Chem 232: Final Exam

December 14, 2017

Name:

Student ID number:

Discussion TA:

Discussion day and time:

Seat Number:

(1) You have 120 minutes to complete your exam.

(2) Put your final answer in the box, when provided, to obtain full credit.
(3) You may use a molecular model kit.
(4) Please turn off any electronic devices.
(5) People caught using electronic devices will have their exams confiscated.

GOOD LUCK!

Page 2 (8 pts):
Page 3 (12 pts):
Page 4 (12 pts):
Page 5 (15 pts):
Page 6 (10 pts):
Page 7 (12 pts):
Page 8 (10 pts):
Page 9 (20 pts):
Page 10 (19 pts):
Page 11 (8 pts):
Page 12 (8 pts):
Page 13 (8 pts):
Page 14 (19 pts):
Page 15 (6 pts):
Page 16 (3 pts):
Page 17 (5 pts):
TOTAL POINTS (Out of 175 pts):
1. Ranking (8 points)

A. Rank in order of increasing acidity (1 = least acidic, 4 = most acidic).

O
Me Me Me Me
SH OH OH CH3

B. Rank in order of increasing number of stereogenic centers (1 = least, 4 = most).

Cl
Cl

Cl Cl Cl
Cl

C. Rank each conformation in order of increasing stability (1 = least stable, 4 = most stable).

H Me Cl Me Cl H
H Cl H Cl
H H
Me H H H H H Me H
H H H H

D. Rank the following in order of increasing oxidation state of the indicated carbon. (1 =
lowest oxidation state, 4 = highest oxidation state)

O O
Me OH Me Me Me OH Me Me

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2. Naming & Configurations

(a) Assign the stereochemical configuration for each indicated structural element. (6 pts)

H 3C Br OH

Cl CH3
O

(b) Draw the enantiomer of the compound in part 2(a). Indicate all stereogenic centers that
changed configuration with a *. (3 pts)

(c) Draw a diastereomer of the compound in part 2(a). Indicate all stereogenic centers that
changed configuration with a *. (3 pts)

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(d) Provide a name for each indicated functional group in the following molecules. (6 pts)

HO

OMe

O
O

(e) Provide an appropriate IUPAC name for the following structure. (3 pts)

(f) Draw a bond-line structure corresponding to the given IUPAC name. (3 pts)

4-bromo-3-ethylheptane

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3. Predict the products for the following transformations. When necessary indicate the
major product and relative stereochemistry.

(a) (5 points)

1. NBS, hv
CH3
2. NaCN
DMSO

(b) (5 points)

O
NaBH4
O

i-PrOH
O

(c) (5 points)

1. m-CPBA
CH2Cl2

2. H2SO4 (cat.)
H 2O

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(d) (5 points)

1. BH3•THF
2. H2O2, NaOH

3. NaH, EtI
DMF

(e) (5 points)

O 1. PhMgBr (xs)
Me
Me O 2. H3O+

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4. (12 points) Provide the necessary reagents to accomplish the desired organic reactions.
Please number the steps and note that some reactions will require more than one step.

(a) (4 points)

Br OMe

racemic

(b) (4 points)

OH
O
Ph
Ph
SMe

(c) (4 points)

Ph OH

H Ph CH3

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5. (10 points) Consider the following molecule.

Me
Me Ph

Me Cl
(a) Draw three staggered conformations of this molecule using Newman projections from the
indicated perspective (one structure per box). (6 pts)

(b) Predict the major product for the following transformation. Be sure to account for
stereochemistry. (4 pts)

Me
Me Ph KOt-Bu

Me Cl t-BuOH
heat

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6. Retrosynthesis. Fill in the boxes to predict the major product or provide the necessary
reagents to accomplish the desired transformations. (20 points)

O
Me
Me
Me
Me

1.
9.

2.

3.

Me OTs

Me

4.
7.

8.

5.

O
Me Me
Me 6.
Me

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7. Resonance. Use arrow formalism to show electron motion that leads to the major
resonance forms contributing to the structures of the shown structures. Draw the most
important resonance structures in the boxes and circle the most important contributor.
Some answers may have multiple equal contributors. (17 points)

(a) (9 pts)

(b) (5 pts)

N
C

(c) (5 pts)

O O

Me N Me
Me

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8. (24 points) Provide a detailed arrow pushing mechanism for the following
transformations.

(a) (8 points)

CH3 1. NaH, DMF CH3 CH3

H 3C SH 2. CH3 H 3C S CH3

Br CH3

Your mechanism should explain the observed stereochemical outcome.

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(b) (8 points)

Br
Br2
CH3 CH3
H 3C H 3C
Br
racemic

Your mechanism should explain the observed stereochemical outcome.

12
(c) (8 points)

O
OH O
O Cr Cl
N
H O
CH2Cl2

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(d) For the following reaction, using your understanding of the mechanism:

Br EtOH OEt
Heat

i. Sketch an accurate energy diagram (4 pts)

Free Energy (G)

Reaction Coordinate
ii. On the energy diagram label the: (9 pts)
• Reactants, products, and any intermediates
(you do not need to draw structures on the diagram)
• Transitions states
• ΔGrxn (overall)
• Ea for each step

iii. Indicate the slowest step on the energy diagram (2 pts)

iv. Draw the structures for any intermediates in the box below (4 pts)

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9. Spectroscopy

(a) (4 points) Predict the product for the reaction given below.

1. MgBr , THF
2. O

H H
H 3. H 3O+

3. O
Cl
Cl , DMSO
O
NEt 3, CH2Cl2

(b) (2 points) For the 1H NMR spectrum illustrated below, label each of the indicated peaks
with the appropriate functional group.

List of 1H NMR resonances: 9.4 ppm (singlet, 1H), 7.6 ppm (multiplet, 2H), 7.5 ppm
(multiplet, 1H), 7.4 ppm (multiplet, 2H)

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(c) (3 points) For the 13C NMR spectrum illustrated below, label each of the indicated peaks
with the appropriate functional group.

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List of C NMR resonances: 177 ppm, 133 ppm, 131 ppm, 129 ppm, 119 ppm, 95 ppm, 88
ppm.

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(d) (2 points) For the IR spectrum illustrated below, label each of the indicated peaks with the
appropriate functional group.

(e) (2 points) Draw the structure of the compound represented by the spectra given above in
the box given below.

(f) (1 point) Did the reaction go to completion? (yes or no?)

The spectra for this problem were reproduced from the National Institute of Advanced Industrial
Science and Technology, http://riodb01.ibase.aist.go.jp/sdbs/ on Jan. 29, 2017.

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