NMR Practice 2 Answers

Question One (four marks)

In the 300 MHz spectrum of a certain compound there are two triplets separated by 3 ppm. The observed coupling
constant is 7 Hz.
i.)
What is this separation in Hz?



3 Hz/MHz x 300 MHz = 900 Hz





ii.) In a 500 MHz instrument, what is the separation between these signals in Hz?
1500 Hz

iii.) In a 500 MHz instrument, what is the separation between these signals in ppm?
3 ppm
iv.) What is the coupling constant? 7 Hz (Coupling constants are indecpendent of field strength)

Question Two (nine marks)

i) Determine the topicity of the groups or atoms shown in bold.
ii) In the boxes provide, give the number of proton and carbon signals you might expect to see.
Diastereotopic Diastereotopic Diastereotopic
CH3 Diastereotopic
HO H H H Ph
H H3CO H
H
*
H H H
O H3CO H
H3CO CH HC OCH
H H 3
Diastereotopic F
H3CO OCH3
CH3 F
Homotopic by C2 rotation. Enantiotopic Diastereotopic

H 4 H 5 H 7 or 9
H 8

3 6 C 4 C 9
C C
Question Three (six marks)

On the chart below, sketch the proton NMR spectrum that you would expect for the molecule shown.

C
O

H3CO

8 7 6 5 4 3 2 1 0
Question Four (three marks)
Below is the 13C NMR spectrum of one of the three xylenes (dimethylbenzenes). Which one? Explain your reasoning.
The triplet at 77 ppm is CDCl3.

Meta-xylene will exhibit a total of 5 lines as observed. Ortho-xylene will show only 4 and para-xylene only 3 lines.
Question Five (five marks)
i) Classify the methyl groups on the molecule N, N-Dimethylformamide as homotopic, enantiotopic or diastereotopic.
One would expect them to be homotopic by C-N bond rotation.
ii) Below are the remarkably similar 13C and proton NMR spectra of this molecule. In another example of molecules
doing as they damn well please in spite of what we think, what is the actual topicity of these methyl groups?
If they have different chemical shifts, then these must be diastereotopic.

C CH3
H N

CH3

iii) Explain why these methyl groups appear in these spectra as they do. You may want to review your Chem 2500
assignments.
O Due to the importance of the charge-separated resonance
O
structure, there is enough double-bond character (you
C CH3 calculated it in 2500) to slow the rotation about the C-N
C CH3 H bond making this appear like an alkene with one methyl
H N N
cis to O and one trans.
H3C H3C
Question Six (ten marks)
Remember to give the spectral evidence for your answers. This is generally the case.
Below is the proton NMR spectrum of p-methoxycinnimaldehye at 400 MHz. Expansions are printed below.
i.) Is this molecule cis- or trans-cinnimaldehyde? Trans: the vinyl coupling constant is 16 Hz.
ii.) Assign all of the protons to their respective signals.
iii) Account for the position of the vinyl protons.

H6 H5
H3 O O
H H
H3CO C C C H3CO C C C

H4 H H

OCH3

H5
CHO H3 H6
H4
Unknown Questions - 15 marks each
Give brief analyses and assign spectra as thoroughly as possible. Spectra are recorded at 400 MHz proton and 100 MHz
13C.
Unknown One C6H6BrN
The IR indicactes that an NH2 is present and the proton NMR shows a broad two proton
NH2 peak integrating to two consistent with this. There are four protons in the aromatic
region of the proton NMR which tells us this is a disubstituted benzene with one
H6 H2 substituent NH2 and one Br. The splitting pattern in the proton NMR exhibits a meta-
coupled triplet which is only possible if there is a single proton flanked by two
substituents, therefore this must be a 1,3-disubstituted benzene.

H5 Br

H4 NH2

H5 H2

H4
H6
NH2

C-NH2
Unknown Two C8H12O2 The proton signal at 3.7 looks like a methyl group attached to O. The other four resonances,
three CH2s and a methyl looks like an n-butyl group. We have three carbons and an O to
account for. The 13C peak at 155 is low for a C=O but possible and there are two downfield
carbons characteristic of unsaturation. We have only enough atoms left for a C=O and a C-C
triple bond:

H3CO

OCH3
O C C
C
Unknown Three - C7H7NO2 Problems with this proton spectrum. The broad peaks at 3.5 and 8.5 integrate too low.
We can only assume that they are two and one respectively. Four aromatic protons
indicate that this is a disubstituted benzene. The 13C NMR indicates a carbonyl. The
proton NMR show two ortho coupled triplets only possible in a 1,2 disubstituted
benzene. The substituents must include a carbonyl, an NH2 and an OH (the latter based
on the two broad resonances). This leaveas

CO2H CONH2 as possibilities and I accepted

both. It is actually the former
compound. The problem with
this spectrum, I now realize, is
NH2 OH that the peak at 3.5 is actually
a water peak associated with
the NMR solvent. The OH
peak is missing and is
probably downfield somewhere

H2
H3
H5 H3 CO2H
H2 H4

H4 NH2

H5
C=O