《有机化学》课件第18章 碳水化合物

HO
CH2OHO
-D-呋喃果糖基--D-吡喃葡萄糖苷 (-D-吡喃葡萄糖基--D-呋喃果糖苷)
HO
HO OH
O O
C12H22O11
CH2OH
OH CH2OH
非还原糖
分子中无苷羟基
无变旋光现象
不能生成脎
31
蔗糖的水解
C12H22O11 + H2O
H+ 转化反应
C6H12O6 + C6H12O6
蔗糖
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
14
吡喃糖与呋喃糖
O
吡喃(Pyran)
C H 2O H O
OH
HO
OH
OH
-D-吡喃葡萄糖
吡喃糖 (Pyranose)
O
呋喃(Furan)
HOH2C O OH
HO CH2OH
OH
-D-呋喃果糖
呋喃糖 (Furanose)
15
环己烷的构象
所有的C－H键都 处于交叉式的位置
所有化学键的 夹角都是109.5
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
(64%)
[]D=+18.7º
m.p.=150ºC
13
果糖的开链和氧环式结构
-D-果糖
-D-果糖
INTRINSIC CHEMISTRY OF FRUCTOSE Robert S. Shallenberger New York State Agricultural Experiment Station, Cornell University, Geneva, New York 14456, USA Pure & Appi. Chem. Vol. 50, pp.l409-1420.
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
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.
HO
H
HO
H
H
OH
C 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
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
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
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
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
Fundamentals of Organic Chemistry John McMurry
nCO2 + mH2O + 太阳能 叶绿素 Cn(H2O)m + nO2
3
单糖的结构与名称(1)
RH
CHO OH
C H Baidu NhomakorabeaO H
D-(+)-甘油醛 D-(+)-Glyceraldehyde
CHO
HO
HS
C H 2O H
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
OCH3
OH
甲基--D-吡喃葡萄糖苷
糖苷
Glycoside
CH3OH, HCl
CH 2 OH O OCH3
OH HO
OH
甲基--D-吡喃葡萄糖苷
19
单糖的反应－被硝酸氧化
CHO
COOH
CH2OHO HO
H
OH
H
OH
HO
H HNO3 H O
H
H
OH
HO
OH CHOH
H
OH
H
OH
H
OH
D-吡喃葡萄糖
C H 2O H
OH
C H 2O H
D-(–)-核糖 D-(–)-Ribose
C H 2O H
D-(–)-阿拉伯糖 D-(–)-Arabinose
C H 2O H
D-(+)-木糖 D-(+)-Xylose
C H 2O H
D-(–)-来苏糖 D-(–)-Lyxose
戊醛糖(Aldopentose) 6
单糖的结构与名称(4-1)
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
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
H 2C6H5NHNH2 H O
H
2C6H5NHNH2 H O
H
H
OH
H
OH
H
OH
H
OH
H
OH
H
OH
C H 2O H
C H 2O H
C H 2O H
D-葡萄糖
D-葡萄糖脎
D-甘露糖
差向异构体(Epimer)
只有一个碳原子构型不同的非对映体
28
单糖的反应－生成醚
HO
CH2OHO
(CH3)2SO4
HO
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)
D-葡萄糖醇
26
单糖的反应－被硼氢化钠还原
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-葡萄糖
1. NaBH4 2. H2O
CH 2 OH
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-葡萄糖醇
27
单糖的反应－生成脎
CHO
C H NNHC 6 H 5
CHO
H
OH
C NNHC 6 H 5
HO
H
HO
[]D=+66.5º
(转化糖)
D-葡萄糖
D-果糖
[]D=+52.6º []D= –92º
(1:1混合物[]D= –22º)
Sucrose, or ordinary table sugar, is probably the most abundant pure organic chemical in the world. Whether from sugar cane (20% by weight) or from sugar beets (15% by weight), and whether raw or refined, all table sugar is sucrsoe.
(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.
Fundamentals of Organic Chemistry John McMurry
32
Sucrose—John McMurry
Sucrose is a disaccharide that yields 1 equivalent of glucose and 1 equivalent of fructose on hydrolysis. This 1:1 mixture of glucose and fructose is often referred to as invert sugar because the sign of optical rotation changes (inverts) during the hydrolysis from
D-(–)-苏阿糖 D-(–)-Threose
丁醛糖(Aldotetrose)
5
单糖的结构与名称(3)
CHO
CHO
H
OH
HO
H
H
OH
H
OH
C H 2O H
D-(–)-赤藓糖
CHO
CHO
C H 2O H
D-(–)-苏阿糖
CHO
CHO
H
OH
HO
H
H
OH
HO
H
H
OH
H
OH
HO
H
HO
H
H
OH
H
OH
H
OH
H
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。
COOH CHOH CHOH COOH
酒石酸 (Tartaric acid)
C H 2COOH C (OH) COOH C H 2COOH
柠檬酸 (Citric acid)
还原糖(Reducing sugar)
能被费林试剂、托伦斯试剂或本尼迪特试剂氧化的糖
22
单糖的反应－和托伦斯试剂的作用
CHO
H
《有机化学》课件第18章 碳水化合 物
糖的分类
单糖(Monosaccharide) 不能水解成更简单多羟基醛酮的碳水化合物
(葡萄糖，果糖) 低聚糖(寡糖，Oligosaccharide) 水解时能生成2~10个单糖的碳水化合物
(蔗糖，麦芽糖) 多糖(Polysaccharide) 水解时能生成10个以上单糖的碳水化合物