210 Fa 15 Exam 2 KEY

Chem 210 Feldman & Maslak
FORM A KEY
Exam 2 Fall 2015
Chem 210 Sections 001 003

Exam 2
October 7, 2015
Printed Name: KEY___________________________________ Section: _________

PSU eMail: ______________________________________
Signature: _______________________________________
FILL OUT AND TURN IN THIS FRONT PAGE WITH YOUR SCANTRON FORM. WE
WILL NOT PROCESS YOUR SCANTRON WITHOUT THIS COMPLETED AND SIGNED
FRONT PAGE.
1) There are 25 multiple-choice questions on this exam. Make sure that you have them all. Each
question is worth 4 pts.
2) On the Scantron sheet, make sure that you fill in your name (print), section, your student ID
number, and the test form (white cover = Form A, yellow cover = test form B).
3) You may take the exam booklet with you. Your score will be based solely on the information on
your Scantron form.
4) Needed data will be provided. The data values provided with the exam, either with the problem
itself or in the Tables at the back if not listed in the problem, will be the ones that you must use to
arrive at an answer.
5) There is no penalty for guessing.
6) No electronic devices of any kind are allowed. This proscription includes, but is not limited to,
calculators, cell phones, cameras, etc. Exposing such devices during the exam, even if they are
not in use, is grounds for imposing a "zero" grade on the exam.
7) Use of molecular model kits is encouraged.
8) Blank paper is provided at the end of the exam for your convenience. You may not use any other
source of paper during the exam.
9) An answer key will be posted soon after the end of the exam.
1
Copyright 2015 Ken Feldman & Pshemak Maslak Use of this document by any third-party forprofit concern (i.e., PSU KnowHow, Nittany Notes) is in violation of US copyright law. All rights
reserved.
FORM A KEY
Exam 2 Fall 2015
2
reserved.

1.
FORM A KEY
Exam 2 Fall 2015
Which compound is a stereoisomer of 1?
(b)
(a)
(c)
(d)
Answer (d) is the same as 1. Answer (b) has one CH2 more than 1. Answer (a) is a
constitutional isomer of 1. Only answer (c) is a stereoisomer of 1. (c) is the correct answer.
(b)
(a)
constitutional
isomer
2.
R
S
(c)
(d)
different molecule
(dff. # of atoms)
same molecule
How many stereogenic centers are in moronic acid (1)?
H
OH
O
H
O
(a) 6
(b) 7
(c) 8
(d) 9
There are seven stereogenic centers in moronic acid. (b) is the correct answer.
*
O
*
*
*
*
OH
O
3
reserved.

3.
FORM A KEY
Exam 2 Fall 2015
Which arrow designation connecting alcohol 1 and aldehyde 2 is not possible?

O
OH
1
(a)
(b)
(c)
H
(d)
Alcohol 1 and aldehyde 2 are constitutional isomers. They can be, in principle, connected via
a chemical reaction of some type (answers (a), (b), and (c)), but they are not resonance forms
of each other (answer (d)). (d) is the correct answer.
4.
A pair of diastereomers must have which characteristic?

(a) The same atom connectivity.
(b) Optical activity.
(c) At least one stereogenic center for each member of the pair.
(d) A symmetry element (i.e., C2 axis, mirror plane) for each member of the pair.
Diastereomers must have the same connectivity. They do not have to be optically active (i.e.,
they could be racemic diastereomers) and they do not need to be chiral (for example, E/Z
isomers). They can have stereochemical elements (chiral axes) that are not stereogenic
centers. Finally, they do not have to have any particular symmetry, or any symmetry at all. (a)
is the correct answer.
5.
Label the atoms 1 and 2 with either an R or an S designation.

1
H
Cl
O
Cl
2
(a)
(b)
(c)
(d)
atom 1
atom 2
S
R
R
S
S
R
S
R
The R/S assignments are shown below. (b) is the correct answer.
R
H4
2
Cl
1 O1
Cl 2
3
R
H4
4
reserved.
6.
FORM A KEY
Exam 2 Fall 2015
Which structure is a diastereomer of 1?

H
H
Cl
(a)
O
Cl
Cl
O
Cl
(b)
Cl
(c)
O
Cl
Cl
Cl
Cl
(d)
O
Cl
Answer (a) is the same molecule as 1 (rotate 180o about a line going straight down through the
oxygen). Answer (c) is an enantiomer of 1, and answer (d) is the same as answer (c) (via a
180o rotation about a line straight down through the oxygen). Answer (b) is a diastereomer of
1; it only differs in the stereochemistry at one Cl-bearing carbon. (b) is the correct answer.
7.
Which structure is equivalent to 1?

Cl
1
Cl
H CH3
Cl
H CH3
Cl
a)
H3C H
H Cl
H3C H
Cl
Cl
Cl
Cl
H3C H
b)
H CH3
c)
Cl
H3C
H3C H
d)
This type of problem can be solved effectively by building plastic models of 1 and the answers,
and inspecting them visually. Equally effective would be to assign absolute stereochemistry to
each carbon, and compare. (c) is the correct answer.
S
Cl
H CH3
R Cl
Cl R
H CH3
Cl
R
a)
H3C H
S Cl
Cl S
H3C H
b)
H3C H
Cl S
R Cl
H CH3
c)
H Cl
S Cl
H3C S
H3C H
d)
5
reserved.

8.
FORM A KEY
Exam 2 Fall 2015
Assign E or Z stereochemical designations to alkenes 1 3.

Cl
Cl
Cl
Br
Br
Br
1
(a)
(b)
(c)
(d)
(e)
(f)
E
E
E
Z
Z
Z
Z
E
E
Z
E
Z
Z
Z
E
Z
E
E
The priority assignments are illustrated below. (a) is the correct answer.
1 Cl
1 Br
1 Cl
2 Cl
Br
Br
6
reserved.

9.
FORM A KEY
Exam 2 Fall 2015
The inversion barrier for ammonia (1a) is small, about 7 kcal/mol. In contrast, the inversion
barrier in phosphine (3a) is much larger, about 32 kcal/mol.
H ~ 7 kcal/mol
H
H
1a
107o
N H
2
H ~ 32 kcal/mol
H
H
1b
P
H
H
H
90o
3a
P H
4
H
H
P
3b
What is the hybridization change at N and P for the hybrid orbital holding the lone pair upon
going from the starting material to the transition state (i.e., 1a 2 and 3a 4)?
(a)
(b)
(c)
(d)
change at N
change at P
sp2.1 sp3
sp2.1 sp3
sp2.1 p
sp2.1 p
sp3 sp2
s p
sp3 sp2
s p
As usual, geometry specifies hybridization. The 107o bond angle in ammonia calculates out to
a hybrid orbital on N holding the lone pair of sp2.1 (see Lecture 3). You didn't have to
remember this value all of the answers start with sp2.1. The TS is planar, as must be the case
in an inversion. As such, the N is nominally sp2 hybridized, and the hybrid orbital holding the
lone pair in TS 2 must be a pure p orbital. Thus, with 1a, an sp2.1 p hybrid orbital change
occurs upon going to 2. With phosphine, the 90o HPH angle dictates that the phosphorus
uses its pure p orbitals to form bonds to the hydrogens (actually, the real angle is 92o, so there
is some small amount of s-character in the hybrids, but for mathematical simplicity, the 90o
value was used). If pure p orbitals are used for the three PH bonds, then the lone pair must
reside in a pure s orbital in 3a. In TS 4, the lone pair now resides in a pure p orbital, as 4 has
the same geometry as 2. Thus, an s p hybrid orbital changes occurs in going from 3a to 4.
Note that this large hybrid orbital change with phosphine (0% p to 100% p), compared to the
relatively minor hybrid orbital change with 1a (68% p to 100% p) accounts for the much larger
barrier to inversion. (d) is the correct answer.
7
reserved.

10.
FORM A KEY
Exam 2 Fall 2015
The reaction shown below interconverts

HO
HO
N
1
Et
CH3
Et
N CH3
a) an enantiomer into a diastereomer.

b) a diastereomer into an enantiomer.
c) a pair of diastereomers.
d) a pair of enantiomers.
One stereogenic center is fixed and does not change upon going from 1 to 2; the alcoholbearing carbon. The second stereogenic center (at nitrogen) does change (invert) upon going
from 1 to 2. Thus, 1 and 2 are diastereomers. (c) is the correct answer.
11.
What is the relationship between 1 and 2?
(a) They are chiral diastereomers.

(b) They are racemic diastereomers.
(c) They are the same molecule.
(d) They are enantiomers.
1 and 2 are enantiomers, as can be seen by applying the fundamental definition of enantiomers;
non-superimposable mirror images. (d) is the correct answer.
2
mirror plane
8
reserved.

12.
FORM A KEY
Exam 2 Fall 2015
Clockwise rotation by 60o of the front carbon in Newman projection 1 leads to three eclipsing
interactions in the bond rotation transition state. Identify these three interactions.
Ph
Br
Cl
1
H3C
(a) Ph//Cl, H3C//H, H//Br

(b) Ph//Cl, H3C//Br, H//H
(c) Ph//Br, H3C//Cl, H//H
(d) Ph//Br, H3C//H, H//Cl
As illustrated below, Ph//Br, H3C//Cl, and H//H eclipsing interactions arise upon rotation of
the front carbon clockwise by 60o. (c) is the correct answer.
Ph
Br
Cl
1
H3C
13.
Ph
Br
Cl
H3C
HH
What is the most stable conformer (= conformational isomer) on the reaction coordinate for
rotation about the indicated bond in 1?
H
(a)
H
(b)
(c)
H
(d)
Answer (d) has the wrong number of carbons and so it can be discounted. Answer (b) has a
gauche interaction between a methyl group and a larger isopropyl group. Answer (c) has two
gauche interactions; methyl//isopropyl, and methyl//methyl. Answer (a) has only a
methyl//methyl gauche interaction, and so it has the least energetic penalty and it will be the
most stable rotomer. (a) is the correct answer.
H
(a)
H
H
(b)
H
(c)
H
(d)
H
9
reserved.

14.
FORM A KEY
Exam 2 Fall 2015
Calculate the first rotational barrier (in kcal/mol) for the clockwise rotation of carbon a about
the bond indicated in the staggered conformation 1.
1
(a) 6.2
(b) 4.4
(c) 3.5
H
a
60o
(d) 2.5
The math is detailed below. (c) is the correct answer.
Ha
g
g
1
15.
60o
rotation
2.6
H 1
H
H = 6.2 2.7 = 3.5 kcal/mol
3 x g = 2.7 kcal/mol
2.6
2.6 + 2.6 + 1 = 6.2 kcal/mol
G for a bond rotation is 5 kcal/mol. This bond rotation is accompanied by a decrease in

entropy (S < 0). As the temperature is increased, what happens to G for this bond rotation?
(a) G becomes more positive than 5 kcal/mol.
(b) G becomes more negative than 5 kcal/mol.
(c) G stays the same at 5 kcal/mol.
Since G = H TS, as T increases and with S negative, G becomes more positive. (a) is
the correct answer.
10
reserved.
FORM A KEY
Exam 2 Fall 2015
A reaction coordinate diagram for a two-step reaction (A + B C > D) is shown below. The
activation energy for conversion of C back into A and B is
16.
(a) G1 G2
(b) G2
(c) G1
D
A + B
(d) G1 + G2 G1 DG2
G2
A, B
G1
G2
G1
D
reaction coordinate
First of all, you must identify just where on this diagram, exactly, the activation energy for the
conversion of C into A and B resides. This desired quantity, shown as G3 below, can be
seen by inspection to be the difference between G1 and G2. (a) is the correct answer.
G3
E
A, B
A + B
G1
G2
G2
G1
D
reaction coordinate
11
reserved.

17.
FORM A KEY
Exam 2 Fall 2015
The strain energy of propellane (1) is 68 kcal/mol. Assuming that each CH2 unit bears the
same strain as a CH2 unit in cyclopropane, how much strain energy (kcal/mol) can be
assigned to each quaternary carbon (arrows)? To simplify the math, you can use an overall
strain energy for cyclopropane of 28 kcal/mol.
(a) 34
(b) 16
(c) 40
(d) 20
Propellane (1) has three CH2 units, the same as cyclopropane. Thus, the amount of
propellane's total strain due to the CH2's is equal to cyclopropane's strain, 28 kcal/mol.
Since the total strain of propellane is 68 kcal/mol, the amount assignable to the two quaternary
carbons is 68 28 = 40 kcal/mol, or 20 kcal/mol per quaternary carbon. (d) is the correct
answer.
18.
Methylenecyclopropane (1) has about 10 kcal/mol more strain energy than cyclopropane (2).
Which species has more angle strain, and which species has more eclipsing interactions?
CH2
more angle strain

(a)
(b)
(c)
(d)
1
1
2
2
more eclipsing interactions

1
2
1
2
Methylenecyclopropane (1) compresses a nominal 120o angle down to a nominal 60o,

compared to cyclopropane, which compresses a nominal 109.5o angle down to a nominal 60o
(i.e., sp2 hybridization in 1 vs. sp3 hybridization in 2). Thus, 1 has more angle strain than 2.
Cyclopropane (2) has 6 eclipsing CH//CH interactions, whereas 1 only has 4 such
interactions. The p orbital as part of the bond does not align with the adjacent CH bonds,
so there is no eclipsing interaction. Cyclopropane (2) has more eclipsing interactions than
methylenecyclopropane (1). It appears that angle strain overwhelms torsional strain in the 1
vs. 2 comparison. (b) is the correct answer.
12
reserved.

19.
FORM A KEY
Exam 2 Fall 2015
Diaxial 1,3-difluorocyclohexane (2) is calculated to be 1.1 kcal/mol higher in energy than the
diequatorial conformer 1. In addition, all-axial hexafluorocyclohexane (4) is calculated to be
1.8 kcal/mol higher in energy than the all-equatorial conformer 3.
+ 1.1 kcal/mol
+ 1.8 kcal/mol F
F
F
F
F
F
4
What is the energy value, in kcal/mol, of one CF//CF gauche interaction (rounded to the
nearest 0.1 kcal/mol)? Please use 0.1 kcal/mol for fluorine's A-value to simplify the math.
[Hint: First calculate the value of a 1,3-diaxial F//F interaction from the 1/2 information.]
a) 1.8
(b) 0.4
(c) 0.6
(d) 2.0
This calculation has three levels. The first task is to figure out the value of a 1,3-diaxial
difluoride interaction. As illustrated below, this value (labeled "X") can be deduced from the
formula:
1.1 kcal/mol = 0.1 + 0.1 + X 0 (the energy of 1), or X = 0.9 kcal/mol for the F//F diaxial
interaction. The second task is to figure out the strain energy value for the all-axial
hexafluoride 4. That value is 6 x 0.9 kcal/mol = 5.4 kcal/mol. Finally, the value for six
gauche CF//CF interactions can be found from the formula:
1.8 kcal/mol = 5.4 Y, where Y = the value of six CF//CF gauche interactions.
By this math, Y = 3.6 kcal/mol. The value of one CF//CF interaction is then 3.6/6 or 0.6
kcal/mol. (c) is the correct answer.
0.1
H
0.1
F
13
reserved.

20.
FORM A KEY
Exam 2 Fall 2015
Which dimethylcyclohexane isomer can be classified as meso?

(a)
(b)
(c)
(d)
The definition of meso; a molecule with an internal mirror plan that reflects equivalent but
oppositely configured stereogenic centers into each other. By this criterion, both answers (a)
and (b) are not meso since they do not have stereogenic centers. Answer (d) has the same
absolute stereochemistry at both carbons, so it does not have an internal mirror plane. Only
answer (c) has an S center reflected into an R center. (c) is the correct answer.
(a)
(b)
(c)
(d)
21.
How much energy is released (in kcal/mol) in the following reaction?
(a)
(b)
2.8
(c)
5.1
(d)
7.5
(e)
8.3
The reaction re-distributes the strain energy between the different CH2 groups. We can use
data from Table 4 to obtain a total strain of 33.9 kcal/mol on the left side of the equation (6.3 +
27.6 kcal/mol) and a total strain of 26.4 kcal/mol on the right side (0 + 26.4 kcal/mol). The
right side has less strain (more stable) and 7.5 kcal/mol (26.4 33.9 kcal/mol) of heat is
released upon this conversion. (d) is the correct answer.
14
reserved.

22.
FORM A KEY
Exam 2 Fall 2015
Free radical chlorination of cyclohexene (1) can proceed through the allylic radical 2 to give
the allylic chloride 3. However, an alternative pathway can compete for 2; the addition of 2 to
cyclohexene 1 to give the new carbon radical 4:
Cl2
hv
Cl2
Cl
3
2
1
How many CC bonds (carbon-carbon single bonds) are established in the 1 + 2 4

transformation?
How many C=C bonds (carbon-carbon double bonds) are lost in the 1 + 2 4 transformation?
CC bonds established
(a)
(b)
(c)
(d)
C=C bonds lost
2
2
1
1
2
1
2
1
The starting molecule 1 loses its C=C bond in going to 4, and the product 4 has two new C-C
bonds compared to 2 + 1 (count them). (b) is the correct answer.
C=C lost
new CC bonds
15
reserved.

23.
FORM A KEY
Exam 2 Fall 2015
1-Methylcyclohexene (1) undergoes H-atom abstraction to give, in competition, radicals 2 and

3.
Br
Br
HBr
HBr
Which reaction coordinate diagram best describes the energetics of these processes?
(a)
(c)
1
1
E
reaction cordinate
reaction cordinate
(b)
(d)
1
1
E
reaction cordinate
reaction cordinate
The radicals 2 and 3 each can be drawn as a pair of resonance forms, below. Radical 2 is a
mixture of primary and secondary allylic radicals, whereas radical 3 is a mixture of secondary
and tertiary allylic radicals. By virtue of the tertiary allylic radical 3b resonance form, radical
3 is more stabilized than radical 2. Thus, answers (c) and (d), which show 2 as more stabilized
than 3, can be discounted. The Hammond postulate can be used to distinguish between
answers (a) and (b). The more stabilized radical 3 should be formed via the lower energy
transition state. This correlation is indicated in answer (a). (a) is the correct answer.
2b
2a
Br
Br
HBr
HBr
1
3a
3b
most
stabilized
16
reserved.

24.
FORM A KEY
Exam 2 Fall 2015
Decalin (1) can be fluorinated (cautiously!) under conditions where the predominant products
are monofluorides.
F2
hv
monofluoro products
What is the % of tertiary fluorides formed in this mixture of monofluorides? Please use the
selectivity values in Table 5 at the end of the exam.
(a) 11
(b) 33
(c) 13
(d) 20
The selectivity table is illustrated below. The selectivity values (2 for the tertiary H, and 1 for
the secondary H) come from Table 5 at the end of the exam. (d) is the correct answer.
F
F
F2
F
+
hv
1
2 tertiary fluoride
#H
selectivity
# H's x selectivity
%
3 secondary fluorides
2
2
16
1
4
20%
16
80%
= 20
25. Radicals can be compared according to their selectivity in hydrogen abstractions based on the
reactivity-selectivity principle. Consider the following radicals:
(a)
HO
(b)
(c)
Cl
(d)
Br
(e)
Which of the listed radicals would be expected to be the least selective in an H-atom
abstraction reaction?
The most reactive radicals are the least selective. The radical that forms the strongest XH
bond in the hydrogen abstraction process is the most reactive. The fluorine forms the strongest
XH bond. (b) is the correct answer.
17
reserved.
FORM A KEY
Exam 2 Fall 2015
Table 1. BDE's of some common bonds.

XY
BDE
specific BDE's, kcal/mol

H H
H F
H Cl
H Br
H I
H OH
H CH 3
H CH2CH 3
H CH(CH 3)2
H C(CH 3)3
H CH2CH=CH2
H CH2Ph
HPh
H CH=CH2
H CCH
H CN
104
136
103
88
71
119
average BDE's, kcal/mol
H 3CCH 3
H 3CCH2CH 3
H 3CCH(CH 3)2
H 3CC(CH 3)3
H 3CCH=CH2
H 3CCH2CH=CH2
H 3CCH2Ph
H 3COH
H 3CNH2
H 3CCl
H 3CBr
H 3CI
104
98
95
91
87
85
112
108
125
130
88
85
84
81
97
74
72
91
80
84
70
56
H 2C=CH2
150
HCCH
210
C
C
C
C
C
C
N
O
F
Cl
C H
N H
O H
O O
O Cl
BrCl
N N
C=C
CC
85
72
CN
C=N
204
143
91
110
81
98
99
102
35
49
52
65
152
200
N=N
NN
C=O
100
225
175
kcal/mol
Table 2. Conformational
energy values.
CH//CH
eclipsed
1.0
CCH3//CH
eclipsed
1.4
CCH3//CCH3 eclipsed
2.6
CCH3//CCH3 gauche
0.9
CCH2//CCH2 gauche
0.9
Table 3. A-values for cyclohexane axial substituents.
A (axial) strain energy

kcal/mol
H
3
X
1
Van der Waals

radius for just the
non-bonded
atom/group X,
A (axial) strain energy

kcal/mol
CX bond length,
0.12
1.47
1.40
CH3
0.9
Cl
0.25
1.80
1.78
CH2CH3
0.95
Br
0.25
1.95
1.93
CH(CH3)2
1.1
OH
0.5
1.52
1.43
C(CH3)3
2.7
CH3
0.9
2.00
1.54
Ph
1.5
CO2H
0.7
18
reserved.
FORM A KEY
Table 4. Strain energies of common rings.

kcal/mol
cyclopropane
27.6
cyclobutane
26.4
cyclopentane
6.5
cyclohexane
0.0
cycloheptane
6.3
Exam 2 Fall 2015
Table 5. Hydrogen abstraction selectivities on a

per-hydrogen basis.
tertiary HX BDE (kcal/mol)
primary
secondary
136
Cl
3.5
103
Br
80
1600
88
1100
97000
71
19
reserved.

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Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Chem 210 Sections 001 003

Printed Name: KEY___________________________________ Section: _________

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Which compound is a stereoisomer of 1?

How many stereogenic centers are in moronic acid (1)?

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Which arrow designation connecting alcohol 1 and aldehyde 2 is not possible?

A pair of diastereomers must have which characteristic?

Label the atoms 1 and 2 with either an R or an S designation.

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Which structure is a diastereomer of 1?

Which structure is equivalent to 1?

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Assign E or Z stereochemical designations to alkenes 1 3.

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

The reaction shown below interconverts

a) an enantiomer into a diastereomer.

What is the relationship between 1 and 2?

(a) They are chiral diastereomers.

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

(a) Ph//Cl, H3C//H, H//Br

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

The math is detailed below. (c) is the correct answer.

H = 6.2 2.7 = 3.5 kcal/mol

G for a bond rotation is 5 kcal/mol. This bond rotation is accompanied by a decrease in

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

more angle strain

more eclipsing interactions

Methylenecyclopropane (1) compresses a nominal 120o angle down to a nominal 60o,

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Which dimethylcyclohexane isomer can be classified as meso?

How much energy is released (in kcal/mol) in the following reaction?

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

How many CC bonds (carbon-carbon single bonds) are established in the 1 + 2 4

C=C bonds lost

Chem 210 Feldman & Maslak

Exam 2 Fall 2015

Printed Name: KEY___________________________ Section: _