DE1962490C3 - Complex compound of ethylene or 1 ^ -propylene-bis-dithiocarbamic acid detail salts and agent containing them for influencing plant growth - Google Patents

Description

The invention relates to complex compounds of ethylene or 1,2-propylene-bis-dithiocarbamic acid acetate salts and agents for influencing plant growth which use these compounds as an active ingredient contain.

In the DT-AS 10 57 814 complexes of Zinc alkylene bis-dithiocarbarnates described with amines. These compounds are used as pesticides. However, their effect is insufficient and insufficient to control undesirable fungi.

The present invention is therefore based on the task of creating new compounds, the better ones Fungicides are known as the compounds.

The invention relates to complex compounds of ethylene or 1,2-PtOpylcn-bis-dithiocarbamic acid metal salts, their metal from 30 to 100 mol% zinc and 70 to 0 mol% manganese and / or iron and / or cobalt, and an alkanolamine of the general formula

H (N HCH.CH ₂ J _n OH

where η is 2 or 3, in a molar ratio of zinc to alkanolamine of 0.5: 1 to 16: 1.

The invention also relates to an agent for influencing plant growth, comprising a or more of the complex compounds mentioned above.

For the sake of simplicity, the ethylene bis-dithiocarbamate and the 1,2-propylene-bis-dithiocarbamate as "alkylene-bis-dithiocarbamate" designated.

According to the invention, the term “multimetallic, zinc-containing alkylene bis-dithiocarbamate” is intended to mean the polymeric alkylene-bis-dithiocarbamate to be understood, which is formed by reaction of an alkylene-bis-dithiocarbamate ion with an equivalent amount of two or more water-soluble metal salts, of one of which is a zinc salt is obtained. In such compounds, the metals are chemically in abundance bound, which correspond to their initial molar ratios. The zinc ions and other metal ions are at least divalent, with manganese (II) -, iron (II) - of these ions. Iron (III) and cobalt (II) ions should be mentioned. Since the alkylene-bis-dithiocarbamate ion is divalent. the various ions are combined to form a polymeric product.

The invention encompasses compounds in which the metal is in any intermediate value between 30 and 100

Mol% zinc with a corresponding intermediate value of the total amount of further metal between 70 unc 0 mol% occurs, the ratio of zinc to alkanolamine being any intermediate ratio of 0.5: 1 to; 16 ■ 1 can take. The metal preferably consists of at least 70 mol% zinc, where da < The molar ratio of zinc to alkanolamine is 1: 1 to 8: 1.

The compounds defined above are simply referred to as "complex compounds". the individual complex compounds are called Zinkäthy len-bis-dithiocarbamate-alkanolamines or zinc-1,2 called propylene-bis-dithiocarbamate alkanolamines where the mole percentage of zinc or our metal is given in parentheses, which are immediately after the word "zinc" or the designation of the other metal. The molar ratio; from zinc to alkanolamine is given in brackets at the end of the designation. In general, the in the complex compounds according to the invention a set further metals in divalent form, mii Except for iron, used (if the valence of another metal is greater than 2, then the Valence indicated by a Roman number, referring to the designation of such a metal adjoins, while the lack of a Roman numeral suggests that the metal is in the specified Complex compound is present in divalent form For example, "iron" means an iron (II) ion and "iron (III)" means trivalent iron.

The compounds of the invention are generally amorphous or crystalline, solid materials most of these compounds are white but can also take on other colors, in particular when the compound is a multimetallic complex compound. the Complex compounds are very easily soluble in water and organic solvents. The complex compounds form moderately stable dispersions in aqueous solutions of alkanolamines ^ The complex compounds have characteristic melting or liquefaction points or decomposition points. Certain complex compounds visibly decompose when heated without melting or melting beforehand evaporate. When heated, many of the complex compounds appear to melt or liquefy, namely at a temperature which is characteristic of the respective complex compound. A cool down many complex compounds, however, do not always have a solidification at the characteristic melting temperature result. In addition, the melted and resolidified products are not always identical to the respective original complex compound. Under the terms »melting« and "Melting point" is to be understood as the characteristic temperature at which a respective Compound melts, liquefies or appears to melt, this being the temperature of the one The temperature at which a particular complex compound is different without melting or evaporation decomposed.

The complex compounds according to the invention have proven to be useful for changing the growth of Plants proved suitable. The compounds are capable of the growth of lower plants, such as for example fungi, while inhibiting them no noticeable phytotoxicity towards higher plants exercise. The connections can also be there;

To favor the growth of higher plants. The complex compounds according to the invention are particularly suitable for combating a number of fungi, in particular for combating those Fungio ^r organisms that are usually found on the aerial parts or on the seedlings of higher plants, for example for combating cherry leaf rust, apple scab, rice blight, fluff dew species, cottonseed Accumulation disease, Helminthosporium leaf rust on grass, grain and maize, grain rust, Phytium on maize or pea seedlings, Cercospora and Septoria leaf rust and later dry rot. To combat such organisms, a plant or a part of a plant or a plant growth medium is contacted with an amount of one or more complex compounds according to the invention which changes the plant growth.

The complex compounds according to the invention can be applied to growing vegetation or to seedlings higher plants are applied in amounts required for effective fungi control without adversely affecting the plants. The complex compounds are also suitable both to eliminate an already existing fungi infestation and to achieve one ongoing preventive effect against a fungal attack. Furthermore, the complex compounds are distributed easily within the cell structure of plants that have been contacted with these compounds, so that extensive protection of parts of plants to which these compounds have been applied, is achieved. Furthermore, the complex compounds according to the invention can be applied to higher Plants are used in the plant growth changing amounts in an advantageous manner to to stimulate the growth of plants, for example of useful plants, such as. B. grapes, potatoes or celery, even if there is no fungal attack. Another advantage is that the Complex compounds have a low toxicity to warm blooded animals and can therefore be handled without that there is a danger to warm-blooded animals.

Complex compounds preferred for such purposes are those in which the further metal, if present, consists of trivalent iron or divalent manganese or cobalt. A preferred one Group of complex compounds includes those compounds in which the molar ratio of zinc to further metal is 60:40 to 100: 0, and where the other metal consists of bivalent manganese or cobalt or trivalent iron. A preferred one Group of compounds includes those complex compounds in which the molar ratio of Zinc to further metal is 60:40 to 100: 0, the further metal being made up of manganese or iron consists. The molar ratio of zinc to alkanolamine is 1: 1 to 8: 1. Another preferred one The group of compounds includes those compounds in which the alkanolamine is derived from aminoethylethanolamine consists. Another preferred group of compounds includes those compounds in which the molar ratio of zinc to further metal is about 90:10 to 100: 0, the Another metal consists of manganese or fish or of these two elements and the alkanolamine is made up Aniinoäthylälhanolamin composed. It amounts to the molar ratio of zinc to alkanolamine 1: 1 to 4: 1.

The complex compounds according to the invention can by reacting a water-soluble alkali or ammonium alkylene bisdithiocarbamate, more water-soluble Salts of zinc or mixtures of water-soluble salts of zinc and other metals and one Alkanolamine can be prepared according to the above formula. Representative water-soluble alkylenebisd'thiocarbamate starting compounds are for example Äthylenbisdithiocarbamat- or i, 2-Propylenbisdithiocarbamat salts of lithium, sodium, potassium or ammonium. Representative water-soluble salts of zinc or manganese, iron or cobalt are, for example, the chlorides, sulfates, or nitrates Acetates. The alkanolamine reactant is preferably added in the form of the free base, but also the salts can be used, for example the sulfates, phosphates, nitrates, hydrohalides, acetates, Citrates or the like. When the alkanolamine is used in the form of a salt, the acidity becomes the Reaction mixture by adding a base, such as sodium hydroxide, to release the free alkanolamine adjusted.

The complex compounds are formed when the reactants are contacted and mixed in an inert solvent. Representative inert solvents which can be used as reaction media are, for example, water, methanol, ethanol, isopropanol or mixtures thereof, with aqueous media being preferred. The reaction takes place at temperatures between approximately 10 and 50 ^° C. in an aqueous or alcoholic medium and is generally complete after approximately 2-60 minutes. The zinc-containing alkylenebisdithiocarbamate-alkanolamine complex compound product precipitates in the reaction mixture. The precipitated product can be isolated by filtration, by decanting, by centrifugation or by another conventional method. The product can be purified by conventional methods, for example by washing with water, methanol or aqueous methanol, in order to remove any unreacted starting materials that may still be present. The complex compound product can be used directly to control fungi or to increase plant growth, with or without cleaning, but it can also be cleaned by washing and dried at ambient pressure or under reduced pressure at temperatures well below the decomposition point of the respective product lie. Temperatures of approximately 35 to 75 ° C. are advantageously maintained for drying the product.

The reactants combine to form a zinc-containing A Ikylenbisdithiocarba mat complex compound, if they are mixed with one another in any proportions. However, that depends Identity of the product produced in a given case on the particular molar ratios employed Reactants.

In the production of the multimetallic according to the invention Complex compounds should be the water-soluble salts of zinc and the other metal or of the metals in essentially the same molar ratios (based on the metal content of each Salt) as they should be in the end product, be used. Are noticeably less than j (. Mol% of the metal ions through aas / inksal / zur Provided, for example 10 or 20 mol%.

then the product obtained has a corresponding ratio of zinc to further metal and does not have all of the desired properties of the complex compounds according to the invention which change plant growth. The relative proportions of water-soluble alkyloibisduhiocarbamate and water-soluble zinc salts or other metal salts are not critical. An approximately existing unreacted excess of a de ^r reactants can be separated from the complex compound product by customary methods, for example by filtration and washing. When carrying out a preferred procedure, the water-soluble salts of zinc or of the other metals and the water-soluble alkylenebisdithiocarbamate are used in stoichiometric amounts. It is preferred to use an amount of alkylene bisdithiocarbamate sufficient to react with the zinc and metal reactants without using an appreciable excess of alkylene bisdithiocarbamate.

The minimum amount of the alkanolamine reactant to be used is critical to the preparation of the complex compounds. An amount of alkanolamine must be used which is sufficient to provide at least 1/1 mole amount of alkanolamine per mole amount of zinc in the mixed product. If significantly less alkanolamine is used, for example a 0.02 or 0.01 mola <; Amount of alkanolamine per mole of the zinc, then products are obtained which contain little or no alkanolamine and many of the desired properties which change plant growth, such as, for example, a high antifungal effect, are lacking. When one or more other metal salt reactants are used in conjunction with the zinc, the mole content of the zinc alone is taken into account when calculating the amount of alkanolamine. In such a case, the alkanolamine reactant is used in an amount of at least 1 / it. the molar amount of the zinc salt reactant used. If the alkanolamine reactant consists of a mixture of alkanolamines, then the total molar amount of alkanolamine reactants must be at least 1/8 of the molar amount of zinc that is to be present in the desired product. It is generally preferred to use all of the reactants in stoichiometric amounts. In this case it will be ^! / it> up to 2 molar amounts of the alkanolamine reactant per molar amount of the zinc salt reactant used. In most cases the exact amounts of zinc salt reactant and alkanolamine will correspond to the molar ratio of zinc and alkanolamine that is sought in the final product. If the final product is to contain 1-2 moles of alkanolamine per mole of zinc, then the use of an excess of alkanolamine is preferred.

Under given reaction conditions with regard to Temperature, solvent. Molecular concentrations of the reactants and the like can be greater or less smaller excess of alkanolamine may be required to produce a complex compound that contains a has a certain molar ratio of zinc to alkanolamine. In such a case a Flc meritarian analysis of the fixed complicity quickly information as to the molar ratio of / ink to alkanolamine in the obtained Product. Is produced by the Elcnientaranwlyse, ins. that the product has a higher or lower ratio from zinc to alkanolamine as desired, then the excess of alkunolamine used can be increased or decreased in order to get a product with the desired ratio. Simple and routine changes in the amount of alkanolamine will allow the determination of the exact excess of alkanolamine to be used under specified reaction conditions in order to achieve a To get product that has a desired ratio of zinc to alkanolamine.

When performing an expedient procedure for preparing the complex compounds of the invention a water-soluble alkylenebisdithiocarbamate, a water-soluble zinc salt Alkanolamine corresponding to the above formula and optionally one or more further metal salts together with an inert solvent, preferably water, in any order or Way mixed. In a preferred method, the water-soluble alkylene bisdithiocarbamate is used first in the inert solvent and the alkanolamine reactant dissolved, whereupon the water-soluble zinc salt and other water-soluble metal salts of the Solution are added in the required proportions. The amount of inert Solvent is preferably such that 5-25% by weight solids in the final reaction mixture are present. In practicing such a method, the alkanolamine reactant. the water-soluble zinc salt and any other metal salt present with one another in the required proportions mixed with further inert solvents and added as a solution. One can also proceed in such a way that they individually the Alkylenbisdithiocarbanuil solution can be added.

Shall the alkanolamine with a manganese salt before adding the mixture / u the alkylenebisdithiocarbamate Solution are mixed, then it is preferable to dissolve the manganese salt and alkanolamine in methanol / u mix. The reaction mixture is then mixed mechanically and at one temperature kept within the reaction temperature range until the complete compound has precipitated is finished. The product is conveniently separated from the reaction mixture by filtration. The complex compound is obtained as a filter cake. which directly to change the growth of Use plants, including mushroom plants! can be. Optionally, the product can be mixed with water or washed with methanol and dried by customary methods. Will a Koinplcxverbiniliing that Contains manganese, not dried or at I accelerated dried below about 40 "C, the complex compound will generally get that Manganese in the form of a dihydrate. If the product is dried at temperatures of 70 "C or above, then the water of hydration is removed. Complex compounds that are either the hydrated or the Hydrated manganese are similarly used to affect the growth of plants suitable. Since the hydrated manganese complex compounds do not require any special isolation or drying require their production, they are generally used preferentially for the treatment of plants.

lici carrying out another I lersielliingsme (I can linset the complex compounds / img one or more alkanolamines accordingly of the above formula mn a / mkalkylenbisdilhiocarh ainat or mil a iiK-hmmelallischen. / iiikcnthallcn

the alkylenebisdithiocarbamate. These salts can either be used as such or in the form of a wettable powder preparation containing surface-active agents in which the salts are present, be used. The formation of the complex compound occurs when the reactants in one inert aqueous or alcoholic liquid reaction medium, preferably water, are mixed. The reaction takes place at temperatures of 10-50 ° C. and is generally complete after 30-120 minutes. The complex compound can be used directly to influence plant growth by applying the diluted or undiluted reaction mixture can be used on plants or parts of plants. Optional the product can be separated off and purified by customary methods, for example by Filtration and washing.

If a complex compound is to be made which has more than about 1 mole of the alkanolamine per mole of zinc contains, or is intended to be, the preparation immediately after mixing the reactants for the control of fungi or used to promote the growth of higher plants then it is preferable to use one Add excess alkanolamine in amounts of 3-10 moles of the alkanolamine per mole of zinc. The relative In many cases, a larger excess has the effect of removing the zinc-containing alkylenebisdithiocarbamai dissolve or disperse in the reaction medium. The complex compound that is subsequently odc forms in the reaction mixture. It precipitates out, in most cases contains 1–2 mol Alkanolamine per mol of zinc. An elemental analysis of the purified product can be used to to determine the ratio of zinc to alkanolamine obtained in each case. Of the Excess of the alkanolamine to be used, which is used under the respective reaction conditions, can be increased or decreased depending on whether the zinc: alkanolamine ratio in the Product is higher or lower than the exact ratio sought. Routine changes to the used Excess alkanolamine makes it possible to obtain a complex compound as a product that has a desired ratio of zinc to alkanolamine in each case.

In carrying out a convenient method, a zinc-containing alkylene bisdithiocarbamate, an alkanolamine and an inert solvent, preferably water, in any order or Way mixed. The reaction mixture is at a temperature within the reaction temperature range held for a period of time sufficient to terminate the reaction, the Mixing is continued to keep the zinc-containing alkylene bisdithiocarbamate in suspension. the Reaction mixture, which contains the product, can be used directly for the control of fungi and for regulation a plant growth can be used. The product can also be separated off by filtration and cleaned by washing with water or methanol.

The alkanolamine starting materials. those for the preparation of the complex compounds according to the invention can be used by conventional methods by reacting ethylene oxide with an excess on an alkylamino compound. The reaction is made by mixing the Ethylene oxide with the excess of alkylamine in

carried out a lower alcohol as the reaction medium. The reaction is rapid at ambient temperatures and printing, the desired alkanolamine product being obtained by conventional methods can be, for example by stripping off the reaction medium and any existing unreacted starting materials. For example, aminoethylethanolamine can be added by adding ethylene oxide be prepared to an excess of ethylenediamine.

The water soluble ethylene bisdithiocarbamate starting materials can be produced by known methods. In performing a representative method, the soluble alkylenebisdithiocarbamates of, for example, sodium, lithium or potassium or ammonium by reacting Carbon disulfide with ethylenediamine or 1,2-propylenediamine and a base, which may be an alkali hydroxide or ammonium hydroxide. The reaction is in an inert solvent for the ethylenediamine or 1,2-propylenediamine, such as Methanol, ethanol, isopropanol or water, carried out and runs at temperatures of about 25-50 ° C. The alkylene bisdithiocarbamate product is obtained as a solution in the inert solvent medium. The solution of the product can be direct can be used to prepare the complex compounds according to the invention. It can also be in yours Volume by evaporation or distillation to remove some of the solvent or the concentrated whole solvent.

The zinc alkylene bisdithiocarbamate starting materials, which are used to prepare the complex compounds can be made by customary methods getting produced. When performing a representative method, the salt can be doubled by Reaction of a water-soluble zinc salt with a water-soluble Alkylenbisdithiocarbamat produced will. The reaction is carried out in an aqueous solvent as the reaction medium, wherein the insoluble zinc alkylene bisdithiocarbamate is obtained as a precipitate. Optionally, the insoluble Zinkalkylenbisdithiocarbamat by mixing carbon disulfide with an aqueous solution of Ethylenediamine and a water-soluble zinc salt are produced. The zinc alkylene bisdithiocarbamate product is obtained in the form of a precipitate.

The multimetallic zinc-containing alkylene bisdithiocarbamate starting materials are members of a well-known class of polymeric compounds known as "alkylenebisdithiocarbamates produced by joint reaction" can be designated. You can double implementation of a water-soluble Alkylene bisdithiocarbamate salt, such as an alkali or ammonium salt, with a Mixture of water-soluble salts of zinc and of other metals or other metals, such as the chlorides. Sulfates or acetates. The zinc saiz as well as the other metal salts are used in the molar ratio that is sought in the multimetallic product. The reaction is expediently carried out in water as the reaction medium. The product precipitates the reaction mixture and can be purified by customary methods, such as, for example, washing will.

The multimetallic zinc-containing alkylcnbisdithiocarbamal materials can of mixtures

of metal salts due to their physical properties, such as elemental analysis, X-ray diffraction or spectroscopic values, can be distinguished.

The multimetallic zinc-containing alkylene bisdithiocarbamate starting materials can also by reacting ethylenediamine or 1,2-propylenediamine, Carbon disulfide and a mixture of soluble salts of zinc and other metal or other metals are produced. Such a method is analogous to the method used to manufacture it of zinc alkylene bisdithiocarbamates is complied with.

The following examples illustrate the invention.

example 1

21 p. 4 g (0.6 mol) of disodium ethyienbisdithiocarbamate hexahydrate are dissolved in 3 l of water, whereupon the solution is thoroughly mixed with 62.4 g (0.6 mol) of aminoethylethanolamine. The solution is stirred while a solution of 81.77 grams (0.6 moles) of zinc chloride in 125 ml of water is gradually added over a period of approximately one-half minutes. A white precipitate forms in the reaction mixture during the addition of the zinc chloride. The reaction mixture is stirred for an additional 30 minutes, after which the mixture is filtered off. The filter cake is washed twice with water and once with methanol. The washed product is dried at a temperature of 40 ⁰ C in an oven. That

Zinkäthylenbisdithiocarbamat-Aminoäihyläthanolamin (l : 1) Product is obtained in the form of a white, finely divided amorphous solid which is essentially insoluble in water, alcohols and other organic solvents isL The product has a Melting point of about 133-135 ° C. Elemental analysis shows that the product has a carbon, Hydrogen, nitrogen and sulfur content of 25, 11, 4.59, 14.98 and 33.56%, compared to theoretical values of 2536, 4.74, 14.76 and 33.74%.

The procedure described above is repeated, with the exception that aminoethylethanolamine dihydrochloride is used instead of Aminoäthyläthanolamin, with an amount of sodium hydroxide sufficient to adjust the pH of the mixture to about 7, namely immediately before adding the zinc chloride. That

Zinkäthylenbisdithiocarbamat-aminoethylethanolamine (l: 1) product is obtained as a white finely divided solid, which seems to melt when heated to about 133-134 ⁰ C The structure of the product is confirmed by elemental analysis.

The procedure described above is repeated, using 0.028 mol of disodium l, 2-propylene bisdithiocarbamate, 0.02 mol of aminoethylethanolamine and 0.028 mol of zinc chloride can be used. Receives one is a zinc-1,2-propylenebisdithiocarbamate-aminoethylethanolamine (1.4: 1) product in the form of a white, finely divided amorphous solid, which is essentially in Is insoluble in water and organic solvents and decomposes on heating to approximately 129 ° C An elemental analysis of the product shows that the complex compound is a carbon, hydrogen, Nitrogen and sulfur content of 25.4, 4.4, 13.2 and 35.2% compared to the theoretical values of 25.84.4.53.13.14 and 35.34%, calculated for the specified structure.

Example 2

An aqueous suspension of zinc ethylene bisdithioearbamate is prepared in such a way that slowly a solution of 88.59 g (0.65 mol) of zinc chloride in 125 m. Water of a solution of 236.6 g (0.65 mol) of disodium ethylene bisdithiocarbamate hexahydrate in 31 water is added with vigorous stirring. The resulting stirred suspension is then slowly selected

over a period of about 5 minutes A solution of 33.8 g (0.325 mol) of aminoethylethanolamine in 100 ml of water was added. The reaction mixture is then stirred for 30 minutes, after which the solid contained therein is filtered off and washed

is, first with water and then with methanol. All operations are performed under ambient conditions. The washed solid is dried at a temperature of 40 ^{° C. overnight.} This gives 200 g of an insoluble, finely divided white amorphous solid. The structure of the Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (2: 1) product is confirmed by elemental analysis.

2s B e i s ρ i e 1 3

A solution of 0.02 mol of zinc chloride and 0.12 mol of aminoethanolamine in 10 ml of water is treated with a Solution of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate mixed in approximately 10 ml of water. A white crystalline solid slowly precipitates out in the reaction mixture. The mixture will be at Maintained ambient temperature and pressure for 3-4 hours. The filter cu-

It is washed with water, filtered and dried in an oven ^{at 40 ° C. overnight.} The dried Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (0.5: 1) product has a melting point of 123-125 ° C. C, H, N, S, Zn; found: 30.1, 6.1, 18.0, 27.7, 13.1; calculated: 29.8, 6.2, 17.4, 26.5, 13.5%. The product is essentially insoluble in water, but forms stable dispersions in aqueous aminoethylethanolamine.

Using essentially the same methods as those described above and when performing them of Examples 1 and 2 have been complied with, disodium ethylene bisdithiocarbamate, zinc chloride and Aminoäthyläthanolamin for the preparation of the complex compounds given below for

brought to implementation. These compounds are characterized by their melting temperatures as well as by their Characterized elemental analysis values.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (3: 1V F, 163 to! 66 ⁰ C: C, H, N, S, Zn; found:

20,3,3,3, 12,0,41,2; 21,1%; calculated: 20,6, 3.2, 12,0,41,3, 21.1%.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (4: 1), m.p. 174-177 "C; C, H ₁ N ₁ S, Zn; found: 19.7, 2.9, 11.5, 42.1, 21.7%; calculated: 19.9, 3.0, 11.6, 42.5,

to 21.7%.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (6: 1), mp 180-184 ° C; H, S, Zn; found: 2.6, 42.6, 22.1%; calculated: 2.7.43.7.22.3%.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanoi-

amine (8: 1), m.p. 188-190 ° C. C, H, Zn; found: 18.7, 2.6. 22.4%, calculated: 18.4, 2.6, 22.7%.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (12: 1), F. 193-196 ° C; N, H, Zn; found: 10.7.2.6.

22.6%, calculated: 10.7.2.5.23.0%.

Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (lb: 1), F. 198-201 ⁰ C. C, N, Zn; found: 17.9, 10.7, 22.9%, calculated: 18.1,10,6,23,21%.

Example 4

0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate and 0.019 mol of aminoethylethanolamine are dissolved in 100 ml of water. A solution of 0.019 mol of zinc chloride and 0.01 mol of manganese chloride in 3 ml of water is added to the resulting solution with vigorous stirring. After the addition is complete, the mixture is stirred for 30 minutes at ambient temperature. The mixture is filtered, after which the filter cake is carefully washed with water and dried ^{in an oven at 40 ° C. overnight.} That

Zinc (95) manganese dihydrate (5) ethylene bisdithiocarbamate aminoethylethanolamine (l : 1) Product is obtained in the form of a white amorphous powder that melts at 125 ° C. C, H, S, Zn, Mn; found: 25.1.4.7, 34.2, 16,6,0,7; calculated: 25,0,4,7,34,1,16,5,0,7%.

Following essentially the same method, the complex compounds given below are obtained manufactured:

Zinc ^ SJ-Mangandihydrat ^ J-Äthylenbisdithiocarbamat-Amino-ethylethanolamine (8 : 1) is obtained as an insoluble and pale purple amorphous powder (F. 164-167 ° C) by reacting 0.020 mol of disodium ethylene-bis-dithiocarbamate, 0.001 mole of manganese chloride, 0.019 mole of zinc chloride and 0.0024 mole of aminoethylethanolamine produced in aqueous solution.

Example 5

A solution of 0.16 mol of aminoethylethanolamine and 0.02 mol of zinc chloride in 50 ml of methanol is added dropwise to a solution of 0.02 mol of disodium ethylene bis-dithiocarbamate hexahydrate in 75 ml of methanol with vigorous stirring. A white precipitate forms immediately after the addition. The mixture obtained is then stirred for a further 30 minutes and then filtered off. The filter cake is washed with methanol and dried ^{in an oven at 40 ° C. overnight.} The zinc ethylene-bis-dithiocarbamate-aminoethylethanolamine (0.5: 1) product is obtained in the form of a white, amorphous, finely divided solid which is essentially insoluble in water and organic solvents and can be taken up in aqueous aminoethylethanolamine. The product melts at 123-125 ° C. C, H, N, S, found: 29.9.6.0.17.7.27.1; calculated: 29,8,6,2,17.4,26.5%.

The following complex compounds are produced in compliance with (is essentially the same method of operation:

Zinc (95) -cobalt (5) -ethylene-bis-dithiocarbamate-aminoethyethanolamine (3rd : 1) becomes in the form of a green, insoluble powder (m.p. 164 to 166 ° C) by using of 0.019 mol of zinc chloride, 0.007 mol of aminoethylethanolamine and 0.001 mol of cobalt chloride below Obtain compliance with the procedure described above.

Zinc (50) -obalt (50) -ethylene-bis-dithiocarbamate-aminoethylethane-laminate (l : 1) is obtained in the form of a green, insoluble powder that decomposes without melting at 185 to 189 ° C, namely through Use of 0.01 mol each of zinc chloride and aminoethylethanolamine and 0.01 mol of cobah chloride, the procedure described above is adhered to.

s example fc>

0.4 moles of disodium ethylene bis-dithiocarbamate hexahydrate and 0.09 mol of aminoethylethanolamine are dissolved in 2 l of water. This solution is slowly taking

ίο vigorous stirring a solution of 0.36 mol of zinc chloride, 0.020 mol of iron (III) chloride and 0.02 mol of manganese chloride in 60 ml of water were added. After this Addition is complete, the mixture is left at room temperature for a period of about 0.5 hours

is touched. A solid precipitate forms during of mixing and stirring. The mixture is filtered off and the filter cake is washed with water and dried in an oven at 40 ° C overnight.

Zinc (90) manganese dihydrate (5) iron (IIIX5) ethylene bis dithiocarbamate aminoethylethanolamine (4: 1) is obtained in the form of an insoluble powder which is gray in color like activated charcoal (melting point 158 to 161 ° C.).

Zinc (70) -iron (IIIX30) -ethylene-bis-dithiocarbamate-aminoethylethanolamine (l : 1) is in the form of an insoluble powder that is gray in color like activated charcoal (m.p. 138 up to 142 ° C) by using 0.28 mol each Zinc chloride and Aminoäthyläthanolamin and 0.12 mol of iron (III) chloride obtained, with the manganese chloride is omitted when performing the above procedure.

Example 7

0.6 moles of disodium ethylene bis-dithiocarbamate hexahydrate are dissolved in 3 l of water, whereupon the solution obtained is stirred with 0.05 mol of 2- [2- (2-aminoethylamino) ethylamino] ethanol is mixed. A solution of 0.6 mol of zinc chloride in 125 ml of water is the Mixture added with stirring over a period of 10 minutes. After this addition has ended the mixture is stirred for a period of about 0.5 hours. The mix will

Filtered for 4s, whereupon the filter cake is washed with water and dried ^{at a temperature of 40 ° C. overnight.} The zinc ethylene bisdithiocarbamate-2-

[2- (2-Aminoethylamino) ethylamino] ethanol (12: I) product comes in the form of a white insoluble powder

so obtained that melts at 178-181 ° C. C, H, N; found: 18.7,2,6,10,7; calculated: 18.8.2.6.11.0%.

The procedure described above is repeated without noticeable changes, with the exception that that the specified amounts of the mentioned reactants

ss th for the preparation of the following complex compounds can be used. The structure of each product is confirmed by elemental analysis

Zinkäthylenbisdithiocarbamat-2- [2- (2-AminoäthyI-amino) -äthy! Amino] -äthano! (6: 1) is in the form of a white, insoluble powder (F. 171-174 ⁰ C) by using 0.1 mol 2- [2- (2-Aminoäthylaminoäthylamino] ethanol obtained.

Zinkäthylenbisdithiocarbamat-2- [2- (2-Aminoäthylamino) -äthylamino] -ethanol (3 : 1) is in the form of a

6s of white, insoluble powder (m.p. 156-158 ° C) Use of 0.2 mol of 2- [2- (2-Aminoäthylamino) -äthylaminoj-ethanol obtain. H, N, Zn; found: 3.6, 12.4, 19.87! calculated: 3.6.12.95.20.15%.

Example 8

114

0.4 mol of disodium ethylene bisdithiocarbamate hexahydrate and 0.36 mol of aminoethylethanolamine are dissolved in 2 l of water. A solution of 0.36 mol of zinc chloride and 0.04 mol of manganese chloride in 60 ml of water is slowly added to this solution with vigorous stirring. Ambient conditions are observed. After this addition is complete, the mixture is stirred for a period of approximately 0.5 hours. A solid precipitate forms during this period. The mixture is filtered, whereupon the filter cake is washed with water and dried in an oven ^{at 40 ° C. overnight.} That

Zinc ^ OJ-MangandihydratilO ^ Äthylenbisdithiocarbamat-Äminoäthyiäthanoiamin (i : i) Product is obtained in the form of a slightly brown, insoluble amorphous powder which melts at 129 ° C. C, H; found: 24,4,4,6; calculated: 24,55,4,63%.

The procedure described above is repeated without significant changes, with the exception of that the specified amounts of the listed reactants for the preparation of the following complex compounds can be used. The structure of each product is confirmed by elemental analysis.

ZinkieOJ-Mangandihydra ^ Oj-Äthylenbisdithiocarbamat-Aminoäthyläthanolamin (l : 1) is in the form of a light brown insoluble powder (M.p. 142-144 ° C) through Use of 0.32 mol each of zinc chloride and aminoethylethanolamine and 0.08 mol of manganese chloride obtain.

Zinc (70) manganese dihydrate (30) -äthylenbisdithiocarbarnai-aminoethyläihanolamine (1: 1) is in the form of a light brown insoluble powder (F. 141 -i44 "C) by Use of 0.28 mol each of zinc chloride and aminoethylethanolamine and 0.12 mol of manganese chloride obtain.

Zinc (60) manganese dihydrate (40) -ätthylenbisdithiocarbamat-Aminoäthyläthanolamin (1: 1) is in the form of a brown insoluble solid (M. 137-140 ⁰ C) by using 0.24 mol each of zinc chloride and Aminoäthyläthanolamin and 0.16 Moles of manganese chloride obtained.

Zinc (50) manganese dihydrate (50) ethylene bisdithiocarbamate aminoethylethanolamine (3: 1) is in the form of a purple-brown insoluble powder (mp 153-155 ° C) by using 0.20 mol of zinc chloride, 0.067 mol of aminoethylethanolamine and 0.20 mol of manganese chloride obtain.

Zinc (30) manganese dihydrate (70) ethylene bisdithiocarbamate aminoethylethanolamine (3: 1) is in the form of a brown insoluble powder (m.p. 158-161 ° C) through Use of 0.12 mol of zinc chloride, 0.04 mol of aminoethylethanolamine and 0.28 mol of manganese chloride obtain. H, N, Zn; found: 3.3, 10.0, 42.6; calculated: 33.10.1.42.2%.

The complex compounds according to the invention can be used to change the growth of plants, including both mushroom plants and higher Plants, are used. The complex compounds are used in an advantageous manner for control a fungal attack or to stimulate growth or to achieve both of these effects used. Representative examples of higher plants are almond trees, apple trees, and apricot trees. Banana trees, cherry trees, peach trees, pear trees, grapefruit trees, carrots. Tomatoes, cabbage. Gur

ken, cantaloupe, spinach, potatoes, beets, corn, hops, rice, wheat, beans. Cotton, lettuce, Onions, celery. Tobacco or other useful plants as well as ornamental shrubs, flowers and grasses. at the implementation of such measures, the higher plants or the plant parts with a das Plant growth-changing amount of a complex compound according to the invention contacted. One such plant growth altering amount is at least one of an antifungal amount and a growth stimulating amount Amount, depending on the effects to be achieved. It is essential that one such antifungal or growth stimulating amount is below the phytotoxic amount. at when applied to growing plants, for example, amounts of more than 27.8 kg are the Complex compound per hectare generally unnecessary to be good antifungal and growth-stimulating To make an impact. Larger amounts can cause phytotoxic effects and growth inhibit many plants. Excellent fungi control as well as excellent Stimulation of the growth of coarse plants can then be achieved if the complex compounds on the parts of higher plants growing above the ground in quantities of 0.0045-3.36 kg of the Compound compound can be applied per hectare, or if parts growing in the air are higher Plants are contacted with preparations containing 25 - 2400 or more parts by weight of the complex compound contained per million parts by weight of the total preparation. Similarly, has an application of complex compounds on seeds of higher plants in amounts of 0.03-1% by weight of the complex compound, Excellent fungi control without inhibition based on the weight of the seed the germination of the seed and without impairment of the growth from this seed Plants result.

The complex compounds can be used in their unmodified form or in preparations are used which additives and adjuvants, preferably non-phytotoxic adjuvants, contain. The term “non-phytotoxic adjuvant” is to be understood as meaning customary fungicidal adjuvants that have no noticeable adverse effect on plant leaves, stems, flowers or Exercise fruits and not noticeably inhibit the growth of plants when using the invention Complex compounds are applied in amounts that change plant growth. Some preparations may contain 0.0001-2% by weight or more of a complex compound. Liquid preparations may for example contain one or more fungicidal adjuvants, such as aqueous ones Alkanolamines, alcohols, acetone, toluene, petroleum distillates or dimethyl sulfoxide. Dust preparations can be formulated using finely divided solid adjuvants, for example using of powdered walnut shells, pyrophyllite. Lime, talc or gypsum. In addition, these Preparations of solid surface-active dispensing agents, such as, for example, Fuller's earth, bentonite. Contains diatomaceous earth or attapulgite clay. The preparations can also be made as a concentrate which contain about 2 to about 98% of a compound compound. Such preparations are suitable for dilution by mixing

with other adjuvants before use.

These preparations can be formulated as wettable powders, ionic or not contain ionic surfactant dispersants. A preferred group of preparations contains a complex compound and a surface-active dispersant. Under the term "Surface-active dispersing agent" should be understood to mean all agents that are capable of this the interface between the complex compounds and water or an organic liquid as To act dispersing medium and thereby dispersing the complex compound in water or in the organic liquid to facilitate the formation of dispersible concentrate preparations. the preferred preparations of a complex compound and a surface-active dispersant treatment preparations can be that contain 0.0001-2 or more percent by weight of the complex compound contain. It can also be a concentrate preparation containing 2-98% by weight of a complex compound contain. The concentrate preparations can be prepared by adding water or organic solvents. Additives or non-phytotoxic adjuvants for the production of the finished treatment preparations be diluted.

Another preferred group of preparations includes those preparations which contain a complex compound and contain a dispersion stabilizer. Under the term "dispersion stabilizer" those means are to be understood which act to disperse the complex compounds in aqueous or organic liquid systems to favor and the settling of To inhibit solids. These agents generally cause an increase in the viscosity of the liquid Dispersion medium. Such dispersion stabilizers also contribute to the fact that the active Complex compounds are retained on parts of plants when the preparations are used as sprays will. Representative dispersion stabilizers are, for example, alginic acid, blood albumin, carboxymethyl cellulose, Casein, gluten, starch, linear and / or crosslinked polyacrylamides, natural and artificial gums such as gum arabic, guar gum, hydroxypropylmethyl cellulose and Hydroxypropyl cellulose, peptins or gelatin or compatible mixtures of these ingredients. Preparations consisting of a complex compound and 0.25 - 20% of a dispersion stabilizer L> exist, result in excellent plant growth-changing effects in liquid dispersions. Such preparations enable the deposition of increased amounts of the complex compounds Parts of plants if they are applied in the form of sprays for the given amounts to be applied. Spray formulations comprising a complex compound and from about 0.25 to about 20% by weight of a dispersion stabilizer are preferred, in which case the dispersion stabilizer from lower-alkyl and hydroxy-lower-alkyl cellulose ethers consists, with lower-alkyl Metlul. Is to understand ethyl or propyl / u. Hydroxypropylniethyl cellulose is a preferred dispensing measure.

An excellent fight against later Tn> k blight, Phytophthora infcstans. will <l; inn he /. received.

when tomato plants are treated with an aqueous preparation containing any of the following compounds contains: zinc ethylene bisdithiocarbamate-aminoethylethanolamine (1: 1), zincethylene bisdithiocarbamate-aminoethylethanolamine (8 : 1), Zinkäthylenbisdithiocarbamat-Aminoäthy! Ethanolamine (16: 1), Zinkäthylenbisdithiocarbamit-2- [2- (2-Aminoäthylamino) -äthyl] -aminoethanol (2: 1) or zinc-l ^ -propylenebisdithiocarbamate-aminoethylethanolamine (1.4 : 1) as the only active agent, in a concentration of 1200 Parts by weight of the complex compound per million parts by weight of the preparation. Thereby these Preparations in the form of sprays on parts of tomato plants growing above the ground applied, after which the plants are subsequently treated with a suspension of viable Phytophthora spores infestans (late blight) infected graze. Similar plants not that way with a Complex compounds have been treated are infected in a similar manner and serve as control plants. All plants are kept for 4 days under such temperature and humidity conditions, which are conducive to the growth of fungal organisms. An observation of the with a Ben according to the invention Plants treated with complex compounds provide excellent control against fungal attack and also shows that an infestation with late blight is prevented. The treated plants are healthy and grow vigorously, while the untreated comparison plants show signs of severe fungal attack demonstrate.

Similarly, excellent control results of Plasmophora viticola are achieved when the parts of grape vines growing above the ground with aqueous spray preparations which contain one of the compounds listed below as the only active ingredient

Zinc (60) - manganese dihydrate (40) - ethylenebisdithiocarbamate - aminoethylethanolamine (1: 1) or zinc (90) - manganese dihydrateiSJ-EisenilllHSJ -ätthylenbisdithiocarbamat-aminoethylethanolamine (4 : 1) at a concentration of 600 parts per 1 million parts. The plants are then covered with viable spores infected by Plasmophora viticola, the downy meltau organism. The treated planters are observed. It was found that they were strong and healthy throughout the test period grow.

Furthermore, one can use aqueous suspensions which 600 parts per million parts of one of the following specified compounds contain: Zinkäthylenbis dithiocarbamat-AminoäthyläthanolaminO: 1) odei Zinc-1 ^ -propylenebisdithiocarbamate-aminoethylethanolamine (l : I). These suspensions are applied to parts in front of leaves of young bean plants. Tue « Suspensions are broken up in the form of uniform droplets, each containing 50 microliters and left to dry overnight. The bean planters are then spread over the entire surface of the leaves infected away with viable bean rose spores (Uromyces phaseoli) and during a egg Maintained a period of 1 week under conditions conducive to the growth of bean rust Similar imbehandclu- plants are in similar Wise infected and serve as comparison plants. Nact Termination of! - It is clear from the period that di < Comparative plants spread rust pustules the whole of the infected leaf surface

The treated plants show pustule-free zones of the leaf surface, which surround the parts that have been treated with a complex compound and extend approximately 2 cm above such treated parts extend away. These results show that the complex compound extends through the plant structure distributed through it without the antifungal activity being lost in any noticeable manner Performing other experiments are ripe and healthy grape vines of the Carignane type three times during the grape flowering period at approximately 1 week intervals with an aqueous suspension sprayed, the 0.45 kg (0.12 wt .-%) Zinkäthylenbisdithiocarbamat-Aminoäthyläthanolamin (l Contains: 1) per 100 gallons (3801).

The spraying is carried out in a plant growth-changing amount of about 380 l / hectare (100 gallons / acre). Similar grape vines are not treated and are used as comparison vines. It will be in none of the plants found any damage. After the end of the growing season, the Yield and the quality of the fruit are determined. The comparison plants produce approximately 5.5 kg of grapes per vine, with approximately 22.5% of such grapes being classified as No. 1 grapes

Those with zincethylene bisdithiocarbamate-aminoethylethanolamine (l : 1) treated plants produce approximately 9.8 kg of grapes per vine, with approximately 44% of such grapes as grapes with the Grade Ni. 1 can be classified.

The effect of the compounds according to the invention in the control of Candida peUiculosa and Pullaria pullulans was compared with the effect of one of the compounds known from DT-AS 10 57 814.

The test compounds are in isopropyl alcohol solved. The test solutions are diluted with melted agar so that one can obtain a concentration of the testing chemicals at 10 ppm, expressed by weight. The melted mixture is in Petri dishes poured. It can solidify. The test organisms are on the surface of the agar applied and then incubated.

The results are assessed as follows:

100% control - no growth of the test organisms 50% control - reduced growth
0% control - no reduction in growth.

The tests are listed in the table below.

MctallsaU

Mol - '! B amine
metal

Mol- "o control

relationship

Salt / amine Candida pullaria
pclliculosa pullulans

Connection of the DT-AS
i 1057814
: (HSCSNHCHj) ₂ Zn 100 NH ₂ C ₂ H ₄ NH ₂ η 1 0 0 I according to the invention
links
: (HSCSNHCH ₂ ) ₂ Zn 100 H (NHCH ₂ CH ₂ J ₂ OH 12th 1 100 100 \ dtsgl. Zn 100 the same 16 1 100 100 the same Zn 100 the same 1 1 100 100 .3 the same. Zn / M η 60/40 the same 2 1 100 100 X the same. Zn / Mn 60/40 the same 1 I 100 100 % same Zn / Mn 70/30 the same 4th 1 100 100 1 the same Zn / Mn 70/30 the same I. 1 100 100 the same Zn / Mn 80/20 the same 1 I 100 100 the same Zn / Mn 95/5 the same 2 1 100 100 1 the same Zn / Mn 95/5 the same 3 1 100 100 • the same. Zn / Mn 95/5 the same 8th 1 100 100 I the same Zn / Mn 95/5 the same I. 1 100 100 1 the same Zn Mn 90/10 the same 3 1 KX) 100 I the same Zn / Fe 95/5 the same 3 1 50 100 I the same Zn / Co 95/5 the same 4th 1 50 50 \ the same Zn, Fc Mn 90/5/5 the same 2 1 100 100 ^{t the} same. Zn KK) H (NHCH ₂ CH ₂ ), () H 12th ! 100 K) (I. the same Zn KX) destil. 1 KK) 100

CH ₂

HSCSNHC HCH, —NHCSSH Zn

H (NIlCH ₂ CH ₂ I ₂ OH

1: I.

K) O

50

Claims (2)

Patent claims: 1. Complex compound of ethylene or 1,2-Profjylen-bis-dithiocarbamic acid metal salts, their metal content of 30 to 100 mol% zinc and 70 to 0 Mol% manganese, and / or iron and / or cobalt, and an alkanolamine of the general formula H (NHCH ₂ CH ₂ ) _n OH where η is 2 or 3, in a molar ratio of zinc to alkanolamine of 0.5: 1 to 16: 1. 2. Means for influencing plant growth containing a complex compound according to Claim 1.