Name:_____________________________
A
GT Student ID:_____________________________
Third Exam
CHEM 2312
15 March 2017
In taking this examination, you are expected to adhere to the GT academic honor code. At a minimum this requires that
you utilize only the materials supplied to you, and that you do not give help to, or accept help from, others.
(60 points) Multiple choice:
1.
Arrange the following compounds in the order of increasing basicity (least to most) in aqueous solution:
NH 2
i.
NH 2
ii.
iii.
NH
O2N
Cl
a. IV < I < II < III
b. II < I < IV < III
c. III < IV < I < II
2.
d. III < II < I < IV
e. III < IV < II < I
What is the reactant M of the following reaction sequence?
PBr 3
M
i. Mg, Et 2O
ii. CO2
iii. H 3O+
O
nPrOH
O
cat. H 2SO 4
OH
O
OH
a.
3.
NH 2
iv.
b.
c.
d.
H
H
e.
Which of the following reactions would not yield pentan-2-amine?
O
Cl
a.
O
c.
1. NaN 3
e. all of these will work
1. 2-bromopentane
NK
2. H 2O, heat
2. H 2NNH 2
O
1. NaN 3
Br
b.
2. H 2, Pd-C
d.
1. LiBH 3CN
NH 3
O
2. H 2O
O
4. What is the final product P of the following reaction sequence?
1. NaNO 2, HCl
2. CuCN
NH 2
P
3. LiAlH 4
4. H 2O
NH 2
a.
b.
c.
O
H
N
d.
NH 2
NH 2
NH 2
e.
O
5. Predict the major organic product of the following conversion:
O
O
1. CH 3MgBr
(excess)
?
2. H 2O
a.
HO
HO
HO
c.
b.
H 3CO
HO
HO
H 3CO
d.
O
e.
HO
HO
O
6. Which of the following structures is fumaric acid?
a. HOOC
COOH
b.
COOH
COOH
c.
COOH
COOH
d.
HOOC
e.
COOH
7. Which of the following reactions could be used to synthesize acetamide?
a. CH3COCl, excess NH3, 25°C
b. (CH3CO)2O, excess NH3, 25°C
c. CH3COOH, excess NH3, 25°C
d. Answers a), b), and c)
e. Answers a) and b) only
8. Arrange the following compounds in the order of decreasing reactivity towards sodium hydroxide:
O
i.
O
Cl
a. II > I > IV > III
b. I > II > IV > III
c. IV > III > II > I
ii.
O
O
O
iii.
O
NH 2
iv.
d. II > I > III > IV
e. IV > III > I > II
O
COOH
9. What would be the product(s) of the following conversion?
Cl
KNH 2
?
NH 3 (l)
NH 2
Cl
a.
b.
Cl
c.
d.
NH 2
e. mixture of
a) and b)
NH 2
NH 2
10. Choose the reagent(s) that would bring about the following reaction:
O
O
?
NH 2
OEt
a. i) NaOH, heat ii) SOCl2 iii) EtOH
b. i) NaOH, heat ii) EtOH, H2SO4
c. i) P2O5 ii) DIBAL-H iii) EtOH
d. Answers a) and b)
e. Answers a), b), and c)
11. What would be the product F of the following reaction sequence?
COOH
O
COOH
b.
a.
N
H
CH 3NH 2
(excess)
SOCl2
F
O
N
H
c.
O
N
H
Cl
N
d.
e.
N
H
Cl
12. What is the major organic product X of the following reaction sequence?
CHO
NH 2OH
Na
X
EtOH
O
a.
NH 2
NH 2
b.
NH 2
c.
N
OH
d.
OH
CN
e.
13. (20 points) For each of the following reactions fill in the missing reagent(s) or product(s).
a)
H2N
LiBH3CN
CHO
N
H
b)
1. Et2CuLi
2. H2O
Cl
O
O
c)
O
Cl
NH2
Cl
Br2, NaOH
NH2
heat
d)
Cl
NH
O2N
CH3NH2
NO2
O2N
heat
NO2
e)
1. NaNO2, HCl
2. Cu2O, Cu2+, H2O
NH2
OH
14. (8 points) Propose a detailed step-by-step mechanism for the following conversion:
O
1. CH 3MgBr
CN
2. H 3O+
MgBr
H
N
N
H
O
H
H
O
H
H
H
CH3
H
O
H
H
O
H H
H
N
CH3
O
H
N
CH3
CH3
H3C MgBr
H
H
N
H
CH3
H
H
O
H
H
H
H
H
N
O
O
CH3
H
H
N
CH3
O
H
H
O
CH3
15. (12 points) Starting from benzoic acid, propose a multistep synthesis of amide Q. Provide a sequence of
reactions to perform each transformation, showing the reagents and structures of all isolated synthetic
intermediates. All carbon atoms of Q must be derived from benzoic acid; however, you may use any other
reagent as needed. Do NOT provide mechanisms, just the synthetic steps.
O
COOH
N
H
O
COOH
SOCl2
O
Cl
NH2
Q
pyridine
NH3
NH2
1. LiAlH4
2. H2O
O
N
H
NH2