Chemistry-Orgo II Exam 1 Version A (UD) Answer Key

CHEM 3322
Exam I
September 26, 2012
Work four out of five problems. For extra credit you may work all five, but clearly indicate the
extra credit problem.
I. Complete the following reactions
A. Naphthalene
B.
C. 3-nitrophenol
D. ethylbenzene
E.
II. Give a reasonable synthesis of the following from benzene, alcohols of 4 carbons or less,
and any necessary inorganic reagent.
B. p-nitrobenzoic acid C. o-chloronitrobenzene

A
A.
B.
C.
III.
A. Which compound will undergo a faster SN1 reaction? Use resonance structures to
explain your answer.
B. In order to increase the reaction rate of A would you place a methoxy (CH3O-)
substituent onposition 6 or position 7. Use resonance structures to explain your answer.
A B
C. Which will react faster by nucleophilic aromatic substation, 2-chloropyridine or 3-
chloropyridine. Explain with resonance.
2-chloropyridine will react faster to nucleophilic substitution since the intermediate

formed by the addition of the nucleophile has a resonance form placing the negative charge on
nitrogen, which is more electronegative and therefore capable of holding a negative charge more
stably.
The nucleophilic substitution intermediate for 3-chloropyridine, however, has no
resonance form with the negative charge on the nitrogen. Therefore, this intermediate is higher
energy and forms more slowly.
IV.
A. Which of the following compounds are aromatic and which are not? Use molecular
orbital theory diagrams to explain.
The cyclooctatetraene dianion has completely filled bonding and non-bonding orbitals,
but it does not have any electrons in antibonding orbitals (as shown in the Frost circle above).
With a Huckel’s rule number of electrons, this ion will be aromatic if it is planar.
The cyclopentadienyl cation is fully conjugated, but the Frost circle MO diagram shows a
di-radical in two of the bonding orbitals. This would be very unstable and would cause this
molecule to be anti-aromatic if planar. More likely, this ion would adopt a non-planar geometry
to avoid anti-aromaticity.
B. How many electrons are in p orbitals in a benzyl carbocation? Is a benzyl

carbocation aromatic? Explain your answer and be specific.
The benzyl carbocation has 6 electrons in p-orbitals. The benzyl carbocation is aromatic because
it has a Huckel’s Rule number of electrons, and it is completely planar.
C. What functional group is consistent with the following spectrum?
This spectrum is consistent with a carboxylic acid.
D. Give an explanation for the n+1 rule for the splitting of hydrogens in proton NMR. Be
specific; i.e., why does a hydrogen on an adjacent carbon split the signal into a doublet?
The spin of adjacent hydrogens gives them a magnetic moment that is either parallel to the
applied field or anti-parallel. If parallel, the magnetic fields reinforce one another, creating a
stronger deshielding effect on the hydrogen giving the signal. If the magnetic moment on
adjacent hydrogens is anti-parallel to the applied field, the fields oppose one another, causing a
slight shielding effect that pushes the signal upfield. Since each adjacent hydrogen has an equal
probability of being parallel and anti-parallel, a signal with only one adjacent hydrogen will be
split into 2 peaks of roughly equal height.
For a signal with 2 adjacent hydrogens, the following probability diagram shows how 3
signals arise in a 1:2:1 height ratio:
V. The IR spectrum of a compound appears to that of an alkane. The molecular ion signal in
the mass spectrum has peaks at 120 and 122 in a three to one ratio. The proton NMR has
three peaks: a quartet at  3.5, adoublet at  1.8 and a singlet at  1.3 in a ratio of 1:3:9.
What is the structure of the compound?
The mass spectrum 3:1 ratio for the molecular ion indicates the presence of a chlorine atom.
We can subtract the mass of chlorine from the molecular ion mass and use the remaining
weight to determine the number of carbons and hydrogens.
120 − 35 = 85 The H-NMR indicates the presence of 13 H’s (1+3+9).

72
85 − 13 = 72 = 6 𝐶′𝑠 The chemical formula is therefore C6H13Cl.
12
Putting the pieces together, we get the following molecule:

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Chemistry-Orgo II Exam 1 Version A (UD) Answer Key

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What reactions are discussed on pages 1-2?

What topic is discussed on page 3 and what is the main question?

CHEM 3322

I. Complete the following reactions

B. p-nitrobenzoic acid C. o-chloronitrobenzene

2-chloropyridine will react faster to nucleophilic substitution since the intermediate

B. How many electrons are in p orbitals in a benzyl carbocation? Is a benzyl

This spectrum is consistent with a carboxylic acid.

120 − 35 = 85 The H-NMR indicates the presence of 13 H’s (1+3+9).

Putting the pieces together, we get the following molecule:

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