BINDURA UNIVERSITY OF SCIENCE EDUCATION

FACAULTY OF SCIENCE

CHEMISTRY DEPARTMENT

STUDENT NAME : MIKE VHURINOSHARA

REG NUMBER : B1748924
LEVEL : 4.1
COURSE CODE : CH 323
COURSE DESCRIPTION : ADVANCED ORGANIC CHEMISTRY
LECTURER : PROF P. DZOMBA
DUE DATE : 02-10-2020
1. (a) Explain why thioesters are used as chain extenders instead of oxygen esters in the
acetate pathway.
Thioesters are used because they are more reactive towards nucleophilic acyl
substitution than esters. Also, thioesters enol can react with an electrophile to yield an
alpha substitution product that is they enolize readily than esters.
Thioesters are also compared to other chemical components like oxygen esters thermo-
chemically and kinetically. Thermo-chemically, thioester linkages produce a lot of energy
upon hydrolysis compared to oxygen esters. Kinetically, thioester reactivity at the alpha
carbon compares favorably with that of ketones.

Thioester resonance Ester resonance

.. ..
.
.O .O
.
R R
.. ..
S H3C O
H3C .. ..

.. ..
. O-.. . O-.
. . .

R R

+ +
S H3C O
H3C .. ..

(b) Describe the chemical test that can be used to distinguish an alkaloid from a
triterpene.
Presents of alkaloids can be detected using the Dragendroff’s test. A potassium bismuth
iodine solution (Dragendroff’s reagent) is added to a sample and presence of alkaloids can
be indicated by an orange-red precipitate.
(c. i). What type of compound is cholesterol?
Cholesterol is a steroid.
(ii) Describe the functions of cholesterol in in humans.
Cholesterol acts as an intermediate in the biosynthesis of all other steroids in the body. It
also aids in the development of tissues and hardening of arteries. Cholesterol is also
 involved in bile production in the liver and lastly it is used to maintain fluidity of
membranes in the body.
(d) Draw a general structure of a phenolic compound.
OH

phenol

(ii) Using examples describe the use of tannins as medicines.

Tannins are a subgroup of phenolics and are less widely used in medicine due to their
tumorous effects. In a positive way in medicines, tannins act as immunomodulatory
agents in the fighting against diseases for example Galic acid and Ellagic. Moreover,
tannins are used to treat tonsillitis, pharyngitis, hemorrhoids and skin ulcers because of
their styptic and astringent properties.
Tannins are also known to have anti-inflammatory effects and help control gastric,
esophagitis, enteritis, and irritating bowel disorder.
Tannins are also used for immediate relief of sore throats, diarrhea and dysentery. They
are also said to reversibly react with proteins thus complexing within the bacterial
membranes neutralizing the acidity hence the antibacterial activity of tannins particularly
polymeric proanthocynanidins are effective towards E-coli.
2. Outline the biosynthesis of carotenoids.
Carotenoids are tetra terpenes derived from the 40 carbon isoprenoid phytoene. They are
synthesized in all photosynthetic organisms (including plants) and some non-
photosynthetic bacteria and fungi. The first step involves the isomerization of isopentenyl
pyrophosphate (IPP) to dimethyl allyl pyrophosphate (DMAPP) and the sequential
addition of three further IPP molecules to DMAPP. These reactions, catalyzed by prenyl
transferases, yield the C20 compound geranylgeranyl pyrophosphate (GGPP). In
carotenogeneic systems, two GGPP molecules condense head to head to form, via
prephytoene pyrophosphate, phytoene. Phytoene is then desaturated by virtue of
phytoene desaturase enzyme to form phytofluene which is also desaturated further to
form ζ carotene. ζ carotene is desaturated to neurosporine then to lycopene using ζ
carotene desaturase. Lycopene is a carotenoid which can be cyclized to alpha carotene or
beta carotene through lycopene alpha or beta cyclase.
 CH3 H3C

O O O
O

+ +
P P P P
H2C H3C
- - -
- O O
O O

DMAPP
IPP

GGPP Synthase

CH3 CH3 CH3 H3C

O O
H3C +
P P GGPP
- -
O O

Phytoene synthase

CH3 CH3 CH3 CH3

CH3

H3C
CH3 CH3 CH3 CH3

phytoene
Phytoene desaturase

CH3 CH3 CH3

CH3
CH3
H3C
CH3 H3C CH3 CH3

phytofluene
Phytoene desaturase

CH3 CH3 CH3

CH3
CH3
H3C
CH3 H3C CH3 CH3

carotene desaturase carotene

CH3 CH3 CH3
CH3
CH3
H3C
CH3 H3C CH3 CH3
neurosporene
carotene desaturase

CH3 CH3 CH3

CH3
CH3
H3C
CH3 H3C CH3 CH3

lycopene alpha cyclase lycopene

CH3
H3C
H3C CH3 H3C

CH3 CH3 CH3

CH3
H3C alpha carorene
3. Differentiate the acetate pathway from mevalonate pathway
ACETATE PATHWAY MEVALONATE PATHWAY
Is used in the synthesis of fatty acids Is used in the synthesis of isoprenes,
isoprenoids and steroids.
Takes place in the cytosol Takes place in the mitochondria matrix
There is phosphorylation There is no phosphorylation
The acyl carrier is ACP and cysteine The acyl carrier is acetyl coenzyme A

The intermediate is malonyl coenzyme A The intermediate is mevalonic acid

(mevalonate)

4. a) (i) Show the product of the following reaction.

H3C
CH3

H3C
CH3
H3C
CH3 CH3
CH3

H SUNLIGHT

H H
HO H
HO

7-dehydrocholesterol
vitamin D3
CH2

(ii) Describe the application of this reaction in food industries

The product is used in the production of baby food like cerelac.

(iii) Retrosynthetic Analysis

 H3C

CH3

CH3
N HO

CH3 OH

-
- C
CH
+ H3C CH3
C
N -
CH

CH3
O
Li

H3C CH3

N
SYNTHESIS

CH3 CH3
Li Li
+ Cl Cl + HCl

Cl CH3
CH3
Li
Li
ether
+ Mg
2+

Mg
Cl Cl
CH3 CH3
O
H3O
Li Li

+
- H3C CH3
C
Mg H3C CH3
Cl
OH

CH3
Li
CH3 N
H3C + N
HO H3C CH3
CH3
OH
REFERENCES
1. Natural Product Chemistry, Jurt B.G. Torssell, 1983.
2. Medicinal natural products, Paul Dewick, Wiley, 1998.
3. Cholesterol and steroid hormones.htm
4. http://atom.chem.wwu.edu/dept/facstaff/pavia/425pavia.html, Natural products
lecture notes.
5. www.usm.my/pharmacy/ (Liu J and Lu R( 2002)The Alkaloids, ed. A. Brossi, vol.
33, p. 83, Academic Press, New)