Alcohols,ethers and phenols1课件.ppt

Characteristics of the reaction: Condensation(缩合反应) 2. Only for primary alcohols 3. The temperature of condensation is lower than elimination. 4. SN2 mechanism 1,5-Pentanediol (1,5-戊二醇) Oxane ( 烷)(76%) A. Oxidation of primary alcohols 3-Fluoro-1-propanol (3-氟-1-丙醇) 3-Fluoropropanoic acid (3-氟丙酸) (74%) PCC reagent is soluble in CH2Cl2 P 263 9.3.3 Oxidation of alcohols Secondary alcohols [O] ketones B. Oxidation of secondary alcohols PCC doesn’t attack C=C bond Citronellol (香茅醇) Citronellal (82%) (香茅醛) Chromic acid H2CrO4 C. Oxidation of vicinal diols Vicinal diols react with HIO4, the C-C bond is broken to form carbonyl compounds AgNO3 is added to identify the vicinal diols AgIO3 Ch.P225,(3) Cyclohexanol Cyclohexanone(85%) 9.4 Reactions of phenols Acidity Acylation Aromatic Electrophilic substitution Formation of aryl ethers The sites of reactions 9.4.1 Acidity of Phenols pKa = 18 pKa = 9.89 pKa = 4.74 TABLE 1 The acidity constants of phenols Substi- tuents pKa (25℃) o- m- p- -H -CH3 -Cl -NO2 -OCH3 10.20 10.01 10.17 8.11 8.80 9.20 7.17 8.28 7.15 9.98 9.65 10.21 9.89 9.89 9.89 pKa (25℃) 2,4-Dinitro 2,4,6-Trinitro (picric acid) (苦味酸) 3.96 0.38 Substi- tuents P256,8.3 Substituted phenols: Substuents on the position o- or p- Electron - releasing group Acidity is decreased Electron – withdrawing group Acidity is increased pka = 10 Electron delocalization in phenoxide ion: 9.4.2 Electrophilic aromatic substitutions A hydroxyl group is a very powerful activating substituent: Bromination: Sulfonation: Rate control Equilibrium control P266; Ch.P322,(2) 9.4.3 Acylation of phenols Acylating agents: acyl halides and carboxylic acid anhydrides Fries rearrangement: Phenol benzoate p-hydroxylbenzopheone （对-羟基二苯酮）(64%) (9%) Phenolic Esters （酚酯） Conversion of aryl esters to aryl ketones. Ch.P319(丙) 9.4.4 Kolbe-Schmitt reaction: Carboxylaltion of phenols Sodium phenoxide CO2 Heated un