C and 95 to 100% relative humidity under artificial lighting.

After 3 to 4 days, the effectiveness of the funds is determined. For this purpose, the percentage inhibition of infection is calculated from the proportion of necrotic leaf area per leaf disc compared to the controls without added funds

 The results are listed in Table C.

Table C: Action against Phytophthora infestans on tomato leaf discs. Active substance concentration: 5 pg / ml

Compound No. Inhibition of infection in percent

Zineb (known) 5

24 62

, ₂₃ . 2 6 3 6 9 O

Beisgiel_D

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 experimental variant. The cucumber plants are sprayed with active compound preparations 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 active substance concentration.

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

 The results are shown in Table D.

Table D: Effect on the length growth of cucumber plants in blood treatment. Active substance concentration: 1000 mg / l

Compound No. Plant height

in cm relative

Untreated control 23 100 24 14.5 63

Claims (4)

1. Fungicidal agent with additional plant growth-regulating effect, characterized marked by the fact that a mixture of N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether salts and at least 15 percent by weight of N-alkyl-2 , 5-cis- and / or trans-dimethylmorpholiηio-alky] -phenyl ether salts of the general formula I, ό χ / ^ R and in the R is straight-chain or branched alkyl having 6 to 20 C atoms, R is straight-chain or branched alkylene having 1 to 6 C atoms, 2. Method of combating fungi. The name of the product is provided by the fact that, according to point 1, the means according to point 1 are allowed to act on fungi or on objects to be protected against fungal attack. 3. Use of agents according to item J, characterized dadurc h, that they are used to combat fungi. 3 4 5
R, R and R are each, independently of one another or different, hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms, alkoxy having 1 to 4 C atoms, acyl having. up to 4 C atoms, halogen, halogenoalkyl having 1 to 4 C atoms, cycloalkyl having 3 to 7 C atoms, aryl-lower-alkyl having 7 to 12 C atoms, aryl, nitro, cyano, thiocyanato, NHCOR ', COOR 'and / or CONR ¹ R'', wherein R ¹ and R "independently of one another are hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms or aryl-lower-alkyl having 7 to 12 carbon atoms, and X "mean the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or formulation excipients included. 4. Use of funds according to item 1, characterized ge by using them to regulate plant growth.