DE2224244A1 - NEW TRIAZINOBENZIMIDAZOLE - Google Patents

Description

New rfriazinobenzimidazoles The invention relates to triazinobenzimidazoles of the formula in which R is an optionally branched alkyl group with 1 to 18 carbon atoms, an optionally branched alkenyl group with 3 to 18 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, which is also replaced by one or more alkyl groups with 1 to 4 C atoms or the hydroxyl group can be substituted, a radical of the formula (Trocyclo- [5,2,1,02,6] -decyl) a phenalkyl or diphenylalkyl group each having 1 to 6 carbon atoms in the alkylene radical, in which the phenyl nuclei are substituted by halogen, lower alkyl, lower alkoxy or lower alkylthio can, a phenyl or naphthyl group, which can be substituted by lower alkyl, halogen, lower haloalkyl, hydroxy, lower alkoxy, phenoxy or lower alkylthio, a hydroxyalkyl, alkoxyalkyl, polyalkoxyalkyl, alkylmercaptoalkyl, dialkylphosphinylalkyl, furfuryl , Morpholinoalkyl, pyrrolidinoalkyl, piperidinoalkyl or carbalkoxyalkyl groups with 2 to 12 carbon atoms can mean.

The invention also relates to a process for the preparation of compounds of the formula I, which is characterized in that 2-methoxycarbonylamino-benzimidazole of the formula TI with a primary amine of the formula Xl2NR (III) and formaldehyde.

A preferred embodiment of the method is that the 2-methoxycarbonylamino-benzimidazole (ii) is suspended in a solvent or dissolves, adding the molar to twice the molar amount of the amine and stirring adding twice to four times the molar amount of aqueous formaldehyde solution. One works preferably at temperatures of 0-800C, in particular 200-400, but is the temperature range is not critical.

The reaction product normally goes into solution and can in this Separated solution of any 2-methoxycarbonylamino-benzimidazole still present will. By concentrating and treating the residue with an inert solvent such as gasoline or by reprecipitation, e.g. B. from methylene chloride / gasoline, the triazinobenzimidazole can be isolated in pure form.

The reaction also takes place when a deficit of formaldehyde is used with formation of the end product I.

Among the amines of the formula III, preferred reactants are those in which R represents a straight-chain or branched alkyl group with 1 to 15 carbon atoms, or an alkenyl group with 3 to 18 carbon atoms, or a cycloalkyl group with 3 up to 12 carbon atoms, which are also represented by an alkyl group with 1 to 4 Carbon atoms, in particular substituted by a methyl or ethyl group, as well as the Tricyclodecyl group or the phenyl or naphthyl group, one with methyl, ethyl, tert-butyl, chlorine or hydroxy monosubstituted or disubstituted phenyl or naphthyl groups, a phenalkyl group with 7 to 9 carbon atoms, in particular the benzyl group or diphenylalkyl group with 13 to 14 carbon atoms, in which the phenyl group with substituents such as chlorine or Methyl, or an alkoxy or dialkoxyalkyl or alkyl mercaptoalkyl group with 3 to 8, in particular -3 to 4 * carbon atoms or a hydroxyalkyl group with 3 to 7, in particular 3 to 6 carbon atoms, an alkylphosphinylalkyl group with 3 to 9 carbon atoms, in particular 3 to 5 carbon atoms, a morpholino-alkyl group with 5 to 8, in particular with 6 or 7 carbon atoms or a carbalkoxy group with 3 to 12, in particular 4 to 8 carbon atoms.

In addition to the amines used in the examples are accordingly exemplary the following amines are suitable: isoamylamine, iso-octylamine, nonylamine, n-decylamine, iso-decylamine, n-undecylamine, pentadecylamine, hexadecylamine, octadecylamine, n-octadecen-9-ylamine, Cyclobutylamine, 2-methylcyclopentylamine, 3-aminohexahydrotoluene, 4-amino-hexahydro-mxylene, 4-isopropyl-cyclohexylamine, 4-ethylcyclohexylamine, 2,6-diethylaniline, 4-tert.-butylaniline, 2-, 3- and 4-chloroaniline, -2-, 3- and 4-aminophenol, α- and ß-naphthylamine, 3-phenylpropylamine, 2-phenylethylamine, 4-phenyl-butylamine, diphenylmethylamine, 2,2-diphenylethylamine 2-, 3- and 4-chlorobenzylamine, 2- (2L-chlorophenyl) -ethylamine, 2-, 3- and 4-methylbenzylamine, 2-ethylthioethylamine, 4-methylthiobutylamine, 1- and 4-amino-hexanol, dimethyl- (2-aminoethyl ) phosphine oxide, diethyl (4-aminobutyl) phosphine oxide, N-aminomethyl morpholine, N- (3-aminopropyl) morpholine, N-aminoethyl-pyrrolidine, N-aminomethyl- and N-aminoethylpiperidine, furfurylamine, Aminoacetic acid methyl and ethyl ester, 2-aminopropionic acid methyl ester, 3-aminobutyric acid ethyl ester, 6-Amino-caproic acid methyl and ethyl ester, alanine methyl ester : 7 ^ - Aminovaleric acid methyl tar, 7-Aminoval eric acid ethyl ester, 4-methoxy-benzylamine, 4-tert-butyl-cyclohexylamine, 2-amino-1,3,5-trimethyl-benzene, 2-amino-butane, 2-ethylhexylamine, n-tridecylamine and tetradecylamine, iso-tetradecylamine.

As the solvent for the reaction are particularly moderate or weak polar solvents, preferably those with low boiling points, can be used, such as methylene chloride, chloroform, carbon tetrachloride, benzene; Ether like diethyl ether, Diisopropyl ether and tetrahydrofuran; Esters such as methyl acetate and ethyl acetate or Ketones such as acetone or methyl ethyl ketone.

Chloroform or methylene chloride is preferably used.

The 2-methoxycarbonylamino-benzmidazole can according to the in J. Am.

Chem. Soc. 56, 144 (1934) described method by implementing o-Phenylenediamine produced with S-methyl-iso-thiourea-dicarboxylic acid dimethyl ester will. The preparation of the amines required for the reaction is also known from the literature.

The claimed compounds are characterized by fungicidal, in particular systemic effect, so that with their help also those already in the herbal Fungal pathogens that have penetrated tissue can be combated curatively. This is especially important for those fungal diseases that have a long incubation period and not after infection with the usual fungicides more can be fought.

The spectrum of activity of these compounds is very broad and covered a number of important fungal pathogens that are found in fields, fruit, wine, Hops, horticulture and ornamental plants play an important role and of which only a few should be mentioned such as B. Fusicladium, Gloeosporium, Cylindrosporium, Botrytis, Verticillium, Cercospora, Septoria, Mycosphaerella, Cladosporium, Colletotrichum, Rhizoctonia, Fusarium, Cercosporella, Ustilagi, neen, Erysiphaceen, Aspergillaceen, Sclerotinaceae.

They also own a number of them - especially those with long-chain residues R - an excellent effect against Phycomycetes such as Peronospora and Phytophtora species.

Their degree of effectiveness corresponds to that of the active ingredients from the group of Metal salts of dithiocarbamids or trichloromethylthio-phthalimide derivatives and is sometimes even superior to them.

The claimed compounds can also be used to protect stored Fruit and vegetables are used against fungal attack (e.g. Fusarium penicillium species, etc.) will.

In addition, they are suitable for use in the technical area z. B. to protect textiles, wood, dyes and paints against attack with rotting and other fungal organisms.

The subject of the invention are therefore also pesticides, especially fungicidal agents containing the triazinobenzimidazoles of the general Formula 1 as active ingredients, preferably in concentrations of 2 to 95 Vo, in the usual mixtures with solid or liquid inert carriers, adhesive, wetting, Contain dispersing and / or grinding aids.

They can be used as wettable powders, emulsions, suspensions, or dusts Granules are used. They can also be mixed with other fungicides, with which they form compatible mixtures.

Mineral substances such as aluminum silicates can be used as carrier substances. Clays, kaolin, chalks, pebble earths, talc, kieselguhr or hydrated Silicic acid or preparations of these mineral substances with special additives, e.g. chalk greased with sodium stearate.

All common carriers can be used as carriers for liquid preparations and suitable solvents, for example toluene, xylene, diacetone alcohol, cyclohexanone, Isophorone, gasoline, paraffin oils, dioxane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, Tetrahydrofuran, chlorobenzene and others can be used.

Glue-like cellulose products or polyvinyl alcohols are used as adhesives into consideration.

All suitable emulsifiers such as oxyethylated can be used as wetting agents Alkylphenols, salts of aryl or alkylarylsulfonic acids, salts of oleylmethyltaurine, Salts of oxethylated phenylsulfonic acids or soaps can be used.

Cell pitch (salts of lignosulfonic acid) are suitable as dispersants, Salts of naphthalenesulfonic acid or salts of oleylmethyltaurine.

Suitable inorganic or organic 1-cal grinding aids can be used Salts such as sodium sulfate, ammonium sulfate, sodium carbonate, Sodium bicarbonate, Sodium thiosulfate, sodium stearate or sodium acetate can be used.

The compounds of formula 1 also have an anthelmintic effect in veterinary medicine Sector.

The following production and use examples illustrate the Invention: A) PREPARATION EXAMPLES Example 1: 57.3 g (0.3 mol) 2-methoxycarbonylamino-benzimidazole are suspended in 550 ml of methylene chloride, 55.5 g (0.3 mol) of dodecylamine are added and the mixture is heated to 350.degree. At this temperature 68 ml (0.8 mol) of 35% strength aqueous formaldehyde solution are added dropwise with stirring. The mixture is then stirred for 1 hour at 3800, then allowed to cool while stirring.

The unreacted 2-methoxycarbonylaminobenzimidazole is filtered off with suction (after drying 4 g), the aqueous layer is separated and the methylene chloride solution dried over magnesium sulfate.

After concentration, 122.7 g of a crystalline substance of melting point are obtained. 75 ° C.

To remove any still adhering amine, the mixture is stirred with 200 ml of gasoline (30/850 ° C.) and 95 g (79% of theory) of l-methoxycarbonyl-3-dodecyl-s-hexahydro-triazino-benzimidazole of melting point 860 - 87 ° C.

C23H35N4O2 MW 400 calculated: C 69.0; H 9.0%; N 14.0% Found: C 69.3%; H 9.2%; - N 14.0% In the infrared spectrum the compound has a characteristic c>.

Carbonyl absorption at 1720 cm 1, as well as double bond bands at 1620 cm 1 and 1595 cm 1.

Example 2: 38.2 g (0.2 mol) of 2-methoxycarbonylamino-benzimidazole are used suspended in 600 ml of chloroform, mixed with 14.6 g (0.2 mol) of n-butylamine and heated to 35 ° C. At this temperature, 68 ml (0.8 mol) of 35% strength are added with stirring aqueous formaldehyde solution was added dropwise.

The mixture is then stirred at 380 ° C. for 1 hour. The benzimidazole goes with reaction in solution. It is lapped to cool, the aqueous layer is separated off and dried the organic phase over magnesium sulfate.

After filtering and concentrating, an oil is obtained which, after rubbing out solidifies with n-hexane.

Yield: 41 g (71% of theory) of l-methoxycarbonyl-3-n-butyl-shexahydro-triazino-benzimidazole. Mp 109 ° C.

C15H20N4O2 MW 288 calc .: C 62.5%; H 6.94%; N 19.45% found: C 62.8 %; H 7.2%; N 19.5% In the infrared spectrum, the compound has carbonyl absorption at 1745 cm 1, as well as double bond bands at 1620 cm 1 and 1595 cm 1.

Example 3: 57.3 g (0.3 mol) of 2-methoxycarbonylamino-benzimidazole become suspended in 900 ml of methylene chloride, with 26.7 g (0.3 mol) of 3-methoxypropylamine added and heated to 35 ° C.

At this temperature, 68 ml (0.8 mol) of 35% strength are added with stirring aqueous formaldehyde solution was added dropwise. The mixture is then stirred at 38 ° C. for 1 hour.

After cooling, a small amount remains unreacted Starting benzimidazole filtered off. The aqueous phase is separated off and the methylene chloride solution dried over magnesium sulfate.

After filtering and concentrating, an oil is obtained that can be rubbed in when rubbed solidifies with n-hexane.

Yield: 63 g (69% of theory) of 1-methoxycarbonyl-3- (3'-methoxypropyl) -s-hexahydro-triazino-benzimidazole. M.p. 730-710C.

C15H20N4O3 MW 304 calcd .: C 59.2; H 6.6%; N 18.7% found: C 59.3%; H 6.9%; N 18.7% In the infrared spectrum, the compound has carbonyl absorption at 1750 and 1600 cm 1.

The substances of the formula listed in the following table were presented analogously to Examples 1 to 3. Tabel Bespj ~ el R Fp. OC 4 -CH, 138 5 -C2Ha 167-168 6 -c, H, (n) 150-132 7 -c, H, (iso) 7 -C3H; (iso) 112-114 8 -CH-CH = C 106-108 9 --c (CH, 113 . . B ~ ~ 10 6 3-r-: PJ 2 $ CH) 11 -C4 Hg (iso) 138 .12 1-78 13th not 14 -C3H27 (iso) distilling cash 0e1 15 -C6H15 (n) 75-76 Example game OC 16 17 -OH2 -0H-CH OH , CH, OH 18 -CH 128-130 cw, -CH, 19 - (CH, -OH 86-88 19 - (CH2) 5-oH 86-88 20-130-132 20 \ I 21 L 16Ci 22nd 15ci-156 25c '171 24 ~, 145-146 i4 145-146 2 - (CH,), -S-CH, 107-109 26 - (CH2) 3-S-cHs 120-121 27 ~ (CH2) sO ~ c2H5 84-85 28 ~ (CH2) z ~ ° ~ C5 4 66-67 Example ~ ~ C 29 - (FH2) 2- 66-x68 So -CH2-CE2 40-45 -CB2- 3 m 31 A dest hard oil Sa - (CH, 3, -C, TOC, H, sic ~ -OC2H; not iH des-tlix, - de bares Oe3 ~ 33 -C,. ,,. 7th 33 -C7His (n) 73-74 34 <118-120 34 Ül 118-120 35 = I i37-154 CH, ÜÄ. ~ ~ CH3 CH3 36 - CH2-C-CHa 151-152 CH5 CH3 - (OH2) sN 37 -CH () CH2 12 6 \ (CH2 38 - (CH2) aO-cHa 99 ,. . ~. . . . 39 (n) <~,,. ~ 40 -C9H19 (n) Example R OC not 41 - (CH,), -OC, H, des-tillier- hard oil 0 cm, 42 - (OH2 OH3 126-127 OH5 43 CH, 152-153 44½ 112-114 H, C H »C I 55-56 . t ~ 46 -½ 196-197 ~ ~ - 1r8-159 .. ~ r ~. ,. , ~ 48 -ch 77-19 48 -CH 77-79 \ (CH2) 2-coocH3 B) AIXnTENDUNGgSBEISPIBLE Example I: Cucumber plants were grown in pots and in the 2-leaf stage with aqueous suspensions of the compounds according to Examples 4, 5, 6, 7, 8, 9, 2, 10, 11, 12, 13, 1, 14, 15 to runoff treated. New growth of the plants and soil were carefully covered with plastic sleeves before treatment so that they were not hit by the spray mixture.

The application concentrations were 2000, 1000, 500, 250 and 125 mg active ingredient / liter spray liquid. Benomyl (1-N-butyl-carbamoyl-2-methoxycarbonylaminobenzimidazole) was used as a comparison agent.

After the spray coating had dried on, the protective sleeves were removed and put the plants in a greenhouse. As.

the plants had developed the 4th - 5th leaf, they became with conidia of cucumber powdery mildew (Erysiphe cichoracearum) strongly infected and then in a humidity chamber set at 220C and relative humidity of 100 / o. After a residence time of 24 hours, the plants were placed in a greenhouse with high relative humidity (80 - 90 / o) and a temperature of 220 - 230C Here they stayed until the outbreak of the disease.

-The infection evaluation was carried out as usual on the basis of visual inspection. Of the Degree of infestation was expressed in% of infested leaf area compared to untreated, infected control.

As can be seen from the result in Table I, the claimed Compounds have an excellent systemic effect, which the comparison agent clearly is superior.

Example II: Garden soil was with the invention, in Example I mentioned compounds in the application rates of 10, 5, 2.5, 125, 0.6 'and 0.3 mg Active ingredient / kg soil is well missed for 10 minutes in a shaking machine. As a means of comparison Benomyl was used at the same application rates as the test preparations.

The soil treated in this way was poured into pots and each with 10 Grains of winter wheat of the Heine VII variety sown and germinated in a greenhouse brought with high humidity and a temperature of 22 ° C. Avenge the emergence of wheat, the plants were at the 4-5 leaf stage with conidia of wheat powdery mildew (Erysiphe graminis) heavily infected. After an incubation period of 14 days were the plants examined for powdery mildew infestation by visual inspection. The degree of infestation was expressed in% of infected leaf area compared to untreated, infected Control plants.

As can be seen from the test result in Table II, have the claimed compounds have excellent systemic activity and are significantly more effective than the comparison medium.

Example III: Sugar beet plants were in the 6-leaf stage with conidia of the causative agent of leaf spot disease - (Cercospora beticola) strongly infected and dripping wet in a climatic chamber with 2500 and a relative humidity of 100 % posed.

They stayed there for 24 hours and were then put in a greenhouse with a relative humidity of 85 - 90% and a temperature of 240 - Brought to 250C. After a Infection time of 7 days were the Plants with aqueous suspensions of the compounds mentioned in Example I are dripping wet treated.

The application concentrations were 60, 30, 15 and 7.5 mg / liter Spray mixture. As a comparison agent, Benomyl in the same application concentrations.

After the spray coating has dried on, the plants are moved to the greenhouse brought back. After an incubation period of 3 weeks, the plants were raised Infestation with leaf spot disease examined. The infestation evaluation was carried out after inspection. The degree of infection was expressed in terms of leaf area infected based on untreated, infected control plants.

As can be seen from the result in Table III, the claimed have Compounds have an excellent curative effect, which is better than that of the comparison agent.

Example IV: Tomato plants were grown in the fully grown 3-leaf stage heavily infected with conidia of the brown spot disease of the months (Cladosporium fulvum) and dripping wet one day in a climatic chamber with 2500 and a relative humidity set by 100%. Then they were put in a greenhouse with a relative humidity of 85 - 90% and a temperature of 230 - 25 ° C. After a period of 7 days the plants were with aqueous suspensions of the compounds according to Example 16, 17, 18, 19, 20, 21, 22, 23, 24 in the concentrations of 60, 30, 15 and 7.5 mg / liter Treated spray mixture, Benomyl was used as a comparison agent.

After the spray coating had dried on, the plants were moved to the laundry house brought back and after an incubation period of 21 days for infestation with brown spot disease examined. As usual, the infestation rating was based on visual inspection. The degree of infestation was expressed in% infected leaf area based on untreated, infected Control plants.

As can be seen from the test result in Table IV, the claimed compounds an excellent, superior to the comparative agent, curative effectiveness against brown spot disease in tomatoes.

Example V: Wheat plants were grown in pots and in the 2-leaf stage treated to runoff with the compounds mentioned in Example IV. The application concentrations were 2000, 1000, 500, 250 and 125 mg / liter of spray mixture. As a means of comparison Benomyl was used in the same active ingredient concentrations as the test preparations.

After the active substance coating had dried on, the plants were in a Brought to the greenhouse and remained there until the 4th and 5th leaves were formed. At this stage the plants were infected with conidia of wheat powdery mildew (Erysiphe graminis) and the temperature of the greenhouse to 220 - 23 ° C, the Relative humidity set to '80 - 90 ffi to ensure optimal infection conditions for creating wheat powdery mildew.

After an incubation period of 10 days, the plants were tested for powdery mildew examined. The infestation rating was carried out on the basis of visual inspection. The degree of infestation was expressed in infested leaf area based on untreated, infected control plants.

The result is given in Table V and shows that the claimed Compounds have a very good systemic effect and the powdery mildew infestation is stronger reduce than the comparison mean.

Example VI Winter wheat of the Heine VII variety was mixed with the in Example IV compounds mentioned and benomyl in the application rates of 200, 100, 50 and 25 g of active ingredient per 100 kg of seed for 10 minutes in a shaker evenly pickled.

Then the dressed seeds were repeated 5 times Place 10 grains each in earth pots and put them in a greenhouse to germinate.

When the plants had developed the 4th and 5th leaves, they became heavily infected with conidia of wheat powdery mildew (Erysiphe graminis) and the greenhouse to a relative humidity of 80 - 90-ç0 and a temperature of 220 - 23 ° C set.

After an incubation period of 10 days, the plants were infected examined with powdery mildew and the degree of infestation in% of the infested leaf area based on untreated infected control plants expressed.

The result in Table VI shows -daP the claimed compounds have a very good systemic effect and better prevent powdery mildew infestation as the means of comparison.

Example VII: Wheat plants of the cultivar Heine VII were grown in the 3-leaf stage infected with conidia of wheat powdery mildew (Erysiphe graminis) and 3 days after the Infection, with aqueous suspensions of compounds according to Example 25, 26, 3. 27, 28, 29, 30, 51, 32 treated drip hatred. The application concentrate amounts to 1onn 120, 60, 30 and 15 mg of active ingredient / liter of spray liquor Benomyl was used as a comparison agent in the same active ingredient concentrations.

After the active substance coating had dried on, the plants were in a Greenhouse with a relative humidity of 80 - 9Q and a temperature brought from 22a - 23 ° C.

10 days after treatment, the plants were visually examined for wheat powdery mildew infestation. The degree of infestation was expressed in% infected leaf area based on untreated, infected control.

The result of the experiment is given in Table VII.

It emerges from it that the compounds claimed are clearly one have better action against powdery mildew than the comparison agent.

Example VIII: Cucumber plants were in the 2-leaf stage with aqueous Suspensions of the compounds mentioned in Example VII in the use concentrations of 2000, 1000, 500 and 250 mg of active ingredient / liter of spray liquor treated dripping wet, whereby the new growth and the floor are carefully covered with plastic sleeves were that they were not hit by the spray liquid.

Again, benomyl was used as a comparison agent.

After the active substance coating had dried on, the plants came into a Greenhouse and remained there until they had developed the 4th leaf. In this All plants, including untreated control plants, were at stage Cucumber powdery mildew (Erysiphe cichoraccarum) conidia are heavily infected and in a Climatic chamber with 22 ° C and a relative humidity of 100% set ach The plants were in a greenhouse with high humidity and for 24 hours brought to a temperature of 220-23 ° C. After an incubation period of 10 days the plants were examined for cucumber powdery mildew infestation. The degree of infection was expressed in% of infected leaf area based on untreated, infected control plants.

As can be seen from the result in Table VIII, the claimed Compounds have excellent systemic effects and are more effective than that Comparison means.

Example IX: Rice plants were grown in the 4-leaf stage with Piricularia oryzae strongly infected and then placed in a climatic chamber with 250C and a relative Air humidity of 100% given.

After incubation for 24 hours, the plants were placed in a greenhouse with a relative humidity of 85 - 90% and a temperature of 250 - 26O 'brought.

4 days after infection, the plants are treated with those in example VII mentioned compounds in the application rates of 60, 30, 15 and 7.5 mg active ingredient / liter Spray liquid treated dripping wet.

Benomyl was used as a comparison agent in the same active ingredient concentrations like the investigational drugs.

After the spray coating had dried on, the plants were moved to the greenhouse returned after an incubation period of 14 days for infestation with Piricularia oryzae examined visually. The degree of infection was expressed in% more infected Leaf area compared to the untreated, infected control.

As can be seen from the result in Table IX, the claimed Compounds have an excellent curative effect and are more effective than the comparative agent.

Example X: Vine plants which are susceptible to peronospore from cuttings Cultivar Müller-Thurgau were grown in the 4-leaf stage with aqueous suspensions of the compounds according to Example 15, 12, 13, 1, 14 treated to runoff. The application concentrations were 500, 250, 125 and 60 mg of active ingredient / liter of spray mixture. As a means of comparison Benomyl (comparative agent I) and Eolpet (N- (trichloromethylthio) -phthalimide were used; Comparative agent II) in the same active ingredient concentrations as the test preparations.

After the spray coating had dried on, the plants were treated with a Zoosporangia suspension of Peronospora viticola heavily infected and dripping wet in a climatic chamber at a temperature of 200C and a relative humidity set by 100%. After 24 hours, the infected plants were placed in the climatic chamber taken and placed in a greenhouse with a temperature of 23 ° C and a humidity brought from 80 - 90%.

After an incubation period of 7 days, the plants were: moistened Placed in the climatic chamber overnight, causing the disease to break out. The evaluation of the infestation was carried out on the basis of visual inspection. The degree of infestation was in% infected leaf area compared to the untreated, infected control plants and is shown in Table X. As can be seen from this, own the claimed compounds an excellent, equivalent to the comparative product Folpet, partly superior effectiveness.

The comparison agent Benomyl, on the other hand, shows, as was to be expected, no effect against downy mildew.

Example XI: Vine plants obtained from cuttings of the Müller-Thurgau variety were drawn in the 4-leaf stage with the compounds mentioned in Example X. Treated soaking wet. The application concentrations were 20, 10, 5 and 2.5 mg Active ingredient / liter of spray liquid. Benomyl and Folpet in were used as comparison agents the same active ingredient concentrations as the test preparations.

After the active ingredient was dried on, the plants were placed in a greenhouse with a relative humidity of 85 - 90 ffi and a temperature of 230 - Brought to 250C and strong with conidia of powdery mildew of the vine (Oidium tuckeri) infected.

After an incubation period of 14 days, the plants die for infestation examined with Oidium and the degree of infection in / 3 infected leaf area in comparison printed out on untreated, infected control plants.

As can be seen from the result in Table XI, the claimed have Compounds have an excellent effect against oidium of the vine, which is better than the comparison agent Benomyl. The comparative remedy Folpet has a noticeable, however completely inadequate effect on Oidium of the vine, for example tomato plants of the variety Rhineland Ruhm were in the 3-leaf stage with those mentioned in Example X. Connections treated soaking wet. The application concentrations were 500, 250, 120 and 60 mg of active ingredient liters of spray liquid. Benomyl was used as a comparison agent (Comparative agent I) and Zineb (zinc ethylene bisdithiocarbamate; comparative agent II).

After the spray coating had dried on, the plants were treated with a Zoosporangia suspension of Phytophthora infestans heavily infected - and one day long dripping wet in a climatic chamber at a temperature of 1500 and a relative 100% humidity. They were then placed in a cold greenhouse with a temperature of 1500 and a relative humidity of 85 - 95%.

After an incubation period of 7 days, the plants were infected examined with Phytophthora after visual inspection.

The degree of infestation was expressed in ffi infested leaf area im Comparison with untreated, infected control plants.

As can be seen from the Brresult in Table XII, the claimed have Compounds have an effectiveness that is partly clearly superior to the comparative agent Zineb. As was to be expected, the comparison agent Benomyl has no effect against Phytophthora infestans.

Table I Compound% leaf area infested with cucumber powdery mildew according to mg active ingredient / liter spray mixture Example 2000 1000 500 250 125 4 ° 0 5 10 15 5 0 0 3 12 18 6 0 0 5 10 16 7 0 0 5 12 18 8 0 0 5 10 15 9 0 0 3 10 18 10 0 0 5 12 15 2 0 0 5. 1.0 15 11 0 3 8 12 12 0 0 0 5 10 13 0 0 0 5 10 1 0 0 0 5 10 14 0 0 5 10 12 15 0 0 3 5 10 Benomyl 0 5 8 15 20 Control plants 100 100 100 100 100 (untreated) Tabel II compound% leaf area infested with wheat powdery mildew according to mg active ingredient / kg Earth example 10 5 2.5 1.25 0.6 0.3 4 0 0 0 5 12 25 5 0 0 0 5 15 20 6 0 0 0 5 12 20 7 0 0 0 5 10 .20 8 0 0 0 5 10 25 9 0 0 0 5 12 20 2 0 0 0 5 10 20 10 0 0 0 5 12 18 11 0 0 0 5 10 15 12 0 0 0 0 5 12 13 0 0 0 0 5 10 1 0 0 0 0 3 10 14 0 0 0 3 5 12 15 0 0 0 5 8 15 Benomyl 0 3 5 10 20 35 Control plants 100 100 100 100 100 100 (untreated) Table III Compound% Cercospora Infested Leaf area at mg of active ingredient / liter of spray liquor Example 60 30 15 7.5 4 0 0 8 15 5 0 0 8 15 6 0 0 5 10 7 0 0 5 10 8 0 0 5 12 9 0 0 8 15 2 0 0 5 10 10 0 0 5 12 11 0 0 8 12 12 0 0 5 10 13 0 0 3 8 1 0 0 0 5 14 0 0 5 10 15 0 0 8 15 Benomyl 0 3 15 20 control plants 100 100 100 100 (untreated) Tabel IV compound% Cladosporium infected leaf area at mg active ingredient / liter Spray mixture example 60 30 15 7.5 16 0 0 5 10 17 O 0 5 10 18 0 0 3 12 19 0 0 5 10 20 0 0 8 15 21 0 0 5 10 22 0 0 8 15 23 0 0 5 12 24 0 0 8 15 Benomyl 5 12 20 28 control plants 100 100 100 100 (untreated) Table V Compound% infestation with powdery mildew at mg active ingredient / according to liter spray liquor Example 2000 1000 500 250 125 16 0 0 5 10 18 17 0 0 3 8 15 18 0 0 0 10 15 19 0 0 0 5 12 20 0 0 0 8 15 21 0 0 0 5 10 22 0 0 0 5 12 23 0 0 0 3 10 24 0 0 0 5 15 Benomyl 0 3 8 15 28 Control plants 100 100 100 100 100 (untreated) Table VI Compound% powdery mildew after seed treatment with according to g active ingredient / 100 kg seed Example 200 100 50 25 16 0 ° ° 5 12 17 0 0 5 10 18 0 0 3 10 19 0 0 0 5 20 0 0 5 10 21 0 0 0 5 22 0 0 3 8 23 0 0 0 5 24 0 0 3. 10 Benomyl 0 5 10 18 Control plants 100 100 100 100 (untreated) Table VII Compound% wheat powdery mildew infestation at mg active ingredient / according to Liters of spray liquid Example 120 60 30 15 25 0 0 0 8 26 0 0 5 10 3 0 0 3 8 27 0 0 5 10 28 0 0 5 8 29 0 0 8 10 30 0 0 5 10 31 0 0 5 8 32 0 0 3 5 Benmoyl 0 5 8 15 control plants 100 100 100 100 (untreated) Table VIII Compound% Cucumber mildew infestation at mg of active ingredient / according to liters of spray mixture Example 2000 1000 500 250 25 0 o 5 15 26 o o 8 15 3 o 0 3 10 27 0 0 5 10 28 0 0 5 10 29 o o 8 15 30 ° ° 3 10 31 o o 3 10 32 0 0 5 12 Benomyl 3 10 15 28 Control plants 100 100 100 100 (untreated) Table IX Compound% Piricularia infection at mg active ingredient / according to liter of spray mixture Example 60 30 15 7.5 25 o o 3 10 26 0 0 5 12 3 0 0 3 10 27 0 0 5 15 28 o o 3 12 29 0 o 8 -18 30 0 0 5 18 31 o o o 5 32 0 0 3 10 Benomyl 0 5 18 25 control plants 100 100 100 100 (untreated) Table X Compound% Peronosporabfall at mg of active ingredient / according to liters of spray liquor Example 500 250 125 60 15 0 3 5 10 12 0 .0 0 5 8 13 O, 0 3 5 1 0 0 0 3 14 0 0 3 8 VM 1 100 100- 100 100 VM II 0 3 5 10 Control plants 100 100 100 100 (untreated) Table XI Compound% Oidium attack of the vines at mg active ingredient / according to liters of spray mixture Example 20 10 5 2.5 15 0 0 8 15 12 0 0 5 15 13 0 0 0 8 1 0 0 0 8 14 0 0 5 12 VM I 0 8 15 23 VM II 65 80 100 100 control plants 100 100 100 100 (untreated) Table XII Compound% Phytophothora infestation at mg active ingredient / according to liter spray liquor Example 500 250 120 60 15 o 0 0 5 13 12 0 0 5 10 13 0 0 5 8 1 ° 0 3 5 14 0 3 5 10 VM I 100 100 100 100 VM II 0 3 5 12 control plants 100 100 100 100 (untreated)

Claims (5)

Claims 1) Triazinobenzimidazoles of the general formula in which R is an optionally branched alkyl group with 1 to 18 carbon atoms, an optionally branched alkenyl group with 3 to 18 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, which is also replaced by one or more alkyl groups with 1 to 4 carbon atoms Atoms or the hydroxyl group can be substituted, a radical of the formula (Tricyclo- [5,2,1,0,2,6] -decyl) a phenalkyl or diphenylalkyl group each having 1 to 6 carbon atoms in the alkylene radical, in which the phenyl nuclei are substituted by halogen, lower alkyl, lower alkoxy or lower alkylthio can be substituted, a phenyl or naphthyl group which can be substituted by lower alkyl, halogen, lower haloalkyl, hydroxy, lower alkoxy, phenoxy or lower alkylthio, a hydroxyalkyl, alkoxyalkyl, polyalkoxyalkyl, - - - -, -yi - -Alkylmercaptoalkyl, dialkylphosphii / alkyl, furfuryl-morpholinoalkyl, pyrrolidionoalkyl, piperidinoalkyl or carbalkoxyalkyl groups with 2 to 12 carbon atoms can mean. 2) Process for the preparation of triazinobenzimidazoles of the formula I, characterized in that 2-Nethoxycarbonyiamino-benzimidazole with a primary amine of the formula H2Ns-R, and formaldehyde. 3) Method according to claim 2, characterized in that at least 2 moles of formaldehyde used. 4) Pesticides, characterized by their content of triazinobenzimidazoles of the formula I as active ingredients in a mixture with customary auxiliaries and carriers. 5) Pharmaceutical preparations, characterized by a content of a benzimidazole of the formula I as the active ingredient.