CEM 351, Fall 2007

Midterm Exam 2, Version A

Friday, October 26, 2007
1:50 – 2:40 p.m.
Room 138, Chemistry
Name (print)
Signature
Student #

...
Section Number (2 pts extra credit)

Grade?

...
1.(20 pts.)
2.(20 pts.)
3.(20 pts.)
4.(20 pts.)
5.(20 pts.)
6.(20 pts.)
TOTAL (100 pts.)

Score

Note: Answer any 5 questions for a total score of 100 pts. Be sure to look over
all the questions first before beginning the exam, and indicate which five
questions are to be graded by checking the corresponding box.

Recitation Day and Time Instructors: Room

1. T 9:10-10:00 a.m. Alex Predeus 85
2. M 10:20-11:10 a.m. Alex Predeus 281
3. T 10:20-11:10 a.m. Karrie Manes 85
4. Th 10:20-11:10 a.m. Kostas Rampalokos 287
5. T 10:20-11:10 a.m. Alex Predeus 283
6. T 11:30-12:20 p.m. Kostas Rampalakos 283
7. Th 11:30 - 12:20 Kostas Rampalakos 85
8. M 4:10-5:00 p.m. Karrie Manes 110
9. W 4:10-5:00 p.m. Karrie Manes 110
1. (20 pts) Consider compound A at right:
Cl
(a) (3 pts) Name A, being sure to include
Br
stereochemical (R&S) designations. A
(2S,3R)-2-Bromo-3-chlorobutane

(b) (3 pts) On the template below, make a Newman projection of the eyeball’s view of A.
CH3
Cl H

H Br
CH3

(c) (4 pts) Redraw A (upper left) in the table below, together with its three stereoisomers.

A B
Cl Cl

Br Br

C D
Cl Cl

Br Br

(d) (4 pts) On the templates below, make Fischer projections of A-D from part (c).
CH3 CH3 CH3 CH3
H Br Br H H Br Br H
H Cl Cl H Cl H H Cl
CH3 CH3 CH3 CH3

A B C D
(e) (6 pts) Among the four compounds you drew in (d) assign all stereochemical
relationships (enantiomer, diastereomer, etc) by circling the correct term.
A to B Enantiomers Diastereomers Other (define)
A to C Enantiomers Diastereomers Other (define)
A to D Enantiomers Diastereomers Other (define)
B to C Enantiomers Diastereomers Other (define)
B to D Enantiomers Diastereomers Other (define)
C to D Enantiomers Diastereomers Other (define)

2
2. (20 pts) Draw the structures of the major organic product(s) of the following reactions.
Remember that double bonds have two equally reactive faces with exposed π systems.

Br2 , O
OH +
O
Br Br
1 2

H H H
1)BH3*THF
+
2)H2O2, NaOH
OH OH
H H 3
H 4

H2/Pd
+

D D D
5 6

Br
HBr Br
+

Br Br Br
7 8

OH HO
1) Hg(OAc)2/H2O
+
2) NaBH4
9 10

3
3. (20 pts) Alkenes A and B (C6H12) are cis/trans stereoisomers. Upon reaction with Br2, A gives
a single meso compound while B gives a racemic mixture of two compounds, which are both
diastereomers of the product from A. Remembering that Br2 adds trans across a double bond,
deduce the structures of A and B and draw their structures in the boxes below:

Br
Br2
Br
Br Br notice internal
alkene A meso compound mirror plane

Br2
+
Br Br
Br Br
alkene B racemic mixture
no no
mirrors mirrors
Br here Br here

Br Br

4
4. (20 pts.) An unlabeled reaction energy diagram is shown below.

Transition
State

E
N Ea
E
R
G
Y
Starting !Erxn
materials

Products

REACTION COORDINATE
(a) (6 pts) Label the parts of the curve that represent starting materials, transition
states(s), intermediates(s) (if any), and products.

(b) (3 pts) Is the reaction endothermic or exothermic? Circle the correct answer.

endothermic exothermic

(c) (6 pts) Draw in and label the activation energy Ea and the overall reaction energy ΔErxn.

(d) (5 pts) This diagram could represent which one of the following reactions (circle your
answer)? Explain in the boxes at right how you ruled each of the processes out or in. Be sure
to think hard about energies:
Reaction Explanation

This flip is one step, yes, but thermoneutral--

(Chair-chair flip) same energies on both sides; graph above is
not, so it's not this one.

This reaction is one step, but very endo-

I + HOH HI + HO (Acid-Base) thermic. Graph above shows exothermic
reaction, so it's not this one.

CN CN This reaction is one step, and quite exo-

+ (Diels-Alder) thermic; this is the one!

This reaction is exothermic, but takes two

Br steps via the bromonium ion intermediate; so
+ Br2 (Addition) it's not this one!
Br

5
5. (20 pts) (4 pts each) For each pair of isomeric structures in the grid below, circle the more
stable one, and provide a brief explanation. If you need more space, continue below (e.g. if you
need to draw additional structures, etc.)

Compounds Explanation

Within a given framework, double bonds

prefer most substituted sites, so here,
the tetraalkyl beats the trialkyl alkene.

Trans-1,4-dimethylcyclohexane places
both methyls equatorial, so it's lower in E
than the cis, where one methyl has to be
axial.

Four-membered ring introduces much

more strain (ca 25 kcal/mol) than two 5-
membered rings (ca. 2 x 6 = 12 kcal/mol)

When next door to the C(+) site,

O Oxygen's lone pair is shared with O
O C's empty 2p, stabilizing via a
resonance struc with all full octets

Aromatic stabilization energy of 6-!

electrons in a conjugated loop hugely
stabilizes relative to localized double
bonds.

6
6. (a) (14 pts) Show the mechanisms for the formation from A of both products B and C shown
in the reaction below. Don’t worry about stereochemistry, only structural arrangements. Be sure
to draw any intermediate(s) especially carefully, and use arrows to show how the electron pairs
move.

H-Br Br
+

Br
A B C

Br
path a
a Int-2B
b Br
path b
Br
Rearrangement can happen via
Int-1 bond migration (paths a and b) to Int-2C
secondary cation center in Int-1.
Both these paths expand the ring
and form the more stable tertiary
cations in Int-2B and Int-2C. These
are then trapped by the bromide ion
to form products B and C.

(b) (6 pts) Provide the IUPAC names of the starting material (A) and both products (B) and (C).

A: 1,2-dimethyl-1-vinylcyclopentane

B: 1-bromo-1,2,3-trimethylcyclohexane

C: 1-bromo-1,2,6-trimethylcyclohexane or 2-bromo-1,2,3-trimethylcyclohexane