Five-membered 2,3-dioxo heterocycles: XCVII.* Reaction of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones with Fischer's base

Article abstract of DOI:10.1134/S1070428013120099

3-Aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones reacted with 1,3,3-trimethyl-2-methylidene- 2,3-dihydro-1H-indole (Fischer's base) to give (2Z)-1-aryl-2-[3-oxo-3,4-dihydroquinoxalin-2(1H)-ylidene]-5-(1,3,3-trimethyl-2, 3-dihydro-1H-indol-2-ylidene)pentane-1,3,4-triones.

Full text of DOI:10.1134/S1070428013120099

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 12, pp. 1759–1761. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.V. Konovalova, A.N. Maslivets, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 12, pp. 1778–1780.
Five-Membered 2,3-Dioxo Heterocycles:
XCVII.* Reaction of 3-Aroylpyrrolo[1,2-a]quinoxaline-
1,2,4(5H)-triones with Fischer’s Base
V. V. Konovalovaa and A. N. Maslivetsb
a Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
b Perm State National Research University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received July 9, 2012
Abstract—3-Aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones reacted with 1,3,3-trimethyl-2-methylidene-
2,3-dihydro-1H-indole (Fischer’s base) to give (2Z)-1-aryl-2-[3-oxo-3,4-dihydroquinoxalin-2(1H)-ylidene]-5-
(1,3,3-trimethyl-2,3-dihydro-1H-indol-2-ylidene)pentane-1,3,4-triones.
DOI: 10.1134/S1070428013120099
Substituted 4-acyl-1H-pyrrole-2,3-diones, including
those fused by the [e] side to aza heterocycles, readily
react with binucleophiles to produce a variety of fused
heterocyclic and spiro-heterocyclic systems [2–4]. We
previously studied reactions of 4-acyl-1H-pyrrole-2,3-
diones fused to quinoxalin-2-one fragment, 3-aroylpyr-
rolo[1,2-a]quinoxaline-1,2,4(5H)-triones, with primary
enamines. The reactions of pyrroloquinoxalinetriones
with N-alkyl-substituted dimedone imines involved
successive addition of the β-CH and NH groups in the
enamine fragment of the latter (enamine tautomer) to
the C3a and C2 atoms of pyrroloquinoxalinetrione,
respectively, to give bridged 3,10,13-triazapentacyclo-
[10.7.1.01,10.04,9.014,19]icosanes [4, 5]. The reaction of
pyrroloquinoxalinetriones with substituted 1,3,3-tri-
methyl-2-azaspiro[4.5]dec-1-enes stops at the stage of
addition of the β-CH group of the enamine to the C3a
atom of pyrroloquinoxalinetrione [1]. Reactions of
3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones
with secondary enamines were not reported.
By heating 3-aroylpyrrolo[1,2-a]quinoxaline-
1,2,4(5H)-triones Ia–Ie with an equimolar amount of
1,3,3-trimethyl-2-methylidene-2,3-dihydro-1H-indole
(II, Fischer’s base) in boiling anhydrous acetonitrile
for 2–10 min (until disappearance of bright violet color
typical of initial pyrroloquinoxalinetriones) we ob-
tained in good yields the corresponding (2Z)-1-aryl-2-
[3-oxo-3,4-dihydroquinoxalin-2(1H)-ylidene]-5-(1,3,3-
trimethyl-2,3-dihydro-1H-indol-2-ylidene)pentane-
1,3,4-triones IIIa–IIIe (Scheme 1).
Compounds IIIa–IIIe were isolated as orange or
red high-melting (with decomposition) crystalline
substances, which were readily soluble in DMSO and
DMF, poorly soluble in alcohols and chlorinated
hydrocarbons, and insoluble in water and alkanes.
The IR spectra of IIIa–IIIe contained absorption
bands due to stretching vibrations of NH group (3175–
3185 cm–1), NH group involved in intramolecular
hydrogen bond (broadened band, 3093–3098 cm–1),
and carbonyl groups (C3′=O, C4=O, 1678–1688 cm–1;
Scheme 1.
H
N
Me
3''
Me
O
Me
O
4'
HN
1
3'
Me
CH2
COAr
2'
2
5
2''
+
4
1'
N
3
COAr
N
N
N
1''
H
O
O
Me
Me
O
O
Ia–Ie
II
IIIa–IIIe
Ar = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-ClC6H4 (d), 4-BrC6H4 (e).
* For communication XCVI, see [1].
1759

KONOVALOVA, MASLIVETS
1760
ArC=O, 1651–1653 cm–1; C3=O, 1605–1609 cm–1,
broadened band). In the H NMR spectra of IIIa–IIIe
hydro-1H-indol-2-ylidene)pentane-1,3,4-trione
(IIIb). Yield 90%, mp 169–171°C (from EtOAc). IR
spectrum, ν, cm–1: 3175 (NH), 3094 br (NH,
H-bonded), 1678 (C3′=O, C4=O), 1653 (C1=O), 1605
1
we observed signals from aromatic protons, a six-
proton singlet at δ 1.43–1.48 ppm from two methyl
groups in position 3 of the indole fragment, a three-
proton singlet at δ 3.27–3.29 ppm from the NCH3
group, a singlet at δ 5.81–5.83 ppm from the vinylic
proton, a singlet at δ 12.04–12.05 ppm from the NH
proton in position 4 of the quinoxaline ring, and
a singlet at δ 14.46–14.52 ppm from the NH proton
(H-bonded) in position 1 of the quinoxaline fragment.
1
(C3=O, H-bonded). H NMR spectrum, δ, ppm: 1.48 s
(6H, Me), 2.35 s (3H, 4-MeC6H4), 3.28 s (3H, NMe),
5.81 s (1H, CH), 7.02–7.94 m (12H, Harom), 12.04 s
(1H, N4′H), 14.50 s (1H, N1′H). Found, %: C 73.59;
H 5.51; N 8.21. C31H27N3O4. Calculated, %: C 73.65;
H 5.38; N 8.31.
(2Z)-1-(4-Methoxyphenyl)-2-[3-oxo-3,4-dihydro-
quinoxalin-2(1H)-ylidene]-5-(1,3,3-trimethyl-2,3-di-
hydro-1H-indol-2-ylidene)pentane-1,3,4-trione
(IIIc). Yield 92%, mp 195–197°C (from EtOAc). IR
spectrum, ν, cm–1: 3175 (NH), 3098 br (NH,
H-bonded), 1688 (C3′=O, C4=O), 1653 (C1=O), 1608
Presumably, in the described reaction attack by the
=CH2 group of Fischer’s base on the C1 atom of Ia–Ie
is followed by opening of the pyrrole ring via cleavage
of the C1–N10 bond, as described in [2–4] for the reac-
tions of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-
triones with mononucleophiles. No such pathway was
observed previously in reactions of pyrroloquinoxa-
linetriones with enamines.
1
(C3=O, H-bonded). H NMR spectrum, δ, ppm: 1.43 s
(6H, Me), 3.27 s (3H, NMe), 3.32 s (3H, MeO), 5.82 s
(1H, CH), 6.99–7.81 m (12H, Harom), 12.04 s (1H, N4′
H), 14.47 s (1H, N1′H). 13C NMR spectrum, δC, ppm:
21.93 (3″-CH3), 29.82 (CH3N), 48.11 (C3″), 109.14
(C5), 115.41–146.39 (Carom), 154.81 (C3′), 173.74 (C4),
183.57 (C3), 191.11 (C1). Found, %: C 71.30; H 5.26;
N 8.00. C31H27N3O5. Calculated, %: C 71.39; H 5.22;
N 8.06.
EXPERIMENTAL
The IR spectra were recorded on a Bruker IFS 66
spectrometer with Fourier transform from samples
1
dispersed in mineral oil. The H and 13C NMR spectra
(2Z)-1-(4-Chlorophenyl)-2-[3-oxo-3,4-dihydro-
quinoxalin-2(1H)-ylidene]-5-(1,3,3-trimethyl-2,3-di-
hydro-1H-indol-2-ylidene)pentane-1,3,4-trione
(IIId). Yield 90%, mp 191–192°C (from dichloro-
ethane). IR spectrum, ν, cm–1: 3175 (NH), 3093 br
(NH, H-bonded), 1686 (C3′=O, C4=O), 1651 (C1=O),
were measured on a Varian Mercury-300BB spectrom-
eter (300 MHz for H) from solutions in DMSO-d6
1
using hexamethyldisiloxane as internal reference. The
purity of the isolated compounds was checked by TLC
on Sorbfil plates using ethyl acetate–benzene (1:5) or
ethyl acetate as eluent; spots were visualized by treat-
ment with iodine vapor.
1
1605 (C3=O, H-bonded). H NMR spectrum, δ, ppm:
1.43 s (6H, Me), 3.27 s (3H, NMe), 5.82 s (1H, CH),
7.02–7.81 m (12H, Harom), 12.04 s (1H, N4′H), 14.47 s
(1H, N1′H). Found, %: C 68.38; H 4.66; N 7.83.
C30H24ClN3O4. Calculated, %: C 68.50; H 4.60; N 7.99.
(2Z)-2-[3-Oxo-3,4-dihydroquinoxalin-2(1H)-
ylidene]-1-phenyl-5-(1,3,3-trimethyl-2,3-dihydro-
1H-indol-2-ylidene)pentane-1,3,4-trione (IIIa). A so-
lution of 1.0 mmol of compound Ia and 1.0 mmol of
Fischer’s base (II) in 20 mL of anhydrous acetonitrile
was heated for 10 min and cooled, and the precipitate
was filtered off. Yield 89%, mp 177–179°C (from
dichloroethane). IR spectrum, ν, cm–1: 3185 (NH),
3095 br (NH, H-bonded), 1680 (C3′=O, C4=O), 1653
(2Z)-1-(4-Bromophenyl)-2-[3-oxo-3,4-dihydro-
quinoxalin-2(1H)-ylidene]-5-(1,3,3-trimethyl-2,3-di-
hydro-1H-indol-2-ylidene)pentane-1,3,4-trione
(IIIe). Yield 89%, mp 175–177°C (from dichloro-
ethane). IR spectrum, ν, cm–1: 3175 (NH), 3094 br
(NH, H-bonded), 1679 (C3′=O, C4=O), 1651 (C1=O),
1
(C1=O), 1608 (C3=O, H-bonded). H NMR spectrum,
1
1609 (C3=O, H-bonded). H NMR spectrum, δ, ppm:
δ, ppm: 1.47 s (6H, Me), 3.29 s (3H, NMe), 5.83 s
(1H, CH), 7.03–8.02 m (13H, Harom), 12.05 s (1H,
N4′H), 14.52 s (1H, N1′H). Found, %: C 73.12; H 5.25;
N 8.52. C30H25N3O4. Calculated, %: C 73.30; H 5.13;
N 8.55.
1.43 s (6H, Me), 3.28 s (3H, NMe), 5.83 s (1H, CH),
7.00–7.94 m (12H, Harom), 12.04 s (1H, N4′H), 14.46 s
(1H, N1′H). Found, %: C 63.09; H 4.36; N 7.24.
C30H24N3O4Br. Calculated, %: C 63.17; H 4.24; N 7.37.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 12-03-00146, 12-03-00696) and by the Council
for Grants at the President of the Russian Federation
(project no. MK-2998.2011.3).
Compounds IIIb–IIIe were synthesized in a similar
way.
(2Z)-1-(4-Methylphenyl)-2-[3-oxo-3,4-dihydro-
quinoxalin-2(1H)-ylidene]-5-(1,3,3-trimethyl-2,3-di-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 12 2013

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: XCVII.
1761
cheskie svoistva, prakticheskoe primenenie (2,3-Dihydro-
pyrrole-2,3-diones Fused to Various Heterocycles by the
[a] Side and Their Benzo[b] Analogs. Synthesis, Chem-
ical Properties, and Practical Applications), Perm: Perm.
Gos. Sel’skokhoz. Akad., 2003.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 12 2013