IL33346A - Alkylenebisdithiocarbamate complex compounds - Google Patents

Description

AL YLElffiBISDITHIOCARBAMATE COMPLEX COMPOUNDS This invention concerns metal-containing alkylenebisdithiocarbamate. alkanolamine complex compounds and method and composition employing the same.

In particular, this invention provides a metal-contain-ing alkylenebisdithiocarbamate* alkanolamine complex compound wherein the metal is at least 30 mole percent zinc and not more than 70 mole percent of one or more of manganese, nickel, iron, cobalt, and copper; the alkanolamine has the formula H(NHCH2CH2)n0H in which n represents 2 or 3; and the molar ratio of zinc to the alkanolamine is from 0.5:1 to 16:1.

. The term "alkylene" is employed in the present specification and claims to designate ethylene or 1,2-propylene.

Thus, the term "alkylenebisdithiocarbamate':' designates one of ethylenebisdithiocarbamate and 1, 2-propylenebisdithiocarbamate.

The term "polymetallic zinc-containing alkylenebisdithiocarbamate" is employed in the present specification and claims to designate the polymeric alkylenebisdithiocarbamate obtained by the reaction of an alkylenebisdithiocarbamate ion with an equivalent amount of two or more water-soluble metal salts, one of which is a zinc salt. In such compounds, the metals are chemically combined in amounts corresponding to their starting molar ratios. The zinc and additional metal ions are at least divalent such as manganous, ferrous, cupric, nickelous, ferric and cobaltous ions, and since the alkylenebisdithiocarbamate ion is divalent, the several ions are combined to form a polymeric product.

The invention includes and is exemplified by each compound wherein the metal is present at any intermediate value between 30 and 100 mole percent of zinc with a corresponding between 70 and zero mole percent, and wherein the ratio of zinc to alkanolamine is present in any intermediate ratio of from 0.5:1 to 16:1. Preferably, the metal is at least 70 mole per cent zinc and the molar ratio of zinc to the alkanolamine is from 1:1 to 8:1.

For the sake of convenience, the compounds defined above will be referred to herein simply as "complex compounds." Individual complex compounds will be named as zinc ethylenebis-dithiocarbamate-alkanolamines or zinc 1, 2-propylenebisdithio-carbamate^alkanolamines with the molar percentage of zinc or additional metal being given in parentheses immediately following the word "zinc" or the name of the additional metal, and the molar ratio of zinc to alkanolamine being expressed in parenthese at the end of the name. In general, the additional metals em-ployed in the complex compounds are employed in a divalent form, with the exception of iron. When the valence of an additional metal is greater than two, the valence will be indicated by a Roman numeral following the name of such metal, while the absence of a Roman numeral will indicate that the metal is divalent in the complex compound named. E.g., "iron" is ferrous iron, "iron III" is ferric iron and "copper" is cupric copper.

The compounds of the present invention are generally amorphous or crystalline solid materials, most of which are white but which may also have other colors, particularly when the compound is a polymetallic complex compound. The complex compounds are very slightly soluble in water and organic solvents The complex compounds form moderately stable dispersions in aqueous solutions of alkanolamines . The complex compounds evidence characteristic melting or liquefaction points or decomposition points. Certain of the complex compounds visibly heating, many of the complex compounds appear to melt or liquefy at a temperature characteristic of the particular complex compound; however, cooling of many of the complex compounds does not always result in resolidification at the characteristic melting temperature, nor are the melted and resolidified products always identical with the original complex compound. The terms "melting" and "melting point" will be employed herein to designate such characteristic temperature at which a particular complex compound melts, liquefies or appears to melt, as distin-guished from the temperature at which particular complex compounds decompose without melting or evaporating.

The complex compounds of the invention have been found to be useful for altering the growth of plants. The compounds have been found to inhibit the growth of lower plants such as fungi, while exhibiting no significant phytotoxicity to higher plants. The compounds have also been found to enhance the growth of higher plants. The present complex compounds are particularly useful for the control of a wide range of fungi, especially those fungal organisms ordinarily found on the aerial portions or on the seeds of higher plants such as, for example, cherry leaf spot, apple scab, rice blast, downy mildews, damping-off o.f cottonseed, Helminthosporium leaf spot on grasses, cereals and corn, cereal rusts, Pythium on corn or pea seeds, Cercospora and Septoria leaf spots and late blight. For control of such organisms, a plant or plant part or plant growth media is contacted with a plant growth-altering amount of one or more complex compound of the invention.

The complex compounds of the present invention can be applied to growing vegetation or to seeds of higher plants in amounts required for effective fungal control without significant both in eliminating established fungal infestation as well as in providing residual and extended control against fungal attack. Further, the complex compounds exhibit high redistribution potentials, that is, they are readily distributed or translocated through the cellular structure or plant contacted therewith and can thus effect rapid coverage and protection of plant parts when applied thereto. Also, application of the present complex compounds to higher plants in plant growth-altering amounts can beneficially be used to stimulate plant growth on such crop plants as grapes, potatoes and celery, for example, even in the absence of significant fungal disease pressure. It is a yet further advantage that the complex compounds have low mammalian toxicity and can thus be handled with a minimum of danger from accidental mammalian exposure thereto.

For such uses, preferred complex compounds are those wherein the additional metal, when present, is trivalent. iron or divalent manganese, copper, cobalt or nickel. A preferred group of complex compounds includes those wherein the mole ratio of zinc to additional metal is from 60:40 to 100:0 and wherein the additional metal is divalent manganese, copper, cobalt or nickel or ferric iron. A preferred group of compounds includes those complex compounds wherein the mole ratio of the zinc to the additional metal is from.60:40 to 100:0, the additional metal is selected from manganese and iron, the alkanolamino. -ic ono t erein R o.s hydrogen and the molar ratio of zinc to alkanolamine is from 1:1 to 8:1. Another preferred group of compounds . in- .„ eludes those wherein the alkanolamine is aminoethylethanolamine. Another preferred group of compounds includes those wherein the mole ratio of zinc to the additional metal is from about 90:10 to 100:0, wherein the additional metal is manganese or iron or The complex compounds of the invention can be prepared by the reaction of a water-soluble alkali metal or ammonium alkylenebisdithiocarbamate, water-soluble salts of zinc or mixtures of water-soluble salts of zinc and additional metals and an alkanolamine corresponding to the above formula. Representative water-soluble alkylenebisdithiocarbamate starting materials include ethylenebisdithiocarbamate or 1,2-propylene-bisdithiocarbamate salts of lithium, sodium, potassium or ammonium, for example. Representative water-soluble salts of zinc or of manganese, iron, copper,. nickel or cobalt include the chloride, sulfate, nitrate or acetate salts, for example. The alkanolamine reactant is preferably added as the free base, though salts thereof such as the sulfates, phosphates, nitrates, hydrohalides, acetates, citrates and the like can also be em-ployed. When the alkanolamine is employed as a salt, the acidity of the reaction mixture is adjusted by the addition of a base such as sodium hydroxide to liberate the free base alkanolamine.

The complex compounds are formed when the reactants are contacted and mixed in an inert solvent. Representative inert solvents which can be employed as reaction media include water, methanol, ethanol, isopropanol and mixtures thereof, aqueous media being preferred. The reaction proceeds at temperatures between about 10° and 50°G„ in an aqueous or alcoholic medium and is generally complete in from about 2 to 60 minutes. The zinc-containing alkylenebisdithiocarbamate" alkanolamine complex compound product precipitates in the reaction mixture. The precipitated product can be isolated by filtration, decanlJation, centrifugation or other conventional methods and the product can be purified by conventional procedures such as remove any unreacted starting materials which may be present. The complex compound product can be employed to control fungi and enhance plant growth directly with or without purification, . or it can be purified by washing and dried under e'mbient or reduced pressures at temperatures which are well below the decomposition point of the particular product. Temperatures of from about 35° to 75°G. are advantageously employed in drying the product.

The reactants combine to form a zinc-containing alkylenebisdithiocarbamate complex compound when mixed together ι in any proportions; however, the identity of the product produced in a given instance is dependent upon the molar proportions of certain of the reactants employed.

Thus, in the preparation of the polymetallic complex compounds of the invention, the water-soluble salts of the zinc and the - additional metal or metals should be employed in substantially the same molar proportions (based on the metal content of each salt) as are desired to be obtained in the final product. When substantially less than 30 mole percent of the metal ions are provided by the zinc salt, such as 10 or 20 mole percent, the product obtained will contain a corresponding ratio of zinc to the additional metal and will not possess many of the desirable plant growth-altering properties of the complex compounds of the invention. The relative proportions of water-soluble alkylenebisdithiocarbamate and water-soluble zinc or additional metal salts are. not critical and any unreacted excess of either reactant can be separated from the complex compound product by conventional procedures such as filtration and washing. In a preferred procedure, the water-soluble salts of zinc or the additional metals and the water-soluble alkylenebisdithiocarbamate are employed in stoichiometric proportions. Thus, it is react with the zinc and metal reactants without employing a significant excess of alkylenebisdithiocarbamate.

The minimum amount of alkanolamine reactant to be employed is critical to the preparation of the complex compounds. Sufficient alkanolamine must be employed to provide at least one-sixteenth molar proportion of alkanolamine for every molar proportion of zinc in the desired product. When substantially less alkanolamine is employed, such as 0.02 or 0.01 molar proportion of alkanolamine per molar proportion of zinc, products are obtained wfiich contain little or no alkanolamine and which lack many desirable plant growth-altering properties, such as high antifungal potency. When using one or more additional metal salt reactants along with zinc, the molar content of the zinc alone is taken into account when calculating the amount of alkanolamine. In such a case, the alkanolamine reactant is employed in an amount of at least one-sixteenth the molar proportion of zinc salt reactant employed. When the alkanolamine reactant is a mixture of alkanolamines , the total molar quantity of alkanolamine reactants must be at least one-sixteenth the molar quantity of zinc to be present in the desired product.

It is generally preferred to employ all the reactants in stoichio metric amounts, in which case from. one-sixteenth to 2 molar proportions of alkanolamine reactant are employed for every molar proportion of zinc salt reactant. In most cases, the exact proportions of zinc salt reactant and alkanolamine to Jje employed correspond to the molar ratio of zinc and alkanolamine desired in the final product. When the final product is to contain from 1 to 2 moles of alkanolamine per mole of zinc, the use of an excess of alkanolamine reactant is preferred.

Under a given set of reaction conditions of temper V- greater or lesser excess of alkanolamine may be required to produce a complex compound having a particular molar ratio of zinc to alkanolamine. In any such case, elemental analysis of the solid complex compound will readily provide information as to the molar ratio of zinc to alkanolamine in the product obtained. When the product is found by elemental analysis to contain a higher or lower ratio of zinc to alkanolamine than desired, the excess of alkanolamine reactant employed can be increased or decreased, respectively, to produce a product having the desired ratio. Simple and routine variations in the amount of alkanolamine reactant will enable one to determine the exact excess of alkanolamine to be employed under any given set of reaction conditions to obtain a product having a particular ratio of zinc to alkanolamine.

In a convenient procedure for the preparation of the complex compounds of the invention, a water-soluble alkylenebis-dithiocarbamafce, a water-soluble zinc salt, an alkanolamine corresponding to the above formula and, optionally, one or more additional metal salts are mixed together with an inert solvent, preferably water, in any order or fashion. In a preferred procedure, the water-soluble alkylenebisdithiocarbamate is first dissolved in the inert solvent and the alkanolamine reactant, water-soluble zinc salt and additional water-soluble metal salts are added to the solution in the required proportions. The amount of inert solvent employed is preferably such as to provide from .5 to 25 percent by weight of solids in the ultimate reaction mixture. In such procedure, the alkanolamine reactant, the water-soluble zinc salt and any additional metal salt employed can be mixed together in the required proportions with additional inert solvent and added as a solution, or they can be When it is desired to mix the alkanolamine with a manganese salt prior to adding the mixture to the alkylenebisdithiocarba-mate solution, it is preferred to mix the manganese salt and alkanolamine in methanol. The reaction mixture is then mechanically mixed and held at a temperature within the reaction temperature range until precipitation of the complex compound is complete. The product is conveniently separated from the reaction mixture by filtration. The complex compound is obtained as a filter cake which can be employed directly to alter the growth of plants, including fungal plants. Alternatively, the product can be washed with water or methanol and dried by conventional procedures. When a complex compound containing manganese is not dried, or is dried at temperatures less than about 40°C, the complex compound product generally contains the manganese in the form of the dihydrate. Drying the product at temperatures of 70°C. or higher removes the water of hydration. Complex compounds containing either the hydrated or dehydrated manganese are similarly useful for influencing the growth of plants. Since the hydrated manganese complex compounds require no particular isolation or drying steps for their preparation, they are generally more conveniently employed in plant growth-influencing operations.

In an alternate method of preparation, the complex compounds can be prepared by the reaction of one or more alkano-lamines corresponding to the above formula with a zinc alkylene-bisdithiocarbamate or with a polymetallic zinc-containing alkylenebisdithiocarbamate. These salts can be employed either per se or in the form of a wettable powder composition containing surfactants or the like in which the salts are present. The formation of the complex compound proceeds when the reactants reaction medium, preferably water. The reaction proceeds at temperatures from 10° to 50°C. and is generally complete in from 30 to 120 minutes. The complex compound product can be employed directly to influence the growth of plants by the appli-cation of the diluted or undiluted reaction mixture to plants or plant parts. Alterna ively, the product can be separated and purified by conventional procedures such as filtration and washing When it is desired to prepare a complex compound which contains more than about one mole of the alkanolamine per mole of zinc, or when the composition is to be employed immediately after the reactants are mixed to control fungi or promote the growth of higher plants, then the preferred practice is to add excess alkanolamine in amounts of from 3 to 10 moles of alkano-lamine per mole of zinc, the relatively, larger excesses acting in many cases to dissolve or disperse the zinc-containing alkylenebisdithiocarbamate in the reaction medium. The complex compound which thereafter forms in the mixture or is precipitated therefrom will contain from 1 to 2 moles of alkanolamine per mole of zinc in most cases. Elemental analysis of the purified product can be employed to determine the ratio of zinc to alkanolamine obtained in any particular case. The excess of alkanolamine to be employed under particular reaction conditions can be increased or decreased depending upon whether the zinc: alkanolamine ratio in the product is higher or lower than the exact ratio desired. Routine variations in the excess alkanolamine employed will enable one to obtain a complex compound product having a particular ratio of zinc to alkanolamine.

In a convenient procedure, a zinc-containing alkylene-bisdithiocarbamate, an alkanolamine and inert solvent, preferably mixture is held at a temperature within the reaction temperature range for a period of time sufficient for the reaction to go to completion, with mixing being continued to maintain the zinc-containing alkylenebisdithiocarbamate in suspension. The reaction mixture containing the product can be employed directly in antifungal and plant growth regulatory operations, or the product can be separated by filtration and purified by washing with water or methanol.

The alkanolamine starting materials employed to prepare the complex compounds of the invention can be prepared in conventional procedures by the reaction of ethylene oxide with excess alkylamino compound. The reaction is carried out by mixing the ethylene oxide with excess alkylamine in a lower alcohol as a reaction medium. The reaction proceeds readily at ambient temperatures and pressures, and the desired alkanolamine product can be obtained by conventional techniques such as by stripping off the reaction medium and any unreacted starting materials. For example, aminoethylethanolamine can be prepared by adding ethylene oxide to an excess of ethylenediamine.

The water-soluble alkylenebisdithiocarbamate starting materials can be prepared by known methods. In a representative method, the soluble alkylenebisdithiocarbamates of such metals as sodium, lithium, or potassium or of ammonium are prepared by the reaction of carbon disulfide with ethylenediamine or 1,2-propylenediamine and a base which can be an alkali metal hydroxide or ammonium hydroxide. The reaction is carried out in an inert solvent for the ethylenediamine or 1,2-propylenediamine such as methanol, ethanol, isopropanol or water and proceeds at temperatures of from about 25° to 50°G. The alkylenebisdithiocarbamate product is obtained as a solution in the inert solvent. preparation of the complex compounds of the invention, or it can be reduced in volume by evaporation or distillation to remove all or part of the solvent.

The zinc alkylenebisdithiocarbamate starting materials 5 employed to prepare the complex compounds can be prepared by conventional methods. In a representative procedure, the salt can be formed by the metathetic reaction of a water-soluble zinc salt with a water-soluble alkylenebisdithiocarbamate. The reaction is carried out in an aqueous solvent as a reaction medium and the insoluble zinc alkylenebisdithiocarbamate is obtained as a precipitate. Alternatively, the insoluble zinc alkylenebisdithiocarbamate can be prepared by mixing carbon disulfide with an aqueous solution of ethylenediamine and a water-soluble zinc salt. The zinc alkylenebisdithiocarbamate product is obtained as a precipitate.

The polymetallic zinc-containing alkylenebisdithiocarbamate starting materials are members of a known class of polymeric compounds which can be described as "coreacted alkylene- bisdithiocarbamates" „ They can be prepared by the metathetic reaction of a water-soluble alkylenebisdithiocarbamate salt such as an alkali metal or ammonium salt with a mixture of water- soluble salts of zinc and the additional metal or metals such as the chlorides, sulfates, acetates or the like. The zinc and additional metal salts are employed in the molar ratio which ^5 is desired in the polymetallic product. The reaction is conveniently carried out in water as a reaction medium. The product precipitates from the reaction mixture and can be purified by conventional techniques such as washing.

The polymetallic zinc-containing alkylenebisdithiocarba- ^ mate materials can be characterized and distinguished from including elemental analysis, X-ray diffraction and spectroscopic analysis.

The polymetallic zinc-containing alkylenebisdithio- carbamate starting materials can also be prepared by the reaction 5 of ethylenediamine or 1,2-propylenediamine, carbon disulfide and a mixture of soluble salts of zinc and the additional metal or metals. Such procedure is analogous to that employed for the preparation of zinc alkylenebisdithiocarbamates .

The following examples are illustrative of the in- 10 vention.

Example 1 Disodium ethylenebisdithiocarbamate hexahydrate (218.4 grams; 0.6 mole) was dissolved in 3 liters of water and the solution mixed thoroughly with aminoethylethanolamine (62.4 grams; 0.6 mole). The solution was stirred while a solution of zinc chloride (81.77 grams; 0.6 mole) in 125 milliliters of water was added gradually thereto over a period of about ten minutes. A white precipitate formed, in the reaction mixture during the addition of the zinc chloride. The reaction mixture was stirred for an additional thirty minutes after which the mixture was filtered. The filter cake was washed twice with water and once with methanol. The washed product was oven-dried at a temperature of 40°G. The zinc ethylenebisdithiocarbamate · aminoethylethanolamine(l:l) product was obtained as a white, ^5 finely divided amorphous solid which was found to be substantially insoluble in water, alcohols and other organic solvents.

The product has a melting point of about 133-135°C. . The product was found by elemental analysis to have carbon, hydrogen, nitrogen and sulfur contents of 25.11, 4,59, 14.98 and 33,56 3® percent, respectively, as compared with theoretical values of The above procedure was repeated with the sole variations being substitution of aminoethylethanolamine dihydro- chloride for the aminoethylethanolamine and the addition of sufficient sodium hydroxide to adjust the pH of the mixture to about 7 immediately prior to the addition of the zinc chloride. The zinc ethylenebisdithiocarbamate. aminoethylethanolamine (1 : 1) product was obtained as a white finely divided solid which appeared to melt on heating at about 133-134°C. The structure of the product was confirmed by elemental analysis, The above procedure was repeated employing 0.028 mole of disodium 1,2-propylenebisdithiocarbamate, 0.02 mole of aminoethylethanolamine and 0.028 mole of zinc chloride. A zinc 1 , 2-propylenebisdithiocarbamate· aminoethylethanolamine (1.4:1) product was obtained as a white finely divided amorphous solid which was substantially insoluble in water and organic solvents and which decomposed on heating at about 129"G. Elemental , analysis of the product disclosed the complex compound to have carbon, hydrogen, nitrogen and sulfur contents of 25.4, 4.4, 13„2 and 35.2 percent, respectively, as compared to the theoret- ical values of 25.84, 4.53, 13.14 and 35.34 percent, respectively, calculated for the named structure.

An aqueous suspension of zinc ethylenebisdithiocarba- mate was prepared by slowly adding a solution of zinc chloride (88.59 grams; 0.65 mole) in 125 milliliters of water to a solution of disodium ethylenebisdithiocarbamate hexahydrate (236.6 grams; 0.65 mole) in 3 liters of water with vigorous stirring. The addition was carried out over a period of about six minutes. To the resulting stirred suspension was then slowly added, over a period of about five minutes, a solution milliliters of water. The reaction mixture was then stirred for 30 minutes after which the solid present therein was filtered off and washed, first with water and then with methanol. All operations were conducted under ambient conditions. The washed solid was dried overnight at a temperature of 40°C. yielding 200 grams of an insoluble, finely divided, white amorphous solid, The structure of the zinc ethylenebisdithiocarbamate* aminoethylethanolamine (2 : 1) product was confirmed by elemental analysis. Example 3 A solution of 0.02 mole of zinc chloride and 0.12 mole of aminoethylethanolamine in 10 milliliters of water was mixed with a solution of 0.02 mole of disodium ethylenebisdithiocar-bamate hexahydrate in about 10 milliliters of water. A white crystalline solid precipitated slowly in the reaction mixture. The mixture was held at ambient temperature and pressure for 3 to 4 hours. The filter cake was wahsed with water, filtered, and dried overnight in a 40°G„ oven, The dried zinc ethylene-bisdithiocarbamate* aminoethylethanolamine (0.5:1) product was found to melt at 123e-125°C. G, 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 percent. The product is substantially insoluble in water but forms stable dispersions in aqueous aminoethylethanolamine.

In substantially the same procedures as those employed above and in Examples 1. and 2, disodium ethylenebisdithiocarba*-mate, zinc chloride and aminoethylethanolamine were reacted together to prepare the following complex compounds, which are characterized by melting temperatures and by elemental analysis.

Zinc ethylenebisdithiocarbamate- aminoethylethanolamine (3:1), melting at 163-166°C; C, H, N, S, Zn; found: 20.3, 3.3, 12.0, 41.2, 21.1 percent; calculated: 20.6, 3.2, 12,0, 41.3, Zinc ethylenebisdithiocarbamate· aminoethylethanolamine (4:1), melting at 174-177°C. ; G, H, N, S, Zn; found: 19.7, 2.9, 11.5, 42„1, 21.7 percent; calculated^ 19.9, 3.0, 11.6, 42.5, 21.7 percent.

Zinc ethylenebisdithiocarbamate · aminoethylethanolamine (6:1), melting at 180-184°C. ; H, S, Zn; found: 2.6, 43.6, 22.1 percent; calculated: 2„7, 43.7, 22.3 percent.

Zinc ethylenebisdithiocarbamate. aminoethylethanolamine (8:1), melting at 188-190°C. , C, H, Zn; found: 18.7, 2.6, 22.4 percent; calculated: 18.4, 2.6, 22.7 percent.

Zinc ethylenebisdithiocarbamate · aminoethylethanolamine (12:1), melting at 193-196 °C. ; N, H, Zn; found: 10.7, 2.6, 22.6 percent; calculated: 10.7, 2.5, 23.0 percent.

Zinc ethylenebisdithiocarbamate . aminoethylethanolamine (16sl), melting at 198-201°C. ; C, , Zn; found: 17.9, 10.7, 22.9 percent; calculated: .18.1, 10.6, 23.1 percent.

Example 4 0.02 Mole of disodium ethylenebisdithiocarbamate hexahydrate and 0.019 mole of aminoethylethanolamine were dis-solved in 100 milliliters of water. A solution of 0.019 mole zinc chloride and 0.001 mole of manganese chloride in 3 milli-liters of water was added to the resulting solution with vigorous stirring. After the addition was complete, the mixture w.as stirred for 30 minutes at ambient temperatures. The mixture was filtered and the filter cake carefully washed with water and dried overnight in a 40°C. oven. The zinc(95)manganese dihydrate (5)ethylenebisdithiocarbamate. aminoethylethanolamine (1:1) product was obtained as a white amorphous powder melting at 125°C. G, 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 percent.

In substantially the same procedure, the following complex compounds were prepared.

Zinc(95)manganese dihydrate(5)ethylenebisdithiocarba- mate- aminoethylethanolamine(8:1) was prepared as an insoluble faint purple amorphous powder, melting at 164-167°C, by the reaction of 0.020 mole disodium ethylenebisdithiocarbamate, 0.001 mole manganese chloride, 0.019 mole zinc chloride and 0.0024 mole aminoethylethanolamine in aqueous solution.

Zinc (95)copper(5)ethylenebisdithiocarbamate •amino- ethylethanolamine(l:l) was obtained as a tan insoluble powder, melting at 129-132°C, by the reaction of 0.019 mole each of zinc chloride and aminoethylethanolamine, 0.001 mole of cupric chloride and 0.020 mole of disodium. ethylenebisdithiocarbamate . H, N, S; found: 4.5, 14.5, 33.9; calculated: 4.7, 14.6, 34.2 percent.

'■ Example 5 A solution of 0.16 mole of aminoethylethanolamine and 0.02 mole zinc chloride in 50 milliliters of methanol was added dropwise to a solution of 0.02 mole of disodium ethylenebis- dithiocarbamate hexahydrate in 75 milliliters of methanol with vigorous stirring. A white precipitate formed immediately upon the addition. The resulting mixture was then stirred for an additional thirty minutes after which it is filtered. The filter cake was washed with methanol and dried overnight in a 40°G. oven. The zinc ethylenebisdithiocarbamate. aminoethylethanolamine (0.5 : 1) product was obtained as a white, amorphous, finely divided solid which was substantially insoluble in water and organic solvents and which can be taken up in aqueous aminoethylethanolamine. The product was found to melt at 123- 125°G. G, H, N, S; found: 29.9, 6.0, 17.7, 27.1; calculated: In substantially the same procedure, the following complex compounds were prepared.

Zinc (95)cobalt (5)ethylenebisdithiocarbamate · aminoethylethanolamine (3:1) was obtained as a lime green insoluble powder, melting at 164-166°G., by employing 0.019 mole of zinc chloride, 0.007 mole of aminoethylethanolamine and 0.001 mole of cobalt chloride in the above procedure.

Zinc (50)cobalt(50)ethylenebisdithiocarbamate. aminoethylethanolamine (1: 1) was obtained as a green insoluble powder, which decomposes without melting at 185-189°C, by employing 0.01 mole each of zinc chloride and aminoethylethanolamine and 0.01 mole of cobalt chloride in the above procedure.

Example 6 0.4 Mole of disodium ethylenebisdithiocarbamate hexahydrate and 0.36 mole of aminoethylethanolamine were dissolved in 2 liters of water. To this solution was slowly added, with vigorous stirring, a solution of 0.36 mole zinc chloride, 0.012 mole ferric chloride, 0.008 mole cupric chloride and 0.02 mole of: manganese chloride in 60 milliliters of water. After o this addition was complete, the mixture was stirred at room temperature for about 0.5 hour. A solid precipitate formed during the mixing and stirring. The mixture was filtered and the filter cake washed with water and dried overnight in a 40°G. oven. The zinc(90)iron III(3)copper(2)manganese dihydrate (5)-ethylenebisdithiocarbamate* aminoethylethanolamine (1 : 1) product was obtained as a beige-colored, insoluble, amorphous powder which melted at 124-127°C. G, H, N; found: 24.4, 4.4, 14.4; calculated: 24.7, 4.6, 14.4 percent.

The above procedure was repeated without substantial variation other than the designated changes in the named Zinc(90)manganese dihydrate(5)iron III(5)ethylenebis-dithiocarbamate. aminoethylethanolamine(4:1) was obtained as a charcoal gray-colored insoluble powder, melting at 158-161°C, by employing 0.09 mole of aminoethylethanolamine and 0.020 mole of ferric chloride and omitting the cupric chloride in the above procedure.

Zinc(70)iron III(30)ethylenebisdithiocarbamate. aminoethylethanolamine (1:1) was obtained as a charcoal gray-colored Insoluble powder,; melting; at: 138-142°,C., by employing 0.28 mole each of zinc chloride and aminoethylethanolamine and 0.12 mole of ferric chloride and omitting the cupric chloride and manganese chloride in the above procedure.

Zinc (70)nickel(30)ethylenebisdithiocarbamate- aminoethylethanolamine (1:1) was obtained as a green insoluble powder, melting at 124-127°C. , by employing 0.28 mole each.of zinc chloride and aminoethylethanolamine and 0.12 mole of nickel chloride and omitting the manganese, ferric and cupric chlorides in the above procedure. H, N.; found: 4.11, 13.73; calculated: 4.16, 13.75 percent.

Example 7 0.6 Mole of disodium ethylenebisdithiocarbamate hexahydrate was dissolved in 3 liters of water and the resulting solution is mixed with stirring with 0.05 mole of 2- [2- (2-amino-ethylamino)ethylamino]ethanol. A solution of 0.6 mole zinc chloride in 125 milliliters of water is added to the mixture with stirring over a ten minujbe period. After this addition is complete, the mixture is stirred for about 0,5 hour. The mixture is filtered and the filter cake is washed with water and dried overnight at a temperature of 40°C. The zinc ethylenebisdithio-carbamate- 2- [2- (2-aminoethylamino)ethylamino]ethanol (12 : 1) 178-181°G. C, H, N; found: 18.7, 2.6, 10.7; calculated: 18.8, 2.6, 11.0 percent.

The above procedure was repeated without substantial variation other than the designated changes in the amounts of the named reactants to prepare the following complex compounds.

The structure of each product was confirmed by elemental analysis.

Zinc ethylenebisdithiocarbamate.2- [2- (2-aminoethylamino)- ethylamino]ethanol(6 : 1) was obtained as a white insoluble powder, melting at 171-174°C, by employing 0.1 mole of 2- [2- (2-aminoethylamino)ethylamino]ethanol.

Zinc ethylenebisdithiocarbamate* 2- [2- (2-aminoethyl- amino)ethylamino]ethanol(3:l) was obtained as a white insoluble powder, melting at 156-158°C, by employing 0.2 mole of 2-[2-(2- aminoethylamino)ethylamino]ethanol. H, N, Zn; found: 3.6, 12.4, 19.87; calculated: 3.6, 12.95, 20.15 percent.

-Example 8 0.4 Mole of disodium ethylenebisdithiocarbamate hexa- hydrate and 0.36 mole. of aminoethylethanolamine were dissolved in 2 liters of water. To this solution was slowly added, with vigorous stirring, a solution of 0.36 mole zinc chloride and 0.04 mole of manganese chloride in 60 milliliters of water.

Ambient conditions were used. After this addition was complete, the mixture was stirred for about 0.5 hour during which time a solid precipitate forms. The mixture was filtered and the filter cake was washed with water and dried overnight in a 40°G. oven. The zinc(90)manganese dihydrate(10)ethylenebisdithiocarbamate 'aminoethylethanolamine (1:1) product was obtained as a light brown insoluble amorphous powder which melts at 129°C.

G, H; found: 24.4, 4.6; calculated: 24.55, 4.63 percent.

The above procedure was repeated without substantial the named reactants to prepare the following complex compounds. The structure of each product was confirmed by elemental analysis.

Zinc(80)manganese dihydrate(20)ethylenebisdithiocar-bamate.aminoethylethanolamine(1:1) was obtained as a light brown insoluble powder, melting at 142-144°C, by employing 0.32 mole each of zinc chloride and aminoethylethanolamine and 0.08 mole of manganese chloride.

Zinc(70)manganese dihydrate(30)ethylenebisdithiocar-bamate* aminoethylethanolamine(1 : 1) was obtained as a light brown insoluble powder, melting at 141-144°C, by employing 0.28 mole each of zinc chloride and aminoethylethanolamine and 0.12 mole of manganese chloride.

Zinc(60)manganese dihydrate(40)ethylenebisdithiocar-bamate* aminoethylethanolamine(1 : 1) was obtained as a brown insoluble solid, melting at 137-140°C. , by employing 0.24 mole each of zinc chloride and aminoethylethanolamine and 0.16 mole of manganese chloride.

Zinc (50)manganese dihydrate (50)ethylenebisdithiocar-bamate« aminoethylethanolamine(3 : 1) was obtained as a purple-brown insoluble powder, melting at 153-155°C, by employing 0.20 mole of zinc chloride, 0„067 mole of aminoethylethanolamine and 0.20 mole of manganese chloride.

Zinc(30)manganese dihydrate(70)ethylenebisdithiocar-bamate* aminoethylethanolamine (3:1) was obtained as a brown insoluble powder, melting at 158-161°C. , by employing 0.12 mole of zinc chloride, 0.04 mole of aminoethylethanolamine and 0.28 mole of manganese chloride. H, , Zn; found: 3.3, 10.0, 42.6; calculated: 3.3, 10.1, 42.2 percent.

The complex compounds of the invention can be used to higher plants. Thus, the complex compounds are advantageously employed to control fungal attack or stimulate growth or both on such representative higher plants as almond, apple, apricot, banana, cherry, peach, pear, grape, carrot, tomato, cabbage, cucumber, cantaloupe, spinach, potato, beet, corn, hops, rice, wheat, beans, cotton, lettuce, onions, celery, tobacco and other crop plants as well as ornamental shrubs and flowering plants and turf grasses. In such operations, the higher plant or plant part. is contacted with a plant growth-altering amount of a complex compound of the invention. Such plant growth-altering amount. is at least an antifungal amount or a growth-stimulating amount, depending on the effects or combination of effects to1? be produced. It is essential that such antifungal or growth-stimulating amount be less than a phytotoxic amount. For example, when applied to growing plants, application rates in excess of about 25 pounds (27.8 kg.) of complex compound per acre (hectare) is generally unnecessary to obtain good antifungal and growth-stimulating results, and can .produce phytotoxic responses and inhibition of the growth of many higher plants. Excellent control of fungi and stimulation of the growth of higher plants can be obtained when the complex compounds are applied to the above-ground portions of higher plants in amounts from 0.004 to 3 pounds (0.0045-3,36 kg.) of complex compound per acre (hectare) or when aerial portions of higher plants are contacted with compositions containing from 25 to 2400 or more parts by weight of complex compound per million parts by weight of total composition. Similarly, application of complex compounds to seeds of higher plants in amounts of from 0.03 to 1 percent by weight of complex compound based on the weight of seed provides excellent control of fungi without inhibiting 0 The complex compounds can be employed in their unmodified form or they can be employed in compositions comprising additaments and adjuvants, preferably a non-phytotoxic adjuvant. The term "non-phytotoxic adjuvant" refers to con-ventional fungicide adjuvants which are not substantially deleterious to plant leaves, stems, flowers, fruit and the like and not substantially inhibitory to the growth of plants at rates of application of complex compounds consistent with good plant growth-altering activity. Such compositions can contain from 0.0001 to 2 percent or more by weight of a complex compound. Liquid compositions can include one or more fungicide adjuvant such as aqueous alkanolamines, alcohols, acetone, toluene, petroleum distillates, dimethylsulfoxide and the like. Dust compositions can be formulated by employing finely divided solid adjuvants such as powdered walnut shells, pyrophyllite, chalk, talc, gypsum or the like and can include solid surface active dispersing agents such as fuller's earth, bentonite, kieselgiihr, attapulgite clay and the like. The compositions can also be prepared as concentrate compositions containing from about 2 to about 98 percent of a complex compound. Such compositions are adapted to be diluted by admixture with additional adjuvants prior to use.

The complex compounds can also be incorporated with other active agents to provide combinations of effects or syner-gistic results in particular operations. For example, the compositions can include additional fungicides or preservatives such as the phenolic preservatives, halogenated salicylanilides, sulfur, copper fungicides and the like; insecticides, nematocides, fumigants and other pesticides such as dichlorodiphenyltrichloro-ethane, hexachlorocyclohexane, m&lathion, diethyl-p-nitrophenyl- 0-(3,5,6-trichloro-2-pyridyl)phosphorothioate, 4-dimethylamino-3,5-xylyl methylcarbamate and the like; fertilizers including ammonium, phosphate and urea fertilizers and trace mineral plant nutrients; and pre-emergent or post-emergent herbicides such as.. the halogenated phenoxy aliphatic acids, dinitrosecondary-butylphenol, 3- (3,4-dichlorophenyl)-l, 1-dimethylurea and the like. When the complex compounds are employed to treat higher plants, any other active agents are selected to provide a composition which will provide the desired additional effects such as control of insects, slugs, nematodes and weeds without adversely affecting the plant species treated.

The compositions can also be formulated as wettable powders including ionic or non-ionic surface active dispersing agents. A preferred group of compositions includes those com-prising a complex compound and a surface active dispersing agent. The term "surface active dispersing agent" is employed herein to include all agents which are capable of acting as the inter-facial surface between the. complex, compounds and water or an organic liquid as the dispersion medium, facilitating thereby the dispersion of the complex compound in water or organic liquid to form dispersible concentrate compositions or the like. The preferred compositions comprising a complex compound and a surface active dispersing agent can be treating compositions containing from 0.0001 to 2 or more percent by weight of the complex compound, or they can be concentrate compositions containing from 2 to 98 percent by weight of a complex compound.

The concentrate compositions can be diluted by the addition of water, organic solvents, additaments, non-phytotoxic adjuvants and the like to prepare the ultimate treating compositions.

Another preferred group of compositions includes those term "dispersion stabilizer" is employed herein to include those agents which act to promote the dispersion of the complex compounds in aqueous or organic liquid systems and to inhibit the settling of solids therefrom, and which generally act to increase the viscosity of the liquid dispersion medium. Such dispersion stabilizers also contribute to the holding of the active complex compounds on plant parts or the like when the compositions are employed as sprays. Representative dispersion stabilizers which can be employed include alginic acid, blood albumin, carboxy-methyl cellulose, casein, gluten, starch, linear and/or cross-linked polyacrylamides, natural and artificial gums such as gum arabie, guar gum, hydroxypropylmethyl cellulose and hydroxypropyl cellulose, pectins, gelatin and the like and compatible mixtures thereof. Compositions comprising a complex compound and from 0.25 to 20 percent of a dispersion stabilizer provide excellent plant growth-altering results in liquid dispersions. Such compositions provide deposits of increased amounts of complex compounds on plant parts when applied as sprays at given application rates. Spray compositions containing a complex compound and from about 0.25 to about 20 percent by weight of a dispersion stabilizer selected from the lower alkyl and hydroxy lower alkyl cellulose ethers wherein lower alkyl is methyl, ethyl or propyl are particularly preferred, and hydroxypropylmethyl cellulose is a dispersion stabilizer of choice.

In a representative operation, excellent control of late blight organism, Phytophthora infestans, is obtained when tomato plants are treated with an aqueous composition containing one of zinc ethylenebisdithiocarbamate · aminoethylethanolamine (1:1), zinc ethylenebisdithiocarbamate · aminoethylethanolamine (8:1), zinc ethylenebisdithiocarbamate" aminoethylethanolamine ethyl ]aminoethanol(2:1), zinc 1,2-propylenebisdithiocarbamate.-aminoethylethanolamine(1.4:1) as the sole active agent therein and at a concentration of 1200 parts by weight of complex compound per million parts by weight of composition. In such operations, the compositions are applied as sprays to the above-ground portions of tomato plants and the plants are thereafter inoculated with a suspension of viable spores of Phytophthora infestans (late blight). Similar plants not thus treated with a complex compound are similarly inoculated to serve as checks. All the plants are held for four days under conditions of temperature and high humidity conducive to the growth of the fungal organism. Observations of the plants treated with a complex compound of the invention show excellent control of fungal attack and prevention of late blight infestation, the treated plants being healthy and growing vigorously, while the untreated check plants show heavy fungal infestation with attendant injury to the plants.

In a similar representative operation, excellent controls of Plasmophora viticola are obtained when the above-ground portions of grape plants are treated with aqueous spray compositions containing one of zinc(95)copper (5)ethylenebisdi-thiocarbamate · amonoethylethanolamine (1 : 1) , zinc(60)manganese dihydrate(40)ethylenebisdithiocarbamate« aminoethylethanolamine (1:1), zinc(95)nickel(5)ethylenebisdithiocarbamate« aminoethyl-ethanolamine (1 : 1) , or zinc(90)manganese dihydrate(5)iron 111(5)-ethylenebisdithiocarbamate* aminoethylethanolamine( : 1) as the sole active ingredient therein at a concentration of 600 parts per million, and the plants are thereafter inoculated with viable spores of Plasmophora viticola, the downy mildew organism. The treated plants are observed to be in a state of vigorous 6-' In other representative operations, aqueous suspensions containing 600 parts per million of one of zinc ethylenebisdi-thiocarbamate»aminoethylethanolamine(l.l) or zinc 1, 2-propylene-bisdithiocarbamate.aminoethylethanolamine(l:l) are applied to portions of the leaves of young bean plants. The suspensions are applied in uniform droplets of 50 microliters each and allowed to dry overnight. The bean plants are then inoculated over the entire leaf surface with viable spores of bean rust (Uromyces phaseoli) and held for one week under conditions conducive to the growth of bean rust. Similar untreated plants are similarly inoculated and held to serve as checks. At the end of the test period, the check plants show widespread eruption of bean rust pustules over the entire inoculated leaf surface. Observations of the treated plants show pustule-free zones of leaf surface surrounding each portion treated with a complex compound and extending about 2 centimeters beyond such treated portions. Such results indicate redistribution and translocation of the complex compound through the plant. structure without significant loss of antifungal activity. In other representative operations, mature healthy grape plants of the Carignane variety are sprayed three times through the grape blooming period at approximately one week intervals with an aqueous suspension containing one pound (0.12 percent by weight) of zinc ethylenebisdithiocarbamate° aminoethylethanolamine (1 : 1) per 100 gallons, the spray being applied at a plant growth-altering amount of approximately 100 gallons per acre (945 1? /hectare). Similar grape plants are left untreated to serve as checks. No injury to any of the plants is detected and at the end of the growing season, the yield and quality of the fruit is determined. The check plants are found to produce about 12.2 pounds (5.5 kg.) market grade. The plants treated with zinc ethylenebisdithio-carbamate* aminoethylethanolamine(l: 1) are found to produce about 21.7 pounds (9.8 kg.) of grapes per vine, with about 44 percent of such grapes being #1 grade.

Claims (8)

v- WHAT IS CLAIMED IS: THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. . 1. A metal-containing alkylenebisdithiocarbamate- - alkanolamine complex compound wherein the metal is at least 30 mole percent zinc and not more than 70 mole percent of one or more of manganese, nickel, iron, cobalt, and copper; the alkanolamine has the formula H(NHCH2CH2)n0H in which n represents 2 or 3; and the molar ratio of zinc to the alkanolamine is from 0.5:1 to. 16:-lf. the term alkylene designating ethylene or 1 ,2-propylene .

2. A- compound according to Claim 1 wherein the alkylenebisdithiocarbamate is ethylenebisdithiocarbamate.

3. A compound according to Claim 1 or Claim 2 wherein the metal is at least 70 mole percent zinc and the molar ratio of zinc to the alkanolamine is from 1:1 to 8:1.

4. A composition containing a non-phytotoxic adjuvant in admixture with a metal-containing alkylenebisdithiocarbamate · - alkanolamine complex compound wherein the metal is at least 30 mole percent zinc and not more than 70 mole percent of one or more of manganese, nickel, iron, cobalt, and copper; the alkanolamine has the formula in which n represents 2 or 3; and the molar ratio of zinc to the alkanolamine is from 0.5:1 to 16:1.

5. A composition according to Claim 4 wherein the adjuvant is a surface active agent.

6. A composition according to Claim 4 wherein the adjuvant is a dispersion stabilizer.

7. A method for the modification of the growth of plants and plant parts which method comprises applying to the plants or plant parts a growth-altering amount of one or more of the complex compounds according to any one: of Claims 1 to 3 or of a composition according to any one of Claims 4 to 6.

8. A metal-containing alkylenebisdithiocarbamate* -alkanolamine complex substantially as described hereinbefore with reference to any one of the specific Examples.