Some Answers to Hour Examination #1, Chemistry 302/302A, 2004

1. In this variation of the Diels-Alder reaction, both the diene and the dienophile are
cyclic compounds. The first complication is to decide whether the reaction will pass
over an endo or exo transition state. In fact, the cycloadduct has the endo
stereochemistry, and this reaction is normal in that respect
O

H O

note:
endo

C11H10O2

O
You may have noticed that the product of this Diels-Alder reaction still has a double
bond with two attached carbonyl groups. This carbon-carbon double bond is also a
quite reactive dienophile. When this reaction is run in the presence of two equivalents
of 1,3-cyclopentadiene, a 2:1 adduct is readily formed:

H O

H O

C16H16O2

double endo

O
HH

2. Adamantene is unstable because the bond is a very poor one.The orbitals do not
overlap at all well.
very poor overlap
reverse
=
Diels-Alder
1

The reaction succeeds, but the unstable adamantene undergoes a reverse Diels-Alder
reaction. Remember: all cyclohexenes are related to a diene and a dienophile through
the Diels-Alder reaction.

3. Solvolysis gives pentadienyl cation I that closes to a cyclic ion. Addition of water,
followed by deprotonation gives 4 .

OTs
H

H2 O

H2 O

4
H3 C

H H

CH 3

H3 O

H3 O

H3 C

H H
I

CH 3

H3 C

CH 3

Intermediate I is a pentadienyl cation, a four-electron system. Analysis of the HOMO

shows that closure must take place in conrotatory fashion to give the compound with
trans methyl groups. If you cant figure out the MOs, you do know that all thermal 4n
electrocyclic reactions are conrotatory.

HOMO = psi 2, top view + + 0

CH 3

H2 O
4
+

H3 O
H3 C

CH 3

H3 C

4. Compound A is formed through a straightforward Friedel-Crafts alkylation reaction.

CH 3 (CH ) CH
3 2

Cl

AlCl 3

CH 3
(+)

CH 3

H
CH(CH3)2

CH(CH3)2

(+)

+ HCl

CH 3

CH 3

CH 3

AlCl 4

+ AlCl3

What can HCl do? The hint tells you to focus on this product. If the product A is
protonated, we can generate an intermediate in which an alkyl shift moves the
relatively large alkyl groups apart. Thats the key to why this rearrangement happens the relief of steric strain when the thermodynamically more stable 1,3,5-trisubstituted
benzene is formed from a less stable 1,2,4-trialkylbenzene.
CH3

H3C

CH(CH3)2

HCl
CH3

CH(CH3)2 H C
3
(+)

CH(CH3)2 H3C

(+)

CH(CH3)2

(+)

(+)
CH3

CH3

CH3

5a. Straightforward. Friedel-Crafts acylation, sulfonation, reduction.

SO 2OH

CH 3CH 2CH 2

SO 3

Cl

O H2SO 4

AlCl 3

O
CrO3
CH 3CH 2CH 2CH 2OH

CH 3CH 2CH 2

SO 2OH
Zn/HCl

SOCl2
OH

H2O

CH 3CH 2CH 2

Cl

5b. Harder: Indirection must be used because Friedel-Crafts alkylation will not be
effective on the strongly deactivated nitrobenzene. Of course, the tert-butyl group is an
ortho/para director and will not nitrate in the meta position. So, we use the strongly
activating amino group to force nitration into the position adjacent to it, and then
remove the amine. In the answer, we acylate the amine to avoid substitution in the
meta position directed by the protonated amine, but we will let you get away (partially
at least) with an answer without the protection-deprotection sequence.
C(CH 3 )3
C(CH 3 )3
C(CH 3 )3 1. HNO
3
AcCl
H2 SO 4
AlCl
3

(CH 3 )3 CCl

(protection)

2. H2/Pd/C
NH 2

NHAc

SOCl 2

HNO3
H2 SO 4

(CH 3 )3 COH
C(CH 3 )3

C(CH 3 )3
1. HONO/HCl

NO2

KOH/H 2O
NO2 (deprotection)

2. H3PO 2
NH 2
SOCl 2

CH 3 COOH

C(CH 3 )3

AcCl

NO2
NHAc

Alternatively,
NH 2

NHAc
AcCl

1. HNO3 /H2 SO 4

pyridine

2. H2 /Pd/C

(CH 3 )3 C-Cl
AlCl 3
NHAc

as above

C(CH 3 )3
6. Compound 3 is aromatic (4n + 2, n = 4), whereas compound 4 is not (4n, n = 4).
Accordingly, the 12 outside hydrogens in 3 appear far downfield of the normal alkene
position [ B net = Bo + Bi], and the six inside hydrogens are shifted far upfield [Bnet =
Bo Bi]. No such effect is apparent in 4 , of course.
B induced

aromatic ring
Hout

Hin

B induced

B applied

7. Here is a set of structures:

A

B
O

C
O

HOOC
O
Fried el-Craf ts with
th e acyl chlo rid e

ozo no lysis/ oxida tion

of th e d ou ble b on d

E
Cl

Cl
Dou ble Wo lff-Kishn er
red uce s C=O grou ps

a cid ch lorid e formation

a nd an ot her Fried elCraf ts

Cl

Cl

Cl

Ph ot ochlo rin ate all

b enzyl p ositio ns

Cl
Do uble E2
O

F =
Cl