Name ________________________________

1. Rank the molecules below in order of decreasing pKa (increasing acidity) of the
indicated H: (2 points)

H
H
H 3C H H

A B C D

pKa A > D > C > B

least most
acidic acidic

2. Circle the compounds that are aromatic: (4 points)

O H
N N
N N
O
A B C D

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3. Provide the structures of the products of each of the following reactions. Show
stereochemistry where appropriate: (4 points)

a)
!
+

b) O !
+
OEt CO 2Et

c)
!
+

O CN
CN !
d)

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4. Circle the isoprene units in the following terpenes: (2 points)

OH
H O
H

menthol camphor

COOH

cedrene abietic acid

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5. Treatment of nerol with aqueous acid gives rise to terpin. Write a mechanism for its
formation. (4 points)

OH
H +, H2 O
OH

OH

nerol terpin

H-B

OH H

H-B

O O
H H
H
:B
O
H H

H
O O
H H H :B OH

O O
H OH
H

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6. The following transformation occurs at high temperatures. Provide a mechanism and

CO2 Et O
!
O + + A
CO2 Et EtO 2C CO 2Et

H
CO2 Et
O = A
CO2 Et H

7. The following transformation occurs at high temperature and pressure. Propose a

Cl O

O
NaOH

-Cl

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8. The Friedel-Crafts alkylation of benzene with 1-chloropropane yields two products,

Cl

A +
AlCl3
B

a) Product A has the following 1H NMR spectrum (CDCl3, 300 MHz, in ppm):
δ 7.15-7.35 (m, 5H), 2.94 (septet, 1H), 1.29 (d, 6H). Identify the chemical
structure of A and provide a mechanism for its formation: (4 points)

SN1 AlCl4-
Cl

primary carbocation
rearranges to form
more stable
secondary carbocation

H H

cumene

b) The one-proton septet in the 1H NMR spectrum of A (CDCl3, 300 MHz, in ppm)
consists of the following peaks: δ 3.01, 2.99, 2.97, 2.95, 2.93, 2.91, 2.89, 2.87.
Express the coupling constant (J) for this splitting pattern in Hz: (2 points)

J = (0.02 ppm)(300 MHz) = 6 Hz

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9. Compounds A and B are isomers with molecular formula C8H10O. Based on the
following spectroscopic data, assign structures to compounds A and B: (6 points)

Compound A:
IR: 3329, 1046 cm-1
1
H NMR: δ 7.07-7.41 (m, 5H), 3.77 (t, 2H, J=7Hz), 2.82 (t, 2H, J=7),
2.01 (s, 1H, peak disappears in D2O)

Compound B:
IR: 1245 and 1049 cm-1
1
H NMR: δ 6.8-7.22 (m, 5H), 3.96 (q, 2H, J=7Hz), 1.37 (t, 3H, J=7)

A B
OH O

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Name ________________________________

10. Design a synthesis of the molecule below using benzene and starting materials with 3
carbons or less. (6 points)

NO2
H
O
H

Solution:

HNO3 NO2
MeCl, AlCl3

H2SO4
Br2
CCl4
light
NO2 NO2
Na

H2, Lindlar's Br
NO2 mCPBA
Product

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11. For each of the following products, design a synthesis starting from benzene.
(6 points)

a) COOH

Br

CH 3 COOH
CH3
MeCl Br 2 KMnO4

AlCl3 FeBr3 H 2O
Br Br

b)

Cl

SO 3H

Cl SO 3 Cl2 Cl

AlCl3 H 2SO4 FeCl2

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12. Two reaction mechanisms have been suggested to explain the 2+4 cycloaddition
reaction. One is a concerted reaction affording cyclohexane product. The second
mechanism involves the allylic radical intermediate, which could result in two
products, as shown below. However, only cyclohexene is observed.

Draw a reaction energy diagram and provide an explanation for why the lack of
vinylcyclobutane product does not rule out the two-step mechanism. (6 points)

NOT OBSERVED ONLY PRODUCT

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Name ________________________________

13. Please provide a mechanism that explains formation of products A and B, obtained
through reaction of the starting material with HCl. (6 points)

(Hint: Product B requires a 1,2 alkyl shift.)

HCl
Cl
Cl

A B

H2 C
A
Cl
H Cl Cl

H 2C
CH2

Cl

B
Cl

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