Chemistry 303

fall 1994
THIRD EXAMINATION
8:00 am, December 9th, 1994
Duration: 2 hr
Name________________________________________________
Lab TA.______________________________________________

key
This is an "open book" examination; you may use anything which is not alive.
NOTE: if you do not know the complete or specific answer, give a partial or general answer-WRITE SOMETHING
NOTE: write your mechanisms CAREFULLY. A good answer will require precision in the use of the
arrows.
Grade:
1._______/20
2._______/40
3._______/10
4._______/30
total: _____/100
There are 8 pages in this exam; please check now to be sure you have a complete set.

Pledge:_________________________________________________________________________________
I. (20 pts) Choose that reaction of each of the following pairs which proceeds fastest and write the major
product(s) for that reaction. Assume identical conditions where not specified. Write a one-sentence
explanation for your choice, and name the mechanism you have chosen.

A.

1.

+ NaOH

Br
Br

2.

SN2; less hindered reacts faster.

OH

+ NaOH

___________________________________________________________________________________

B.

1.

2.

(CH3)3N:

(CH3)3N:

CH 3CH2I

CH 3CH2I

CH3OH

(CH3)3NCH 2CH3

SN2 Increased charge in the transition state

better stabilized by the more polar, H-bonding
solvent

hexane

_______________________________________________________________________________________

C. 1.

2.

N: + CH3 CH2I

..

(CH3)2NH + CH3 CH2 I

CH3OH

CH3OH

SN2 Less tightly held electron pair is better

nucleophile; sp3 more reactive than sp2.

(CH3)2NHCH2 CH3

_______________________________________________________________________________________

D. 1. n-butyl methyl ether

2. n-butyl ethyl ether

+ HI

Write a mechanism
for your choice.

+ HI
H+

I
Me
O
H
SN2 after activation by acid; reacts at less hindered carbon.

O
H

+ Me-I

_______________________________________________________________________________________

E.

ether

MgBr

O +

SN2 to give favorable reaction due to the release

of strain energy.

ether

MgBr

O +

MgBr

II. (40 pts) Consider the following rate and product data: reaction (B) is much faster than (A) under the
same conditions. Reaction (A) gives only one product (C) while reaction (B) gives a mixture C + D,
favoring D.
(A)

Cl

K+ -OC(CH3)3
ether

A
(B)

CH3

Cl
B

C, C7H12

K+ -OC(CH3)3
ether

C + D, both C7 H12

D is the major product

CH3

Note also that reaction of either A or B with silver nitrate in ethanol gives a mixture of C + D and
substitution products (same mixture from either reactant):

(C)

Cl

AgNO3
EtOH

mixture of C+ D
and substitution
products

AgNO3
EtOH

Cl

A
CH3
CH3 B
__________________________________________________________________________
1. (4 pts) Draw the more stable chair form of each of the starting materials, A and B. Which is of higher
energy (less stable)? Discuss any ambiguity. Indicate on one of your structures whether the CH3 group and
the Cl are axial or equatorial.

both equatorial

Cl (ax)

Cl
CH3
A

Cl

or

CH3
(eq)

CH3

A is more stable than B

cannot easily know which of these two is the more stable.
because it has no axial
substituents, and therefore
no additional gauche interactions
with the cyclohexane ring carbons

2. (4 pts) Suggest structures for C and D. Point out two features from each NMR spectrum which clearly
differentiate the structures. NMR spectra data:
C: 0.9 ppm, doublet with J = 7Hz area 3H; series of multiplets between 1.2-2.2 ppm, area 7H;
5.6 ppm, multiplet, area 1H; 5.7 ppm, multiplet, area 1H.
D: 1.5 ppm, multiplet, area 4H; 1.7 ppm, singlet, area 3H; 1.9 ppm, multiplet, area 4H;
5.4 ppm, broadened singlet, area 1H.

CH3
C

CH3
D

There are two alkene type H in C (5.6 and 5.7 ppm), and only one in D (5.4, 1H)
The Me group is upfield and a doublet in C, due to the adjacent methine H; the Me group is shifted a little
downfield (1.9 ppm) and is a singlet in D.
3. Using the usual arrow formalism, write a mechanism for reaction (A).
Diaxial isomer is needed for the E2 mechanism to operate: H and the leaving group must be antiperiplanar
Cl
E2

Cl
CH3

CH3

CH3

RO

4. Write a mechanism for reaction (B) which shows clearly the formation of both products.

Cl

HH

E2

CH3

CH3

RO
Cl

HH

CH3

E2
CH3

RO

5. Using the usual reaction coordinate diagrams, compare reaction (A) and reaction (B). Indicate the
position of the reactant, product(s), transition state(s), and intermediates (if any). Take care to show the
relative energies which justify the difference in rate [reaction (B) is faster than ( A)].
both are E2, one step [A' is the diaxial chair isomer of A]

!G#

!G#

A'

B
alkene

C
D

Conformational change to the higher energy, diaxial

derivative, then good E2 TS to product.

6. (2 pts) Explain why product D is preferred over C in reaction (B).

D is more stable, and this shows up in a slightly lower energy TS; otherwise, the mechanisms are
identical.
5

7. (6 pts) Write a mechanism for substrate A in reaction (C). In addition to C and D, three different
substitution products are likely. Write them and indicate how each forms in your mechanism.

OH
CH3

H
Cl
CH3

+ Ag+

CH3
E1

OH

SN1

CH3
H

H-shift

H
+

CH3

HO- add

CH3

CH3 H
OH
8. (4 pts) Using your mechanism, predict whether A or B will be more reactive with silver nitrate in
ethanol. Explain briefly.
They give the same cationic intermediate, so the relative activation energy is directly related to the
reactant energy. A is more stable and therefore is slower to reach the transiion state; reacts slower.
_____________________________________________________________________________________
III. (10 pts) Consider the reaction of X under the conditions specified.

CH3
R
N(CH3 )2
HO
H
Y

H3C
N:
H
X

CH3
a. CH3-I

H3C

CH3

N
H

CH3

-H
H
H
b. water,
heat

What is the configuration of the

stereogenic carbon in X?
R or S

H3C

H
O
H

CH3
N

R H

CH3

Write the usual stepwise mechanism for the reaction. Show all intermediates. Is the product Y most likely
to be optically active (primarily one enantiomer)? If so, is it the result of inversion or retention? Be sure
your mechanism is consistent with the result.
Analogy with bromination, and Br- addition to a bromonium ion; this is water addition to an ammonium
ion, adding at the best cation site with one face blocked by the N.

IV. (30 pts). In an early mechanistic study, the following data were collected on compound E. Reaction of
E with thionyl chloride (SOCl2) produces compound F as the organic product. Treatment of F with sodium
hydroxide gives G. Oxidation with CrO3 of either E or G leads to H. Reaction of E with ZnCl2/HCl gives a
product, J, with the same NMR spectrum as F but zero molecular rotation. A startling mechanistic
conclusion (since proven wrong) was deduced from these reactions and the molecular rotation data given
below.
[J] [!] D 0o
ZnCl2
HCl

CH3

H
OH

SOCl2

[F]
[!] D +43o

NaOH

[!] D +10o

CrO3

[G]
[!] D -10o

CrO3

[H] [!] D 0o

[H] [!] D 0o
________________________________________________________________________________________________________
_

A. (3 pts) What is the absolute configuration of E in the R/S system?

(circle best)

B. (9 pts) Draw structures for F, G, and H. Assign absolute configuration (R/S) to F and G.

H3C

H
HO

Cl

CH3

CH3

O
H

F
R

C. (3 pts) Why is H optically inactive? It has a plane of symmetry

D. (3 pts) Why is J optically inactive? It is a racemic mixture
E. (6 pts) Propose a mechanism for the conversion of E to F with thionyl chloride which is consistent with
the relative configurations implicated by the data above.
H3C

H
OH

SOCl2

H3C

Cl
O

H3C

H
Cl
+

O
+ HCl

SO2

Retention mechanism

F. (6 pts) The mechanistic conclusion brings into question the reliability of the experimental data,
especially the rotation value for G. Suggest a mechanism more in line with general theory for this sort of
reaction and indicate how it would require different rotation data.

H3C

Cl
OH

SOCl2

H3C

Cl
O

Cl

S
O

This is the typical SN2 mechanism, requiring clean inversion.

CH3