DD298723A5 - BIOZIDE MEDIUM - Google Patents

Abstract

The invention relates to biocidal agents which can be used to combat microorganisms in agriculture and horticulture. The biocidal agents contain as active ingredient * of the general formula I. The meaning of R1 to R6 and X is taken from the description. Formula (I) {Biocidal agent; * Microorganisms; combating; Agriculture; Horticulture}

Description

in the

R ^{1 is} straight-chain or branched alkyl having 8 to 18 C atoms, R ^{2 is} straight-chain or branched alkylene having 1 to 6 C atoms, R ^{3 is} hydrogen or alkyl having 1 to 4 C atoms,

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

R ⁵ and R ⁶ independently of one another or different hydrogen, straight-chain or

branched alkyl having 1 to 4 carbon atoms or halogen and Χ ^θ mean the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or formulation auxiliaries included.

2. A method for controlling microorganisms, characterized in that means according to claim 1 are allowed to act on microorganisms or the objects to be protected against microorganism infestation.

3. Use of mit aln according to claim 1, characterized in that it is used for controlling microorganisms.

Field of application of the invention

The invention relates to novel N-alkyl-piperidino-alkanecarboxylic acid -NMalkoxycarbonyl-alkyO-anilide salts and their use as biocidal agents in agriculture.

Characteristic of the known state of the art

It is known that long-chain N-alkylpiperidines have a fungicidal activity (Angewandte Chemie 77 [1965], pp. 327-333). Furthermore, quaternary salts of piperidino-alkanecarboxylic acid anilidone with lower alkyl, alkenyl, alkynyl or substituted alkyl groups are known as plant growth regulators (DE-PS 2657728, DE-PS 2915250, DD-PS 150423, DD-PS 151036). However, the action of the compounds mentioned is not always completely satisfactory in certain indication areas, in particular at low application rates and concentrations. 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 biocidal activity and a process for their preparation and of biocidal agents containing such compounds, and the use of such biocidal agents in agriculture and horticulture.

Explanation of the essence of the invention

The invention has for its object to provide novel N-alkyl-piperidino-alkanecarboxylic acid-N'-falkoxycarbonyl-alkyD-anilide salt-containing biocidal agent with good efficacy and broad spectrum of activity and the highest possible plant compatibility.

To solve this problem, biocidal agents are proposed, which are characterized in that they contain at least one N-alkyl-piperidino-alkanecarboxylic acid-N'-lalkoxycarbonyl-alkyO-anilide salt of the general formula I,

CO-N

CH-COOiT

in the

R ¹ straight-chain or branched alkyl having 8 to 18 C atoms, R ^{2 is} ge-adketted or branched alkylene with up to 6 C atoms, R ^{3 is} hydrogen or alkyl having 1 to 4C atoms, R ^{4 is} hydrogen or alkyl having 1 to 4 carbon atoms, R ⁵ and R ^{e are} independently of each other the same or different hydrogen, straight or branched alkyl

with 1 to 4 C atoms or halogen and Χ ^Θ the anion of a non-phytotoxic acid,

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

Surprisingly, it has been found that the N-alkyl-piperidino-alkanecarboxylic acid-N'-lalkoxycarbonylalkyD-anilide salts of general formula I according to the invention have a strong biocidal behavior and a broad spectrum of activity and are particularly suitable for controlling phytopathogenic fungi on crops and vegetable crops. The active compounds show a 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-alkanecarboxylic acid-N '- (alkoxycarbonyl-alkyl) -anilide salts of other ring size, whose rings may also be substituted, have similar biocidal and growth-regulating properties as the active compounds according to the invention.

Furthermore, it has been found that the N-alkyl-piperidino-alkanecarboxylic acid-N'-lalkoxycarbonyl-alkyD-anilide salts of the general formula I are obtained by reacting an N-alkyl-piperidine of the formula II,

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

R - CO-N

CH-COOR ^

wherein R ² to R ^{5 have} the meaning given in the general formula I and X is halogen, or alternatively a piperidino-alkanecarboxylic acid-N-taloxycarbonyl-alkyD-anilide of the formula IV,

N - R - CO - N

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

R ¹ - X (V)

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

N-Alk / 1-piperidines of formula II are e.g. n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, 1,5,9-trimethyldecyl, n-hexadecyl

or n-octadecylpiperidine.

Haloalkanecarboxylic acid N-falkoxycarbonyl-alkyD-anilides of the formula III are, for example, chloroacetic acid-N-

(methoxycarbonyl-methyl) -anilide, chloroacetic acid-N-t-methoxycarbonyl-methyl-d-chloroanilide-chloroacetic acid N- (methoxycarbonylmethyl) -2,6-dimethylanilide, N-methoxy-carbonyl-ethoxy-chloroacetic acid anilide, chloroacetic acid-N- (1'-methoxycarbonyl-ethyl) -4-chloroanilide, chloroacetic acid-N-d-methoxycarbonyl-ethyl-1-yl-dimethylanilide, 2-bromopropionic acid.

N- (1'-methoxycarbonyl-ethyl-M-chloroanilide, 2-bromo-caproic acid N-d '-methoxycarbonyi-ethyl-M-chloroanilide or 6- Bromcapronic acid N-methoxycarbonyl-ethyl-M-chloroanilide, if appropriate as a mixture of enantiomeric forms

be used.

Piperidino-alkanecarboxylic acid-N-lalkoxycarbonyl-alkyD-anilides of the formula IV are, for. B. piperidinoacetic acid N-

(Methoxycarbonyl-methyl) anilide, acetic acid-N-fmethoxycarbonyl-methyD-'i-chloroanilide -acetic acid-N-lmethoxycarbonylmethyl) -2,6-dimethylanilide, acetic acid-N-lrrethoxycarbonyl-methyD-SB-dichloroanilide, - acetic acid N-d'-methoxycarbonyl--ethyl-anilide, acetic acid-N-d'-methoxycarbonyl-ethyD ^ -chloranilid, acetic acid-N-d'-methoxycarbonyl-ethyD ^ -methyM-chloroanilide -acetic acid N-di-methoxycarbonyl-ethyl-1-dimethylanilide, -propionic acid-N-d-methoxycarbonyl-ethyl) -chloranilide, -capric acid-N-d-methoxycarbonyl-ethyl-d-chloroanilidoderecaproic acid-N -li'-methoxycarbonyl-ethyl) ^ - chloroanilide. The compounds of formula IV, which may occur in optically active forms, are used as a racemic mixture.

Alkyl halides of the formula V are, for example, n-hexyl bromide, n-octyl bromide, n-decyl bromide, n-dodecyl chloride, n- Tridecyl chloride, iso-tridecyl chloride, 1,5,9-trimethyldecyl chloride, n-hexadecylbromide or n-octadecylbromide. The conversion to the active compounds of the formula I are optionally in the presence of a solvent or diluent

at a temperature in the range between 10 and 18O ⁰ C, preferably between 30 and 15O ⁰ C performed. The starting materials of the formula II or of the formula IV are in stoichiometric amounts with a compound of the formula II or 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 above the stoichiometric amount, based on the starting materials of the formula II or of the formula IV.

As preferred solvents or diluents, for example, aliphatic or aromatic, optionally

halogenated hydrocarbons, such as n-pentane, cyclohexane, benzene, toluene, chlorobenzene, chloroform or methylene chloride, aliphatic ketones, such as acetone, methyl ethyl ketone or cyclohexanone; Ethers, such as diethyl ether, tetrahydrofuran or dioxane;

Alcohols, such as methanol, ethanol, propanols, butanols or hexanols; Nitriles, such as acetonitrile; Esters, such as methyl acetate

or N-methyl-pyrrolidone; Dimethyl sulfoxide or water or mixtures of these solvents can be used. The

Isolation of the active compounds of the general formula I from the reaction mixtures is not absolutely necessary since they too

can be used without further purification operation for the preparation of biocidal preparations.

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

to combat fungal pathogens in agriculture and horticulture. The active ingredients may be used to control undesirable fungi found on plants or parts of plants. The active ingredients are general

Formula I are also suitable as mordants for the treatment of seeds and plant cuttings to protect against fungal infections

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

The biocidal agents of the invention are useful for controlling economically important pathogenic fungi, such as Erysiphe, Botrytis, Phytophthora, Pythium, Fusarium, Mucor, Alternaria species, and others. a. suitable. . Furthermore, the biocidal agents also provide good activity against wood-discoloring and wood-destroying fungi, such. B. Pullaria pullulans, Aspergillus niger, Polystictus versicolor or Chaetomium globosum. Furthermore, the active compounds of general formula I show good activity against molds, such. B. PeniciUium, Fusarium

or Aspergillus species that spoil high-moisture agricultural products or

Processing products of agricultural products during storage or intermediate storage. Such

to be treated products include z. Apples, oranges, tangerines, lemons, grapefruits, peanuts, cereals and

Cereal products or legumes and meal. The active ingredients are, in addition to their broad spectrum of fungicidal activity, also different from phytopathogenic bacteria,

such as Xanthomonas or Erwinia species.

Some active ingredients zeiqen also an effect against human pathogenic fungi, such. B. Trichophyten and Candida species. The biocidal agents according to the invention are also suitable for controlling resistant S.'ämme of fungal pathogens, the

show resistance to known fungicidal agents resistance.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, foams, pastes, soluble powders, granules, natural and active substances impregnated with active substance

Synthetic substances, ultra-fine encapsulations in polymeric materials and in coating compositions for seeds as well as ULV-KaIt- and

Warm mist formulations. The preparation of these formulations can be carried out in a known manner, for. B. by mixing or grinding the active ingredients

of the general formula I with solvents and / or carriers, optionally with the use of surfactants, such as emulsifiers and / or dispersants.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by mass. The active compounds may be prepared as such, in the form of their formulations or by further dilution therefrom Application forms in a conventional manner, for. By casting, dipping, spraying, spraying, atomizing, injecting, silting, Spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting, applied

become.

In the treatment of parts of plants, the drug concentrations in the use forms in a larger Range can be varied. They are generally between 0.001 and 1 wt .-%, preferably between 0.01 and 0.5 Ma .-%. The Wirkstoffaufwandmengsn are dependent on the specific application and are generally between 0.1 and 3kg Active ingredient per hectare. In seed treatment, in general, amounts of active ingredient are from 0.0001 to 50 g per kilogram of seed, vorz'-osweise

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 inventive method for controlling microorganisms is characterized in that biocidal agent

with the active compounds of the general formula I to microorganisms or to be protected against microorganism infestation

Allow objects to act in an effective amount. The active compounds of the general formula I can be used in the formulations or in the various forms of application

other known active substances, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides,

Growth regulators, plant nutrients and soil conditioners are mixed and applied. In

In many cases when mixing with fungicides, a widening of the fungicidal activity spectrum is obtained. At a

Number of mixtures of the biocidal agents according to the invention with known fungicides also have synergistic effects

on, wherein the fungicidal activity of the combination product is greater than that of the added effectiveness of the

Individual components. The following examples are intended to further illustrate the invention without, however, limiting it, and the effect of

prove compounds of general formula I according to the invention.

Ausführiingsbelsplele The following examples illustrate the preparation of the compounds of the invention. The starting compounds for the preparation of the compounds according to the invention are known or can be prepared per se

known methods are produced.

example 1 N-iso-tridecyl piperidinio-acetic acid N '- (1'-methoxycarbonyl-ethyl) -4-chloroanilide chloride

5.4 g of N-iso-tridecyl-piperidine and 5.8 g of chloroacetic acid N-d-methoxycarbonyl-ethyl-M-chloroanilide are heated to reflux with addition of a catalytic amount of sodium iodide in 15 ml of n-propanol for 48 hours. Then allowed to cool and distilled off the solvent in vacuo.

The residue is directed with hexane. The product is dissolved in a little acetone and with η-hexane for complete separation

added. The oily phase is separated and freed from solvent residues in vacuo. This gives 7.3 g of a tan

Resin (Compound No.7). IR spectrum (film) / cm.sup.V: 2950, 2870, 2630, 255, 2440, 1745, 1675, 1600, 1550, 1490, 1455, 1380,

1 250,1090,1060,1010,950,830

Example 2 N-n-dodecyl-piperidinio-acetic acid-N'-lmethoxycarbonyl-methylM-chloroanilide bromide

5.1 g of Nn-dodecyl-piperidine and 5.5 g of chloroacetic acid-N-lmethoxy-carbonyl-methylM-chloroanilide are dissolved in 20 ml of n-propanol and heated under reflux for 36 hours with the addition of a catalytic amount of sodium iodide. After cooling, the solvent is distilled off in vacuo. The residue is repeatedly directed with η-hexane. The product is dissolved in a little acetone and η-hexane is added until complete precipitation as an oily phase. Finally, the solvent residues are removed in vacuo. There are obtained 6.5 g of a yellow resin (Compound No. 3). IR Spoktrum (Film) / cm " ¹ /: 2950.2860, 2640, 2540-2500, 1745.1 680, 1600.1 540, 1495, 1460, 1380, 1210, 1090, 1050, 1020, 960, 880, 830

Table 1: N-Alkyl-piperidinio-alkanecarboxylic acid N'-lalkoxycarbonyl-alkyD-anilide salts

R ² -CO-Ν '

R ¹ CH-COOR ⁴ R ³ R ⁴ R ⁵ R ⁶ (I) Verb. R ² X No. nC _e -H ₁₇ CH ₃ CH ₃ 2-CH ₃ 6-CH ₃ 1 ISO-C ₁₃ Hj ₇ CH ₂ H CH ₃ H H br 2 n-C) jHj6 CHj H CH ₃ 4-CI H Cl 3 ISO-Ci ₃ Hj ₇ CH ₂ H CH ₃ 4-CI H Cl 4 ISO-C ₁₃ H ₂₇ CH ₂ CH ₃ CH ₃ H H Cl CTI nC ₁₂ H ₂₅ CH ₂ CH ₃ CH ₃ 4-CI H Cl 6 ISO-C ₁₃ H ₂₇ CH ₂ CH ₃ CH ₃ 4-C H Cl 7 ISO-C ₁₃ H ₂₇ CHj CH ₃ CH ₃ 3-C 5-CI Cl 8th iso-C ₁₃ H ₂₇ CH ₂ CH ₃ CH ₃ 2 Chi 4-CI Cl 9 IsO-C ₁₃ Hj ₇ CH ₂ CH ₃ CH ₃ 3-CI 4-CI Cl 10 CH ₂ Cl

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

!.Example

Solution concentrates: 80 parts by weight of compound 3 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.Beispiel

Emulsifiable concentrates: 25 parts by weight of compound 7 are mixed with 2.5 parts by weight of epoxidized vegetable oil, 10 parts by weight of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts by weight of dimethylformamide and 57.5 parts by weight of xylene. From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

III. example

Injection powder: 40 parts by weight of compound 1 are mixed well with 5 parts by weight of the sodium salt of a Llgnlnsulfonsäure from a sulfite liquor, 1 part by weight of sodium di-isobutylnaphthalene-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

Granules: 5 parts by weight of compound 1 are mixed with 0.25 part by weight of epichlorohydrin and dissolved with 6 parts by weight of acetone. Thereafter, 3.5 parts by weight of polyethylene glycol and 0.25 parts by weight of cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

Example A

Wheaty mildew test (Erysiphe graminis / wheat)

Potted-grown wheat plants of the variety 'Alcedo' are dewatered sprayed in the single-leaf stage with active compound preparations 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 plants are pollinated with conidia (spores) of the wheat powdery mildew (Erysiphe graminis var. Tritici).

Subsequently, the test plants for a period of 2 to 3 hours at 90 to 100% relative humidity in an incubation cabin and then placed 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 funds is then calculated according to ABBOTT. The experiments show that, for example, the compounds Nos. 3 and 7 show a better effect (efficiency 87 or 92%) when using an active substance concentration of 100 mg χ Γ ¹ than the known fungicide saprol (N, N-bis ( 1-formamido-2,2,2-trichlorothyl) -piperazine (efficiency 85%).

Example 8

Botrytis test (Botrytis cinerea / broad bean IVicia fabal leaflet)

Cut off leaves of field bean plants (Vicia faba) of variety 'Fribo' in the four-leaf stage are briefly immersed in active ingredient preparations 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 away 12 to 16-day-old fungal cultures on malt agar 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 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 Verbuche showed that the compounds Nos. 3 and 7 when used in a drug concentration of 500 mg χ Γ ¹ a better effect (efficiency of 100 or 80%) than the known active ingredient dicloran (2,6-dichloro-4 nitraniline) (efficiency 65%).

Claims (1)

1. Biocidal agent, characterized in that it comprises at least one N-alkyl-piperidinoalkanecarboxylic acid N '- (alkoxycarbonyl-alkyl) -anilide salt of the general formula I, ₃ 5 \ / \ r ² - co-n (D 3 CH-GOOR