Chemistry 31-Summer 2017

Organic Chemistry I

Problems Packet

Dr. Brian McNelis

Chemistry Department
Santa Clara University
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.
a. CH3CH2CH2CH(CH3)2
b. CH3CH2CHBrCH2C(CH3)3
c.
H3C O

H3C CH2 CH C OH
d.
CH2
CH2 CH

CH2 CH
C

CH2

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 C S N N N
S

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: _______ C2: _______ C3 _______ O4 _______

Chem 31 Problems pg 2
b. What is the geometry at each of these atoms? (Ignore distortions.)

C1: _______ C2: _______ C3 _______ O4 _______

c. Fill in all nonbonding electrons and H's on the structure below. (Assume neutral charge.)

OCH3 O OCH3

O
H3CO O

Cl H3C

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.

b a
a O
OH
b Prostaglandin E2
O
b
HO OH

a
a

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.

Chem 31 Problems pg 3
b. Given what you know about the effects of electronegative atoms, which compound is more stable?
Briefly explain why.

6. Consider acetylene anion, shown below.

H C C

a. Give the hybridization of all carbon atoms.

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

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

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

O O
Cl Cl
O HO OH

O O NH2 O

O O

Chem 31 Problems 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.

OH
O
O

Br

O O NH2
OH
OCH3 H
N
O
H

O O N
N
C O

OH

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.

OH

O O O

meperidine norethindrone

Chem 31 Problems pg 5
11. Convert the following skeletal structures to Lewis structures. Make sure to include all atoms and
lone pairs.
O

O
O Cl H2N

12. Convert the following Lewis structures to skeletal structures.

H O
H
O H H C C H
HH O H H C C O
H H
C C C C C C
H C C C C N H H C O
H H H H
H C C H H H C
H N
H H C O
H H
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.
O

Cl

N OH

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.
a
a
O
OH

O Prostaglandin E2

HO c
OH
b
b
c

Chem 31 Problems pg 6
 c
O
N c
O
Novocain
b NH2
a
b a

Cholesterol

HO b

c a
a

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

17. Calculate the degree of unsaturation, and draw three constitutional isomers for the molecular
formula C6H10.
18. Calculate the degree of unsaturation, and draw three constitutional isomers for the molecular
formula C6H8.
19. Calculate the degrees of unsaturation and draw two reasonable structures for each of the following
molecular formulas.
a. C6H6
b. C3H4

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.

Chem 31 Problems pg 7
21. For the compounds below, determine which are isomers of each other. What kind of isomers are
they?

22. Label the functional groups in the molecules below.

NH2 NH2
Br CH3
H
O
H3C Br O
OH

O
O O OH O
HO OCH3 O O

O
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.
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.
a.

OH

b.

c.
O

H2N
d.

e.

N
H

f.

OH

Chem 31 Problems pg 8
g.

O O

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.

Chem 31 Problems pg 9
b.

c.

26. Draw and name a constitutional isomer of methylcyclohexane.

Chem 31 Problems pg 10
27. Name the following compounds using IUPAC nomenclature.
a.

b.

c.

Cl

28. Name the following compounds using IUPAC nomenclature.

a.

b.

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

b. 5-(1-methylpropyl)octane

Chem 31 Problems pg 11
30. Name the following compounds using IUPAC nomenclature. Be sure to include stereochemistry
when appropriate (i.e. cis, trans)
a.

H
H

b.

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
c. 3-(1-methylcyclopropyl)-4-propylheptane
d. cis-2-ethyl-1,1,3-trimethylcyclopentane

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

a. 3-ethyl-5-methyloctane
b. 1-bromo-3-isopropylcyclohexane

33. Rank the following compounds from lowest boiling point to highest boiling point. Justify your
answers with brief explanations.
butane; 2-methylpropane; pentane; propane

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.

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 Problems pg 12
36. Consider the molecule 2,3-dimethylbutane:
H3C CH3

H3C CH3
a. Draw the eclipsed Newman projections for the conformations of this molecule.
b. Draw the staggered Newman projections for the conformations of this molecule.
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?

Steric interactions Eclipsing (0o) Staggered (60o)

H-H 1.0 0
CH3-H 1.4 0
CH3-CH3 2.5 0.9
Energies in kcal/mol
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
each pair of counterparts, indicate which you expect to be higher in energy, and briefly explain your
reasoning.
38. Consider the all cis isomer of 1,3,5-tribromo-2,4,6-trimethylcyclohexane.
a. Draw the molecule as a skeletal structure.
b. Draw a sawhorse representation of each of the two possible chair forms.
c. Which chair conformation do you expect to be more stable? Briefly explain why.

39. Consider the all cis isomer of 1-tert-butyl-2,4,6-trimethylcyclohexane.

a. Draw the molecule as a skeletal structure.
b. Draw a sawhorse representation of each of the two possible chair forms.
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?
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.

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

Chem 31 Problems pg 13
41. For the following molecule, perform a complete conformational analysis using the data provided in
tables in the course packet. 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.

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

43. For each set, identify which compounds are isomers, and indicate what type of isomers they are.
a.

b.
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

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.
13
formula C NMR peaks
C 3H 6 1
C6H10 3
C4H10O 3
C5H9Br 3
C 6H 8 6
C 6H 8 4

Chem 31 Problems pg 14
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?
CH3 CH3 CH3

CH3 CH3
H3C H3C
H3C
CH3

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

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

Br

Br

Chem 31 Problems pg 15
49. For the following pairs of cyclohexane chair conformations, circle the conformer that you expect to
be more stable. Briefly explain your reasoning.
a.

b.
CN

H3C
CH3 CN

CH3 CH3
c.

H3C CH3

CH3 CH3
CH3
CH3

50. Identify the more stable conformation in each of the following pairs, and briefly explain your
reasoning.
a.

b.
CH3
H CH3

H H
H H H

H H

Chem 31 Problems pg 16
c.
CH3

CH3
CH3
CH3

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

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.

O
O 1
1 O
O

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.
d. Is there anything unusual about your findings above that may go against conventional wisdom in
such conformational analyses? Explain briefly.

Chem 31 Problems pg 17
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
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.
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

Br Br

HO

OH

Chem 31 Problems pg 18
56. Identify the following pairs of compounds as enantiomers, diastereomers, constitutional isomers, or
the same.
a.
Br Br Br
Br

b.
HO

OH

57. Identify the stereocenters in the following molecules, and indicate whether they are R or S.
H NH2
OH
Cl
HO OH

H O

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.
Br O

OH
CH3 OH NH2

CH3 OH HO OH

CH3

59. Circle those molecules below that are chiral.

Cl OH

Cl

HO O Cl Cl CH3
Cl
CH3

Chem 31 Problems pg 19
60. Name the compound below. Be sure to include R,S designations.
CH3

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

Br Br

b.
NH2 NH2

NH2 NH2
c.
OH

HO
d.
OH OH OH OH

Br Br
e.
CH3 CH3

CH3 H3C
f.

OH OH OH OH

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

b. Draw all possible resonance forms, showing formal charges.
c. What experimental method could you use to determine which resonance form is the most
important? How would it help?

Chem 31 Problems pg 20
63. Do you expect AlBr3 to be a weaker or stronger Lewis acid than AlCl3? Explain.
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
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.

O H O
O
N
OH N
O

N H O H O
N N
O
H O

S N SH
O N
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

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.

Chem 31 Problems pg 21
 CH3 O H O
N N
O
NH3

CH3
+2 H3C CH3 N
S O
N N N
O CH3

O
N N
Cl N
O N

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 O O

more stable more stable

68. For the following reactions, predict on which side the equilibrium should lie. Give a brief explanation
for your reasoning.

O OH OH O
+ +

NH2 + + PH2
PH3 NH3

+ +

Chem 31 Problems pg 22
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.

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

O O

more stable more stable

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 conbributor

O O
acetone

major conbributor

2-methylpropene

"only" contributor Why don't we draw

this resonance form?

Chem 31 Problems pg 23
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 O

H3C CH3 H3C CH3

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 O

pKa = 16 pKa = 5.1

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?
b. Which of the above acids are strong enough to react with NaOH (pKa of H2O = 15.7)?
c. Which conjugate base of any of the acids above could deprotonate acetic acid (pKa = 4.8)?
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.

76. Draw the conjugate bases for the following acids.

Acid pKa Conjugate Base
O
H3C 4.8
OH

H C C H 25

H2O 15.7

NH4 9.2

H-F 3.2

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
Chem 31 Problems pg 24
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:

b. Draw out the acid-base reaction using one of the bases you chose. Use mechanistic arrows to show
the flow of electrons.
c. Draw the subsequent mechanism for the substitution reaction using mechanistic arrows. Identify the
molecules as nucleophiles and electrophiles.

77. a. Show the products of the following acid/base reaction and indicate whether it would occur. In
addition, try to draw the mechanism of the acid-base reaction using the curved arrow notation. Show
the "deprotonation" by the base taking an H+ from the acid using a pair of electrons.
pKa: Protonated form of trimethylamine = 9.8; Formic Acid = 3.7
O
N +
H3C CH3 H OH
CH3

trimethylamine formic acid

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

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.
c. Why do you think toluene is so much more acidic?

Chem 31 Problems pg 25
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.
OH OH
O O O
H
H
H H H

pKa = 10 pKa = 20 pKa = 10 pKa = 16

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.

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

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.
b. Do you expect the equilibrium to lie towards the right or the left?
c. Draw an energy diagram consistent with your mechanism and prediction of the equilibrium.

Chem 31 Problems pg 26
82. For the following pairs, determine which compound is more stable, and briefly explain why.

O O

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

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

c.
O

O Na O
+ NaBr
Br O

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

Br

Chem 31 Problems pg 27
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

b.
I
I
CH3 HI CH3 CH3
+

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

b.

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

Br + SH +
SH Br

Br + + H2O
OH

87. Based on the mechanistic arrows and the starting materials shown, show the expected products for
the following transformations.

Br

Chem 31 Problems pg 28
 O

CN

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

a.
HBr

b.
HBr

c.

excess HBr

89. Determine the products of the following reactions.

a.

HBr

b.

HBr

c.

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?
a.
NaOCH3
Br

b.

Chem 31 Problems pg 29
 Br KNH2

c.

Li C CH
Br

d.
Br
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.
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.
c. Draw the structure(s) of the transition state(s) using the standard conventions.
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?

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

b.
PPh3

OSO2CH3
c.

NH2
Cl
Chem 31 Problems pg 30
d.

SH
OSO2Ph
OH
e.
O
Br
O

Br
f.

Cl CN

Cl
g.
CN F
Br

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

O
Cl

b.
Br
OH

H
c.
Br
OH

H
d.
OSO2Ph
NH2

Chem 31 Problems pg 31
e.

Cl CH3

Cl
f.

Br
g.

Br
O

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

b.

Br
c.
CH3

I
CH3

d. CH3I

96. Give the expected products for the following reactions, and when possible indicate the type of
mechanism by which the reaction proceeds.
a.
O
NaCN
Br

b.
OSO2Ph NaOAc

Chem 31 Problems pg 32
c.
H2SO4
OH

d.

Cl CH3ONa

e.
Br NaC≡CH

f.

I
CH3OH

g.
Cl

H2O

h.

NaNH2
OSO2Ph

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

b.

Br (CH3)3CO Na

c.

Cl CH3O Na

Chem 31 Problems pg 33
d.
Br
CH3S Na

e.
NaOH

Br
f.

OH NaCN

g
Br
NaOCH3

h.
NaNH2
Br
i.

O Na CH3Br
H

j.
I O

O Na

(NaOAc)

k.

Br t-BuONa

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

Chem 31 Problems pg 34
b.
Br
NaOCH3

c.
Cl
NaCN
H3C
CH3
d.
OH

HCl

e.
O
Br
H NaO H

CH3
H3C
f.
Cl OH

g.
CH3
H
CH3
KOH
Br

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

Chem 31 Problems pg 35
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.
OSO2Ph
NaN3

b.

NaOH

Cl
c.

HO
HBr

d.
Br
NaOCH3

e.
NaNH2
Br
f.
Br
HOCH3

g.
OH
H2SO4

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

Chem 31 Problems pg 36
b.
H Br
NaOCH3

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
b.
H
CH3 CH3
CH3O Na
Cl
H
H

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

Chem 31 Problems pg 37
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
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
105. Rank the following species in order of their strength as nucleophiles.
O O
S O CH3O CF3CH2O
O O

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)?

F Cl

Br Br

b. Which is a stronger acid (3 different sets)?

O O

OH OH
F

OH OH

OH NH2

Chem 31 Problems pg 38
c. Which is a better nucleophile (3 different sets)?

N NH2
H

OH NH2

CF3
N N
H H

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
HBr

b.
CN OSO2CH3
Br

c.
Br
OH

d.
OH
H2SO4

H
e.

OSO2Ph
O

f.
Br
OH

Br

Chem 31 Problems pg 39
g.
OSO2Ph
CN

h.

HBr

Cl
i.

OH
Cl

j.

Cl O

Cl
k.
Cl

SH

l.
HBr

m.
PPh3
I

n.
O
NH2
OH
o.

OH HBr

Chem 31 Problems pg 40
p.

N3

Br
q.
O

OH O
OSO2Ph

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

b. Which is a stronger acid (2 different sets)?

NH2 NH2

SH OH

109. Name the following compounds using IUPAC nomenclature. Don't forget to include stereochemical
designations where appropriate.
a.
Cl

b.

Br

Chem 31 Problems pg 41
110. Name the following compounds using IUPAC nomenclature. Don't forget to include stereochemical
designations where appropriate. (e.g. E, Z, cis, trans)
a.

b.

c.

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.

HBr

b.

OH HBr

c.
OH
H2SO4

Chem 31 Problems pg 42
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.
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.
c. Draw the structure(s) of the transition state(s) using the standard conventions.

114. Consider the following reaction.

H Cl

HCl

a. Draw a reasonable mechanism that accounts for the observed product. Show all steps and
intermediates.
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.
c. Draw the structure(s) of the transition state(s) using the standard conventions.

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
?

b.

?
Br
Br
c.

?
OH O

Chem 31 Problems pg 43
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.
??
+
Br

b.
H2O

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.

HBr
C C

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

2. NaOH, H2O2

b.
Br
?

c.

H2, Pd/C

O
d.

1. Hg(OAc)2, H2O

2. NaBH4

Chem 31 Problems pg 44
e.
1. O3 H O

2. Zn, HOAc O H

f.

H2O
CH3
H2SO4

g.
OH
?

Br
h.
1. BH3-THF OH

2. NaOH, H2O2

i.
Br2

j.
H2, Pd/C

k.
1. OsO4 (excess)

2. NaHSO3

l.

1. O3

2. Zn, HOAc

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

Chem 31 Problems pg 45
118. Give the missing products, reactants, or reagents for the following reactions.
a.
?
OH

OH
b.
OH
1) BH3, THF

2) HOOH, -OH

c.
H2, PtO2

d.
1) O3 O O

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

f.
HCl

g.
Br2, H2O

h.

1) Hg(OAc)2, H2O

2) NaBH4

i.

H2, Pd/C

j.
Cl2, CCl4

Chem 31 Problems pg 46
k.
?
OH

Br
l.

1) BH3, THF

2) HOOH, -OH

m.

H2, Pd/C

n.

mCPBA

o.

1) O3

2) Zn, H3O+

p.

Cl2, CCl4

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

I N3
N3

b.
OH
H2SO4

Chem 31 Problems pg 47
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

121. Draw a reasonable mechanism to explain the outcome of the following reaction. Be sure that your
mechanism explains the observed stereochemistry.
Br
O Br2
O
OH O
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
Br2 , H2O
??
CH3

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

H3C CH3 2. NaHSO3

b.
H CH3 1. OsO4, pyridine

H3C H 2. NaHSO3

Chem 31 Problems pg 48
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
b.

? H
Br
O
c.

?
Br
Br
d.

?
OH
OH
e.

OH ?

OH
f.
Cl ?

g.

? SCH3

h.

? O O
I
H H

Chem 31 Problems pg 49
125. Propose syntheses to accomplish the following transformations. Each transformation can be done
in two or three steps.
a.
Br ? OH

b.
Br
Br ?
OH
c.
OH
?
+
OH OH

(can't avoid the mixture of these two compounds)

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.
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.

b.

129. Give the missing products, reactants, or reagents for the following reactions.
a.
H2, Pd/C

b.
CN OSO2CH3
Br

Chem 31 Problems pg 50
c.
1 eq. Br2, CCl4

d.
1) O3 O O

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

f.
Cl HC CNa

g.

h.

1) Hg(OAc)2, H2O

2) NaBH4

i.
OSO2Ph
CN

j.

HBr

Cl
k.

OH
Cl

l.
1) BH3, THF O

2) HOOH, -OH

Chem 31 Problems pg 51
m.
PPh3
I

n.
Na, NH3

o.
HgSO4, H2SO4, H2O

p.

N3

Br
q.
O

OH O
OSO2Ph

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.

?
OH

Br
b.
Br
?

c.

1) BH3, THF

2) HOOH, -OH

d.
2 eq. HBr

Chem 31 Problems pg 52
e.
1 eq. Br2

f.
1 eq. HBr

g.

HgSO4, H2SO4

H2O

h.
1) BH3, THF O

2) HOOH, NaOH
i.
H2, Pd/C

j.

O H2, Pd/C

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

2) HOOH, NaOH

b.
1) excess O3

2) Zn, HOAc

Chem 31 Problems pg 53
c.
Li, NH3

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

e.
HO NaC≡CH
Br

f.
Br NaC≡CH

g.
1) BH3, THF O

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

H2 gas

i
O
? ?
?
j.

C CH
C C

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.
Br2, H2O

b.
HgSO4, H2O

H2SO4

Chem 31 Problems pg 54
c.
1) O3 H O

2) Zn, H3O+ O OH
d.

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

2)
I
f.
HBr Br Br

g.

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
b.

?
H
Br
O

Chem 31 Problems pg 55
c.

? H
Br
O
d.
Br
?
Br
e.

?
OH
f.

?
HC CH

g.

?
Br
OH
h.

i.

? Br H Br
H

j.

? O
Br

k.

? H
Br
O

Chem 31 Problems pg 56
134. Synthesize the following compounds from acetylene (HC≡CH) and any primary (1°) alkyl halide(s)
(RCH2X, where X = Cl, Br, or I).
a.
O

H
b.

OH
c.
Cl

Cl
d.

Br
OH
e.

f.

O
g.
HO

135. Synthesize the following molecules using acetylene and any alkyl halide(s).
a.
OH

b.
O

OH
c.

Chem 31 Problems pg 57
d.

e.
O

H
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.
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.
138. Draw a resonable mechanism to explain the reaction below. Show all steps and intermediates.
1 eq. Br2 O

H2O Br

Chem 31 Problems pg 58