Chemistry 143B Spring, 2015

NAME:

Exam #1 (4-22-15)

Total Points: 75

Ima KEY

TA Name: ___________ ____________

USE INK FOR RECORDING ANSWERS (if using pencil, no re-grades will be allowed)
1. (10 points) The following procedure is followed in the laboratory. Read it
CAREFULLY and answer the questions that follow.
Place aniline (5 mmol), water (12 mL) and concentrated hydrochloric acid (0.5 mL) in a
25 mL Erlenmeyer flask. Add a stir bar and carefully stir the content to dissolve the
aniline. Add acetic anhydride (1.0 mL) to the stirred solution. Allow the reaction mixture
to stir for one hour.
Below, draw the EXACT structure of ALL of the organic compounds that would be
present following the above procedure:

2. (15 points) The following procedure is followed in the laboratory. Read it

CAREFULLY and answer the questions that follow.
Add glacial acetic acid (4 mL) to a 25 mL Erlenmeyer flask containing a stir bar and add
two mL of toluene (methylbenzene) with stirring. Once a solution is formed, add tetra-Nbutylammonium tribromide (calculate and add one equivalent based on toluene amount)
with stirring and heat the slightly orange mixture at 60oC. Analyze the reaction by TLC.
Be sure to run three lanes; one with starting material, reaction, and co-spot. Also be sure
to completely evaporate the acetic acid from the plate before developing. Record the TLC
in your notebook. After 20 minutes, quench by adding water (15 mL) and a saturated
solution of sodium bisulfite (2 mL). Add an additional mL of the bisulfite solution if the
orange color persists. Stir the solution for 5 minutes. Work up the reaction in an
appropriate manner and identify the compounds which are present.

Below, draw the EXACT structure of all of the organic compounds that would be present
following the above procedure:

What was the purpose of adding sodium bisulfite?

To remove (destroy) unreacted bromine (Br2)

(4 points)

Write the balanced chemical equation to show how the sodium bisulfite acted as you
described in the previous question.

3. (28 points) The following procedure is followed in the laboratory. Read it

CAREFULLY and answer the questions that follow.
To a mixture of 0.7 g (an excess) of sodium acetate trihydrate in 3 mL of anhydrous
DMSO in a 10 mL round bottomed flask containing a stir bar is added 500 L (0.5 mL)
of 1-bromo-3-methylbutane, via syringe. The flask is fitted with a water-cooled condenser
and the solution heated to 100C for 30 min. The resulting clear, colorless solution is
cooled to room temperature during which a precipitate of NaBr forms. Water (5 mL) is
added, and the contents of the reaction flask are transferred to a test tube. The reaction
flask is rinsed a second time with 5 mL of water, and this wash combined with the first.
Pentane (2 mL) is added mixture and the contents mixed well with a Pasteur pipette. The
pentane layer is transferred to a clean, dry test tube. A second pentane wash (2 mL) of
the aqueous layer is similarly transferred to the test tube. The combined pentane layers
are washed once with 4 mL of water, once with 4 mL brine, dried over Na2SO4, and
filtered into a 25 mL round bottomed flask. The pentane is carefully removed in vacuo at
room temperature.

The above reaction was worked-up utilizing a liquid-liquid extraction. What was the
purpose of the water wash? (note: the answer given during lecture was NOT complete):

What was the purpose of the brine wash?

to remove the bulk of the water (3 points)
You used DMSO as a solvent for this reaction. Draw the structure of DMSO and give its
full name. Next, provide the structure and full names of 3 other polar aprotic solvents that
are commonly used on SN2 reactions (from Volhardt and Shore, Table 6-5):

Provide the COMMON name of the alcohol you would use to prepare the above product
via a Fischer esterification.
Isoamyl alcohol or Isopentyl alcohol (3 points)
4. (14 points) The following procedure is followed in the laboratory:
Dissolve 4-bromo-2-nitroacetanilide in 18O-labeled methanol (H3C18OH) (2.0 mL), and
bubble in gaseous hydrochloric acid. Add a boiling chip or stir bar and attach a reflux
condenser. Reflux the reaction mixture for about 10 minutes and check the reaction
progress by TLC. To do this, remove a small amount (0.5 mL) of the reaction solution
with a pipette. Place this in a small vial and add ether. Mix the layers by drawing the
liquid in and out of the pipette several times. Analyze the organic layer by TLC (note:
continue to reflux your reaction throughout this analysis). Record these TLC's in your
notebook. When the starting material is no longer present by TLC, cool the reaction to
ambient temperature.

Show ALL the organic products that would be present following the above procedure:

.
TLC plates consist of a polar adsorbent on a solid support. We routinely utilize silica as
the polar adsorbent in the lab. Name the other common polar adsorbent that is used and
was discussed (and used) in the MIT video on TLC.
ALUMINA

(4 points)

RANK IN ORDER OF DECREASING REACTIVITY IN ELECTROPHILIC

AROMATIC SUBSTITUTION REACTIONS: