CH512188A - Alkyl-substd 2-benzimidazole carbamate transition metal complexes - fungicides, arachnicides - Google Patents

Abstract

Complexes of transition metals and alkyl substd. 2-aminobenzimidazolecarbamates X=H, alkyl (C1-4), nitro or alkoxy (C1-4), R1=methyl, ethyl, isopropyl or sec. butyl; R2=alkyl (C1-12), alkenyl (C3-12), alkynyl (C3-12), cycloalkenyl (C4-8), cycloalkyl (C3-8) substd. with methyl, methoxy or Cl; (cycloalkyl)-alkyl (C7-8), phenyl opt. substd. with methyl, ethyl, methoxy, ethoxy, nitro, CF3, CH3SO2 or halogen, benzyl opt. substd. with methyl, nitro, methoxy or halogen; or H; R3=H, alkyl (C1-12) opt. substd. with cyano, OR1 acetoxy, Cl or F; alkenyl (C3-10), alkynyl (C3-10), cycloalkyl (C3-8) or Z=alkyl (C1-3) opt. substd. with Cl; phenyl opt. substd. with nitro, methyl or Cl; benzyl opt. substd. with nitro, methyl or Cl; Me=Zn, Cu, Ni, Mn, Co, Cd, Fe or Cr, n=0, 1/2, 1, 1 1/2, 2 or 3. (I) have fungicidal- and ovicidal activity against arachnids as well as curative properties; they may be used against fungus diseases of all parts of plants during growth as well as during handling, storing etc.

Description

  

  
 



  Pesticides containing transition metal complexes of substituted alkyl 2-benzimidazole carbamates
The present invention relates to new pesticides containing complexes formed between transition metal cations and substituted 2-aminobenzimidazoles, processes for their production, and the use of these pesticides for preventing or attenuating the damage to plants and inanimate organic substances by fungi and mites.  In the context of the present patent, protection for the use of the pesticides according to the invention is only claimed insofar as it does not concern any finishing of raw or processed textile fibers which is suitable for the textile industry. 



   For a long time, man's viability was largely dependent on his ability to protect plants and their products, which satisfy his basic needs, from the various influences of destruction.  With the world's rapidly growing population, it is imperative that the effectiveness of the materials and processes used to achieve this protection continue to be greatly improved.  This improvement may be in the form of effective control of multiple species of pests or in the form of requiring less material or labor.  The substances and processes according to the invention have distinct advantages with regard to these two possible forms of improvement, as will be explained in detail below. 



   It has now been found that the use of the pesticides according to the invention surprisingly completely excludes or reduces damage to plants and inanimate organic substances both by fungi and by mites.  Fungal mycelia are killed or prevented from further development by the presence of one or more of the complexes contained in the pesticides, i. E.  H. , the complexes are fungicidal or fungistatic.  The complexes also prevent or minimize or eliminate mite populations from expanding by preventing the normal development of their eggs;  H. , they are mite-ovicid. 



   The pesticides and methods of operation according to the invention also enable the damage caused by both fungi and mites to be controlled with an astonishingly small amount of chemicals and with surprisingly little effort.  These advantages are largely due to the fact that, when used correctly, the complexes can enter and move around plants.  This means that an entire plant can be protected from mites and fungi with a simple application of the chemical to only part of it, i.e.  H.  the complexes are systemic.  In addition, if the pesticides are used after a pathogenic fungus is already in a plant, the complexes can enter the tissues and clear the infection;  H.  the complexes are healing. 

  In this way, in many cases, the need for application prior to the actual onset of the disease is eliminated. 



   The invention relates to a pesticide which has the above-mentioned excellent fungicidal and milbenovicidal activity and which is characterized in that it contains at least one complex of the formula I as an active ingredient in addition to an inert carrier
EMI2. 1
 where Q is the meaning
0 0 -C-NHR2, t or -SZ, X has hydrogen, halogen, alkyl with 1 to 4 carbon atoms, nitro or alkoxy with 1 to 4 carbon atoms, R1 methyl, ethyl, isopropyl or sec. -Butyl, R2 alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 12 carbon atoms, alkynyl with 3 to 12 carbon atoms, cycloalkenyl with 4 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, with methyl,

   Methoxy or chlorine-substituted cycloalkyl with 3 to 8 carbon atoms, (cycloalkyl) -alkyl with 7 or 8 carbon atoms, phenyl, with methyl, ethyl, methoxy, ethoxy, nitro, CF:,.       CH1SO or halogen-substituted phenyl, benzyl, benzyl or hydrogen substituted with methyl, nitro, methoxy or halogen, R:

  : Hydrogen, alkyl with 1 to 12 carbon atoms, with cyano, -OR1, acetoxy, chlorine or fluorine substituted alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, cycloalkyl with 3 to 8 carbon atoms or the group of the formula
EMI2. 2
 Z alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted with chlorine, phenyl, phenyl substituted with nitro, chlorine or methyl, benzyl or benzyl substituted with nitro, chlorine or methyl, Me zinc, copper, nickel, manganese, cobalt , Cadmium, iron or chromium and n means zero, 1/2, 1, 11/2, 2 or 3. 



   Among the compounds of the formula I, the compounds with the following formula II are preferred because of their greater pesticidal activity:
EMI2. 3
 where Q1 is the meaning
EMI2. 4th
 or - SCC13, R1 'denotes methyl or ethyl, Ro' denotes alkyl with 1 to 8 carbon atoms, Me denotes zinc or manganese and n denotes zero, 1, 1l / or 2. 



   Among the compounds of the formula I, the following complexes are most preferred because of their activity:
The 2: 1 zinc complex of 1- (butylcarbamoyl) -2benzimidazole carbamic acid methyl ester and the 2: 1 manganese complex of 1- (butylcarbamoyl) 2-benzimidazole carbamic acid methyl ester. 



   The present invention also relates to new processes for the preparation of the complexes according to formula I. 



  In these processes, the benzimidazole carbamate starting compound is reacted with the suitable metal salt in a system consisting of a) an aqueous solution of the metal salt, b) a suitable organic solvent and c) the benzimidazole carbamate, which is initially mainly in undissolved solid form in the organic solvent is present, and, if necessary, d) an aqueous solution of a base. 

 

   The system is vigorously stirred and, after a suitable period of time, the complex product is separated off by pouring the mixture into water and then filtering or by direct filtration of the reaction mixture, depending on the type of reaction used. 



   The invention is described in detail below. 



   The novel complexes according to the invention are prepared by reacting a benzimidazole carbamate with the suitable metal salt.  The benzimidazole carbamate reactants used have the general formula
EMI3. 1
 where Q is the meaning
EMI3. 2
 or -SZ has, X is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, nitro or alkoxy with 1 to 4 carbon atoms, R1 is methyl, ethyl, isopropyl or sec. -Butyl, R2 alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 12 carbon atoms, alkynyl with 3 to 12 carbon atoms, cycloalkenyl with 4 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, methyl, methoxy or chlorine-substituted cycloall:

  : yl with 3 to 8 carbon atoms, (cycloalkyl) -alkyl with 7 or 8 carbon atoms, phenyl, with methyl, methyl, methoxy, ethoxy, nitro, CFs, CH3SO- or halogen substituted phenyl, benzyl, with methyl, nitro, methoxy or Halogen-substituted benzyl or hydrogen, R3 hydrogen, alkyl with 1 to 12 carbon atoms, cyano, -OR1, acetoxy, chlorine or fluorine-substituted alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or the group
EMI3. 3
 and Z alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted with chlorine, phenyl, phenyl substituted with nitro, chlorine or methyl benzyl or with nitro,

   Signify chlorine or methyl substituted benzyl. 



   Among the benzimidazole arbamates, the compounds in which X is hydrogen, Q is the meaning
EMI3. 4th
 or - has SCCl5, R1 has methyl or ethyl and R; Mean alkyl having 1 to 8 carbon atoms, preferred in view of the high activity of the complex product. 



   In view of the highest activity of the resulting complexes, the following compounds are most preferred:
1 -Butylcarbamoyl-2-benzimidazole carbamic acid methyl ester, 1 - hexylcarbamoyl - 2 - benzimidazole carbamic acid methyl ester, 1 - octylcarbamoyl - 2-benzimidazole carbamic acid methyl ester,
1 - (o - Methoxyphenylcarbamoyl) - 2 -benzimidazolecarbamic acid methyl ester, 1-trichloromethylthio-2-benimidazolecarbamic acid methyl ester and 1-trichloromethylthio-2-benzimidazolecarbamic acid ethyl ester. 



   The benzimidazole carbamate reactants can be prepared in accordance with the prior art, for example as described in Belgian Patent No.  698 071 is described. 



   You can thus by reacting a 2-benzimidazole carbamate of the formula
EMI3. 5
 with 1 equivalent of an alkylchlorothiol formate, alkylchlorothionoformate, alkylchlorodithioformate, isocyanate, acyl chloride or a sulfenyl chloride in an inert solvent.  The 2-benzimidazole carbamates can be prepared according to U.S. Patent No.  3,010,768. 



   The transition metal salts used in the preparation of the metal complexes according to the invention are salts of zinc, manganese, nickel, cobalt, copper, cadmium, iron and chromium.  The salts can be acetates, chlorides, sulfates, nitrates, citrates and the like. 



  Complexes containing zinc and manganese are preferred because of their high fungicidal activity. 



   The complexes may in some cases have different structures, for example they may be 1: 1 complexes instead of 2: 1 complexes, and they may contain anions such as acetate ions when the complex is made from a metal acetate, and the like.  However, such complexes are usually obtained by procedures other than the novel processes of the invention.  For example, they can be obtained by reacting the benzimidazole derivative and the metal salt in an organic solvent such as ethyl acetate in the absence of water.  The products thus obtained have the disadvantage of being unstable in the presence of water and are therefore not preferred. 



   The novel complexes according to the invention can be prepared either by known procedures or by the novel processes according to the invention. 



  In a known preparation, as described in Example 6, the benzimidazole carbamate derivative is dissolved in a suitable solvent such as dimethylformamide and one molar equivalent of sodium methylate is added to convert the benzimidazole carbamate to its sodium derivative.  Half a molar equivalent of the desired metal salt in the form of a solution in dimethylformamide is added to the solution thus obtained.  After stirring for a suitable period of time, e.g. 15 minutes, the reaction mixture is poured into a mixture of ice and water with stirring, and the product is isolated by filtering, washing and drying. 



   In contrast to this known process, one of the novel procedures according to the invention allows the slurry instead of dissolving the benzimidazole carbamate and the heavy metal salt in dimethylformamide, which greatly reduces the amount of dimethylformamide required.  In addition, concentrated aqueous sodium or potassium hydroxide or carbonate is used in the new process instead of the much more expensive sodium methylate, or it can tert. Lower alkylamines or tetra-lower alkylammonium hydroxides can be used, and in addition the cheaper metal salts of inorganic acids, for example sulfates, chlorides or nitrates, can be used instead of the much more expensive salts of organic acids, for example acetic acid, for which reference is made to Example 10. 



   In other embodiments of the novel process according to the invention, the dimethylformamide used as solvent is replaced by acetone (Example 11) or methyl ethyl ketone (Example 12), and the heavy metal salt is added in the form of a highly concentrated or saturated aqueous solution.  The use of methyl ethyl ketone has the advantage that the metal complex can be isolated by simple filtration without it being necessary to pour the reaction mixture into water.  The methyl ethyl ketone recovered in the filtration can be used as such in the preparation of the next batch of metal complex.  It is clear to the person skilled in the art that these procedures, in particular when using methyl ethyl ketone, can be carried out continuously. 



   In another novel procedure according to the invention, the benzimidazole carbamate is reacted with the metal salt in a three-phase system which consists of the aqueous solution of the metal salt, a suitable, water-immiscible organic solvent, such as ethyl acetate, and the benzimidazole carbamate, which is mainly in undissolved solid form in the organic solvent is present.  The use of a base is avoided in this procedure.  The three-phase system is stirred vigorously and after a suitable stirring time, which depends on the reaction conditions used, the solid phase has passed from the organic phase into the aqueous phase, which means that the reaction is complete.  This phenomenon can be checked by interrupting the stirring process for a moment in order to allow the liquid phases to separate. 

  The product is separated off by filtration or the like and the two liquid phases in the filtrate can be used directly in the preparation of the next batch of product.  It is clear to the person skilled in the art that this new procedure is extremely suitable for continuous operation, for example in a tubular reactor. 



   In the more detailed description of this method of operation according to the invention, Example 1 below can be chosen as a starting point.  In this example, a substantially saturated solution of 6 molar equivalents of zinc acetate dihydrate in water with about 10 wt. % slurry of 1 molar equivalent molar equivalent of 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester mixed in ethyl acetate at room temperature.  The volumes of the two liquid phases are the same and are each about 3200 cms per mole of benzimidazole carbamate.  Provided that stirring is vigorously and effectively so that the stirred mixture has the appearance of an emulsion, the conversion to the metal complex occurs almost immediately under these conditions. 



  These or similar conditions are therefore particularly suitable for a continuous process, for example in a tubular reactor. 



   If the stirring is stopped, the two liquid phases separate practically immediately.  The two phases can first be separated and then the aqueous phase can be filtered in order to obtain the product, or the three-phase system can be filtered as such without prior separation.  In either case, the two phase filtrate can be used as such for the preparation of the next batch of metal complexes by simply adding the required amounts of benzimidazole carbamate and metal salt. 



   The conditions described in Example 1 can be varied within wide limits.  For example, the amount of zinc acetate dissolved in the aqueous phase can be reduced from 6 molar equivalents to 1 molar equivalent (which is an excess of 100% over theory).  At this concentration of zinc acetate, the conversion in the metal complex no longer takes place immediately, but it is still very rapid.  However, if the amount of zinc acetate is reduced even further, for example to a 10% excess over theory, with the other conditions remaining the same, the conversion proceeds so slowly that it is still incomplete after 6 hours of stirring with a normal laboratory stirrer. 

  It should be noted that the use of specially designed high speed stirrers, Waring mixers and the like will of course lead to a reduction in the time required for complete conversion. 



   The concentration of zinc acetate in the aqueous phase can be below the saturation value.  For example, if, as above, 1 molar equivalent of zinc acetate (100% excess) is used in twice the amount of water (about 6400 cm3 per mol of benzimidazole carbamate), the conversion will still take place but will take 1 to 2 hours. 



   The volume of water and ethyl acetate used can both be decreased or increased.  However, it is preferred not to reduce the volume levels below the point at which effective mixing of the phases is hindered.  Increasing these volumes increases the duration of the reaction and generally offers no great advantages. 



   However, water and ethyl acetate must both be present.  As discussed above, the use of ethyl acetate alone leads to the formation of a 1: 1 zinc acetate complex which is unstable in water and is therefore not preferred.  The use of water alone, even for long reaction periods, does not lead to any appreciable conversion.  The ethyl acetate can be replaced by other suitable water-immiscible esters and ethers, for example amyl acetate, diethyl ether, but the use of hydrocarbons, chlorinated hydrocarbons and the like, for example benzene, hexane, chloroform, generally leads to poor or slow conversions, which is why the latter Solvents are not preferred.  

  The use of water-miscible ethers, such as tetrahydrofuran, results in the formation of rather difficult-to-work-up mixtures which, while having fungicidal toxicity, are not preferred. 



   As already mentioned above, ethyl acetate can also be replaced by such water-miscible or partially water-miscible solvents such as dimethylformamide, acetone or methyl ethyl ketone, but in these cases the presence of a base is necessary in order to obtain high yields.  It has also already been mentioned that the heavy metal sulfates, for example, work just as well as the acetates. 



   In the procedure of Example 1, the pH of the reaction mixture plays a role in the ease and extent of the reaction, as can be seen from the fact that the reaction is much less easy with zinc chloride than with zinc acetate.  It is advisable to determine the optimal pH conditions for each benzimidazole carbamate and for each metal salt and, if necessary, to adjust the pH to the optimal value and maintain it. 



   With regard to all the novel working methods according to the invention, it should be noted that the temperature at which the conversion is carried out can generally vary between the freezing point and the boiling point of the reaction mixture.  Elevated temperatures can be advantageous, for example, in cases where the metal salt used has low water solubility.  However, the 1-subst used as starting materials according to the invention. -Benzimidazolcarbamidsäureester to varying degrees thermal instability at elevated temperatures, which depends on the nature of the substituent in the 1-position. 



  In cases in which this thermal instability is pronounced, it is recommended that the other reaction conditions are chosen so that the reaction takes a minimum of time and that the temperature is kept below, for example, 500 ° C.  The reactions are preferably carried out at room temperature without external heating or cooling.  Depending on the solubility of the product in the organic solvent, it is in some cases of some advantage with regard to the yield to cool the reaction mixture to, for example, 0 to 30 ° C. before filtering. 



   Another factor that affects the ease of conversion and the yield is the particle size of the organic starting material.  For example, it has been found that micro-comminution of the starting material can in some cases increase the yield of metal complex by 15 under otherwise identical conditions. 



   The novel complexes according to the invention prepared by the known processes and by the new processes explained above are usually obtained in the form of dihydrates under normal drying conditions, for example when spreading in air or drying in a vacuum oven at somewhat elevated temperatures, for example up to 500 ° C. .  The substances can, however, be converted into forms that contain less water, for example into the corresponding monohydrates, hemihydrates or the completely anhydrous forms.  The monohydrates and the anhydrous forms are by far the most commonly preserved forms. 



   They are obtained, for example, by vacuum drying at elevated temperatures, for example 60 to 1000 ° C., or by drying in solution or suspension.  These procedures are illustrated in Examples 13-16.  In some cases, the conversion of the dihydrates into the corresponding monohydrates or anhydrous forms not only leads to increased antifungal and miteicidal activity, but also to a significantly increased storage stability. 



   This is the case in particular with the 1-carbamoyl compounds according to the invention.  As discussed in Examples 13-16, drying the dihydrates of this type to the corresponding monohydrates or anhydrous forms leads to changes in the IR spectra, for example the appearance of a peak at 5.8 p which, together with the increased stability, indicate a structural rearrangement in the metal complex, as a result of which the group -COOR1 in the 2-position no longer takes part directly in the binding of the metal atoms and this binding function is taken over by the carbamoyl group in the 1-position.  It should therefore be noted that the corresponding compounds of the formula I or II, in which n is zero, 1/2 or 1, have structures of the following type:
EMI5. 1
 and the like. 



   For reasons of expediency, however, the compounds according to the invention are still referred to as compounds of the formula I or II. 



   The following examples illustrate the preparation of compounds of formula I.  The amounts given in parts are parts by weight, unless otherwise stated.  In some examples, both parts by weight and parts by volume are mentioned, in these cases the units of measurement such as g to ml, kg to liter and the like correspond. 



   Example 1 Preparation of 1- (butylcarbamoyl) -l-benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate
14.5 parts of methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate and 144 parts (160 parts by volume) of ethyl acetate are added to a practically saturated solution of 66 parts of zinc acetate dihydrate in 160 parts of water.  This mixture contains 6 moles of zinc acetate dihydrate per mole of organic starting material.  The mixture is a three-phase system in which the solid organic starting material in the ethyl acetate layer is mainly in undissolved form.  The mixture is vigorously stirred at room temperature.  After a few minutes the stirrer is stopped and the mixture is allowed to separate into its phases. 

  It is observed that the solid material is now in the aqueous layer, which means that the reaction is complete.  Under the conditions of the present example, the reaction occurs practically immediately.  The reaction mixture is cooled to 0 to 5 ° C. in order to increase the yield, filtered and the solid is washed with cold ethyl acetate and cold water and dried.  The product weighs 15.3 parts (90%).     It is found that the ethyl acetate layer contains 1 part of organic starting material on evaporation, so that the yield is 97.0%, based on the converted starting material. 



   The IR spectrum shows the following characteristic changes in comparison with the IR spectrum of the organic starting material: The characteristic peaks shown by the parent compound at about 5. 8 and p. 8 / z have disappeared and there are new ones
Peaks at around 60, 6. 6 and S, 7 w before. 



     NMR spectrum: the product has a triplet at --0. 88; - with a coupling constant J = 5.1 Hz.  This absorption is due to the proton attached to the N in the 1-butylcarbamoyl group.  The same triplet is in the parent compound and occurs at -0. 45 to with a coupling constant of J = 5.1 Hz. 



   The presence in the product of the essentially unchanged absorption of the proton linked to the N in the 1-butylcarbamoyl group is strong evidence of the lack of a relationship between the butylcarbamoyl group of the molecule and the metal atom. 



   The spectrum of the starting compound shows an absorption at -2.28 (broad), which is assigned to the proton which is linked to the nitrogen in the 2-position.  This peak is no longer present in the product, indicating that this proton has been replaced by the metal. 



   The rapid exchange of the two protons discussed above is hindered in deuterodimethylsulfoxide (when used as a solvent), which allows observation of their separate absorption positions and, if appropriate, their coupling constants. 



   There is no other absorption below 1.5 y in either the product or the starting compound. 



  Changes in the absorption pattern of the aromatic hydrogens support the assignment of an association of the nitrogen in the 3-position with the metal. 



   Analysis C2sU-iN8OsZn: calc. : C 49.5 H 5.6 N 16.5 Zn 9.6% found. : C 59.50 H 5.61 N 16.42 Zn 9.59 Scl2melzpwlk-t: The product melts over a very wide range, as is to be expected for a compound of this type. 



     DelzAdratisierlslg: As described in more detail in one of the examples below, the product loses two molecules of water when heated in a vacuum oven to 60 to 65 C. 



     Structural formula: The above data is in accordance with the following structural formula:
EMI6. 1

Example 2 Production of
1- (Butylcarbamoyl) -2-benzimidazole-carbamate-2: 1-manganese complex dihydrate to a solution of 74 parts of manganese acetate tetrahydrate in 220 parts of water are added 14.5 parts of 1 (butylcarbamoyl) -2-benzimidazole-carbamate and 171 parts (190 parts by volume) of ethyl acetate.  The mixture is stirred vigorously at room temperature for 2 hours and then filtered.  The solid is washed with ethyl acetate and water and dried. 

  Spectral and elemental analyzes of the type discussed in Example 1 show that under the conditions used the conversion is not complete and that the material obtained is a mixture of about 55S manganese 2: 1 complex dihydrate and about 45% starting compound.  The starting compound is removed by slurrying the material with chloroform, filtering and washing with chloroform.  The insoluble solid consists of the desired complex. 



   The IR spectrum shows the absence of peaks at 5.8 and 8.8 j which are characteristic of the starting material and the presence of peaks at 6.0, 6.6 and 8.7 / e which are characteristic of the desired one Manganese 2: 1 complex dihydrate are characteristic. 



   Analysis C2sH38N808Mn: calc. : C 50.25 H 5.7 N 16.8% found. : C 50.47 H 5.75 N 16.75
The structural formula of this material is the same as in Example 1, with the difference that the zinc atom has been replaced by a manganese atom. 

 

   Example 3 Preparation of 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester-2: 1-copper complex
29 parts of methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate and 405 parts (450 parts by volume) of ethyl acetate are added to a solution of 60 parts of copper III acetate dihydrate in 850 parts of water.  The mixture is vigorously stirred at room temperature for 3 hours and then filtered.  The solid is washed with ethyl acetate and water and dried.  It consists of a light green powder and weighs 28 parts.  The IR spectrum shows characteristic peaks at 5. 95, 6.5 and 8.7 it.    



  There are no peaks at 5.8 and 8.8 u.   



   Analysis Ce8H34N806Cu: calc. : C 52.45 H 5.4 N 17.5% found. : C 52.49 H 5.47 N 17.33
Example 4 Preparation of 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester-2: 1 nickel complex trihydrate
14.5 parts of methyl 1 (butylcarbamoyl) -2-benzimidazole carbamate and 171 parts of ethyl acetate are added to a solution of 75 parts of nickel acetate tetrahydrate in 220 parts of water.  The mixture is vigorously stirred at room temperature for 2 hours.  The mixture is then filtered and the solid is washed with ethyl acetate, water and acetone and dried.  It weighs 11 parts. 



   The infrared spectrum shows the presence of a small amount of starting material and also clearly shows the characteristic peaks of the desired product at 6.0.     6.6 and 8.7.     The product is a light greenish blue powder. 



   Elemental analysis, calculated for a 9: 1 mixture of product and starting material: calc. : C 49.63 H 5.84 N 16.51% found. : C 49.69 H 5.80 N 16.06
Example 5 Preparation of 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 cobalt complex dihydrate
14.5 parts of methyl 1 (butylcarbamoyl) -2-benzimidazolecarbamate and 171 parts of ethyl acetate are added to a solution of 75 parts of cobalt acetate tetrahydrate in 220 parts of water.  The mixture is vigorously stirred at room temperature for 2 hours.  The mixture is then filtered, washed with ethyl acetate, water and acetone and dried.  The light pink powder weighs 16 parts. 

  The infrared spectrum shows characteristic peaks at 6.0, 6.6 and 8.7, and the like.     It also shows the presence of a small amount of starting material. 



   Elemental analysis, calculated for a 9: 1 mixture of product and starting material: calc. : C 50.80 H 5.76 N 16.87 Co 7.87% found. : C 50.89 H 5.87 N 16.62 Co 7.56
Example 6 Preparation of the manganese complex of Example 2 by a known method
29 parts (1 molar equivalent) of methyl 1- (butylcarbamoyl) -2benzimidazole carbamate are added to 19 parts of dimethylformamide.  The mixture is stirred while 5.4 parts (1 molar equivalent) of sodium methylate are added.  The organic material dissolves.  Then a solution of 12.2 parts (0.5 molar equivalents) of manganese acetate tetrahydrate in 50 parts of dimethylformamide (dissolved by gentle heating) is added while stirring at room temperature.  After stirring for a further 15 minutes, the mixture is poured into 3000 parts of ice and water with stirring. 

  After stirring for a further 30 minutes, the mixture is filtered, washed with water and dried.  The product is identical to the product of Example 2 in all respects. 



   Example 7 Preparation of the product of Example 1 in diethyl ether and water
The method of preparation of Example 1 is repeated, with the difference that the 160 parts by volume of ethyl acetate are replaced by an equal volume of diethyl ether. 



   The reaction proceeds in essentially the same manner and the product is identical to that of Example 1 in all respects. 



   Example 8 Preparation of the product of Example 1 in amyl acetate and water
The method of preparation of Example 1 is repeated with the difference that the 160 parts by volume of ethyl acetate are replaced by an equal amount by volume of n-amyl acetate.  The reaction proceeds in essentially the same manner and the product is identical to that of Example 1 in all respects. 



   Example 9
Using the procedure of Example 1, the organic substances compiled in the table below are reacted with zinc acetate in water / ethyl acetate in the same molar amounts as in Example 1, resulting in the products listed. 



   Table of starting material Product Infrared spectrum 1- (n-Hexylcarbamoyl) -2- 1 - (n-Hexylcarbamoyl) -2-benzimidazole - characteristic methyl benzimidazole carbamic acid - carbamic acid - 2: 1-zinc com peaks at 5.96, methyl ester plex dihydrate 6.55 and 8,7, 1 - (n-octylcarbamoyl) -2 1 - (n-octylcarbamoyl) -2-benzimidazole - characteristic benzimidazolearbamic acid - carbamic acid methyl ester - 2 1- peaks at 5.93, methyl ester ziek complex dihydrate 6.53 and 8, 7u 1- (S9-decenylcarbamoyl) -2- 1- (d 9-decenylcarbamoyl) - Zbenz- characteristic benzimidazole carbamic acid imidazole carbamids acid methyl ester - peaks at 5.96, methyl ester 2:

  : 1-zinc complex dihydrate 6.55 and 8.72 cm 1- (allylbamoyl) -2-benz- 1- (allylcarbamoyl) -2-benzimidazole - characteristic methyl imidazole carbamic acid earbamic acid - 2: 1 - peaks at 6.0, methyl ester zinc complex -dihydrate 6.5 and 8.63
Table (continued) Starting material Product Infrared spectrum 1- (methylcarbamoyl) -2-benz- 1 - (methylcarbamoyl) -2-benzimidazole - characteristic iínidazole carbamic acid methyl carbamic acid methyl ester-2:

   1-zinc peaks at 5.92, methyl ester complex sesquihydrate 6.55 and 8.7! T l- (cyclohexylcarbamoyl) -2- 1 - (cyclohexylcarbamoyl) -2-benzimidazole - characteristic benzimidazole carbamic acid methyl carbamic acid 2: 1- Zinc peaks at 5.95, methyl ester complex dihydrate 6.5 and 8.7 is 1- (Benzylcarbamoyl) -2- 1 - (B enzilcarbamoyl) -2-benzimidazole - characteristic benzimidazole carbamic acid methyl carbamate-2:

   1-zinc com peaks at 5.92, methyl ester plex sesquihydrate 6.5 and 8.7 1 - (p-methoxybenzylcarbamoyl) - l- (p-methoxybenzylcarbamoyl) -2-benz- characteristic 2-benzimidazole carbamic acid imidazole carbamic acid methyl ester peaks at 5.98, methyl ester 2: l-zinc complex dihydrate 6.57 and 8.7, u 1- (p-methoxyphenylcarbamoyl) - l- (p-methoxyphenylcarbamoyl) -2- characteristic 2-benzimidazole carbamic acid - benzimidazole carbamic acid methyl ester - peaks at 5, 95, methyl ester 2:

   1-zinc complex dihydrate 6,6 and 8,8al 1 - (trichloromethylthio) -2- 1 - (trichloromethylthio) -2-benzimidazole- new peak at benzimidazolecarbamic acid methyl carbamate-2: 1 -zinkkom- 6.46, u methyl ester plex -dihydrate 1 - (methylcarbamoyl) -2- 1 - (methylcarbamoyl) -2-benzimidazole - characteristic benzimidazole carbamic acid - carbamic acid isopropyl ester-2:

   1-zinc peaks at 5.92, isopropyl ester complex dihydrate 6.55 and 8.7p
Example 10 Preparation of the product of Example 2 in dimethylformamide and water in the presence of a base
A slurry of 5.8 parts of 1- (butylcarb amoyl) -2-benzimidazole carbamate and 1.7 parts of manganese sulfate monohydrate in 34 parts by volume of dimethylformamide is stirred and 1. 6 parts of 50% aqueous sodium hydroxide were added.  After stirring for 1 hour, the mixture is poured into 200 parts by volume of a mixture of ice and water with stirring.  The mixture is stirred for 15 minutes and filtered.  The solid is washed with water and dried.  The product weighs 6. 5 parts and is identical to the product of Example 2 in all respects. 



   Example 11 Preparation of the product of Example 2 in acetone and water in the presence of a base
A slurry of 5.8 parts of methyl 1- (buty] carbamoyl) -2-benzimidazole carbamate in 100 parts by volume of acetone is stirred vigorously and 1.6 parts of 50 molar aqueous sodium hydroxide are added dropwise.  Stirring is continued for 1 hour. 



  A solution of 1.7 parts of manganese sulfate monohydrate in 4 parts of water is added dropwise with stirring to the acetone suspension of the sodium derivative of 1 - (butylcarbamoyl) -2-benzimidazolcarbamide methyl ester thus obtained. 



   After the addition is complete, large drops of the aqueous phase are visible in the acetone phase.  Stirring is continued for 3 hours.  Then wec 'pour the mixture into 250 parts of water with stirring.  After stirring for 15 minutes, the suspension is filtered and the solid is washed and dried.  The product weighs 6.2 parts and is identical to that of Example 2 in all respects. 



   Example 12 Preparation of the product of Example 2 in methyl ethyl ketone and water in the presence of a base
A slurry of 5.8 parts of 1- (butylcarbamoyl) -2-benzimidazole carbamate in 50 parts by volume of methyl ethyl ketone is stirred vigorously and 1.6 parts of 50% aqueous sodium hydroxide are added dropwise.  Stirring is continued for 1 hour.  To the suspension of the sodium derivative of 1- (butylcarbamoyl) -2-benzimida- zolcarbamidsäuremethylesters thus obtained in methyl ethyl ketone, a solution of 1.7 wt. share manganese fulfate monohydrate in 3 parts water.  The two liquid phases (which contain the third, solid phase) are clearly visible.  Stirring is continued for 3 hours. 

  The mixture is then cooled in ice with stirring and filtered.  The solid is washed with methyl ethyl ketone and water and dried.  The product weighs 6.2 parts and is identical to the product of Example 2 in all respects.    

 

   Example 13 Preparation of 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester -2: 1 - zinc complex - monohydrate
10 parts of the dihydrate of Example 1 are mixed with 50 parts by volume of concentrated aqueous ammonia and the mixture is stirred for 2 hours.  The mixture is filtered and the solid is dried. 

  It weighs 9 parts and, calculated for the 2: 1 zinc complex monohydrate, shows the following analysis:
Analysis C28Hs0N807Zn: calc. : C 50.8 H 5.5 N 16.95 Zn 9.85% found. : C 5 (), 41 H 5.34 N 17.74 Zn 9.96
The infrared spectrum of the monohydrate product differs from that of the dihydrate mainly in that it has a peak at 5.8 µ and that the peak at 2.9 jt (H2O) is absent.  The monohydrate also lacks a peak at 6.0 At.     The monohydrate is converted back into the dihydrate when treated with water. 



   Example 14 Preparation of 1- (butylcarbamoyl) -2-benzimioazole-carbamic acid methyl ester - 2: 1 - zinc complex (anhydrous form)
Ten parts of the dihydrate from Example 1 are placed under high vacuum (0.25 mm Hg) in a laboratory rotary evaporator.  The temperature is gradually increased to 600 ° C. and held at this value for 1 hour. 

  The anhydrous product obtained weighs 9 parts and shows the following analysis, calculated for the anhydrous 2: 1 zinc complex:
Analysis C2gHg4NgO6Zn: calc. : C 52.3 H 5.3 N 17.4% found. : C 52.25 H 5.10 N 17.34
The infrared spectrum of the anhydrous product differs from that of the dihydrate mainly in that the peak at 2.9 liters attributable to water has disappeared and that there is a new peak at 5.8 liters.  The water-free material converts back into the dihydrate when treated with water. 



   Example 15 Preparation of 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex monohydrate
10 parts of the dihydrate from Example 2 are placed under high vacuum (0.25 mm Hg) in a laboratory rotary evaporator.  The temperature is gradually increased to 603 C and held at this value for 3 hours. 

  The monohydrate obtained weighs 9 parts and shows the following analysis, calculated for the 2: 1 manganese complex monohydrate:
Analysis CssH36N807Mn: calc. : C 51.5 H 5.6 N 17.2% found. : C 51.83 H 5.73 N 17.12
The infrared spectrum of the monohydrate product differs from that of the dihydrate mainly in that it contains a new peak at 5.8 lt and that the peak at 2.9, U, which is attributable to water, has completely disappeared, although the molecule is still Contains 1 mole of water.  When treated with water, the monohydrate is converted back into the dihydrate. 



   Example 16 Preparation of 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester - 2: 1-manganese complex (anhydrous form)
10 parts of the dihydrate from Example 2 and 5 parts of Linde molecular sieve type 3A are added to 50 parts by volume of dimethylformamide.  The mixture is stirred for 1/2 hour and filtered.  The filtrate is placed in a laboratory rotary evaporator and concentrated in a high vacuum (0.25 mm Hg) at 500 ° C.  After most of the dimethylformamide has been removed, the temperature is increased to 700 ° C. and drying is continued until the residue is a dry powder. 

  The product weighs 9 parts and, calculated for the anhydrous 2: 1 manganese complex, shows the following analysis:
Analysis C28H34Ns06Mn: calc. : C 53.1 H 5.4 N 17.7% found. : C 52.90 H 5.72 N 17.81
If this drying attempt is repeated in the absence of Linde molecular sieve, the same product is obtained.  In other words, treatment of the dihydrate with dimethylformamide and removal of this solvent by evaporation in vacuo at elevated temperature are sufficient to remove 2 moles of water of hydration.  However, the presence of the drying agent is advantageous in that it produces a dry dimethylformamide distillate which can be used as such for drying the next batch of material. 



   The infrared spectrum of this anhydrous material is similar to that of the monohydrate of Example 15 in that both spectra (unlike that of the dihydrate of Example 2) have a peak at 5.8 At and no peak at 2.9 lt O).  The spectrum of the anhydrous product has an extra peak at 5.95. When treated with water, the anhydrous material is converted back to the dihydrate. 



   Example 17
The following zinc complexes can also be prepared by replacing the 1- (butylcarbamoyl) -2benzimidazole carbamic acid methyl ester of Example 1 with the corresponding 2-benzimidazole carbamic acid alkyl ester reactants. 



   1 - dodecylcarbamoyl-2-benzimidazole carbamate acid methyl ester 2: 1 zinc complex dihydrate, I- (d -dodecenylcarbamoyl) -2-benzimidazole carbamide acid methyl ester 2: 1 zinc complex dihydrate,
1- (Propynylcarbamoyl) - 2 - benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate,
1- (Dodecinylcarbamoyl) -2-benzimidazole carbamic acid, ethyl ester-2: 1-zinc complex dihydrate, 1 - (cyclopropylcarbamoyl) -2-benzimidazole carbamide acid sec. -butyl ester 2: 1 zinc complex dihydrate, l- (cyclooctylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate,
1 - (p-Methylcyclohexylcarbamoyl) -2-benzimidazole carbamide isopropyl ester-2: 1 -zinc complex dihydrate, i - (cyclohexylmethylcarbamoyl) -2-benzimidazole carbamide methyl ester-2:

   1-zinc complex dihydrate,
1 - (m-Methoxycyclohexylcarbamoyl) - 2 - benzimidazole carbamic acid methyl ester -2: 1 - zinc complex dihydrate, 1 - (p - chlorocyclohexylcarbamoyl) -2-benzimidazolcarbamide acid methyl ester-2: -zinc complex dihydrate, 1 - (2 - cyclopentenyl) -2- benzimidazole carbamide acid methyl ester-2: 1 zinc complex dihydrate,
1- (2-Cyclohexenylcarbamoyi) -2-benzimidazolecarbamidic acid methyl ester-2:

   1-zinc complex dihydrate,
1 - (2-Cyclooctenylcarbamoyl) -2-benzimidazole carbamide acid-sec. -butyl ester 2: 1 zinc complex dihydrate,
1 - (2-Cyclobutenylcarbamoyl) -2-benzimidazole carbamide acid methyl ester-2: 1-zinc complex dihydrate,
1 - (Norbornylmethylcarbomoyl) -2- benzimidazolcarbamide acid methyl ester-2: 1-zinc complex dihydrate, 1 - (cyclohexylethylcarbamoyl) -2-benzimidazolcarbamide-acid methyl ester-2: 1-zinc complex-dihydrate, I - (Phenylcarbamideme) -2-benzimidazole- methyl ester-2: 1-zinc complex dihydrate, 1 - (butylcarbamoyl) -4-methyl-2-benzimidazole carbamide acid methyl ester-2:

   1-zinc complex dihydrate, 1- (butylcarbamoyl) - 5 - butyl-2-benzimidazole carbamide acid ethyl ester-2: 1-zinc complex dihydrate, 1- (m-tolylcarbamoyl) -4-bromo-2-benzimidazole carbamide acid methyl ester-2: 1 -zinc complex dihydrate,
1- (p-Tolylcarbamoyl) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (p-ethylphenylcarbamoyl) -5-chloro-2-benzimidazole carbamic acid methyl ester -2: l-zinc complex dihydrate,
1- (Butylcarbamoyl) - 5 -fluoro-2-benzimidazole carbamide acid methyl ester 2: 1 zinc complex dihydrate,
1- (Butylcarbamoyl) - 4 -fluoro-2-benzimidazolecarbamidic acid methyl ester-2:

   1-zinc complex dihydrate, 1- (octylcarbamoyl) - 4 - nitro-2-benzimidazole carbamate acid methyl ester-2: 1 zinc complex dihydrate, 1- (ethylcarbamoyl) -4 - methoxy - 2-benzimidazole carbamide acid methyl ester-2: 1- zinc complex dihydrate,
1 - (Allylcarbarnoyl) -5-butoxy-2-benzimidazole carbamide acid isopropyl ester-2: 1-zinc complex dihydrate,
1- (p-Methoxyphenylcarbamoyl) -2-benzimidazole carbamide acid methyl ester-2: 1-zinc complex dihydrate,
1- (p-Ethoxyphenylcarbamoyl) -2-benzimidazole-carbamide acid methyl ester-2: 1-zinc complex dihydrate,
1- (p-Nitrophenylcarbamoyl) -2-benzimidazole carbamide acid methyl ester-2:

   1-zinc complex dihydrate, 1- (m-trifluoromethylphenylcarbamoyl) -2-benzimidazole carbamic acid ethyl ester-2: 1-zinc complex dihydrate, 1- (p-methylsulfonxylphenylcarbamoyl) -2-benzimidazole carbamic acid isopropyl hydrate, 1-zinc complex, 1- - (p-Chlorophenylcarbamoyl) -2-benzimidazolecarbamide acid methyl ester-2: 1-zinc complex dihydrate, 1- (3,4-dichlorophenylcarbamoyl) -2-benzimidazolcarbamoyl acid methyl ester-2: 1-zinc complex dihydrate, l - (m-bromophenylcarbamoyl ) -2-Benzimidazole carbamate-2: 1-zinc complex dihydrate, 1 - (o -fluorophenylcarbamoyl) -2-benzimidazole-carbamate-2:

  : 1-zinc complex dihydrate, 1 - (benzylcarbamoyl) -2-benzimidazole carbamic acid methyl ester-2: 1 zinc complex dihydrate, 1- (benzylcarbamoyl) -5-nitro-2-benzimidazole carbamide-acid isopropyl ester-2: 1 zinc complex dihydrate ,
1- (o-Methylbenzylcarbamoyl) -2-benzimidazolecarbamidic acid methyl ester-2: 1-zinc complex dihydrate,
1 - (p-Methylbenzylcarbamoyl) -2-benzimidazole-carbamate-acid methyl ester-2: 1-zinc complex-dihydrate, 1- (p-nitrobenzylcarbamoyl) -2-benzimidazole-carbam-acid-methyl-ester-2: 1-zinc-complex-dihydrate, 1- (p-methoxy-benzyl ) - 2 -benzimidazolcarbamide acid methyl ester-2:

   1-zinc complex dihydrate, 1- (o-fluorobenzylcarbamoyl) - 2 - benzimidazole carbamido acid methyl ester 2: 1 zinc complex dihydrate, 1 - (p -chlorobenzylcarbamoyl) -2-benzimidazole carbamide acid methyl ester 2: 1 zinc complex dihydrate, 1 - (m-Bromobenzylcarbamoyl) -2-benzimidazole carbamate acid methyl ester-2: 1-zinc complex dihydrate,
1- (Carbamoyl) -2- benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate,
1- (Formyl) -2- benzimidazole carbamic acid methyl ester- 2: ex-dihydrate,
1- (Acetyl) -2- benzimidazole carbamic acid methyl ester- 2: 1 zinc complex dihydrate,
1- (Propionyl) -2- benzimidazole carbamic acid methyl ester-2:

   1-zinc complex dihydrate, 1- (dodecanoyl) -2- benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate,
1 - (Cyanoacetyl) -2-benzimidazole carbamic acid sec. -butyl ester 2: 1 zinc complex dihydrate, 1- (3-methoxypropionyl) - 5-nitro-2-benzimidazole carbamide acid methyl ester 2: 1 zinc complex dihydrate,
1 - (3 sec. -Butoxypropionyl) - 2 - benzimidazole carbamide acid methyl ester-2: 1-zinc complex dihydrate, 1 - (acetoacetyl) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1 - (levulinyl) -2-benzimidazole-methyl carbamate
2:

   1-zinc complex dihydrate, 1- (4-chlorocaproyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate, 1- (trifluoroacetyl) -2-benzimidazolcarbamislic acid methyl ester 2: 1 zinc complex dihydrate,
1- (Acroyl) -2- benzimidazole carbamic acid ethyl ester 2:

   1-zinc complex dihydrate,
1 - (# 9-Decenoyl) -2- benzimidazole carbamic acid isopropyl ester-2: 1-zinc complex dihydrate,
1- (Cyclopropylcarbonyl) -2-benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate, 1- (cyclooctylcarbonyl) -2 - benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate, 1- (propargyl) - 2 - benzimidazole carbamic acid -2: 1-zinc complex dihydrate, 1 - (benzoyl) -2 -benzimidazole carbamic acid methyl ester
2:

   1-zinc complex dihydrate, 1- (p-chlorobenzoyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1-zinc complex dihydrate, 1- (m-bromobenzoyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1-zinc complex dihydrate, 1 - (p-Fluorobenzoyl) -2-benzimidazole-carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (p-methylbenzoyl) -2-benzimidazole-carbamic acid methyl ester-2: 1-zinc complex-dihydrate, 1 - (p-sec. -Butylbenzoyl) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (m-nitrobenzoyl) -2-benzimidazole carbamic acid methyl ester-2:

  : 1-zinc complex dihydrate, 1 - (p-methoxybenzoyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate,
1 - (p-Butoxybenzoyl) -2-benzimidazole carbamic acid methyl ester-2: 1 zinc complex dihydrate,
1- (Methylthio) -2- benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (isopropylthio) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate,
1- (Propylthio) -2- benzimidazole carbamic acid methyl ester-2:

   1-zinc complex dihydrate, 1- (trichloromethylthio) - 2 - benzimidazole carbamic acid methyl ester 2: 1 zinc complex dihydrate, 1- (trichloromethylthio) - 2 - benzimidazole carbamic acid ethyl ester-2: 1-zinc complex dihydrate, l- (trichloro) - 2 - benzimidazole carbamic acid isopropyl ester 2: 1-zinc complex dihydrate, I - (3-chloropropylthio) -2-benzimidazole cara acid methyl ester 2: 1 zinc complex dihydrate, 1 - (pentachloroethylthio) -2-methylbenzimidazole carbamate : 1-zinc complex dihydrate,
1- (Phenylthio) -2- benzimidazole carbamic acid methyl ester-2:

   1-zinc complex dihydrate, 1 - (benzylthio) - 2 - benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (o-nitrophenylthio) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1 - ( 2,4-Dinitrophenylthio) 2- benzimidazole carbamide acid methyl ester-2: 1 -zinc complex dihydrate,
1 - (p-Chlorophenylthio) -2- benzimidazole carbamic acid methyl ester-2: 1 zinc complex dihydrate, 1 - (m-Tolylthio) - 2 - benzimidazole carbamids acid methyl ester-2: 1 zinc complex dihydrate,
1- (o-Nitrobenzylthio) -2-benzimidazole carbamic acid methyl ester-2: 1-zinc complex dihydrate, 1- (p-chlorobenzylthio) -2-benzimidazole carbamic acid methyl ester-2:

   1-zinc complex dihydrate, 1 - (p-methylbenzylthio) - 2 -benzimidazole carbamic acid sec. butyl ester 2: 1 zinc complex dihydrate and 1- (o-nitrobenzylthio) -2-benzimidazole carbamic acid isopropyl ester 2: 1 zinc complex dihydrate. 



   Example 18
The zinc complexes of Example 17 are dried in the manner described in Example 14.  The corresponding anhydrous forms of the products of Example 17 are obtained. 



   Example 19
The following manganese complexes can be prepared by adding equivalent amounts of the corresponding alkyl 2-benzimidazole carbamate for the
1- (Butylcarbamoyl) -2-benzimidazolcarbamidsäureme thylester in Example 2 are used. 



  1 - (Benzylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex dihydrate, 1- (methylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex dihydrate,
1- (Octylcarbamoyl) - 2 - benzimidazole carbamids acid methyl ester 2: 1 manganese complex dihydrate, 1 - (Allylcarbamoyl) - 2 - benzimidazole carbamic acid methyl ester 2: manganese complex dihydrate,
1 - (Hexylcarbamoyl) - 2 -benzimidazolcarbamic acid methyl ester-2: 1-manganese complex dihydrate,
1 - (p-Nitrophenylcarbamoyl) - 2 -benzimidazole carbamide acid methyl ester-2: 1-Manganese complex dihydrate 1 (butylcarbamoyl) - 2 - benzimidazole carbamic acid isopropyl ester-2:

   1-manganese complex dihydrate,
1 - (p-Methoxyphenylcarbamoyl) - 2 - benzimidazole carbamide acid methyl ester - 2: 1 - manganese complex - dihydrate, 1- (norbornylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex dihydrate,
1 - (Cyclohexylcarbamoyl) -2- benzimidazole carbamide acid methyl ester-2: 1-manganese complex dihydrate,
1 - (Phenylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex dihydrate, 1 - (Cyclopropylcarbonyl) -2-benzimidazole carbamic acid methyl ester 2: 1 manganese complex dihydrate,
1 - (Propionyl) - 2 - benzimidazole carbamic acid methyl ester-2: 1-manganese complex dihydrate, 1 - (benzoyl) - 2 -benzimidazole carbamic acid methyl ester
2:

   1-manganese complex dihydrate, 1- (trichloromethylthio) -2- benzimidazole carbamic acid methyl ester-2: 1-manganese complex dihydrate, 1- (trichloromethylthio) -2- benzimidazole carbamic acid isorpopyl ester-2: 1-manganese complex dihydrate, 1 - (cyclohexylmethylmethyl) 2- benzimidazole carbamide acid methyl ester -2: 1 - manganese complex - dihydrate,
1 - (2,4 - Dinitrophenylthio) 2-benzimidazole carbamide acid mes, methyl ester 2: 1 manganese complex dihydrate and
1 - (2,4 - Dinitrophenylthio) - 2 - benzimidazole carbamide acid isopropyl ester 2: 1 manganese complex dihydrate. 



   Example 20
The dihydrates of Example 19 are dried following the procedure of Example 16.  The corresponding anhydrous forms are obtained. 



   Example 21
The following copper complexes can be prepared by using equivalent amounts of the corresponding alkyl 2-benzimidazole carbamate for methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate in Example 3. 



      1 nzylcarbamoyl) 2 benzimidazole carbamides acid methyl ester 2: 1 copper complex,
1 - (methylcarbamoyl) -2-benzimidazole carbamide acid methyl ester 2: 1 copper complex, 1- (octylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2: 1 copper complex,. 



     
1 - (Allylcarbamoyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1 copper complex,
1 - (Hexylcarbamoyl) -2-benzimidazole carbamic acid methyl ester 2.     1 copper complex, 1 - (p-nitrophenylcarbamoyl) -2 -benzimidazole carbamide- 5 acid methyl ester-2: 1 -copper complex,
1 - (p-Methoxyphenylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester-2 1 -copper complex, 1 - (cyclohexylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester-2: 1-copper complex, 1- (phenylcarbamoyl) -2-benzunidazole -copper complex, 1 - (cyclohexylmethylcarbamoyl) -2- benzimidazolcarbamide acid methyl ester-2:

   1-copper complex,
1- (Cyclopropylcarbonyl) -2-benzimidazole carbamic acid methyl ester 2: 1 copper complex,
1 - (Propionyl) - 2 - benzimidazole carbamic acid methyl ester-2: 1-copper complex,
1 - (Benzoyl) -2-benzimidazole carbamic acid methyl ester
2: 1 copper complex,
1- (Trichloromethylthio) -2-benzimidazole-carbamic acid methyl ester-2: 1-copper complex, 1- (2,4-dinitrophenylthio) 2- benzimidazole-carbamide-acid methyl ester-2: 1 -copper complex and 1- (acetyl) -2-benzimidazole-carbamic acid methyl ester
2: 1 copper complex. 



   Example 22
The following nickel complexes can be prepared by adding equivalent amounts of the corresponding alkyl 2-benzimidazole carbamate for the
1- (Butylcarbamoyl) 2- benzimidazole carbamate can be used in Example 4. 

 

   1 - (Allylcarbamoyl) - 2 - benzimidazole carbamic acid methyl ester 2: 1 nickel complex trihydrate,
1 - (Hexylcarbamoyl) - 2 -benzimidazolcarbamidsäureme thylester-2: 1 -nickel complex trihydrate, 1 - (propionyl) - 2 - benzimidazolcarbamidsäuremethylester-2: -nickelcomplex-trihydrate,
1 - (p-Methoxyphenylcarbamoyl) -2- benzimidazole carbamide acid methyl ester-2: 1 -nickel complex trihydrate,
1 - (Benzoyl) -2-benzimidazole carbamic acid methyl ester
2: 1-nickel complex trihydrate, 1 (trimethylthio) -2-benzimidazole-carbamate-2: 1-nickel-complex-trihydrate and 1 - (2,4-dinitrophenylthio) 2- benzimidazole-carbamide-acid-methyl-ester-2: 1-nickel-complex-trihydrate. 



   Example 23
The following cobalt complexes can be prepared by adding equivalent amounts of the corresponding alkyl 2-benzimidazole carbamate for the
Methyl 1- (butylcarbamoyl) 2- benzimidazole carbamate can be used in Example 5. 



   1 - (Hexylcarbamoyl) - 2 -benzimidazolcarbamidsäureme thylcster-2: 1 cobalt complex dihydrate,
1- (Octylcarbamoyl) - 2- benzimidazolcarbamidsäureme thylester-2: 1-cobalt complex dihydrate,
1 - (p-NIethoxyphenylcarbamoyl) - 2 - benzimidazole carbamide acid methyl ester-2: -cobalt complex dihydrate,
1 - (Benzylcarbamoyl) benzimidazole carbamic acid methyl ester-2:

   1-cobalt complex dihydrate, 1- (cyclohexylcarbamoyl) -2-benzimidazole carbamidic acid methyl ester-2: 1-cobalt complex dihydrate, 1 - (acetyl) -2- benzimidazole carbamic acid methyl ester-
2: 1 cobalt complex dihydrate, 1- (trichloromethylthio) -2- benzimidazole carbamic acid methyl ester 2: l cobalt complex dibydrate,
1 - (p-Nitrophenylcarbamoyl) - 2 -benzimidazole carbamide acid methyl ester 2: 1 cobalt complex dihydrate,
1- (Cyclopropylcarbonyl) -2-benzimidazole carbamic acid methyl ester 2: 1 cobalt complex dihydrate, 1- (benzoyl) -2-benzimidazole carbamic acid methyl ester
2:

   1-cobalt complex dihydrate and 1 - (2,4-dinitrophenylthio) -2- to benzimidazole carbamide acid methyl ester-2: 14 cobalt complex dihydrate.    



   Example 24
The following transition metal complexes can be prepared by using equivalent amounts of the corresponding soluble salts for the zinc acetate dihydrate in Example 1. 



     1- (Butylcarbamoyl) -2- benzimidazole carbamates acid methyl ester 2: 1-iron complex dihydrate, 1- (butylcarbamoyl) -2-benzimidazole carbamates acid methyl ester-2: 1-caumium complex dihydrate and 1- (butylcarbamoyl) 2-benzimidazole -chrome complex dihydrate.    



   As already mentioned above, it has been found that the complexes according to the invention have excellent fungicidal and milbenovicidal activity when they are used to prevent or reduce damage to plants and inanimate organic substances.  The usefulness of the present invention will now be described in detail. 



   The complexes according to the invention combat a large number of fungal diseases of leaves, fruits, stems and roots of growing plants without damaging the host plant.  Fruits, bulbs, onions, roots, seeds and other parts of plants that are harvested for food, animal feed or other purposes are protected from exposure to fungi during processing, distribution and storage.  Seeds, bulbs, saplings and other plant propagation materials are protected from attack by fungi during handling and storage, as well as after planting in the soil.  Wood, fabric, fiberboard, paper and other industrial materials are protected from unsightly stains and devastating deterioration caused by fungi.  Luggage, shoes, shower or 

  Rain curtains, carpets, mats, clothes and other useful household, public and industrial items are protected from rot, fungal stains and mold growth.  Painted surfaces are protected from staining and discoloration by incorporating a complex according to the invention into the paint formulation. 



   The many fungi against which the complexes according to the invention are active can be illustrated by the ones given below, although the list is not intended to represent a restriction:
Venturia inaequalis, which causes apple scab, Podosphaera leucotricha, which causes apple powdery mildew, Uromyces phaseoli, which causes bean rust, Cercospora apii, which causes premature dry rot in celery, Cercospora beticola, which causes leaf spots on sugar beet, Sclerotinia sclerotiorum in vegetables , Beans, carrots and celery, causes, Colletotrichum spp. , which causes anthracnose in fruits and vegetables such as beans, tomatoes and coffee, Septoria apii, which causes late blight of celery, Cercospora musae, which causes Sigotoka's disease in bananas, Piricularia spp. ,

   which causes Johnson stain on bananas, Erysiphe cichoracearum, which causes powdery mildew on cantaloupe and other pumpkin fruits, Penicillium digitatum, Phomopsis spp.  and Diplodia natalensis, which cause fruit rot in citrus fruits, Ceratostomella ulmi, which causes Dutch elm disease, Sphaerotlleca humuli, which causes powdery mildew on roses, Diplocarpon rosae, which causes star soot in roses, Ramularia spp. , which causes leaf spots on ornamental plants, Botrytis cinerea, which causes flower and fruit rot in ornamental plants, fruits and vegetables, Uncinula necator, which causes powdery mildew on grapes, Guignardia bidwellii, which causes black rot, Melonconium fuligineum, Coccomyces, which causes white rot in grapes ,

   which causes cherry leaf spots, Cytospora spp. which causes tree cancer, Cladosporium carpophilum which causes peach scab, Fusicladium effusum which causes pecan scab, Erysiphe graminis which causes powdery mildew on cereals, Monolinia (Sclerotinia) laxa, and M.  fructicola.     cause the brown rot of stone fruits such as peaches, cherries and apricots, Pseudopenziza ribes, which causes leaf spots on gooseberries, Piricularia oryzae, which causes rice blight, Puccinia recondita, P.  coronata and P. 

   glumarum, which causes leaf rust in wheat, oats and grasses, Puccinia graminis tritici, which causes stem rust in wheat, Claviceps purpurea, which causes ergot in rye and grass, Aspergillus niger, which causes cotton boll rot and post-injury rot in many plant tissues, Aspergillus terreus, which is commonly found in the soil and attacks plant material, Tilletia caries and other Tilletia species that cause common wheat blight, Ustilago tritici, Ustilago nigra, Ustilago avena (and other Ustilago species), the open burns on wheat, barley and oats cause, Urocystis tritici and other Urocystis species that cause open wheat blight, Sphacelotheca sorghi, which causes covert fire in sorghum, Ustilago hordei and Ustilago kollerie,

   which cause covert burns in barley and oats, Pithomyces chartorum, which is present in lawns, pastures and other grass areas and which is known to have several side effects, various species of Rhizoctonia, Fusarium and Verticillium that are present in the soil and which Attack roots and other underground parts as well as the vascular system of a large number of plants, various types of Penicillium that grow on objects such as fabrics, fiberboard, leather items and paint, and Myrothecium species that affect objects such as shower curtains or  Attack rain curtains, carpets, mats and clothing. 



   The milbenovicidal activity of the complexes according to the invention is useful in preventing the development of harmful mite populations or in the gradual reduction of existing populations.  The movement of mites is limited.  As a result, an increase in population or the continuity of a high population at a particular location depends to a large extent on the development of the eggs that are laid at that location. 



   Mite eggs do not develop to produce live young when these eggs are treated with one of the complexes of the invention or when they are laid on a surface containing a complex of the invention.  In addition, the eggs do not develop if they are laid by a female mite that has come into contact with a complex according to the invention, or if they are laid by a female mite that eats or has recently consumed food such as vegetable sap, which contains a complex according to the invention.  This disorder in egg development prevents the population from increasing significantly beyond the size at the time of treatment. 

  This ovicidal effect, in connection with the high natural mortality rate of adult animals, can eliminate mites in an already infested area to a high degree in a relatively short period of time.  As long as the complexes are present on the surface on which the mites are located or as long as the complexes remain in the food supplied to them, no new populations can develop. 



   Many types of mites, which cause damage to fruits, crops, vegetables and ornamental plants under a wide variety of circumstances, are controlled by the complexes and modes of operation according to the invention.  The extent of the practical usefulness of the mite control achieved is illustrated by the following list of specific sensitive mites, whereby the type of damage they can cause is also listed, although the list is not intended to be a limitation:

  :
Panonychus ulmi (European red mite) and Tetranychus urticae (two-spotted mite), commonly called orchard mites, attack a wide variety of deciduous fruits including apples, pears, cherries, plums and peaches, Tetranychus atlanticus (Atlantic mite or strawberry Leaf spider mite), T.  einnabarinus (carmine spider mite) and T. 

   pacificus (Pacific spider mite), which attack cotton and numerous other crops, Paratetranychus citri (red citrus mite) and others which attack citrus fruits, Phyllocoptruta sleivora, which causes citrus rust, Bryobia praetiosa (clover mite), which attacks clover, alfalfa and other crops, aceria neocynodomis, which attacks grasses and other plants, Tyrophagus lintneri, which is a serious pest on stored food and cultivated fungi, and Lepidoglyphus destructor, which damages Kentucky cattle grass seeds in storage. 



   The complexes according to the invention, if they are used according to certain working methods according to the invention, enter the plants and move freely in the plants, i.  H. , they are systemic.  In this way, both fungi and mites can be controlled in parts of the plant that are away from the application site.  In view of this activity, the complexes can be applied to seeds.  In this way, treatment of cucumber seeds with a few grams of a complex according to the invention per 50 kg of seeds enables control of powdery mildew (Erysiphe cichoracearum) and of leaf spider mites such as Tetranychus urticae on the resulting plants for periods of more than 40 days. 

  Applications to the soil also provide control of certain leaf diseases and mites on plants growing in the treated soil.  Spray or dust treatments of plant leaves and stems provide protection from both fungi and mites to the other parts of the plant that have not actually been sprayed and new, later developing leaves. 



   An additional valuable property of the complexes according to the invention is their ability to prevent the spread of a fungal infection or to kill a fungal infection that is already present in a plant;  H. , they are healing.  Thus, the complexes need not be applied until conditions have developed which allow the fungi to actually start the attack.  This means that under certain circumstances it is possible to avoid the use of a chemical agent throughout the life of the crop.  In other cases, only part of the normal full pesticide application is required. 



   With compounds that have systemic and curative modes of action, great savings are thus possible both in terms of chemical costs and in terms of the work involved in the application.  A further saving is given with the complexes according to the invention insofar as both fungi and mites are controlled by using a single chemical agent. 



   The complexes according to the invention provide protection against damage by fungi, mites or both when they are applied at the appropriate site by means of the methods described below and in an amount sufficient to exert the desired fungicidal and milbenicidal effect.  They are particularly suitable for protecting living plants such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable fruits, horticultural plants (including ornamental plants, small fruits and berries), fiber plants, grain and seed plants, sugar cane, sugar beet, pineapple, fodder and hay plants, beans, peas, soybeans, peanuts, potatoes, sweet potatoes, tobacco, hops, turf, and pastures.    

 

   Living plants can be protected from fungi and mites by placing one or more complexes according to the invention on the soil in which they grow or in which they are subsequently sown or planted, or on seeds, tubers, bulbs or other parts of the plant reproduction before planting and on leaves , Stems and fruits of the living plant are applied.  Live plants can also be protected by immersing the root system or by physically injecting the chemical or chemicals in roots or stems,
Applications to the soil are made with dusts, granules, granules, slurries or solutions. 



  Preferred amounts for the application of the complexes according to the invention on soils in which plants grow or will grow are in the range from 0.01 to 500 ppm by weight of the soil in which the roots grow or will grow.  More preferred use levels are in the range from 0.1 to 50 ppm and the most preferred amounts are in the range from 0.25 to 25 ppm. 



   Preferred amounts for use on seeds, tubers, bulbs or other parts of plant reproduction are in the range from 0.03 to 6000 g of the active complex according to the invention per 50 kg of treated plant material.  More preferred amounts are in the range of zero. 3 to 3000 g of active complex per 50 kg, while the most preferred amounts are in the range of 2.8 to 1500 g per 50 kg. 



   The applications are carried out with dusts, slurries or solutions.  Such treatments protect the treated parts themselves from damage by fungi mites or both, and also give the resulting new plants extensive protection against both types of pests. 



   Preferred amounts for the use of the complexes according to the invention on leaves, stems and fruits of living plants are in the range of 0. 012 to 60 kg of active ingredient per hectare. 



  More preferred amounts are in the range of 0.025 to 30 kg per hectare, while the most preferred amounts are in the range of 0.05 to 15 kg per hectare.  The optimal amount within this range depends on a number of variables known to those skilled in the crop protection art.  These variables include the disease to be controlled, the anticipated weather conditions.  the type of plant, the stage of development of the plant and the interval between applications, although this list is not a limitation.  It may be necessary to repeat applications within the specified range once or many times at intervals of 1 to 60 days.  The applications are made with dusts, slurries or solutions. 



   Preferred amounts for application to the roots of living plants by immersion are in the range of 0.5 to 18,000 grams of active ingredient per 380 liters of water or other liquid vehicle.  More preferred amounts are in the range of 4. 5 to 9,000 grams per 380 liters, while the most preferred amounts range from 45 to 4,500 grams per 380 liters. 



   Preferred amounts for injection into the roots or stems of living plants are in the range of 0.01 to 10,000 ppm of water or other liquid vehicle.  More preferred amounts are in the range from 0.1 to 5000 ppm, while the most preferred amounts are in the range from 1 to 1000 ppm. 



   Parts of plants such as fruits, tubers, onions, leaves.  Roots and the like obtained as food or fodder are protected from rot and other deterioration caused by fungi or mites by treatment with an active complex of the present invention during processing, distribution and storage.  The parts of plants to be protected in this way can be immersed in a liquid bath containing the active ingredient, dusted with a finely divided preparation of the active ingredient, sprayed on, misted with an aerosol containing the compound, or they can be encased in wrapping or packaging materials impregnated with the active compound. 



   When a liquid bath is used, it can contain an amount of the active ingredient in the range of 1 to 5000 ppm by weight of the liquid.  A more preferred range for the bath is 5 to 2500 ppm, while the most preferred range is 10 to 1000 ppm. 



   Dusts as well as wrapping or packaging materials used for this type of application can contain 0.01 to 10X of the active ingredient.  More preferred amounts are in the range of 0.1 to 5%, while the most preferred amounts are in the range of 0.2 to 2.5%. 



   Wood, leather, fabric, fiberboard, paper and other industrial materials of an organic nature can be protected from decomposition or discoloration by fungi and from mite infestation by coating or impregnating them with or incorporating them with an effective amount of one or more complexes according to the invention.  The coating can be achieved by dipping, spraying, pouring over, nebulising (for example with an aerosol) or dusting the material to be protected with a suitable composition which contains the active ingredient.  The preferred application amounts for the active ingredient in the treatment preparation that is actually applied to the material to be protected is in the range of 0.025 to 95 Ges. %.    



  More preferred amounts are in the range from 0.05 to 50% while the most preferred amounts are in the range from 0.1 to 25%. 



   If incorporation or impregnation methods are to be used, application levels can be expressed as the amount of active ingredient introduced into the material to be protected.  The preferred application amounts for these application types are in the range from 0.001 to 30 wt. % of active ingredient in the final product. 



  More preferred amounts are in the range of 0.005 to 15/0, while the most preferred amounts are in the range of 0.01 to 7%; lie. 

 

   Luggage, shoes, shower or  Rain curtains, carpets, mats, clothes and other useful items for household, public or industrial use are protected from rot, fungal stains and unsightly mold growth and from attack by mites by the active complexes according to the invention. 



  Here, too, surface protection or deep protection can be achieved.  The surface treatment is done by dipping, washing, spraying, with aerosols or by applying dust.  Deep treatment is achieved through penetrating solutions.  Sprays, dipping liquids and washing liquids contain the active compound according to the invention in amounts of 10 to 5000 ppm.  Liquids for aerosol application and dusts contain 0.1 to 20 wt. %.  Penetrating solvent solutions contain such an amount of the active ingredient that there is a deposit of 5 to 20,000 ppm in the material to be protected. 



   Painted surfaces can be protected from unsightly stains and mold growth by incorporating 5 to 20,000 ppm of an active complex according to the invention into the paint formulation before use.  More preferred amounts are in the range of 10 to 10,000 ppm, while the most preferred amounts are in the range of 20 to 5000 ppm.  Such treatments with the complexes according to the invention also protect the paint from damage by fungi while it is still in the can. 



   Damage to stored organic products such as grains, seeds, onions, tubers, meat or animal skins by mites is minimized if the floors, walls, compartments and other parts of department stores or other buildings are treated with one or more active complexes .  The application takes place using dusts, sprays or aerosols with preferred application amounts in the range of 0. 05 to 1000 of the active complex according to the invention per 93 mw surface, which is to be kept free from excessive mite populations. 



   The healing control of plant diseases with the complexes according to the invention is improved if the treated parts of the plant are moist for one or more periods of time from 2 to 12 hours each soon after the application of the active complex.  Often this is achieved by slow drying with an original spray treatment or by naturally occurring rain, fog or dew.  In other cases, for example during dry periods or in shelters such as greenhouses, it is necessary to keep the plants moist through special work in order to achieve the best results. 



   When the complexes according to the invention are used, their activity can be increased if certain auxiliary substances are used, for example in the water in which they are dispersed. 



  These excipients can be surfactants.  Be oils, humectants, enzymes, carbohydrates and organic acids.  They improve the effectiveness of tubers, leaves, treatments used for immersion application to the roots of living plants, in the case of liquids used for injection into roots or stems of living plants, or in mixtures containing be used to treat fruits, tubers, onions, roots and the like after harvest. 



   Surface-active agents which improve the control of fungi and mites by the compounds according to the invention include sulfonated and sulfated amines and amides, diphenylsulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, ethoxylated fatty acid esters and oxides, polyethylene oxides / combinations, polyethylene oxides, polyethylene oxides, polyethylene oxides, combinations , surface-active fluorocarbon agents, glycerol esters, ethoxylated alcohol sulfates, glycol esters, isethionates, sulfated ethoxylated alkylphenols, lanolin derivatives, lecithin and lecithin derivatives, alkanolamides, phosphate derivatives, monoglycerides and derivatives, quaternary compounds, sulfated, sulfated, sulfated, sulfated, sulfated fatty acid esters, alcohol and sorbitol derivatives and fatty acids, alkylbenzenesulfonates, imidazolines, taurates,

   Ethoxylated mercaptans, ethoxylated amines and amides, modified phthalic acid-glycerine-alkyd resins and similar substances.  The oils include non-phytotoxic aliphatic spray oils and triglycerides, either with or without an emulsifier to enable dispersion in water.  Humectants such as glycerine or ethylene glycols, enzymes such as bromelain, and carbohydrates such as glucose, lactose and dextrose are also useful.  Organic acids of interest include glycolic and gluconic acids. 

  Although the exact way in which these additives improve the mode of action of the fungicides according to the invention is not known, the effect is nonetheless astonishing and it is possible that these additives prevent the fungicides according to the invention from penetrating into the plant or the transport of substances through the Improve plant. 



   Surfactants preferred for improving the fungicidal and milbenovicidal activity of these compounds are products such as dioctyl sodium sulfosuccinate (Aerosol OT and Aerosol OT-B), mixtures of aromatic sulfonates and ethylene oxide derivatives (Agrimul GM, Agrimul A-100, Agrimul N-100, Emcol H50A , Emcol H53), polyoxyethylene sorbitoleate / laurate (Atlox 1045A), sodium lauryl sulfate (Duponol ME), polyoxyethylated vegetable oils (Emulphor EL719), conductive binder derivatives (Emultex R), acidic complex organic phosphate esters (Gafac RE-610, Victawet), aliphatic alkyl sulfonate Base LL), oleic acid ester of sodium isethionate (Igepon AP78), sodium N-methyl-N-oleyl taurate (Igepon T77),

   the sodium salt of sulfated lauryl and myristylcolamide (Intramine Y), polyethylene glycol 400 oleic acid ester (Nonisol 210), sodium dodecylbenzenesulfonate (Sul-Fon-Ate AA 10, Ultrawet K), polyoxyethylene ether with long-chain alcohols (Surfonic LR 30, Alfonic 1012-6 , Brij 30, Tergitol TMN), ethylene oxide condensates with propylene oxide / ethylene diamine condensates (Tetronic 504), polyhydroxy alcohol esters (Trem 014), modified phthalic acid-glyceral alkyd resins (Triton B 1956), quaternary products (Zelec-nodenshate 9N4No-dowaxol), alkylphenol , Hyonic 9510, Tergitols) and the like.  The examples given in brackets are only intended to serve as an illustration and do not exclude other commercial products not mentioned. 

  Examples of other surfactants in each of these different categories are found in Detergents and Emulsifiers, 1965 Annual or 1966 Annual, edited by John W.  McCutcheon, Inc. , 236 Mt.  Kemble Avenue, Morristown, New Jersey. 

 

   Preferred oils include aerosol oils such as Orchex 796 made emulsifiable with Triton X-45, castor oil made emulsifiable with Triton X-114, corn oil made emulsifiable with Triton X-114, Volck Oil No.  70, Sunoco Oil No.  7E, and similar non-phytotoxic spray oils of vegetable, animal or mineral origin. 



   The complexes of the invention and the oils, surfactants, humectants, enzymes, carbohydrates, and acids useful in increasing the fungicidal and miticidal activity of these complexes can be brought together in a number of ways.  For example, the activity enhancing additive can be mixed with the complexes of the invention when preparing spray slurries.  It is often also possible and expedient to prepare formulations in which the additive and the complex according to the invention are both present in the composition, which is then convenient to use.  Such compositions can be powders, granules, suspensions or also solutions, which depends on the physical and chemical properties of the components that are to be incorporated into the preparations. 

  On the basis of the teaching according to the invention, it is readily apparent to the person skilled in the art that the proportions of the active complex constituent to additives can vary widely.  Thus, the additive in such mixtures can be present in a range from 33 to 10,000 parts per 100 parts of complexes according to the invention.  More preferred are ratios of 40 to 5000 parts of additive per 100 parts of active ingredient, while a ratio range of 50 to 3500 per 100 parts of complex is even more preferred. 



   The compositions according to the invention are formulated by mixing a complex according to the invention with one or more surface-active agents. 



   The surfactants used in the present invention can be wetting, dispersing or emulsifying agents.  They can act as wetting agents for wettable powders and dusts, as dispersants for wettable powders and suspensions and as emulsifiers for emulsifiable concentrates.  Surfactants can also increase the biological activity of the complexes of the invention.  Such surfactants can include those anionic, cationic and nonionic agents as heretofore generally used in herbicides of similar types.  Suitable surfactants are described, for example, in Detergents and Emulsifiers Annual1967 by John W.  McCutcheon, Inc. described. 

  Other surface-active agents which are not listed in the above reference but which are still effective dispersants due to a protective colloid effect include methyl cellulose, polyvinyl alcohol, hydroxyethyl cellulose and alkyl-substituted polyvinylpyrrolidones. 



   Suitable surface-active agents for use in compositions according to the invention include polyethylene glycol esters with fatty and resin acids, polyethylene glycol ethers with alkyl phenols or with long-chain aliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acid esters and polyoxyethylene thioethers. 

  Other suitable surfactants include amine, alkali, and alkaline earth metal salts of alkylarylsulfonic acids, amine, alkali, and alkaline earth metal fatty alcohol sulfates, dialkyl esters of alkali metal sulfosuccinates, fatty acid esters of amine, alkali and alkaline earth metal disodium salts, alkali metal salts, alkali metal salts, alkali metal salts, alkali metal salts, alkali metal salts, alkali metal salts, amine alkali metal salts, alkali metal taurates, amine alkali metal salts, alkali metal salts, amine alkali metal taurates, amine alkali metal salts and amine alkali metal taurates or hydroxyethylated cellulose, polyvinyl alcohols, alkyl-substituted polyvinylpyrrolidone, amine, alkali and alkaline earth metal salts of polymerized alkylnaphthalene sulfonic acids and long-chain quaternary ammonium complexes.  Anionic and nonionic surfactants are preferred. 



   Among the preferred wetting agents are sodium alkylnaphthalene sulfonates, sodium dioctyl sulfosulfonate, sodium dodecylbenzenesulfonate, ethylene oxide condensates with alkylated phenols such as octyl, nonyl and dodecyl phenol, sodium lauryl sulfate and trimethyl nonyl polyethylene glycol.  Among the preferred dispersants are sodium.  Calcium and magnesium lignin sulfonates, low viscosity methyl cellulose, low viscosity polyvinyl alcohol, alkylated polyvinylpyrrolidone, polymerized alkylnaphthalene sulfonates, sodium N-oleyl or N-lauryl isethionates, sodium N-methyl-N-palmitoyl taurate and dodecylphenol polyethylene glycol. 



   The preferred emulsifiers are ethylene oxide adducts of lauric, oil, palmitic or stearic acid esters of sorbitan or sorbitol, polyethylene glycol esters with lauric, oleic, oleic, palmitic, stearic or resin acids, oil-soluble alkylarylsulfonates, oil-soluble polyoxyethylene and dodecylphenol, polyoxyethylene adducts with long chain mercaptans, and mixtures of these surfactants. 



   If desired, the compositions according to the invention also contain surface-active agents for the production of wettable powders.  Dusts, granules or emulsifiable liquids, solid or liquid diluents. 



  A.    Powders that can be added
Wettable powders are compositions which usually contain inert solid diluents in addition to surfactants.  These inert diluents can serve several purposes.  They can act as grinding aids to prevent smearing of the grinder and clogging of the sieve, they can support rapid dispersion of the mixture after it has been placed in water, they can adsorb liquid or low-melting solid active material to produce a free-flowing solid product They can prevent agglomeration into lumps upon prolonged storage in the heat and they can enable the manufacture of compositions with a controlled amount of active ingredient so that an appropriate dose can be easily measured by the consumer. 



   Suitable diluents can be either inorganic or organic in origin.  These include natural clays, diatomaceous earths, synthetic mineral fillers derived from silicon dioxide or silicates, barite or barium sulfates, insoluble salts produced by precipitation in flaky form, for example tricalcium phosphate or calcium carbonate, and powdered organic diluents such as shell flour, wood cob flour, corn Carbohydrates.  Preferred fillers for the compositions of the invention include kaolin clays, attapulgite clays, non-swelling calcium magnesium montmorillonites, synthetic silicas, synthetic calcium and magnesium silicates.    Diatomaceous earth, sucrose, corn flour and barium sulfate. 

 

   Wettable powders usually contain both a wetting agent and a dispersing agent.  For dry wettable powders, the anionic and nonionic surfactants which are in solid form are most preferred.  Occasionally, a liquid nonionic surfactant, normally considered an emulsifier, can be used to effect both wetting and dispersion. 



   In wettable powders according to the invention, wetting agents and dispersants together make up about 1.0 to 8.0 wt. % of the total composition.  The active ingredient is present in a concentration of about 25 to 80%, the remainder up to 100: 0 consists of diluent.  If necessary, a corrosion inhibitor or a foam inhibitor can be added in an amount of 0.1 to 1.0%, the amount of diluent being correspondingly reduced. 



  B.  Dusts
Dust compositions are intended for use in dry form with suitable dusting equipment.  Since downwind is undesirable when dusts are applied, the most suitable dust diluents are those that are dense and settle quickly.  These include kaolinites, talc, pyrophyllites, ground phosphate rock, sericite and ground tobacco stalks.  Dusts, however, are usually most easily produced by diluting an existing highly concentrated wettable powder with a dense diluent so that the final dust often contains some light, absorbent diluent as well as the more desirable dense filler. 



   In dust formulations, a wetting agent is desired to improve adhesion to the dew-covered leaves.  Dusts made from wettable powders usually contain sufficient wetting agent, while dusts made directly from a non-formulated active material usually contain an added wetting agent. 



  Dry, solid anionic or nonionic wetting agents are preferred. 



   Dust formulations usually contain 5.0 to 25 wt. S active material, 0.005 to 1.0% wetting agent, and 3 to 20% light grinding aid diluent and residual dense, rapidly settling diluent.  When the dust formulations are prepared by diluting an already prepared wettable powder, they also contain a small amount of dispersant which does not play an active role when the composition is used as a dry dust. 



  C.  Emulsifiable liquids
Emulsifiable liquids are formulated by combining the complexes according to the invention with a suitable emulsifying agent and with an organic liquid with low water solubility. 



  The active component can be completely dissolved in the organic liquid or it can form a finely ground suspension in a liquid solvent.  Suitable organic liquids include alkylated naphthalenes, xylene, high molecular weight ketones such as isophorones and dibutyl or diamyl ketone, esters such as amyl acetate, straight chain paraffins or iso-paraffins, and purified colorless oils.  The most preferred emulsifiers are mixtures of oil-soluble sulfonates and nonionic polyoxyethylene glycol esters or ethers of fatty acids or alkylated phenols. 



   The active component is in emulsifiable concentrates in an amount of 10 to about 40 wt. % in front. 



  The combined emulsifiers are in an amount of 3 to about 10 wt.     before and the remainder consists of an organic carrier liquid or an organic solvent. 



  D.    Granules
Soil treatments with fungicides, either before or after emergence, are often easiest to do with granules.  Granular products with the complexes of the invention can be made in a number of ways.  The active ingredients can be dissolved in a volatile carrier and sprayed onto pre-formed granules.  They can be mixed as a powder with suitable diluents and binders, then moistened and granulated and then dried.  Powders can also be applied to coarse porous granules by tumbling them together and applying some non-volatile liquid, such as oil, glycol, or a liquid nonionic surfactant, to act as a binder. 

  The rate of grain dissolution and dispersion of the active material in the moist soil can be regulated by the choice of surfactants added or the choice of binders used to form the granules. 



   Suitable preformed granules include those made from attapulgite clay, granular expanded vermiculite, ground corn on the cob, ground nutshells, or preformed kaolinite granules. 



  When the active fungicide is applied to such carriers, the concentration can range from 1 to 25 liters.  However, it is difficult to prevent the active material and carrier from separating in the case of preformed granules at concentration ranges above about 10%.    When higher concentrations of active material are desired, the best results are obtained when powdered active material, diluent, binder and surfactant are mixed beforehand and then granulated so that the active material is distributed in the grain, not just on its surface. 



   Suitable diluents for the manufacture of granules by granulation or extrusion include kaolin clays, non-swelling Ca, Mg montmorillonites and gypsum.  Cohesion into a solid grain is usually achieved by wetting, compacting and drying with or without some binder. 



  Kaolin clays form solid granules when combined with gelatinous agents such as methyl cellulose, natural gums or swelling bentonite.  Ca, Mg bentonites do not require a binding agent and plaster of paris can be brought into a form that forms solid granules either by adding plaster of paris or certain salts such as ammonium sulfate, potassium sulfate or urea, which form double salts with gypsum. 

 

   The active content of the granules formed can range from 1 to 90%, although 75% active material is the upper limit when controlled dissolution of the granules in moist soil is desired. 



  The regulation of the dissolution rate is achieved by regulated compaction, e.g. by regulated extrusion pressure, and by the addition of inert water-soluble compounds, e.g. sodium sulfate, which can be washed out.   



   In addition to the component according to the invention, such compositions can contain conventional insecticides, mites, bactericides, nematocides, fungicides or other agricultural chemicals such as fruit-set agents, fruit-thinning compounds, fertilizer components and the like, so that the Compositions can serve useful purposes in addition to controlling fungal and mite infestations. 



   For illustration purposes, agricultural chemicals are listed below that can be incorporated into the compositions or sprays that contain one or more active complexes can be added. 



   1.2. 3,4,10,10- hexachlor -1 94,4a, 5,8,8a-hexahydro-1,4- endoexo-5,8-dimethanonaphthalene (Aldrin), 1,2,3,4,5,6- Hexachlorocyclohexane (lindane), 3,3,4,5,6,7,8,8-0ctachlor-4,7-methano-tetra hydroindane, 1,1,1-trichloro-2,2-bis (p-chlorophenyl ) -ethane (DDT),
1,2,3,4,10,10- hexachlor - 6,7-epoxy-1, 4,4a5,6,7,8,8a- octahydro -1,4 - endo -exo-5,8-dimethanonaphthalene ( Dieldrin), 1,2,3,410,1 O-hexachlor - 6,7 - epoxy-1,4,4a, 5,6,7,8,8a- octahydro- 1,4-endo-endo-5,6- dimethanonaphthalene (endrin),
1 (or 3a), 3,5,6,6,7,7-heptachloro-3a, 4,7,7a-th
4,7-methanoindene,
1,1,1-trichloro-2,2-bis (p-methoxyphenyl) -ethane (methoxychlor),

   1,1-dichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated camphene with a chlorine content of 67 bis
69 9, 2-Nitro-1,, 1-bis- (p-chlorophenyl) -butane, 1-naphthyl-N-methylcarbamate (Sevin D) methyl carbamic acid ester with 4- (dimethylamino) -3,5-dimethyl-phenol, methyl carbamic acid ester with 1,3-dithiolan-2-one oxime,
O, O-diethyl-O- (2 - isopropyl-4-methylpyrimid-6-yl) thiophosphate, O, O-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate,
O, O-dimethyl-S- (1,2-dicarbethoxyethyl) -dithiophosphate (malathion)
0.0 - Dimethyl -O-p-nitrophenyl-thiophosphate (methyl parathion), O, O-dimethyl-O- (3-chloro-4-nitrophenyl) -
O, O-diethyl-O-p-nitrophenyl-thiophosphate (parathion),

   dl-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclo-penten-1-one-chrysanthemat, O, O-dimethyl-O- (2,2-dichlorovinyl) -phosphate (DDVP), mixture of 53 , 3% Bulan, 26.7% Prolan and 20.0% related complexes,
O, O-dimethyl-O- (2,4,5-trichlorophenyl) -phosphorothioate, 0,0 -dimethyl-S- (4-oxo-1, 2,3-benzotriazine-3 (4H) -yl-me- thyl) phosphorodithioate (Guthion e bis (dimethylamino) phosphonous anhydride, O, O-diethyl-O- (2-keto-4-methyl-7-a'-pyranyl) thiophosphate, O. O-diethyl- (S-ethyl-mercaptomethyl) -dithiophore calcium arsenate, sodium aluminofluoride, dibasic lead arsenate, 2'-chloroethyl -1-methyl-2- (p-tert. -butylphenoxy) ethyl sulfite, azobenzene,

   2-Hydroxy-2,2-bis (4-clllolphenyl) -acetic acid ethyl ester, O, O-diethyl-O [2 (ethyl mercapto) ethyl] thiophosphate, 2,4-dinitro-6-sec. -butylphenol, toxaphen, O-ethyl-Op-nitrophenylbenzene thiophosphonate, 4-chlorophenyl-4-chlorobenzenesulfonate, p-chlorophenyl-phenylsulfone, tetraethylpyrophosphate, 1,1-bis- (p-chlorophenyl) -ethanol, 1,1-bis- ( chlorophenyl) -2,2,2-trichloroethanol, p-chlorophenyl-p-chlorobenzyl sulfide, bis (p-chlorophenoxy) methane, 3- (1-methyl-2-pyrrolidyl) pyridine, mixed ester of pyrethrolone and cinerolone keto alcohols and 2 chrysanthemum acids, cube and derris, both whole roots and powdered, ryanodine, alkaloid mixture,

   known as veratrine, dl-2-allyl-4-hydroxy-3-methyl-2-cyclopentell-l-one, esterified with a mixture of cis- and trans-dl chrysanthemum monoarboxylic acids, butoxypolypropylene glycol, p-diehlobenzene, 2-butoxy-2 '-thiocyanodiethylether, naphthalene, methyl-O-carbamylthiolacetohydroxamat, 1,1-dichloro-2,2-bis- (p-ethylphenyl) -ethane, methyl-O- (methylcarbamyl) -thiolacetohydroxamat, p-dimethylaminobenzoldiazo-sodium sulfone oxyaminobenzo-oxohydrazone, tetraalkylthiuram disulfide, such as tetramethylthiuram disulfide or tetraethylthiuram disulfide, metal salts of Äthylenbisdithiocarbamic acid, z.  B. 



   Manganese, zinc, iron and sodium salts, pentachloronitrobenzene, n-dodecylguanidine acetate (dodine), N-trichloromethylthiotetrahydrophthalimide (captan), phenylmercuric acetate, 2,4-dichloro-6- (o-chloroaniline) -s-triazine (Dyrene t ' ), N-methylmercury-p-toluenesulphonanilide, chlorophenolmercuric hydroxides, nitrophenol-mercury hydroxides, ethyl-mercury acetate, ethylmercury-2, 3-dihpdophyl mercaptide, methylmercuric acid, methylmercury-2,3-bis-propsilveracetate (tetrahydrofuran, 3,3-bis-propsilveracetate, methyl mercury-3,3-bis-4,6 -dimethyl-2H-1,, 3,5 thiodiazine-2-thione), methylqueekilverdiyandiamide, N -ethylmercury-p-toluenesulfonanilide, 1,4-dichloro-2,5-dimethoxybenzene, metal- (e.g. 

  B.    Iron, sodium and zinc), ammonium and amine salts of dialkyldithioearbamic acids, tetrachloronitroanisole, hexachlorobenzene, hexachlorophene, methylqueekilberitrile, tetraehlorquinine, N-trichloromethylthiophthalimide, 1,2-dibromo-3-chloro-3-chloroprene, Dichloropropane / dichloropropene mixture, ethylene dibromide, trichloronitromethane, sodium dimethyldithiocarbamate, tetrachloroisophthalonitrile, 1-benzimidazolecarboxylic acid-2-earboxyamino-dimethyl-ester, streptomycin, 2- (2,4,5-trichloro-phenoxy-acetylenic acid, -chlorophthalic acid, 2- (2,4,5-trichlorophenoxy) -propionic acid, 2- (2,4,5-trichloro-phenoxy) -chloro-propionic acid, 2- (2,4,5-trichlorophenoxy) -propionic acid N- (1-napthyl) acetamide.    



   The agricultural chemicals compiled above are only examples of compounds which can be mixed with the active complexes according to the invention, and this list is not intended to limit the invention in any way. 



   The use of pesticides such as those listed above in combination with a compound of the invention sometimes appears to greatly increase the activity of the active complex.  In other words, an unexpected level of activity is sometimes observed when another pesticide is used in conjunction with the active complex. 



   The complexes of the invention are also useful in that their addition to irrigation wastewater increases the rate of wastewater decomposition.  When the complexes are added to the soil, they increase the rate at which the nitrogen present in fertilizers is converted into usable plant food. 



   The complexes of the invention are also useful in that they reduce the rate of breakdown of chlorophyll and keep plants in an effective photosynthetic state for longer.  The lengthening of the photosynthesis span or the anti-aging activity leads to increased expansion in many types of grain, fruits and vegetables.  In the case of green leafy vegetables, certain ornamental plants, green cut fodder and the like, the shelf life is also increased. 



   The usefulness of the complexes according to the invention is illustrated by the following examples. 



  All parts are parts by weight unless otherwise specified. 



  Wettable Ptllver
Example 25 1 - (Butylcarbamoyl) - 2-benzimidazole carbamic acid methyl ester 2: 1 complex with
Zinc, dihydrate 70%
Dioctyl Sodium Sulphosuccinate 4%
Oleyl ester of sodium isethionate 3%
Diatomaceous earth 23%
The above wettable powder is prepared by mixing the components together, then micropulverizing them in a hammer mill, and then air milling them to further reduce the particle size. 



   The above composition is added to water in such an amount that there is 300 ppm of the active ingredient of the present invention. 



  This compound is then sprayed on alternate trees in an apple orchard in Virginia.  It is known that the trees were infected with the apple scab pathogen two days before the first treatment.  On some leaves of each tree, the beginning of powdery mildew growth also appears and the overwintering population of leaf spider mites begins to infest the orchard. 



   Spraying is carried out on 15-year-old apple trees in an amount of 50 liters per tree in the pink stage of early flowering.  During spring and summer, the sprayings are repeated every three weeks.  At harvest time, the leaves on the sprayed trees are healthy and free of spider mites, and the fruit is full-size with good color and smooth skin.  In contrast, the untreated trees are severely affected by scab and powdery mildew and are bronze-colored due to a high population of leaf spider mites.  The fruit on untreated trees is small and deformed by scab injuries. 

  The composition according to the invention applied in the manner described thus destroys both apple scab and mildew-causing fungi and prevents an accumulation of leaf spider mites, whereby disease and damage caused by them are prevented. 



   All of the complexes described in Examples 2 to 24 can be formulated in the above manner and give similar results when used. 



   Example 26
1 -Butylcarbamoyl- 21r benzirnidazolcarbamide acid methyl ester-2: 1-Z-complex with
Manganese, dihydrate 50
Dodecylphenol condensate with 9 moles of ethylene oxide 3% Sodium N-methyl-N-oleoyl taurate 1%
Kaolin clay 46%
The above mixture is mixed and milled in the same manner as in Example 25. 



   The above composition is added to water.  The amount of the composition used is such that 300 ppm of the active complex according to the invention are present in the finished aqueous preparation.  Selected spots in a sugar beet field in Minnesota are sprayed with the above preparation at 2-day intervals at an amount of 600 liters per hectare.  During the three months after the test began, the weather is favorable for frequent sugar beet leaf spotted fungus infections.  At harvest time, the beets in the treated spots are large and strong with healthy leaves.  The beets in the untreated areas surrounding the treated spots, on the other hand, are over small and the leaves are stained and dying due to numerous infections by the sugar beet leaf spot fungus. 

 

   Example 27
1-Hexylcarbamoyl-2-benzirnidazolcarbamide acid methyl ester -2: 1 complex with
Zinc, dihydrate 70%
Sodium lauryl sulfate 2%
Sodium lignosulfonate 2%
Corn on the cob meal with a particle size below 0.053 mm (-270 mesh) 20S
The above composition is mixed and then ground in the pin mill until the active ingredient becomes an average particle size of about 10 Cc. 



   The above composition is added to water in an amount which contains 300 ppm of a modified phthalic acid glycerol alkyd resin as a surface-active agent (Triton B 1956) that 300 ppm of the active complex according to the invention are present.  This aqueous preparation is sprayed on alternate trees in a peach garden in North Carolina in an amount of 15 liters per tree.  Spraying is started in the pink stage of the flower and repeated at 14-day intervals until harvest time.  The remaining trees in the plantation are left untreated. 



   There are several warm, humid periods during the flowering and early growing season, and fungus pathogens have a good opportunity to infect the flowers and fruit.  At harvest time, the treated trees are healthy and the fruit is free from disease.  In contrast, the fruit on the untreated trees is badly rotten due to the brown rot fungus and disfigured by peach scab. 



   Example 28 1 - (p-Methoxybenzylcarbamoyl) -2-benz- imidazolecarbamic acid methyl ester - 2-1-
Complex with zinc, dihydrate 50%
Diamyl sodium sulfosuccinate 4% dehydrated, partially desulfonated
Sodium lignosulfonate 46%
The above components are mixed and milled in a jet mill until the active ingredient is essentially all less than 5µ. 



   The above composition is added to water containing 500 ppm of modified phthalic acid-glycerol alcohol resins (Triton B 1956).  The amount of the composition used is such that 250 ppm of the active complex according to the invention are present in the finished aqueous preparation.  This preparation is then sprayed onto alternate rose bushes with enough water to thoroughly wet the leaves.  The rose bushes are selected in a plantation that is heavily infested with star soot and powdery mildew and infested with leaf spider mites. 



  The plants are sprayed every 7 days during the growing season and the alternate plants are left unsprayed. 



   Two months after starting the treatments, the treated roses are healthy, growing vigorously and producing flowers in abundance.     The untreated canes, on the other hand, are almost completely defoliated by disease and only have a few small flowers.  The few remaining leaves are covered with powdery mildew or damaged by mites or star soot infections. 



   All of the complexes of the invention can be formulated in the same manner with similar results. 



   Example 29
1- (Butylcarbamoyl) - 2 - benzimidazole carbamide acid methyl ester -2: 1 complex with
Manganese, monohydrate 50%
Dioctyl sodium sulfosuccinate 85% with
Sodium Benzoate (Aerosol OTB) 3%
Low viscosity methyl cellulose 0.75%
Cane sugar 46.25%
The above components are mixed and micropulverized and then air-milled until virtually all of the particles are 5 p or less. 



   A uniform field of cantaloupe in North Carolina is inoculated with powdery mildew (Erysiphe cichoracearum).  After 10 days this organism has established itself well in the plants.  At this point, alternate rows are sprayed with water containing a suspension of the wettable powder prepared in the manner described above. 



  The concentration of this chemical suspension is such that 27 g of the active compound according to the invention are present per 378 liters of water (0.06%).  The spraying is carried out in a volume of 1410 liters per hectare.  The other rows remain unsprayed. 



   After another 15 days, the unsprayed rows are badly damaged by powdery mildew and some plants are dying.  In contrast, the sprayed rows are healthy and grow rapidly.  The results show that the active compound of the suspension acts as a healing fungicide. 



   Example 30 1 - (Butylcarbamoyl) - 2-benzimidazole carbamide acid methyl ester - 2: 1 complex with
Manganese 50%
Sodium lauryl sulfate 2%
Nonylphenoxy-poly- (ethyleneoxy) -ethanol (40 Mol lait20)
Pentaerythritol 44%
The above composition is mixed, then micropulverized and then air-milled to further reduce the particle size until virtually all of the material consists of particles smaller than 5.     are measured by Andersen pipette sedimentation. 



   Six field boxes of oranges are picked from a commercial tree stand in Florida.  Three boxes of oranges are immersed for three minutes in a water bath containing a suspension made from the above formulation in an amount to provide 300 ppm by weight of the active ingredient of the invention.  The remaining three boxes are submerged in water in a similar manner.  All boxes are placed in a citrus warehouse for three weeks. 



   After this period of time, all fruits are checked.  The fruits which have been subjected to an immersion treatment with the compound according to the invention are still in good condition, while the fruits not protected in this way are badly rotten by the blue mold fungus (Penicillium digitatum). 



   Example 31 1 - (Butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 2: 1 complex with
Zinc 60%
Alkyl naphthalene sulfonate, sodium salt 3 SS
N-methyl-N-palmitoyl taurate, sodium salt 2%
Cane sugar 35%
The above components are mixed, micropulverized and air-milled to a particle size of 5 st or less as determined by microscopic examination of aqueous dispersions of the formulation. 



   The above 50% wettable powder formulation is dispersed in water so that there is a concentration of 3.6 g of active ingredient per liter of water.  Eight uniform apple trees of the same variety are selected for the test.  Four of these are sprayed at weekly intervals during the growing season with the above formulation until they run off, which requires about 2850 liters per hectare, and the other four trees are left unsprayed. 



   At the end of the season, very high populations of orchard mites have developed on the unsprayed trees, and the unsprayed trees are heavily infested with apple scab, Venturia inaequalis.  Due to the mite infestation, the leaves are rust-brown and fall off prematurely.  The untreated trees also show poor branch growth and have small, blotchy fruits.  The trees sprayed with the complex according to the invention are essentially free from mites, their eggs and apple scab.  As a result of the excellent mite control, the sprayed trees have leaves with a healthy, dark green color and show good branch growth and good fruit size. 



  Granules
Example 32 1-Butylcarbamoyl-2-benzimidazole-carbamide acid methyl ester 2: 1 complex with
Zinc, monohydrate 10%
Alkylnaphthalenesulfonic acid, sodium salt 1% expanded vermiculite granules, 0.59 to
0.25mm (30 to 60 mesh) 89%
The active material and surfactant are taken up in acetone and tumbled onto the vermiculite, after which the acetone is evaporated. 



   A cucumber planting is made by inserting three cucumber seeds into 3 cm deep holes in the ground that are 1 m apart in the row. 



  The rows are 3 m apart.  Alternating rows are treated by placing 2 g of the granules described above in the planting holes.  The adjacent rows remain untreated. 



  6 weeks after sowing, the plants in the treated rows are completely healthy.  The plants in the untreated rows are severely affected by powdery mildew. 



   This illustrates disease control by the active complex according to the invention when it is taken up from the soil by the roots and transported systemically into the leaves. 



   All of the complexes of the invention can be formulated in the same manner with similar results. 



   Example 33 1- (Butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester 2: 1 complex with
Manganese 10%
Dodecylphenol condensed with 9 moles of ethylene oxide 5% expanded vermiculite granules, 0.59 to
0.25mm (30 to 60 mesh) 85%
The active component is first air-milled to the smallest particle size and then briefly mixed with the vermiculite.  The surfactant is then sprayed into the mixture while mixing and mixing is continued for a few minutes. 



  The surfactant acts as a binder to prevent separation of the powder and granules and also assists in rapid release when the granules are placed in moist soil. 



   A field in California is sown with cotton in the normal manner, with the exception that granules made in the manner described above are added to alternate rows.  These granules are distributed so that some fall into the furrow and some are mixed with the covering soil.  The granules are used in such an amount that 0.45 kg of active chemical according to the invention are used per 3600 m of linear series.  The remaining rows remain untreated. 



   Six weeks after planting, in the rows without the granules, many plants are dead and others show pathological injuries caused by Rhizoctonia solani and strong populations of the Pacific mite (Tetranychus pacificus).  In the rows that received the granules, all plants remain alive and are healthy and free from mites.  The effect on mites is clearly systemic. 



  Wettable powder
Example 34
1- (Butylcarbamoyl) 2-benzimidazolcarbamide acid methyl ester -2: 1 - complex with
Zinc, dihydrate 50%
Dioctyl Sodium Sulphosuccinate 3%
Sodium N-methyl-N-palmitoyl taurate (Igepon TN 74) 4%
Sucrose 43%
The above components are mixed, pulverized and then air-milled until virtually all of the particles are 5% or less. 



   A rice planting field in Louisiana becomes infected with rice blight in the early part of the growing season.  Many older leaves become ill and the rice brandy fungus is present with such intensity that good grain production is in danger.  At the time of head formation, when the rice flowers are in the lowest leaf-bearing section of the stem, selected sections are sprayed. 



   The spray is an aqueous preparation containing the above-described wettable powder in an amount to provide 30 ppm of the active complex and 500 ppm of a modified phthalic acid-glyceral alkyd resin (Triton B 1956) as a surfactant.  The spray is applied at a rate of 300 liters per hectare.  Two weeks later, when the rice head has formed, a second treatment is carried out on the selected sections as well as the first.  At harvest time, the rice is healthy in the treated sections and does not show any rot between the roots and the stalk.  The untreated rice surrounding these sections is badly diseased, the heads are broken off, and most of the grain is affected by rice blight and lost. 

 

  dust
Example 25
1 - Octylcarbamoyl - 2 - benzimidazole carbamic acid methyl ester - 2: 1 complex with
Zinc, monohydrate 10%
Diatomaceous silica 10% Glimmertalk 80%
The active compound and the silica are first mixed and ground together and then mixed with talc in a ribbon blender. 



   In potash, a vineyard with a stage of development in which the shoots are about 20 to 30 cm long is selected.  The older leaves have active powdery mildew colonies.  Individual plants are dusted with the above composition early in the morning during a very calm period, with very little dust being blown onto the neighboring unpolluted vines.  The dust application rate is 2000 g per 0.4046 hectare (1 acre).  The dust treatment is repeated in three weeks.  When the grapes are ripe, the treated vines have healthy leaves and fruits. 



   The neighboring vines that are untreated have deformed saplings covered with powdery mildew, and the fruits are discolored and split open due to the severe powdery mildew infection. 



     Pourable oil note concentrate
Example 36
1 -Trichloromethylthio-2-benzimidazolcarbamide acid methyl ester - 2: 1 - complex with
Zinc, dihydrate 25% colorless mineral oil, viscosity 50 to 60 70%
Mixture of oil-soluble sulfonates and
Polyoxyethylene ethers 5%
The above components are mixed and then sand milled until the insoluble active component is below 5 lbs.  The oil dispersion thus formed can be emulsified in water. 



   1 liter of the above composition is suspended in 1000 liters of water.  This preparation is then sprayed onto apple trees in an amount of 40 liters per tree.  The trees are in the early flowering stage (pink) and have been exposed to a warm period for two days, which has led to a severe infection by apple scab.  The powdery mildew infections from last year are visible on some saplings and some spider mites are active on the older leaves.  The spray treatments are repeated at weekly intervals up to 1 month before harvest.  Unsprayed apple trees adjacent to the trees treated in the above manner show signs of disease in the middle of the season.  Leaves with apple scab patches begin to turn yellow and fall off.  The saplings stop growing and are dusty white from powdery mildew. 

  The untreated trees are bronze-colored by leaf spider mite damage and the fruits are deformed by scab injuries. 



   The trees that undergo regular treatments stay healthy and produce large, flawless fruits with good color and fine quality.  The treatments are both curative and preventive in terms of combating apple disease. 



   PATENT CLAIM 1
Pesticides, characterized in that, in addition to an inert carrier, there is at least one complex of the formula as an active ingredient
EMI22. 1
 where Q is the meaning
EMI22. 2
 or -SZ has, X is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, nitro or alkoxy with 1 to 4 carbon atoms, R1 is methyl, ethyl, isopropyl or sec. -Butyl, Ro alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 12 carbon atoms, alkynyl with 3 to 12 carbon atoms, cycloalkenyl with 4 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, with methyl, methoxy or chlorine substituted cycloalkyl with 3 to 8 carbon atoms, (cycloalkyl) -alkyl with 7 or 8 carbon atoms, phenyl,

   phenyl, benzyl substituted with methyl, methyl, methoxy, ethoxy, nitro, CFs, CHssSOo- or halogen, benzyl or hydrogen substituted with methyl, nitro, methoxy or halogen, Rs hydrogen, alkyl with 1 to 12 carbon atoms, with cyano, -OR1 , Acetoxy, chlorine or fluorine substituted alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, cycloalkyl with 3 to 8 carbon atoms or the group
EMI22. 3
 Z alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted with chlorine, phenyl, phenyl substituted with nitro, chlorine or methyl, benzyl or benzyl substituted with nitro, chlorine or methyl, Me zinc, copper, nickel,

   Manganese, cobalt, cadmium, iron or chromium and n zero, 1 / ;, 1, 1t / ¯, 2 or 3 mean. 



   SUBCLAIMS
1.  Pesticide according to claim I, characterized in that it contains complexes of the formula II as the active ingredient

** WARNING ** End of DESC field could overlap beginning of CLMS **. 



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. The active compound and the silica are first mixed and ground together and then mixed with talc in a ribbon blender. In potash, a vineyard with a stage of development in which the shoots are about 20 to 30 cm long is selected. The older leaves have active powdery mildew colonies. Individual plants are dusted with the above composition early in the morning during a very calm period, with very little dust being blown onto the neighboring unpolluted vines. The dust application rate is 2000 g per 0.4046 hectare (1 acre). The dust treatment is repeated in three weeks. When the grapes are ripe, the treated vines have healthy leaves and fruits. The neighboring vines that are untreated have deformed saplings covered with powdery mildew, and the fruits are discolored and split open due to the severe powdery mildew infection. Pourable oil note concentrate Example 36 1 -Trichloromethylthio-2-benzimidazolcarbamide acid methyl ester - 2: 1 - complex with Zinc, dihydrate 25% colorless mineral oil, viscosity 50 to 60 70% Mixture of oil-soluble sulfonates and Polyoxyethylene ethers 5% The above components are mixed and then sand milled until the insoluble active component is below 5 lbs. The oil dispersion thus formed can be emulsified in water. 1 liter of the above composition is suspended in 1000 liters of water. This preparation is then sprayed onto apple trees in an amount of 40 liters per tree. The trees are in the early flowering stage (pink) and have been exposed to a warm period for two days, which has led to a severe infection by apple scab. The powdery mildew infections from last year are visible on some saplings and some spider mites are active on the older leaves. The spray treatments are repeated at weekly intervals up to 1 month before harvest. Unsprayed apple trees adjacent to the trees treated in the above manner show signs of disease in the middle of the season. Leaves with apple scab patches begin to turn yellow and fall off. The saplings stop growing and are dusty white from powdery mildew. The untreated trees are bronze-colored by leaf spider mite damage and the fruits are deformed by scab injuries. The trees that undergo regular treatments stay healthy and produce large, flawless fruits with good color and fine quality. The treatments are both curative and preventive in terms of combating apple disease. PATENT CLAIM 1 Pesticides, characterized in that, in addition to an inert carrier, there is at least one complex of the formula as an active ingredient EMI22.1 where Q is the meaning EMI22.2 or -SZ has, X hydrogen, halogen, alkyl with 1 to 4 carbon atoms, nitro or alkoxy with 1 to 4 carbon atoms, R1 methyl, ethyl, isopropyl or sec-butyl, Ro alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 12 carbon atoms, alkynyl with 3 to 12 carbon atoms, cycloalkenyl with 4 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, methyl, methoxy or chlorine-substituted cycloalkyl with 3 to 8 carbon atoms, (cycloalkyl) -alkyl with 7 or 8 carbon atoms, phenyl , phenyl, benzyl substituted with methyl, methyl, methoxy, ethoxy, nitro, CFs, CHssSOo- or halogen, benzyl or hydrogen substituted with methyl, nitro, methoxy or halogen, Rs hydrogen, alkyl with 1 to 12 carbon atoms, with cyano, -OR1 , Acetoxy, chlorine or fluorine substituted alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, cycloalkyl with 3 to 8 carbon atoms or the group EMI22.3 Z alkyl with 1 to 3 carbon atoms, alkyl with 1 to 3 carbon atoms substituted with chlorine, phenyl, phenyl substituted with nitro, chlorine or methyl, benzyl or benzyl substituted with nitro, chlorine or methyl, Me zinc, copper, nickel, Manganese, cobalt, cadmium, iron or chromium and n zero, 1 / ;, 1, 1t / ¯, 2 or 3 mean. SUBCLAIMS 1. Pesticide according to claim I, characterized in that it contains complexes of the formula II as the active ingredient EMI23.1 where Q1 is the meaning O | -C-NHR2 ', or -SCC13, R1' is methyl or methyl, R 'is alkyl having 1 to 8 carbon atoms, Me is zinc or manganese and n is zero, 1, 11/2 or 2. 2. Pesticide according to claim I, characterized in that it contains methyl 1- (butylcarbamoyl) -2-benzimidazole carbamic acid 2: 1 zinc complex dihydrate as the active ingredient. 3. Pesticide according to claim I, characterized in that it contains 1 - (butylcarbamoyl) -2-benzimidazole carbamate methyl ester-2: zinc complex monohydrate as the active ingredient. 4. Pesticide according to claim I, characterized in that it contains 1- (butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester-2: 1 zinc complex as the active ingredient. 5. A pesticide according to claim 1, characterized in that it contains 1 - (butylcarbamoyl) -2-benzimidazole carbamate methyl ester 2: 1 manganese complex dihydrate as the active ingredient. 6. Pesticide according to claim I, characterized in that it contains 1 - (butylcarbamoyl) -2-benzimidazole carbamate methyl ester 2: 1 manganese complex as the active ingredient. 7. Pesticide according to claim I, characterized in that it contains 1 - (butylcarbamoyl) benzimidazole carbamate methyl ester 2: 1 manganese complex monohydrate as the active ingredient. PATENT CLAIM II Process for the production of the pest control agent according to claim I, characterized in that a three-phase system of a) an aqueous solution of the acetate, chloride, sulfate, nitrate or citrate of zinc, manganese, nickel, cobalt, copper, cadmium, iron or chromium, b ) a water-immiscible organic solvent and c) a solid benzimidazole carbamate of the general formula EMI23.2 wherein Q, X, R1 have the meanings given in claim I, prepares in this solvent, moves the three-phase system until the solid phase passes from the organic phase into the aqueous phase, the resulting complex wins and mixed with an inert carrier. SUBCLAIMS 8. The method according to claim II, characterized in that the aqueous solution is a zinc acetate or manganese acetate solution. 9. The method according to dependent claim 8, characterized in that the water-immiscible organic solvent is ethyl acetate, amyl acetate or diethyl ether. 10. The method according to dependent claim 9, characterized in that the benzimidazole carbamate is methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate. PATENT CLAIM III Use of the pesticide according to patent claim I for preventing damage by mites or fungi, with the exception of the use for the finishing of raw or processed textile fibers in the textile industry, characterized in that an effective amount of the pesticide is applied to the area to be protected.