D. J.

Wardrop
Chem 232 wardropd@uic.edu

Problem Set 7 Answers

Question 1.

c. Rank each carbocation in order of increasing stability (1 = least stable; 4 = most stable)

2 3 1 4 5

e. Rank in order of increasing heat of hydrogenation (∆Hhydrog) (1 = lowest ∆Hhydrog, least exothermic; 5 =
highest (∆Hhydrog, most exothermic).

1 4 3 6 5 2

Question 2.
Toluene (1) undergoes benzylic bromination when heated with N-bromosuccinimide (NBS, 2). Before
toluene (1) reacts though, NBS (2) generates both bromine radicals (Br•) and diatomic bromine (Br2).
First, draw the product of this reaction. Second, draw the mechanism for the homolysis of NBS to
provide a bromine radical. Third, draw a mechanism involving a termination step that shows how Br2 is
formed in the reaction. Finally, draw the mechanism for the radical bromination of toluene (1) using the
bromine radical and Br2 generated from NBS (2).

O O
CH3 hv
+ N Br Br N H
CCl4, heat
O O
1 2
Question 2 (contd).
Question 3.
Draw the major organic product in the boxes provided for each reaction scheme below. If the reaction is
regioselective, only draw the major product. Be sure to indicate the correct relative stereochemistry (i.e.
dashes & wedges or axial & equatorial bonds) where appropriate.

Me O
O 1,3-pentadiene H
heat KOt-Bu
O O
Br THF
H O
O
single isomer single isomer

CH3 Me
1. C2H2 (acetylene)
heat HBr H
Br
2. Pd/C, H2 25 °C
CH3 Me (thermodynamic
single isomer control) single isomer

O Br
heat H
HBr Br
N Br
CHCl3
-80 °C
O
(kinectic control)

O
O
OH Zn(Hg) OH
H heat
H O O HCl O

Br2 (no light) Br

NBS, CHCl3 Br
1,4-addition
H heat

Me
O Me O
H
Me Me O O
Me NBS, BzOOBz Me Me
Me
heat heat Me
H Me Br
O O
Question 4.
Write the name for the principle functional group present in each molecule (e.g. ketone, alcohol, amine,
etc.). If there appears to be more than one functional group present, name them singularly (e.g. vicinal
chlorhydrin rather than alkyl chloride and alcohol). Do not write the IUPAC name or common name for
the molecule, just the functional group name.

O
ketone alkene
H3C CH3

H3C OH ketone H3 C CH3 alkyne

O
Br alkyl bromide H3 C Cl
acid chlorde

OH O
phenol CH3 ester
H3C O

OH
H3C NH2
amide bromohydrin
O Br

O O
acid anhydride H3 C O CH3 ether
H3C O CH3

O OTs
aldehyde alkyl sulfonate
H3 C H

OH
CH3SCH3 thioether/sulfide enol
H3 C CH2

O
H
N amine carboxylic acid
H3 C CH3 H3 C OH

O
H3 C C N nitrile epoxide
Question 5.
For each of the molecules shown below, use electron-counting and Huckel's rule to determine whether
they are aromatic, anti-aromatic or neither. Note that where heteroatoms are shown with a lone pair, this
atom contributes two electrons to the pi-bonding system.

H H H
Me
N
Me H H NA(SC)*
AA
NA A NA
H H H
H
H
try drawing
Br
NA some resonance
H H structures!
AA A AA
H
H H H
2-
NA

H
A AA
AA A

Me

Me

NA AA A

Although one resonance form is

* non-aromatic, this compound
NA A has another which houses NA = Non-aromatic
aromatic cycloheptrienyl cation A = Aromatic
and cyclpentadienyl anion: AA = Antiaromatic
despite being composed of only SC = Special Case
NA C and H, this compound has a
very large dipole moment
Question 6.
Using the Frost Circle mnemonic, draw the molecular orbital diagram for a cyclopentadienyl carbanion
(energy levels only). Indicate which MOs are bonding, non-bonding and antibonding. Use up and down
arrows to represent the electrons present in each orbital. State whether a cyclopentadienyl carbanion is
aromatic, antiaromatic or neither. Use your diagram to explain.

6 Pi-Electrons in Bonding System (4n+2, when n = 1)

H
H H

H H Antibonding MOs
Aromatic Anion
Bonding MOs