Chapter 13Structure Determination: Nuclear Magnetic Resonance

Spectroscopy

SHORT ANSWER

1. For a nucleus to exhibit the nuclear magnetic resonance phenomenon, it must be magnetic.
Magnetic nuclei include:

a. all nuclei with even numbers of neutrons and protons

b. all nuclei with odd numbers of protons
c. all nuclei with odd numbers of neutrons
d. both b and c

ANS:
d

2. Nuclear magnetic resonance spectroscopy provides information about a molecule's:

a. conjugated pi electron system.

b. size and formula.
c. carbon-hydrogen framework.
d. functional groups.

ANS:
c

3. Explain why all protons in a molecule do not absorb rf energy at the same frequency.

ANS:
All nuclei in molecules are surrounded by electron clouds. When a uniform external magnetic field
is applied to a molecule, the circulating electron clouds set up tiny local magnetic fields of their
own. These local magnetic fields act in opposition to the applied field, so that the effective field
actually felt by a nucleus is a bit smaller than the applied field.

Beffective = Bapplied Blocal

This effect is termed shielding. Each nucleus is shielded to a slightly different extent, so each
unique kind of proton in a molecule resonates at a slightly different frequency and gives rise to a
unique NMR signal.

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

Exhibit 13-1
The following question(s) pertain to the charting of NMR spectra. MATCH a term to each
description below. Place the letter of the term in the blank to the left of the description.

a. TMS e. low-field or downfield side

b. high-field or upfield side f. chemical shift
c. MHz g. specific absorption
d. delta ()

4. _____ When looking at an NMR chart the right-hand part of the chart is the _____.

ANS:
b

5. _____ The exact place on the chart at which a nucleus absorbs is called its _____.

ANS:
f

6. _____ The calibration standard for 1H and 13C NMR is _____.

ANS:
a

7. _____ The NMR charts are calibrated using an arbitrary scale that is divided into _____
units.

ANS:
d

Exhibit 13-2
For each of the compounds below tell how many signals you would expect the molecule to have in
its normal, broadband decoupled 13C NMR spectra.

8.

ANS:

three

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9.

ANS:

two

10.

ANS:

five

11.

ANS:

six

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

12.

ANS:

five

13.

ANS:

three

14.

ANS:

five

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15.

ANS:

three

Exhibit 13-3
Identify the indicated sets of protons as unrelated, homotopic, enantiotopic, or diastereotopic.

16.

ANS:
homotopic

17.

ANS:
enantiotopic

18.

ANS:
diastereotopic

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

19.

ANS:
unrelated

Exhibit 13-4
For each compound below tell how many types of nonequivalent protons there are.

20.

ANS:

four

21.

ANS:

one

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22.

ANS:

four

23.

ANS:

four

24.

ANS:

four

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

25.

ANS:

two

26.

ANS:

five

27.

ANS:

four

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Exhibit 13-5
Predict the splitting patterns you would expect for each proton in the molecules below.

28.

ANS:
No. of adjacent
Proton Protons Splitting
1 1 doublet

2 6 septet

29.

ANS:

No. of adjacent
Proton Protons Splitting
1 0 singlet

2 3 quartet

3 2 triplet

30.

ANS:

No. of adjacent
Proton Protons Splitting
1 0 singlet

2 1 doublet

3 1 doublet

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

31. The 1H NMR spectrum of styrene oxide shows that protons 1, 2, and 3 all have different
chemical shift values. Proton 1 is coupled to both proton 2 (J = 5.8 Hz) and proton 3 (J = 2.5
Hz). Draw a tree diagram for the proton 1 signal.

ANS:

Exhibit 13-6
Refer to the structure of 3-methyl-2-butanone below to answer the following question(s).

32. Refer to Exhibit 13-6. What is the splitting pattern for the hydrogens in 3-methyl-2-butanone
labeled a.?

a. septet
b. quartet
c. doublet
d. singlet

ANS:
d

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33. Refer to Exhibit 13-6. What is the splitting pattern for the hydrogens in 3-methyl-2-butanone
labeled b.?

a. septet
b. quartet
c. doublet
d. singlet

ANS:
c

34. Refer to Exhibit 13-6. The carbonyl-carbon resonance of 3-methyl-2-butanone occurs at

208.7 ppm downfield from TMS. How many hertz downfield from TMS would this
carbonyl-carbon absorb if the spectrometer used to measure this absorption were operating
at 200 MHz?

ANS:

35. Treatment of tert-butyl alcohol with hydrogen chloride yields a mixture of tert-butyl
chloride (SN1 product) and 2-methylpropene (E1 product). After chromatographic
separation, how would you use 1H NMR to help you decide which was which?

ANS:
2-Methylpropene has two kinds of hydrogens. It will have a vinylic absorption (4.56.5 )
representing two hydrogens and an unsplit signal (1.01.5 ) due to the six equivalent
methyl hydrogens.

tert-Butyl chloride has only one kind of hydrogen, which results in one unsplit signal.

Exhibit 13-8
Below are three isomeric chlorobutanes and their 13C NMR spectral data. MATCH the spectral
data to the correct structures by placing the letter of the spectrum in the blank to the left of the
corresponding structure.

a = , 55.4, 36.2, 19.3

b = , 56.2, 35.3
c = , 56.0, 36.0, 24.2, 8.2

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

36. _____

ANS:
b

37. _____

ANS:
c

38. _____

ANS:
a

Exhibit 13-8
Propose structures for compounds that fit the following 1H NMR data.

39. C8H9Br
3H doublet at 2.0 , J = 7 Hz
1H quartet at 5.0 , J = 7 Hz
5H singlet at 7.3

ANS:

40. C7H14O
6H triplet at 0.9 , J = 7 Hz
4H sextet at 1.6 , J = 7 Hz
4H triplet at 2.4 , J = 7 Hz

ANS:

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41. C3H6Br2
2H quintet at 2.4 , J = 6 Hz
4H triplet at 3.5 , J = 6 Hz

ANS:
BrCH2CH2CH2Br

42. C10H14
6H doublet at 1.2 , J = 7 Hz
3H singlet at 2.3
1H septet at 2.9 , J = 7 Hz
4H singlet at 7.0

ANS:

43. C6H14
12H doublet at 0.8
2H septet at 1.4

ANS:

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

Exhibit 13-9
To answer the following question(s), consider the data and 1H NMR spectrum below:

The mass spectrum of this compound shows a molecular ion at m/z = 113, the IR spectrum has
characteristic absorptions at 2270 and 1735 cm1, and the 13C NMR spectrum has five signals.

Spectrum obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

44. Refer to Exhibit 13-9. Based on the mass spectral data and the IR data, what functional
groups are present in this compound?

ANS:
A molecular ion of mass 113 indicates an odd number of nitrogen atoms in the compound.
Coupled with the IR absorption at 2270 cm1, a nitrile functional group is indicated. The IR
absorption at 1735 cm1 indicates a carbonyl group, possibly an ester.

45. Refer to Exhibit 13-9. How many types of nonequivalent protons are there in this molecule?

ANS:
three

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46. Refer to Exhibit 13-9. Describe the signal at 3.5 in terms of its integration, splitting pattern
and chemical shift.

ANS:
The integration of the signal at 3.5 indicates that it is due to two equivalent hydrogens, probably
a CH2 group. Since the signal is a singlet (not split) there are no nonequivalent hydrogens
attached to the atoms adjacent to the carbon to which these two hydrogens are bonded. The
chemical shift to 3.5 indicates that this CH2 group has at least one electronegative atom or
group bonded to it, possibly a carbonyl group.

47. Refer to Exhibit 13-9. Describe the signals at 4.35 and 1.3 in terms of their integration,
splitting and chemical shift.

ANS:
The signal at 4.35 is owing to two equivalent hydrogens split by three adjacent hydrogens or a
CH2 next to a CH3. It is shifted by attachment to an electronegative atom like oxygen. The
signal at 1.3 is three equivalent hydrogens split by two adjacent hydrogens of a CH3 next to a
CH2. It is shifted slightly downfield by the presence of an electronegative atom bonded to the
adjacent CH2.

48. Refer to Exhibit 13-9. What is the significance of the 13C NMR data?

ANS:
The 13C NMR has five signals, which means that there are five different kinds of carbon in this
compound.

49. Refer to Exhibit 13-9. Propose a structure for this compound.

ANS:
By compiling all the information deduced from the data provided, we note that this compound is a)
a nitrile and an ester [two carbons accounted for], and b) has two CH2 groups and one CH3 group
[three more carbons accounted for]. One of the CH2 groups is attached to the oxygen of the ester
and one is attached to the carbonyl of the ester. The singlet CH2 is also bonded to the nitrile. Based
on the chemical shifts, the singlet CH2 must be bonded to the carbonyl and the quartet CH2 must
be bonded to the oxygen of the ester. So the compound is ethyl cyanoacetate:

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

50. How would you use 1H and 13C NMR to help you distinguish between these two isomeric
structures?

ANS:

# peaks Distinguishing Absorptions

1
H 5 methyl doublet at 1.5 (overlaps other
methylene signals), no vinyl protons
13
C 6 one carbonyl carbon, no vinyl carbons
1
H 4 split vinylic peak; rel. area 2
methyl singlet between 3.54.0
13
C 4 one vinylic carbon, no carbonyl carbon

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Exhibit 13-10
Answer the question(s) for the compound whose 1H NMR spectra is shown below.

C4H8O

Spectrum obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

51. Refer to Exhibit 13-10. Describe each signal in terms of its integration, splitting and
chemical shift.

ANS:
The signals at 1.05 and 2.45 are characteristic, in their integration and splitting (a 2H quartet and
a 3H triplet), for an ethyl group. The shift of the CH2 to 2.45 indicates that the ethyl group is
attached to a carbonyl group. The signal at 2.1 , a 3H singlet, is characteristic for a CH3 attached
to a carbonyl group.

52. Refer to Exhibit 13-10. Propose a structure for this compound.

ANS:
2-butanone, CH3COCH2CH3

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

Exhibit 13-11
Answer the question(s) for the compound whose 1H NMR spectra is shown below.

C5H12O

Spectrum obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

53. Refer to Exhibit 13-11. Calculate the degree of unsaturation for this compound.

ANS:
The base formula for this compound is C5H12, which corresponds to a saturated compound, so
there is no unsaturation in this compound.

54. Refer to Exhibit 13-11. Describe each signal in the 1H NMR in terms of its integration,
splitting and chemical shift.

ANS:
In looking at the spectrum, it is important to note that the relative number of hydrogens for each
signal adds up to four. The formula of the compound indicates that there are a total of 12
hydrogens. Therefore, the integration of 3:1 corresponds to 9H:3H. The signal at 1.2 is a 9H
singlet, which is characteristic for a tert-butyl group. The slight downfield shifts indicates that this
group is attached to an electronegative atom, in this case, oxygen. The signal at 3.2 is a 3H
singlet which is characteristic of a methyl group bonded to an oxygen.

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55. Refer to Exhibit 13-11. Propose a structure for this compound.

ANS:
tert-butyl methyl ether, (CH3)3COCH3

Exhibit 13-12
Answer the question(s) for the compound whose 1H NMR spectra is shown below.

C8H7ClO

Spectrum obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

56. Refer to Exhibit 13-12. Calculate the degree of unsaturation in this compound.

ANS:
The base formula for this compound is C8H8; the saturated formula is C8H18; the degree of
unsaturation is five [(18 8) 2].

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

57. Refer to Exhibit 13-12. Describe the signals that occur between 7 and 8 in terms of
integration, splitting and chemical shift.

ANS:
The chemical shift of the signals between 7 and 8 indicates that these hydrogens are aromatic.
The integration of four hydrogens and the splitting pattern of two doublets is characteristic of a
para disubstituted aromatic compound.

58. Refer to Exhibit 13-12. Describe the signal at 2.6 in terms of integration, splitting and
chemical shift.

ANS:
This signal is a 3H singlet shifted by attachment to a carbonyl group; a methyl ketone, probably.

59. Refer to Exhibit 13-12. Propose a structure for this compound.

ANS:

4-chloroacetophenone

60. Propose a structure for a compound, C6H14O, with the following 13C NMR spectral data:

Broadband decoupled 13C NMR: 23.0, 68.4

DEPT-90: 68.4
DEPT-135: positive peaks at 23.0, 68.4 ; no negative peaks

ANS:

61. Propose a structure for Compound X, which has M+ = 120 and (M + 2) = 122 of
approximately equal intensity in its mass spectrum and has the following 13C NMR spectral
data:

Broadband decoupled 13C NMR: 32.6, 118.8, 134.3

DEPT-90: 134.3
DEPT-135: positive peaks at 134.3 ; negative peaks at 32.6, 118.8

ANS:

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 Chapter 13

62. Propose a structure for Compound Z, which has the following spectroscopic properties:

MS: M+ = 88
IR: 3380 cm1
1
H NMR: 0.85 (6H doublet); 1.40 (3H multiplet); 2.68 (1H singlet); 3.55 (2H
triplet)

Broadband decoupled 13C NMR: 22.7, 25.0, 41.8, 60.5

DEPT-90: 25.0
DEPT-135: positive peaks at 22.7, 25.0 ; negative peaks at 41.8, 60.5

ANS:
(CH3)2CHCH2CH2OH

63. Describe how you could differentiate the following compounds using a DEPT NMR
experiment.

ANS:
Both compounds contain two different kinds of carbon, so an ordinary broadband decoupled 13C
NMR spectrum of either compound will show two peaks. The DEPT-90 spectrum, however, will
show no peaks for 1,4-dichlorobutane while the DEPT-90 spectrum of 2,3-dichlorobutane will
show one peak. The DEPT-135 spectrum for 1,4-dichlorobutane will show two negative peaks,
while the DEPT-135 spectrum of 2,3-dichlorobutane will show two positive peaks.

64. Which structure of molecular formula C4H8Cl2 fits both the 1H NMR and 13C NMR spectra
shown below?

a.

b.

c.

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

d.

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 Chapter 13

Spectra obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

ANS:
b

MULTIPLE CHOICE

1. Which of the following provides information about the carbon framework of a molecule?
a.

b.

c.

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

d.

ANS: A

2. Which signal(s) remain(s) when a DEPT-90 spectrum is run?

a. CH3
b. CH2
c. CH
d. quaternary C
e. a, b, c
ANS: C

3. Which of the following occurs when a DEPT-135 spectrum is run?

a. CH3, CH carbons appear as positive signals
b. CH2 carbons appears as a negative signal
c. quaternary carbon signals are absent
d. a and b
e. all of the above
ANS: E

4. Consider the following structure. Atoms other than carbon and hydrogen are labeled. The
carbon atoms are designated by numbers.

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 Chapter 13

Which carbon atom(s) will produce a signal in a DEPT-90 spectrum?

a. 1, 6 and 7
b. 2 and 5
c. 3
d. 4
e. All will produce a signal.
ANS: D

5. Consider the following structure. Atoms other than carbon and hydrogen are labeled. The
carbon atoms are designated by numbers.

Which carbon atom(s) will produce a signal in the broadband decoupled, the DEPT-90, and the
DEPT-135 spectra?
a. 1, 6, and 7
b. 2 and 5
c. 3
d. 4
e. All carbons atoms will appear these spectra.
f. None of the carbon atoms appear in all these spectra.
ANS: D

6. Consider the following structure. Atoms other than carbon and hydrogen are labeled. The
carbon atoms are designated by numbers.

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

Which carbon atom will produce a signal the furthest downfield in the broadband decoupled 13C
NMR spectrum?
a. 1
b. 2
c. 3
d. 4
e. 5
f. 6
g. 7
ANS: C

7. What type of NMR spectrum is the following?

a. broadband decoupled
b. DEPT-90
c. DEPT-135
d. It is not possible to judge given just the spectrum.
ANS: C

8. The following is the tree diagram for the protons on a specific carbon.

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 Chapter 13

Which of the following signals in a proton NMR could correspond to these protons?
a.

b.

c.

d.

e. None of these due to the coupling constants.

ANS: E

9. How many signals would appear the proton NMR for the following substance? Atoms other
than carbon and hydrogen are labeled.

a. 2 c. 4
b. 3 d. 5
ANS: B

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Structure Determination: Nuclear Magnetic Resonance Spectroscopy

10. Identify the splitting pattern of the numbered protons. Atoms other than hydrogen and
carbon are labeled.

a. 1: doublet, 2: triplet c. 1: quartet 2: quartet

b. 1: triplet, 2: triplet d. 1: singlet, 2: triplet
ANS: C

11. Identify the two numbered hydrogen atoms as:

a. unrelated c. enantiotopic
b. homotopic d. diastereotopic
ANS: A

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