Name: _________________________________
CHEM 322. Midterm 3
Spring 2014
Watson, Hietbrink
Please write your answers clearly in the boxes provided. If your answer is illegible or
outside the box, it will not be graded. You may use the back of test pages for scratch
work.
You may use molecular models.
Use of calculators, cell phones, headphones, or any other electronic device during this
exam is prohibited.
No notes or books may be used during this exam. Data tables are provided on pages 12
and 13 of this exam.
You may raise your hand to ask a question if you are not sure what is being asked of
you.
There are 15 pages in this exam. Please check that your test has 15 pages before you
begin. The last 2 pages are blank and may be used as scratch paper.
Please circle your lecture:
Hietbrink 8:00 am class
Hietbrink 11:15 am class
Watson class
Question
Points
1
_____ /32
2
_____ /56
3
_____ /24
4
_____ /24
5
_____ /50
6
_____ /24
7
_____ /40
Total
_____ /250
1
Name: _________________________________
1. (32 points) Please fill in the missing starting materials or products of the following reactions.
O
O
O
N
H
N
cat. H+
OH
cat. H+
O
O
OH
1) 2 LiAlH4
2) H3O+
O
Me
Me
OH
O
OMe
1) 2 MeLi
2) H3O+
OH
OH
Me
Me
2
Name: _________________________________
2. (56 points) Please provide the necessary reagents to complete the following transformations.
HS
NaCN
SH
cat. H+
O
H
S
S
Br
Br
O
O
(1) LiAlH4
(2) H2O
Cl
S
Ph
or
S
S
NH2
S
CN
Ph
HO
DCC
NaH or NaOH
BrCH2CH3
S
S
S
H
N
H3C
N
S
O
O
Hg2+
H2O
O
H3C
N
H
O
Na2Cr2O7
H2SO4, H2O
O
HO
H3C
N
O
3
Name: _________________________________
3. (24 points) Please fill in the products of the following reactions. If no reaction is expected,
state “No Reaction”.
HO
CrO3
O
Ph3P
CO2Me
MeO2C
N
(or PCC)
LiAlH4, then H3O+
HO
Pd/C, H2
HO
4
Name: _________________________________
4. (24 points) Please fill in the products of the following reactions. If no reaction is expected,
state “No Reaction”.
O
HO
H3C
CH3
cat. H+
HO
H3C
O
H3C
O
O
Cl
AlCl3
O
H3C
O
H3C
O
O
NaOH, H2O
OMe
H3C
O
H3C
O
OH
O
H3C
O
H3C
O
OMe
HNEt2, DCC
O
NEt2
HCl, H2O
HO
NEt2
HO
5
Name: _________________________________
5. (50 points) Dr. Oops wanted to prepare the dimethyl acetal of benzaldehyde. She found an
old bottle of benzaldehyde on her lab shelf and ran the following reaction. She observed 2
products from this reaction. Confused, she checked her starting material (benzaldehyde) and
found that it contained an impurity. Spectra for A and B are shown on the following pages.
Based on these spectra and your chemical knowledge, please answer the following questions.
O
A
+
benzaldehyde
OCH3
cat. H+, H3COH
OCH3
unknown
impurity
(C7H6O2)
B
+
unknown
product
(C8H8O2)
benzaldehyde
dimethyl acetal
(desired product)
(a) Please draw a reasonable arrow-pushing mechanism for the formation of benzaldehyde
dimethyl acetal from benzaldehyde (i.e., Dr. Oops’ desired reaction).
Ph
H+
O
H3C
Ph
Ph
O
O
CH3
H3C
O
O
H
H
H
CH3
Ph
O
Ph
H
O
CH3
CH3
OH
Ph
O
O
H
O
CH3
H
O
CH3
O
CH3
Ph
H
O CH
3
CH3
H
OH
O
Ph
O
H
CH3
CH3
OH2
(b) For impurity A, what does the IR peak at 1690 cm–1 indicate?
C=O
(c) For impurity A, what does the 1H NMR peak at ~ 12 ppm indicate?
O
C
O
H
6
Name: _________________________________
(d) For impurity A, what does the 13C NMR peak at 172 ppm indicate?
X
O
C
X = heteroatom (in this problem, an oxygen)
(e) What is the structure of impurity A?
O
OH
(f) For product B, what does the 1H NMR peak at 3.9 ppm indicate?
O CH3
(g) For product B, what does the 13C NMR peak at 168 ppm indicate?
X
O
C
X = heteroatom (in this problem, an oxygen)
(h) What is the structure of product B?
O
O
CH3
7
Name: _________________________________
Unknown Impurity A:
IR
(2H)
(3H)
1
H NMR
(1H)
13
C NMR
8
Name: _________________________________
Unknown Product B:
IR
(3H)
1
H NMR
(3H)
(2H)
13
C NMR
9
Name: _________________________________
6. (24 points) Please provide a reasonable arrow-pushing mechanism for the following reaction.
Me
O
H3O+
NH Me
Me
N
Me
O
O
NH Me
H
H
O
O
O
H
NH Me
Me
Me
O
Me
N
O
O
H
H
Me
Me
OH
Me
N
O
H
H
Me
Me
Me
N
Me
N
O
O
OH2
H
O
H
Me
OH
Me
N
H
O
H
O
Me
Me
N
O
10
Name: _________________________________
7. (40 points) Please suggest a synthesis of diamine 3 starting from either cyclohexene (1) or
dibromide 2. Clearly indicate which starting material (1 or 2) you have chosen in your answer.
NH2
H2N
1
Br
Br
3
2
From 1:
O
O
KMnO4
or
O3; then H2O2
HO
O
1
SOCl2
OH
Cl
Cl
O
A
NH3
NH3, DCC
O
NH2
H2N
LiAlH4
H2N
NH2
O
3
From 2:
NaCN
Br
Br
CN
NC
LiAlH4
NH2
H2N
3
2
Mg
BrMg
MgBr
CO2
1. NH3, DCC
2. LiAlH4
O
HO
OH
O
A
(Same intermediate as
in synthesis from 1 above)
or
1. SOCl2
2. NH3
3. LiAlH4
Please note: No arrow-pushing mechanism was required for this question.
11
Name: _________________________________
Approximate IR Absorption Frequencies
–1
Bond
Frequency (cm ) Intensity
O–H (alcohol)
3650–3200
Strong, broad
O–H (carboxylic acid)
3300–2500
Strong, very broad
N–H
3500–3300
Medium, broad
C–H
3300–2700
Medium
2260–2220
Medium
C≡N
2260–2100
Medium to weak
C≡C
C=O
1780–1650
Strong
C–O
1250–1050
Strong
1
Approximate H NMR Chemical Shifts
Hydrogen
δ (ppm)
CH3
0.8–1.0
CH2
1.2–1.5
CH
1.4–1.7
C=C–CHx
1.7–2.3
O=C–CHx
2.0–2.7
Ph–CHx
2.3–3.0
2.5
≡C–H
R2N–CHx
2.0–2.7
I–CHx
3.2
Br–CHx
3.4
Cl–CHx
3.5
F–CHx
4.4
O–CHx
3.2–3.8
C=CH
4.5–7.5
Ar–H
6.8–8.5
O=CH
9.0–10.0
ROH
1.0–5.5
ArOH
4.0–12.0
RNHx
0.5–5.0
CONHx
5.0–10.0
RCOOH
10–13
13
Approximate C NMR Chemical Shifts
Carbon
δ (ppm)
Alkanes
Methyl
0–30
Methylene
15–55
Methine
25–55
Quaternary
30–40
Alkenes
C=C
80–145
Alkynes
70–90
C≡C
Aromatics
110–170
Benzene
128.7
Alcohols, Ethers
C–O
50–90
Amines
C–N
40–60
Halogens
C–F
70–80
C–Cl
25–50
C–Br
10–40
C–I
–20–10
Carbonyls, C=O
R2C=O
190–220
RXC=O (X = O or N)
150–180
12
Name: _________________________________
pKa TABLE
compound
Bu-H
Ph-H
H2
iPr2N-H
pKa
48
43
~36
~35
O
Me N
Me
25
CH3
(amide α-H)
O
tBuO
CH3 (ester)
24
O
Me
CH3 (ketone)
17-20
O
N Me
H
(amide N-H)
Me
iPrOH
H2 O
+
Et3N-H
~18
16-18
16
10
O
Me
OH (carboxylic acid)
+
H3 O
HCl
-1-6
–2
–8
13
Name: _________________________________
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14
Name: _________________________________
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15