RR`C=NOH

RCONHR (OR) R`CONHR

OH

C=N
R

..

R HO

C=N ..

RCONHR`

..

That it is always the antigroup which migrates has been confirmed by the rearrangements of the two isomeric oximes of 2-bromo-5nitroacetophenone.

Me | C

Me

O2N
| OH

O2N
Br

Cold NaOH
O

(I)
Me | C

(III)

O2N
Br

DH

NaOH

No reaction

(II)

RR`C=NOH

18 H2O
H

18 O

R-C-NHR`

I I

.. . C=N

H OH HO

R R

.. C=N

H2O OH2

C=N / R

..

.. C=N R

H2O

H2O

C=NR
R

-H

C=NR
R

O R-C-NHR

R
R

.. C=N

PhSO2CI -HCI

R
R

.. C=N OSO2Ph

-PhSO2O

C=N R

..

RRCNOH

RCONHR H2O

RNH2+RCOOH

H CH=CH

OH C=N P2O5

CH

CH NH

CH HO- C H

CH N

O=C

CH -H2O
Isoquinoline

CH N

RCON3

R-N=C=O+N2

(a) RCOCI+NaN3
Sodium azide

RCON3+NaCI
Acyl azide

(b) RCOOC2H2

NH2NH2

RCONHNH2
Acyl hydrazide

HNO2

RCON3+2H2O

.. .. R-C-N=N=N

.. .. R-C-N-N N ..

.. , C6H6 R-C-N -N2

R-N=C=O
Isocyanate

..

..

..

..

urethane

R-N=C=O + HOH

O R-NH-C-OH
Carbamic acid

RNH2+ CO2

1.NH2NH2 C6H5CH2COOC2H5 2.HNO2 Ethylphenyl acetate

C6H5CH2CON3

1.

, C6H6 2. H2O

C6H5CH2NH2
Benzylamine

RCOOH + N3H

H2SO4

RNH2 + CO2 + N2

R2CO + N3H

H2SO4

RCONHR +N2

RCHO +N3H

H2SO4

RCN and RNHCHO

Nitrile N- formyl derivative (major) (minor)

R-C

H R-C H OH

OH

.. H-N-N N ..

OHH

O H
-H2O
R-C=N-N N

R-C-N-N N
OH

..

-N2-H

R-N=C=OH2O RNH2 + CO2

CH3`CO`CHR`COOC2H5

N3H H2SO4

CH3CONHCHR`COOC2H5

H2O H

RCH(NH2)`COOH

Note that the reaction with ketones is virtually the insertion of NH group between the carbonyl group and the alkyl group of the ketone.