Elsy Saravia RIU – CHEM 14C – FALL 2024

d06-219-639

Problem Set #5 (Due Date: 11/13/2024)

I) Multiple Choice: For each question, choose the best answer and write your answer
in the box(es) provided. For True or False questions, write T for True and F for False.

1) The relative peak intensities of multiplets can be described with the “Pascal
P triangle.” Using the Pascal triangle, what is the correct ratio of the intensities of a
quartet?

A) 1:1:1:1 B) 1:2:2:1 C) 1:1:2:2 D) 1:3:3:1 E) 1:4:4:1

P 2) Which statement about “shielding” is correct?

A) The more shielded a nucleus, the higher is the effective magnetic field at the nucleus
and the higher is the level splitting.
B) he more shielded a nucleus, the higher is the effective magnetic field at the nucleus
and the lower is the level splitting.
C) The more shielded a nucleus, the lower is the effective magnetic field at the nucleus
and the higher is the level splitting
& D) The more shielded a nucleus, the lower is the effective magnetic field at the nucleus
and the lower is the level splitting.

P 3) Which of the following isotopes is NMR inactive?

15 19 33
A) N B) F C) S D) 16O E) 2H F) These can all be studied using NMR

FALSE 4) True or False: A “downfield” peak appears at a lower ppm value.

5) True or False: 1H-decoupled 13C NMR spectra of hydrocarbons only exhibit

FALSE singlets because of the low natural abundance of 13C.

pg. 1
 RIU – CHEM 14C – FALL 2024

II) NMR Spectroscopy:

A) How many different signals would you expect in the 1H and 13C NMR spectra for
each of the following molecules.
HH

·m
H
, HN O
*
.....
C O
in -
Cl
H
-
H

H met
-

H
H
O
HH
M H
# of 1H
NMR 4 4 S 4 I
Signals:

# of 13C
NMR 4 6 5 7 S
Signals:

B) What is the predicted splitting pattern (multiplicity) of the indicated hydrogens in

the following molecules and expected peak integral of each H-type, reported in number
of hydrogens? You may either write out the full words or use the proper abbreviations.

Multiplicity: Peak Integral (#H):

Ha: ________________
septet ________________
It
Hb O Hc
Hb: ________________
doublet ________________
3H
YH
C CH Hd Hc: ________________
quartet ________________
It
O ↑

T
Hd: ________________
triplet ________________
37
Ha HH

Ha
Multiplicity: Peak Integral (#H):
C
Ha: ________________
singlet ________________
It

Hb: ________________
singlet ________________
3H
Hb C O ________________ ________________
IH
HH
Hc: whariet

H
T
-H Y
Hd Hd: ________________
triplet ________________
3H

O
H

F Cl Hc
HH

pg. 2
 RIU – CHEM 14C – FALL 2024

C) Rank the following protons according to their expected 1H NMR chemical shift.

Ha Hb Hc

Cl Me2N Deshielded _____

Ha > _____ HC Shielded
Hp > _____

Cl

O O O

He > _____
Deshielded _____ Ha > _____
Ha Shielded

Ha Hb Hc

III) NMR Spectroscopy Con.: Unknown amines A and B are constitutional isomers
with molecular formula C8H11N and result in the following NMR spectroscopic data
(singlet = s, m = multiplet, t = triplet, br = broad):

Amine A:
1
H NMR: 6.80 (s, 1H), 6.77 (2H), 5.28 (2H, br), 2.28 (6H, s) ppm.
13
C NMR: 147.2, 139.1, 120.9, 113.0, 21.6 ppm

Amine B:
1
H NMR: 7.25 (m, 2H), 7.24 (m, 2H), 7.19 (m, 1H), 2.98 (2H, t), 2.83 (2H, t), 1.6 (2H, br) ppm.
13
C NMR: 139.4, 128.6, 127.7 125.9, 41.9, 39.0 ppm

a) What is the double bond equivalents (DBE) value for each of these amines: 4

b) Based on the NMR data, draw the structures of amine A and B below.

Amine A Amine B
HzC CH3

N "
.
HN CH3

I
I

=
18 - 11 = 1+ 1 8/2 4 =
pg. 3
10 + 2

8 2 +2 11 0
=
1
-
. -
+
=
4
DBE =
2

16 2+ -
11 + 1

18 -
11 + 1
7+ 1 =
 RIU – CHEM 14C – FALL 2024

c) For amine A, explain why the 1H NMR signals between 6.80-6.77 ppm are more
shielded than typical protons of this class (no more than one sentences). You may also
include drawings in box below to support your explanation.

The 'H NMR signals in amine A are more shielded

because of the nitrogen lone pair !!

d) While studying the molecules above, you notice a small peak at 0 ppm in both NMR
spectra. Draw the molecule that is causing that signal, then explain its presence (no
more than one sentence).

which is commonly used as

Caused by TMS the

H32/CHE) an internal standared.

Si
Hyd CH3

pg. 4
 RIU – CHEM 14C – FALL 2024
↑

IV) NMR Spectroscopy Con.: Provided below is the 1H NMR spectrum of an alkyl
bromide. Each of the carbons in the structure are labelled with capital letters to represent
the hydrogens attached to that carbon. Each of the peaks in the 1H NMR spectrum are
labelled with lower case letters. The light blue “pedestals” above each peak gives its
integration. ⑥ domblet
Hi

- 2 -
H

&H quartet 6
( /-
H
,,
C
+

& It seplet C
-H
IH sextet
X
M
C

H
dombite
O
H
# tripleStelded 3
q
-

T
2 H

zhaninter 2
34 triplet
2
1
1

f
1/g
c d
ASC
a
& b
& e
......
nouber >
-
6 H doubler
anarret

I t
aninter

minetriplet
septet sextet

G
Xcepset
anaret
criplet
3.5 3.0 2.0 1.5 1.0 H

In taminer
H F
G B
E D
Match the protons on each carbon atom to their peak by writing the capital letter onto
the line next to the appropriate lower-case letter. At least one peak will have multiple
letters assigned to it.

H
a. ___________ ⑬
d. ___________ g. ___________
A, C

b. ___________
G e. ___________
D

c. ___________
E F
f. ___________

pg. 5
 RIU – CHEM 14C – FALL 2024

V) Noncovalent Interactions: Answer the following question about the molecules

shown below.

F
O
I Cl Ne

F F ~
A B C ~ X
D

H
O O
Cl Cl
S CO2
O O
~
E F~ X
G H

i) Which molecules exhibit intermolecular dipole-dipole interactions (separate

A, B C , E , F , H
each letter using a comma):__________________________________________
,

ii) One of the molecules also exhibits an intramolecular dipole-dipole interaction.

&

Draw the molecule and intramolecular interaction (using a dotted line) in the
box below.

p --- Ho iii) Name of this dipole-dipole

interaction:
_______________
Hydrogen Bonding

pg. 6
 RIU – CHEM 14C – FALL 2024

1
H and 13C NMR Tables:
Note that NMR peaks may lay outside of the listed ranges due to other effects, such as
the electronegativity of nearby atoms

pg. 7