Practice Final Exam B

8:30 — 11:30 a.m.

Name:

Important Notes:

1. This exam consists of 18 problems on 18 pages, plus this cover sheet, and two pages for scratch work
at the end of the exam.

2. All answers must be written in the spaces provided. Do not write anything in red ink. Answers
written on the back of a page will not be graded. Anything written on the scratch pages will not be graded.

3. You are allowed to use a set of molecular models for this exam.

Problem Score Problem Score

1. ____________ / 16 10. ____________ / 18

2. ____________ / 16 11. ____________ / 18

3. ____________ / 16 12. ____________ / 18

4. ____________ / 16 13. ____________ / 18

5. ____________ / 14 14. ____________ / 18

6. ____________ / 14 15. ____________ / 16

Total Score:
7. ____________ / 18 16. ____________ / 16

8. ____________ / 18 17. ____________ / 16

______________
9. ____________ / 18 18. ____________ / 16 / 300
 1 Name:
1. Each of the following transformations can be carried out in no more than three steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" through that step.

OH 1. OH
a)

2.

3.

1.
b)
2. O2N

3.

1.
c)
HO OH
2. S

3.

1. Br
d)
HO
2. O

3.

_______ / 16
 2 Name:
2. Each of the following transformations can be carried out in no more than three steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" through that step.

Cl
1. Cl
a)

2.

3.

1.
b)
2. O

3.

O OH

1.
c)
2.

3.

CO2Et
1.
d) O

2. CO2Et

3. (+/-)

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 3 Name:
3. Fill in each box with the single major organic product of the indicated transformation. Be sure to indicate
stereochemistry where relevant!

a)
CO2H Br2
HO2C

1. Br2, H2O
b)
2. NaOH

Cl

F
c) NaOEt

NO2

d) 1. OsO4, H2O

2. CrO3, pyridine

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 4 Name:
4. Fill in each box with the starting material of the indicated transformation. Be sure to indicate
stereochemistry if it is relevant! For full credit, all reagents must be used in a meaningful way.

CN
1. PBr3
a)
2. NaCN

h
b)
D

OH
Ph Et
1. BH3, THF
c)
2. NaOH, H2O2 Me H
H

(+/-)

1. NH2OH, pH 5
NH
d)
2. H+
O

_______ / 16
 5 Name:
5. You have just synthesized a new compound, and the following spectroscopic data is obtained:
• From the mass spectrum, you deduce that the molecular formula is: C12H19N
• The infrared spectrum is:

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 450
WAVENUMBERS

From the infrared spectrum, circle the functional From the infrared spectrum, circle the functional
groups that are definitely present: groups that are definitely absent:

O H C O C C C N O H C O C C C N

• The proton NMR spectrum (with expansions) is:

9H

6H
7.2 ppm 6.8 ppm

2H 2H

12 11 10 9 8 7 6 5 4 3 2 1 0

Draw your best choice for the structure of this molecule in the box below.

_______ / 14
 6 Name:
6. You have just synthesized a new compound, and the following spectroscopic data is obtained:
• From the mass spectrum, you deduce that the molecular formula is: C5H7NO2
• The infrared spectrum is:

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 450
WAVENUMBERS

From the infrared spectrum, circle the functional From the infrared spectrum, circle the functional
groups that are definitely present: groups that are definitely absent:

O H C O C C C N O H C O C C C N

• The proton NMR spectrum (with expansions) is:

2H

3H

4.1 ppm 1.2 ppm

2H

12 11 10 9 8 7 6 5 4 3 2 1 0

Draw your best choice for the structure of this molecule in the box below.

_______ / 14
 7 Name:

7. Consider the following reaction, cycloaddition of a nitrile oxide to an alkyne to form an isoxazole:
Br Br
C
+
N N
cycloaddition
O O

nitrile an isoxazole
oxide

a) Draw a complete Lewis structure of the nitrile oxide pictured above, showing all formal charges and lone
pairs. Include the two best resonance structures for the molecule. Then draw out all the molecular
orbitals of the nitrile oxide, clearly indicating which is the HOMO and which is the LUMO.

b) Your classmate suggests that this nitrile oxide could react with dienes in a similar cycloaddition, as
shown below. Provide a complete curved-arrow mechanism for this proposed reaction.

Br N
Br C N O
O

c) Using a frontier molecular orbital (FMO) argument, briefly explain why the reaction shown in part (b) would not be
expected to proceed as shown.

_______ / 18
 8 Name:

8. Alkenes can be epoxidized by the reagent trifluoroperoxyacetimidic acid, whose structure is shown
below. This reagent can be generated from nitriles in basic peroxide solution.
NH
H2O2
F3C C N O
NaOH F3C O H
trif luoroperoxyacetimidic acid
a) Provide a complete curved-arrow mechanism for the formation of trifluoroperoxyacetimidic acid as shown
above.

b) Provide a complete curved-arrow mechanism for the epoxidation of the alkene shown below by
trifluoroperoxyacetimidic acid. Draw the structure of the epoxide intermediate and its hydrolysis product in the
boxes provided; remember to account for stereochemistry!
NH

O
F3C O H O H3O+
+
F3C NH2

Epoxide Intermediate Hydrolysis Product

c) Draw the structures of all stereoisomers expected for the final product, and label all stereocenters with
the proper R/S configuration.

_______ / 18
 9 Name:

9. Provide a complete curved-arrow mechanism for all steps of the following multistep transformation.

O
OH Ph Me
H3O+ 1. Me2CuLi
Ph
O 2. O
Ph
OH
H H
3. H+ workup

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 10 Name:

10. Provide a complete curved-arrow mechanism for all steps of the following multistep transformation.

O
O 1. LDA (2 equiv.)
S
OH 2. S
S
S

3. H+

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 11 Name:

11. Provide a complete curved-arrow mechanism for all steps of the following multistep transformation.
O
O

1. h ,

2. NaOH, H2O
OH
O

_______ / 18
 12 Name:

12. Provide a complete curved-arrow mechanism for all steps of the following multistep transformation.

EtO O EtO O EtO O

H+ H3O+

CN
NH O

_______ / 18
 13 Name:

13. Draw a curved-arrow mechanism for each step in the following multistep transformation. Identify and
classify all pericyclic reactions. For example, "[4s+2s], 6 e-, thermal, cycloaddition".
O H
O
H + 1. KOtBu,
H
O
OH NH
N N 2. H+ workup
H

_______ / 18
 14 Name:

14. Provide a complete curved-arrow mechanism for the following transformation.

O

O
O
O O 1. NaOEt, EtOH,
OEt

OEt 2. H+ workup
O O

_______ / 18
 15 Name:

15. Provide a multistep synthesis for the desired product. You may use any inorganic reagents and any
acyclic organic compounds with six or fewer carbons. The best answer will require four or fewer steps.

Starting material:

any acyclic organic compounds

with six or fewer carbons

NH

Desired product

_______ / 16
 16 Name:

16. Provide a multistep synthesis for the desired product from the indicated starting material. You may use
any inorganic or organic reagents you wish. The best answer will require seven or fewer steps.

Starting material:

O O

EtO OEt

OCH3

OCH3
Desired product

_______ / 16
 17 Name:

17. Provide a multistep synthesis for the desired product from benzene. You may use any inorganic reagents,
and any organic reagents containing two or fewer carbons. The best answer will require seven or fewer
steps.
Starting material:

plus any organic reagents

containing two or fewer carbons

HO N

Desired product

_______ / 16
 18 Name:

18. Provide a multistep synthesis for the desired product from the indicated starting material. You may use
any inorganic or organic reagents you wish. The best answer will require five or fewer steps.

Starting material:

O2N NO2

plus any inorganic

or organic reagents

NO2
O

O NO2

(mixture of
diastereomers)

Desired product

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SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED
SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED