CHEM 203

Midterm Exam 2
November 13, 2014

Your name:

This a closed-notes, closed-book exam

You may use your set of molecular models

This document contains 7 pages

Time: 1h 30 min

1. ________ / 10

2. ________ / 15

3. ________ / 15

4. ________ / 20

5. ________ / 20

6. ________ / 20

TOTAL ________ / 100

This exam counts for 18.75% of your CHEM 203 final grade
Chem 203 midterm exam 2 p. 2 of 7

1. (10 pts.) The compounds shown below are similar – though clearly not identical – to
particular reagents that were discussed in class. On the basis of analogy, indicate the likely
use of each (write your answers in the appropriate boxes):
probably used as / for probably used as / for

N
N O O
N
N
N Cl

probably used as / for probably used as / for

OH
Na
N
Si Si

OCH3

2. (15 pts.) Inside the appropriate boxes, draw:

a. The structure of an alkane that is a poor substrate for radical chlorination, but a good one
for radical bromination, and one that is a poor substrate for radical bromination, but a
good one for radical chlorination:
poor for chlorination, good for bromination poor for bromination, good for chlorination

b. The structure of an alkyl halide that is likely to react with H C C–Na by the SN2
mechanism, and one that is likely to react with the same reagent by the E2 mechanism.
likely to react by SN2 likely to react by E2
Chem 203 midterm exam 2 p. 3 of 7

c. The structure of two carbonyl compounds that yield product A when treated with an
excess of CH3MgBr , followed by mild H3O+:

CH3MgBr OH
or
then mild
H3O+
A

d. The structure of a chiral alkyne that yields a chiral product when treated with H2 and
Lindlar catalyst, but an achiral product when treated with H2 and finely divided platinum:

e. The product obtained from alkene B upon reaction with HBr, followed by CH3Li and
CuBr:

1. HBr

2. CH3Li
B CuBr

3. (15 pts.) Write an accurate mechanism for the following known reaction:

CH3SH CH3S

radical
initiator
Chem 203 midterm exam 2 p. 4 of 7

4. (20 pts.) Provide the structure of the major product expected from the following reaction
sequences. If no overall change is expected, answer "NO REACTION." Important:
compounds incorporating multiple stereogenic centers must be drawn with the correct
relative configuration.
Note: it is understood that chiral compounds will be obtained as racemic mixtures.

1. Br2, CH3OH
a.
2. NaN3
3. Zn, H+

1. H2SO4, 180 °C
2. HI
b. OH
3. Na CH3
4. Na, liq. NH3

1. HBr, radical
initiator
c.
2. CH3MgBr
CuBr

1. HCl
d. and (2 products)
2. CH3OH, heat

1. NBS, hν
CH3
2. Mg
e.
3. CO2
4. mild H2O+
Chem 203 midterm exam 2 p. 5 of 7

5. (20 pts.) Propose a method to achieve the transformations shown below. Indicate all the
reagents, in the correct order, that are required to induce each transformation. Present your
answer as a numbered list displayed above / below each reaction arrow. If a product appears
to be unavailable from the indicated starting material by any method known to you, write
"INACCESSIBLE" on the reaction arrow
Note: it is understood that chiral compounds will be obtained as racemic mixtures.

a.

OH

Br
H
b.
H
Br

c.

d.

O
e. OH
SCH3
Chem 203 midterm exam 2 p. 6 of 7

6. (20 pts.) Propose a method for the preparation of compounds a. – e. below starting ONLY
with methane (CH4) and acetylene (H–C≡C–H) as the source of carbon atoms. You may use
any additional reagent that might be needed (e.g., borane, HCl, Mg, H2O2, potassium tert-
butoxide, etc.). Present your answer as a clear flowchart that shows all intermediate steps and
products. Substances obtained in a prior sequence may be used in later sequences. It is not
necessary to draw mechanisms

OH
a.

O
b.
H
Chem 203 midterm exam 2 p. 7 of 7

c. OH

OCH3
d.

CH3O
e.