台灣大學開放式課程

有機化學乙
蔡蘊明 教授

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Chapter 22 Carbohydrates

※ Introduction
General formula: Cx(H2O)y
Simple carbohydrates:
sugars, saccharides (醣類)
例 sucrose
glucose -ose ending
maltose
Viewed from functional groups
polyhydroxy aldehydes or ketones
Classification
monosaccharides 單醣 (無法進一步水解)
disaccharides
trisaccharides
oligosaccharides (2-10 單醣)
polysaccharides (>10 單醣)

1 maltose H+ 2 glucose
H2O
disaccharide

1 sucrose H+ 1 glucose + 1 fructose

H2O
 starch
composed of n glucose
cellulose

H2O
monosaccharide no hydrolytic cleavage

 Biologically
enzyme
xCO2 + yH2O + solar E carbohydrates + xO2

carbohydrates + xO2 xCO2 + yH2O + E

E
ADP ATP

ATP ADP
E
※ Monosaccharides
◎ Classification

CH2OH
CHO
C O
CHOH
CHOH
CHOH
CHOH
CH2OH
CH2OH
a ketose an aldose
a ketopentose an aldotetrose triose
hexose
functional number of etc.
group carbons
◎ D and L designation

glyceraldehyde
CHO CHO CHO
H HO
OH H
*CHOH :
CH2OH CH2OH CH2OH

an aldotriose

CHO CHO
H OH HO H
CH2OH CH2OH

R-(+) S-(−)
Designate as: D L
Use D- and L-glyceraldehyde as a reference
for other sugars

CHO
CHOH
CHOH
H C OH
CH2OH
Highest numbered chiral carbon:
same configuration as D-glyceraldehyde
CH2OH : an D-aldopentose
C O
CHOH
CHOH
HO C H Same configuration as L-glyceraldehyde
CH2OH : an L-ketohexose
 ◎ Structure (Emil Fischer)
D-(+)-glucose
Diastereomers: differed by only
one carbon
CHO CH2OH CH2OH
H OH OH
O O
HO H OH + OH
H OH
a hemiacetal
OH OH OH carbon or
H OH OH OH
Haworth
CH2OH
projection
anomeric
carbon
CH2OH CH2OH
HO O HO O
HO H HO OH
HO HO
OH H

α-D-(+)-glucopyranose β-D-(+)-glu-----
the two
C-1 (anomeric) OH
isomers are
and C-6 are trans
A shorthand C-1 OH and C-6 anomers
representation for writing are cis 變旋異構
◎ Mutarotation
Ordinary D-(+)-glucose crystallized from water at rt
 mp 146 oC, [α] = +112o
Crystallized at 98 oC
 another form: mp 150 oC, [α] = +19 o
In solution: both turn into +52.7 o
Reason: CHO
CH2OH H OH CH2OH
HO O HO H O
HO
HO H HO OH
H OH
HO HO
OH H OH H
α CH2OH α
mp 146 oC mp 150 oC
at equilibrium
[α] = +112o [α] = +19o
[α] = +52.7o
 36% α + 64% β
more stable
 HO OH HO OH
HO O O
HO
HO H HO OH

OH H

α-D-mannopyranose β-D-mannopyranose
69% 31%
more stable
(anomeric effect)
◎ Glycosides (醣苷 )
CHO
HO H OH
HO O HO H
HO OH
H OH
HO
H OH
CH2OH
CH3OH, HCl

HO HO
HO O O
+ HO
HO HO OCH3
HO OCH HO
3

acetals
methyl α-D-glucopyranoside methyl β-D-glucopyranoside
mp 165 oC, [α] = +158o mp 107 oC, [α] = −33o
Mechanism:

HO HO HO
O H+ O −H2O O β
HO HO HO
HO OH HO OH2 HO
HO HO HOCH3
HO
α
 Glycosides:
no mutarotation
stable in basic condition
hydrolyzes in acidic condition
HO HO
O H+, H2O O
HO HO
HO OR HO OH + ROH
HO HO
aglycone

例 HO
O CH2OH
HO salicin
HO O
HO from willow bark

aglycone
※ Reactions
◎ Isomerization of monosaccharides
CHO O− OH
H OH OH O−
−
HO H OH
HO H HO H
H OH
H OH H OH
H OH
H OH H OH
CH2OH
CH2OH CH2OH

CHO CH2OH
HO H C O
HO H HO H
H OH H OH
*Formation of glycosides H OH H OH
stops this isomerization CH2OH CH2OH
D-mannose D-fructose
◎ Methylation
HO H3CO
O NaOH H3CO O
HO
HO OCH3 H3CO OCH3
CH3OSO3CH3
HO CH3O
exhaustive methylation
a pentamethyl derivative

CHO H3O+
H OCH3
H3CO H H3CO
H3CO O
H OCH3
H3CO OH
H OH
CH3O
CH2OCH3
◎ Ester formation
HO AcO
O Ac2O O
HO AcO
HO py AcO
HO OH AcO OAc

◎ Other protection
HO O
OH O OH
O O
HO H2SO4 O
HO OH OO
D-galactopyranose

Only the cis diols form

cyclic acetals with acetone
 acetonides
◎ Oxidation CO2H
 Bendict’s reagent: Cu2+ complex of citrate HO CO2H
CO2H
Fehling’s reagent: Cu2+ complex of tartrate
O citric acid

R H
aldose
reducing
Cu2+ + or sugars
blue
R
OH
O
ketose
Cu2O
brick-red

 Positive Tollen’s test

 reducing sugars
 hemiacetals the open form

can be oxidized
But
acetals are non-reducing sugars

R'O OR" R''O OR"'

R R R'
 Bromine water oxidation
CHO Br2 COOH
(CHOH)n (CHOH)n
H2O
CH2OH CH2OH
aldose pH = 6.0 aldonic acid
Mechanism:
HO HO HO
HO O O Br O
HO HO
HO OH HO O HO
HO H HO H HO O
B−

CH2OH COOH
HO H H OH
O
HO H
OH O
H OH
H OH
OH
CH2OH
D-glucono-γ-lactone D-gluconic acid
α-form does not react
HO
HO O
HO H
H HO
H Br O
antiperiplanar requirement for
elimination

sterically unfavorable
 Nitric acid oxidation
CHO HNO3 COOH
(CHOH)n (CHOH)n
CH2OH COOH
aldose aldaric acid

例
CHO COOH
H OH H OH
HO H HNO3
HO H
H OH H OH
H OH H OH
CH2OH COOH

D-glucaric acid
 O COOH
COOH C
CHOH
CHOH CHOH
HC
CHOH −H2O O
CHOH or CHOH or δ-lactone
CHOH HC O
CHOH
CHOH CHOH
C
COOH COOH O

γ-lactone
  Periodate oxidation

C OH HIO4 C O
+ HIO3 + H2O
C OH
C O

−
O
C O
I O
C O
O

例
H H
C O C O
CH2OH CH2OH HO
HIO4 H 2HIO4 H
CHOH CHOH C O
CH3 H CH2OH H H
C O C O
H3C H
 H
H O C O
C 2 IO4− HO HO
CHOH C O
CH2OH H H
C O
H H
C O
CH2OH 2 IO4− H
C O CO2
CH2OH H
C O
H
CH2OH IO4−
CH2 NR
CH2OCH3
CH2OH IO4−
CHOH NR
CH2R
 1 1
H C OCH3 H C OCH3
CHOH 2 IO4− CHO
O O + HCOOH
CHOH
CHOH CHO
H 5C H 5C
CH2OH CH2OH

Br2/H2O
SrCO3

1
H C OCH3

Sr2+ O
C
O O All α-D-hexopyranosides
O
C
O gives the same salt
H 5C
CH2OH
Because they have the
same configuration at
C-1 and C-5
◎ Reduction

CHO NaBH4 CH2OH

(CHOH)n (CHOH)n
or
CH2OH CH2OH
H2/Pt

例
CHO CH2OH
HO H OH H OH
O HO H NaBH4
HO HO H
HO OH H OH H OH
HO H H OH H OH
CH2OH CH2OH

D-glucitol
(or D-sorbitol)
 ※ Synthesis and degradation CHO
H OH
of monosaccharides D-(−)-erythrose
H OH
CH2OH
◎ Kiliani-Fischer synthesis Na-Hg
H2O, pH 3-5
1) Ba(OH)2 COOH
CN O
+
H OH 2) H3O H OH HO O
H OH H OH
CH2OH HO
CHO CH2OH
HCN
H OH epimeric aldonic acid γ-aldonic lactone
CH2OH COOH
CN O
D-glyceraldehyde HO H HO H O
H OH 1) Ba(OH)2 H OH
CH2OH 2) H3O+ CH2OH HO OH

Na-Hg
H2O, pH 3-5

CHO
HO H
D-(−)-threose
H OH
CH2OH
Q: A simple method to determine which is erythrose and
which is threose?
CHO CHO
H OH HO H
H OH H OH
CH2OH CH2OH
erythrose threose
[O] [O]

COOH COOH
H OH HO H
aldaric acid
H OH H OH
COOH COOH
optically optically
inactive active
(meso)
◎ Ruff degradation

CHO COOH
H OH H OH CHO
Br2 H2O2
H OH H OH H OH + CO
2
H2O Fe2(SO4)3 H OH
H OH H OH
CH2OH CH2OH CH2OH

D-(−)-ribose D-(−)-erythrose

All D-series can be correlated via chemical methods

L-series likewise
※ Fischer’s proof of the configuration
of D-(+)-glucose

Four chiral centers  24 = 16 isomers

Arbitrarily consider D only  8 possibility

1 2 3 4 5 6 7 8
Experiments:
1) HNO3  optically active aldaric acid
−1, −7
 1 2 3 4 5 6 7 8
2) Degradation  HNO3  optically active aldaric acid
−2, −5, −6

1 2 3 4 5 6 7 8
 1 2 3 4 5 6 7 8
HCN HNO3
3) (−)-Arabinose two sugars both are
including glucose optically
plus mannose active

(−7), −8
4) There is an L-sugar  glucaric acid  D-glucose

3 4
COOH COOH

COOH COOH

same as 4

L-gulose
D-glucose
※ Disaccharides
◎ Sucrose
Structure
1) C12H22O11  a disaccharide

2) Acid hydrolysis  D-glucose + D-fructose

CH2OH
O HO 6
O OH
HO H 2
5 HO a furanose
H OH 4 CH2OH
H OH 3 1
OH
CH2OH
D-fructose β-fructofuranose
3) Negative Bendict’s & Tollen’s
 non-reducing sugar
 no hemiacetal structure
 must be connection between C-1 of glucose
and C-2 of fructose

4) Hydrolyzed by α-glucosidase (an enzyme)

 α-configuration for glucopyranoside
Hydrolyzed by sucrase (hydrolyze β-fructofuranosides)
 β-configuration for fructofuranoside

• Exhaustive methylation  octamethyl derivatives

hydrolysis
2,3,4,6-tetra-O-methylglucose
+ 1,3,4,6-tetra-O-methylfructose
 Must be pyranoside + furanoside
Sucrose:
HO 6
OH
5 O H 1 O H
2
4 OH 1 HO 5
2
HO O
3 3
4 6 OH
OH OH

α-glucosidic linkage β-fructosidic linkage

Proved also by X-ray and synthesis cf. 6

HO O OH
2
5 HO
4 CH2OH
3 1
OH
◎ Maltose
1) Hydrolysis  two D-(+)-glucose
2) Positive Fehling’s, Bendict’s and Tollen’s test
 reducing sugar
3) Two anomeric forms:
α-maltose [α] = +168o o
136
β-maltose [α] = +112o
 one glucose must be a hemiacetal
another glucose must be a glucoside
HO HO
O H O
OH OH OH
HO O
OH OH
α C-4
◎ Cellobiose (纖維雙醣 )
disaccharides from cellulose
HO
O
HO
OH OH (2 D-(+)-glucose)
O O
OH OH
HO
OH β-linkage: the only difference from
maltose
4-O-(β-D-glucopyranosyl) β-D-glucopyranose
(α)
Conformation: HO 3 OH
HO O 2
OH
HO 1
HO O 4 5 O
OH HO 6
◎ Lactose (in milk)
 D-glucose + D-galactose

HO
O
HO A reducing sugar
OH OH
HO O O
OH OH

OH β-glycosidic linkage

D-galactose: CHO
H OH
HO H
HO H
H OH
CH2OH
※ Polysaccharides

Starch, glycogen, cellulose

 Polymers of D-glucose
◎ Starch
HO
Amylose (10-20%) HO O
Amylopectine (80-90%) HO
HO
O
Amylose (直鏈澱粉 ) OH
HO
C-1 and C-4
α-linkage O
100-100,000 units helical
HO
structure O
Amylopectin (分枝澱粉 )
n
with branching at C-6 every 24-30 unit
(~400,000 units, larger than amylose)
Helical amylose
◎ Glycogen
similar to amylopectin
with more branching

A rapid source of E
enzyme hydrolyzes from the end group

Stored in the cell

has high MW
 no osmotic pressure problem

cf. Fats: can store more E

but slow for use: insoluble in water
O conc. in cell is low
O O R
R O O
O R
◎ Cellulose
D-glucose linked in 1,4-fashion using β-linkage
Can not be hydrolyzed by human

Linear shape with hydrogen bonding between chain

HO OH
HO O O
HO
HO O O
OH HO
n
 Cellulose derivatives
NaOH S
cellulose-OH + CS2
cellulose O S− Na+

cellulose-OH H+ soluble in water

formation of a fiber or a sheet
(Rayon or cellophane)
Linear cellulose