Reactions of thiosulfonic acid esters with amines

Tetrahedron Letters No.48, PP, 4291-4293, 1965. Pergamon Preae Ltd. Printed in Great Britain,

REACTIONS

OF THIOSULFONIC

ACID

E. Dunbar

Joseph

and

E. C. Britton The

Dow Chemical

Company,

ESTERS

Joan

WITH

AMINES

H. Rogers

Laboratory Midland,

Michigan,

U.S.A.

(Received 7 September 1965)

In a recent reported

the reaction

hydrazine mides

communication

with

RS02SR'

of primary

esters

(II) and amine

salts

that aryl

esters esters

aromatic

of this

amines

reaction

to observations

in our not

In addition When

methyl

metric there

entirely

RS02H.H2NR"

days even

H, 8.22;

(m.p.

H, 7.04:

N, 5.76. runs

to their

with

their

the reaction

for C5HllNOS:

126-127.5". Found:

of varying

N, 10.37)

temperature,

at 100 to 110".

prior

was

in ether

minutes,

within

at room

and

Studies

publication

led

results.

to be reversible.

treated

solution

4-(methylthiojmorpholine

Calcd.

sulfinate

R' react

in accord

found

of morpholine

C, 44.97;

of several

to react

laboratory

we have

obtained

n25 D 1.4977. Found:

several

p-toluenethiolsulfonate

amount was

fail

sulfena-

III

(I) of aliphatic require

and

They

(III).

II

reported

that

+

ammonia

(I) to form

acids

R'-S-NHR"

Kolesnikova

amines,

acids

of sulfinic

I

whereas

and

aliphatic

of thiosulfonic

2H2NR"+

+

(1) Boldyrev

with at room

(b.p.

C, 45.08:

a stoichiotemperature,

48-49"/5mm.;

H, 8.33;

and morpholinium

N, 10.52. -p-toluene-

c, 54.29: Calcd. for C11H17N03S: . C, 54.41; H, 7.22; N, 5.44). In each lengths

4291

of time

the same

amount

of

No.48

4292

zhiosulfonate

unreacted reaction

was

morpholine in ethyl

was

demonstrated

with e?her

variety will

yield.

Equilibrium

of thiolsulfonates

be reported

in a later

amines

that

unsubstituted

at approxix,ately when

0.05

room

temperature

(V) was two

hours

mide

with

to give

(m.p.

l38-140';

sulfenamide

(m.p.

benzenesulfenamide reaction anilinium

the

as do alkyl

mole

(VI)

and

react

(m.p.

with

amines

thiolsulfonates.

in ether,

one minute,

33-36')

Thus,

(IV) is treated

of morpholine in about

we have

the salt

and

(3) was

at

after

isolated

in

yield.

to the reported

that

o-nifrophenyl

in e-than01 at reflux

aniline

of a

determined

authors,

benzenethiolsulfonate

regard

we ;lave shown

are being

of the cited

to precipitate

with

in 30% of the

of the reactions

thiolsulfonates

rate

0.20

theoretical

Finally,

and

same

the sulfenamide

90% of the

reacts

aryl

rrole of phenyl

observed

amines,

the

methyl

publication.

Contrs.ry to the observations found

to give

(2) isolated

constants

with

-p-toluenesulfinate

for 20 hours

56-59")

(m.p.

of the

of 4-(methylthio)-

of morphilinium

temperature

p-toluenettdolsulfonate theoreticai

reversibility

by the treatment

an equivalent at room

The

isolated.

temperature

unreactivity

of aromatic

benzenethiolsulfonate with -p-anisidine,

-p-toluidine

the N-(p-methoxyphenyl)-o-nitrobenzenesulfena51%

yield)

136-138"; (m.p.

sulfenamide

bcnzenesulfinatk

89%

94-97") was

(4): N-(p-tolyl)-o-nitrobenzene_ yield)

(5), respectively.

isolated

(m.p.

(5) and N-phenyl-o-nitro-

132')

in very (6) was

small

In the yield,

obtained

latter but

in 52%

the

No.40

yield.

4293

The driving force for the formation of the sulfenamide

and the sulfinic acid salt is therefore enhanced not only by increased'basicity of the amine, but also by decreased electron density about the divalent sulfur atom of the thiolsulfonate group.

REFERENCES

1.

B. G. Boldyrev and S. A. Kolesnikova, Zh. Obshch. Khim. 3, -

198 (1965).

2.

D. T. Gibson, J. Chem. Sot. =1931, 2637.

3.

R. C. Kinstler, U. S. Patent 2,840,556, June 24, 1958.

4.

J. H. Billman and E. O'Mahoney, J. Am. Chem. Sot. 2340 (1939).

5.

T. Zincke and F. Farr, -Ann. 391, 80 (1912).

6.

H. Bredereck and E. Bider, Chem. Ber. E,

129 (1954).