New route of reaction of 4-acyl-1H-pyrrole-2,3-diones with 1,3-CH,NH-binucleophile

Full text of DOI:10.1134/S1070428013080290

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 8, pp. 1248−1249. © Pleiades Publishing, Ltd., 2013.
Original English Text © P.S. Silaichev, N.V. Bubnov, V.O. Filimonov, E.S. Denislamova, A.N. Maslivets, 2013, published in Zhurnal Organicheskoi Khimii,
2013, Vol. 49, No. 8, pp. 1260−1261.
SHORT
COMMUNICATIONS
New Route of Reaction of 4-Acyl-1ꢀ-pyrrole-2,3-diones
with 1,3-СН,NH-Binucleophile
P. S. Silaicheva,b, N. V. Bubnova,b, V. O. Filimonova, E. S. Denislamovaa, and A. N. Maslivetsa,b
aPerm State National Research University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bInstitute of Natural Sciences at Perm’State National Research University, Perm, Russia
Received March 3, 2012
DOI: 10.1134/S1070428013080290
Reactions are described of 1-aryl-4-aroyl-5-
methoxycarbonyl-1Н-pyrrole-2,3-diones with
acyclic [1], carbocyclic [2] and heterocyclic [3]
1,3-СН,NH-binucleophiles leading to the formation of
spirobisheterocyclic or bridging heterocyclic systems due
to the involvement of pyrrolediones in these reactions
by atom С5 and methoxycarbonyl group or atom С3
respectively.
methyl-5-[2-oxo-2-(4-tolylamino)acetyl]-1-phenyl-1H-
pyrazolo[3,4-b]pyridine-4-carboxylates IIIа, IIIb.
The formation of compounds IIIа, IIIb occurs
apparently through primary addition of the β-СН group
of the enamino fragment of compound II to the atom С5
of pyrrolediones Ia, Ib followed by the intramolecular
reaction of the primary amino group with the carbonyl
group of the acyl substituent in the position 4 and by the
opening of the pyrrole ring at the N1–C5 bond.
At boiling substituted 5-methoxycarbonyl-1-(4-tolyl)-
1Н-pyrrole-2,3-diones Iа, Ib and 5-amino-3-methyl-1-
phenyl-1Н-pyrazole (II) in 1:1 ratio in anhydrous benzene
for 1–1.5 h (TLC monitoring) we obtained methyl 6-R-3-
The described reaction is an example of the new route
of the reaction between 1-aryl-4-acyl-5-methoxycarbonyl-
1Н-pyrrole-2,3-diones and 1,3-СН,NH-binucleophiles,
Me
N
R
O
NH2
O
N
NH2
OH
Ph
O
R
Ph
II
N
N
O
O
O
N
N
MeO
Ar
Me
Ar
Ia, Ib
O OMe
R
MeO
O
OH
O
N
Me
N
H
N
Ph
Ar
N
N
O
_H2O
N
O
N
O
N
R
Ar
Me
Ph
OMe
IIIa, IIIb
Ar = 4-MeC6H4, R = Ph (а), Ph-CH=CH (b).
1248

NEW ROUTE OF REACTION OF 4-ACYL-1Н-PYRROLE-2,3-DIONES
1249
and also a convenient method of building up the hetero-
cyclic system of 1H-pyrazolo[3,4-b]pyridine with previ-
ously inaccessible combination of substituents.
δ, ppm: 15.01 (Ме), 20.38 (Ме), 53.05 (OМе), 110.43
(С3С), 120.25–138.27 (Сarom), 143.07 (МеС3), 150.25
(N1C), 152.86 (C4), 159.13 (С6), 164.40 (СООMe),
191.18 (С5C=O). Found, %: С 72.47; Н 4.93; N 10.54.
С32H26N4O4. Calculated, %: С 72.44; Н 4.94; N 10.56.
Methyl 3-methyl-5-[2-oxo-2-(4-tolylamino)-
acetyl]-1,6-diphenyl-1H-pyrazolo[3,4-b]pyridine-
4-carboxylate (IIIа).Asolution of 1 mmol of compound
Ia and 1 mmol of amine II in 10 ml of anhydrous benzene
was boiled for 1 h, cooled, the separated precipitate was
filtered off. Yield 84%, mp 195–196°С (benzene). IR
spectrum, ν, cm–1: 3364 (NН), 1727 (COOMe), 1698 (C5–
С=О), 1686 (CONH). 1Н NMR spectrum, δ, ppm: 2.26 s
(3H, Ме), 2.64 s (3H, Ме), 3.94 s (3H, OMe), 7.12–8.24
group of signals (14H, 2Ph + 2С6Н4), 10.74 s (1Н, NН).
13C NMR spectrum, δ, ppm: 14.47 (Ме), 20.49 (Ме),
53.38 (OМе), 110.45 (С3–С), 120.40–138.60 (Сarom),
142.89 (МеС3), 150.17 (N1C), 158.16 (C4), 159.24 (С6),
164.89 (СООМе), 191.48 (С5C=O). Found, %: С 71.42;
Н 4.79; N 11.10. С30H24N4O4. Calculated, %: С 71.42;
Н 4.79; N 11.10.
IR spectra of compounds obtained were recorded on
a spectrophotometer Perkin Elmer Spectrum Two from
1
mulls in mineral oil. Н and 13С NMR spectra were
registered on a spectrometer BrukerAM-400 at operating
frequencies 400 (1Н) and 100 MHz (13С) in DMSO-d6,
internal reference TMS. The homogeneity of compounds
synthesized was proved by TLC on Silufol plates, eluent
benzene–ethyl acetate, 5 : 1, development in iodine vapor.
REFERENCES
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Methyl 3-methyl-5-[2-oxo-2-(4-tolylamino)-acetyl]-
6-styryl-1-phenyl-1H-pyrazolo[3,4-b]-pyridine-4-
carboxylate (IIIb). Yield 80%, mp 219–220°С (toluene).
IR spectrum, ν, cm–1: 3328 (NН), 1719 (COOMe), 1697
(C5–С=О), 1669 (CONH), 1636 (C6–CH=CH). 1Н NMR
spectrum, δ, ppm: 2.29 s (3H, Ме), 2.64 s (3H, Ме), 3.88 s
(3H, OMe), 7.19–8.30 group of signals (16H, 2Ph +
С6Н4 + CH=CH), 10.94 s (1Н, NН). 13C NMR spectrum,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013