Photochemical (2 + 2) cycloaddition of and thermal decomposition to n-methylacridone and acetone: chemiluminescence as a probe of possible formation of 1,2-dioxetanes

Photochemical (2 + 2) cycloaddition of and thermal decomposition to n-methylacridone and acetone: chemiluminescence as a probe of possible formation of 1,2-dioxetanes

Tetrahedron Letters,Vol.23, Printed in Great Britain No.l,pp 95-96,1982 oo40-4039/82/alOO95-O2$03.OO/o @Pergamon Press Ltd. PHOTOCHEMICAL (2 + 2) ...

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Tetrahedron Letters,Vol.23, Printed in Great Britain

No.l,pp

95-96,1982

oo40-4039/82/alOO95-O2$03.OO/o @Pergamon Press Ltd.

PHOTOCHEMICAL (2 + 2) CYCLOADDITION OF AND THERMAL DECOMPOSITION CHEMILUMINESCENCE

AS A PROBE OF POSSIBLE

Nobutaka Department

Suzuki,*

Yoshihiko

of Industrial

AND ACETONE:

OF 1,2-DIOXETANES

Kazui, and Yasuji

Chemistry,

Mie University,

TO N-METHYLACRIDONE

FORMATION

Izawa

Faculty of Engineering,

Tsu, Mie 514, JAPAN

Irradiation of N-methylacridone @MA) in an acetone solution at -78 "C in the argon atmosphere afforded light emission (@CL: low6 - 10m8 e' Instein/mol) upon warming-up to room temperature. The final products were NMA and acetone exclusively. Photochemical oxetanes,l Similar

(2 + 2) cycloaddition

cycloaddition

reactions

1,3-dioxetanes

(cyclic acetals),

are considered

as the reverse

between

between

accompanying

such photochemical

1,2-dioxetane

carbonyls

two molecules

two carbonyl

molecules

but there was no literature

reactions

moles of carbonyls

emission

reactions

are well known as well as those between

of the thermal

chemiluminescence formation

as a probe of the formation

could yield

cyclobutanes.

1,2-dioxetanes

We now describe

the photochemical

and/or

to the two

the first example

of

using chemiluminescent products

2

The reactions

of 1,2-dioxetanes

from two moles of ketones

upon warming-up

to yield

giving

about the reactions.

decomposition

(CL).

and olefins

of olefins

light

at -78 "C to

room temperature.

2

NMA(1)

1,2-dioxetane

(3)

l* 4

A solution 5 min before

(1: 10s2 M) in acetone (Wako Chem. Co.), flushed with 02, N2, or Ar for

of NMA3

irradiation,

was irradiated

through

solution

gave light emission

chemiluminescence with PL spectrum

compound

(probably

showed

(PL) spectra

is 1.

3)p which

of the irradiated

under the similar

that no other compound

that irradiation

1,2-dioxetane,

species

being irradiated

up from 77 K to room temperature

of 1 (Xmax 525 nm) in acetone

These data suggest

The emitting

when warmed

(CL) and phosphorescence

of the spent solution TLC.5

at -78 "C with a 100 W high-pressure

Hg lamp (Eikosha: The irradiated

a Pyrex dewar flask in a Pyrex test tube (0 1.8 cm) for 5-30 min.

PlH-100)

decomposed

thermally

NMA, acetone, and irradiation

were

were repeatable

several

95

times.

were identical

used for CL.

Analyses

than 1 and acetone by GLC5 and

gave an unstable

again at -78 "C after CL, the spent solution

ation/chemiluminescence

conditions

was detectable

of 1 in acetone

The

(Table I).4 solution

chemiluminescent

to 1 and acetone revealed

exclusively.

to be essential.

gave light emission.

When

The irradi-

96

Table quenches

I shows that presence

radicals

of 02 decreased

or triplet excited

state of the C=O product) decomposition.8

states

(@CL) of 1,2-dioxetanes

Thus, O2 quenches

of 3.

in a range of the similar

1,2-dioxetanes _ in the literatures.Y

Similar

irradiation

CH2C12 gave weaker

of 43 produced two molecules

photochemically

The present an another synthesize emission

reaction

radical

cycload-

9-methylene-lo-methylacridanes Yields of CL a) from NMA

Ar

N2

02

1.0 x 10-6

3.1 x 10-8

0.7 x 10-8

in CH2C12

provides

route to 6b,lO 1,2-dioxetanes.

Quantum

I.

in Me2C0

of 1.

at the photochemical

from substituted

solv.

from

of CL (from S,

its non-chemiluminescent,

CL reactions

Table

of 1 in

decomposition

It has been known that 02

of quantum yield

The half life time (T,,~: ~a. 60 set at 0 "C) is

derived

CL which seems to

result from the thermal

of CL.

suppressing

the successive

dition stage as well as the thermolysis

appeared

the amounts

(Tl)7 and enhances

-

-

a) Relative

to the Hasting's

0.7 x lo-g

Standard

(see ref. 4).

general

We also aware that the photoirradiation/chemiluminescent

system might compose possibly

a photo-energy-storage/discharge

system,

light

if the reactions

would be more effective. We thank Dr. T. Kondo and Professor and the valuable the financial

discussions

support

T. Goto, Nagoya

and the Ministry

and K. D. Legg, J.

4) acL values were measured

by using a photomultiplier

mesh)

standard

[J. W. Hastings

Yanagimoto

in a steinless

13C-NMR

at -80"

of Japan for

1, 283 (1967).

1, 197 (1967); D. J. Trecker,

3) K.-W. Lee, L. A. Singer,

5) GLC Conditions:

for taking and Culture

AND NOTES

and G. Lenz, org. Photochemistry,

2) G. J. Fonken, org. Photochemistry,

to the Hasting's

Science,

(Grant-in-Aid). REFERENCES

1) 0. L. Chapman

University,

of Education,

tube (Hamamatsu

R-105UH)

and G. Weber, J. opt. SOC. Amer.,

Yanaco G-18OF

steel column

ibid., 2, 63 (1969).

org. Chem., 41, 2685 (1976).

(FID), 10% Silicone

GE-SE-30

and are relative

53, 1410 (1963)].

on Diasolid

L (60-80

(0.8 m x $ 3 run); Col. temp. 250 "C; inj. temp. 280 "C, carrier

Silica gel PF254 -gipshaltig (Merck), 0.25 mn (CHC13). TLC Conditions: 13 C-NMR signal of the quarternary carbons of 3 supposed should 6)(a) As the referee suggested, the 6b However, the solubility limitation at -6O%-80 "C, in that appear in the range of 6 89-95 ppm. gas (N2) 40.0 ml/min.

range 3 would be stable, stability

made it difficult

of the instruments

7) N. J. Turro,

"Modern

p. 354; "Free Radicals" 8) T. Wilson

available;(b)

Molecular

the signals

and was out of the sensitivety/

W. Adam, Adv. Heterocycl.

Photochemistry",

Chem.,

Benjamin/Cumnings,

Vol. 1, ed by J. K. Kochi, Wiley,

21, 437 (1977).

Menlo Park, CA., 1978,

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I. Beheshti,

A. Burford,

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Chem. Lett.,

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cited therein.