1、 构象异构同分异构构型异构顺反异构对映异构立体异构构造异构碳架异构官能团异构位置异构互变异构 (动画)左旋乳酸，由蔗糖发酵得到右旋乳酸，由肌肉运动产生实物镜子镜象CHOHCOOHH3CCHCOOHCH3HOCH3-CH-COOHOHCH3-CH-CH-CH3OHCH3CH3-CH-CH2-CH3Br*CH3H3C无对称面CCHH3CHCH3对称面对称面H3CCH3HHOCOHCOOHHHCHHHCl三个二个一个多个 CH3H3CCOOHCH3CH3COOHHHHHii 偏振光光源观察Nicol棱 镜检偏镜Nicol棱 镜起偏镜I=I Cos 20I0I Nicol棱 镜检偏镜Nicol棱 镜起
2、偏镜光源盛液管观察偏振光旋转后的偏振光I0I式中：Clt 6.4.1 对映体和外消旋体的性质对映体和外消旋体的性质6.4.2 构型的表示方法构型的表示方法6.4.3 构型的标记方法构型的标记方法 实物镜子镜象CHOHCOOHH3CCHCOOHCH3HOCCH3BrCH3CH2HCCH3BrCH2CH3H实物镜子镜象 透视式：直观，但书写麻烦，不适用于复杂化合物Fischer投影式：使用方便，适用于简单和复杂化合物两种方法CHOHCOOHH3C透视式投影式FischerCH3COOHOHHCCOOHCH3OHH观察COOHCH3OHH 构型不变(b)(b)CH3COOHHHOCH3COOHOHH
3、。180构型改变(b)CH3COOHOHHCH3COOHOHH与 不同(b)（）90。构型改变(b)（）CH3OHHHOOCCH3COOHOHH与 不同(b)270。构型改变(b)(b)CH3COOHHHO与 不同(b)CH3COOHOHH脱离纸面旋转CH3COOHHHO与 不同(b)CH3COOHOHH脱离纸面旋转。180。180 CH3COOHOHHCOOHHCH3OHHOHH3CHOOC=(S)(S)(S)(R)(S)OHHCOOHCH3CH3COOHOHH(S)HOOCHOHCH3CH3COOH构型改变HCOOH构型改变 甘油醛CHOCH2OHOHH(+)-CHOCH2OHHHO甘油醛
4、(-)-D-型L-型标准：CH2OHOHHCOOHOHHCOOHCH3HCOOHCH3H2NHCOOHH2NCH2OHL丝氨酸L丙氨酸D甘油酸D乳酸OHHCOOHCH3Na-HgD-(+)-D-(-)-甘油醛乳酸CHOCH2OHOHHCH2OHOHHCOOHOHHCOOHCH2NH2OHHCOOHCH2BrNaNO2+HBrHNO2HgO 和(a)(b)CHCOOHCH3HOCHOHCOOHH3C (a)(b)CHCOOHCH3HOCHOHCOOHH3C观察观察OHCOOHCH3OHCOOHCH3 顺时针方向为逆时针方向为R型S型例2CHCOOH观察ClBrCOOHBrCl 顺时针方向为R型：
5、为逆时针方向S型CH观察ClCl：例3CH3CH2OHCH2OHCH3 顺时针方向为R型CH：例CH2OHCH2OH4CHOOHOHCHO观察 CH2OHOHHCHORCH3HCOOHOHRSHOHCH3HCOOHHOSOHCOOHCH3CHOOHCHOCH2OHCH2OH乳酸甘油醛乳酸甘油醛CH3CH2CH3CH2OHHSCH2OHCH2CH3CH3HOCOOHC6H5OHCHCH2CH3CH3CHCH2OHHSHOHCOOHC6H5S COOHCOOHOHHHClCOOHHOHClCOOHHOHCOOHCOOHHHClCOOHCOOHHOHHCl()I()I I()I I I()IV(2R
6、,3R)(2S,3S)(2R,3S)(2S,3R)CH2OHHCHOHOHOHOHCH3CH3HHClHOCH2OHCHOHHOHClCH3CH3HHOH赤藓糖苏阿糖赤式苏式相同的原子在同侧相同的原子不在同侧 赤式苏式赤式前后ClH3CHCH3ClHCH3HClClOHHHOClHCH3HCH3ClHHCH3OHH3C苏式前后前后前后前后碳旋转方向不同前后碳旋转方向相同 (2R,3S)(2S,3R)I I II IV VCOOHCOOHOHHHHOCOOHCOOHHOHHOHOHCOOHCOOHHHOHHHCOOHHOCOOHHOI I(2R,3R)(2S,3S)I I I I CH3CH2C
7、H2CH3CH3CHCH2CH3ClCl2+其他产物产生第一手性碳前手性碳*外消旋体 如果在一个旋光体分子里生成第二个手性碳原子，生成非对映体的量是不相等的。例如：手性环境(2S,3S)-二氯丁烷(2S,3R)-二氯丁烷29%71%非对映体，产量不等+HClCH3CH3HHHClCH3CH3ClHHClCH3CH3HClCl2(2S)-氯丁烷 (羰基处于非手性环境,a方式与b方式机会相等)abCH3CHCOOHOH(外消旋体)2-羟基丙酸NaBH4C=OHOOCH3C但：CH3-C-COOHOH2NC6H5HCH3+COCOCH3HNC6H5HCH3NaBH4手性胺(羰基处于手性环境,a方式与
8、b方式机会不等)abC CONH CC6H5CH3HCH3HHO+含量不等的非对映体C CONH CHCH3HCH3C6H5HO水解 分离CH3HHOC COOH+(+)-2-羟基丙酸(-)-2-羟基丙酸CH3HOHHOOC C +(-)-R3N(+)-RCOOH(-)-RCOOH(-)-R3N(-)-R3N(+)-RCOOH(-)-RCOOH外消旋体溶解度相同重结晶不能分离非对映体混合物溶解度不同重结晶可分离旋光性生物碱(+)-RCOOH(-)-RCOOH(-)-R3N(-)-R3N(+)-RCOOH(-)-R3N(-)-RCOOH(-)-R3N(+)-RCOOH(-)-R3N+HCl(-)
9、-RCOOH(-)-R3N+HCl重结晶HClHCl(-)-R3N非对映体COOHCOOR-(+)R3N-(-)COOR-(-)COOH R3N-(-)分离水解水解(-)-ROH(+)-ROH(+)-ROH(-)-ROH+OOOCOOHCOOR-(+)COOR-(-)COOH外消旋体外消旋体 CH3HHCH3CH3HHCH3即反-1,4-二甲基环己烷 顺-1,4-二甲基环己烷 即HHCH3CH3HCH3HCH3 H3C稳定CH3CH3CH3HHHH稳定不CH3CH3反-1,4-二甲基环己烷 顺-1,4-二甲基环己烷 HHHHHHHH顺式十氢萘反式十氢萘HHHHHHHH空间障碍大，能量高空间障碍
10、小，能量低Pd-C催化剂。530 C，91%9%顺式与反式十氢萘互为构型异构体，是两种不同的化合物，它们在室温下不能相互转变。但在530、Pd-C催化剂存在下，两者可达到动态平衡：HHCOOHHOH2CHHCH2OHHOOCHHCOOHHOH2CHHCH2OHHOOC()I()I I()I I I()IV顺式对映体顺式反式反式对映体 CH3HHCH3CH3CHHH3CHHCH3H3对映体反式反式HHCOOHHHHOOCCOOHHOOC()I I()I I I顺式HHCOOH()IHOOC内消旋体COOHCO2HHHCOOHHOOCHHHOOCCOOHHH顺式反式对映体内消旋体反式(有 )HHC
11、H3CH3HHHHCH3H3CHHH3CHHH3CHHCH3HHCH3HH邻位交叉式部分重叠式互为实物与镜像构象对映体互为实物与镜像构象对映体HHCH3HHCH3HHCHCH3HH3HHCCH3HHH3CH3HHHHCH3邻位交叉式对位交叉式部分重叠式全重叠式非实物与镜像的关系构象非对映体非实物与镜像的关系构象非对映体 两个双键相互垂直，构成了手性轴spC CC CC Csp2sp2HCH3CH3H3CH3CHHH无对称面无对称面对映体CCCCCC CH3HHCH3CH3HHCH3 位阻作用COOHHOOCNO2O2NCOOHHOOCNO2O2N对映体手性分子手性分子 BrClBrClBrClBrCl 例例1：对烯烃加溴反应机理的验证：对烯烃加溴反应机理的验证：CCBrBr+CCBrCCBrBr慢快Br-烯烃+Br2CH3CH3HHCH3CH3HHCH3HHCH3赤式赤式CCBrBrCCBrBrC=CBrBrCH3HCH3HBrBrCH3CH3HHCH3BrBrCH3HHBr2Br2+CCBrBrCH3CH3HHCCBrBrCH3CH3HHC=CCH3HHCH3苏式苏式BrBrCH3HCH3HBrBrCH3CH3HHCH3BrHCH3HBrCH3BrHCH3HBrBr2CH3BrHCH3HBrCH3BrHCH3HBr+
