CEM252, Fall 2007
Midterm #1
CEM 252, Fall 2007
Tue, Thurs 8:00–9:20 am
Midterm #1
September 27, 2007
Name:______________________________
Section:____________
PID: _______________________________
TA: _______________
This is a closed book and note examination. If boxes are provided for your answers, only
what is written in the boxes will be graded. You have 80 minutes to complete the test.
Section 1
Section 2
Section 3
Section 4
Section 5
Section 6
Section 7
Section 8
Section 9
Section 10
Section 11
Section 12
M
W
W
M
F
M
F
M
Th
F
W
Th
8:00 – 8:50 AM
8:00 – 8:50 AM
1:50 – 2:40 PM
11:30 – 12:20 PM
9:10 – 10:00 AM
11:30 – 12:20 AM
3:00 – 3:50 PM
9:10 – 10:00 AM
4:10 – 5:00 PM
8:00 – 8:50 AM
9:10 – 10:00 AM
1:50 – 2:40 PM
Monica
Dan
Dan
Toyin
Stewart
Monica
Stewart
Monica
Toyin
Stewart
Dan
Toyin
1
Question
1
2
3
4
5
6
7
8
9
Bonus
Total
Points
16
6
5
6
5
34
6
18
4
6
106
Score
CEM252, Fall 2007
Midterm #1
1. Provide a name or a structure for the following compounds (16 pts, 2 pts each box)
a. Quinoline
N
O
b. Isopropyl phenyl ether
c. Cyclopentene oxide
O
O
d. m-Chloroperbenzoic acid
O
O
H
Cl
e.
OH
2-ethoxy-cyclopentanol
O
f.
2,3 epoxy-4,5 diethyl heptane
O
g.
O
O2N
h.
NH2
2-methoxy-4-nitro-aniline
O
H
p-bromo-benzaldehyde
Br
2
CEM252, Fall 2007
Midterm #1
2. (6 pts)
a. Which of the following compounds is aromatic? (Circle the correct compound) (3 pts)
H
H
O
b. Draw an orbital picture to show how the molecule you chose above is aromatic.(3 pts)
O
3. Put the following compounds in order of increasing pKa (5 pts)
OH
OH
OH
O2N
OH
NO2
NO2
H2O
NO2
NO2
A
low
pKa
B
C
NO2
D
C
D
B
3
A
E
E
high
pKa
CEM252, Fall 2007
Midterm #1
4. Determine where the chlorine would add to the following substituted benzenes (it could
be more than one compound). (6 pts, 2 pts each box)
O
O
Cl2
FeCl3
Cl
SO3H
SO3H
Cl
Cl
OH
Cl
OH
Cl2
FeCl3
OH
Cl
Cl2
FeCl3
Cl
Cl
SH
SH
5. Show a detailed mechanism of the following aromatic chlorination. (5 pts)
Cl
Cl2
FeCl3
δ
δ
Cl Cl
Cl
FeCl3
Cl
H
FeCl4
Cl
H
H
Cl
+ HCl + FeCl3
4
CEM252, Fall 2007
Midterm #1
6. Provide the major product or the reaction conditions for the following reactions. (34 pts, 2
pts each box)
OH
1. PCC
2. PhMgBr
3. H3O+
OH
a.
OH
OH
OH O
Cl
KMnO4
b.
OH
AlCl3
NO2
c.
NO2
1. HNO3
H2SO4
2. H2/Pd
O
d.
NO2
NH2
OH
1. LiAlH4
2. H3O+
mCPBA
O
Name the reaction for
2 bonus points
250 oC
e.
Claisen
O
f.
H2SO4, heat or
POCl3, pyr
OH
1. OsO4, pyr
2. NaHSO3, H2O
OH
OH
5
CEM252, Fall 2007
Midterm #1
O
g.
OTMS
1. CH3CH2MgBr
2. H3O+
3. TMSCl, Et3N
1. Hg(OAc)2, CH3CH2OH
2. NaBH4
h.
O
1. SOCl2
2. Mg, Ether
i.
OH
j.
O
k.
OH
O
3.
4. H3O+
OH
OH
1. CH3CH2MgBr
2. H3O+
1. H2SO4, heat
2. BH3, THF
3. H2O2, NaOH
OH
1. NaH
2.
O
SO3H
O
SO3H
Cl
l.
O
m.
Cl
Williamson
Name the reaction for
2 bonus points
Friedel Crafts Acylation
AlCl3
O
OH
Name the reaction for
2 bonus points
(KSO3)2NO
O
6
CEM252, Fall 2007
Midterm #1
7. Determine the structure of the following compound based on the 1H-NMR spectrum and
IR data given. Put your final structure in the box. (show work for partial credit). (6 pts)
C10H14O2
OH
3
O
3
2
2
2
1
1
8
7
6
5
4
PPM
3
2
1
0
IR: broad, medium peak at 3600 cm-1; strong peaks at 1300 cm-1 and 1100 cm-1.
1H-NMR: 0.90 ppm (t, 3H); 1.91 ppm (pentet, 2H); 3.85 ppm (broad singlet, 1H); 3.90
ppm (s, 3H); 4.41 ppm (t, 1H); 7.25 ppm (d, 2H); 6.92 ppm (d, 2H).
7
CEM252, Fall 2007
Midterm #1
8. As written the following syntheses have flaws. What is wrong with each of them? (4 pts,
2 pts each)
O
a.
1. Br2, FeBr3
2. KMnO4
OH
Br
Step 1: Bromination cannot be meta
b.
HO
TMSO
O
1. CH3CH2MgBr
2. H3O+
3. TMSCl
OTMS
Step 1: Cannot form Grignard reagent in the presence of a free –OH.
8
CEM252, Fall 2007
Midterm #1
9. Provide a reasonable synthesis for the following molecules using the given starting
material and any other carbon containing compound you need with 3 Carbon atoms or less.
Several steps are required. (Show work for partial credit) (18 pts, 6 pts each)
NO2
a.
O
NO2
HNO3
H2SO4
NO2
CH3Cl (or any other RCH2Cl)
AlCl3
NO2
NO2
1. LiAlH4
2. H3O+
O
OH
1. NaH
2. Cl
KMnO4
H2O, heat
OH
SOCl2, pyr
NO2
NO2
NO2
OH
NaH
O
Cl
9
O
CEM252, Fall 2007
Midterm #1
O
b.
OH
OH
SOCl2 (or PBr3)
pyr
Cl
Mg, ether
MgCl
1.
O
2. H3O+
O
OH
PCC or Jones
10
CEM252, Fall 2007
Midterm #1
c.
O
O
HO
O
HO
SOCl2
pyr
O
Cl
1. CH3CH3MgBr
2. H3O+
O
NaH
11
OH
Cl
CEM252, Fall 2007
Midterm #1
Scratch Sheet: Needs to be turned in with the test (if missing, the test will not be graded)
12