Five-membered 2,3-dioxoheterocycles: XCV.*recyclization of 4-benzoyl-5-phenylfuran-2,3-dione at the action of substituted 1,3,3-trimethyl-2-azaspiro[4.5]dec-1-enes. crystal and molecular structure of substituted 5-(2-Azaspiro[4.5]dec-1-ylidene)cyclopent-3

Article abstract of DOI:10.1134/S1070428013110110

4-Benzoyl-5-phenylfuran-2,3-dione reacts with 2',5',5'-trimethyl-4',5'- dihydro-4H-spiro[naphthalene- 1,3'-pyrrol]-4-one and 8-(2-methoxy-5- methylphenyl)-1,3,3,9-tetramethyl-2-azaspiro[4.5]deca-1,7-dien-6-one with the formation of (Z)-3-benzoyl-5-(5',5'-

Full text of DOI:10.1134/S1070428013110110

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1628−1631. © Pleiades Publishing, Ltd., 2013.
Original English Text © V.V. Konovalova, Yu.V. Shklyaev, P.A. Slepukhin, A.N. Maslivets, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 11, pp. 1648−1650.
Five-Membered 2,3-Dioxoheterocycles: XCV.* Recyclization
of 4-Benzoyl-5-phenylfuran-2,3-dione at the Action
of Substituted 1,3,3-Trimethyl-2-azaspiro[4.5]dec-1-enes. Crystal
and Molecular Structure of Substituted
5-(2-Azaspiro[4.5]dec-1-ylidene)cyclopent-3-ene-1,2-dione
V. V. Konovalovaa, Yu.V. Shklyaeva, P. A. Slepukhinb, and A. N. Maslivetsc
aInstitute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
bPostovskii Institute of Organic Synthesis, Ural Branch of Russian Academy of Sciences, Ekaterinburg, Russia
cPerm State National Research University, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received July 7, 2012
Abstract—4-Benzoyl-5-phenylfuran-2,3-dione reacts with 2',5',5'-trimethyl-4',5'-dihydro-4H-spiro[naphthalene-
1,3'-pyrrol]-4-one and 8-(2-methoxy-5-methylphenyl)-1,3,3,9-tetramethyl-2-azaspiro[4.5]deca-1,7-dien-6-one
with the formation of (Z)-3-benzoyl-5-(5',5'-dimethyl-4-oxo-4Н-spiro[naphthalene-1,3'-pyrrolidin]-2'-ylidene)-
4-phenylcyclopent-3-ene-1,2-dione, whose structure was proved by XRD analysis, and of (Z)-3-benzoyl-5-{8-
(2-methoxy-5-methylphenyl)-3,3,9-trimethyl-6-oxo-2-azaspiro[4.5]dec-7-en-1-ylidene}-4-phenylcyclopent-3-
ene-1,2-dione.
DOI: 10.1134/S1070428013110110
5-Arylfuran-2,3-diones at heating suffer a thermal
decarbonylation providing aroylketenes, which are
involved in intermolecular reactions of cycloaddition
with active dienophiles [2, 3] and acylate weak
nucleophiles giving aroylacetyl derivatives [2, 4]. At
the same time the proper furandiones are capable of
acylating nucleophilic reagents at a temperature that is
lower than the temperature required for aroylketenes
generation leading to the formation of aroylpyruvoyl
derivatives [2, 5]. We described formerly the reaction
between 5-arylfuran-2,3-diones and 1,3,3-trimethyl-2-
azaspiro[4.5]dec-1-ene (2',5',5'-trimethyl-4',5'-dihydro-
4H-spiro[naphthalene-1,3'-pyrrol]-4-one) affording
the products of β-СН-acylation with the furandiones
of the tautomeric enamino form of the spiropyrrolone,
(2Z,5Z)-1-aryl-3-hydroxy-5-(5',5'-dimethyl-4-oxo-
2'Н,4H-spiro[naphthalene-1,3'-pyrrolidin]-2'-ylidene)
__________________
pent-2-ene-1,4-diones [6]. In extension of these studies
we attempted to modify the structure of furan-2,3-diones
aiming at changing the regiodirection of their reaction
with substituted 1,3,3-trimethyl-2-azaspiro[4.5]dec-1-
enes.
The reaction of 4-benzoyl-5-phenylfuran-2,3-
dione (I) with 2',5',5'-trimethyl-4',5'-dihydro-4H-
spiro[naphthalene-1,3'-pyrrol]-4-one (IIа) and 8-(2-me-
thoxy-5-methylphenyl)-1,3,3,9-tetramethyl-2-azaspi-
ro[4.5]deca-1,7-dien-6-one (IIb) in the ratio 1 : 1 at
boiling in anhydrous benzene for 30–60 min (till the
disappearance of the bright yellow color of the initial
furandione) afforded in good yield 5-substituted (Z)-3-
benzoyl-4-phenylcyclopent-3-ene-1,2-diones IIIа, IIIb.
The structure of compound IIIа was confirmed by XRD
analysis.
Compound IIIа is dark red, compound IIIb is dark
violet crystalline substances, they are readily soluble
in DMSO and DMF, sparingly soluble in alcohols and
*For communication XCIV, see [1].
1628

FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: XCV.
1629
Me
CH2
Me
Me
Me
Me
N
NH
PhCO
Ph
O
O
IIа, IIb
A
COPh
CHCOCOCH
COPh
O
I
Me
Me
NH
Me
COPh
H
COPh
O
MeO
O
OH
Ph
Ph
Me
Me
Me
_H2O
O
O
Me
Me
Me
Me
O
. . . O
NH
Me
Me
Me
Me
NH
N
N
IIIа, IIIb
IIa
IIb
haloalkanes, insoluble in water and alkanes.
of the naphthalene or cyclohexadiene fragment as a broad
band at 1655–1661 cm–1, and the keto carbonyl group
С1=O involved in the formation of the intramolecular
hydrogen bond at 1611–1614 cm–1.
The IR spectra of compounds IIIа, IIIb contain the
bands of stretching vibrations of NH group involved into
the formation of intramolecular hydrogen bond (HB) as
a broad band at 3263–3265 cm–1, of the keto carbonyl
group С2=O as a broad band at 1689–1692 cm–1, of the
keto carbonyl group PhС=O and the keto carbonyl group
1
In the Н NMR spectra of compounds IIIа, IIIb
alongside with the proton signals of the aromatic rings and
the groups attached thereto two singlets are present from
the protons of the two methyl groups of the pyrrolidine
fragment in the region 1.15–1.50 and 1.19–1.53 ppm, a
doublet of doublets from the СН2 group of the pyrrolidine
fragment (1.94–2.27 ppm), and a singlet of the proton of
the NH group at 10.74–10.81 ppm.
According to the XRD data (see the figure) the
dark red crystals of compound IIIа crystallize in the
centrosymmetrical space group Р-1 of the triclinic crystal
system. The unit cell is formed by two crystallographically
independent molecules of similar geometry. The bond
lengths and bond angles of the molecules possess close
values approaching the standards. The bond lengths in the
conjugated system of С–С bond of the dioxocyclopentene
fragment (the bond lengths with substituents included)
are to a large extent leveled (1.37–1.49 Å). At the same
time the length of the С15–С16 bond between two keto
groups is 1.55 Å, the value close to the standard length
of the ordinary С–С bond, indicating the absence of
the conjugation of the π-electron density between
General view of the molecule of (Z)-3-benzoyl-5-(5',5'-
dimethyl-4-oxo-4Н-spiro[naphthalene-1,3'-pyrrolidin]-2'-
ylidene)-4-phenylcyclopent-3-ene-1,2-dione (IIIа) according
to XRD data..
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

KONOVALOVA et al.
1630
these moieties. The pyrrole fragment is nonplanar.
Its orientation with respect to the dioxocyclopentene
fragment is governed by the intramolecular hydrogen
bond NH⋯О.
tometer Xcalibur 3 with a ССD-detector by a standard
procedure (MoKα-radiation, 295(2) K, ω-scanning, step
of scanning 1є) [7]. The correction for extinction was not
introduced due to its negligible value (μ 0.086 mm–1).
Within the scattering angles 2.66 < θ < 28.28° 24707 re-
flections were collected, 11991 among them independent
(Rint 0.0255), 5591 reflections with I > 2σ(I). Crystal sys-
tem triclinic, a 9.8236(8), b 14.7005(10), c 18.8767(13)
Å, α 101.190(6), β 98.939(6), γ 104.011(7) deg, space
group Р-1. Completeness for θ < 26.00° 97.1%. The
structure was solved by the direct method and refined
with the use of software SHELXTL [8] with respect to
F2 in the anisotropic approximation for the nonhydrogen
atoms (the hydrogen atoms were introduced into the re-
finement in the rider model in the isotropic approximation
with dependent thermal parameters). The final refinement
parameters are as follows: R1 0.0553, wR2 0.1475 [for
reflections with I > 2σ(I)], R1 0.1204, wR2 0.1630 (for
all reflections) for Z 4, GOOF 1.015. The peaks of the
residual electron density 1.063 and –0.316 ēÅ–3.
Apparently in the course of the reaction under consid-
eration the β-CH group of the tautomeric enamino form
А of the substituted 1,3,3-trimethyl-2-azaspiro[4.5]dec-
1-enes IIа, IIb undergoes the acylation by the carbonyl
group in the position 2 of 4-benzoyl-5-phenylfuran-2,3-
dione (I), the furandione ring opens at the О1–С2 bond
and the successive intramolecular cyclization occurs
with water elimination. The reaction presented is an ex-
ample of building up a stereoregular ensemble from two
polyfunctional systems based on a direct recyclization of
4-benzoyl-5-phenylfuran-2,3-dione under the action of
substituted 1-methyl-2-azaspiro[4.5]dec-1-enes.
The introduction of an additional benzoyl group into
the position 4 of the furandione ring led to the change in
the previously described reactions.
EXPERIMENTAL
(Z)-3-Benzoyl-5-{3,3,9-trimethyl-8-(5-methyl-2-
methoxyphenyl)-6-oxo-2-azaspiro[4.5]dec-7-ene-1-
ylidene}-4-phenylcyclopent-3-ene-1,2-dione (IIIb)
was analogously obtained. Yield 92%, mp 207–209°С
(decomp., ethyl acetate). IR spectrum, cm–1: 3265 br
(NH in HB), 1692 (С2=O), 1661 br (PhС=O, COcyclohex),
1614 (С1=O in HB). 1Н NMR spectrum, δ, ppm: 0.93 d
(3Н, 9-Мe), 1.15 s, 1.19 s (6H, 2Мe), 1.94, 1.98 d.d (2Н,
С4Н2, J 5.1 Hz), 2.10 t (2Н, С10Н2, J 13.4 Hz), 2.30 s
(3Н, 5-Ме), 3.32 br.s (1Н, Н9), 3.80 s (3H, ОМe), 6.13 s
(1H, H7), 6.75–7.74 group of signals (13H, 2Ph + C6H3),
10.81s (1H, NH). Found, %: С 77.87; H 6.02; N 2.22.
С38Н35NO5. Calculated, %: С 77.93; H 6.02; N 2.39.
IR spectra of compounds obtained were recorded
on an IR Fourier spectrophotometer IFS 66 (Bruker) in
mineral oil. 1Н and 13С NMR spectra were registered on
a spectrometer Mercury-300BB (300 MHz) in CDCl3,
internal reference HMDS. The homogeneity of com-
pounds synthesized was confirmed by TLC on Sorbfil
plates, eluents ethyl acetate–benzene, 1 : 5, ethyl acetate;
spots visualized with 0.5% chloranil solution in toluene.
(Z)-3-Benzoyl-5-(5',5'-dimethyl-4-oxo-4Н-
spiro[naphthalene-1,3'-pyrrolidin]-2'-ylidene)-
4-phenylcyclopent-3-ene-1,2-dione (IIIа).Asolution of
1.0 mmol of 4-benzoyl-5-phenylfuran-2,3-dione (I) and
1.0 mmol of reagent IIa in 30 ml of anhydrous benzene
was boiled for 60 min, cooled, the separated precipitate
was filtered off. Yield 89%, mp 218–219°С (decomp.,
ethyl acetate). IR spectrum, cm–1: 3263 br (NH in HB),
1689 (С2=O), 1655 br (PhС=O, COnaphth), 1611 (С1=O in
HB). 1Н NMR spectrum, δ, ppm: 1.50 s, 1.53 s (6H, 2Мe),
2.21, 2.27 d.d (2H, СН2, J 13.8 Hz), 5.88 d (1Hnaphth),
6.89 d (1Hnaphth), 6.95–7.81 group of signals (14H, 2Ph,
C6H4), 10.74 s (1H, NH). Found, %: С 79.19; H 5.16;
N 2.61. С33Н25NO4. Calculated, %: С 79.34; H 5.04; N 2.80.
ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grants
nos. 12-03-00146, 12-03-00696, 12-03-33135) and of the
Council of grants of the President of the Russian Federa-
tion (МК-2998.2011.3).
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