DK154980B - N-3 '- (P-TERT.-BUTYLPHENYL) -2'-METHYL-PROPYL-1'-PIPERIDINE DERIVATIVES, FUNGICIDES CONTAINING THESE AND PROCEDURES TO FIGHT FUNGI - Google Patents

Abstract

1. Claims for the contracting states : BE, CH, LI, DE, FR, GB, IT, LU, NL, SE An N-(3'-(p-tert.-butylphenyl)-2'-methyl-prop-1'-yl)-piperidine derivative of the general formula see diagramm : EP0056461,P6,F5 where R is acetyl or propionyl, or a salt thereof. 1. Claims for the contracting state : AT A fungicide containing an N-(3'-(p-tert.-butylphenyl)-2'-methyl-prop-1'-yl)-piperidine derivative of the general formula see diagramm : EP0056461,P6,F6 where R is acetyl or propionyl, or a salt thereof.

Description

DK 154980 B

The invention relates to novel valuable N-3 '- (p-tert.-butylphenyl) -2'-methyl-propyl-1'-piperidine derivatives and their salts with good fungicidal activity, fungicides containing these compounds, and a process for combating fungi with these compounds.

It is known to use N-3 '- (p-tert.-butylphenyl) -2 methyl-propyl-1'-3-hydroxymethylpiperidine as a fungicide (DE-OS 27 27 482). It is also known to use N-3 '- (p-10-tert.-butylphenyl) -2'-methylpropyl-1,1-piperidine and the corresponding -4-hydroxypiperidine as fungicides (DE-OS 2 752 135).

The compounds of the invention are esters of N-3 '- (p-tert-butylphenyl) -2'-methyl-propyl-1'-3-hydroxymethylpiperidine of the formula set forth in claim 1. It has been found that these compounds have a good fungicidal effect which is superior to the fungicidal action of the known hydroxy compound.

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Salts are e.g. the salts with inorganic or organic acids, e.g. chlorides, fluorides, bromides, iodides, sulfates, nitrates, phosphates, acetates, propionates or with acids of surfactants, e.g. dodecylbenzenesulfonic acid.

The preparation of the compounds according to the invention takes place e.g. by reacting 3-hydroxymethyl-piperidine with 3-p-tert-butyl-phenyl-2-methylpropanal in the presence of a reducing agent, e.g. formic acid at temperatures from 50 to 110 ° C and esterification of the hydroxy compound with acetanic anhydride or propionic anhydride in the usual manner.

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The following examples illustrate the preparation of the new compounds.

The starting compounds can be prepared as follows.

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Regulation 1

Synthesis of N-3 '- (p-tert.-butylphenyl) -2'-methyl-propyl-1'-3-hydroxymethyl-piperidine.

Into a 1 liter flask are introduced 204 g of 3- (4'-tert.-butyl-phenyl-1 ') -2-methylpropanol and with stirring 115 g of 3-hydroxymethylpiperidine are added. On cooling, 50 g of 98% formic acid is then added. The batch is then heated to boiling, thereby causing a strong formation of CC> 2. After 12 hours of heating to 120 to 140 ° C, the synthesis is completed.

To purify the product, distill under a pressure of 3 mbar. After a course of 44 g which goes up to a temperature of 169 ° C / 3 mbar and which according to the gas chromatographic analysis (GC) contains 27% of the final product, 260 g of the final product passes between 169 and 174 ° C . According to the GC analysis, there is an approx.

25 95% pure product. The yields for the two starting products are 84%. The NMR analysis shows the expected signals.

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3

Example 1

Synthesis of N-3 '- (p-tert-butylphenyl) -2'-methyl-propyl-1'-3-acetoxymethyl-piperidine (I) In a 250 ml round-bottom flask, 30 g of N-3' - (p tert-butyl-phenyl) -2'-methyl-propyl-1'-3-hydroxymethylpiperidine and 50 g of acetanic anhydride are added. As a catalyst for the esterification, 1 ml of pyridine is added dropwise. For 10 complete reaction, the reaction mixture is heated at reflux for 20 minutes. To purify the product I, the reaction mixture is distilled at 3 mbar. Up to a temperature of 153 ° C, 10 g passes (56% purity according to GC analysis). The bulk of the product goes between 153 and 155 ° C. According to the GC analysis, a product with 99% purity is available. The NMR analysis shows the expected signals.

C calc .: 76/16% H calc .: 7.99% C calc .: 8.45% N calc .: 7.40% 20 fd: 76.0% fd .: 7.9% fd .: 8.9% fd: 7.3%

Example 2

Synthesis of N-3 '- (p-tert.-butylphenyl) -2'-methyl-propyl-1'-3-propionoxymethyl-piperidine (II)

By reaction of 30 g of N-3 '- (p-tert.-butylphenyl) -2'-methyl-propyl-1'-3-hydroxymethylpiperidine with 60 g of propionic anhydride in the presence of catalytic amounts of 30 pyridine (1 ml) the product is prepared II. The purification is also carried out by distillation under a pressure of 3 mbar. 24 g of product II passes in the temperature range between 169 and 172 ° C at 3 mbar. According to the GC analysis, a product has a purity of more than 35

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4 98%. The NMR analysis shows the expected signals.

C calc .: 16.03% H calc .: 10.37% C calc .: 8.90% N calc .: 3.90% fd .: 76.5% fd .: 10.2% fd .: 9 , 20% fd: 3.9% -5

The active substances according to the invention and the fungicides produced therefrom are particularly suitable for the control of plant diseases, e.g. Erysiphe graminis (real mildew) in grains, Erysiphe cichoracearum (real mildew) in pumpkin-10 plants, Podosphaera leucotricha in apples, Onicinula ne-cator in wine, Erysiphe polygony in beans, Sphaerotheca pannosa in roses, Microshpaera querci in roses -nera in strawberries, wine, Mycosphaerella muscola in bananas, Puccinia species (rust fungi) in cereals, Uromyces appendicu-latus and u.phaseoli in beans, Hemileia vastratrix in coffee and Rhizoctonia solani. They are systemically active; they are absorbed both through the root and through the leaves and transported into the plant tissue.

20 When using the new active substances for the treatment of plants against fungal infections, the amounts used are between 0.025 and 5 kg of active substance / ha surface.

For the purpose of surface protection of trees and fruits, the active substance may also be used in conjunction with 25 plastic dispersions at a concentration of 0.25% to 5%, calculated in relation to the weight of the dispersion. The fungicides generally contain between 0.1 and 95% by weight of the active substance, preferably between 0.5 and 90%. The active substance can be mixed with other known fungicides. In 30 many cases does this result in an increase in the fungicidal spectrum of action? for a number of fungicide mixtures in the weight ratios of 1:10 to 10: 1, synergistic effects also occur, ie. the fungicidal activity of the combination product is greater than the added fun 5

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gicidal activities of the individual components. Active substances for such mixtures are, for example: dithiocarbamates and their derivatives such as zinc dimethyl dithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylenediamine bis-dithiocarbamate, zinc ethylene bisdithiocarbamate, -ethylene bis-dithiocarbamate) and 10 N, N1-polyethylene bis (thiocarbamoyl) disulfide, zinc (N, N'-propylene bis (thiocarbamoyl) disulfide, zinc (N, N ') propylene bis-dithiocarbamate), ammonia complex of zinc (N, Ν'-propylene bis-dithiocarbamate), and N, N'-polypropylene bis (thiocarbamoyl) disulfide; heterocyclic compounds such as N- trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide, N- (1,1,2,2-tetrachlorethylthio) -tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methyloxycarbonyl -dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 5-butyl-2- dimethylamino-4-hydroxy-6-m ethyl pyrimidine, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene and various other fungicides such as dodecylguanidine acetate, N-dichlorofluoromethylthio-N ' , N1-dimethyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, 6

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2-Iodobenzoic acid anilide, 2-bromobenzoic acid anilide, 3-nitroisophthalic acid diisopropyl ester, 1- (1,2,4-triazolyl-1-11) -1- (4'chlorophenoxy) -3,3-dimethyl-butane -2-one, 1- (1-imidazolyl) -2-allyloxy-2- (2,4-dichlorophenyl) -ethane, piperazine-1,4-diyl-bis-1- (2,2,2-trichloroethyl) 1) -formamide, 2,4,5,6-tetrachloro-isophthalonitrile, 10,2-dimethyl-3,5-diphenyl-pyrazoliniuramethyl sulfate.

The use is made, for example, in the form of directly extrudable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders, sprinklers, granules by spraying, misting, atomization, spraying, pickling or pouring. The forms of use are entirely directed to the purposes of use: in each case they must ensure the finest possible distribution of the active substances according to the invention.

*

For the preparation of direct sprayable solutions, emulsions, pastes and oil dispersions, medium to high boiling point mineral oil fractions such as kerosene or diesel oil, in addition coal oil, etc., as well as vegetable or animal origin oils, aliphatic, cyclic and aromatic hydrocarbons, e.g. . benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g. methanol, ethanol, propanol, butanol, chloroform, tetrachlorocarbon, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., highly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are considered.

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Aqueous dispensing forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders) or oil dispersions by the addition of water. For preparing emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil of the solvents can be homogenized in water by wetting, adhesive, dispersing or emulsifying agents. But concentrates may also be made up of active substance, wetting agent, adhesive, dispersing or emulsifying agent and optionally solvent or oil, which concentrate is suitable for dilution with water. Examples of surfactants may be cited: alkali metal and alkaline earth metal salts, salts of sulphated hexane decanols, heptadecanols, octadecanols, salts of sulphated fatty alcohol glycol ethers, condensation products of sulphonated naphthalene and naphthalene ethanol-phenyl-oxydehyde, condensation products of naphthalene or naphthalene isooctylphenol, octylphenol, nonylphenol, alkyl phenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil ether, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene auryl alcohol polyglycol ether acetal, sorbitester, lignin, sulfite waste liquor and methyl cellulose.

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Powders, emulsifiers and powders can be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. envelope, impregnation and homo granules can be prepared by bonding the active substances to solid carriers. Solid carriers are e.g. mineral soils, such as silica gel, silica, silica gels, silicates, talc, kaolin, aggregates, limestone, lime, chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled molds, fertilizers, such as e.g. ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as cereal, wood bark, wood and nut shell flour, cellulose powder and other solid carriers.

To the mixtures or individual active substances may be added oils of various types, herbicides, fungicides, nematodicides, insecticides, bactericides, trace elements, fertilizers, antifoam agents (eg silicones), growth regulators, antidotes or other active substances. compounds.

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For the following experiments, the following known comparison compounds were used.

H CH

5 CH, X J

\ -o CH3 N == / \ - '10 Hv CH,

CH, t ^ C OH

h3c -) - £ ^ ί £, ch2- / ~ V (b) CH3 '- Ή 15 J "j \ .Λ« 2 «v-0 <' v» c> 20 'CH3 · ·

Wheat Milk Activity 25 Leaves of wheat Jubilar-driven wheat seedlings are sprayed with aqueous emulsions of 80% (wt.%) Of active substance and 20% emulsifier (calculated relative to the dry matter) and, after initial drying of the spray coating, are sprayed with 30 oidia (spores) of wheat mildew (Erysiphe graminis var. Tritici). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and at a relative humidity between 75 and 80%. After 10 days, the extent of the development of the mildew is assessed.

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In this experiment, the new active substances I and II, using active agent spray fluids at a concentration of 0.012, 0.006, 0.003 and 0.0015%, respectively, showed a better fungicidal activity than the known active substance A.

5 For documentation of this, refer to the table below.

Activity against wheat mildew 10 Active substance Attack of the leaves after spraying with spray liquid with a concentration of active substance of x% 0.012 0.006 0.003 0.0015 15 I 0 0 0 1 II 0 0 0 1

Comparative compound A 0-112 2-3 20 Control (untreated) 5 0 = no fungal attack, escalated to 5 = total attack

Leaves of wheat-grown wheat plants of the variety 25 "Jubilar" are artificially infected with spores of wheat brown (Puccini's recondita) and set up for 48 hours at 20 to 25 ° C in a steam-saturated comb. Then, the plants are sprayed with aqueous spray liquids containing a mixture of 80% of the active substance to be tested, 30 and 20% sodium lignin sulfate (based on the dry matter), which mixture is dissolved in the water or emulsified therein, and they are stored in a greenhouse. at temperatures between 20 and 22 ° C at a relative humidity of between 75 and 80%. After 10 days, the development of 35 11 is judged

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rust fungus.

In this experiment, the new active substances I and II, using sprays with an active substance concentration of 0.025, 0.012 and 0.006%, respectively, showed a better fungicidal effect than the known active substances A, B and C. As evidence thereof please refer to the table below.

10 Wheat brown rust activity

Active substance Attack of the leaves after spraying with spray liquid with an active substance concentration of x% 15 0.025 0.012 0.006 I 0 0 2 II 0 0 1

Comparative Compound A 1 1-2 3 20 Comparative Compound BO 2 3-4

Comparative compound C 2 3 3

Control (untreated) 5 0 = no fungal attack, escalated to 5 = total attack 25

Example a

90 parts by weight of compound I are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution suitable for use in very small droplets is obtained.

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Example b 12

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10 parts by weight of compound II are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the preparation product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-mono-ethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil.

By pouring and finely distributing the solution, an aqueous dispersion is obtained.

Example c 20 parts by weight of compound I are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the product of 40 moles of ethylene oxide for 1 mole of castor oil. By pouring and finely distributing the solution 20 in water, an aqueous dispersion is obtained.

Example d 20 parts by weight of compound II is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ° C and 10 parts by weight of the preparation product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in water, an aqueous dispersion is obtained.

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Example e 13

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80 parts by weight of the active substance I are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulphonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel and ground in a hammer mill. By splitting the mixture into water, a spray liquid is obtained.

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Example f 3 parts by weight of compound II is thoroughly mixed with 97 parts by weight of finely divided kaolin. Similarly, a powder containing 3% by weight of the active substance is obtained.

Example g 30 parts by weight of Compound I is thoroughly mixed with a 20 mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesiveness is obtained.

Example H 40 parts by weight of the active substance II are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water.

30 A stable aqueous dispersion is obtained. Dilution with water gives an aqueous dispersion.

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Example i

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14 parts of the active substance 4 are thoroughly mixed with 2 parts calcium salt of dodecylbenzenesulfonic acid, 8 parts fatty alcohol 5 polyglycol ether, 2 parts sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

10 15 20 25 30 35

Claims (3)

N-3 '- {p-tert.-butylphenyl) -21-methyl-propyl-1'-piperidine derivatives, characterized in that they have the general formula CH5 CH3 CH20R CH2 -c2} -ch2 wherein R is an acetyl or propionyl group and salts thereof. Fungicide, characterized in that it contains a compound according to claim 1. Method for controlling fungi, characterized in that the fungi are treated with a compound according to claim 1 or that before the fungal attack 25, the articles to be protected are treated with a compound according to claim 1. 30