Curtius-rearrangement of “rigid” azides

Curtius-rearrangement of “rigid” azides

Tetrahedron Letters No.44, Printed in Great Britain. pp. 3285-3288, 1964. CURTIUS-REARRANGEMENT Walter Thomas Department Since 1914, azides, a...

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Tetrahedron Letters No.44, Printed in Great Britain.

pp.

3285-3288,

1964.

CURTIUS-REARRANGEMENT Walter Thomas Department

Since

1914,

azides,

azides latter

which class

by heat

19 August

the carbonyl they

azides

are

RO-CO-N,,

1.

T.

Curtius,

A.

Bertho,

F. L.

Scott,

T. Curtius

of these

Z,

Angew.

J. prakt. Chem. and A.

azides

Chem., Chem.,

and Ind., Burkhardt,

Corm.

been divided

I’ ‘I3

The classic

-/C-CO-

‘I3

i2s5

” 3

such as Ar-NH-COexplanation

given.

Chem.

of

the azido-

(1914).

959.

J. prakt.

for the

A number

rearrange,

Ar-SO,-N3,

No convincing

27, 111, 213 = 120, 89 (1928). = 1954, V

example

also

azides,

as yet been

and non-rigid

>C-NCO.

ArRN-CO-N,,

carbamoyl

1964)

Upon decomposition

N3.

azides,

U. S. A.

into two classes:

upon decomposition,

the arylsulfonyl

and certain

Scheiffele

form 17 September

to isocyanates,

azides,

Ltd,

AZIDES

New Haven,

have

azides,

and R,N-CO-N,.

behavior

2. 3.

azides

rearrange

carbamoyl

N3. 4 R-NH-CO-N3,

4.

the organic

in revised

rearrangement.

rigid

different

1964;

University,

undergo

aryl-substituted

formates,

Yale

press

DeMauriac,

and Ekkehard

do not rearrange

or light,

Typical

Jr.

which

are

OF “RIGID”

Richard

Mattingly,

of Chemistry,

(Received

Rigid

W.

Lwowski,

Pergmon

2,

205

(1898).

for the

Vo,‘i4

3286

5.

w.

Lv-r>nski

and

work

and

T. W.

tu hc published.

Mattingly,

Jr.

,

Tetrehcdron

Letters

,_ l96_2,

277:

No, 44

3287

azide

decomposition

mole)

of diethyl

yield

of urethane

in methanol

peroxydicarbonate, EtO-CONH,,

Monophenyl-, radiated

tra,

they

were

methanol,

little,

however,

isocyanates

were

the >d.dition products

azide,

produced

hydrazine.

26% of the theory

the solvent.

to the corresponding

gave

and diethyl yield

identified

In

alkylamino-

of the azide,

solution

did not yield

Ann. ~

of N-

Ethylcarba-

carbamoyl

azide,

(CZH5)aN-

of N-diethyl-N’-carbomethoxy-

by their

azide

hydrazine,

with an authentic

followed

water

a 65% yield

elemental was

analyses, also

n. m. r.

compared

6

of N, N-diethyl

by comparison

Heller,

IR spec-

N-ethyl-N’-carbomethoxyhydrazine,

of diethylcarbamoyl

then decarboxylates.

G.

were

sample.

whi-h

6.

to their

from

N-Phenyl-N’-carbomethoxyhydrazine

Photolysis

ment

in 57% yield

The products

with an authentic

identified

gave

63% of the theoretical

and IR spectra.

derived

ir-

and benzene).

C&Is-NH-NH-COOCH,.

C,H,-NH-CO-N,,

C,H,-NH-NH-COOCH, CO-N,

According

C&,-NH-CO-N,,

phenyl-N’-carbomethoxy-hydrazine, azide,

a 78%

obtained.

Phenylcarbamoyl

moyl

(l/2

were

cyclohexene

weight.

groups

produced

carbamoylazide,

(cyclohexane,

if any,

amounts

carbamates.

and diethyl

solvents

by large

reaction

and no alkoxy

of high molecular

contained

be induced

but this

monoethyl-

in hydrocarbon

The products

could

by addition

in an aqueous isolated

gives

Interestingly,

photolysis

rearrangement

products.

263, 281 z=z=z=

(1891).

as the oxalate Apparently,

sample.

of water,

emulsion

gave and

rearrange-

Et,N-NH-COOH, in a 1: 1 acetoneIt appears

that the

3288

x0.44

organic

component,

iorms

ii closed

Acknowledgements: through

the

i~!lovvship

7.

L. S. (1963)

grants for

and

We are

NIH GM 08762 from

T. W. M.,

Yagozhinskli

solvate

and A.

references

grateful

and

shell

around

for

NSF‘ GP

support 649 and

the National

Institutes

Ya.

J. Gen.

cited

Berlin, therein.

the

aaide,

of this ior

pr,~-

work

a p:eedoctoral

oi Health.

Chem.

USSR, __

13, Z

3078