Chemistry 216

First Examination
November 6, 2007 Name ______Key__________
Please Print
Dr. Andrew Karatjas
(2 hrs, 100 points) Signature _______________________

Student ID # _____________________
Please CHECK OFF your lab section.
____section #_________GSI_____________ ____section #____GSI____________
_____130 Thomas Sundberg _____170 Kapil Karki
_____131 Peter Mai _____171 Ben Thompson
_____172 Peter Mai
_____132 Peter Ung _____173 Therese Dorau
_____133 Therese Dorau _____174 Joseph Jankolovits
_____134 Candice Paulsen _____175 Christopher Taylor
_____135 Ahleah Rohr _____176 Christopher Taylor
_____136 Justin Lomont
I 6
_____150 Kapil Karki II 3
_____151 Ben Thompson
III 7
_____152 Thomas Sundberg
_____153 Candice Paulsen IV 12
_____154 Peter Ung V 8
_____155 Joseph Jankolovits
VI 12
_____156 Ahleah Rohr
VII 16

This exam has 14 pages including this cover VIII

page. The last 3 pages include a periodic table, 9
tables of characteristic IR absorption
IX 12
frequencies of common chemical bonds, and
pKa values for representative acids. X 15

Total 100
I. One of the more common uses of TLC is monitoring the progress of a reaction. Using the TLC
plate diagrams below, draw in the spots on the plate (after development) for the following
reaction. Plate # 1: At the start of the reaction. Plate # 2: At 50% completion. Plate #3: When
the reaction is finished. Each plate should have a lane for SM, a co-spot, and the reaction
mixture (6 points).
O LiAlH4 ;
acidic workup
OCH 3 OH

Starting Reaction Starting Reaction Starting Reaction

Material co-spot Mixture Material co-spot Mixture Material co-spot Mixture

At start of reaction At 50% completion At 100% completion

II. Rank the following compounds on the basis of increasing Rf (3 points).

O N
CO 2H OH

A B C D

A
Smallest R f
< C < D < B
Largest Rf
 III. Draw a proper setup for a refluxing reaction. Label all of the equipment needed for this setup.
Why would you setup a reaction in this way? (7 points)

In order to allow the reaction solvent to boil but

still retain the volume of solvent you started
with. water out

condenser

water in

f lask

stirbar
heating bath

IV. In experiment 1, we did the acylation of aniline derivatives. The same type of reaction can be
done with phenols. When done with salicylic acid, the product is acetylsalicylic acid or aspirin.
The reaction is shown below. Answer the following questions about this reaction. Show all
work. (12 points)

O O O O
H2 SO4
OH O OH

OH O

O
MW = 138 MW = 102 9M MW = 180
density = 1.08 g/mL
(a) If you start with 1.5 g of salicylic acid, 2 mL of sulfuric acid, and 2 mL of acetic
anhydride, what is the limiting reagent?
Salicylic acid: 1.50 g / 138 g/mol = 10.9 mmol ---- LIMITING REAGENT
Acetic anhydride: 2 ml * 1.08 g/mL = 2.16 g / 102 g/mol = 21.1 mmol
Sulfuric acid: 2 mL * 9 mmol/mL = 18 mmol

(b) What is the theoretical yield of this reaction?

10.9 mmol * 180 g mmol = 1.96 g

 (c) From this reaction, 1.70 g of aspirin were recovered. What is the actual yield?

Yield = 100 * (1.70 g / 1.96 g) = 87%

V. For the following sets of compounds, circle the one that is the stronger base (8 points).

(a) MeO NH 2 (b) NH 2 O2 N NH 2

NH 2

O O O O
-
(c) O O- (d) O- O-
NO2 Br

VI. The goal of recrystallization is to obtain purified material with a maximized recovery. For the
following items, explain why this goal would be adversely affected (12 points).
(a) In the solution step, an unnecessarily large volume of solvent is used.

Upon cooling, there will still be too much solvent and more (all) of the product will still be in solution.

(b) The crystals recovered are washed with additional hot solvent.

The hot solvent will redissolve some of the crystals.

(c) The solution is allowed to cool before the gravity filtration to remove insoluble
impurities.

Some of the products will have come out of solution and will also get filtered during the gravity
filtation.
(d) Crystallization is accelerated by immediately placing the flask of hot solution into an
ice-water bath.

May get poor crystallization due to the speed – some impurities may crash out as well. or The flask
may break from the extreme temperature difference.
VII. Fill in the box with the expected outcome of the reaction, or the correct starting materials (16
points).

(a)
O
O O
NaOH
+ H

(b)

O O
H 2 SO 4 O
OH

OH

(c)
OH No reaction - tertiary alcohol.
NaOCl
The hypochlorite would also be an
acceptable answer here.
O
Cl

(d)

H2 N
HN NO2 N
O +
HN NO2
O2 N
O2 N
VIII. In experiment 1, we made acetylated derivatives of various anilines to make
the corresponding acetamides. In a similar fashion, one can make the benzamide derivatives
using benzoyl chloride. Draw the full mechanism of the conversion of aniline to its benzamide
derivative in the box below (9 points).

Cl

H
NH 2 benzoyl chloride N

O
B:

+H Cl H H
N Ph N+
H
O- O
IX. For the following pairs of compounds, explain briefly how you could use IR spectroscopy to
distinguish them (12 points).
(a)
O O

The presence of the methoxy group gives the carbonyl on the right additional single bond character
and will shift it to lower wavenumbers.

(b)
O O

OH Si

The silicon is less electronegative than oxygen and therefore will donate more electron density
toward the carbonyl. This will increase its single bond character and push it to lower
wavenumbers.

(c)
O O

Higher ring strain – higher wavenumbers – cyclopropanone will be at higher wavenumbers than
cyclobutanone.
 X. For the following 5 IR spectra, there are 12 possible structures, assign the appropriate structure
to its spectrum (15 points).
(a)

(b)

A
(c)

(d)

J
(e)

E
 O
A G H
Cl

O
NH2
B OH H

OH H
N
C I

O
D CN J

O O
E O K

H
N
F L
O