New pathway of the reaction of hetareno[a]pyrrole-2,3-diones with NH nucleophiles

Full text of DOI:10.1134/S1070428012010253

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 1, pp. 145–146. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.V. Kuslina, I.V. Mashevskaya, P.A. Slepukhin, A.N. Maslivets, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 1, pp. 149–150.
SHORT
COMMUNICATIONS
New Pathway of the Reaction of Hetareno[a]pyrrole-2,3-diones
with NH Nucleophiles
L. V. Kuslinaa, I. V. Mashevskayab, P. A. Slepukhinc, and A. N. Maslivetsa,b
a Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
c Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. S. Kovalevskoi 20, Yekaterinburg, 620219 Russia
Received January 4, 2011
DOI: 10.1134/S1070428012010253
It was shown previously that 4-acyl-1H-pyrrole-
2,3-diones fused at the N1–C5 bond to various hetero-
cycles (hetareno[a]pyrrole-2,3-diones) react with
mono- and difunctional nucleophiles via initial addi-
tion at the C1 or C3a carbon atom of the hetareno[a]-
pyrrole skeleton [1].
Although the possibility for other (than those in-
dicated above [1]) direction of nucleophilic attack on
4-acyl-1H-pyrrole-2,3-diones fused at the N1–C5 bond
to various heterocycles was theoretically predicted
about 20 years ago [2], products of such reactions were
isolated for the first time.
By reactions of 3-benzoylpyrrolo[1,2-a]quinoxa-
line-1,2,4(5H)-trione (Ia) with phenylhydrazine and of
3-benzoyl-1H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-
1,2,4-trione (Ib) with 2-hydrazinobenzoic acid (reac-
tant molar ratio 1:1, anhydrous acetonitrile, 1–3 min
under reflux; TLC monitoring), we obtained products
resulting from nucleophilic attack at the C2 carbon
atom, (Z)-3-benzoyl-2-(2-phenylhydrazono)pyrrolo-
[1,2-a]quinoxaline-1,4(2H,5H)-dione (IIa) and
(Z)-2-{2-(3-benzoyl)-1,4-dioxo-1H-benzo[b]pyrrolo-
[1,2-d][1,4]-oxazin-2(4H)-ylidenehydrazino}benzoic
acid (IIb). The product structure was proved by X-ray
analysis of compound IIb.
(Z)-3-Benzoyl-2-(2-phenylhydrazono)pyrrolo-
[1,2-a]quinoxaline-1,4(2H,5H)-dione (IIa). A solu-
tion of 1.0 mmol of phenylhydrazine in 10 ml of anhy-
drous acetonitrile was added to a solution of 1.0 mmol
of compound Ia in 30 ml of anhydrous acetonitrile.
The mixture was heated for 3 min under reflux and
cooled, and the precipitate was filtered off. Yield 69%,
mp 241–243°C (from DMF). IR spectrum, ν, cm–1:
3350, 3200 (NH); 1680 (C1=O); 1660 (C4=O); 1630
1
(COPh). H NMR spectrum, δ, ppm: 6.99–7.68 m
(11H, Harom), 8.03 d (2H, o-H in COPh, J = 7.4 Hz),
8.69 d (1H, 9-H, J = 7.4 Hz), 11.22 s (1H, 5-H),
13.31 s (1H, NHPh). Found, %: C 70.53; H 3.91;
H
NHNH2
N
O
X
N
O
O
O
N
O
N
O
O
O
PhNHNH2
X = NH
COOH
X = O
N
Ph
Ph
Ph
O
O
O
N
H
N
H
N
COOH
Ph
IIa
Ia, Ib
IIb
X = NH (a), O (b).
145

KUSLINA et al.
146
N 13.75. C24H16N4O3. Calculated, %: C 70.58; H 3.95;
N 13.72.
independent (Rint 0.0304) and 2438 reflections were
characterized by I > 2σ(I). No correction for absorp-
tion was introduced. Triclinic crystal, space group P-1;
unit cell parameters: a = 8.463(2), b = 11.609(3), c =
12.8717(19) Å; α = 83.952(16), β = 76.505(17), γ =
85.75(2)°. Final divergence factors: R1 = 0.0394, wR2 =
0.0775 for reflections with I > 2σ(I); goodness of fit
S = 1.004; maximal and minimal residual electron
densities 0.347 and –0.185 ē/Å3.
2-[(Z)-2-(3-Benzoyl-1,4-dioxo-1H-benzo[b]pyr-
rolo[1,2-d][1,4]oxazin-2(4H)-ylidene)hydrazino]-
benzoic acid (IIb). A solution of 1.0 mmol of 2-hy-
drazinobenzoic acid hydrochloride in 30 ml of a 10:1
mixture of anhydrous acetonitrile and DMSO was
added to a solution of 1.0 mmol of compound Ib in
30 ml of anhydrous acetonitrile. The mixture was
heated for 1 min under reflux and cooled, and the
precipitate was filtered off. Yield 47%, mp 275–277°C
(from acetonitrile). IR spectrum, ν, cm–1: 3300 br,
3200 (OH, NH), 1732 (C1=O), 1669 (COOH), 1636
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
1
The H NMR spectra were obtained on a Bruker AM-
400 instrument (400 MHz) using DMSO-d6 as solvent
and tetramethylsilane as internal reference.
1
(COPh). H NMR spectrum, δ, ppm: 7.23–8.12 m
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
(12H, Harom), 8.63 d (1H, 9-H, J = 8.0 Hz), 10.24 s
(1H, 5-H), 13.70 s (1H, COOH), 14.87 s (1H, NH).
Found, %: C 66.21; H 3.29; N 9.24. C25H15N3O6. Cal-
culated, %: C 66.23; H 3.33; N 9.27.
REFERENCES
The X-ray diffraction data for compound IIb were
acquired on an Xcalibur S automatic diffractometer
[λ(MoKα) 0.71073 Å, temperature 295(2) K, ω-scan-
ning through a step of 1°, crystal to detector distance
50 mm] according to standard procedure. Total of
7184 reflections were measured, 5783 of which were
1. Mashevskaya, I.V. and Maslivets, A.N., Khim. Getero-
tsikl. Soedin., 2006, p. 3.
2. Maslivets, A.N., Mashevskaya, I.V., Krasnykh, O.P.,
Shurov, S.N., and Andreichikov, Yu.S., Zh. Org. Khim.,
1992, vol. 28, p. 2545.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012