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Chemistry 304B Spring 2012

First Examination

March 5th, 2012

7:30-9:30 pm

Name (as listed on Blackboard and please print)_______________________________________________________

This is an "open book" exam; you may use anything which is not alive nor connected to the internet.

There are 11 pages in this exam; please check to be sure you have a complete copy.

State your assumptions and show your logic. Write complete answers (e.g., if you claim resonance effects, be sure to draw the
relevant structures to illustrate your point).

Use arrows to show mechanisms with precision. Sloppy arrows will not be given full credit.

For radical reactions, be sure to use the half-headed arrows carefully.

Drawing mechanisms is a means of communication; if it is sloppy, the grader may not understand you.

No matter what, do something! We love to give at least partial credit.

p2.______/13 p3.______/14 p4. ______/17 p5. ______/10

p6.______/12 p7.______/10 p8._______/12 p9.______/12

Lecture total:_____________/100 Lab Total:________/14

Pledge_________________________________________________________________________________
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I. (19 pts). Note the following three reactions involving related substrates and conditions, but quite different product types.
Example A is a straightforward reaction, as discussed in class, but B and C are not…

A. (07 pts).
1. Draw the best mechanism for the formation of Z and clearly label the product structure as Z. Clearly show the role of the
peroxide as a catalyst. Note the 13C NMR spectrum of Z shows 5 distinct signals [proton coupled: two quartets, two triplets, and one
doublet in off-resonance decoupling].
2. What about the stereochemistry of Z? no stereocenter racemic S configuration R configuration
(circle best answer)

RO-OR
+ HBr (cat) Z
!

B. (06 pts). Draw the best mechanism for the formation of the product, Y. Some steps are the same as above; you need not repeat
them. Why is this product favored in this case instead of simple addition to the alkene?
RO-OR CH2Br
(cat)
+ HBr
!
CH3
Y

Continued….
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C. (06 pts). Draw the best mechanism for the formation of the product, X. Why is this product favored in this case instead
of simple addition to the alkene?

RO-OR
+ HBr (cat)
Br
! X

II. (08 pts). Note the molecule M, which is unstable and rapidly rearranges into N. Compound N is also interesting as it
undergoes a very favorable reaction with dicycanoacetylene to give P and Q.
CN
CN
N + [R] +
CN
M N CN Q
P

A. (02 pts). From an analysis of pi elecron count alone, would you expect M to be aromatic? Explain in one sentence.

B. (02 pts). Give the single most important reason why M is quite unstable.

C. (04 pts). Draw the pathway for the reaction of N with dicyanoacetylene to give P and Q. Show intermediate R, but you need not
write arrows/mechanism.
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III. (11 pts). Bisphenol A has made the news in the last few years because it is a common component of polymers such as
polycarbonate and epoxy resins, and it seems to have some negative biological activity. It is attractive economically because it is so
easy to make from phenol and acetone, with stannic chloride as a catalyst. The process begins by formation of intermediate T, but
continues spontaneously under the same conditions to give bisphenol A,
Write a careful mechanism for this process, showing all intermediates and the activating role of the SnCl4.
OH HO
HO
O OH
SnCl4 SnCl4 + H2O
+ OH

phenol T bisphenol A

_____________________________________________________________________________________________________
IV. (06 pts). Consider the molecule shown here. Does it satisfy the criteria for Me Me
aromaticity? Explain carefully. Me Me
Me Me
C
C
Me Me
Me Me
Me Me
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V. (10 pts). Ketones are normally extremely weak bases; however, there are exceptions. Compare the basicities of
molecules X , Y and Z. Molecule X is much more basic than Y which, in turn, is significantly more basic than Z. In fact, X is
sufficiently basic that one can isolate a stable conjugate acid.
O O O

O MeO OMe
X Y Z

A. (04 pts). Draw the conjugate acids of Y and Z. Explain carefully with pictures why Y is more basic than Z.

B. (06 pts). Draw the conjugate acid of X and explain carefully with pictures why X is much more basic than Y and Z.
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VI. (12 pts). The following reaction sequences were considered as a route to the target OCH3
molecule, X. Identify the best synthesis route (A or B) for target compound X and draw the most
likely product from each step. For the other route, which would not be successful, draw the most NO2

likely product from each step and draw the single most likely product at the end of that sequence.

HNO3 HNO3 Br2 NaOCH3

A. NO2
[a] [b] [c] X? X
H2SO4 H2SO4 FeBr3 CH3OH

Br2 HNO3 HNO3 NaOCH3

B. [d] [e] [f] X?
FeBr3 H2SO4 H2SO4 CH3OH

VII. (05 pts). Consider the following pair of reactions. Identify which is the faster reaction by writing the major product
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expected for that reaction. Explain why you think that one is faster, in terms of the mechanism.

CN
Cl
+
N
NC H

CN

+
N
H
NC Cl

_______________________________________________________________
VIII. (05 pts). Consider the following pair of equilibrium reactions. Identify which one is more favorable by writing the
product for that reaction. Explain why you think that one is more favorable.

O
H2 O
Me

O 2N

O
H2 O
Me

MeO
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IX. (12 pts). Consider the observation represented by the reaction below. Treatment of 1-bromo-2-phenylethane
with aluminum tribromide at low temperature gives an intermediate, Y. Addition of water produces 1-hydroxy-2-phenyethane. The
intermediate Y is a cation (AlBr4- counter ion) and cannot be isolated at room temperature, but observation by 13C NMR spectroscopy
shows 5 signals for Y.
Br AlBr3 H2O OH
Y
-78 oC

When the starting bromide is prepared with 13C enriched at the site indicated below, the 13C label now reveals that there are actually
two products, differing in the location of the label.

Br a. AlBr -78 oC OH • OH
• 3
b. H2O
• +

50 : 50
• = 13C label

Write a structure for Y and a mechanism for its formation, using the usual arrow formalism, which shows clearly the role of the
AlBr3. Complete the mechanism for the conversion of Y into the alcohols, and explain carefully why there are two products when the
13C label is included.
[Clue: think about the reaction of ethyl bromide with benzene, with AlBr3 catalyst]
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X. (12 pts). Propose a synthesis of L from any precursors with two carbons or fewer. Show each step in the
sequence and write the appropriate reagents above the arrow. Shorter, more convergent sequences are better. You may use any of the
reagents and methods which we have discussed in class so far (Chem 303 and 304B), such as: HCl, HBr, CrO3, OsO4, RCO3H,
SOCl2, Br2, Me3SiCl, pyridine, NaOH, KOtBu, Zn/HCl, Mg, Li, ROOR, NaSCH3, [Carbon atoms in protecting groups do not count
in the 2-carbon limit.]

S-CH3

XI. (14 pts). [lab related question].

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In 1978, Lee and Herndon examined the reaction of maleic anhydride (M) and furan (F) by H NMR spectroscopy. In acetonitrile
(CH3CN) solution at 40 °C, with initial concentrations of M and F both equal to 1.50 M, a small amount of adduct A was initially
formed and identified by its 1H NMR spectrum. At the end of 24 minutes, the concentration of adduct A and a new adduct B were
equal, and the concentration of adduct B increased relative to that of adduct A thereafter. Adduct A essentially disappeared after 48
hours to be replaced exclusively by adduct B. By studying this reaction at different concentrations, the following rate constants (k)
were derived:
k1
M + F A
k-1

k2
M + F B
k-2

k1 = 7.29 x 10-3 L m-1 s-1

k-1 = 4.37 x 10-2 s-1
k2 = 1.60 x 10-5 L m-1 s-1
k-2 = 4.40 x 10-6 s-1

A. (02 pts). What is the structure

of adduct A? (A three-dimensional
representation of adduct A would
be appreciated here.)

B. (02 pts). What is the structure

of adduct B? (A three-dimensional
representation of adduct B would
be appreciated here.)
A B

C. (03 pts). Adduct A is the kinetic product of the reaction of maleic anhydride (M) and furan (F). Based on the rate constant data,
shown above, how much faster is adduct A formed than adduct B?

D. (02 pts). Why is adduct A formed faster than adduct B?

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E. (03 pts). The formation of both adducts A and B are reversible (to give the starting materials M and F). Based on the rate
constant data, shown above, how much faster does adduct A revert to starting materials than adduct B?

F. (02 pts). Adduct B is the thermodynamic product of the reaction of maleic anhydride (M) and furan (F). Adduct B is estimated to
be 1.9 kcal/mol more stable than adduct A. Why is adduct B more stable than adduct A?

End Exam 1