PROBLEM SESSION PROBLEM ANSWERS -- CHEM 31

1. Draw reasonable skeletal (line/angle) formulas for the following condensed formulas/structures. Next,
draw good 3D structures by adding wedges and dashes to your simple skeletal structures.
The answers include the 3D of the skeletal and an expanded idea of the 3D structure with the
hydrogens added back in (essentially hybrids of the skeletal and Lewis).
a. CH3CH2CH2CH(CH3)2
H
H H
H H
H
H H

H H H
H H H
b. CH3CH2CHBrCH2C(CH3)3
H
H H H
H H Br H
Br Br H H
H
H
H
H H H H H
c.
H3C O

H3C CH2 CH C OH

H H O
O O
H
OH
OH OH
H H H
H H
H
d.
CH2 H H
CH2 CH H H
H
CH2 CH H
C H H

CH2 H H

Chem 31 Answers pg 1
2. For the following molecules, draw a valid Lewis structure, and indicate the formal charge on each
atom. Use the templates provided for the arrangement of the atoms.
SO32- CS2 N3-

O
S S C S N N N
O O

3. The molecule shown below is Griseofulvin, an antifungal compound.

OCH3 O OCH3

O
H3CO O
Cl H3C 1
3
4 2
a. Give the hybridization of carbons 1, 2, 3 and oxygen 4.
C1: sp3 C2: sp3 C3 sp2 O4 sp3
b. What is the geometry at each of these atoms? (Ignore distortions.)
C1: tetrahedral C2: tetrahedral C3 trigonal planar O4 tetrahedral
c. Fill in all nonbonding electrons and H's on the structure below. (Assume neutral charge.)

OCH3 O OCH3
H
H
O
H3CO O
H
Cl H3C H H

4. For the molecule shown give the information corresponding to each letter as indicated below.
a. give the hybridization of these atoms.
b. give these bond angles.

sp2
sp2
120°
O
OH
120°ˇ Prostaglandin E2
O
109.5°
HO OH

sp3
sp3

Chem 31 Answers pg 2
5. Consider the molecules 1 and 2 below:

Cl C Cl H C H
Cl H

1 2
a. Draw a three-dimensional picture of 1 and 2 using wedges and dashes. Show any nonbonding
electrons residing in an orbital, and give the formal charge on carbon.

C Cl C H

Cl H
Cl H
b. Given what you know about the effects of electronegative atoms, which compound is more stable?
Briefly explain why.
The first compound is more stable -- anion is more stable on a carbon that is electron poor due
to the effects of the highly electronegative Cl atoms attached.

C Cl C H

Cl H
Cl H

6. Consider acetylene anion, shown below.

H C C
a. Give the hybridization of all carbon atoms.

H C C
sp sp
b. In what type of orbital does the nonbonding pair of electrons reside?
sp orbital

Chem 31 Answers pg 3
7. For the following structures, draw in all pertinent bond dipoles and show the net dipole for the
molecule. Be sure to ignore C-H dipoles and consider the nonbonding electrons where appropriate.

H Cl
O O
H3C CH3
H Cl

net dipole

net dipole net dipole

8. The following molecules only have a single functional group. Identify to which class of organic
compounds each molecule belongs based on its functional group.

OH O O

H O

alcohol aldehyde ester

O O
Cl Cl
O HO OH

alkyl halide ketone carboxylic acid

O O NH2 O

O O

ester amine ether

Chem 31 Answers pg 4
9. Label the functional groups in the molecules below. For each compound, fill in the assumed
nonbonding electron pairs and the assumed hydrogens. All atoms are neutral unless a charge is
shown. For additional practice, assign the hybridization/geometry for each atom.
ketone
ketone
OH
O
O alcohol
alkene

Br
halide
aromatic ring or arene ring
O amine
O NH2

OCH3 OH
H
N ester aldehyde O
H
carboxylic acid
amine
nitro

O
ketone

O N carboxylic acid
O
N
O
C

nitrile OH

aromatic ring or arene ring

assumed hydrogens given with 3-D perspective

OH OH
H H
H H H H
H H H H
H H
H O O H H H
H H Br H Br
H H H HH H HH
H H H
H
H H H H H H H OR
H OH
H OH
H H
H H H H
H H H
H H
H
H Br H Br
H HH H HH

Stereoisomers

Chem 31 Answers pg 5
 H H H
H H
H
H H
H
H N H O NH2
H
H H HH O OH
H
OR H OCH3 H H O
H
H H H H H OR
H H
H
H
H O NH2
H H
H OH
H N H H
H H H H O

Stereoisomers
Stereoisomers

O N H
O
N O
H C
H
HH HH OH
H H

10. Below are shown two common pharmaceuticals: meperidine (Demerol), which is an analgesic
(pain-killer), and norethindrone, a synthetic hormone used in birth control pills.
a. For each, circle and name any functional groups you can identify.
b. For each atom marked with an arrow, determine the local geometry.
c. Determine the molecular formula for each compound.

alcohol
trigonal planar tetrahedral
OH
aromatic tetrahedral alkyne
ring N amine linear

O O trigonal planar
O
ester ketone trigonal planar
alkene

meperidine
norethindrone
C15H21NO2 C20H26O2

11. Convert the following skeletal structures to Lewis structures. Make sure to include all atoms and
lone pairs.

Chem 31 Answers pg 6
 H H
H H
H C HH O
H C C H H C C
H C C C C C
Cl O
C C C C C
O C C H N C C
H H H
H H H H H
H H
12. Convert the following Lewis structures to skeletal structures.

O OH OH

NH2 O

N O
H

13. In the following molecule, identify all atoms that have a trigonal planar geometry. Can you make any
correlations between obvious structural features and the geometries? Explain.

Cl

N OH

All the atoms here that are invovlved in double bonds have trigonal planar geometry and will be best
described as sp2-hybridized. This trend is generally true (note allenes as special cases). The key
feature overall is that large regions of the molecule are flat. Interconnected groups of trigonal planar
atoms lead to planar regions of a molecule. Moreover, as we think about the orbital pictures, we
recognize that these planar regions have electrons residing above and below them because the p-
orbitals used to make the pi bonds lie perpendicular to the plane with the sigma bonds. Interesting
chemistry will result from these electron clouds.

Chem 31 Answers pg 7
14. For the molecules below, give the information requested by the letter scheme.
a. name these functional groups.
b. give the degree of substitution for these carbons.
c. give the hybridization of these atoms.

carboxylic acid
ketone
O
OH

O Prostaglandin E2

HO sp2
OH
3°
2°
sp3

sp2
O
N sp3
O
Novocain
1° NH2
amine
1° ester

sp3

4°

Cholesterol

HO 2°
sp2 alkene
alcohol

15. BH3 and NH3 have similar formulas and might be expected to have similar properties. However, BH3
has no observed dipole moment but NH3 has an observed dipole moment of 1.47 D.
a. Use your knowledge of structure and bonding to explain this difference. Draw pictures.
Boron has three valence electrons and normally forms three bonds with no lone pairs left over.
With three "things" attached, we describe it as sp2-hybridized. As a result, all the B-H bonds are in a
plane -- we have trigonal planar geometry. Any dipoles for these bonds would cancel each other, so it is
not a surprise that BH3 has no overall dipole moment.
Nitrogen has five valence electrons and normally forms three bonds with one lone pair left over.
With four "things" attached, we describe it as sp3-hybridized. As a result, we have tetrahedral geometry.
Chem 31 Answers pg 8
Any dipoles for the N-H bonds would not cancel each other. Moreover, the lone pair is on one side of
the molecule. We would expect an overall dipole moment.

lone pair
H
B no lone pair; sp2 N
H H H H
trigonal planar H sp3; tetrahedral

bond dipoles cancel bond dipoles sum

b. If you mixed BH3 and NH3 together, what would you expect to happen? Would they react with each
other or remain inert? Explain your answer. Would you want to store them in the same cabinet?
This question is a preview of acid-base chemistry. Boron would like to have a full octet, and
therefore it is a lone pair acceptor (Lewis acid). The nitrogen of ammonia has a lone pair that can be
donated (Lewis base). If I mixed BH3 and NH3, I would see the lone pair donated to form a bond from the
nitrogen to the boron. Although I have formal charges, the new complex provides each atom with a full
octet. I've illustrated it in pictures below. Needless to say, I wouldn't want to store mutually reactive
substances in the same cabinet.
H H H H
H B N H H B N H
H H H H

16. For the molecules below, determine the number of 1°, 2°, 3°, and 4° substituted carbons.

1° _2_ 2°_7_ 3°_2_ 4°_1_ 1°_4_ 2°_7_ 3°_2_ 4°_2_

17. Calculate the degree of unsaturation, and draw three constitutional isomers for the molecular
formula C6H10.
2° of unsaturation; possibilities include:

Chem 31 Answers pg 9
18. Calculate the degree of unsaturation, and draw three constitutional isomers for the molecular
formula C6H8.
3° of unsaturation; possibilities include:

19. Calculate the degrees of unsaturation and draw two reasonable structures for each of the following
molecular formulas.
a. C6H6
4° of unsaturation:

b. C3H4
2° of unsaturation

20. Draw all the possible isomers of dimethylcyclobutane, MF: C6H12. Two of the constitutional isomers
you have drawn can exhibit stereoisomerism as well. Draw the two possible stereoisomers for each of
these compounds.

cis trans cis trans

21. For the following compounds below determine which are isomers of each other. What kind of isomers
are they?
There are two sets of constitutional isomers, A and B.

C6H14 C6H12 C6H12 C6H14 C5H12 C5H10

22. Label the functional groups in the molecules below.

Chem 31 Answers pg 10
 NH2 NH2
Br CH3
H
O
H3C Br O
OH

amine, alcohol, amide alkyl halide alkene, aldehyde

O
O O OH O
HO OCH3 O O

O
carboxylic acid, ketone
alcohol, ester alkene, ether, anhydride
aromatic ring/arene ring

23. You find a bottle on the shelf only labeled C3H6O. You take an IR spectrum of the compound and
find major peaks at 2950, 1720, and 1400 cm-1. Draw a molecule that might be the compound in the
bottle.

O
The peak at 1720 indicates a C=O bond (carbonyl). One possibility is acetone:

24. For each of the following compounds, draw an isomer that changes the functional groups in the
molecule. Name all the functional groups. Indicate the major absorbances you would expect to find in
the IR spectrum for each isomer, and highlight how you could use IR to tell them apart.
In each case I have shown just one possibility. Others will exist. Remember to check the
molecular formulas to make sure you have created isomers.
a.
O
OH

alcohol O-H at 3500 ketone C=O at 1720

b.

alkene C=C bands near 1600 terminal alkyne C≡C band near 2200
alkyne C-H near 3300

Chem 31 Answers pg 11
c.
O
O

H2N N

amide N-H bands near 3300 amine and ether

C=O band near 1680 C-N and C-O bands in the fingerprint region
d.
O
O
H

alkene and ether aldehyde C-H at 2700, 2900

C=C bands near 1650 C=O at 1730
C-O bands in the fingerprint region
e.

N N
H

amine and alkene

C-N bands in the fingerprint region nitrile C≡N at 2250
C=C bands near 1650
f.

OH O

alcohol (and aromatic ring) ketone (and alkene)

O-H at 3500 C=O at 1720
I got a little crazy on this one. Note that it would not be easy to identify the difference between C=C
bonds of the aromatic ring in the first compound and the alkene in the second.
g.

OH
O O

ether C-O bands in the fingerprint region carboxylic acid

(actually a special kind of ether-like O-H at 2500-3200
functionalgroup called an acetal) C=O at 1720

Chem 31 Answers pg 12
25. For the three infrared spectra below, pick out the molecule from the list that would correspond to the
spectrum for that compound.
N
O O OH
C N O
CH3
OH

a. With O-H stretch at 3414 cm-1, aliphatic C-H, and aromatic/vinyl C-H (below and above 3000 cm-1),
must be:
OH
CH3

b. With C=O peak at 1687cm-1 (C=O in conjugation), aliphatic C-H, and aromatic/vinyl C-H (below and
above 3000 cm-1), must be:
O

c. With only aliphatic C-H, must be:

N

because no aromatic/vinyl C-H (above 3000cm-1), can't be:

O

because no C≡N at about 2200 cm-1, can't be:

N
C

26. Draw and name a constitutional isomer of methylcyclohexane.

Here's one: cycloheptane

Chem 31 Answers pg 13
27. Name the following compounds using IUPAC nomenclature.
a. 2,5,5-trimethylheptane

b. trans-1-methyl-2-(2-methylpropyl)cycloheptane

c. 5-chloro-3-methyl-4-propyloctane

Cl
28. Name the following compounds using IUPAC nomenclature.
a. 3-methylhexane

b. 2-iodobutane

29. The names given for the following structures are wrong. Specify the errors in naming, and give the
correct names.
a. 2,2,5-methylheptane

correct name: 2,2,5-trimethyl-heptane; tri was missing

b. 5-(1-methylpropyl)octane

correct name: 3-methyl-4-propyloctane; parent is chosen to maximize branching/substituents, and

numbering is chosen to give lowest numbers

Chem 31 Answers pg 14
30. Name the following compounds using IUPAC nomenclature. Be sure to include stereochemistry
when appropriate (i.e. cis, trans)
a. trans-1-isopropyl-4-propylcycloheptane

H
H

b. 3-ethyl-2,2,6-trimethyloctane

31. Draw the skeletal (line/angle) formulas for the following.

a. 3-ethyl-5-methyl-4-(1-methylethyl)octane

b. 2-bromo-1-ethyl-3-propylcyclohexane

Br

c. 3-(1-methylcyclopropyl)-4-propylheptane

d. cis-2-ethyl-1,1,3-trimethylcyclopentane

32. Draw the skeletal(line/angle) formulas for the following.

Chem 31 Answers pg 15
a. 3-ethyl-5-methyloctane

b. 1-bromo-3-isopropylcyclohexane
Br

33. Rank the following compounds from lowest boiling point to highest boiling point. Justify your
answers with brief explanations.

< < <

propane 2-methylpropane butane pentane

First trend: the larger the molecule (higher molecular weight), the higher the boiling point. Second
trend, for 2-methylpropane vs butane (which are isomers): isomers that are more spherical have lower
boiling points since they have weaker attractive forces between the molecules. The strength of
dispersion forces between molecules depends on how much surface area is available where they
collide; spherical molecules have less surface area for these weak attractive forces.

34. Consider 1,3-dimethylcyclobutane. Do you expect the trans isomer or cis isomer to be more stable?
Offer an explanation using the ideas of conformational analysis developed for cyclohexane.
First, we should draw the two possibilities as flat projections:

Now, we need to remember what we learned about cyclobutane conformations. Cyclobutanes usually
adopt puckered conformations (increasing ring strain) in order to lessen the torsional strain from
eclipsing interactions. When we draw the rings in these conformations, we create pseudo-axial and
equatorial positions at each carbon. Similar to cyclohexane, having equatorial substituents creates less
strain. As a result, we'd rather have the isomer that can place both the methyls in equatorial positions.
That isomer is the cis-1,3-dimethylcyclobutane.
CH3

H3C CH3 CH3

cis -- diequatorial trans -- one axial, one equatorial

35. Sighting along the C2-C3 bond, draw all the possible staggered conformations (as Newman
projections) of 3-methylpentane. Which is the lowest energy conformation? Draw a sawhorse projection
of the lowest energy conformation of the entire molecule.

Chem 31 Answers pg 16
 CH3 CH3 CH3
H3C Et H CH3 Et H

H H H H H H
H Et CH3

A B C
A has two gauche interactions, while B and C each have only one. Between B and C, we can
safely estimate that a methyl-ethyl gauche is slightly worse than a methyl-methyl gauche interaction. I'd
rate B as the lowest energy conformation.
For the last question, the answer is easy if we realize that skeletal drawings naturally put linear
chains in their lowest energy conformations -- all anti-butane type conformations. Just add on the
methyl!

36. Consider the molecule 2,3-dimethylbutane:

H3C CH3

H3C CH3
a. Draw the eclipsed Newman projections for the conformations of this molecule.
H3C H H3C
CH3 CH3 CH3

H H H
H H3C CH3 H3C H3C CH3 H3C H3C H

1 x H-H, 2 x CH3-CH3 2 x CH3-H, 1 x CH3-CH3 2 x CH3-H, 1 x CH3-CH3

1 + (2 x 2.5) = 6 kcal/mol (2 x1.4) + 2.5 = 5.3 kcal/mol (2 x1.4) + 2.5 = 5.3 kcal/mol
The second two are more stable than the first by 0.7 kcal/mol
b. Draw the staggered Newman projections for the conformations of this molecule.
H3C H3C H3C
H CH3 H3C H H3C CH3

H CH3 H CH3 H CH3

CH3 CH3 H
3 x CH3-CH3 gauche 2 x CH3-CH3 gauche 3 x CH3-CH3 gauche
3 x 0.9 = 2.7 kcal/mol 2 x 0.9 = 1.8 kcal/mol 3 x 0.9 = 2.7 kcal/mol
middle is most stable (by 0.9 kcal/mol of course!)

c. Calculate the energy of each of the conformations/Newman projections you drew for a. and b. using
the information provided below. For each set, indicate which of the conformations is more stable?
calculations done above
37. Consider the conformational isomers along the C1-C2 bond of 1-bromopropane. Draw all the
distinct eclipsed and staggered conformations. For each, indicate the types of strain, if any, that you
think may be incurred. Compare these conformers with their counterparts in our analysis of butane. For
Chem 31 Answers pg 17
each pair of counterparts, indicate which you expect to be higher in energy, and briefly explain your
reasoning.
H3C Br Br HBr Br
H CH3 H H

H H H CH H H
H
H H H
H
H H 3 CH3

A B C D

steric and steric torsional none

torsional
like gauche like anti
butane butane

All the counterparts for butane simply have a methyl group where the bromine is. The bromine-carbon
bond here is longer than the counterpart carbon-carbon bond in butane. Moreover, even though
bromine is a bigger atom than carbon, it has no attached hydrogens like the methyl group does. As a
result, the steric interactions should be less, and certainly the A and B conformers here should be
lower in relative energy than the similar conformers in the butane case.

38. Consider the all cis isomer of 1,3,5-tribromo-2,4,6-trimethylcyclohexane.

a. Draw the molecule as a skeletal structure.
Br

Br Br

b. Draw a sawhorse representation of each of the two possible chair forms.

Br Br
Br
Br
Br Br

bromines equatorial methyls equatorial

methyls axial bromines axial

c. Which chair conformation do you expect to be more stable? Briefly explain why.
For the same kinds of arguments as in (37) above, the diaxial interactions between the
bromines should be much less than between the methyl groups. Expect the second conformation
(bromines axial) to be much more stable.
39. Consider the all cis isomer of 1-tert-butyl-2,4,6-trimethylcyclohexane.
a. Draw the molecule as a skeletal structure.

Chem 31 Answers pg 18
b. Draw a sawhorse representation of each of the two possible chair forms.

A B
t-butyl equatorial methyls equatorial
methyls axial t-butyl axial
c. Given that a single CH3-CH3 1,3 diaxial interaction has a cost of 15 kJ/mol, which chair conformation
do you expect to be more stable? By how much?
A has 3 CH3-CH3 1,3 diaxial interactions for a total cost of 45 kJ/mol. B has only the t-butyl
diaxial cost of 23 kJ/mol. B should be more stable by 22 kJ/mol.
d. If you add another cis methyl at carbon 3, how might this change the picture? Draw the chair forms
and make a guess as to which is more stable. Explain your reasoning.
picture would now be modified to:

A B
Energy cost for A is still 45 kJ/mol. The cost for B is now t-Bu-H at 11.5 + CH3-H at 4 + whatever the
cost of the t-Bu-CH3 interaction is. If that interaction is greater than 30 kJ/mol, A would now be more
stable than B. Knowing that CH3-CH3 costs 15 kJ/mol, it's a good guess that t-Bu-CH3 is more than
twice as much and greater than 30. I'd guess that A is now more stable.
40. Draw the two possible chair conformations for 3-methyltetrahydropyran (shown below). Indicate
which is more stable. Estimate the relative populations of the two chair forms relative to those for
methylcyclohexane.

3-methyltetrahydropyran
O

O
O

A B
A, with the equatorial methyl, is more stable. Relative to methylcyclohexane, though, having the methyl
axial does not cost as much energy. The oxygen has no attached hydrogens, so we have removed one
of the diaxial interactions. The cost might be estimated as about 4-5 kJ/mol rather than 7.6 kJ/mol. (The
assumption is that any interaction with a lone pair is a lot less than with the hydrogen.) An energy
Chem 31 Answers pg 19
difference of 7.6 kJ/mol gives us a ratio of about 95% equatorial/5 % axial. Reducing that to 5 kJ/mol
would give us a ratio of more like 85% equatorial/15% axial.
41. For the following molecule, perform a complete conformational analysis using the data provided in
tables in the course packet (or in the book). Follow the steps below to complete the analysis.
CH3
CH3
CH3
CH3
a. Draw the two chair conformations possible for the compound.
b. Calculate the energy difference between the two chair conformations.
c. Estimate the ratio of most stable to least stable conformation for a sample of this compound at 25 °C.

2 x 1,3 diaxial 2 x 1,3 diaxial

H CH3
H
H H
anti -- 180°, no steric interactions
CH3
H H
CH3 CH3-CH3 CH3
gauche (60o)
2 x 1,3 diaxial
1,2 disubstituted
2 x isopropyl-H 1,3 diaxial 4 x CH3-CH3 1,3 diaxial
1 x CH3-CH3 gauche no CH3-CH3 gauche, CH3-CH3 angle is 180°
isopropyl equatorial, no steric interactions

(2 x 1.1) + 0.9 = 3.1 kcal/mol 4 x 0.9 = 3.6 kcal/mol

more stable conformation less stable conformation by 0.5 kcal/mol

0.5 kcal/mol gives a ratio of about 70:30 (just estimate knowing that 0.65 is 75:25)

42. Draw a pair of substituted cyclobutane stereoisomers. Name them.

Here is one possibility:
Cl Cl

cis-1-chloro-2-methylcyclobutane trans-1-chloro-2-methylcyclobutane
43. For each set, identify which compounds are isomers, and indicate what type of isomers they are.
a. constitutional (structural) isomers

b. constitutional (structural) isomers

Chem 31 Answers pg 20
 OH H3C

OH
OH
CH3 OH

44. For each of the following compounds, indicate how many peaks you would expect in its 13C NMR
spectrum and the approximate location of each peak.
OH O
O O OH

H H OH

4 peaks 3 peaks 9 peaks 3 peaks

all in 0-100 ppm 2 in 0-100 ppm 6 in 0-100 ppm all in 0-100 ppm
1 in 160-220 ppm 2 in 100-160 ppm
1 in 160-220 ppm
45. For each set below, draw an isomer of the given formula that would show the given number of
peaks in its 13C NMR spectrum.
I have given one possibility for each case -- there are often others.
13
formula C NMR peaks

C 3H 6 1

C6H10 3

C4H10O 3 OH

C5H9Br 3 Br

C 6H 8 6

C 6H 8 4
46. You have been given a sample of one of the C6 compounds shown below. You take the 13CNMR
and find 2 peaks in the spectrum. Which compound do you have?

Chem 31 Answers pg 21
 CH3 CH3 CH3

CH3 CH3
H3C H3C
H3C
CH3

3 peaks 1 peak 4 peaks 2 peaks!! 5 peaks 3 peaks

47. You have an unknown that you are told is one of the four compounds below, and it exhibits the
following spectral data. Which compound do you have?
13
C NMR: 3 peaks
IR major peaks:
• 1710cm-1 Large and Sharp
• 3300cm-1 Large and Broad
• 3000cm-1 C-H Aliphatic (mostly obscured by 3300cm-1 broad peak).

O O
N OH
OH C OCH3

C=O, O-H peaks for acid in IR; 3 peaks in 13C NMR

note: even if the O-H confused you, just the C=O plus 3 NMR peaks is enough for the identification

48. For the following pairs of cyclohexane chair conformations, circle the conformer that you expect to
be more stable. Briefly explain your reasoning.

t-butyl is much bigger than methyl, more important to be equatorial.

t-butyl is still bigger than phenyl, more important to be equatorial.

Chem 31 Answers pg 22
 H H
H HH
H

The cyclohexyl substituent can get out of the way -- the interaction isn't actually any worse than that of
a methyl group. However, any orientation of the phenyl has atoms much closer. I've shown this
arrangement, but even the 90° rotation of the phenyl ring has more problems than a methyl would.

Br

Br

Bromine has no attached H's and it is attached to the ring via a longer bond. It will interact less with the
diaxial H's and is better to have axial than the methyl would be.
49. For the following pairs of cyclohexane chair conformations, circle the conformer that you expect to
be more stable. Briefly explain your reasoning.
a.

Biggest, most sterically demanding group (-C6H5) is equatorial. If you are unsure about which group,
the benzene ring or the isopropyl, is sterically larger, see the table in the class packet: C6H5 has 1.5
kcal/mol (6.5 kJ) steric strain energy, isopropyl is only 0.95 kcal/mol (4 kJ).
b.

CN

CH3 H3C CN

CH3 CH3

2 groups axial vs. only one group axial

c.

Chem 31 Answers pg 23
 H3C CH3

CH3 CH3 CH3

CH3

The first conformation has 2 CH3 groups axial on the same side of the ring, leading to 2 CH3-H diaxial
interactions and also a very costly CH3-CH3 diaxial interaction (see problem 39 for an estimate). The
second conformation has a single CH3 group axial, which only leads to the 2 CH3-H diaxial interactions.
Note that both conformations also have a CH3-CH3 gauche interaction.
50. Identify the more stable conformation in each of the following pairs, and briefly explain your
reasoning.
a.

Ring is in preferred "envelope" conformation, which reduces all the eclipsing interactions around the
ring and allows the isopropyl to adopt a psuedo-equatorial position.
b.

CH3 H CH3
H H
H H H

H H

Good practice for working with different 3-D perspectives. The left conformation is eclipsed, while the
right one is staggered, and in fact anti.

Chem 31 Answers pg 24
c.
2 CH3-H diaxial interactions

H H
CH3

CH3

CH3
CH3

2 CH3-CH2 diaxial interactions

The CH3-CH2 diaxial interactions cost much more than the CH3-H diaxial interactions.
d. A tough one -- draw the most stable chair forms for both and then compare their stability
HO HO

HO HO
O O

HO OH HO OH
OH OH

OH OH
O O
HO HO
HO OH
1 HO
OH OH 1
OH

The -OH at carbon one is more stable when equatorial. All other groups are the same for both
molecules.
51. For the molecule below, follow the steps to perform a complete conformational analysis. Use the
energy data provided in the course handout packet. Assume no distortion of the ring due to the
oxygens, and assume no steric strain due to the electron pairs on oxygen.

O
H3C
1
Ph O H

Note: Ph = C6H5 on Conformational Analysis Table in packet

a. Draw the two chair conformations possible for the compound. For convenience, fill in the appropriate
substituents on the chairs below.

Chem 31 Answers pg 25
 2 CH3-H diaxial interactions

CH3 H H
H O
1
Ph O
1 H H3C O
O H
Ph H

2 Ph-H diaxial interactions

b. Calculate the energy difference between the two chair conformations drawn above.
c. Estimate the ratio of more stable to less stable conformation for a sample of this compound at 25 °C.
Left: 2 (3.8) = 7.6 kJ/mol
Right: 2 (6.5) = 13 kJ/mol
Right is more stable by 5.4 kJ/mol, which we might estimate giving a 88:12 ratio of more
stable:less stable.
d. Is there anything unusual about your findings above that may go against conventional wisdom in
such conformational analyses? Explain briefly.
The preferred, lower energy conformation has the big t-butyl group in the axial position!? The reason is
that no H's on the oxygen atoms means no 1,3 diaxial interactions. Crazy!
52. The energy of the boat conformation of cyclohexane is 7 kcal/mol (29 kJ/mol) higher than the chair
conformation. Calculate the steric strain due to the Ha-Hb interaction in the boat using what you know
about the other destabilizing interactions in this molecule. A model might be helpful here.

H Ha Hb
H
H
H
H
H
H H
H H
There are 4 H-H eclipsing interactions for the lower 4 H's (bottom of the boat): 4 x 1 kcal/mol (4 kJ/mol)
= 4 kcal/mol (16 kJ/mol) for H-H eclipsing; therefore the Ha-Hb interaction costs 3 kcal/mol (13 kJ/mol).
53. Circle the chiral centers in the following compounds.

O
OH

HO OH
HO

Cholesterol Prostaglandin E2
54. Label with a "*" all the chiral centers in the following molecules.

Chem 31 Answers pg 26
 O CH3
N O
NHCO2CH3
CH3
* O
H C C * H
* *
* C C O
*
H3CSSS H OR H
O

calecheamicin cocaine

55. Identify the following pairs of compounds as enantiomers, diastereomers, or the same.
Br Br OH OH

diastereomers enantiomers

Br Br

HO

OH
diastereomers
enantiomers
56. Identify the following pairs of compounds as enantiomers, diastereomers, constitutional isomers, or
the same.
a. diastereomers
Br Br Br
Br

b. enantiomers
HO

OH

57. Identify the stereocenters in the following molecules and indicate whether they are R or S.
H NH2
OH
Cl S
R S HO OH
R S
S
H O
not a stereocenter!
58. Using the tests for chirality we have learned, determine whether the following molecules are chiral.
Determine the configuration (R or S) of any chiral centers in the molecules.

Chem 31 Answers pg 27
 Br O
R R
S OH
S
CH3 OH NH2

chiral chiral chiral

CH3 OH HO OH
S S R
R
CH3
achiral achiral achiral
meso no stereocenter meso

59. Circle those molecules below that are chiral.

Cl OH

Cl

HO O Cl Cl CH3
Cl
CH3

60. Name the compound below. Be sure to include R,S designations.

CH3

S-3-methylhexane
61. Determine the relationship between the following pairs of molecules: enantiomers, diastereomers,
identical, or structural isomers.
a. structural isomers

Br Br

Chem 31 Answers pg 28
b. diastereomers
NH2 NH2

NH2 NH2
c. identical -- no chiral center
OH

HO
d. enantiomers
OH OH OH OH

Br Br
e. identical -- draw flat and see -- compound is meso
CH3 CH3

CH3 H3C
f. identical -- meso

OH OH OH OH

62. a. Draw a Lewis structure for carbon monoxide, CO. C O

b. Draw all possible resonance forms, showing formal charges.

C O C O

c. What experimental method could you use to determine which resonance form is the most important?
How would it help?
You could determine the dipole moment. In the resonance structure on the left, the dipole would
point toward the carbon. In the structure on the right, the dipole would point toward the oxygen.
Measuring the actual dipole moment and its direction would indicate where the electrons really lie and
which resonance form is the bigger contributor.
63. Do you expect AlBr3 to be a weaker or stronger Lewis acid than AlCl3? Explain.
A Lewis acid is an electron pair acceptor. Here the Al is electron deficient because it has three
bonds and no lone pairs. It is disposed to accept an electron pair. The attached halogen atoms also pull
electrons away from the Al and make it an even better electron pair acceptor. The more electronegative
halogen will be better at pulling electrons away. Cl is more electronegative than Br and will cause the Al
to be more electron deficient. The more deficient, the more it wants a lone pair, and the better the Lewis
acid it is. AlCl3 is stronger.

64. For the following compounds, determine the formal charge for all the heteroatoms (O, N, and S). All
nonbonding electrons are shown. For carbon atoms, assume zero charge and fill in the correct number

Chem 31 Answers pg 29
of assumed hydrogens. Note: there are no assumed electrons on carbon; they have to be explicitly
shown with nonbonding electrons and/or with a charge notation.
heteroatoms with no indicated formal charge have a charge of 0.
H H
O H H H H O H
H H H H H O H
H H H H
H N H
OH H H H
H O H H N
H H
H H H H
H H H H H H H
H H H H
H H
H H H
H H
H H H H H H
H N H H O H
H H O
H
H H N N
H H H
H O H H H H O
H H H H
H H
H H
H H H
H H H H H H
H H H H
H H N
H H H
H S H H H H SH
O H N H H
H H H HH H H H
H H

65. For the following compounds, determine the charge for all the atoms, and assign formal charges to
any atoms that need them. All normally-assumed hydrogens and nonbonding electrons are shown.
H H
O
CH3 N H
H H CH3 H
H3C
H3C CH3
H H CH3 H
H

H H
CH3
Br CH3 CH3 CH3
H3C H3C O
H3C CH3
H

Chem 31 Answers pg 30
66. For the following compounds, all charges are shown as they might typically be in texts or the
chemical literature. Add to these structures the correct number of normally-assumed nonbonding
electrons and hydrogens consistent with the formal charges as shown. Recall from the drawing
conventions that hydrogens are always shown on heteroatoms (O, N, and S); only hydrogens on
carbons are assumed and need to be added to the structures below. As always, assume zero charge
unless a charge is shown.
CH3 H
H H H O
H H H H O
N H H N H H
H H
H H O H
H H H H
H H H NH3 H H H
H H H H H
H H H
H
H
H H H H
H H CH3 H
H H
H +2 S H H3C CH3 H N
O N N N H
H
O H CH3 H
H H H H
H H
H
H H
O H H H H H H
H H
H H H H N
H N Cl N
H H H N
O H H H H H H H H
H H

67. For the following sets of resonance structures, use mechanistic arrows to show how one can be
converted to the other. Each pair has one structure listed as more stable. Give a brief explanation why
it is the more stable form.

O O

H H more stable
Because oxygen is more electronegative than carbon, having a negative charge on the oxygen is better
than having it on the carbon. The resonance form on the right should be a bigger contributor to the
overall picture.

O O

more stable
The resonance form on the left is better because all the atoms have full octets with 8 electrons. The
resonance form on the right is reasonable because the lone pair goes to the more electronegative
atom, but the carbon has only 6 electrons. Note that a resonance form with the lone pair moving to the
carbon would be unreasonable -- it has essentially no contribution to the overall picture.
68. For the following reactions, predict on which side the equilibrium should lie. Give a brief explanation
for your reasoning.
Chem 31 Answers pg 31
 O OH OH O
+ +

O
no resonance

vs
H
O O
plus other resonance forms

The extra electrons on the oxygen are better stabilized when they have additional places to go -- which
is what occurs by resonance. That makes the bottom (or right side) base more stable than the top (or
left side) base. Equilibrium should be on the right.

NH2 + + PH2
PH3 NH3

Here the base and conjugate base are the neutral molecules. Is the lone pair better on the
phosphorous or the nitrogen? Phosphorous is bigger, more diffuse, and better stabilizes electron pairs
(more kids to start with). It is less likely than nitrogen to feel the need to donate its lone pair to a proton.
Use the periodic trend. It is less basic, and the equilibrium lies on the right.

+ +
H

The difference in the two bases here is whether the lone pair is held in an sp2 orbital (left) or an sp3
orbital (right). the more s-character, the more stable the lone pair. An sp2 orbital at 33% s is better than
an sp3 orbital at 25% s. Equilibrium lies on the left.

Chem 31 Answers pg 32
69. For the following pairs of compounds, decide which one is more stable, and briefly explain why.
Draw out any structures that would justify your selection.
more stable more stable
resonance resonance

empty
p-orbital

pi bond
pi bond and empty p-orbital are
orthogonal, so electrons can't move
between them
more stable
resonance
O more stable
more resonance

70. Give an explanation why the labeled anion of each pair is more stable.
more stable

O O

Both structures have resonance, but the one on the left can delocalize the lone pair to a more
electronegative atom (O more electronegative than C).
more stable

O O
O O O

no resonance for the one on the left, lots of resonance for the one on the right.

Chem 31 Answers pg 33
71. The major contributor is labeled in each set of resonance structures. Explain why that resonance
form is "better" than the other. Although a resonance form is shown for 2-methylpropene, we generally
consider it so "bad" that we don't bother to draw it. Explain why we don’t draw the second resonance
form for 2-methylpropene but we do consider a similar resonance form for acetone.

O O

major contributor has the negative charge on the more

electronegative atom

major conbributor
major contributor avoids charge separation; the only reason
that the minor one isn't silly is that it puts a negative charge
O O on the more electronegative atom, and we know the bond is
polarized to start. (We'll see that it also explains a lot of the
reactivity of ketones.)
major conbributor

Simultaneously creating carbon anions and cations from a

neutral structure is so bad it sends shivers down our spines.
Bond has no polar character to make us think this structure
would appear in anything other than our nightmares.
"only" contributor Why don't we draw
this resonance form?

72. For the following carbocations, the oxygen containing molecule is significantly more stable. Explain
why the -OCH3 group would be better able to stabilize the carbocation than a -CH3 group.
CH3 CH3
CH3 O O

H3C CH3 H3C CH3 H3C CH3

no resonance cation is stabilized by resonance

The lone pairs of the oxygen can be donated by resonance to stabilize the cation. Nothing similar is
possible with just a methyl group.

Chem 31 Answers pg 34
73. Indicate where the equilibrium would lie for the following reaction. Explain your answer briefly.
O O
H3C O H3C O
H
H + CH3OH + CH3O
H3C O H3C O H

O pKa=16 O
pKa=5.1
O
H3C O
H
H3C O
O
plus one more
A simple answer is that reactions favor to the weaker acid/base, which correlates with higher pKa's, so
the equilibrium must be on the left. Could you do it if we hadn't given you the pKa's? It's a tougher call
because the initial anion is on carbon vs. oxygen. However, the anion on the left is stabilized by
multiple resonance forms, including two where the charge is on an oxygen. At a minimum, this
assessment allows us to make sense of the experimental data.
74. Use the pKa values below to answer the following questions.
HF 3.2 H2SO4 -5.4 CH3CH2OH 18
a. Which acid is the strongest? Which acid is the weakest?
strongest, H2SO4 weakest, CH3CH2OH
b. Which of the above acids are strong enough to react with NaOH (pKa of H2O = 15.7)?
HF and H2SO4
c. Which conjugate base of any of the acids above could deprotonate acetic acid (pKa = 4.8)?
only, the conjugate base of ethanol,

75. Trifluoromethanol, CF3OH, has a much lower pKa than methanol, CH3OH. Does that make CF3OH
more acidic or less acidic? Briefly explain why the pKa of trifluoromethanol is lower.
base
H3C OH H3C O

F F
base
F C OH F C O
F F

The strongly electronegative fluorines withdraw electrons from the carbon and inductively stabilize the
anion on oxygen, so trifluoromethanol is more acidic. Note that this example is really just theoretical
because the anion shown would immediately decompose to other products. Trifluoromethanol itself is
highly unstable.
76. Draw the conjugate bases for the following acids.

Chem 31 Answers pg 35
 Acid pKa Conjugate Base
O O
H3C 4.8 H3C
OH O

H C C H 25 H C C

H2O 15.7 HO

NH4 9.2 NH3

H-F 3.2 F

a. In the following reaction scheme, compound A (pKa = 10) must be deprotonated to form anion B with
the appropriate base. Compound B then reacts with CH3Br to form a new carbon-carbon bond. From
the list of acids and their pKa's given above, which conjugate base(s) would you chose to deprotonate
A? Be sure to give all the bases that would be appropriate for this reaction.
O O O O O O
+ CH3Br
Base + H-Base
H H
H H CH3
A B
Draw the structure of the appropriate bases below:

H C C HO

b. Draw out the acid-base reaction using one of the bases you chose. Use mechanistic arrows to show
the flow of electrons.
O O
O O

HO H H
H

c. Draw the subsequent mechanism for the substitution reaction using mechanistic arrows. Identify the
molecules as nucleophiles and electrophiles.
O O O O

+ Br
H H CH3
H3C Br
nucleophile
electrophile

Chem 31 Answers pg 36
77. a. Show the products of the following acid/base reaction and indicate whether it would occur.
pKa: Protonated form of trimethylamine = 9.8; Formic Acid = 3.7
H
O O
N + N +
H3C CH3 H OH H3C CH3 H O
CH3 CH3

trimethylamine formic acid

pKa = 3.7 pKa = 9.8

Reactions go to the weakest acid and base. The trimethylammonium ion is a much weaker acid than
formic acid. Difference of 6 pK units corresponds to a an equilibrium constant of about 106. The
reaction will definitely occur.
b. Which of the following acids would react with N(CH3)3?
i) H2S, pKa 7.0 ii) H2CO3, pKa 6.4 iii) CH3CH2OH, pKa 18 iv) NH3, pKa 36
We will get a reasonable reaction with anything that is at least a few pKa units below 9.8, the pKa for
the trimethylammonium ion. That means H2S and H2CO3, but neither of the other two.
78. Toluene (methylbenzene) has a pKa of 41, while methylcyclohexane has a pKa ~ 50.
CH3 CH3
toluene methylcyclohexane
pKa ~41 pKa ~50

a. Draw the conjugate base for each molecule.

b. Draw all possible resonance structures for each base.
H
CH3 CH2 CH2 CH2 CH2 CH2

H
H
acid conj. base

CH3 CH2
no resonance

acid conj. base

c. Why do you think toluene is so much more acidic?
The conjugate base of toluene is stabilized by resonance, while the conjugate base of
methylcyclohexane is not. The better stabilized the conjugate base, the stronger the corresponding
acid.

Chem 31 Answers pg 37
79. For each pair of compounds, circle the one that is more acidic. Briefly explain why your choice is
the more acidic one. Your answer should involve basic principles (not just the pKa's given), and you
should probably include some pictures.

O O O O
O O O O
base

H H
H

O O
O
H base
H
H H
H
Resonance forms are similar, so the more the better. Resonance with two carbonyls is better than one.

OH O O O O

base

OH O

base
no resonance

One anion is stabilized by resonance, and the other isn't

Chem 31 Answers pg 38
80. Consider an acid/base reaction between dimedone and sodium methoxide (NaOCH3).

pKa ~ 10
H H
O O
CH3OH pKa ~ 16

dimedone methanol
a. Draw a mechanism for the reaction.

OCH3
H H H
O O O O
+ CH3OH

b. Do you expect this reaction to go to completion? Explain.

Reactions go to the weakest acid and base. Methanol is a much weaker acid than dimedone.
Difference of 6 pK units corresponds to a an equilibrium constant of about 106. The reaction will
definitely occur and go to completion.
c. Draw an energy diagram that represents your reaction mechanism. Give an estimate for the energy
difference between the reactants and products. Is it exothermic or endothermic?

energy H H
O O

+ OCH3

H
O O

+ CH3OH

reaction coordinate

The reaction is exothermic. An equilibrium constant of 106 corresponds to an energy decrease of about
40 kJ/mol from reactants to products.

Chem 31 Answers pg 39
81. A reaction of alkenes catalyzed by acid is their isomerization. Consider the reaction of 1-butene
isomerizing to 2-butene, shown below.
H+

a. Draw a mechanism that could explain the reaction going from left (1-butene) to the right (2-butene).
Draw on your knowledge of the reaction mechanism of the electrophilic addition reaction of alkenes
with mineral acids like HCl and HBr.

H H
H+ H - H+
H
H
H H H H
b. Do you expect the equilibrium to lie towards the right or the left?
More substituted alkenes are more stable. Expect the equilibrium to lie to the right.
c. Draw an energy diagram consistent with your mechanism and prediction of the equilibrium.
The key difference from the previous problem is that here we have an intermediate.

H H
H
H
H
H H H H

energy
+ H+

+ H+

reaction coordinate

82. For the following pairs, determine which compound is more stable, and briefly explain why.
2 R groups 4 R groups

cis trans-more stable

more highly substituted
double bond

biggest groups trans

resonance no resonance
stabilized stabilization

Chem 31 Answers pg 40
 O O

resonance resonance pi bonds are not in resonance

no resonance so no resonance stabilization
stabilized stabilization stabilized

83. Label the following reactions as addition, elimination, substitution, or rearrangement.

a.
CH3Br + CH3SNa S + NaBr
H3C CH3
substitution
b.
O O
Heat

rearrangement
c.
O

O Na O
+ NaBr
Br O
substitution

d.
Br2
Br
+ HBr
H2O OH
addition
e.
Br2 Br

Br
addition

Chem 31 Answers pg 41
84. Using the stability arguments we have learned, label which product would be major in the following
reactions. Briefly explain why.
a.
Br
CH3 CH3
NaOH

major
more substituted
double bond
b.
I
I
CH3 HI CH3 CH3
+

major
more substituted
cation intermediate

85. Using the stability arguments we have recently learned, indicate whether the product or the reactant
would be favored. Briefly explain why.
a.

product: biggest groups are trans, which reduces steric strain

b.

reactant: more substituted carbocation is more stable

86. For the following transformations, fill in mechanistic arrows to show the mechanism.

Br + SH SH +
Br

H
+ OH
+ H2O
Br

Chem 31 Answers pg 42
87. Based on the mechanistic arrows and the starting materials shown, show the expected products for
the following transformations.

O
O
+
Br

Br

O
O CN
CN

88. Predict the major product(s) for the following reactions.

a.
HBr Br

b.
Br
HBr
+

Br
both cation intermediates are 2°, so we get both possible products
c.

excess HBr Br

Br

89. Determine the products of the following reactions.

a.

HBr

Br
b.

HBr
Br
c.

Chem 31 Answers pg 43
 Br
HBr

90. For the following substitution reactions, determine the nucleophile and electrophile, and predict the
product. For extra fun, draw the mechanism of these reactions. Note that the last one has an interesting
stereochemical outcome. Recalling what we discussed to be the best approach to displace the Br, what
should be the stereochemistry of the product?

In all cases, the electrophile is the starting halide compound, and the nucleophile is over the
reaction arrow. All the mechanisms are SN2.
a.
NaOCH3
Br OCH3

b.
Br KNH2 NH2

c.

Li C CH
Br

d.
Br N3
Na N N N

91. Consider the following substitution reaction.

O
Br O O
O Na NaBr
+

a. Draw a reasonable mechanism that accounts for the observed product. Show all steps and
intermediates.
O
δ− O
Br O Na O
δ+ + NaBr

O
inversion of stereochemistry
O indicates that mechanism is SN2

Nucleophile must approach from

the opposite side of the leaving
group -- 180o approach
b. Draw a reaction coordinate diagram for the reaction. Label the transition state(s), intermediate(s), the
energy of activation(s), and the energy of reaction.

Chem 31 Answers pg 44
 δ-
Br
TS picture

TS O δ-

ΔG ΔG

H Br ΔGrxn O
O H

Progress of Reaction
c. Draw the structure(s) of the transition state(s) using the standard conventions.
Note: we can't really show the change in stereochemistry
Bond with dashed/partial bonds (a dashed-wedge or
breaking δ- a dashed-dash?), so we show the stereochemistry
Br change using the modified pictures below

first rotate

Bond H Br H
forming O δ-
rotate
Br
O 60o

Mechanism:
O H O H
O δ-
H
O Br O
O δ- S
Br
R
TS picture that shows
sterechemistry changing
d. Carefully examine the stereochemistry of the product. How would you describe the change of
stereochemistry that occurred from the reactant to the product? To produce the stereochemistry of the
product, how did the nucleophile, CH3CO2Na, approach the reactant, (R)-2-bromobutane -- from the top
face or the bottom face of the molecule?
SN2 reactions cause inversion of stereochemistry as seen here. The nucleophile approaches
the carbon from the opposite side ( 180° relative approach angle) of the leaving group. As drawn, the Br
was coming out toward us, which can be considered being on the top face. As a result, the acetate
must have approached from the bottom face.

92. Rank the following alkyl halides in order of increasing SN2 reaction rate as electrophiles (when
reacted with a nucleophile).

Chem 31 Answers pg 45
 Cl
Cl Br Cl
Cl

1 = slowest 3 2 5 = fastest 4
no SN2 at 3° 1° halide with 2° halide 1°, and Br is 1° halide, no
carbons beta branching better leaving beta branching
group than Cl

93. Give the expected major products for the following SN2 reactions. Draw the movement of electrons
for each reaction using mechanistic arrows.
a.

N3
I N3

b.

PPh3

OSO2CH3 PPh3

c.

NH2
Cl NH2

d.

SH
OSO2Ph SH
OH OH
no reaction at the alcohol -- not a good leaving group
e.
Br O Br
O
O
Br O

no reaction at the 3° bromide

Chem 31 Answers pg 46
f.

CN
Cl CN

Cl Cl
2
no reaction at the aromatic halide (sp carbon, no SN2)
g.
CN F
Br
no reaction

no good leaving groups in the substrate

94. Give the expected major products for the following E2 reactions. Draw the movement of electrons
for each reaction using mechanistic arrows.
a.

H
O
Cl

b.

Br H

OH

H
can't be anti-periplanar to the bromine
c.
Br

H OH

more substituted alkene product

d.
OSO2Ph

H NH2

Chem 31 Answers pg 47
e.
H

Cl CH3

Cl Cl

f.

H
O

Br

g.

Br

H O
more substituted alkene product

95. When the following substrates are reacted with NaOH, will they participate in a SN2 reaction, an E2
reaction, both, or neither? Briefly explain why.
a.
Br

2° substrate, expect E2 with basic nucleophile

b.

Br
1° substrate, expect SN2 -- good nucleophile
c.
CH3

I
CH3
3° substrate, SN2 not possible -- NaOH is strong base, so expect E2

d. CH3I
no elimination possible, so expect SN2

Chem 31 Answers pg 48
96. Give the expected products for the following reactions, and when possible indicate the type of
mechanism by which the reaction proceeds.

a.
O O
NaCN
Br CN

1° halide; good nucleophile (weak base) -- SN2

b.
OSO2Ph O
NaOAc OAc
= Ac

Good leaving group, 2° substrate; good nucleophile, weak base -- SN2; note inversion of
stereochemistry
c.
H2SO4
OH

3° alcohol, sulfuric acid -- special case of deliberate E1; note most substituted double bond is major
product
d.
Cl CH3ONa OCH3

1° halide; good nucleophile (strong base, but ok with 1°) -- SN2

e.
Br NaC≡CH

2° halide; good nucleophile but very strong base (conj. acid pKa 25) -- E2
f.

I OCH3
CH3OH

3° halide; weak nucleophile, but weak base -- SN1

g.
Cl OH OH

H2O +

2° halide but benzylic on both sides (special case); weak nucleophile, weak base -- SN1; note
racemization owing to cation intermediate
h.

Chem 31 Answers pg 49
 NaNH2
OSO2Ph

3° substrate, good leaving group; very strong base (conj. acid pKa 35) -- E2; note most substituted
double bond
97. Give the major product of the reaction and the mechanism by which it is produced (SN2 and E2
only for this set of reactions; we will add in SN1 /E1 later). Be sure to include the stereochemical
outcome.
a.

Br CH3O Na OCH3

1° halide, good nucleophile, SN2

b.

Br (CH3)3CO Na

special case: 1° halide but non-nucleophilic, strong base, E2

c.

Cl CH3O Na

3° halide, SN2 not possible; with strong base, E2 (conjugate acid pKa >15)
d.
Br SCH3
CH3S Na

2° halide, but non-basic (conj. acid pKa <12), good nucleophile, so SN2 -- note inversion of
stereocenter
e.
NaOH

Br
2° halide, strong base, E2
f.

OH NaCN
no reaction

No good leaving group plus 3°, so no SN2. Nucleophile not in class that can cause any other
reaction we know.
g
Br
NaOCH3

2° halide, strong base, E2; note more substituted double bond product
Chem 31 Answers pg 50
h.
NaNH2
Br NH2
1° halide, good nucleophile, SN2
i.

O Na CH3Br OCH3
H H

methyl substrate can't eliminate, so SN2; note that reaction is not occuring at the stereocenter,
so the stereochemistry remains unchanged.
j.
I O O

O Na O
(NaOAc)

2° halide, with weak base/good nucleophile, so SN2; note stereochemical inversion

k.

Br t-BuONa

special case: 1° halide but non-nucleophilic, strong base, E2

98. Give the major product of the reaction and the mechanism by which it is produced (SN1, SN2, E1,
E2). Be sure to include the stereochemical outcome.
a.
Br

NaOH
no reaction

no SN2 possible at an sp2 carbon; no current reaction we know works with an aromatic halide
b.
Br
NaOCH3

2° halide, strong base, E2

c.
Cl CN
NaCN
H3C H3C
CH3 CH3
2° halide, good, non-basic nucleophile, SN2; note inversion of stereochemistry
d.

Chem 31 Answers pg 51
 OH Cl Cl

HCl
+

special case: this substitution occurs by an SN1 mechanism; substrate is just good enough at 2°
with resonance stabilization; carbocation intermediate leads to racemic mixture
e.
O
Br H
H NaO H O

CH3 CH3
O
H3C H3C
2° halide, good, non-basic nucleophile, SN2; note inversion of stereochemistry
f.

Cl OH O

3° halide with a weak nucleophile, weak base, SN1

g.
CH3
H
CH3
KOH
Br

3° halide with strong base, E2; stereochemistry allows formation of most substituted double
bond

Chem 31 Answers pg 52
99. Assume that both of the following compounds happen to undergo an SN1 reaction. Draw what the
intermediate would be for each compound. Which, if either intermediate, is more stable? Why? As a
result, which should be formed faster?

Br Br

intermediate is stabilized by resonance no resonance

The allyl cation is a more stable intermediate because it is stabilized by resonance. In the energy
diagram on the right, the lower curve might represent the SN1 reaction profile for the 3-
bromocyclohexene (left, A), and the higher curve would then represent the SN1 reaction profile for the
bromocylcohexane (right, B). We know that the energy gap between the starting material and the
intermediate is less if the intermediate is more stable, so that distance is less on the profile for A. The
Hammond postulate says that a transition state most closely resembles the intermediate nearest to it in
energy. If the intermediate is more stable for A, the transition state for forming that intermediate is also
more stable than the corresponding transition state for B. That means that the activation energy (Δ G‡)
is lower for the reaction of A than it is for the reaction of B, and therefore 3-bromocyclohexene reacts
faster.
100. Give the expected major product for each of the reactions shown below. Indicate the type of
mechanism by which it is formed. Draw out the mechanism by which it is formed.
a.

N3
OSO2Ph N3

NaN3

SN2 reaction -- inversion of stereochemistry; 2° substrate; weak base, good nucleophile

b.

OH
H
NaOH

Cl

E2 reaction -- I emphasized that the anti hydrogen is removed; 2° substrate, strong base
c.
Chem 31 Answers pg 53
 H Br H
HO H O Br
Br

+ Br + H2O

SN1 reaction; note that first step is to make OH into a good leaving group; 3° alcohol;
protonation gives us good leaving group; very non-basic
d.

Br
OCH3
H

E2 reaction; major product is most substituted double bond; 3° substrate; strong base
e.

NH2
Br NH2
SN2 reaction; 1° substrate, good nucleophile
f.
H
Br O OCH3
HOCH3 CH3 -H
HOCH3

+ Br

SN1 reaction; 3° substrate, non-basic, weak nucleophile

g.

OH H

H O H -H
H

+ H2O

E1 reaction; special case of 3° alcohol and sulfuric acid

101. Using what you know about the mechanism, predict the elimination product. Be sure to clearly
show the stereochemistry of the proposed product.
a.
Chem 31 Answers pg 54
 Br H
CH3CH2ONa

Remember that the elimination only occurs when the Br and H are anti-periplanar. That means
that you have to rotate to that conformation to accurately predict the stereochemistry of the
resulting double bond.
b.
H Br H
NaOCH3

H H
The bridgehead hydrogen (at the 3° carbon next to the Br) can never be antiperiplanar to the Br.
The rings make that conformation impossible. As a result, we get the less substituted double
bond.
102. Using what you know about the mechanism, predict the elimination product. Be sure to clearly
show the stereochemistry of the proposed product.
a.
H3C Br
CH3O Na

CH3

H3C Br
H3C Br
rotate 180° to get H3C
Br and H antiperiplanar H3C
O H
H CH3

Chem 31 Answers pg 55
b.
Ha
CH3 CH3
CH3O Na can't be a true chair
with double bond, so
Cl we show it flat
Hb
H
Ha is cis to Cl -- can't be antiperiplanar
Hb will be removed -- but must be from
antiperiplanar conformation

ring flip so Hb, Cl

are antiperiplanar

Cl
E2

H3C Ha Ha
H3C
H
Hb CH3 CH3

H3C O

103. Consider the following reaction and its associated kinetic data.
Cl

+ NaCN ??

A B

Change in Reactant Concentration Effect on Rate

2 x [A] rate doubles
2 x [B] no change in rate
2 x [A], 2 x [B] rate doubles
4 x [A] rate quadruples (x 4)
a. Determine the reaction mechanism (SN1, SN2, E1 or E2), provide a reasonable rate expression, and
predict the reaction product.
Only the concentration of the substrate A affects the reaction rate, so we have a unimolecular
reaction. Of the choices, that means SN1 or E1. With A, no elimination is possible, so it must be SN1. A
reasonable rate expression is rate = k[A], and our predicted product is:

Chem 31 Answers pg 56
 Cl CN

+ NaCN

A B
b. Draw a reasonable, stepwise reaction mechanism. Be sure to show all of the steps!!!

Cl CN

-Cl

C N

c. Draw a reaction coordinate diagram for the reaction. Label the transition state(s) and intermediate(s),
and draw structures that are reasonable estimates of the transition state(s).
δ-Cl δ-CN
δ+ δ+

TS1 TS2

ΔG

intermediate
Cl

CN

Progress of Reaction

Chem 31 Answers pg 57
104. Explain the following observations. These problems are difficult but interesting.
a. In the following reaction, the only product had the relative stereochemistry shown. Why? Use your
knowledge of the E2 mechanism to explain.

Br2 Br

CCl4
Br

Br
Let's start by looking at the most stable conformation for the
product. We know that the tBu must be equatorial, so both the
bromines are axial. As a result, they are anti and periplanar (more
Br simply antiperiplanar). How would this product have been formed?
We have to look at the mechanism.
most stable conformation

b
Br The reaction goes via the
Br2 bromonium ion, as we've
Br
learned previously. This
intermediate can react with
the bromide in two ways.
a Both are from underneath
Br the ring, but a is axial and
b is equatorial.

If bromide does the axial attack via a, we get the experimentally observed product. If bromide
attacks equatorially via b, we would get the unobserved diequatorial product. Why is a favored?
Only by this pathway can there be an overlap of all the orbitals involved in the forming of the
new bonds and the breaking of the pi bond. Why is this question even on the problem set?
This example is completely analogous to what we learned about E2 eliminations and their
requirement for antiperiplanar H and leaving group. Essentially, this reaction can be thought
of as a reverse reaction for the elimination. Microscopic reversibility tells us that what is
true for the forward reaction is also true for the reverse.
b. Workers studying nucleophilic substitutions reacted optically active 2-iodobutane with radioactive
iodine (I*) as shown below. When they stopped the reaction, they found that the product was 40%
radioactive, but only 20% enantiomerically pure (20% ee). Does this result confirm or contradict the
SN2 mechanism we would have predicted? Explain.

NaI*

I I*
no radioactivity 40% radioactive
100% ee 20% ee

Chem 31 Answers pg 58
 This result is exactly what we would expect, and in fact it was used to confirm the mechanism
for the SN2 reaction. Let's see why. Everytime we substitute with I*, we both incorporate
radioactivity and invert the stereochemistry of the chiral center, as shown below.

NaI*

I I*

Now, if the reaction has gone to 40% completion, we have 60% starting material (not
radioactive) and 40% product (radioactive).

NaI*
60% 40%
I I*
Now, let's think about the stereochemistry. This mixture is the same as 20% of the original
isomer and a 80% racemic mixture -- 40% product and 40% starting isomer. This combination
therefore exhibits a 20% enantiomeric excess. As a result, 40% radioactivity and 20% ee is
exactly what we expect for a mechanism that always involves inversion -- as we said was
true for SN2

20% 40% 40%

I I I*

excess racemic mixture

105. Rank the following species in order of their strength as nucleophiles.
O O

S O CH3O CF3CH2O
O
O

conjugate acid pKa -7 16 12 5

nucleophilicity rank 4 1 2 3
As a first approximation, we can simply make our ranking based on the basicities. Because in each
case we have an oxygen anion, the more basic anions will be more nucleophilic. The basicity can be
judged by the pKa of the conjugate acids, which leads us to the ranking above. At the same time, it is
useful to consider in more general terms why some anions are more basic than the others. A useful
concept is that to whatever degree an anion is better stabilized (happy at home), it is less likely to be
donated in a reaction (leave the house). In this group we have the methoxide anion, which is the most
basic because it has no additional stabilization (other than being on the electronegative oxygen). Next
is the trifluoroethoxide anion, which is somewhat stabilized by the inductive withdrawal of the highly
electronegative fluorine atoms. Following is the acetate anion, which is stabilized by resonance. Last
comes the benzenesulfonyl anion, which is stabilized both be several resonance forms and special
characteristics of the sulfur. For practice, I suggest taking the time to draw pictures that represent these
effects -- particularly the resonance forms. It is also worth noting a general trend: resonance is a more
stabilizing force than inductive effects.
106. Evaluate the sets of compounds according to the given criterion and explain your reasoning. I like
these questions a lot, and you can expect to see them regularly on exams.
a. Which substrate reacts faster in SN2 reactions (2 different sets)?

Chem 31 Answers pg 59
 F Cl

Chloride ion (conj. acid pKa -2) is a much better leaving group than fluoride ion (conj. acid pKa 3). The
arguments can be complicated and depend somewhat on the solvent, so we'll leave it at that.

Br Br

Both are primary and unbranched, so sterics isn't really a factor. The positive charge on the carbon in
the transition state can be stabilized by conjugation with the pi bond of the alkene. The idea is more
complicated than but similar to why the allyl substrate is better for an SN1 reaction. In that case we can
draw direct resonance.
b. Which is a stronger acid (3 different sets)?

O O

OH OH
F

The fluorine atom is highly electronegative and inductively withdraws electrons. That withdrawal helps
stabilize the oxyanion of the conjugate base. For the other acid, if anything the methyl group is
inductively donating.

O We can let the picture do the talking. Both conjugate bases

are oxygen anions. One is stabilized by resonance, and the
OH OH other is not. The more stable conjugate base correlates with
the stronger acid.

O
O
O

O no resonance

OH NH2

pKa 16 pKa 40

When we look at the conjugate bases, we see an oxygen anion vs. a nitrogen anion. They are in the
same row of the periodic table, so we can use the periodic trend that for elements in the same row, the
charge is much better stabilized on the more electronegative atom, which is oxygen. Because oxygen
and nitrogen are in the same row of the periodic table, size isn't a factor.
c. Which is a better nucleophile (3 different sets)?
Chem 31 Answers pg 60
 N NH2
H

The basicities of the two amines should be about the same, so that isn't the deciding factor. The sterics,
however, differ greatly. The extra alkyl group on the secondary amine can get in the way for the
nitrogen lone pair to be donated as a nucleophile. As a result, the primary amine is the better
nucleophile.

OH NH2

Because oxygen and nitrogen are in the same row of the periodic table, we can use electronegativity as
the judge of which atom is more willing to donate electrons. Oxygen is more electronegative than
nitrogen, which means that it holds on to its lone pairs more tightly. If you hold on tighter, you're less
willing to give them up, which is what you need to do to be a good nucleophile. The amine is therefore
the better nucleophile.

CF3
N N
H H
Sterics are roughly the same, and they're both amines. Here we return to a difference based on
inductive effects. The highly electronegative fluorine atoms withdraw some of the electron density of the
nitrogen lone pair. In a sense that makes it less negative and certainly less available for donation as a
nucleophile. The non-fluorinated amine should be better.

107. Give the expected major products for the following reactions, and when possible indicate the type
of mechanism by which the reaction proceeds.
a.
OH Br
HBr protonation
then SN1

b.
CN OSO2CH3 CN Br
Br
SN2

c.
Br
OH
E2

d.
OH
H2SO4
E1

H
e.

Chem 31 Answers pg 61
 OSO2Ph
O
E2
Z only

f.

Br O
OH
SN1
Br Br
g.
OSO2Ph CN
CN
SN2

h.

Br
HBr

Cl Cl
i.

OH
Cl OH SN2

j.

Cl O O
SN2
Cl Cl
may be slow, but no elimination is possible
k.
Cl SH

SH
SN2

l.
Br

HBr

the cation intermediate for this product also has resonance

m.

Chem 31 Answers pg 62
 PPh3
I PPh3 SN2

n.
O O
NH2
OH O
o.

OH HBr Br protonation
then SN1
p.

N3
SN2
Br N3
q.
O

OH O OH SN2
OSO2Ph O

O
108. Evaluate the sets of compounds according to the given criterion and explain your reasoning.
a. Which substrate reacts faster in SN1 reactions?

Cl

Cl
in the top case, the cation intermediate has resonance, but it the second case it doesn't (both are 2°).
Expect the more stable cation to be formed faster, which means a faster SN1 reaction.
b. Which is a stronger acid (2 different sets)?

H
NH2 NH NH
etc.

NH2 NH

better conjugate base is the one stabilized by resonance. more stable conjugate base correlates with
the stronger acid.

Chem 31 Answers pg 63
 SH S

OH O

O and S are in the same column of the periodic table. Therefore, the charge is better stabilized on the
larger atom, so the thiol will be more acidic.
109. Name the following compounds using IUPAC nomenclature. Don't forget to include stereochemical
designations where appropriate.
a.
Cl

(3E,6S)-6-chloro-4-methyl-3-octene
b.

Br
5-bromo-2,4-dimethyl-1,6-heptadiene
110. Name the following compounds using IUPAC nomenclature. Don't forget to include stereochemical
designations where appropriate. (e.g. E, Z, cis, trans)
a.

(Z)-4-ethyl-3-heptene
b.

(Z)-4-isopropyl-1-methyl-1-cyclooctene
c.

(Z)-3-methyl-1,3-hexadiene

Chem 31 Answers pg 64
111. Draw the skeletal structures corresponding to the following names. Make sure to clearly indicate
stereochemistry.
a. (Z)-4-methyl-1,4-octadiene

b. (E)-5-methyl-1,4-heptadiene

112. Using mechanistic arrows, draw a detailed mechanism for the following reactions.
a.

Br
H Br Br

b.
H
OH O H Br
H Br - H2O Br

c.
H H
OH O
H - H2O -H

H H
H
113. Consider the following rearrangement reaction. Although we have not studied rearrangements,
use what you know about HBr addition to alkenes to understand this reaction and answer the following
questions.
CH2
H H3C CH3
CH3
H3C H (catalyst) H3C CH3
CH3
a. Draw a reasonable mechanism that accounts for the observed product. Show all steps and
intermediates. Hint: H+ is not consumed in the overall reaction.

Chem 31 Answers pg 65
 H
CH2
H H3C CH3
CH3
H3C H (catalyst) H3C CH3
CH3

+H -H
H3C CH3

H
H3C
CH3
b. Draw a reaction coordinate diagram for the reaction. Label the transition state(s), intermediate(s), the
energy of activation(s), and the energy of reaction.

TS1 TS2

ΔG2

H3C CH3
ΔG ΔG1
H
H3C
CH3

CH2 ΔGrxn
CH3 H3C CH3
H3C H
CH3 H3C CH3

Progress of Reaction

Chem 31 Answers pg 66
c. Draw the structure(s) of the transition state(s) using the standard conventions.
H δ+
H3C δ+ CH3
H2C CH3
H
H3C δ+
δ+ H CH3
H3C
CH3

transition state #1 transition state #2

114. Consider the following reaction.
H Cl

HCl

a. Draw a reasonable mechanism that accounts for the observed product. Show all steps and
intermediates.

H Cl
H H H
H
+H
=

+Cl

Cl

b. Draw a reaction coordinate diagram for the reaction. Label the transition state(s), intermediate(s), the
energy of activation(s), and the energy of reaction.

TS1 TS2
TS3
ΔG2
ΔG1
ΔG3
ΔG H H

H ΔGrxn

Cl

Progress of Reaction

Chem 31 Answers pg 67
c. Draw the structure(s) of the transition state(s) using the standard conventions.
δ-
δ+ Cl
H
δ+ δ+
H H
δ+ δ+

transition state #1 transition state #2 transition state #3

115. Provide a synthetic sequence to go from the given starting material to the desired product. Show
all reagents and synthetic (not reaction) intermediates. All these syntheses can be accomplished in two
steps.
a.
OH N3
?

CH3SO2Cl, NEt3
OSO2CH3 N3

b.

?
Br
Br

HBr
O

c.

?
OH O

HBr
OH

Br

Chem 31 Answers pg 68
116. Supply the missing reagent or product. If more than one product can formed, give all possible
products, and indicate which would be the major product. Be sure to indicate the stereochemistry and
regiochemistry of the products where appropriate.
a.
NaOCH3
+
Br or any other strong base

major -- favored because

double bond is in conjugation
with the benzene ring; think
about resonance stabilization
b.
OH
H2O
analogous to HBr addition
H2SO4

c. Although we have not covered reactions of alkynes yet, use what you know about HBr addition to
predict the product. What is the sterochemistry of the double bond in the product? Assume one mole of
HBr adding to one mole of the alkyne.
Br
HBr
C C trans product
H

117. Supply the missing reagent, reactant, or product. If more than one product can formed, give all
possible products, and indicate which would be the major product. Be sure to indicate the
stereochemistry and regiochemistry of the products where appropriate. The last three are particularly
challenging.
a.

1. BH3-THF H
OH
2. NaOH, H2O2 syn addition of H, OH

b.
Br
NaOCH3

c.

H2, Pd/C

O O
note: these conditions only reduce ordinary alkenes -- not carbonyls or benzene rings
d.

Chem 31 Answers pg 69
 1. Hg(OAc)2, H2O OH

2. NaBH4

e.
1. O3 H O

2. Zn, HOAc O H
f.

H2O
CH3 CH3
H2SO4
OH
carbocation intermediate at more substituted carbon, so OH ends up there
g.
OH
Br2, H2O

Br
anti addition (but product is racemic mixture)
h.
1. BH3-THF OH

2. NaOH, H2O2
note that 1-butene would give 1-butanol, not 2-butanol as given
i.
Br
Br2

Br
anti addition (but product is racemic mixture)
j.
H2, Pd/C

H2 gas always in excess, so both π bonds will react

k.
1. OsO4 (excess) HO OH HO OH
+
2. NaHSO3
HO OH HO OH

major product
syn addition for each diol; second addition more likely from opposite side
l.

Chem 31 Answers pg 70
 O O
1. O3
H
+ H
2. Zn, HOAc
O O

ozone always in excess; 2 moles of each product are formed

m.
H3C CH3 H3C CH3
H3C CH3 1. BH3-THF H3C CH3
CH3 CH3
2. NaOH, H2O2
H

OH
borane addition from less sterically-hindered side of alkene
118. Give the missing products, reactants, or reagents for the following reactions.
a.
1) OsO4 OH
2) NaHSO3
OH
b.
OH
1) BH3, THF

2) HOOH, -OH

c.
H2, PtO2

d.
1) O3 O O

2) Zn, H3O+ H H
e.
Br
Br2, CCl4
Br

Chem 31 Answers pg 71
f.
Cl
HCl
+

Cl
g.
Br
OH
Br2, H2O

h.

OH
1) Hg(OAc)2, H2O

2) NaBH4

i.

H2, Pd/C

j.
Cl
Cl2, CCl4

Cl
k.
Br2, H2O
OH

Br
l.

1) BH3, THF
OH
2) HOOH, -OH

m.

H2, Pd/C

n.

mCPBA
O + O

o.

Chem 31 Answers pg 72
 1) O3 O O

2) Zn, H3O+ H

p.

Cl
Cl2, CCl4

Cl
119. Using mechanistic arrows, draw a detailed mechanism for the following reactions.
a.
I
I
I N3 N3
N3

b.

loss of
OH H OH2 H
H+

loss of H hydride
protonation
H2O shift

120. Draw a reasonable mechanism to explain the outcome of the following reaction. Be sure that your
mechanism explains the observed stereochemistry.
OH O
H2SO4

+H -H

OH O

H
H

Chem 31 Answers pg 73
121. Draw a reasonable mechanism to explain the outcome of the following reaction. Be sure that your
mechanism explains the observed stereochemistry.
Br
Br2
O
O

OH O
H
Br
Br

Br
O
O
Br OH
O
H H

122. Given the results from the oxymercuration reaction below, predict the products from treating the
same alkene with Br2 and H2O. Draw a mechanism that explains the regiochemistry and
stereochemistry of the product.
H3C CH3 H3C CH3
1. Hg(OAc)2, H2O
OH
CH3 2. NaBH4
CH3
H3C CH3
H3C CH3 H3C CH3
Br2 , H2O OH
CH3
CH3
CH3
Br
Br

bromine must add to bottom face, so water must add from the top
123. Give the stereochemical relationship of the products formed (i.e. enantiomers, diastereomers, etc)
in the reactions below. Recall that the method we use is to look at the products from both top and
bottom face attacks and then to determine the stereochemical relationship between them.
a.
H H 1. OsO4, pyridine HO OH HO OH
+
H3C CH3 2. NaHSO3 H3C CH3 H3C CH3
the two products are the same -- so product is single, achiral, meso compound
b.

Chem 31 Answers pg 74
 H CH3 1. OsO4, pyridine HO CH3 HO CH3
+
H3C H 2. NaHSO3 H3C OH H3C OH
(R, R) (S, S)
The two products are enantiomers; overall we get a racemic mixture
124. Provide a synthetic sequence to go from the given starting material to the desired product. Show
all reagents and synthetic (not reaction) intermediates. All these syntheses can be accomplished in two
or three steps.
a.

? OH
Br

OH

KOtBu 1) OsO4
2) NaHSO3

b.

? H
Br
O

KOtBu 1) O3
2) Zn, H+

c.

?
Br
Br

KOtBu HBr

d.

?
OH
OH

1) Hg(OAc)2,
CH3SO2Cl, NEt3 H2O, THF
2) NaBH4

KOtBu
OSO2CH3
e.

Chem 31 Answers pg 75
 ?
OH

OH

H2SO4
1) BH3, THF
2) HOOH, -OH

f.
Cl ?

KOtBu H2, Pd/C

g.

? SCH3

HBr
NaSCH3

Br

h.

? O O
I
H H

KOtBu 1) O3
2) Zn, H+

Chem 31 Answers pg 76
125. Propose syntheses to accomplish the following transformations. Each transformation can be done
in two or three steps.
a.
Br ? OH

1) Hg(OAc)2,
KOtBu 1) BH3, THF
or H2O, THF
2) HOOH, -OH
2) NaBH4

b.
Br
Br ?
OH

KOtBu Br2, H2O

c.
OH
?
+
OH OH

1) Hg(OAc)2,
CH3SO2Cl,
H2O, THF or 1) BH3, THF
NEt3 2) HOOH, -OH
2) NaBH4

KOtBu

O SO2CH3

Chem 31 Answers pg 77
126. Treatment of compound A (C6H14O) with H2SO4 gave two alkene products, with B as the major
product. Catalytic hydrogenation of B gave 2-methyl-pentane as the only product. Hydroboration (1.
BH3-THF; 2. H2O2, NaOH) of B gave a single compound, alcohol C. Ozonolysis of B gave a ketone and
an aldehyde (no formaldehyde): compounds D and E. Show the structures of all the compounds: A, B,
C, D, and E.

H2SO4 H2, Pd/C

A B C
Alcohol
Alcohol Alkene Alkane
Dehydration

OH 1.BH3-THF
2. H2O2, NaOH
1. O3
2. Zn, HOAc
Alcohol C

Alkene B
must be O O
+ OH
R R R H

E D

O O
D and E must be:
H

127. Draw the skeletal structure corresponding to each of the following names. Make sure that
stereochemistry is clearly indicated.
a. 2-methyl-3-hexyne

b. (Z)-2-butene

c. 5-methyl-2-heptyne

128. Name the following molecules. Make sure to include E/Z designations as appropriate.
a.

1-hexyne
b.

(E)-2-hexene

Chem 31 Answers pg 78
129. Give the missing products, reactants, or reagents for the following reactions.
a.
H2, Pd/C

b.
CN OSO2CH3 CN Br
Br
SN2

c.
1 eq. Br2, CCl4 Br

Br
d.
1) O3 O O

2) Zn, H3O+ H H
e.
2 eq. HBr Br Br

f.
Cl HC CNa

g.
1) NaNH2

2) Br
h.
OH
1) Hg(OAc)2, H2O

2) NaBH4

i.
OSO2Ph CN
CN
SN2

j.

Br
HBr

Cl Cl

Chem 31 Answers pg 79
k.

OH
Cl OH SN2

l.
1) BH3, THF O

2) HOOH, -OH
m.

PPh3
I PPh3 SN2

n.
Na, NH3

o.
O
HgSO4, H2SO4, H2O

p.

N3
SN2
Br N3
q.
O

O OH SN2
OH
O
OSO2Ph

O
130. Give the missing reagent(s), reactant(s), or product(s) for the following reactions. If more than one
product would be formed, provide all expected products, and when possible indicate which would be
the major product. Be sure to indicate the stereochemistry and regiochemistry of the products as
appropriate.
a. Review: bromohydrin formation, -OH goes to more highly substituted side just like in oxymercuration

Br2, H2O OH

Br
o
b. Review: E2 with 2 halide -- many other strong bases also work here
Br
KOtBu

Chem 31 Answers pg 80
c.

1) BH3, THF H
OH
2) HOOH, -OH

d.
Br Br
2 eq. HBr

e. Trans addition of Br's

Br
1 eq. Br2

Br
f. Trans addition of H and Br -- cation intermediate
Br
1 eq. HBr

H
g. Via enol intermediate
O
HgSO4, H2SO4

H2O

h. Starting material must be internal alkyne, else hydroboration/oxidation would lead to the aldehyde
1) BH3, THF O

2) HOOH, NaOH
i. All ordinary π bonds reduce with Pd/C. (Note that π bond in benzene rings are not reduced.)
H2, Pd/C

j. The π bonds of benzene rings and ordinary ketones are not reduced.

O H2, Pd/C O

k. Step 1 is deprotonation to form the alkyne anion; Step 2 is an SN2 reaction.

1) CH3Li (or NaNH2)
C CH C C
2)
Br

Chem 31 Answers pg 81
131. Give the missing reagent(s), reactant(s), or product(s) for the following reactions. For
stereoselective reactions, indicate the relative stereochemistry of the products.
a.

1) BH3, THF H

2) HOOH, NaOH O

b.
O
1) excess O3 O
+ H + CO2
OH
2) Zn, HOAc H
O
c.
Li, NH3

d.
O
O O
1) excess O3
H + + CO2
2) Zn, HOAc H3C OH

e.

HO NaC≡CH O
Br Br + HC≡CH

f.
Br NaC≡CH
+ HC≡CH

g.
1) BH3, THF O

2) HOOH, NaOH H OH
h.
Lindlar catalyst
(Pd/CaCO3, quinoline)

H2 gas

Chem 31 Answers pg 82
i.

after 1)
Br
1) Br2 HgSO4 O

2) KOtBu H2SO4, H2O

Br

j.
1) NaNH2
C CH
C C
2) Br

132. Supply the missing reagents, products, or starting materials for each of the reactions shown
below. Make sure to indicate stereochemistry and regiochemistry when appropriate.
a.
OH
Br2, H2O

Br
b.
O
HgSO4, H2O
+ 1:1
H2SO4
O
c.
1) O3 H O

2) Zn, H3O+ O OH
d. Step 1 also possible with H2, Lindlar.

1) Li, NH3
Br
2) Br2
Br
e.
1) NaNH2 Li, NH3

2)
I
f.
HBr Br Br

g.

Chem 31 Answers pg 83
 H2, Pd/C

h.

H2, Lindlar catalyst

133. Provide a synthetic sequence to go from the given starting material to the desired product. Show
all reagents and synthetic (not reaction) intermediates. All these syntheses can be accomplished in two
or three steps.
a.
Br
Br ?
Br

KOtBu
1 eq. Br2

b.

? H
Br
O

HC CNa 1) O3
2) Zn, H3O+

Na, NH3

c.

? H
Br
O

HC CNa 1) BHR2
2) H2O2, NaOH

Chem 31 Answers pg 84
d.
Br
?
Br

Li, NH3
Br2

e.

?
OH

CH3SO2Cl, NEt3

OSO2CH3
f.

?
HC CH

1) NaNH2
1) NaNH2
2) CH3I 2)
Br

g.

?
Br
OH

NaOtBu 1) Hg(OAc)2, H2O

2) NaBH4

Chem 31 Answers pg 85
h.

Br2 Br
NaOtBu

Br
i.

? Br H Br
H

Li, NH3 Br2

j.

? O
Br

NaC CH HgSO4, H2SO4, H2O

k.

? H
Br
O

NaOtBu 1) O3
2) Zn, H3O+

134. Synthesize the following compounds from acetylene (HC≡CH) and any primary (1°) alkyl halide(s)
(RCH2X, where X = Cl, Br, or I) you would like to use.
a. Note for all of these: NaNH2 is given as the base, but CH3Li and BuLi are equally good.
1) NaNH2 O
1) BH3, THF
HC CH
2) H
Br 2) HOOH, -OH

Chem 31 Answers pg 86
b.
1) NaNH2 Na, NH3
HC CH
2)
Br 1) Hg(OAc)2, H2O
2) NaBH4

OH
c.
1) NaNH2 1) NaNH2 H2/ Lindlar
HC CH
2) 2)
Br Br Cl2
Cl

Cl
d.
1) NaNH2 Na, NH3 Br2, H2O
HC CH Br
2)
Br OH

e.
1) NaNH2 1) NaNH2 Li, NH3
HC CH
2) 2)
Br Br
f.
1) NaNH2
HgSO4, H2SO4, H2O
HC CH
2) O
Br
g.
1) NaNH2
Na, NH3
HC CH
2)
Br 1) BH3, THF
2) HOOH, -OH

HO

Chem 31 Answers pg 87
135. Synthesize the following molecules using acetylene and any alkyl halide(s).
a. Note for all of these: NaNH2 is given as the base, but CH3Li and BuLi are equally good.
OH

1) Hg(OAc)2,
1) NaNH2 H2 OH
H2O
HC CH
2) Lindlar 2) NaBH4
Br
b.
O

OH

O
1) NaNH2 O3
HC CH
2) OH
Br
c.

Can't make this one;

explain why!
O

1) NaNH2 1) NaNH2 HgSO4

HC CH
2) CH3I 2) H2SO4
O
Br H2O

d.

1) NaNH2 1) NaNH2 H2
HC CH
2) 2) Lindlar
Br Br

Chem 31 Answers pg 88
e.

1) NaNH2 1) BH3, THF O

HC CH
2) 2) H2O2, NaOH H
Br

136. Compound A (C4H6) absorbs two molar equivalents of H2 gas on catalytic hydrogenation with
palladium on carbon. Upon reaction with H2SO4 and H2O, a ketone is formed. Give the two possible
structures for compound A.
"Compound A (C4H6) absorbs two molar equivalents of H2 gas" means there are two π bonds in A.
"Upon reaction with H2SO4 and H2O, a ketone is formed." Alkynes hydrate to form ketones!
or

137. Compound B has the molecular formula C4H6O. When treated with H2 and a palladium catalyst, B
absorbs one equivalent of H2. Compound B also has a strong IR peak at 1715 cm-1. Draw a possible
structure for B that is consistent with this information.
Compound has one C-C π bond (absorbs one equivalent of H2) and a carbonyl (IR peak at 1715). A
possible structure is:
O

138. Draw a resonable mechanism to explain the reaction below. Show all steps and intermediates.
H

1 eq. Br2 O O
-H
Br
H2O
Br

Br

Br +H

H H
H H
H O
O O -H H

H
Br Br

Br

Chem 31 Answers pg 89