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1、第十六章碳水化合物多糖概述糖：多羟基醛、多羟基酮化合物糖单糖葡萄糖、果糖低聚糖蔗糖、麦芽糖、乳糖淀粉、纤维素16.1 葡萄糖的结构一、开链结构C6H12O61. HIP还原生成正己烷直链结构2. 与乙酸酐反应消耗5mol酸酐五个羟基3. 与HCN反应生成一元羟基腈一个羰基4. 与溴水反应生成一元羧酸一个醛基HOCH2CHCHCHCHCHOOHOHOHOH*5. Fischer投影式：Fischer假定(+)葡萄糖为D型CHOOHOHOHOHCH2OHCHOOHOHOHCH2OHHOCHOOHOHOHCH2OHHO（1） （2） （3）（4）HHHHHHHHHHHHCHOHOHOHCH2OHHO
2、HOHHHCHOOHOHHOHCH2OHCHOOHHOHCH2OHHOCHOOHHOHCH2OHHO（5） （6） （7）（8）HHHOHHHHOHHHHOHCHOHHOHCH2OHHOHOHHOHFischer确定葡萄糖结构1. HNO3氧化得到旋光性的葡萄糖二酸（1）与（7）不符合2. 葡萄糖降解后得到()阿拉伯糖，用HNO3氧化得到旋光性二酸（2）、（5）与（6）不符合3. ()阿拉伯糖升级后得到()葡萄糖和()甘露糖，二者氧化后得到旋光性糖二酸（8）不符合4. 将（3）中CHO与CH2OH互换，得到另一种糖，氧化后得同种二酸CHOOHOHOHCH2OHHOCH2OHOHOHOHCHOH
3、OCHOCH2OHHOHOOHHOOCOOHOHOHOHCOOHHOHHHHHHHHHHHHHHHH5. 将（4）中CHO与CH2OH互换，为原来化合物，如果有另外一种己醛糖氧化生成葡萄糖二酸，则()葡萄糖的结构为（3）CHOOHCH2OHHOOCOOHOHOHOHCOOHHOHOHOCOOHOHCOOHHOHOHOHHHHHHHHHHHHL()古罗糖葡萄糖的Fischer投影式CHOCH2OHCHOOHOHOHCH2OHHOHHHH二、环状结构1.变旋光现象：常温水中重结晶：m.p. 145 C，D=112 110C重结晶m.p. 150 C，D=19 放置,比旋光度逐渐变成52.7 2.
4、形成糖苷时, 只与1mol甲醇反应3. 不与NaHSO3反应CHOOHOHOHCH2OHHOHHHHOHOHOCH2OHHOHHHHOHOHOHOHOCH2OHHOHHHHOHOH+-D-(+)-吡喃葡萄糖m.p. 148150CD=+18.7-D-(+)-吡喃葡萄糖m.p. 146CD=+11263.6% 36.4%CHOOHOHOHCH2OHHOHHHHCOHOHOCH2OHHOHHHHHOHCH3OHCOHOHOCH2OHHOHHHHHOCH3半缩醛式 甲基葡萄糖苷（缩醛）葡萄糖的Haworth式OCH2OHHHOHOHHHOHHOHOCH2OHHHOHOHHHOHOHH-D-(+)-吡
5、喃葡萄糖-D-(+)-吡喃葡萄糖CHOOHOHOHCH2OHHOHHHH123456CH2OHCHOHOHHOHOHHHOH654321旋转C4C5OHCHOCH2OHHHOHOHHHOH654321OCH2OHHHOHOHHHOHHOHOCH2OHHHOHOHHHOHOHH-D-(+)-葡萄糖-D-(+)-葡萄糖-D-(+)-吡喃葡萄糖-D-(+)-吡喃葡萄糖OHHOHHOHHOH2CHOHOHHOHHOHHOHHOH2CHOHHOHCH2OHOHOHCH2OHHOHHHOD-(-)果糖16.2 果糖的结构OHHOHHOHOHHOHHHOHHOHOHHCH2OHOHHHOCH2OHOHHHO
6、HHOHOHHOHCH2OHOHOHCH2OHHOHCH2OHOHHOHOHCH2OHHCH2OHOHOHH-D-(-)呋喃果糖-D-(-)呋喃果糖-D-(-)吡喃果糖-D-(-)吡喃果糖甲基-D-(+)-吡喃葡萄糖苷16.3 单糖的化学性质一、成苷反应OCH2OHHHOHOHHHOHHOH CH3OH无水HClHCl水溶液OCH2OHHHOHOHHHOHHOCH3CHOHOHCH2OHHOHNaBH4CH2OHHOHCH2OHHOHD()苏阿糖二、还原反应CHOOHOHCH2OHHOHHHOHHAg(NH3)2+COOHOHOHCH2OHHOHHHOHH+ Ag菲林试剂COOHOHOHCH2
7、OHHOHHHOHH+ Cu2O三、氧化反应还原糖还原糖CH2OHOHOHCH2OHHOHHHOAg(NH3)2+或菲林试剂AgCHOOHOHCH2OHHOHHHOHHCCOHOHCH2OHHOHHHOHHOHCH2OHOHOHCH2OHHOHHHOCHOOHOHCH2OHHOHHHOHHBr2, H2OCOOHOHOHCH2OHHOHHHOHHCOOHOHOHCOOHHOHHHOHHHNO3CHOOHOHCH2OHHOHHHOHH5HCOOH + HCHOHIO4OHCHOHCH2OH+POOHOHHOOHCHOHCH2OPOOHOHD-甘油醛-3-磷酸酯四、成酯反应五、脱水反应CHOOHO
8、HCH2OHHOHHHOHH浓酸OHOH2CCHO5羟甲基糠醛CHOOHOHCH2OHHOHHHOHHCH2OHOHOHCH2OHHOHHHOCHOOHOHCH2OHHOHHHHHO3C6H5NHNH2HCCOHOHCH2OHHOHHHNNHC6H5NNHC6H53C6H5NHNH23C6H5NHNH2黄色晶体鉴别糖六、成脎反应CHOOHOHCH2OHHOHHHCNCNOHOHCH2OHHOHHHOHHCNOHOHCH2OHHOHHHHHOH3OOHOCH2OHHOHHHOHHONa(Hg)pH=3.5-4CHOOHOHCH2OHHOHHHOHHCHOOHOHCH2OHHOHHHHHO七、递升
9、反应CHOOHOHCH2OHHOHHHOHHBr2COOHOHOHCH2OHHOHHHOHHCa(OH)2COO-OHOHCH2OHHOHHHOHH2Ca2+H2O2,Fe3+COOHOHOHCH2OHHOHHHOCHOOHOHCH2OHHOHHH八、递降反应Ruff降解法16.4 二糖和多糖一、二糖1. 麦芽糖C11H22O11水解：生成2分子葡萄糖可用-葡萄糖苷酶水解还原糖变旋现象：D=+168D=+112变为D=+136麦芽糖的结构OHHOHHOHHOH2CHOHOHOHHHOHHOH2CHOHOHH-1,4-苷键OHHOHHOHHOH2CHOHOHOHHHOHHOH2CHOHOHHOHHOHHOHHOH2CHO
