Practice Problems for Midterm Exam

Q1. EI-MS of compound 1 (C8H16O, M = 128) shows fragment ion peaks at m/z = 99, 72,
and 57. Identify each of the fragment ions with illustration of the mechanism of its formation.
O

Q2. EI-MS of compound 2 (C7H14, M = 98) shows fragment ion peaks at m/z = 83 and 69.
Identify each of the fragment ions with illustration of the mechanism of its formation.

Q3. EI-MS of compound 3 (C7H16O, M = 116) shows fragment ion peaks at m/z = 101 and
59. Identify each of the fragment ions with illustration of the mechanism of its formation.
OH

3
Q4. Predict how molecular ion peaks in the EI-MS of ortho-dibromobenzene (5) will look like.
Also discuss how one can distinguish 5 from its meta- and para-isomers by 1H and 13C NMR.
Br

Br
4

Q5. Compare compounds 57 in terms of the 1H NMR chemical shift of the asterisked proton
(which has the smallest (or largest) chemical shift and why?).

N NO2
H* H* H*

5 6 7
Q6. An unknown compound 8 consists of C, H, and O, and shows the following spectral data.
EI-MS: 90 (M), 45 (M45).
1
H NMR (ppm): 3.39 (s, 6H), 3.55 (s, 4H) (s = singlet).
13
C NMR (ppm): 59.0, 71.9.
Deduce the structure of 8 and identify the fragment ion of m/z = 45.

Q7. An unknown compound 9 shows the following spectral data.

EI-MS: 101 (M), 86 (M15), 44 (M57).
1
H NMR (ppm): 1.04 (d, 12H), 2.91 (septet, 2H), 3.20 (s, 1H) (d = doublet, s = singlet).
13
C NMR (ppm): 23.5, 45.3.
Deduce the structure of 9 and identify the fragment ion of m/z = 86.
Q8. 1H and 13
C NMR spectra of compound 10 (C9H11NO) are shown below (italicized
numbers refer to integrations; app. s = apparent singlet, brs = broad singlet). Its EI-MS
shows fragment ions at m/z = 105 and 77.

10 (1H NMR) 10 (13C NMR)

5 (app. s)

6 (brs)
3 signals

(ppm) (ppm)

(a) Deduce the structure of 10.

(b) Identify the fragment ions of m/z = 105 and 77.
1
(c) The above H NMR spectrum was measured at room temperature. When the
temperature is lowered, what change will be observed in the 1H NMR spectrum?
Q9. 1H and 13
C NMR spectra of compound 11 (C5H8O2) are shown below (italicized numbers
refer to integrations; t = triplet, q = quartet, dd = doublet of doublets). Its EI-MS shows a
fragment ion at m/z = 55.

11 (1H NMR) 3 (t) 11 (13C NMR)

1 (dd) 2 (q)

1 (dd) 1 (dd)

(ppm) (ppm)

(a) Deduce the structure of 11.

(b) Identify the fragment ion of m/z = 55.
(c) Below is a magnified image of 5.8-6.4 ppm region of the 1H NMR spectrum. Assign
signals a, b, and c to the corresponding protons of 11.
a b c

6.4 5.8
Q10. 1H NMR, 13
C NMR, and EI-MS spectra of compound 12 are shown below (italicized
numbers refer to integrations; s = singlet).

12 (1H NMR) 12 (13C NMR)

2 (m)
2 (m)

2 (brs)

(ppm) (ppm)

12 (EI-MS) 171 (M) 173 (M+2)

92
65

m/z

(a) Deduce the structure of 12.

(b) Identify the fragment ion of m/z = 92.
1 13
(c) Completely assign each of the H and C NMR signals to the corresponding
proton/carbon.
Q11. 1H and 13
C NMR spectra of compound 13 (C8H14O4) are shown below (italicized
numbers refer to integrations; s = singlet, t = triplet, q = quartet).

13 (1H NMR) 4 (s) 6 (t) 13 (13C NMR)

4 (q)

10 9 8 7 6 5 4 3 2 1 0
(ppm) (ppm)

(a) Deduce the structure of 13.

(b) Depict how DEPT135 spectrum of 13 will look like.
Q12. 1H and 13
C NMR spectra of compound 14 (C8H14O4) are shown below (italicized
numbers refer to integrations; d = doublet, t = triplet, q = quartet).

14 (1H NMR) 14 (13C NMR)

6 (t)
two signals
3 (d) are overlapped

4 (q)

1 (q)

10 9 8 7 6 5 4 3 2 1 0
(ppm) (ppm)

(a) Deduce the structure of 14.

(b) Depict how DEPT135 spectrum of 14 will look like.