加州大学伯克利分校有机化学第八章.pptVIP

? University of California ? Univesity of California Structure Hydrophobic-Hydrophilic Alkoxides RO Synthesis of Alcohols R-OH Retrosynthetic Analysis Roadmaps Ethanol Chapter 8: Alcohols R OH O H H O CH3 CH3 δ+ O H CH3 δ+ δ+ δ+ δ+ δ+ δ-- δ-- δ-- Water Alcohol Ether 1. Find the longest chain containing the –OH function: alkane ? alkanol. Note: This may not be the longest chain in the molecule! 2. Number such as to give HO-C lowest # 3. Other rules same as in alkanes 4,4-Dimethyl-1-nonanol 5-Bromo-3-propyl- 2-heptanol OH OH Br 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 Names 7 OH OH CH3 HO Cyclohexanol Cis-3-methyl-cyclohexanol 1-Ethylcyclo-pentanol -OH as a substituent is called hydroxy -OR is alkoxy: Ethers R-O-R’, alkoxyalkanes RCH2OH RCHOH R’ RCOH R’ R’’ Primary Secondary Tertiary alcohol Cyclic alcohols are called cycloalkanols: Defined as C1, # is not part of name 1 1 3 O can be thought of as sp3-hybridized, “tetrahedral”, i.e. bent, not linear. DHo (O H) = 119 kcal mol-1 H H3C O Most striking: Relatively high melting and boiling points, and water solubility. Why? Hydrogen Bonding O R H H O R δ- δ- δ+ δ+ 5 kcalmol-1 Extensive network: Methanol tetramer Water hexamer Increases inter- molecular interactions. Allows for solvation by water. R OH Water solubility: Decreases with size of R R is hydrophobic; –OH is hydrophilic ROH + H2O RO- + H3O+ pKa’s H2O CH3OH CH3CH2OH (CH3)2CHOH 15.7 15.5 15.9 17.1 (CH3)3COH ClCH2CH2OH CF3CH2OH CF3CH2CH2OH 18 14.3 12.4 15.4 Steric effect “Inductive” electronic effect. Tapers off with distance. K Sterics and solvation Acidity CH3OH + Na NH2 CH3O Na + NH3 CH3CH2OH + Na OH CH3CH2O Na + H2O K ~ 1 pKa 15.5 35 K 15.9 15.7 + - + - + - + - K K = 1019.5 Preparation: When CH3CH2OH is solvent, equilibrium is displaced to the right. Lone e-pairs can be protonated. Molecules which are both acids and bases are called