Photochemistry of 9,10-diphenylanthracene endoperoxide

Tetr.&edron

Letters

Pergamon

No. 7, pp 687 - 690, 1970.

PHOTOCHEMISTRY

ENDOPEROXIDE

Jean RIGAIJDY, Claire BRELIERE Laboratoire

de Recherches

(Recejved

It is well oxygen

analogues,

such as &,

originate

diepoxides

xides of naphthalenes

isomers

by v.p.c.,

where

irradiation

-la was submitted

to UV irradiation

concurrently

by t.1.c. on silica

- 9,10-diphenylanthracene

2a -'

three isomers

experiments

gel. These are

have shown that these

intermediates

: the meso-

with l-4 endopero1,2-3,4 diepoxidest

under various proportions,

conditions.

6.80-7.18

(CH30H)

:

from photo-dissociation

5a resulting ._'

from a degradation

process,

:

- i4.M.R. (lH), 61E13.:

(m,lOH,phenyls)

M/e (70ev.)

- UV (ether)

6.76(m,4H

An,axnm(logE)

: H6H7H8Hg),

: 272(3.60)

5,

7.34 (s,~H

; 266(3.54)

: H1H2H3H4),

; 261 (3.40)

: 362 (M+).

- 6,11-diphenyl-6,11-dihydro-6,11-epoxydibenzo~,eloxepin (CH30H)

Five

were always detected

- 4b,lOa-diphenyl-4b,lUa-dihydro-benzo~,4~cyclobuta~,2-b]benzo~~,4~dioxan m.p. 166-167°C

pro-

of -la.

in variable

arising

- lo-hydroxy-lo-phenylanthrone

to degradation

leads to isolable

behaviour

molecular

-lb or meso-alkylated

leading

of primary

1977)

-la releases

3 . Because of the similarities

the photochemical

which are produced

and the following

endoperoxide

tine unsubstituted

transformations

and anthracenes,

CEilEX 05 29 December

an O-O bond homolysis,

in these conditions

or isolated

de l'E.S.P.C.I.

publication

for

whereas

1

75231-PARIS

of types S and -10 *. Trapping

in studying

Endoperoxide main products,

upon heating,

from tiie subsequent

6_, unstable

we were interested

1?77; accepted

suffer essentially

ducts or to rearranged isomers

Organiques

known that 9,10-diphenylanthracene

almost quantitatively

Britain.

and Pierre SCRIBE

- 10, rue Vauquelin,

in UK 3 Decenber

in Great

OF

9,10-DIPHENYLANTHRACENE

(E.R.A.W'l70)

Printed

Press.

- UV (ether) hmaxnm(logE)

acid-catalyzed

isomerization

: 286(3.48) of -la 536.

; 279(3.44).

&,

previously

m.p. 169-170°C obtained

from the

- 4b,9b-dipbenyl-4b,9~-dihydro-benzofuroC3,2-b7benzofuran (C2H50H)

- N.M.R.

282(3.85)

(13C) hTMS : 103.0ppm CDC13 - M/e (70 ev,) : 362 (M+).

-12a, resulting

from the migration

12a , m.p. 199-200°C (only one kind of sp3C) - UV (ether) hmaxnm(logE)

of both side-nucleus

example

of this kind, not found up to now in the thermolysis 7 endoperoxides . A wavelength understood

effect

on tne distribution

if one takes into account

the following

to oxygen,

or photolysis

of these products considerations

is the first of anthracenic

was observed.

:

It can be

:

No. 7

68k

R

R

R = R =

C,H,

6) c)

R =

CH,

a)

1

il

1

1 hu

\ ‘/ [&fiq O

-

/

+ NMM

\

k

4

R

0

H

689

I?o. 7

- The three photoisomers, region

as photo-oxide

tion with

(in particular

the others,

a high-pressure

Extended

coefficient irradiation

resulting

products

it is recovered nearly unchanged

of photo-oxide

is difficult

to evaluate

;

alone to irradia-

above 350 nm whose

owing to unavoidable

traces of -2a.

of -la under conditions

where

the

Table

(Runs 1, 2 and 3) that photodissociation

promoting,

isomerization

besides,

isomer -12a, and to a lesser

to -8a predominates.

Accordingly,

Conditions

253,7 a

conditions

yields.

: Yields of detected or isolated photoproducts

Solvent

1

precisely

to prepare -12a (Run 4) and -8a (Run 5) in reasonable

Table

I

the

are photostable.

extent -10a. At long wavelengths

I

rates during

when submitted

in this region does induce photolysis

only at short wavelengths,

could be adjusted

at different

-12a is the most photostable

-la shows a weak tail absorption

It is clear from the accompanying is important

decomposed

at 253 nm). However

in the same spectral

Hg lamp in a Pyrex vessel.

- The UV spectrum extinction

a strong absorption

-la (A<310 nm), can be further

course of the irradiations in contrast with

which exhibit

ether

Products

Temp.

Time

("C)

(Hrs)

20

2

(%)

-la 5

40

14

2

i

i

5

15

-

30

2

> 280 b

ether

-70

18

13

Ii

115 I48

1 -

I

18

I

3

> 400 c

ether

20

30

23

2

2

60

i

5

-

8

3

32

11

10

25

-

8

2

15

50

i

i

-

18

4

> 280 d

cyclohexane

20

4

10 -

5

> 350 e

benzene

20

33

14

h

4

1

6

1

-

a Rayonet

R-U-L.235,7

nm lamp

lamp - solid glass filter

; e Mazda halogen lamp 500 W ; f

t.1.c.

; i traces.

It was probable fl-methyl-maleimide

(30 moles)

4

-

2

3

I

I

I

I

I

I

(4

11

( 1

16

159

1

22

1

d

Philips SP 500 lamp - Pyrex h based on v.p.c. analysis ; based on preparative

that -8a derived

of -la under conditions

72

; b Osram X-O-B Xenon lamp - Pyrex filter ; ’ Osram X-O-B Xenon

: Sovirel type VjV3 ;

filter

diation

14

water-cooled

from the intermediate

giving -Ca (Run 6) in the presence (Run 7) led to an adduct

diepoxide

G

; in fact, irra-

of a large excess

(60%), C31H2304N,

of

Finst 317-318°C

@IO

No.

(EtOH), for which the steric structure from the following (q,2H,H2,H3), 259(3.00),

spectral

acetic acid by Zn and KI t NaOAc,

in aqueous

(AcOEt)- NMR 6;E13

3.03 (t,2H,HlI,H12)

: 2.88 (s,3H,N-CH3),

; UV (ether) h,,xnm(logs)

with one of the two stereoisomeric 8 220°C in a sealed tube . A closer insight photooxide

adducts

6.13 265(3.03),

obtained

tions leading

it is noteworthy

through

only -8a. When the warming

states

is in accord with 9 of endoperoxides .

J. RIGAUDY

France,

IUPAC Congress,

Boston

p. 493 and references

of

by

only -10a and and that it

photoisomeriza-

primarily

to disso-

made on the behaviour

and NOTES

Contributed

Pure and Applied

on Photochemistry,

paper N"84, p.268. See also,

Chem., Special

lectures

at the XXIIIrd

1971, Vol. 1, p.383.

M.C. PERLAT,

3) J. RIGAUDY,

leading

predictions

at the VIth IUPAC Symposium

July 19-23,1976.

and J.J. BASSELIER,

2) J. RIGAUDY,

a solution

up was preceded

containing

it undergoes

effect,

the theoretical

results have been presented

Aix-en-Provence,

at

-9a and -lla.

intermediates

REFERENCES I) Preliminary

of NMM on 2,

first at long wavelengths,

that the wavelength

or homolysis,

of excited

(q,2H,H2,H3),

is identical

by irradiating

a mixture was obtained

through -7a, to -8a. At short wavelengths,

to -10a and -12a possibly

Moreover

, which

l-4 addition

could be obtained

afforded

at short wavelengths,

thermally,

4.50 (m,2H,HI,H4),6,50

by direct

-12a. One can then infer that diepoxide -6a is formed rearranges

14a, C31H2302N,

of Run 3, but at -7O"C, in order to stop at -6a. Simply war-

to room temperature

irradiation

13a gives

; 295(3.99),286(4.03)

into the mechanism

fh in the conditions

ming up a fraction

280,

2,78 (m,2H,H1,H4),

253(2.93).

Finst 285-286°C

ciation

to the known -13b 3, could be deduced

; UV (ethe?) +,,,xnm(loge) : 279(3.04), 272(3.04),

3.61 (t,2H,H11,H12)

Reduced

a second

13a, analogous

; NMR TFls $...,C, : 2.89 (s,3H,N-CH3),

data

7

D. SIMONand NGUYEN

KIM CUONG, Bull. Sot. Chim. Fr., 1976,

therein.

J. BARANNE-LAFONT,

A. DEFOIN and NGUYEN

KIM CUONG, C.R.Acad.Sci.

Paris,

1975,

Serie C, p. 527.

4) For various examples, 5) J. RIGAUDY

see

and C. BRELIERE,

6) An analogous

bicyclic

: J. RIGAUDY, Pure and Applied Chem., 1968, I&, p. 169. Bull. Sot. Chim. Fr., 1972, p.

acetal has been found also during

dimethyl-benz(a)anthracene.

M.K. LOGANI,W.A. AUSTIN

1390.

the photooxygenation

and R.E. DAVIES, Tetr.

of 7,12 Letters,

1977

p. 2467. 7) Chemical

evidence

in complete

They will be reported 8) For other examples

agreement

in a forthcoming

of l-4 additions

with the proposed

and A.U. KHAN, Photochem.

have been obtained.

paper.

of dienophiles

J. RIGAUDY and NGUYEN KIM CUONG, C.R.Acad.Sci. 9) D.R. KEARNS

structures

on 9,10_diphenylanthracene,

Paris,

and Photobiol.,

1961, 253,

1969, lo,

p. 1705.

p. 193.

see

: