Five-Membered 2,3-Dioxo Heterocycles: LXXV.* Reaction of Methyl 1-Aryl-3-aroyl-4,5-dioxo-4,5-dihydro- 1H-pyrrole-2-carboxylates with 1,3-Diphenylguanidine. Crystalline and Molecular Structure of 9-Benzoyl-8-hydroxy-2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3, 6-triazaspiro-[4.4]non-8-ene-4,7-dione

Article abstract of DOI:10.1134/S1070428011040099

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 1,3-diphenylguanidine to give the corresponding 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4, 7-diones. The molecular and crystalline structures of 9-benzoyl-8-hydroxy-2- imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione were determined by X-ray analysis. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070428011040099

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 4, pp. 523–526. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.V. Bubnov, E.S. Denislamova, Z.G. Aliev, A.N. Maslivets, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 4,
pp. 526–528.
Five-Membered 2,3-Dioxo Heterocycles:
LXXV.* Reaction of Methyl 1-Aryl-3-aroyl-4,5-dioxo-4,5-di-
hydro-1H-pyrrole-2-carboxylates with 1,3-Diphenylguanidine.
Crystalline and Molecular Structure of 9-Benzoyl-8-hydroxy-
2-imino-6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro-
[4.4]non-8-ene-4,7-dione
N. V. Bubnova, E. S. Denislamovab, Z. G. Alievc, and A. N. Maslivetsa,b
a Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Perm State University, ul. Bukireva 15, Perm, 614990 Russia
c Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received April 7, 2010
Abstract—Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 1,3-diphenyl-
guanidine to give the corresponding 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-
8-ene-4,7-diones. The molecular and crystalline structures of 9-benzoyl-8-hydroxy-2-imino-6-(4-methyl-
phenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione were determined by X-ray analysis.
DOI: 10.1134/S1070428011040099
Monocyclic 1H-pyrrole-2,3-diones are known to
react with difunctional nucleophiles to produce various
five-, six-, and seven-membered nitrogen-containing
heterocycles, as well as fused and spiro heterocyclic
systems [2, 3]. We previously showed that methyl
1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-
carboxylates react with N-alkyl- and N-aryl-substituted
acyclic, cyclic, and heterocyclic enamino ketones
(ethyl 3-phenylaminobut-2-enoates [4], 3-alkylamino-
and 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones
[5], 1-methyl-3,4-dihydrobenzo[f]isoquinolines [6]) as
1,3-C,N-binucleophiles according to the scheme in-
volving initial attack by the β-CH group in the
enamino fragment on the C2 atom in the pyrrole ring
and subsequent closure of new pyrrole ring via intra-
molecular attack by the NH group of enamino ketone
on the ester carbonyl carbon atom of dioxopyrrole and
elimination of methanol. These reactions lead to the
formation of spiro heterocyclic systems, such as
1,7-diazaspiro[4.4]nonane [4], spiro[indole-3,2′-pyr-
role] [5], and spiro[benzo[h]pyrrolo[2,1-a]isoquino-
line-2,2′-pyrrole] derivatives [6]. Reactions of mono-
cyclic 1H-pyrrole-2,3-diones with 1,3-N,N-binucleo-
philes were not studied previously.
By reactions of methyl 1-aryl-3-aroyl-4,5-dioxo-
4,5-dihydro-1H-pyrrole-2-carboxylates Ia–Ig with
an equimolar amount of 1,3-diphenylguanidine (II) on
heating in boiling anhydrous 1,2-dichloroethane over
a period of 1–2 h (until the bright red color intrinsic to
the initial dioxopyrrole disappeared) we obtained the
corresponding 6-aryl-9-aroyl-8-hydroxy-2-imino-1,3-
diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-diones
IIIa–IIIg [7] whose structure was proved by the X-ray
diffraction data for compound IIIb.
Compounds IIIa–IIIg are colorless or light yellow
high-melting crystalline substances, which are readily
soluble in DMSO and DMF, poorly soluble in other
common organic solvents, and insoluble in saturated
hydrocarbons and water; they showed a positive color
test (cherry color) with an alcoholic solution of
iron(III) chloride.
* For communication LXXIV, see [1].
523

BUBNOV et al.
524
Scheme 1.
O
O
Ar1
O
O
Ar1
OH
OH
Ar1
MeO
O
8
NH
9
Ph
4
7
+
Ph
Ph
MeOCO
N3
2
5
6
N
O
–MeOH
O
N
N
1
N
O
Ph
N
H
H
N
N
Ar2
NH
Ar2
O
Ar2
HN
Ph
IIIa–IIIIg
Ph NH
Ia–Ig
II
Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-ClC6H4 (d); Ar1 = 4-MeC6H4, Ar2 = Ph (e); Ar2 = 4-MeC6H4,
Ar1 = 2,4-Me2C6H3 (f), 4-EtOC6H4 (g).
The IR spectra of compounds IIIa–IIIg contain
molecule IIIb fall into the corresponding standard
absorption bands due to stretching vibrations of the
OH and NH groups (a broad band at 3050–3080 cm–1),
lactam carbonyl group C4=O in the imidazole frag-
ment (1780–1790 cm–1), lactam carbonyl group C7=O
in the pyrrole fragment (1725–1735 cm–1), and aroyl
carbonyl group (1620–1630 cm–1). Compounds IIIa–
ranges.
Presumably, compounds IIIa–IIIg are formed via
addition of the secondary amino group of diphenyl-
guanidine II to the C2 atom of pyrrole Ia–Ig with
subsequent closure of imidazole ring as a result of
intramolecular nucleophilic attack by the second PhNH
group on the ester carbonyl carbon atom and elimina-
tion of methanol. The described reaction may be
regarded as a novel method for building up function-
alized 1,3,6-triazaspiro[4.4]non-8-ene heterocyclic
system.
1
IIIg displayed in the H NMR spectra signals from
protons in the aromatic rings and substituents attached
thereto and a broadened singlet at δ 9.29–9.48 ppm
belonging to the OH and NH protons. According to the
X-ray diffraction data (see figure), all bond lengths in
EXPERIMENTAL
C17
C16
C15
C23
The IR spectra were recorded on FSM-1201 and
Bruker IFS-66 spectrometers from samples dispersed
in mineral oil. The 1H NMR spectra were measured on
a Bruker AM-400 spectrometer (400 MHz) from solu-
tions in DMSO-d6 using tetramethylsilane as internal
reference. The purity of the isolated compounds was
checked by TLC on Silufol plates using ethyl acetate
and ethyl acetate–benzene (1:5) as eluents; spots were
visualized by treatment with iodine vapor.
C24
C25
C22
C18
C21
C13
C14
C19
N3
C20
O4
C1
C3
N2
C4
O3
C5
C12
N1
C2
O1
C11
C10
N4
C7
9-Benzoyl-8-hydroxy-2-imino-1,3,6-triphenyl-
1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione (IIIa).
A solution of 1 mmol of compound Ia and 1 mmol of
1,3-diphenylguanidine (II) in 10 ml of anhydrous
1,2-dichloroethane was heated for 1 h under reflux.
The mixture was cooled, and the precipitate was
filtered off. Yield 71%, mp 254–255°C (from 1,2-di-
chloroethane). IR spectrum, ν, cm–1: 3050 br (OH,
NH), 1790 (C4=O), 1735 (C7=O), 1630 (COPh).
1H NMR spectrum, δ, ppm: 7.10–7.70 m (20H, Harom),
9.42 br.s (2H, NH, OH). Found, %: C 72.34; H 4.38;
N 10.86. C31H22N4O4. Calculated, %: C 72.36; H 4.31;
N 10.89.
C6
C8
C31
O2
C26
C27
C9
C30
C29
C28
C32
Structure of the molecule of 9-benzoyl-8-hydroxy-2-imino-
6-(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-
8-ene-4,7-dione (IIIb) according to the X-ray diffraction
data.
Compounds IIIb–IIIg were synthesized in a simi-
lar way.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXV.
525
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 (IIIb). Yield 79%, mp 243–244°C (from 1,2-di-
chloroethane). IR spectrum, ν, cm–1: 3070 br (OH,
NH), 1790 (C4=O), 1730 (C7=O), 1630 br (COPh).
1H NMR spectrum, δ, ppm: 2.41 s (3H, Me), 7.10–
7.71 m (19H, Harom), 9.43 br.s (2H, NH, OH). Found,
%: C 72.73; H 4.50; N 10.67. C32H24N4O4. Calculated,
%: C 72.72; H 4.58; N 10.60.
9-Benzoyl-6-(4-chlorophenyl)-8-hydroxy-2-
imino-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-ene-
4,7-dione (IIId). Yield 78%, mp 253–254°C (from
1,2-dichloroethane). IR spectrum, ν, cm–1: 3080 br
(OH, NH), 1790 (C4=O), 1735 (C7=O), 1620 (COPh).
1H NMR spectrum, δ, ppm: 7.08–7.73 m (19H, Harom),
9.48 br.s (2H, NH, OH). Found, %: C 69.84; H 3.88;
N 10.16. C31H21ClN4O4. Calculated, %: C 67.82;
H 3.86; N 10.21.
X-Ray analysis of compound IIIb. Colorless
crystals, C32H24N4O4 ·1.5C2H5OH; monoclinic crystal
system, space group C2/c; unit cell parameters: a =
19.939(3), b = 18.560(5), c = 18.910(2) Å; β =
115.60(1)°; V = 6311(2) Å3; M 594.59; dcalc = 1.252 g×
cm–3; Z = 8. The X-ray diffraction data were acquired
on a KM-4 (KUMA Diffraction) automatic four-circle
diffractometer with χ-geometry (monochromatized
MoKα irradiation, ω/2Θ scanning, 2Θ ≤ 50°). Total of
5674 reflection intensities were measured, 4836 of
which were independent (Rint = 0.0374). No correction
for absorption was introduced (μ = 0.086 mm–1). The
structure was solved by the direct method using SIR92
program [8], followed by a series of calculation of
electron density maps. The positions of hydrogen
atoms were set on the basis of geometry considera-
tions. The positions of non-hydrogen atoms were
refined by the least-squares procedure in full-matrix
anisotropic approximation (SHELXL-97 [9]) up to
R1 = 0.0985 [2511 reflections with I ≥ 2σ(I)] and R1 =
0.1771 (all 4836 reflections); 396 refined parameters;
goodness of fit 1.165. Crystals of IIIb reflect weakly,
so that only 50% of the measured reflection intensities
were significant; as a result, the divergence factor was
fairly large, and thermal vibration coefficients of the
peripheral carbon atoms in the benzene rings were also
high. Molecules IIIb in crystal are packed in such
a way that channels along the [101] direction are
formed, where statistically disordered solvent mole-
cules are located (they were not identified completely).
A series of least-squares refinements with different
atom weights and populations led us to presume that
the solvent is ethanol and that its concentration ap-
proaches 1.5 per molecule IIIb.
8-Hydroxy-2-imino-9-(4-methylbenzoyl)-1,3,6-
triphenyl-1,3,6-triazaspiro[4.4]non-8-ene-4,7-dione
(IIIe). Yield 74%, mp 247–248°C (from 1,2-dichloro-
ethane). IR spectrum, ν, cm–1: 3070 br (OH, NH), 1790
(C4=O), 1735 (C7=O), 1625 br (ArCO). 1H NMR spec-
trum, δ, ppm: 2.34 s (3H, Me), 7.08–7.69 m (19H,
Harom), 9.42 br.s (2H, NH, OH). Found, %: C 72.58;
H 4.49; N 10.59. C32H24N4O4. Calculated, %: C 72.72;
H 4.58; N 10.60.
9-(2,4-Dimethylbenzoyl)-8-hydroxy-2-imino-6-
(4-methylphenyl)-1,3-diphenyl-1,3,6-triazaspiro-
[4.4]non-8-ene-4,7-dione (IIIf). Yield 81%, mp 222–
223°C (from 1,2-dichloroethane). IR spectrum, ν,
cm–1: 3050 br (OH, NH), 1789 (C4=O), 1733 (C7=O),
1
1621 br (ArCO). H NMR spectrum, δ, ppm: 2.03 s,
2.26 s, and 2.40 s (3H each, Me); 6.81–7.69 m (17H,
Harom); 9.48 br.s (2H, NH, OH). Found, %: C 73.41;
H 4.99; N 10.19. C34H28N4O4. Calculated, %: C 73.37;
H 5.07; N 10.07.
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 (IIIg). Yield 75%, mp 251–
252°C (from 1,2-dichloroethane). IR spectrum, ν, cm–1:
3050 br (OH, NH), 1790 (C4=O), 1730 (C7=O), 1625 br
1
(ArCO). H NMR spectrum, δ, ppm: 1.35 t (3H,
CH3CH2, J = 7.0 Hz), 2.40 s (3H, Me), 4.08 q (2H,
OCH2, J = 7.0 Hz), 6.85–7.81 m (18H, Harom), 9.29 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.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
9-Benzoyl-8-hydroxy-2-imino-6-(4-methoxy-
phenyl)-1,3-diphenyl-1,3,6-triazaspiro[4.4]non-8-
ene-4,7-dione (IIIc). Yield 89%, mp 237–238°C (from
1,2-dichloroethane). IR spectrum, ν, cm–1: 3065 br
(OH, NH), 1780 (C4=O), 1725 (C7=O), 1630 (COPh).
1H NMR spectrum, δ, ppm: 3.85 s (3H, OMe), 7.13–
7.69 m (19H, Harom), 9.39 br.s (2H, NH, OH). Found,
%: C 70.88; H 4.53; N 10.61. C32H24N4O5. Calculated,
%: C 70.58; H 4.44; N 10.29.
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