DD296819A5 - FUNGICIDAL AGENT WITH ADDITIONAL PLANT GROWTH-REGULATORY EFFECT (I) - Google Patents

Abstract

The invention relates to fungicidal compositions having additional plant growth-regulating action, the N-alkylpyrrolidinio-carbonsaeureamid salts of the general formula I and can be used for the control of fungal pests in agriculture and horticulture. In addition, the compositions of the invention have plant growth regulating properties. The meaning of R1, R2, R3, R4 and X in the formula (I) can be taken from the description. Formula (I) {fungicidal agent; plant growth-regulating effect; N-Alkylpyrrolidinio-carboxylic acid amide salts; fungal pathogens; combating; Agriculture; Horticulture}

Description

Field of application of the invention

The invention relates to novel N-alkylpyrrolidinio-carboxamide salts and their use as fungicidal agents in agriculture and horticulture with additional plant growth-regulating properties.

Characteristic of the known state of the art

It is known to use N-aralkylpyrrolidines and their acid addition salts as fungicides (DE-PS 2727482, DE-PS 2830127, Angewandte Chemie 92 [1980], p. 17 & -181).

It is also known that quaternary ammonium compounds of long-chain N-alkylpyrrolidines with lower alkyl substituents are fungicidally effective (CS-PS 190691).

Furthermore, it is known that N-alkyl, N-alkenyl or N-alkynyl-substituted N-Aralkylpyrrolidinium salts are described in the means for regulating plant growth (DE-PS 2952382).

Furthermore, quaternary salts of pyrrolidino-alkanecarboxylic acid anilides with lower alkyl, alkenyl, alkynyl or

Substituted alkyl groups known as plant growth regulators (DE-PS 2657728, DE-PS 2915250, EP-PS 0014223, DD-PS 151036).

Furthermore, it is already known to use N, N'-bis (1-formamido) trichloroethylpiperazine (triforine) or 2,6-dichloro-4-nitraniline (diclorane) as active ingredients in fungicidal agents for combating 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 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.

Object of the invention

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

Explanation of the essence of the invention

The invention has for its object to provide novel N-alkylpyrrolidinio-carboxamide salt-containing fungicidal compositions with good efficacy and broad spectrum of activity and the highest possible plant tolerance and additional plant growth-regulating properties.

According to the invention fungicidal agents are proposed with additional plant growth-regulating effect, which are characterized in that they contain at least one N-alkylpyrrolidinio-carboxamide salt of the general formula I,

(D

in which

R ¹ straight-chain or branched alkyl having 6 to 20 C atoms,

R ² straight-chain or branched alkylene with up to 6 C atoms,

R ³ and R ⁴ independently of one another are identical or different hydrogen, straight-chain or branched alkyl having 1 to 20 C atoms, a straight-chain radical substituted by hydroxyl, alkoxy having 1 to 4 C atoms, cyano or dialkylamino having 2 to 16 C atoms or branched alkyl having 1 to 6 carbon atoms, an optionally halogen-substituted alkenyl having 3 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, aryl which is mono- or polysubstituted by identical or different straight-chain or branched alkyl 1 to 6 C atoms, alkoxy having 1 to 4 C atoms, aryl lower alkyl having 7 to 12 C atoms, cycloalkyl having 3 to 7 C atoms, acyl having 1 to 4 C atoms, alkoxyalkyl with 1 to 8 C atoms, aryl, halogen, halogenoalkyl having 1 to 4 C atoms, halogenoalkoxy having 1 to 4 C atoms, alkylthio having 1 to 4 C atoms, halogenoalkylthio having 1 to 4 C atoms, nitro, cyano, thiocyanates, NHCOR ', NHCONR'R ", COOR', CONR'R", SO ₂ R 'and / or SO ₂ NR ¹ R ", where R' and R" independently represent water toff, straight-chain or branched alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 7 C atoms, aryl or aryl-lower-alkyl having 7 to 12 C atoms, may be substituted aryl-lower-alkyl with 7 to 12 C atoms, which are monosubstituted or polysubstituted, identically or differently, by 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, haloalkyl having 1 up to 4 C atoms, nitro and / or cyano can be substituted,

R ³ and R ⁴ together with the nitrogen atom represents a five- or six-membered heterocyclic ring which is optionally mono- or disubstituted by alkyl having 1 to 4 C atoms and / or halogen and optionally also contains one or two further heteroatoms, and

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

Surprisingly, it has been found that the N-alkylpyrrolidinio-carboxamide salts of the general formula I according to the invention have a strong fungicidal activity and a broad activity spectrum and are particularly suitable for controlling phytopathogenic fungi on crop plants and vegetable stocks.

The active compounds show good plant compatibility in the amounts required for controlling plant diseases. In addition, the compounds according to the invention, with their growth-regulating properties, can positively influence crop plants in the desired manner.

N-alkyl-cycloammonio-carboxamide salts of other ring size, whose rings may also be substituted, have similar fungicidal and growth-regulating properties as the active compounds according to the invention.

Furthermore, it has been found that the N-alkylpyrrolidinio-carboxamide salts of the general formula I are obtained by reacting an N-alkylpyrrolidine of the formula II

о-

(II)

wherein R ^{1 has} the meaning given in the general formula I, with a compound of formula III,

R ³

X - R ² - CO - N ^ _(|||)

R ⁴

wherein R ² , R ³ , R * have the meaning given in the general formula I and X is halogen reacted

or alternatively a pyrrolidino-carboxamide of the formula IV,

N-R-CO-N

(IV)

in which R ² , R ³ and R ^{4 have} the meaning given in the general formula I, with a compound of the formula V,

R'-X (V)

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

N-alkylpyrrolidines of the formula II are e.g. n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, pentadecyl or n-didecylpyrrolidine. Halogenocarboxamides of the formula III are, for example, chloroacetamide, chloroacetic acid-N-C 1 -C 4 -alkylamide, -N-2-cyanoethylamide, -Ν, Ν-diethylamide, -N, N-bis (2-cyanoethyl) -amide, -N- cyclohexylamide, anilide, 4-chloroanilide, 3,5-dichloroanilide, 3,5-dichloro-4-methoxy-anilide 1 H-1,2,4-triazol-1-yl-amide, 2-bromopropionic acid 3,5-dichloroanilide, -2,6-dibromo-4-nitranilide, -N-methyl-2,6-dichloro-4-cyanoanilide or ^, e-dibromo-nitroanilide, -N-methyl ^ .fJ-dichloM-cyanoanilide or -2,6-dibromo-4-thiocyanato-anilide.

Pyrrolidino-carboxamides of the formula IV are z. B. Pyrrolidinoacetic acid amide, acetic acid NC ^ Caoalkylamide, acetic acid bis (2-cyanoethyl) amide, acetic acid N-cyclohexylamide, acetic acid anilide, acetic acid 4-chloroanilide, acetic acid S ^ -dichloroanilide-acetic acid-SS-dichloro-methoxyanilide. ^ -Propionic acid-S, -dichloroanilide, -g-ргоріопваиге-г.б-агЬто-А-nitroanilide,--propionic acid,--dibromo-thiocyanato or--propionic acid -N-methyl ^ .e dichloM-cyanoanilid. Alkyl halides of the formula V are, for example, n-octyl 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 solvent or diluent at a temperature in the range between 10 and 180 ⁰ C, preferably between 30 and 15O ⁰ C. The starting materials of the formula II or of the formula IV are used in stoichiometric amounts with a compound of the formula III or of the formula V or preferably with an excess of 10 to 100% of a compound of the formula III or of the formula V over the stoichiometric amount also, based on the starting materials of the formula II or the formula IV, implemented.

As preferred solvents or diluents, for example, aliphatic or aromatic, optionally halogenated hydrocarbons, such as n-pentane, cyclohexane, benzene, toluene, chlorobenzene, chloroform or methylene chloride; aliphatic ketones, such as acetone, methyl ethyl ketone or cyclohexanone; Ethers, such as diethyl ether, tetrahydrofuran or dioxane; Alcohols, such as methanol, ethanol, propanols, butanols or hexanols; Nitriles, such as acetonitrile; Esters, such as methyl acetate; 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 to prepare fungicidal preparations. The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared by known processes.

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 treating seed and plant patches for protection against fungal infections and can be used against phytopathogenic fungi occurring in the soil. In addition, the active ingredients in their application influence the growth processes of crops in a positive way.

The active compounds according to the invention are particularly suitable for the prevention and cure of plant diseases caused by fungi, such as. B. Erysiphe graminis (powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Erysiphe polygoni (bean powdery mildew), Podosphaera leucotricha (apple powdery mildew), Sphaerotheca pannosa (rose mildew), Uncinula necator (vineyard mildew); Rust diseases, such as those of the genera Puccinia, Uromyces or Hemileia, in particular Puccinia graminis (cereal rust 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 different effective against phytopathogenic fungi, such. B. Ustilago avenae (flare), Ophiobolus graminis (cereal foot diseases), Septoria nodorum (cereal and fennel tan), Venturia inaequalis (apple scab) and other fungal pathogens, such as Rhizoctonia, Tilletia, Helminthosporium, Peronospora, Pythium, Alternaria, Mucor, Sclerotinia, Fusarium, Pseudocercosporella and Cladosporium. 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 plants, of cion applied to the plants or their environment, and the mode of administration. Furthermore, the active ingredients also provide good activity against wood-discoloring and wood-destroying fungi, such. Pullaria pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum.

Furthermore, the active compounds of the general formula I according to the invention show a good activity against molds, such. 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, mandarins, lemons, grapefruits, 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 effective against phytopathogenic bacteria, such as, for example, Xanthomonas or Erwinia species.

Some of the active ingredients also show an action against human pathogenic fungi, such. B. Trichophyten and Candida species. A part of the active compounds of the general formula I is distinguished not only by the protective action but also by a systematic development of activity. 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 also suitable for controlling resistant strains of fungal pathogens which are resistant to known fungicidal active compounds, such as. B. Active ingredients from the group of dicarboximide fungicides, such as 5-methyl-5-vinyl-SO ^ -DichlorphenyD ^^ - dioxo-i ^ -oxazolidinlVinclozolinJoderS-methyl-S-methoxymethyl-SO ^ -DichlorphenyD-IS-oxazolidin- 2,4-dione (myclozoline); Active substances from the group of the benzimidazole or thiophanate fungicides, such as, for example, i-in-butylcarbamoy-D-benzimidazole-1-methylcarboxylate fbenomyl), benzimidazol-2-yl-carbamic acid methyl ester (carbendazim) or 1,2-bis (3-ethoxycarbonyl) 2-thioureido) -benzene (thiophanate); Agents from the group of azole fungicides, such as 1- (4-chlorophenoxy-3,3-dimethyl-1- (1 H-1,2,4-triazol-1-yl) -butan-2-one (Triadimefon ) or 1/2 '- (2 ", 4" -dichlorophenyl) -2' - (propenyloxy) ethyl / -1,3-imidazole (imazalil); active compounds from the group of aromatic hydrocarbons containing fungicides, such as 2 , 5-dichloro-1,4-dimethoxybenzene (chloroneb) or 2,6-dichloro-4-nitroaniline (dichloran); acylalanine fungicide group active ingredients such as DL-N- (2,6 -dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester (metalaxyl) or DL-N- (2,6-dimethylphenyl) -N- (2-furoyl) alanine methyl ester (Furalaxyl) or agents from the group of pyrimidine Fungicides, such as 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine (dimethirimol) or 2-chlorophenyl-4-chlorophenyl-pyrimidin-5-yl-methanol (fenarimol) show resistance phenomena.

The anions X listed in the general formula I the novel active ingredients ^- 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 substance, very fine encapsulations in polymeric substances and in encapsulants Seeds and ULV KaIt and warm mist formulations.

The preparation of these formulations can be carried out in a known manner, for. B. by mixing or Vermählender the active compounds of general formula I according to the invention with solvents and / or carriers, optionally with the use of surfactants, 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, e.g. B. 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. As 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 finely divided silica, alumina and silicates. As solid carriers for granules z. B. crushed and fractionated natural minerals, such as calcite, marble, pumice, dolomite and synthetic granules of inorganic or organic meals, and granules of organic materials, such as sawdust, cellulose powder, tree bark and Nussschalenmehl be used.

As an emulsifying agent can ζ. As non-ionic and anionic emulsifiers, such as alkali metal, alkaline earth metal or ammonium salts of Ligninsulfonic acid, naphtholsulfonic acids, phenolsulfonic acids, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and Alkaline earth salts of dibutylnaphthalenesulfonic acid.Lauryl ether sulfate, fatty alcohol sulfates, fatty alkali and alkaline earth salts, salts

sulfated hexadecanols, heptadecanols or octadecanols, salts of sulfated fatty alcohol glycol ethers,

Condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of Naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyethylene-octylphenolether, Alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, Laurylalkoholpolyglykoletheracetal and sorbitol esters, are used. Suitable dispersants are, for example, lignin-sulphite liquors and methylcellulose. Adhesives, such as carboxymethyl cellulose, natural and synthetic latex polymers, may be included in the formulations.

such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

As further additives dyes and trace nutrients may be included in the formulations of the active ingredients. The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by mass. The inventive method for controlling fungi is characterized in that fungicidal agents with the

active compounds of the general formula I according to the invention act on fungi or the objects to be protected against fungal attack in an effective amount.

The active compounds may be prepared as such, in the form of their formulations or by further dilution therefrom Application forms in a conventional manner, for. By casting, dipping, spraying, spraying, atomizing, injecting, silting, Spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting, applied

become.

In the treatment of parts of plants, the drug concentrations in the use forms in a larger Range can be varied. They are generally between 0.0001 and 1 mass%, preferably between 0.5 and 0.001 mass%. The drug application rates are dependent on the specific application and are generally between 0.1 and

3kg of active ingredient per hectare.

In the case of seed treatment, in general, amounts of active substance are from 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 or processed products

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

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

required at the place of action.

The following examples are intended to illustrate the invention further, but without limiting it and the effect of

prove compounds of general formula I according to the invention.

ExampIes examples The following examples illustrate the preparation of the compounds of the invention. example 1 N-iso-tridecyl pyrrolidinio acetamide chloride

25.4 g of N-isotridecylpyrrolidine and 9.4 g of chloroacetamide are added with the addition of a catalytic! Amount of sodium iodide in 100ml

Acetonitrile heated to reflux for 24 hours. It is cooled and the solvent is distilled off in vacuo. The product will

dissolved in a little acetone and mixed with η-hexane until complete deposition. After concentration in vacuo to give 28geines yellow-brown resin (compound no.7).

IR spectrum (film): C = O absorption 1670 cm ^-1 Example 2 N-iso-tridecyl pyrrolidinio-acetic acid-S ^ -dichloranilid chloride

25.4 g of N-isotridecylpyrrolidine and 24 g of chloroacetic acid 3,5-dichloroanilide are refluxed in 100 ml of n-butanol with the addition of a catalytic amount of sodium iodide for 24 hours. It is cooled and the solvent is distilled in

Vacuum off. The remaining product is dissolved in a little acetone and until completely precipitated with n-hexane

added. The oily phase is separated and freed from solvent residues in vacuo. This gives 41 g of a tan

Resin (Compound No. 79). IR spectrum (film): C = O absorption 1700 cm ^-1 Example 3 N-iso-tridecyl pyrrolidinio-acetic acid ^ -chloranilid chloride

24 g of pyrrolidinoacetic acid 4-chloroanilide and 22 g of isotridecyl chloride (mixture of various C 1 -C 4 -alkyl chlorides containing 60 to 70% of n-tridecyl chloride) in 100 ml of n-butanol are heated to reflux for 24 hours. After cooling, the

Distilled off solvent in vacuo. The crude product is dissolved in a little acetone and until complete deposition with

η-hexane added. The oily phase is separated and freed from solvent residues in vacuo. This gives 48 g of a light brown resin (compound no.55).

IR spectrum (film): C = 0 absorption 1695cm "'. In a corresponding manner, the following compounds of general formula I are prepared, which in the Generally yellow to brown viscous oils or resins, in polar solvents, e.g. Alcohols, acetone, Dimethylformamide and dimethyl sulfoxide, are readily soluble and characterized by IR spectra. The starting compounds for preparing the compounds of the invention are known per se or may according to

known methods are produced.

IT-GO-N

R ⁴

1 n-hexyl CH ₂ 2 n-octyl CH ₂ 3 n-decyl CH ₂ 4 n-dodecyl CH ₂ 5 n-tridecyl CH ₂ 6 1,5,9-trimethyldecyl CH ₂ 7 iso-tridecyl CH ₂ 8th iso-tridecyl CH ₂ 9 iso-tridecyl CH ₂ 10 iso-tridecyl CH ₂ 11 iso-tridecyl CH ₂ 12 iso-tridecyl CH ₂ 13 iso-tridecyl CH ₂ 14 iso-tridecyl CH ₂ 15 iso-tridecyl CH ₂ 16 iso-tridecyl CH ₂ 17 iso-tridecyl CH ₂ 18 iso-tridecyl CH (CH ₃ ) 19 iso-tridecyl CH (CH ₃ ) 20 iso-tridecyl CH (C ₂ H ₆ ) 21 iso-tridecyl C (CH ₃ I ₂ 22 iso-tridecyl CH (C ₅ H ₁₁ ) 23 iso-tridecyl (CH ₂ ) ₃ 24 iso-tridecyl (CH ₂ ) _e 25 IvC ₁₅ H ₃₁ CH ₂ 26 NC ₂₀ H ₄₁ CH ₂ 27 iso-tridecyl CH ₂ 28 iso-tridecyl CH ₂ 29 iso-tridecyl CH (CH ₃ ) 30 iso-tridecyl CH ₂ 31 n-octyl CH ₂ 32 iso-tridecyl CH ₂ 33 iso-tridecyl CH ₂ 34 iso-tridecyl CH ₂ 35 iso-tridecyl CH (CH ₃ ) 36 iso-tridecyl CH ₂ 37 iso-tridecyl CH ₂ 38 iso-tridecyl CH ₂ 39 iso-tridecyl CH ₂ 40 iso-tridecyl CH (CH ₃ ) 41 iso-tridecyl CH (CH ₃ ) 42 iso-tridecyl CH ₂ 43 iso-tridecyl CH ₂ 44 iso-tridecyl CH ₂ 45 iso-tridecyl CH ₂ 46 iso-tridecyl CH ₂ 47 iso-tridecyl CH ₂ 48 iso-tridecyl CH ₂ 49 iso-tridecyl CH ₂ 50 iso-tridecyl CH (CH ₃ ) 51 iso-tridecyl CH ₂ 52 iso-tridecyl CH ₂ 53 iso-tridecyl CH ₂ 54 iso-tridecyl CH ₂ 55 iso-tridecyl CH ₂ 56 iso-tridecyl CH ₂

H H H H H H H H H H H H H H H methyl H ethyl H sec-butyl H 2-ethylhexyl H n-dodecyl H n-octadecyl H 3-hydroxypropyl H 3-ethoxypropyl H 2-cyanoethyl H 2-diethylaminoethyl H H H n-dodecyl H n-butyl H n-butyl H n-butyl H n-butyl H n-butyl H n-butyl H n-butyl ethyl ethyl n-octyl n-octyl n-butyl n-butyl 2-hydro- 2-hydroxyethyl xyethyl 2-cyano 2-cyanoethyl ethyl 2-cyano 2-cyanoethyl ethyl methyl 3-cyanopropyl H allyl allyl allyl methyl crotyl methyl 4-chlorobut-2-en-1-yl methyl propargyl H cyclopropyl H cyclopentyl H cyclohexyl H cycloheptyl ethyl cyclohexyl H phenyl methyl phenyl n-propyl phenyl allyl phenyl propargyl phenyl benzyl phenyl allyl phenyl H naphth-1-yl H biphen-2-yl H 3-fluorophenyl H 3-fluorophenyl H 4-chlorophenyl H 4-bromophenyl

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Br Br Br Br Br Cl Br Cl Cl Cl Cl Br Cl

Cl Cl

57 iso-tridecyl CH ₂ H 4-ethylphenyl Cl 58 iso-tridecyl CH (CH ₃ ) methyl 4-n-butoxyphenyl br 59 iso-tridecyl CH (CH ₃ ) methyl 4-formylphenyl br 60 iso-tridecyl CH (CH ₃ ) methyl 4-acetphenyl br 61 iso-tridecyl CH ₂ H 3-nitrophenyl Cl 62 iso-tridecyl CH ₂ H 4-cyanophenyl Cl 63 iso-tridecyl CH ₂ H 3-trifluoromethylphenyl Cl 64 iso-tridecyl CHj H 4-thiocyanatophenyl Cl 65 iso-tridecyl CHj H 4-acetaminophenyl Cl 66 iso-tridecyl CH ₂ H 4-methoxycarbonylphenyl Cl 67 iso-tridecyl CH ₂ H 4-N, N-dimethylamidocarbonylphenyl Cl 68 iso-tridecyl CH ₂ H 4-N, N-dimethylureidophenyl Cl 69 iso-tridecyl CH ₂ H 4-N, N-dimethylamidosulfenylphenyl Cl 70 iso-tridecyl CH ₂ H 4-phenylsulfonylphenyl Cl 71 iso-tridecyl CH ₂ H 2,3-dichlorophenyl Cl 72 iso-tridecyl CH ₂ H 2,4-dichlorophenyl Cl 73 iso-tridecyl CH ₂ H 2,5-dichlorophenyl Cl 74 iso-uidecyl CH ₂ H 2,6-dibromophenyl Cl 75 iso-tridecyl CH ₂ H 3,4-dichlorophenyl Cl 76 n-octyl CH ₂ H 3,5-dichlorophenyl Cl 77 n-octyl CH ₂ methyl 3,5-dichlorophenyl Cl 78 n-octyl CH (CH ₃ ) H 3,5-dichlorophenyl br 79 iso-tridecyl CH ₂ H 3,5-dichlorophenyl Cl 80 iso-tridecyl CH (CH ₃ ) H 3,5-dichlorophenyl br 81 iso-tridecyl CH (CH ₃ ) methyl 3,5-dichlorophenyl br 82 iso-tridecyl CH (CH ₃ ) allyl 3,5-dichlorophenyl br 83 iso-tridecyl CH ₂ H 3,5-dibromophenyl Cl 84 iso-tridecyl CH (CH ₃ ) H 3,5-dibromophenyl br 85 iso-tridecyl CH (CH ₃ ) methyl 3,5-dibromophenyl br 86 iso-tridecyl CH ₂ H 2,6-dimethylphenyl Cl 87 iso-tridecyl CH ₂ H 3,4-dimethylphenyl Cl 88 iso-tridecyl CH ₂ H 3,5-dimethylphenyl Cl 89 iso-tridecyl CH ₂ H 2-nitro-4-trifluoromethylphenyl Cl 90 iso-tridecyl CH ₂ H 2-methyl-4-chlorophenyl Cl 91 iso-tridecyl CN (CH ₃ ) H 2-methyl-4-chlorophenyl br 92 iso-tridecyl CH ₂ H 2-cyano-4-nitrophenyl Cl 93 iso-tridecyl CH ₂ H 3,5-dinitrophenyl Cl 94 iso-tridecyl CH ₂ H 2,6-dibromo-4-nitrophenyl Cl 95 iso-tridecyl CH ₂ methyl 2,6-dibromo-4-nitrophenyl Cl 96 iso-tridecyl CH (CH ₃ ) H 2,6-dibromo-4-nitrophenyl br 97 iso-tridecyl CH (CH ₃ ) methyl 2,6-dibromo-4-nitrophenyl br 98 iso-tridecyl CH ₂ H 2,6-dichloro-4-cyanophenyl Cl 99 iso-tridecyl CH ₂ methyl 2,6-dichloro-4-cyanophenyl Cl 100 iso-tridecyl CH (CH ₃ ) H 2,6-dichloro-4-cyanophenyl br 101 iso-tridecyl CH (CH ₃ ) methyl 2,6-dichloro-4-cyanophenyl br 102 iso-tridecyl CH ₂ H 3,4,5-trichlorophenyl Cl 103 iso-tridecyl CHj methyl 3,4,5-trichlorophenyl Cl 104 iso-tridecyl CH ₂ H 2,4,6-trichlorophenyl br 105 iso-tridecyl CH ₂ H 2,4,6-trichlorophenyl br 106 iso-tridecyl CH ₂ H 2,6-dibromo-4-thiocyanato-phenyl Cl 107 iso-tridecyl CH ₂ methyl 2,6-dibromo-4-thiocyanato-phenyl Cl 108 iso-tridecyl CH (CH ₃ ) H 2,6-dibromo-4-thiocyanato-phenyl br 109 iso-tridecyl CH (CH ₃ ) methyl 2,6-dibromo-4-thiocyanato-phenyl br 110 iso-tridecyl CH ₂ H 3,5-dichloro-4-methoxyphenyl Cl 111 iso-tridecyl CH ₂ methyl 3,5-dichloro-4-methoxyphenyl Cl 112 iso-tridecyl CH (CH ₃ ) H 3,5-dichloro-4-methoxyphenyl br 113 iso-tridecyl CH ₂ H 3,4-diethoxyphenyl Cl 114 iso-tridecyl CH ₂ H benzyl Cl 115 iso-tridecyl CH (CH ₃ ) H phenethyl br 116 iso-tridecyl CH (CH ₃ ) methyl 4-chlorobenzyl br 117 iso-tridecyl CH ₂ H 4-methylbenzyl Cl 118 iso-tridecyl CH ₂ H 4-tert-butylbenzyl Cl 119 iso-tridecyl CH ₂ H 4-methoxybenzyl Cl 120 iso-tridecyl CH ₂ H 3-trifluoromethylbenzyl Cl 121 iso-tridecyl CH ₂ methyl 4-cyanobenzyl Cl 122 iso-tridecyl CH (CH ₃ ) H 4-nitrobenzyl br 123 iso-tridecyl CH ₂ H 3,4-dichlorobenzyl Cl

No. R ¹ R ² R ³ R ⁴ X

124 iso-tridecyl CH ₂ H, 2,3,4-trichlorobenzyl IR spectra (film) / cm ^-1 / Cl 125 iso-tridecyl CH ₂ aziridin-1-yl Cl 126 iso-tridecyl CH ₂ pyrrol-1-yl Cl 127 iso-tridecyl CH ₂ pyrrolidin-1-yl Cl 128 iso-tridecyl CH ₂ pyrazol-1-yl Cl 129 iso-tridecyl CH ₂ 1H-imidazol-1-yl Cl 130 iso-tridecyl CH ₂ 1H-1,2,4-triazol-1-yl Cl 131 iso-tridecyl CH ₂ piperidin-1-yl Cl 132 iso-tridecyl CH ₂ 3,5-dimethylpiperidine-i-yl Cl 133 iso-tridecyl CH ₂ 4-methylpiperazin-1-yl Cl 134 iso-tridecyl CH (CH ₃ ) tetrahydro-1,4-oxazin-4-yl br 135 iso-tridecyl CH (CH ₃ ) 2,6-cis / trans-dimethyl-tetra-hydro-1,4-oxazin-4-yl br 136 iso-tridecyl CH (CH ₃ ) tetrahydro-1,4-thiazin-4-yl br 137 iso-tridecyl CH (CH ₃ ) 2,6-cis / trans-dimethyl-tetra-hydro-1,4-thiazon-4-yl br 138 iso-tridecyl CH ₂ oxazolidin-3-yl Cl 139 iso-tridecyl CH ₂ thiazolidin-3-yl Cl As an example, the compounds according to the invention are characterized by their IR spectra: Verb.-Nr.

7 3300.2 960, 2930, 2870, 1700, 1564

12 3 350.3 200.2 960.2 930.2 850.1 670.1 560.1 470.1 380

44 3 380.2 960.2 930.2 870.1 700.1 610.1 560.1 505.1 450.1 320.1 260

55 3 370.2 955.2 930.2 870.1 700.1 615.1 560.1 500.1 465.1 310.1 255.1 100.835

79 3 380.2 965.2 925.2 880.1 705.1 600.1 565.1450

104 3 380.2 965.2 935.2 880.1 700.1 540.1 460.1 380

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

I. Example

Solution concentrates: 80 parts by weight of compound 12 are mixed with 20 parts by weight of N-methyl-2-pyrrolidone. A solution is obtained which is suitable for use in the form of very small drops.

II. Example

Emulsifiable concentrates: 25 parts by weight of compound 55 are mixed with 2.5 parts by weight of epoxidized vegetable oil, 10 parts by weight of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts by weight of dimethylformamide and 57.5 parts by weight of xylene. From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

III. example

Spritzpuler: 40 parts by weight of compound 79 are mixed well with 5 parts by weight of the sodium salt of a lignosulfonic acid 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.

IV. Example

Dusts: 5 parts by weight of compound 79 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.Beispiel

Granules: 5 parts by weight of compound 44 are mixed with 0.25 part by weight of epichlorohydrin and dissolved with 6 parts by weight of acetone. Thereafter, 3.5 parts by weight of polyethylene glycol and 0.25 parts by weight of cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

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

Example A

Botrytis test (Botrytis cinerea / field bean [Vicia faba] leaffed)

Cropped leaf spring of potted bean plants (Vicia faba) of the variety "Fribo" in the four-leaf stage are briefly dipped in active ingredient preparations, which are prepared from 1 part by weight of active ingredient, 100 parts by weight of acetone and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired active ingredient concentration After the spray coating has dried on, the leaves are inoculated with a conidia suspension of Botrytis cinerea, which is obtained by washing 12 to 16-day-old fungal cultures on malt agar nutritive medium (2% malt) in an incubation cabin in dishes Temperature of 22 ° C and maintained at 90 to 100% relative humidity.

After 2 days, the Botrytis infestation of field bean leaflet is determined. The infections were counted and multiplied by a factor for the strength of infection (rating scale from 1 = no infestation, to 5 = very severe infestation). The resulting value was given in% Infektionsangang and calculated in relation to the untreated control of the efficiency.

The results of the experiments showed that, for example, the compounds Nos. 44.55 and 104 when used in an active compound concentration of 500 mg χ Γ ¹ a better effect (efficiency of 90 to 100%) than the known active ingredient diclorane (2,6- Dichloro-4-nitraniline) (efficiency 65%) reach.

Example B Test against Phytophthora infestans on tomato leaf disks The active ingredients are dissolved in a little DMF and distilled with dist. Water adjusted to the desired concentration. To perform the test, leaf disks are punched out of adult leaves of tomato plants. The zoospore suspension needed for the infection becomes more susceptible to swelling fungal turf halves Produced potato varieties. The treatment with the active ingredients and the infection take place simultaneously by adding certain drug concentrations Zoosporensuspension of Phytophthora infestans are added and these mixtures after shaking on the in Petri dishes

designed leaf discs are poured. After 2 hours, the supernatant liquid is poured off. The dishes are stored at 15 to 20 ^° C under exposure. After 3 to 4 days, the evaluation is carried out by determining the proportion of necrotic leaf area per leaf disc. From the testing of a concentration series, the infection inhibition is determined.

The results of the experiments showed that, for example, the compounds Nos. 44 and 55 at a drug concentration of

5mg x Γ ^{1 achieved} a 90 to 100% effect.

Example C Plant growth regulatory test Cucumber plants of the variety "Eva" are in pots in humus soil, which is sufficiently supplied with nutrients, up to a Growth height of 9 cm used in the greenhouse. 10 plants are used per experimental variant. The cucumber plants

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

After a growth time of 14 days after the application of the medium, the treated plants and the

untreated control plants length measurements made.

The results of the experiments showed that, for example, the compound No. 104 in an active ingredient concentration of

1 250mg χ Γ ¹ inhibited the growth of cucumber plants by 5%.

Claims (3)

1. Fungicidal agent with additional plant growth-regulating effect, characterized in that it comprises at least one N-alkyl-pyrrolidinio-carboxamide salt of the general formula I. ^ ^A (I) -CO-N in the R ¹ straight-chain or branched alkyl having 6 to 20 C atoms, R ² straight-chain or branched alkylene having 1 to 6 C atoms, R ³ and R ⁴ are each, independently or differently, hydrogen, straight-chain or branched alkyl having 1 to 20 C atoms, a straight-chain or hydroxyl-substituted alkoxy having 1 to 4 C atoms, cyano or dialkylamino having 2 to 16 C atoms branched alkyl having 1 to 6 carbon atoms, an optionally halogen-substituted alkenyl with 3 to 6 C atoms, cycloalkyl having 3 to 7 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 having 7 up to 12 C atoms, cycloalkyl having 3 to 7 C atoms, acyl having 1 to 4 C atoms, alkoxyalkyl having 1 to 8 C atoms, aryl, halogen, halogenoalkyl having up to 4 C atoms, halogenoalkoxy having 1 to 4 C atoms, Alkylthio having 1 to 4 C atoms, Halogenalkylthiomiti bis4C atoms, nitro, cyano, thiocyanato, NHCOR ', NHCONR'R ", COOR', CONR'R", SO ₂ R 'and / or SO ₂ NR'R ", where R 'and R "independently of one another represent hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 7 C atoms, aryl or aryl-lower-alkyl having 7 to 12 carbon atoms, may be substituted, aryl-lower-alkyl having 7 to 12 carbon atoms, which is mono- or polysubstituted by identical or different 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, halogenoalkyl having 1 to 4 C atoms, nitro and / or cyano may be substituted, R ³ and R ⁴ together with the nitrogen atom represents a five- or six-membered heterocyclic ring which is optionally monosubstituted or disubstituted by alkyl having 1 to 4 C atoms and / or halogen and optionally also contains one or two further heteroatoms, and X ~ denote the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or formulation excipients included. 2. A method for controlling fungi, characterized in that means according to item 1 is allowed to act on fungi or the objects to be protected against fungal attack. 3. Use of agents according to item 1, characterized in that they are used to combat fungi.