Birla Institute of Technology & Science-Pilani, K. K.

Birla Goa Campus

Second Semester 2016-2017, Comprehensive Exam (Open Book)
COURSE TITLE: Organic Chemistry IV COURSE NO: CHEM F342
TOTAL MARKS: 40 Duration: 90 min Date: 10/05/17

Answer all the parts of a question together.

Marks will be awarded only for completely correct answers.

Q1 Write the IUPAC nomenclature for the following compounds [2]

(i) S O
N
(a) (b)
N
S
(ii) Draw the structure of the following compounds [2]
(a) 1,3,2,4-diazaphosphasiletidine
(b) Benzo[b]thiophene

Q2 (i) The carbonyl peak in IR for aziridinone, 2-azetidinone and butanamide were observed
in the regions 1830-1859, 1745-1765 and 1640 cm-1 respectively. Identify these
vibrational frequencies and give reason for the observed order. [2]
O
O
NH2
NH
NH
O
aziridinone azetididone buatanamide
(ii) Arrange pyridazine, pyrazine and pyrimidine in decreasing order of their aromaticity
with logical explanation for the observed order. [3]

Q3 (i) Predict the product and propose the mechanism for the following reaction [4]
NH OMe

POCl3
O ?
MeO Reflux, 2h
OH

(ii) Suggest three different ways in which you can differentiate between the structures of A
and B given below [3]
O
O

O
O
A= B=

(ii) Complete the following reactions by identifying the major product(s) with correct
stereochemistry wherever applicable [1x4]
Ph
O
 Cl
N ? Cl
(a) CCOOEt (b) S
?

EtOOC COOEt CCOOEt

O
H (i) Br2/ PBr3
N ?
(i) CH3I (ii) H2O
(c) ? + ? (d) OH
NMe2 (ii) Na-Hg, EtOH (iii) NH 3, Excess

P.T.O.

1
Q4 Answer the following questions about the BASF continuous citral process.

(i) Identify all the name reactions in the overall synthetic sequence. [2]
(ii) Draw the structures of the precursor molecules involved in formation of the main acetal
intermediate. [2]
(iii) Provide arrow pushing mechanism for the following step [3]
heating
+ HO
O O O

Q5 Carry out the synthesis of the following terpenoid in only two steps from 2-methyl-1,3-
butadiene and isopropyl vinyl ketone and any other suitable reagent you may require. [3]
HO

Q6 Provide all reagents for the following 5 step steroidal transformation. [5]

O
HO HO

Q7 Explain using the structure of vitamin C why it is a useful natural anti-oxidant. [1]

Q8 Explain mechanistically using curved arrows how in the synthesis of vitamin A (retinol) its
precursor retinal is reduced by the co-enzyme NADH. [4]
Adenosine
N

CHO CH2OH
H2NOC

END