New York University Prof.

Ron Callahan
CHEM UA 226

PRACTICE EXAMINATION I

NAME ____________________________________

N# _____________________________________

PLEASE WRITE ALL ANSWERS ON THIS EXAMINATION PAPER. PLEASE READ

I _____

II _____

III _____

IV _____

V _____

TOTAL ___________
I Complete the following reactions. Always indicate the major product(s) 32 points

1. Cl

AlCl3

NO2

CH3 CH3

2. CH3CHCH2CH2Cl

AlCl3

NO2

3.
SO 3
H2SO 4
OH

HCl
4. CH3 CH CH CH CH CH3
-60OC

HCl
5. CH3 CH CH CH CH CH3
800C

2
6)
O O
NH2NH C NH2

pH 5

7) O

CH3CH2 NH CH2CH3

pH 5

O
O
8) CH3 C O O H

Cl O
1) CH3CH2CH2 C Cl , AlCl3
9)
2) NH2NH2 , OH

O 2 OH

10) CH3 C CH3

NO2

11) NO2 OCH2CH3

3
12) O

+ heat
O

O O
CH3 C CH3
13) heat
A + B
CH3 C CH3
O

1) MgBr
O
C
14)
2) H , H2O

15) CrO3
CH3CH CH2OH
H
CH3

1) Ph3P
16) CH3CH2CH2CH2Br
2) n-butyl lithium
3) 2-butanone

4
 II) MECHANISM AND THEORY (30 points)

1a) Using Frost circles and molecular orbital theory, explain why 1,3-cyclobutadiene is not
aromatic (using Huckel’s rule will NOT get you any credit) (2 points)

1,3-cyclobutadiene

1b) would the structure below be a good base? Why or why not? (2 points)

NH

1c) Indicate using Huckel’s rule whether the following is aromatic or not. (2 points)

(here is a case where the Huckel’s rule determination does not agree with nature.
What might be the reason the compound acts differently than the expected result from Huckel’s
rule?

5
2) Give the product and write a mechanism for the following:(6 points)

O
CH3CH2 C CH2CH3 + NH2OH pH 5

6
3a) Show using resonance structures how the SO3H group directs an electrophile meta. (Do not
attach the electrophile to the benzene ring). Briefly explain your structures. (2 points)

O
O S OH

3b An ethyl group is an ortho para director on benzene. If you add bromine to ethylbenzene,
show why the addition is ortho and para to the ethyl group. Use resonance structures derived
from addition of the bromine. Be sure to explain why the ethyl group stabilizes the system.(4
points)

7
4) Write a mechanism for the following: (6 points)

O
HOCH2CH2CH2OH O O
H

8
5) The reaction below forms 2 monchlorinated products of formula C5H9Cl. Indicate the 2
products and a mechanism for their formation. State which product is the major one and why. (6
points)

CH3
HCl
CH3 C CH CH2OH
low temp

9
III) SYNTHESIS (30 points)

1) Synthesize the following from benzene: (6 points)

CH2CH2CH3

NO2 NO2

2) Synthesize the following by a Wittig reaction using toluene and any needed inorganic reagents
(6 points)

CH CH

10
3) Synthesize the following from cyclohexane and methane, as the only carbon sources and any
other needed inorganic reagents. (8 points)

OH
CH3 C

11
4) Carry out the following conversion using the starting material, carbon compounds of 3
carbons or less and any needed inorganic reagents. (5 points)

O OH O
BrCH2CH2CH2 C CH3 CH3 C CH2CH2CH2 C CH3
CH3

12
5) Carry out the following: (5 points)

OH

NH2

13
IV) Find Structures consistent with the following NMR and IR data (10 points)

a) Compound A (C7H13O2Cl)
NMR IR
1.0ppm triplet 3H 1700cm-1
0.9ppm singlet 6H 1100cm-1
2.5ppm quartet 2H
4.0ppm singlet 2H

b) Compound B (C16H16O2)

NMR IR
9.1ppm singlet 1H 1700cm-1
7.2-7.8ppm multiplet 10H 3500cm-1
4.0ppm triplet 2H
3.2ppm singlet 1H
1.5ppm triplet 2H

14
V) Compound A (C4H10) reacts with bromine and light to form compound B (C4H9Br).
Compound B reacts with t-butoxide anion to form compound C (C4H8). Compound C
reacts with bromine and light to form compound D (C4H7Br). Compound D reacts with
KOH to form compound E (C4H6). Compound B also reacts with KOH to form compound
F (C4H8), a structural isomer of C. F reacts with 2 Br2 and light to form compound G
(C4H6Br2). G reacts with 2 moles of KOH in DMSO then PCC to form compound H
(C4H4O2) Compounds E and H react by a Diels-alder process to form the structure below.
What are structures A-H? (8 points)

O
C H

C H
O

15