1. Name or draw structures for the following compounds.
(a)
isopropylbenzene
Ph
(b)
2-methyl-1-phenyl-2-butene
OH
(c)
o-bromophenol
Br
CH3
CHO
(d)
4-hydroxy-2-methylbenzaldehyde
HO
NO 2
(e) m-fluoronitrobenzene
F
CH 3
(f) (3R, 4R)-4-methyl-3-phenylnonane
CH 2CH 3
(g) p-Ethylphenol
NH 2
(h) aniline
OH
Ph
2. Predict the major organic product(s) of each of the following reactions. If no reaction will occur, write “N.R.”
NO2
(a)
CH3Cl
N.R.
AlCl3
Cl
(b)
Cl
Cl
Cl
Cl
Cl
Cl2
FeCl3
Cl
Cl
3. Provide reagents by each arrow below to complete the following reaction scheme.
Br
CH3Cl
Br2
AlCl3
h
1. Mg, Et2O
2. CH3CHO
3. H3O+
1. CH3CH2C(O)Cl
2. H2, Pt
Zn(Hg)
HCl
PCC
O
OH
4. (i) Draw the major product of the following reaction.
NO 2
HNO3
H2SO4
(ii) Draw the major product formed from the reaction of the compound you drew in part (i) with
another electrophile (E+).
NO 2
E
(iii) Draw the intermediate of the reaction described in part (ii). Include all valid, contributing
resonance structures of this intermediate in your answer.
NO 2
NO 2
NO 2
H
H
E
H
H
E
H
E
H
(iv) Explain why the isomer you drew in part (ii) is the major product of this reaction (rather than any
other isomers).
A resonance structure for the ortho,para substitution have a positive charge on the carbon bearing
the nitro group. This is very unstable because two positive charges are adjacent to one another.
The resonance structures for the meta substitution are more stable, so the meta product is more
likely to form.
5. Circle the letter that corresponds to the correct answer for each question. There is only one correct
answer for each question.
(i) Which of the statements is TRUE regarding the nitration reaction of isopropylbenzene?
A.
B.
C.
D.
A 50:50 mixture of ortho and para products will be formed.
A greater amount of the para product will be formed.
A greater amount of the ortho product will be formed
Only the meta product will be formed.
(ii) Which of the following sets of substituents are ALL ortho/para directing groups in electrophilic
aromatic substitution?
A.
B.
C.
D.
Cl, CN, NO2
CH3, OCH3, C(O)CH3
Cl, NH2, CH3
CN, NO2, C(O)CH3
6. Aniline reacts with nitrous acid, HNO2, to yield a stable diazonium salt.
This diazonium salt undergoes electrophilic aromatic substitution on activated aromatic rings to yield brightly
colored azo compounds that are widely used as dyes. The intermediate structures for the mechanism of this
reaction are given below. Show all electron flow with arrows for this mechanism on the structures provided.
7. Name or draw structures for the following compounds.
OH
(a)
(R)-1,3-butanediol
OH
HO
Cl
(b)
trans-3-chlorocyclohexanol
OH
(c)
3-isopropyl-1-hexanol
(d)
4-penten-2-ol
OH
(i)
isobutyl alcohol
(j)
(E)-2-buten-1-ol
OH
OH
(k)
(2R, 4R)-2,4-hexanediol
(l)
cis-3-ethylcyclobutanol
OH
OH
HO
CH 2CH 3
8. Consider the following reaction.
HO
CH3
HBr
0°C
(a) What is the stereochemistry of the starting material?
(b) What is the solvent in this reaction?
S
Water
(c) Draw the first step of the reaction mechanism.
HO
CH 3
H2O
H
(d) Why is this step necessary?
CH 3
OH2
To make the –OH a better leaving group
(e) What type of reagent must be present for this step to occur in any reaction? Why? Strong acid to
protonate the weak base.
(f) Draw the second step of the reaction mechanism.
H2O
CH 3
+ H2O
(g) Does the carbocation intermediate rearrange? Why or why not? No. It is stable as a 3° carbocation.
(h) Draw the final step of the reaction mechanism.
Br
CH3
Br
(i) What is the stereochemistry of the major organic product? Why? Racemic mixture. Bromide ion
is equally likely to attack either side of planar carbocation.
9. Draw the major organic products formed in the following reactions, clearly showing all appropriate
regio- and stereochemistry.
(a)
PBr3
HO
Br
OH
OTs
TsCl
(b)
pyridine
H2SO4
(c)
OH
O

excess
MgBr
(d)
O
OH
H3O+
ether
Cl
OH
SOCl2
(e)
dioxane
O
OH
O
OH
(f)
O
OH
1. NaBH4
2. H3O+
O
O
(g)
OH
OH
1. LiAlH4
OH
2. H3O+
O
CH 2OH
PCC
(h)
H
CH2Cl2
Na2Cr2O7
(i)
H2SO4
OH
O
10. The following alcohol can be synthesized by three different combinations of a Grignard reagent and a
ketone. Show all three possible combinations. (You do not need to show any mechanisms).
HO CH3
O
+
CH3MgBr
+
CH3CH2MgBr
O
O
+
CH3CH2CH2MgBr
11. Provide starting materials in the boxes below to complete the following reactions.
CH2OH
O
1. PhMgBr
(a)
2. HCl, H2O
C
H
H
OH
O
1. PhMgBr
(b)
H
2. HCl, H2O
O
(c)
OH
1. PhMgBr
2. HCl, H2O
12. Each of the following conversions requires more than one step. Show reagents and experimental
conditions necessary to bring about each conversion.
OH
OH
(a)
OH
OH
H2SO4, 
H2O, H2SO4
O
(b)
Br 2
h
OH
Br
Mg
ether
MgBr
1. CH3CHO
2. HCl/H2O
PCC
O
13. Name the following compounds
CHO
(a)
(R)-3-hydroxy-2-methylpropanal
H
H3C
CH2OH
O
(b)
2-methyl-3-pentanone
CHO
(c)
(d)
(2S)-2-ethyl-3-methylpentanal
O
CH3
(R)-3-methylcyclopentanone
14. Draw structures for the following compounds.
(m) 5-oxohexanal
O
O
H
O
(n) 3-methyl-3-buten-2-one
(o) isopropyl methyl ketone
O
CHO
(p) trans-4-hydroxycyclohexanecarbaldehyde
OH
15. Identify any nucleophilic and/or electrophilic atoms in the following molecules.
(a)
Ph3P
E
CH2
N
ON
E
(b)
N
(c)
E
CH3CH2
MgBr
16. Give the major organic product(s) for the following reaction.
O
O
O
HOCH2CH2CH2OH
HCl
Br
Br
17. Provide structures in the empty boxes below to complete the following reaction scheme.
H
H
O
+
NH3
H+
N
H2
H
N
Ni
18. The following alkene can be synthesized using the Wittig reaction. Show both possible routes,
including formation of the phosphonium ylide.
O
1. PPh3
CH3CH2Br
2. BuLi
CH3CH-PPh3
+
19. Show reagents and experimental conditions necessary to bring about each of the following conversion.
Et
N
(a)
OH
O
PCC
OH
CH2Cl2
H
1. (CH3)2CHMgBr
2. H3O+
OH
O
N
H2CrO4
H2NCH2CH3
H+
O
(b)
OH
OH
OH
O
1. CH3MgBr
PCC
2. H3O+
CH2Cl2
OH
H
H+
OH
1. BH3-THF
2. H2O2, NaOH
OH
H2CrO4
O
20. Name the following compounds.
Cl
(a)
propanoyl chloride
O
O
(b)
isopropyl acetate
O
N
(c)
N-ethyl-N-methylacetamide
O
O
C
(d)
O
phenyl benzoate
CH3
(e)
H
HO
(S)-3-hydroxybutanoic acid
CH2CO2H
O
(f)
E-2-methyl-2-butenoic acid
HO
(g)
2-ethyl-4-methylhexanoic acid
CO2H
O
O
(h)
acetic butanoic anhydride
O
21. Draw structures for the following compounds.
O
(q) Octanoyl chloride
Cl
OH
O
(r) Ethyl 3-hydroxybutanoate
O
(s) N-Cyclohexylpentanamide
O
N
H
(t) Propanoic anhydride
O
O
O
(u) Formic propanoic anhydride
O
H
O
O
22. Each of the following conversions requires more than one step. Show reagents and
experimental conditions necessary to bring about each conversion.
CH3
CH2CO2CH2CH3
(a)
CH 3
CH 2Br
CH 2MgBr
Br 2
Mg
h
Et 2O
1. CO2
2. H3O+
CH 2CO 2CH 2CH 3
CH 2CO 2H
CH3CH2OH
H+
CH3
O
(b)
C
NO2
H2N
Cl
CH 3
CH 3
CH 3
Cl
HNO3
Cl2
H2SO4
FeCl3
NO 2
NO 2
1. KMnO4, OH-, 
2. H+
C(O)NH 2
CO 2H
C(O)Cl
Cl
Cl
Cl
SOCl2
2 NH3
NO 2
NO 2
NO 2
23. What is the order of decreasing activity (most reactive = 1, least reactive = 4) towards
nucleophilic acyl substitution for the following carboxylic acid derivatives?
O
H3C
C
O
O
1
C
O
CH3
H3C
C
4
O
N(CH3)2
H3C
C
2
O
O
CH3
(CH3)2CH
C
3
O
CH3
24. Draw the major organic products formed from the following reactions or sequences of reactions.
O
OH
1. LiAlH4, ether
2. H3O+
(a)
C
O
CH 2OH
O
O
O
(b)
OH
HCl
OCH3
+ CH3OH
H2O
excess
O
MgBr
(c)
Cl
OH
H3O+
CH3CH 2
C
CH 2CH 2CH3
ether
CH 2CH 2CH3
H
N
(d)
25.)
26.)
27.)
CO2H
SOCl2
LiAlH4
H3O+
N
28.)
29.)
30.)
31.)
32.)
33.)
34.)
35.)