OChem2 Course Pack

Practice Problems by Chapter

Practice Exams
 

 
 
Chemistry 3720 
Problem Sets 
Dr. Peter Norris OChem 2

Klein Chapter 13 Problems : Alcohols and Phenols

1. Provide each of the following molecules with an acceptable name. You may use IUPAC or “common” names 
for substituents. Be sure to include any stereochemical descriptors where needed (R/S, cis/trans).  
 

2. Give the (major and minor) product(s) expected to be formed from each step under each of the following 
sets of reaction conditions. Include any stereochemical issues that might be important in each outcome. 
 

3. Provide  detailed  mechanisms  for  each  of  the  following  conversions  that  include  all  important  resonance 
structures for any intermediates that are formed. Include any stereochemical changes that might take place. 
 

4. Rank the following molecules in terms of their increasing acid strength; 1 = weakest acid, 4 = strongest acid. 
Give brief explanations for your choices. 
 

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Dr. Peter Norris OChem 2

Klein Chapter 13 Problems : Alcohols and Phenols - Answers

1. “Provide each of the following molecules with an acceptable name. You may use IUPAC or “common” names 
for substituents. Be sure to include any stereochemical descriptors where needed (R/S, cis/trans).”  
 

2. “Give the (major and minor) product(s) expected to be formed from each step under each of the following 
sets of reaction conditions. Include any stereochemical issues that might be important in each outcome.” 
 

3. “Provide detailed mechanisms for the following conversions that include all important resonance structures 
for any intermediates that are formed. Include any stereochemical changes that might take place.” 
 

 
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Dr. Peter Norris OChem 2

c. OTMS OH
1. MeMgBr, THF
2. H+ quench
O 3. n-Bu4NF, THF Me OH
Me MgBr

:F

TMS
OTMS O
H

Me O Me OH  
 

4. “Rank the following molecules in terms of their increasing acid strength; 1 = weakest acid, 4 = strongest acid. 
Give brief explanations for your choices.” 
 

1 is a simple alcohol in which the conjugate base will have the negative charge localized on O; 2 is an enol so the conjugate
base charge will be stabilized by resonance; 3 is a phenol so the conjugate base is stabilized significantly by delocalization
into the phenyl ring; 4 is a phenol with a strongly electron-withdrawing NO2 group that stabilizes better than CH3 in 3.
 
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Dr. Peter Norris OChem 2

Klein Chapter 14 Problems : Ethers & Epoxides ; Thiols & Sulfides

1. Provide each of the following ethers with an acceptable name. You may use IUPAC or “common” names for 
substituents. Be sure to include any stereochemical descriptors where needed (R/S, cis/trans).  
 

a. b. c. OCH3 d.
O O O
Et Pr OH
Et Pr

2. Give the (major and minor) product(s) expected to be formed from each step under each of the following 
sets of reaction conditions. Include any stereochemical issues that might be important in each outcome. 
 

3. Provide  detailed  mechanisms  for  each  of  the  following  conversions  that  include  all  important  resonance 
structures for any intermediates that are formed. Include any stereochemical changes that might take place. 
 

4. Provide viable, efficient syntheses of the products shown from the starting materials provided in each case. 
You may use any of the chemistry and reagents seen so far in Organic 1 and Organic 2. 
 

 
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Dr. Peter Norris OChem 2

Klein Chapter 14 Problems : Ethers & Epoxides ; Thiols & Sulfides - Key
1. “Provide each of the following ethers with an acceptable name. You may use IUPAC or “common” names for 
substituents. Be sure to include any stereochemical descriptors where needed (R/S, cis/trans).”  
 

a. b. c. OCH3 d.
O O O
Et Pr OH
Et Pr

cyclohexyl 2,2-diethyl-3,3-dipropyloxirane (1R,2R)-2-methoxy- (R)-sec-butoxybenzene

isopropyl or cyclopentan-1-ol
ether 3-ethyl-4-propyl-3,4-epoxyheptane

2. “Give the (major and minor) product(s) expected to be formed from each step under each of the following 
sets of reaction conditions. Include any stereochemical issues that might be important in each outcome.” 

SH 1. SNa 2. S
a. 1. NaOCH3
(+ CH3OH)
2. CH3CH2Br

b. O xs HBr Br

Br

Br Br
c. NaH, THF O
OH O

O 1. O 2. OH
d. 1. NaSCH3, THF
2. H+ quench SCH3 SCH3

3. “Provide detailed mechanisms for the following conversions that include all important resonance structures 
for any intermediates that are formed. Include any stereochemical changes that might take place.” 
 
a. O xs HI
I
I
H I

H I
H H
O O I OH2

I I I
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Dr. Peter Norris OChem 2

b. O HBr Me OH
Me Me
Me H Br Br

H
H
O +
O
Me +
Me
Me Br Me Br

c. 1. NaSH, DMF
Br SCH3
2. NaH, THF
3. CH3Br

SH Br
CH3

S H S

d.
O H NaH
THF
O
Br
H

Br

4. “Provide viable, efficient syntheses of the products shown from the starting materials provided in each case. 
You may use any of the chemistry and reagents seen so far in Organic 1 and Organic 2.” 
 

xs HBr xs NaSCH3
a. Br Br H3CS SCH3
O

O NaN3 OH NaH O CH3Br OCH3

b. Me
H+ w/up Me Me Me
Me Me N3 Me N3 Me N3
 

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Dr. Peter Norris OChem 2

Klein Chapter 15 Problems : IR Spectroscopy & MS Spectrometry

1. In each of the following situations, which one of the molecules matches the  given IR spectrum?  Match as 
many frequencies as you can from the spectroscopy sheet to back up your answers.  
 
a) 
O O O

HO HO

HO HO

HO HO

 
b) 

O OH

NH2
O

c) 
O O

OCH3 Cl

O O

OH H

O CH2

CH3 H

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Dr. Peter Norris OChem 2

2. In each of the following situations, which one of the molecules matches the given mass spectrum? Match as 
many fragments as you can to back up your answers. 
 
a) 
OH
Cl

CH3 Br

Cl I

 
 
 
b) 

O S

Br Cl  

 
 
c) 

Cl I

OH NH2

F Br  

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Dr. Peter Norris OChem 2

3. A pharmaceutical compound has the formula C9H8O4 and the following IR and mass spectral characteristics. 
The  pKa  of  the  most  acidic  proton  on  the  compound  was  found  to  be  ~5.  Calculate  the  degrees  of 
unsaturation present in the molecule and then suggest a structure that agrees with the data given. 
 

 
 
Important IR signals: 3100, 3000, 2850, 1740, 1700, 1620, 1300, 1175, 900, 750 cm‐1.  
  
 

 
Important MS signals: m/z 180, 162, 138, 122, 121, 94, 44. 

 
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Dr. Peter Norris OChem 2

Klein Chapter 15 Problems : IR Spectroscopy & MS Spectrometry - Key

1. In each of the following situations, which one of the molecules matches the  given IR spectrum?  Match as 
many frequencies as you can from the spectroscopy sheet to back up your answers.  
 
a) 
O O O

HO HO

HO HO
3320 = OH; 3000 = C-H; 1680 = C=C;
1480 and 1350 = C-H; 1025 = C-O
O

HO HO

 
b) 

O OH

2920 and 2850 = C-H;

1710 = C=O; 1460 = C-H
NH2
O

c) 
O O

OCH3 Cl

O O

OH H

1710 = C=O; 1200 = C-O

O 700 and 740 = monosub benzene

CH3 CH2

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Dr. Peter Norris OChem 2

2. In each of the following situations, which one of the molecules matches the given mass spectrum? Match as 
many fragments as you can to back up your answers. 
 
a) 
OH
Cl

CH3 Br

Cl I

m/z = 112, 114 (3:1);

77 (C6H5)
 
b) 

 
c) 

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Dr. Peter Norris OChem 2
3. A pharmaceutical compound has the formula C9H8O4 and the following IR and mass spectral characteristics. 
The  pKa  of  the  most  acidic  proton  on  the  compound  was  found  to  be  ~5.  Calculate  the  degrees  of 
unsaturation present in the molecule and then suggest a structure that agrees with the data given. 
 
Degrees of Unsaturation = [#C – (#H/2) – (#X/2) + (#N/2)] + 1 
 
9‐4+1 = 6 cycles or multiple bonds (benzene ring = 4; C=O = 2) 
 
 
 
 
 
O OH

aspirin

 
 
Important IR signals: 3100 (OH), 3000 (C‐H), 2850 (C‐H), 1740 (C=O), 1700 (C=O), 1620 (C=C),  
1300 (C‐O), 1175 (C‐O), 900, 750 (m‐disubstituted) cm‐1.  
  
                          

O OH

aspirin  

Important MS signals: m/z 180 (M+), 162 (M‐OH), 138 (M‐CH3CO), 122 (M‐CH3CO2H),  
121 (M‐CH3CO2), 94 (PhOH), 44 (CH3CO). 
 
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Dr. Peter Norris OChem 2

Klein Chapter 16 Problems : Nuclear Magnetic Resonance Spectroscopy

1. In each of the following situations, which one of the molecules matches the given 1H NMR spectrum? Match 
as many signals as you can from the spectroscopy sheet to back up your answers.  
 
a) 

9 8 7 6 5 4 3 2 1 0
PPM

O H O OH O O  
 
 
b) 

5 4 3 2 1 0
PPM

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Dr. Peter Norris OChem 2

c) 

8 7 6 5 4 3 2 1 0
PPM

d) 

2. How many individual signals do you expect to appear in the 13C spectra of each of the following? 
 

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Dr. Peter Norris OChem 2
 
3. In each of the following situations, which one of the molecules matches the given 13C NMR spectrum? Match 
as many signals as you can from the spectroscopy sheet to back up your answers.  
 
a) 

 
 
 
b) 

 
 
 
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Dr. Peter Norris OChem 2
 
c) 

 
 
 
d) 

 
 
 

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Dr. Peter Norris OChem 2

Klein Chapter 16 Problems : NMR Spectroscopy – Answers

1. In each of the following situations, which one of the molecules matches the given 1H NMR spectrum? Match 
as many signals as you can from the spectroscopy sheet to back up your answers.  
 
a) 

5.25
H
6.72
H
H 5.76
7.45 7.45

7.85 7.85

O 2.50

9 8 7 6 5 4 3 2 1 0
PPM

 
 
 
b) 

O
1.79 4.21
2.33
0.94 O 1.21

1.12

5 4 3 2 1 0
PPM

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Dr. Peter Norris OChem 2

c) 

O
5.14
H 3.31

4.32
7.34
H O

8 7 6 5 4 3 2 1 0
PPM

d) 

2. How many individual signals do you expect to appear in the 13C spectra of each of the following? 
 

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Dr. Peter Norris OChem 2
 
3. In each of the following situations, which one of the molecules matches the given 13C NMR spectrum? Match 
as many signals as you can from the spectroscopy sheet to back up your answers.  
 
a) 

 
 
 
b) 

 
 
 
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Dr. Peter Norris OChem 2
 
c) 

 
 
 
d) 

 
 
 

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Dr. Peter Norris OChem 2

Klein Chapter 17 Problems : Conjugated Pi Systems & Pericyclic Reactions

1. For each of the following reactions, decide which product is major and which is minor and then provide a 
mechanistic  rationale  for  your  choices  that  includes  arrow  pushing  and  discussions  of  any  intermediate 
structure or stereochemical factors necessary.  
 

2. In each of the following instances, provide the major and minor products (where applicable) that you expect 
to be formed under the conditions provided. 
 

 
3. Within each pair of molecules below, which one do you expect to absorb at the longer wavelength in UV‐
Visible spectroscopy? Briefly explain your choices.  
 

 
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Dr. Peter Norris OChem 2

Klein Chapter 17 Problems : Conjugated Pi Systems - Answers

1. For each of the following reactions, decide which product is major and which is minor and then provide a 
mechanistic  rationale  for  your  choices  that  includes  arrow  pushing  and  discussions  of  any  intermediate 
structure or stereochemical factors necessary.  
 
 
H+
a) OH
H2SO4,
+

minor major
(trisubstituted) (tetrasubstituted)

Ha Carbocation can lose

OH2
- H2O H+ from two sites to
give alkenes - more
substituted is more
stable major (Zaitsev)
Hb

Br
b) H H
KOtBu
+

major minor
(Hofmann) (Zaitsev)
Br
Left proton is anti H Right proton is syn
co-planar with Br H co-planar with Br;
leaving group; also also less accessible
more accessible using the large base

Br
c) HBr, 50 oC Br
+

H H
minor major
H Br (disubstituted) (trisubstituted)

Process can equilibrate

at higher temperatures;
the more highly subst'd
alkene becomes major
H H

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Dr. Peter Norris OChem 2

2. In each of the following instances, provide the major and minor products (where applicable) that you expect 
to be formed under the conditions provided. 
 

 
3. Within each pair of molecules below, which one do you expect to absorb at the longer wavelength in UV‐
Visible spectroscopy? Briefly explain your choices.  
 
 

2
Chemistry 3720 Ch. 13-19 Synthesis Problems

These problems are typical of those that will be on the upcoming exams in 3720.

1. From Chapters 13-19: Show retrosynthetic analyses for each of the following molecules that go back
only to the starting materials given below. Then, using any chemistry seen in 3719 and 3720 so far,
give an efficient synthesis of each molecule showing the products formed in each step. Assume that
you have access to any of the usual reagents such as Br2, AlCl3, Fe, HBr, HNO3, H2SO4, etc.

a. OH b. OH c. OH

d. e.
OH OH
O2N

start ing mater ials

O
CH 3Cl
H

O O
Br
Cl

2. From 13 and 14: Give structures of the products from each step within the following “roadmap” and
match the spectral data to the product.

Br2, heat Mg, ether H

Na2Cr 2O 7 H 3O+

H 2SO 4
H2O
(13C 200 ppm) (IR 3300 cm-1)
3. From 13-19: Give structures of the products from each step in the following reaction sequences.

a.
1. Br 2, heat
2. 2 Li, ether
3. CH 3CHO

4. H 3O +
5. HBr

b.
1. CH3COCl, AlCl3
2. LiAlH 4, ether
3. H 3O +
4. NaH, ether
5. CH 3CH 2Br

c.
1. NaBH4, CH3OH
O 2. HBr
3. 2 Li, ether

4. CH 3CH 2CHO
5. H3O+

d.
1. H2SO4, H2O
2. Na 2Cr2O7, H 2SO 4
3. PhMgBr, ether

4. H 3O +
5. NaH, ether
6. CH 3CH2CH 2Br

e.
OH 1. PDC, CH2Cl2
2. CH 3Li, ether
3. H3O+
4. Na2Cr 2O7, H2SO4
5. PhMgBr, ether
6. H 3O +

f.
1. CH 3COCl, AlCl3
2. HNO3, H2SO4
3. NaBH 4, CH 3OH

4. NaH, ether
5. CH3CH 2CH 2Br
4. From 1-19: Design syntheses of the following molecules using any of the chemistry seen so far in
3719 and 3720 and using only the sources of carbon shown below. Again, assume that you have
access to all of the common inorganic reagents (Br2, AlCl3, Fe, HBr, etc.).

a.
O
O
HO
Cl

NH 2

b.

HO OH
OH

c.

O
O
OH
OCH3
CH 3Br

d.

Br H H

e.

OH
CH3 CH 2 OH
Chemistry 3720 ChapterV 16 - Spectroscopy Problems

1. (10 pts) An unknown organic compound has the molecular formula C5H12O, in the mass spectrum, M+
= 88.09. Given the following 1H and 13C data, give the structure of the unknown and assign all of the 1H
and 13C signals.

4 3 2 1 0
PPM

1
H NMR (ppm) 1.14 (t, 3H, J = 7.2 Hz), 1.09 (d, 6H, J = 7.0 Hz), 3.19 (septet, 1H, J = 7.0 Hz),
3.50 (q, 2H, J = 7.2 Hz)

70 60 50 40 30 20 10 0
PPM

13
C NMR (ppm) 15.5, 22.3 (double), 64.8, 71.8

1
2. (10 pts) Draw the approximate 13C NMR spectrum of the following molecule. Include approximate
chemical shifts and indicate which signal corresponds to which carbon(s) in the molecule.

O
O
H3C
O
O
CH 3

3. (10 pts) A chemist produces a new compound with the following spectral characteristics and considers
the new material to be one of the possibilities shown below. Which structure is correct and why?
Include a complete assignment of all of the spectral data in your answer.
1
H NMR (ppm) 1.32 (t, 3H, J = 7.0 Hz), 3.30 (s, 3H,), 4.09 (q, 2H, J = 7.0 Hz), 4.63 (s, 2H), 7.10
(m, 2H), 7.83 (m, 2H)
13
C NMR (ppm) 14.8, 57.2, 64.6, 81.2, 126.1, 129.4 (double), 129.7 (double), 163.8, 198.3

IR (cm-1) 1740, 810

O OCH3 O OCH 3
O

O
OCH 3
O
OH

O OH

O
O O

O
O O O

2
4. (10 pts) Draw the expected 1H and 13C NMR spectra of the following molecules. Include chemical
shifts and line shapes (singlet, doublet, etc.) in the 1H spectra and intensities in the 13C spectra. Also
indicate which signal corresponds to which proton(s) and carbon(s).

a.
O

b.
O

c.
O

d.
O

5. (10 pts) An unknown organic compound has the molecular formula C11H14O2. Given the following
spectral data, provide a structure for the unknown that agrees with the data, and then assign the data.
1
H NMR (ppm) 2.50 (s, 3H), 2.75 (t, 2H, J = 7.2 Hz), 3.30 (s, 3H), 2.52 (t, 2H, J = 7.2 Hz), 7.37-
7.76 (m, 4H)
13
C NMR (ppm) 26.6, 35.3, 59.3, 73.0, 126.0, 127.7, 128.5, 132.1, 1391, 139.2, 197.0

Mass spectrum (m/z) 178.10 (M+)

Infra Red (cm-1) 1730, 760, 690

6. (10 pts) An unknown organic compound has the molecular formula C12H16O2 and, in the mass
spectrum, M+ = 192.12. Given the following 1H and 13C data, give the structure of the unknown and
then assign all of the 1H signals.
1
H NMR (ppm) 1.20 (d, 6H, J = 7.0 Hz), 1.29 (t, 3H, J = 7.1 Hz), 2.87 (septet, 1H, J = 7.0 Hz),
4.30 (q, 2H, J = 7.1 Hz), 7.41 (d, 2H), 7.97 (d, 2H)
13
C NMR (ppm) 14.1, 23.3 (double), 33.2, 60.9, 126.0 (double), 127.3, 129.6 (double), 155.7,
165.9

3
Chemistry 3720 Chapter 19 - Benzene Synthesis Problems

Provide an efficient synthesis of each of the following substituted benzenes from benzene
itself. Use any of the reagents seen in Chemistry 3719/3720 so far and pay careful
attention to the order of steps. Assume that mixtures may be separated.

CH3

O
Br

CO 2H

NH2

SO3H

CO 2H

CH3
SO3H

O OH

O
Chemistry 3720 Chapters 19-23 Synthesis Problems

These problems are typical of those that will be on the next exams in 3720. You should be comfortable
with each reaction in the forward direction, how to think about each reaction in a retrosynthetic manner,
and then be able to complete multi-step syntheses.

1. Give the major organic product(s) from each of the following reaction sequences and then a detailed
mechanism for each reaction. Be careful with any regiochemical issues.

a. b. O
xs CH3OH xs CH3OH

Cl O cat. H + OH cat. H+

O O O
c. HOCH2CH2OH d xs CH 3OH

H OCH 3
cat. H+ cat. H+

Br O O
e. xs EtOH f. xs MeOH
MeO
cat. H+ cat. H+
O

2. Give the major organic product(s) from each step of the following synthetic scheme.

1. CH 3COCl, AlCl3
2. Br2 , Fe
3. HOCH 2CH 2OH, cat. TsOH
4. Mg, ether

5. H2 C=O, ether
6. aq. NH 4 Cl (quench)
7. PCC, CH2 Cl2
8. (CH3 )2 CHLi, THF
9. aq. NH 4 Cl (quench)
10. PDC, CH 2 Cl2
11. PhMgBr, THF
12. aq. NH 4Cl (quench)
13. NaH, ether
14. PhCH 2Br, ether
15. 5% HCl, 3 h, RT
16. NaBH 4, CH 3 OH
17. HBr
18. NaOCH 3 , CH 3 OH
19. m-CPBA, CH 2Cl2
20. PhMgBr, ether
21. aq. NH 4Cl (quench)
3. In the boxes provided, give the products from each step in the following “road-map” scheme.

O
PCC xs. MeOH 2 CH3Li
MeO OH
CH2Cl2 cat. H+ THF

CH3Br NaNH2 H3O+

THF (quench)

5% HCl PhMgBr H 3O+

THF THF (quench)

m-CPBA PCC

CH2Cl2 CH 2Cl2

13C = 175 ppm

4. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.

O
O
a.
OH
Cl
NH 2

N OH
b. HO NH 2

O O
O
c. Ph
O
Chemistry 3720 Chapters 20-22 Synthesis Problems

These problems are from various parts of 3719 and 3720 and deal with the two main synthetic issues
studied; C-C bond formation and manipulation of functional groups.
.

1. Give the major organic product(s) from each of the following aldol reactions as well as a detailed
mechanism for each case. Be careful with any regiochemical issues.

a. O
b.
NaOH
O
KOH
CH3OH, ∆ CH3OH, ∆
O

O O O
KOH NaOH
c. d.
H H
EtOH, reflux CH3OH, ∆

O O O
e. KOH f. NaOH

EtOH, reflux H O CH3OH, ∆

2. Draw all of the possible aldol condensation products formed under the following conditions.

O
O NaOH, H 2O
+
reflux

3. Provide the reagents required to make each of the following compounds via 1,4-addition chemistry.

O
O

4. In the following Robinson annulation, 3 aldol products are possible; draw them and then explain
why only the one shown below is formed. Give a complete mechanism for the reaction including
important resonance structures.

NaOH, H 2O

O O
OH
5. Give the major products from each step of the following reaction sequences.

a. OH b. 1. Na2Cr 2O 7, H2O
1. PCC, CH2Cl2 H2SO4
OH
+
2. m-CPBA, CH2Cl2 2. CH3OH, H

O
c. 1. Ph3P=CH2
d.
1. m-CPBA, CH2Cl2

2. H2, Pd 2. CH3OH, cat. H+

6. Provide complete mechanisms for the following conversions. Include all resonance structures for
any intermediates that may be formed.

O O O O
NaOH

O
O

O O
CH 3OH, H+
OH OCH 3

7. Give structures for each of the products in the following “roadmap.”

PCC NaOH, EtOH Et2CuLi

OH
CH2Cl2 reflux THF

Na2Cr2O 7 aq. NH4Cl

H2SO 4, H2O (quench)

xs CH3OH, H+

2 PhLi aq. NH4Cl

ether (quench)
8. The polyether compound chauncydermolide G (shown below) was recently isolated by Triplet
Pharmaceuticals Inc. and found to have promising antibiotic properties. In order to prove the
structure unequivocally, a total synthesis beginning with the shown starting material was carried out.
Give structures for each of the products in the synthetic sequence.

1. NaH, THF
2. PhCH2 Br
3. PhLi, THF
4. aq. NH4 Cl (quench)
5. PCC, CH 2Cl2
6. xs CH3 OH, cat. H +
7. H 2, Pt
8. PDC, CH 2Cl2
9. (CH 3) 2CHCH 2MgBr, ether
O 10. aq. NH 4Cl (quench)
11. NaH, THF
H 12. CH 3CH2 CH2 Br Br

13. 5% HCl, 3 h, RT OMe

OH 14. Br2 , Fe
15. (CH2 OH)2 , cat. H + O
16. 2 Li, THF
17. H2 C=O chauncy der molide G
18. aq. NH 4 Cl (quench)
19. PCC, CH2 Cl2
20. Ph3P=CH2 , ether
21. m-CPBA, CH 2Cl2
22. (CH3 )2 CHMgBr, ether
23. aq. NH 4 Cl (quench)
24. PCC, CH2 Cl2
25. Br2 , H 2O, THF
26. NaOCH3 , CH3 OH
27. CH 3CH 2CH2 MgBr, ether
28. aq. NH 4 Cl (quench)
29. NaH, THF
30. CH 3Br
31. CH 2I2 , Zn, THF
32. 5% HCl, 3 h, RT
33. LDA, THF, -78 o C
34. CH 3CH 2Br
35. , THF
PPh 3

36. dil. H 2SO 4

37. HBr
Chemistry 3720 Chapters 21-22 Additional Synthesis Problems

1. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.

a.
O H

O O CO 2

b. O O

O HO

O
c.
O

d. O OH
O
CH3OH
OCH3 OH

e. H
N
HO CH3OH
O

2. Give the major organic product(s) from each step of the following synthetic sequence.

1. Na 2Cr2 O7 , H 2SO4
2. xs CH 3OH, cat. H2 SO4
3. NaOCH 3 , CH3 OH
4. aq. NH 4Cl (quench)
OH
5. NaOCH3 , THF
6. CH 3 CH 2Br
7. NaOH, aq. THF
8. dil. HCl (quench)
9. 180 oC (-CO2 )
10. LDA, THF, -78 oC
11. PhCH 2 Br
3. In the boxes provided, give the products from each step in the following “road-map” scheme. Predict
the 1H NMR spectra of each of the organic products from each step.

Br 2 Mg

Fe ether
CO 2

xs CH3OH dil. HCl

cat. H2SO4 (quench)

HNO3
H2SO4

2 x CH 3Li aq. NH4Cl

THF (quench)
NaH
THF

Sn, HCl CH3Br

4. Give complete mechanisms, including any important resonance structures for intermediates where
applicable, that explain the bond-making and bond-breaking events, in each step of the following
conversions.

O O
a. 1. NaOCH 3, CH 3OH
OCH 3
H 3 CO Ph
2. dilute HCl (quench)
O 3. NaOCH 3, THF
4. PhCH 2Br
5. NaOH, aq. THF
6. dilute HCl (quench)
7. 180 o C (-CO 2)
b. O O
1. Na2 Cr 2O 7, H2 SO4
OH
OH
2. xs CH3 OH, cat. HCl
3. NaOCH 3, CH 3OH
4. dilute HCl (quench)
5. NaOH, aq. THF
6. dilute HCl (quench)
Chemistry 3720 Further Synthesis Problems 1

1. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.

a.
OH
HO PPh3

b. OH OH

Br
c.
O
HO
Cl

d. O OH
OH

Ph

e. OH OH
HO

2. Give the major organic product(s) from each step of the following synthetic scheme.

1. PCC, CH2 Cl2

2. NaOH, EtOH, reflux
OH
3. (CH3 )2 CuLi, ether
4. aq. NH 4 Cl (quench)

5. PhMgBr, ether
6. aq. NH 4 Cl (quench)
7. NaNH 2, THF
8. CH 3Br
3. In the boxes provided, give the products from each step in the following “road-map” scheme.

OH
PCC PhMgBr

CH2Cl2 THF
aq. NH4Cl
(quench)

(CH 3)2CuLi PCC

THF CH2Cl2
aq. NH4Cl
(quench)

CH3Br

Br2 NaOCH3

CHCl 3 CH3OH
(CH3)2CuLi
THF

NaBH4 aq. NH4Cl

CH3OH (quench)

4. Give complete mechanisms, including any important resonance structures for intermediates where
applicable, that explain the bond-making and bond-breaking events in the following conversions.

O OH
a. 1. m-CPBA, CH2 Cl2
OH
+ Ph
2. 2 PhMgBr, THF Ph
3. aq. NH4 Cl (quench)

O O
1. HNO3 , H 2SO 4 OH
b.
o
2. LDA, THF, -78 C Ph
3. O
Ph NO 2
4. aq. NH 4 Cl (quench)
 

 
 
Chemistry 3720 
Problem Set Keys 
Chemistry 3720 Chapters 1-19 Synthesis Problems - Key

These problems are typical of those that will be on the upcoming exams in 3720.

1. From Chapters 1-19: Show retrosynthetic analyses for each of the following molecules that go back
only to the starting materials given below. Then, using any chemistry seen in 3719 and 3720 so far,
give an efficient synthesis of each molecule showing the products formed in each step. Assume that
you have access to any of the usual reagents such as Br2, AlCl3, Fe, HBr, HNO3, H2SO4, etc.
a
Retrosynthesis
.
OH OH O
Li
H

Br

Synthesis

Br2, heat Br 2 Li, ether Li

O
H

OH OLi
H 3O+

b
Retrosynthesis

OH OH
O
Li

Br

Synthesis

Br 2, Fe Br 2 Li, ether Li

OH OLi
+
H3O
c.
Retrosynthesis

OH OH O
Li
H

Br

Synthesis

Br 2, Heat Br 2 Li, ether Li

O
H

OH OLi
H 3O +

d.
Retrosynthesis

OH OH O

MgBr

Br O

Synthesis Cl
O OMgBr
CH 3COCl MgBr

AlCl3 ether
H3 O+

Mg OH
Br MgBr
ether
e.
Retrosynthesis

OH OH O
O2 N O2 N O2 N

MgBr

O
O

Cl
Br
Synthesis
O O
CH 3COCl HNO3 O2 N

AlCl3 H 2SO 4

CH 3Cl AlCl3

CH 3
Br2 Br Mg MgBr ether
heat ether

OH BrMgO
O 2N H 3O+ O 2N

2. From 13 and 14: Give structures of the products from each step within the following “roadmap” and
match the spectral data to the product.

Br 2 , heat Br Mg, ether MgBr H

O Na 2Cr2 O7 OH OMgBr
H 3O +

H2 SO4
H 2O

( 13 C 200 ppm) (IR 3300 cm-1)

3. From 13-19: Give structures of the products from each step in the following reaction sequences.

a.
1. Br 2 , heat Br Li LiO HO Br
2. 2 Li, ether
1. 2. 3. 4. 5.
3. CH 3CHO

4. H 3O +
5. HBr

b.
1. CH 3COCl, AlCl3 O O Al OH ONa O
2. LiAlH4 , ether 2. 3.
1. 4. 5.
3. H3 O+ Li+
4. NaH, ether
5. CH 3CH2 Br 4

c.
1. NaBH 4, CH 3OH LiO HO
O 2. HBr OH Br Li
3. 2 Li, ether 1. 2. 3. 4. 5.

4. CH3 CH 2CHO
5. H 3O+

d.

1. H 2SO 4, H2 O
2. Na2 Cr 2 O7, H2 SO4 OH O Ph Ph
OMgBr OH
3. PhMgBr, ether 1. 2. 3. 4.

4. H 3O+
5. NaH, ether
6. CH3 CH 2CH 2Br Ph Ph
ONa O
5. 6.

e.
1. PDC, CH 2Cl2 Ph Ph
OH H O OLi OH O OMgBr OH
2. CH3 Li, ether
1. 2. 3. 4. 5. 6.
3. H 3O +
4. Na 2Cr 2O7 , H 2SO 4
5. PhMgBr, ether
6. H3 O+

f.
1. CH 3COCl, AlCl3
O O OH ONa O
2. HNO3 , H2 SO4
3. NaBH 4, CH 3 OH 1. 2. 3. 4. 5.

4. NaH, ether
5. CH3 CH 2 CH 2Br NO2 NO 2 NO2 NO 2
4. From 1-19: Design syntheses of the following molecules using any of the chemistry seen so far in
3719 and 3720 and using only the sources of carbon shown below. Again, assume that you have
access to all of the common inorganic reagents (Br2, AlCl3, Fe, HBr, etc.).

a.
Design (Retrosynthesis)

O
O
HO
Cl

NH2

Br HO
+ OH
O OH

NH2 NH 2 NO2

HO Br Li
O O + OH OH

NO 2 NO2 NO2 NO2

O
O
+
Cl

Construction (Synthesis)

HBr 2 Li
HO Br Li
ether
O O
O
Cl HNO 3
ether
AlCl3 H2 SO4
NO2

O O ONa OH

Sn Br NaH

HCl ether
NH 2 NO 2 NO2 NO2
b.
Design (Retrosynthesis)

HO OH
OH

HO HO
O HO

OH Br Li

OH H
MgBr
O

Br

Construction (Synthesis)

HBr 2 Li
OH Br Li
Br 2 ether
heat
Br
OH PDC O
Mg ether
CH 2Cl2
ether H
MgBr

PDC H 3O +
ether
CH2 Cl2
O HO LiO

BrMgO H 3 O+ HO
c.
Design (Retrosynthesis)

O
O
OH
OCH 3
CH3 Br

Br HO
O

OH O
+ CH 3MgBr CH 3 Br
H 3CO
3 o alcohol
(2 equiv. subst.)

Construction (Synthesis) O

Mg 0.5 OCH3 OMgBr

CH 3 Br CH 3MgBr
ether ether

HO
H 3O+
HBr

O Br ONa NaH OH
ether

d.
Design (Retrosynthesis - several ways to do this one)

Br H H

Li Br
O OH
OH OH
d. (cont’d.)

OH
Br Li

O OH OH O

H H H H H

Li Br

Construction (Synthesis)
Br Br Br
Br2 Br 2 Br2

heat heat Fe

2 Li ether 2 Li ether 2 Li ether

Li Li Li

O
ether
Li H H

OLi O OH OLi
PCC H 3O +
H H H
ether CH 2Cl2

H 3 O+
Li
OH O
PCC

CH 2Cl2 ether OLi

H 3O +

HBr
Br OH
e.
Design (Retrosynthesis)

OH
CH3 CH 2 OH

OH OH Li Br

Li Br HO

H OH
OH
OH O

Construction (Synthesis) Br Li

HBr 2 Li Br 2 2 Li
HO Br Li
ether Fe ether

OH H
PCC Li H 3O +
O ether OLi OH
CH2Cl2 (quench)

dil. H 2SO4
Li
(E1 )
OLi m-CPBA
O
ether CH2 Cl2
"steric contr ol"
(E/Z) isomers
H 3 O+ (quench)

OH major product :
dil. H 2SO4 tetrasubstituted
(E ) isomer, alkene
(E1 ) conjugated with ring
Chemistry 3720 &KDSWHUVSpectroscopy Problems - Key

1. (10 pts) An unknown organic compound has the molecular formula C5H12O, in the mass spectrum, M+
= 88.09. Given the following 1H and 13C data, give the structure of the unknown and assign all of the 1H
and 13C signals.

4 3 2 1 0
PPM

1
H NMR (ppm) 1.14 (t, 3H, J = 7.2 Hz), 1.09 (d, 6H, J = 7.0 Hz), 3.19 (septet, 1H, J = 7.0 Hz),
3.50 (q, 2H, J = 7.2 Hz)

70 60 50 40 30 20 10 0
PPM

13
C NMR (ppm) 15.5, 22.3 (double), 64.8, 71.8

3.50 (q)

HH CH 3 1.10 (t) 22.3 64.8

15.5
O 1.13 (d)H 3C CH3
O
H3C O CH 3 71.8
H 22.3
3.19 (sept)

1
2. (10 pts) Draw the approximate 13C NMR spectrum of the following molecule. Include approximate
chemical shifts and indicate which signal corresponds to which carbon(s) in the molecule.

205.5 O 127.4
29.3 104.1 14.8
O
H3C 153.6 64.9
127.4 153.6
O
205.5 104.1
O
CH 3
64.9
29.3 14.8

220 200 180 160 140 120 100 80 60 40 20 0

PPM

3. (10 pts) A chemist produces a new compound with the following spectral characteristics and considers
the new material to be one of the possibilities shown below. Which structure is correct and why?
Include a complete assignment of all of the spectral data in your answer.
1
H NMR (ppm) 1.43 (t, 3H, J = 7.0 Hz), 3.47 (s, 3H,), 4.11 (q, 2H, J = 7.0 Hz), 4.76 (s, 2H), 7.17
(m, 2H), 7.83 (m, 2H)
13
C NMR (ppm) 14.8, 57.2, 64.6, 81.2, 126.1, 129.4 (double), 129.7 (double), 163.8, 198.3
IR (cm-1) 1740, 810
O OCH3 O OCH 3
O

O
OCH 3
O
OH

O OH

O
O O

O
O O O

4.09 64.6
O 1.32 O 14.8
163.8
7.10 7.10 129.7 129.7

7.83 7.83 129.4 129.4

3.30 126.1 57.2
198.3
O O
O O
4.63 81.2

IR: 1740 = C=O, 810 = para disubstitution

2
4. (10 pts) Draw the expected 1H and 13C NMR spectra of the following molecules. Include chemical
shifts and line shapes (singlet, doublet, etc.) in the 1H spectra and intensities in the 13C spectra. Also
indicate which signal corresponds to which proton(s) and carbon(s).

a.
1.13
O
1.06 3.62 3.19

2.47
O 1.13
3.09

4 3 2 1 0
PPM

22.3
O
7.9 210.8 62.6 71.8
O 22.3
35.9 45.1

220 200 180 160 140 120 100 80 60 40 20 0

PPM

3
b.

1.19
O 1.19
1.06 3.62

2.70 O 1.19
3.09
1.06

4 3 2 1 0
PPM

213.6 28.2
O 28.2
17.6 60.4 73.8

41.0 O 28.2
42.9
17.6

220 200 180 160 140 120 100 80 60 40 20 0

PPM

4
c.

1.13
O
1.20 3.62 3.19
O 1.13
1.20 3.09
1.20

4 3 2 1 0
PPM

22.3
44.3 O
25.9 63.2 71.8

40.1
O 22.3
25.9 213.8
25.9

220 200 180 160 140 120 100 80 60 40 20 0

PPM

5
d.

O
1.06 3.62 3.50

2.70
O 1.10
3.09
1.06

4 3 2 1 0
PPM

213.6 O
17.6 65.4 66.3

41.0
O 15.2
42.3
17.6

220 200 180 160 140 120 100 80 60 40 20 0

PPM

6
5. (10 pts) An unknown organic compound has the molecular formula C11H14O2. Given the following
spectral data, provide a structure for the unknown that agrees with the data, and then assign the data.
1
H NMR (ppm) 2.50 (s, 3H), 2.75 (t, 2H, J = 7.2 Hz), 3.30 (s, 3H), 2.52 (t, 2H, J = 7.2 Hz), 7.37-
7.76 (m, 4H)
13
C NMR (ppm) 26.6, 35.3, 59.3, 73.0, 126.0, 127.7, 128.5, 132.1, 1391, 139.2, 197.0
Mass spectrum (m/z) 178.10 (M+)
Infra Red (cm-1) 1730, 760, 690
1
H NMR data

O CH 3 2.50

7.71 7.76
3.30 3.52
7.37
O
2.75 7.48

8 7 6 5 4 3 2 1 0
PPM
13
C NMR data

O CH 3 26.6
197.0
139.1
127.7 126.0
59.3 73.0
128.5
O 139.3
35.3 132.1

200 180 160 140 120 100 80 60 40 20 0

PPM

(m/z) 178.10 (M+): this means that C11H14O2 is the actual formula of the unknown

Infra Red (cm-1): 1730 corresponds to C=O; 760, 690 correspond to meta substitution

7
6. (10 pts) An unknown organic compound has the molecular formula C12H16O2 and, in the mass
spectrum, M+ = 192.12. Given the following 1H and 13C data, give the structure of the unknown and
then assign all of the 1H signals.
1
H NMR (ppm) 1.20 (d, 6H, J = 7.0 Hz), 1.29 (t, 3H, J = 7.1 Hz), 2.87 (septet, 1H, J = 7.0 Hz),
4.30 (q, 2H, J = 7.1 Hz), 7.41 (d, 2H), 7.97 (d, 2H)
13
C NMR (ppm) 14.1, 23.3 (double), 33.2, 60.9, 126.0 (double), 127.3, 129.6 (double), 155.7,
165.9

1
H NMR data

1.29
O O
4.30
7.97 7.97

7.41 7.41
2.87
1.20 1.20

9 8 7 6 5 4 3 2 1 0
PPM

13
C NMR data

14.1
O O
60.9 165.9
127.3
129.6 129.6

126.0 126.0
152.7
33.2
23.3 23.3

180 160 140 120 100 80 60 40 20 0

PPM

M+ = 192.12 means that C12H16O2 is the actual formula of the compound

8
Chemistry 3720 Chapter 19 - Benzene Synthesis Problems - Key

Provide an efficient synthesis of each of the following substituted benzenes from benzene
itself. Use any of the reagents seen in Chemistry 3719/3720 so far and pay careful
attention to the order of steps. Assume that mixtures may be separated.

CH3

1. CH3Cl, AlCl3 Put CH3 on f irst then send next

gr oup o/ p major and separate the
2. CH3COCl, AlCl3 isomers

Br
1. Br2, Fe Br and CH3 both o/ p dir ectors but
CH3 is acti vating - probably a cl eaner
2. CH3Cl, AlCl3 reacti on (f ewer over-substi tuted products
(separate from o-isomer) if Br goes on f ir st - have to oxid ize l ast
3. KMnO4 CO2H as -CO2H i s a meta director

NH2
Putti ng NO2 or the acyl group on
1. CH3CH2COCl, AlCl3
f i rst would send the next gr oup to
the meta position (ei ther would d o)
2. HNO 3, H2SO4
and then reduction would gi ve the
3. Sn, HCl
d esi red product
4. Zn, HCl

SO3H

1. CH3Cl, AlCl3 Put CH3 on f irst (o/p d irector) then

bri ng i n SO3H gr oup (m d irector) -
2. SO3, H2SO 4 oxi dize CH 3 to CO2H (m dir ector)
(separate from o-isomer)
3. KMnO 4 CO 2H

CH3
SO 3H Introduce CH3 f i rst (o/ p di rector),
1. CH3Cl, AlCl3
separate i somers, then bring i n
2. SO3, H2SO4 SO3H gr oup (m d irector)

O OH

1. CH3Cl, AlCl3 Put CH3 on f i rst (o/ p di rector) then

bring in acyl gr oup (m d irector) -
2. CH3COCl, AlCl3
separate f rom o-isomer - then oxi dise
(separate from o-director)
the CH 3 group to CO2H
3. KMnO4 O
Chemistry 3720 ChDSWHUV 1-23 Synthesis Problems Key

These problems are typical of those that will be on the next exams in 3720. You should be comfortable
with each reaction in the forward direction, how to think about each reaction in a retrosynthetic manner,
and then be able to complete multi-step syntheses.

1. Give the major organic product(s) for each of the following sets of reaction conditions and then a
detailed mechanism for each reaction. Be careful with any regiochemical issues.

a.
OCH 3 OCH3
xs CH3OH - H+
OCH 3 OCH3
+
Cl O cat. H Cl Cl H
ketone gives acetal
H CH3
O
H Cl is completely unreactive under
these conditions
CH 3
O

Cl O Cl
H HOCH 3

HOCH 3
H CH 3 CH 3 CH 3
O +
O O
H trans. -H 2O

Cl O Cl O Cl O Cl
H H H H

b.

H CH 3
O H
O O O
H xs CH3OH - H+
OH cat. H+
OCH 3 OCH3
carb. acid gives ester

H
O
H O CH 3
O

OH H
O
H
O
O H
OCH 3

H H H
O O H+ trans. O -H 2O
OH OH2
OH
O O
CH3 H CH 3
HOCH 3
c.

O HOCH2CH2OH - H+
O O O O H
H cat. H +
H H
H R aldehyde gives acetal
O
H
The aldehyde is much more reactive than the alkene
under these conditions so the alkene survives
H O
O
OH
H H

OH
HO H
H H+ trans. H H - H 2O OH
O O O O
H H
H OH OH
H O O H

d.

H CH 3
O
O O CH 3O O CH 3O O
H xs CH3OH - H+
OCH3 CH 3O OCH 3 CH 3O OCH3
cat. H+
H
ketone gives acetal

ester could also react but overall there would be

no net change (OCH3 swapped for OCH 3)
H
O O CH 3O O

OCH3 OCH 3

H H H+ trans.
H H - H 2O
O O O O O O CH3O O

OCH3 OCH 3 OCH3 OCH 3

CH3 O CH 3O
H
HOCH 3 HOCH 3
e.
H R H
O
Br O Br EtO OEt Br EtO OEt
H
xs EtOH - H+
+
cat. H

ketone gives acetal

the bromide is completely unreactive

H under these reaction conditions
Br O Br OEt

H H H H HOEt
Br O Br O H+ trans. Br O - H2O Br EtO
H
O OEt
Et
HOEt

f.

O O O
xs MeOH - H+
MeO MeO MeO
cat. H+ MeO OMe
O MeO OMe
ketone gives acetal H
H Me
O
H the ester would not change overall even if
it did react under these conditions
O O

MeO MeO
O OMe
H

HOMe
HOMe
O O H Me O Me O
O + O - H2O
H trans.
MeO MeO MeO MeO
O O O O
H H H H Me
2. Give the major organic product(s) from each step of the following synthetic scheme.

O O
1. CH 3COCl, AlCl3 O O
2. Br2 , Fe
3. HOCH 2CH 2OH, cat. TsOH 1. 2. 3.
4. Mg, ether
Br Br
5. H2 C=O, ether
6. aq. NH 4 Cl (quench)
7. PCC, CH2 Cl2 O O O O O O
8. (CH3 )2 CHLi, THF
9. aq. NH 4 Cl (quench) 4. 5. 6.
10. PDC, CH 2 Cl2
11. PhMgBr, THF
12. aq. NH 4Cl (quench) MgBr
13. NaH, ether H OLi H OH
H H
14. PhCH 2Br, ether
15. 5% HCl, 3 h, RT
16. NaBH 4, CH 3 OH O O O O O O
17. HBr
18. NaOCH 3 , CH 3 OH 7. 8. 9.
19. m-CPBA, CH 2Cl2
20. PhMgBr, ether
21. aq. NH 4Cl (quench)
H O OLi OH
H H

O O O O O O

10. 11. 12.

O OMgBr OH
Ph Ph

O
O O O O

13. 14. 15.

ONa OCH2 Ph OCH 2Ph

Ph Ph Ph

OH Br

16. 17. 18.

OCH 2Ph OCH2 Ph OCH 2Ph

Ph Ph Ph

OMgBr OH
O

19. 20. 21.

Ph Ph

OCH 2Ph OCH2 Ph OCH 2Ph

Ph Ph Ph
3. In the boxes provided, give the products from each step in the following “road-map” scheme.

O
PCC O H xs. MeOH O OMe 2 CH3Li
MeO OH
MeO O MeO OMe
CH2Cl2 cat. H+ THF

CH3Br ONa OMe OH OMe OLi OMe

NaNH2 H3O+
Me OMe Me OMe Me OMe
Me THF Me (quench) Me

OMe OMe 5% HCl OMe H PhMgBr OMe OMgBr H 3O+

Me OMe THF Me O THF Me Ph (quench)

Me Me Me

OMe O OMe O OMe OH

m-CPBA PCC
Me OPh CH2Cl2 Me Ph Me Ph
Me Me CH 2Cl2 Me

13C = 175 ppm

4. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.

O
O
a.
OH
Cl
NH 2
Br OH
O

MgBr
NH2

OH OH

NH2 NH 2
O

NH 2 NH2

O O OH

NO 2 NH 2 NH 2

O
O

Cl

Synthesis

HBr Mg
OH Br MgBr
ether

O O O OH

Cl HNO 3 NaBH 4

AlCl3 H2SO4 CH 3OH

NO 2 NO2
OMgBr
O
H 3PO4 m-CPBA MgBr aq. NH4Cl

heat CH 2Cl2 ether (quench)

NO 2 NO2 NO2

OH ONa O O
NaH Br Sn

THF THF HCl

NO2 NO2 NO 2 NH2
OH
N
b. HO
NH 2

OH
BrMg
O
NH 2
BrMg

OH OH
O

Synthesis

HBr Mg
HO Br BrMg
ether

OH
H3PO4 O
m-CPBA
ether
heat CH2Cl2

O OH OMgBr
PCC H3O+

CH 2Cl2 (quench)

cat. H +

NH 2
N
O O
O
c. Ph
O

Br
O
Ph
O HO OH

H
H
MgBr
Ph
O OH
Ph Ph
OH H
H

Synthesis

Br MgBr O
Br 2 Mg OMgBr
Fe ether ether H
H

O NaBH4 OH
aq. NH 4Cl (quench)
CH3OH

O Na2Cr 2O 7 OH
cat. H+
OH H 2SO 4 H
H

O
Chemistry 3720 Chapters 20-22 Synthesis Problems – Key

These problems are from various parts of 3719 and 3720 and deal with the two main synthetic issues
studied; C-C bond formation and manipulation of functional groups.

1. Give the major organic product(s) from each of the following aldol reactions as well as a detailed
mechanism for each case. Be careful with any regiochemical issues.

O
a. O NaOH, CH 3OH, ∆
Intramolecular aldol is much
faster than the intermolecular
H O reaction, therefore a cycle is
formed. Refluxing the mixture
HO promotes loss of H2O in the
HO final step and formation of the
O O
O α,β-unsaturated product. There
H are two types of α-H but loss of
the other type would lead to an
O unstable 3-membered ring.
O OH
CH 3O H

b. O
O KOH, CH 3OH, ∆ Intermolecular aldol reaction is
the only possibility here since
there isn’t a second carbonyl in
H the substrate. The use of KOH
as base ensures that both some
HO CH 3O H enolate and some of the starting
HO ketone are present. Running
O O
H these reactions at higher temp
O O usually results in loss of H2O,
especially when conjugation is
O OH possible.

c.
O KOH, EtOH, reflux O
Again, intermolecular aldol
H H reaction is the only possibility
here since there isn’t a second
H carbonyl in the substrate. The
H
use of KOH as base ensures that
HO both some enolate and some of
the starting aldehyde are
O RO O
O O H present. Carrying out these
H H reactions at higher temp usually
H H results in elimination of H2O to
O HO form α,β-unsaturated product.
H
H OEt
d.
O O O
NaOH, CH 3OH, ∆
H The intramolecular aldol is
much faster than intermolecular
H
reaction, therefore a cycle is
formed. There are two types of
HO α-H in the starting material,
however only one cyclization
leads to a stable ring. Refluxing
O HO O (boiling) the mixture promotes
O O H loss of H2O in the final step.

H H H
O HO

H OCH3

e. O
O O
KOH, EtOH The intramolecular aldol much
faster than the intermolecular
reflux reaction, therefore a cycle is
H
formed. There are several types
of α-H in the starting material;
HO so several cyclization paths may
be possible. The reaction is
reversible and will yield the
H-OEt O HO O most stable product, the one
O shown. Refluxing the mixture
H
promotes loss of H2O in the
O O HO
final step.

f.
O O
NaOH, CH 3OH, ∆
The intramolecular aldol much
faster than the intermolecular
H O reaction, therefore a cycle is
formed. Two types of α-H but
only one pathway leads to a
HO HO
stable product, in this case a
CH 3 O H five-membered ring. Refluxing
O O
O H the mixture promotes loss of
H2O in the final step.

O O HO
2. Draw all of the possible aldol condensation products possible in the following reaction.

O
O NaOH, H 2O O O
+
reflux

A B
C-A C-B
NaOH
O O

O O
O
O
+ D-A D-B

C D
followed by protonation O
and elimination O
O O

E-A E-B
E F

O O

F-A F-B

3. Provide the reagents required to make each of the following compounds via 1,4-addition chemistry.

O
O

O
O

CuLi CuLi
CuLi
2 2 2
4. In the following Robinson annulation, 3 aldol products are possible; explain why only one is formed.

O O

NaOH, H 2O
H2 H3
O O O
OH
H1

O
H 2O
O

O O O
H1

H2
O O
O O
O H1
H1

Since there are 3 different types of α-H there are 3 different enolates possible here. The outcome
of the reaction is governed by thermodynamics (i.e. stability) since the steps are reversible,
therefore the most stable product will result. The enolate formed by removal of H1 would
generate a bicylic system (somewhat strained), the one formed by removal of H2 would only
afford a 4-membered ring (quite strained), whereas the enolate generated by removal of H3 would
give the favourable 6-membered ring shown above.

5. Give the major products from each step of the following reaction sequences.

O O
OH 1. 2.
a. 1. PCC, CH2Cl2
O
2. m-CPBA, CH 2Cl 2

1. Na2Cr2O7, H2O
H 2SO 4 O O
b. 1. 2.
OH
2. CH3OH, H+ OH OCH 3

O CH 2 CH 3
c. 1. Ph 3P=CH2 1. 2.

2. H 2, Pd

OCH 3
1. m-CPBA, CH2Cl2 O
d. 1. 2. OH
+
2. CH 3OH, cat. H
6. Provide complete mechanisms for the following conversions. Include all resonance structures for
any intermediates that may be formed.

O O O OH O O
NaOH

O
H
O O
enol form keto form
OH

O O
O
H-OH

O O O O

O O
O O

H+
O O
+
CH 3OH, H
OH OCH 3

H
- H+ O

OCH3
H
O

OH
OH

OCH3

H H H H
O O O
OH OH
OH
O CH O CH
3 3
HOCH 3 H
7. Give structures for each of the products in the following “roadmap.”

H
PCC H NaOH, EtOH Et 2CuLi
OH O
CH2Cl2 O reflux THF
H

OH H H
Na2Cr2O7 aq. NH4Cl
O O OLi
H2SO4, H 2O (quench)

xs CH3OH, H +

OCH 3 2 PhLi Ph Ph aq. NH4Cl Ph Ph

O OLi OH
ether (quench)

8. The polyether compound chauncydermolide G (shown below) was recently isolated by Triplet
Pharmaceuticals Inc. and found to have promising antibiotic properties. In order to prove the
structure unequivocally, a total synthesis beginning with the shown starting material was carried out.
Give structures for each of the products in the synthetic sequence.

O O OLi OH O
1. 2. 3. 4. 5.
H H

ONa OCH 2Ph OCH 2Ph OCH2Ph OCH 2Ph

6. H 3CO OCH 3 7. H3CO OCH 3 8. H3CO OCH 3 9. H 3CO OCH3 10. H 3CO OCH3

OCH 2Ph OH O OMgBr OH

11. H 3CO OCH3 12. H 3CO OCH3 13. O 14. O

Br

ONa O O O
15. 16. 17. OLi 18. OH
O O O O O O O O
Br Li
H H
H H

O O O O

19. O 20. CH 2 21. 22.

O O O O O O O O O OMgBr
H H H H

O O O O

23. 24. 25. Br 26.

O O OH O O O O O O
H O O O

O O O O

27. 28. 29.

O O O O O O

OMgBr OH ONa

O O O

30. 31. 32. O

O O O O

OMe OMe OMe

O O O

33. OLi 34. O 35.

OMe OMe OMe

O O O

36. 37.
OH Br

OMe OMe

O O
Chemistry 3720 Chapters 21-22 Additional Synthesis Problems Key

1. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.
a. Retrosynthesis

O H

O O CO2

O
H
O HO O

O O

X OH

X = OH, Cl, OCOPh

Br MgBr O

OH CO 2

Synthesis

Br2
Br Mg MgBr

Fe ether CO2

H NaBH4 O
HO
O CH 3OH OMgBr

O O
xs HO dil. HCl
O OH (quench)

cat. H2SO 4

If the alcohol is inexpensive and readily available then the Fischer esterification works well, however if
the alcohol is expensive, it is better to convert the carboxylic acid to the acid chloride (X = Cl) using
SOCl2/pyridine or the anhydride (X = OCOPh) by heating and removing H2O. Both of these reactive
carboxylic acid derivatives require 1 equivalent of alcohol to give the ester (with pyridine as a base).
b.
Retrosynthesis

O O

O HO

O O O

O HO

Synthesis
O O O
Na2Cr2O7 heat
HO O
H2SO 4 HO (- H 2O)

The most straightforward way to make an anhydride from a volatile (i.e. easily distillable) carboxylic acid
is to heat it up with a small amount of a mineral acid and remove the water that is formed. You could also
form the acid chloride from a portion of the carboxylic acid (using SOCl2/pyridine) and then react that
with more of the remaining carboxylic acid.

c.
Retrosynthesis
O

O OH

Synthesis
OH O O
dil. H 2SO4 Na2Cr2O7 m-CPBA O
H2SO 4 CH2Cl2

All of the required carbon atoms for the product are found in the given starting material, which needs to
be manipulated to introduce oxygen. The system has to be oxidized to produce the lactone (cyclic ester)
so the Baeyer-Villager oxidation is appropriate.
d.
Retrosynthesis

O OH
O
CH 3OH
OCH 3 OH

O
O CO2 CH 3 CO2 H
CH3 OH
OCH3 CO2 CH3 CO2 H

Synthesis

Na2Cr2O 7 CO2H xs CH3OH CO 2CH3

OH
OH H2SO 4 cat. H 2SO4
CO2 H CO2CH 3

NaOCH3
CH3OH

O O
O dil HCl O

OCH3 (quench) OCH 3

e.
Retrosynthesis
H
N
HO CH3 OH
O

NH Cl HO
HO
O O O

NH2 HO
CH 3OH H 2C=O

HO Br Li

NO2
Synthesis

PCC 2 Li HBr HO
Li Br
CH3 OH H2 C=O
CH2Cl 2 THF

aq. NH4Cl Na2Cr2O7 HO

LiO HO
(quench) H 2SO4
O

SOCl 2
NO 2 NH 2 pyridine
HNO3 Sn

H2SO 4 HCl Cl

O
pyridine

H
N

2. Give the major organic product(s) from each step of the following synthetic sequence.

1. Na 2Cr2 O7 , H 2SO4 O O
1. O 2. O 3.
2. xs CH 3OH, cat. H2 SO4
3. NaOCH 3 , CH3 OH OH OCH 3
OCH3
4. aq. NH 4Cl (quench)
OH
5. NaOCH3 , THF O O O O
4. H 5.
6. CH 3 CH 2Br
OCH3 OCH 3
7. NaOH, aq. THF
8. dil. HCl (quench)
9. 180 oC (-CO2 )
O O O O
10. LDA, THF, -78 oC 6. 7.
11. PhCH 2 Br OCH3 ONa

O O O
8. 9.
OH

OLi O
10. 11.

Ph
3. In the boxes provided, give the products from each step in the following “road-map” scheme. Predict
the 1H NMR spectra of each of the organic products from each step.

Br2 Br Mg MgBr

Fe ether
CO 2

CO 2CH 3 xs CH3OH CO 2H dil. HCl CO2MgBr

cat. H2SO4 (quench)

HNO3
H 2SO4

OLi OH
CO2 CH 3 2 x CH 3Li aq. NH 4Cl

THF (quench)
NaH
NO2 THF
NO 2 NO 2

OCH3 OCH3 ONa

Sn, HCl CH3Br

NH2 NO2 NO 2

7.44 7.66
7.18 Br 7.26 MgBr
7.22 7.44 7.19 7.66
7.18
7.26

8 6 4 2 0 8 6 4 2 0
PPM PPM

MgBr O
O 7.66
8.21

7.66
8.21
OH12.74
O 7.79 8.21
7.79 8.21 7.66
7.66

8 6 4 2 0 12 10 8 6 4 2 0
PPM PPM
O 8.44
O
8.05 3.89 3.89
7.82
7.56
O O
7.66 8.05 8.47 8.60
7.56
N+
O O-

8 6 4 2 0 8 6 4 2 0
PPM PPM

Li
O 5.52
7.93 OH
7.64 7.93
1.30 7.64
1.30 1.30
8.19 8.25
8.19 1.30
8.25
N+
O O- N+ -
O O

8 6 4 2 0 8 6 4 2 0
PPM PPM

3.30
ONa 7.93
O
7.93
7.64 7.64
1.30 1.30
1.30 1.30
8.19 8.25 8.19 8.25

N+ - N+ -
O O O O

8 6 4 2 0 8 6 4 2 0
PPM PPM

3.30
O
6.90
7.13
1.30
6.56 1.30
6.68

NH 2
5.32

8 6 4 2 0
PPM

4. Give complete mechanisms, including any important resonance structures for intermediates where
applicable, that explain the bond-making and bond-breaking events in the following conversions.
O O
a. 1. NaOCH 3 , CH3 OH
OCH3
H3 CO 2. dilute HCl (quench) Ph
H O 3. NaOCH 3 , THF
4. PhCH 2 Br
CH 3O 5. NaOH, aq. THF
6. dilute HCl (quench)
7. 180 o C (-CO2)
O O
OCH 3 OCH 3
H 3 CO H 3CO
O O

CH3O
O O OCH3 O H O

H3 CO H 3 CO contd....
H 2O H
O O O O O O

H3 CO H3 CO H 3 CO

Br

CH3O Ph
O O O O O O
H
H3 CO H3 CO H 3 CO

HO O O HO O O O O

H3 CO H3 CO H 3 CO

Ph Ph

H2O H
HO O O O O O O
H
O O O

Ph Ph Ph

H
O O O O

O HO

Ph Ph

OH O
tautomerism
Ph Ph
b. 1. Na2 Cr 2 O7, H2 SO4
O O
OH
OH
2. xs CH3 OH, cat. HCl
3. NaOCH 3, CH 3OH
4. dilute HCl (quench)
5. NaOH, aq. THF
6. dilute HCl (quench)

O
Na2 Cr 2O 7 + H2 SO4 HO Cr OH chromic acid
O
H OH 2 H H HOCH 2R H
O O O HO O CH2 R
HO Cr OH HO Cr OH HO Cr OH HO Cr OH
O O O O

H 2O
O H H CH 2R
O HO O CH 2R HO O
HO Cr O R
HO Cr OCH 2R HO Cr HO Cr OH 2
O H
O O O
H 2O

H OH 2 H H
O H 2O H
R O R O
O OH
H H
H H
R H
H2 O

CHROH H H
HO O HO O CHROH O HO OH
HO Cr OH 2 HO Cr OH HO Cr OH
O R H
O O

H 2O
H
HO O CHROH O O OH
HO Cr HO Cr OCHROH HO Cr O R
O O O H

H 2O
CH 3OH
H 3C H H H
O O
R O R O
R OH
H OCH3
OH OH OH OH
H
CH 3 OH

H 3C H
O O
R OH R O
R OH 2
OCH 3
OH OCH3 OCH 3
contd....
O
Ph
OCH 3 H 3CO
H H 3CO O O
O O Ph
Ph Ph OCH 3
OCH 3 OCH 3 Ph

O
Ph
OCH3

O O O O O O
Ph Ph Ph
OCH3 OCH3 OCH 3
Ph Ph H Ph
CH 3O
H 2O H

O O O O O O OCH3
Ph Ph Ph
OCH3 OCH3 OH
Ph H Ph H Ph
OH

H 2O H
O O O O O O OCH 3
Ph Ph Ph H
OH O O
H Ph H Ph H Ph
Chemistry 3720 Further Synthesis Problems 1 - Key

1. Give retrosynthetic analyses for the following molecules that go back to the given starting materials,
and then provide the synthesis in the forward direction. Assume you have access to the usual other
reagents (HBr, HNO3, NaBH4, etc.) in the lab.

a.
Retrosynthesis

OH
HO PPh3

Ph3 P Ph3 P Br

Br PPh3
O OH

HO

Synthesis

HBr PBr3
HO Br Ph 3P Br
ether

OH O n-BuLi THF
PCC

CH2Cl 2

Ph 3P

It would also be possible to use organometallic chemistry in this synthesis (e.g. turn one piece into a Grignard
reagent and then add to a ketone, followed by acid-catalyzed elimination), however that might not give you this
alkene as the major isomer in the elimination step. The Wittig route puts the double bond in the right place
without any complications.
1
b. Retrosynthesis

OH OH

OH
OH MgBr Br

O OH OH

Synthesis

O BrMgO
OH HBr Br Mg MgBr

ether

OH PCC O aq. NH4Cl

(quench)
CH 2Cl2

H 3PO4
OH

80 oC

One could also make the Grignard reagent from the cyclopentanol and the ketone from the isopropanol or even
use Wittig chemistry here. Since the product is the most highly substituted alkene anyway, both methods work.

c. Retrosynthesis

Br
O
HO
Cl

OH O O

Br
O O O

Cl
HO
2
Synthesis

O O OLi
Cl LDA

AlCl3 THF, -78 oC Br

HBr
HO Br O

Br OH
HBr NaBH 4

CH3OH

The limitation here is the starting materials that are given; the 2-carbon alcohol limits what type of chemistry
can be applied and the only logical way really is to recognize that the alpha-carbon of the ketone may be
deprotonated to form the nucleophilic enolate.

d. Retrosynthesis

O OH
OH

Ph

O O
OH OH O
H
Ph Ph Ph

OH O
OH

Synthesis

OH O
PCC PCC O
OH
H
CH2Cl2 CH2Cl2 Ph

O
NaOH, EtOH
reflux H
Ph

Ph

Logical to use crossed-aldol here since the alkene is alpha to the ketone carbonyl. Heating ensures elimination.
3
e. Retrosynthesis

OH OH
HO

OH O O O

OH OH

Li Br HO OH O

Synthesis

OH PCC O NaOH O

CH2Cl2 EtOH, ∆

HBr 2 Li
HO Br Li
ether

OH aq. NH4Cl OLi

(quench)

Given the two alcohols here the logical first disconnection is the ethyl group, which reveals a 6-carbon fragment
that is then accessible by a simple intermolecular aldol reaction. Heating the aldol step ensures that elimination
occurs to give the required α,β-unsaturated product.

2. Give the major organic product(s) from each step of the following synthetic scheme.

1. PCC, CH2 Cl2 O O OLi

2. NaOH, EtOH, reflux
OH 1. 2. 3.
3. (CH3 )2 CuLi, ether
4. aq. NH 4Cl (quench)

5. PhMgBr, ether
6. aq. NH 4Cl (quench) O BrMgO Ph HO Ph
7. NaNH 2, THF
8. CH 3Br 4. 5. 6.

NaO Ph CH3 O Ph
7. 8.

4
3. In the boxes provided, give the products from each step in the following “road-map” scheme.

OH O OMgBr
PCC PhMgBr
H Ph
CH2Cl2 THF
aq. NH4Cl
(quench)

OLi O OH
(CH3)2CuLi PCC
Ph Ph Ph
THF CH2Cl2
aq. NH4Cl
(quench)

O O O
Br2 Br NaOCH3
Ph Ph Ph
CHCl3 CH3OH
(CH3)2CuLi
THF

OH O OLi
NaBH4 aq. NH4Cl
Ph Ph Ph
CH3OH (quench)

4. Give complete mechanisms, including any important resonance structures for intermediates where
applicable, that explain the bond-making and bond-breaking events in the following conversions.

a.
O OH
R O H 1. m-CPBA, CH 2Cl2
OH
+ Ph
2. 2 PhMgBr, THF Ph
3. aq. NH 4Cl (quench)

H
H H H
O O O O
O
O O
O H O O O
HO OCAr H δ - δ+
Ar O Ar O Ph MgBr

OH OMgBr OMgBr
Ph
OH H 3O + Ph Ph O
+ Ph
Ph Ph OMgBr O OMgBr
δ - δ+
Ph MgBr

5
b. O O
1. HNO 3, H2 SO4
OH
o
2. LDA, THF, -78 C Ph
3. O
Ph NO2
O
4. aq. NH4 Cl (quench)
O

O O - H2O
HO 3S O H H O N H 2O N O N O
O O
H NO2

H2O
O O O
O
H

Ph N(i-Pr)2
NO 2 NO2 NO 2
O H NO 2

O O
O
OLi H NH3 OH

Ph Ph

NO2 NO2 H NO2

6
 

 
 
Chemistry 3720 
Practice Exams 
and 
Answer Keys 
Chemistry 3720, Spring 2014 Exam 1 Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

1. (8 pts) Give a detailed explanation for the different regiochemical outcomes in the following two epoxide-
opening reactions.

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical changes where applicable.

O
1. NaBH4, CH3OH
a.
2. NaH, THF
3. CH3CH2Br

CH3
1. H B
b.
2. NaOH, H2O2
3. PDC, CH2Cl2

CH3 1. m-CPBA, CH2Cl2

c.
2. NaCN, DMF
3. H3O+ (quench)

1. (CH3)3SiCl, Et3N
2. PhMgBr, ether
O
d.
OH H 3. H3O+ (quench)
4. (C4H9)4N+ F-

SH 1. NaOCH2CH3
e.
2. CH3CH2CH2Br
CH3

2
3. (9 pts) Give the product expected under the following conditions. Then draw a complete mechanism for the
conversion being careful with the overall sequence of events as the ether is converted to the product.

4. (9 pts) For the following conversion, provide a complete mechanism that describes all of the major events
on the way from starting material to product.

3
5. (16 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and molecular formula clues might help you come up with answers.

6. (8 pts) Give the expected major product from each step of the following reaction sequence. No need to show
any mechanisms.
1. NaBH4, CH3OH
2. PBr3
3. Mg, ether
O 4. O

H
5. H3O+ (quench)
6. PCC, CH2Cl2
7. PhMgBr, ether
8. H3O+ (quench)

4
7. (6 pts) Give the expected product from each of the following oxidation reactions, and then provide a brief
explanation for why each alcohol gives a different result.

8. (8 pts) Which of the following molecules does the IR spectrum below match? Explain your choice here by
pointing out important signals that helped you to decide (Use the spectroscopy sheet for numbers).

5
9. (8 pts) From the molecules shown below, choose which one matches the following mass spectrum. Then
explain your choice, including reasons for why you didn’t pick the other possible answers. Atomic masses
(in atomic mass units, a.m.u.) are as follows: C = 12 ; H = 1 ; Cl = 35.45 ; Br = 79.90.

OH Cl CH3 Br
a) b) c) d)

10. (8 pts) Provide a retrosynthesis for the following ether that goes back to the sources of carbon shown. Then
show how you would make the target molecule using any of the reactions seen so far in Chemistry 3719/
3720. Include a product from each of your synthetic steps.

6
Youngstown State University
Organic Chemistry Spectral Data Sheet

Approximate 1H NMR Chemical Shifts (δ, ppm)

R3C-H (alkyl) 0.9-1.8 R3N-C-H (N neighbor) 2.2-2.9

C=C-C-H (allylic) 1.6-2.6 Cl-C-H (Cl neighbor) 3.1-4.1

O=C-C-H (α to C=O) 2.1-2.5 Br-C-H (Br neighbor) 2.7-4.1

NC-C-H (α to CN) 2.1-3.0 -O-C-H (O neighbor) 3.3-3.7

C C H (alkyne) 2.5 R2N-H (amine) 1-3

Ar-C-H (benzylic) 2.3-2.8 RO-H (alcohol) 0.5-5

C=C-H (alkene) 4.5-6.5 Ar-O-H (phenol) 6-8

Ar-H (benzene) 6.5-8.5 -CO2H (carboxylic acid) 10-13

O=C-H (aldehyde) 9-10

Approximate 13C NMR Chemical Shifts (δ, ppm)

RCH3 (alkyl) 0-35 RCH2Br (alkyl bromide) 20-40

R2CH2 (alkyl) 15-40 RCH2Cl (alkyl chloride) 25-50

R3CH (alkyl) 25-50 RCH2NH2 (alkyl amine) 35-50

R4C (alkyl) 30-40 RCH2OR (alcohol or ether) 50-65

R C C R (alkyne) 65-90 RCN (nitrile) 110-125

R2C=CR2 (alkene) 100-150 RCO2R (acid, ester) 160-185

Benzene C (aromatic) 110-175 RCHO, R2CO (aldehyde, ketone) 190-220

Approximate IR Absorption Frequencies (cm-1)

Stretching Vibrations

-O-H (alcohol) 3200-3600 C=C (alkenes) 1620-1680

-O-H (carbox. acid) 2500-3600 C=O (ald., ketones) 1710-1750
R2N-H (amine) 3350-3500 C=O (acyl halides) 1770-1815
sp C-H (alkynes) 3310-3320 C=O (esters) 1730-1750
sp2 C-H (alkenes) 3000-3100 C=O (amides) 1680-1700
sp3 C-H (alkanes) 2850-2950
sp2 C-O (carbonyls) 1200 triple bond (alkynes) 2100-2200
sp3 C-O (alcoh., ethers) 1025-1200 triple bond (nitriles) 2240-2280

Bending Vibrations

RCH=CH2 (alkenes) 910, 990 Monosubstituted benzene 730-770, 690-710

R2C=CH2 (alkenes) 890 ortho-disubstituted benzene 735-770
R2C=CHR’ (alkenes) 790-840 meta-disubstituted benzene 750-810, 680-730
para-disubstituted benzene 790-840
Chemistry 3720, Spring 2014 Exam 1 - Key Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

1. (8 pts) Give a detailed explanation for the different regiochemical outcomes in the following two epoxide-
opening reactions.

O H-Br (1 mol) OH
Under acidic conditions the epoxide is first
Br protonated to produce the oxonium ion. This
species will prefer to spread more of the charge
H H
onto the 3o carbon, which will flatten out and
O O be accessible for attack; the 3o bromide is formed
+

Br

O 1. PhMgBr OH
+ In this case the conditions are highly basic so the
2. H3O+ Ph
nucleophile will approach the epoxide in the rate-
determing step. Here the 1o carbon is much more
Ph-MgBr accessible and so the reaction occurs there to give
H+
OMgBr the 3o alcohol.

Ph

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical changes where applicable.

O 1. H 2. H 3.
H
OH ONa OCH3
1. NaBH4, CH3OH
a.
2. NaH, THF
3. CH3CH2Br
(+/-) (+/-) (+/-)

CH3
1. H CH 2. H CH 3. H CH
1. H B B 3 3 3
b. HO O
2. NaOH, H2O2
3. PDC, CH2Cl2
+ enantiomer + enantiomer + enantiomer

CN CN
1. O 2. ONa 3. OH
CH3 1. m-CPBA, CH2Cl2 CH3
c. CH3 CH3
2. NaCN, DMF
3. H3O+ (quench)
+ enantiomer + enantiomer + enantiomer

1. 2.
O OMgBr
1. (CH3)3SiCl, Et3N Ph
2. PhMgBr, ether (CH3)3SiO H (CH3)3SiO H
d. O
(+/-)
OH H 3. H3O+ (quench)
4. (C4H9)4N+ F- 3. 4.
OH OH
Ph Ph
(CH3)3SiO H OH H
(+/-) (+/-)

SH 1. NaOCH2CH3 1.
SNa SCH2CH2CH3
2.
e.
2. CH3CH2CH2Br CH3
CH3 CH3

2
3. (9 pts) Give the product expected under the following conditions. Then draw a complete mechanism for the
conversion being careful with the overall sequence of events as the ether is converted to the product.

Br

O HBr (excess) OH

H Br Br

H
O

The ether features a primary benzylic and phenolic oxygen. The HBr will
protonate the oxygen to make it a better leaving group and the bromide
anion will attack at the primary/benzylic carbon to give the benzylic
bromide. The phenolic OH will not react despite the excess HBr.

4. (9 pts) For the following conversion, provide a complete mechanism that describes all of the major events
on the way from starting material to product.

Ph MgBr
O OH
1. PhMgBr (excess) Ph
O
Ph
2. H3O+ (quench)
OH

H
O H
Ph O H O
Ph
O
Ph
O
Ph MgBr
O
H H
Ph O
H
OMgBr

3
5. (16 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and molecular formula clues might help you come up with answers.

H CH3
OH PDC CH3MgBr
O OMgBr
CH2Cl2 ether

IR : 1720 cm-1 C8H9BrMgO

H3O+
(quench)

CH3 CH3 CH3

CH3CH2 CH3CH2MgBr Na2Cr2O7
OMgBr O OH
H2SO4 H2SO4
(+/-)

IR : 1740 cm-1 IR : 3300 cm-1

H3O+
(quench)

CH3 CH3 CH3

CH3CH2 NaH CH3CH2 CH3Br CH3CH2
OH ONa OCH3
ether ether
(+/-) (+/-) (+/-)

IR : 3350 cm-1 C10H13ONa Final product:

Molecular formula = C11H16O
7 signals in 1H NMR spectrum

6. (8 pts) Give the expected major product from each step of the following reaction sequence. No need to show
any mechanisms.

1. NaBH4, CH3OH 1. OH 2. Br 3. MgBr

2. PBr3
H H H
3. Mg, ether H H H
O 4. O
OMgBr OH O
H +
5. H3O (quench) 4. 5. 6. H
6. PCC, CH2Cl2
7. PhMgBr, ether H H H
H H H
8. H3O+ (quench)
OMgBr OMgBr
7. Ph 8. Ph

H (+/-) H (+/-)
H H

4
7. (6 pts) Give the expected product from each of the following oxidation reactions, and then provide a brief
explanation for why each alcohol gives a different result.

8. (8 pts) Which of the following molecules does the IR spectrum below match? Explain your choice here by
pointing out important signals that helped you to decide (Use the spectroscopy sheet for numbers).

Each of the options contains C-C and C-H single bonds to sp3 carbons so those
signals would not be useful here. The absorbances highlighted help solve the
problem: the broad signal at ~3340 cm-1 corresponds to an alcohol group, which
precludes options b), c), and e). The absorbance at 1660 cm-1 corresponds to a
C=C group, which d) has but a) does not. The signal at 1030 would fit both a)
and d), however the absorbance at 900 cm-1, for sp2 =CH2, would only fit a
terminal olefin, i.e. option d).

5
9. (8 pts) From the molecules shown below, choose which one matches the following mass spectrum. Then
explain your choice, including reasons for why you didn’t pick the other possible answers. Atomic masses
(in atomic mass units, a.m.u.) are as follows: C = 12 ; H = 1 ; Cl = 35.45 ; Br = 79.90.

OH Cl CH3 Br
a) b) c) d)

By simply adding up the atomic masses in each molecule, the answer is quickly revealed as being
chlorobenzene, b). The M+ signals at 112 and 114 a.m.u. match only this compound and reveal the
natural abundance isotopic ratio of Cl35 and Cl37. While each of these different compounds might
reasonably be expected to exhibit the 77 a.m.u. fragment, which corresponds to the phenyl radical
cation, only chlorobenzene would have the correct mass and two M+ signals in this (75:25) ratio.

10. (8 pts) Provide a retrosynthesis for the following ether that goes back to the sources of carbon shown. Then
show how you would make the target molecule using any of the reactions seen so far in Chemistry 3719/
3720. Include a product from each of your synthetic steps.

6
Chemistry 3720, Spring 2014 Exam 2 Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

HDI/Unsaturation Number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (8 pts) Provide a detailed mechanism for the following reaction that includes all resonance structures for any
intermediate(s) that is/are formed. Which mechanism is this and which step is rate-determining?

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical information where applicable.

1. Br2, FeBr3
a.
2. Mg, ether
3. D2O

O
1. Cl , AlCl3
b.
2. LiAlH4, ether
3. H+ (quench)

OH
1. PCC, CH2Cl2
c.
2. Na, NH3, CH3OH
3. NaBH4, CH3OH

O O O
1. , heat
d. O
2. H2, Pd

1. (CH3)2CHCl, AlCl3
e.
2. HNO3, H2SO4
3. Na2Cr2O7, H2SO4,

2
3. (15 pts) An unknown organic compound is found to have the molecular formula C12H15BrO and the
following spectral data. Draw the expected structure of the unknown and match the 1H NMR and IR signals
to your molecule. IR : 1720, 1200, 800, 690 cm-1

1
H NMR (CDCl3): 1.16 (d, 6H, J = 6.9 Hz), 3.05 (t, 2H, J = 7.0 Hz), 3.20 (septet, 1H, J = 6.9 Hz), 3.63 (t, 2H, J = 7.0 Hz),
7.32 (t, 1H, J = 6.8 Hz), 7.39 (d, 1H, J = 6.8 Hz), 7.79 (s, 1H), 7.93 (d, 1H, J = 6.8 Hz)

13
C NMR (CDCl3): 18.1 (q, double intensity), 31.6 (t), 35.1 (d), 39.0 (t), 126.0 (d), 127.7 (d), 128.5 (d),
132.1 (d), 136.6 (s), 139.3 (s), 202.1 (s)

3
3. (9 pts) Give the major product expected under the following conditions. Then draw a complete mechanism
for the conversion that includes important resonance structures for any intermediate(s).

4. (9 pts) Indicate whether each of the following molecules is expected to be aromatic or not aromatic and
then draw Frost Circles of molecular orbitals for each system to back up your answers.

4
5. (14 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and molecular formula clues might help you come up with answers.

O
Cl Br2

AlCl3 FeBr3

IR : 1740 cm-1 IR = 690, 800 cm-1

Zn, HCl

O
H H Mg, ether

M+ = 228, 230 C8H9BrMg 8 signals in 13C NMR

Final product:
PCC Molecular formula = C9H10O
signal at 9 ppm in 1H NMR spectrum
CH2Cl2
signal at 190 ppm in 13C NMR spectrum

IR : 3300 cm-1 IR : 1720 cm-1

6. (8 pts) In the addition of HBr to 1,3-butadiene, the product distribution depends greatly on the temperature
at which the reaction is run. Give a mechanism for this process and explain the expected outcomes at low
temperature and high temperature.

5
7. (9 pts) A new antibiotic compound is thought to have one of the structures shown below. From the spectral
data, which structure corresponds to the drug? Match the proton NMR data to your answer.

UV : 290 nm M+ = 205 a.m.u. IR : 1720, 1640, 1200, 800 cm-1

1
H NMR : 1.08 (t, 3H, J = 7.0 Hz), 2.98 (q, 2H, J = 7.0 Hz), 6.54 (d, 1H, J = 12.0 Hz),
7.91 (d, 1H, J = 12.0 Hz), 8.03 (d, 2H, J = 6.8 Hz), 8.37 (d, 2H, J = 6.8 Hz).
13
C NMR : 7.9 (q), 34.0 (t), 123.8 (double intensity, d), 126.2 (d), 129.0 (double intensity, d),
141.3 (s), 142.8 (d), 147.1 (s), 200.4 (s).

8. (8 pts) Give the major product(s) expected under the following conditions. Then provide a complete
mechanism for the conversion that includes important resonance structures for any intermediate(s). Briefly
explain the regiochemical outcome of the reaction.

6
Youngstown State University
Organic Chemistry Spectral Data Sheet

Approximate 1H NMR Chemical Shifts (δ, ppm)

R3C-H (alkyl) 0.9-1.8 R3N-C-H (N neighbor) 2.2-2.9

C=C-C-H (allylic) 1.6-2.6 Cl-C-H (Cl neighbor) 3.1-4.1

O=C-C-H (α to C=O) 2.1-2.5 Br-C-H (Br neighbor) 2.7-4.1

NC-C-H (α to CN) 2.1-3.0 -O-C-H (O neighbor) 3.3-3.7

C C H (alkyne) 2.5 R2N-H (amine) 1-3

Ar-C-H (benzylic) 2.3-2.8 RO-H (alcohol) 0.5-5

C=C-H (alkene) 4.5-6.5 Ar-O-H (phenol) 6-8

Ar-H (benzene) 6.5-8.5 -CO2H (carboxylic acid) 10-13

O=C-H (aldehyde) 9-10

Approximate 13C NMR Chemical Shifts (δ, ppm)

RCH3 (alkyl) 0-35 RCH2Br (alkyl bromide) 20-40

R2CH2 (alkyl) 15-40 RCH2Cl (alkyl chloride) 25-50

R3CH (alkyl) 25-50 RCH2NH2 (alkyl amine) 35-50

R4C (alkyl) 30-40 RCH2OR (alcohol or ether) 50-65

R C C R (alkyne) 65-90 RCN (nitrile) 110-125

R2C=CR2 (alkene) 100-150 RCO2R (acid, ester) 160-185

Benzene C (aromatic) 110-175 RCHO, R2CO (aldehyde, ketone) 190-220

Approximate IR Absorption Frequencies (cm-1)

Stretching Vibrations

-O-H (alcohol) 3200-3600 C=C (alkenes) 1620-1680

-O-H (carbox. acid) 2500-3600 C=O (ald., ketones) 1710-1750
R2N-H (amine) 3350-3500 C=O (acyl halides) 1770-1815
sp C-H (alkynes) 3310-3320 C=O (esters) 1730-1750
sp2 C-H (alkenes) 3000-3100 C=O (amides) 1680-1700
sp3 C-H (alkanes) 2850-2950
sp2 C-O (carbonyls) 1200 triple bond (alkynes) 2100-2200
sp3 C-O (alcoh., ethers) 1025-1200 triple bond (nitriles) 2240-2280

Bending Vibrations

RCH=CH2 (alkenes) 910, 990 Monosubstituted benzene 730-770, 690-710

R2C=CH2 (alkenes) 890 ortho-disubstituted benzene 735-770
R2C=CHR’ (alkenes) 790-840 meta-disubstituted benzene 750-810, 680-730
para-disubstituted benzene 790-840
Chemistry 3720, Spring 2014 Exam 2 Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

HDI/Unsaturation Number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (8 pts) Provide a detailed mechanism for the following reaction that includes all resonance structures for any
intermediate(s) that is/are formed. Which mechanism is this and which step is rate-determining?

OH Br
H Br

Br

OH2
Br

SN1 reaction; carbocation

formation is rate-determining

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical information where applicable.

1. Br2, FeBr3 2. 3.
1.
a.
2. Mg, ether
3. D2O

Br MgBr D

O H H
O O OH
1. Cl , AlCl3 1. 2. 3.
b.
2. LiAlH4, ether
3. H+ (quench)

H
OH O O OH
1. PCC, CH2Cl2 1. 2. 3.
c.
2. Na, NH3, CH3OH
3. NaBH4, CH3OH

O O O
H O H O
1. , heat 1. 2.
d. O O O O O
2. H2, Pd
H O H O

endo major

O OH
1. (CH3)2CHCl, AlCl3 1. 2. 3.
e.
2. HNO3, H2SO4
3. Na2Cr2O7, H2SO4,
NO2 NO2

2
3. (15 pts) An unknown organic compound is found to have the molecular formula C12H15BrO and the
following spectral data. Draw the expected structure of the unknown and match the 1H NMR and IR signals
to your molecule. IR : 1720, 1200, 800, 690 cm-1

1H NMR (CDCl3): 1.16 (d, 6H, J = 6.9 Hz), 3.05 (t, 2H, J = 7.0 Hz), 3.20 (septet, 1H, J = 6.9 Hz), 3.63 (t, 2H, J = 7.0 Hz),
7.32 (t, 1H, J = 6.8 Hz), 7.39 (d, 1H, J = 6.8 Hz), 7.79 (s, 1H), 7.93 (d, 1H, J = 6.8 Hz)

13C NMR (CDCl3): 18.1 (q, double intensity), 31.6 (t), 35.1 (d), 39.0 (t), 126.0 (d), 127.7 (d), 128.5 (d),
132.1 (d), 136.6 (s), 139.3 (s), 202.1 (s)

3
3. (9 pts) Give the major product expected under the following conditions. Then draw a complete mechanism
for the conversion that includes important resonance structures for any intermediate(s).

NO2
HNO3, H2SO4

O O O
N H O S OH N O N O
O OH O OH2
O

H2O
H NO2 H NO2 H NO2

O N O

4. (9 pts) Indicate whether each of the following molecules is expected to be aromatic or not aromatic and
then draw Frost Circles of molecular orbitals for each system to back up your answers.

not aromatic aromatic aromatic

diradical species all electrons in all electrons in

bonding M.O. bonding M.O.

4
5. (14 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and molecular formula clues might help you come up with answers.

O
O O
Cl Br2 Br
AlCl3 FeBr3

IR : 1740 cm-1 IR = 690, 800 cm-1

Zn, HCl

O
H OMgBr
H H BrMg Mg, ether Br
H

C9H11BrMgO C8H9BrMg 8 signals in 13C NMR

H OH O Final product:
PCC Molecular formula = C9H10O
H H
signal at 9 ppm in 1H NMR spectrum
CH2Cl2
signal at 190 ppm in 13C NMR spectrum

IR : 3300 cm-1 IR : 1720 cm-1

6. (8 pts) In the addition of HBr to 1,3-butadiene, the product distribution depends greatly on the temperature
at which the reaction is run. Give a mechanism for this process and explain the expected outcomes at low
temperature and high temperature.

H H
HBr Br
+ The addition reaction goes through an allylic
Br carbocation that is represented by resonance
H Br C D structures A and B. Attack of the bromide ion
at C-2, the kinetic process, gives the product
of 1,2-addition, i.e. C. Attack at C-4 produces
the more stable 1,4- isomer, D. At low temp.
H H the kinetic product, C, will be major since the
Br system is less likely to reverse; at higher
temp. equilibrium will be established in which
A B the more stable product, D, will predominate.
Br

5
7. (9 pts) A new antibiotic compound is thought to have one of the structures shown below. From the spectral
data, which structure corresponds to the drug? Match the proton NMR data to your answer.

H O O H H H
H O2N H

H H
O2N O2 N O2N O O

UV : 290 nm M+ = 205 a.m.u. IR : 1720, 1640, 1200, 800 cm-1

1
H NMR : 1.08 (t, 3H, J = 7.0 Hz), 2.98 (q, 2H, J = 7.0 Hz), 6.54 (d, 1H, J = 12.0 Hz),
7.91 (d, 1H, J = 12.0 Hz), 8.03 (d, 2H, J = 6.8 Hz), 8.37 (d, 2H, J = 6.8 Hz).
13
C NMR : 7.9 (q), 34.0 (t), 123.8 (double intensity, d), 126.2 (d), 129.0 (double intensity, d),
141.3 (s), 142.8 (d), 147.1 (s), 200.4 (s).

7.91
H
8.03 6.54
8.37 H
-
O 8.03
N+ 2.98
O
8.37
O
1.08

J value of 12 Hz matches cis alkene

8. (8 pts) Give the major product(s) expected under the following conditions. Then provide a complete
mechanism for the conversion that includes important resonance structures for any intermediate(s). Briefly
explain the regiochemical outcome of the reaction.

Having the Br go in the meta position avoids positive charge developing next to the
highly electron-withdrawing CF3 group in the intermediate.

6
Chemistry 3720, Spring 2014 Exam 3 Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

HDI/Unsaturation Number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (8 pts) Provide a detailed mechanism for the following reaction sequence that includes resonance structures
for any intermediate(s) that is/are formed.

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical information where applicable.

HO CH3
1. Na2Cr2O7, H2SO4
a.
2. HN(CH3)2, cat. H+

O
1. Cl , AlCl3
b.
2. H2C=PPh3, ether

OH
1. Na2Cr2O7, H2SO4
c.
2. SOCl2
3. CH3CH2OH, pyridine

O OH
1. PBr3
d.
2. Br2
3. H2O

Br 1. HNO3, H2SO4
e.
2. HN(CH2CH3)2, heat

2
3. (10 pts) Design a retrosynthesis for the following molecule that goes back to the starting materials shown.
Then give the synthesis in the forward direction assuming that you have access to any of the reagents seen
in Chemistry 3719 and 3720.
Br CH3

HO

4. (8 pts) Give the major product expected to be formed under the following conditions, and then draw a
mechanism for the conversion that includes important resonance structures for any intermediate(s).

3
5. (8 pts) Provide the major product expected from the following reaction and then a detailed mechanism that
includes all important resonance structures for any intermediates that are formed.

O
xs CH3CH2OH
H
cat. H+

6. (14 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and nomenclature clues might help you come up with answers.

OH PCC CH3MgBr

CH2Cl2 ether

IR : 1740 cm-1 organic salt

H+ (quench)

m-CPBA Na2Cr2O7

CH2Cl2 H2SO4

13
C : 175 ppm IR : 1720 cm-1 6 signals in 13C NMR

xs NH3

One product: pKa = 10

+
Second product: acetamide

two products

4
7. (10 pts) Provide a detailed mechanism for the following Wolf-Kischner reduction sequence. Include all of
the resonance structures for any intermediates that are formed.

8. (8 pts) Methyl benzoate, benzoyl chloride and benzamide are all derivatives of benzoic acid with quite
differing reactivity towards nucleophiles. Draw structures for each of the molecules, then indicate which is
the most reactive and which is the least reactive in reactions with nucleophiles. Explain your choices.

5
9. (6 pts) For each of the following molecules, identify any alpha protons and then draw all of the possible
enolates that would be formed when each molecule was reacted with a strong base.

10. (8 pts) Give a detailed mechanistic interpretation for the following conversion. Be sure to show all of the
resonance structures for any intermediates that are formed.

O O
1. Br2, cat. H+

2. KOt-Bu, THF

6
Chemistry 3720, Spring 2014 Exam 3 - Key Student Name:

“Y” Number:

This exam is worth 100 points out of a total of 700 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. The spectroscopy sheet is attached at the back of the exam. Good Luck!

HDI/Unsaturation Number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (8 pts) Provide a detailed mechanism for the following reaction sequence that includes resonance structures
for any intermediate(s) that is/are formed.

1
2. (20 pts) Provide the expected major products from each step of the following reaction sequences. Be sure to
include any stereochemical information where applicable.

HO CH3 O CH3 (H3C)2N CH3

1. Na2Cr2O7, H2SO4
a. 1. 2.
2. HN(CH3)2, cat. H+

O
O CH2
1. Cl , AlCl3
b. 1. 2.
2. H2C=PPh3, ether

OH O OH O Cl O OEt
1. Na2Cr2O7, H2SO4 1. 2. 3.
c.
2. SOCl2
3. CH3CH2OH, pyridine

O OH O Br O Br O OH
1. PBr3 1. 2. Br 3. Br
d.
2. Br2
3. H2O

Br Br NEt2 NEt2
Br 1. HNO3, H2SO4 1. NO2 2. NO2
e.
2. HN(CH2CH3)2, heat
+ +

NO2 NO2

2
3. (10 pts) Design a retrosynthesis for the following molecule that goes back to the starting materials shown.
Then give the synthesis in the forward direction assuming that you have access to any of the reagents seen
in Chemistry 3719 and 3720.
Br CH3

HO
Retrosynthesis

HO CH3 HO

O O O O

CH3 CH3 Cl CH3 HO CH3

HO CH3

BrMg Br
HO CH3

Synthesis

Br2, Br Mg BrMg then H+ quench

HBr
ether
O Br CH3
Na2Cr2O7 O SOCl2 O
HO CH3
H2SO4 HO CH3 Cl CH3 AlCl3

4. (8 pts) Give the major product expected to be formed under the following conditions, and then draw a
mechanism for the conversion that includes important resonance structures for any intermediate(s).

H+ O O
xs CH3CH2OH
OH OCH2CH3 + H2O
cat. H+

HO
H H
O O OH H
O
OH OH O
OEt
H
HO
H
HO OH HO O H OH OH
H+ trans.
OEt OEt OEt OEt
H

3
5. (8 pts) Provide the major product expected from the following reaction and then a detailed mechanism that
includes all important resonance structures for any intermediates that are formed.

6. (14 pts) In the boxes below, provide the product from each step of the following sequence. Using the
spectroscopic and nomenclature clues might help you come up with answers.

O OMgBr
OH PCC CH3MgBr
H CH3
CH2Cl2 ether H

IR : 1740 cm-1 organic salt

H+ (quench)

O OH
O m-CPBA Na2Cr2O7
CH3 CH3
O CH3 CH2Cl2 H2SO4 H

13
C : 175 ppm IR : 1720 cm-1 6 signals in 13C NMR

xs NH3

O One product: pKa = 10

+
OH H2N CH3
Second product: acetamide

two products
4
7. (10 pts) Provide a detailed mechanism for the following Wolf-Kischner reduction sequence. Include all of
the resonance structures for any intermediates that are formed.

H+ NH2
O N H H
NH2NH2 KOH, H2O

cat. H+ heat

H H NH2
O O N

H hydrazone

NH2NH2

H H
OH O H NHNH2 NNH2
H+ trans.
NH2 NHNH2
NH2

H
N NH N H N H
N H OH N N N

H
OH
H H
O

N
H H H H N
O
- N2
alkane
H H

8. (8 pts) Methyl benzoate, benzoyl chloride and benzamide are all derivatives of benzoic acid with quite
differing reactivity towards nucleophiles. Draw structures for each of the molecules, then indicate which is
the most reactive and which is the least reactive in reactions with nucleophiles. Explain your choices.

Benzoyl chloride is the most reactive whereas benzamide is the least reactive. The former is not
stabilized much by lone pair donation from the large Cl whereas benzamide will benefit from
donation by the NH2 group. Also, Cl is a much better leaving group than NH2.

5
9. (6 pts) For each of the following molecules, identify any alpha protons and then draw all of the possible
enolates that would be formed when each molecule was reacted with a strong base.

10. (8 pts) Give a detailed mechanistic interpretation for the following conversion. Be sure to show all of the
resonance structures for any intermediates that are formed.

H+ O O
1. Br2, cat. H+

2. KOt-Bu, THF

H H
O O :B O
H Br

H
:B Ot-Bu

H H H
O O O
Br Br
Br Br

6
Chemistry 3720 Practice Exam 1 Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam and you may use the attached spectroscopy sheet as needed. Good Luck.

1. (8 pts) Give the major final products from the following and explain the different regiochemical outcomes in
terms of the mechanism(s) operating.
(Klein Chapter 14)

a.
O
1. PhMgBr, ether

2. H3O+ (quench)

b. O
CH3OH

catalytic H+

1
2. (20 pts) Give the major organic product(s), including any stereochemical issues, expected from each step in
the following reactions. You do not have to show any mechanisms.
(Klein Chapters 13 and 14)

O
a.  1. CH3MgBr, ether
 
  2. H+ quench
  3. H2, Pd
 
 
 
 
 
  OH
b. 
1. H3PO4, heat
 
  2. m-CPBA, CH2Cl2
 
3. NaOH, H2O
 
 
 
 
 
 
OH 1. NH+ [(O Cr) O]-
c.  3 2
  2

 
  2. LiAlD4, ether
  3. aq. NH4Cl
 
 
 
 
 
d. 
  O
1. NaBH4, CH3OH
  H
  2. NaNH2, THF
  3. CH3CH2CH2Br
 
 
 
 
 
  SH
e.  1. NaOCH3, THF 1.

2. (CH3)2CHBr
3. xs H2O2, aq. THF

2
3. (16 pts) Give the expected major product from each step of the following reaction sequence. No need to
show any mechanisms.
(Klein Chapter 13)

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 

4. (9 pts) Give the expected final product(s) formed in each of the following cases. (Klein Chapter 14)
 
a.
O excess HBr

b.
excess HBr
O

c.
O excess HI

3
5. (7 pts) Give the expected major product formed under the following reaction conditions, and then a detailed
mechanism for the conversion. How would you tell the product is an alcohol by IR spectroscopy?
(Klein Chapters 13-15)

6. (8 pts) A recently isolated microbial metabolite is found to have the empirical formula C4H7O and its mass
spectrum shows M+ = 142. Significant signals are seen in the IR spectrum at 1740 and 1650 cm-1. The 1H
NMR spectrum, collected in CDCl3, is given below. Provide a structure for the organic compound that
matches the data, and then match the protons in the molecule to the 1H NMR signals. (Klein Chapter 15)
 
Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1 
 

1
H NMR (ppm): 1.06 (d, 6H, J = 7.1 Hz), 1.36 (t, 3H, J = 7.0 Hz), 2.52 (octet, 1H, J = 7.1 Hz), 
4.20 (q, 2H, J = 7.0 Hz), 5.83 (d, 1H, J = 16.0 Hz), 6.88 (dd, 1H, J = 7.1, 16.0 Hz)

4
7. (12 pts) Provide a retrosynthetic plan for the molecule below that uses only the given starting materials as
sources of carbon. Then give a detailed synthesis of the compound that shows each product formed along
the way. You have access to all of the usual reagents in the lab (HBr, HNO3, NaBH4, Zn, Mg, etc.), as well
as techniques for separating isomers and byproducts (i.e. distillation, chromatography, etc.) as needed.
(Klein Chapters 13-14)
 

from and H
O

5
8. (20 pts) Give the major organic product(s) expected from each step in the following reactions. You do not
have to show any mechanisms. (Klein Chapters 13 and 14)

O
a.  1. NaBH4, CH3OH
 
  2. PBr3
  3. NaN3, DMSO
 
 
 
 
 
 
b.  Cl
  1. Mg, ether
 
2. CH3CHO
 
  3. dil. aq. NH4Cl
 
 
 
 
 
c.  OH
  1. H2SO4,
 
  2. OsO4, H2O2, NaOH
3. HIO4
 
 
 
 
 
 
d. 
  1. Br2, H2O
 
  2. NaNH2, THF
  3. NaSCH3, DMF
 
 
 
 
 
 
O
e.  1. LiAlH4, ether

2. dil. aq. NH4Cl

3. CH3COCl, pyridine

6
Chemistry 3720 Practice Exam 1 - Key Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam and you may use the attached spectroscopy sheet as needed. Good Luck.

1. (8 pts) Give the major final products from the following and explain the different regiochemical outcomes in
terms of the mechanism(s) operating.
(Klein Chapter 14)

1
2. (20 pts) Give the major organic product(s), including any stereochemical issues, expected from each step in
the following reactions. You do not have to show any mechanisms.
(Klein Chapters 13 and 14)

H3C
a.  O H3C OMgBr H3C OH H OH
  1. CH3MgBr, ether 1. 2. 3.
 
2. H+ quench
 
3. H2, Pd H
 
racemic
 
 
 
 
 
b.  OH H OH
O
  1. H3PO4, heat 1. 2. 3. OH
H
 
  2. m-CPBA, CH2Cl2
  3. NaOH, H2O
  meso racemic
 
 
 
 
c.  OH 1. NH+ [(O Cr) O]- O D OAlR3 D OH
3 2
  1. 2. 3.
2
 
  2. LiAlD4, ether
  3. aq. NH4Cl
  racemic racemic
 
 
 
 
d. 
  O OH ONa O
1. NaBH4, CH3OH 1. 2. 3.
 
  H H H H
2. NaNH2, THF H H H
 
  3. CH3CH2CH2Br
 
 
 
 
  SH SNa SCH(CH3)2 SO2CH(CH3)2
e.  1. 2. 3.
1. NaOCH3, THF

2. (CH3)2CHBr
3. xs H2O2, aq. THF

2
3. (16 pts) Give the expected major product from each step of the following reaction sequence. No need to
show any mechanisms.
(Klein Chapter 13)

 
 
 
 
 

4. (9 pts) Give the expected final product(s) formed in each of the following cases. (Klein Chapter 14)
 
 
a.
O excess HBr OH Br
+

b.
excess HBr
O Br

Br

c.
O excess HI I I
+

 
 
 

3
5. (7 pts) Give the expected major product formed under the following reaction conditions, and then a detailed
mechanism for the conversion. How would you tell the product is an alcohol by IR spectroscopy?
(Klein Chapters 13-15)

The product would have a broad absorption at ~3600 cm‐1 in the IR spectrum 

6. (8 pts) A recently isolated microbial metabolite is found to have the empirical formula C4H7O and its mass
spectrum shows M+ = 142. Significant signals are seen in the IR spectrum at 1740 and 1650 cm-1. The 1H
NMR spectrum, collected in CDCl3, is given below. Provide a structure for the organic compound that
matches the data, and then match the protons in the molecule to the 1H NMR signals. (Klein Chapter 15)
 
Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1 
 

O
5.83 4.20
H
O 1.36
1.06 Unsat = 8-7+1 = 2
2.52
H 6.88

1.06

8 7 6 5 4 3 2 1 0
PPM
1
H NMR (ppm): 1.06 (d, 6H, J = 7.1 Hz), 1.36 (t, 3H, J = 7.0 Hz), 2.52 (octet, 1H, J = 7.1 Hz), 
4.20 (q, 2H, J = 7.0 Hz), 5.83 (d, 1H, J = 16.0 Hz), 6.88 (dd, 1H, J = 7.1, 16.0 Hz)

4
7. (12 pts) Provide a retrosynthetic plan for the molecule below that uses only the given starting materials as
sources of carbon. Then give a detailed synthesis of the compound that shows each product formed along
the way. You have access to all of the usual reagents in the lab (HBr, HNO3, NaBH4, Zn, Mg, etc.), as well
as techniques for separating isomers and byproducts (i.e. distillation, chromatography, etc.) as needed.
(Klein Chapters 13-14)
 

5
8. (20 pts) Give the major organic product(s) expected from each step in the following reactions. You do not
have to show any mechanisms. (Klein Chapters 13 and 14)

O 1. OH 2. Br 3. N3
a.  1. NaBH4, CH3OH
 
  2. PBr3
  3. NaN3, DMSO
  r acemic r acemic r acemic
 
 
 
 
  ClMgO HO
b.  Cl 1. MgCl 2. 3.
  1. Mg, ether
 
2. CH3CHO
 
3. dil. aq. NH4Cl
 
  r acemic r acemic
 
 
 
 
c.  OH 1. 2. OH OH 3.
  1. H2SO4, O
  CHO
2. OsO4, H2O2, NaOH
 
3. HIO4
 
r acemic
 
 
 
 
 
d. 
1. Br 2. 3. SCH3
  1. Br2, H2O
  O
  2. NaNH2, THF
  3. NaSCH3, DMF OH ONa
 
r acemic meso r acemic
 
 
 
  O
  OAlR3 OH O
O 1. 2. 3.
e.  1. LiAlH4, ether

2. dil. aq. NH4Cl

3. CH3COCl, pyridine
r acemic r acemic r acemic

6
Chemistry 3720 Practice Exam 2 Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam and you may use the attached spectroscopy sheet as needed. Good Luck.

Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (10 pts) Give the expected major product(s) from the following nitration reaction, and then give a complete
mechanism for the conversion that includes resonance structures for the intermediate(s) formed. Explain
why you only get certain isomer(s) as the major product(s) in this reaction. (Klein Chapter 19)
 

1
2. (8 pts) Give the structure of an unknown organic compound with the formula C7H14O2 and the following
spectral characteristics, and then match the 1H signals to your structure:
 
1
H NMR (CDCl3): 0.90 (t, 3H, J = 7.0 Hz), 1.14 (d, 6H, J = 6.9 Hz), 1.73 (sextet, 2H, J = 7.0 Hz), 2.67
(septet, 1H, J = 6.9 Hz), 4.13 (t, 2H, J = 7.0 Hz)
13
C NMR (CDCl3): 10.3 (q), 19.1 (q, double intensity), 21.9 (t), 34.0 (d), 66.5 (t), 177.0 (s)

(Klein Chapter 16)

3. (10 pts) Provide the expected major product(s) from the following reaction, and then give a complete
mechanism for the process that includes any important resonance structures. (Klein Chapter 19)

 
CO2H
Br2, FeBr3

2
4. (20 pts) Give the major organic product(s) expected from each step in the following reaction sequences.
You do not have to show any mechanisms here. (Klein Chapters 17-19)

1. H2C=CHCO2Et
a. 
2. LiAlH4, ether
 
  3. H+ (quench)
 
 
 
 
 
 
 
b. 
1. CH3COCl, AlCl3
 
 
2. Zn, HCl
 
3. Br2, heat
 
 
 
 
 
 
 
c. 
  1. (CH3)3CCl, AlCl3
 
2. Br2, FeBr3
 
3. 2Li, ether
 
  4. D2O
 
 
 
 
d. 
  1. SO3, H2SO4
 
  2. Cl2, AlCl3
  3. NaOH
 
 
 
 
 
  1. (CH3)2CHCl, AlCl3
e.  2. Br2, FeBr3

3. HNO3, H2SO4
4. NaOCH3, CH3OH

3
5. (12 pts) Provide syntheses of the compounds below, starting from benzene, that show each product formed
along the way. You have access to all of the usual reagents in the lab (e.g. HNO3, Br2, NaOH, AlCl3, etc.),
as well as techniques for separating any isomers and byproducts as needed. (Klein Chapter 19)
 
a. 
CO2H

NH2  
 
 
 
 
 
 
 
b. 
HO

CH(CH3)2

6. (12 pts) Give the products from each step of the following synthetic sequence and then, on the NMR axis
given below, draw the expected 1H spectrum of the final product. (Klein Chapters 13 and 16)
 

 
4
7. (12 pts) Consider the following reaction and then answer the questions below related to the mechanism.
(Klein Chapter 17)

Draw a reaction profile (on the axes given below) that describes energy changes during the reaction.

 
 
 
 
 
 
 
Energy  
 
 
 
 
 
 
 
 
 
 
 
 
 
Reaction coordinate
 

In the space below, draw diagrams of all transition states and reactive intermediates (including resonance
structures), and indicate where they appear on the graph above. Indicate the rate-determining step, and
label that step as unimolecular or bimolecular. Finally, explain why the major product is formed here.
 
 
 
 
 
 
 
 
 
 

5
8. (10 pts) Provide a retrosynthetic plan for the molecule shown that goes back only to the organic
compounds provided, and then show how you would build the molecule using chemistry seen in 3719 and
3720. (Klein Chapter 19)
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
9. (6 pts) Indicate which of the following molecules are aromatic and explain your choices based on applying
Hückels’rule. (Klein Chapter 16)
 
 

6
Chemistry 3720 Practice Exam 2 Key Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam and you may use the attached spectroscopy sheet as needed. Good Luck.

Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1

1. (10 pts) Give the expected major product(s) from the following nitration reaction, and then give a complete
mechanism for the conversion that includes resonance structures for the intermediate(s) formed. Explain
why you only get certain isomer(s) as the major product(s) in this reaction. (Klein Chapter 19)
 

1
2. (8 pts) Give the structure of an unknown organic compound with the formula C7H14O2 and the following
spectral characteristics, and then match the 1H signals to your structure: (Klein Chapter 16)
 
1
H NMR (CDCl3): 0.90 (t, 3H, J = 7.0 Hz), 1.14 (d, 6H, J = 6.9 Hz), 1.73 (sextet, 2H, J = 7.0 Hz), 2.67
(septet, 1H, J = 6.9 Hz), 4.13 (t, 2H, J = 7.0 Hz)
13
C NMR (CDCl3): 10.3 (q), 19.1 (q, double intensity), 21.9 (t), 34.0 (d), 66.5 (t), 177.0 (s)

a = 0.90 (t, 3H, J = 7.0 Hz)

b = 1.73 (sextet, 2H, J = 7.0 Hz)

c = 4.13 (t, 2H, J = 7.0 Hz)

d = 1.14 (d, 6H, J = 6.9 Hz)

e = 2.67 (septet, 1H, J = 6.9 Hz)

3. (10 pts) Provide the expected major product(s) from the following reaction, and then give a complete
mechanism for the process that includes any important resonance structures. (Klein Chapter 19)
 
 
CO2H CO2H
Br Br

FeBr3
Br

Br Br FeBr3

Br Br FeBr3

CO2H CO2H CO2H

Br FeBr3

H H H
Br Br Br

2
4. (20 pts) Give the major organic product(s) expected from each step in the following reaction sequences.
You do not have to show any mechanisms here. (Klein Chapters 17-19)

a.  1. H2C=CHCO2Et
  2. LiAlH4, ether
1. 2. 3.
 
3. H+ (quench)
 
EtO2C LiOCH2 HOCH2
 
 
 
 
 
  H Br
O CH3 H CH3 H CH3
b. 
  1. CH3COCl, AlCl3
  1. 2. 3.
  2. Zn, HCl
  3. Br2, heat
 
 
 
 
 
 
c.  C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
  1. (CH3)3CCl, AlCl3
  1. 2. 3. 4.
  2. Br2, FeBr3
  3. 2Li, ether
  4. D2O Br Li D
 
 
 
 
d. 
SO3H SO3H SO3Na
  1. SO3, H2SO4
 
1. 2. 3.
  2. Cl2, AlCl3
  3. NaOH Cl Cl
 
 
 
 
 
 
1. (CH3)2CHCl, AlCl3 CH(CH3)2 CH(CH3)2 CH(CH3)2 CH(CH3)2
e. 
2. Br2, FeBr3
1. 2. 3. 4.
3. HNO3, H2SO4 NO2 NO2
4. NaOCH3, CH3OH Br Br OCH3

3
5. (12 pts) Provide syntheses of the compounds below, starting from benzene, that show each product formed
along the way. You have access to all of the usual reagents in the lab (e.g. HNO3, Br2, NaOH, AlCl3, etc.),
as well as techniques for separating any isomers and byproducts as needed. (Klein Chapter 19)
 

6. (12 pts) Give the products from each step of the following synthetic sequence and then, on the NMR axis
given below, draw the expected 1H spectrum of the final product. (Klein Chapters 13 and 16)
 

4
7. (12 pts) Consider the following reaction and then answer the questions below related to the mechanism.
(Klein Chapter 17)

Draw a reaction profile (on the axes given below) that describes energy changes during the reaction.

 
In the space below, draw diagrams of all transition states and reactive intermediates (including resonance
structures), and indicate where they appear on the graph above. Indicate the rate-determining step, and
label that step as unimolecular or bimolecular. Finally, explain why the major product is formed here.

-
+ H Br
H H
+

first step T.S. intermediate

-
Br +
H H
+
-
Br
second step T.S.
 
 
First step is R.D.S. and it is bimolecular (diene and HBr are involved); major product is the thermodynamic 
outcome since reaction is reversible at higher temperatures and more substituted alkene is favoured. 
 
5
8. (8 pts) Provide a retrosynthetic plan for the molecule shown that goes back only to the organic compounds
provided, and then show how you would build the molecule using chemistry seen in 3719 and 3720. (Klein
Chapter 19)
 
OH O
? OH
H
and

Retr osynthesis
OH O

Li Br OH

Synthesis OLi OH
OH Br 2 Li Li PhCHO NH4Cl
HBr
ether ether
 
 
 
 
 
9. (6 pts) Indicate which of the following molecules are aromatic and explain your choices based on applying
Hückels’rule. (Klein Chapter 16)
 
 

N O

1 = No 2 = Yes 3 = Yes

For 1 : 8 pi electrons so 4n+2 = 8 ; n = 3/2 ; not lat, not aromatic

For 2 : 6 pi electrons so 4n+2 = 8 ; n = 1 ; flat and aromatic

For 3 : 6 pi electrons so 4n+2 = 8 ; n = 1 ; flat and aromatic  

6
Chemistry 3720 Practice Exam 3 Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. Good Luck.

1. (8 pts) Provide a complete mechanism, including all important resonance structures, for the following:
(Klein Chapter 22)

1
2. (20 pts) Give the major organic product(s), including any stereochemical issues, expected from each step in
the following reactions. You do not have to show any mechanisms. (Klein Chapters 20-22)

O
a. 
OH 1. xs CH3OH, cat. H+
 
  2. Sn, HCl
 
  NO2
 
 
 
 
 
 
  OH
b.  1. PCC, CH2Cl2
 
2. xs NaOH, xs I2
 
 
 
 
 
 
 
 
  O
c.  1. SOCl2, pyridine
  OH
  2. HNEt2, pyridine
 
 
 
 
 
 
 
  O
d.  1. Ph3P=CH2, THF
  H
  2. H2, Pd
 
 
 
 
 
 
 
  O
e.  1. LDA, THF

2. CH3CH2CH2Br

2
3. (14 pts) Provide the major organic product from each step of the following synthetic sequence (in the boxes
provided). The spectroscopic clues along the way might help. (Klein Chapters 13-22)
 
 

O (CH3)2CuLi H3O+

H THF (quench)

IR : 1700 cm-1

CH3MgBr
THF

Na2Cr2O7 H3O+

H2SO4 (quench)

IR : 1700 cm-1 IR : 3200 cm-1

PhMgBr
THF

Final product:
H3O+
Molecular formula = C11H16O
(quench) IR : 1700 cm-1

 
 

4. (6 pts) Number the following compounds in order of their decreasing reactivity with nucleophiles; 1 = most
reactive, 3 = least reactive. Then explain your reasoning. (Klein Chapter 21)

3
5. (8 pts) Provide a complete mechanism that describes the following conversion. Include all resonance
structures for any intermediates that are formed. (Klein Chapter 21)

6. (8 pts) Provide a complete mechanism for the following annulation that includes any important resonance
structures along the way. (Klein Chapter 22)

4
7. (8 pts) Provide a retrosynthetic analysis for the following molecule that leads back only to 1-propanol as the
source of carbon. Then show an actual synthesis in the forward direction. (Klein Chapters 13-22)
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
8. (8 pts) Provide a complete mechanism for the following ester saponification sequence: (Klein Chapter 21)
 
O O
i. KOH, EtOH,
O OH +
HO
ii. dilute aq. HCl

5
9. (20 pts) Give the major organic product(s) expected from each step in the following reactions. You do not
have to show any mechanisms. (Klein Chapters 20-22)

O
a.  1. Br2 in H2O
 
  2. NaCN in DMF
 
 
 
 
 
 
 
  O
b.  1. PhMgBr, THF
 
2. dilute HCl (quench)
 
 
 
 
 
 
 
 
 
O
c. 
  O 1. 2 CH3MgBr, THF
  2. dilute HCl (quench)
 
 
 
 
 
 
 
  O
d. 
  1. NH2NH2, cat. H+
 
2. KOH, heat
 
 
 
 
 
 
 
 
 
O
e.  1. excess NaOD/D2O

2. NaBD4, CH3OD

6
Chemistry 3720 Practice Exam 3 - Key Name:

This exam is worth 100 points out of a total of 600 points for Chemistry 3720/3720L. You have 50 minutes to
complete the exam. Good Luck.

1. (8 pts) Provide a complete mechanism, including all important resonance structures, for the following:
(Klein Chapter 22)

O O
1. NaOEt, EtOH H OEt
OEt
OEt 2. H+ (quench) O O
O
H
O
H+
OEt
O
OEt
O O
O O
OEt OEt
OEt OEt O
O O OEt
O O
O O

OEt
O OEt O O
OEt H OEt OEt

O O O O O O

Dieckmann Cyclization
1
2. (20 pts) Give the major organic product(s), including any stereochemical issues, expected from each step in
the following reactions. You do not have to show any mechanisms. (Klein Chapters 20-22)

O O O
a.  1. 2.
  OH 1. xs CH3OH, cat. H+ OCH3 OCH3
 
2. Sn, HCl
 
  NO2 NO2 NH2
 
 
 
 
 
 
  OH O O
b.  1. PCC, CH2Cl2 1. 2.
  ONa
2. xs NaOH, xs I2
 
+ CHI3
 
 
 
 
 
 
 
  O O O
c.  1. SOCl2, pyridine 1. 2.
  OH Cl NEt2
  2. HNEt2, pyridine
 
 
 
 
 
 
 
  O CH2
d.  1. Ph3P=CH2, THF 1. 2. CH2CH3
  H H
  2. H2, Pd
 
 
 
 
 
 
 
  O OLi O
e.  1. LDA, THF 1. 2.

2. CH3CH2CH2Br

NO2 NH2

2
3. (14 pts) Provide the major organic product from each step of the following synthetic sequence (in the boxes
provided). The spectroscopic clues along the way might help. (Klein Chapters 13-22)
 
 

O (CH3)2CuLi H3O+
OLi O
H THF (quench)
H H

IR : 1700 cm-1

CH3MgBr
THF

O Na2Cr2O7 OH H3O+ OMgBr

H2SO4 (quench)
CH3 CH3 CH3

IR : 1700 cm-1 IR : 3200 cm-1

PhMgBr
THF

Final product:
H3O+
OMgBr OH
Molecular formula = C11H16O
H3C Ph (quench) H3C Ph IR : 1700 cm-1

 
 

4. (6 pts) Number the following compounds in order of their decreasing reactivity with nucleophiles; 1 = most
reactive, 3 = least reactive. Then explain your reasoning. (Klein Chapter 21)

O O O

OCH3 NHCH3 Cl

2 3 1

The acid chloride is the most reactive since it is least stabilized by resonance
from the leaving group; Cl is unable to delocalize a lone pair as well as O or N
due to its larger size. Cl is also a much better leaving group than O or N. The
ester is next most reactive since it is not as stabilized as the amide (O is more
electronegative and holds it lone pair tighter), additionally the O leaving group
is better than the N leaving group, again due to O being more electronegative.

3
5. (8 pts) Provide a complete mechanism that describes the following conversion. Include all resonance
structures for any intermediates that are formed. (Klein Chapter 21)
O
1. CH3MgBr, ether
C N: CH3
2. aq. HCl (quench)
3. H2SO4, H2O,

CH3MgBr - H+

H+ H
NMgBr O OH H3N OH
CH3 CH3 CH3 CH3

H + tr ansf er
H+
NH NH2 NH2 H2N OH2
OH2
CH3 CH3 CH3 CH3

6. (8 pts) Provide a complete mechanism for the following annulation that includes any important resonance
structures along the way. (Klein Chapter 22)

Cl
Cl
H
KOH, EtOH,
O
H H3CO
H3CO O
O H O
CH3O
CH3O
O
HO

R1 R1 R1
R1 H
H H H
R2 R2 R2 O
O O O O O O R2
HO
O
H
O
HO

R1 R1 R1 H
H H
O
R2 R2 R2
O O O
O O
O O RO H O

Michael/Robinson sequence

4
7. (8 pts) Provide a retrosynthetic analysis for the following molecule that leads back only to 1-propanol as the
source of carbon. Then show an actual synthesis in the forward direction. (Klein Chapters 13-22)
 
O

H
F.G.I.
O OH O OH O
Retrosynthesis:
H H H

F.G.I. F.G.I.

F.G.I. O
HO HO
H

Synthesis:
PCC O NaOH O
HO aldol
H H pr oduct
CH2Cl2 H2O,
 
 
 
 
 
 
8. (8 pts) Provide a complete mechanism for the following ester saponification sequence: (Klein Chapter 21)
 
O O
i. KOH, EtOH,
O OH +
HO
ii. dilute aq. HCl

HO H+

O O O

O O O
OH HO

O H
O

Saponification

5
9. (20 pts) Give the major organic product(s) expected from each step in the following reactions. You do not
have to show any mechanisms. (Klein Chapters 20-22)

O O O
a.  1. 2. CN
1. Br2 in H2O Br
 
  2. NaCN in DMF
 
 
 
 
 
 
 
  O BrMgO Ph HO Ph
b.  1. PhMgBr, THF 1. 2.
 
  2. dilute HCl (quench)
 
 
 
 
 
 
 
 
O BrMgO HO
c.  CH3 CH3
  1. 2 CH3MgBr, THF 1. 2.
O CH3 CH3
 
2. dilute HCl (quench)
  OMgBr OH
 
 
 
 
 
 
H H
  O NNH2
d. 
1. NH2NH2, cat. H+ 1. 2.
 
  2. KOH, heat
 
 
 
 
 
 
 
 
 
e. 
O O HO D
1. excess NaOD/D2O 1. 2.
D D
2. NaD4, CH3OH D D

6
 

 
 
Chemistry 3720 
Practice Exams 
Chemistry 3720 PRACTICE EXAM QUESTIONS

(12 pts) An unknown natural product has the formula C11H12O2 and its mass spectrum shows M+ = 176.
Important signals are seen in the IR spectrum at 1740, 760, and 690 cm-1. The compound dissolves in
CDCl3 for the NMR spectra shown below. Give a structure for the organic compound that matches the
data and then try to match the protons in the molecule to the 1H NMR signals.
 

1
H NMR (ppm): 2.05 (d, 3H, J = 7.0 Hz), 3.89 (s, 3H), 5.63 (dq, 1H, J = 12.0, 7.0 Hz),
6.35 (d, 1H, J = 12.0 Hz), 7.35 (m, 2H), 7.81 (d, 1H), 7.93 (d, 1H)

13
C NMR (ppm): 12.8 (q), 51.5 (q), 124.4 (d), 127.3 (d), 128.5 (d), 129.1 (d),
130.5 (d), 131.1 (s), 132.8 (d), 137.9 (s), 165.9 (s)

 
3720 Exam 1 2013 (Chapter 16 in Klein)
(8 pts) Each of the following molecules shows only one signal in its 1H NMR spectrum. Draw the
structure of each compound based on its chemical shift and unsaturation number.
 
 

3720 Exam 1 2013 (Chapter 16 in Klein)

(8 pts) Explain in detail the vastly different equilibrium constants for the hydration processes shown in
the equations below.

3720 Exam 2 2013 (Chapter 20 in Klein)

(14 pts) Provide the major organic product from each step of the following synthetic sequence (in the
boxes provided). The spectroscopic clues along the way might help.
 
 
O

Cl NaBH4

AlCl3 CH3OH

IR : 1700 cm-1

H3PO4,

PhMgBr m-CPBA

ether CH2Cl2
then H+ quench
-1
IR : 3400 cm

Na2Cr2O7
H2SO4

Final product:
xs. CH3OH
Molecular formula = C16H18O2
cat. H+ Carbon NMR: 11 13C signals

13
C NMR : 200 ppm  

3720 Exam 2 2013 (Chapters 13-16 in Klein)

(8 pts) Provide a complete mechanism for the following acetal synthesis that includes any important
resonance structures along the way.
 

3720 Exam 2 2013 (Chapter 20 in Klein)

(14 pts) Provide a retrosynthetic analysis for each of the following molecules that leads back only to the
sources of carbon shown in the box below. Then show an actual synthesis in the forward direction for
each.

a. 

 
     
 
 
 
 
 
 
 
 
 
 
 
 
b. 
 

3720 Exam 2 2013 (Chapters 13-20 in Klein)

(9 pts) Give the expected major product(s) under the following conditions, and then give a brief mechanistic
explanation for your choice. The use of pertinent resonance structures will help in your answer.
 
OH
O P OH
HNO3, H2SO4

3720 Exam 1 2011 (Chapter 19 in Klein)

(8 pts) The four isomeric compounds shown below are very closely related pharmaceuticals that have
quite similar NMR, MS, UV, and IR properties. Indicate which molecule matches the 13C spectrum
below and explain why you chose that molecule. There will be no credit for simply guessing a
compound.

3720 Exam 1 2011 (Chapter 16 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

1. Br2, FeBr3
2. Mg, ether
a. 
  3. H2C=O
4. H3O+
 
 
 
 
 
 
 
1. (CH3)2CHCl, AlCl3
  2. CH3COCl, AlCl3
b. 
  3. KMnO4, heat
  4. NaOH
 
 
 
 
 
 
  1. HNO3, H2SO4
c.  2. Sn, HCl
  3. Cl2, FeCl3
 
 
 
 
 
 
 
  1. CH3CH2Cl, AlCl3
d.  2. Br2, heat
  3. NaOCH3, heat
  4. D2, Pt
 
 
 
 
 
 
  1. CH3COCl, AlCl3
  2. SO3, H2SO4
e. 
3. Zn, HCl
4. NaOCH2CH3

3720 Exam 1 2011 (Chapter 19 in Klein)

(12 pts) A newly produced organic pharmaceutical compound is found to have the formula C13H15NO2
and its mass spectrum shows M+ = 217. Significant signals are seen in the IR spectrum at 2250, 1730,
800, and 720 cm-1. The compound is soluble in organic solvents such as ethyl acetate, acetone, as well as
CDCl3 with the NMR spectra below being taken in the latter. Provide a structure for the organic
compound that matches the data, and then match the protons in the molecule to the 1H NMR signals.
 
Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1 
 

9 8 7 6 5 4 3 2 1 0
PPM
1
H NMR (ppm): 1.13 (d, 6H, J = 6.9 Hz), 2.72 (t, 2H, J = 7.0 Hz), 3.19 (septet, 1H, J = 6.9 Hz), 3.53 (t, 2H, J = 7.0 Hz), 
7.71 (t, 1H, J = 6.5 Hz), 8.10 (d, 1H, J = 6.5 Hz), 8.25 (d, 1H, J = 6.5 Hz), 8.42 (s, 1H) 

13
C NMR (ppm): 22.3 (double), 41.3, 63.1, 75.5, 112.5, 118.6, 129.3, 132.0, 133.1, 136.6, 137.4, 198.1 
 
 
3720 Exam 1 2011 (Chapter 16 in Klein)
(12 pts) Give the expected major product(s) from the following acylation reaction, and then a complete
mechanism for the conversion that includes resonance structures for the intermediate formed.
 

3720 Exam 1 2011 (Chapter 19 in Klein)

(15 pts) Provide a retrosynthetic plan for the molecule below that uses only the given starting materials
as sources of carbon. Then give a detailed synthesis of the compound that shows each product formed
along the way. You have access to all of the usual reagents in the lab, as well as techniques for
separating isomers and byproducts (i.e. distillation, chromatography, etc.) as needed.
 

OH
O O
from OH
Cl H
NH2

3720 Exam 1 2011 (Chapters 13-19 in Klein)

(12 pts) Provide the products from each step of the following synthetic scheme and then, on the NMR
axis given below, draw the expected 1H spectrum of the final product.
 
1. (CH3)3CCl, AlCl3
O
2. , AlCl3
Cl

3. NH2NH2, KOH,
4. Br2, heat
5. 2 Li, ether
6. D2O

3720 Exam 1 2011 (Chapters 13-19 in Klein)

(10 pts) Give the expected major product formed under the following reaction conditions, and then give
a detailed mechanism for the conversion. (Hint – the major organic product has the formula C10H18O).
 

3720 Exam 2 2011 (Chapters 13-14 in Klein)

(10 pts) In the boxes provided, give the expected major product from each step of the following reaction
sequence. The spectroscopic clues might help you work out structures.
 
 

Cl Br2

AlCl3 FeBr3

13
C = 6 signals
1. Mg, ether
2. D2O

excess CH3OH KMnO4, heat

cat. H+

1
H = 3 signals IR = 3400, 1750 cm-1  

3720 Exam 2 2011 (Chapters 13-21 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

O
1. NaBH4, CH3OH
2. HBr
a. 
  3. NaOCH3, CH3OH,
  4. OsO4, NaOH, H2O2
 
 
 
 
 
 
  1. m-CPBA, CH2Cl2
b.  2. PhMgBr, ether
 
3. H3O+ (quench)
 
4. PCC, CH2Cl2
 
 
 
 
 
 
  CH2OH
1. Na2Cr2O7, H2SO4
c.  2. xs CH3OH, cat. H+
 
  3. 2 eq. PhMgBr, ether
  4. H3O+ (quench)
 
 
 
 
 
  1. CH3COCl, AlCl3
d.  2. NaBD4, CH3OH
 
  3. NaH, ether
  4. CH3CH2CH2CH2Br
 
 
 
 
 
  O
  1. LiAlH4, ether
e.  2. H3O+ (quench)

3. H3PO4, heat
4. Zn, CH2I2, ether

3720 Exam 2 2011 (Chapters 13-19 in Klein)

(8 pts) Explain the vastly different equilibrium constants observed for the following two hydration
processes.
 

3720 Exam 3 2011 (Chapter 20 in Klein)

 
 
(10 pts) In the boxes provided, give the expected major product from each step of the following
synthetic scheme. The spectroscopic clues might help you work out structures.
 

O KOH, EtOH (CH3)2CuLi

H reflux THF

1
H singlet 9 ppm
H3O+ (quench)

NaOH Na2Cr2O7

aq. EtOH H2SO4

m.p. = 200 oC IR = 3400, 1750 cm-1 IR = 1750 cm-1  

3720 Exam 3 2011 (Chapter 22 in Klein)

(9 pts) Provide a detailed mechanism, including resonance structures where appropriate, for the
following Baeyer-Villager reaction and then explain the regiochemical outcome.
 

3720 Exam 3 2011 (Chapter 20 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

OH
1. PCC, CH2Cl2
2. Br2, FeBr3
a. 
  3. LDA, THF, -78 oC
  4. CH2=CHCH2Br
 
 
 
 
 
 
  1. Br2, low temp.
b.  O 2. NaOCH3, CH3OH
 
3. Ph2CuLi, THF
 
4. H3O+ (quench)
 
 
 
 
 
 
  CH3 1. Na2Cr2O7, H2SO4
c.  2. xs CH3OH, cat. H+
 
  3. HNO3, H2SO4
  4. Sn, HCl
 
 
 
 
 
  O Br 1. xs CH3OH, cat. H+
d.  2. Mg, ether
 
  3. H2C=O, ether
  4. H3O+ (quench)
 
 
 
 
 
  O
  1. PhMgBr, ether
e.  H 2. H3O+ (quench)

3. PCC, CH2Cl2
4. Ph3P=CH2, ether

3720 Exam 3 2011 (Chapters 13-22 in Klein)

(9 pts) Provide a synthesis of the molecule below that uses only the given starting materials as sources of
carbon. You have access to all of the usual reagents in the lab (HBr, HNO3, NaBH4, Zn, Mg, PPh3, CuI,
etc.), as well as techniques for separating isomers (i.e. distillation, chromatography, etc.) as needed. No
need to show a retrosynthesis unless it helps.
 

3720 Exam 3 2011 (Chapters 13-23 in Klein)

(9 pts) Give a detailed mechanism for the following conversion that includes important resonance
structures for intermediates that are formed.
 
 

3720 Exam 3 2011 (Chapter 22 in Klein)

(9 pts) Give the expected major product formed under the following reaction conditions, and then give a
detailed mechanism for the synthetic sequence that includes important resonance structures for
intermediates.
 
 

3720 Exam 3 2011 (Chapter 20 in Klein)

(12 pts) Give the expected major product from each step of the following reaction sequence. No need to
show any mechanisms.
 
1. PCC, CH2Cl2
2. LDA, THF, -78 oC
OH 3. CH3CH2CH2Br

4. NaBH4, CH3OH
5. NaH, THF
6. CH3CH2CH2Br

3720 Exam 3 2011 (Chapters 13-22 in Klein)

(8 pts) Provide a complete mechanism for the following conversion that includes resonance structures
for intermediates that are formed.

3720 Exam 3 2011 (Chapter 22 in Klein)

(6 pts) The following sequence fails to give the product shown; explain why and then give a modified
procedure (showing all intermediate products) that results in the formation of the desired compound.

3720 Exam 3 2011 (Chapter 20 in Klein)

 
(6 pts) The following spectral data belong to one of the five compounds shown below; circle the correct
structure and match the 1H NMR data to that molecule.
1
H NMR (ppm): 2.34 (s, 3H), 3.30 (s, 3H), 4.80 (s, 2H), 7.16-7.48 (m, 4H)
13
C NMR (ppm): 21.6, 58.9, 74.8, 124.4, 128.1, 128.5, 129.3, 138.3, 138.7
IR (cm-1): 760, 700

3720 Exam 1 2009 (Chapter 16 in Klein)

(12 pts) An unknown organic compound has the formula C6H12O2 from mass spectrometry data and the
following signals in the 1H and 13C spectra. Give a structure for the unknown compound that agrees with
the NMR data and then match the 1H NMR signals to the protons in your answer.
1
H NMR (ppm): 1.13 (d, 6H, J = 6.9 Hz), 2.57 (q, 2H, J = 7.0 Hz), 3.19 (septet, 1H, J = 6.9
Hz), 3.67 (t, 2H, J = 7.0 Hz), 9.72 (t, 1H, J = 7.0 Hz)
13
C NMR (ppm): 22.3 (double intensity), 43.5, 61.2, 75.5, 202.2

3720 Exam 1 2009 (Chapter 16 in Klein)

(12 pts) In the lab you have a bottle of benzene and all of the usual reagents and catalysts required to do
organic synthesis. Beginning with benzene, provide an efficient synthesis of the following compounds
by using any of the reactions and reagents seen thus far in Chemistry 3719 and 3720. Show the organic
product(s) from each step of your syntheses; you may assume that isomer mixtures are separable.

NH2

CO2H

HO3S

3720 Exam 1 2009 (Chapter 19 in Klein)

(20 pts) Give mechanistic explanations for the formation of the products and the regiochemical
outcomes in the following reactions (i.e. draw the mechanisms and use resonance structures to explain
the products).

3720 Exam 1 2009 (Chapter 19 in Klein)

(8 pts) Give a detailed mechanism (including resonance structures for the intermediate) for the formation
of the product in the following reaction.

3720 Exam 1 2009 (Chapter 19 in Klein)

(9 pts) Give the major product formed under the following conditions and then a complete mechanism
for its formation. How many signals do you expect to see in the 13C NMR spectrum of the product?

3720 Exam 2 2009 (Chapter 14 in Klein)

(10 pts) On the axis given below, draw the approximate 1H NMR spectrum for the following molecule.
Label which signals belong to which protons.

3720 Exam 1 2009 (Chapter 16 in Klein)

(10 pts) Give the major products from each step of the following reaction sequence. What will the
upfield region of the 1H NMR spectrum of the final product look like (signal shapes and integration
values)?

Exam 2 2009 (Chapter 13 in Klein)

(16 pts) Give the products A through H from the following sequence. The molecular formula data and
the spectral information might help as clues.

Br2, FeBr3 2 Li

ether

A = C6H5Br B = C6H5Li

Na2Cr2O7 H3O+

H2SO4 (quench)

E IR = 1720 cm-1 D IR = 3200 cm-1 C = C10H13LiO

CH3CH2MgBr, THF
then aq. NH4Cl

NaNH2 CH3CH2Br

THF THF

F IR = 3200 cm-1 G C12H17NaO H 11 signals in 13C

3720 Exam 2 2009 (Chapter 13-19 in Klein)

(9 pts) Provide the major organic product, as well as a complete mechanism for its formation, for the
following reaction. How many signals do you expect to see in the 1H NMR spectrum of the product?

3720 Exam 2 2009 (Chapter 14 in Klein)

(18 pts) Provide a retrosynthesis for each of the following target compounds that goes back to the given
starting materials the sources of carbon. Then give step-by-step syntheses of the target compounds,
showing products from each step along the way.

a.

b.

from and HO
O

3720 Exam 2 2009 (Chapters 13-14 in Klein)

(18 pts) Provide mechanisms for both of the following transformations that include all intermediates and
any important resonance structures.

a.

b.

3720 Exam 2 2009 (Chapters 13 and 21 in Klein)

(20 pts) Give the major organic products from each step of the following reaction sequences (i.e. when
there is more than one step, a product from each is expected).

a.

b.

c.

d.

e.

3720 Exam 2 2009 (Chapters 13-14 in Klein)

(10 pts) Give a complete mechanism for the following transformation that includes any important
resonance structures for intermediates that may be formed.

3720 Exam 2 2009 (Chapter 20 in Klein)

(9 pts) Give a complete mechanism for the formation of the product in the following transformation that
includes resonance structures where applicable. What role do you think the MgSO4 is playing here?

3720 Exam 2 2009 (Chapter 21 in Klein)

(9 pts) Provide a complete mechanism for the formation of the product in the following reaction. How
many signals do you expect to see in the 13C NMR spectrum of the product?

O O
KOH, ethanol

O reflux

3720 Exam 2 2009 (Chapter 22 in Klein)

(10 pts) Provide a step-by-step synthesis, showing products from each step along the way, of the
following target compound using only the given starting materials as the sources of carbon. Although
you do not have to show a retrosynthesis, using this technique might help you to solve the problem.

3720 Exam 2 2009 (Chapter 22 in Klein)

(20 pts) Give the major organic products from each step of the following reaction sequences (i.e. when
there is more than one step, a product from each is expected).

a.

b.

c.

d.

e.

O
1. LDA, THF

2. CH3CH2CH3Br
3720 Exam 2 2009 (Chapters 22-23 in Klein)
(16 pts) Give the products A through H from the following sequence. The molecular formula data and
the spectral information might help as clues.

Cl Br2

AlCl3 FeBr3

A 13C NMR 200 ppm B = C9H9BrO

1. LDA, THF
2. CH3CH2Br

Mg (CH2OH2)

THF cat. H+

E = C13H17BrMgO2 D = C13H17BrO2 C IR = 1720 cm-1

CO2
then H+ quench

SOCl2 dilute HCl

then CH3OH
pyridine

F 13C NMR = 175 ppm G = C15H20O4 H = C13H16O3

3720 Exam 2 2009 (Chapters 13-23 in Klein)

(8 pts) Provide a major product from each step of the following reaction sequence.

3720 Exam 2 2009 (Chapter 22 in Klein)

(9 pts) Order the following compounds in terms of their relative reactivity with nucleophiles (1 = most
reactive, 3 = least reactive) and then give a brief explanation for your choices.

OCH3

Cl

NHCH3

3720 Exam 2 2009 (Chapter 21 in Klein)

(9 pts) Order the following compounds in terms of their relative boiling points (1 = highest, 3 = lowest)
and then give a brief explanation for your choices.

3720 Exam 2 2009 (Chapter 21 in Klein)

Chemistry 3720 PRACTICE EXAM QUESTIONS KEY

(12 pts) An unknown natural product has the formula C11H12O2 and its mass spectrum shows M+ = 176.
Important signals are seen in the IR spectrum at 1740, 760, and 690 cm-1. The compound dissolves in
CDCl3 for the NMR spectra shown below. Give a structure for the organic compound that matches the
data and then try to match the protons in the molecule to the 1H NMR signals.

1
H NMR (ppm): 2.05 (d, 3H, J = 7.0 Hz), 3.89 (s, 3H), 5.63 (dq, 1H, J = 12.0, 7.0 Hz),
6.35 (d, 1H, J = 12.0 Hz), 7.35 (m, 2H), 7.81 (d, 1H), 7.93 (d, 1H)

13
C NMR (ppm): 12.8 (q), 51.5 (q), 124.4 (d), 127.3 (d), 128.5 (d), 129.1 (d),
130.5 (d), 131.1 (s), 132.8 (d), 137.9 (s), 165.9 (s)

B
O OCH3
A
CH3
E H
C
H
D  
 
[A 2.05 (d, 3H, J = 7.0 Hz)], [B 3.89 (s, 3H)], [C 5.63 (dq, 1H, J = 12.0, 7.0 Hz)],
[D 6.35 (d, 1H, J = 12.0 Hz)], [E 7.35 (m, 2H), 7.81 (d, 1H), 7.93 (d, 1H)] 
 
3720 Exam 1 2013 (Chapter 16 in Klein)
(8 pts) Each of the following molecules shows only one signal in its 1H NMR spectrum. Draw the
structure of each compound based on its chemical shift and unsaturation number.
 
a. C8H18 0.9 ppm b. C8H8 5.8 ppm

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

c. C2H4Cl2 3.7 ppm d. C12H18 2.2 ppm

CH3
Cl Cl H3C CH3
H H
Cl Cl H3C CH3
CH3  

3720 Exam 1 2013 (Chapter 16 in Klein)

(8 pts) Explain in detail the vastly different equilibrium constants for the hydration processes shown in
the equations below.

O K = 22,000 HO OH O K = 0.0014 HO OH
F3C CF3 F3C CF3 H3C CH3 H3C CH3

Considering the left hand side of each equation, the ketone on the left is a lot less
stable than the one on the right because the CF3 groups are powerfully electron-
withdrawing whereas the CH3 groups on the right are lectron-dontating, which
serves to stabilize the electron-poor carbonyl group. Both acetals will suffer from
steric compression in which the large alkyl groups will repel, however the overall
equilibrium constant is a balance between the stabilities of the species on either side
of the equation i.e. the ketone and the hydrate. In the left equation the ketone is
significantly destabilized, in the right the ketone is favoured.

3720 Exam 2 2013 (Chapter 20 in Klein)

(14 pts) Provide the major organic product from each step of the following synthetic sequence (in the
boxes provided). The spectroscopic clues along the way might help.
 
O
O OH
Cl NaBH4

AlCl3 CH3OH H

IR : 1700 cm-1

H3PO4,

H OH
H H
PhMgBr
O m-CPBA
H H
ether H CH2Cl2
H
then H+ quench
IR : 3400 cm-1

Na2Cr2O7
H2SO4

O H3CO OCH3
Final product:
xs. CH3OH
Molecular formula = C16H18O2
cat. H+ Carbon NMR: 11 13C signals

13
C NMR : 200 ppm  

3720 Exam 2 2013 (Chapters 13-16 in Klein)

(8 pts) Provide a complete mechanism for the following acetal synthesis that includes any important
resonance structures along the way.
 
3720 Exam 2 2013 (Chapter 20 in Klein)

(14 pts) Provide a retrosynthetic analysis for each of the following molecules that leads back only to the
sources of carbon shown in the box below. Then show an actual synthesis in the forward direction for
each.
a. Cl OH OH BrMg
FGI C-C

FGI O Br
HO H

Synthesis:
Br2, Br Mg BrMg
ether

PCC O
HO CH2Cl2 H

Cl SOCl2
OH NH4Cl
OMgBr

 
     
 
OH OH O
b.
FGI C-C H

FGI

FGI Br FGI Li HO

Synthesis:
Br2 Br 2 Li Li

FeBr3 ether

PCC O
HO CH2Cl2 H

H3PO4 OH NH4Cl OLi

3720 Exam 2 2013 (Chapters 13-20 in Klein)

(9 pts) Give the expected major product(s) under the following conditions, and then give a brief mechanistic
explanation for your choice. The use of pertinent resonance structures will help in your answer.
 

3720 Exam 1 2011 (Chapter 19 in Klein)

(8 pts) The four isomeric compounds shown below are very closely related pharmaceuticals that have
quite similar NMR, MS, UV, and IR properties. Indicate which molecule matches the 13C spectrum
below and explain why you chose that molecule. There will be no credit for simply guessing a
compound.

The highlighted compound has two symmetrical aromatic rings so there will be double signals in 
the 13C spectrum. The other three compounds will have 15 signals each in their spectra  
3720 Exam 1 2011 (Chapter 16 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

OMgBr OH
1. Br2, FeBr3 Br MgBr
1. 2. 3. 4.
a.  2. Mg, ether
 
3. H2C=O
  4. H3O+
 
 
 
 
 
 
O OH O ONa
  1. (CH3)2CHCl, AlCl3
1. 2. 3. 4.
b.  2. CH3COCl, AlCl3
 
  3. KMnO4, heat
  4. NaOH
  O O
O
 
 
 
 
  NO2 NH2 NH2 NH2
1. HNO3, H2SO4 1. 2. 3.
c. 
2. Sn, HCl Cl
 
  3. Cl2, FeCl3
+
 
  Cl
 
 
 
  D
  Br D
d.  1. CH3CH2Cl, AlCl3 1. 2. 3. 4.
2. Br2, heat
 
  3. NaOCH3, heat
  4. D2, Pt
 
 
 
 
 
  O O
  1. CH3COCl, AlCl3
1. 2. 3. 4.
e.  2. SO3, H2SO4

3. Zn, HCl
4. NaOCH2CH3 SO3H SO3H SO3Na

3720 Exam 1 2011 (Chapter 19 in Klein)

(12 pts) A newly produced organic pharmaceutical compound is found to have the formula C13H15NO2
and its mass spectrum shows M+ = 217. Significant signals are seen in the IR spectrum at 2250, 1730,
800, and 720 cm-1. The compound is soluble in organic solvents such as ethyl acetate, acetone, as well as
CDCl3 with the NMR spectra below being taken in the latter. Provide a structure for the organic
compound that matches the data, and then match the protons in the molecule to the 1H NMR signals.
 
Unsaturation number = [#C atoms – ½#H atoms – ½#Halogen atoms + ½#N atoms] + 1 
 

1
H NMR (ppm): 1.13 (d, 6H, J = 6.9 Hz), 2.72 (t, 2H, J = 7.0 Hz), 3.19 (septet, 1H, J = 6.9 Hz), 3.53 (t, 2H, J = 7.0 Hz), 
7.71 (t, 1H, J = 6.5 Hz), 8.10 (d, 1H, J = 6.5 Hz), 8.25 (d, 1H, J = 6.5 Hz), 8.42 (s, 1H) 

13
C NMR (ppm): 22.3 (double), 41.3, 63.1, 75.5, 112.5, 118.6, 129.3, 132.0, 133.1, 136.6, 137.4, 198.1 
 
Mass spectrum shows that the formula of the compound is C13H15NO2 as given and the IR 
signal at 2250 suggests a nitrile (cyano) group (unsat’n of 2). IR signal at 1730 and 13C NMR 
signal at 198.1 ppm indicates a ketone (unsat’n of 1). IR signals at 800 and 720, as well as 
signals  at  7.5‐8.5  and  112‐137  in  the  1H  and  13C  spectra  respectively,  point  a  meta‐
disubst’d aromatic ring (unsat’n of 4).  
 
 
3720 Exam 1 2011 (Chapter 16 in Klein)
(12 pts) Give the expected major product(s) from the following acylation reaction, and then a complete
mechanism for the conversion that includes resonance structures for the intermediate formed.
 

3720 Exam 1 2011 (Chapter 19 in Klein)

(15 pts) Provide a retrosynthetic plan for the molecule below that uses only the given starting materials
as sources of carbon. Then give a detailed synthesis of the compound that shows each product formed
along the way. You have access to all of the usual reagents in the lab, as well as techniques for
separating isomers and byproducts (i.e. distillation, chromatography, etc.) as needed.
 
3720 Exam 1 2011 (Chapters 13-19 in Klein)

(12 pts) Provide the products from each step of the following synthetic scheme and then, on the NMR
axis given below, draw the expected 1H spectrum of the final product.
 

1. (CH3)3CCl, AlCl3
O
2. , AlCl3 1. 2. 3.
Cl

3. NH2NH2, KOH,
4. Br2, heat
O
5. 2 Li, ether
6. D2O

4. 5. 6.

Br Li D

1.35
1.35 1.35

7.41 7.41

7.21 7.21
0.90 2.8
D
1.7

8 7 6 5 4 3 2 1 0
PPM

3720 Exam 1 2011 (Chapters 13-19 in Klein)

(10 pts) Give the expected major product formed under the following reaction conditions, and then give
a detailed mechanism for the conversion. (Hint – the major organic product has the formula C10H18O).
 

3720 Exam 2 2011 (Chapters 13-14 in Klein)

(10 pts) In the boxes provided, give the expected major product from each step of the following reaction
sequence. The spectroscopic clues might help you work out structures.
 
 

3720 Exam 2 2011 (Chapters 13-21 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

O OH Br OH
1. NaBH4, CH3OH 1. 2. 3. 4.
2. HBr OH
a. 
  3. NaOCH3, CH3OH,
  4. OsO4, NaOH, H2O2
 
 
 
 
 
 
OMgBr OH O
  1. m-CPBA, CH2Cl2
1. O 2. 3.
Ph Ph 4. Ph
b.  2. PhMgBr, ether
 
3. H3O+ (quench)
 
4. PCC, CH2Cl2
 
 
 
 
 
 
  CH2OH OH OCH3 Ph Ph Ph Ph
1. Na2Cr2O7, H2SO4 1. 2. 3. 4.
c.  2. xs CH3OH, cat. H+ O O OMgBr OH
 
  3. 2 eq. PhMgBr, ether
  4. H3O+ (quench)
 
 
 
 
 
  1. CH3COCl, AlCl3 1. 2. OH 3. ONa 4. O(CH2)3CH3
d.  2. NaBD4, CH3OH O D D D
 
  3. NaH, ether
  4. CH3CH2CH2CH2Br
 
 
 
 
 
  O OH
1. LiAlH4, ether H O-AlX3 H
  1. 2. 3. 4.
e.  2. H3O+ (quench) H
3. H3PO4, heat
4. Zn, CH2I2, ether

3720 Exam 2 2011 (Chapters 13-19 in Klein)

(8 pts) Explain the vastly different equilibrium constants observed for the following two hydration
processes.
 

For the ketone the equilibrium heavily favours the carbonyl and not the 
hydrate;  the  carbonyl  is  stabilized  by  electron  donation  from  the  two 
alkyl groups and the hydrate experiences strain due to the two bulky alkyl 
groups.  In  the  case  of  the  aldehyde  the  carbonyl  is  less  stabilized  with 
only one alkyl group and the hydrate is not as crowded since the H is very 
small.  

3720 Exam 3 2011 (Chapter 20 in Klein)

 
 
(10 pts) In the boxes provided, give the expected major product from each step of the following
synthetic scheme. The spectroscopic clues might help you work out structures.
 
O OLi
O KOH, EtOH (CH3)2CuLi
H H
H reflux THF
H CH3

1
H singlet 9 ppm
H3O+ (quench)

O O O
NaOH Na2Cr2O7
ONa OH H
aq. EtOH H2SO4
CH3 CH3 CH3

m.p. = 200 oC IR = 3400, 1750 cm-1 IR = 1750 cm-1  

3720 Exam 3 2011 (Chapter 22 in Klein)

(9 pts) Provide a detailed mechanism, including resonance structures where appropriate, for the
following Baeyer-Villager reaction and then explain the regiochemical outcome.
 
O
O Cl OH
O O
O

CH2Cl2

O
Cl OH
O
O H
O

B:
H O
Cl
O O O
OH
O

H
O O
H+ transfer HO O O
Cl
HO O O
Cl

The more highly substituted (and hence more electron‐rich) group 
migrates to the electron‐poor oxygen. 
 

3720 Exam 3 2011 (Chapter 20 in Klein)

(20 pts) Give the major organic product(s) expected from each step in the following conversions. You
do not have to provide mechanisms.

a. 
 
 
 
 
 
 
 
 
 
b. 
 
 
 
 
 
 
 
 
 
c. 
 
 
 
 
 
 
 
 
 
d. 
 
 
 
 
 
 
 
 
 
 
e. 

3720 Exam 3 2011 (Chapters 13-22 in Klein)

(9 pts) Provide a synthesis of the molecule below that uses only the given starting materials as sources of
carbon. You have access to all of the usual reagents in the lab (HBr, HNO3, NaBH4, Zn, Mg, PPh3, CuI,
etc.), as well as techniques for separating isomers (i.e. distillation, chromatography, etc.) as needed. No
need to show a retrosynthesis unless it helps.
 

3720 Exam 3 2011 (Chapters 13-23 in Klein)

(9 pts) Give a detailed mechanism for the following conversion that includes important resonance
structures for intermediates that are formed.
 
 
O O NaOCH3, CH3OH
O
+
H
reflux
H

OCH3

O O OH O

H
O H OCH3

H O O OCH3

H
 

3720 Exam 3 2011 (Chapter 22 in Klein)

(9 pts) Give the expected major product formed under the following reaction conditions, and then give a
detailed mechanism for the synthetic sequence that includes important resonance structures for
intermediates.
 
 

1. :PPh3, ether
Br
2. Li , THF
3. O

- Ph3P=O

Li Ph3P
H O

PPh3 Br

Ph3P
O
PPh3 PPh3
 

3720 Exam 3 2011 (Chapter 20 in Klein)

(12 pts) Give the expected major product from each step of the following reaction sequence. No need to
show any mechanisms.
 
1. PCC, CH2Cl2
2. LDA, THF, -78 oC
OH 1. O 2. OLi
3. CH3CH2CH2Br

4. NaBH4, CH3OH
5. NaH, THF
6. CH3CH2CH2Br
3. O 4. OH

5. ONa 6. O

3720 Exam 3 2011 (Chapters 13-22 in Klein)

(8 pts) Provide a complete mechanism for the following conversion that includes resonance structures
for intermediates that are formed.

O O O
KOH, EtOH

H reflux
O O

RO

O O O O

O O O

O
O
OH
H
O
O
H OR RO

3720 Exam 3 2011 (Chapter 22 in Klein)

(6 pts) The following sequence fails to give the product shown; explain why and then give a modified
procedure (showing all intermediate products) that results in the formation of the desired compound.

O O
1. Mg, ether

2. O
Br OH

3. H3O+
H3O+ (hydrolysis)
O
H3CO OCH3
xs CH3OH
cat. H+
BrMg
good chance of intr amolecular OH
r eaction so ketone needs to be
pr otected f ir st
H3O+ (quench)

H3CO OCH3 H3CO OCH3 O H3CO OCH3

Mg, ether

Br BrMg
OMgBr

3720 Exam 3 2011 (Chapter 20 in Klein)

(6 pts) The following spectral data belong to one of the five compounds shown below; circle the correct
structure and match the 1H NMR data to that molecule.
1
H NMR (ppm): 2.34 (s, 3H), 3.30 (s, 3H), 4.80 (s, 2H), 7.16-7.48 (m, 4H)
13
C NMR (ppm): 21.6, 58.9, 74.8, 124.4, 128.1, 128.5, 129.3, 138.3, 138.7
IR (cm-1): 760, 700

3720 Exam 1 2009 (Chapter 16 in Klein)

(12 pts) An unknown organic compound has the formula C6H12O2 from mass spectrometry data and the
following signals in the 1H and 13C spectra. Give a structure for the unknown compound that agrees with
the NMR data and then match the 1H NMR signals to the protons in your answer.
1
H NMR (ppm): 1.13 (d, 6H, J = 6.9 Hz), 2.57 (q, 2H, J = 7.0 Hz), 3.19 (septet, 1H, J = 6.9
Hz), 3.67 (t, 2H, J = 7.0 Hz), 9.72 (t, 1H, J = 7.0 Hz)
13
C NMR (ppm): 22.3 (double intensity), 43.5, 61.2, 75.5, 202.2

3720 Exam 1 2009 (Chapter 16 in Klein)

(12 pts) In the lab you have a bottle of benzene and all of the usual reagents and catalysts required to do
organic synthesis. Beginning with benzene, provide an efficient synthesis of the following compounds
by using any of the reactions and reagents seen thus far in Chemistry 3719 and 3720. Show the organic
product(s) from each step of your syntheses; you may assume that isomer mixtures are separable.

O O O
Cl HNO3

AlCl3 H2SO4
NH2 NO2
(+ trace amounts of o/p isomers -
separate)

O
Sn Zn

HCl HCl
NH2 NH2
3720 Exam 1 2009 (Chapter 19 in Klein)

(20 pts) Give mechanistic explanations for the formation of the products and the regiochemical
outcomes in the following reactions (i.e. draw the mechanisms and use resonance structures to explain
the products).

a)

only isomer f ormed

o
H2SO4, 0 C

The t-butyl group is an o/p

director since it stabilizes
H the carbocation f ormed in
O those case (one resonance
H H
structure has 3o character);
only the p isomer is formed
here becuase the o positions
are crowded by the very big
t-butyl group.
H
O
H
H

3o character
3720 Exam 1 2009 (Chapter 19 in Klein)

(8 pts) Give a detailed mechanism (including resonance structures for the intermediate) for the formation
of the product in the following reaction.

3720 Exam 1 2009 (Chapter 19 in Klein)

(9 pts) Give the major product formed under the following conditions and then a complete mechanism
for its formation. How many signals do you expect to see in the 13C NMR spectrum of the product?

Product is symmetrical so you would see 6 signals in its 13C spectrum.

3720 Exam 2 2009 (Chapter 14 in Klein)

(10 pts) On the axis given below, draw the approximate 1H NMR spectrum for the following molecule.
Label which signals belong to which protons.

3720 Exam 1 2009 (Chapter 16 in Klein)

(10 pts) Give the major products from each step of the following reaction sequence. What will the
upfield region of the 1H NMR spectrum of the final product look like (signal shapes and integration
values)?

3H doublet at ~1 ppm for CH3; 1H quartet at ~2.5 ppm for benzylic CH

D is not magnetically active so it does not show up

Exam 2 2009 (Chapter 13 in Klein)

(16 pts) Give the products A through H from the following sequence. The molecular formula data and
the spectral information might help as clues.

Br2, FeBr3 Br 2 Li Li

ether

A = C6H5Br B = C6H5Li

O OH OLi
+
Na2Cr2O7 H3O

H2SO4 (quench)

E IR = 1720 cm-1 D IR = 3200 cm-1 C = C10H13LiO

CH3CH2MgBr, THF
then aq. NH4Cl

OH ONa O
NaNH2 CH3CH2Br

THF THF

F IR = 3200 cm-1 G C12H17NaO H 11 signals in 13C

3720 Exam 2 2009 (Chapter 13-19 in Klein)

(9 pts) Provide the major organic product, as well as a complete mechanism for its formation, for the
following reaction. How many signals do you expect to see in the 1H NMR spectrum of the product?

Product is symmetrical so you would see 7 signals in its 13C spectrum.

3720 Exam 2 2009 (Chapter 14 in Klein)

(18 pts) Provide a retrosynthesis for each of the following target compounds that goes back to the given
starting materials the sources of carbon. Then give step-by-step syntheses of the target compounds,
showing products from each step along the way.

a.

OH
from
OH

O
OH
Li Br

Synthesis:
O OH Br Li
Na2Cr2O7 HBr 2 Li

H2SO4 ether

aq. NH4Cl

OLi OH
b.

from
OH

OH O

MgBr Br

Synthesis:
m-CPBA HBr Br Mg MgBr
O
CH2Cl2 ether

O aq. NH4Cl

OMgBr OH

3720 Exam 2 2009 (Chapters 13-14 in Klein)

(18 pts) Provide mechanisms for both of the following transformations that include all intermediates and
any important resonance structures.

a.
b.
O OH
1. 2 CH3Li, THF
O + HO
2. aq. NH4Cl
- +
CH3Li

H2O H
OLi OLi

O
+ LiO

O - + H OH2
CH3Li

LiO

3720 Exam 2 2009 (Chapters 13 and 21 in Klein)

(20 pts) Give the major organic products from each step of the following reaction sequences (i.e. when
there is more than one step, a product from each is expected).

a.

b.

c.

d.

e.

3720 Exam 2 2009 (Chapters 13-14 in Klein)

(10 pts) Give a complete mechanism for the following transformation that includes any important
resonance structures for intermediates that may be formed.

Br 1. PPh3, THF
Ph3P: 2. CH3CH2CH2CH2Li

3. O

- Ph3P=O

PPh3 O
Ph3P H - Ph3P
+
Li
Br

O
Ph3P Ph3P

3720 Exam 3 2009 (Chapter 20 in Klein)

(9 pts) Give a complete mechanism for the formation of the product in the following transformation that
includes resonance structures where applicable. What role do you think the MgSO4 is playing here?

3720 Exam 3 2009 (Chapter 21 in Klein)

(9 pts) Provide a complete mechanism for the formation of the product in the following reaction. How
many signals do you expect to see in the 13C NMR spectrum of the product?

O O
H K+ -OH, ethanol

O reflux

O O OR

H
O
O OH
O

O H OR
O

Expect to see 10 signals in the 13C spectrum of the product

3720 Exam 3 2009 (Chapter 22 in Klein)

(10 pts) Provide a step-by-step synthesis, showing products from each step along the way, of the
following target compound using only the given starting materials as the sources of carbon. Although
you do not have to show a retrosynthesis, using this technique might help you to solve the problem.

O OH
from OH +
H

O O O O

H H H H

OH HBr Br 2 Li Li CuI
CuLi
ether ether 2

PCC O KOH, EtOH O

OH
CH2Cl2 H 50 oC H

O OH OLi
aq. NH4Cl
H H H

Note: the retrosynthesis was not required but is included here to show how the problem is solved

3720 Exam 2 2009 (Chapter 22 in Klein)

(20 pts) Give the major organic products from each step of the following reaction sequences (i.e. when
there is more than one step, a product from each is expected).

a.

b.

c.

d.

HO O NCH2Ph
1. PCC, CH2Cl2 1. 2.

2. PhCH2NH2, cat. H+

oxidation product imine formation

(2o OH to ketone) (1o amine used)

e.

3720 Exam 3 2009 (Chapters 22-23 in Klein)

(16 pts) Give the products A through H from the following sequence. The molecular formula data and
the spectral information might help as clues.

O O
O
Cl Br2 Br
AlCl3 FeBr3

F-C acylation meta bromination

A 13C NMR 200 ppm B = C9H9BrO

1. LDA, THF
2. CH3CH2Br

O
O O Mg O O (CH2OH2)
BrMg Br Br

THF cat. H+

Grignard formation acetal formation -alkylation

E = C13H17BrMgO2 D = C13H17BrO2 C IR = 1720 cm-1

CO2
then H+ quench

O O O O
O O SOCl2 O O dilute HCl
HO H3CO H3CO
then CH3OH
pyridine
Nuc addition to CO2 esterification via acid chloride acetal hydrolysis

F 13C NMR = 175 ppm G = C15H20O4 H = C13H16O3

3720 Exam 3 2009 (Chapters 13-23 in Klein)

(8 pts) Provide a major product from each step of the following reaction sequence.

1. PCC, CH2Cl2 H
2. (CH3)2C=O, KOH, CH3OH,
OH 1. O
stops at aldehyde
3. (CH3CH2)2CuLi, THF
4. aq. NH4Cl (quench)
H O
2. crossed aldol reaction

OLi
3. 1,4- cuprate addition

O
3. via the enol form

3720 Exam 2 2009 (Chapter 22 in Klein)

(9 pts) Order the following compounds in terms of their relative reactivity with nucleophiles (1 = most
reactive, 3 = least reactive) and then give a brief explanation for your choices.

O
The molecule is stabilized by lone pair donation from the O(CH3) group; the highly E.N. O is of similar
2 size to the carbonyl C so overlap is good, however donation is not as significant as with the less E.N.
OCH3 N in the amide (3). The OCH3 group is a better L.G. than NHCH3 but not as good as Cl.

O
The molecule is stabilized somewhat by lone pair donation from the Cl; the highly E.N. Cl is larger than
1 the carbonyl C so overlap is not as good; donation is not as significant as with the O of the ester (2) or
Cl the N in the amide (3). The Cl species is a better L.G. than both NHCH3 and OCH3.

O The molecule is stabilized by lone pair donation from the NH(CH3) group; the E.N. N atom is of similar
3 size to the carbonyl C so overlap is good, however donation is more significant than with the more E.N.
NHCH3 O in the ester (2). The NHCH3 group is a worse L.G. than both OCH3 and Cl.

3720 Exam 3 2009 (Chapter 21 in Klein)

(9 pts) Order the following compounds in terms of their relative boiling points (1 = highest, 3 = lowest)
and then give a brief explanation for your choices.

O Significant dipoles and strong H-bonding possibilites lead to strong intermolecular interactions
1 and consequently a higher temperature needed to overcome those interactions and turn the
OH material from being a liquid to a gas.

O Significant dipoles but no real H-bonding possibilites lead to weaker intermolecular interactions
2 and consequently a lower temperature needed to overcome those interactions and turn the
OCH3 material from being a liquid to a gas.

Less significant dipoles and no real H-bonding possibilites result in much weaker intermolecular
OCH3 3 interactions and consequently a lower temperature needed to overcome those interactions and
turn the material from being a liquid to a gas.

3720 Exam 3 2009 (Chapter 21 in Klein)