Reaction of 1-(4-methylphenyl)-5-phenyl-2,3-dihydro-1H-pyrrole-2,3-dione with tris(diethylamino)phosphine. A new synthesis of 3,3′-bipyrrolylidene- 2,2′-dione derivatives

Full text of DOI:10.1134/S1070428014070227

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 7, pp. 1058–1059. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © L.I. Musin, A.V. Bogdanov, V.F. Mironov, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 7, pp. 1073–1074.
SHORT
COMMUNICATIONS
Reaction of 1-(4-Methylphenyl)-5-phenyl-2,3-dihydro-
1H-pyrrole-2,3-dione with Tris(diethylamino)phosphine.
A New Synthesis of 3,3′-Bipyrrolylidene-2,2′-dione Derivatives
L. I. Musin, A. V. Bogdanov, and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: abogdanov@inbox.ru
Received January 29, 2014
DOI: 10.1134/S1070428014070227
3
13
Heterocyclic α-diketones are used as starting mate-
rials for the synthesis of new heterocyclic compounds
possessing useful properties, from those exhibiting
specific biological activity to new functional materials
[1–3]. A particular place is occupied by pyrrole-2,3-
dione and 3,3′-bipyrrolylidene derivatives which have
recently found increasing application in the preparation
of synthetic analogs of natural chromophore systems
[4], as well as in organic semiconducting and photo-
voltaic devices [5].
Up to now, several procedures have been reported
for the synthesis of 3,3′-bipyrrolylidene-2,2′-diones
from furan-2,3-dione derivatives [6, 7]. We previously
showed that derivatives of another heterocyclic α-dike-
tone, isatin, undergo mild deoxygenation by the action
of tris(diethylamino)phosphine to give symmetrically
substituted isoindigos in high yields [8–10].
at δC 170.14 ppm (d, JCH = 8.8 Hz) in the C NMR
spectrum of the product indicated that deoxygenation
involved only the C3=O carbonyl group.
Our results suggest prospects in further develop-
ment of this simple one-step synthesis of 3,3′-bipyr-
rolylidene-2,2′-dione derivatives.
1,1′-Bis(4-methylphenyl)-5,5′-diphenyl-1H,1′H-
3,3′-bipyrrolylidene-2,2′-dione (II). A solution of
0.985 g of (3.8 mmol) 1-(4-methylphenyl)-5-phenyl-
2,3-dihydro-1H-pyrrole-2,3-dione (I) [11] in 20 mL of
anhydrous methylene chloride was cooled to –70°C,
and 0.929 g (3.8 mmol) of tris(diethylamino)phosphine
was added dropwise. During the addition, the original-
ly red solution changed to dark violet. The mixture was
allowed to warm up to room temperature and was kept
for 8 h. The solvent was removed under reduced pres-
sure (18 mm), and the residue (violet powder) was
purified by column chromatography on silica gel using
benzene as eluent. Yield 0.67 g (73%), mp >300°C. IR
spectrum, ν, cm–1: 1687, 1580, 1545, 1491, 1262,
The present communication reports on the reaction
of tris(diethylamino)phosphine with 1-(4-methyl-
phenyl)-5-phenyl-2,3-dihydro-1H-pyrrole-2,3-dione
(I), which afforded 3,3′-bipyrrolylidene-2,2′-dione
derivative II and hexaethyltriamidophosphate (CH2Cl2,
δP 24 ppm). The presence of only one downfield signal
1
1187, 1095, 1029, 802, 735, 696. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.29–7.04 m (9H, 4-H, 7-H,
8-H, 11-H, 12-H, 13-H), 2.22 s (3H, CH3). 13C NMR
Me
13
12
O
4
5
10
6
11
3
N
P(NEt2)3, CH2Cl2, –60°C
–(Et2N)3P=O
O
2
N
N
O
O
7
9
Me
8
Me
I
II
1058

REACTION OF 1-(4-METHYLPHENYL)-5-PHENYL-2,3-DIHYDRO-1H-PYRROLE-2,3-DIONE
1059
spectrum (CDCl3), δC, ppm (J, Hz) (the signal multi-
plicity in the proton-decoupled spectrum is given in
parentheses): 170.14 d (s) (C2, 3JCH = 8.8), 128.76 d (s)
REFERENCES
1. Lashgari, N. and Ziarani, Gh.M., Arkivoc, 2012, part (i),
2
1
(C3, JCH = 2.6), 103.73 d (s) (C4, JCH = 182.7),
p. 277.
151.87 m (s) (C5), 135.00 m (s) (C6), 126.69 d.d (s)
2. Singh, G.S. and Desta, Z.Y., Chem. Rev., 2012, vol. 112,
1
3
(C7, JCH = 162.1, JCH = 7.3), 131.11 d.m (s) (C8,
p. 6104.
1JCH = 158.8), 136.66 m (s) (C9, JCH = 5.5), 130.46 m
3
3. Wee, X.K., Yang, T., and Go, M.L., Chem. Med. Chem.,
(s) (C10, overlapped by a component of the C8 signal),
2012, vol. 7, p. 777.
127.47 d.d.d (s) (C11, JCH = 161.0, JCH3 = 6.6, 5.9),
1
3
4. Hashimoto, H., Shiratori, K., Kawakita, K., Tanaka, T.,
Sekine, R., and Irikawa, H., Heterocycles, 2005, vol. 65,
p. 1385.
128.42 d.d (s) (C12, JCH = 161.8, JCH = 5.9),
1
129.73 d.t (s) (C13, JCH = 161.0, JCH = 6.6), 18.17 q
1
3
1
5. Flores, J.-Ch., Berens, U., Bienewald, F., Kirner, H.J.,
(s) (CH3, JCH = 127.3). Found, %: C 82.30; H 5.02;
and Turbiez, M.G.R., US Patent no. 20100297405.
N 5.37. C34H26N2O2. Calculated, %: C 82.57; H 5.30;
N 5.66.
6. Ried, W. and Valentin, J., Chem. Ber., 1968, vol. 101,
p. 2117.
The H, 31P–{1H}, and 13C NMR spectra were
1
7. Treibs, A., Jacob, K., and Dietl, A., Justus Liebigs Ann.
recorded on a Bruker Avance-400 spectrometer at 400
Chem., 1967, vol. 702, p. 112.
(1H), 161.0 (31P), and 150.9 MHz (13C) from solutions
8. Bogdanov, A.V., Mironov, V.F., Musin, L.I., and
in CDCl3; the H and 13C chemical shifts were meas-
1
Musin, R.Z., Synthesis, 2010, no. 19, p. 3268.
ured relative to the residual proton signal and carbon
signal of the solvent. The IR spectrum was obtained on
a Bruker Vector-22 instrument from a sample of II dis-
persed in mineral oil. The elemental composition was
determined on a EuroVector 2000 CHNS-O analyzer.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 14-03-31717-mol_a).
9. Bogdanov, A.V., Mironov, V.F., Musin, L.I., Mu-
sin, R.Z., Krivolapov, D.B., and Litvinov, I.A.,
Monatsh. Chem., 2011, vol. 142, p. 81.
10. Bogdanov, A.V., Yusupova, G.G., Romanova, I.P., Laty-
pov, Sh.K., Krivolapov, D.B., Mironov, V.F., and Sinya-
shin, O.G., Synthesis, 2013, vol. 45, p. 668.
11. Cobas, A., Guitih, E., and Castedo, L., J. Org. Chem.,
1993, vol. 58, p. 3113.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014