Sodium hydride unsaturated hydrocarbons

It will be remembered that acid esters of sulphuric acid can be prepared by the action of the acid on unsaturated hydrocarbons. The preparation of alcohols from unsaturated hydrocarbons through the esters of sulphuric acid is a convenient method, as the esters of acids which contain oxygen are much more easily hydrolyzed than are the esters of the halogen hydrides. Acid ethyl sulphate is readily hydrolyzed when boiled with water. Ethyl acetate is converted into ethyl alcohol and sodium acetate when warmed with an aqueous solution of sodium hydroxide. 

Much more conveniently, even a,)S-unsaturated esters can he transformed into a,)S-unsaturated alcohols by very careful treatment with lithium aluminum hydride [1073], sodium bis(2-methoxyethoxy)aluminum hydride [544] or diiso-butylalane [1151] (Procedure 18, p. 208). An excess of the reducing agent must be avoided. Therefore the inverse technique (addition of the hydride to the ester) is used and the reaction is usually carried out at low temperature. In hydrocarbons as solvents the reduction does not proceed further even at elevated temperatures. Methyl cinnamate was converted to cinnamyl alcohol in 73% yield when an equimolar amount of the ester was added to a suspension of lithium aluminum hydride in benzene and the mixture was heated at 59-60° for 14.5 hours [1073]. Ethyl cinnamate gave 75.5% yield of cinnamyl alcohol on inverse treatment with 1.1 mol of sodium bis(2-methoxy-ethoxy)aluminum hydride at 15-20° for 45 minutes [544]. 

It follows from this discussion that all solvents and monomers used must be carefully purified. Hydrocarbons should be stirred over sulphuric acid for many days and ethers refluxed over sodium—potassium alloy or sodium fluorenone before fractionation. Traces of unsaturated materials in aliphatic hydrocarbons can be removed by silica gel. After fractionation, a preliminary drying over calcium hydride can be followed by storage over sodium—potassium alloy for ethers, or a treatment with butyllithium or similar non-volatile reactive organometallic reagent for hydrocarbons. Monomers cannot be treated quite so drastically, but fractionation followed by a pre-polymerization in vacuum over butyl-... 

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