NO127152B - - Google Patents

Description

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It has now been shown that the use of the complex compounds according to the invention surprisingly completely excludes or reduces

ter damage to plants and dead organic materials due to fungi and mites. Fungus, mycelia are destroyed or prevented from

develop further due to the presence of one or more of the complex compounds, i.e. that the complex compounds are fungicidal or fungistatic. The complex compounds also prevent mite colonization

nines from developing or they reduce these to a low level or even destroy them by preventing the normal development of their eggs, i.e. the complex compounds are middovicides.

The complex compounds also make it possible to control damage due to both fungi and mites using a surprisingly small amount of chemical and with surprisingly little labour.

effort. These advantages are largely due to the fact that, when the complex compounds are used correctly, they can enter and be fed around plants. This means that an entire plant can be protected against mites and fungi by a simple application of the chemical to only part of the plant, i.e. that the complex compounds are systemic. Moreover, the complex compounds, if they are supplied after a disease-causing fungus has already established itself in a plant, can enter the tissues and destroy the infection, i.e. that the complex compounds are curative

end. The need for application for the disease has occurred is eliminated so-

is led in several cases.

The invention thus relates to complex compounds of 2-benzimidazolcarbamic acids with midvicidal or fungicidal action which are particularly

characterized by having the general formula:

where Q is

or -SZ, B.-^ ér methyl, ethyl, isopropyl or

sec.butyl, R2 is alkyl' with 1-8 carbon atoms or benayl substituent

is methoxy, Z is alkyl of 1-3 carbon atoms substituted with chlorine, Me is zinc, copper, nickel, manganese, cobalt, cadmium, iron or chromium, and n is 0, 0.5, 1, 1.5, 2 or 3.

Of the new compounds, the following are the most preferred

due to their action: methyl ester 2:1 zinc complex mono or dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methylester 2:1 zinc complex of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester-2:1-manganese complex-mono- or dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methylester-2:1-manganese complex of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid .

The invention also relates to a method of manufacture

of the complex compounds, and the method is characterized by the fact that a system of

a) a slurry of a solid benzimidazole carbamate of the formula:

where Q, R-^, R2 and Z are as indicated above, .in a solvent consisting of dimethylformamide, acetone or methyl ethyl ketone, and 0.5 molar equivalent of acetate, chloride, sulphate or nitrate of zinc, manganese, nickel, cobalt, copper , cadmium, iron or chromium,

b) one molar equivalent of aqueous sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, and the system is reformed, and the

formed complex compound is recovered.

Of the benzimidazole carbamates, the compounds are where 0 is

or -SCC1-., R-^ is methyl or ethyl, and R2 is alkyl with

1-8 carbon atoms, preferred as starting compounds.

Due to the strong action of the complex compounds obtained, the following compound is the most preferred: the methyl ester of 1-(butylcarbamoyl)-2-benzitnidazolecarbamic acid, the methyl ester of 1-(hexylcarbamoyl)-2-benzimidazolcarbamic acid, the methyl ester of 1-(octylcarbamoyl) )-2-benzimidazolecarbamic acid, .v-;: the methyl ester of 1-(o-methoxybenzylcarbamoyl)-2-benzimidazolecarbamic acid,

the methyl ester of l-trichloromethylthio-2-benzimidazolecarbamic acid and the ethyl ester of l-trichloromethylthio-2-benzimidazolecarbamic acid.

v' f i The benziiftidazole carbamate reactants can be prepared in a known manner such as, e.g. described in Belgian Patent No. 698,071.

They can thus be prepared by reacting a 2-benzimidazole carbamate with the formula:

with one equivalent of an alkylchlorothiolformate, alkylchlorothioformate, alkylchlorothioformate, isocyanate, acyl chloride or a sulfenyl chloride in an inert solvent. The 2-benzimidazole carbamate can be prepared as described in US patent no. 3-010,768.

The transition metal salts used for the production of the metal complex compounds according to the invention are salts of zinc, manganese, nickel, cobalt, copper, cadmium, iron and chromium. The salts can be acetates, chlorides, sulphates or nitrates. Due to their high fungicidal action, complex compounds containing zinc and manganese are preferred.

The new complex compounds according to the invention can be prepared either in a known manner or by using the new method according to the invention. In a known preparation, the benzimidazole carbamate derivative is dissolved in a suitable solvent, such as dimethylformamide, and a molar equivalent of sodium methoxide is added to convert the benzimidazole carbamate to its sodium derivative. Half a molar equivalent of the desired metal salt is added in the form of a solution in dimethylformamide to the solution thus obtained. After stirring for a suitable time, e.g. 15 minutes, the reaction mixture is poured into a mixture of ice and water with stirring, and the product is separated by filtration, washing and drying.

In contrast to this known method, the new method according to the invention uses a slurry of the benzimidazole carbamate and the heavy metal salt in dimethylformamide instead of a solution, and this makes it possible to use a much smaller amount of dimethylformamide. Moreover, the new method uses concentrated aqueous sodium or potassium hydroxide or carbonate instead of the far more expensive sodium methoxide, and also the cheaper metal salts of inorganic acids, e.g. sulphates, chlorides or nitrates, or acetates, instead of the far more expensive salts

ter of other organic acids.

In different embodiments of the new method, the dimethylformamide used as solvent is replaced with acetone (example 2) or with methyl ethyl ketone (example 3), and the heavy metal salt is added in the form of a highly concentrated or saturated aqueous solution. The use of methyl ethyl ketone offers the advantage that the metal complex compound can be recovered by simple filtration without it being necessary to pour the reaction mixture into water. The methyl ethyl ketone recovered by filtration can be used as such for the production of the next batch of metal complex compound. It will be clear to the person skilled in the art that these methods, and especially the method where methyl ethyl ketone is used, can be carried out continuously.

For the new method - according to the invention - it can be established that the temperature at which the conversion is generally carried out can vary between the freezing point and the boiling point of the reaction mixture. Too-high temperatures can e.g. be advantageous if the metal salt used has a low solubility in water. However, the 1-substituted benzimidazolecarbamic acid esters used as starting materials according to the invention have different degrees of thermal instability at elevated temperatures depending on the nature of the substituent in the 1-position.

In those cases where this thermal instability is prominent, it is thus recommended to choose the other reaction conditions so that the conversion requires a very short time, and that the temperature is kept below e.g. 50 C. It is preferred to carry out the reactions at room temperature without external heating or cooling. Depending on the solubility of the product in the organic solvent, it is in some cases advantageous for the yield to cool the reaction mixture to e.g. 0 - 3°C for filtration.

Another factor that affects the ease of the reaction and the yield is the particle size of the organic starting material. It has e.g. it has been shown that fine pulverization of the starting material will in some cases increase the yield of metal complex compound by up to 15% under otherwise identical conditions'.

The new complex compounds according to the invention are usually obtained in the form of dihydrates under normal drying conditions, such as e.g. by spreading the product in air or by drying in a vacuum oven at slightly elevated temperatures of e.g. up to 50°C. However, the materials can be converted into forms containing less water, e.g. to the corresponding monohydrates, hemihydrates or even to completely anhydrous orjnérV The monohydrates and the aqueous forms are the forms most frequently obtained...

These are achieved e.g. by vacuum drying at higher temperatures' of e.g. 60 - 100°C or by drying; in solution or, suspension ion-, . These methods are described in examples k - 6. In some cases, conversion of the dihydrates into de. corresponding monohydrates or anhydrous forms not only to a enhanced fungicidal and midvicidal effect, but also to. a greatly improved storage stability...

This applies in particular to the 1-carbamoyl compounds according to the invention. As described in examples k - 6, conversion of the dihydrates of this type to the corresponding monohydrates or anhydrous forms leads to changes in the infrared spectra, e.g. a peak occurs at 5>8 μm, which, together with the increased stability, indicates a structural rearrangement in the metal complex compound whereby the -COOR-^ group in the 2-position no longer directly takes part in the binding of the metal atoms , and this bond is taken over by the carbamoyl group in position I. It should therefore be noted that the compounds where n is 0, 0.5 or 1 can have such structures as: a) The preferred compound methylester-2:1-zinc-complex-dihydrate of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid has an infrared spectrum with the following characteristic changes compared to the infrared spectrum for the organic starting compound methyl ester of 1-(butylcarbamoyl)-2-benzimidazoliccarbamic acid:' the characteristic peaks for the starting compound at about 5?8 and 8.8 iim have disappeared, and new peaks appear at about 6.0, 6.6 and 8.7 /^m Nuclear magnetic resonance spectrum The compound has a triplet at 0.88Ttned a coupling constant T - 5, 1 eps. This absorption is due the proton attached to the N of the 1-butylcarbamoyl group. This same triplet was present in the starting compound and occurred at 0.5T with a coupling constant of J" = 5?1 eps.

The presence in the product of the substantially unchanged absorption of the proton bound to N in the 1-butylcarbamoyl group constitutes strong evidence that the molecule's butylcarbamoyl group has no connection to the metal atom.

The spectrum of the starting compound has an absorption at -2.28T (broad) which is written from the proton bound to the nitrogen in the 2-position. For the product, this peak is no longer present, and this indicates that this proton has been replaced by the metal.

A rapid exchange of the two above-mentioned protons is prevented

in deuterium dimethylsulfoxide which is used as a solvent, and this makes it possible to observe their individual absorption positions and possibly their coupling constants.

There is no other absorption below 1.5 T in either the product or the starting compound. Changes in the absorption monsters. for the aromatic hydrogen atoms supports the indication that the 3-nitrogen atom is connected to the metal.

Elemental analysis:

Melting point: The product melts over a very wide range, and this was expected for a compound of this type.

Dehydration: As described in more detail in one of the following examples, the product loses two molecules of water when heated in a

o

oven to 60 - 65 C.

Structural formula: The above is consistent with the following structural formula: b) The infrared spectrum for the preferred compound methyl ester-2:i-manganese complex dihydrate of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid shows that no peaks occur at 5 .8 and 8.8 /Lim which are characteristic of the starting compound the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, but there are peaks at 6.0, 6.6 and 0.7 /Ltm which are characteristic of the desired 2:1 manganese complex dihydrate compound.

Elemental analysis:

This compound has the structural formula shown above, but with the difference that a manganese atom replaces the zinc atom.

c) The compound methyl ester-2:1-copper complex of 1-(butyl-carbamoyl)-2-benzimidazolecarbamic acid is a light green powder. Its

infrared spectrum has characteristic peaks at 5.95, 6.5 and 8.7 /Lim. There are no peaks at 5.8 and 8.8 ^m.

Elemental analysis:

d) The compound methylester-2:1-nickel complex-dihydrate of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid has an infrared spectrum

which indicates that a smaller amount of starting material is present and also clearly has the characteristic peaks at 6.0, 6.6 and 8.7 /Lim. The product is a light, greenish-blue powder.

Elemental analysis:

Calculated for a 9:1 mixture of product and starting material:

e) The compound 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid methyl ester-2:1-cobalt-carbon complex dihydrate is a faint pink powder. -

Its infrared spectrum has characteristic peaks at 6.0, 6.6 and 8.7 im. It also indicates that a small amount of starting material is present.

Elemental analysis:

Calculated for a 9:1 mixture of product and starting material:

The organic starting materials indicated in the following table have a fast reaction to the products indicated in the table.

In the following examples, the amounts are based on parts by weight, unless otherwise stated. In some of the examples, both parts by weight and parts by volume are indicated, and in these cases the units of measurement correspond to each other such as grams to milliliters, kilograms to liters etc.

Example 1

A slurry of 5.8 parts of methyl ester of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid and 1.7 parts of manganese sulfate monohydrate in 3^ parts by volume of dimethylformamide was stirred and 1.6 parts of 50% aqueous sodium hydroxide was added dropwise. After stirring for 1 hour, the mixture was poured under stirring into 200 parts by volume of a mixture of ice and water. The mixture was stirred for 15 minutes and filtered.

The solid was washed with water and dried. The product weighing 6.5 parts was exactly the same as product b) above.

Example 2

A slurry of 5.8 parts of methyl ester of 1-(butylcarbamo-yl)-2-benzimidazolcarbamic acid in 100 parts by volume of acetone was vigorously stirred and 1.6 parts of 50% aqueous sodium hydroxide added dropwise. Stirring was continued for 1 hour. A solution of 1.7 parts of manganese sulfate monohydrate in water was added dropwise to the acetone suspension with stirring, the sodium derivative of the methyl ester of 1-(butyric acid).

Large dr„A to.nphase after the addition has been completed..more. The mixture was then poured into 250 parts v^. etc. After stirring for 15 minutes, the suspension was filtered, and the remaining material was washed and dried. The product weighing 6.2 parts was exactly the same as product b) above.

Example

A slurry of 5.8 parts of methyl ester of 1-(butylcarbamo-yl)-2-benzimidazolcarbamic acid in 50 parts by volume of methyl ethyl ketone was vigorously stirred and 1.6 parts of 50% aqueous sodium hydroxide added dropwise. Stirring was continued for 1 hour. A solution of 1.7 parts by weight of manganese sulphate monohydrate in 3 parts of water was added with stirring to the suspension in methyl ethyl ketone of the thus obtained sodium derivative of the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid. The two liquid phases containing the third, solid phase were clearly visible. Stirring was continued for 3 hours. The mixture was then cooled in ice with stirring and filtered. The solid was washed with methyl ethyl ketone and water and dried. The product that weighed

6.2 parts," yar.-noyakt the same as the product b) above.

Example k

Anhydrous methyl ester-2:1-zinc complex of 1-(butylcarbamo-yl)-2-benzimidazolcarbamic acid 10 parts of the dihydrate a) above were placed in a rotary laboratory evaporator under a high vacuum of 0.25 mm Hg. The temperature was gradually increased to 60°C and held at this temperature for 1 hour. The anhydrous product obtained weighed 10 parts and had the following analysis:

Calculated for the anhydrous 2:1 zinc complex:

The infrared spectrum of the anhydrous product differed from that of the dihydrate mainly in that the peak at 2.9 µm due to water had disappeared and in that a new peak at 5.8 µm appeared. On treatment with water, the anhydrous material reverted to the dihydrate.

Example 5

Preparation of methyl ester 2:1-manganese complex monohydrate of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid

10 parts of the dihydrate b) above were placed in a rotary laboratory evaporator under a high vacuum of 0.25 mm Hg. The temperature was gradually increased to 60°C, and this temperature was maintained for 3 hours. The obtained monohydrate weighed 9 parts and had the following analysis: Calculated for the 2:1 manganese complex monohydrate:

The infrared spectrum of the monohydrate product differed from that of the dihydrate mainly in that it contained a peak at 5.8 µm and in that the peak at 2.9 Mra due to water had completely disappeared despite the molecule still containing .1 mole of water. ■ When treated with water, the monohydrate returned to the dihydrate.

Example 6

Preparation of anhydrous methyl ester-2:1-manganese complex of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid 10 parts of the dihydrate b) above and 5 parts of Linde Molecular Sieve Type 3A were added to 50 parts by volume of dimethylformamide. The mixture was stirred for 1.5 hours and filtered. The filtrate was placed in a laboratory rotary evaporator and concentrated under a high vacuum of 0.25 mm Hg at 50°C. After removing most of the dime-thylf ormamide, the temperature was increased to <7>0°C and drying continued until the residue was a dry powder. The product, which weighed 9 parts, had the following analysis:

Calculated for the anhydrous 2:1 manganese complex:

By repeating this tdrkeforsdk, but without applying Linde

Molecular Sieve, the same product was obtained. In other words, a treatment of the dihydrate with dimethylformamide and removal of this solvent. by evaporation under vacuum at the prehdyet temperature sufficient to remove the 2 moles of water of hydration. However, the presence of a drying agent is advantageous in that it gives a dry dimethylformamide distillate which can be used as such for drying the next batch of material.

The infrared spectrum for this anhydrous. material resembled the infrared spectrum of the monohydrate according to Example 5 in that both spectra, in contrast to the spectrum for the dihydrate b)' above, had a peak at 558 µm and no peak at 2.9 µm (R 2 O). The spectrum. for the anhydrous product had an additional peak at 5?95/im. When treated with water went. the aqueous material back to the dihydrate.

Example 7

The following zinc-complex compounds can be prepared in a similar manner by replacing the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid with the corresponding alkyl ester reactants of 2-benzimidazolecarbamic acid.

methyl ester 2:1 zinc complex dihydrate of 1-(trichloromethylthio )-2_-benzimidazolecarbamic acid, ethyl ester 2:1 zinc complex dihydrate of 1-(trichloromethylthio)-2-benzimidazolecarbamic acid, isopropyl ester 2:1- zinc complex dihydrate of 1-(trichloromethylthio).-.. 2-benzimidazolcarbamic acid,

methyl ester 2:1-zinc complex dihydrate of 1-(3-chloropropylthio)-2-benzimidazolecarbamic acid and

methyl ester 2:1-zinc complex dihydrate of 1-(p-methboxybenzylcarbamoyl)-2-benzimidazolecarbamic acid.

Example ;8,:) A

The zinc complex compounds according to Example 7 were dried as described in Example k. The corresponding anhydrous forms of the products according to Example 7 were obtained.

Example 9

The following manganese complex compounds can be prepared by replacing the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid with equivalent amounts of the corresponding alkyl esters of 2-benzimidazolecarbamic acid: methyl ester 2:1-manganese complex dihydrate of 1-( methylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1-manganese complex dihydrate of 1-(octylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1-manganese complex dihydrate of 1-(allylcarbamoyl)-2- benzimidazolecarbamic acid, methyl ester 2:1-manganese complex dihydrate of 1-(hexylcarbamoyl)-2-benzimidazolecarbamic acid,

isopropyl ester 2:1-manganese complex dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1-manganese complex dihydrate of 1-(p^-methoxybenzylcarbamoyl)-2-benzimidazolcarbamic acid, methyl ester 2:1-manganese complex dihydrate of, 1-(trichloromethylthio )-2- benzimidazolecarbamic acid and isopropyl ester 2:1-manganese complex dihydrate of 1-(trichloromethylthio)-2-benzimidazolecarbamic acid.

Example 10

The dihydrates according to example 9 were dried using the method according to example 6. The corresponding anhydrous forms were obtained.

Example 11

The following copper complex compounds can be prepared by replacing the ethyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid with equivalent amounts of the corresponding alkyl esters of 2-benzimidazolecarbamic acid: methylester-2:1-copper complex of 1-(methylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester-2:1-copper complex of 1-(octylcarbamoyl)-2-.benzimidazolecarbamic acid, methylester-2:1-copper complex of 1-(allylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complex of 1-(hexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complex of 1-(p-methoxybenzylcarbamoyl)-2-benzimidazolecarbamic acid and

methyl ester 2:1 copper complex of 1-(trichloromethylthio)-2-benzimidazolecarbamic acid.

Example 12

The following nickel-complex^ compounds can be prepared by replacing the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid with equivalent amounts of the corresponding alkyl esters of 2-benzimidazolecarbamic acid: methylester-2:1-nickel-complex-trihydrate of 1- (allylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 nickel complex trihydrate of 1-(hexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1-nickel complex trihydrate of 1-(p-methoxybenzylcarbamoyl)-2-benzimidazolecarbamic acid and

methyl ester 2:1-nickel complex trihydrate of 1-(trimethylthio)-2-benzimidazolecarbamic acid.

Example 13

The following cobalt complex compounds can be prepared by replacing the methyl ester of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid with equivalent amounts of the corresponding alkyl esters of 2-benzimidazolecarbamic acid: methyl ester 2:1 cobalt complex dihydrate of 1- (hexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex dihydrate of 1-(octylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex dihydrate of 1-(p-methoxybenzylcarbamoyl)-2-benzimidazolecarbamic acid and

methyl ester 2:1 cobalt complex dihydrate of 1-(trichloromethylthio)-2-benzimidazolecarbamic acid.

Example lk -

The following transition metal complex compounds can be prepared by replacing zinc acetate dihydrate with equivalent amounts of the appropriate soluble salts: methyl ester 2:1 iron complex dihydrate of 1-(butylcarbamoyl)-2-benzimidazolcarbamic acid, methyl ester 2:1- cadmium complex dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 chromium complex dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid.

The complex compounds according to the invention have a very good fungicidal and midvicidal effect when they are used to prevent or reduce damage to plants and dead organic materials. The usefulness of the compounds according to the invention is described in more detail in the following paragraphs.

The complex compounds according to the invention can be used to control a wide range of fungal diseases in leaves, fruit, stems and roots of plant crops without damaging the plant itself. Fruit, root tubers, pods, roots, seeds and other plant parts that are harvested to be used as food and animal feed or for other purposes are protected against degradation due to fungal attack during processing, distribution and storage. Seeds, root tubers, cuttings and other plant growth propagating materials are protected against fungal attack during handling and storage and in the soil after planting. Wood, woven fabric, fibreboard, paper and other industrial products are protected against unsightly staining and destructive degradation caused by fungi. Luggage, shoes, shower curtains, carpets, mats, clothes and other useful household, communal or industrial products are protected against rot, fungal stains and mold growth. Painted surfaces are protected against stains and discoloration by using a complex compound according to the invention in the paint formulation.

The long range of fungi against which the complex compounds according to the invention are active can, without this being limiting, be represented by the following: Venturia inaequalis which causes scab on apples, Podosphaera leucotricha which causes powdery mildew on apples, Urpmyces phaseoli which causes bone rust, Cercosppra apii, which causes early emergence .of celery, Cercospora betieola; which causes leaf spots on sugar beets, Sclerotinia sclerotiorum which causes rot in vegetables, such as leaf lettuce, beans, carrots and celery,: Colleto-trichum spp. which causes disc spots in fruits and vegetables, such as beans, tomatoes and coffee, Septoria apii which causes late blight of celery, Cercospora musae which causes Sigotoka disease in bananas, Piricularia spp. which causes Johnson spot on bananas, Erysiphe cichoracearum which causes powdery mildew on cantaloupe due to other cucumber plants, Penicillium digitatum, Phomppsis spp. and Diplodia natalensis which cause aker rot in citrus fruit, Cerato-stomella ulmi which causes elm disease, Sphaerotheca humuli which causes powdery mildew on roses, Diplocarpon rosae which causes black spots on roses, Ramularia spp. which causes leaf spots on ornamental shrubs, Botrytis cinerea which causes rot in flowers and fruit from ornamental shrubs', in fruit and vegetables, Uncinula necator which causes powdery mildew on grapes, Guignardia bidwellii which causes black rot in grapes, Melonconium fuligineum which causes white rot in grapes, Cbccomyces hiemalis which causes rot in cherry leaves, Cytospora spp. which causes cancer in trees, Cladosporium carpophilum which causes scab on peaches, Fusicladium effusum which causes scab on American walnuts, Erysiphé giraminis which causes powdery mildew on cottonwoods, Monolinia (Sclerotinia) laxa and M. fructicola which causes brown rot in stone fruits, which peaches, cherries bg apricots, Pseudopnenziza ribes sbm causes leaf spot r on gooseberries, Piricularia oryzae which causes rice wilt, Pucciniå recondita, P. coronåta and P. glumarum which cause aphids on wheat, oats and grass respectively, Puccinia graminis tritici spm which causes stem rust in wheat, Claviceps purpurea which causes downy mildew on rye and grass, Aspergillus niger which causes rot in bpmullsfrb capsules and decomposition after damage to a number of plant tissues, Aspergillus terreus which is common in soil and attacks vegetables, Tilletia caries and other Tilletia species s<p>m cause common,, . wheat blight, Ustilago tritici, Ustilago nigra, Ustilago

avena <p>g other Ustilag<p> species that cause Ibs blight in wheat, barley and oats respectively, Urocystis tritici and other Urpcystis species that cause loose blight in wheat, Sphacelqtheca sprghi which L causes covered blight in sorghum , Ustilago hordei pg Ustilago kolleri which causes covered barley blight and oat blight respectively,

Pithomyces chartorum which is present in lawns, pastures and other areas of grass and which is known to have several secondary effects, various species of Rhizoctonia, Fusarium and Verti-cillium which are present in soil and attack the roots or other parts of the soil and the vascular system in a number of plants, and various species of Penicillium which grow on such materials as textiles, fiber plants, leather goods and paint, and species of Myrothecium which attack such objects as shower curtains, carpets, rugs and clothing.

The midticidal effect of the compounds according to the invention is useful for preventing the development of a harmful mite spread or for effecting a gradual reduction of a present spread. The movement of the mites is restricted. Thus, a break in the spread or a continuation of a strong spread in a particular place is largely dependent on the development of eggs that have been laid in that place.

Midge eggs are not developed in such a way that they will produce living specimens if the eggs are treated with one of the complex compounds according to the invention or if the eggs are laid on a surface containing one of these complex compounds. The eggs will also not develop if they are laid by a female mite that has been in contact with one of the complex compounds or laid by a female mite that takes in or has recently taken in food, such as plant sap, containing one of these complex compounds. This impact on the development of eggs prevents a reduction in the distribution to a significant extent in relation to the distribution during the treatment. This ovicidal effect, together with the high natural virulence of adult specimens, can to a large extent eradicate mites from an already infected area in the flea: in a relatively short time. Moreover, new colonies cannot develop as long as the complex connections are. present on the mite-infested surface or occurring-in their food supply.

Several mite species which cause damage to fruit, field crops, vegetables and ornamental shrubs under a variety of conditions can be controlled by using the complex compounds and methods according to the invention. The extent of the practical benefit of the achieved mite control can be represented, without being limiting, by the following indication of particular susceptible mites together with the types of damage they can cause: Panonychus ulmi (European rbd mite) and Tetranychus urticae (two-spotted mite) which is commonly referred to as "fruit tree mite" and which attacks a variety of deciduous tree fruits including apples, pears, cherries, plums and peaches, Tetranychus atlanticus (Atlantic or strawberry spider mite), T. cinnabarinus (carmine spider mite) and T. pacificus (Pacific spider mite) which attacks cotton and a number of other cultivated plants, Paratetranychus citri (citrus rbd mite) and others which attack citrus, Phyllocoptruta sleivora which causes citrus rust, Bryobia praetiosa (cluster mite). which attacks clover, lucerne and other cultivated plants, Aceria neocynodomis which attacks grass and other plants, Tyrophagus lintneri which is a serious pest in stored foods and on cultivated mushrooms, and Lepido-glyphus destructor which damages Kentucky turnip grass seed during storage.

When the complex compounds according to the invention are used in certain ways, they enter and move freely in the plants, i.e. that they are systemic. Thus, both fungi and mites can be controlled in plants in parts that are far away from the place of application. Because of this effect, the complex compounds can be used in conjunction with frb', and treatment of cucumber frb with a few grams of a complex compound according to the invention per 50 kg of fro' is thus sufficient to control powdery mildew (Erysiphe cichoracearum) and spider mites, which Tetranychus urticae on the treated plants for a period of over 40 days. An application to soil also provides control of certain leafhoppers and mites on plants growing in the treated soil. Sproy tea or dust treatment of plant leaves and stems protects other parts of the plant that have not been directly sprayed and new leaves that develop later, against both fungi and mites.

It is a further valuable property of the complex compounds according to the invention that they are capable of preventing the spread of or destroying an already established fungal infection in a plant, i.e. that they are healing. The complex compounds thus do not need to be used after conditions have developed which enable incipient fungal attack. This means that under certain circumstances it is possible to avoid the use of any chemical during the entire life of the cultivated plant. In other cases, only part of the usual, full plan for pesticide application is necessary.

Large savings both in terms of chemical costs and labor in connection with the application are therefore possible when using compounds with systemic and healing properties. The complex compounds according to the invention also result in a further saving due to the fact that both fungi and mites can be controlled by using a single chemical.

The complex compounds according to the invention provide protection against damage caused by fungi, mites or both when applied in the right place by the methods described later and in a sufficient quantity to give the desired fungicidal and midvicidal effect. They are particularly suitable for the protection of living plants, such as fruit-bearing trees, fruit-bearing trees, ornamental shrubs, forest trees, vegetable plants, flowering plants including ornamental plants, small fruit trees and berry bushes, fiber crops,. cereal and seed crops, sugar cane, sugar beet, pineapple, forage and high crops, beans, peas, soya beans, potatoes, potatoes, sweet potatoes, tobacco, hops, lawns and pastures.

Living plants can be protected against fungi and mites by adding one or more of the complex compounds according to the invention to the soil where they grow or where they will later be sown or planted, or by adding to seeds, root tubers, pods or other plant propagating parts for planting, and also when added to the living plant's leaves, stems and fruit. Living plants, can also be protected by dipping the root system or by mechanically injecting the chemical or chemicals into roots or stems.

For soil treatment, pellets, grains, pellets, slurries or solutions are used. Preferred amounts for treating soil where plants grow or are to grow, when using the complex compounds according to the invention are 0.01 - 500 parts by weight per million parts by weight of soil where the rats grow or will grow. It is preferred to use amounts of 0.1 - 50 parts per million, and 0.25 - 25 parts per; million is the most preferred amount.

Preferred amounts for use in connection with seeds, tubers, pods or other plant propagating parts are 0.03 -

6000 g active complex compound according to the invention per 50 kg of treated plant material. More preferred amounts are 0.3 - 3000 g of active complex compound per 50 kg, and the most preferred quantities are 2.8 - 1500 g per 50 kg.

For the treatments, dust, suspensions or solutions are used. With such treatments, the treated parts are protected from damage by fungi, mites or both, and they also protect the formed new plants against both types of plague.

Preferred quantities for use of the complex compounds according to the invention when treating the leaves, stems and fruits of living plants are 0.012 - 60 kg of active ingredient per hectares. More preferred amounts are 0.025 - 30 kg per hectare, and the most preferred quantities are 0.05 - 15 kg per hectares. The optimum amount in this area depends on a number of variables which are well known to those skilled in the field of plant protection. These variables include, but are not limited to, the disease to be controlled, the expected weather conditions, the plant type, the plant's developmental stage and the time between applications. It may be necessary to repeat the applications within the indicated area one or a number of times at intervals of 1 - 60 days. Dusts, slurries or solutions are used for the treatments.

For the immersion of live plant rats, it is preferred to use a quantity of 0.5 - 18,000 g of active ingredient per 380 liters of water or another liquid carrier material. More preferred quantities are 4.5 - 9000 g per 380 litres, and the most preferred quantities are 45 - 4500 g per 380 litres.

For injecting into the roots or stems of living plants, it is preferred to use a quantity of 0.01 - 10,000 parts per parts per million of water or another liquid carrier material. More common quantities are 0.1 - 5000 parts per million, and the most preferred quantities are 1 - 1000 parts per million.

Plant parts, such as fruit, root tubers, pods, foliage, roots and the like that are hosted for use as food or for, are protected by treatment with an active complex compound according to the invention against decomposition and other deterioration due to fungi or mites during processing, distribution and storage . The plant parts to be protected in this way can be dipped in a liquid bath containing an active ingredient, dusted with a finely divided preparation of the active ingredient, sprayed, misted with an aerosol containing the compound or wrapped in wraps or wrapping materials impregnated with the active compound.

If a liquid bath is used, it may contain 1 - 5000 parts by weight of active ingredient per million parts by weight of liquid. A more preferred quantity for the bathroom is 5,2500 parts per million, and the most preferred quantity is 10 - 1000 parts per million.

Dust and covers or wrapping materials used for this type of treatment may contain 0.01 - 10 7. of the active ingredient. More preferred amounts are 0.1 - 5 7„, and the most preferred amounts are 0.2 - 2.5 7.-

Wood, leather, woven fabrics, fibreboards, paper and other organic industrial products can be protected against splitting or discolouration due to fungi and against attack by mites by being coated, lined or impregnated with an effective amount of one or more of the complex compounds according to the invention . The coating can

carried out by dipping, spray changing, over-stressing, fog treatment, e.g. with an aerosol, or coating the material to be protected with a suitable mixture containing the active ingredient. The preferred, usable amounts of the active ingredient in the treatment preparation applied to the material to be protected are 0.025 - 95% by weight. More preferred amounts are 0.05 50 7., and the most preferred amounts are 0.1 - 25 7«.

If an introduction or impregnation is to be used, the amounts used can be expressed as the amount of active ingredient introduced into the material to be protected. The preferred usable amounts for these treatment types are 0.001 - 30 wt.7. active ingredient in the final product. More preferred amounts are 0.005 - 15 70, and most preferred amounts are 0.01 - 7" L.

Luggage, shoes, shower curtains, carpets, mats, clothes and other useful household, communal or industrial objects are protected against rot, fungal stains and unattractive mold growth and also against attack by mites by using the active complex compounds according to the invention. Again, either a surface protection or a deeper protection can be achieved. The surface treatment is carried out by dipping, washing, spraying, aerosol application or polishing.

A deep treatment is achieved by using penetrating solutions. Spray replacement fluids, immersion solutions and washing solutions contain the active compound according to the invention in an amount of 10 - 5000 parts per million. Fluids for aerosol application and bestbvning contain 0.1 - 20 wt70. Penetrating solvent solutions contain an amount of the active ingredient that gives a deposit of 5-20,000 parts per million in the material to be protected.

Painted surfaces can be protected against unsightly stains and mold growth by introducing 5-20,000 parts of an active complex compound according to the invention into paint formulations for use. million. More preferred quantities are 10 - 10,000 parts per million, and the most preferred quantities are 20 - 5000 parts per million. Such a treatment with complex compound fleece according to the invention also protects paint in cans against degradation due to fungi.

Damage due to mites of stored, organic products, such as grains, seeds, pods, root tubers, fruits or animal skins is kept to a minimum by treating the floors, walls and other parts of warehouses or other buildings with one or more of the active complex compounds . The treatments are carried out by using dust, spray liquids or aerosols containing a preferred amount of 0.05 - 1000 e of the active complex compound according to the invention per 93 m surface that must be kept free from too strong midge spread.

A curative control of plant diseases when using the complex compounds according to the invention is improved if the treated plant parts are moist for one or more periods of 2-12 hours each immediately after using the active complex compound. This will often be achieved due to the slow absorption of an original spray treatment or due to naturally occurring rain, mist, fog or dew. Under other conditions, such as during periods of drought or under protection, e.g. in greenhouses, to achieve the best results it is necessary to take measures to keep the plants moist.

When the complex compounds according to the invention are used, their effect can be improved by using certain additives, e.g. in the water in which they are dispersed. These additives can be surfactants, oils, wetting agents, enzymes, carbohydrates and organic acids. They enhance the effect on root tubers and foliage, of treatments for dipping live plant rots, when using liquids for injection into live plant rots or stems or in mixtures used to treat fruit, root tubers, pods, rots and the like after harvest.

Surfactants that improve fungal control and mite control when using the compounds according to the invention include sulfonated and sulfated amines and amides, diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, ethoxylated fatty esters and oils, polyethylene oxide/polypropylene oxide combinations, alkyl sulfonates, surface-active fluorocarbons, glycerol esters, ethoxylated alcohol sulfates, glycol esters, isethionates, sulfated ethoxylated alkylphenols, lanolin derivatives, lecithin and lecithin derivatives, alkanolamides, phosphate derivatives, monoglycerides and derivatives, quaternary ammonium compounds, sorbitan and sorbitol derivatives, sulfosuccinates, alcohol sulfates, sulfated fatty esters, sulfated and sulfonated oils and fatty acids , alkylbenzene sulfonates imidazolines, taurates, ethoxylated mercaptans, ethoxylated amines and amides, modified phthalic acid glycerol alkyl barpices and similar materials. The oils include non-phytotoxic aliphatic spray oils and triglycerides either with or without emulsifiers to enable the preparation of dispersions in water. Humectants, such as glycerol or ethylene glycols, enzymes, such as bromelain, and carbohydrates, such as glucose, lactose and dextrose, can also be used. Of the organic acids that can be used, mention may be made of glycolic and gluconic acids. Although the exact way in which these additives improve the effect of the fungicides according to the invention is not known, the effect is nevertheless very surprising, and it is possible that these additives improve the penetration into the plant or a spread in the plant of the fungicides according to the invention.

Preferred surfactants to enhance the fungicidal and midvicidal action of these compounds are products such as dioctyl disodium sulfosuccinates ("Aerosol" OT and "Aerosol" OT-B), mixtures of aromatic sulfonates and ethylene oxide derivatives ("Argrimul" GM, "Argrimul" A-100, " Agrimul" N-100, "Emcol", H50A, "Emcol" H53), polyoxyethylene sorbitol oleate/laurate ("Atlox" 1045A), sodium lauryl sulfate ("Duponol" ME), polyoxyethylated vegetable oils ("Emulphor" EL719), lecithin derivatives ("Emultex " R), acid-complex organic 6-phosphate esters ("Gafac" RE-610, "Victawet"), aliphatic amide alkyl sulfonates ("Hyfoam" Base LL), oleic acid esters of sodium isethionate ("Igepon" AP78), sodium N-methyl- N-oleoyl taurate ("Igepon" T77), sodium salt of sulfated lauryl and myristincolamide ("Intramine" Y), polyethylene glycol 400 oleic acid ester ("Nonisol" 210), sodium dodecylbenzene sulfonate ("Sul-Fon-Ate" AA 10, "Ultrawet " K), polyoxyethylene ether with long-chain alcohols ("Surfonic" LR 30, "Alfonic" 1012-6, "B rij" 30, "Tergi-tol" TMN), ethylene oxide condensates with propylene oxide/ethylenediamine condensates ("Tetronic" 504), esters of polyhydric alcohols ("Trem" 014), modified phthalic acid glycerol alkyd resins ("Triton" B 1956), quaternary compounds ( "Zeléc" DP), alkylphenol-ethylene oxide condensates ("Dowfax" 9N4, "Dowfax" 9N10, "Hyonic" 9510, "Tergitols") and the like. The examples in brackets; is illustrative only and does not exclude other products not mentioned in the male section available. Examples of other surfactants within each of these categories are set forth in "Detergents and Emulsifiers", 1965 Annua1, or 1966 Annua1, published by John W. McCutcheon, Inc., 236 Mt. Kemble Avenue, Morris-town, New Jersey.

The preferred ones include spray oils such as "Orchex" 796 which has been emulsified with "Triton" X-45, castor<p>oil which has been emulsified with "Triton" X-114, corn oil which has been emulsified with " Triton" X-114, Volck Oil ^70, Sunoco Oil No. 7E and similar non-phytotoxic spray oils of vegetable, animal or mineral origin.

The complex compounds according to the invention and the surfactants, surfactants, wetting agents, enzymes, carbohydrates and acids which can be used to improve the fungicidal and middovicidal effect of the complex compounds can be connected in a number of ways. An additive that will improve the effect can e.g. mixed with complex compounds according to the invention for the production of spray slurries. It is also often possible and advantageous to prepare mixtures where the additive and the complex compound according to the invention will both be present in the mixture, which is then easy to use. Such mixtures can be powders, grains, suspensions or even solutions depending on the physical and chemical properties of the components to be produced. A person skilled in the art will understand on the basis of the above teaching that the relationship between the active ingredient of. complex compound and additives can vary greatly. The additive can thus be present in such mixtures in an amount of 33 - 10,000 parts per 100 parts of the complex compounds according to the invention. Amounts of 40 - 5000 parts additive per 100 parts active ingredient is more preferred, and a quantity of 50 - 3500 parts per 100 parts complex compound is even more preferred.

The mixtures are prepared by mixing a complex compound according to the invention with one or more surfactants.

The surfactants

can be wetting, dispersing or emulsifying agents. The

can act as wetting agents for wettable powders such as dust, as dispersants for wettable powders such as suspensions and as emulsifiers for emulsifiable concentrates. The surfactants can also improve the biological effect of the complex compounds

according to the invention. Surface-active agents can be used such anion-active, cation-active and non-ionic agents as have hitherto been generally used in similar plant control mixtures. Suitable surfactants are indicated in e.g. "Detergents and Emulsifiers Annual - 1967" by John W. McCutcheon, Inc. Other surfactants not mentioned by McCutcheon, but which are nevertheless effective dispersants because of their protective colloidal action, include methylcellulose, polyvinyl alcohol, hydroxyethylcellulose and alkyl substituted poly-vinyl pyrrolidones.

Suitable surfactants are

polyethylene glycol esters with fatty and rosin acids, polyethylene glycol ethers with alkylphenols or with long-chain aliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acid esters and polyoxyethylene thioethers. Other suitable surfactants include amine salts and alkali metal and alkaline earth metal salts of alkylaryl sulfonic acids, amine and alkali metal and alkaline earth metal fatty alcohol sulfates, dialkyl esters of alkali metal sulfosuccinates, fatty acid esters of amine and alkali and alkaline earth metal isothionates and taurates, amine and alkali metal and alkaline earth metal salts of ligninsulfonic acids, methylated or hydroxyethylated cellulose, polyvinyl alcohols, alkyl-substituted polyvinylpyrrolidone, amine and alkali metal and alkaline earth metal salts of polymerized alkylnaphthalenesulfonic acids and long-chain quaternary ammonium complex compounds. Anionic and nonionic surfactants are preferred.

Preferred wetting agents include sodium alkylnaphtha-1enesulfonates, sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, ethylene oxide condensates with alkylated phenols such as octyl-, nonyl- and dodecylphenol, sodium lauryl sulfate and trimethylnonylpolyethylene glycols. 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-palmityl pyltaurate pg dodecylphenol polyethylene glycol esters

are examples of preferred dispersants.

Preferred emulsifiers include ethylene oxide adducts of lauric, oleic, palmitic or stearic acid esters of sorbitan or sorbitol, polyethylene glycol esters with lauric, oleic, palmitic, stearic or rosin acids, oil-soluble alkylaryl sulphonates, oil-soluble polyoxyethylene ethers with octyl , nonyl and dodecylphenol, polyoxyethylene adducts to long-chain mercaptans and mixtures of these surfactants.

The mixtures can, in addition to surface-active agents, contain solid or liquid diluents for the production of wettable powders, dust, grains or emulsifiable liquids.

A. Wettable powders

Wettable powders are materials which, in addition to surfactants, usually contain inert, solid diluents. These inert, solid diluents can serve several purposes. They can act as a grinding aid to prevent sticking in the mold and clogging of sieves, they can help achieve a rapid dispersion of the mixture 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 after longer heat storage, and they can make it possible to produce materials containing a controlled amount of active ingredient so that the correct dose can be easily measured by the consumer.

The suitable diluents can be either inorganic or organic in origin. These include the natural clays,

kieselguhr, synthetic mineral fillers derived from silicon dioxide or silicates, blanc fixe or barytes, insoluble salts produced by precipitation in light form of compounds such as tricalcium phosphate or calcium carbonate, and powdered organic diluents such as husk flour, wood flour, corn cob flour or carbohydrates.

Preferred fillers for the compounds according to the invention include kaolin clays, attapulgite clays, non-swelling calcium magnesium montmorillonites, synthetic silicon dioxides, synthetic calcium and magnesium silicates, diatomaceous earth, sucrose, corn cob flour and barium sulfate *

The wettable powders will generally contain both a wetting agent and a dispersing agent. The solid anionic and nonionic surfactants are the most preferred for dry, wettable powders. Occasionally, a liquid, non-ionic surfactant, which is generally considered an emulsifying agent, can be used for both wetting and dispersing.

The total amount of wetting and dispersing agents used in the wettable powders according to the invention is approx. 1.0. -. 8.0

weight 7o ay the total, material. The active ingredient is present:

in a concentration of approx. 25 - 80 7. with the diluent making up the remainder up to 100%. If necessary, a corrosion inhibitor or anti-foaming agent can be added in an amount of 0.1 - 1.0% with a corresponding reduction in the amount of diluent.

B. Dust

The scaffolding materials must be used in a dry state together with suitable scaffolding equipment. As wind drift is undesirable when dust is used, the most suitable dust thinners are dense and quick-setting. Among these diluents can be mentioned kaolinites, talcums, pyrophyllites, ground phosphate mineral, Sericite and ground tobacco stalks. Dust, however, is usually most easily produced by diluting an available high-strength wettable powder with a dense diluent so that the finished dust will often contain a fraction of light, absorbent diluent and the more preferred dense filler.

It is desirable in base compositions to use a wetting agent to improve adhesion to uncoated foliage. Dust produced from wettable powders will usually contain sufficient wetting agent, but dust produced directly from an unmixed active ingredient will usually contain an added wetting agent. That fore? is drawn to use dry, solid anion-active or non-ionic wetting agents.

The Stbv compositions generally contain 5.0

25 weight7. active material, 0.005 - 1.0 7. wetting agent and 3 - 20 7. of a light diluent which facilitates the painting, the rest being dispensed by a dense, quick-setting diluent. If it has been produced by diluting a treated wettable powder, the stbv composition also contains a small amount of dispersing agent which plays no active role when the material is used as dry stov.

C. Emulsifiable liquids

Emulsifiable liquids are produced by bringing together the complex compounds according to the invention with a suitable emulsifying agent, such as an organic liquid with low solubility in water. The active ingredient may be completely dissolved in the organic liquid or it may be a finely ground suspension in a non-dissolving liquid. Suitable organic liquids include alkylated riaphthalenes, xylene, ketones with a high molecular weight such as isbphorones and dibutyl or diamyl ketone, esters such as amyl acetate, n- or iso-paraffins and purified white oils. Mixtures of oil-soluble sulfonates and nonionic polyoxyethylene glycol esters or ethers of fatty acids or alkylated phenols are the most preferred emulsifiers.

The active ingredient is present in emulsifiable concentrates in an amount of LO'..- approx. 40 weight7". Combined emulsifiers are present in an amount of 3 -r approx. LO weight?" the remainder being an organic carrier liquid or a solvent.

D. Corn

Soil treatment with fungicides either before or after germination can often be fertilized with grain in the simplest way. Granulated products containing the complex compounds according to the invention can be produced in a number of ways. The active materials can be dissolved in a volatile carrier and sprayed onto previously formed grains.

They can be mixed as powders with suitable diluents and binders and then moistened and granulated followed by drying. Powders can also be applied to coarse, porous grains by tamping and applying a non-volatile liquid, oil, glycol or a liquid, non-ionic surfactant that acts as a binder. The rate of breakdown of grains and dispersion of active material in moist soil can be regulated by choosing added surfactants or by the binding agents used in the formation of the grains.

Suitable preformed grains include grains made from attapulgite clay, granulated expanded vermiculite, ground corncobs, ground nbutte husks, or preformed kaolinite grains. Active fungicide can be applied to such carrier materials in a concentration of 1 - 25 7„. However, it is difficult to avoid. segregation of active ingredient and carrier at concentrations above approx. 10 7. in advance they form grains. If it is desirable to use higher concentrations of active ingredient, the best results are obtained by pre-mixing powdered active ingredient, diluents, binders and surfactants and then granulating these so that the active ingredient will be distributed throughout the grain and not just on its surface.

Suitable diluents for the production of grains by granulation or extrusion include kaolin clays, non-swelling Ca, Mg-montmorillonites and gp s. Bonding into a solid grain is usually achieved by wetting, compression and twerking with or without a binder. Kablin clays give solid grains if they are bound together with gelatinous agents, such as methylcellulose, natural gums or swelling bentonite. It is not necessary to use any binder for Ca, Mg bentonites, and calcium sulphate can be brought to form solid grains either by adding gypsum or certain salts, such as ammonium sulphate, potassium sulphate or urea as double salts with calcium sulphate.

The content of active ingredient in the shaped grains is 1 -

90 7o, although a quantity of 75% active ingredient is the upper limit if controlled breakdown of the grain in moist soil is desirable. A control of the rate of decomposition is achieved by a controlled compression, i.e. by using a controlled extrusion pressure, and by adding inert, water-soluble ingredients, such as sodium sulfate, which can be leached.

Such compositions may, in addition to the active ingredient according to the invention, contain common insecticides, miticides, bactericides, nematocides, fungicides or other agricultural chemicals, such as fruiting agents, fruit thinning compounds, fertilizer components and the like, so that the compositions can thereby be used for other purposes in addition for a control of fungal and mite infestation.

The following agricultural chemicals are representative of chemicals that can be used in the mixtures or that can additionally be added to spray agents containing one or more of the active complex compounds according to the invention.

1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4-endoexo-5,8-dimethannafthaiene (aldrin),

1,2,3,4,5,6-hexachlorocyclohexane (lindane),

2,3,4,5,6,7,8,8-octachloro-4,7-methane-3a-4,7,7a-tetrahydroindane,

1,1,1-trichloro-2,2-bis-(p-chlorophenyl)-ethane (DDT),

1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,5a-5,6,7,8,8a-octahydro-1,4-endo-exo-5,8- dimethanenaphthalene (dieldrin), 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a-5,6,7,8,8a-octahydro-1,4-endo-endo -5,6-dimethanenaphthaene (endrin), 1 (or 3a), 4,5,6,6,7,7-heptachloro-3a^4,7,7a-tetrahydro-4,7-methanindene,

1,1,1-trichloro-2,2-bis-(p-methoxyphenyl)-ethane-(methoxychloro),

1,1-dichloro-bis-(p-chlorophenyl)-ethane,

chlorinated camphene with a chlorine content of 67 - 69

2-nitro-1,1-bis-(p-chlorophenyl)-butane,

1-naphthyl-N-methylcarbamate ("Sevin" °^ ),

methylcarbamic acid with phenol, 4-(dimethylamino)-3,5-dimethyl,

methylcarbamic acid with 1,3-dithiolan2-one-oxime,

0,0-diethyl-0-(2-isopropyl-4-methylpyrimid-6-yl)-thiophos fat,

0,0-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate,

0,0-dimethyl-S-(1,2-dicarbethoxyethyl)-dithiophosphate (malathion),

0,0-dimethyl-O-p-nitrophenylthiophosphate (methylparathion),

0,0-dimethyl-0-(3-chloro-4-nitrophenyl)-thiophosphate,

0,0-diethyl-O-p-nitrophenylthiophosphate (parathion), dl-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopenten-1-one-chrysanthemumate,

0,0-dimethyl-0-(2,2-dichlorovinyl)-phosphate (DDVP),

mixture containing 53.3 7. "Bulan", 26.7 7. "Prolan" and 20.0 7. related complex compounds,

0,0-dimethyl-0-(2,4,5-trichlorophenyl)-phosphorothioate,

0,0-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-yl-methyl)-phosphorus dithioate ("Guthion"),

bis-(dimethylamino)-phosphonic acid anbydride,

0,0-diethyl-0-(2-keto-4-methyl-7-a'-pyranyl)-thiophosphate,

0,0-diethyl-(S-ethylmercaptomethyl)-dithiophos fat,

calcium arsenate,

sodium aluminum fluoride,

dibasic lead arsenate,

2'-chloroethyl-1-methyl-2-(p-tert.butylphenoxy)-ethylsulfite,

azobenzene,

ethyl 2-hydroxy-2,2-bis-(4-chlorophenyl)-acetate,

0,0-diethyl-0-(T-(ethylmercapto)-ethyl7-thiophosphate,

2,4-dinitro-6-sec. butylphenol,

toxaphene,

O-ethyl-0-p-nitrophenylbenzenethiophosphonate,

4-chlorophenyl-4-chlorobenzenesulfonate,

p-chlorophenyl-phenylsulfone,

tetraethyl pyrophosphate,

1,1-bis-(p-chlorophenyl)-ethanol,

1,1-bis-(chlorophenyl)-2,2,2-trichloroethanol,

p-chlorophenyl-p-chlorobenzyl sulphide,

bis-(p-chlorophenoxy)-methane,

3-(1-methyl-2-pyrrolidyl)-pyridine,

mixed ester of pyrethrolone and cinerolone keto alcohols and two chrysanthemum acids,

chopped sugar and derris both as whole root and in powdered form,

ryanodtn,

mixture of alkaloids known as veratrine, dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one esterified with a mixture of cis and trans dl-chrysanthemum monocarboxylic acids,

butoxy polypropylene glycol,

p-dichlorobenzene,

2-butoxy-2'-thiocyanodiethyl ether,

oil shark,

methyl-O-carbamylthiolacetohydroxamate,

1,1-dichloro-2,2-bis-(p-ethylphenyl)-ethane,

methyl O-(methylcarbamyl)-thiolacetohydroxamate,

sodium p-dimethylaminobenzenediazosulfonate,

quinonoxyaminobenzooxohydrazone,

tetraalkylthiuram disulfides, such as tetramethylthiuram disulfide or tetraethylthiuram disulfide,

metal salts of ethylene-bis-dithiocarbamic acid, e.g. mangam zinc, iron and sodium salts,

pentachloronitrobehzen,

n-dodecylguanidine acetate (dodine),

N-trichloromethylthiotetrahydrophthalimide (captan),

phenylmercuric solvacetate,

2,4-dichloro-6-(o-chloroaniline)-s-triazine ("The Animals" Ti ),

N-methylmercury-p-toluenesulfonanthlide,

chlorophenol mercuric hydroxides,

nitrophenol mercuric hydroxides,

ethyl mercury acetate,

ethylmercury*2,3-dihydroxypropyl mercaptide,

methylmercury acetate,

tnethylmercury-2,3-dihydroxypropyl mercaptide,

3,3'-ethylene-bis-(tetrahydro-4,6-dimethyl-2H-1,3,5-thiodiazin-2-thione),

methylmercurydicyandiamide,

N-ethylmercury-p-toluenesulfonanilide,

1,4-dichloro-2,5-dimethoxybenzene,

metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids,

tetrachloronitroanisole,

hexachlorobenzene,

hexachlorophene,

methylmercurynitrile,

tetrachloroquinine,

M-trichloromethylthiophthalimide,

1,2-dibromo-3-chloroprene,

1,2-dibromo-3-chloropropene,

dichloropropane - dichloropropene mixture,

ethylene dibromide,

chlorpicrin,

sodium dimethyldithiocarbamate,

tetrachloroisophthalnitrile,

1- benzimidazole carboxylic acid, 2-carboxyamino, dimethyl ester,

streptomycin,

2-(2,4,5-trichlorophenoxy)-propionic acid,

p-chlorophenoxyacetic acid,

1-naphthalene acetamide, and

N-(1-naphthyl)-acetamide.

The above-mentioned agricultural chemicals are only examples of the complex compounds that can be mixed with the active complex compounds and shall not limit the invention in any way.

The use of pesticides, such as those indicated above, together with a compound according to the invention sometimes appears to greatly improve the action of the active complex compound. In other words, an unexpected degree of effectiveness can be obtained when another pesticide is used together with the active complex compound.

The complex compounds according to the invention can also be used for addition to sewage and provide a faster sewage decomposition. When added to soil, the complex compounds increase the rate at which nitrogen in fertilizers is converted into usable plant nutrients.

The complex compounds according to the invention are also useful in that they can reduce the breakdown rate of chlorophyll and keep plants in an active photosynthetic state for longer. The extension of the photosynthetic period or the effect against ageing, gives increased yields of a number of cereals, fruits and vegetables. In addition, the storage time for green leafy greens, certain ornamental plant materials, green cuttings and the like is increased.

Some examples of the usefulness of the complex compounds according to the invention are given in the following examples, where all parts are based on weight unless otherwise stated.

Wettable powders

A wettable powder was prepared containing 70 7% methyl ester 2:1 zinc complex dihydrate of 1-(butylcarbamoyl)-2-. benzimidazolecarbamic acid, 4% dioctyl sodium sulfosuccinate, 3 7, oleyl ester of sodium isethionate and 23 7" diatomaceous earth by mixing the ingredients together and then micropulverizing these in a hammer mill followed by air grinding to further reduce the particle size.

The above-mentioned mixture was added to water in such a quantity that 300 parts of active ingredient according to the invention were obtained, per million. This preparation was then sprayed on various trees in an apple orchard in Virginia. The trees had been attacked by the apple scab pathogen two days before the first treatment. There were also signs of incipient powdery mildew growth on a couple of the leaves of each tree, and the overwintering spider mites had begun to attack the garden.

The spray agent was sprayed on 15-year-old apple trees in a quantity of 50 liters per three months ago the trees were in early bloom. Repeated sprayings were applied every three weeks during the spring and summer. At harvest, the leaves of the spr-changed trees were healthy and free of spider mites, and the fruit was full-sized and of a good color and smooth surface. The untreated trees, on the other hand, were heavily contaminated with scab and powdery mildew and were bronze-coloured due to a large number of spider mites. The fruit on the untreated trees was small and uneven with scab damage. The materials according to the invention thus destroy, when used in the manner described, both apple scab and fungi which cause powdery mildew and prevent a build-up of spider mites and therefore also diseases and injuries caused by these organisms.

Any of the complex compounds described in Examples 2-24 can be used for the preparation of mixtures in the manner indicated above, and they will give similar results when applied.

A mixture was prepared consisting of 50% methylester-2:1-manganese complex dihydrate of l-butylcarbamoyl-2-benzimidazolecarbamic acid, 3 7" dodecylphenol condensate with 9 molecules of ethylene oxide, 1 7, sodium-N-methyl, N- oleoyl taurate and 46 7o kaolin clay.

The mixture was added to water. A sufficient amount of mixture was used so that 300 ppm of the active complex compound according to the invention was obtained in the finished aqueous preparation. Selected locations in a sugar beet field in Minnesota were sprayed with this preparation at 21-day intervals in a quantity of 600 liters per hectares.

During the first 3 months after the experiment had been started, the weather was favorable for frequent attacks by fungi that caused leaf spots on sugar beet. At harvest, the sugar beets grown on the treated sites were large and vigorous with healthy foliage. The sugar beets in the untreated areas around the treated sites, on the other hand, were small and the leaves were spotted and discolored due to a series of attacks by the sugar beet leaf spot fungus.

A mixture consisting of 70% methyl ester 2:1-zinc complex dihydrate of 1-hexylcarbamoyl-2-benzimidazolecarbamic acid, 2% sodium lauryl sulfate, 2% sodium lignin sulfonate and 26% corncob flour with a particle size of -270 mesh was prepared. The ingredients were mixed and then ground in a spiked bowl until the active ingredient had an average particle size of approx. 10 y..

The mixture was added to water containing 300 ppm of a surfactant consisting of a modified phthalic acid glycerol-alkyd resin ("Triton" B 1956) in an amount sufficient to obtain 300 ppm of the active complex compound according to the invention. This aqueous preparation was in a quantity of 15 liters per tree sprouted on different trees in a peach orchard in North Carolina. The seed change was started while the plants were in pink flowering and repeated at 14-day intervals until harvest. The remaining trees in the planting field were not treated.

There were several hot, humid periods during flowering and the early growing season, and fungal pathogens had ample opportunity to attack the flowers and fruit. At harvest, the treated trees were healthy, and the fruit had no disease. The fruit on the untreated trees, on the other hand, was severely rotted by the brown rot fungus and had a damaged shape with peach scab.

A mixture was prepared consisting of 50% methyl ester-2:1-zinc complex dihydrate of 1-(p-methoxybenzylcarbamoyl)-2-benzimidazolecarbamic acid, 4 "U diamyl sodium sulfosuccinate and 46 7" dehydrated and partially desulfonated sodium lignin sulfonate. The components were. mixed and then ground in a jet mill until substantially the entire amount of active ingredient had a particle size below 5 µl.

The mixture was added to water containing 500 ppm modified phthalic acid glycerol alcohol resins ("Triton" B 1956). The mixture was used in an amount sufficient to give 250 ppm active complex compound according to the invention in the finished aqueous preparation. This was then sprinkled on various rose bushes with sufficient water so that the foliage was well moistened. The rose bushes were chosen in a planting field that was heavily attacked with black spots, powdery mildew and. of spider mites. The same plants were seeded every 7 days during the growing season, while the other plants were not seeded. 2 months after treatment had begun, the treated roses were healthy, grew vigorously and produced a rich bloom. The untreated bushes, on the other hand, were almost completely leafless due to disease and only had a couple of small flowers. The few remaining leaves were covered with powdery mildew or damaged by mites or with black spots.

Mixtures of all complex compounds according to the invention can be prepared in the same way and give similar results.

A mixture was prepared consisting of 50 7. methyl ester-2:1-manganese complex monohydrate of l-(butylcarbamoyl)-2-benzimidazolecarbamic acid, 3% of a mixture of 85 7. dioctyl sodium sulfosuccinate with sodium benzoate (Aerosol 0TB), 0.75 7. methylcellulose with low viscosity and 46.25 7> rbr sugar. The ingredients were mixed and micropulverized and then ground with air until substantially all particles had a particle size of 5 y or less.

An even planting field of cantaloupe in North Carolina was contaminated with a fungus (Erysiphe cichoracearum), which causes powdery mildew. After 10 days, this organism had gained a firm hold in the plants. At this time, different rows were sprayed with water containing a suspension of the wettable powder prepared as described above. The chemical suspension was used in such an amount that 227 g of the active compound according to the invention was obtained per 378 liters of water (0.06 7.). The spray replacement fluid was applied in a quantity of 1410 liters per hectares. The remaining rows were not changed.

After a further 15 days, the unsprayed leaves were heavily damaged by powdery mildew, and some of the plants were dead. However, the sprbyted rows were healthy and grew quickly. The results thus indicate that the active compound in the suspension acts as a curative fungicide.

A mixture was prepared, consisting of 50 7. methyl ester-2:1-manganese complex of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, 2 7. sodium lauryl sulfate, 4 7«. nonylphenoxypoly-(ethylene-oxy)-ethanol with 40 mol Et^O and 44% pentaerythritol. Inventory? the parts were mixed and then micropulverized followed by milling in air to further reduce particle melting until substantially all material consisted of particles less than 5 µ in size as measured by Andersen pipette deposition.

Six field boxes of oranges were picked from a commercial plantation in Florida. Three boxes of oranges were dipped for 3 minutes in a water bath containing a suspension prepared from the above mixture in an amount sufficient to give 300 parts by weight of the active ingredient according to the invention per million parts by weight. The remaining three boxes were similarly dipped in water. All crates were set aside for 3 weeks in a citrus warehouse.

All fruit was then examined. Fruit which had been treated by immersion with the compound according to the invention was still in good condition, but the fruit which had not been protected in this way, was badly rotted by the fungus (Penicillium digitatum) which caused blue mould.

A mixture was prepared consisting of 60 7. methylester-2:1-zinc complex of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid, 3 °U sodium alkylnaphthalene sulfonate, 2 '% sodium N-methyl-N-palmitoyl taurate and 35' % cane sugar. The ingredients were mixed, micropulverized and ground in air to a particle size of 5 µ or less as determined by microscopic examination of aqueous dispersions of the mixture.

The above-mentioned composition containing 50 g of wettable powder was dispersed in water to a concentration of 3.6 g of active ingredient per liters of water. Eight uniform apple trees of the same species were selected for investigation. Four of these were sprayed with the above-mentioned composition until runoff, and for this it took approx. 2850 liters per hectare, with an interval of 1 week during the growing season, and the other four trees were not sprung.

At the end of the season, the untreated trees were heavily attacked by orchard mites and apple scab (Venturia inaequalis).

Due to being eaten by the mites, the foliage was reddish brown and fell off prematurely. The untreated trees also had poor branch growth and small, spotted fruit. The trees sprayed with the complex compound according to the invention were essentially free of mites, mite eggs and apple scab. Because of the excellent mite control, the sprayed trees had foliage of a healthy, dark brown color, and they had good branch growth and fruit size.

Grain

Grains were prepared consisting of 10 °U methyl ester-2:1-zinc complex monohydrate of 1-butylcarbamoyl-2-benzimidazolcarbamic acid, 1% sodium alkylnaphthalene sulfonate and 89 7" expanded vermiculite grains with a grain size of 30-60 mesh. The active material and surface-active agent were taken up in acetone and sprayed onto the vermiculite under stirring, after which the acetone was evaporated.

Cucumbers were planted by placing three cucumber plants in soil holes with a depth of 3 cm and with a distance of 1 meter in the row. The rows had a distance of 3 metres. Every other row was treated by placing 2 g of the above described grains in the planting holes. The neighborhoods were not treated. Six weeks after planting, the plants in the treated rows were completely healthy. The plants in the untreated rows were heavily attacked by powdery mildew. This shows that the active complex compound according to the invention can control disease when it is taken up from the soil by the rats and transported in the plants to the foliage.

All complex compounds according to the invention can be used for the preparation of preparations in the same way and give similar results.

Grains were produced consisting of 10% methylester-2:1-manganese complex of l-(butylcarbamoyl)-2-beirzimidazolcarbamic acid, 57o dodecylphenol condensed with 9 molecules of ethylene oxide and 85% expanded vermiculite grains with a grain size of 30 - 60 mesh. The active ingredient was first ground in air to a very small particle size and then briefly mixed with the vermiculite. The surfactant was then sprayed onto the mixture, and mixing was continued for a few minutes. The surfactant acted as a binder to prevent segregation of powder and grains and also facilitates a rapid release when the grains are placed in moist soil.

A field in California was sown with cotton in the usual manner, except that grain prepared as described above was added to every second row. The grains were dropped in such a way that some fell into the furrow and some were mixed with the topsoil. The grains were applied in such a quantity that 0.45 kg of active chemical according to the invention was obtained per 3600 linear radmetres. The remaining rows were not processed.

Six weeks after planting, several of the plants in the rows without the grains were dead, <p>g others had stem damage in the form of sick areas caused by Rhizoctonia.solani and were also heavily attacked by the Pacific mite (Tetranychus pacificus). All plants in the rows that had been treated with the grains were alive and healthy and free of mites. The effect on mites is thus clearly systemic.

Euctable powder

A wettable powder was prepared consisting of 50% methyl ester 2:1 zinc complex dihydrate of l-(butylcarbamoyl)-2-benzimidazolecarbamic acid, 3% dioctyl sodium sulfosuccinate, 4 7o sodium N-methyl-N-palmitoytaurate ( " I<g>e<p>o<n>" TN 74) and 43-7" sucrose. The ingredients were mixed and pulverized and then ground in air until substantially all particles had a particle size of 5 y or less.

A rice field in Louisiana was infested with rice blast in the early part of the growing season.~ Several old leaves were attacked,

and the rice blight fungus was present in such quantity that a good rice production was threatened. During germination, when the rice flowers were enveloped, selected locations were sprung.

The spray change agent was an aqueous preparation containing the wettable powder described above in such an amount that 300 ppm of the active complex compound and 500 ppm of a. surfactant of a modified phthalic acid glycerol alkyd resin ("Triton" B 1956). The spray agent was added in a quantity of 300 liters per hectares. Two weeks later during germination, the selected locations were subjected to another treatment similar to the first. At harvest, the rice in the treated areas was healthy without neck rot. The untreated rice around these places was very badly attacked by disease and the tops were broken off. and most of the rice had been lost due to. rice blast attack.

Stove ' -••

A stock was prepared consisting of 10 7. methylester-2:1-zinc-complex-monohydrate of 1-oethylcarbamoyl-2-benzimidazolecarbamic acid, 10 7„ silica gel bg 80% mica talc. The active compound and diatomaceous earth were first mixed together and ground and then mixed with the talc in a ribbon mixer.

A vineyard in California was chosen where the vines

had come so far that the shots were approx. 20 - 30 cm long. The old leaves were attacked by active powdery mildew. Certain plants were dusted with the above-described mixture during a very calm period in the early morning when very little dust was blown away to unsprayed neighboring vines. The starch was applied in an amount of 494 g per acres. The Stbv treatment was repeated after three weeks. When the grapes were ripe, the treated vines had fresh leaves and fruit.

The neighboring vines that had not been treated had twisted shoots covered with powdery mildew, and the fruit was discolored and split due to heavy powdery mildew attack.

Emulsifiable oil concentrate barrel

An emulsifiable oil concentrate was prepared consisting of 25% methyl ester-2:1-zinc complex dihydrate of 1-trichloromethylthio-2-benzimidazolecarbamic acid, 70 70 white mineral oils with a viscosity of 50 - 60 and 5% of a mixture of oil-soluble sulphonates and polyoxyethylene ether. The components were mixed and co-ground until an insoluble, active component had a particle size of less than 5 u. The oil dispersion thus formed was emulsifiable in water. 1 liter of the above mixture was suspended in 1000 liters of water. This preparation was then sprayed on apple trees in a quantity of 40 liters per three. The trees were in early pink bloom and had been exposed to hot rain for 2 days which produced a heavy attack of apple scab. Some of the shoots had clear signs of powdery mildew attack from the previous year, and a few spider mites were active on the older leaves. The spray replacement treatment was repeated at 2-acre intervals up to one month before harvesting. Unplanted apple trees near those that had been treated in the manner described above showed mid-season signs of disease. Leaves spotted with apple scab began to turn yellow and fall off. The shoots stopped growing and were powdery white with powdery mildew. The untreated trees became bronze colored due to spider mite damage, and the fruit was misshapen due to scab damage.

• The treated trees. stayed fresh and gas- large, clean fruit •• with good color and surface. The 'treatments' were thus both healing. and preventive for the control of apple disease.- -

Claims (7)

1. "Complex compounds of 2-benzimidazolecarbamic acids with midvicidal or fungicidal" action, characterized in that they have the general formula: in which Q is or -SZ, R, is methyl, ethyl, isopropyl or • sec.butyl, R2 is alkyl with 1-8 carbon atoms or benzyl substituted with methoxy, Z is alkyl with 1-3 carbon atoms substituted with chlorine, Me is zinc, copper, nickel, manganese, cobalt, cadmium, iron or chromium, and n is 0, 0.5, 1, 1.5, 2 or 3. 2. Complex compound according to claim 1, characterized in that it is methylester-2:1-zinc-complex-mbno- or dihydrate of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid. 3. Complex compound according to claim 1, characterized. at <.>at. it is methyl ester-2:l-zinc complex of 1-{but<y>lcarbamoyl)-2-benzimidazolecarbamic acid..... h. Complex compound according to claim 1, characterized in that it is methyl ester-2:1-manganese complex mono or dihydrate of 1-(butylcarbamoyl)-2-benzimidazoTcarbamic acid. 5. Complex compound according to claim 1, characterized in that it is a methylester-2:1-manganese complex of 1-(butylcarbamoyl)-2-benzimidazolecarbamic acid. 6. Procedure for the preparation of the complex compounds according to claims 1-5, characterized in that a system is prepared of a) a slurry of a solid benzimidazole carbamate with the formula: where Q, R-p R2 and Z are as stated in claim 1, in a solvent consisting of dimethylformamide, acetone or methyl ethyl ketone, and 0.5 molar equivalent of acetate, chloride, sulphate or nitrate of zinc, manganese, nickel, cobalt, copper, cadmium , iron or chromium, b) a molar equivalent of aqueous sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, and the system is stirred, and the complex compound formed is recovered. 7. Method according to claim 6, characterized in that an aqueous solution of zinc sulphate or manganese sulphate is used.