CH301 Tutorial Solutions

UV Spectroscopy

1. The reaction shown below was studied using a high pressure liquid
chromatograph (HPLC) instrument, equipped with a UV detector, operating at a
single wavelength of 254 nm. Which products (if any) would be detected and
which would not be detected and why?
O O
MBr OH
+
+
Et2O

Not detected, since acyclic butadiene = 217nm Not detected,

It is not a conjugated 1 alkyl subs. +5nm not conjugated
or aromatic system 1 exo C=C +5nm or aromatic
ext. conj. +30nm
257nm

Note: Woodward-Fieser Rules which we will apply to three specific chromophores:

i. Conjugated dienes
ii. Conjugated dienones
iii. Aromatic systems

2. Calculate the max for the following compounds

CHO
O

a d MeO Cl
b c e

a) acyclic butadiene = 217nm b) Heteroannular (transoid) = 214nm

3 alkyl subs. +15nm 3 alkyl subs. +15nm
232nm 1 exo C=C +5nm
234nm

c) acyclic butadiene = 217nm d) acyclic enone = 215nm

1 exo C=C +5nm 2 x β-alkyl subs. +24nm
2 alkyl subs. +10nm 239nm
232nm

e) substituted benzene = 250nm

m-Cl +0
m-O-CH3 +7
257nm
3. The ketones below have max at 234, 244, 254 nm. Which ketone has which
absorption?

acyclic enone = 215nm cyclic enone = 215nm cyclic enone = 215nm

1 x α- alkyl subs. +10nm 2 exo C=C +10nm 2 x β-alkyl subs. +24nm
1 x β-alkyl subs. +12nm 2 x β-alkyl subs. +24nm 1 exo C=C +5nm
237nm 249nm 244nm

4. A diene, C11H16, was proposed to have the structure . Its UV-Vis

spectrum showed max = 263nm, with A = 0.85.

a) Determine if the structure is correct using woodward-fieser rules

Heteroannualr diene = 214nm
4 alkyl subs. +20nm
1 exo C=C +5nm
239nm

b) If the structure is not correct, using the same carbocyclic skeleton, draw a
structure that satisfies the spectrum
max = 253 + 2(5) = 263nm

c) If the cell used for the recording is 1 cm, with 3 mg of compound in 250ml of
ethanol, determine max.
The molecular weight of C11H16 (Mr) = 148 g/mol

Concentration of the solution = 3mg/0.25L = 12 mg/L = 12 x 10-3 g/L

Molarity of the solution = 12 x 10-3 g/L = 12 x 10-3 g/L = 8.108 x 10-5 mol/L
Mr 148g/mol

As absorbance (A) = ϵcl; ϵ = A/cl and as l = 1 cm,

ϵ = A/c
= 0.85/ 8.108 x 10-5 mol/L
= 10483 L mol-1 cm-1

d) Is it an allowed or forbidden transition?

e) What is the transition that is causing this transition?
Refer to lecture notes
5. Calculate the molar absorptivity for the compound shown below. max given is
given as 257 nm and pathlength of the cell is 1 cm.
O
Conc (mgL-1) max (A)

8.9 257 (1.05)

OH

max = 257 nm, A = 1.05

The molecular weight of compound (Mr) = 134 g/mol

Concentration of the solution = 8.9 mg/L = 8.9 x 10-3 g/L

Molarity of the solution = 8.9 x 10-3 g/L = 8.9 x 10-3 g/L = 6.64 x 10-5mol/L
Mr 134g/mol

As absorbance (A) = ϵ cl; ϵ = A/cl and as l = 1 cm,

ϵ = A/c
= 1.05/ 6.64 x 10-5 mol/L
= 15809 L mol-1 cm-1