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United States Patent Office Patented Nov 3,221,026 United States Patent Office Patented Nov. 30, 1965 2 3,221,026 prepared by reaction of a dicyanoketene acetal of the SALTS OF 1,1-DCYANO-2,2,2-TRIALKOXY formula ETHANES Owen W. Webster, Wilmington, Del, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Feb. 13, 1962, Ser. No. 172,875 wherein R2 and R3 have the meanings defined above in the 2 Claims. (C. 260-340.9) general formula for the products of this invention, with This invention relates to salts of polycyano compounds, one molar equivalent of an alkali metal alkoxide of an and more particularly, to salts of polycyanopolyalkoxy alcohol having 1-8 carbon atoms at a temperature below ethanes and a process for their preparation. 10° C., and preferably at a temperature between 0 and The salts are derivatives of tetracyanoethylene which -80° C., in the presence of an inert reaction medium, is a very reactive compound that has received considerable e.g., an excess of the alcohol from which the alkoxide is study during the last few years. A large number of new 5 derived, or an ether such as diethyl ether, dioxane, tetra and valuable compounds have been prepared from it, and hydrofuran, ethylene glycol dimethyl ether and the like. now a new class of polycyano compounds is provided by As in the case of the reaction starting with tetracyano the present invention. ethylene, the reaction mixture in this case should also The novel compounds of this invention are salts of the be anhydrous to obtain the best results. formula While the reaction between the alkali metal alkoxide 20 and the tetracyanoethylene or dicyanoketene acetal takes CN OR1 place in the stoichiometric proportions discussed above, i.e., 3 moles of alkoxide to 1 mole of tetracyanoethylene soon&N &R! I or 1 mole of alkoxide per mole of dicyanoketene acetal, it wherein M is a cation, n is the valence of the cation M, 25 is generally preferred to use a small excess of the alkoxide, R, R2, and R3 are alkyl of 1-8 carbon atoms or R3 and e.g., a 10-20% excess, to obtain the best results. R3 taken together can be an alkylene radical of 2-6 car The reaction of the alkali metal alkoxide with tetra bon atoms. cyanoethylene or with the dicyanoketene acetal takes The cation M in the products of this invention can be place at ordinary pressures; however, superatmospheric the ion of any metal, the ammonium ion, or an alkyl sub 30 or subatmospheric pressures can be employed, if desired. stituted ammonium ion in which each alkyl group con At the temperature of reaction, defined above, the reac tains from one through four carbon atoms. The metals, tion is completed in periods of time ranging from one to according to the Periodic Table in Deming's "General several hours, e.g., 1-5 hours. Chemistry,' 5th edition, chapter 11, John Wiley & Sons, In a modification of this reaction that is useful when Inc., and in Lange's "Handbook of Chemistry,” 9th edi 35 alkali metal methoxides are employed as reactants, there tion, pp. 56-57, Handbook Publishers, Inc. (1956), are can be used a methanolic solution of an alkali metal the elements of Groups I, II, VIII, III-B, IV-B, V-B, cyanide in place of a methanolic solution of alkali metal VI-B, VII-B, and the elements of Groups III-A, IV-A, methoxide. Thus, potassium 1,1-dicyano-2,2,2-trimethox V-A and VI-A which have atomic numbers above 5, 14, yethanide can be prepared by the reaction of tetracyano 33 and 52, respectively. These metals include both light 40 ethylene with a molar equivalent of potassium cyanide dis and heavy metals. The light metals are also known as solved in excess methanol at a temperature below 10° C. the alkali metals and the alkaline earth metals. The Apparently, potassium methoxide is formed from the re heavy metals include brittle, ductile and low melting action of potassium cyanide with methanol and this in metals as described in the above-mentioned Periodic turn reacts with the tetracyanoethylene as described here Table in Lange's Handbook of Chemistry. Thus, the light 45 inbefore. metals include lithium, sodium, potassium, rubidium, The salts of this invention which are less soluble than cesium, beryllium, magnesium, calcium, strontium, and the alkali metal salts can be prepared from the alkali barium; and the heavy metals include copper, silver, zinc, metal salts by double decomposition. Thus, the addition cadmium, mercury, iron, cobalt, nickel, titanium, vana of an aqueous solution of soluble alkali metal salt of the dium, chromium and manganese. The ammonium and 50 dicyanotrialkoxyethane anion to an aqueous solution of a alkyl substituted ammonium cations include ammonium, water-soluble salt of that metal or alkyl substituted am dimethylammonium, tetramethylammonium, ethylammo monium cation whose dicyanotrialkoxyethane salt is de nium, tetrabutylammonium, trimethylbutylammonium, sired results in the precipitation of the desired salt from and the like. the reaction mixture. For example, when an aqueous 55 solution of potassium dicyanotrimethoxyethanide is mixed The salts of this invention in which the cation is an with an aqueous solution of silver nitrate, the less soluble alkali metal ion can be prepared directly by reaction of Silver dicyanotrimethoxyethanide precipitates from the re tetracyanoethylene with three molar equivalents of a action mixture. The precipitated salt is then filtered from metal alkoxide of the formula M'OR, wherein M' is an the reaction mixture and dried. By this method salts of alkali metal, e.g., lithium, sodium, potassium, rubidium dicyanotrialkoxyethanes with metals such as magnesium, or cesium, and R is an alkyl radical of 1-8 carbon atoms, 60 calcium, barium, copper, silver, zinc, cadmium, mercury, at a temperature below 10° C. and preferably at a tem titanium, vanadium, chromium, iron, cobalt and nickel, perature between 0 and -80 C. An excess of the alcohol and from highly substituted ammonium cations such as from which the alkali metal alkoxide is derived is pref tetrabutylammonium, can be prepared from the more wa erably included in the reaction mixture. It is also pref ter Soluble alkali metal Salts. erable that the reaction medium should be anhydrous in 65 Alternatively, the salts of this invention which are more order to avoid undesired side reactions. Soluble in Water than barium sulfate can be prepared by The alkali metal salts of this invention can also be reacting an aqueous solution of a barium 1,1-dicyano 3,221,026 3 4 2,2,2-trialkoxyethanide with an equeous solution of the Stirring is continued for an additional 2 hours at -40° sulfate of a desired cation. In such a reaction, barium sul C. The soltuion is then added to 500 ml. of dry diethyl fate precipitates quantitatively as a byproduct which is ether and refrigerated overnight. Filtration of the reac readily filtered off, leaving a solution of the salt of the tion mixture gives 4.8 g. (48% of theory) of an off-white, cation which was introduced in the form of a suffate. water-soluble solid identified as sodium 1,1-dicyano-2,2,2- In this manner the ammonium and tetramethylammonium, trimethoxyethanide by infrared analysis. for example, salts of 1,1-dicyano-2,2,2-trialkoxyethanides EXAMPLE IV canThe be tetracyanoethyleneobtained. used in the process of this in Sodium 1,1-dicyano-2,2,2-iriethoxyethanide from 1,1-di vention can be prepared by known methods; for example, IO cyanoketene diethyl acetal and sodium ethoxide by heating sulfur monochloride with malononitrile, suit To a solution of 1.6 g. of sodium metal in 100 ml. of ably in the presence of an inert liquid diluent. The di absolute ethanol cooled to 0° C. by means of an ice bath cyanoketene acetal used as starting material in the alterna is added dropwise over 3 hours a solution of 1.5 g. of di tive process can be made by heating tetracyanoethylene cyanoketene diethyl acetal in 50 ml. of absolute ethanol. with an alcohol or a glycol at a temperature between 5 The mixture is then added to 500 ml. of dry diethyl ether. room temperature and 200 C. and preferably at a tem The mixture is chilled to -10° C. and filtered. There perature between 50 and the B.P. of the alcohol or the is obtained 4.02 g. (68% of theory) of slightly yellow, glycol, optionally in the presence of a catalyst Such as a water-soluble crystals of sodium 1,1-dicyano-2,2,2-tri tertiary amine, urea or a metal salt. The preparation of ethoxyethanide. After recrystallization from acetonitrile, dicyanoketene acetals is described in greater detail in U.S. 20 the compound decomposes at temperature above 250 C. Patent 2,980,698 to Heckert and Middleton, and by Mid Analysis.-Calcd. for CH5NONa: C, 57.27%; H, dleton and Engelhart in J. Am. Chem. Soc., 80, 2788 6.45%; N, 11.96%. Found: C, 57.40%; H, 6.61%; N, (1958). 12.15%. The products and process of this invention are illus EXAMPLE V trated in further detail by the following examples in which 25 Preparation of sodium 1,1-dicyano-2-ethoxy-2,2-ethylene the proportions of ingredients are expressed in parts by dioxyethanide from dicyanoketene ethylene acetal weight unless otherwise stated. and sodium ethoxide EXAMPLE I The procedure of Example IV is repeated using 1.6 g. Preparation of potassium 1,1-dicyano-2,2,2-trimethoxy 30 of sodium, 75 ml. of absolute ethanol and 6.8 g.
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