3. (28 pts). Consider each of the following four pairs of molecules in turn.

For each pair, give ONE

form of spectroscopy (UV, IR, MS, 1H NMR) which will clearly distinguish the two. You may use each
form of spectroscopy only ONCE. Explain carefully the single most important spectral feature which
will distinguish the molecules.
O

A.

Me

Me
Cl

Cl

Only possibility is 1H NMR. In particular, the Me group will appear around 3.5 ppm in the molecule on the left, while the Me
in the right molecule will appear at about 2.3 ppm. Similar predictions can be made about the -CH2- group next to the C=O on the
left (2.6 ppm) compared to the one next to the O in the one on the rught (3.6 ppm).

O
O

B.
a

This is a good place to use IR. The C=O stretch in (a) appears at 1720 cm-1 (like any simple ketone) while the C=O stretch
for (b) will be at lower frequency due to conjugation, about 1680 cm-1. UV would also work: molecule (b) is a conjugated
ketone and will show a strong pi-to-pi* peak and weak n-to-pi* in the observable region, while (a) will show only the very weak
n-to-pi* peak. 1H NMR would show numerous differences.
No difference in the mass spec molecular ion pattern.

C.
HN

NH

CH3

Same nominal molecular weight, so MS is not too useful. One could make careful analysis of the M+2 peak height, but not very reliable.
1H NMR and IR would both be useful, but UV is obviously useful. (b) has long conjugation, very long wavelength !
max compared
to (a).

D.

Cl

HO

HO

Only real difference is in the mass spec molecular ion. (b) has I while (a) has Cl. Difference in mass of 92.