Chemistry

2332H

Exam 3
May 5, 2014

Prof. Douglas

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First Name: _____________________

Student ID: _____________________

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General Instructions & Tips:

1) Use pen, cross out anything you dont want us to grade.
2) Electronic Devices of any kind are not allowed: turn off and stow.
3) Carefully read all instructions for questions.
4) Model kits, calculators, and stencils are not allowed.
5) Maximize partial credit by first attempting questions you feel you can answer correctly, rather
than tackling problems in sequence.
6) Clear drawings make it easy to assign full/partial credit.
7) There is at least one problem on each page except this one: dont miss any!

Last Name: _____________________ (1 bonus point)

First Name: _____________________
Student ID #__________________

Point Tally:

Bonus Point
/1
Problem 1. (Reactions)




/20


Problem 2. (Curved Arrow Mechanism)

/20


Problem 3. (Draw Products & Conditions)
/25


Problem 4. (Synthesis Proposals)


/25


Problem 5. (Acid/Base Effects)



/5
Problem 6. (Polymer synthesis)


/5
















Total:
/100

Problem 1: (20 points) Draw the structures of the products for each reaction. You can assume all
products are racemates, if applicable.

a. (2 pts each)





b. (2 pts each)

NH 2
O

1) I 2, NaOH
H 2NPh
2) pH = 3
note arrow
300 C
direction
CH 2N 2
O
(diazomethane)
pyridine
Ph
OH
O
Cl
benzoic acid
CH3
EtOH, H 2O
O
H 2SO 4
Cl
Cl
product IR:
O
~ 1800 cm-1

c. (2 pts each)
O

POCl 3
product IR: ~ 2200 cm-1

1) n-BuLi
2) H 3O+

O
i) [Ph 2Cu]Li

i) LDA
ii)

ii) H 3O+

Br

Problem 2: (20 points)

a. The reaction below prepares a compound known as Hagemanns Ester, which is an important
intermediate in the synthesis of many other compounds. Draw a curved arrow mechanism and
show each reasonable reactive intermediate (15 points)

O
Me

O
OEt

NaOEt
Me

O
O
EtO

()
Me
Hagemann's Ester

assume neutralizing
work-up

b. The mechanism for this reaction found in Wade (page 1090) relies on an extremely unfavorable
acid/base equilibrium (delta pKa 9), which Wade ignores. Draw this equilibrium out. (5 points)
FYI/Hint: you need not have drawn this equilibrium above to get full credit for part a.

Problem 3 (25 pts, 5 each) Predict the major product(s) of the following reactions. You may
ignore stereochemistry in these problems. You need not draw byproducts and you can assume
neutralizing work up.

a.)


O
OH

1) SOCl2
2) AlCl3

b.) Prepares the insecticide known as Sevin

OH

Me

N C O

c.)

Me
CO 2Me
N
O

H 2, Pd/C

H
O

d.)

O

Br 2, PBr 3

HO

CH3

e.) Fill in the reagents for the 2 steps; you dont need to draw the intermediate.

O
Me
Me
H

O
Me

Me
H
Me

Me
Intermediate

H
O

Me

Me
H

Me
progesterone

Problem 4 (25 points) Propose multistep synthesis routes using the starting materials shown and
any other reagents/reactants you need. To maximize partial credit, be sure to draw out the
products of each reaction you propose.

a. (10 pts)
O
MeO 2C

MeO 2C

O
O

b. (15 pts)
O
+

other reactants
with 3-carbons
or less

O
Me
OMe

Problem 5: (5 points)

Given the structure of ascorbic acid (vitamin C):

OH
HO
HO

ascorbic acid
(vitamin C)

OH

a) Is ascorbic acid a carboxylic acid? (1pts) Circle your answer: yes/no
b) Which OH is most acidic? (2pts) Circle the appropriate H on the structure above.
c) Ascorbic acids pKa is 4.71. Draw the form most present in the body (pH = 7.4). (2 pts)




Problem 6: (5 points)

The polymer Lexan is used in bullet-proof glass and bike helmets. It is synthesized in 2 steps
from 3 molecules containing 6 carbons in each.
O

CH3

C O

CH3

O
O C O

CH3

n
Lexan, a polycarbonate

CH3

a) Draw the three starting materials (3 pts).







b) The intermediate after step one of the synthesis is called bisphenol A. Draw its structure and
suggest conditions to prepare it from two of your starting materials above. (2 pts)