Chemistry 213
Clark College
Exam 2 Review Sheet
The following questions have been pulled from various exams and review sheets from some of my
previous classes. The review is not complete! Make sure you study the assigned homeworks, go
through suggested problems and read through the Chapter Notes and your lecture notes.
Topic Outline
You should feel comfortable with the following topics:
Ch. 19 Amines
• Nomenclature of substituted amines (IUPAC and non-IUPAC methods).
• Basicity of amines.
• Preparation of amines via:
o Direct alkylation of an amine with R-X via an SN2 mechanism.
 Overalkylation with a large excess of R-X.
 Monoalkylation with a large excess of amine.
o Formation of imines and enamines followed by reductions.
o Addition of cyanide, followed by reduction to add –CH2NH2.
o Addition of sodium azide (NaN3), followed by reduction.
o The Gabriel synthesis of 1° amines with phthalimide/KOH followed by hydrazine.
• Reactions of an aromatic diazonium salt.
o Preparation from anline with sodium nitrite and HCl.
o Reaction with CuX (X = Br, Cl, CN) to substitute the X group.
o Reaction with KI to add I to the ring.
o Reaction with HBF4 to add F to the ring.
o Reaction with ROH, H+ to form phenols and phenolic ethers.
o Reaction with H3PO2 to substitute a hydrogen.
o Using the directing effects of the nitro and amino substituents, followed by a diazonium
reaction to make substituted benzenes.
Ch. 20 and 21 Carboxylic Acids and Derivatives
•
•
•
•
•
•
•
•
•
•
•
Nomeclature of acids and derivatives.
Physical properties of acids – dimerization.
Reactivity of acids and derivatives – leaving group ability, basicity, resonance structures.
Fischer esterification; reaction and mechanism.
Formation of acid chlorides with SOCl2 or PCl3, in pyridine; reaction only.
Conversion of acid chlorides to other derivatives; nucleophiles, mechanisms, solvent
requirements/stoichiometry.
Conversion of esters to other esters and amides; reactions and mechanisms.
Hydrolysis reactions – acid-catalyzed, base-catalyzed (saponification); mechanisms.
Use of esters as protecting groups, limitations of esters as protecting groups.
Reactions of esters, acid chlorides with carbon nucelophiles.
Reductions of acids and derivatives with LiAlH4 and DIBALH.
Review Problems
1. Road map. Provide the intermediates for the synthesis of Buproprion, better known by the trade
names Wellbutrin® or Zyban®. [18]
O
1) Cl
AlCl3
2) H2O
Exam 1
A
Cl2
FeCl3
B
HBr
C
OH
HO
Spring 2007
H+
H2N
D
TEA
E
H3O+
F
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Chemistry 213
Clark College
2. Flutamide (Eulexin®) is a drug that is used in the prevention and treatment of prostate cancer by
reducing the amount of testosterone and androsterone in target cells. Propose a synthesis of
flutamide from (trifluoromethyl)benzene.
CF3
CF3
O2N
O
N
H
3. Synthesize the following molecule from benzene.
CH3
O
F
4. Complete the following Diels-Alder reaction, provide a mechanism and give a product that is
consistent with the following observation: an IR of the product shows a broad peak centered at
3000 cm-1. [8]
OH
O
Heat
O
C10H12O4
O
5. Each of the following compounds can be hydrolyzed back to butanoic acid when treated with acid
and water. Which will react the most rapidly? Completely explain your answer. [10]
O
O
O
O
N
H
O
O
6. Provide the mechanisms for the following reactions.
O
O
O
Exam 1
OH-
1)
2) H+
C5H10O3
O
Cl
2 CH3NH2
Spring 2007
N
H
CH3NH3+Cl-
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Chemistry 213
Clark College
7. Determine the structure of Compound A below. Then, give the structures of the two starting
materials that, when heated in the presence of acid, will form compound A. [13]
Compound A
C7H14O2
6H, d
3H, t
2H, d
2H, q
1H, m
Spectrum obtained from http://www.aist.go.jp/RIODB/SDBS/cgi-bin/cre_index.cgi, SDBS Spectral Database of Organic
Compounds, (accessed April 25, 2007).
H+
heat
Compound A
8. What is the correct IUPAC name for the following molecule?
O
OEt
a. E-ethyl-3-methyl-2-pentenoate
b. Z-3-methyl-2-pentenoic acid, ethyl ester
c. Ethyl Z-3-methyl-3-penten-5-oate
d. Ethyl E-3-methyl-2-pentenoate
Exam 1
Spring 2007
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Chemistry 213
Clark College
9. Which of the following is the correct product for the following reaction?
O
O
CH3OH
H+
H3CO
O
H3CO
O
O
OCH3
HO
OH
H3CO
H3CO
OH
O
10. What statement best explains why an amide can’t be synthesized directly from the carboxylic acid?
a. The amine will deprotonate the carboxylic acid proton and will no longer be a nucleophile
b. The reaction proceeds faster from the ester.
c. The amine is not a strong enough nucleophile to attack the carbonyl carbon.
d. We did not learn the reaction specifically in class.
11. Nomenclature.
a. Name the following molecules using the IUPAC naming system.
O
O
F
Br
OH
N
O
O
O
O
O
H
H3C
Cl
CH3
O
Cl
NH2
HN
F
O
H
N
O
b. Draw the following molecules from the IUPAC names.
i. 3,3–dimethylhexanoyl chloride
ii. 2–methyl–1,4–butanedioic acid
iii. trans-3-(ethylamino)cyclohexanol
Exam 1
Spring 2007
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Chemistry 213
Clark College
12. Fill in the blanks I.
O
O
OH
O
O
N
H
pyridine
O
O
O
H
N
1) NaBH4
2) H3O+
O
O
O
OH
Cl
1) DIBALH, -78°C
2) H2O
O
O
H
1) (CH3CH2)2CuLi
-78°C
2) H2O
Cl
H
N
O
OEt
H+, heat
HO
OH
O
O
HCl
H2O
O
O
O
Cl
Exam 1
Give both organic products.
N H
pyridine
Spring 2007
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Chemistry 213
Clark College
13. More fill in the blanks.
NH2
NH2
1) NaNO2
HCl, 0°C
2) CuCN
3) H2, Pt
Excess Et-I
NH2
F
O
O
NH2
Br
O
Br
N K+
1)
O
2) N2H4, !
14. Road Maps. Give the identities of the compounds in the following synthetic pathways.
O
OH
O
H
1) BrMg
2)
H3O+
HBr
H2O2
A
A
NH3
DMSO
H2CrO4
B
SOCl2
Pyridine
OH
HO
B
H+
C
C
heat
Pyridine
1) Hg(OAc)2,
H2O
2) NaBH4
D
D
SOCl2
pyr
G
C12H21N
Exam 1
Spring 2007
H+
F
CH3NH2
DMSO
E
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