Professional Documents
Culture Documents
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.
Score:
p 2___________/12
p3___________/11
p4___________/08
p5___________/14
p6___________/10
p7___________/15
p8___________/10
p9___________/ 12
p10__________/08
Lecture Total:
/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
(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
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
C. (03 pts).
Me
a. OsO4
b. reduction
tBu
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
undefined configuration
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.
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
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".
10
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.
11
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.)
12