Chem33 Week 5 Extra Practice

1) For the following questions, write the letter of all answers that apply on the line below:
I. What common factor do Carbon Carbon single bonds possess that multiple bonds do not?
Answer:__B,D
a.
The ability to position the molecule in multiple configurations
b.
Free rotation about the bond.
c.
Direct overlap of two hybridized orbitals.
d.
longer bond length between the atoms
II. What are represented in constitutional isomers? Answer:
a.
b.
c.
d.
e.

___A, B

Two or more chemicals that have the same molecular formula.

Two or more substances that have the different physical properties.
Two or more materials that can be E/Z isomers.
Two or more chemicals that can be created by rotation about a single
bond.
Two or more molecules that are mirror images of each other.

III. What do meso compounds have that enantiomers lack? Answer: ___C , E
a.
The ability to rotate light.
b.
a cis/trans isomer
c.
Superimposability, making them identical molecules.
d.
a single chiral center
e.
an internal mirror plane
IV. For the following, circle the capitalized word that best completes the statement.
(a) For a reaction that has a favorable thermodynamic driving force as written, the
products are LOWER or HIGHER in energy than the starting materials.
(b) A reaction that has greater opportunity (occurs faster) has a LOWER or HIGHER
activation energy.
(c) When Keq >1, equilibrium favors the PRODUCTS or the REACTANTS.
(d) Endothermic reactions favor formation of PRODUCTS or REACTANTS.
(e) The transition state is defined as the species with the HIGHEST or LOWEST energy
in an energy diagram.

2) 2-hydroxypropanoic acid or Lactic acid is found in many sour milk products like
yogurt and cottage cheese. It is also added to a variety of processed food to adjust pH or
as a preservative. Lactic acid has two optical isomers: (S)-lactic acid and (R)-lactic acid,
however only the first, (S)-lactic acid, is biologically important.
A. The atom connectivity for lactic acid is shown below. Using clear wedge and dash
line notation, draw the biologically important form of lactic acid below.
O

1
2

OH

OH

OH

OH

S-lactic acid
B. Please give the hybridization and approximate bond angle on the atoms indicated:
1 (C) hybridization _______sp2_________ angle _________120_____________

2 (C) hybridization _______sp3_________ angle __________109.5____________

C. Lactic acid will lose only one proton in solution. Indicate in the box whether proton #
3 or 4 will be lost:
Proton
#3
Give a short explanation and justify your answer with resonance structures:
If proton 3 is lost, there are two resonance structures which allow the negative charge left
to be delocalized over the two oxygens, thus stabilizing the deprotonated form. If proton
4 is lost, there is no such stabilization.
O-

OOH

O
OH

D. Methanesulfonic acid and methanethiol are two other examples of organic monoprotic
acids. Remember that a stronger acid is more likely to lose its proton. Below rank these
three acids from strongest (1) to weakest (3) and briefly explain your answer in the box
provided.
O
O
S

SH

OH

OH
OH

____1_____

_____3____

_____2____

The deprotonated form of 1 is stabilized by three resonance structures, thus it will be most
stable. #2 has two resonance structures to stabilize the deprotonated form, while there is no
resonance structure to stabilize methanethiol, #3.

3) Calcitriol, shown below, is the active form of vitamin D. Your body is able to
carefully synthesize this exact stereoisomer with the help of sunlight. Lack of
vitamin D has been implicated in an increased risk of MS and other diseases, which
tend to be more prevalent in areas that have colder or harsher climates that might
limit peoples exposure to the sun.
a) How many chiral carbon centers are present in Calcitriol?
b) On the structure below, clearly label each stereocenter as R or S.
c) Label each double bond as Z or E, if possible.

R
R
S
H

E
Z

R
HO

S
OH

H
OH

4) Identify the relationship between the following pairs of compounds: diastereomers (D),
enantiomers (E), same (S), completely unrelated (X).
O

OH

OH
OH

HO

HO
O

OH O

OH
OH

Me
Et

Me

Et

Me
Cl

iPr

H
D

HO

i Pr

Me

OH
Cl

Cl

OH

X
Cl

OH

Br
H

Cl
Br

C
Cl
D

For each question, circle the statements that are true. If a statement is false, write a corrected
statement in its place.
5) A strong acid:
a) is more likely to be in the protonated form deprotonated
b) will have a large pKa will have a small pKa (large Ka value)
c) will have a relatively weak conjugate base
d) the conjugate base is relatively stable
6) A weak base:
a) will have a conjugate acid with a relatively small pKa
b) is stable and therefore less reactive
c) is more likely to be protonated remain in the deprotonated state
d) will have a relatively reactive conjugate acid
For each set of acids draw a mechanism for the reaction of the first acid with water. Then
explain the differences between the pKa values for the three acids.
7)
H
N
NH 3

NH3

pKa = 10.5

pKa = 38

pKa = 3.4

8)

H
O

O
H

pKa = -2.9

pKa = 4.75

O
O

pKa = 16

+
H

H
O
O

+
H

9) In Organic synthesis we often come across compounds that look similar to simple acids and
bases that we have studied, therefore they are likely to have similar properties and pKas.
L-Dopa is a drug used in the treatment of Parkinsons disease. Thinking about the acids you just
worked with on page 1, identify the four most acidic protons on this molecule and rank them in
order of increasing acidity. Predict how the protonation states of L-Dopa would change when
going from the stomach to the bloodstream.

10) On each molecule, circle the most acidic proton and briefly justify your answer

A)

NH 2

O is more electronegative
than N, thus better stabilizes
the charge on the conjugate base

The negative charge lef t on the N near the

ketone, can be stabilized by resonance between
B) the N and O.
O

N
H

OH

C)

3-aminobutanol
OH near the electron
withdrawing
F's will f orm a more
F3 C
CF3
stable conjugate base

N
H

N-methyl-3-(methylamino)propanamide
H

D)

sp orbital better than sp2 at

stabilizing charge

OH
HO

H
H

1,1,1-trif luoro-5-methyl-2-(trif luoromethyl)hexane-2,5-diol

pent-1-en-4-yne

11) 1-methylguanidine has the connectivity shown below.

NH

N
H

NH 2

a. Complete the Lewis dot structure for this compound based on the connectivity
given. (NOTE: no additional atoms should be added to the structure here, only any
electrons that are not yet shown.)
b. Approximately what is the N-C-N bond angle?

>120

c. It is possible for each of the nitrogens in 1-methylguanidine to accept an additional

proton, however one of these nitrogens is much more basic than the others. Please
draw the three ions that result from monoprotonation of each of the nitrogens in the
molecule shown above. For each structure, make sure to also show any important
resonance structures.
NH

N
H2

NH 2

NH2

N
H

NH

N
H

NH2

NH 2

N
H

NH 3

NH2

NH 2

N
H

NH2

NH 2

N
H

d. On the neutral starting structure below, please circle which nitrogen atom is the
most basic. Explain your answer in 1-2 sentences.
NH

H3C

H
N

NH2

The positive charge resulting from protonation

of this nitrogen can be very well stabilized over
4 different resonance structures. There are no
resonance structures available to stabilize the
positive charge of the other two nitrogens.

NH 2