MT S VN V SACCARIT TRONG GING DY

CC LP CHUYN HA HC PH THNG
Th.s. Cao vn Giang.
Trng THPTchuyn HSP H ni
LI NI U
Trong qu trnh ging dy cho cc lp chuyn Ha hc phn cacbohydrat, chng ti nhn thy
rng: hc sinh rt lng tng trong phn cu trc phn t, cc danh php tng i v tuyt i,
vn dng gii cc bi tp. Nhm trao i tho g bt cc lng tng , chng ti ly monosaccarit
lm c s cho vic nghin cu saccarit. Trong phm vi bi vit ny chng ti ch trnh by cc
vn sau:
1.Mt s khi nim m u.
2. Phn loi.
3. Cu trc ca monosaccarit
4.Cc phn ng tiu biu
5. Gii thiu mt s bi tp c tuyn ch t thi hc sinh gii mn Ha hc cp quc gia,
quc t.
CACBOHIRAT.
I.

MT S KHI NIM M U.

Cacbohidrat l nhm hp cht hu c tp chc , c nhiu trong thin nhin, c bit trong thc
vt (chim trn 80% khi lng kh)
I.1. Cc tn gi khc nhau ca cacbohydrat
1. Cacbohidrat
Cng thc phn t ca chng c dng Cn(H2O)m , nn c gi l cacbohidrat. Tuy nhin
chng khng phi l hiddrat ca cacbon. Cacbon khng tan trong nc..
2. ng
ng ( sugar). T sugar c xut x t ting Phn. su ngha l ngt gar ngha l ct.,
tc l ct ngt.
3. Saccarit
Ting Latinh saccharum cng c ngha l ng v t t saccarit c dng thay cho
t cacbohidrat.
4. Gluxit
Tn ny c xut x t ting Hi-lp glucus) ngha l ngt.
Tm li cacbohidrat, ng, saccarit l ba tn gi khc nhau ca cng mt loi hp cht hu c.
I.2. Phn loi:
Cacbohirat c phn thnh ba nhm chnh sau y:
1. Monosaccarit (monoz): l nhm cacbohirat n gin nht, khng th thy phn c. V d:
glucoz, fructoz (C6H12O6) .
Monosaccarit dng mch h nu thuc loi polihidroxiandehyd th gi l andoz, cn nu
thuc loi polihidroxixeton th gi l xetoz. Chng u c ui oz ( ting Anh ose)
Ty vo s nguyn t cacbon trong phn t m monosaccarits c gi l :
3C- Trioz ( andotrioz hoc xetotrioz)
4C- tetroz, 5C- pentoz, 6C- hexoz, 7C- heptoz
104

2. Oligosaccarit (oligoz): l nhm cacbohirat m khi thy phn hon ton sinh ra 2 - 10 phn t
monosaccarit. V d: saccaroz, mantoz (C12H22O11) , rafinoz,melexitoz (C18H32O16)
3. Polisaccarit: l nhm cacbohirat phc tp m khi thy phn n cng sinh ra nhiu hn 10
phn t monosaccarit. V d: tinh bt, xenluloz (C6H10O5)n
Polisaccarit c chia thnh 2 loi: homopolisaccarit v heteropolisaccarit.
homopolisaccarit khi b thy phn hon ton cho nhiu hn 10 monosaccarit cng loi v d
tinh bt, xenluloz.
Heteropolisaccarit khi b thy phn n cng cho 2 hay nhiu loi monosaccarit khc nhau v
d aga-aga.
II- CU TRC PHN T.
Cn phi ni r hn v khi nim cu trc phn t, n bao gm cu to phn t v hnh dng
khng gian ca phn t thng hiu l cu hnh phn t
1. Cu to dng mch h ca monosaccarit.
Cu to dng mch h ca monosaccarit v d ca glucozo c xc nh bng thc nghim.
C th tm tt bng s cc phn ng sau
[Ag(NH3)2]+; t0
(CH3CO)2O
C6H12O6
(glucozo)

HI du
HCN

Ag + ....

(1)

C6H7O(OCOCH3)5

(2)

CH3(CH2)4CH3 + I2 +H2O
C5H11O5CHOH-CN

HOH,H+

HIdu

(3)

C5H11O5CHOH-COOH (4)
CH3(CH2)4COOH

T cc th nghim suy ra :
(1) glucozo c chc andehyd CHO
(2) glucozo c 5 nhm OH , thuc ru 5 chc
(3) v (4) suy ra gluco c mch cacbon khng phn nhnh. Vy cu to dng mch h ca
glucoz nh sau
H2C6
OH

5H 4 H 3 H 2
C
C
C
OH OH

OH

H1
C

H
C

OH

OH

CHO

Vit gn l CH2(OH)(CHOH)4CHO
2. Cu hnh ca monosaccarit. ng phn quang hc
a. Cu hnh ca andohexoz
Ta ly polihidroxiandehyd n gin nht l glixerandehyd hay 2,3-dihidroxipropanal lm v
d in hnh kho st. Phn t n c mt nguyn t cacbon bt i (C*) hay cn gi l c 1
trung tm bt i nn c 2 enantiome hay hai i quang

105

Cu hnh S :

OH > CHO >CH2OH > H

106

107

Anohexoz c 4C* ( 4 nguyn t cacbon bt i s c 24 = 16 ng phn gm c 8 ng

phn dy D v 8 ng phn dy L. Tuy nhin trong t nhin ch gp cc ng phn dy D.
V d
CHO
H
OH
H
OH
H
H

CHO
HO
H
H

OH
OH
CH2OH

D-Alloz

CHO

H
OH
OH

H
HO
H

OH
CH2OH

D-Altoz

OH
H
OH
OH
CH2OH

D-glucoz

CHO

CHO
HO
H
HO
H
H
H

OH
OH
CH2OH

H
H
HO
H

D-mannoz

OH
OH
H
OH
CH2OH

D-Guloz

CHO
HO
H
H
OH
HO
H
H

OH
CH2OH

D-Idoz

CHO
H
OH
HO
HO
H

H
H
OH

CHO
HO
H
HO
H
HO
H

CH2OH

H
OH
CH2OH

D-Galactoz

D-Taloz

Ch !
*Cc andohexoz ch khc nhau cu hnh ca mt nguyn t C* c gi l ng phn
epime ca nhau th d cc cp ng phn epime C2 l D- glucoz v D- mantoz; C4 l Dglucoz v D-galactoz.
c
p
ng ph
n epime
nguyn t C2

H
HO
H
H

CHO
OH
H
OH
OH
CH2OH
D-glucozo

HO
HO
H
H

CHO
H
H
OH
OH
CH2OH

D-mantozo

c
p
ng ph
n epime
nguyn t C4
H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

H
HO
HO
H

D-glucozo

CHO
OH
H
H
OH
CH2OH
D-galactozo

* cu hnh tng i l cu hnh dng glixerandehyd lm chun gn vi danh php D/L.

Cu hnh tuyt i l cu hnh gn vi trung tm bt i v gn vi danh php R/S.
b.Cu hnh ca xetohexoz
Tng t nh andoz, xetoz ly 1,3,4-trihidroxibutan-2-on-lm chun cho danh php D/L
CH2OH

CH2OH

C O
1,3,4-Trihydroxy-butan-2-on

H C OH
CH2OH

C O

HO C H
CH2OH

D-Eritruloz

L-Eritruloz
D-eritruloz lm chun cho dy D
Cc xetohexoz c cng thc cu to

Phn t c 3 nguyn t C* nn co 23 = 8 ng phn quang hc. 4 dy D v 4 dy L.

4 ng phn dy D ca xetohexozo
108

CHO
H

OH

H
H

CHO
H
OH

CHO

OH

HO
H

H
OH

HO

OH

OH

CH2OH

CH2OH

H
OH
CH2OH

CHO
HO

HO

OH
CH2OH

D(-)-Lixozo
D(+)-Xilozo
D(-)-Arabinozo
Trong thin nhin Arabinoz tn ti ch yu dng L(+)-arabinoz.
3. Cu trc mch vng ca monosaccarit-ng phn anome.
a.Cu hnh
trng thi rn, cc monosaccarit tn ti ch yu dng mch vng 5, cnh hoc 6 cnh.
Nh bit phn xicloancan, vng 6 cnh l ch yu.Vng 5 cnh gi l furanoz , 6 cnh gi
l pyranoz. V d i vi D- glucoz l
D( ) glucozopyranozo
D(-)-Ribozo

CHO

D() glucozofuranozo

H
HO

OH
H

H
H

OH
OH
CH2OH

D() glucozopyranozo

D( ) glucozofuranozo

Dng vng c to ra do nguyn t H ca nhm OH C5 tch ra cng vo nhm cacbonyl

C=O C1 to ra nhm C1-OH, nhm OH ny c gi l nhm hidroxyl semiaxetal (hay
hemiaxetal). ng phn c nhm hemiaxetal nm bn phi gi l ng phn , cn nm bn tri
gi l . Hai ng phn ny ch khc nhau cu hnh C1( nguyn t C* mi hnh thnh) c gi
l hai ng phn anome.
Ty tng monosaccarit m hm lng tng ng phn anome trong cn bng cng khc
nhau. ng phn anome no c nng lng nh hn s chim hm lng cao hn.
V d: i vi glucoz v galactoz, t l : l 3 6 : 64, trong khi i vi manoz t l ny
l 68:32.
Dng vng ca monosaccarit c biu din dng chiu Haworth ( c l Havooc). Vng
5,6 cnh c qui c chiu xung mt phng thng gc vi mt phng trang giy. Nguyn t O
trong vng c vit nh bn phi xa mt ta. Trong dung dch nc cc andohexoz tn ti
ng thi c dng mch h v c hai loi vng 5 cnh 6 cnh, cc dng ny chuyn ha cho nhau
theo mt cn bng.
Cng thc chiu Haworth ca cc dng andohexoz

109

cH2OH
5

OH
3

O H

H
1

2
OH

OH

OH

OH

H
C1
H
HO
H
H

OH
H
OH
O
CH2OH

D () glucozopyranozo
H
HO

CHO
OH
H

OH

D( ) glucozofuranozo
6

CH2OH

H 4 OHO

H
1

H OH
H

HOH
2

OH

cH2OH
5

H
4
OH

2
OH H

D() glucozopyranozo

OH
CH2OH

OH

OH

OH

C11
H 2 OH
HO 3 H
H 4O
H 5 OH
6 CH OH
2

D () glucozofuranozo
6 CH OH
2
5

OHO

H OH
3

OH
HH

OH

Ch ! Trn c s cu trc vng c th gii thch mt s hin tng sau:

Hin tng 1:Ha tan ng phn -(D)-glucoz tinh khit c gc quay cc ring
D 1120 vo nc; hoc ha tan -(D)-glucoz tinh khit c gc quay cc ring

D 18, 70 vo nc. Khi t ti cn bng u thu c dung dch c D 52, 70 .

Hin tng ny xy ra l do s chuyn ha gia hai ng phn anome trong dung dch cn gi
l s quay h bin. Ta c th tm c % s mol mi ng phn trng thi cn bng nh
sau:
Gi s mol v ln lt l x, y. ta c h x+y=1 v 112x + 18,7y=52,7. T tm c x=
0,36, y-0,64.
Hin tng 2: Cho hoc -(D)-glucoz pyranoz tc dng vi CH3OH c mt ca kh HCl
khan xc tc, thy ch c 1 nhm OH phn ng, l nhm semiaxetal tm thnh
metylglucozit

Khi nhm OH C1 chuyn thnh nhm OCH3, dng vng khng th chuyn sang dng
mch h c na.
- Phn ng ny dng chng minh dng mch vng ca glucoz
b.Cu dng Tng t nh xiclohexan cac hexopiranoz tn ti dng gh: dng C1 v 1C.
110

V d:
4

5 O

C1

-(D)-glucozpyranoz

1c
-(D)-glucozpyranoz

OH

H OH

H
HO
HO

HO
H

HO
HO

HO

OH
OH
H
H
H
Cu trc vng ca xetohexoz cng c xem xt tng t nh andohexoz
H

OH
OH

III. MT S PHN NG TIU BIU

III.1. Phn ng ca nhm hydroxyl
a. Phn ng vi Cu(OH)2, trong mi trng kim to thnh phc cht mu xanh lam ging
poliancol.
b. Phn ng to este. Ging ancol, cc monosaccarit tc dung vi clorua axit hoc anhydrit
axit, s to thnh este

111

c. Phn ng to glicozit
Do nh hng ca nguyn t oxy trong vng m nh -OH semiaxetal c kh nng phn ng
cao hn cc nhm OH khc v d to metyglicozit.

d. Phn ng to thnh ete

112

e. Phn ng to axetal vng v xetal vng.

113

114

III.2. Phn ng ca nhm cacbonyl.

a. Phn ng oxy ha gi nguyn mch cacbon.
Nhm chc an dehyd ca monosaccarit b oxi ha bi ion Ag+ trong dung dch amoniac,
(thuc th Tollens), ion Cu2+ trong mi trng kim hoc thuc th Fehling, nc brom vv
to thnh axit andonic hoc mui ca chng.
CH2OH[CHOH]4CHO + 2[Ag(NH3)2]OH

CH2OH[CHOH]4COONH4 + 2Ag + 3NH3 + H2O

(amoni gluconat)
- Vi dung dch Cu(OH)2 trong NaOH, un nng (thuc th Felinh)
CH2OH[CHOH]4CHO + 2Cu(OH)2 + NaOH

CH2OH[CHOH]4COONa + Cu2O
(natri gluconat)
( gch)

- Vi dung dch nc brom:

CH2OH[CHOH]4CHO + Br2 + H2O

+ 2H2O

CH2OH[CHOH]4COOH + 2HBr

Khi oxi ha bng dung dch HNO3 long c nhm CHO ln nhm CH2OH cui mch cng b oxi
ha thnh axit anddaarric hoc saccaric. V d

115

b.Phn ng oxy ha ct mch cacbon

116

b. phn ng kh.

c. Phn ng tng mch cacbon

117

Theo phng php ca Kiliani-Fischer, cho monosaccarit tc dung vi HCN, ri qua mt

chui phn ng s thu c monosaccarit tng thm 1 nguyn t cacbon

d. Phn ng ct ngn mch cacbon

d.1. Phng php thoi phn ca Ruff

Phng php ny cho hiu sut thp.

d.2. Phng php Wohl

118

6.Ph
e. Phn ng to ozazon

119

III.3. Phn ng ln men .

Nh tc dng xc tc ca cc enzim khc nhau, monosaccarit c th to ra nhiu sn phm
khc nhau.
V d: Glucoz ln men nh sau
1. ln men ru.
enzim
C6H12O6
2C2H5OH + 2CO2
2.

3.

ln men lactic
C6H12O6

enzim

ln men butyric
enzim
C6H12O6

4. ln men xitric
C6H12O6

enzim

2CH3-CH(OH)-COOH
axit lac tic
CH3CH2CH2COOH + 2CO2 +2H2
axit butyric
COOH
HOOC-CH2- C-CH2-COOH + 2H2O
COOH
axit xitric

120

VI.MT S BI TP TUYN CHN V SACCARIT.

Bi 1 ( cu 4.2 thi chon HSGQG-2011)

Hng dn gii

121

Bi 2 ( QG 2010 cu 10.2 v 10.3)

10.2. Inulin (mt cacbohirat c trong r cy actis) khng phn ng vi thuc th Felinh; khi b thu
phn c mt -glucoziaza cho 2 mol glucoz v mt polisaccarit gm cc D-fructoz kt cu theo kiu (21)D-fructofuranoz. Phn t khi tng i ca inulin khong 5200 u.
V cng thc Havooc (Haworth) ca inulin.
10.3. Phng php bo v nhm hiroxyl (-OH) thng c s dng khi chuyn ho gia cc
monosaccarit.
H
OCH3
O

Vit s phn ng iu ch -D-perosinamid

v cc cht cn thit.
Hng dn gii
10.2. Cng thc ca Inulin:

HO
OH

O
O O
CH2
O O

28
n v

CH2
O O
CH2

OO

(Hoc v 2 gc glucoz cng mt u)

10.3.

122

CH3

NH2
H

HO

OH
t

HO

OH
OH

3.
O

HO

HO

OH

HO

1. MeOH/H+
2. CH3COCH3/H+

OH

H3C

OCH3

OCH3

HO

H3C

OCH3

TsO

O 1. NaBH4, EtOH, H2O

OH

OH

OCH3

H2N

OH
OH

NH2

HO

OH

CH3

OCH3
H

H2N

OH

OCH3

H3C

OCH3

N3

(Hirua u tin

2. TsCl, Et3N

OH
H3C

OCH3

LiAlH4

OH

O
tn cng vo v
trequatorial)

NaN3

MeOH/H+

TsO

H3C

1. TsCl, Et3N
2. LiAlH4
3. RuO4

O
O

OH
H3C

OH

Bi 3 (Cu V.1 v cu V.2 thi chn TQG d thi IChO-2009).

Cho s chuyn ho sau:
CH3

HO

O
OMe
OH OH A

HIO4/H2O

C6H12O5
B

O
/Ag 2
H 3I

2 /N

i, t

C8H16O5 C
CH2OH
H

OCH3
O

H3 C

H
CH2OH

a) Vit cng thc cu trc ca A (c biu din cu hnh ca tng nguyn t cacbon bt i). A
CH
thuc dy no (D hay3 L) v dng -glicozit hay -glicozit? O C8H16O5
g2
I/A cha nhm cacbonyl. Gii thch s
HO thc cu
O to ca B v C bit rng B khng
b) Vit cng
CH 3
HIO4/H2O
CH2OH
OMe
C6H12O5
to thnh B.
H
H
OCH3
c) V sao B khng cha nhm cacbonyl m vn b kh
2 /N bi hiro?
i, t o
Hng dn gii: OH OH (A)
C
O
a) Cu trc ca A l
N thuc dy L, loi -glicozit.

HO
CH3
OH

HC
H
O 3 OMe
CH2OH

OH

b) Sau khi phn ng vi HIO4, mt nhm anehit b hirat ho thnh gem iol, cht ny to vng
vi nhm anehit th hai, tip theo l phn ng metyl ho.
123

O OMe

HO
CH3

O OMe

HIO4
H2O

HC CH3
O

OH

OH

HO

O OMe
HC CH3
HO O CH

CH
OH

O OMe
CH3I
Ag2O

HC CH3
MeO O CH

OH

OMe

c) Di tc dng ca nhit, B m vng, b ehirat ho tr li anehit v do b kh.

Bi 4 ( cu V.2 thi chn TQG d thi IchO-2008)
V.2. Vit s phn ng oxi ha D-glucoz to thnh axit anonic v axit anaric, cng thc
Haworth cc mono v i -lacton ca chng v gi tn cc lacton y.
Hng dn gii
Cc sn phm oxi ho D-glucoz v cc lacton ca n
O
COOH

CHO

OH

OH
HO
OH
OH
CH2OH
HNO3

COOH
OH
HO
OH
OH
COOH

Br2

HO

H2O

OH

O
OH

OH
OH

D- -gluconolacton

OH

HO

CH2OH

CH2OH
axit gluconic
COOH
OH
O

CH2OH
OH
O

OH

OH
COOH
O
OH HO

OH
O

O
O

O
O

OH
1,4-lacton ca axit glucaric
1,4:3,6-dilactonca axit glucaric
3,6-lacton ca axit glucaric
OH

Bi 5 ( Cu 21 bi tp chun b cho IchO-41)

Cc xetoz l mt nhm c bit trong cc ng. Cc dn xut ca D-ribuloz ng mt
vai tr quan trng trong tng hp quang ha. Mt -metyl glycosit ca D-ribuloz (A) c th
c iu ch t D-ribuloz bng cc x l vi metanol v xc tc axit. un nng A trong axeton
c mt HCl dn n s to thnh B l mt dn xut ca propyliden. Axeton to thnh axetal vi
cc vic-diol nu hai nhm OH c nh hng khng gian thch hp.

124

H2C
O

OH

HO

CH2OH
HO

CH2OH

OH

HO

acetone/H+

O OCH3

H
OH

D-ribulose

OOCCH3

acetic anhydride
(cat.)

H2O/H+

CH3-OH/H+

OCH3
HO

HO

1-O-methyl--D-ribulose<2.5>
A

a) Trong qu trnh tng hp B th c th to thnh hai cu trc. V cu trc ca chng v cho

bit u l sn phm chnh.
B phn ng vi anhydrit axetic (c mt xc tc) to thnh C. D c to thnh C bng
cch un nng trong axit long. D phn ng vi metanol c mt axit to thnh E.
b) V cu trc ca cc cht t C-E.
c) Liu c th xc nh c cu dng ca nguyn t cacbon C1 trong E?
Mc d s to thnh cc axetonit l mt phng php gi tr bo v nhm OH quan trng
nhng trong nhiu trng hp n cho nhiu sn phm (hay thnh phn sn phm ph thuc nhiu
vo iu kin phn ng). Ni chung y l trng hp hay gp i vi cc ng c cu trc
vng 6 cnh.
Ngi ta chng minh rng khng h c s to thnh axetonit khi hai nhm OH k nhau
chim v tr axial. Tuy nhin cc vic-diol c nhm OH chim hai v tr equatorial hay mt axial
mt equaorial u phn ng c vi axeton/HCl.
d) V hai cu dng gh ca 1-O-metyl-6-O-acetyl--D-galactoz<1.5> (F). nh du cc
nhm OH v tr axial (a) hay equatorial (e). Xc nh cu dng bn nht.
e) C bao nhiu ng phn axetonit c th c to thnh t hp cht ny v c bao nhiu
cu dng gh khc nhau ca cc axetonit ny tn ti c?
f) V cng thc chiu Haworth ca L-galactoz <1.5>
Hng dn gii
a)

125

S to thnh ng phn 1,3 t ph hp hn (do cc nhm th vi tr trans khng thun li cho

vic to vng) nn sn phm chnh s l 3,4-acetonide
b)

c) Khng, v D c nhm OH cha b kha cho nn trong qu trnh tng hp E th c th to

thnh c c hai ng phn v . Thnh phn cc ng phn ny ph thuc nhiu vo iu
kin phn ng:
d)

e)

126

Nh vy ng phn 3,4-axetonide c hai cu dng gh khc nhau cn ng phn 2,3 ch mt:

f)

127