Chemistry of acyl(imidoyl)ketenes. 7. Synthesis and thermolysis of 5-aryl-4-quinoxalinyl-2,3-dihydrofuran-2,3-diones

Article abstract of DOI:10.1023/A:1016097120253

3-Aryl-Z-2-aroylmethylidene-1,2-dihydroquinoxalines react with oxalyl chloride to form 3-aryl-2-(2-aryl-4,5-dioxo-4,5-dihydro-3-furyl)quinoxalines, whose thermal decarbonylation generate 5-aryl-2-(3-arylquinoxalin-2-yl)-4-aroyl-3-aroyloxy-1H-pyrido[1,2-a]

Full text of DOI:10.1023/A:1016097120253

850
Russian Chemical Bulletin, International Edition, Vol. 51, No. 5, pp. 850—853, May, 2002
Chemistry of acyl(imidoyl)ketenes
7.* Synthesis and thermolysis of 5ꢀarylꢀ4ꢀquinoxalinylꢀ
2,3ꢀdihydrofuranꢀ2,3ꢀdiones
a
a
a
b
b
A. N. Maslivets,a N. Yu. Lisovenko, O. P. Krasnykh, O. P. Tarasova, Z. G. Aliev, and L. O. Atovmyan
ꢀ
аPerm State University,
15 ul. Bukireva, 614000 Perm, Russian Federation.
Fax: +7 (342 2) 39 6367. Eꢀmail: koh@psu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
14 Institutskii prosp., 142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (096) 515 3588. Eꢀmail: aliev@icp.ac.ru
3ꢀArylꢀZꢀ2ꢀaroylmethylideneꢀ1,2ꢀdihydroquinoxalines react with oxalyl chloride to form
3ꢀarylꢀ2ꢀ(2ꢀarylꢀ4,5ꢀdioxoꢀ4,5ꢀdihydroꢀ3ꢀfuryl)quinoxalines, whose thermal decarbonylation
generate 5ꢀarylꢀ2ꢀ3(arylquinoxalinꢀ2ꢀyl)ꢀ4ꢀaroylꢀ3ꢀaroyloxyꢀ1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ
1ꢀones. The crystal and molecular structures of one of them (Ar = Ph) were established by
Xꢀray diffraction analysis.
Key words: 2,3ꢀdihydrofuranꢀ2,3ꢀdiones, aroyl(imidoyl)ketene, cycloaddition, crystal strucꢀ
ture, molecular structure, Xꢀray diffraction analysis.
The reaction of primary βꢀenamino ketones with
It is most likely that the first stage of the reaction is
the acylation of the CH group of the enamino ketone
fragment in compounds 1a—c, which is characteristic of
βꢀenamino ketones, followed by the intramolecular ring
closure of acid chlorides 4a—c to furandiones 3a—c.
The ring closure of acid chlorides 4a—c to pyrrolediones
2a—c does not occur, likely, due to steric hindrances
from the bulky aryl and aroyl groups. This reaction is the
first example of the synthesis of 2,3ꢀdihydrofuranꢀ2,3ꢀ
diones containing the heterocyclic substituent in poꢀ
sition 4.
It is known that the modes of stabilization of acylꢀ
ketenes generated by decarbonylation of 2,3ꢀdihydroꢀ
furanꢀ2,3ꢀdiones depend on the character of substituꢀ
ents in the furan ring. For example, aroylketenes formed
from 5ꢀarylꢀ,8 5ꢀarylꢀ4ꢀhalogenꢀ,9 5ꢀarylꢀ4ꢀmethylꢀ,10
4ꢀbenzoylꢀ5ꢀphenylꢀ,11 and 4,5ꢀdiarylꢀ2,3ꢀdihydrofuranꢀ
2,3ꢀdiones12 are stabilized by intermolecular [4+2]ꢀcycloꢀ
addition, and in one ketene molecule the ArCOC=C
fragment plays the role of a heterodiene, while in anꢀ
other molecule the C=C bond of ketene plays the role of
a dienophile. In the case of cycloadducts from 5ꢀarylꢀ,
4ꢀbenzoylꢀ5ꢀphenylꢀ, 4,5ꢀdiarylꢀ2,3ꢀdihydrofuranꢀ2,3ꢀ
diones, the reaction is usually accompanied by the
[1,3]ꢀmigration of the proton or aroyl group. The
similar [4+2]ꢀcyclodimerization of dipivaloylketene
formed from 5ꢀtertꢀbutylꢀ4ꢀpivaloylꢀ2,3ꢀdihydrofuranꢀ
2,3ꢀdione involves the C=О bond of the pivaloyl or ketene
fragments.13 Aroyl(imidoyl)ketenes formed from
oxalyl chloride is the most common method for the synꢀ
thesis of substituted 4ꢀacylꢀ2,3ꢀdihydropyrroleꢀ2,3ꢀ
diones.2 This method was used to synthesize substituted
4ꢀacylꢀ2,3ꢀdihydropyrroleꢀ2,3ꢀdiones from heterocyclic
enamino ketones, viz., substituted 1ꢀacylmethylideneꢀ
1,2,3,4ꢀtetrahydroisoquinolines,3 3ꢀacylmethylideneꢀ3,4ꢀ
dihydroꢀ2Hꢀ1,4ꢀbenzoxazinꢀ2ꢀones,4 2ꢀacylmethylideneꢀ
3,4ꢀdihydroꢀ2Hꢀ1,3ꢀbenzoxazinꢀ4ꢀones,5 and 3ꢀacylꢀ
methylideneꢀ1,2,3,4ꢀtetrahydroꢀ2ꢀquinoxalones.6
This work is devoted to the study of an unusual route
of the reaction of enamino ketones with oxalyl chloride,
which resulted in the preparation of the first representaꢀ
tives of the class of 5ꢀarylꢀ4ꢀheterylꢀ2,3ꢀdihydrofuranꢀ
2,3ꢀdiones, and to the study of their thermolysis.
Results and Discussion
The reaction of 3ꢀarylꢀZꢀ2ꢀaroylmethylideneꢀ1,2ꢀ
dihydroquinoxalines (1а—с) with oxalyl chloride affords
3ꢀarylꢀ2ꢀ(2ꢀarylꢀ4,5ꢀdioxoꢀ4,5ꢀdihydroꢀ3ꢀfuryl)quinꢀ
oxalines (3a—c)** (Scheme 1) instead of the expected
4ꢀarylꢀ3ꢀaroylꢀ1,2ꢀdihydropyrrolo[1,2ꢀa]quinoxalineꢀ
1,2ꢀdiones (2a—c). The spectroscopic characteristics of
furandiones 3а—с (see Experimental) and substituted
2,3ꢀdihydrofuranꢀ2,3ꢀdiones8—14 are in good agreement.
* For Part 6, see Ref. 1.
** For preliminary report, see Ref. 7.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 785—788, May, 2002.
1066ꢀ5285/02/5105ꢀ850 $27.00 © 2002 Plenum Publishing Corporation

Synthesis of 1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ1ꢀones
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
851
Scheme 1
Ar = Ph (a), 4ꢀMeC6H4 (b), 2,5ꢀMe2C6H3 (c)
4ꢀ[αꢀ(arylimino)benzyl]ꢀ5ꢀphenylꢀ2,3ꢀdihydrofuranꢀ2,3ꢀ
diones undergo intramolecular ring closure due to the
acylation of the orthoꢀposition of the Nꢀaryl ring by the
ketene fragment.14 This type of intramolecular ring cloꢀ
sure is impossible for 3ꢀarylꢀ2ꢀquinoxalinyl(aroyl)ketenes
(5a—c) generated by the thermolytic decarbonylation of
furandiones 3a—c but other methods of participation in
intermolecular cycloaddition are available.
When solutions of furandiones 3a—c are kept in
pꢀxylene at 138—140 °С for 20 min, 4ꢀaroylꢀ3ꢀaroyloxyꢀ
5ꢀarylꢀ2ꢀ(3ꢀarylꢀ2ꢀquinoxalinyl)ꢀ1Hꢀpyrido[1,2ꢀa]quinꢀ
oxalinꢀ1ꢀones (5a—c) are formed.* Ketenes 6a—c formed
by the thermal decarbonylation of furandiones 3a—c are
most likely stabilized through [4+2]ꢀcyclodimerization
followed by the [1,3]ꢀmigration of the aroyl group in
cycloadducts 7a—c.
1.301(3), N(7)—C(41) 1.321(2), and N(8)—C(42)
1.317(2) Å correspond to the double C=C bond lengths.
The distances C(10)—C(11) 1.362(3) and C(12)—C(13)
1.375(3) Å are much longer than the standard value for
the C=C double bond (1.34 Å), which can indicate conꢀ
siderable delocalization of the double bonds in the pyriꢀ
dine ring of the tricyclic fragment of the molecule. At
the same time, this ring has an envelope conformation:
the inflection along the N(5)...C(10) line is 19.5°, and
the deviation of the C(9) atom from the plane of other
five atoms is 0.26 Å. Taking into account that the ordiꢀ
nary C(11)—C(12) bond of 1.410 Å is also strongly shortꢀ
ened and the N(5)—C(13) bond of 1.402 Å corresponds
to the ordinary bond, we can assume that delocalization
takes place in the C(10)...C(11)...C(12)...C(13) chain.
Other bond lengths in the molecule do not differ from
standard values. The pyrazine ring fused with pyridine
has a boat conformation: the inflections along the
N(5)...C(14) and N(6)...C(16) lines are 18.4° and 10.3°,
and the deviations of the C(13) and C(15) atoms are
0.24 and 0.12 Å, respectively.
The structure of compound 5а was established by
Xꢀray diffraction analysis. The general view of molecule
5а is shown in Fig. 1. The bond lengths N(6)—C(14)
* For preliminary report, see Ref. 12.

852
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
Maslivets et al.
C(25)
C(6)
C(24)
C(23)
C(30)
C(31)
C(29)
C(33)
C(21)
N(6)
C(22)
O(4)
C(28)
C(14)
C(32)
C(15)
C(27)
C(12)
C(11)
C(20)
C(13)
N(5)
C(19)
O(2)
C(34)
O(3)
N(7)
C(49)
C(16)
C(36)
C(18)
C(10)
C(17)
C(9)
C(37)
C(38)
O(1)
C(35)
C(47)
C(41)
C(48)
C(43)
C(40)
C(39)
C(46)
C(42)
N(8)
C(50)
C(45)
C(44)
C(51)
C(54)
C(53)
C(52)
Fig. 1. Molecular structure of compound 5а.
m.p. 170—171 °С (with decomp., from a 1 : 3 chloroꢀ
form—hexane mixture). Found (%): C, 76.68; H, 4.45; N, 7.02.
C26H18N2O3. Calculation (%): C, 76.83; H, 4.46; N, 6.89. IR,
Experimental
IR spectra of the compounds synthesized were recorded on
1
1
a URꢀ20 instrument in Nujol. H NMR spectra were recorded
ν/cm–1: 1830 (C(2)=Оfuran); 1720 (C(3)=Оfuran). H NMR, δ:
on a Bruker AMꢀ400 spectrometer (400 MHz) in CDCl3 or
DMSOꢀd6 using Me4Si as the internal standard. Mass spectra
were obtained on an MKhꢀ1310 instrument (70 eV).
Compounds 1a—c were synthesized by the reaction of
diaroylacetylenes with оꢀphenylenediamine according to a preꢀ
viously described method.15
2.30, 2.36 (both s, 3 H, Me); 6.70—8.10 (m, 12 H).
2ꢀ[2ꢀ(2,5ꢀDimethylphenyl)ꢀ4,5ꢀdioxoꢀ4,5ꢀdihydroꢀ3ꢀfuryl]ꢀ
3ꢀ(2,5ꢀdimethylphenyl)quinoxaline (3с) was prepared similarly
in 90% yield, m.p. 132—133 °С (with decomp., from a 1 : 3
chloroform—hexane mixture). Found (%): C, 77.56; H, 5.10;
N, 6.47. C28H22N2O3. Calculated (%): C, 77.40; H, 5.10;
N, 6.45. IR, ν/cm–1: 1820 (C(2)=Оfuran); 1720 (C(3)=Оfuran).
4ꢀBenzoylꢀ3ꢀbenzoyloxyꢀ5ꢀphenylꢀ2ꢀ(3ꢀphenylquinoxalinꢀ2ꢀ
yl)ꢀ1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ1ꢀone (5а). A solution of furanꢀ
dione 3a (0.38 g, 1 mmol) in anhydrous pꢀxylene (5 mL) was
kept for 20 min at 138—140 °С, the solvent was distilled off to
3 mL, and the remaining solution was cooled. The precipitate
that formed was filtered off, and compound 5а was obtained in
85% yield (0.30 g), m.p. 270—271 °С (from MeCN). Found (%):
C, 78.83; H, 4.00; N, 7.99. C46H28N4O4. Calculated (%):
C, 78.84; H, 4.03; N, 8.00. IR, ν/cm–1: 1745 (CОО); 1662
(CО). 1H NMR, δ: 7.00—7.94 (m, 27 H); 8.12 (d, 1 H, C(10)H,
J = 8.4 Hz).
2ꢀ(4,5ꢀDioxoꢀ2ꢀphenylꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ3ꢀphenylꢀ
quinoxaline (3а). A solution of compound 1a (3.00 g, 10 mmol)
and oxalyl chloride (0.85 mL, 10 mmol) in dry CHCl3 (40 mL)
was refluxed for ∼1.5 h and concentrated to half its volume.
Dry hexane (50 mL) was added, the solvent was distilled off to
a volume of 20 mL, the resulting solution was cooled, the
precipitate that formed was filtered off, and quinoxaline 3а was
obtained in 87% yield (3.29 g), m.p. 142—143 °С (with decomp.,
from a 1 : 3 chloroform—hexane mixture). Found (%): C, 76.03;
H, 3.74; N, 7.42. C24H14N2O3. Calculated (%): C, 76.18;
H, 3.73; N, 7.40. IR, ν/cm–1: 1825 (C(2)=Оfuran); 1730
1
(C(3)=Оfuran). H NMR, δ: 7.03 (d, 1 H, оꢀCH, J = 7.0 Hz);
7.15—8.25 (m, 13 H). MS, m/z (Irel (%)): М+ 378 (10), 350
(35), 321 (100), 305 (10), 293 (30), 105 (25), 77 (20).
5ꢀ(4ꢀTolyl)ꢀ2ꢀ[3ꢀ(4ꢀtolyl)quinoxalinꢀ2ꢀyl)ꢀ4ꢀ(4ꢀtoluoyl)ꢀ
3ꢀ(4ꢀtoluoyloxy)ꢀ1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ1ꢀone (5b) was obꢀ
tained similarly in 80% yield, m.p. 310—311 °С (from MeCN).
Found (%): C, 79.34; H, 4.79; N, 7.41. C50H36N4O4. Calcuꢀ
2ꢀ[(4,5ꢀDioxoꢀ2ꢀ(4ꢀtolyl)ꢀ4,5ꢀdihydroꢀ3ꢀfuryl)]ꢀ3ꢀ(4ꢀ
tolyl)quinoxaline (3b) was synthesized similarly in 90% yield,

Synthesis of 1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ1ꢀones
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
853
lated (%): C, 79.35; H, 4.79; N, 7.40. IR, ν/cm–1: 1750 (CОО);
1665 (CО). H NMR, δ: 2.15, 2.23, 2.33, 2.39 (all s, 3 H, Me);
2. Khimiya pyatichlennykh 2,3ꢀdioksogeterotsiklov [Chemistry
of Fiveꢀmembered 2,3ꢀDioxoheterocycles], Ed. Yu. S.
Andreichikov, Perm University, Perm, 1994, 91 (in
Russian).
3. T. Sano, J. Toda, N. Maehara, and Y. Tsuda, Canad.
J. Chem., 1987, 65, 94.
4. A. N. Maslivets, I. V. Mashevskaya, O. P. Krasnykh, S. N.
Shurov, and Yu. S. Andreichikov, Zh. Org. Khim., 1992, 28,
2545 [Russ. J. Org. Chem., 1992, 28 (Engl. Transl.)].
5. G. Kollenz, R. Theuer, W. Ott, and E. Ziegler, Ann.,
1977, 1964.
6. A. N. Maslivets, O. V. Golovnina, O. P. Krasnykh, and
Z. G. Aliev, Khim. Geterotsikl. Soedin., 2000, 113 [Chem.
Heterocycl. Compd., 2000 (Engl. Transl.)].
7. A. N. Maslivets, N. Yu. Lisovenko, O. V. Golovnina,
E. S. Vostrov, and O. P. Tarasova, Khim. Geterotsikl.
Soedin., 2000, 556 [Chem. Heterocycl. Compd., 2000 (Engl.
Transl.)].
8. Yu. S. Andreichikov, Yu. A. Nalimova, A. P. Kozlov, and
I. A. Rusakov, Zh. Org. Khim., 1978, 14, 2436 [Russ. J. Org.
Chem., 1978, 14 (Engl. Transl.)].
9. Yu. S. Andreichikov, N. V. Gel´t, and A. P. Kozlov, Zh. Org.
Khim., 1984, 20, 1749 [Russ. J. Org. Chem., 1984, 20 (Engl.
Transl.)].
10. E. V. Pimenova, V. V. Zalesov, S. S. Kataev, and D. D.
Nekrasov, Zh. Obshch. Khim., 1997, 67, 674 [Russ. J. Gen.
Chem., 1997, 67 (Engl. Transl.)].
1
7.04—7.86 (m, 23 H); 8.10 (d, 1 H, C(10)H, J = 8.4 Hz).
4ꢀ(2,5ꢀDimethylbenzoyl)ꢀ3ꢀ(2,5ꢀdimethylbenzoyloxy)ꢀ5ꢀ
(2,5ꢀdimethylphenyl)ꢀ2ꢀ[3ꢀ(2,5ꢀdimethylphenyl)quinoxalinꢀ2ꢀyl]ꢀ
1Hꢀpyrido[1,2ꢀa]quinoxalinꢀ1ꢀone (5с) was obtained similarly
in 70% yield, m.p. 230—231 °С (from MeCN). Found (%):
C, 79.55; H, 5.44; N, 6.90. C54H44N4O4. Calculated (%):
C, 79.78; H, 5.46; N, 6.89. IR, ν/cm–1: 1750 (CОО); 1680
1
(CО). H NMR, δ: 1.68, 1.69, 1.95, 2.00, 2.02, 2.07, 2.26, 2.35
(all s, 3 H, Me); 6.88—7.89 (m, 19 H); 8.10 (d, 1 H, C(10)H,
J = 8.1 Hz).
Xꢀray study of compound 5а. For the Xꢀray study, a sample
of compound 5а was additionally recrystallized from pꢀxylene
to give well faced yellow crystals in the form of tetrahedral
prisms. The crystals C46H28N4O4•0.5(pꢀMeC6H4Me) are
monoclinic, space group Р21/n, a = 20.812(4), b = 16.202(3),
c = 11.857 Å, β = 98.03(3)°, V = 3958.9(12) Å3, M = 753.80,
dcalc = 1.265 g cm–3, Z = 4. The unit cell parameters and set of
experimental reflections were measured on a KMꢀ4 automated
fourꢀcircle diffractometer (KUMA DIFFRACTION) with
χꢀgeometry using the ω—2θ scan mode and monochromated
CuꢀKα radiation in the angle interval 3.47° < 2θ < 80.24°. On
the whole, 7723 independent reflections were measured, 3099 of
them had I ≥ 2σ(I). No correction for absorption was applied
(µ = 0.649 mm–1). The structure was solved by the direct
statistical method followed by a series of calculations of the
electron density maps.
Hydrogen atoms were specified geometrically after the R
factor achieved 0.065 by the leastꢀsquares refinement in the
anisotropic approximation. The final refinement gave R1 = 0.039.
The GOOF parameter was 0.902. All calculations were perꢀ
formed on a РС/AT using the SHELXꢀ97 program complex.16
The atomic coordinates were deposited with the Cambridge
Structure Data Bank.
11. C. Wentrup, H.ꢀW. Winter, G. Gross, K.ꢀP. Netsch,
G. Kollenz, W. Ott, and A. G. Biedermann, Angew. Chem.,
1984, 96, 791.
12. N. Yu. Lisovenko, O. P. Krasnykh, Z. G. Aliev, E. S.
Vostrov, O. P. Tarasova, and A. N. Maslivets, Khim.
Geterotsikl. Soedin., 2001, 556 [Chem. Heterocycl. Compd.,
2000 (Engl. Transl.)].
13. C. O. Kappe, G. Färber, C. Wentrup, and G. Kollenz,
J. Org. Chem., 1992, 57, 7078.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 01ꢀ03ꢀ32641
and 02ꢀ03ꢀ96411).
14. G. Kollenz, G. Penn, W. Ott, K. Peters, E.ꢀM. Peters, and
H. G. von Schnering, Chem. Ber., 1984, 117, 1310.
15. M. J. Haddadin and M. A. Atfah, J. Org. Chem., 1982,
47, 1772.
16. G. M. Sheldrick, SHELXꢀ97, Programs for Crystal Structure
Analysis, University of Göttingen, Germany, 1997.
References
1. Z. G. Aliev, A. N. Maslivets, O. V. Golovnina, O. P.
Krasnykh, and L. O. Atovmyan, Izv. Akad. Nauk, Ser. Khim.,
2001, 1255 [Russ. Chem. Bull., Int. Ed., 2001, 50, 1317].
Received September 3, 2001;
in revised form December 28, 2001