US1752016A

US1752016A - Catalyst for the production of ethylene glycols and ethylene hydrocarbons

Info

Publication number: US1752016A
Application number: US109961A
Authority: US
Inventors: Alexander T Maximoff
Original assignee: Naugatuck Chemical Co
Current assignee: Uniroyal Chemical Co Inc
Priority date: 1926-05-18
Filing date: 1926-05-18
Publication date: 1930-03-25
Anticipated expiration: 1947-03-25

Description

Patented Mar. 25, 1930 UNITED STATES PATENT OFFICE ALEXANDER T. maxmorr, OF'NEW YORK, N. Y., ASSIGNOB TO THE NA'UGATUCZ CHEMICAL COMPANY, OF NAUGATUCK, CONNECTICUT, A COBPOMTION' 01' CON- NECTICUT CATALYST FOR THE PRODUCTION OF ETHYLENE GLYCOLS AND Mmm muo- CABBONB Io Drawing.

The present invention relates to the production of homologues of ethylene glycol and ethylene hydrocarbons, and to the production of pinacol from acetone. More particu- 6 larly the invention relates to the activation of an aluminum reagent by the formation of a thin layer of an active amalgam upon the surface of the aluminum.

The ordinary method of amalgamating 10 aluminum for use in the reduction of organic compounds does not impart to it sufficient activity. According to the present invention the introduction of a third metalunto the amalgam greatly .increases the activity thereof and at the same time permits carrying out reactions which are impossible with aluminum activated b the usual methods. The metal introduce into the ordinary aluminum-mercury amalgam is preferably zinc. Other metals, such as cadmium etc. may also be employed. While the invention is not limited to any particular method of forming the reagent, the following may serve as illustrations. The amalgamation may be conducted by the use of soluble salts of mercury and of the third metal, these saltsbe ng precipitated upon aluminum which is 1mmersed or suspended in the solution of these salts. Another method of forming the amalgam of this invention is to melt the aluminum and third metal together thus forming an alloy which may then be ground to any desired degree and subsequently amalgamated on its surface by treatment with the mercury salts. When acetone and other ketones and derivatives thereof are treated with the improved reagent it will be found that the nature of the reaction is dependent upon the amount of third metal present in the amalgam. When ketones are treated with aluminum, upon which is deposited an aluminummercury-zinc amalgam containing 1 to 2% of zinc, a direct addition of aluminum to the ketone occurs, with the formation of Application filed Kay 18, 1828. Serial Io. 109,961.

aluminum lycolates according to the followmg genera reaction:

If the glycolate thus obtained be treated with water, a glycol and aluminum hydroxide are obtained:

Y Yam When acetone is treated with the improved reagent the end product will be tetramethyl ethylene glycol or pinacol.

If the amount of third metal be increased to 7 30% by weight of the aluminum, ethy lene hydrocarbons are produced when ketones are treated. For example acetone will yield propylene:

The above equations describe reactions which take place in a non-aqueous medium. If water be introduced into the reacting mixture, nascent hydrogen is evolved. This nascent hydrogen will lead to the formation of a series of reduction products. Under such conditions ketones will produce secondary alcohols:

(311 60.611, 2H= CH,.GH.OH.CHa

tacky material is formed in which, the zinc may act as a cementing substance to keep the aluminum and mercury together. By 1ncreasing the percentage of zinc, say up to 30% in the aluminum zinc alloy, a large percentage of propylene will appear in the reaction when acetone is used as the starting material. When an alloy contains 7% of zinc, propylene continues to appear in large quantities in this reaction. When the amount of zinc is reduced to 2% or less, very l1ttle propylene will appear, and pinacol is obtained as the main product.

The same results may be obtained by using mixtures of zinc and mercuric salts with aluminum in the preparation of the amalgam.

For instance if amalgamation of the aluminum is carried out by using a solution of 5% of zinc chloride and 10% mercuric chlo ride, the treatment of acetone with such amalgamated aluminum yields pinacol in large quantities, and relatively free from propylene and other products.

The advantage gained by the present invention is that any kind of aluminum may be employed, and the aluminum may be used in the form of filings or even in the form of rough shavings. Moreover it has been the experience of organic chemists that not all makes of pure aluminum may be employed in carrying out these catalytic reactions. Indeed it is the general experience that there is but one kind of aluminum a product made in Germany which will yield pinacol as the product of the reduction of acetone. By'practicing the present invention, however, any kind of aluminum may be employed and even better results obtained than with the abovementioned foreign product. The percentage of zinc present in the alloy may be varied within wide limits, depending upon the product desired. For the production of pinacol approximately 3% or less of zinc will give excellent results. If propylene or other ethylene hydrocarbons are desired, a higher amount of zinc, even up to 30%, may be used to advantage, although quantities of the unsaturated hydrocarbon will be obtained. with 7% of zinc. It is understood, of course, that the percentage of zinc is figured as metallic zinc. If a zinc compound is employed, cal culations are made accordingly. For example zinc chloride will analyze'a little less than 50% of zinc as metal. It will thus be seen that the reduction of organic oxygencontaining substances particularly the ketones and other compounds which are ordinarily reduced by nascent hydrogen formed y amalgamated aluminum in the presence of water, can be carried out much more eco nomically and with better results than has hitherto been possible. Furthermore the invention possesses the advantage that any type of aluminum can be employed and that it is not essential to have the aluminum in a very which the improved aluminum amalgam may be put. It will be understood, however, that the reagent may be variously employed in reduction reactions in the presence of water, as

wellas in reactions where the aluminum forms a compound with all or part of the reacting material. The claims are therefore to be interpreted broadly. The expressions metallic element, metal and zinc as used in the claims, are descriptive of these mate- 7 rials as single elements, but the terms include also compounds of the elements, and the percentages given in the claims refer to percent ages of the metal, not of its salt. It is to be understood therefore that salts of zinc and the other metals which may be employed are comprehended by the claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is: I

1. An improved reagent for the treatment of organic compounds, namely, an amalgam consisting solely of mercury, aluminum and a metal of the group consisting of zinc and cadmium.

2. An improved reagent for the treatment of organic compounds, namely, an amalgam consisting solely of mercury, aluminum and zinc.

Signed at New York, New York, this 4th day of May, 1926.

ALEXANDER T. MAXIMOFF.

CERTIFICATE OF CORRECTION.

Patent No. 1,752,016. Granted March 25, 1930, to

ALEXANDER T. MAXIMOFF.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line 54, in the first formula for R' R" second occurrence read R' R; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th day of April, A. D. 1930.

M. J. Moore, (Seal) Acting Commissioner of Patents.