CHEM 234, Spring 2008

Third Midterm

PRINTED
FIRST NAME

Ian R. Gould

PRINTED
LAST NAME

Person on your LEFT (or Aisle)

ASU ID or
Posting ID

Person on your RIGHT (or Aisle)

nomen
Mxn
1__________/9 .........................9__________/20.........................

!PRINT YOUR NAME ON EACH PAGE!

EAS
2__________/15.........................

READ THE DIRECTIONS CAREFULLY!

Keq
3__________/12.........................

USE BLANK PAGES AS SCRATCH PAPER

Stork
4__________/14.........................

work on blank pages will not be graded...

Reactions
5__________/32
.........................

WRITE CLEARLY!

Retro
6__________/38.........................

MOLECULAR MODELS ARE ALLOWED

Benene R
7__________/20.........................

DO NOT USE RED INK

Claisen Mxn
8__________/20.........................

DON'T CHEAT, USE COMMON SENSE!

Total (incl Extra)________/180+5

Extra Credit_____/5

He

Li Be

Ne

Na Mg

Al Si P

Cl

Ar

Ga Ge As Se Br

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

~1.0

Kr

H/Me

In Sn Sb Te I

Xe

Me/Me

Tl Pb Bi Po At

Rn

Me/Et

N H

10
200

OR

R C OH

~8

8
160

~2

H
NR2

1650

OCH2

C CH3
H2C NR2

7
140

6
120

5
100

R2C
Aromatic

CR2

C CH

4
80

3
60

RC

CR

Alkyl
3Y > 2Y > 1Y

2
40

OCH2

R C N

~15

C C

1500

NMR Correlation Charts

2000

~2

C C

C CH2

O
C

~10
H

1600

Aromatic Ar H
mainly 8 - 6.5

9
180

~7

H
C C

1710

NH2 variable and condition

OH dependent, ca. 2 - 6 !

11
220 O

H H

H2C X

(!, ppm)

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

1735

CH

2500

O
C H

~2.7

C C

2200

3000

O
R C OH

t-Bu/Me

1680

broad ~3000

amine R
alcohol R

16001660

O
C O H

3500

~2.9

H
C

28502960

(cm )

~1.1

O H

-1

~0.95

i-Pr/Me

broad with spikes ~3300

broad ~3300

Et/Me

~2.6

2200

~1.4

27202820
2 peaks

3000
3100

~0.9

Infrared Correlation Chart

3300

Me/Me

usually
strong

Gauche

Eclipsing
H/H

C H

Interaction Energies, kcal/mol

1
20

0
0

Alkyl 3Y > 2Y > 1Y

C X

C NR2

-2-

CHM 234, Spring 2008, Midterm #3

NAME

Question 1 (9 pts.) Give an unambiguous IUPAC or common name for the following
compounds. Be sure to use cis/trans, E/Z or R/S where appropriate.

OH
[6S]-hydroxy-2-methyloct-1-en-4-one

Question 2 (15 pts). Rank in order of increasing rate of electrophilic aromatic

substitution at the carbons indicated by the arrows. Give a BRIEF explanation.
B
A

C
C

CH3
B
slowest

<

<

A
fastest

Reaction at both A and C is faster than at B, because both are activated by strong (amine) and
weak (aryl) donating groups on the ring. Reaction at A is activated more than at C because the
donating group stabilizes the intermediate more at this position it is o- and p-directing). Reaction at
B is deactivated by the by the strongly withdrawing nitrile group.

-3-

CHM 234, Spring 2008, Midterm #3

NAME

Question 3 (12 pts).

a) Rank the following reactions in order of increasing equilibrium constant for formation of product
and give a BRIEF explanation
O
O

HO OH

O
HO OH
O

HCl cat.

O
HO OH

<

<

smallest

HCl cat.

largest

O
O

C
O

HCl cat.

O
as far as the C=O is concerned, the O in A is strongly donating which decreases
reactivity, the O in B is mildly withdrawing due to the inductive effect which increases
reactivity, in C the O effect is negligible and the alkyl groups are weakly donating,
intermdiate reactivity

Question 4 (14 pts) In the boxes, fill in the missing reagents/conditions in the following reaction
sequence

+
N H cat.
+
H (not H3O )

Br
N

H3O+

-4-

CHM 234, Spring 2008, Midterm #3

NAME

Question 5 (32 pts.) provide the reaction products or reagents/conditions as required

O
O

1. EtO +Na/ EtOH

a)
EtO

2. H3O+

N
HCl (cat.)

b)

H2N

O
Zn/Hg
c)

HCl/H2O

O
O

1. BuLi
2. CH3Br
d)

3. BuLi
4. CH3CH2Br
5. H3O+

-5-

CHM 234, Spring 2008, Midterm #3

NAME

Question 6 (38 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.

a)

NBS/h!
Ph3P

CH2
O

Br
1. Hg(OAc)2 / H2O
2. NaBH4

K+ O-t-Bu

OH

PCC

O
b)

Ph

OH

O
1 Equiv.
HO

H+

OH

1. EtMgBr
2. H3O+

O
H

Ph
O

Ph
O

1. N2H4
2. KOH/heat

Ph
O

H3O+

-6-

CHM 234, Spring 2008, Midterm #3

NAME

Question 7 (20 pts.) Synthesize the (target) molecule on the right from the starting
molecule 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.
NO2
CO2H

O
Cl

AlCl3

SO3H

1. KMnO4/OH/boil
2. H3O+
SO3/H2SO4

NO2
Zn(Hg)

HNO3
H2SO4

HCl/H2O
SO3H

SO3H

SO3H

Extra credit question (5 pts). A photochemical 2 + 2 cycloaddition reaction occurs in

DNA

Hemoglobin

Vitamin C

from weekly work #12

peroxidase

CHM 234, Spring 2008, Midterm #3

-7-

NAME

Question 8 (20 pts.) Give a complete arrow-pushing mechanism for the following TWO reactions.

Show exactly where each proton comes from and goes to.
Add non-bonding electrons and hydrogen atoms as necessary
Indicate the lewis acid/base for each INTERmolecular step (LB or LA) and whether they are
also Brnsted bases/acids (LB/BB or LA/BA)
SHOW ALL RESONANCE STRUCTURES OF THE INTERMEDIATES

1. Na+ OCH3/CH3OH
H

H3CO

H3CO

2. H3O+
CH3O
O
O

H3CO
H3CO

O
O

O
H3CO

H3CO
O+ H

OCH3

H3CO

O
H3CO

O
OCH3

H3CO
CH3O

-8-

CHM 234, Spring 2008, Midterm #3

NAME

Question 9 (20 pts.) Give a complete arrow-pushing mechanism for the following reaction.

Show exactly where each proton comes from and goes to.
Add non-bonding electrons and hydrogen atoms as necessary
Indicate the lewis acid/base for each INTERmolecular step (LB or LA) and whether they
are also Brnsted bases/acids (LB/BB or LA/BA)
SHOW ALL RESONANCE CONTRIBUTORS OF THE INTERMEDIATES
O
LA
LB H2N

OH

NH

HCl (cat.)
LA/BA

LB/BB

Cl
OH H
H
N
O

H O

NH

Cl

LA/BA
LB/BB
LA/BA
OH

H
N

OH

HCl
O

OH

H
N

LB/BB

LA/BA
OH

H
N

HCl
OH
LB/BB

OH

H
N

OH2