DE2221090A1 - Zinc-contng metallic alkylenebis-dithiocarbamate-ethylene - polyamine complexes - antifungal plant growth promoters - Google Patents

Abstract

Novel title complexes are prepd. by reacting, in an inert solvent, a water-soluble ammonium or alkali metal alkylenebis-dithiocarbamate, an ethylenepolyamine as the free base having formula NH2(CH2CH2NH)nH (where n = 1-5) and a water-soluble metallic salt(s) (where the metal consists of 30-100 molar % zinc and 70-0 molar % of a supplementary metal selected from Mn, Ni, Fe, Co and Cu). The molar ratio of Zn ethylenepolyamine is 0.5-8:1 with the condition that when n = 1 or 2 the Zn:ethylenepolyamine ratio si 2-8:1.

Description

Process for the preparation of alkylene bisdithiocarbamate complex compounds.

The present invention relates to a method of manufacture of zinc-containing alkylene bisdithiocarbamate: ethylene polyamine complex compounds.

Many known antifungal agents give when applied to the above-ground parts of higher plants provide effective fungal control; However harm they also have flowers and young fruits with which they come in contact so that they do not can be used in all cases with the desired success. In other cases antifungal agents have been used because of their low phytotoxicity, which, however, neither guarantee rapid nor complete protection against fungi. Other antifungal agents have low potential for distribution (i.e.

the migratory properties are through the cell structure of the plant bad), so that several days are required before they are of the immediate Contact zone on the plant migrate to the outside and thus all surfaces in front of the Fungal attack are protected. During this distribution period, activity increases of the remedy to a considerable extent, so that an effective control of the fungus is not obtained, especially in the case of severe fungal attack. Other antifungal agents have high toxicity in mammals and are therefore in a number of cases dangerous to use.

The present invention relates to a method of production of zinc-containing alkylene bisdithiocarbamate: ethylene polyamine complex compounds, characterized in that one is water-soluble in the presence of an inert solvent Alkali or ammonium alkylenebisdithiocarbamate, an ethylene polyamine of the general Formula NH2 (CH2CH2NH) nH, in which n is a number from 1-5, and a water-soluble one Metal salt converts, where the metal consists of 30-100 mol .-- 'zinc and 70-0 mol .-% t? An-n, Nickel, iron, cobalt or copper and the molar ratio zinc / ethylene polyamine 0.5: 1 to 8: 1, in the event that n is the number 1 od-'cr 2 means the zinc / ethylene polyanine molar ratio is 2: 1 to 8: 1.

The products of the process are useful as antifungal agents and promote the growth of higher plants. They are stable and have a high level of antifungal properties Efficacy and good migration properties, have low phytotoxicity and low mammalian toxicity0 For the sake of simplicity, the following both monoethylene diamine and polyethylene polyamines sometimes as ethylene polyamines designated. The term "alkylene" is used as a designation in the present application of ethylene or 1,2-propylene are used; the term "alkylene bisdithiocarbamate" thus denotes ethylene bisdithiocarbamate and 1,2-propylene bisdithiocarbamate.

The expression "zinc-containing alkylene bisdithiocarbamate'1 is used in the present application for the designation of polymeric alkylene bisdithiocarbamates used, which can be obtained by reacting an alkylene bisdithiocarbamate ion with a equivalent amount of two or more water-soluble metal salts, of which one is a zinc salt. In these compounds, the metals are chemically in one combined in such an amount as corresponds to the nol ratios used.

The ions of zinc and other metals are at least divalent, such as manganese-II, iron-copper-II, nickel-II, iron-III and cobalt-II ions; there the alkylene bisdithiocarbamate ion is divalent, the different ions react to form a polymeric product.

The maximum molar ratio of zinc / ethylene polyamine in the invention Complex compound is 8: 1, the preferred molar ratio is 6: 1 to 3: 1. That to achieve minimum zinc / ethylene polyamine molar ratio required for the desired results depends on the particular ethylene polyamine used. Within the inaximal and minimum zinc / ethylene polyamine ratios in the various ethylene polyamine components any intermediate molar ratio can be used.

Examples of such intermediate molar ratios of Zinc to other metals are, for example, 31:69, 52.5: 47.5; 66.33: 33.67; 72.73: 27.57 and 99.5: 0.5. Examples of intermediate molar ratios of zinc / ethylene polyamine are 1.33: 1; 0.7: 1; 2.5: 1; 0.93: 1 etc.

For the sake of simplicity, the products of the process are described below simply referred to as "complex compounds". Individual complex compounds are as zinc ethylene bisdithiocarbamate: ethylene polyamine or zinc 1,2-propylene bisdithiocarbamate: Ethylenepolyamines, where the mole percent of zinc and other metal in each case in brackets immediately after the name of the metal and the mole percent of zinc / ethylene polyamine in brackets at the end of the name. In general, the other Metals used in the complex compounds in divalent form, with the exception of iron. If the value of the other ITetal is greater than 2, then the value is indicated by a Roman number after the name of the metal; the absence a Roman number means that the metal in the complex compound is divalent is. For example, "iron" means an iron-II-ion, "iron-III" means a ferric ion and "copper" a copper (II) ion. If the other metal is in hydrogenated form, such as manganese dihydrate, thus the water of hydration is characterized by the term "dihydrate". In complex compounds with zinc as the only metal (i.e. ratio zinc: other metal = 100: 0) the zinc / other metal molar ratio is of course not given.

The ethylene polyamine can be 1-5 of the five different ethylene polyamines use the formula given above. In general, it is preferred that one only a single ethylene polyamine is used. If the complex compound is more than contains a type of ethylene polyamine, each half is expressed separately, where the Molar ratio of each ethylene polyamine to zinc in parentheses immediately after the name of the ethylene polyamine is given, e.g. zinc-ethylene-bisdithiocarbamate-triethylenetetramide (3: 1). Tetraethylene pentamine (3: 1).

The novel compounds of the present invention are general amorphous or crystalline solids; mostly they are white, but they can also be different Have colors, especially if the compound is a polymetal complex. The complex compounds are very easily soluble in water and organic solvents. You educate moderately stable dispersions in aqueous solutions of the polyamines.

The complex compounds according to the invention show no characteristic Smear or liquefaction points when heated, rather they decompose visibly.

In general, such complex compounds are used where any other metal present, trivalent iron or divalent manganese, Is copper, cobalt or nickel. Have a preferred group of complex compounds the molar ratio of zinc / other metal from 60:40 to 100: 0, with the optional existing other metal from divalent manganese, copper, cobalt or nickel or Iron (III) or mixtures thereof. Such complex compounds are examples mentioned in which-the molar ratio of zinc to any other present Metal is 60:40 to 100: 1, with the further metal consisting of manganese or iron or

Mixtures of the same exist as ÄthYlenpolyamin-Pentaäthylenhelrarnin is used and the zinc / ethylene polyamine molar ratio is 1: 1 to 4: 1. One Another preferred group of compounds are those in which, as ethylene polyamine Triethylenetetramine is used. The most preferred group of compounds are those in which the molar ratio of zinc to any other present Metal is about 90: 1 to 100: 0, with manganese or iron or Mixtures of the same and, as ethylene polyamine, ethylene diamine, diethylene triamine or Triethylenetetramine is used, the molar ratio of zinc / ethylene polyamine is about 3: 1 to 6: 1.

The complex compounds according to the invention are obtained by reaction of a water-soluble alkali or ammonium alkylenebisdithiocarbamate, with water-soluble Zinc salts or Mixtures of water-soluble salts of zinc and the further metal and an ethylene polyamine of the formula given above Examples of water-soluble alkylenebisthiocarbamates as starting materials are Ethylene bisdithiocarbamate or 1,2-propylene bisdithiocarbamate salts of lithium, Sodium, potassium or ammonitinis. Examples of water-soluble salts of zinc or manganese, iron, copper, nickel or cobalt are the chlorides, sulfates, Nitrates or acetates. The ethylene polyamine component is preferably used as a free Base used, but you can also use their salts, e.g. the sulfates, phosphates, Nitrates, hydrohalides, acetates and citrates. If you use a salt, it becomes the acidity of the reaction mixture by adding a base, e.g. sodium hydroxide, adjusted so that the free ethylene polyamine is released.

The complex compounds form as soon as the reaction takes place come into contact or are mixed in an inert solvent. Examples for inert solvents which are used in the reaction according to the invention are water, methanol, ethanol, isopropanol, and mixtures thereof; the aqueous medium is preferred. The reaction takes place at temperatures between 10 and 50 0C in an aqueous or alcoholic medium, it is generally from 2-60 Finished minutes. The zinc-containing alkylene bisdithiocarbamate: ethylene polyamine complex precipitates out of the reaction mixture when a liquid is used in which the product is insoluble. In this regard, water is the preferred solvent for the production of complexes with ethylenediamine, diethylenetriamine and triethylenetetramine in all molar ratios of zinc / amine component, the same applies to manufacture of complexes with tetraethylene pentamine and pentaethylene hexamine at relatively high zinc / amine ratios such as 2-8 moles of zinc per mole of the ethylene pol; sramine component. The complex compounds of tetraethylene pentamine or pentaethylene hexamine, which contain relatively large amounts of these compounds (e.g. 0.5-1.5 or even 2 mol Zinc per mole of the amino compound, on the other hand, have considerable solubility in water. Accordingly, the latter complex compounds are preferred under use made of a non-aqueous solvent, particularly good results are obtained with methanol. The precipitated products can by filtering, decanting, centrifuging, or other common methods to be isolated; the cleaning of the product is carried out in the usual way, e.g. by Washing with water, methanol, aqueous methanol, etc. to remove any remove unreacted starting materials.

The complex compounds can be used for fungus control and growth promotion can be used directly without cleaning; but you can also clean them by washing and then dry under normal pressure or reduced pressure at temperatures such as which are well below the decomposition point of the specific product. Temteratures from 35-75 ° C are preferably used to dry the products.

Form the zinc-containing alkylene bisdithiocarbamate complex compounds oh, if you mix the reaction components in any proportions; however, the identity of the product formed in each case depends on the molar Quantities of certain reaction components.

So it is with the production of polymetallic complex compounds critical and important that the water-soluble salts of zinc and other metal in practically the same molar ratio (based on the metal content of each salt) can be used as desired in the end product.

The water-soluble salts of zinc used as a waste product or mixtures of zinc and other metal are therefore used in such proportions used that zinc ions in an amount of about 30-100 mol% in the reaction mixture of all of the metal ions are present. If substantially less than 30 mol% of the metal ions consist of zinc, e.g. 10-20 mil-%, the end product will contain a corresponding one Zinc / other metal ratio and therefore has many of the desired plants The growth-changing properties of the complex compounds according to the invention do not. The relative l: tengen ratio of water-soluble alkylenebisdihiocarbamate and water-soluble Salts of zinc or other metals. not critical any unconverted Any reactant's surpluses can in usual Way, e.g. by filtering and washing, separated from the complex flow will. A preferred method uses the water soluble salts of zinc or other metals and the water-soluble Alkylenbisdihtiocarbamat in stoechiometric proportions.

It is expedient to use so much Alkylenbisdithiocarbamat that the Amount is sufficient to react with the zinc and other metal components without that one uses a significant excess of Alkylenbisdithiocarbamat.

The minimum amount of ethylene polyamine used is also critical for the preparation of the complex compounds according to the invention; there must be one sufficient amount of the amine can be used so that at least 1/8 mole of ethylene polyamine is present per mole of zinc of the desired product, if much less is used Ethylene polyamine, e.g. 0.1-0.05 moles per mole of zinc, is absent from the products obtained many desirable plant growth-changing properties, e.g. high antifungal properties Effectiveness. When using one or more other metal salts together with In addition to zinc, only the molar amount of zinc has to be taken into account when considering the wants to calculate the amount of ethylene polyamine to be used. In these cases the latter is used Component used in an amount of at least 1/8 mole per mole of the zinc salt will. If the amine component consists of a mixture of two or three ethylene polyamines, so the total molar amount of the amino components must be at least 1/8 mole per mole Zinc of the desired product. In general, it is convenient to use all reaction components in stoechiometric amounts, with 1/8 to 2 moles of ethylene polyamine can be used per mole of zinc salt. In most cases the exact ones are the same The proportions of zinc salt and ethylene polyamine correspond to the desired molar ratio of zinc and ethylene polyamine in the end product. However, when using triethylenetetramine, Tetraethylene pentamine, pentaethylene hexamine or mixtures thereof as the ethylene polyanline component in many cases it is necessary to use an excess of this component, if you get a product with a special molar ratio zinc / ethylene polyamine want.

If the ethylene polyamine component is used in excess, so is the use of an organic solvent instead of water is recommended - At least in those cases in which a metal is used that leads to a non-desired higher valence level can be oxidized. In this context it can under given reaction conditions (temperature, solvent, molar concentration the reaction participant) it may be necessary that one is more or less sized Excess of ethylene polyamine is used when you have a complex compound with a wants to obtain special molar ratio zinc / amine. In any case, you get through Elemental analysis of the solid complex compound easily provides the required information in terms of the molar ratio of zinc / ethylene polyamine in the compound obtained.

A preferred process for the preparation of the complex compounds according to the invention is that the water-soluble Alklenbisdithiocarbamat first in the inert solvent and then the ethylene polyamine, the water-soluble zinc salt and adding the water-soluble salts of the other metals in the required amounts. The amount of the inert solvent is preferably about 5-25% by weight of the solids in the final reaction mixture. In this process, the ethylene polyamine, the water-soluble zinc salt and the other metal salt in the required proportions mixed with additional inert solvent and then together to form the solution are given; or they can be added individually to the alkylene bisdithiocarbamate solution give.

If you want to combine the ethylene polyamine with the other metal salt (e.g. a Manganese salt) before adding the mixture to the alkylene bisdithiocarbamate solution are, the mixing of these components is preferably carried out in methanol. The reaction mixture is then mixed mechanically and over a range of temperatures held until the precipitation of the complex compound is complete. The product is usually separated off from the reaction mixture by filtration. As Torture cake obtained complex compound can directly change the growth used by plants or fungi. Alternatively, you can use the product with Wash with water or methanol and dry in the usual way.

If a manganese-containing complex is not dried or at temperatures dried below about 40 ° C., the complex compound generally contains the manganese in the form of the dihydrate.

By drying the product at temperatures of? Ooo or higher it will removed the water of hydration. Both the complex compounds with hydrated as even those with dehydrated manganese are used to influence plant growth useful; as the hydrated manganese complex compounds in their production do not require any special insulation or drying, they are generally used for Preference is given to influencing plant growth.

As starting materials for the preparation of the invention Polyethylene polyamines used in complex compounds are commercially available Chemicals produced in the usual way by the reaction of ethylene dichloride with ammonia under suitable temperature and pressure conditions in the presence of sodium hydroxide getting produced. These polyethylene polyamines are formed by restriction the added amount of ammonia, one being the unreacted ethylenediamine and Diethylenetriamine circulates. The desired products are made by distillation isolated.

The zinc-containing alkylenebisdithiocarbamates used as starting materials are a known class of polymeric compounds; they are called "coreacted" Alkylenbisdithiocarbamate referred to. It is obtained through methathetic reaction a water-soluble alkylene bisdithiocarbamate salt such as an alkali or ammonium Salt, with a mixture of water-soluble salts of zinc and other metals, e.g. of chlorides, sulfates or acetates. The zinc and other salts are in the Molar ratio used that is desired in the polymetallic product. The reaction is usually carried out in water as the reaction medium.

The product precipitates out of the reaction mixture and can in the usual Way, e.g. by washing.

The zinc-containing alkylenebisdithiocarbamates are characterized and differ from mixtures of Metal salts through their physicochemical properties, e.g. in elemental analysis, X-ray diffraction or spectroscopy.

The polymetallic zinc-containing alkylenebisdithiocarbamates are obtained also by reacting ethylenediamine or 1,2-propylenediamine, carbon disulfide, Sodium hydroxide or ammonium hydroxide and a mixture of the soluble salts of Zinc and other metals. This procedure is analogous to that for the production of zinc alkylenebisdithiocarbamates is used.

The complex compounds according to the invention are used to change the Plant growth used, both the growth of mushrooms and of higher plants. If complex compounds are used to control fungal infestation, so the fungi or their hosts become tight with a change in plant growth (which is also an antifungal amount) of the complex compounds brought into contact. The term "host" is used here in the broadest sense and includes higher plants as well as parts of plants, growth zones and other areas or surfaces with which the mushrooms come in contact. The term "higher plant" includes those containing chlorophyll Plant parts with leaves, stems, roots, etc., such as the Angiospermae and Gymnospermae. If one uses the complex compounds as growth stimulants, one brings Parts of the higher plants (e.g. the leaves, stems, seeds, flowers or fruits) with an amount that changes the plant growth (which is also a growth-stimulating Amount is) of connections in contact. When using the compounds for control fungal attack on higher plants or parts of plants is generally one antifungal amount also a growth-stimulating amount for the higher plant, so that by contacting the higher plant with an antifungal amount of a complex compound the growth of the higher plant is also stimulated and improved.

When used on growing plants, for example, there are usually quantities About 27.8 kg / hectare of complex compounds unnecessary if you have good antifungal and We want to achieve growth-stimulating effects; one would get by too large amounts only phytotoxic reactions and growth inhibition received in some higher plants. Excellent control of mushrooms and. Growth stimulation of the higher plants is observed when the complex compounds on the aerial parts of the higher plants in an amount of 0.0045-3.36 k / hectare or when the airborne parts of the higher plant contacted with compositions containing about 25-2,400 parts by weight or more of the complex compounds per million parts by weight of the total composition. similarly, by applying the complex compounds in an amount of about 0.35-11.2 g / kg on seeds of higher plants an excellent control of the Mushrooms without the germination of the seeds and the growth of the resulting Plants is prevented.

If one only wants to achieve a fungus control, the effects on higher plants are negligible (e.g.

when treating wood, storage containers, paper, fabric, etc.), or if one does not want to combat fungus - in the airborne lines of higher ones Carry out plants (e.g. when treating the soil or orchard soil), so the ~ coriaplex compounds are used in a growth-changing amount, which is also an antifungal amount. In this process, the compositions applied in an amount of 0.0045-112 kg / hectare or in such an amount, that the complex compound in the host of the fungus in a concentration of at least 1 part by weight per million parts by weight of the substrate is present. During a soil treatment it is usually not necessary then to apply more than about 112 kg / hectare; in most cases excellent antifungal results are obtained on application from 0.0045-5 <kg / hectare. In other processes, the complex compounds on mushrooms or their growth media or hosts (wrapping paper, storage container etc.) used in the form of compositions, which at least one or more parts by weight the complex compound per million parts by weight of the growth medium or host (e.g. Floor, wood or paper) included.

The complex compounds can be used in their unmodified form be, or as compositions, which additives and adjuvants (preferably non-phytotoxic Adjuvants) included. usually the additives go straight to the unmodified one Given the reaction mixture and the reaction mixture plus additives are used directly as an antifungal and growth-regulating composition. The term "non-phytotoxic Adjuvant "refers to the common adjuvants of pungicides, which are practical no harmful effects on parts of plants (leaves, stems, flowers, fruits etc.) and the growth of plants in the together with the complex compounds practically does not affect the amount used. Such compositions can be 0.0001 or less to 2 or more percent by weight of a complex compound. Liquid Compositions contain one or more fungicide adjuvants, such as aqueous alcohols, Acetone, toluene, petroleum distillates, dimethyl sulfoxide, etc. Powdery compositions are formulated using finely divided solid adjuvants, such as powdered Walnut shells, pyrophyllite, lime, talc, gypsum, etc .; They can be solid surfactants Contain dispersants, such as fuller's earth, bentonite, montmorillonite, diatomaceous earth, Attapulgite clay etc. The compositions can also be made as concentrates, which contain 2-98% of a complex compound. These compositions must be before of use can be diluted by adding additional adjuvants.

The complex compounds can also be used together with other active ingredients process so that one can achieve combinations of effects or synergistic results certain procedures achieved. For example, the compositions can contain other fungicides or preservatives, insecticides, nematocides, fumigants, fertilizers and herbicides (before or after casserole) included. If one uses the complex compounds for the treatment of higher plants, every other active ingredient must be selected so that the composition obtained has the desired additional effects (e.g. control of insects, snails, nematodes and weeds) without new time Effects on the plant species treated.

The compositions can also be formulated as a wettable powder, by admixing ionic or non-ionic surfactant dispersants. Compositions with a content of complex compounds and a surface-active Dispersants are preferred. The term "surface-active dispersant" denotes here all means which act as the interface between the complex compound and the water or an organic liquid used as a dispersion medium can act, whereby the dispersion of the complex compound in the water or in the organic liquid is facilitated, so that dispersible concentrates are formed.

Examples of surface-active dispersants are bentonite, montmorillonite, Fuller's earth, attapulgite and other clays, condensation products of alkylene oxides with phenols and organic acids, alkylarylsulfonates, fatty acid esters of sugars and ethylene oxide derivatives thereof, polyoxyethylene derivatives of sorbitol esters, complexes Alcohols, mahogany soaps, etc. Particularly good results are obtained when using them of lignosulfonates, e.g. the calcium, magnesium, sodium or potassium salts, or when using "Goulac" (a mixture of magnesium lignosulfonate, calcium ligninsulfonate and pentose sugar); These lignin additives can be used alone or together with non-phytotoxic compounds containing polyvalent metal ions (e.g. sulfates, sulfites or chlorides iron or zinc) as well as with other wetting and dispersing agents and with dispersion stabilizers The preferred compositions contain a complex compound and a surfactant dispersant in an amount of 0.0001 or less up to 2 or more% by weight (based on the complex compound), or they are concentrates, which contain 2-98% by weight of the complex compound. These concentrates, which are 0.01 or less to 20 or more N by weight of dispersant are added by adding of water, organic solvents, additives, or non-phytotoxic adjuvants diluted if one wants to produce the final treatment composition.

Another preferred group of compositions contains besides the Complex compound a dispersion stabilizer.

The term "dispersion" StaDilizer "refers here to such agents, which the dispersion of the complex compounds in aqueous or organic liquid Promote systems and prevent solids from settling therefrom; in general increase the viscosity of the liquid dispersion medium, such dispersion stabilizers also help to keep the active complex compound on the plant parts etc.

sticks better if the compositions are used as sprays.

Examples of dispersion stabilizers are alginic acid, blood albumin, Carboxymethyl cellulose, paraformaldehyde, casein, gluten, starch, linear and / or cross-linked polyarylamides, natural and artificial gums, such as gum arabic, guar gum, Hydroxypropylmethyl cellulose and hydroxypropyl cellulose, e, pectins, gelatin etc, and compatible mixtures thereof. Excellent plant growth-changing results in liquid dispersions one obtains with formulations which, apart from the complex compound 0.25-20% by weight of a dispersion stabilizer. Such compositions lead to the fact that increased amounts of the complex compounds are deposited on the plant parts if you spray them on in a certain application amount. Particularly Spray composites are preferred which, in addition to the complex compound, contain 0.25-20% by weight. contain a dispersion stabilizer made of alkyl or hydroxyalkyl cellulose ethers where alkyl is ethyl, ethyl or propyl; Hydroxypropyl methyl cellulose is the dispersion stabilizer of choice.

The Komplerzerbindungen and compositions containing them can are applied to plants, fungi or growth media in the usual way, e.g. by spraying, dipping, dusting, or by rolling onto plant seeds, Soil treatment with or without subsequent incorporation using discs, etc., impregnation, Dispersion in irrigation water etc. You can use the compositions in different Apply amounts depending on the concentration of the complex compound and the desired Effect.

The invention is explained in more detail in the following examples. 1 example 1 Dissolve 0.005 mol (0.3 g) triethylenetetramine in a solution of 0.02 mol (,?, 28 g) Disodium-Ethylenbisthiocarbamat-hexahydrate in 50 ml of water and add this Solution slowly with 0.02 mol (2.72 g) zinc chloride dissolved in 10 ml of water. The solution is added during the addition of the zinc chloride and then for another 30 minutes touched. The resulting white solid precipitate is filtered off, three times with Washed with water and dried at 40 ° C. The material obtained has a decomposition point of about 166 ° C and is insoluble in water and organic solvents. According to the elemental analysis, the product has the constitution of zinc xthylenebisdithiocarbamate: Uriethylenetetramine (4: 1).

Analysis calculated C 21.1% H 3.2% N 13.3% S 38.46% found 21.15% 3.37 % 13.46% 41.03% Example 2 A solution of 0.02 moles (7.28 g) disodium ethylene bisdithiocarbamate hexahydrate in 75 ml of methanol, 0.02 mol (5.78 g) of tetraethylene pentamine is added. then a filtered solution of 0.02 mol (2.72 g) zinc chloride in 25 ml of methanol is added slowly while stirring into the solution. Stirring is continued for another half hour, whereupon the cream-colored precipitate is filtered off, washed with methanol and with 40 ° C dries. The product obtained in this way decomposes at 15,000 and is sparingly soluble in water and organic solutions. The elemental analysis of the solid is in accordance with the constitution of a Zinkthylenbisdithiocarbamat: Tetrartholm pentotmins (1: 1).

Analysis calculated C 31.0% H 6.25% N 21.1% S 27.56% found 29.8 6.0% 20.9% 28.3% Example 3 The procedure of the example is repeated 1, but instead of tetraethylene pentamine, an equivalent amount of pentaethylene hexamine used. In this way you get a cream-colored solid that turns out to be 167 ° C and is insoluble in water and organic solvents. He has the constitution of a zinc ethylene bisdithiocarbamate: pentaethylene hexamine (2: 1).

Analysis calculated C 29.59% H 5.11% N 17.89% S 32.71% found 29.0% 5.0 % 17.7% 31.8% Example 4 A solution of 0.014 moles (1.9 g) zinc chloride and 0.006 mol (1.19 g) of manganese chloride tetrahydrate in 10 ml of water is slowly within 5 minutes in a solution of 0.02 mol (7.28 g) disodium ethylene bisdithiocarbamate hexahydrate and 0.014 mol (2.04 g) of triethylenetetramine in 75 ml of water, after combination of the two solutions, the mixture is stirred for a further half an hour and filtered the precipitate obtained was washed with water and dried at 40.degree will. In this way, a cream-colored solid is obtained, which at 160 ° C decomposes and is practically insoluble in water or organic solvents. The elemental analysis agrees with the composition zinc (70) manganese dihydrate (30) ethylene bisdithiocarbamate: triethylenetetramine (1.33: 1).

Analysis found C 24.04% H 4.0% N 13.9%.

- Example 5 The procedure of Example 4 is repeated using of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate, 0.006 mol of triethylenetetramine, 0.006 moles of zinc chloride and 0.014 moles of manganese chloride tetrahydrate. In this way a tan-colored solid is obtained, which is at about 206 ° C decomposes and is practically insoluble in water and organic solutions. The elemental analysis this compound is in agreement with the composition zinc (30) manganese dihydrate (70) ethylenebisdithiocarbamate: triethylenetetramine (1.25: 1).

Analysis found C 0 21.42% H 3.6 ffi N 12.56.

.B e i s p i e l 6 The procedure of Example 4 is repeated under Use of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate, 0.019 mol Triethylenetetramine, 0.019 mol of zinc chloride and 0.001 mol of iron (II) chloride tetrahydrate. In this way, a gray solid is obtained which decomposes at 148.degree. C. and is insoluble in water and organic solvents.

The elemental analysis is in agreement with the composition Zinc (95) iron (5) ethylene bisdithiocarbamate: triethylenetetramine (1.36: 1).

Analysis found G 26.6% H 5.04 N 17.6 N Example 7 Repeat this Procedure of Example 4 using 0.02 moles of disodium ethylene bisdithiocarbamate hexahydrate, 0.012 mol of triethylenetetramine, 0.012 mol of zinc chloride and 0.008 mol of copper (II) chloride dihydrate. Here, an aqueous solution of the zinc and copper salts with concentrated hydrochloric acid treated in an amount sufficient to clarify the solution; only this solution becomes the solution of the disodium ethylene bisdithiocarbamate hexahydrate and given triethylenetetramine. A reddish-brown solid is obtained which decomposes at 15400 and completely insoluble in water and organic solutions is.

The elemental analysis is in agreement with the composition Zinc (60) -copper (40) -ethylene bisdithiocarbamate: triethylenetetramine (1.2: 1).

Analysis found C 24.06% H 4.47% N 15.2% S 34.74%.

EXAMPLE 1 8 The procedure of Example 4 below is repeated Use of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate, 0.02 mol Triethylenetetramine, 0.018 mol of zinc chloride, 0.001 mol of iron (III) chloride hexahydrate and 0.001 moles of manganese chloride tetrahydrate. The tan product obtained decomposes. at about 143 ° C. This product is insoluble in water and organic solvents. The elemental analysis is in agreement with the composition zinc (90) iron III (5) manganese dihydrate (5) ethylene bisdithiocarbamate: triethylenetetramine (1.33: 1).

Analysis found C 25.39% H 4.7% N 14.8% S 30.6%.

Example 9 The procedure of Example 4 is repeated using of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate, 0.018 mol of triethylenetetramine, , -0.018 moles of zinc chloride and 0.002 moles of sobalt chloride hexahydrate. In this way an olive-colored solid is obtained which decomposes at 15500 and in water and is insoluble in organic solvents. The elemental analysis is in agreement with the composition zinc (90) cobalt (10) - {thylenebisdithiocarbamate: riethylenetetramine (1.5> analysis found G 25.13% H 4.28 ffi N 16.44% S 32.04 4.

EXAMPLE 1 10 The consumption of Example 4 is repeated below Use of 0.02 mol of disodium ethylene bisdithiocarbamate hexahydrate, 0.016 mol Triethylenetetramine, 0.016 mol of zinc chloride and 0.004 Mrl of nickel chloride hexahydrate. The light green solid obtained decomposes at 155 ° C and is in but and organic Solvent insoluble. The element analysis is in agreement with the composition Zinc (80) nickel (20) ethylene bisdithiocarbamate: triethylenetetraamine (1: 1). f Example 11 The procedure of Example 4 is repeated using of 0.025 mol (?, 5 g) of the disodium salt of 1,2-propylene bisdithiocarbamic acid, 0.030 mol of triethylenetetramine and 0.025 mol of zinc chloride, giving a white solid obtained, which decomposes at 135 C and in water and organic solvents is insoluble. The elemental analysis of the product is in accordance with the Composition of zinc propylene bisdithiocarbamate: triethylenetetramine (1.33: 1).

Analysis found C 28.5% H 5.3 96 N 17.5%.

EXAMPLE 12 The procedure of Example 11 is repeated whereby 0.01 mol (1.46 g) of triethylenetetramine is first mixed with 0.08 mol (29.12 g) of disodium ethylene bisdithiocarbamate hexahydrate in 150 ml of water and then reacted with 0.08 mol (10.88 g) of zinc chloride. After washing and drying the precipitate gives a white amorphous precipitate which decomposes around 19,000 and is insoluble in water and organic solvents is. The elemental analysis is in agreement with the constitution of a zinc ethylene bisdithiocarbamate: triethylenetretramine (8: 1).

EXAMPLE 13 The mixture is added to a solution of 0.02 while stirring Mol (5.5 g) of 93% disodium ethylene bisdithiocarbamate hexahydrate in 100 ml of distilled Water 0.005 mole (0.3 g) xthylenediamine. 10 ml are then left with further stirring an aqueous solution of 0.019 mol (5.46 g) zinc sulfate hepta hydrate and 0.001 mol Add dropwise (0.17 g) of manganese sulfate dihydrate. One continues to stir for half an hour, what to the precipitated product is filtered off and washed with water and dries at 40 ° C. In this way you get dihydrate (5) -ethylenebisdithiocarbamate: ethylenediamine (4.2: 1) in the form of a light red solid that dissolves in water and organic solvents is practically insoluble and decomposes at 153 C. The elemental analysis of the product is in accordance with the specified structure.

Analysis calculated. C 18.52% H 2.8% N 12.0 ffi found. 18.6% 2.8% 12.1 ffi EXAMPLE 14 A solution of 0.02 moles (7.28 g) of disodium ethylene bisdithiocarbamic acid hexahydrate in 75 ml of distilled water is stirred with 0.01 mol (1.03 g) of diethylenetriamine offset. With further stirring, 6 ml of an aqueous solution of 0.02 mol is allowed Add dropwise (2.73 g) zinc chloride and stir for a further 1/2 hour. That. precipitated product is filtered off, washed with water and dried at 40 ° C. The zinc ethylene bisdithiocarbamate is obtained: diethylenetriamine (2: 1) in the form of a white solid that dissolves in water and organic solvents is practically 'insoluble and decomposes at 14200. The elemental analysis is complete in accordance with the stated constitution.

Analysis calculated: C 22.05% H), 83% N 15.0% found. 22.4% 3.6% 15.1% B e i 5 -p i e 1 15 The effect of the products on the process is investigated downy powdery mildew, Plasmorphara viticola, being the aerial parts of Grapevines treated with aqueous spray compositions, which one of the following Compounds contain: Zinc ethylene bisdithiocarbamate: triethylenetetramine (1: 1) @ Zinc ethylene bisdithiocarbamate: tetraethylene pentamine (1: 1) Zinc ethylene bisdithiocarbamate: pentaethylene hexamine (2: 1); Zinc-Ethylenbisdithiocarbuat: TetraäthylenpentEmin (5: 1); Zinc Xthylenebisdithiocarbamate: Pentaethylene hexamine (»Hink (95) manganese dihydrate (5) -Xthylenebisdithiocarbamate; uriethylenetetramine (1.23: 1); Zinc (70) manganese dihydrate (3Q) ethylene bisdithiocarbamate: uriethyleptetramine (1.3v Zinc (30) 'manganese dihydrate (70): ethylene bisdithiocarbamate; Triethylenetetramine (1.25: 1); Zinc (95) iron (5) ethylene bisdithiocarbamate: triethylenetetramine (1.36: 1); Zinc (60) copper (40) ethylene bisdithiocarbamate: triethylenetetramine (1.2: 1); Zinc (90) iron III (5) manganese dihydrate (5) ethylene bisdithiocarbamate: triethylenetetramine (1.33: 1); Zinc (90) cobalt (10) ethylene bisdithiocarbamate: triethylenetetramine (1.66: 1); the concentration of the active ingredient is 150 parts by weight per million parts by weight of the total composition. Zinc ethylene bisdithiocarbamate: triethylenetetramine are used as further active ingredients (2: 3), zinc ethylene bisdithiocarbamate: triethylenetetramine (4: 1), zinc (80) nickel (20) ethylene bisdithiocarbamate : Triethylenetetramine (1: 1), zinc-1,2-propylenebisdithiocarbamate: triethylenetetramine (1.33: 1) and zinc-ethylene bisdithiocarbamate: triethylenetetramine (8: 1) in one concentration of 600 ppm. The treated plants (as well as untreated controls) are then inoculated with live spores of Plasmophara viticola. All plants are kept 4 days under such temperature and humidity conditions that the growth of the Promote fungal organisms.

If one observes the treated with the complex compounds according to the invention Plants show excellent fungal control and prevention the powdery mildew infestation; the treated plants are healthy and grow lively, while the untreated control plants showed violent fungal infestation and protection show on the plant, B e i 5 p i e 1 The effect of the process products is investigated versus downy mildew Plasmorphers viticola, whereby one the above-ground parts of grapevines treated with aqueous spray compositions, which contain one of the following compounds: Zinc 95) manganese dihydrate (5) -Xthylenebisdithiocarbamate: ethylenediamine (6.3: 1); Zinc (95) manganese dihydrate (5) ethylene bisdithiocarbamate: ethylene diamine (4.2: 1); Zinc (95) manganese dihydrate (5) ethylene bisditkiorbamate: diethylenetriamine (4.2: 1)); Zinc (95) manane dihydrate (5) ethylene bisdithiocarbamate: iiethylene triamine (6.3: 1); Zinc ethylene bisdithiocarbamate: diethylenetriamine (2: 1); Zinc ethylene bisdithiocarbamate: diethylenetriamine (3: 1); Zinc ethylene bisdithiocarbamate : Diethylenetriamine (4: 1); and zinc ethylene bisdithiocarbamate: diethylenetriamine (6: 1), at a concentration of 600 parts by weight per million parts of the final Composition. Then the treated plants (as well as untreated controls) inoculated with living spores of Plasmophara viticola. All plants are kept 4 days under such temperature and humidity conditions that growth promote the fungal organisms.

If one observes the treated with the complex compounds according to the invention Plants show excellent fungal control and prevention the mildew infestation; the treated plants are healthy and grow vigorously, while the untreated control plants suffered severe fungal infestation and damage show on the plant.

EXAMPLE 17 This experiment gives an excellent one Control of Phytophthora infestans when looking at the aerial parts of tomato plants Treated with aqueous spray compositions, which zinc-Äthylenbisdithiocarbamat: triethylenetetramine (1: 1), zinc ethylene bisdithiocarbamate: triethylene tetramine (4: 1) or zinc (95) manganese dihydrate (5) ethylene bisdithiocarbamate: triethylenetetramine (1.23: 1) at a concentration of 37 ppm, whereupon the plants with a Suspension of live spores of Phytophthora infestans (later powdery mildew) inoculated. In contrast to the untreated control plants, the treated plants show during the vigorous healthy growth throughout the test.

Example 18 An aqueous suspension with 600 ppm of zinc (95) manganese dihydrate (5) ethylenebisdithiocarbamate: triethylenetetramine (1.23: 1) is applied to leaf parts of young bean plants, namely intForm equal droplets of 50 microliters each, whereupon they dry overnight leaves. The bean plants are then alive on the whole leaf surface Bean rust spores (Uromyces phaseoli) inoculated and placed under conditions for a week which are conducive to the growth of the bean rust. Similar untreated Plants are also inoculated and kept as controls. At the end of the trial period the control plants show widespread eruptions of the bean rust pustules of the entire inoculated leaf surface. The treated plants show pustule-free Zones on the leaf surface which each treated with the complex compound Surround zones and extend approximately 3.75 cm beyond the treated portions. This results in the distribution and migration of the complex compounds through the leaf structure apparent without significant loss of antifungal effectiveness, B e i s p i e l 19 Adult healthy vines of the Carignane variety are grown three times during sprayed with an aqueous suspension at intervals of approx. 1 week during the flowering period, which contains 112 kg / hectare of zinc ethylene bisdithiocarbamate: triethylenetetramine (1: 1). Similar vines are left untreated as controls, at the end of the growing season if no damage to the plants is found, and the yield and are determined Quality of the fractions. The control plants yield about 5.5 kg of grapes Per Vine, with about 22.5% of these grapes having market level No. 1. With Zinc-Äthylenbisdithiocarbamat: Tri äthylenetetramin (1: 1) provide treated plants about 7.6 kg of grapes per vine, with about 47 ß of these grapes being market grade no. 1 have.

Claims (5)

P a t e n t a n s p r ü c h e 1. Process for the production of zinc-containing alkylene bisdithiocarbamate: ethylene polyamine complex compounds, characterized in that one is water-soluble in the presence of an inert solvent Alkali or ammonium alkylene bisdithiocarbamate, an ethylene polyamine of the general Formula NH2 (CH2CH2NH) nH, in which n is a number from 1-5, and a water-soluble one Metal salt converts, the metal consisting of 30-100 mol% zinc and 70-0 mol% manganese, Nickel, iron, cobalt or Kunfer and the molar ratio zinc / ethylene polyamine 0.5: 1 to 8: 1, in the event that n is the number 1 or 2, the molar ratio Zinc / ethylene polyamine is 2: 1 to 8: 1. 2. Procedure. according to claim 1, characterized in that as inert solvent water, methanol, ethanol or isopropyl alcohol is used. 3. The method according to claims 1 or 2, characterized in that the reaction is carried out at a temperature of 10-50 ° C. 4. Process according to Claims 1-3, characterized in that one used as ethylene polyamine triethylenetetramine. 5. Process according to Claims 1-4, characterized in that one Ethylenebisdithiocarbamate is used as the alkylene bisdithiocarbamate.