DD150839A5 - FUNGICIDAL AGENT - 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

22 1 274 ί-

Fungicides for plant protection - '

Field of application of the invention

The new fungicides can be used in agriculture as fungicides.

Characteristic of the known technical solutions From the DE-OS 27 52 135 it is known that 3 - (^ '- tert-butyl-cyclohexyl-1 ¹ ) -2-methyl-l-piperidino-propanes and their salts to combat phytopathogenic fungi can be used.

Object of the invention

The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but the crops are not damaged.

DESCRIPTION OF THE NATURE OF THE INVENTION The object of the invention is to provide chemical compounds with fungicidal activity.

It has been found that the trans compounds of formula

CH ₃ CH ₃

CHL-C < VcH ₀ -CH-CH ₅ -R

CH ₃ ^

in which R is the radical of a nitrogen-bonded saturated 5-, 6- or 7-membered nitrogen-containing heterocyclic radical, which is optionally monosubstituted or polysubstituted by methyl and which is optionally in the ^ position to the nitrogen atom instead of the methylene radical. an oxygen atom or the C = O radical, or the salts of the trans compound has a better fungicidal action than the

, Sws / BL " ^J

- 2 - O. Z. 0050/033880

have corresponding cis connection. It is surprising that the trans compounds are more fungicidally active than cereals and beans in relation to rust fungi (Puccinia species) on cereals and beans, inter alia, by 10 to 100 times more than the corresponding cis compounds. The trans compound means both the pure trans compound and mixtures containing more than 50 % (wt. %) Of the trans compound. Examples of the radical R are, for example, the radicals of piperidine, hexamethyleneimine, 3> 5-dimethyl-4-piperidone and 2,6-dimethylmorpholine. Salts are, for example, the salts with hydrogen halide acids, for example hydrochloric acid, hydrobromic acid, or salts with sulfuric acid, acetic acid, p-toluenesulfonic acid.

The trans compounds are obtained by reacting the cis-trans mixture obtained in the hydrogenation of the corresponding 1,4-disubstituted phenyl compound to form the cyclohexane compound after distilling off the solvent used for the hydrogenation by fractional distillation at a pressure at the top of the column , 05 to 50 Torr at a 10-100-bödigen column under a reflux ratio of 1: 1 to 1: 100 enriched by fractionation to a trans content of about 85 % and the pure trans isomers after conversion into an acid addition salt to a is allowed to crystallize strong acid solvents and crystallization in an organic solu- ² ^.

production method

1. Preparation of cis- and trans-3 - (^ - tert -butyl-cyclo- ^3- hexyl-1) -2-methyl-1- (3'-methyl-1-piperidino) -propane

2 2 127 A

O.Z. ΟΟ5Ο / Ο3338Ο

a) Synthesis of the aromatic amine:. "" In a 2-1 three-necked flask, 306 g of 3- (prtert.-butyl-phenyl) -2-methyl-propanal presented and added dropwise 72.5 S 98 # ige (wt. *) Formic acid.

Thereafter, in the course of three hours, 149 g of 3-methylpiperidine are added dropwise. The temperature increases from 25 to more than 50 ⁰ C. Then, the reaction mixture is heated for a further 12 hours at reflux, with C0 ₂ -situation occurs.

After completion of the reaction is .Fraktioniert distilled under reduced pressure. After a flow of 47 g, which is up to a temperature of. 130 ⁰ C passes at 0.2 Torr, the distilled

3- (p-tert-butylphenyl) -2-methyl-1- (3'-methyl-1'-piperidino) -propane between 130 to 133 ° C at a pressure of 0.2 Torr over. There are obtained 355 g, which corresponds to a yield, based on the aldehyde used, of 82.4 % .

b) Hydrogenation to the cyclohexane derivative:

In a 3-1 roll autoclave, 309 g of 3- (p-tert-butylphenyl) -2-methyl-1- (3'-methyl-1'-piperidino) -propane are dissolved in 1000 g of dioxane using 0, 5 g

hydrogenated. At a hydrogen pressure

p3

of 100 bar and a temperature of 120 ⁰ C no hydrogen is taken up after 3 hours. Subsequently, at 14O ° C and 120 bar H ₂ pressure within 12 hours, a pressure drop of

35 bar and after readjustment of the hydrogen pressure to 160 bar at a temperature of loO C in the course of further

10 hours again a pressure drop of 10 35

- 4 - O. Z. OC5O / O3388O

registered. If the hydrogen pressure is raised further to 160 bar and the temperature reaches 180 ° C, there is no longer any increase in hydrogen concentration.

c) Fractional distillation:

The reaction mixture, 1310 g, is fractionally distilled via a sieve tray column with 10 sieve trays at a pressure of 10 mbar. After distilling off the dioxane are at a

fä reflux ratio of 1: 5 following fractions

1 to 185 ^° C. 27 g containing 85 % ice and 10 %

trans compound (balance of 5 % is lead) • 2. at 185 ^° C. 114 g containing 75 % cis and .25 % trans compound

3. to 186 ⁰ C 60 g containing 40 % ice and 60%

trans compound to 187 ° C 55 g i trans compound

up to 187 ° C 55 g containing 30 % ice and 70 %

The distillation residue of ^ O g is subjected to a short-path distillation at 10 mbar and 187 ⁰ C. There are obtained 38 g of the composition 92 * trans and only 8 % ice. There remain 2g of distillation residue.

The cis-trans ratio is determined in each case by gas chromatography.

504 g according to the method described above

notified 3- ^(4-f tert 3utyl-cyclohexyi-l ^r -) - 2- methyl-l -propane _i (3-methyl-l'-piperidino ^t) the 5 ^% cis and 46% trans Cyclohexane derivative (total 425 g) are added to a column

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fractionated with 20 sieve trays. A ^T return ratio of 1: 3 is set.

Up to a transition temperature of 192 ⁰ C go over 70 g flow. Thereafter, the following fractions are obtained: 1. to 197 ° C / 28 mbar 13 g containing: 85 % ice and

3 % trans (rest of 12 % is lead)

"2. to 198 ° C / 26 mbar 52 g containing: 93 % ice and 7 % trans

3. to 197 ° C / 25 mbar 87 g containing: 90 % ice and 10 % trans

4. to 192 ° C / 22 mbar 82 g containing: 85 % ice and 15 % trans

5. to 196 ° C / 22 mbar 3l g containing: 80 % ice and

20 % trans

β. to 2O2 ° C / 28 mbar 87 g containing: 30 % ice and 70 % trans.

7. to 196 ° C / 22 mbar 73 "g containing: 97 % trans. And 3 % ice.

The distillation residue of 27 S is subjected to short-path distillation. There are obtained 24 g with a content of trans compound of over 98 %.

d) Preparation of the H3r salt of the pure cis form: The further purification of the starting and / or final fractions to give the pure cis form is carried out by conversion.

crystallization of the Kydrobromids in acetic acid / water and in the case of the trans-connection made with the help of hydrogen chloride in methanol: 35

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25 g of the first fraction obtained above are mixed with 20 g of aqueous 48 ^ hydrobromic acid. Thereafter, 50 g of acetic acid are added and the entire crystals are brought into solution by heating. Crystallized on cooling

the hydrobromide of the cis-form. The NMR analysis confirms the presence of the pure cis form. There are 28 g with a melting point of 210 ⁰ C. ' , receive

C on: 64.15 % F .: 64.5 %; Hb .: 10.77 % ₉

found: 10.3 %

N calc .: 3.74% Found .: 3.60%; He calculates: 20.34 %, •. found: 20.6 %

e) Preparation of the HCl salt of the pure trans form: 35 g of fraction 5 obtained above are added in methanol with 60 g of hydrogen chloride. Upon cooling, 28 g of hydrochloride crystallize with .a melting point of 168 ° C from. The NMR analysis confirms the presence of the trans form.

2) Preparation of cis- and trans-3- (4'-tert-butylcyclohexy1-1 ') - 2-methyl-1- (3', 5'-dimethy1-1'-piperidino) -propane ,

a) 361 g of 3 ~ (p-tert-butylphenyl) -2-methyl-propanal are reacted as described in Example 1 with 200 g of 3,5-dimethyl-piperidine and 86 g of 98% formic acid. The purification of the amine is carried out by fractional distillation at a

Pressure of 0.2 mbar over a 10-plate column causes. At 136 ⁰ C go over 406 g of pure amine.

b) Hydrogenation to the Cyclohexane Compound:

In a shaking autoclave with. a reaction

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Volume of 250 ml 70 g of 3- (p-tert-butylphenyl) -2-methyl-l- (3 ', 5'-dimethyl-1'-piperidino) -propane are mixed with 80 g of dioxane. As the hydrogenation catalyst, 0.5 g of ruthenium oxide hydrate is added. At 100 bar of hydrogen and 120 ⁰ C 358 bar nachgepreßt within 37 hours.

The fractional distillation of Reaktionsaus-. inert (139.g) gives 64.g of the cyclohexanderi-,. It is distilled over at a pressure of 3 Torr between 136 "to 146 ⁰ C. Gas chromatographic analysis shows that it is an isomeric mixture of the two forms, ice and trans, of the cyclohexane derivative.

c) Fractional distillation:

562 g of the aromatic amine dissolved in 1000 g of dioxane with the aid of Ru ₂ O _3. Hydrate at I ² JO bar

₂₃ 'hydrogen pressure and at 120 ⁰ C within

Was hydrogenated for 20 hours, is separated in the fractionation through a column with 10 sieve bottom at a reflux ratio of 1: 5,

as described in Example 1. 25

The over 90 3is cis-cyclohexane derivative is at a pressure of 0.1 Torr between 124-125 ⁰ C over. The over 90 % enriched trans-cyclo

hexane derivative passes between 129-131 ° C. 30

A repetition of the fractional distillation over a 80 cm long with wire mesh netting In stocked column at a pressure of

12-13 Torr allows the extraction of 154 g 35

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of over 90 % enriched cis compound. ^Zwischen An intermediate run of 13o g consisted of a mixture of 1: 1 cis-trans-cyclohexane derivative. 93 g of trans-enriched cyclohexane derivative (enriched to over 90 %) will be recovered.

The intermediate run is used again for fractionation. Residue formation occurred only to a very small extent in the fractional distillation of the cis-trans isomeric

Mixtures are formed from 390 g only 2 g · higher boiling components. At a pressure of 12 Torr · the cis derivative between 193-195 ° C and the enriched trans product between 199-200 ⁰ C over.

d) Crystallization of the pure cis compound via the HCl salt:

20 g of the more than 90 % enriched cis- ro product are taken up in 25 g of methanolic hydrogen chloride solution, whereby the solution is heated to almost boiling. Upon cooling, 12 g of hydrochloride crystallize out (active ingredient No. 19). The melting point of the recrystallized cis-cyclohexane derivative is 24O ⁰ C.

Sample of the salt decomposed with KOH showed "to be trans-free cis compound by gas chromatographic analysis." · 30

e) Crystallization of the pure trans compound via the KCl salt:

20 g of the over 90 % enriched trans-inerts are taken up in 30 g of ethanolic hydrogen chloride solution. Upon cooling, crystalline

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Siert the hydrochloride of the pure trans-connection "by Pp = 202 ⁰ C (active ingredient Mr. 20). There are obtained 13 g. The free base, which is obtained by decomposing a sample of salt shows at gaschroraatographischen investigation that it is around

cis-free trans compounds. The NMR analyzes of the two crystals confirm the statements already obtained by the .GC analysis.

^ 3) Preparation of cis- and trans-3- (V-tert-butylcyclohexyl-1 ') - 2-methyl-1- (2', 6'-cis-dimethyl-morpholyl) -propane

a) The preparation of 3- (p-tert-butylphenyl) -2-methyl-1- (2 ', 6'-cis-dimethyl-morpholyl) -propane

carried out according to the procedure described in Example 1 by reacting 3- (p-tert-3utylphenyl) -2-methyl-propanal with 2,6-cis-dimethylmorpholine and formic acid. The cleaning of the. aromatic amine is made by distillation.

The amine is at 3.0 mbar between 17O-175 ° C over.

b) Hydrogenation to Cyclohexane Compound:

^£ 720 g of the above-described morpholine derivative

are added with 500 g of dioxane. As the hydrogenation catalyst, 0.5 g of ruthenium oxide hydrate is added. The hydrogenation is at a water pressure of 120 bar and at a temperature

^ ^{0 performed} by 140 ⁰ C. Within 24 hours

In the hydrogenation carried out in the 2,6-1-roll autoclave, a total of 130 bar of hydrogen are injected.

  22 ^ 2 74 -10- AP A 01 H / 221 274

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c) fractional distillation:

623 g of the resulting cis-trans isomer mixture, which consists of 60 % of cis and 40 % of trans compound, are in a 80 cm filled with silver wire net spirals column at a. ^D ruck fractionally from 3.0 mbar "When reflux ratio will be 1: 5th The cis-compound is between 144 to 145 ⁰ G "at 3.0 Torr. The enrichment of the cis-Yerbindung in the first three fractions each of about 70 g is performed to more than 90%, the last three fractions containing the enriched trans- Compound «71 g, 54 g and 38 g The trans proportion is over 85 % ·

d) crystallization of the pure cis- and trans-HCl salt: compartment can be the pure hydrochloride of the cis-compound with ethanolic ChI orv / ass only off solution win "Pp to the method described in Examples 1 and 2 161 ⁰ C (. Drug no. 23).

The pure trans compound forms a hydrochloride with a melting point of 199 ⁰ C (drug no. 24).

The gas chromatographic analysis, the free bases prepared from both salts by reaction with KOH, confirms the unity of the bases. The .so pre-purified cis-cyclohexane derivative contains less than 0.5 % trans product; the trans product contains less than 1 % cis compound. The NMR analysis confirms the finding of the GC analysis.

Similarly ^w else the other active ingredients are made "

') Q ! I! I in η, -,

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list R ι the active ingredients pyrrolidine active substance pyrrolidine pyrrolidine 1 pyrrolidine 2 piperidine 3 piperidine 4 5 6

Pp / Kp ⁰ C ice base Kp ₁ ^ = 177

₁ ^

trans base bp = 130 Eis HCl salt Pp 170 trans HCl salt Pp 208 ice base Kp ₁₀ = 180 trans base Kp ^ = 135

7 4-Methyl-piperidine ice base Kp _0n = 205 to

^dü 206

8 4-methyl-p-eridine trans base Kp-> = 146 to

^ 147

9 hexamethyleneimine ice base Kp _no = 151

10 hexamethyleneimine trans base Kp _n p ⁼ 153

11 3,5-dimethyl-4-

piperidone ice base Kp, "144

12 3,5-dimethyl-4-

piperidone trans base Kp-, = 148

13 4-ethyl-piperidine ice base Kp, = 157

14 4-ethyl-piperidine trans base bp = 159

15 4-ethyl-piperidine ice HCl salt Pp 214

16 4-ethyl-piperidine trans HCl salt Fp 240

17 3,5-dimethylpiperi

din ice _% Base Kp ₁₈ 195

18 3,5-dimethylpiperidinidine base

19 3,5-Diniethylpiperidi

din ice HCl SAIZ pp 240 3,5-dimethylpiperidine trans HCl SAIZ pp 202 cis-2,6-dimethylmorpholine ice base Kp ₃ = 145 Cis-2,6-dimethylmorpholine trans base Kp ₃ = 148 cis-2,6-dimethyl-inorpholine ice HCl SAIZ pp 161 cis-2,6-dimethyl-cymethylmorpholine trans HCl SAIZ pp 199

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The fungicides are particularly suitable for controlling ^"one plant diseases, such as Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoriacearum (powdery mildew) on cucurbits, Podosphaera leucotricha on apples, Uncinula necator in grapevines, Erysiphe polygoni of beans. Sphaerotheca pannosa of roses , Microsphaera querci on oaks, Botrytis cinerea on strawberries, vines, Mycosphaerella inusicola on bananas, Puccinia species (rust fungi) on cereals, Uromyces appendiculatus and U. phaseoli on beans, -Hemileia vastatrix ^ on coffee and Rhizoctonia solani.They are systematically active they are taken up via the roots as well as over the leaves and transported in the plant tissue.

In the application of the active ingredients for the treatment of plants against fungal infections, the application rates between 0.025 and 5 kg active ingredient / ha surface, For surface protection of trees or fruits, the active ingredients in conjunction with plastic dispersions 0.25 / ^ Ig to 55 »ig> based on the weight of the dispersion. The fungicides generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90 %.

The active ingredients can be mixed with other known fungicides. In many cases, this results in an enlargement of the fungicidal activity spectrum; synergistic effects also occur in a number of fungicide mixtures in the weight ratios 1:10 to 10: 1, i.e., the fungicidal activity of the combination product is greater than that of the added efficiencies of the individual components. Fungicides which can be combined with the compounds according to the invention are, for example:

Dithiocarbamates and their derivatives, such as zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate,

2 2 ί 2 7 k

- 13 - 0.2. 0050/033380

Manganese-zinc-ethylenediamine-bis-dithiocarbamate,, ⁿ

Zinkäthylenbisdithiocarbamat,

Tetrajnethylthiuramdisulfid,

Ammonia complex of zinc-CNjN-ethylenebis-dithiocarbamate) and

NjN'-Polyethylene-bis-CthiocarbainoyD disulfide, zinc (N, N'-propylene-bis-dithiocarbamate), ammonia complex of zinc-CNjN'-propylene-bis-dithiocarbamate)

UNAE

¹ ^ NjN'-polypropylene-bis-CthiocarbamoyD disulfide; heterocyclic compounds, such as

N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide,

N- (I, 1,2,2-tetrachloroethylthio) -tetrahydrophthalimide, '' 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methyloxycarbonylamino-benzimidazole, 2,3-dihydro-5-carboxanilido-6-niethyl- l, ^ - oxathiin - ^, 4- dioxide,

2,3-Dihydro-5-carboxanilido-o-methyl-1,4-oxathiin, 5-3-butyl-2-dimethylamino- ¹ -hydroxy-6-methylpyrimidine, 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-M ¹ , N'-di-ethyl-N-phenyl-sulfuric acid diamide,

2,5-Dimethy1-furan-3-carboxylic acid anilide, 2,5-dimethyl-fuΓan-3-catebo-cyclohexylamide, 2-iodobenzoic anilide,

2-Brombenzoesäureanilid,

3-nitro-isophthalic acid diisopropyl ester, 1- (1,2,4-triazolyl-1 ') - yl .- (M'-chlorophenoxy) ~ | -3,3-dimethylbutan-ii-one,

1- (1-imidazolyl) -2-allyloxy-2- (2,4-dichlorophenyl) -ethane, piperazine-1,4-diyl-bis-1- (2,2,2-trichioroethyl) -formamide,

- l4 - O. Z. 0050/032880

^ j ^> 5,6-tetrachloroisophthalonitrile: Ll,. "*

1.2 "Dimethy1-3,5-diphenyl-pyrazoliniummethylsulfat.

The application is e.g. In the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering, egg whites or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils, etc., and oils of vegetable or animal origin, aliphatic ^, cyclic and aromatic hydrocarbons, for example benzene, Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, for example, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents, eg Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration. The salts can be used in the form of their aqueous solutions.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), oil dispersions by addition of water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of 'effective substance, wetting agent, adhesive, dispersing or emulsifying agent' and possibly solvent or oil Kon¬

2 212 7 4

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• prepared for dilution with water.

Surfactants include: Alkali, alkaline earth, ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylarylsulfonates, alkylsulfates, alkylsulfonates, alkali and alkaline earth salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty alkali and alkaline earth salts, sulfated salts Hexadecanoles, heptadecanols, octadecano-Ie, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthaiine. derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonphenol, alkylphenol polyglycol ether. Tributylphenylpolyglykoläther, Alkylarylpolyätheralkohole, Isotridecylalkohol, Fettalkoholäthylenoxid-Kcndensate, ethoxylated castor oil, Polyoxyäthylenalkyläther, ethoxylated polyoxypropylene, Laurylalkoholpolyglykolätheracetal, sorbitol esters, lignin, liquors and methylcellulose.

»

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths such as silicas, silicates, talc, kaolin, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate

phat, ammonium nitrate, ureas and vegetable products,

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0.2. OO5O / O3388O

such as cereal flours, bark, hops and nutshell flour, cellulose powders and other solid carriers.

Oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoaming agents (e.g., silicones), growth regulators, antidote agents or other active compounds may be added to the mixtures or single agents.

10 trial 1

  Efficacy against wheat powdery mildew

Leaves of wheat seedlings grown in pots "Jubilar" are sprayed with aqueous emulsions of 80 % (weight percent) of active ingredient and 20 * emulsifier and dusted after drying the spray coating with oidia (spores) of wheat powdery mildew (Erysiphe graminis var. Tritici). The test plants are then placed in the greenhouse at temperatures between 20 and 22 ⁰ C and 75 to 80 % relative humidity. After 10 days, the extent of mildew fungus development is determined

t.

25

35

active substance

Infestation of the leaves after spraying with xiger active ingredient broth

0.006 0.003 0.0015 0.0007

9 (cis form) 0 2 5 3 3 10 (trans-form) 0 0 0 0 23 (cis-shape) · 0 2 2-3 2-3 30 24 (trans-form) 0 0 0 · 0 Control (untreated)

0 =. no infestation, graded to 5 = total infestation

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Trial 2

20 25

Efficacy against wheat brown rust

Leaves of potted wheat plants are artificially infected with spores of the wine brown rust (Puccinia recondita) and placed for 48 hours at 20 to 25 ⁰ C in a water vapor-saturated chamber. Thereafter, the plants are sprayed with aqueous spray liquors dissolved or emulsified in the water containing a mixture of 80 % of the active substance to be tested and 20 % sodium lignosulfonate and in the greenhouse at temperatures between 20 and 22 ° C. and at 75 to 80 %. relative humidity. After 10 days, the extent of rust fungus development is assessed.

active substance

Infestation of the leaves after spraying with x2iger active ingredient broth

0.012 0.006 0.003 0.0015

χ =

5 (cis form) 2-3 5 2-3 • 2-3 0 4 4 3 4-5 6 (trans-form) 0 0 0 2 11 (cis form) 2 2-3 3 4 12 (trans-form) 0 0 0 0 21 (cis form) 2 3 5 5 22 (trans-form) 0 0 0 2 23 (cis form) 3 5 24 (trans-form) 0 0 Control (untreated)

0 = no infestation, graded to 5 = total infestation 30

Exemplary embodiments Example 1

90 parts by weight of compound 10 are mixed with 10 parts by weight.

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^r weight parts of N-methyl pyrrolidone and a solution is obtained, ^"1 which is suitable for application in the form of microdrops.

Example 2

20 parts by weight of compound 6 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium

IQ salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of ¹ JO mol ethylene oxide to 1 mol of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 percent by weight of the active ingredient

Contains J5.

Example 3

20 parts by weight of compound 12 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 adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 weight percent of the active ingredient.

Example 4

, ,

20 parts by weight of compound 22 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a .Mineralölfraktion boiling 210 to 28O ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and

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to finely distribute 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

20 parts by weight of the active ingredient 6 are mixed with 3 parts by weight of

  17 parts by weight of the sodium salt of diisobutylnaphthalene-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water to obtain a spray mixture containing 0.1 percent by weight of the active ingredient.

Example 6

3 parts by weight of compound 12 are intimately mixed with 97 parts by weight of finely divided kaolin. Obtained in this way a dust containing 3 percent by weight of the active ingredient.

Example 7

30 percent by weight of the compound 22 v / erden with a mixture of 92 parts by weight of powdered silica gel

  and 8 parts by weight of paraffin oil, which has been sprayed onto the surface of this silica gel, intimately mixed. This gives a preparation of the active substance with good adhesion.

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Example 8

40 parts by weight of the active compound 6 are intimately mixed with 10 parts of sodium salt of phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of V / asser. 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

 1G

Example 9

20 parts of the active ingredient 4 are intimately mixed with 12 parts of calcium dodecylbenzenesulfonic acid, 3 parts of polyhydric alcohol polyacetyl ether, 2 parts of sodium salt of a phenolsulfonic urnst'offrformaldehyd condensate and 68 parts of a paraffinic mineral oil. This gives a stable oily dispersion.

Claims (1)

22 1274 - 21 - O. Z. 0050/033330 * Invention claim A fungicidal composition characterized by a content of a solid or liquid carrier and a trans compound of the formula CH ₃ -C · / VCH ₂ -CH-CH ₂ -R CH ₃ ' in which R is the radical of a nitrogen-bonded saturated 5-, 5- or 7-membered nitrogen-containing heterocyclic radical which is optionally monosubstituted or polysubstituted by methyl and which optionally in the 4-position to the nitrogen atom instead of the methylene radical is an oxygen atom or den C = 0 radical, or the salts of the trans compound.