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有機化學 22 PDF
有機化學 22 PDF
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
H2O
monosaccharide no hydrolytic cleavage
Biologically
enzyme
xCO2 + yH2O + solar E carbohydrates + xO2
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
R H
aldose
reducing
Cu2+ + or sugars
blue
R
OH
O
ketose
Cu2O
brick-red
can be oxidized
But
acetals are non-reducing sugars
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
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
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
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
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
A rapid source of E
enzyme hydrolyzes from the end group
HO OH
HO O O
HO
HO O O
OH HO
n
Cellulose derivatives
NaOH S
cellulose-OH + CS2
cellulose O S− Na+