Name: 07/03/2021

Student ID:
Instructor: Yunus Emre Türkmen

CHEM 232 Organic Chemistry II - 2021 Spring Semester –

Midterm 1 (Remote Exam) Solutions
(Overall 100 Points, Duration: 2 h)

1) (20 points) a) Based on the reaction scheme given below, determine the
structures of compounds A-D. (16 points)

Hint: In its structure, compound D has 9 sets of chemically equivalent hydrogens,

and therefore is expected to exhibit 9 signals in its 1H-NMR spectrum.

O
CN
CH3 NBS (1 equiv) A Me
AIBN: Me N CN
(major NBS: N Br N
Me
(PhCO2)2 (5%) product) Me
Br O
heat

NBS (1 equiv) B NaHS 1) NaOH (1 equiv)

CH3 D
(major C (C16H16S)
AIBN (5%) product) 2) Compound A
heat or light

Solution: Each correct answer is 4 points.

CH3 NBS (1 equiv)

Br

Br (PhCO2)2 (5%)
Br
heat
A

NBS (1 equiv) NaHS

CH3
Br SH
AIBN (5%)
heat or light
B C

Br
D

b) In the preparation of A, (PhCO2)2 acts as a radical initiator. Draw the

mechanism(s) of the reaction(s) using curved arrows for the generation of radical(s)
when (PhCO2)2 is heated. (4 points)

1
Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen

Solution: Each step is 2 points.

O
O
heat O +
O 2 2 2CO2
O
O

2) (20 points) a) Determine the number of signals you would expect from the
13C{1H}-NMR (1H-decoupled 13C-NMR) spectra of the following compounds. (12

points)

CH3
CH3 CH3 CH3
H 3C CH3

H 3C
CH3

Solution: Each correct answer is 3 points.

CH3
CH3 CH3 CH3
H 3C CH3

H 3C
CH3
6 signals 7 signals 7 signals 6 signals

b) In an undergraduate laboratory experiment, when students recorded the IR

spectrum of air, they observed a strong signal at ~2300 cm-1. Among N2, O2, CO2 and
argon, which are major components of air, which one(s) do you think might be
responsible for this signal? Explain your reasoning. (8 points)

Answer: Ar does not have a vibrational motion since it is a mono-atomic gas. N2 and
O2 are homonuclear diatomic molecules. Since the stretching vibrational motion
does not cause a change in the net dipole moment, these two molecules do not
exhibit a signal in their IR spectra. The signal at ~2300 cm-1 results from the
unsymmetrical stretching vibration of CO2.

2
Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen

3) (20 points) a) Compound A has a molecular formula of C7H14O2, and its 1H-NMR
spectrum is shown below. Propose a plausible structure for A. (10 points)

Answer:

O
A

3
Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen

b) Compound B has a molecular formula of C13H18, and its 1H-NMR spectroscopic

data are given below. Propose a plausible structure for B. (10 points)

1H-NMR Data for B

Chemical shift
Multiplicity Integration
(ppm)
1.28 singlet 9H
2.27 singlet 3H
6.37 doublet 1H
6.43 doublet 1H
7.16 doublet 2H
7.25 doublet 2H

Answer:

CH3 CH3
CH3
CH3 or H 3C
H 3C
H 3C CH3

4) (20 points) a) Propose a detailed mechanism for the following transformation

using curved arrows. Please indicate initiation, propagation and termination steps
explicitly. (12 points)

CH3 H 3C O heat CH3

+ Cl H 3C OH
H 3C +
H 3C CH3 CH3 H 3C H 3C CH3
CH3 Cl

4
Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen
Solution:

Initiation:

H 3C O heat H 3C O +
Cl Cl
H 3C H 3C
CH3 CH3

Propagation:

H 3C OH CH3
H 3C O + H CH3
H 3C +
H 3C H 3C CH3 CH3 H 3C CH3
CH3

CH3 O CH3 CH3 H 3C O

Cl CH +
H 3C CH3 CH3 3 H 3C
H 3C CH3 CH3
Cl

Termination:
Cl + Cl Cl2

CH3 CH3

H 3C CH3 Cl H 3C CH3
Cl

CH3 CH3 H 3C CH3

H 3C CH3 H 3C CH3
H 3C CH3 H 3C CH3

b) When compound H is irradiated in the presence of 1 equivalent of Br2, K and L,

which are diastereomers of each other, are obtained as major products. Draw the
structures of K and L by paying attention to stereochemical details. (8 points)

CH3
Br2
H 3C CH3 K + L
light
Br
H
single enantiomer
Solution: Each correct structure is 4 points.

Br CH3 H3C Br
H 3C CH3 H 3C CH3

Br Br

K L

5
Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen

5) (20 points) Assume that you want to convert X to Y and Z selectively, and analyze
the reaction outcome by mass spectrometry. Draw the expected signal patterns with
the corresponding m/z values for the molecular radical cation (M+•) in their low-
resolution mass spectra. Provide the intensity ratios of all major peaks that belong
to the molecular ions. Please pay attention to the major isotope distributions.

HO OH OH
B B Br Br Br B
HO OH OH
Z X Y

Approximate
Element Major Isotopes Natural Abundance (%)
Atomic Mass
C 12C 98.9 12
H 1H 99.9 1
O 16O 99.8 16
79Br 50.7 79
Br 81Br 49.3 81
10B 19.9 10
B 11B 80.1 11

Solution:
Ratio = 1:2:1

79Br81Br

79Br79Br 81Br81Br
Br Br

X
234 236 238

(m/z)

Ratio = 1:4:1:4

79Br11B 81Br11B

OH
Br B
79Br10B 81Br10B
OH
Y

199 200 201 202

(m/z)

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Name: 07/03/2021
Student ID:
Instructor: Yunus Emre Türkmen

Ratio = 1:8:16

11B11B

10B11B

HO OH
10B10B
B B
HO OH
Z
164 165 166
(m/z)