CHM556

TUTORIAL 2
SPECTROSCOPY (NMR & IR)

1.
a) Isopropyl alcohol can be oxidized to acetone via hot oxidation of sodium dichromate.

Na2Cr2O7.2H2O

conc. H2SO4
Isopropyl heat Acetone
alcohol

I. Sketch a predicted 1H NMR spectrum for isopropyl alcohol with signals in estimated chemical
shift ranges and with expected splitting pattern.
II. Give the integral values as a whole number ratio for the signals in the 1H NMR spectrum of
isopropyl alcohol.
III. How many 13C NMR signals would you predict for isopropyl alcohol?
IV. How many sets of peaks would you expect to observe in the 1H NMR spectrum of acetone?
V. State one oxidizing agent for the above reaction other than sodium dichromate.

2.
a) Two aromatic compounds (A and B) have the same molecular formula of C9H10O. They
both show infrared spectra with a strong absorption at 1710 cm-1. Determine the structures
of the compounds if they show the following 1H-NMR data.

Compound A Compound B
2.0 ppm, singlet, 3H 0.98 ppm, triplet, 3H
3.7 ppm, singlet, 2H 2.3 ppm, quartet, 2H
7.4 - 7.6 ppm, multiplet, 5H 7.4 - 7.6 ppm, multiplet, 5H

3.
a) Compound E with a molecular formula of C4H8O, gives a positive iodoform test and has the
following 1H-NMR data.

Compound E
Triplet, 1.3 ppm
Singlet, 2.1 ppm
Quartet, 2.7 ppm

i) Suggest the structure of E.

ii) Outline an equation for the reaction between compound E and the iodoform test
reagents.

iii) Compound E could also be reduced by sodium borohydride, NaBH4, in methanol. State
how you would confirm that the reduction has taken place using IR spectroscopy.
4.
a) Consider the following reactions.

LiAlH4 DiBAL-H
Ester A

Benzyl alcohol Benzaldehyde

i) Having a sharp singlet at the chemical shift of 3.73 ppm on the 1H NMR spectrum, indicate the
structure of the starting ester A.
ii) What is the distinguished feature in the IR spectra that can differentiate the two products above?
iii) Why DiBAL-H reduces ester A to benzaldehyde and not to its corresponding alcohol?

b) Outline a stepwise synthesis of succinic acid, HOOCCH2CH2COOH from ethylene, CH2=CH2.

5.
Under different reaction media, vanillin undergoes esterification with acetyl chloride yielding
two different products.

Basic or
?
acidic medium

Vanillin

i) Based on the IR spectrum of vanillin, at what range should you observe the absorption signal
of the hydroxyl group?
ii) Draw the structures of the major products for the esterification of vanillin with acetyl chloride
in:
I. 10% NaOH solution
II. 1.0 M H2SO4 solution