5

Carbohydrates

(ii) A six-proton singlet at the highest field (-11 or -89) is posible due to presence of isopropyl
group where the two methyl groups are attached to same carbon. This shows that one fragment of the
compound will be

CH3 . These are marked as a.

C
CH3

(iii) A three-proton singlet at -21 or -79 indicates that a methyl group is attached to a C=O
group. This means another fragment of the compound is CH3CO group. These are marked as b.
(iv) A two-proton singlet at -26 or -74 indicates that a methylene group is present which has
proton free carbons attached to it. This means on one side of it we have a C=O group and on other side
of it we have

CH3. These are marked as c.

C
CH3

(v) A single-proton singlet at -39 or -61 indicates that a hydroxyl group is attached to carbon
having no proton. It is marked as d.
On combining the above information the following structure can be assigned to the compound :
a
O
CH3
b
c
a
H3C C CH2 C CH3
d
OH
The name of the compound is diacetone alcohol or 4-hydroxy-4-methylpentan-2-one.
Solved Problem 4. Elemental analysis of a compound (molecular mass 137) shows the
presence of carbon, hydrogen and bromine. The PMR spectrum of the compound using TMS as
the reference shows the following three peaks : (i) Doublet, -104 or -896 (ii) Complex multiplet,
-195 or -805 and (iii) Doublet, -333 or -667. The ratio of areas under the peak is 6 : 1 : 2.
Assign the structure to the molecule.
Solution. The compound has bromine and its molecular formula is 137. This means we can have
only one bromine atom in the compound because the atomic weight of bromine is 80. The remaining
weight of the compound will be due to carbon and hydrogens. The sum of the ratios of the areas under
the peaks show presence of 9 protons (6 + 2 + 1). This means there will be four carbons. This is
because the total weight due to carbons will be (137 80 9 = 48). So, the molecular formula of the
compound will be C4H9Br.
This molecular formula can be represented by four structural isomers i.e. 1-bromobutane, 2bromobutane, 1-Bromo-2-methylpropane and 2-Bromo-2- methylpropane. Structures of all the compounds
are shown below
a
H3C

b
CH2

c
CH2

d
CH2

1-Bromobutane

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Br

a
H3C

b
CH2

Br
c
CH

d
CH3

2-Bromobutane

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