NZ198418A - Metal oxycarboxylates - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 98418 Priority Datefs;; . X\lP. .'I7. ".'A '?P.

Complete Specification Filed: CplCO-R -, C-oT-il) coic.^1) ccncs% Class: Publication Date: ..

P.O. Journal, IMo: .. .'.Vf.

WW* Nfj NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION METAL OXYCARB CXYLAT.E s and method of making same jc/We' BIO-SYSTEMS RESEARCH, INC,, a, corporation of. Colorado, of 109 W. Rainbow Drive, Salida, Colorado 81201.,. United States of America, hereby declare the invention for which i: / we pray that a patent may be granted to 5^/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- 1 N.Z. PATENT OFFICE 3 0 JAN 1984 1954l$ Background of the Invention The invention relates to a method of making natal oxycarboxylates and to uses therefor.

Zinc oxyacetate (zinc, hexakis (acetato) oxotetra) having the empirical formula C]_2Hi_8°13Zn4 anC^ t*le structura-"- formula Zn^O(CH^CC^)6, has been described in the literature. See The Bulletin of the Chemical Society of Japan, March 1954, Volume 27, Number 2, pages 112-114. In this literature article, and in others, the compound is prepared by slowly distilling powdered anhydrous zinc acetate in a high vacuum. Zinc oxyacetate sublimes gradually and is collected as a crystalline crust on a cool place in the container. This method is time consuming and expensive.

It is an object of the present invention to go some way towards overcoming these disadvantages or at least to provide the public with a useful choice.

In accordance with the present invention there is provided a rrethod for making metal axycarboxylates-which comprises reacting a metal; acetic acid, and hydrogen peroxide in an aqueous reaction mixture, precipitating the metal oxycarbaxylate, and separating the precipitated metal oxycarbaxylate Preferred metals include beryllium, magnesium, chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium and mercury. Mixture or alloys'of metals, such as manganese and zinc, may be used. Preferred carboylic acids include aliphatic carboxylic acids containing up to eight carbon atoms, such as formic, acetic, propionic and butyric.

Further in accordance with the invention, the metal Qxyoarboxylateprovides an effective vehicle for supplying the metal to plants, animals and humans. The metal oxycarboxylate is J 984 18 effectively applied to soil for assimilation by plants, and is effectively fed to animalB or humans as a food supplement or in food compositions.

Detailed Description of the Invention The metal which is used as a reactant is free metal and is preferably in finely divided form, such as shot or powder, for facilitating reaction. The carboxylic acid is utilized in any convenient concentration, but relatively strong concentrations are preferred because it is preferred that the third reactant, hydrogen peroxide, is added in dilute aqueous solution and because it is preferred to minimize the total amount of water in the reaction mixture. Where the acid is acetic, glacial acid is readily available and readily usable. The amount of acid used is preferably not in excess of stoichiometric.

Since it is a relatively simple matter to remove unreacted metal - which remains undissolved - it is preferred to use the metal in an amount in excess of stoichiometric relative to the acid. An excess of about 1.2 to 3 times stoichiometric is preferred.

Hydrogen peroxide is preferably used in excess of stoichiometric. A weight ratio of about.0.1 to 0.5 parts by weight of ^2°2 ^er Part ky weight of metal is preferred. The hydrogen peroxide is preferably used in dilute solution of up to 10% H2°2* A 3% solution is preferable in some situations such as when using glacial acetic acid, since the total amount of water in the aqueous reaction mixture is appropriate when introduced in this manner. The amount of water in the system can vary widely and is , preferably at least sufficient to prevent boiling without additional cooling. It is preferred that the amount of water lis sufficient to prevent the temperature of the reaction mixtli?J^" ^ J ^ from rising about about 90°C without additional cooling.

The reaction is preferably carried out at atmospheric pressure for reasons of economy and at temperatures below the boiling point of the reaction mixture. In general, a temperature of from room temperature up to about 130°C is preferred.

After the reaction is complete, excess metal is preferably removed by filtration or by decantation of the liquid phase. Precipitation is preferably achieved by adding acetone and cooling, but may be effected by careful evaporation of the aqueous reaction mixture. The amount of acetone is preferably about 1-5 volumes per volume of the aqueous phase and the aqueous phase is preferably cooled, or permitted to cool, to at least room temperature before the addition of the acetone in order to minimize evaporation of acetone. The solution is then preferably chilled, preferably to a temperature of less then 50°F, to precipitate the metal oxycarboxylate. While chilling can be carried much lower, it is generally not necessary, in order to precipitate substantially all of the metal axycarbaxylate> to cool below about 30°F.

The precipitated metal axycarbaxylate is recovered by filtration or the like and drying.

While the structure of the zinc axycarbaxylate has been confirmed to be Zn40(R-C02), and that of the manganese as Mn^O (R-C02)g, wherein R is hydrogen or alkyl, the structure of reaction products of all of the other metals and acids has not yet been confirmed. However, the following general information is attributed.

Mx°(r-C02)6 where M is a metal, x is an integer of 2 to 8, and R is hydrogen or alkyl.

Examples of the invention follow: \ N&^ - 4 - ^ __ ^ / Example I. Preparation of Zinc Oxyacetate i y#q-n Into a 600 milliliter beaker are placed 50 grams (0.76 5 gram-atoms) of zinc metal shot. Then 45 milliters (0.767 moles) of glacial acetic acid is added. To this mixture is added 400 milliliters of 3% hydrogen peroxide. This mixture is stirred at room temperature for 1 hour.

The reaction liquid mixture is decanted to remove the unreacted zinc shot. Then 1200 milliliters of acetone is added to the decanted liquid, and the solution is cooled to 40°F. After one hour, the precipitate is filtered to yield 50 grams of white product (Hexakis (acetato) oxotetra zinc) .

Example II'. Preparation of Zinc Oxyacetate Into a 2000 milliliter beaker is placed 100 grams (1.53 g-atoms) of zinc metal shot. Then 90 milliliters (1.57 moles) of glacial acetic acid is added. To this mixture is added 800 milliliters of 3% hydrogen peroxide. The mixture is heated to 94°C for 30 minutes with stirring. The unreacted zinc is removed, and the solution is chilled overnight in a larger container after adding 2400 ml acetone to yield 115 grams of white product (hexakis (acetato) oxotetra zinc).

As mentioned above, the metal .eocycasbaxylate can be added to soil as such or in admixture with a suitable carrier such as a fertilizer composition containing other fertilizer values such as N, P or K. The compound is also suitable for supplying metals to animals or humans and can be supplied in tablet or other convenient form in admixture with a suitable carrier such as a water soluble wax or other solid excipient. The compound can also be admixed with a food product for human or animal consumption, such as breakfast cereal, animal foods, and the like. a y./MTENT office. t924-\8 The amount of compound that is administered will, of course, depend on the amount of metal which is desired to be added to the plant or ingested by the animal or human. For agricultural use, the amount of metal which is to be used may be determined by the amount by which the soil is considered deficient in a particular metal or by the amount by which the plant is considered deficient in that metal. Similarly, for animal or human use, the metal dosage may be determined by a dietary metal deficiency or by a metal deficiency in blood plasma, in body tissues, or the like. The dosage can vary widely for a particular metal, particularly for agricultural purposes. For zinc, dosages, in general, would typically be as follows: USE DOSAGE oo o <C -5 O ro II,: : C ■! I-. " Agricultural 2-12 ppm in the soil Animal 50-2 50 mg. per day Human 50-150 mg. per day Examples III - XVI.

Example I is followed except that the zinc metal shot is replaced with 50 grams of the following finely divided metals: III - beryllium; IV - magnesium; V - chromium; VI - manganese; VII - iron; VIII - cobalt; IX - nickel; X - palladium; XI -platinum; XII - copper; XIII - silver; XIV. - gold; XV - cadmium; XVI - mercury. The recovered metal oxyacetate reaction products are useful, in the manner indicated above for the zinc oxyacetate reaction product, for supplying the metal to plants, animals, and humans. The amount of the metal to be supplied will, of course, depend on the metal; desirable amounts of each to be supplied are well known for particular applications.

Examples XVII - XX Example I is followed except that the glacial acetic acid is replaced with an equivalent amount of the following acids: XVII - formic acid; XVIII - propionic acid; XIX - n-butyric acid; XX - isobutyric acid. The recovered zinc cxycarbaxylatepro-

Claims (20)

ducts are useful as indicated above. 1984 18 Example XXI The compound of Example VI is analyzed and found to have the following structural formula: Mn^O(CH^-CC^)g. \ - 7 - 198418 WHAT WE CLAIM" IS:

1. A method of preparing a metal cmycarbaxylate which comprises reacting a metal, a carboxylic.-acid, and hydrogen peroxide in an aqueous reaction mixture, precipitating metal axycarbaxylate, and separating the precipitated metal axycarbaxylate.

2. A method according to claim 1 wherein said metal is • * v. • zinc.

3. A method according to claim 1 wherein said metal is : selected from the group, consisting of beryllium, magnesium, chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, silver, gold, cadmium and mercury.

4. A method according to claim 1 wherein said carboxylic acid is an aliphatic carboxylic acid containing from 1 to 8 carbon atoms.

5. A method according to claim 4 wherein said acid is selected from the group consisting of formic, acetic, propionic and butyric acids.

6 . A method according to claim 5 wherein said acid is acetic acid.

7. A method according to claim 1 wherein the metal axycarbaxylate is precipitated by adding acetone to said reaction mixture.

8. A method according to claim 1 wherein the amount of hydrogen peroxide is from 0.1 to 0.5 parts by weight per part by weight of metal.

9. A method according to claim 1 wherein said hydrogen peroxide is added to the reaction mixture as a dilute aqueous solution.

10. A method according to claim 1 wherein the temperature of said reaction mixture is maintained below 130°C. - 8 " 21 MAY 1984 RECBVED ^ 193418

11. A method according to claim 7 wherein the temperature of said reaction mixture is not in excess of - room temperature at the time of the addition of said acetone. Ai p a c "

12. A method according to claim 1-2"wherein the reaction i-h 9^ i4°(R-co2)5 mixture is cooled to a temperature not in excess of 50°F to facilitate said precipitation.

13. A method of preparing a metal oxycazbcxylate of formula where M is a metal cation selected from the group consisting of Zn, Co, Mn, Cr, Cd, Hg and Ni, and r is hydrogen or alkyl, which method comprises reacting any M (as defined above) ,. a carboxylic acid, and hydrogen peroxide in an aqueous reaction mixture, precipitating metal axycarbcocylate, and separating the precipitated metal axycarbaxylats.

14. A method according to any one of claims 1 to 13 substantially as herein described.

15. A product produced by the process of any one of claims 1 to 14 .

16. A product as claimed in claim 15 having the formula ■Mx°(r-C02>6 wherein M is a metal cation, x is an integer of from 2 to 8, and r is hydrogen or alkyl.

17 . Manganese axycarbaxylates.

18. Manganese oxyacetate.

19 . A metal axycarbaxylate having the formula m4o(r-co2)6 wherein M is a metal cation selected from the group consisting of Mn, Cr, Cd, Hg and Ni, and r is hydrogen or alkyl.

20. A compound as claimed in any one of claims 17 to 19 substantially as herein described. 3" GX'f : IV A. j, in 29FEB1984. . wh 9 ~ Psr