CS211371B2 - Fungicide means - Google Patents

Abstract

1. A fungicide for crop protection, containing a trans compound of the formula see diagramm : EP0019769,P11,F1 where R denotes the radical of a saturated, 5-, 6- or 7-membered nitrogenous heterocyclic radical which is attached at the nitrogen, is unsubstituted or mono- or polysubstituted by methyl, and may bear, in the 4-position to the nitrogen atom, an oxygen atom or a C=O radical instead of the methylene radical, or a salt thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicidal plant protection product which comprises the trans-isomer of 3- (p-tert-butylcyclohexyl) -2-methylpiperane or a salt thereof, which in position 1 is bound to a nitrogen nitrogen atom. containing heterocycle.

It is known from DE-OS 27 52 135 that 3- (4'-tert-butylcyclohexyl) -2-methyl-1-piperidinopropane and its salts can be used for combating fungi pathogenic to plants.

Said compounds may exist with respect to both cyclohexane ring substituents at the 1, 4 position in the form of the clsa trans-isomers.

It has now been found that trans-compounds of general formula

CH, CP 3 - CH - CH 2 R

CH ₅ where R is a nitrogen-bonded saturated 5-membered, 6-membered or 7-membered nitrogen-containing heterocyclic radical containing one nitrogen atom and optionally substituted one or more times with methyl and optionally in the 4 position to the nitrogen atom containing a methylene group oxygen or the C-O residue or salts of these trans compounds have a better fungicidal effect than the corresponding cis compounds. It is surprising that trans-compounds are, inter alia, ten to 100 times more fungicidally effective than the corresponding cis-compounds against rusts (Puccinia species) on cereals and beans.

By trans-compound is meant both pure trans-compound but also mixtures containing more than 50% (w / w) of the trans-compound. Examples of radical R are those of piperidine, hexamethyleneimine, 3,5-dimethyl-4-piperidone and 2,6-dimethylmorpholine.

As salts, for example, salts with hydrohalic acids such as hydrochloric acid, hydrobromic acid or salts with sulfuric acid, acetic acid or p-toluenesulfonic acid are used.

The trans compounds were prepared by lacquering that the cis-trans mixture formed in the hydrogenation corresponding to the 1,4-disu-substituted phenyl compound to the cyclohexane compound was fractionally distilled at the top of the column after distilling off the solvent used for the hydrogenation.

6.6 to 6665 Pa on a 10 to 100-foot column from a reflux of 1: 1 to 1: 1000, in which the trans portion is enriched to 85% and the pure trans isomer is obtained by conversion to a strong acid salt and crystallization from an organic solvent.

Preparation method;

1. Preparation of cis- and trans-3- (4-tert-butylcyclohexyl-1-2-methyl-1- (3 (-methyl-1-piperidino) propane)

a) Synthesis of aromatic amine

306 g of 3- (p-tert-butylphenyl) -2-methylpropanol are placed in a 2 L three-necked flask and 72.5 g of 98% w / w are added dropwise. % j formic acid. Then 149 g of 3-methylpiperidine are added dropwise over three hours. The temperature is raised from 25 to 50 ° C. The reaction mixture was heated at reflux for 12 hours while releasing CO 2.

After completion of the reaction, the reaction mixture was traction distilled under reduced pressure. After the front 47 g which was distilled at 130 ^Q C at a pressure of 26.6 Pa, distilled 3- (p-tert-butylphenyl) -2-methyl-l- (3'-methyl-l-piperidino) propane between 130 133 ° C at 26.6 Pa. 355 g are obtained, corresponding to a yield of 82.4% based on the aldehyde used.

bj Hydrogenation to cyclohexane derivative

In a 3 liter rotary autoclave, 309 g of 3- (p-tert-butylphenyl) -2-methyl-1- (3'-methyl-1'-piperidinoylpropane) are placed in 1000 g of dioxane and hydrogenated in the presence of 0.5 g of Ru2O3-hydrate At 10 MPa of hydrogen and 120 degrees Celsius, there is no more hydrogen consumption after 3 hours, then at 140 ° C and 12 MPa of hydrogen the pressure drops by 3.5 MPa after 12 hours and after the hydrogen pressure is reset to 16 MPa at The pressure drops to 160 ° C over the next 10 hours in MPa, further hydrogen pressure is not increased to 16 MPa and the temperature to 180 ° C.

(c) Fractional distillation

The reaction mixture, 1310 g, was fractionally distilled through a 10-bed sieve column at 10 mbar. After the dioxane has been distilled off, the following fractions are obtained at a reflux ratio of 1: 5:

1. up to 185 ° C 27 g containing 85% cis and 10 per cent of the trans compound (the remainder 5% being the front),

2. at 185 ° C 114 g containing 75% cis and% trans-compounds,

3. to 186 ° C 60 g containing 40% cis- and% trans-compounds,

4. to 187 ° C 55 g containing 30% cis-α

70% of the trans compound.

The distillation residue of 40 g was distilled without column at 10 mbar and 187 ° C. 38 g of a 92% trans- and only 8% cis compound are obtained. 2 g of distillation residue remained.

The ratio of cis and trans compounds is determined by gas chromatography.

504 g of 3- (4'-tert-butylcyclohexyl-1'-) 2-methyl-1- (3'-methyl-1-piperidino) propane containing 54% cis- and 46% trans- cyclohexander derivative (425 g total) is fractionally distilled on a 20-mesh sieve column. A reflux ratio of 1: 3 is used.

70 g of the front were collected at a temperature of 192 ° C. The following fractions are then collected.

1. to 197 ° C / 2.8 kPa 13 g containing 85% of cic and 3% of the trans-compound (the remainder 12% being the front),

2. up to 198 ° C / 2.6 kPa 52 g containing 93% cis and 7% trans-compound,

3. up to 197 ° C / 2,5 kPa 87 g containing 96% cis and 10 o / o trans compounds,

4. up to 192 ° C / 2,2 kPa 82 g containing 85% cis and 15 o / o trans compounds,

5. db 196 ° C / 2.2 kPa 81 g containing 80% cis- and 20% trans-compounds,

6. to 202 ° C / 2.8 kPa 87 g containing 30% cis and 70% trans compounds,

7. to 196 ° C / 2.2 kPa 73 g containing 97% trans compound and 3% cis compound.

The distillation residue of 27 g was distilled to give 24 g of a product consisting of a trans compound (> 98%).

d) Preparation of the HBr salt of the pure cis form

Further purification of the starting and / or terminal fractions to the pure cis form is accomplished by crystallization of the hydrobromide in acetic acid-water and, in the case of the trans compound, with hydrogen chloride in methanol.

g of the first fraction obtained above was treated with 20 g of aqueous 48% hydrobromic acid.

50 g of acetic acid are then added and the crystalline fraction is dissolved by heating. Upon cooling, the hydrobromide of the cis form crystallizes. NMR analysis confirmed the presence of the pure cis form. 28 g of product are obtained, m.p. 210 ° C.

calculated:

64.15% C, 10.77 O / o H, 3.74% N,

20,34% Br, pts] р7рпгу

64.5% C, 10.3% H, 3.60% N,

20.6 bps Br.

e] Preparation of HCl salt of pure transform.

g of fraction 5 obtained above is reacted with 60 g of hydrogen chloride. Upon cooling, 28 g of hydrochloride of m.p. 168 DEG C. are obtained. NMR analysis confirmed the presence of the trans form.

2) Preparation of cis- and trans-3- (4'-tert-butyl) cyclohexyl-1'-2-methyl-1- (3'‘, 5'-dimethyl-1'-piperidino] propane

a] 361 g of 3- (p-tert-butylphenyl] -2-methyl-lpropanol the procedure of Example 1 was reacted with 200 g of 3,5 _dimettΊy] piperidine and 86 g of 98% formic acid. Purification of the amine is carried out by fractional distillation at a pressure of 20 Pa on a 10-bed column, 406 grams of pure amine are obtained at 136 ° C.

b] Hydrogenation of the cyclohexane compound 70 g of 3- (p-tert-butylphenyl) -2-methyl-1- ([eta] < 5 &gt; -dim (4 &apos; 1 &lt; 1 &gt;)] - are placed in a 250 ml shake autoclave. ^s -piperazine: piperidino] propane in 80 dioxane .g. bydrogenační as catalyst. 0.5 g RuzCh-hhdrátu. at a pressure of 10 bar of hydrogen and 120 ° C during 37 hours there was added 35.8 psi of hydrogen.,

Fractional distillation of the reaction product (139 g) yielded 64 g of the cyclohexane derivative distilled at 136-146 [deg.] C. at a pressure of 0.4 kPa The gas chromatography showed that it was an isomeric mixture of both forms of cis- and trans-cyclohexane derivatives.

(c) Fractional distillation

562 g of the aromatic amine in 1000 g of dioxane are hydrogenated for 20 hours with RU2O3 hydrate at 14 MPa hydrogen. at 120 ° C and then fractionally distilled on a 10-mesh tray at a reflux of 1: 5 as described in Example 1.

The fraction containing more than 90% of the cis-cyclohexander derivative distils at a pressure of 13.3 Pa between 124 and 125 ° C. The fraction containing more than 90% of the trans-cyclohexane derivative distilled between 129-131 ° C.

Repeat fractional distillation on a 80 · cm long column filled with silver cot. netting at 1.6-1.7 kPa allows to obtain 154 grams of cis compound containing more than 90 percent. An intermediate fraction of 136 g consists of a 1: 1 mixture of cis- and trans-isomers of the cyclohexander derivative. The enriched trans-cyclohexane derivative (enriched over 90%) was obtained in a yield of 98 g.

The intermediate fraction is again subjected to fractional distillation. The formation of the distillation residue in the fractional distillation of the mixture of cis and trans isomers is very limited and only 2 g of the high-boiling fraction is produced from 390 g. At a pressure of 1.6 kPa, the cis derivative distills between 193-195 ° C and the enriched trans-isomer between 199-100 ° C.

d] Crystallization of the pure cis-compound via HCl salt 20 g of the cis-enriched product over 90% are dissolved in 25 g of methanolic hydrochloric acid solution and the solution is heated rapidly to boiling. Upon cooling, 12 g of hydrochloride (active ingredient no. 19) crystallized. The melting point of the recrystallized cis-cd-hexane derivative · lies at 240 ° C. A sample of the salt which was decomposed with KOH showed that it was a trans-isomer-free cis compound when analyzed by gas chromatography.

ej Crystallization of pure trans-compound via WEATHING SALT .......... ......

g of a trans compound enriched in over 90% is dissolved in 30 g of ethanolic hydrochloric acid. On cooling, the pure trans-compounds crystallized at 202 DEG C. (active substance No. 20) to give 13 g of pure product, and the free base prepared by the decomposition of the salt sample showed that it was cis-free according to gas chromatography. The N-analysis of both crystalline fractions confirms the results obtained by gas chromatography analysis.

3. Preparation of cis- and trans-3- (4'-terc.butylcyklohexyll Γ-2-methylll- (2 ^', 6'-cis-dimethylmorfolyl] propane.

a] Preparation of 3- (p-tert-butylphenyl] -2-methyl-1- (2 ', 6 ^d -cis-ols dimethdlmorf 1] propane is conducted as described in Example 1 by reacting 3- (p-tert. butylphenyl] 2-methylpropanol with 2,6-dimethylmorpholine and formic acid The aromatic amine is purified by distillation and the amine is distilled at 170 to 175 ° C / 300 Pa.

b) Hydrogenation to a cyclohexane compound

720 g of the above-described mole -inder derivative are dissolved in 500 g of dioxane. 0.5 g of RU2O3 hydrate is added as hydrogenation catalyst. Hydrogenation is carried out at a hydrogen pressure of 12 MPa at 140 ° C. Within 24 hours to

A 2.6 liter rotary autoclave allows 13 MPa of hydrogen.

(c) Fractional distillation

623 g of the obtained mixture of cis- and trans-isomers, reduced from 60-% cis- and 40% trans-acid, are fractionally distilled in an 11a · 80 cm column packed with silver mesh rings at a pressure of 300 Pa and back 5. distills at 144-145 ° C / 300 Pa. The enrichment of the cis-compound in the first three fractions, containing about 70 g, is greater than 90%. The last three fractions contain the enriched trans-compound. These fractions contain 71 g, 54 g and 38 grams. The trans compound content is greater than 85%.

Crystallization of pure hydrochlorides of cis trans compounds

Following the procedure described in Examples 1 and 2, the pure cis-compound hydrochloride is reacted with a solution of ethanolic hydrochloric acid. Mp. 161 ° C (active ingredient no. 23).

Pure, trans-compound · forms hydrochloride

mp 199 ° C (active substance, n ° 24).

The free bases prepared from both salts by reaction with KOH are sufficiently pure bases, according to gas chromatography analysis. The cis-cyclohexane derivative thus purified contains less than 0.5% of the trans product; trans211371

The product then contains less than 1% cis

-compounds. NMR analysis confirms the data of the active compound.

obtained from gas chromatography.

List of active substances:

active R isomer m.p. ° C substance 6.

1 pyrrolidine cis base m.p. 2.1 kPa 177 2 pyrrolidine trance base t. 533 Pa 130 3 pyrrolidine cis HCl-salt 1.1. 170 4 pyrrolidine trance HCl-salt 1.1. 208 5 piperidine cis base m.p. 1.3 kPa 180 6 piperidine trance base t./ 400 Pa 135 7 4-Methyl-piperidine cis base m.p. 2.7 kPa 205-206 8 4-Methyl-piperidine trance base t. v. 400 Pa 146—147 9 hexamethylenimine cis base t., 26.6 Pa 151 10 hexamethylenimine trance base t., 26.6 Pa 153 11 3,5-dimethyl-4-piperidone cis base t./ 400 Pa 144 12 3,5-dimethyl-4-piperidone trance base t./ 400 Pa 148 13 4-ethylpiperidine cis base t./ 400 Pa 157 14 4-ethylpiperidine trance base T. 533 Pa 159 15 Dec 4-ethylpiperidine cis HCl-salt t. 214 16 4-ethylpiperidine trance HCl-salt 1.1. 240 17 3,5-dimethylpiperidine cis base bw 2.4 kPa 195 18 3,5-dimethylpiperidine trance base mp 2.4 kPa 199 19 Dec 3,5-dimethylpiperidine cis HCl-salt T. 240 20 May 3,5-dimethylpiperidine trance HCl-salt 202 21 cis-2,6-dimethylmorpholine cis base t./ 400 Pa 145 22nd cls-2,6-dimethylmorpholine trance base t./ 400 Pa 148 23 cis-2,6-dimethylmorpholine cis HCl-salt 1.1. 161 24 cis-2,6-dimethylmorpholine trance HCl-salt 1.1. 199

Fungicides are particularly useful for combating plant diseases such as Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichorlacearum (powdery mildew) on pumpkins, Podosphaera leucotricha (apple powdery mildew) on apple trees, Uncinyla necator (vine mildew) on vine, polygoni on beans, Sphaerotheca pannosa on roses, Microsphaera querci on oak, Botrytis cinerea on strawberries, vines, Mycosphaerella musicola on bananas, Puccinia-grain rust species, Uromyces appendiculatus and U. phaseoli on beans, Hemileia vastatoc. they are systemically effective, both roots and leaves are taken up and transported in plants.

When the active ingredient is used after treatment of the plants against fungal infection, an amount of 0.025-5 kg of active ingredient per hectare is used. For the surface treatment of trees or fruit, the active compounds can also be used in conjunction with 0.25% to 5% dispersion plastic, based on the weight of the dispersion. The fungicide normally contains between 0.1 and 95 wt. %, preferably 0.5 to 90%.

The active ingredient may be mixed with other known fungicides. In many cases, an enlargement of the fungicidally effective spectrum is achieved. With the amount of fungicidal compositions in a weight ratio of 1:10 to 10: 1, synergistic effects also occur, i.e. the fungicidal activity of the combination products is greater than the sum of the activities of the individual components.

Fungicides which may be combined with the compounds of the invention are, for example: zinc dithiocarbamates and derivatives thereof, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, zinc ammonium ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, , N, N'-polyethylene-bis- (thlokarbamoyl) disulfide,

Zinc N, N'-propylene-bis-dithiocarbamate, zinc-ammonia N, N'-propylene-bis-dithiocarbamate complex, N, N'-polypropylene-bis- (thlokarbamoyl) disulfide, heterocyclic compounds such as Ν-ϋΓίαϋΓ1θΐΊηίη -1θ1ΓαΓιγύΓθί1Ηϋηιίό,

N-Trichloromethylthio-phthalimide

N- (1,1,2,2-tetrroChemo-thio) -tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester,

2-methyloxycarbonylaminobenzimidazole,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathirine,

5'-Allyl-2-dimethylphenyl] -4- (4-hydroxy-6-methylpyrimidine), 1,1'-bis- (3'-cyclohexyl-21hrouroidD) -benzene,

1,2-bis- (i-methoxycarbonyl-2-thioureido) -benzene, and various other fungicides such as dodeclguamination, N-dichlorofluoromethylthio-N, N- ^4- dimethyl-N-phenyl sulfonic acid diamide, 2,5-dimethyl anilide -furan-3-carboxylic acid, 2,5-dimethyl-3-furan-3-carboxylic acid cyclohexylamide, 2-iodobenzoic acid anilide, 2-bromobenzoic acid anilide, 3-nitroisophthalic acid diisopropyl ester,

1- (1,2,4 - [(4-O-11)) - [1- (4'-chlorophenoxy]] - 1- (1-imidazolyl) -2- [1,1'-b] -2- (2,4- Dichlorophenynyl ethane, piperazine-1,4-dibisbis-1-methyl-amide,

2,4, Z, 6 - orrachlooistrtalonitrile,

1,2-dimethyl-3,5-diphenylpyrazolinium methylsulfate.

The fungicidal composition is used, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, granules, which are sprayed, misted, sprayed, scattered, urinated or watered. The use forms depend entirely on the intended use, in each case the finest possible distribution of the active ingredient according to the invention is to be achieved.

To prepare directly; for sprayable solutions, emulsions, pastes of oil dispersions, suitable are mineral oil fractions of medium to high boiling point, such as kerosene, naphtha, coal tar oil and the like, as well as vegetable or animal oils, aliphatic, cyclic aromatic hydrocarbons, such as, for example, benzene, toluene, xylene, paraffin, tetrasodonaphthalene, alkyl naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexzazole, cyclohexanone, chlorobenzene, isophorone and the like strongly polar solvents such as dimethylformamide; dimethblsulfoxide, N-methylpyrrolidone, water and the like. The salts can be used in the form of aqueous solutions.

The aqueous solutions used can be used from emulsion concentrates, pastes or wettable powders (sprayable powders), oil dispersions by the addition of water For the preparation of emulsions, pastes or oil dispersions, the compounds can be used as such or dissolved in oil or solvent or homogenized in water Concentrates consisting of the active ingredient, wetting agent, sizing agent, dispersing agent or emulsifying agent, optionally from a solvent or an oil, which are suitable for dilution with water, may also be prepared, such as a surfactant, a dispersing agent or an emulsifying agent.

The surfactants include: alkali metal, ammonium alkaline earth metal salts, ligninsulfonic acid salts, naphthalenesulfonic acids, phenolsulfonic acids, alkylarlsulfonates, alkylsulfonates, alkaline earth metal salts of dibutylnaphthalenesulfonic acids, laurblethersulfate, fatty alcohol sulfates from alkaline-earth fatty acids, sulphate acid · hexadecanol, heptadecanol, octadecanol, sulphate · fatty acid glycol ether · alcohol, condensation products of sulphonated · n-naphthalene from derivatives of n-naphthalene with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol, , ethoxylovzný isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, alkylaryl polyglycol ethers 1bg1bL tributb1ferlblpo ^1, a1kb1arb1po1betheralkoho'1b, isotridecyl alcohol, fatty alcohol condensate from ethyleneoxy iodine, ethoxylated castor oil, polyoxybethylene alkyl ether, ethoxylated polyoxypropylene, 1a-urea-alcohol-alcohol-ether, sorbitol ester, lignin, sulfite leaches from methylcelluloses.

Powders, dusts from the spreading agents can be prepared by mixing or comminuting the active ingredients with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredient to a solid carrier. As solid carriers, for example, mineral clays such as silicic acid, silicates, talc, kaolin, limestone, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as for example, ammonium sulfate, ammonium phosphate, ammonium disulphate, urea and plant products such as ground grain, ground tree bark, ground wood- and ground nut shells, powdered cellulose and other solid carriers.

Oils of various types, herbicides, fungicides, nematicides, insecticides, bactericides, trace elements, fertilizers, antifoams (silicones), growth regulators, antidotes or other active compounds may be added to the mixtures or individual active substances.

Experiment 1

Effect on powdery mildew

The leaves in pots of germinated 'Jubilar' wheat are sprayed with an aqueous emulsion of 80% (w / w) active ingredient and 20% emulsifying agent and inoculated with spores of powdery mildew (Erysiphe graminis var. Tritici). The test plants are then placed in a greenhouse at a temperature between 20-22 ° C with a relative humidity of 75-80%. After 10 days, grass powdery mildew is evaluated.

active ingredient infestation of leaves after spraying x% solution (suspension) of active ingredient

x = 0.006 0.003 0.0015 0.0007 9 (cis-form) 0 2 3 3 10 (trans-form) 0 0 0 0 23 (cis-form j 0 2 2—3 2—3 24 (trans-form) 0 0 0 0

control (untreated) 5 = no attack graded to 5 = complete attack.

P o k u s 2

Effect on rust wheaten

The leaves in a pot of cultivated wheat plants are artificially infected with spores of wheat rust (Puccinia recondita) and placed in a water-saturated chamber at 20-25 ° C for 48 hours. The plants are then sprayed with an aqueous solution or aqueous emulsion of a mixture containing 80% active ingredient and 20% sodium lignin sulphonate and placed in a greenhouse at 20-22 ° C and 75-80% relative humidity. After 10 days, the development of wheat rust was evaluated.

active ingredient infestation of leaves after spraying x% active ingredient x = 0.012 0.006 0.003 0.0015

5 (cis-form) 2—3 2—3 2—3 4 6 (trans-form) 0 0 0 3 11 (cis-form) 2 2—3 4 4—5 12 (trans form) 0 0 0 2 31 - (cis-form) 2 3 3 4 22- (trans-form) 0 0 0 0 23 (cis-form) 3 5 5 5 24 (trans-form) 0 0 0 2 inspection (untreated) 5

= no attack graded to 5 = complete attack.

Example 1

Compound No. 10 (90 parts) is mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution that is suitable for use as the smallest droplets.

Example 2 parts by weight of Compound No. -6 are dissolved in a mixture containing 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per mole of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid. 40 moles of ethylene oxide per mole of castor oil. Pouring and finely distributing the solution into 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 3 parts by weight of compound 12 are dissolved in a mixture containing 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide per mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor oil. . Pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 4 parts by weight of compound 22 are dissolved in a mixture containing 25 parts by weight of cyclohexanol, 60 parts by weight of a mineral oil fraction, m.p. 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles ethylene oxide per mole castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.

Example 5 parts by weight of the active substance No. 6 are well dispersed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of lignin sulphonic acid sodium salt from sulphite leaches and 60 parts by weight of powdered silica and ground in a hammer mill. A finely divided mixture in 20,000 parts by weight of water gives a suspension containing 0.1% by weight of active ingredient.

Example 6 parts by weight of Compound No. 12 are intimately mixed with 97 parts by weight of kaolin. A dust containing 3% by weight of the active ingredient is obtained.

Example 7% by weight of Compound No. 22 is intimately mixed with a mixture comprising 92 parts by weight of powdered silica and 8 parts by weight of paraffin oil sprayed onto the surface of the silica. In this way, a composition having good adhesion is obtained.

Example 8 parts by weight of active ingredient No. 6 are intimately mixed with 10 parts of sodium condensate prepared from ¹ phenol sulfonic acid, urea and formaldehyde, 2 parts silica gel and 48 parts water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of active ingredient.

Example 9 parts by weight of the active substance No. 4 are intimately mixed with 12 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid condensate, urea and formaldehyde and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Claims (1)

SUBJECT OF THE INVENTION A fungicidal plant protection product comprising a solid or liquid carrier and a trans-isomer of a compound of the formula 5-, 6- or 7-membered nitrogen-containing heterocyclic radical containing one nitrogen atom and optionally substituted one or more times with methyl and optionally in the 4-position to the nitrogen atom, the methylene radical contains an oxygen atom or a C = O radical or the corresponding salt of the trans-isomer.