CH2102: Organic Chemistry & Spectrophotometry

(CA 12 March 2013) Answer ALL parts 1. Whereas H3PO4 is a triprotic acid, H3PO3 is a diprotic. Draw structures for these two acids and account for this differences. Which is the stronger acid & why? (7 marks) There are four dimethylcyclopropane isomers, (a) Write three-dimensional formulas for these isomers, (b) Which of the isomers are chiral? (c) If a mixture consisting of 1 mol of each of these isomers were subjected to simple gas chromatography (an analytical method that can separate compounds according to boiling point), how many fractions would be obtained and which compounds would each fraction contain? (d) How many of these fractions would be optically active? (18 marks) Cortisone is a natural steroid that can be isolated from the adrenal cortex. It has antiinflammatory properties and is used to treat a variety of disorders (e.g., as a topical application for common skin diseases). (a) Identify all of the chirality centers in cortisone, (b) Assign the appropriate (R) or (S) designation for the configuration of each chirality center. Propose a mechanism for the following:
Br EtOH warm + OEt + HBr

3.

HO O H H O H

OH

Cortisone

(12 marks) 4.

(7 marks) 5. Provide a concise explanation why the following molecule cannot undergo an E2 reaction:
H

Br Me

(6 marks) END OF PAPER

Answers
Question 1 H3PO4

O HO P OH OH

H3PO3

O HO P H OH

H3PO4 has 3 & H3PO3 has 2 protons (in red) which can be deprotonated. Thus they would be a triprotic & diprotic acid respectively. H3PO4 would be expected to be a stronger acid since there are more electron withdrawing oxygen atoms which can stabilize the resulting anion(s) upon losing proton(s).

Question 2 (a)

(b) (c)

(3) and (4) are chiral and are enantiomers of each other. Three fractions: a fraction containing (1), a fraction containing (2), and a fraction containing (3) and (4) [because, being enantiomers, (3) and (4) would have the same vapor pressure], None

(d)

Question 3

HO O *
R S

* H
S

*
S

OH
(* = chiral centre)

* H

* H

Question 4
Br EtOH warm + OEt + HBr

- Brrelief of ring strain going fm 4 to 5 membered ring

-H+ -H+

OEt H

.. EtOH ..

Question 5 The anti-coplanar or syn-coplanar arrangement for the adjacent C-H & C-Br undergoing elimination MUST be attainable. Otherwise E2 is NOT possible.

H H Br

Drawing the given cis-decalin derivative in the chair form, it can be seen that none of the adjacent C-H bonds are in a coplanar arrangement to C-Br, except the C-Me bond. (C-Br and C-Me in red in anti-coplanar). Thus elimination of HBr is not possible.

H Me H