mean = 94/150

sigma = 20

CHEMISTRY 241 Section 004

EXAMINATION I
TUESDAY, October 11, 2005
10:30 - 11:50 AM
Professor William P. Dailey

NAME:_____________________________________________________________
Student ID number :__________________________________________

QUESTIONS POINTS SCORE

1. 16 ______
2. 10 ______
3. 12 ______
4. 12 ______
5. 12 ______
6. 8 ______
7. 9 ______
8. 9 ______
9. 15 ______

10. 8 ______
11. 8 ______
12. 12 ______
13. 10 ______
14. 9 ______
TOTAL ______

READ ALL QUESTIONS CAREFULLY BEFORE ANSWERING THEM.

1. (16 Points) Provide correct IUPAC names for the following compounds.

2-Methyl-1-(1-methylcyclopentyl)heptane

2,3,6,7,7-pentamethyloctane

5-(1,1-dimethylethyl)-1-methyl-2-(1-methylethyl)cyclohexane

Bicyclo[1.1.1]pentane

2. (10 Points) The value for the heat of combustion of cycloheptane is –1108.3 kcal/mol while
the molar heat of combustion of cyclohexane is –944.5 kcal/mol. Recall that cyclohexane has no
strain energy. Calculate the total amount of strain energy found in cycloheptane. Propose the
reason(s) for this ring strain.

Enthalpy per CH2 for cyclohexane = -944.5/6 = -157.4 kcal/mol

Enthalpy per CH2 for cycloheptane = -1108.3/7 = -158.3 kcal/mol
Difference =0.9 kcal/mol/per CH2
So strain in cycloheptane = 7x0.9 = 6.3 kcal/mol

Models show some eclipsing C-H bonds and some ring strain.

3. (12 Points) Consider the reaction between 2-methylpropane and chlorine (Cl2). Draw all of
the monochlorinated products. Assume that the relative reactivity of primary:secondary:tertiary C-
H bonds towards chlorination is 1:3:8. Predict the relative amounts of each different
monochlorinated product and clearly show your calculations.

2
Cl
Cl

primary tertiary

9 equivalent primary H's so relative amount product is 9x1 = 9

1 tertiary H, so relative amount of tertiary product is 1x8 = 8

So % primary = 9/(9+8)% = 53%

% tertiary = 8/(9+8)% = 47%

4. (12 Points) Consider the following trimethyl-substituted cyclohexane shown below. It can
exist is two chair conformations that differ in energy by 4.4 kcal/mol. Draw the two possible chair
conformations, note all the axial methyl groups and predict which one of the chair conformations is
the most stable. In one of these conformations, there exists a severe 1,3-diaxial methyl-methyl
interaction , a numerical value for which we have not determined. However you can derive a value
for this interaction by carefully analyzing the difference in energy of the two conformations.
two gauche

H 3C

CH3
gauche gauche gauche
CH3 H 3C CH3
CH3 gauche
CH3
CH3 1,3-diaxial methy-methyl
all methyls are equatorial

CH3 All methyls are axial

The chair with all methyls equatorial is most stable. The energy of the left chair is
due to 4 gauche interactions and one 1,3-diaxial methyl-methyl interaction. The
energy of the right chair has 2 gauche. So equating the two with the 4.4 kcal/mol
energy difference gives

4 gauche + 1,3-diaxial = 2 gauche + 4.4 kcal/mol

4(0.9) + 1,3-diaxial = 2(0.9) + 4.4 kcal/mol
1,3-diaxial = 2.6 kcal/mol

3
5. (12 Points) Draw representations of the following

a. A Newman projection along the central C-C bond of trans-decalin

H
H
H2 C CH2

H2 C CH2
H H

b. A Newman projection along one of the C-C bonds in cyclopropane

H
H
CH2

H
H
(eclipsed)
c. A Newman projection along the 3,4 C-C bond in the most stable conformation of 3-
ethyl-4-methylpentane.

H
H3 C CH3

H3 CH2 C CH2 CH3

H
d. A Newman projection of the highest energy conformation of 1,2-dichloroethane.
H
H
Cl

H
H
(eclipsed)
6. (8 Points) Number the following compounds from 1 to 5 in order of increasing boiling
point. (1 is lowest boiling, 5 is highest)
O O
OH

2 5 4 3 1
Clearly state the reason(s) for this ordering.

Greater surface area (more van der Waals interaction) makes 2 higher boiling than 1.
Greater dipole moment makes 3 boil higher than 2 and 1. Even greater dipole moment
makes 4 boil higher than 3. Hydrogen bonding in 5 makes it boil highest.

4
7. (9 Points) Write the best Lewis structure for the following molecules and show all formal
charges.

a). CH3ONO
..

..
..
O O..
H3 C N
..
b) HNNN
.. +

..
N N N .. _
H

c) HCNO
+
.. _
H C N

..
..O
8. (9 Points) a) Draw a qualitative (no numbers needed) energy profile for rotation about the C-C
bond of 1,2-dichloroethane, ClH2CCH2Cl. Draw the conformation that corresponds to each
minimum and maximum on the diagram. Label all the transition states.

Same relative energy diagram as butane but without any energy values. The
transition states are the three maxima.

b) The experimental dipole moment of 1,2-dichloroethane is 1.0 D. Which of the following

statements is false ? Explain.

a. 1,2-Dichloroethane exists totally in the gauche form.

b. 1,2-Dichloroethane exists totally in the anti form.
c. 1,2-Dichloroethane exists as a mixture of the gauche and anti forms.

In the anti form there is no dipole moment. Since the molecule has a dipole moment,
it must therefore exist in some other conformation at least partially.

9. (15 points) Label the reactants in these acid-base reactions as Lewis acids or Lewis bases.
Complete the reactions using the curved arrow formalism.

a.

5
 F H
F F .. H +
B N F B- N H
F H H F H
LA LB

F- Br Br F Br -
Br
LB LA

Br+
.. -
Br Br Br

LA LB

b. Predict the products of the following reactions using the curved arrow formalism.

H3 C
.. _
O O+ BF3
H3 C CH3 + BF 3
H3 C

O .. O +
+ NH3 CH3 NH4
CH3 _
O H O

10. (8 points) Chlorination and bromination of alkanes can be useful reactions in organic
synthesis. On the other hand, iodination is generally not successful. Using the table below, as well
as what you know about the mechanism of halogenation, offer an explanation for the lack of
success of this reaction.

Cl-Cl 58 kcal/mol H-Cl 103 C-Cl 83

Br-Br 46 H-Br 88 C-Br 70
I-I 36 H-I 71 C-I 56

For the two propagation steps in radical halogenation, the sum (the overall reaction)
is endothermic for iodination. So it usually doesn't work.

11. (8 Points) Compare and contrast the structure and bonding in carbocations with that found
in carbanions. Describe how alkyl subsitution affects the stability of each species.

6
Carbocation stability follows the trend that tertiary is more stable than secondary is
more stable than primary.
Carbanion stability follows the opposite trend. Primary is more stable than secondary
than tertiary.

Electron-donation via hyperconjugation from alkyl groups will stabilize a positive

charge but destabilize a negative charge.

12. (12 points) a. Predict which one of the following compounds will have the more Lewis
basic oxygen atom. Clearly explain your reasoning.
O _
O O
N N
+

The dipolar resonance structure for the amide is much more important than the
corresponding form of ketone, so the oxygen will have a greater negative charge and
be more basic.

b. Predict which one of the following alkenes will have the most Lewis acidic carbon atom
and predict which carbon atom it is. Clearly explain your reasoning.
_
O O
+

The most important resonance structure that has a positive charge on carbon is
shown.

c. Predict which one of the following compounds containing N-H bonds will be the stronger
Bronsted acid. Clearly explain your reasoning.
_
N O O +
N N
H
H H

This resonance structure is more

important with C=O rather than C=C since O is more electronegative. This makes the
hydrogen more acidic.

13. (10 points) The simplest example of a compound known as an allene is H2C=C=CH2.
Draw the Lewis structure for this compound, predict its geometry, draw and note the hybridization

7
of the orbitals on the carbon atoms, and draw where the valence electrons are located in these
orbitals.
sp

sp2

H H
C C C
H H

14. (9 points) Draw the mirror image of each compound below and determine whether it is the
same or different from the original structure.

Same

Br Br
Different
Cl Cl (enantiomer)

Different
(enantiomer)