–

H O H
+
N H H N H H H H
H H2O2 heat
+ HO N
H
H H H H H H
H H H H

Note: peroxyacids (e.g. mCPBA) can hydroxyl group is a stronger base than
also be used for the oxidation step the protonated N-oxide

H3C H3C O H3C –

HO OH HO
–
O
CH3 CH3 + H CH3 +
N N N
CH3 CH3 CH3
H2O2

H
+ H2O
H H H
H H H
H H H

"N-oxide"
Tertiary amine

H3C –
O CH3
CH3 +
Bonds Formed: C-C (π), O-H
N H3C
CH3 OH
Bonds Broken C-H, C-N
heat + N
CH3
H hydroxyl amine
H
H
H H
H

N-oxide Alkene
H3C – CH3
O H
CH3 +
H N the C-H bond anti to the N-oxide remains
CH3
H
H
heat
H
H H H
H
H the C-H bond syn to the N-oxide breaks
H

C-H bond anti to the Br breaks (giving Zaitsev) Major Minor

CH3 CH3
CH3 H
H Br
H
H NaOEt +
EtOH, heat H
H H H
H H
H H
H H
H
H C-H bond anti to the Zaitsev product "Hofmann product"
Br breaks (Hofmann) (more substituted alkene) (less substituted alkene)
break C-H form C-C (pi)
H H
H H H H
H H break C-N
H H
H H

H +
H
H
–
N
+
+ HO N
H
N H H
O H
–
O H 11

Transition state
form O-H

H3C H
CH3 H3C H3C
H +
O H
N
H3C –
O H + N
CH3
heat
H H
Bonds Formed: C-C (π), O-H
H H H
H
H Bonds Broken C-H, C-N
H