Mild addition of 2-pyrene to pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione

Full text of DOI:10.1134/S107042800805028X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 5, pp. 774−775. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.V. Babenysheva, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 5, pp. 779−780.
SHORT
COMMUNICATIONS
Mild Addition of 2-Pyrene
to Pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione
A. V. Babenysheva and A. N. Maslivets
Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received April 9, 2007; final version October 23, 2007
DOI: 10.1134/S107042800805028X
compound I as it has been described for reactions of
pyrrolobenzoxazinetriones I with OH- and NH-mono-
nucleophiles [1, 2]. A probable alternative mechanism
(route b) involves the [4+2]-cycloaddition of olefin II at
the system of conjugated bonds O=C–C3=C4 as is
characteristic of acyl-substituted 1H-pyrrole-2,3-diones
[3, 4] to form compound IV with a subsequent [1,5]-
prototropic shift in the latter.
Reactions of olefins addition to 1H-pyrrole-2,3-
diones, in particular, fused at the [a] side with
azaheterocycles, were not previously reported.
In reaction of 3-benzoyl-2,4-dihydro-1H-pyrrolo-
[2,1-c][1,4]benzoxazine-1,2,4-trione (I) with 2-pyrene
(II) in a ratio 1:2 at boiling in anhydrous toluene for 100–
120 min we unexpectedly obtained in good yield 3-benzo-
yl-2-hydroxy-3a-(3,4-dihydro-2H-pyran-5-yl)-1H-
pyrrolo[2,1-C][1,4]benzoxazine-1,4(3aH)-dione (III).
The described reaction is a mild method of a carbon-
carbon bond formation occurring without intermolecular
activation and previously not observed with five-member-
ed 2,3-dioxoheterocycles.
The formation of compound III may be attributed to
the extremely easy nucleophilic addition (route a) of
a polarized olefin II to the most electrophilic site of
O
O
N
O
O
N
O
O
II
a
COPh
COPh
O
O
OH
O
I
III
[1,5]-H
O
O
O
[4+2]
O
b
N
Ph
O
O
IV
774

MILD ADDITION OF 2-PYRENE
775
Benzoyl-2-hydroxy-3a-(3,4-dihydro-2H-pyran-5-
yl)-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,4(3aH)-
dione (III). A solution of 3.3 mmol of compound I and
6.7 mmol of 2-pyrene (II) in 15 ml of anhydrous toluene
was boiled for 120 min (till decoloration), the mixture
was cooled, the separated precipitate was filtered off.
Yield 84%, mp 126–128°C (from hexane). IR spectrum,
ν, cm–1: 3025 br (OH), 1777 (C4=O), 1713 (C1=O), 1655
(COPh). 1H NMR spectrum, δ, ppm: 0.86 t (1H, C4'H,
J 6.7 Hz) 1.60, 1.78 d.m (2H, C5'H), 3.70, 3.87 d.m (2H,
C6'H), 6.26 s (1H, C2'H), 7.33–7.90 group of s (9H,
C6H4 + Ph), 11.80 s (1H, OH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 17.06 (C4'), 20.90 (C5'), 65.12 (C6'),
67.44 (C3a), 106.51 (C2'), 116.46–143.42 (CAr), 161.41,
162.81 (C1, C4), 190.00 (COPh). Found, %: C 68.38;
H 4.27; N 3.57. C23H17NO6. Calculated, %: C 68.50;
H 4.23; N 3.46.
spectra were registered on a spectrometer Bruker WP-
400, solvent DMSO-d6, internal reference TMS. The
homogeneity of compound synthesized was proved by
TLC on Silufol plate, eluent ethyl acetate, development
in iodine vapor.
The study was carried out under a financial support
of the Russian Foundation of Basic Research (grant no.
08-03-01032).
REFERENCES
1. Maslivets, A.N., Mashevskaya, I.V., Krasnykh, O.P.,
Shurov, S.N., and Andreichikov, Yu.S., Zh. Org. Khim.,
1992, vol. 28, p. 2545.
2. Maslivets, A.N., Mashevskaya, I.V., and Andreichi-
kov, Yu.S., Zh. Org. Khim., 1993, vol. 29, p. 2056.
3. Sano, T., J. Synth. Org. Chem. Jpn., 1984, vol. 42, p. 340.
4. Penn, G., Kollenz, G., and Peters, K., Osterr. Chem.-Zeit.,
1983, p. 234.
IR spectrum was recorded on a spectrophotometer
1
13
FMS-1201 from mull in mineral oil. H and C NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008