Photo-Fries rearrangements in N-sulphonyl carbazoles

Tetrahedron

Vol

45

16

No

5059

pp

to 5064

1989 0

Prmted I” GreatBrltam

PHOTO-FRIES

Amit

REARRANGEnENTS

Chakrabarti,

Department

of

Goutam

Chemistry,

K.

Bose

(Recewed

Pbstrect

: -When

benzene

or

photo-Fries

methanol

respectively

in

rearrangements

to

Though aromatic

amides

has

glvan

bean

unexplored mides,

the

were

Irradiation (Scheme, ture)

clearly

2(a-c)_

and

rearranged zoles

afforded

l-

and

accompanied

(Scheme,

be

from

the

nitrogen-sulphur

the 2

and

2

/‘1,5_7 may the

from

migratation undergo

discuss

no

be the

in

methanol tampara-

photoproducts of

photo-

N-sulphonylcarbestarting

s

material.

remained

photo-rearranged

unsuccess-

product8

a

fast

homolytic

N-sulphonylcarbszola

could

by

the

and

hydrogen(H4

of

i-1,

RSO>,(Scheme).

from

3-7

Part

radicals neighbour

generating

photo-products

intramolecular

carbazola

cleavage

thereby

Formation

(Scheme).

radical, 1

or

formation

unraacted

underwent

sulphonyl to

N-

Id.

l-l”,7

rationalisad

recombination

migrated

cases

respective of

of

results.

benzene

S-7

all

amount

sulphona-

atmosphera(room

I-1,

expected of

to

almost

behaviour the

and

of

which

i-A-7 frofr

leak

molecules

and

thereby

carbazole.

presence L-1,

and

of

relation

l(a-c)in

In

l-A-7

abstract

Since

of

of

cage

solvent-cage

producing

in

could

l-A-7

in

N-benzoylcarbazola

bond

intermediate

of 3 7

and

photo-Fries light j-1,

and

rearrangements In

absence

5 7 mlorated

2

similar

attention

consideration

nitrogen

from

axclted

covalant

solvent-caqed

and

esters

little

photochamic8l

will

in

small

photolysata

Photochemically of

we

3-7

with and

undergo

phenolic

vary

In

the

(Table).

and

in

1 2

not

in

carbazolas

365nm

L-1,

experiment

did

studied,

3-8ulphonylcarba2oles

Exparlmantal)

isolated

or

the

carbatola

Similar ful

of

respactlvely

3(a-cl

s

rearrangements

report

254

csrbazoles

3-sulphohylcarbatoles

N-sulphonylcarbazoles

at

India

N-sulphonyl

and

studying

present

of

Experimental)

in

Chakraborty*

products.

bahaviour

In

in l-

photochemistry.

interdstad

sulphonylcarbazolea.

D.P.

Calcutta-700009,

extensively

sulphonamide

CARBAZOLES

UK 10 May 1989)

WI

Fries

been

photochemical we

Institute,

expected

have

to

and

N-benzoylcarbazole

photo&emical 192

Biswas

afforded

yield,

glva

N-SULPHONYL

rearrangements

smoothly

29-555

IN

$3 OOf 00 004&4020/89 1989 Pergamon Press plc

of

have any

been

catalytic

sulphonylcarba7@It=s 5059

found

to

reaoent3, 2(a-c)

occur

only

formation and

3(a-cl

A

5060

respectively

from

CHAKRABARTI

N-sulphonylcerbazoles

et (11

l(a-cl

constitute

the

examples

of

true photo-Fries rearrangement, hitherto not investigated in carbazole system. Interestingly such photochemicalrearrangementsin N-sulphonylof

carbazoles and by

l(a-cl

provide

5-sulphonylcarbazoles conventional

synthetic

us

with

which

an have

easy

access

been

found

to

the

synthesis

difficult

to

synthesise

stratagem.

SCHEFIE-1

2.

b,

or ml : lrradlatlon 'it. 254 nm ln benzene or methanol

b2 or

m2

: lrracilatloncjt365 nm In benzene or

methanol

s02R

l-

Photo-Fnes rearrangements

5061

TABLE-l RESULTS

OF

IRRADIATION

OF N-SIJLPHDNYLCARBAZDLES

Wavelenqth

Entrv

Time

Solvent

1.

a

254 254 365 365

nm nm nm nm

Benzene methanol Benzene Methanol

2.

I!

254 254 365 365

nm nm nm nm

Benzene methanol Benzene methanol

3.

c

254 254 365 365

nm nm nm nm

Benzene flethanol Benzene methanol

a:

Compounds

A:

Yields are referred to the amount Compounds 2!a-c) by chromatography. mlcroanalytical data were obtained

=:

Car.

=

l(a-c),

were

prepared

by

methods

described

in

the

($

vield)b

experimental

of crystallised products obtained and 3(a-cl are all new. Satisfactory for new compounds 2(a-c) and 3(a-c).

Cerbazole.

are ACKNDWLEDCEflENTS : The authors t 8 Institute for his Interest. il~‘k~er~~x, Mr. Jaganmoy Guln and fir. Thanks

Product

also

due

to

Mr.

Normal

thankful to The authors Tapan Dutta Das for assistance

K.

Prof. B.0. Biswas, Direcare grateful to Dr. Dilip Por MS end 1~ NMR spectra. during experiment.

EXPERIMENTAL Spectroscopic

grade

photolyeis well

photochemical

254

nm medium

fitted

with

Toshniwal recorded using 30

(Merck)

reactor

pressure

melting on

a

point

Elmer

methanol

was

400-W,

quartz

Bruker

end

(Applied

and

protector

a Perkin

benzene Irradiation

experiments.

365

CXP

(300

instrument.

flHz)

are

(70

m mole-7

in

IR ev)

solvents

in

with

mercury

a

16-W,

vapour on

H NMR spectra

lamps a were

discs)

were

obtained

obtained

with

a AEIMS

DMF-benzene

(1:l)

were

the

immersion

determined 1

(KBr

as quartz

England)

were

uncorrected.

Instrument.

a

pressure

points

flS

used in

Ltd.,

nm medium

PIeltrng and

782

out

Photophysics

tubes.

apparatus

were

carried

spectrometer.

Synthesis

of

startlnq

compounds

Carbazole round

bottom

0-5’C

under

nylchlorlde

~‘l.Og;

flask

was

mechanical (0.8

ml;

5.9

treated

stlrrlno. 6 m mole),

l(a-d)_:

with

To the

50

ml

In

150

sodium

hydride

(0.168g;

7.0

cold

stirred

solution

benzenesulpho-

p-toluenesulphonylchloride

(1.12g;

m mole)

5.9

ml at

m mole),

5062

A

methanesulphonylchloride 6.0

m mole)

experimental rature

for

about acid

ml

sodium

added

in

conditions.

sulphuric (100

(0.4

were

in

The

4 hrs.

end

graphed

over

columns

with

n-hexane-ethyl

crystalline

starting

After

silica

compounds

(0.959; 1100 (6H,

m),

7.51

Hz),

8.41

(IH,

d,

(300

(4H, J =

m), 7.6

(0.9og; 1130,

(IH,

d,

7.96

(IH,

d,

Hz),

J =

Hz);

8.2

‘H

J I

8.8

8.16

cm

Hz),

(IH,

;

d,

ml)

for

the

same

wave

length

chemical the in

each

(60-120

mesh)

J =

12O’C;

IR

:

1390,

the afforded

1355,

7.19

(IH,

d,

7.9

Hz),

7.95

(IH,

:

1595,

(Ker)

7.53

(OH,

Hz),

6.39

(IH,

d,

m),

1Ol’C; flHz,

7.81 flS

m.p.

compounds

and

J =

1400,

(ppm): m),

7.9

7.78 HZ);

J -

1140, 8.6

d,

1330,

2.34 (IH,

fls

IR

(KBr):1600,

CDC13)

(ppm)

:

6.0

Hz),

(lH,

:

m/z

:

98’C

period

was were

l(a-d)

l(a-d)

were

d, 245

J =

Hz),

J -

8.5

d,

:

1300,

(SH,

m/z

J = 321

a),

7.15

7.6

Hz),

(t’l+).

1410, 2.36

1331, (3H,

7.88

1290,

s),

(lH,

1140,

7.10 d,

(lH,

d,

J = 7.7

Hz),

benzene

or

(fl+).

-

I)

removed subjected

using

(I.09

254

of

time

under

were

(Llt4.

at

lrredistsd (same

Table

run

up

(f’l+).

m),

90%),

reactions

solvent

d,

(5H,

Hz);

Compounds (300

enhydrous

(Id):

of

nol

7% benzene

chromato-

elution

work

tempe-

(1~):

8.1

(0.909; Irradiation methanol

(lH,

7.42

m.p.:

N-benzoylcarbazole

On

1590,

(ppm)

COC13)

(4H,

J =

:

over were

flerck).

(KRr):l600,

fiS: 307

:

H NRR (300

7.46

extracts

follows

KHz,

(O.!;g;,89%), 1120

with

extracts

subsequent

NRR (300

N-methanesulphonylcarbazole

1127,

with

extracted

benzene

and

COC13)

7.80

m.p.

cm -I;

J = 8.0

room

(1 b),:

go%),

1110

IR

Wz,

N-p-toluenesulphonylcarbazole

1150,

as

at

ml;

similar

decomposed

were

the

(0.69

under

stirred

then

mesh;

(9:l)

m.p.:180°C;

’ H NflR

7.39

the

up

(la),:

95%),

cm”;

was

(60-120

l(e-d)

set

products

drying

gel

benzoylchloride

were

concentration,

acetate

N-benzanesulphonylcarbezole

1125,

mixtures

reaction

and

of

and

experimental

sodiumhydride

the

filtration

columns

m mole)

reaction

experiment).

sulphate,

6.0

separate

Excess

solution

each

ml;

four

et al

CHAKRABARTI

N2

under tc

n-hexane-ethyl

nm as

each)

were at

irradistlon

atmosphere by

vacua.

et

chromatography acetate

as

at

365

dissolved

in well

room

After red

as

254 wes

T.L.C. The

98’C)

well

separately of

monitored

m.p.

nm es

maintained

benzene as

tempereture. completion photolysates

over

columns eluent.

The of

of

or

at

under

oily

the

nm in

365 a

methanm

fixed photo-

irradiation thus

silica

obtained gel

Photo-Fnes Photoproducts rately) cal

at by

time

254

work

of

up

obtained

nm as

well

under

eimilar

irradiation

tively)

as

as

as

the

conditions

have

been

Photoproducts in benzene

or

two

ehown

Carbazole

in

of in

by

of

benzene

wave

the -

were

The

variation

(254

under

sepa-

found

and

365

different

identi-

in

the

rtm respect-

experimental

1.

irradiation

of

(n-hexane-ethyl

(la-lc,

methanol

lengths

products

Table

compounds

or

condition.

different

yields

obtained methanol:

irradiation

365

experimental

under

well

by

at

5063

rearrangements

&

at

acetate

254

9:?)

nm as

:

m.p.

well

ae

241’C

at

365

nm

m.p.

(Lit

245’C). I-benzenesulphonylcarbarole so1id:m.p.

172’C;

1150,

cm -’ ;

1140

7.97

(IH,

d,

(IH,

b8,

020

J t

(2al: IR

‘H

1150, 8.02

8.0

Hz),

AHz,

8.11

exchangible)

1130

cm -’ ; m),

exchangible)

‘H

8.18

or

d,

307

obtained methanol

1100;

m-p. ‘H

7.87

(IH,

(IH,

8,

NflR d, D20

1130,

m.p.

7.52

(4H,

(IH,

S,

by

:

irradiation Carbazola

Carbazole

KHz,

CDCi3)

(ppm):2.37

Hz),

7.94

m),

1110

m.p. cm -1 ;

98’C; I H NIIR

IA (300

1585,

(St?,

and

Hz)

1330,

m)

9.86

and

1300,

ml,

(3H, bs)

1270,

7.54

(SH,

(IH,

s,

9.95

m), 020

8.28

as

at

acetate:9:?) 1340,

s),

(IH,

7.34 d,

3 =

nm

crystalline

1310, (3H, 7.9

365

1145, m);

1135,

7.53

Hz)

and

(4H,

(n-hexane-ethyl 1630,

1600,

COC13)

9.90

(IH,

d,

321

(m+).

irradiation

acetate:7:3):crystaIIine 1595,

1427,

(ppm):2.35

8.16

of

J -

3

8.0

at

HZ),

254

1345,

(3H,

s),

8.65

(IH,

nm as

well

1300, 7.37 s)

as

at

1140, (3H,

and

365

m), 9.91

nm in

acetate:g:l) (2~1: (KBr):3395, MHz,

(n-hexane 1600,

COC13)

m)

(II+).

MS:m/t by

nm as well acetate:9:1)

1435,

(3H,

m),

321 (3b):

I-methanesulphonylcarbazole solid;

(2H,

flS:m/t

exchangible);

(n-hexane-ethyl

(lH,

(n-hexane-ethyl

(300

obtained methanol:

1400,

of lb at 254 (n-hexane-ethyl

(2bl:

(2H,

7.9

1280,

7.57

acetate:7:3):crystaIIine 1580,

8.77

1620,

7.97

J -

(ppm):7.30

Hz),

(KBr):3385,

exchangible);

m), 020

Photoproducts benzene or

COC12)

8.0

228’C; IR (K8r):3390, -1 I cm ; H Nf’lR (300 RH2,

1120

d,

1350,

m),

(N+).

3-p-toluenesulphonylcarbazole solid;

1600,

IR

8.6

(IH,

1340,

(3H,

(IV+>.

20O’C;

J =

1430,

(n-hexane-ethyl

flHr,

I-p-toluenesulphonylcarbazole solid;

8.34

1630,

J =

acetate:9:l):crystalline 1580,

(ppm);7.38

m), 307

:3320,

NFlR (300 (lH,

; p1S:m/z

Photoproducts in benzene

(2H,

; flS:m/z

(KOr)

1600,

COC13)

(3a)_:

205’C;IR

(2H,

1620,

Nt’lR (300

3-benzeneaulphonylcarbazole so1i.d:m.p.

(N-hexane-ethyl

(KBr):5390,

1420, (ppm)

ethyl

acetate:9:?)

1340, 2.31

(3H,

1229, s),

1300, 7.28

crystelllne 1140, (3H,

1132, m),

7.72

A CHAKRABARTI et al

5064

(IH, d, J = 8.0 Hz), 7.78 (2H, m), 8.07 (IH, d, 3 = 8.0 Hz) and 9.86 (lH, ba, D20 exchingible); RS:m/t 245 (fl+). (n-hexene-ethyl acetate:8:2):cryatalline

3-methanesulphonylcarbazole (3~): llII°C;

solid; m.p. 1115

cm -I

(2H,

m),

gible);

;

‘H

IR

NIIR

(300

(lH,

d,

7.95 PIS:m/z

245

No L-1, obtained at

254

carbatole

by

(KBr):3385,

1600,

CDC13)

RHz, J = 6.2

Hz),

8.45

3-7

and/or of

5-7

L-1,

(IH,

s)

however

benzoyl

1331,

1290,

1140,

(3H,

a),

7.29

(3H,

and

9.84

(IH,

s,

migrated

N-benzoylcarbazole

well as at 365 nm under

was

1345,

1126,

m), D20

7.62 exchin-

(VI+).

irradiation

nm as

1420,

(ppm):2.30

N2

(ld) atmosphere

photoproducts

in

benzene

at

room

or

were methanol

temperature.

Some

isolated. REFERENCES

1.

2.

3.

a.

Bellus. D.,

Adv.

b.

Bellus.

Hrdlovic.

a.

Anderson.

C;

b.

Finnegan.

A.R.;

March.

D.;

J.,

Clarke. and

Reese.

T.H.,

Duantitetlvel,

Chem.

B.C.,

Mattlce.

1977,

1971,

P.,

‘Advanced

structure’, 4.

Photochem.

J.

Rev.

Chem.

J.J., Organic

f3,

109-159. 1967,

SOC.

67,

1963,

Tetrahedron

599-609. 1781.

1965,

2,

Chemistry:Reection,

lDl5.

mechanism

and

506.

'A Handbook Edward

of

Drganlc

Arnold,

Analysis London,

4th

:

QualltatlVe

Ed.,

1949,

207.