CHEM 234, Spring 2008

Final Exam

PRINTED
FIRST NAME

Ian R. Gould

PRINTED
LAST NAME

ASU ID or
Posting ID

Person on your LEFT (or Aisle)

Person on your RIGHT (or Aisle)

1__________/18 .......................9__________/72.........................

!PRINT YOUR NAME ON EACH PAGE!

2__________/14.........................10__________/22.........................

READ THE DIRECTIONS CAREFULLY!

3__________/10.........................11__________/20.........................

USE BLANK PAGES AS SCRATCH PAPER

4__________/12.........................12__________/40.........................

work on blank pages will not be graded...

5__________/12 .......................13__________/25.........................

WRITE CLEARLY!

6__________/12........................14__________/50.........................

MOLECULAR MODELS ARE ALLOWED

7__________/20........................15__________/40.........................

DO NOT USE RED INK

8__________/18........................

DON'T CHEAT, USE COMMON SENSE!

Total (incl Extra)________/385+5

Extra Credit_____/5

He
B

Ne

Na Mg

Al Si P

Cl

Ar

H/H

~1.0

Me/Me

~0.9

Ga Ge As Se Br

Kr

H/Me

~1.4

Et/Me

~0.95

In Sn Sb Te I

Xe

Me/Me

~2.6

i-Pr/Me

~1.1

Tl Pb Bi Po At

Rn

Me/Et

~2.9

t-Bu/Me

~2.7

Ca

Sc Ti V

Cr Mn Fe Co Ni Cu Zn

Rb Sr

Zr Nb Mo Tc Ru Rh Pd Ag Cd

Cs Ba

Lu Hf Ta W

small range
range of values
broad peak

Re Os Ir Pt Au Hg
O H

C N

N H

C O

Interaction Energies, kcal/mol

Li Be

C
H

OR

1735

CH

NR2

1650

3000

2000

2500

11
220 O

10
200

R C OH

O
C

O
C CH3
H2C NR2

C CH2
8
160

7
140

6
120

5
100

Aromatic

CR2

C CH

4
80

3
60

RC

CR

Alkyl
3Y > 2Y > 1Y

2
40

OCH2

R C N
R2C

~15

C C

1500

OCH2

NMR Correlation Charts

Aromatic Ar H
mainly 8 - 6.5

9
180

~2

1710

H2C X

(!, ppm)

~8

~2

C C

2200

NH2 variable and condition

OH dependent, ca. 2 - 6 !
O
C H

~10
H

1600

broad ~3000

O
R C OH

H
C C

O
C O H

3500

H
C

28502960

amine R
alcohol R

~7

C C

1680

O H

(cm )

H H

broad with spikes ~3300

-1

2200

broad ~3300

16001660

27202820
2 peaks

3000
3100

N H

3300

Approximate Coupling
Constants, J (Hz), for
1
H NMR Spectra

Infrared Correlation Chart

usually
strong

C H

Gauche

Eclipsing

1
20

0
0

Alkyl 3Y > 2Y > 1Y

C X

C NR2

CHM 234, Spring 2008, FINAL EXAM

NAME

- 2-

Question 1 (18 pts.) Provide IUPAC names for the following structures, do not forget to use E/Z
and R/S as appropriate.
a)

CO2H

O
b)

Question 2 (14 pts.) For the following three structures:

a) Clearly indicate the location of the most acidic hydrogen atom on the line-angle structures
b) Indicate the order of increasing Bronsted acidity for A, B and C. Give a BRIEF explanation.
O

O
O
A
<

least
acidic

<

most
acidic

Question 3 (10 pts.) Rank the following three structures in order of increasing Bronsted acidity.
Give a BRIEF explanation.
O
O
O
F
F
OH
F

OH

A
least
acidic

OH

B
<

C
<

most
acidic

CHM 234, Spring 2008, FINAL EXAM

-3 -

NAME

Question 4 (12 pts.) Rank the following in order of increasing basicity, give a BRIEF
explanation.
N

C
C

least
basic

<

<

most
basic

Question 5 (12 pts) Explain why sodium borohydride (NaBH4) will reduce a ketone but will not
reduce an ester. Draw minor resonance structures of the ketone and ester to support your BRIEF
explanation.

NaBH4/EtOH

OH

NaBH4/EtOH

no reaction

Question 6 (12 pts) Give the product of the following acid/base reaction, give a BRIEF explanation
for your choice of product
O
O

1 Equiv. HCl

CHM 234, Spring 2008, FINAL EXAM

-4-

NAME

Question 7 (20 pts.) Provide the reactants that can be used to synthesize the following two
structures using a malonic ester or ethylacetoacetate synthesis, i.e. give the structure of
malonic ester or ethyloacetoacetate and give the structures of the two bromides. You do not
need to provide a reaction sequence, or any other reagents/conditions.

CO2H

Ph

Question 8 (18 pts.) Give the reagents/conditions to perform the following alkylation using a Stork
enamine reaction

Br

Br

b) Give the reagents/conditions to perform the following alkylation using the LDA method, AND give
the unwanted side-product that you would also expect to form under these conditions (you do not
have to indicate which you woiuld expect to be the major product).
O
Br
Br

unwanted side-product

NAME

-5-

CHM 234, Spring 2008, FINAL EXAM

Question 9 (72 pts)

Provide the missing products, reagents/conditions or reactants, as required. Do not forget
to include stereochemistry as appropriate.

a)

1. excess CH3I

NH2

2. Ag2O/ H2O
3. heat

HO

O
b)
EtO

1 Equiv.

NH2
c)
Ph

d)

H3C

C
Cl

OH

heat

+
CN

O
e)

Cl

-6-

CHM 234, Spring 2008 FINAL EXAM

NAME

Question 9, Contd...
Provide the missing products, reagents/conditions or reactants, as required. Do not forget
to include stereochemistry as appropriate.

Br2/FeBr3

O
f)
O

OH
1. PhMgBr
g)
2. H3O+

h)

i)

NH2

Br

NO2

Ph

1. SO3/H2SO4
2. H2/Pd/C
3. HNO3/H2SO4
3. HONO
4. H3PO2

-7-

CHEMISTRY 234, Spring 2008 FINAL EXAM

NAME

Question 10 (22 pts) For EACH of the TWO bonds indicated, A and B, provide the best
SYNTHONS, and also appropriate "actual reagents"

OH

A (C-O bond)
=

B (C-C bond)
Reagents for A

Synthons for A

Reagents for B

Synthons for B

Question 11 (20 pts) For the cycloaddition reaction below:

a) Draw the curved arrow-pushing that describes product formation
b) will the stereochemistry of the expected product be cis- or trans-? Give a BRIEF explanation.
Me

Me

Me

()

MeO

Me

MeO

Me

OR

()
MeO

c) Draw the HOMO and LUMO of the reactant cation ON TOP of the structures that are
redrawn below
Me
Me

MeO
HOMO

Me

MeO

LUMO

Me

Me

CHEMISTRY 234, Spring 2008 FINAL EXAM

-8-

NAME

Question 12 ( 40 pts.) a) Give a curved arrow-pushing mechanism for the following reactions
You can give an "abbreviated mechanism, i.e. you may use +H+ and -H+
BUT, draw all resonance structures for the intermediates
Add non-bonding electrons and CH bonds as necessary
O
a)

OET

O
b)

H3O+

OCH3

OH

H3O+

HO

H
O

+ HOEt

+ CH3OH

NAME

-9-

CHEMISTRY 234, Spring 2008 FINAL EXAM

Question13 ( 25 pts.) b) Give a curved arrow-pushing mechanism for the following reaction
SHOW WHERE EVERY PROTON COMES FROM AND GOES TO (no +H+ or -H+)
DO NOT DRAW RESONANCE STRUCTURES for the intermediates
Add non-bonding electrons and CH bonds as necessary
At each INTERMOLECULAR step, INDICATE THE Lewis acid and base (LA or LB)
and whether they are also Bronsted acids and bases (BA or BB) as appropriate
O

O
1. Na+ OEt/EtOH

O
OEt

2. H3O+
OH

OEt
O

Extra Credit Question (5 pts). Hydrolysis of which functional groups is used to make soap?
amine

ester

amide

aldehyde

CHM 234, Spring 2008 FINAL EXAM

- 10 -

NAME

Question 14 (50 pts.) Show how you would make the target componds on the right form the
starting compounds on the left. Show reagents and conditions where appropriate, and the
structures of important intermediate compounds. Do not show any (arrow pushing)
mechanisms. For question a) you must indicate steps that require separation of isomers
Cl
a)
Br
NH2

THE NEXT TWO SYNTHESIS PROBLEMS, b) and c), USE ONLY THE "SIMPLE SET OF
REACTIONS" PROVIDED RECENTLY ON THE CLASS WEB PAGE!
OH
b)

Ph
c)
O

CHM 234, Spring 2008 FINAL EXAM

- 11 -

NAME

Question 15 (40 pts.) In each case, synthesize the (target) molecules on the right from the
starting molecules the left. this can not be done in one reaction. Give reagents and conditions
and the intermediate molecules at each step. Do not show any mechanisms or transient
intermediates.
O

a)

b)

OH
HO

OH

(ignore stereochemistry)

N
H