ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 12, p. 1891. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.V. Bubnov, E.S. Denislamova, Z.G. Aliev, A.N. Maslivets, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 12, p. 1876.
SHORT
COMMUNICATIONS
Spiro Heterocyclization of Methyl 3-Aroyl-1-aryl-4,5-dioxo-
4,5-dihydro-1H-pyrrole-2-carboxylates by the Action
of Diphenylguanidine
N. V. Bubnova, E. S. Denislamovaa, 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 January 4, 2010
DOI: 10.1134/S1070428010120201
Reactions of monocyclic 1H-pyrrole-2,3-diones
with guanidines were not reported. We examined re-
actions of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihy-
dro-1H-pyrrole-2-carboxylates Ia and Ib with 1,3-di-
phenylguanidine (II) at a molar ratio of 1:1 in boiling
anhydrous 1,2-dichloroethane (reaction time 1–2 h;
TLC monitoring) and isolated 6-aryl-9-aroyl-8-hy-
droxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-
8-ene-4,7-diones IIIa and IIIb whose structure was
confirmed by X-ray analysis. Presumably, compounds
IIIa and IIIb are formed via addition of one secondary
amino group in diphenylguanidine II at the C2 atom of
pyrroledione Ia or Ib, followed by closure of imida-
zole ring as a result of intramolecular attack by the
second secondary amino group in II on the ester car-
bonyl group and elimination of methanol molecule.
and 1 mmol of diphenylguanidine II in 10 ml of anhy-
drous 1,2-di-chloroethane was heated for 1 h under
reflux. The mixture was cooled, and the precipitate
was filtered off. Yield 79%, mp 243–244°C (from
1,2-dichloroethane). IR spectrum, ν, cm–1: 3070 br
(OH, NH), 1790 (C4=O), 1730, 1700 (C7=O), 1615 br
(9-C=O). 1H NMR spectrum, δ, ppm: 2.41 s (3H, Me),
7.10–7.69 m (19H, Harom), 9.44 br.s (2H, NH, OH).
Found, %: C 72.73; H 4.50; N 10.67. C32H24N4O4. Cal-
culated, %: C 72.72; H 4.58; N 10.60.
9-(4-Ethoxybenzoyl)-8-hydroxy-2-imino-6-
(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro-
[4.4]non-8-ene-4,7-dione (IIIb) was synthesized in
a similar way. Yield 75%, mp 251–252°C (from 1,2-di-
chloroethane). IR spectrum, ν, cm–1: 3050 br (OH,
NH), 1790 (C4=O), 1730, 1700 (C7=O), 1610 br
1
(9-C=O). H NMR spectrum, δ, ppm: 1.35 t (3H,
O
O
Ar
CH3CH2, J = 7.0 Hz), 2.40 s (3H, Me), 4.08 q (2H,
CH2O, J = 7.0 Hz), 6.85–7.81 m (18H, Harom), 9.28 br.s
(2H, NH, OH). Found, %: C 71.38; H 4.88; N 9.70.
C34H28N4O5. Calculated, %: C 71.32; H 4.93; N 9.78.
The IR spectra were recorded on an FMS-1201
spectrometer from samples dispersed in mineral oil.
The 1H NMR spectra were measured on a Bruker WP-
400 instrument from solutions in DMSO-d6 using
tetramethylsilane as internal reference. The purity of
the products was checked by TLC on Silufol plates
using ethyl acetate as eluent; spots were visualized by
treatment with iodine vapor.
O
O
Ar
Ph
OH
O
PhNHC(=NH)NHPh (II)
N
O
–MeOH
O
N
N
N
HN
MeO
C6H4Me-4
Ia, Ib
Ph
C6H4Me-4
IIIa, IIIb
Ar = Ph (a), 4-EtOC6H4 (b).
The described reaction may be regarded as a novel
method for building up polyfunctionalized spiro-fused
heterocyclic 1,3,6-triazaspiro[4.4]nonane system.
9-Benzoyl-8-hydroxy-2-imino-6-(4-methylphen-
yl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-
dione (IIIa). A solution of 1 mmol of compound Ia
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-96036).
1891
Bubnov
