1.

This Diels-Alder reaction yields two adducts, endo and exo:

A and B
25 °C

H CN
CN

CN H
endo C9H11N exo C9H11N



The Diels-Alder reaction is reversible, and at high temperature the reverse reaction
is favored because of the TΔS term. In this case, not only can starting material be
reformed, but new products appear. Here is the arrow formalism for formation of
the new products, shown only for the endo isomer. Of course both adducts can
undergo the reversal.

400 °C
H CH2

CH2
CN
CN

















 2. In each case, the two products come from 1,2 and 1,4 addition. Here are the
arrow formalisms:

H Cl

+
+ H
H

– –
Cl Cl

C14H 23Cl
H H
Cl Cl

In this example, the circled product of 1,2 addition is also the more stable product
(trisubstituted double bond vs. disubstituted double bond), and thus will be the
major product at all temperatures.














 3. Only isomer B gives an aromatic anion when deprotonated. Thus, it will be
far more acidic then the either A or C, neither of which gives an aromatic
anion.

–

H :B –

–
=
–

aromatic

4. There are, of course, many possible correct answers to this one. Here are
some. By the way, this one is in the book, so …………

Note that all lone pairs are shown in the figure below, but those in the sigma system
do not contribute to the pi system’s aromatic sextets.
O
(c) N
(a) or (b)

B
H B N
B H H
H

(d) N (e) O
O
N
or N or
O O N
B B
H H









5. Formation of B is a reverse Diels-Alder reaction (6 electrons, 4 + 2) and is
thermally possible. Formation of C is a reverse 4 + 4 (8 electrons) reaction
and will not be possible thermally. The HOMO-LUMO interactions in the
formation of B allows for two bonding interactions,. Whereas the HOMO-
LUMO interactions in the formation of C require one antibonding interaction.
reverse
4+2

reverse
4+4

Here are the orbitals:

4 + 2 4 + 4

HOMO diene HOMO diene

antibond
LUMO ene

LUMO diene






6.

H Cl

+
A

(+) (+)

H
+
C –Cl

C10H12