Chemistry 303

fall, 2009

THIRD EXAMINATION
7:30 PM, DECEMBER 16TH, 2009
Duration: 2.5 hr
Name___________________________________________________________

This is an open book examination; you may use anything that is not alive or connected to the Web.
Note: if you do not know the complete or specific answer, give a partial or general answer
We love to give partial credit.
If there seems to be more than one good answer, explain your thinking.
If you invoke resonance delocalization as part of your answer, draw the relevant resonance structures.
If you draw a chair cyclohexane, be sure to orient the bonds carefully.
If you do not know a structure and need to write a mechanism, write a general mechanism for partial credit.
You need not draw transition states as part of a mechanism unless expressly instructed to do so.

USE THE ARROW FORMALISM CAREFULLY FOR ALL MECHANISMS. SHOW ALL INTERMEDIATES.
BE SURE TO INCLUDE ALL FORMAL CHARGES.

Write only in the space provided for each question.

Score:
p 2___________/12

p3___________/11

p4___________/08

p5___________/14

p6___________/10

p7___________/15

p8___________/10

p9___________/ 12

p10__________/08

Lecture Total:

Lab question _________/14

/100

There are 12 pages in this exam; please check now to be sure you have a complete set.

Pledge:_________________________________________________________________________________

I. (12 pts). Consider the reaction of Z-2-butene under the conditions shown.
Br2
H 2O

C4H9BrO
(two stereoisomers)
M1 and M2

NaH

C4H8O; (one stereoisomer)

(base)

+ H2 + NaBr

N
[IR: no peaks 4000-3200 cm-1]

A. (06 pts). Write the mechanism for formation of the stereoisomers M1 and M2, drawing both carefully using
the sawhorse or Newman projection.
Are they:
enantiomers diastereomers a racemic mixture meso isomers (circle all correct answers)?

B. (06 pts). Write the mechanisms for the formation of N from M1 and M2, drawing the structure carefully
using the sawhorse projection. Circle true characteristics about N. (circle all correct answers)
Racemic mixture

meso isomer

zero optical rotation

II. (11 pts). Consider the simple SN1 reaction (no rearrangements) of the
secondary p-toluenesulfonate esters represented by X, and the relative rate data for
the cases where both R = Me, and where both R = tert-butyl.

R
OTs
R

H2O

50o C

rates
R = Me =
1
R = t-Bu = 10,000

A. (03 pts). Draw the mechanism for the reaction involving R = Me.

B. (03 pts). Explain in terms of the mechanism the single most important reason why the case with R = t-butyl
is much faster.

C. (05 pts). Now consider the SN1 reaction of substrate Y under the same
conditions with a very different outcome in relative rates.
Explain in terms of mechanism why Y with R = t-butyl
is much slower than than Y with R = Me.

Br
R

H2O

50o C

rates
R = Me = 600
R = t-butyl = 1

III. (08 pts). Draw the structure of an alkyl bromide having molecular formula C5H11Br that
fits the criterion for each part (different structure for each answer; in each case, explain in one sentence why
your structure is a particularly good choice). There may be more than one correct answer; give only one.
A. (02 pts). Undergoes E1 elimination at the fastest rate (also draw the alkene).

B. (02 pts). Is incapable of reacting by the E2 mechanism (not just very slow).

C. (02 pts). Yields only a single alkene on E2 elimination (also draw the alkene).

D. (02 pts). Yields the most stable alkene upon E2 elimination (also draw the alkene).

IV. (14 pts). A. (07 pts). Write the best mechanism to account for the following conversion
of G to H and J.
H+

G
H

B. (07 pts). Draw one reaction coordinate diagram to represent this process, leading to both products. Be
sure to indicate the relative energy of intermediates and products carefully.

reaction progress

V. (10 pts). Provide the starting material, reagent(s), or major product for each reaction below.
A. (02 pts).
O

1. O3

Me

2. Zn

O
Cl

B. (03 pts).

one mole

OEt
one mole

pay attention to exact stereochemistry

C. (03 pts).

Me

a. OsO4
b. reduction
tBu

most stable chair form

D. (02 pts).

H
H

H
H

H
H

H
H

O
O

Br

OEt

VI. (15 pts). Consider the selective formation of L from H under the conditions shown.
O
COOH

a. NaHCO3

Et3N

b. I2

[13C
I

C9H12O2

+ Et3NH I

NMR: ! 23, 25, 29, 31, 42,

82, 122, 132, 176 ppm]

undefined configuration

A. (01 pts). What is the absolute configuration of H?

R or S

circle one

B. (06 pts). Draw a mechanism for the reaction that accounts for formation of L as a single diastereomer.
Show clearly the stereochemistry of the substituents.

C. (02 pts). Draw L in its lowest-energy

conformation using the chair version.
D. (06 pts). Draw the mechanism for the conversion
of L to M, showing clearly the structure of M.
Explain why this particular alkene is formed in terms
of the mechanism. Use the appropriate chair
representation of L.

VII. (10 pts). Consider the following reactions of A to give B and the enantiomers C1 and C2.
While B appears as a single enantiomer with the cis configuration, C is actually a racemic mixture of isomers
with the trans configuation. No specific configuration is implied by structure C1/C2 shown here.
NMe2
OEt

NMe2

Ag2CO3
EtOH
A

C1/C2

Cl

NMe2
SEt
THF

SEt

racemic trans isomers

[!] = +19.5o
[!] = +8o
[!] = 0o
A. (02 pts). Draw the best mechanism to rationalize the formation of B from A, including the selective
formation of the isomer shown. What is the name of this mechanism?

B. (02 pts). Draw the two isomers C1 and C2

that constitute the racemic mixture
represented by C1/C2, in their most stable
chair forms.

C. (06 pts). Draw the best mechanism to rationalize the formation of the racemic C1/C2; show clearly why a
racemic mixture with the trans configuation is formed .

VIII. (12 pts). Trialkylammonium ions such as F and G can undergo E2 eliminations, as shown here.
The selectivity is not always as advertised for this mechanism, as suggested by the mixtures obtained.
H

Me NMe3

Et

tBuOK

NMe3
H

Me

DMSO

Et

Et

95%

iPr

Ph

Me

tBuOK

iPr

5%
Ph

+
DMSO

Ph

32%

iPr

Me
iPr = isopropyl,

Me

68%

A. (02 pts). Why is E2 preferred over E1/SN1 and SN2 under these conditions? Explain briefly

B. (05 pts). Based on the data above, draw the two Newman projections for F that account best for the two
products shown. Circle the conformation that leads to the major product. Explain why this conformation is
favored, using the arrow formalism to show electron flow.

C. (05 pts). Based on the data above, draw the two Newman projections for G that account best for the two
products shown. Circle the conformation that leads to the major product. Explain why this conformation is
favored.

IX. (08 pts). A. (04 pts). Draw here all four stereoisomers of 1,2,4-trimethylcyclopentane and
label them 1, 2, 3 and 4. Then answer the following questions using your labels. If the answer is "none", write
"none".

B. (01 pts). Give one pair of enantiomers.

C. (01 pts). Give one pair of diastereomers.
1,2,4-trimethylcyclopentane
(no stereochemistry
intended)

D. (01 pts). Give one meso structure.

E. (01 pts). List all chiral structures.

_______________________________________________________________________________________

End Lecture Exam Portion

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X. (14 pts). Laboratory: Hugh B. DeMann, former orgo lab student, attempted to prepare 3methyl-2-butenyl acetate (2) from 1-chloro-3-methyl-2-butene (1) and acetic acid, as shown below.
H3C

C H3C O2H

H3C

Cl

H3C
+
H3C

O C C H3
2

To his chagrin, the reaction also produced isomer 3. The 1H NMR spectrum of isomer 3 is summarized below:
Isomer 3

H NMR (CDCl3, 400 MHz): " 1.52 (s, 6H), 1.99 (s, 3H), 5.07 (dd, J = 10.9 Hz, J = 0.9 Hz, 1H)
5.17 (dd, J = 17.5 Hz, J = 0.9 Hz, 1H), 6.08 (dd, J = 17.5 Hz, J = 10.9 Hz, 1H)

Hint: read both parts of the question before analyzing the data. The mechanism and the spectral data should
work together to help you.
A. (11 pts). Deduce the structure of isomer 3. Draw the structure of isomer 3 and label each unique
hydrogen on your proposed structure. Under the structure, indicate your chemical shift assignments for the
resonances at ! 5.07, 5.17, and 6.08 ppm. Also, carefully explain the splitting patterns and make coupling
constant assignments for these resonances.

Continued.

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B. (3 pts). Tell Hugh (and us) why he should not have been surprised to obtain two isomeric products from
this reaction. (Hint: Formal mechanisms are not required here, but a brief mechanistic analysis of the reaction
seems warranted.)

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