The reaction of anti-methyl-3-(1-methyl-indolyl) ketoxime with toluene-p-sulphonyl chloride

Tetrahedron

Letters

No.25,

THE REACTION

pp.

2165-2166,

1970.

Pergamon Press.

Printed

OF ANTI-METHYL-3-(l-METHYL-INDOLYL) WITH

TOLUENE-p-SULPHONYL Maurice

Birmingham

University,

in Great Britain.

KETOXIME

CHLORIDE

Cohen Edgbaston,

Birmingham,

England’ (Received in UK 16 April Many cases

acoepted

for

publication

or Neber

the oxime 0-toluene-p-sulphonate

rearrangement,

In connection with an investigation of such compounds, 3 (I) was treated with toluene-p-sulphonyl ketoxime The resulting

crystalline

compound (IV),

chlorine,

but sulphur was absent.

indicated

the molecular

Theu.v., exhibited

1970)

i.r..

formula

spectra

chloride,

v CHaC1z 1600, max

dCDCl

Ketoxime

CH&l, Vmax

QDCl,

1558,

I

On heating with aqueous hydrochloric

contained nitrogen

and molecular

and

to those

8.47

(s),

7.32,

7. 22 (m),

3.67

(8).

2.33

(s).

8.08

(s),

7. 14.

7. 12 (m).

3. b7

(8).

2.33

(6).

acid,

shown by chromatography

liberated

a potassium

(IV) yielded

1 -methyl-3-(

to be oxygen,

structure H,NCl

(IV) explains t H@

1 -methyl-indolyl)

was evolved.

iodide solution in aqueous tetrahydrofuran,

temperature. The assigned

at

weight determinations

of compound (IV) were very similar

ketone (V) and a gas, iodine from

112-113’,

in dry pyridine,

(I):

Compound (IV);

(I);

m. p. analysis

isolable.

to be C1tH1tNaCl.

andn.m.r.

by its precursor

Elemental

is usually

anti-methyl-3-(l-methyl-

indolyl) -5”.

30 April

of the reaction of toluene-p-sulphonyl chloride with oximee are recorded 2 and although, in some cases, the product is that expected from a

in the literature Beckmann

1970;

the data presented.

+ NH, t HOCl;

2165

2HOCl

+ 2HCl t Oa.

It also at room

No.25

2166

~:&!&$$$&~cI

I

II

CH3

As illustrated which itself potassium

above,

hydrolyses iodide or,

Such behaviour prepared

hydrolysis to ammonia

upon heating,

producing

mechanism

ester

The fact that the isomeric

analogous proceed

to be formed

anion by the electrons

medium,

normally

the postulated

initially,

followed

of the hetero-ring,

by thus

is attacked by the most

namely the chloride

anion,

to open the three

(IV).

anti-methyl-Z-(1

way supports

, which are, however,

is shown above.

(11) is presumed

ring and yield the N-chloroketimine

in an analogous

4

This spiran intermediate

in the reaction

ketone (V) and chloramine,

The latter would oxidise

with ketones5.

for this unusual reaction

cation (ill).

nucleophile

membered

acid.

V

3

yield oxygen gas.

of the toluene-p-sulphonate

an azirine

powerful

IV

would yield the observed and hypochlorous

of chloramine

The toluene-p-sulphonate displacement

3

has been noted for N-chloroketimines

by condensation

A possible

III

CH3

-methyl-indolyl) mechanism,

to spiran (HI) could not be formed.

The Neber

ketoxime’

did NOT react

for in this case,

an intermediate

rearrangement

is known to

through aairine intermediates’.

Acknowledgements I would like to thank Dr. Council Education

Department

References

and Notes

1. Present

address

2. D. J. Cram 3. M.p.

E. J. Forbes

for a maintenance

- Chemistry

and M. J. Hatch,

138-139’.

m.p.

Reid and D. B. Sharp.

5. C.R.

Hauser

6. M.p.

163-164”.

and E.

Department,

Moore,

satisfactory

Bar-Ilan

158-159’.

J.Org.Chem., J.Amer. analysis.

and Birmingham

City

grant.

J.Amer.Chem.Soc.,

of benaoate,

4. S.L.

for his helpful advice

University, 15,

33 (1953).

Both analyses 26,

Chem.Soc.,

Ramat-Can,

satisfactory.

2567 (1961). 5,

4526 (1933).

Israel.

CH3