Old CH 231 Exams

The questions on these old exams are typical of the kinds of questions
you can expect on the exams in CH 231 this semester.
For the midterm exam, you should know all of the material in
chapters 1-5, with one exception: you will not be tested on Fischer
projections (section 5-4).
The absence of questions about any particular topics on the old exams
does not imply that questions on those topics will also be absent on the
midterm exam this fall.
The overall degree of difficulty of the midterm exam this fall will be
comparable to that on the old exams, although there will undoubtedly be
some variations in the degree of difficulty of individual questions on
specific topics.
You should be able to answer all of the questions on old exam 1 and
all of the questions except 9, 12, 13, and the bonus on old exam 2.

L. T. Scott
10/12/2004
 B OS TON C OL L E GE
Chem 231 - Organic Chemistry I
Exam I - September 27, 2000

name

Please write your answers on the exam.

Do not spend too much time on any one question.

question points
1. (06 points)
2. (06 points)
3. (04 points)
4. (08 points)
5. (05 points)
6. (06 points)
7. (04 points)
8. (06 points)
9. (06 points)
10. (06 points)
11. (06 points)
12. (10 points)
13. (10 points)
14. (06 points)
15. (05 points)
16. (06 points)
total
Chem 231 Exam I - September 27, 2000

1. (6 points) Draw a molecular structure for each of the following compounds:

(a) t-butylcyclopentane (b) 3-(1-chloroethyl)heptane

2. (6 points) Write the IUPAC name for each of the compounds shown below.

H F
F H

3. (4 points) In the drawing to the right, identify

each of the labeled carbon atoms as primary,
secondary, tertiary, or quaternary.

4. (8 points) For each of the organic species below, (a) indicate the hybridization of the
atoms marked with an arrow and (b) indicate the best description of the geometry at
each of the atoms marked with an arrow, choosing from the following list of
descriptors: linear, bent, planar, pyramidal, or tetrahedral.

Br (CH3)2CCH2CH3
H3C N C O

5. (5 points) Circle the most acidic proton of those shown explicitly H

in the molecular structure to the right. O
H
H
N H
H
H

- 2 of 5 -
Chem 231 Exam I - September 27, 2000

6. (6 points) Every covalent bond in the molecule shown to the right can be described
as resulting from the overlap of an atomic orbital on
one atom with an atomic orbital on the attached N
atom. For the bonds marked by arrows, indicate C
what atomic orbitals are overlapping to make the
bond.

7. (4 points) In the group of five compounds shown below, (a) circle the compound
that should have the lowest boiling point and (b) draw a box around the compound
that should have the highest boiling point.

8. (6 points) The C2 H4 Br cation is known to have a

cyclic structure (3-membered ring). Draw the most
reasonable Lewis structure for this cation. Show all
the valence electrons around every atom, and be sure
to indicate which atoms bear formal charges.

9. (6 points) The heat of combustion of

methylcyclopentane is –942.1 kcal/mol, and the heat
of combustion of cyclohexane is –937.7 kcal/mol.
Which of these two C6 H1 2 hydrocarbons is the
thermodynamically more stable isomer? Draw a
potential-energy diagram that shows the potential-
energies of each of these two hydrocarbons plus
oxygen relative to the potential-energies of their
combustion products.

10. (6 points) The halogenation of methane under the influence of heat or light is
actually a reversible reaction (equation shown below). When X=Br, the equilibrium
constant is greater than 1.0 (Keq > 1.0). When X=I, however, Keq < 1.0. Is the change in
Gibbs standard free energy (ΔG°) for the bromination of methane positive or negative?
What is the equation that relates Keq to ΔG°?

CH4 X2 CH3-X H-X

- 3 of 5 -
Chem 231 Exam I - September 27, 2000

11. (6 points) Which of the following four reactions will be the FASTEST?
(a) ΔG° = +4.9 kcal/mol and Ea = +2.3 kcal/mol.
(b) ΔG° = +4.1 kcal/mol and Ea = +8.7 kcal/mol.
(c) ΔG° = -6.8 kcal/mol and Ea = +4.2 kcal/mol.
(d) ΔG° = 0.0 kcal/mol and Ea = +5.7 kcal/mol.

12. (10 points) Free radical chlorination of 2-methylpropane (“isobutane”) gives two
products with the molecular formula C4 H9 Cl in a ratio of about 2:1. If that mixture of
products is then irradiated (hυ) in the presence of elemental bromine, those two
compounds are converted to a mixture of four products with the molecular formula
C 4 H8 BrCl.
(a) Draw bond-line formulas for the two compounds formed with molecular formula
C 4 H9 Cl.

(b) Draw bond-line formulas for the four compounds formed with molecular formula
C 4 H8 BrCl.

(c) Two of the four C4 H8 BrCl compounds make up more than 99% of the product
mixture formed by this sequential halogenation procedure. Circle them.
(d) When the order of the halogenation steps is reversed, i.e., the bromination is
performed before the chlorination, a single compound of formula C4 H8 BrCl makes
up more than 99% of the product mixture. Draw a box around it.
[Hint: It might or might not be the same as one of the compounds you have already
circled.]

- 4 of 5 -
Chem 231 Exam I - September 27, 2000

13. (10 points) Draw a Newman projection for the lowest energy conformation of
2–bromobutane (looking down the C2-C3 bond). Then draw a plot of potential energy
vs torsional angle from 0° to 360° around the C2-C3 bond, with the torsional angle
defined so that the lowest energy conformation corresponds to 0°. You do not have to
draw Newman projections for any of the other conformations, but be careful to show
which energy maxima are higher than others, which energy minima are lower than
others, and which conformations have the same energy.

14. (6 points) A Lewis structure for the cyanate ion is shown below. (a) Draw a second
reasonable Lewis structure for the cyanate ion, being sure to indicate which atoms bear
formal charges. (b) Circle whichever Lewis structure contributes more to the actual
structure of the cyanate ion. (c) Briefly justify your answer to part (b).

O C N

15. (5 points) Which of the compounds below will have the largest dipole moment?
Briefly show why.

H H
Cl-C C-Cl CH2Br2 CS2
H H

16. (6 points) The bond-dissociation energy of H2 O is 119 kcal/mol, whereas the bond-
dissociation energy of HCl is 103 kcal/mol. When the •Cl radical abstracts a hydrogen
atom from an alkane, will it exhibit higher or lower selectivity than the •OH radical in
choosing tertiary vs secondary vs primary hydrogen atoms? Briefly tell why.

- 5 of 5 -
 B OS TON C OL L E GE
Chem 231 - Organic Chemistry I
Exam 2 – October 18, 2000

name

discussion section (time or TA)

Please write your answers on the exam.

Do not spend too much time on any one question.

question points
1. (04 points)
2. (04 points)
3. (04 points)
4. (06 points)
5. (08 points)
6. (06 points)
7. (06 points)
8. (06 points)
9. (04 points)
10. (12 points)
11. (06 points)
12. (12 points)
13. (14 points)
14. (08 points)
bonus (10 points)
total
Chem 231 Exam 2 – October 18, 2000

1. (4 points) Draw a molecular structure for each of the following compounds:

(a) trans-1-chloro-3-isopropylcyclobutane (b) 4,4-bis(fluoromethyl)heptane

2. (4 points) Write the IUPAC name for each of the compounds shown below.

Cl
Br

3. (4 points) In the group of five compounds shown below, (a) circle the compound
that should have the highest boiling point and (b) draw a box around the compound
that should have the lowest boiling point.

Cl Cl I CF4 Br
Cl

4. (6 points) The heat of combustion for methylspiropentane (compound 1 below) is

–782.0 kcal/mol, and the heat of combustion for cyclopropylcyclopropane (compound 2
below) is –778.3 kcal/mol. (a) Which of these two C6 H1 0 hydrocarbons is the more
stable one? (b) What aspect of the structure of the less stable isomer would you
conclude is causing that compound to be less stable than the other isomer?

- 2 of 7 -
Chem 231 Exam 2 – October 18, 2000

5. (8 points) For each of the cyclohexane derivatives below,

(a) Tell whether the groups are cis or trans,

(b) flip the ring and draw the other chair conformation, and

(c) circle the more stable conformation for each compound (i.e., the original drawing vs
yours).
Cl CH3
OH

6. (6 points) A colorless crystalline compound isolated from guaiac wood has been
given the name “guaiol.” Its molecular formula (C1 5H2 6O) and structure strongly
suggest that guaiol is a sesquiterpene. Given this information, which of the following
structures is most likely correct for guaiol? Show your reasoning.

HO

HO OH

7. (6 points) The groups on each stereogenic carbon atom below are labeled in order of
decreasing priority according to the Cahn-Ingold-Prelog system (i.e., highest priority =
a ... lowest priority = d). Indicate for each center whether it has the R or the S
configuration.

b b a
d a a c b d
c d c

- 3 of 7 -
Chem 231 Exam 2 – October 18, 2000

8. (6 points) Circle the “substituent” in each set below that has the highest priority in
the Cahn-Ingold-Prelog system for assigning stereochemistry (R vs. S), and draw a
square box around the “substituent” in each set that has the lowest priority.

O CH2CH3 CH2CH2CF3 C OOH

O

CH2OH C OOH N(CH3)2

N
CN N
S
CH3

9. (4 points) Fischer projections are shown below for four of the stereoisomers of 2,3,4-
trichloropentane.

CH3 CH3 CH3 CH3

H Cl Cl H H Cl H Cl
H Cl H Cl Cl H H Cl
H Cl H Cl H Cl Cl H
CH3 CH3 CH3 CH3

A B C D
Some questions below may have more than one correct answer; circle ALL the correct
answers to each question.

(a) Which isomers are chiral? A B C D

(b) Which isomers are meso? A B C D

- 4 of 7 -
Chem 231 Exam 2 – October 18, 2000

10. (12 points) For each pair of compounds in the list below, circle the word that best
describes their structural relationship. Assume that the rings are planar.

O H H O O H H O
CH3 CH3 CH3 CH3
H H CH3 CH3
CH3 O O CH3 H O O H

mirror mirror
A B C D

A&B identical enantiomers diastereomers

A&C identical enantiomers diastereomers
A&D identical enantiomers diastereomers
B&C identical enantiomers diastereomers
B&D identical enantiomers diastereomers
C&D identical enantiomers diastereomers

11. (6 points) Refer to the compounds above in question 10. Which of the following
samples would be optically active? (Circle all the correct answers).

pure A pure D 1:1 mixture of A and B

1:1 mixture of A and D 1:1 mixture of C and D 3:1 mixture of C and D

12. (12 points) Write the major organic product expected from each of the following
proposed reactions. If no reaction will occur, write NO REACTION.

DMSO
(a) (CH3)2CHCH2-Br Na CN
CH3OH
(b) Cl-CH2CH2CH3 K SCN

DMF
(c) CH3-I Na OCH(CH3)2

- 5 of 7 -
Chem 231 Exam 2 – October 18, 2000

12. (continued)
DMF
(d) CH3-I NH3

CH3OH
(e) CH3CH2CH2CH3 Na Cl

H DMSO
(f) H3C C CH3 Na CN
OH

13. (14 points) Predict the effect of the changes given below on the rate of the reaction:

CH3OH
CH3-Cl O CH3 CH3-O-CH3 Cl

Circle one answer only for each question.

(a) Change substrate from CH3 Cl to CH3 I. faster slower no change
(b) Change nucleophile from CH3 O– to CH3 S– . faster slower no change
(c) Change nucleophile from CH3 O– to CH3 OH. faster slower no change
(d) Change nucleophile from CH3 O– to (CH3 )2 CHO– . faster slower no change
(e) Change substrate from CH3 Cl to (CH3 )2 CHCl. faster slower no change
(f) Change solvent from CH3 OH to (CH3 )2 SO. faster slower no change
(g) Double the concentration of CH3 O– . faster slower no change

14. (8 points) Bromination of pure (3R,4S)-3,4-dimethylhexane (shown below) with one

molar equivalent of elemental bromine under the influence of light produces 3-bromo-
3,4-dimethylhexane in good yield. Consider carefully how this reaction would occur
and then circle all of the products in the list below that you would expect to be formed.

(3R,4R)-3-bromo-3,4-dimethylhexane
H CH3
(3R,4S)-3-bromo-3,4-dimethylhexane
(3S,4S)-3-bromo-3,4-dimethylhexane
H3C H
(3S,4R)-3-bromo-3,4-dimethylhexane

- 6 of 7 -
Chem 231 Exam 2 – October 18, 2000

Bonus. (10 points) When pure cis-1-t-butyl-4-iodocyclohexane is added to a solution of

sodium iodide in acetone (propanone) at room temperature, some trans-1-t-butyl-4-
iodocyclohexane is formed. Likewise, when pure trans-1-t-butyl-4-iodocyclohexane is
added to a solution of sodium iodide in acetone (propanone), some cis-1-t-butyl-4-
iodocyclohexane is formed.

(a) Draw structural representations for the two stereoisomers of 1-t-butyl-4-

iodocyclohexane in their most stable conformations, indicating clearly the 3-
dimensional arrangement of atoms in each, and then use the curved arrow notation to
show how sodium iodide could convert each isomer into the other.

(b) When starting with the pure cis isomer, the reaction “stops” after only 70% of the
starting material has been used up. Even in the presence of excess sodium iodide, about
30% of the cis isomer always remains unconverted to trans. When starting with the
pure trans isomer, the reaction “stops” after only 30% of the starting material has been
used up. Explain (briefly) why these reactions do not convert the starting materials
100% into the product.

(c) Can you explain why one reaction gives 70% conversion to the product, while the
other goes only 30% of the way?

- 7 of 7 -