Five-membered 2,3-dioxoheterocycles: LXXXIV. [4+2]-cycloaddition of styrene to 4,5-diaroyl-1h-pyrrole-2,3-diones. Crystal and molecular structures of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethylphenyl)-1-(4-methoxyphenyl)-6-phenyl-7, 7a-dihydropyrano[4,3-b]- pyrrole-2,3(1H,6H)-dione

Article abstract of DOI:10.1134/S1070428012020157

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones react with styrene to form substituted 7,7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)-diones whose structure was confi rmed by XRD analysis. The crystal and molecular structure of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethyl-phenyl)-1-(4-methoxyphenyl)-6-phenyl-7, 7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)dione was examined. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012020157

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 253−256. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © P.S. Silaichev, N.V. Kudrevatykh, Z.G. Aliev, A.N. Maslivets, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 2,
pp. 263−266.
Five-Membered 2,3-Dioxoheterocycles: LXXXIV.*
[4+2]-Cycloaddition of Styrene to 4,5-Diaroyl-1H-pyrrole-
2,3-diones. Crystal and Molecular Structures of 7a-(2,5-
Dimethylbenzoyl)-4-(2,5-dimethylphenyl)-
1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b]-
pyrrole-2,3(1H,6H)-dione
P. S. Silaicheva,b, N. V. Kudrevatykhb, Z. G. Alievc, and A. N. Maslivetsa,b
aInstitute of Natural Sciences at Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bPerm State University, Perm, Russia
cInstitute of Problems of Chemical Physics, Russian Academy of Sciences,Chernogolovka, Russia
Received May 8, 2011
Abstract—1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-dionesreactwithstyrenetoformsubstituted7,7a-dihydropyrano[4,3-b]
pyrrole-2,3(1H,6H)-diones whose structure was confirmed by XRD analysis. The crystal and molecular structure
of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethyl-phenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b]
pyrrole-2,3(1H,6H)dione was examined.
DOI: 10.1134/S1070428012020157
1H-Pyrrole-2,3-diones exhibited a considerable re- the ratio 1:1.5 in m-xylene solution over 5–8 h (TLC
activity in the Diels–Alder reactions [2, 3]. Polar olefins monitoring) afforded 1,4-diaryl-7a-aroyl-6-phenyl-7,7a-
took part in the [4+2]-cycloaddition at the conjugated dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-diones IVa–
bonds system C5=C4–C=O of the 4-benzoyl-1-phenyl-5- IVg whose structure was proved by XRD analysis by an
ethoxycarbonyl-1H-pyrrole-2,3-dione that was applied to example of compound IVe.
the building up of the heterocyclic system of pyrano[4,3-
b]pyrrole [4, 5]. The olefins cycloaddition to 4,5-diaroyl-
1H-pyrrole-2,3-diones was not formerly investigated.
Compounds IVa–IVg are light-yellow or colorless
crystalline substances of high melting points, readily
soluble in the common organic solvents, insoluble in
With the goal to investigate the influence of the intro- alkanes and water.
duction of an aroyl fragment into the position 5 of the 1H-
The IR spectra of compounds IVa–IVg contain the
pyrrole-2,3-diones on the direction of the cycloaddition absorption bands of the stretching vibrations of lactam
we studied the reactions of 1-aryl-4,5-diaroyl-1H-pyrrole- C2=O and ketone C3=O carbonyl groups as one broad or
2,3-diones Ia–Ig with styrene. Pyrrolediones Ia–Id [1] two narrow bands at 1698–1725 cm–1 , and of the aroyl
were prepared by known procedures, and pyrrolediones carbonyl group in the region 1684–1688 cm–1.
If, Ig were obtained for the first time by the reaction of
In the 1H NMR spectra of compounds IVa–IVg along-
(Z)-1,4-diaryl-2-arylaminobut-2-ene-1,4-diones IIa, IIb side the signals of the protons of the aromatic rings and
with oxalyl chloride. Compounds IIa, IIb were obtained of the groups connected thereto multiplets are present of
in their turn by the reaction of diaroylacetylenes IIIa, IIIb the methine proton (5.36–5.67 ppm) and of the protons of
[6, 7] with p-toluidine.
the methylene group in the region 2.63–2.98 ppm forming
a typical ABX system.
The boiling of pyrrolediones Ia–Ig and styrene in
The 13C NMR spectra of compounds IVa, IVg along-
side the signals of the carbon atoms of the aromatic rings
______________
* For Communication LXXXIII, see [1].
253

SILAICHEV et al.
254
Ar1
Ar1
H
C
Ar1
COAr1
O
O
O
Ar1
O
Ar2 NH2
C
C
N
PhCH=CH2
(COCl)2
_HCl
Ar1OCC CCOAr1
Ph
O
.
.
O
.
H
Ar2
N
O
N
Ar2
Ia_Ig
Ar1
Ar2
IVa_IVg
O
O
IIIa, IIIb
IIa, IIb
I, IV, Ar1 = Ar2 = Ph (a); Ar1 = C6H3Me2-2,5, Ar2 = Ph (b); Ar1 = Ph, Ar2 = C6H4OMe-4 (c); Ar1 = C6H4Me-4, Ar2 = Ph
(d); Ar1 = C6H3Me2-2,5, Ar2 = C6H4OMe-4 (e); Ar1 = Ph, Ar2 = C6H4Me-4 (f); Ar1 = Ar2 = C6H4Me-4 (g); II, III, Ar1 =
Ph, Ar2 = C6H4Me-4 (a); Ar1 = Ar2 = C6H4Me-4 (b).
and of the groups connected thereto contain the carbon
signals of the aroyl carbonyl group (197.52–198.60 ppm),
keto and lactame carbonyls of the pyrroledione ring
(177.64–177.67 and 162.05–162.17 ppm respectively),
and also the signals of the carbon atoms in the positions
6, 7, and 7a of the pyrano[4,3-b]pyrrole-2,3-dione ring
(79.48–79.51, 34.62–35.09, and 66.05–66.10 ppm re-
spectively).
groups connected thereto are very similar to those of
previously described (3R*, 4aR*)-4,4a,6,7-tetrahydro-
6,7-dioxo-1,3,5-triphenyl-4a-ethoxycarbonyl-5H-
pyrano[4,3-b]pyrrole [4].
By the XRD data (see the figure) the pyran ring of the mol-
ecule of compound IVe exists in the envelop conformation.
The bend at the line C1⋯C6 is 49.6°, and the deviation
of the C7 atom from the plane of the rest five atoms is
0.67 Å. All bonds and angles in the molecule have the
values common for the corresponding atoms. The bond
C2=C5 is a localized double bond, 1.354(5) Å. The pyrrole
ring is planar within 0.01 Å and forms with the plane of
five pyran atoms a dihedral angle of 153.4°. No hydrogen
bonds and shortened contacts were found in the crystal.
The formation of compounds IVa–IVg occurs evidently
due to the involvement of the conjugated bond system
O=C–C4=C5 of pyrrolediones Ia–Ig in the thermally in-
duced reaction of the [4+2]-cycloaddition to the polarized
C=C bond of styrene.
The spectra characteristics of compounds and of the
EXPERIMENTAL
IR spectra of compounds obtained were recorded on
a spectrophotometer FSM-1201from mulls in mineral oil.
1H and 13C NMR spectra were registered on a spectrom-
eter BrukerAM-400 [ operating frequencies 400 (1H) and
100 (13C) MHz) in DMSO-d6, internal reference TMS.
The homogeneity of compounds obtained was confirmed
by TLC on Silufol plates, eluents benzene–ethyl acetate,
5:1, ethyl acetate, development in iodine vapor or under
UV irradiation.
4,5-Dibenzoyl-1-(4-tolyl)-1H-pyrrole-2,3-dione
(If). To 0.01 mol of compound IIa in 50 ml of anhydrous
benzene was added dropwise a solution of 0.011 mol of
freshly distilled oxalyl chloride in 10 ml of anhydrous
benzene, the mixture was boiled for 80 min, cooled,
General view of the molecule of 7a-(2,5-dimethylbenzoyl)-
4-(2,5-dimethylphenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-
dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-dione (IVe).
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FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: LXXXIV.
255
the separated precipitate was filtered off. Yield 67%,
mp 215–216°C (decomp., benzene). IR spectrum, cm–1:
1769 (C2=O), 1727 (C3=O), 1671 (C4–C=O), 1649 (C5–
13C NMR spectrum, δ, ppm: 34.62 (C7), 66.05 (C7a),
79.48 (C6), 104.60 (C3a), 126.43–138.50 (Carom), 162.05
(C2), 166.23 (C4), 177.64 (C3), 198.60 (C7a–CO). Found,
%: C 79.13; H 4.74; N 2.84. C32H23NO4. Calculated, %:
C 79.16; H 4.77; N 2.88.
1
C=O). H NMR spectrum, δ, ppm: 2.26 s (3H, Me),
7.15–8.14 group of signals (14H, 2Ph + C6H4). Found,
%: C 75.92; H 4.37; N 3.55. C25H17NO4. Calculated, %:
C 75.94; H 4.33; N 3.54.
Compounds IVb–IVg were prepared in analogous
way.
4,5-Di(4-toluoyl)-1-(4-tolyl)-1H-pyrrole-2,3-dione
(Ig) was similarly synthesized. Yield 65%, mp 222–223°C
(decomp., benzene). IR spectrum, cm–1: 1775 (C2=O),
1725 (C3=O), 1672 (C4–C=O), 1645 (C5–C=O). 1H NMR
spectrum, δ, ppm: 2.24 s (3H, Me), 2.33 s (3H, Me), 2.38 s
(3H, Me), 7.14–8.04 group of signals (12H, 3C6H4).
Found, %: C 76.54; H 5.03; N 3.33. C27H21NO5. Calcu-
lated, %: C 76.58; H 5.00; N 3.31.
7a-(2,5-Dimethylbenzoyl)-4-(2,5-dimethyl-phenyl)-
1,6-diphenyl-7,7a-dihydropyrano[4,3-b]-pyrrole-
2,3(1H,6H)-dione (IVb). Yield 73%, mp 254–255°C
(ethyl acetate–acetone–benzene, 1 : 1 : 1). IR spectrum,
1
cm–1: 1725 (C2=O, C3=O), 1686 (C7a–C=O). H NMR
spectrum, δ, ppm: 2.08 s (3H, Me), 2.12 s (3H, Me),
2.17 s (3H, Me), 2.28 s (3H, Me), 2.72 t (1H, CH2,
J 12.8 Hz), 2.95 d.d (1H, CH2, J 12.8, J 3.2 Hz), 5.41 d.d
(1H, CH, J 12.8, J 3.2 Hz), 6.93–7.54 group of sig-
nals (16H, 2Ph + 2C6H3). Found, %: C 79.77; H 5.71;
N 2.55. C36H31NO4. Calculated, %: C 79.83; H 5.77;
N 2.59.
(Z)-2-(4-Tolylamino)-1,4-diphenylbut-2-ene-1,4-
dione (IIa). Asolution of 0.01 mol of dibenzoylacetylene
(IIIa) [6] and 0.01 mol of p-toluidine in 30 ml of anhy-
drous benzene was boiled for 5 min (TLC monitoring),
30 ml of warm petroleum ether (40–70) was added, the
mixture was cooled, the separated precipitate was filtered
off.Yield 91%, mp 153–154°C (benzene–petroleum ether,
1 : 1). IR spectrum, cm–1: 3150 br. (NH), 1678 (C1=O),
1600 br. (C4=O in intramolecular hydrogen bond).
1H NMR spectrum, δ, ppm: 2.33 s (3H, Me), 6.56 s (1H,
CH), 6.92–8.03 group of signals (14H, 2Ph + C6H4),
12.43 br.C (1H, NH). Found, %: C 80.94; H 5.58; N 4.13.
C23H19NO2. Calculated, %: C 80.92; H 5.61; N 4.10.
7a-Benzoyl-1-(4-methoxyphenyl)-4,6-diphenyl-
7,7a-dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-dione
(IVc). Yield 78%, mp 239–240°C (toluene–ethyl ac-
etate–acetone, 1 : 1 : 1). IR spectrum, cm–1: 1717 (C2=O),
1
1700 (C3=O), 1688 (C7a–C=O). H NMR spectrum, δ,
ppm: 2.67 t (1H, CH2, J 12.4 Hz), 2.95 d.d (1H, CH2,
J 12.4, J 3.6 Hz), 3.76 s (3H, OMe), 5.62 d.d (1H, CH,
J 12.4, J 3.6 Hz), 6.99–7.75 group of signals (19H, 3Ph +
C6H4). Found, %: C 76.85; H 4.86; N 2.68. C33H25NO5.
Calculated, %: C 76.88; H 4.89; N 2.72.
(Z)-1,4-Di(4-tolyl)-2-(4-tolylamino)but-2-ene-1,4-
dione (IIb) was similarly synthesized. Yield 89%, mp
169–170°C (benzene–petroleum ether, 1 : 1). IR spec-
trum, cm–1: 3160 br. (NH), 1665 (C1=O), 1605 br. (C4=O
4-(4-Tolyl)-7a-(4-toluoyl)-1,6-diphenyl-7,7a-
dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-dione (IVd).
Yield 84%, mp 249–250°C (ethyl acetate). IR spectrum,
cm–1: 1719 (C2=O), 1700 (C3=O), 1684 (C7a–C=O).
1H NMR spectrum, δ, ppm: 2.40 s (6H, 2Me), 2.65 t (1H,
CH2, J 12.4 Hz), 2.96 d.d (1H, CH2, J 12.4, J 3.6 Hz),
5.64 d.d (1H, CH, J 12.4, J 3.6 Hz), 7.10–7.66 group of
signals (18H, 2Ph + 2C6H4). Found, %: C 79.43; H 5.25;
N 2.65. C34H27NO4. Calculated, %: C 79.51; H 5.30;
N 2.73.
1
c CCC). H NMR spectrum, δ, ppm: 2.17 s (3H, Me),
2.36 s (6H, 2Me), 6.13 s (1H, CH), 6.91–7.87 group of
signals (12H, 3C6H4), 12.43 br.s (1H, NH). Found, %:
C 81.25; H 6.30; N 3.75. C25H23NO2. Calculated, %:
C 81.27; H 6.27; N 3.79.
7a-Benzoyl-1,4,6-triphenyl-7,7a-dihydropyrano-
[4,3-b]pyrrole-2,3(1H,6H)-dione (IVa). To a solution
of 1.0 mmol of compound Ia in 25 ml of anhydrous
m-xylene was added a solution of 1.5 mmol of styrene
in 10 ml of anhydrous m-xylene, the mixture was boiled
for 8 h, cooled, the separated precipitate was filtered
off. Yield 87%, mp 232–233°C (toluene). IR spectrum,
cm–1: 1723 (C2=O), 1698 (C3=O), 1678 (C7a–C=O).
1H NMR spectrum, δ, ppm: 2.69 t (1H, CH2, J 12.4 Hz),
2.98 d.d (1H, CH2, J 12.4, J 3.6 Hz), 5.67 d.d (1H, CH,
J 12.4, J 3.6 Hz), 7.16–7.76 group of signals (20H, 4Ph).
7a-(2,5-Dimethylbenzoyl)-4-(2,5-dimethylphenyl)-
1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydro-
pyrano[4,3-b]pyrrole-2,3(1H,6H)-dione (IVe). Yield
76%, mp 264–265°C (toluene). IR spectrum, cm–1: 1723
(C2=O, C3=O), 1688 (C7a–C=O). 1H NMR spectrum, δ,
ppm: 2.06 s (3H, Me), 2.13 s (3H, Me), 2.18 s (3H, Me),
2.27 s (3H, Me), 2.71 t (1H, CH2, J 12.8 Hz), 2.90 d.d (1H,
CH2, J 12.8, J 3.2 Hz), 3.78 s (3H, OMe), 5.36 d.d (1H,
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SILAICHEV et al.
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1,4-Di(4-tolyl)-7a-(4-toluoyl)-6-phenyl-7,7a-
dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-dione (IVg).
Yield 82%, mp 212–213°C (toluene). IR spectrum, cm–1:
CH, J 12.8, J 3.2 Hz), 6.93–7.50 group of signals (15H,
Ph + C6H4 + 2C6H3). Found, %: C 77.69; H 5.79; N 2.40.
C37H33NO5. Calculated, %: C 77.74; H 5.82; N 2.45.
1
1725 (C2=O), 1705 (C3=O), 1685 (C7a–C=O). H, δ,
XRD analysis of compound IVe. Colorless bulky
crystals of C37H33NO5 belong to the monoclinic crystal
system: a 13.803(3), b 11.607(2), c 18.969(4) Å,
β 91.88(3)°, V 3037.4(11) Å3, M 571.64, dcalc 1.250 g cm–3,
Z4, space group P21/C. The set of experimental reflections
was obtained on an automatic four-circle diffractometer
QM-4 (KUMADIFFRACTION) with the χ-geometry by
the method of ω/2Θ scanning in the monochromatized
MoKα-radiation (2Θ ≤ 50°). Overall 6057 reflections were
measured, among them 4775 independent (Rint 0.0714).
No correction for extinction was introduced (μ 0.083
mm–1). The structure was solved by the direct method
with the use of SIR92 software [8] followed by the series
of electron density maps calculations. Hydrogen atoms
were placed geometrically. Full-matrix anisotropic (for
nonhydrogen atoms) least-squares refinement along the
software SHELXL-97 [9] was ended at R1 0.0726 for
2044 reflections with I ≥ 2σ(I) and R1 0.1913 for all
reflections. Refined parameters 389, Δρmax 0.218 Å–3.
GOOF 0.955. The crystallographic data are deposited
in the Cambridge Crystallographic Data Center (CCDC
no. 827017).
ppm: 2.30 s (3H, Me), 2.40 s (6H, 2Me), 2.63 t (1H, CH2,
J 12.8 Hz), 2.96 d.d (1H, CH2, J 12.8, J 3.6 Hz), 5.62 d.d
(1H, CH, J 12.8, J 3.6 Hz), 6.98–7.67 group of signals
(17H, Ph + 3C6H4). 13C NMR spectrum, δ, ppm: 20.50
(Me), 20.97 (Me), 21.20 (Me), 35.09 (C7), 66.10 (C7a),
79.51 (C6), 104.48 (C3a), 126.44–143.10 (Carom), 162.17
(C2), 166.26 (C4), 177.67 (C3), 197.52 (C7a–CO). Found,
%: C 79.59; H 5.50; N 2.62. C35H29NO4. Calculated, %:
C 79.68; H 5.54; N 2.65.
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7a-Benzoyl-1-(4-tolyl)-4,6-diphenyl-7,7a-
dihydropyrano[4,3-b]pyrrole-2,3(1H,6H)-dione (IVf).
Yield 79%, mp 243–244°C (O-xylene). IR spectrum,
cm–1: 1721 (C2=O), 1701 (C3=O), 1688 (C7a–C=O).
1H NMR spectrum, δ, ppm: 2.31 s (3H, Me), 2.66 t (1H,
CH2, J 12.2 Hz), 2.97 d.d (1H, CH2, J 12.2, J 3.5 Hz),
5.64 d.d (1H, CH, J 12.2, J 3.5 Hz), 7.02–7.74 group of
signals (19H, 3Ph + C6H4). Found, %: C 79.30; H 5.00;
N 2.77. C33H25NO4. Calculated, %: C 79.34; H 5.04;
N 2.80.
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