The Role of Neighboring Groups in Replacement ... - ACS Publications

ROLEOF THE BENZAMIDO GROUPIN REPLACEMENT REACTIONS

Oct., 1950

[CONTRIBUTION FROM THE CHEMISTRY

DEPARTMENT OF THE

4669

UNIVERSITY OF CALIFORNIA, LOS ANGELES]

The Role of Neighboring Groups in Replacement Reactions. XVII. Complex Neighboring Groups. The Benzamido Group' BY S. WINSTEINAND ROBERT BOSCHAN R

The participating acyloxy group is, in a sense, one of the more complex' neighboring groups. To illustrate, solvolysis of tram-2-acetoxycyclohexyl p-toluenesulfonate2 I gives rise to the intermediate I1 with Walden inversion a t C,. The nature of the final products depends on the conditions; in dry or basic2 acetic acid solution I1 turns up as trans-l,2-diacetoxycyclohexane 111 with a second Walden inversion at either C, or Cg. In acetic acid containing water,2 cis-monoacetate V is produced by way of CHa

i

O/%O

CHa

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- OTs-

I

/-7\ LEo/ I

CHa \m/ OEt

/"\ 0 0 I '

> c-&
C@---Ca

0

0

CiS

l i > c-c
c-c
c-c < acylamino case is an oxazolinium ion VI11 I which is, in general, capable of isolation OAc as a salt or as the free oxazoline. For

9 CH,

I

C

H-&"

C

\O

I

I

> c-c


c-c

a '

I