Recyclization of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones by the action of benzohydrazide

Full text of DOI:10.1134/S1070428009120276

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 12, pp. 1877–1878. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © I.V. Mashevskaya, M.L. Klinchina, I.G. Mokrushin, Z.G. Aliev, A.N. Maslivets, 2009, published in Zhurnal Organicheskoi Khimii,
2009, Vol. 45, No. 12, p. 1878.
SHORT
COMMUNICATIONS
Recyclization of 3-Aroylpyrrolo[1,2-a]quinoxaline-
1,2,4(5H)-triones by the Action of Benzohydrazide
I. V. Mashevskayaa, M. L. Klinchinaa, I. G. Mokrushina, Z. G. Alievb, and A. N. Maslivetsa
a Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received July 10, 2009
DOI: 10.1134/S1070428009120276
Reactions of 3-aroylpyrrolo[1,2-a]quinoxaline-
1,2,4(5H)-triones with hydrazides were not reported
previously. We have found that 3-aroylpyrrolo[1,2-a]-
quinoxaline-1,2,4(5H)-triones Ia and Ib react with
an equimolar amount of benzoic acid hydrazide on
heating in boiling anhydrous acetonitrile (reaction time
1–3 min; the progress of the reactions was monitored
by thin-layer chromatography) to give N-[2-aryl-2,4-
dihydroxy-5-oxo-3-(3-oxo-3,4-dihydroquinoxalin-
2-yl)-2,5-dihydro-1H-pyrrol-1-yl]benzamides IIa and
IIb. The structure of the products was proved by X-ray
analysis.
the carbonyl carbon atom in the aroyl group leads to
closure of new pyrrole ring.
N-[2,4-Dihydroxy-5-oxo-3-(3-oxo-3,4-dihydro-
quinoxalin-2-yl)-2-phenyl-2,5-dihydro-1H-pyrrol-1-
yl]benzamide (IIa). A solution of 1.0 mmol of benzo-
hydrazide was added to a solution of 1.0 mmol of
compound Ia in 30 ml of anhydrous acetonitrile. The
mixture was heated for 2 min under reflux and cooled,
and the precipitate was filtered off and recrystallized
from MeCN. Yield 59%, mp 229–231°C (decomp.). IR
spectrum, ν, cm–1: 3370, 3150 (OH, NH); 1760 (C5=O);
1
1680 (C3′=O); 1650 (CONH). H NMR spectrum, δ,
ppm: 6.60 s (1H, 2-OH), 7.14–7.95 m (14H, Harom),
10.50 s (1H, CONH), 13.26 s (1H, 4′-H), 14.50 s
(1H, 4-OH). Found, %: C 66.13; H 4.03; N 12.38.
C25H18N4O5. Calculated, %: C 66.08; H 3.99; N 12.33.
N-[2,4-Dihydroxy-2-(4-methylphenyl)-5-oxo-
3-(3-oxo-3,4-dihydroquinoxalin-2-yl)-2,5-dihydro-
Compounds IIa and IIb are likely to be formed as
a result of initial attack by the nitrogen atom of the
primary amino group in benzohydrazide on the carbon
atom in position 1 of the pyrroloquinoxaline system.
The subsequent cleavage of the pyrrole ring in I at the
C1–N10 bond and attack by the same nitrogen atom on
H
H
N
O
N
O
PhCONHNH2
O
COAr
N
N
H
O
H
N
Ar
O
N
Ph
O
O
H
O
Ia, Ib
H
N
O
HO
Ar
N
NHCOPh
N
O
HO
IIa, IIb
Ar = Ph (a), 4-MeC6H4 (b).
1877

MASHEVSKAYA et al.
1878
1H-pyrrol-1-yl]benzamide (IIb) was synthesized in
a similar way. Yield 91%, mp 218–220°C (decomp.,
from dioxane). IR spectrum, ν, cm–1: 3380, 3130 (OH,
NH); 1725 (C5=O); 1685 (C3′=O); 1655 (CONH).
1H NMR spectrum, δ, ppm: 2.25 s (3H, CH3), 6.61 s
(1H, 2-OH), 7.05–7.79 m (13H, Harom), 10.43 s (1H,
NHCO), 13.31 s (1H, 4′-H), 14.54 s (1H, 4-OH).
Found, %: C 66.43; H 4.22; N 11.99. C26H20N4O5. Cal-
culated, %: C 66.66; H 4.30; N 11.96.
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
The H NMR spectra were obtained on a Bruker
AM-400 spectrometer (400 MHz) from solutions in
DMSO-d6 using TMS as internal reference.
1
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 07-03-96036, 08-03-01032).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009