Novel desulfurization of thiocarbonyl compounds into their corresponding oxo-derivatives using a peroxy-sulfur intermediate generated from 2-nitrobenzenesulfonyl chloride and superoxide anion.

0040-4039/85 $3.00 + .OO 01985 Pergamon Press Ltd.

Tetrahedron Letters,Vol.26,No.8,pD 1079-1082,1985 Printed in Great Britain

NOVEL DESULFURIZATIOH CORRESPONDING GENERATED

Yong

Hae

COMPOUNDS

OF THIOCARBOHYL

0X0-DERIVATIVES

A PEROXY-SULFUR

USING

FROM Z-NITROBENZENESULFONYL

Bong

Kim*,

Chul

Chung,

CHLORIDE

and

Hae

llepartment of Chemistry,

Korea Advanced

P.O. Box 150 Chong-yang,

Seoul, Korea

Thiocarbonyl

Sumnary.

-thiocarbamates is generated superoxide

were

compounds found

to convert

Sung

THEIR INTERMEDIATE

AND SUPEROXIDE

ANION.

Chang

Institute of Science and Technology

such as substituted-thioureas,

to react

by the treatment

INTO

of

with

a peroxysulfur

2-nitrobenzenesulfonyl

into the corresponding

-thioamides,

intermediate chloride

cat-bony1 compounds

and

(3) which

with potassium in quantitative

yield at -3J°C in acetonitrile.

Considerable derivatives

interest

using

superoxide

oxidative

desulfurizations

are

to occur

known

there

is

no

direct

(3)

excellent

an

olefins.'

We

thioamides,

and

quantitatively substrates

for

oxidizing now

found

thiocarbamates

by addition

and potassium

any

for

thiouracil,

desulfurizations alkaline

oxygen

reaction

facile

and

chloride

into

though

which

is

intermediate

epoxidation

such

their

since

thiobarbital

superoxide

of

as

thioureas,

carbonyl

compounds

to the reaction mixture

of the

The work up is simple:

by t.1.c. on silica gel, filtration

1079

thiourea

compounds

regioselective

derivatives

desulfurized

sulfonyl

give a highly pure product.

and

reported that a peroxysulfur

super-oxide (02*-) at -3S°C in acetonitrile.

the complete

carbonyl like

of

autoxidation4

ethionamide

corresponding

thiocarbonyl

readily

of Z-nitrobenzene

the

activated

the

various

on

system of

the

We recently

reagent

were

of

to form

involving

that

focused

thioureas

in living cells.5a6

have

after monitoring

cyclic

been

and a related

metabolism

evidence

widely

recently

anionle3

of

in vivo --

distributed is

has

and concentration

1080

In a general

a solution

procedure,

of

mtrol) and 4-(p-nitrothiobenzoyl)-morpholine heterogeneous -3S°C

under

stirring, layer

dry

the

gave

afforded

other

potassium

mixture

After

side

pure

amide

(0.0889, Further

products.

(0.159,

being

filtered,

was

for

chloride

mmol;

CH3CN,

cd.

S.Oh

98%)

sulfur

purification

ml)

1.0

at

-35OC

(58,

O.O14g,

were identified

at

with

concentration

from

good

without hot-water

by comparing

Results obtained

ca.

of CH3CN

88%)

by recrystallization

samples.

0.68

1.5 ml) was added to a

with CH3CN:

and

(0.1519,

CH3CN,

and washed

and Imp. with those of authentic

and lH n.m.r,

2.045

stirred

The products obtained

(0.0829, 91%).

sulfonyl

(i,.O9g, 0.47 mmol;

superoxide

atmosphere.

highly

pure amide

in Table

of

argon

reaction

the

accompanying

i.r.

solution

P-nitrobenzene

their

are summarized

I.

S R-&NH

P a”’

+

K02

R’ .

g -359:

NO2

5) R-C-NHR’

+

SO3K

5

,O

Q-

4’1 II’0

? R-C-NH

0

to

the

previous

results2s3

obtained

from

with 02*- in the absence of 1 at 25OC, our new method and

quantitative

analogues appears by

a

conversion

without

attack

to oxidize

of

2 to 4 though

4 may

reaction

quickly

thioureas

with

ureas

mechanism

by 02'and

starting material

2,3

of thiones

for instance,

25OC,

sulfur

of

but

1, where

nor

3 which is formed have

confirmed.8

was recovered

not

The sulfine

intermediates.'

from that of the direct

did

an oxidizing

desulfurization

the sulfine

sulfate

desulfurization

was obtained

occur

oxyyen

The desulfrization

5 by a intramolecular

potassium

thioureas

corresponding

1 and may

isolated

desulfurization

diphenylthiourea

their

intermediate, of

of

to result in a clean

at -35OC.

to the ketones through different

desulfurization

into

formation

been

to the products,

is apparently

at

sulfonyl

R’

takes an advantage

with a peroxysulfur

the

absence

the

compounds

products

3 has neither

convert

in the

guanidines

on

02'-

like the case of the oxidation

of

thiocarbonyl

to be initiated -via the oxidation

intermediate,

The

the

the side or intermediate

nucleophilic

ability

of

‘43 Se

NO2

o-0

In contrast

+

at

quantitatively.

-35OC:

together namely

1081

however

our

new

reaction

results

It is noteworthy

quantitatively. ethylthiourea

(run -9

88%)

transformation various

peroanganate,13

the

acid21

for

Table

as

nitric

manganese

sulfur

1.

acid,lO

with

use

in view

of oxidation

Desulfurization

Substrates

;1 4-No*-c6H4-c-h ca

of

only

into

have

the

been

their

quite

scope

of

intensive

selenium

benzeneselenic

chemical

hindrance yield

studies

dioxide,12

on

yield

and

usiny

dnd

sheds

further

hy 02*-.

of Thiocarbonyl

Compounds

Reaction Time (h)

1:K02:2

at -35OC in Acetonitrile

Product

Referenceb

5(%)a

5.0

1:3:0.6

91(98)'

22

II

6.5

1:1.5:0.6

90(98)'

3

C6H5-!-NHCH3 c

5.0

1:3:0.6

86

23

4

C6H5-&NH-nPr

5.5

1:3:0.6

92

24

5

C6ti5-.-hh-C6ti5 ?

6.5

1:3:0.6

91

25

6

$ 4-Cl-C H -C-NHCH3 G4

4.5

1:3:0.6

86

26

7

CH3-&NH-C6H4-N02-4

5.0

1:3:0.6

95

26

8

s C,H,Nti-C;NHEt

5.5

1:3:0.6

91

27

9

Ph(Et!N-?-NHPh

6.5

1:3:0.6

88

28

10

PhNH-?-NH -u

6.0

1:3:0.6

89

29

11

Ph-S-t-ND

5.0

1:3:0.6

93

x)

12

Ph-S-?-N2

8.5

1:1.5:0.6

87

13

Ph-CH2NH+

7.0

1:3:0.6

92

s

6 -1IHCH2Ph

a) Isolated yields (purified by crystallization) h) The data of all the products are identical with those from c) Crude yields without crystallization

Acknowledgment: generous

financial

We suport.

thank

In-

may be more

2

S

the

potassium

anhydride$a) herein

of

of the

oxo-analogues

The work described and

compounds

1,3-diphenyl-l-

excellent

corresponding

acetate,ll

success.

carbonyl

due to the steric

the new reaction yielded

mercuric

of

and

desulfurization

probably

alkylnitrites,"

some degree

(88%)

the usual

There

groups

dioxide,l'l

synthetic

light on the mechanism

1

though

conditions.

thiocarbonyl

such

chloroperbenzoic

Run

that

and ethyl ones,

tinder mild

of

reagents

advantageous

elementary

gave a poor yield of the urea analogue

the bulky groups of diphenyl urea

in

Professor

Shigeru

Oae

for

helpful

known compounds

suggestion

and

KAIST

for

1082

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(Received in Japan 27 November 1984)