NaOH
OH CHOH
D-葡萄糖
CH3 O
CH2 OCH3 O
CH3 O
CHOCH3 OCH3
五甲基-D-葡萄糖
29
单糖的反应－生成酯
HO
CH2OHO
HO
OH
OPO3H2
1-磷酸-D-葡萄糖酯
(五乙酰基-D-葡萄糖)
OPO 3H2
HO
CH2 O
HO
OH CHOH
6-磷酸-D-葡萄糖酯
30
二糖－蔗糖(Sucrose)
16
直立键(a键)与平伏键(e键)
17
吡
喃
葡
(-D-吡喃葡萄糖)
萄
糖
的
构
象
(-D-吡喃葡萄糖)
18
单糖的反应－生成糖苷
C H 2O H O
OH HO
OH OH
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
C H 2O H O OH
OH HO
OH
CH3OH, HCl
C H 2O H O
OH HO
CHO
H
OH
H
OH
H
OH
C H 2O H
D-(–)-核糖
CHO
H
OH
H
OH
H
OH
H
OH
C H 2O H
D-(+)-阿洛糖 D-(+)-Allose
CHO
HO
H
H
OH
H
OH
H
OH
C H 2O H
D-(+)-阿卓糖 D-(+)-Altrose
CHO
HO
H
H
OH
H
OH
C H 2O H
D-(–)-阿拉伯糖
CHO
H
OH
C H 2O H
C H 2O H
Some diabetes self-test kits sold in drugstores for home use employ Benedict’s test.
Fundamentals of Organic Chemistry John McMurry
24
9
缩醛与半缩醛
(半缩醛)
(缩醛)
10
葡萄糖的开链和氧环式结构
哈沃斯投影式 (Haworth projection)
-D-葡萄糖
-D-葡萄糖
正位异构体(Anomer,异头体) 11
葡萄糖的开链结构和性质
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-(+)-葡萄糖 D-(+)-Glucose
碳骨架 用钠汞齐还原生成己六醇；用HI进 一步还原生成正己烷。
CHO
HO
H
HO
H
HO
H
H
OH
C H 2O H
D-(+)-太罗糖 D-(+)-Talose
己醛糖(Aldohexose) 8
单糖的结构与名称(5)
C H 2O H O
C H 2O H
二羟基丙酮 Dihydroxyacetone
C H 2O H O
HO
H
H
OH
H
OH
C H 2O H
D-(–)-果糖 D-(–)-Fructose
HO
HHOH来自HOHC H 2O H
D-(–)-来苏糖
CHO
H
OH
H
OH
HO
H
H
OH
C H 2O H
D-(–)-古罗糖 D-(–)-Glulose
CHO
HO
H
H
OH
HO
H
H
OH
C H 2O H
D-(–)-艾杜糖 D-(–)-Idose
CHO
H
OH
HO
H
HO
H
H
OH
C H 2O H
D-(+)-半乳糖 D-(+)-Galactose
(淀粉，纤维素)
2
糖的来源
Carbohydrates are everywhere; they occur in every living organism and are essential to life. The sugar and starch in food, and the cellulose in wood, paper, and cotton are nearly pure carbohydrate. Modified carbohydrates form part of the coating around living cells, other carbohydrates are found in the DNA that carries genetic information, and still others are used as medicines.
OH
HO
H
H
OH
H
OH
C H 2O H
D-葡萄糖
托伦斯试剂
COOH
H
OH
HO
H
+ Ag+ (银镜)
H
OH
H
OH
C H 2O H
D-葡萄糖酸
23
单糖的反应－和费林(本尼迪特)试剂的作用
CHO
COOH
H
OH
H
OH
HO
H
本尼迪特试剂 H O
H
H
O H (或托伦斯试剂) H
O H + Cu2O(红色)
H
OH
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-(+)-葡萄糖 D-(+)-Glucose
CHO
HO
H
HO
H
H
OH
H
OH
C H 2O H
D-(+)-甘露糖 D-(+)-Mannose
己醛糖(Aldohexose)
7
单糖的结构与名称(4-2)
CHO
H
OH
HO
H
H
OH
C H 2O H
D-(+)-木糖
CHO
单糖的反应－被高碘酸氧化
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
5IO4－
HCOOH
+
HCOOH
+
HCOOH
+
HCOOH
+
HCOOH
+
HCHO
反应定量进行
25
单糖的反应－催化加氢
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-葡萄糖
CH 2 OH
H
OH
H2
HO
H
Ni
H
OH
H
OH
C H 2O H
醛基 可以与羟胺、苯肼等羰基试剂作用。 用溴水氧化，得到己酸。
五个羟基 与乙酸酐作用生成五酰基衍生物。
12
葡萄糖的氧环式结构和性质－变旋（光现象）
-D-葡萄糖
(36%)
[]D=+112.2º
m.p.=146ºC
变旋光现象
任何纯净的葡萄糖水溶 液的比旋光最终都变为
[]D=+52.6º的现象
-D-葡萄糖
COOH
D-葡萄糖
D-葡萄糖二酸
20
单糖的反应－被溴水氧化
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-葡萄糖
COOH
H
OH
Br2
HO
H
H2O
H
OH
H
OH
C H 2O H
D-葡萄糖酸
21
费林试剂、托伦斯试剂和本尼迪特试剂
斐林试剂(Fehling’s reagent)：硫酸酮和碱性酒石酸钾钠 托伦斯试剂(Tollens’ reagent)：硝酸银的氨水溶液 本尼迪特试剂(Benedict’s reagent)：柠檬酸、硫酸铜、碳酸钠
L-(–)-甘油醛 L-(–)-Glyceraldehyde
丙醛糖(Aldotriose, an aldose)
4
单糖的结构与名称(2)
CHO
H
OH
H
OH
C H 2O H
D-(–)-赤藓糖 D-(–)-Erythrose
CHO
H
OH
C H 2O H
D-(+)-甘油醛
CHO
HO
H
H
OH
C H 2O H
sucrose, []D=+66.5º, to a glucose/fructose mixture, []D=22º. Insects such as honeybees have enzymes
called invertases that catalyze the hydrolysis of sucrose to glucose + fructose. Honey, in fact, is primarily a mixture of glucose, fructose, and sucrose.