Hydrogen halides reactions with ethers

Reactions of Alcohols and Ethers with Hydrogen Halides Reaction of the C-0 Bond by Nucleophilic Substitution... 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

When applied to the synthesis of ethers the reaction is effective only with primary alcohols Elimination to form alkenes predominates with secondary and tertiary alcohols Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric acid at 140°C At higher temperatures elimination predominates and ethylene is the major product A mechanism for the formation of diethyl ether is outlined m Figure 15 3 The individual steps of this mechanism are analogous to those seen earlier Nucleophilic attack on a protonated alcohol was encountered m the reaction of primary alcohols with hydrogen halides (Section 4 12) and the nucleophilic properties of alcohols were dis cussed m the context of solvolysis reactions (Section 8 7) Both the first and the last steps are proton transfer reactions between oxygens... 

Both reactants m the Williamson ether synthesis usually originate m alcohol pre cursors Sodium and potassium alkoxides are prepared by reaction of an alcohol with the appropriate metal and alkyl halides are most commonly made from alcohols by reaction with a hydrogen halide (Section 4 7) thionyl chloride (Section 4 13) or phosphorus tri bromide (Section 4 13) Alternatively alkyl p toluenesulfonates may be used m place of alkyl halides alkyl p toluenesulfonates are also prepared from alcohols as their imme diate precursors (Section 8 14)... 

Just as the carbon-oxygen bond of alcohols is cleaved on reaction with hydrogen halides (Section 4 8) so too is an ether linkage broken... 

The first step in the reaction of an alkyl aryl ether with a hydrogen halide is pro tonation of oxygen to form an alkylaryloxonium ion... 

FIGURE 16.4 The mechanism for the cleavage of ethers by hydrogen halides, using the reaction of diethyl ether with hydrogen bromide as an example. 

Ethers are the least reactive of the functional groups. The cleavage of C-O bond in ethers takes place under drastic conditions with excess of hydrogen halides. The reaction of dialkyl ether gives two alkyl halide molecules. 

Analytically, epoxy groups are determined by the reaction with hydrogen halide and back titration with a standard base. Other functional groups present may cause interference problems and result in poor end points. Pyridinium chloride-pyridine is a recommended reagent for the analysis of bisphenol-diglycidyl ether resins [22,23],... 

Alkyl halides are almost always prepared from corresponding alcohols by the use of hydrogen halides (HX) or phosphorus halides (PX3) in ether (see Section 5.5.3). Alkyl chlorides are also obtained by the reaction of alcohols with thionyl chloride (SOCI2) in triethylamine (Et3N) or pyridine (see Section 5.5.3). 

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