CHM136 Problem Set 2 – Spectroscopy

To be attempted after completion of slide deck 2.

A. Degree of Unsaturation

1. What is the degree of unsaturation for Histrionicotoxin 283A (shown below), which is a toxin
used by poisonous tree frogs as a defense mechanism against predators?

H
N
HO

(a) (b) (c) (d) (e)

6 8 9 10 12

2. What is the degree of unsaturation for the molecule shown below?

NH2

N N
O
N
C
N
HO OH

(a) (b) (c) (d) (e)

3 4 7 8 9

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3. Provide the degree of unsaturation for each of the molecules below.

Molecule Degree of unsaturation

C10H11NO2

C10H13FO

C4H4O3S2

5-chloro-4-oxohex-2-enal

N,N-dimethylpent-3-enamide

oct-5-yn-3-one

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B. Mass Spectrometry

4. The mass spectrum of cyclopentanol is shown below. Decide whether the following statements
about the spectrum are TRUE or FALSE and provide a BRIEF (1-2 sentence) explanation.

OH

(a) The base peak represents the molecular mass of cyclopentanol. TRUE FALSE
Explanation:

(b) The M+ signal has an m/z value of 86. TRUE FALSE

Explanation:

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5. Assign the molecular ion and base peaks for the mass spectrum of 1-phenylpentane (shown
below).

1-phenylpentane

Molecular ion peak Base peak

(a) 149 91
(b) 148 91
(c) 149 92
(d) 148 92
(e) 92 148

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C. Infrared Spectroscopy

6. Which characteristic signals(s) would you expect in the IR

spectrum of prednisone?

(i) ~2700-3600 cm-1 (strong, broad)

(ii) ~2100-2260 cm-1 (medium, sharp)
(iii) ~1700-1800 cm-1 (strong, sharp)

(a) (b) (c) (d) (e)

Only one of i, ii, or iii All of i, ii, and iii Only i and ii Only i and iii Only ii and iii

7. Which compound best matches the IR spectrum shown?

OH
O
H 2N HO O
HO

(a) (b) (c) (d) (e)

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8. What compound best matches the IR spectrum shown?

O
HO HO
OH
(a) (b) (c) (d) (e)

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9. Shown below is the IR spectrum of an unknown organic compound with a molecular formula of
C2H4O2. Answer the questions below about this compound.

(a) What is the degree of unsaturation of this compound?

(b) Based on the IR spectrum, which functional group(s) is/are likely present in the molecule? Reference
speci`ic signals from the IR in your answer.

(c) Propose a structure for the unknown.

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10. What DISTINCT signal(s), if any, do you expect to observe in the IR spectrum for the following
compounds in the speci`ied regions? Be speci`ic and indicate the functional group and bond involved
in producing each signal(s). If a compound does not show a signal in a wavenumber range, clearly
indicate NONE:

Compound A Compound B

Wavenumber
O OH
Range (cm-1) N N
O Cl

> 3000

2100-2260

1680-1800

1500-1680

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11. Match each compound with its corresponding IR spectrum. Provide a BRIEF (1-2 sentence)
explanation why you selected your answer.

O O O

OH O NH2
OH NH2

A B C D E

Spectrum 1 Compound and Explanation

Spectrum 2

Spectrum 3

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 Spectrum 4

Spectrum 5

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D. Nuclear Magnetic Resonance Spectroscopy

12. Identify the structure of the compound represented in the 1H-NMR spectrum below, with molecular
formula C6H10O2:

O O O O O O OH
O
H H OH
O
(a) (b) (c) (d) (e)

13. Which compound corresponds to the following 1H NMR spectrum?

OH
HO O O HO

(a) (b) (c) (d) (e)

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14. Consider the 1H NMR spectrum for the compound shown below. For the compound below, predict
the number of unique 1H NMR signals, and the integration for each signal.

(a) 6 signals with the following integrations: 1H, 1H, 1H, 1H, 3H, 9H
(b) 6 signals with the following integrations: 1H, 1H, 2H, 3H, 3H, 9H
(c) 7 signals with the following integrations: 1H, 1H, 1H, 1H, 2H, 4H, 6H
(d) 7 signals with the following integrations: 1H, 1H, 1H, 1H, 3H, 3H, 6H
(e) 8 signals with the following integrations: 1H, 1H, 1H, 1H, 3H, 3H, 3H, 3H

15. Draw an isomer of C6H12O that contains an sp2-hybridized oxygen atom and produces a 1H NMR
spectrum with only 2 unique signals having the following characteristics: 1.13 ppm (integrates to
9H) and 2.14 ppm (integrates to 3H).

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16. Indicate the number of 1H NMR signals expected for each of the following compounds.

Compound Number of 1H NMR signals

O
OH

O
O

O O

OH

HO OH

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17. Match each compound with its corresponding 1H NMR spectrum. Provide a BRIEF (1-2 sentence)
explanation why you selected your answer.

O O O O
O
O O

A B C D E

Spectrum 1 Compound and Explanation

Spectrum 2

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 Spectrum 3

Spectrum 4

Spectrum 5

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E. Structure Solving using IR and NMR Spectroscopy

18. Which compound corresponds to the following IR and 1H NMR spectra?

H
N H
NH2 OH O N

(a) (b) (c) (d) (e)

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19. Answer the following questions about an unknown compound X that produced the IR and 1H NMR
spectra shown below. Unknown compound X has a molecular formula of C3H6O2.

IR spectrum

1H NMR spectrum

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(a) Do the spectra show evidence that any functional groups are present that contain sp2-hybridized
atom(s), and if so, which signals show this evidence? Be speci`ic and indicate the functional
group/bond involved and where it is found in the spectrum.

Yes No Evidence

IR ❏ ❏
1H NMR ❏ ❏

(b) How many degrees of unsaturation are present in unknown compound X?

(c) Draw the most likely structure for unknown compound X.

(d) CIRCLE the most deshielded proton(s) on the structure of compound X.

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20. Answer the following questions about an unknown compound Y that produced the IR and 1H NMR
spectra shown below. Unknown compound Y has a molecular formula of C8H11N.

1H NMR Spectrum (integrations shown above each signal):

IR data: 3300 cm-1 (weak, broad)

(a) Propose a structure for compound Y.

(b) What functional group is responsible for the weak, broad signal at 3300 cm-1 in the IR spectrum?

(c) Name ONE other important absorbance signal you would expect in the IR spectrum of compound
Y, along with the functional group responsible for it.

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21. Answer the following questions about an unknown compound Z that produced the IR and 1H NMR
spectra shown below. Unknown compound Z has a molecular formula of C8H8O2.

IR Spectrum

1H NMR Spectrum

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(a) Do the spectra show evidence that any functional groups are present that contain sp2-hybridized
atom(s), and if so, which signals show this evidence? Be speci`ic and indicate the functional
group/bond involved and where it is found in the spectrum.

Yes No Evidence

IR ❏ ❏
1H NMR ❏ ❏

(b) How many degrees of unsaturation are present in unknown compound Z?

(c) Draw the most likely structure for unknown compound Z.

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