Name_______________________________

Identification # ___ ___ ___ ___

EXAM #1
CHEMISTRY 351
FALL 2014
INSTRUCTOR: P. B. SAVAGE
DATE: SEPTEMBER 30TH AND OCTOBER 1ST
MATERIALS NEEDED FOR THE EXAM: A pencil or pen is all that is required. You may use models.
You may not use a calculator.
Please write your name and ID # at the top of each page.
If any answers are written on the back of a page, you must indicate it on the front of the page. Otherwise, the
answer will not be graded. Please make your answers as concise and clear as possible. You will be graded not
only on your answers, but also on the means by which you communicate them. In drawing structures you must
use the rules we discussed in class (i.e., include Hs on heteroatoms and if you draw Cs, include the Hs).
Relax, think and have fun.

Name_______________________________

Identification # ___ ___ ___ ___

1. (20 pts) A. Draw Newman projections of the three energy

minima of 2-butanamine, looking down the central C2-C3 bond.
An amine has a smaller A value than a methyl group.
B. Circle the most stable conformation.
C. Draw a square around the least stable conformation.

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checked

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2. (20 pts) A. Draw cyclohexanol in its most stable chair conformation.

B. Draw all of the hydrogens on the carbons in their correct orientation (axial or equatorial).
C. Circle each hydrogen that is axial and draw a square around each hydrogen that is equatorial.
D. Draw cyclohexanol in its least stable chair conformation.
E. Explain why the first structure (with circled and squared hydrogens) is stabler than the second structure you
drew.

3. (24 pts) Consider the following reaction between water and H-Br.
A. Indicate which molecular orbital on water is the HOMO, draw the orbital on the water molecule below, and
explain why it is relatively high in energy.
B. Indicate which molecular orbital on H-Br is the LUMO, draw the orbital on the H-Br molecule below, and
explain why it is relatively low in energy.
C. An alternate reaction could conceivably occur (but doesnt). It is in parentheses. Draw the products that
would be formed from the reaction and explain why it does not occur.
H
O
H

O
H

Br

Br

O
H

Br
H

4. (10 pts) The pKa of H2S is about 7.0. Now consider H2Se. What is the shape of the molecule? Draw H2Se
as it would appear at pH 6.5.
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Name_______________________________

Identification # ___ ___ ___ ___

5. (12 pts) Tyrosine (Y) is an amino acid we will discuss in Chemistry 352. It has a phenolic -OH group
(phenol and tyrosine are drawn below). The phenolic -OH group has a pKa of 10. Other relevant pKa values
are given in the next problem.
A. Draw the structure of tyrosine as it would appear at pH 12 and draw it as it would appear at pH 7.2.
B. Typical R-OH groups have pKa values of ca. 16. Explain why the OH on phenol and on tyrosine have pKa
values of 10 and not 16. (Hint: this explanation will require drawings of the conjugate base).
HO
OH
OH

H 2N
phenol

O
tyrosine
pH 12

pH 7.2

6. (14 pts) Glutamic acid (E) is another amino acid. The monosodium form of glutamic acid is monosodium
glutamate (MSG). Note that glutamic acid has two acid groups, and their pKa values are different (given
below). Remember that the pKa for R-NH3+ is 10.
A. Explain why the two carboxylic acid groups in glutamic acids have different pKa values.
B. Draw the structure of MSG, taking care to draw the functional groups in MSG in the correct protonation
states. Please remember that there is ONE sodium ion in MSG. You do not need to draw the sodium ion.
C. Give the pH range in which the functional groups in MSG will have the protonation states you drew for
question B.
O

OH pKa = 4.1

OH pKa = 2.1

H 2N
O

7. (24 pts) Provide IUPAC names for the three molecules shown below.
Cl

OH

Cl

OH
OH

Br

NH 2

8. (30 pts) For each of the following molecules, indicate which orbitals (nb, C-Cl *, etc.) are the frontier
molecular orbitals (i.e., HOMO and LUMO)
Br

H
O

HOMO
LUMO
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2

OH

H Br

Name_______________________________

Identification # ___ ___ ___ ___

9. (24 pts) Draw any missing formal charges in the following molecules. All hydrogens and lone pairs have
been indicated. Indicate the hybridization of all atoms other than hydrogen.
CH 3
O
H
CH
H 3C
CH 3

CH 3
H 3C

H 3C

CH 3

C
CH2

H 3C

O
C
CH2

F
F
B
F
O
C
CH 3
H 3C

10. (18 pts) Below is a reaction that we will encounter this semester. In the first step of the reaction, highenergy electrons in the alkene (2,3-dimethyl-2-butene) attack the LUMO in H-Br. Molecules that use their
electrons to attack are called nucleophiles, while those that are attacked are called electrophiles. So the alkene
is the nucleophile and H-Br is the electrophile.
A. Explain why the electrons in the bond are relatively high in energy.
B. Draw an arrow showing electron flow in the first step of the reaction (reaction of 2,3-dimethyl-2-butene with
hydrogen bromide).
C. After the first step, a molecule called a carbocation (carbon with a plus charge) is formed. Explain why this
molecule is very reactive.
D. Draw an arrow to show how electrons flow in the reaction of bromide with the carbocation (the second step)
to give the final product.
E. Circle the nucleophile and draw a square around the electrophile in the second step of this reaction.
H
H-Br

Br

Br

11. (4 pts) Methyl lithium (CH3Li) is a very reactive species (the pKa of methane is about 50). It can rapidly
pull a proton off of ammonia (NH3 (pKa of 36)). When reactions are performed, compounds that react are
typically dissolved in a solvent. Explain why it would not be a good idea to use ethanol as a solvent if we want
to react methyl lithium with ammonia.

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