Synthesis and photoarylotropic rearrangement of 10-phenoxynaphthacenokeramidonine

Full text of DOI:10.1023/A:1020978215981

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1212 1213. From Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1263 1264.
Original English Text Copyright
2002 by Sokolyuk, Pisulina.
SHORT
COMMUNICATIONS
Synthesis and Photoarylotropic Rearrangement
of 10-Phenoxynaphthacenokeramidonine
N. T. Sokolyuk1 and L. P. Pisulina2
1Research Institue of Fine Organic Synthesis at TOS Stock Company, Ivanovo, Russia
2Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, 153045 Russia
Received July 4, 2000
We showed formerly that photoarylotropic re-
arrangements [1] occurred also with compounds of
para-quinone imine structure: pyrazolanthrones [2, 3],
pyrazolenaphthocenones [4]. Phenoxy derivatives of
these compounds in the light undergo reversible
transformation into ana-quinone imine isomers.
distribution of bonds in a molecule, 10-phenoxy-
naphthacenokeramidonine (III) (2-butyl-10-phenoxy-
11H-naphtho[3, 2, 1-kl]benzo[h]acridin-11-one).
Naphthacenokeramidonine III was synthesized by the
nucleophilic substitution with phenoxy group of a
chlorine in naphthacenokeramidonine II prepared by
cyclization of naphthacenequinone I in the melt of
aluminum chloride sodium chloride mixture along
procedure [5].
In extension of the study on structural factors
effect on the photoarylotropy we synthesized a photo-
arylotropic compound with the ana-quinone imine
The structural similarity, the resemblance of
spectral characteristics of naphthacenokeramidonines
II, III and keramidonines [6] which possess ana-
quinone imine bond distribution in the molecule
suggest that naphthacenokeramidonines II and III
also have the ana-quinone imine structure.
The presence of an isobestic point in the group of the
spectral curves originating from photochromic transi-
tions of naphthacenokeramidonine III evidences the
presence of two photoforms. Naphthacenokeramido-
nine II with no phenoxy group in the peri-position
with respect to a carbonyl is photostable. The above
data suggest that the photochromism of phenoxy-
naphthacenokeramidonine III is due to a photoarylo-
tropic rearrangement consisting in the reverse migra-
tion of the phenyl ring to the peri-located oxygen of
the carbonyl group. The rearrangement produces a
reversible transformation of ana-quinone imine struc-
ture III into para-quinone imine structure IIIa.
Naphthacenokeramidonine III possesses photo-
chromic properties.
At irradiation of a benzene solution of compound
III with visible light (
450 nm) in the electron
act
absorption spectra of compound III the optical density
of the longwave band decreases and simultaneously
appears an absorption band in the shortwave region
6-(4-Bytylphenylamino)-11-chloro-5,12-naphtha-
cenequinone (I) was prepared by boiling for 6 h 3 g
(9.17 mmol) of 6,11-dichloro-5,12-naphthacene-
at
340 nm. The subsequent irradiation of this
max
solution with shortwave UV light (
result in the restoration of the initial spectral curve.
300 380 nm)
act
1070-4280/02/3808-1212$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS AND PHOTOARYLOTROPIC REARRANGEMENT
1213
quinone [7] with 15 ml of butylaniline in 150 ml of
toluene. Under these conditions alongside product I
formed also disubstituted compound 6,11-di(4-butyl-
phenylamino)-5,12-naphthacenequinone (IV).
keramidonine III estimated from its mass spectrum
was 479. calculated M 479.55.
Electron absorption spectra were measured on
spectrophotometer Specord M-40, IR spectra on
spectrophotometer Specord M-80. Mass spectra were
registered on Varian Match-6 instrument. The melt-
ing points were measured on PTP device (production
standard TU 25-11-1144-76). The solutions of the
compounds under study were irradiated in airtight
quartz cells (l = 1 cm) with a lamp DRK-120. The
necessary spectral range was obtained with the use of
standard light filters (State standard GOST 9411-66).
2-Butyl-10-chloro-11H-naphtho[3,2,1-kl]ben-
zo[h]acridin-11-one (II) was obtained by treating
0.14 g (0.318 mmol) of compound II with molten
mixture of 1.11 g (8.32 mmol) of anhydrous
aluminum chloride and 0.12 g (1.98 mmol) of sodium
chloride at 130 140 C for 10 min. On completion of
the reaction the melt was treated with saturated water
solution of oxalic acid in keeping with [8].
REFERENCES
2-Butyl-10-phenoxy-11H -naphtho[3,2,1-kl]benzo-
[h]acridin-11-one (III) was synthesized by treating
0.048 g (0.115 mmol) of naphthacenokeramidonine II
at 130 140 C for 20 min with phenol-phenolate melt
prepared from 1 g of phenol and 0.05 g (0.545 mmol)
of potassium carbonate. Compounds I IV were
isolated in the individual state by chromatography on
silica gel 40 100 , eluent benzene. Further purifica-
tion was carried out by recrystallization from hexane
benzene mixture, 2: 1. Below are given: compound
number; its yield, %; melting point, C; IR spectrum
1. Organicheskie fotokhromy (Organic Photochroms),
El,tsov, A.M., Ed., Leningrad: Khimiya, 1982,
pp. 224 233.
2. Sokolyuk, N.T., Pisulina, L.P., and Kozhevniko-
va, E.I., Zh. Org. Khim., 1992, vol. 28, no. 10,
pp. 2193 2200.
3. Sokolyuk, N.T. and Pisulina, L.P., Izv. Vuz. Khim. i
Khim. Tekhn., 1993, vol. 36, no. 12, pp. 12 15.
4. Sokolyuk, N.T. and Pisulina, L.P., Zh. Org. Khim.,
1994, vol. 30, no. 3, pp. 447 452.
5. Waldman, H. and Hindenburg, K.G., J. Pr. Chem.,
1940, vol. 156, pp. 157 168.
6. Ektova, L.V., Shishkina, Z.P., and Fokin, E.P., Izv.
SO Akad. Nauk SSSR, Ser. Khim. Nauk, 1977, no. 3,
no. 7, pp. 158 161.
7. Gerasimenko, Yu.E., Poteleshchenko, N.T., and
Romanov, V.V., Zh. Org. Khim., 1980, vol. 16, no. 9,
pp. 1938 1945.
1
taken in KBr pellets, , cm , (C=O); electron
absorption spectrum in benzene, max, nm (log ). (I):
66.1; l25 l26 (from benzene ethanol, 2: 1); 1670;
408 (3.91), 504 (3.99). (II): 57.5; ; 1652; 347 sh
(4.10), 408 sh (4.20), 427 (4.34), 452 sh (4.05) (in
toluene). (III): 52.9; 229 230; 1648; 346 sh (4.02),
405 sh (4.17), 426 (4.32), 451 sh (4.07). (IV): 6.5;
176 177; 1625; 477 (3.99), 584 (4.13), 613 sh (4.11).
The elemental analyses are consistent with the cal-
culated data. The molecular weight of naphthaceno-
8. Sokolyuk, N.T. and Pisulina, L.P., Zhurn. Nauchn. i
Prikl. Fotograf., 1998, vol. 43, no. 5, pp. 59 65.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002