Processes of preparing of high molecular weight substituted ethinyl carbinols

摘要

529,794. Ethinyl carbinols. TENNANT, W. J. (Armour & Co.). May 26, 1939, No. 15762. [Class 2 (iii)] High molecular weight hydrocarbon substituted ethinyl carbinols are prepared by reacting in a non-aqueous solvent an alkali metal acetylide or a substituted alkali metal acetylide with a ketone of the formula where R is an alkyl radical of at least 10 carbon atoms, and R1 is an alkyl radical of at least 10 carbon atoms or an aryl radical, followed by hydrolysis of the alkali metal derivatives as formed. The preferred solvent is liquid ammonia, and the preferred conditions for the reaction are room temperature at a raised pressure. The products of the reaction correspond to the general formulae When liquid ammonia is used as the solvent, the alkali metal acetylide is not isolated, but reacted directly with the ketone. In examples (1) Acetylene is passed into a solution of sodium metal in liquid ammonia until the blue colour is discharged. Myristone is then added and the reaction mixture allowed to attain and remain at room temperature in a steel bomb for 48 hours. The product is hydrolysed with ice after the removal of the ammonia to give 1:1-ditridecyl- 2-propyn-1-ol. (2) Laurone is added to a solution of ethinyl sodium prepared as in example (1) and the product worked up as before to give 1:1-diundecyl-2-propyn-1-ol. If desired this example may be carried out using ether as a solvent, in which case the reaction is allowed to proceed for four days. (3) Stearone is added to a solution of ethinyl sodium prepared as in example (1) and the product worked up as before to give 1:1-diheptadecyl-2-propyn-1-ol. (4) p-Diphenyl heptadecyl ketone is added to a solution of ethinyl sodium prepared as in example (1) and the product worked up as before to give 1-diphenyl-1-heptadecyl-propyn- 1-o1. (5) Laurone is added to a solution of sodium vinyl acetylide prepared in an analogous manner to the ethinyl sodium of example (1) and the product worked up as before to give 1:1-diundecyl-3-vinyl-2-propyn-1-ol. (6) A solution of laurone in liquid ammonia is added to a suspension in liquid ammonia of sodium carbide and the product worked up as before to give 1:1:4:4-tetra-undecyl-2-butyn-1:4-diol.