Practice Final Exam C

Chemistry S-20

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 molecuar 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. ____________ / 18 14. ____________ / 18

6. ____________ / 18 15. ____________ / 16

7. ____________ / 14 16. ____________ / 16 Total Score:

8. ____________ / 14 17. ____________ / 16

9. ____________ / 18 18. ____________ / 16 ______________ / 300

 1 Name:
1. Each of the following transformations can be carried out in three or fewer steps. Fill in the reagents or
conditions required for each step. If a step is not needed, please put an "X" through that step.

1.
a)
2.

3.

1.

b) OCH3
2.

3.

OH O
1.

c) O
2.

3.

OH 1. NH2

d)
2.

3.

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 2 Name:
2. Each of the following transformations can be carried out in three or fewer steps. Fill in the reagents or
conditions required for each step. If a step is not needed, please put an "X" through that step.

O O
1.
CN
a)
2.

3.

1. Br Br

b)
C CH 2.
Br Br

3.

1.
OH
c)
2.

3.

1. O O
O
d) OCH3
OCH3 2.

3.

_______ / 16
 3 Name:
3. Fill in each box with the single major organic product of the indicated transformation. For full credit, your
answer must conform to the molecular formula, if given. Be sure to indicate the correct stereochemistry if it is
relevant!

1. O3
a)
2. (CH3)2S

H
N

O , pH 5
b)

(Mol. Form. C12H21N)

c) 1. Zn, HCl, Δ

2. AlCl3,
Cl

O
O

d) 1. NaOCH3,

2. CuLi
O
2
3. H+ workup
(Mol. form. C13H18O2)

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 4 Name:
4. Fill in each box with the starting material or single major organic product of the indicated
transformation. For full credit, you must use each reagent in a reasonable way. Be sure to indicate
stereochemistry if it is relevant!

OH
Et Me
a) 1. BH3, THF

2. H2O2, NaOH Me H
H
(+/–)

1. Na0, liq. NH3 CH3

2. NBS, CCl4 S
b)
3. NaSCH3
(+/-)

1. mCPBA
2. CH3OH, H+
c)
3. TsCl
4. NaCN

O O

1. H+ , OH
d)
HO 2. NaBH4, EtOH

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 5 Name:

5. In the following question, we will explore the preparation of nitrile oxides.

O
OH OH N
O N N
NH2OH oxidation NEt3 C
Ph H Ph H
pH 5 Ph Cl Ph
benzaldehyde oxime oxime chloride nitrile oxide

a) Draw a complete curved arrow mechanism for the formation of the oxime from benzaldehyde.

b) Draw a complete curved arrow mechanism for the formation of the nitrile oxide from the oxime chloride.
O
OH
N NEt3 N

C
Ph Cl
Ph

c) Only the (Z)-oxime chloride reacts as you showed in part b. Explain with clearly labeled diagrams why the
(E)-oxime does not undergo this reaction. Label any relevant FMOs.

OH
N NEt3
no reaction
Cl Ph

(E)-oxime chloride

_______ / 18
 6 Name:

6. In the following question, we will explore the reactivity of nitrile oxides.

O
a) Provide a full FMO analysis of the conjugated pi-system of the nitrile oxide. Please
include all pi-orbitals and identify the HOMO and LUMO. You should ignore the phenyl N
group and consider only the conjugated pi system of the C-N-O atoms.
C
FMO Analysis:
Ph

nitrile oxide

b) Nitrile oxides are known to dimerize (react with itself) under thermal conditions. You and your study buddy
come up with two possible dimerization reactions. On the structures below, show the curved arrow
mechanism for the formation of each of the possible products.

Pathway 1: Pathway 2:

Ph Ph O
O
O C Δ O N
O N Δ N
O
N N N C Ph
N O N
C O C Ph
Ph Ph Ph
Ph

c) Only one of these reaction pathways is observed. Predict below the pathway that should be favored under
thermal conditions.

circle one: PATHWAY 1 or PATHWAY 2

d) Show the FMO orbital analysis for the interactions that would be required in each of these pathways:
Pathway 1: Pathway 2:

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 7 Name:
7. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C10H12O2
• The infrared spectrum is:

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 is:

6H

5H 1H

8 7 6 5 4 3 2 1 0
PPM
Draw your best choice for the structure of this molecule in the box below.

_______ / 14
 8 Name:
8. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C5H10O
• The infrared spectrum is:
MICRONS NICOLET 20SX FT-IR
2.5 2.6 2.7 2.8 2.9 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 21 22
100 0.0

90 .05

80 0.1

70
%
T
0.2
R A
60 A B
N S
S O
M R
50 0.3
I B
T A
T N
A C
40 0.4
N E
C
E
0.5
30
0.6

20 0.7

0.8
0.9
10 1.0

0 2.0
4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 6 00 450
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 is:

3H 3H

1H 1H 1H 1H

6 5 3 2 4 1 0
PPM
Draw your best choice for the structure of this molecule in the box below.

_______ / 14
 9 Name:

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

O
O O
O
1. Br2 , H+ 2. Ph H

Ph
KOtBu, tBuOH

_______ / 18
 10 Name:

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

Me
Me
1. CHCl3 2. LDA Cl

N KOtBu, tBuOH
H N

_______ / 18
 11 Name:

11. Provide a complete curved-arrow mechanism for the following transformation. A key intermediate is
provided below.

O O O O

Ph H

NaCN CN Ph
KOtBu, tBuOH
HO Ph O

key intermediate

_______ / 18
 12 Name:

12. Provide a complete curved-arrow mechanism for all steps in the following transformation.
Me

Me NO2 1. AlCl3 Me NO2

Cl
+
2. NaOH
O Cl O

_______ / 18
 13 Name:

13. Aromatic amines can be converted into phenols using the following two-step transformation:

NH2 N2 Cl OH

1. HCl, 2. H2O

NaNO2

a) Provide a complete curved-arrow mechanism for the first step of the above mechanism (the formation of
the diazonium salt).

b) Your friend suggests that the second step of the above mechanism (reaction with water) could proceed
through an SN1 mechanism. Provide the curved arrows for this proposed mechanism, and then explain briefly
why this mechanism is not likely to be the correct mechanism.

_______ / 18
 14 Name:

14. Phenol can be converted into an interesting product using the following two-step transformation. Provide
a complete curved-arrow mechanism for both steps. If your mechanism contains any pericyclic reactions,
please provide the complete classification (e.g. electrocyclic, 6πe–, thermal, disrotatory).

OH Note: You may represent TsCl as:

O O O
1. TsCl, pyr
S
O Ar Cl
2. NaNH2,
NH3 (l) where Ar = para-toluene

_______ / 18
 15 Name:

15. Provide a complete synthesis of the following desired product from the indicated starting materials. You
may use any other inorganic and organic reagents that you need, but all of the carbon atoms from the starting
materials must end up in the product. You do not need to show any mechanisms. Be sure that your synthesis
accounts for the stereochemistry of the product. The best answer will require eight or fewer total steps.

Starting Material:

and HO

(+/−)

Desired Product

_______ / 16
 16 Name:

16. Provide a complete synthesis of the following desired product from the starting materials with four or
fewer carbon atoms. You may use any inorganic reagents. You do not need to show any mechanisms. Be
sure that your synthesis accounts for the stereochemistry of the product. The best answer will require seven
or fewer total steps.
Starting Material:

anything with 4 or
fewer C's

plus, any inorganic

reagents

CN

OCH3
H3CO

CN

(+/−)

Desired Product

_______ / 16
 17 Name:

17. Provide a complete synthesis of the following desired product from the acyclic starting materials. You
may use any inorganic reagents. You do not need to show any mechanisms. The best answer will require six
or fewer total steps.

Starting Material:

any ACYCLIC reagents

plus, any inorganic

reagents

Me
N

H
N

(+/−) O

Desired Product

_______ / 16
 18 Name:

18. Provide a complete synthesis of the following desired product from the the given starting material and
any other organic or inorganic reagents you need. You do not need to show any mechanisms. The best
answer will require eight or fewer total steps.

Starting Material:

O
H3CO

(+/−)

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