--KEY--Chemistry 108B Exam #1-Winter 2015--KEY-You are planning the synthesis of 4-chloro-2-propylnitrobenzene, A.

Your initial retrosynthetic analysis begins with

three possible precursors to the desired product. Thoroughly but concisely explain whether any of the proposed
one-step reactions will proceed as shown. If yes, explain why; if no, explain why not. A yes or no answer gets you
no credit!
Cl

HNO3/H2SO4

McMurry 16.22c

Cl

NO2

15 = 3@ expl; 6 = synthesis

This pathway WILL work: the propyl group is an o,p-director as is the Cl so we have an example
of additive directive effects placing the NO2 group ortho to the propyl group and para to the Cl.
You will have to invoke the sep o,p incantation, however.
Cl

Cl, AlCl3

Cl

NO2

NO2

This pathway WILL NOT work: the Friedel-Crafts addition of the propyl group is not possible in
the presence of the powerful resonance electron-withdrawing NO2 group.
Cl2, FeCl3

Cl

NO2

NO2

This pathway WILL NOT work: although the electrophilic aromatic chlorination reaction WILL
add Cl to the benzene ring, the NO2 group is a m-director and will cause the Cl to add para to the
propyl group and meta to the NO2 group. The propyl group is an o.p-director and will also cause
the Cl to add to the wrong position on the benzene ring: ortho or para to the propyl rather than the
required meta position.
(b) Use the best initial step from (a) to create a complete your retrosynthetic analysis and propose a multi-step
synthesis of 4-chloro-2-propylnitrobenzene, A, from benzene. If NONE of the of the initial steps in (a) give any of
the precursors shown, propose your own multi-step synthesis of A.
Cl

NO2

HNO3
H2SO4

O
Cl

Cl

AlCl3
H2/Pd
O

Cl2
FeCl3

O
Cl