Last Name (print): ____________________________________ Chemistry 345

Spring 2016
First Name (print): ____________________________________ Exam I

Circle Your TA’s Name: Manar Alherech Moira Esson Brian Graham

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

A. Identify the molecule with the most intense absorption in the infrared region between 2100 and
2300 cm-1.

B. Identify the starting material below that will react with a mixture of HNO3 / H2SO4 to produce the
largest amount of a meta substituted product.

C. Identify the substituent that will have the most effective overlap between a lone pair and an
adjacent aromatic  system.

D. Identify the molecule that you would expect to have the largest coupling value evident in its 1H-NMR
spectrum.

E. Identify the molecule that would result in the most 13C-NMR signals.

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II. The disubstituted aromatic compound 4’-methoxyacetophenone can be oxidized or substituted by
household bleach (sodium hypochlorite) depending upon the pH of the reaction mixture. Answer
the questions below about this reaction and interpret the associated EI-MS, IR, and NMR spectra.
(28 pts total)

To a 25 mL round bottom flask 4'-methoxyacetophenone (0.15 g, 1.0 mmol) glacial acetic acid (1 mL),
and aq. 6% sodium hypochlorite solution (2 mL) are added. The mixture is stirred at room temperature
for 30 min, during which time a solid precipitates.

A. The acidified bleach solution creates an electrophile appropriate for chlorination, [H2OCl]+. Provide
the electron-pushing arrows for the reaction of benzene with [H2OCl]+. Explicitly show the leaving
group after the reaction, place a box around the nucleophilic molecule, and circle the electrophilic
molecule. (2 pts)

B. There are two regioisomeric arenium cations that can be generated; they are depicted below with
their respective calculated relative energy. Provide a series of resonance structures of the most
stable arenium cation that justifies its stability. (6 pts)
Cl

O
A O

0.0 kcal/mol

Cl

B O

13.1 kcal/mol

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C. Draw a potential energy surface that depicts the rate-determining step of this reaction. Clearly
identify the portion of the potential energy surface that determines the regiochemical outcome of
this reaction and explain your choice. (4 pts)

D. The 1H-NMR spectrum for the product of the reaction described above is provided on the
subsequent page and clearly shows two EAS products. Assign each of the 1H-atoms in the molecule
to their corresponding 1H-NMR signals using the A, B, C, etc. signal designations on the spectrum. It
is critical to your assignment that you observe that signals B and C are an accidental overlap
between signals from two different molecules. Place your structures with assignments in the boxes
below. The 13C-NMR spectrum of the crude reaction mixture is also provided, but does not need
to be analyzed for credit. (8 pts)

E. The two EAS products observed in the 1H-NMR spectrum are not produced in this reaction in equal
amounts. Using the integrations from the 1H-NMR spectrum, determine the approximate ratio of
the major to minor product. Express the ratio as a decimal rounded to the nearest hundredth. (4
pts)

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 B

E G
F H
D

C
A

4
The 13C-NMR spectrum is also provided, but does not need to be analyzed for credit. Analysis
of it may help confirm your identification of both the major and minor EAS products.

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F. Confirm that your identification and 1H-NMR assignments of the Major EAS and Minor EAS products
are correct using the EI-mass spectra below. For the Major product only, provide an electron-
pushing mechanism showing the formation of the ions responsible for the signals at m/z = 171, 169,
143, and 141 from the molecular ion(s) (m/z = 186, 184). (4 pts)

Major EAS Product

Minor EAS Product

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III. Analyze the IR, EI-MS, 13C-NMR, and 1H-NMR spectra for a molecule with a chemical formula of
C7H14O2 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. (18 pts total)

A. Calculate the number of double bond equivalencies, unsaturation number, or the index of hydrogen
deficiency for this molecule using the equation provided. (2 pt)

2𝐶 + 𝑁 − 𝐻 − 𝑋 + 2
𝐼𝐻𝐷 =
2

B. 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 C7H14O2 and your
calculated IHD above. (2 pts)

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C. Using your analysis of the IHD and IR spectrum, determine the structure of the molecule using the
1
H-NMR spectrum below of C7H14O2. Place your determined structure in the box on page 10.

Draw part structures for each of the signals marked in the expanded spectra below. Circle the H
atoms responsible for the signal. The signal locations in Hz are provided on the original spectrum.
(4 pts)

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D. Using the EI-MS shown below of C7H14O2, provide the structure of the most likely ion responsible for
the base peak. The molecular ion peak m/z = 130 was too small for detection. (2 pts)

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E. Using the 13C-NMR shown below of C7H14O2, determine the number of carbon environments in the
molecule and assign the likely hybridization of each 13C-atom. Additionally, identify any key
functional groups signals. (3 pts)

F. Draw a structure of the complete molecule. Put your final answer in the box below. (5 pts)

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IV. Show the complete reaction mechanism for the mono-nitration of anisole with a mixture of sulfuric
and nitric acid leading to the major product. (12 pts) Predict the major dinitro- and trinitro-anisoles
that would be produced from subsequent nitration reactions. (2 pts) Be sure to show all
appropriate arrows, lone pairs, formal charges, intermediates, stereochemistry, bonds, resonance
structures, etc… (14 pts total)

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V. Predict the major product(s) of the following reactions or fill in the missing reagents as appropriate.
(30 pts total)

A.

B.

C.

D.

E.

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F.

G.

H.

I.

J.

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Last Name (print): ____________________________________ Chemistry 345
Spring 2015
First Name (print): ____________________________________ Exam I

Circle Your TA’s Name: Manar Alherech Moira Esson Brian Graham

Question Points

I. _______ (10 pts)

II. _______ (28 pts)

III. _______ (18 pts)

IV. _______ (14 pts)

V. _______ (30 pts) _______ & _______

Total _______ (100 pts)

_______ (math double-check)

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