DE2233292A1 - Dialkyl 1,1'-(hydrocarbylenebiscarbamoyl)-bis(2- - benzimidazolecarbamates) - useful as fungicides and acaricides - Google Patents

Abstract

Cpds. (I) (where R and R' are each Me, Et, isoPr or sec.-Bu; X and X' are each H, halogen, Me or MeO; A is 1-18C alkylene, (opt. oxa, N-methylaza or thia-substd) alkenylene, cycloalkylene, bis (cyclohexylene) methylene, alkylcyclohexylene, alkenylene cyclohexane alkyl cyclohexylene substd. by oxa or methylaza gps. N-alkylene aza cyclohexane, bicycloalkylene phenylene, methylphenylene or bis (phenylene) methylene) are prepd. by reacting a benzimidazolyl carbamic acid ester or a mixt. of esters with a diioscyanate OCN-A-NCO.

Description

1,1 '- (Hydrocarbylene-bis-carbamoyl) -bis- (2-benzimidazolecarbamic acid dialkyl ester) optionally substituted on the hydrocarbylene group There are several Beneimidazo3carbamic acid esters that are an excellent fungicide Have activity. Examples of this are the US patent documents 2 933 502, 2,933,504 and 3,631,176.

The invention relates to a new group of on the hydrocarbylene group optionally substituted 1,1 '- (hydrooarbylan-bis-carbamoyl) -bis- (2-benzimidazoloarbamic acid dialkyl esters) as well as the use of these compounds to prevent or alleviate the damage of plants and inanimate organic matter through fungi and mites. The invention also specifically refers to the use of these new compounds for protection of paints and also includes procedures for making the compounds. Fungus myoel is killed by one or more of the compounds according to the invention or prevented from further development; the yerbindun genes hence they are referred to as fungicides or fungistats.

It has been found that excellent fungicidal and milbenovicidal activity can be achieved if the site of infection and / or infestation is treated with compounds of general formula I.

Herein mean: the radicals R, which can be the same or different, Methyl, ethyl, isopropyl or sec-butyl radicals, X a hydrogen or halogen atom, a methyl or methoxy radical and A a divalent group with 1 to 18 carbon atoms, namely an alkylene group, oxa-, N-methylaza- or thia-substituted alkylene group, Alkenylene group, cycloalkylene group, bis (cyclohexylene) methylene group, alkylated Cyclohexylene group, alkylenated cyclohexane group, oxa or methylaza-substituted alkylated cyclohexylene group, N-alkylenated azacyclohexane group, Bicycloalkylene group, Phenylene group, methylated phenylene group or bis (phenylene) methylene group.

Because of the ease of their preparation, the compounds are preferred in which A is a hydrocarbylene group.

Under hydrocarbylene groups or hydrocarbylene radicals are in the present Description to understand generally divalent hydrocarbon residues.

Because of their biological activity, as a fungicide and mite ovicide those compounds of general formula 1 are preferred in which R is a Methyl group and X is a hydrogen atom.

In the same sense, the following compounds are particularly preferred: methyl 1- {5- [2- (methoxycarbonylamino) -1-benzimidazolecarbunylamino] -1,3,3-trimethylcyclohexsylmethylcarbamoyl-2-benzimidazolecarbamic acid methyl ester 1,1 '- (2,2,4-Trimethylhexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) 1,1 '- (4-Methyl-m-phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) 1,1 '- (p-Phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) and 1,1 '- [methylenedi- (p-phenylcarbamoyl)] - his- (2-benzimidazolecarbamic acid dimethyl ester) If two molecules of a 2-benzimidazole cachamino acid alkyl ester (Ii) are bonded to one another with the aid of a diisocyanate (LII), compounds (1) are obtained according to the invention, which have proven to be effective fungicides and mite acidicides. This implementation can be represented as follows: X, R and A have the above meanings.

When the two 2-benzimidazole carbamic acid alkyl ester molecules (II) are the same, the parts a and b in the product (I) are the same. The two Molecules do not need the same to be, and as a result can parts a and b in the molecule of product (I) may also be different. It was found that a large variety of different diisocyanates (III) can be used for production of the products (I) can use, and that these products are consequently the most diverse Groups may have old as connecting links.

The invention also includes the methods of making the above connections described.

The compounds according to the invention, in which the two groups R are the same, can be prepared by reacting two equivalents of a 2-benzimidazole carbamine alkali ester (II) with 1 equivalent of an optionally substituted hydrocarbylene diisocyanate (III) according to the following reaction scheme: The compounds I, in which the two groups R are different, can be prepared by reacting 1 mol of a 2-benzimidazolecarbamic acid alkyl ester (II) with 1 mol of an optionally substituted hydrocarbylene diisocyanate (III) and then reacting the intermediate (IV) with another 2- Prepare benzimidazole carbamic acid alkyl ester (II), which differs from the former in that it has a different group R or a different substituent X. The compounds of the general formula 1 in which the groups R and the substituents X are the same in both parts of the molecule are preferred because they are easier to prepare. The meanings of R, X mid -A here are the same as described above. The above intermediate has the following general formula: The alkyl 2-benzimidazole carbamate (II) used as starting materials can be prepared by known methods, for example by the three-stage reaction process described in US Pat. No. 3,010,968.

The hydrocarbylene diisocyanates can be converted by reacting the appropriate Manufacture diamines with phosgene (cf. Siefken, 1Annalen der Chemie ", Volume 562, 1948, Page 76).

The following examples illustrate the preparation of the compounds explained in more detail according to the invention. The parts relate if nothing otherwise stated is based on weight.

B e i s'p i e l 1 Preparation of 1,1 '- (hexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid methyl ester) A mixture of 19.1 parts of methyl 2-benzimidazole carbamate and 0.1 part Triethylenediamine in 300 parts of acetone is slowly mixed with 8.4 parts of hexamethylene diisocyanate with stirring offset. The reaction is slightly exothermic and the mixture becomes very thick. The reaction mixture is stirred overnight at room temperature and the solid filtered off. The 27.1 parts of 1,1 '- (hexamethylenedicarbamoyl) bis (2-benzimidazolecarbamic acid dimethyl ester) obtained as product are washed with acetone and dried in vacuo at room temperature; F 322-324 ° C (decomposed).

Analysis Calculated for C26H30N806: C = 56.85%; H =, 50%; N = 0.20 ; found: C = 56.69%; H = 5.54%; ; = 19.92%.

Example 2 Preparation of 1- {5- [2- (methoxycarbonylamino) -1-benzimidazoly] carbonylamino] -1,3,3-trimethylcyclohexylmethylcarbamoyl} -2-benzimidazolecarbamic acid methyl ester A mixture of 19.1 parts of methyl 2-benzimidazole carbamate and 0.1 part Triethylenediamine in 300 parts of chloroform is slowly added to 11.1 parts with stirring 5-isocyanato-1- (isocyanatomethyl) -1,3,3-trimethylcyclohexane was added. The reaction mixture is stirred overnight at room temperature, then filtered and the solvent stripped from the filtrate under reduced pressure. The residue of the filtrate is stirred with hexane and the product is filtered off.

28.5 parts of 1- {5- [2- (methoxyocarbonylamino) -1-benzimidazolylcarbonylamine are obtained S-1,3,3-trimethylcyclohexylmethylcarbamoyl [-2-benzimidazole carbamic acid methyl ester; F 82-83 ° C.

B'eispi-eL ~ 3 Production of 1,1 '- (2,2,4-trimethylhexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) -A mixture of 19.1 parts of 2-renzimidazole carbamic acid methyl ester and 0.1 parts Triethylenediamine in 300 parts of chloroform is slowly mixed with 2,2,4-trimethylhexamethylene diisocyanate while stirring offset. The reaction mixture is stirred overnight at room temperature, then filtered and the solvent was evaporated from the filtrate under reduced pressure. The firm one The residue of the filtrate is ground in hexane and the product is filtered off. Man receives 27 parts of 1,1 '- (2,2,4-trimethylhexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester); F 78-80 ° C.

EXAMPLE 4 Preparation of 1- {6- [2- (isopropoxycarbonylamino) -1-benzimidazolylcarbonylamino] -hexamethylenecarbamoyl} -2-benzimidazolecarbamic acid methyl ester A solution of 16.8 parts of hexamethylene diisocyanate and 0.1 part of triethylenediamine in 600 parts of cetone is slowly mixed with 21.9 parts of 2-benzimidazole carbamic acid isopropyl ester with stirring offset. The reaction mixture is stirred at room temperature for 1 hour and then 1991 parts of 2-benzimidazole carbamic acid methyl ester were slowly added. Daj's reaction mixture and then stirred overnight at room temperature, filtered and the solvent stripped from the filtrate under reduced pressure. The residue of the filtrate is stirred with hexane and the product is filtered off. 1- {6- [2- (Isopropoxycarbonylamino) -1-benzimidazolylcarbonylamino] -hoxamethylene carbamoyl} -2-benzimidazole carbamine is obtained acid methyl ester.

EXAMPLE 5 Preparation of 1,1 '- (4-methyl-m-phenylenedicarbamoyl) -bis-2-benzimidazolecarbamic acid dimethyl ester0 A mixture of 19.1 parts of methyl 2-benzimidazole carbamate and 0.1 part Triethylamine in 300 parts of methyl ethyl ketone is slowly added to 8.7 parts with stirring 4-methyl-mphenylene diisocyanate is added to 20 parts of methyl ethyl ketone.

The reaction mixture is stirred for 1 hour at room temperature and filtered. The solid filter residue is air-dried, and one obtains 27.3 parts of 1,1 '- (4-methyl-mphenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester); F 203-205 C.

Example 6 Preparation of 1,1 '- (p-phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) A mixture of 19.1 parts of methyl 2-benzimidazole carbamate and 0.1 part Triethylamine in 300 parts of methyl ethyl kotone is slowly added to 8 parts with stirring p-phenylene diisocyanate is added to 20 parts of methyl ethyl ketone. The reaction mixture is stirred overnight at room temperature. The solid product is released from the reaction mixture filtered off and air dried. 26 parts of 1,1 '- (p-phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) are obtained; F 3500 c ..

Example 7 Preparation of 11 methylenedi- (p-phenylcarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) A mixture of 19.1 parts of methyl 2-benzimidazole carbamate and 0.1 part Triethylamine in 300 parts of chloroform is slowly added to 12.5 parts with stirring Methylenedi- (p-phenyl isocyanate) added. The reaction mixture is kept overnight at Room temperature stirred. The one obtained by filtering solid filter residue is air dried. 30 parts of 1,1 '- [methylenedi- (p-phenylcarbameyl)] - bis (2-benzimidazoloarbamic acid dimethyl ester) are obtained in this way; F 330-3344 C.

B e i s p 1 e 1 8 The following compounds can be made according to the procedure of Example 3, if one uses the methyl 2-benzimidazole carbamate and the 2,2,4-trimethylhexamethylene diisocyanate by the corresponding alkyl 2-benzimidazole carbamate or substituted or unsubstituted hydrocarbylene diisocyanate.

1,1 '- (Hydrocarbylene-bis-carbamoyl) -bis- (2-benzimidazolecarbamic acid dialkyl ester which is optionally substituted on the hydrocarbylene group) Compound 1 1,1 '- (Dodacamethylene dicarbamoyl bis (2-benzimidazole carbamic acid dimethyl ester) 2 1'1 '- (Ethylenedicarbamoyl) -bis- (2-bonzimidazolcarbamic acid dimethyl ester) 3 1,1' - (1,1-Dimsthylethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) 4 1,1 '- (2,2-Dimethyltrimethylenedicarbamoyl) -bis- (2-benzimidazoloarbamic acid dimethyl ester) 5 1,1 '- (1,4-Cyolohexylcndicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) 6 1,1 '- (1,4-Cyclohexylenedimethylenedicarbamoyl) -bis- (2-benzimidasolcarbamic acid dimethyl ester) 7 1,1 '- (1,3-Cyclohexylenedicarbamoyl) -bis-8 1,1' - [Mothylen-bis-94-eyclohexylcarbamoyl)] - bis- (2-benzimidazolecarbamic acid dimethyl ester) 9 1,1 '- [bis- (1,4-cyclchexylene) -dicarbamoyl] -bis- (2-benzimidazolecarbamic acid dimethyl ester) 10 1,1 '- (DecAhydro-1,5-naphthylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) 11 1,1 '- (2-buten-1,4-ylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) link 12 1,1 '- (tetramethylenedicarbamoyl) -bis- (2-in the case of dimethyl imidazole carbamate) 13 1,1 '- (Octamethylenedicarbamoyl) -bis- (2-ben: dimethyl imidazole carbamate) 14 1,1 '- (1,2-Dimethylethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester 15 1,1 '- (2-Methyltetramethylenedicarbamoyl) -bi (2-benzimidazole carbamic acid dimethyl ester.

16 1,1 '- (1,3-Cyclohexylenedicmethylenedicarbamoj bis- (2-benzimidazolecarbamic acid dimethylet 17 1- {4- [2- (methoxycarbonylamino) -1-benzimidazolylcarbonylamino] -1-methylcyclchexj methylethyl} -2-benzimidazolecarbamic acid methyl ester 18 1,1 '- (1,2-cyclobutylenedicarbamoyl) bis- (2-benzimidazolecarbamic acid dimethyl ester) 19 1,1 '- (1,2-Cyclohexylenedicarbamoyl) bis (2-benzimidazolecarbamic acid dimethyl ester) 20 1,1 '- (Isopropylidene-bis-1,4-cyclohexyl-carbamoyl) -bis- (2-benzimidazole-arbaminse dimethyl ester) 21 1,11 - (Oxydiethylenedicarbamoyl) -bis- (2-benzimidazolcarbamic acid dimethyl ester) 22 1,1 '- (1-Methyläthylenedicarbamoyl) -bis- (2-1 jimidazolcarbamic acid dimethyl ester) 23 1,1 '- (1,4-piperazinylene-bis-trimethylenedi- = carbamoyl) -bis- (2-benzimidazole carbamic acid dimethyl ester) 24 1,1 '- (2,2,4,4-totramethyl-1,3-cyclobutylene carbamoyl) -bis- (2-benzimidazole carbamic acid dimethyl ester) 25 1,1 '- (2-methyl-1,3-cyclohexylenedicarbamoyl bis (2-benzimidazole carbamic acid dimethyl ester) 26 1,1 '- [methyliminodi- (trimethylene0-dicarbamoj bis- (2-benzimidazolecarbamic acid dimethyl esters 27 1,1 '- [2,2,4,4-tetramethyl-1,3-cyclobutylene-1 (oxytrimethylene) dicarbamoyl] bis (2-benzimidazolecarbamic acid dimethyl ester) 28 1,1 '- (2-methyl-1,5-cyclohexylenedicarbamoyl) - (2-benzimidazolecarbamic acid dimethyl ester) link 29 1,1 '- (3-methyl-1,4-cyclohexylenedicarbamoyl) (2-benzimidazolecarbamic acid diethyl ester) 30 1,1 '- (Octadecamethylenedicarbamoyl) -bis- (2-bimidazolcarbamic acid dimethyl ester) 31 1,1 '- (hexamethylenedicarbamoyl) -bis- (4-chloro-2-benzimidazolecarbamic acid dimethyl ester) 32 1,1 '- [methylene-bis- (1,4-cyclohexylene) -dicarbamoyl] -bis- (5-fluoro-2-benzimidazole carbs acid dimethyl ester) 33 1,1 '- (1,3-Cyclohexylenedicarbamoyl) -bis- (4-b 2-benzimidazole carbamic acid dimethyl ester) 34 1,1 '- (Dodecamethylene dicarbamoyl) bis (5-iodo benzimidazole carbamic acid dimethyl ester) 35 1,1 '- (1,4-Cyclohexylenedicarbamoyl) -bis- (4-thyl-2-benzimidazolecarbamic acid dimethyl ester) 36 1,1 '- (tetramethylenedicarbamoyl) -bis- (6-met 2-benzimidazolecaroamic acid dimethyl ester) 37 1,1 '- (hexamethylene dicarbamoyl) bis (5-meth benzimidazole carbamic acid dimethyl ester) 38 1,1 '- [bis (1,4-cyclohexylenedicarbamoyl)] - b (4-nitro-2-benzimidazole carbamic acid dimeth ester) 39 1,1 '- (p-Phenylenedimethylenedicarbamoyl) -b (2-benzimidazolecarbamic acid dimethyl esters 40 1,1 '- (m-PhenylenedimethylenedicArbamoyl) -b (2-benzimidazolecarbamic acid dimethyl esters 41 1,1 '- (o-Phenylenedimethylenedicarbamoyl) -b (2-benzimidazolecarbamic acid dimethyl esters 42 1,1 '- [(4-methyl-m-phenylene) -dimethylenedi-carbamoyl] -bis- (2-benzimidazole-carbamate) dimethyl ester) 43 1,1 1- (vinylenedicarbamoyl) -bis- (2-benzimidazole carbamic acid dimethyl ester) 44 1,1 '- (hexamethylenedicarbamoyl) -bis- (2-b imidazolecarbamic acid diethyl ester) 45 1,1 '- (Hexamethylenedicarbamoyl) -bis-2-imidazolecarbamic acid diisopropyl ester) 46 1,1- (Hexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid di-sec. butyl ester) 47 1,1 '- [(2-bromo-p-phenylene) -dimethylenedicarba moyl] -bis- (2-benzimidazolecarbamic acid dimet ester) Compound 48 1,1 '- [(2-iodo-p-phenylene) -dimethylene dicarbame bis- (2-benzimidazolecarbamic acid dimethyl ester 49 1,1 '- [(2-chloro-p-phenylene) -dimethylenedicarbamoyl] -bis- (2-benzimidazolecarbamic acid dimethyl ester) 50 1,1 '- [(2-fluoro-p-phenylene) -dimethylenedicarba moyl-bis- (2-benzimidazoloarbamic acid dimeth ester) 51 1,1 '- [(2,3,5,6-tetrachloro-p-phenylene) -dimeth lendicarbamoyl] -bis- (2-benzimidazolecarbamic acid dimethyl ester) 52 1,1 '- [(2,3,5,6-Tetrafluoro-p-phenylene) -dime lendicarbamoyl] -bis- (2-benzimidazole carbami acid dimethyl ester) 53 1,1 '- [(2-butoxy-p-phenylene) -dimethylandi bamoyl] -bis- (2-benzimidazole carbamic acid methyl ester) 54 1,1 '- [(2-Nitro-p-phenylene) -dimethylenedicarbamic] -bis- (2-benzimidazolecarbamic acid dimet ester) 55 1,1 '- [2,6-dinitro-p-phenylene) -dimethyle carbamoyl] -bis- (2-benzimidazolecarbamine) dimethyl ester) 56 1,1 '- [(2-cyano-p-phenylene) -dimethylenedicarbe bis- (2-benzimidazolecarbamic acid dimethyl ester 57 1,1 '- [(2-methoxy-p-phenylene) -dimethylenedica moyl] -bis- (2-benzimidazole carbamic acid dimet ester) 58 1,1 '- (Thiodiethylenedicarbamoyl) -bis- (2-b imidazolcarbamic acid dimethyl ester) 59 1,1 '- {methylene-bis - [(3,5-dibromo-p-phenylene) -dimethylenedicarbamoyl]} - bis- (2-benzimidazolecarbamic acid dimethyl ester) 60 1,1 '- {methylene-bis - {(3-iodo-p-phenylene) -dimethylenedicarbamoyl]} - bis- (2-benzimidazolcar dimethyl ester) 61 1,1 '- (2-cyclopenten-1,4-ylenedicarbemoyl) bis (2-benzimidazole carbamic acid dimethyl ester) 62 1,1 '- (2-Cyclododec-1,4-ylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl esters 63 1,1 '- (1,4-Cyclododecylenedicarbamoyl) -b (2-benzimidazole carbamic acid dimetyles link 64 1,1 '- (m-Phenylenedicarbamoyl) -bis- (2-benzimidazolearbamic acid dimethyl ester) 65 1,1 '- (2-Methyl-m-phenylenedicarbamoyl) -bis- (2-benzimidzenecarbamic acid dimethyl ester).

The compounds according to the invention can be used to combat a great variety of fungus diseases of leaves, fruits, stems and roots can be used by growing plants without harming the host plants. Fruits, tubers, onions, roots, seeds and others, as food or feed or parts of plants harvested for other purposes are used for processing, distribution and storage protected against damage by fungi. Seeds, tubers, and saplings other goods intended for the reproduction of plants are used when handling and Protected against fungus infestation during storage as well as in the ground after planting.

Wood, textile materials, fiberboard, paper and other technical goods are protected against ugly stains and rot caused by fungi. Luggage, Shoes, shower curtains, carpets, mats, clothing and other household items or technical goods are protected against rot, fungus stains and mold. Painted surfaces are protected against stains and discoloration, by adding one of the compounds according to the invention to the paint.

The milbenovicide effect of the compounds according to the invention makes is noticeable in that it prevents the development of noxious nile colonies or the gradual shrinking of pre-existing colonies. -The Movement of the mites is limited. The increase in the number of mites or the continuation an extensive colony of mites at a certain point therefore largely depends from hatching the eggs laid at this point.

Mite eggs do not develop into live young if they are with any of these compounds are treated, or when placed on a surface that contains one of these compounds. The eggs also develop then not if they are placed by a female mite that has one of these Has been in contact with compounds, or nutrients, such as vegetable juices, that contain, consume or have recently consumed any of these compounds Has. This disruption of the hatching of the eggs prevents mite colonies from growing increase significantly beyond what they are at the time of treatment. Because of this ovicidal effect in connection with the high natural mortality of the fully grown mites, the mites can move from an already infested place in proportion be eradicated in a short time. As long as the connections are on the surface, ingested by the mites or left in their diet can spread do not develop new colonies of mites.

If the compounds according to the invention by certain methods are applied according to the invention, they enter the plants and move freely within them, i.e. they work systemically. Therefore, both fungi and also fight mites in parts of plants that are far from the place of application of the compounds are away. In view of this activity, the compounds can be used to treat to be used by seeds. By treating cucumber seeds with just a few Grams of a compound according to the invention per 50 kg of seed are obtained, for example Suppression of powdery meltau (Erysiphe cichoracearum) and spider mites, such as Tetranychus urticea, on the plants in question for periods longer than 40 days. The treatment of the soil leads to the suppression of certain leaf diseases Tens and mites on plants growing in the treated soil. The spraying or dusting the leaves and stems of plants leads to protection other parts of the plant that have not been sprayed and new leaves, which develop later, both against fungi and against mites.

Another valuable property of the compounds according to the invention is their toughness, the spread of fungus infections of which the plants are already infested, prevent or kill the fungi, i.e. the compounds act as a remedy. They therefore only need to be applied when there are conditions have developed that allow pungus infestation. This means that it is under In some circumstances it is possible to treat the crops with any chemical Avoid substance throughout its life. In other cases it is only one Part of the normal full pest control program necessary.

Hence, one can make significant savings in both chemical costs and in labor costs if one can use compounds that have both have a systemic as well as a healing effect. Another saving results with the compounds according to the invention from the fact that both fungi as well as mites can be controlled by treating with a single compound.

Live plants can be protected against fungi and mites by the soil in which they grow or are then sown or planted, or seeds, tubers, onions or others responsible for the propagation of the plants Divide before planting or the foliage, the trunks and the. Fruits of living Plants treated with one or more compounds according to the invention. Living Plants can also be protected by putting the root system in the pesticide dips or injects the agent into the roots or stems of the plants.

Soil treatment is carried out with dusts, grains, tablets, slurries or solutions. The treatment density of the soil in which the Plants grow or will grow soon, with the compounds according to the Invention 0.01 to 500 parts per million parts by weight of the soil in which the roots are grow or will grow. Preferred densities range from 0.1 to 50 ppm, particularly preferred densities in the range from 0.25 to 25 ppm.

Preferred ~ concentrations for the treatment of seeds, tubers, Bulbs or other parts responsible for the reproduction of plants with the compounds according to the invention are in the range from 0.03 to 6000 g Active ingredient per 50 kg of plant material. Particularly preferred concentrations lie in the range from 0.3 to 3000 g of active ingredient per 50 kg, in particular in the range from 2.8 up to 1500 g / 50 kg. The application takes place in the form of dusts, slurries or Solutions. Such treatments protect the plant parts themselves against damage by fungi and / or mites and also give the developing new plants long-term protection against both types of pests.

Preferred densities for the. Treatment of the leaves, stems and branches of living plants with the compounds according to the invention are in the range from 0.012 to 60 kg of active ingredient per ha. A preferred range is 0.025 to 30 kg / ha, in particular 0.05 to 15 kg / ha. The cheapest amount within this range depends, as those skilled in the art know, on a number of variables. About these variables include, for example, the disease to be combated, the expected weather conditions, the type of crops, the stage of development of the plants and the time intervals between treatments. Treatments in the density ranges given above may need to be repeated one or more times at intervals of 1 to 60 days will. The application takes place in Forui of dusts, slurries or solutions.

Preferred concentrations for immersing the roots of living. Plants are in the range from 0.5 to 18,000 g of active ingredient at 380 liters of water or other Carrier liquid. Particularly preferred concentrations are in the range of. 4.5 up to 9000 g / 380 1, in particular in the range from 45 to 4500 g / 580 1.

Preferred concentrations for injection into the roots.

or strains of living plants range from 0.01 to 10 000 parts of active ingredient per million parts of water or other carrier liquid. Particularly preferred concentrations are in the range from 0.1 to 5000 ppm, in particular from 1 to 1000 ppm.

Parts of plants, such as fruits, tubers, onions, leaves, roots and the like, which are harvested as food or feed, are used in the Processing, distribution and storage against rot and other deterioration protected as a result of pungus or mite infestation. when treated with an active ingredient be treated according to the invention. The parts of the plant to be protected in this way can be immersed in a liquid bath; that contains the active ingredient you can dusted with a finely divided preparation of the active ingredient, sprayed, with one of the Aerosol containing the active ingredient is misted or in an aerosol impregnated with the active ingredient Wrapping or packing to be wrapped.

If you work with a liquid bath, this can contain the active ingredient contained in concentrations of 1 to 5000 parts per million parts by weight of liquid. A preferred range for the bath is 5 to 2500 ppm, especially 10 to 1000 ppm.

Dusts and wrapping or packaging materials for the application of the Active ingredients according to the invention can contain 0.001 to 1.0% active ingredient. Preferred Concentrations are in the range from 0.01 to 0.5, in particular from 0.002 to 0.25%.

Wood, leather, textiles, fiberboard, paper and other technical Products of an organic nature can protect against decomposition and discoloration by fungal or mite infestation can be protected by treating them with an effective amount of a or more compounds according to the invention coated or impregnated or store such a compound in them. The coating can be done by dipping, spraying, Flooding, fogging (e.g. with an aerosol) or dusting of the to be protected Material made with a suitable agent that contains the active ingredient. The preferred Active ingredient concentrations, based on the material to be treated, are included in the range from 0.025 to 95 percent by weight, more preferably in the range from 0.05 to 50 percent by weight and in particular in the range from 0.1 to 25 percent by weight.

If the connections are made by impregnation or incorporation into brings in the substances to be protected, the preferred active ingredient concentrations are based on the final product, 0.001 to 30 percent by weight, more preferred Way 0.005 to 15 percent by weight and especially 0.01 to 7 percent by weight.

Luggage, shoes, shower curtains, carpets, mats, clothing and other household items or technical products are protected against rot, Fungus stains and ugly mold infestation as well as against mite infestation through the active ingredients protected according to the invention. Again, you can use a surface protection or achieve deep protection. The surface treatment is done by dipping, Washing, spraying, misting with aerosols or dusting.

The deep treatment is carried out by penetrating Ijösungen.

Sprüi, dipping and washing preparations contain the active ingredient according to the Invention in concentrations of 10 to 5000 ppm.

Contains liquids for use in the form of aerosols and dusts the active ingredient in concentrations of 0.1 to 20 percent by weight. Penetrating solutions contain the active ingredient in such concentrations that an active ingredient deposition in the material being treated in amounts of 5 to 20,000 parts per million parts of the material to be protected.

Surfaces that have been painted with parquet can be used against ugly ceilings and mold can be protected by applying a paint to the paint before painting Active ingredient according to the invention added in concentrations of 5 to 20,000 ppm.

Preferred concentrations are 10 to 10,000 ppm, in particular 20 to 5000 ppm. Such treatment with these compounds also protects the Paint itself, while it is still in the can, before verdeyben by Fungi.

They are suitable for protecting paints against fungi and mites of the compounds of general formula I, especially those in which R a methyl group and X a metal atom, in particular 1,1 '- (4-methyl-m-phenylenedicarbamoyl ) -bis- (2-benzimidazolecarbamic acid dimethyl ester).

In the case of certain products, such as fiberboard, paper, textiles, Resin and plastic parts, paints, etc., can be a connection according to the Invention are stored in the objects in question during their manufacture. For example, pulp can be used in paper production or color premixing a slurry or solution of a compound prior to milling and dispersing add according to the invention.

The damage to organic products in stock, such as grain, seeds, tubers, onions, meat or animal hides and skins, caused by mites is kept to a minimum when looking at the footbaths, walls and other parts of the warehouses or other components with one or more of the Treated active ingredients. The treatment is carried out with the help of dusts, sprays or aerosols in preferred densities of 0.05 to 1000 g of active ingredient according to the Invention per 100 m2 of the surface to be protected against dust.

The compounds according to the invention are suitable for combating a large variety of mite or pungus diseases in warm-blooded animals.

The compounds according to the invention can be used to achieve the fungicidal or milbenovicidal action according to the invention presented in any suitable manner will. The compounds can be used externally, for example, as ointments, creams, pastes Liquids, lotions, dusting powders or aerosols can be applied.

The dosage of the compounds according to the invention on hot goods depends on the type of animal in question, the fungus in question, the frequency of the Administration and other factors known to those skilled in the art. Generally leaves Fight the fungus effectively by treating the infected area with an agent treated that an active ingredient according to the invention in concentrations of 0.025 to 95 percent by weight, preferably from 0.05 to 50 percent by weight, in particular from 0.1 to 25 percent by weight.

In addition to the active ingredient according to the invention, the agent contains one solid or liquid, nontoxic pharmaceutical carriers for the active ingredient. If suitable sterile products are used, the compounds according to the inventor also as ophthalmic preparations, e.g. in the form of of ointments, topical fluids, lotions, etc. can be applied.

According to one embodiment, the compound according to the invention can be formulated as an ointment, cream or paste. In these products is the active ingredient generally contained in concentrations of 0.01 to 10 percent by weight, while the rest consists of a pharmaceutical base.

Examples of such bases are hydrophilic petrolatum U.S.P., hydrophilic ointment U.S.P., polyethylene glycol and ointment U.S.P. Others, the specialist known bases can also be used.

These remedies are made by putting the active ingredient in the base material or a part of the base material dissolves or suspends and the mixture by a The ointment mill runs.

According to another embodiment, the active ingredient can be external liquid to be used. Such a liquid generally contains 0.01 to 10 percent by weight active ingredient and the remainder consists of a liquid carrier.

The liquid carrier can be aqueous, alcoholic or aqueous-alcoholic Be a liquid, e.g. a mixture of ethanol and water.

This agent is made by dissolving the active ingredient in the solution, Mixing and filtering made.

The compounds can also be formulated as lotions.

The lotions usually contain the active ingredient in amounts of 0.01 up to 10 percent by weight and the remainder consists of a liquid phase. The liquid one Phase can be an aqueous solution containing suitable wetting and suspending agents, or it can be an oil-in-water emulsion stabilized with a suitable surfactant be.

The lotion can be made by turning the active ingredient into one smooth paste and then carefully add the rest of the liquid phase. To obtain better dispersions, high-speed mixers or homogenizers can be used be used.

The compounds can also be formulated as a dusting powder, which generally contain the active ingredient in concentrations of 0.01 to 10 percent by weight and the rest of the powder.

The powder is usually talc U.S.P .; however, you can also Powders known in the art for similar purposes can be used. The powder can too Contains additives such as magnesium stearate to increase its puffiness.

Aerosol dispensers can be applied to deliver the funds in porm of To dispense ointments, creams, pastes, liquids, lotions or powders. The aerosols are produced in a known manner.

The one practiced by the increasing population in the world Coercion combined with the need for more economical agricultural practices has resulted in grains, including corn, being harvested earlier today. Often the grain is stored without proper drying or on grain elevators delivered. Under these circumstances the grain can spoil quite quickly, whereby toxins and other substances that are very harmful or even fatal for animals form Safe and effective feed additives that meet such a Countering spoilage are therefore of great importance for agriculture.

The compounds according to the invention can be used to prevent fodder spoilage. When mixed with the feed, they provide more effective and longer lasting protection without harming the livestock. The compounds according to the invention can be used in various ways for this purpose can be formulated quietly, and these funds can be added directly to the fodder, fresh added to harvested hay and freshly harvested grain or oil seeds. These Compounds prevent the spoilage of corn, millet, wheat, barley, oats, rye and other grains and oil seeds used as fodder.

Under normal circumstances, these bonds can be found in the food For excellent results, added in amounts from 0.01 to 0.25 percent by weight will. Higher concentrations may be required in very humid conditions be.

The compounds can also be used to enhance the effects of others Feed additives, like sodium propionate, improve by taking the two types of Mixing additives directly with one another or by adding them separately to the feed.

The compounds according to the invention offer the further advantage that they are highly persistent. Benzimidazole derivatives decompose under certain circumstances chemically over time, especially at high humidity and high temperature.

The compounds according to the invention are remarkably stable and are therefore easier to formulate and store.

Agents according to the invention are formulated by adding a compound according to the invention with one or more densi den undZoder a thinning carrier.

The surfactants to be used according to the invention can be wetting, dispersing or emulsifiers. They can be used as wetting agents for wettable powders and dusts, as a dispersant for wettable powders and suspensions and as an emulsifier work for emulsifiable concentrates. The surfactants also increase the biological Activity of the compounds according to the invention. Such surfactants are e.g. anionic, Cationic and non-ionic surfactants, such as those already used in crop protection products of a similar nature can be used. Suitable surfactants are e.g. in the factory! 1Detergents and Emulsifiers Annual - 1968 "compiled by John W. McCutcheon, Inc. Other Surfactants that are not listed in this work, but also as a result of them Protective colloid effects act as dispersants are methyl cellulose, polyvinyl alcohol, Hydroxyethyl cellulose and alkyl-substituted polyvinylpyrrolidones.

The agents according to the invention contain, in addition to the enside, solid ones or liquid diluents, in order to obtain wettable powders, dusts, grains, as desired or to obtain emulsifiable liquids.

Wettable powders usually contain inert solids in addition to surfactants Thinning agent. These inert diluents serve several purposes. she can act as grinding aids, avoiding grinder smearing and clogging Prevent the sieves, they can favor the rapid distribution when mixing is introduced into water, they can be liquid or low-melting solids Adsorb active ingredient, so that a free-flowing, solid product is created, them can prevent the product from clumping during prolonged storage in the heat agglomerates, and they can produce agents with controlled amounts of active ingredient enable, so that the end user can easily measure the correct dosage. Suitable Diluents are known and can be inorganic or organic in nature.

Wettable powders usually contain both a wetting agent and also a dispersant. For dry wettable powders, those will be anionic and non-ionic surfactants which are in solid form are particularly preferred. Yes, yes One can use a liquid, non-ionic surfactant that is normally regarded as an emulsifier will be used to achieve both wetting and dispersion.

The concentration of the wetting and dispersing agents in the wettable Powders according to the invention amount to a total of about 0.5 to 5.0 percent by weight, based on the total mean.

The active ingredient is present in a concentration of about 25 to 85%, and the diluent makes up the remainder that is still missing 100%. If necessary, can one corrosion retarder; Anti-foaming agents, dyes, spray markers and the like in amounts of 0.1 to 1.0% each at the expense of the diluent to add.

The active ingredients according to the invention are very strong fungicides that fight the fungi effectively when using conventional spraying equipment be sprayed as aqueous dispersions in concentrations of 200 to 600 ppm. Considering the improved methods of distributing droplets and the more economical In terms of operation, however, it has been found to be desirable to use the 3- to 20 times the concentrations previously used in conventional devices to work and still spray the same amount of active ingredient per hectare. These concentrates g of low volume "or" of ultra-low volume "are with the wettable powders according to the invention, because for pest control only a little active ingredient is required and concentrates of low viscosity themselves can be easily produced with relatively high levels of pesticides.

Dusts are for application in dry form with the help of dusting devices certainly. Since the wind drift is undesirable during pollination, these are best suitable dust thinners are those that are dense and settle quickly. These include kaolinites, talc, pyrophyllites, ground rock phosphate, sulfur, Serecite and ground tobacco stalks. Dusts, however, are usually the lightest manufactured by using an already existing, highly concentrated wettable Powder diluted with a dense thinner, so the finished dust often only a fraction of a lightweight, absorbent diluent and more which contains cheaper, dense filler.

Dusts also expediently contain a wetting agent, so that the dust adheres well to the leaves. Contains dusts made from wettable powders Sufficient wetting agent from the start; but dusts that come directly from pure Active ingredient produced usually contain an added wetting agent. Dry, solid, anionic or non-ionic wetting agents are preferred.

Dusts usually contain 2.0 to 25 percent by weight of active ingredient, 0.005 to 1.0 percent by weight wetting agent and up to 20 percent by weight light Seam aids. The rest usually consists of the dense, rapidly settling Thinning agent. When made by diluting a wettable powder they also contain some dispersant that does not play an active role, when the 5 track is used as dry dust.

Emulsifiable liquids are made by making the compounds according to the invention-with a suitable emulsifier and an organic liquid of poor water solubility mixes. The active ingredient can be completely organic Liquid dissolved or in finely divided form as a suspension in a non-solvent acting liquid are distributed. Suitable organic liquids are alkylated Naphthalenes, xylene, high molecular weight ketones such as isophorone and dibutyl or diamyl ketone, esters such as amyl acetate, and straight or branched chain paraffins. Particularly preferred emulsifiers are mixtures of oil-soluble sulfonates and non-ionic polyoxyethylene glycol esters of fatty acids o, der-Xthern of aliphatic Alcohols or alkylated phenols.

The active ingredient is in concentrations in emulsifiable concentrates from 10 to about 40 percent by weight. The proportion of combined emulsifiers is 3 to about 10 percent by weight, while the remainder is organic Carrier liquid or an organic solvent consist of solutions of the active ingredients in solvents or dispersions of the active ingredients in non-aqueous fluids are most convenient for aerial or ground application in "niodrigem" Volume "or" ultra-low volume. "When formulated with emulsifying agents, can these mixtures as such or to the extent desired with water or oil can be used diluted. If they are only at "low volume" or "ultra-low Volume 'are to be applied, the emulsifying agent can of course be omitted will.

Soil treatment with fungicides before or after emergence leaves often easiest to run through with grains. Granular products can be with the connections acc of the invention in various ways produce. The active ingredients can be melted or dissolved in a volatile carrier and sprayed onto preformed grains. You can use suitable as -powder with Thinners and binders mixed, then moistened and granulated and finally to be dried. Powder can also be applied to preformed grains by tipping them together and the addition of further binders, such as non-volatile oils or glycol, or a liquid, non-ionic surfactant, or a lignosulfonate will. The rate of disintegration and the distribution of the active ingredient in moist -Floor can be made by the choice of added surfactants or by the choice of Manufacture of the binders used by Kerner can be controlled.

Suitable grains consist of attapulgite, granular, flaky Vermiculite, ground corn on the cob, ground nutshells or kaolinite grains. The fungicidal active ingredient can be on such carriers in concentrations of 1 to 25 i0 exist. However, if the active ingredient is not applied in a molten state it is difficult to separate the drug and carrier at concentrations of Prevent more than about 10% on preformed grains. When higher drug concentrations are desired, the best results are obtained by using the powdered active ingredient premixed with thinners, binders and surfactants and then granulated so that the active ingredient is distributed throughout the grains and not just on their surface is present.

The active ingredient content of these granules can range from 1 to 90%; however, an active ingredient concentration of 75 ffi is about the upper limit, who one wants to achieve a controlled disintegration of the grains in the moist soil. The control of the disintegration rate is achieved by controlled compaction, e.g. through controlled extrusion pressure, and through the addition of inert, water-soluble Components like Sodium sulfate or surfactants, which im Leached soil.

Watery. Dispersions of fungicides are the most wettable powders preferable if only devices are available with which a minimum dimension movement can be achieved, but precise dosing is essential. Even the The best and finest wettable powders do not disperse completely in water. Rather, what remains is small agglomerates that settle more quickly. When the pesticide is in an aqueous phase in the presence of dissolved surfactants is ground, each individual particle develops an adsorbed layer, which repels the neighboring particles, and a permanent complete dispersion is obtained. However, this still does not prevent it from slowly settling on the bottom of the storage container forming a dense tone that is difficult to resuspend leaves. A practical aqueous dispersion concentrate can be used for long periods of storage do not form such a sediment. This type of discontinuation works in an effective way hydrated by certain acrylic acid polymers and treated by shear Prevents attapulgite.

Suitable aqueous dispersions of the compounds according to the invention are made by grinding the active ingredient with one or more dispersants and an anti-settling agent in the silica mill or in the sand mill in Water prepared until the particle size of the active ingredient is less than 10, preferably less than 5. For use in cold climates where there is freezing antifreeze agents, such as mixtures of glycols and water, can be considered coherent Use phase.

The means according to the invention can besides those according to the invention Active ingredients conventional insecticides, mite killers, Bactericide, Nematocides, fungicides or other agricultural chemicals, such as fruit treatment agents, Fertilizers and the like, so that they can be used except for the control of Fungus and mite infestations can also be used for other useful purposes can.

In the following examples showing the activity of the compound of the general formula I explain, the parts relate, unless otherwise is indicated on the weight.

Example L ~ e3 9% by weight 1,1 '- (hexamethylene dicarbamoyl) bis (2-benzimidazole carbamic acid dimethyl ester) 50 Sodium alkylnaphthalene sulfonate 3 Sodium N-methyl-N-palmitoyl taurate 2 Diatomaceous earth 45 The ingredients are mixed and micropulverized and then air milled Grind down to particle sizes below 5 W.

The wettable powder thus obtained is in an active ingredient concentration of 500 ppm added to water. This suspension is used to every second Spray tree in an apple plantation to drain. The spraying takes place at one-week intervals from April 25th to June 6th.

From June 6th until the end of the ripening period, the spray treatments are carried out done every two weeks. The remaining trees in the plantation are left untreated.

At the beginning of September, all trees are carefully examined. With Trees sprayed with the compound according to the invention are healthy and free from mite infestation and fungus damage. the There are fruits on the sprayed trees immaculate and of good size. The leaves of the unsprayed trees, on the other hand are strong from 'the apple scab fungus (Venturia inaequalis) - and the - powdery Meltaufungus (Podosphaera leucotricha) infested.

Furthermore, the leaves of the unsprayed trees are very different from the European ones Infested red mite (Panonychus ulmi). The fruits on the unsprayed trees are spotty with scab and small.

B e i s p i e 1 10% by weight 1,1 '- (tetradecamethylene dicarbonyldicarbamoyl) bis (2-benzimidazole carbamic acid diethyl ester) 10 Sodium diamyl sulfosuccinate 0.5 Pyrophyllite 89.5 The active ingredient, the wetting agent and an equal weight of pyrophyllite are first mixed and micropulverized and grind in the air mill. Then the powder with the rest of the pyrophyllite mixed.

A uniform cherry planting in Michigan is used for the test selected. Every other tree is every 14 days in, a density of 900 g per tree treated with the above dust. The remaining trees remain untreated.

On September 1st, the trees will be examined. The trees that come with the Compound according to the invention have been pollinated; are green and healthy, and all the leaves have remained on the trees. At the same time the leaves are of unprotected trees as a result of infestation by the leaf spot fungus (Coccomyces hiemalis) and the two-spotted mite (Tetranychus urticae) largely discolored. A large part of the leaves of the untreated trees is due to the effect of this both pests fell off.

For example, 11% by weight 1,1 '- [1,4-cyclohexylenedicarbonyl-bis- (thiocarbamoyl) 7-bis- (2-benzimidazolecarbamic acid diisopropyl ester) 30 Condensation product of polyethylene oxide and lauryl alcohol 10 Isoparaffin oil ("Soltrol 170 ") 60 The above ingredients are mixed together and ground in the sand mill, until the active ingredient is comminuted to a particle size below 10 T. The oil suspension can be diluted with water to form a sprayable emulsion or immediately as a concentrate be injected using an "ultra-low volume" equipment.

The formulation of this example is suitable for combating the the fungus Cercospora musae caused Sigatoka disease in bananas. this will explained in a field experiment in which certain areas of a banana plantation are treated with 400 g of active ingredient according to the invention per hectare, the active ingredient splashed in enough water to ensure good distribution. The treatment is carried out every 14 days.

Four months after the start of the test, the banana planting is in the treated plots free from the disease, while the untreated plants are severely affected by Sigatoka disease.

Example 1 12 A latex paint for household use contains the following components: parts of hydroxyethyl cellulose (2.5 percent solution) water 68.5 non-ionic dispersant, 25% 15 ("Tamol 73111 from Rohm & Haas) wetting agent 2.5 ( "Triton CF-10" from Rohm & Haas) Antifoam 1 ("Nopco NDW" from Nopco) ethylene glycol 25 non-exuding rutile 250 (titanium dioxide) talc 203.7 fungicide: 1.1 '- (4-methyl-m-phenylenedi- 1,2 carbamoyl) -bis- (2-benzimidazolcarbamic acid dimethyl ester) The above ingredients are ground in a high speed mill and then diluted at a slower speed with the following substances: Parts Acrylic resin, 50 percent 459.8 ("Rhoplex AC-388") Antifoam agents 1 ("Nopco NDW ') Ammonium hydroxide (28 0)) 2 Tributyl phosphate 11.5 Propylene Glycol # Premix 35 Water and / or hydroxyethyl cellulose (2.5%) 17.5 Tinting agent: "Cal / Ink GP8814E Phthalo Blue" -0.05 "Ca; / Ink GP8807B" lamp soot 0.05 The latex paint is applied in two coats to rhatman filter paper no. The first coat is left to dry for 24 hours before the second coat is applied. A square of the coated paper with a side length of 38 mm is heated to 700 ° C. for 24 hours and then treated with running tap water for 24 hours. The paint sample thus obtained is applied to the surface of malt agar in a petri dish and inoculated with an aqueous suspension of Pullularia pullulans (the main fungus isolated from meltau on a paint paint). After four weeks, the paint sample has completely inhibited the growth of the fungus, while a second sample, which has been coated with the same paint but without containing the fungus, is completely covered with the fungus.

If you use the 1,1 '- (4-methyl-m-phenylenedicarbamoyl) -bisbenzimidazolecarbamic acid dimethyl ester) in the latex paint by the same weight amount of one of the following compounds replaced, the paints have a similar inhibitory effect on the growth of Fungi on: 1,1 '- (p-Phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester)> 1,1 '- [methylene-di- (p-phenylcarbamoyl)] - bis- (2-benzimidazole carbamic acid dimethyl ester), 1,1 '- [methylene-bis- (4-cyclohexylcarbamoyl)] - bis- (2-benzimidazolecarbamic acid dimethyl ester), 1,1 '- (m-Phenylenedicarbamoyl) bis (2-benzimidazolecarbamic acid dimethyl ester), 1,1' - (2-Methyl-m-phenylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester).

EXAMPLE 13 A household oil paint made from the The following components are used for the experiment described below used.

Parts of titanium dioxide ("TI-Pure R-966") 300 Talc 315 Oil-extended Alkyd Resin 400 ("Dyel XAC-C129" from Sherwin-Williams Co.) 24 percent lead naphthenate 6.9 6 percent manganese naphthenate 1.4 heavy gasoline 169 1000 parts of the above paint are mixed with 1 part of finely ground 1,1 '- (4-methyl-m-phenylenedicarbsamoyl) -bis- (2-benzimidazole carbamic acid dimethyl ester) with particle sizes of 'less than 35 µ added.

A roof shingle side can be painted with this fungicidal oil paint can be provided with an ordinary painting brush. When the paint has dried the clapboard is resistant to fungus infestation.

Claims (15)

Claims 1. Compound characterized by the general formula in the the radicals R can be identical or different and are methyl, ethyl, isopropyl or sec-butyl radicals, X is a hydrogen or halogen atom or a methyl or methoxy group, and A is a divalent group with 1 to 18 Carbon atoms, namely an alkylene group, oxa-, N-methylaza- or thia-substituted alkylene group, alkenylene group, cycloalkylene group, bis (cyclohexylene) -methylene group, alkylated cyclohexylene group, alkylenated cyclohexane group, oxa or methylaza-substituted alkylated azo-cyclohexylene group, alkyl-alkylene-acylene group, N-alkycyleneacylene group, alkylated cyclohexylene group Denotes phenylene group, methylated phenylene group or bis (phenylene) methylene group. 2. A compound according to claim 1, characterized in that A is a means divalent hydrocarbon group. 3. A compound according to claim 1, characterized in that R den Methyl radical and X is a water stiff atom. 4. Compound according to claim 3, characterized in that it contains 1- {5- [2- (methoxycarbonylamino) -1-benzimidazolylcarbonylamino] -1,3,3-trimethyloyclohexylmethylcarbamoyl} -2-benzimidazolecarbamic acid methyl ester is. 5. A compound according to claim 3, characterized in that it contains 1,1 '- (2,2,4-? Rimethylhexamethylenedicarbamoyl) -bis- (2-benzimidazolecarbamic acid dimethyl ester) is. 6. A compound according to claim 3, characterized in that it contains 1,1 '- (4-methyl-m-phonylandicarbamoyl) -bis- (2-benzimidazolcarbamic acid dimethylesterj) is. 7. Process for the preparation of compounds of the pure formula in which the radicals R can be identical or different and are methyl, ethyl, isopropyl or sec-butyl radicals, X is a hydrogen or halogen atom or a methyl or methoxy group, and A is a divalent group with 1 to 18 carbon atoms, namely an alkylene group, e oxa, N-methylaza or thia-substituted alkylene group, alkenylene group, cycloalkylene group, bis- (cyclohexylene) -methylene group, alkylated cyclohexylene group, alkylenated cyclohexane group, oxa or methylaza-substituted alkylated cyclohexylene group, methylated, phenyl alkylene group, phenoxyalkylenated azacycylene group, N-alkycylenated azacycylene group Phenylene group or bis (phenylene) methylene group means, characterized in that about 2 equivalents of a 2-benzimidazole carbamic acid alkyl ester of the general formula in which R and X have the meanings given above, with about one equivalent of a diisocyanate of the formula O = C = N- (A) -N = C = O in which A has the meaning given above. 8. Process for the 'preparation of a compound of the general formula in which R and R 'are identical or different and represent methyl, ethyl, isopropyl or sec-butyl radicals, X and X' are identical or different and represent a hydrogen or halogen atom or a methyl or methoxy group and A is a divalent group with 1 to 18 carbon atoms, namely an alkylene group, oxa-, N-methylaza- or thia-substituted alkylene group, alkenylene group, cycloalkylene group, bis- (cyclohexylene) -methylene group, alkylated cyclohexylene group, alkylenated cyclohexane group, oxa or methylaza-substituted alkylated cyclohexylene group N-alkylenated azacyclohexane group, bicycloalkylene group, phenylene group, methylated phenylene group or bis (phenylene) methylene group, characterized in that about one equivalent of a compound of the general formula first with about one equivalent of a diisocyanate of the formula O = C = NAN = C = O and then with about one equivalent of a compound of the general formula implements 9. The method according to claim 7, characterized in that R is methyl and X means hydrogen. 10. The method according to claim 9, characterized in that the diisocyanate Is 5-isocyanato-1- (isocyanatomethyl) -1,7,3-trimethylcyclohexane. ll. The method according to claim 9, characterized in that the diisocyanate Is 2,2,4-trimethylhexamethylene diisocyanate 12. The method according to claim 9, characterized characterized ,, that the diisocyanate is 4-methyl-m-phenylene diisocyanate. 13. The method according to claim 9 ,, characterized in that the diisocyanate is p-phenylene diisocyanate. 14. The method according to claim 9, characterized in that the diisocyanate Methylene di (p-phenyl isocyanate) is. 15. Mites aicides or fungicides, consisting essentially of from an effective amount of a compound according to claim 1 with a diluent.