Chemistry 14C Winter 2008 Midterm Exam 2 Page 1

For any question on this exam worth three or more points, you have two choices: answer the question as
written or you may write and circle the phrase “one point”. If you write “one point” you will receive one
point (and only one point) of credit for the question. “One point” overrides anything you have written for
that question, regardless of its accuracy.

Example: (10) Briefly explain everything about organic chemistry. One point

1. (2) Circle the formula(s) that are consistent with the following mass spectrum: m/z = 164 (M; 100%), m/z = 165
(11.2%), m/z = 166 (0.42%).
C10H12O2 C10H12S C10H14NO C11H18O C10N2O

2. (6) The mass spectrum of a molecule whose formula is C11H15Br was found to include peaks at m/z = 225, 226,
227, 228, and 229 (among others).
(a) Circle one or more peaks that are due to molecular ions:
224 225 226 227 228 None of these Cannot determine

(b) Circle one or more peaks that are due to fragments:

224 225 226 227 228 None of these Cannot determine

(c) Circle one or more peaks that are base peaks:

224 225 226 227 228 None of these Cannot determine

3. (6) Deduce the molecular formula(s) that are consistent with the given mass spectrum. Write your answer(s) in
the boxes below (one formula per box). There may be more boxes than formulas, but there are not more
formulas than boxes.
Mass spectrum: m/z = 181 (M; 100%), m/z = 182 (13.75%), m/z = 183 (0.35%)

Work space:
 Chemistry 14C Winter 2008 Midterm Exam 2 Page 2
Hydroxyzine is an antihistamine that works by antagonizing (blocking) the H1 receptor. It also has antiemetic and
mild anxiolytic (anti-anxiety) properties. Cetirizine, a major human metabolite of hydroxyzine, also has
antihistamine properties. (These two drugs illustrate nicely the concept that similar molecules often have somewhat
similar biological properties.) Questions 4-8 concern the spectroscopy of these antihistamines.

metabolism

OH
N O N O

N OH N O
Cl Cl

Hydroxyzine Cetirizine

4. (6) You may recall from the first Chem 14C midterm that metabolism of hydroxyzine (an antihistamine) gives
cetirizine (another antihistamine). This process was mimicked in the laboratory, and the IR spectrum of the
product is shown below.

What does the IR spectrum show? Circle “present” or “not present” in each case. Explain each conclusion.

Hydroxyzine: Present/Not present Explanation (fifteen words or less):

Cetirizine: Present/ Not present Explanation (fifteen words or less):

 Chemistry 14C Winter 2008 Midterm Exam 2 Page 3
5. (6) Consider the mass spectrum of hydroxyzine.
(a) Give a number: For M, m/z =

(b) Give a number to one decimal place: When M = 100%, the best estimate for the intensity of M+1 is...

(c) When M = 100%, the best estimate for the intensity of M+2 is (circle one):
0% 1% 5% 10% 15% 20% 25% 30% 35% 40% More than 40%

6. (5) Mass spectrometry might also be used to determine the absence or presence of hydroxyzine and cetirizine in
the product.
(a) Complete this sentence in twenty words or less: To determine if cetirizine is present in the mixture, in the
mass spectrum we look for...

(b) Complete this sentence in thirty words or less: Mass spectrometry is not a reliable method to determine if
there is any hydroxyzine present in the reaction product because...

7. (10) When hydroxyzine is converted into cetirizine, how does the 1H-NMR spectrum change? Write the
integrals and splitting patterns (but not chemical shifts) for the signals that disappear and appear. See examples
below. Assume for this question that the smallest integral = 1. There may be more boxes than signals.

As the reaction proceeds, these signals disappear from the hydroxyzine NMR spectrum:

Example:
6H singlet

As the reaction proceeds, these signals appear in the cetirizine NMR:

Example:
6H singlet

8. (16) Complete each sentence by writing a number in the blank. For this problem the smallest integral = 1.
(a) Ignoring splitting (i.e., considering a triplet as one signal), ___________ signals in the 1H-NMR spectrum of
hydroxyzine have a chemical shift of less than 6.5 ppm.
(b) Of the signals in part (a), ___________ are singlets, ___________ are doublets, and ___________ are
triplets.
(c) Of the signals in part (a), ___________ have integral =1, ___________ have integral = 2, and ___________
have integral of three or more.
(d) In the 1H-NMR spectrum of cetirizine, ___________ protons whose chemical shift > 6.5 ppm are not
equivalent to any other protons in the molecule.
 Chemistry 14C Winter 2008 Midterm Exam 2 Page 4
9. (13) Perform a five-zone analysis on the following IR spectrum. Molecular formula = C11H14O2

1721 cm-1
 Chemistry 14C Winter 2008 Midterm Exam 2 Page 5
1
10. (12) A substance with unknown structure has the following H-NMR spectrum: 7.65-7.30 ppm (multiplet;
integral = 5), 4.28 ppm (triplet; integral = 2), 1.85 ppm (pentet; integral = 2), 1.70 ppm (sextet; integral = 2),
and 1.03 ppm (triplet; integral = 3). Through other tests, the structure of the unknown was narrowed down to the
four molecules shown below. Circle “consistent” if the molecule is consistent with the 1H-NMR spectrum. If the
molecule is not consistent with the 1H-NMR data, complete the explanation.

O Consistent

O This structure is not consistent because (fifteen

(a) words or less)...

O Consistent

(b) O This structure is not consistent because (fifteen

words or less)...

O Consistent

(c) O
This structure is not consistent because (fifteen
words or less)...

O Consistent
O
(d) This structure is not consistent because (fifteen
words or less)...
 Chemistry 14C Winter 2008 Midterm Exam 2 Page 6
11. (6) Using fifty words or less explain why the carbonyl stretching O
frequency for acetone is greater than the carbonyl stretching frequency O
for acetophenone. CH3
H3C CH3

Acetone Acetophenone

12. (4) For each part draw a molecule composed only of any number of hydrogens, any number of oxygens, but no
more than eight carbons.
(a) Complete the structure of a molecule so that (b) Complete the structure of a molecule so that
the hydrogen shown has the greatest amount the hydrogen shown has the least amount of
of splitting, but the 1H-NMR spectrum splitting, but the 1H-NMR spectrum contains
contains the least number of signals overall. the least number of signals overall.

H–C H–C

13. (2) Circle the molecule whose methyl group has the highest 1H-NMR chemical shift:

CH3CH2OH CH3CH2OCH3 CH3OCH2OCH3 CH3CH2OCH2CH2OCH2CH3

14. (2) Circle the molecule whose methyl group is the most highly deshielded:

CH3CH2OH CH3CH2OCH3 CH3OCH2OCH3 CH3CH2OCH2CH2OCH2CH3

15. (2) Complete this sentence in ten words or less: In order for a functional group to influence chemical shift by
magnetic induction, the functional group must have...

16. (2) Complete this sentence in ten words or less: TMS has a lower 1H-NMR chemical shift than (CH3)4C
because...