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)

nomen
reactions
1__________/18
.......................9__________/72.........................

!PRINT YOUR NAME ON EACH PAGE!

synthons
acidity 1
2__________/14.........................10__________/22.........................

READ THE DIRECTIONS CAREFULLY!

acidity 2
pericyclic
3__________/10.........................11__________/20.........................

USE BLANK PAGES AS SCRATCH PAPER

mxns 1
basicity
4__________/12.........................12__________/40.........................

work on blank pages will not be graded...

reactivity
mxns 2
5__________/12
.......................13__________/25.........................

WRITE CLEARLY!

synth 1
basicity 2
6__________/12........................14__________/50.........................

MOLECULAR MODELS ARE ALLOWED

synth 2
malonics
7__________/20........................15__________/40.........................

DO NOT USE RED INK

Stork
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)

(2S),5-dimethyloct-(5E)-enoic acid

CO2H

O
b)

ethyl propanoate

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
A

B
<

least
acidic

C
<

most
acidic

the anion in A is destabilized by the O of the ester, which acts as a resonance

donating group to the enolate anion, the oxygen in B acts as a weak inductive
withdrawing group to the enolate

Question 2 (10 pts.) Rank the following three structures in order of increasing Bronsted acidity.
Give a BRIEF explanation.
O
O
O
F
F
OH

OH

OH

F
A
least
acidic

B
C

<

<

C
A

most
acidic

the carboxylate is stabilized by the fluorines via the inductive effect, the further the F
from the anion, the weaker the inductive effect

CHM 234, Spring 2008, FINAL EXAM

-3 -

NAME

Question 4 (12 pts.) Rank the following in order of increasing basicity, give a BRIEF
explanation.
sp2
sp
sp3
N
N
N
C
H
A

least
basic

<

<

most
basic

non-bonding electrons are lower in energy the more s-character the A.O., lower in energy
means less reactive, less 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.
O
O
OH
NaBH4/EtOH

NaBH4/EtOH

no reaction

BH4 is a Lewis base, the carbonyl carbon is Lewis acidic in the ketone (see
resonance structure), the carbonyl carbon is less Lewis acidic in the ester due to
the presence of the oxygen.
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

O
O

the minor resonance contributor shows that the carbonyl

oxygen has a partial negative charge and is thus more
basic, and the ester oxygen has a partial positive charge
and is thus less basic

-4-

CHM 234, Spring 2008, FINAL EXAM

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.

Br

Br

+ EtO2C

CO2Et

CO2H

malonic ester
O
Br

Br

+
Ph

EtO2C

COCH3

ethyl acetoacetate

Ph

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

Br

1.

N
H

Br

2. BuBr
3. H3O+
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
Br

Br

O
1. 1 Equiv. LDA
2. BuBr

+
O

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

EtO +Na/EtOH

b)
EtO

1 Equiv.

NH2
c)

d)

H3C

Ph

C
Cl

NH

H3C
Ph

OH

OH

CN

heat

+
CN

O
e)

1.

Cl

N
2. LiAlH4
3. H3O+

-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

f)

Br
O

OH

1. PhMgBr

g)
2. H3O+

h)

Br

Ph

1. Na+ CN

NH2

2. LiAlH4
3. H3O+

NO2
i)

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

NO2

SO3H

-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"
Na+ OH
OH

Br

OH

A (C-O bond)

=
B (C-C bond)
Reagents for A

Synthons for A

OH
H

MgBr
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

Me

TRANS-, this is a 4-electron reaction, the allowed reaction proceeds via a conrotatory Mobius
transition state which puts the methyl groups on opposite sides of the cyclic product
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

CHEMISTRY 234, Spring 2008 FINAL EXAM

NAME

-8-

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)

H3O+
OET

H+

+H+

O H

OET

+ HOEt

OH

O H

OH

OH

OET

OH

H
O

O
H

OH

OET

H+

OH

H
H3O+

OCH3

+H+
OET

O
H

Et

OH

HO

+ CH3OH

b)
O
+H+
H
O

H
O

OCH3

O
H

H
O

OCH3

OCH3

OCH3
O

O H
H

+H+
H
O

H
OCH3
O H
H

H+

OCH3
O
H

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
LB/BB

OEt

1. Na+ OEt/EtOH

H
LA/BA

O
OEt

2. H3O+
OH

OEt
O

O
O

O
OEt

LB/BB

OEt

OH

LA/BA
Et

OEt

OEt

O H O
OEt

OEt

O
LB/BB
H
LA/BA

LB/BB

LA/BA

OH

O
Et

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

NAME

- 10 -

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
HNO3/H2SO4

NH2
Br2/FeBr3

separate
isomers

Cl
Cl2/AlCl3
Cl

NO2

NH2

H2/Pd/C
NO2

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

MgBr 1.

Br Mg.THF

HBr
ROOR

OH

2. H3O+

Ph
c)
O
PCC

1. Hg(OAc)2/H2O
2. NaBH4/EtOH
PCC
OH

1. PhMgBr

H
O

2. H3O+

Ph
OH

CHM 234, Spring 2008 FINAL EXAM

NAME

- 11 -

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)
Br2, h!
Br
HN(CH3)2
MgBr

Mg . THF

COCl

CO2H
1. CO2

SOCl2

2. H3O+

b)

OH

OH

HO

(ignore stereochemistry)

H
NaBH4
EtOH

PCC
O
O

O
H

H
H+

1 Equiv.
HO

H3O+

OH
O

O
H

MeNH2 / H+
N
H2/Pd/C

O
H