Spiro heterocyclization of 4,5-diaroyl-1H-pyrrole-2,3-diones with heterocyclic enamine

Full text of DOI:10.1134/S1070428013060298

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 6, pp. 945–946. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © P.S. Silaichev, A.N. Maslivets, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 6, pp. 958–959.
SHORT
COMMUNICATIONS
Spiro Heterocyclization of 4,5-Diaroyl-1H-pyrrole-2,3-diones
with Heterocyclic Enamine
P. S. Silaichev and A. N. Maslivets
Perm State National Research University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received February 16, 2012
DOI: 10.1134/S1070428013060298
We previously described recyclization of 4,5-di-
aroyl-1H-pyrrole-2,3-diones by the action of a difunc-
tional 1,3-N,N-binucleophile (3-amino-4,6-dimethyl-
2H-pyrazolo[3,4-b]pyridine) with formation of sub-
stituted pyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidine
[1]. There are no published data on reactions of
4,5-diaroyl-1H-pyrrole-2,3-diones with heterocyclic
amines capable of acting as 1,3-C,N-binucleophiles.
in the aroyl substituent on C5 in the dioxopyrrole
fragment.
This reaction may be regarded as the first example
of direct spiro heterocyclization of substituted 4,5-di-
aroyl-1H-pyrrole-2,3-diones with heterocyclic en-
amine, leading to difficultly accessible spiro[pyrrole-
2,5′-pyrrolo[2,3-d]pyrimidine] system.
4-Hydroxy-1′,3′-dimethyl-3-(4-methylbenzoyl)-
1,6′-bis(4-methylphenyl)spiro[pyrrole-2,5′-pyrrolo-
[2,3-d]pyrimidine]-2′,4′,5(1H,1′H,3′H)-trione (IIIa).
A solution of 1.0 mmol of compound I and 1.0 mmol
of pyrroledione IIa in 80 ml of anhydrous 1,2-di-
chloroethane was heated for 3 h under reflux. The
solvent was distilled off, 20 ml of ethyl acetate was
added to the residue, the mixture was heated to the
boiling point, and the undissolved material was filtered
off. The filtrate was evaporated, and the residue was
recrystallized from toluene. Yield 55%, mp 263–
264°C. IR spectrum, ν, cm–1: 3180 (OH), 1721
(C2′=O), 1707 (C4′=O), 1647 (C5=O, 3-C=O). 1H NMR
spectrum, δ, ppm: 2.20 s (3H, Me), 2.34 s (3H, Me),
2.40 s (3H, Me), 3.13 s (3H, Me), 3.50 s (3H, Me),
7.09–7.98 m (12H, Harom), 12.75 s (1H, OH). Found,
%: C 70.72; H 5.07; N 9.96. C33H28N4O5. Calculated,
%: C 70.70; H 5.03; N 9.99.
In continuation of our studies on nucleophilic
recyclizations [1–4] and spiro heterocyclizations [5] of
4,5-diaroyl-1H-pyrrole-2,3-diones [6], we now report
on their reaction with 6-amino-1,3-dimethylpyrimi-
dine-2,4(1H,3H)-dione (I). By heating a solution of
equimolar amounts of 1-aryl-4,5-bis(4-methylben-
zoyl)-1H-pyrrole-2,3-dione IIa or IIb and enamine I
in boiling anhydrous 1,2-dichloroethane for 3–4 h
(TLC) we obtained 1-aryl-4-hydroxy-3-(4-methylben-
zoyl)-6′-(4-methylphenyl)-1′,3′-dimethylspiro[pyrrole-
2,5′-pyrrolo[2,3-d]pyrimidine]-2′,4′,5(1H,1′H,3′H)-tri-
ones IIIa and IIIb. Compounds IIIa and IIIb are
likely to be formed via initial addition of the enamine
β-CH group in molecule I to C5 of 1H-pyrrole-2,3-
dione II, followed by intramolecular closure of new
3H-pyrrole ring as a result of nucleophilic attack by
the primary amino group on the carbonyl carbon atom
O
Ar2
OH
O
O
O
O
N
Ar1
Ar1
Me
O
O
Me
O
Me
O
COAr1
Ar1
Ar2
O
OH
N
N
N
N
N
+
O
N
O
H2N
N
N
N
COAr1
O
Ar2
Me
Me
Ar1
Me
NH2
IIa, IIb
I
IIIa, IIIb
Ar1 = Ar2 = 4-MeC6H4Me (a); Ar1 = 4-MeC6H4, Ar2 = 4-MeOC6H4 (b).
945

SILAICHEV, MASLIVETS
946
4-Hydroxy-1′,3′-dimethyl-6′-(4-methoxyphenyl)-
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation, by the Ministry of Education of
Perm Krai (International Research Teams Competi-
tion), and by the Russian Foundation for Basic
Research (project nos. 12-03-31157, 12-03-00696).
3-(4-methylbenzoyl)-1-(4-methylphenyl)spiro-
[pyrrole-2,5′-pyrrolo[2,3-d]pyrimidine]-
2′,4′,5(1H,1′H,3′H)-trione (IIIb) was synthesized in
a similar way. Yield 58%, mp 250–251°C (from tolu-
ene). IR spectrum, ν, cm–1: 3195 (OH), 1725 (C2′=O),
1
1719 (C4′=O), 1651 (C5=O), 1635 (3-C=O). H NMR
spectrum, δ, ppm: 2.34 s (3H, Me), 2.40 s (3H, Me),
3.14 s (3H, Me), 3.50 s (3H, Me), 3.67 s (3H, OMe),
7.75–8.00 m (12H, Harom), 12.73 s (1H, OH). 13C NMR
spectrum, δC, ppm: 21.16 (Me), 21.40 (Me), 27.39
(Me), 30.73 (Me), 55.20 (OMe), 79.11 (C2), 96.28
(C4′a), 114.61 (C3), 115.79–145.06 (Carom), 151.70
(C7′a), 156.92 (C2′), 158.98 (C5), 161.19 (C4′), 165.78
(C6′), 184.69 (C4), 188.21 (5-C=O). Found, %:
C 68.69; H 4.87; N 9.74. C33H28N4O6. Calculated, %:
C 68.72; H 4.89; N 9.72.
REFERENCES
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The IR spectra were recorded on a Perkin Elmer
Spectrum Two spectrometer from samples dispersed
1
in mineral oil. The H and 13C NMR spectra were
5. Silaichev, P.S., Kudrevatykh, N.V., and Maslivets, A.N.,
Russ. J. Org. Chem., 2011, vol. 47, p. 1602.
measured on a Bruker AM-400 spectrometer at 400
and 100 MHz, respectively, using DMSO-d6 as solvent
and tetramethylsilane as internal reference.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013