Last Name (print): ____________________________________ Chemistry 345

Spring 2018
First Name (print): ____________________________________ Exam I

Circle Your TA’s Name: Steven Chapman Moira Esson Dan SantaLucia

I. Circle the best choice from each series that best completes the exercises below. (10 pts)

A. Identify the molecule that is the most difficult to synthesize with only a simple set of EAS reactions from
benzene.

B. Identify the molecule with the lowest pKa.

C. Identify the molecule with the fewest 1H-NMR signals.

D. Identify the molecule that does not possess a medium to large intensity IR absorption between 1500 cm-1 and
1800 cm-1.

E. Identify the molecule with two nearly equal intensity, large molecular ion signals produced in electron-impact
mass spectrometry.

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II. The mononitration of tyrosine has been reported (2005) as an example of green chemistry in the
undergraduate organic chemistry laboratory. Tyrosine is a naturally-occuring amino acid, is non-toxic, and
water soluble. A single mono-nitrated product is isolated in good yield ~60% after a gentle heating to 40 °C
for 30 minutes upon reaction with an HNO3/H2SO4 mixture. (12 pts total)

A. The generation of a powerful electrophile is critical in all EAS reactions, provide an electron-pushing
mechanism to show the formation of the electrophile in this reaction. Justify the first step of the mechanism
using pKa values. (2 pts)

B. Draw a potential energy surface for the rate-determining step of this reaction leading to the formation of the
arenium cations leading to both isomer I and II. (2 pts)

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C. Which of the two products would you expect to be the major one isolated in this reaction? Justify your choice
with a correct use of Hammond’s Postulate, your answer from part b, and any necessary chemical reasoning.
(6 pts)

D. In which isomer, I or II, would you expect the 1H-NMR signal for Ha to be more downfield, explain. (2 pts)

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III. Analyze the IR and 1H-NMR spectra for a molecule with a chemical formula of C13H16O2 and answer the
questions below. To receive full credit, make sure that you write down part structures and reasoning.
Structures or answers without showing your work may receive no credit. (20 pts total)

2𝐶 + 𝑁 − 𝐻 − 𝑋 + 2
𝐼𝐻𝐷 =
2

A. In the infrared spectrum below identify any key spectral features that may indicate the presence or absence
of a particular functional group that is possible with a formula of C13H16O2. (4 pts)

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B. Using your analysis of the IR spectrum, determine the structure of the molecule using the 1H-NMR spectrum
below of C13H16O2. Assign each one of the signals to its corresponding 1H-atoms using the assignments
provided on the spectrum. Place your answer in the box provided. Note that the signals at 7.47 are two
signals with an accidental overlap. Expansions of each signal are provided in part C. (10 pts)
300 MHz ¹H NMR
In C DC l3
1.2

1.1

1.0

3.08 0.9
2.00

A B C 0.8

0.7

0.6

9.23 0.5

0.4

0.3

3.08 0.2
2.00 0.1
1.09 1.06
0.0
A BC D E F
-0.1
8 7 6 5 4 3 2 1 -0
© 2014, Sigma-Aldrich Co.
ALL RIGHTS RESERVED

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C. It is recommended that you draw part structures for each of the signals marked in the expanded spectra
below. Circle the 1H-atoms responsible for the signal in each part structure. For extra clarity, the x-axis scale
has been changed to Hz from high (left) to low (right).
7.47 7.47
 8.03 (signals peak picked on left) (signals peak picked on right)

A B C

5.05 4.67 1.33

D E F

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D. Using the 13C-NMR shown below of C13H16O2, determine the number of carbon environments in the molecule,
identify any key functional group signals, and assign the likely hybridization of each carbon atom signal by its
13
C-NMR chemical shift. (6 pts)

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IV. Analyze the EI-MS, IR, 13C-NMR, and 1H-NMR spectra for a molecule with a chemical formula of C6H10O2 and
answer the questions below. Structures or answers without showing your work may receive no credit. (16
pts total)

A. In the infrared spectrum below identify any key spectral features that may indicate the presence or absence
of a particular functional group that is possible with a formula of C6H10O2. (2 pts)

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B. Using your analysis of the IR spectrum, determine the structure of the C6H10O2 molecule using the 1H-NMR
spectrum below. Assign each of the 1H-atoms in the molecule to their corresponding 1H-NMR signals using
the signal assignments provided on the spectrum. Draw your final answer in the box below. (7 pts)
300 MHz ¹H NMR
300 MHz ¹H NMR
In C DC l3 In C DC l3
2.183
1.2
2.183
1.2
1.1
1.1
1.0

0.9 1.0
2.704
0.8
0.9
0.72.704

0.6
0.8
5.98 0.5 0.7
0.4
4.00 0.6
0.3

0.2 0.5
0.1
0.4
0.0
A B 0.3
-0.1
2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1
© 2013, Sigma-Aldrich Co. 0.2
ALL RIGHTS RESERVED

0.1

0.0
A B
-0.1
8 7 6 5 4 3 2 1 -0
© 2013, Sigma-Aldrich Co.
ALL RIGHTS RESERVED

9
C. Confirm that your 1H-NMR assignment of C6H10O2 is correct using the 13C-NMR spectrum below. Determine
the number of carbon environments present in the molecule, identify any key functional groups, and assign
the likely hybridization of the corresponding carbon atom to each signal. (3 pts)

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D. Further confirm that your 1H-NMR assignment of C6H10O2 is correct using the EI-mass spectrum below. Draw
and clearly label the species produced in the mass spectrometer that are likely responsible for the signals at
m/z = 114, 99, 43, and 15. (4 pts)
43

99

15 114

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V. Show the complete reaction mechanism for the acylation of bromobenzene with acetyl chloride and
aluminum chloride. Two (of the three possible) mono-acylated products are formed in unequal amounts;
draw a reaction mechanism that accounts for the major organic product. Be sure to show all appropriate
arrows, lone pairs, formal charges, intermediates, stereochemistry, bonds, resonance structures, etc… (12
pts)

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VI. Predict the major product(s) of the following reactions. (30 pts total)

A.

B.

C.

D.

E.

13
F.

G.

H.

I.

J.

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15
Last Name (print): ____________________________________ Chemistry 345
Spring 2018
First Name (print): ____________________________________ Exam I

Circle Your TA’s Name: Steven Chapman Moira Esson Dan SantaLucia

Question Points

I. _______ (10 pts)

II. _______ (12 pts)

III. _______ (20 pts)

IV. _______ (16 pts)

V. _______ (12 pts)

VI. _______ (30 pts) _______ & _______

Total _______ (100 pts)

_______ (math double-check)

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