Name ________________________________ February 10, 2010

Please write your name on all pages

Ch 41b Midterm

Instructions:

You have 1 hour to complete the exam. The exam is closed book and closed notes.
Calculators are permitted. Good luck!



Problem 1 (4 points) ____________________

Problem 2 (6 points) ____________________

Problem 3 (8 points) ____________________

Problem 4 (8 points) ____________________

Problem 5 (8 points) ____________________

Problem 6 (8 points) ____________________

Problem 7 (3 points) ____________________

Problem 8 (3 points) ____________________

Problem 9 (4 points) ____________________

Problem 10 (8 points) ____________________

TOTAL (60 points) ____________________





Name ________________________________
2

1. Rank the following molecules in order of decreasing pK
a
(increasing acidity).
(4 points)


R
H
R
H
R
H
R
H
O
A B C D







> > > pK
a
A B C D














Name ________________________________
3


2a. Provide the reagents necessary for the following transformation (2 points):


H
O
BH
2
2. H
2
O
2
, NaOH




2b. Draw the structure of the major organic product of the following reaction (2 points):




H
2
Pd/C
Pyridine






2c. Draw the structure of the major organic product of the following reaction (2 points):




Na/NH
3



Name ________________________________
4


3. Propose a mechanism for the following transformation. (8 points)


H
Br
2
H
2
O
O
Br






Br
H
Br
Br
H
Br
H
O
H
Br
Br
Br
H
O
H H
Br
Br
H
O
H
H
Br
Br
H
O
H
H
Br
H
bromonium
vinyl cation

Name ________________________________
5


4. Design a synthetic scheme for epoxide B starting from the alkyl halide A. Show
synthetic intermediates and reagents (Organic molecules with 4 carbons or less may
be used as reagents). (8 points)



Br
O
H
H
A B




Na
A
1)
, THF
2) H
3
O
+
1) NaNH
2
, NH
3
2)
Na
Br
mCPBA
B
Na
0
, NH
3
(liq)

Name ________________________________
6


5. Design a synthetic scheme for diol B starting from acetylene A. Show synthetic
intermediates and reagents. (Organic molecules with 4 carbons or less may be used as
reagents). (8 points)



H H
HO OH
H H
A B






Br
NaNH
2
Pd/C (poisoned)
-or-
Lindlar's Catalyst
1) OsO
4
HO OH
H H
A
Br
NaNH
2
H
2
2) H20 NaHSO3
-or-
reductive workup
B

Name ________________________________
7


6. Suppose you were able to cool a sample of 1-bromo-1,1,2-trichloroethane enough that
rotation about the carbon-carbon bond becomes slow on the NMR time scale. What
changes in the NMR spectrum would you anticipate? Be explicit. (8 points)

(Hint: Draw Newman projections)

Cl
H Cl
Br
Cl H
1-bromo-1,1,2-trichloroethane







At room temperature: rapid equilibrium, NMR is a singlet


At low temperature: one line for conformation A and two doublets for conformations B
and C, for a total of five lines (assuming no overlaps)


Loudon, prob 13.28

Name ________________________________
8


7. In the
1
H NMR spectrum of propylbenzene (CDCl
3
, 300 MHz, in ppm), the two-
proton triplet consists of the following peaks: 2.60, 2.57, 2.54. Express the
coupling constant (J) for this splitting pattern in Hz. (3 points)



propylbenzene





(300 MHz)(0.03 ppm) = 9 Hz








8. A solution of 4-methyl-3-penten-2-one in ethanol shows an absorbance of 0.52 at 236
nm in a cell with a 1-cm light path. Its molar absorptivity in ethanol at that
wavelength is 12,600 M
-1
cm
-1
. What is the concentration of the compound?
(3 points)


O

4-methyl-3-penten-2-one



A = cl

M x
cm cm M l
A
c
5
1 1
10 4
) 1 )( 600 , 12 (
52 . 0

Name ________________________________
9

9. The
1
H NMR spectrum of bromocyclohexane shows a downfield peak (1H) at 4.16.
This signal is a single peak at room temperature, but at -75C separates into two
peaks at 3.97 and 4.64. Explain this observation. (4 points)





Br
H
H
Br
axial Br equatorial Br









10. Determine the structures of the stereoisomeric 1,3-dibromo-1,3-dimethylcyclobutanes
A and B from the spectroscopic data below. (8 points)

Isomer A:
1
H NMR peaks: 2.13 (6H, s), 3.21 (4H, s)
Isomer B:
1
H NMR peaks: 1.88 (6H, s), 2.84 (2H, d), 3.54 (2H, d)
(Hint: doublets have equal spacing)


Br
Br Br
Br
Isomer A
rotational
axis
Isomer B
reflection
plane
(H are diastereotopic)

Stoltz Ch 41c Midterm 1
Chem 41c Midterm Exam
Stoltz, Spring 2011, April 29, 2011
The exam begins when you turn to page 2. You have 55 minutes to complete the exam. This is a closed note
and closed book exam with no collaboration. You may use the periodic table at the front of the room or the
one on the last page of this packet. You may also use a model kit if you like. You may not use any other
materials. The exam has a total of 60 points. Good luck.
There are 11 pages in this exam packet.
Be sure to write your name on every page!
Name:_________________________________________
Stoltz Ch 41c Midterm 2
Chem 41c Midterm Exam
Stoltz, Spring 2011, April 29, 2011
The exam begins now. You have 55 minutes to complete the exam. This is a closed note and closed book
exam with no collaboration. You may use the periodic table at the front of the room or the one on the last
page of this packet. You may also use a model kit if you like. You may not use any other materials. The
exam has a total of 60 points. Good luck.
There are 11 pages in this exam packet.
Be sure to write your name on every page!
THERE ARE 5 PROBLEMS WORTH 10-15 POINTS EACH ON THIS EXAM.
1. (10 points)
2. (10 points)
3. (15 points)
4. (10 points)
5. (15 points)
TOTAL
PLEASE WRITE ALL ANSWERS IN SPACES PROVIDED; USE BACKS IF NECESSARY.
ONLY THESE WILL BE GRADED
GOOD LUCK!
Stoltz Ch 41c Midterm 3
1. Predict the major organic products of the following reactions or sequences. (2 points each)
a.
OEt
O
1. CH
3
MgBr (2 equiv), THF
2. H
3
O
+
, H
2
O
OH
b.
O
OH
H
OH
H
1. H
+
, HS SH
2. Raney-Ni
c.
OH
O
O
Cl O
i-Pr
2
NEt, CH
2
Cl
2
O
O
O
O
d.
O
O
H
H
OCH
3
O O
1. LiAlH
4
, Et
2
O
2. PDC, CH
2
Cl
2
3. THF, 0 C
P(Ph)
3
H
H
OCH
3
O O
HINT:
heating the product
in PhCH3 at 150 C
leads to this product
PhCH
3
150 C
O O
CH
3
H
3
CO
H
H
e.
O
OEt
O
OEt
O
EtO
O
NaOEt, HOEt
Stoltz Ch 41c Midterm 4
2. Propose a mechanism for the following reactions. (5 points each)
a.
Br
O
O
O
KOH
H
2
O, THF
O
O
HO
2
C
MECHANISM
b.
MECHANISM
O
O
OH
O H
C
O
Ph
3
P
Br
O
O
O
K
OH
Br
O
O
O
K
OH
Br
O
O
O
O
H
O
O
O
OH
H
O
KOH
H
2
O, THF
O
O
O
O
O
O
HO
2
C
ii. H
+
O
PPh
3
O
O
H
O
O
OH
O H
C
O
Ph
3
P
Ph
3
P C
O
OH
PPh
3
O
C O
O
PPh
3
O
O
O
PPh
3
O
O
Stoltz Ch 41c Midterm 5
3. Provide the missing products in this multi-step synthesis scheme (15 points).
HBr
A
C
6
H
11
Br
B
C
7
H
12
O
2
1. Mg, Ether
2. CO
2
3. H
2
O, H
3
O
+
1. SOCl
2
2. HOCH
3
, DMAP,
Et
3
N
C
C
8
H
14
O
2
1. LiAlH
4
2. H
2
O, H
3
O
+
D
C
7
H
14
O
E
C
9
H
16
O
2
O
Cl
Et
3
N
Br CO
2
H
CO
2
Me
OH O
O
Hint: Below is the
1
H NMR spectrum of compound E acquired in CDCl
3
.
0 1 2 3 4 5 6 7 8
PPM
2H
3H
1H
10H
Stoltz Ch 41c Midterm 6
4. Glycoside derivatives of the terpene steviol (1) are naturally occurring molecules that have an extremely
sweet taste and are used in a variety of soft drinks and other products as low calorie sweeteners. The
conversion of steviol (1) to its methyl ester 2 is a slow reaction under acid catalyzed esterification reaction
conditions. Why would you expect this to be so? Under what conditions would you expect a rapid reaction
to occur? Provide reagents and draw a mechanism for the successful reaction. (10 points)
OH
HO
O
Steviol (1)
H
H
OH
O
O
2
H
H
H
3
C
CH
3
OH, HCl
slow reaction
reaction is slow due to sterics
CH
2
N
2
or MeI, Base (K
2
CO
3
) would work better. Mechanism as in class for either.
MECHANISM
OH
HO
O
H
H
R
1
HO
O
R
2
R
1
O
O
R
2
H
3
C I
K
2
CO
3
, MeI
acetone
OH
MeO
O
H
H
CO
3
2
OH
HO
O
H
H
R
1
HO
O
R
2
N N
H
H
N N
H
H
R
1
O
O
R
2
H
3
C N N
diazomethane
OH
MeO
O
H
H
N
2
Stoltz Ch 41c Midterm 7
5. We have discussed the so-called Weinreb amide a number of times this term. Show how you could
use such an approach to prepare aldehyde 4 from carboxylic acid 3. Explain mechanistically how the
Weinreb amide functions and how the chemistry observed differs from what would occur using a standard
amide. Finally, propose a synthesis of hydroxyester 5 (15 points)
OH
O
H
O
3 4
OH
OEt
O
Ph
5
OH
O
3
OH
OEt
O
Ph
5
a variety of
possibilities
N
O
O
DIBAL
or LiAlH
4
H
O
stabilizes tetrahedral intermediate
N
O
O
AlR
2
H
OH
O
3
4
OEt
O
1. LDA
2. add 4
3. mild H
+
quench