生物化学 Chapter 13 Spectroscopy 2.ppt

Chapter 13  Spectroscopy Chemical Shifts of Representative Types of Protons 1 Chapter 14 Organometallic Compounds Chapter 15 Alcohols,Diols,and Thiols Phosphorous Tribromide: PBr3 仲醇氧化成酮，并易被高锰酸钾进一步氧化使碳碳键断裂，故很少用于合成酮。 叔醇在中性，碱性下不易被KMnO4氧化，在酸性条件下脱水成烯，尔后继续氧化，碳碳键断裂，生成小分子化合物 在碱性条件制得的，新制的MnO2可将碳上为不饱和键的伯，仲醇分别氧化为相应的醛酮，不饱和键不受影响。 Dehydration of Diols Al2O3/△ —醇脱水反应条件:不会发生重排反应 §15.20 Pinacol Rearrangement SN2 type Reactions of Epoxides( Reaction under the Basic catalyst) SN1 type Reactions of Epoxides(Reaction under the acidic catalyst) 14.5.2 Claisen Rearrangement of Allyl Aryl Ethers o-Nitrophenol: have boiling points that significantly lower than those of the meta and pare isomer because of its intramolecular hydrogen bond. The Effect of R- in SN1 reactions of alcohols: Reactivity order : ? (CH3)3C-? ? (CH3)2CH-?? ? CH3CH2-? ? CH3- Step 1 Step 2 Step 3 SN1 Mechanism The Effects of R- in SN2 reactions of alcohols: Reactivity order :? CH3-? ? CH3CH2-? ? (CH3)2CH- ? (CH3)3C- Mechanism:(SN2) 1 ° 2 ° 3 ° ROH ZnCl2 + C. HCl 室温下不反应 5分钟内反应 立即反应（出现混浊） Thionyl(亚硫酰) chloride 81% 82 % Thionyl chloride: SOCl2 2-Ethyl-1-butanol 1-Chloro-2-ethylbutane 2-Octanol Phosphorous acid Isobutyl alcohol Isobutyl bromide Cyclopentanol Cyclopentyl bromide 作为氧化剂的铬酸形式有： Na2Cr2O7 + 40 ~ 50% H2SO4 CrO3 + HAC CrO3吡啶络合物 选择性氧化剂:可在室温下将醇氧化成醛(C5H5N)2CrO3PCCPDC KMnO4: 醇在冷，稀，中性高锰酸钾下不被氧化 在较强烈条件下（如加热）下可氧化伯，仲醇 Mechanism For? Of Alcohol Condensation To Give An Ether 不饱和键不受影响。 Pinacol 频那醇 Pinacolone 频那酮 Chapter 16 Ethers, Epoxides Epoxides are significantly more reactive than simple ethers. 过氧化物的检验： 加入等体积 2 % KI/HAc +淀粉溶液 Spectroscopic Analysis of Ethers IR? - presence of C-O Absorbance (cm-1) Interpretation 1200 -1250 (strong, broad) C-O stretch 1H NMR -? H-C-O-C unit is the most easily recognized (similar to H-COH of alcohols) Resonance (ppm) Interpretation 3.3 - 4.0? H-C-O (deshielding due to O) Mass Spectrometry Loss