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Problem Set 3 - Spectroscopy (answers)

Calculus for the Life Sciences II (University of Ottawa)

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CHM 2120
Problem set 3 – ANSWERS

Part A.

1. Associate each of the following IR spectra with one of the

following compounds and justify your answer.
a. Propanoic acid: look for a carbonyl stretch and a broad
OH stretch
b. 2-Pentanol: look for an OH peak (broad). No carbonyl
peak, no sp2 CH’s.
c. Benzyl alcohol; Look for an OH peak and sp2 CH’s. No
carbonyl peak.
d. Acetophenone: Look for a carbonyl peak and sp2 CH’s. No
OH peak.
Note: the key functional groups must be identified. Identifying the
peaks on the spectrum directly is an straightforward way to do this.

sp3 CH’s
OH

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Problem set 3 - Answers

sp3 CH’s

OH sp2 CH’s

sp2 CH’s

C=O

OH

sp3 CH’s

C=O

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Problem set 3 - Answers

Associate each of the following IR spectra with one of the
following compounds and justify your answer.
e. 2-Propyn-1-ol: Look for an alkyne peak C≡C plus an OH
peak (broad) and a ≡CH.
f. 1-Pentyne: Look for an alkyne peak C≡C plus ≡CH. No
other key groups.
g. 4-Methylpentanenitrile: Look for a C≡N. No OH, C=O or
≡CH.
h. p-Acetylbenzonitrile: Look for C=O, sp2 CH’s and C≡N. No
≡CH.

Note: the key functional groups must be identified.

Identifying the peaks on the spectrum directly is an
straightforward way to do this.

sp3 CH’s

C=O

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Problem set 3 - Answers

sp3 CH’s

OH

C≡C

sp3 CH’s
C≡C-H

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Problem set 3 - Answers

2. Give the number of peaks expected for the indicated protons in
each of the following structures:
Note: s = singlet, d = doublet, t = triplet, q = quartet
a) b) c)
O H O
H 3C C O
CH3 H2
H3 C C Cl CH 3
H2
3 (t) H
3 (t)
2 (d) 5 (quintet)
2 (d) 2 (d)
d) e) 4 (q) f)
H 3C H2N CO2 H
H2 H CH3
CH3 C H
1 (s) H H 3C O
H O
1 (s) 1 (s) 4 (q) 2 (d)
2 (d) Note: usually a broad
singlet

3. How many signals would be expected in the following

molecules?
CH3 O
a) b) O c)
H O
CH CH3
H3 C C C H3C CH3 CH 3
H2 H2 Cl
1 signal H
5 signals
3 signals
d) HB e) f)
H2
H 3C HA H2
O C CH3
C H
H 3C O H 3C C O
CH3 H2
HB
2 signals
HA O 3 signals
4 signals

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Problem set 3 - Answers

4. Explain the following differences in chemical shift.
Me Me The "H" at 7.7 ppm is deshielded
a) Me Me by resonance. Another way to put
O O this is that resonance with the
H H H H carbonyl group removes electron
density from the proton.
 = 7.1  = 7.7 ppm

 = 6.7 ppm
b)
H O
H O The "H" at 6.7 ppm is strongly deshielded
by resonance. The proton at 6.1 ppm is
deshielded only by proximity to the
H
H electron-withdrawing carbonyl group. This
inductive effect is less powerf ul than the
 = 6.1 ppm resonance ef fect.

c) O  = 4.41 ppm
H2 O H2
C O C O
O C CH 3 O C CH 3
H2 H2

 = 3.6 ppm
The oxygen of the ester is even more electronegative
than the oxygen of the ether because resonance in the
ester is strongly drawing electron density to the
carbonyl oxygen. Electron density is consequently
pulled more strongly away from the H's at 4.41 ppm.

d) Me Me
N H  = 5.6 ppm N H

H  = 4.2 ppm H

Resonance with the nitrogen pushes electron density onto the H at 4.2
ppm, effectively "shielding" it with electrons.

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Problem set 3 - Answers

5. Determine the structure of the following unknowns using the
table to fill in your answers.
a.

Signal  Integration Multiplicity Comments

A ~4.3 1H m (multiplet) CH next to O (based on )
or septet
B ~2.0 3H s CH3 next to C=O

C ~1.3 6H d 2 x CH3 (identical) next to CH (i.e. an isopropyl

group)

DU = [5(2) + 2 – 10]/2 = 1

Integration: (6 mm + 18 + 34)/10H = 5.8 mm/H

The pieces:
CH3 O

CH ?
H3 C O ? CH 3

The molecule:
CH3 O

CH C 5H 10 O2
H3C O CH 3

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Problem set 3 - Answers

b.

D E
A B

Signal  Integration Multiplicity Comments

A ~7.8 2H (CH2 or 2 d Not all the 2H’s can be CH2 or there wouldn’t be
x CH) enough carbons accounted for in the molecule
(there are 10 carbons in the molecule);
These H’s are in the aromatic region—they can’t
be CH2’s – only CH group exist on aromatic rings.
Each CH is next to another CH
H
X H

H Y
H plane of symmetry
The red H has one neighbor (n = 1)
and is therefore a doublet.
B ~7.2 2H (CH2 or 2 d See explanation above
x CH)
C ~2.7 2H (CH2 or 2 q CH2 next to CH3 (b/c the peak is a quartet); not
x CH) directly next to O, could be next to C=O (based on
)
D ~2.6 3H s CH3 next to C=O (based on ) or on phenyl ring
(which acts like an electron-withdrawing group)
E ~1.2 3H t CH3 next to CH2

DU = [10(2) + 2 -12]/2 = 5
HINT: DU of 4 = phenyl ring…
In this molecule, there is probably a phenyl ring (DU = 4) + one ring
or one double bond
Integration: (11 mm + 11 + 11 + 17 + 17)/12H’s = 5.6 mm/H

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Problem set 3 - Answers

H
E
The pieces: X H
O ? CH 3
D C
C H Y H2
CH3 ? ? A
? H C
B
? = carbonyl or phenyl

The molecule:

O H O H
C H H 3C C H
H3 C C
OR H2
CH3
H C H CH3
A H2 A
H H
B B

Note: Carbonyl group should be placed at "X". We can tell this because H A is the most deshielded of the
aromatic protons (by resonance with the carbonyl group).

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Problem set 3 - Answers

c.

E
B

A
C

Signal  Integration Multiplicity Comments

A ~3.4 2H d CH2 (probably not 2 x CH, but keep this in mind, just
in case), next to the CH, next to O (based on )
B ~3.3 3H s CH3 isolated, next to O (based on )

C ~1.8 1H m CH multiplet (hard to say what the neighbors are)

D ~1.3 4H m 2 x CH2 (identical—symmetry exists in the

molecule); hard to say what the neighbors are
E ~0.9 6H t 2 x CH3, identical in chemical environment, each
next to CH2 (also identical)

DU = [ 7(2) + 2 – 16 ]/2 = 0  no rings or double bonds

Integration: (12 mm + 17 + 6 + 23 + 34) / 16 H’s = 5.8 mm/H

E
The pieces: The molecule:
CH3
? D
C
O CH O H2 C
? C ? H3C ?
H2 B C
B O A CH CH3
A
H 3C C C E
Note: the formula contains only one oxygen H2 H2
E D
? CH 3 x 2
C
D H2
C 7H16O

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Problem set 3 - Answers

6. Determine the most likely structure of a compound, with the

molecular formula C9H12, which gave a 1H NMR spectrum
consisting of:
a doublet at  1.25
a septet at  2.90 and
a multiplet at  7.25

I II III IV V
]

7. A compound with the molecular formula C10H13Cl gave the

following 1H NMR spectrum:
singlet,  1.6
singlet,  3.1
multiplet,  7.2 (5H)

The most likely structure for the compound is:

Cl Cl
Cl
I II III
Cl
Cl

IV V

8. Determine the likely structure for a compound A (C6H10O),

which is found to decolorize bromine in carbon tetrachloride.
Its spectral data is as follows:

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Problem set 3 - Answers

1
H NMR IR
triplet, 1.0 singlet, 2.4 2200 cm-1
(sharp)
singlet,  1.4 singlet, 3.4 3300 cm-1
(sharp)
quartet,  1.6 3500 cm-1
(broad)

OH
OH OH

I II III

OH
OH
IV V

9. Briefly explain how you might distinguish between the following

substances by comparing their 1H-NMR spectra:
O
O
O
O
I II
The main difference would likely be in the chemical shift of the methine proton of
the isopropyl group. The methine proton in I is likely to be more deshielded, and
produce a signal (septet) at about 3.5 ppm, while the analogous proton in II is
likely to be found, also as a septet, at about 2.3 ppm.
O
O
O
O
I ~3.5 ppm II ~2.3 ppm

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Problem set 3 - Answers

10. An unknown compound has the formula C6H12O. Elucidate
the structure of the molecule by scrutinizing its IR, 1H NMR and
13
C NMR spectra, shown below.

C=O

B
E

A C
D

Signal  Integration Multiplicity Comments

A ~2.4 2H Triplet (t) CH2 next to CH2 (based on multiplicity) and next to
C=O (based on )
B ~2.1 3H Singlet (s) CH3 next to C=O (based on )

C ~1.6 2H Multiplet (m) CH2

D ~1.3 2H Multiplet (m) CH2

E ~0.9 3H Triplet (t) CH3 next to CH2 (based on multiplicity)

DU = [ 6(2) + 2 – 12]/2 = 1  C=O (based on IR)

Integration: (9 mm + 13 + 10 + 10 + 14) / 12 H’s = 4.7 mm/H

The molecule:
C
E
O H2
C C CH3
H 3C C C
H2 H2
B
A D

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Problem set 3 - Answers

An unknown compound, I, has the formula C3H7NO2. Elucidate the
structure of I by scrutinizing its IR, 1H NMR and 13C NMR spectra,
shown below.

NOT a
C=O

C
A
B

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Problem set 3 - Answers

Signal  Integration Multiplicity Comments
A ~4.4 2H Triplet (t) CH2, next to CH2 (based on multiplicity), next to O
or NO2 (based on )
B ~2.0 2H M CH2

C ~1.0 3H t CH3, next to CH2

DU = [ 3(2) + 2 +1 – 7 ] /2 = 1  NOT a C=O based on IR… maybe NO2?

Integration: (17 mm + 17 + 26 ) / 7H’s = 8.6 mm/H

The molecule:
B
H2 O
C N
H3 C C O
H2
C
A

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Part B. Identify the compound represented in each of the 1H NMR spectra

1. 2-pentanone

2. Pentanal

3. 3-pentanone

4. Methyl propanoate

5. Ethyl acetate

6. Butanoic acid

7. 3-methyl butan-2-one

8. isopropyl acetate

9. methyl isobutyrate

10. isopropyl propionate

11. ethyl isobutyrate

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Assignment 6 – NMR, IR
ANSWERS

12. ethyl butyrate

13. propyl propionate

14. pentyl formate

15. hexanoic acid

16. butyl acetate

17. methyl pentanoate

18. N,N-dimethylpropionamide

19. butyramide

20. N-methylbutyramide

21. 1-propanol

22. 2-propanol

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Assignment 6 – NMR, IR
ANSWERS

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Assignment 6 – NMR, IR
ANSWERS
23. propanal

24. 1-bromobutane

25. 2-iodobutane

26. 1-chloro-2-methylpropane

27. 2-chloro-2-methylpropane

28. propylbenzene

29. isopropylbenzene

30. 1-ethyl-4-methylbenzene

31. 1,3,5-trimethylbenzene

32. (4-chlorobutyl)benzene

33. (2-chloro-2-methylpropyl)benzene

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Assignment 6 – NMR, IR
ANSWERS
34. 1-(3-chloropropyl)-4-methylbenzene

35. (2-chlorobutan-2-yl)benzene

36. 3-methylpent-1-yn-3-ol

37. pent-3-yn-1-ol

38. pent-2-yn-1-ol

39. 2-methylbut-3-yn-2-ol

40. pent-4-yn-1-ol

41. 1-methoxypropane

42. ethoxyethane or diethyl ether

43. N-methylpropan-1-amine

44. methyl 4-aminobenzoate

45. 4-aminophenyl acetate

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Assignment 6 – NMR, IR
ANSWERS

46. benzoyl bromide

O

Br

47. 4-chlorobenzoic acid or p-chlorobenzoic acid

O
Cl
OH
48. 1-(4-bromophenyl)propan-1-one
O
Br

49. butyryl chloride

50. 4-chlorobutan-2-one

51. 2-aminopropanoic acid or alanine

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