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Monozaharide - Proprietati chimice

Reducere
H2 /cat, electrochimic, [H]

Emulgatori, vitamina C,
umectanti, indulcitori, organogelifianti

Guma de mestecat

Oxidare
oxidare blnd - cu ap de clor sau brom, oxid umed de argint Ag2O, reactiv
Fehling, sau ap oxigenat acizi aldonici
CHO

COOH

H C OH

H C OH

HO C H
H C OH

oxid.

H C OH
CH2OH
D-Glucoza

HO C H
-H2O

H C OH
H C OH

O
H
HO
H
H

CH2OH
Acid D-Gluconic

C
C OH O
C H
C
C OH
CH2OH
-Lactona

oxidare energic - cu acid azotic concentrat - acizi zaharici

CHO

COOH

H C OH
HO C H
H C OH
H C OH
CH2OH
D-Glucoza

H C OH
HNO3

HO C H
H C OH
H C OH
COOH
Acid zaharic

oxidare enzimatica - acizi uronici

CHO

CHO

H C OH

H C OH
HO C H
H C OH

[O]

ox. C6

H C OH

COOH
Acid D-glucuronic

D-Glucoza

HO C H
H C OH
H C OH
COOH
Acid zaharic

CHO

CO

H C OH
-H2O

H C OH O
HO C H
H C
H C OH
COOH
-Lactona

H C OH
H C OH

CH2OH

COOH

HO C H

H C OH
2[H]

HO C H
H C OH
H C OH
COOH
Acid D-glucuronic

Aciunea acizilor i bazelor asupra monozaharidelor

Acizii minerali, la cald

CHOH

CHOH

CH2OH CHOH

HCl
-3H2O

CHO

HOCH2

CHOH

CHOH

CHOH

CHOH

CHO
O
Furfurol

HCl
-3H2O

HOCH2

CHO

CHO
H3C CO CH2 CH2 COOH + HCOOH
Acid levulic

Epimerizarea - baze slabe ( lapte de var)


Monozaharide epimere difera prin configuratia primilor 2 atomi de carbon
(glucoza, fructoza, manoza)

HO

C1H2OH

C1H-OH

C2 O

C2 O

HO C H

HO C H

C1H OH
C2 O
HO C H

C1H O
C2 OH
HO C H

D-Fructoza

C1HO
C2 OH
HO C H

C1HO
HO C2
H2O
+ HO C H

C1HO
C1HO
H C2 OH HO C2 H
HO C H + HO C H + HO
D-Glucoza

D-Manoza

Reaciile monozaharidelor cu fenilhidrazina


CHO

CH=N-NH-C6H5

H C OH
HO C H

C6H5-NH-NH2

H C OH
H C OH

- H2O

CH2OH
D-Glucoza

H C OH
HO C H
H C OH
H C OH

H C OH
H C OH
CH2OH

C6H5-NH-NH2
(exces)
- C6H5-NH2
- NH3

CH2OH
Fenilhidrazona D-Glucozei

C O
HO C H
H C OH
H C OH
CH2OH

CH=N-NH-C6H5

CH=N-NH-C6H5
C O
HO C H

CH=N-NH-C6H5

C6H5-NH-NH2
- H2O

C N NH-C6H5
HO C H
H C OH
H C OH
CH2OH
Osazona

Monozaharidele epimere dau aceeasi osazona !

C1HO

C1H=N-NH-C6H5

2
HO C H

HO C H

C6H5-NH-NH2

C1H=N-NH-C6H5
C2 O

2
HO C H C6H5-NH-NH2

- H2O

D-Manoza

HO C H

(exces)

HO C H

- C6H5-NH2
- NH3

Fenilhidrazona

C1H2OH

C1H2OH

C2 O

C1H N-NH-C6H5

C2 N-NH-C6H5 C6H5-NH-NH2

C2 N-NH-C6H5

HO C H

C6H5-NH-NH2
- H2O

(exces)

HO C H

D-Fructoza

- C6H5-NH2

HO C H
Osazona

Fenilhidrazona

Aplicatie - transformarea unei aldoze in cetoza epimera


C1H N-NH-C6H5

C1HO

C1H2OH

C2 N-NH-C6H5

C2

C2 O

HO C H
Osazona

H2O

HO C H
Osona

2 [H]

HO C H
Cetoza

Eterificarea grupelor hidroxil din monozaharide


Hidroxilul glicozidic - alcool metilic n prezen de acid clorhidric uscat
Grupe hidroxil poz. 2-6 - iodur de metil n prezen de oxid de argint, sau sulfat de metil i
hidroxid de sodiu

H C OH

H C OCH3

H C OH

H C OH

HO C H

CH3OH
+

HO C H

H C OCH3
4CH3I
Ag2O

H C OCH3
O
H3CO C H

H C OH

H C OH

H C OCH3

H C

H C

H C

CH2OH

CH2OCH3

CH2OH

1,2,3,4,6-pentametil-D-Glucoza
H C OH

H C OCH3
H C OCH3
O
H3CO C H

H2O
+

H C OCH3
O
H3CO C H

H C OCH3

H C OCH3

H C

H C

CH2OCH3

CH2OCH3

2,3,4,6-D-tetrametilglucoza

Utilizare - stabilirea naturii piranozice sau furanozice a ciclurilor


H C OCH3
H C OCH3
O
H3CO C H

H2O

H C OH

CHO

H C OCH3
O
H3CO C H

H C OCH3
H3CO C H

H C OCH3

H C OCH3

H C OCH3

H C

H C

H C OH
CH2OCH3

CH2OCH3

CH2OCH3

[O]

Ciclu piranozic

COOH
H C OCH3
H3CO C H
H C OCH3
H C OH
CH2OCH3

COOH

CO

-H2O

H
H3CO
H
H

C OCH3
O
C H
C OCH3
C
CH2OCH3

lactona

H C OCH3
ox.

H3OC C H
H C OCH3
COOH
Acid trimetoxiglutaric
(xiloglutaric)

Cetalizarea grupelor hidroxil - Reactie de protejare


H C O

H C OH
H 3C

H C OH
HO C H

CH3
C

H C O

H3 C

H 3C

C
H 3C

HO C H

CH3
O

O C H
O C H
H C

H C

CH2OH
1,2,3,4-Diizopropilidengalactopiranoza

CH2OH
Galactopiranoza

CH2OH
OH
O

H3C
H3C

OH
OH
OH

C O

H3C
H3C

O
C

CH2OH
O
O
O
O C

CH3
CH3

CH2OH

CHO
H C
HO C

Exemplusinteza
Vitaminei C

OH

H C

H2/Ni

HO C

OH

H C

OH

H C

OH

H C

OH

H C

OH

Acetobacter
xylinum

HO

C H

CH3COCH 3

C OH

C H
CH2OH

KMnO 4/HO

HO C

C H

HO C

C OH

CH2 O
2,3:4,6-di-O-isopropiliden-a-L-sorbofuranoza
O
C
COOH

O C

HO

C H

C H

COOH

O C H

H2SO4

CH2OH
a-L-sorbofuranoza

OH

O C

C H

O C H

H C

HO

CH2OH
L-sorboza
CH2OH

CH2OH
HO

CH2OH
sorbitol

CH2OH

OH

HO

[O]

H C

CH2OH
D-glucoza

CH2OH

MeONa/MeOH
HCl

C H
CH2 O
acid 2,3:4,6-di-O-isopropiliden-2-ceto-L-gulonic

HO
H
HO

C OH
C H

CH2OH
acid 2-ceto-L-gulonic

H C
HO

C H

CH2OH
acid -L-ascorbic

Esterificarea grupelor hidroxil din monozaharide


Acetilare - reactie stereoselectiva

CH2OH

CH2OAc

O
OH
OH
OH
a-D-Glucoza

OH

Ac2O
Py

OAc

OAc
OAc
OAc
-D-Glucoza-pentaacetat

ZnCl2 ,0o C

Aplicatii - sinteze de glicozide fenolice

SN2
inversie

SN2
inversie

Reacii de interconversie ale monozaharidelor


Reacii de scurtare de caten (reacii de degradare)
CHO
H
HO
H
H

CN

CH=N-OH

C OH
C H H2N-OH
- H2O
C OH
C OH
CH2OH

H
HO
H
H

D-Glucoza

C OH
Ac2O
C H
- H2O
C OH
C OH
CH2OH
Oxima

C OH
C H
C OH
C OH
CH2OH

D-Glucoza

C OAc
C H
2) - HCN
C OAc
C OAc
CH2OAc

CHO
HO C H
H C OH
H C OH
CH2OH

Wohl

D-Arabinoza

COOH

CHO
H
HO
H
H

H
AcO
H
H

1)+ 5 CH3OH /
CH3O-Na+
- 5 CH3COOCH3

ox.

H
HO
H
H

C OH
C H
C OH
C OH
CH2OH

CHO
H2O2
Fe(OAc)3

Acid D-gluconic

Sare de calciu

HO C H
H C OH
H C OH
CH2OH
D-Arabinoza

Ruff

Reacii de lungire de caten


CN
HC O
HO C H
H C OH
H C OH
CH2OH

HCN

H
HO
H
H

CN

C OH
C H
C OH
C OH
CH2OH

HO
HO
H
H

C H
+H2O
C H
C OH
C OH
CH2OH

D-Arabinoza

COOH
H
+ H2O HO
H
H

COOH

C OH HO C H
C H + HO C H
H C OH -H2O
C OH
H C OH
C OH
CH2OH
CH2OH

H
HO
H
H

CO

CO

HO
C OH
C H O + HO
H
C
H
C OH
CH2OH

C H
C H O
C
C OH
CH2OH

-Lactone

Acizi aldonici

CHO

CHO
Na(Hg)

H C OH
HO C H

HO C H
HO C H

Kiliani-Fischer
D-Glucoza

D-Manoza

Transformri biochimice ale hidrailor de carbon


Fermentatia alcoolica

C6H12O6

- procese anaerobe
- procese aerobe

2 C2H5OH + 2 CO2