有机化学Chapter15AlcoholsDiolsandThiols.pptVIP

Chapter 15 Alcohols,Diols,and Thiols;烷烃分子中的氢原子被羟基取代后的化合物，称为醇。 烷烃分子中一个氢原子被羟基取代的，称一元醇，用 ROH表示；几个氢被取代的，称多元醇。 羟基所连接的碳原子 为一级碳原子，称为一级醇（伯醇）； Primary alcohol 为二级碳原子, 称为二级醇（仲醇）； Secondary alcohol 为三级碳原子, 称为三级醇（叔醇） Tertiary alcohol;§15.1 Sources of Alcohols;糖;????15.1.1 ? 烯烃的水合作用;15.1.2 碳水化合物的发酵 ;§15.2 Overview of Preparation of Alcohols;Oxymercuration- Demercuration (羟汞化) of Alkenes;Hydrolysis of Alkyl Halides;Organometallics with Easters ;Reductions of Easters;§15.3 Hydration of Alkenes;Summary;§15.4 Hydroboration / Oxidation of Alkenes;Summary;§ 15.5 Oxymercuration-Demercuration (羟汞化) of Alkenes;Mechanism for Reaction of Alkenes With Hg(OAc)2 / H2o;Regioselectivity predicted by Markovnikovs rule (most highly substituted alcohol) Reaction proceeds via the formation of a cyclic mercurinium ion (compare with bromination of alkenes) The mercurinium is opened by the attack of water to complete the oxy-mercuration Demercuration is effected by a reduction using sodium borohydride, NaBH4;§15.6 Synthesis of Alcohols Using Grignard Reagents;Reaction usually in Et2O followed by H3O+ work-up. 若用水，则生成的Mg(OH)X为胶状物，难以处理。通常用稀酸(HCl,H2SO4)处理;15.6.1 The substituents on the carbonyl dictate the nature of the product alcohol;Addition to ketones gives tertiary alcohols;Reactions of RMgX with Esters;Reactions of RMgX with Epoxides; Organolithium or Grignard reagents react with the carbonyl group, C=O, in aldehydes or ketones to give alcohols. Addition to methanal (formaldehyde) gives primary alcohols. Addition to other aldehydes gives secondary alcohols. Addition to ketones gives tertiary alcohols. The acidic work-up converts an intermediate metal alkoxide salt into the desired alcohol via a simple acid base reaction.;Step 1: The nucleophilic C in the organometallic reagent adds to the electrophilic C in the polar carbonyl group, electrons from the C=O move to the electronegative O creating an