Synthesis of new heterocyclic enamines and their cyclization with oxalyl chloride

Full text of DOI:10.1134/S1070428011030274

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 3, pp. 466–467. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.Yu. Lisovenko, A.E. Rubtsov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 3, pp. 465–466.
SHORT
COMMUNICATIONS
Synthesis of New Heterocyclic Enamines and Their Cyclization
with Oxalyl Chloride
N. Yu. Lisovenko and A. E. Rubtsov
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: lisovn@mail.ru
Received June 28, 2010
DOI: 10.1134/S1070428011030274
Substituted furan-2,3-diones are convenient syn-
thons exhibiting high reactivity and unusual chemical
behavior toward various reagents [1, 2]. Heterocyclic
ensembles derived from these compounds were found
to possess versatile biological activity [3]. Functionally
substituted furan-2,3-diones can be synthesized by
reaction of heterocyclic β-enaminoketones with oxalyl
chloride [4–6].
By reaction of diaroylacetylenes Ia and Ib with bi-
phenyl-3,3′,4,4′-tetraamine (II) according to the proce-
dure described in [7] we obtained new heterocyclic
enamines, 2,2′-(3,3′-diaryl-1,1′,2,2′-tetrahydro-6,6′-bi-
quinoxaline-2,2′-diylidene)bis(1-arylethanones) IIIa
and IIIb (Scheme 1). Heating of compounds IIIa and
IIIb with oxalyl chloride in boiling anhydrous chloro-
form led to the formation of new representatives of the
furan-2,3-dione series, 4,4′-(3,3′-diaryl-6,6′-biquinoxa-
line-2,2′-diyl)bis(5-aryl-2,3-dihydrofuran-2,3-diones)
IVa and IVb (Scheme 2).
(IIIa). A solution of 4.68 g (20 mmol) of compound Ia
in 10 ml of acetonitrile was added to a solution of
2.14 g (10 mmol) of tetraamine II in 20 ml of aceto-
nitrile, and the mixture was heated to the boiling point
and cooled. The precipitate was filtered off and recrys-
tallized from acetonitrile. Yield 5.75 g (89%), orange–
red crystals, mp 252–254°C (from acetone). IR spec-
trum, ν, cm–1: 3034 br (NH), 1580 br (C=O). 1H NMR
spectrum, δ, ppm: 6.29 s (2H, CH), 6.93–7.90 m (26H,
Harom), 15.70 s (2H, NH). Found, %: C 81.74; H 4.60;
N 8.67. C44H30N4O2. Calculated, %: C 81.71; H 4.68;
N 8.66.
2,2′-[3,3′-Bis(4-methylphenyl)-1,1′,2,2′-tetrahy-
dro-6,6′-biquinoxaline-2,2′-diylidene]bis[1-(4-meth-
ylphenyl)ethanone] (IIIb) was synthesized in a simi-
lar way. Yield 5.98 g (85%), orange–red crystals,
mp 223–225°C (from acetone). IR spectrum, ν, cm–1:
1
3024 br (NH), 1586 br (C=O). H NMR spectrum, δ,
ppm: 2.34 s (6H, Me), 2.50 s (6H, Me), 6.35 s (2H,
CH), 6.90–7.92 m (22H, Harom), 15.76 s (2H, NH).
Found, %: C 82.09; H 5.43; N 7.95. C48H38N4O2. Cal-
culated, %: C 82.03; H 5.45; N 7.97.
Presumably, bis-furandiones IVa and IVb are
formed via initial acylation of compounds IIIa and
IIIb with oxalyl chloride at the exocyclic =CH frag-
ments to give intermediate acyl chlorides [8] which are
converted into hydroxyenimine structure with subse-
quent intramolecular cyclization.
4,4′-(3,3′-Diphenyl-6,6′-biquinoxaline-2,2′-diyl)-
bis(5-phenyl-2,3-dihydrofuran-2,3-dione) (IVa).
Oxalyl chloride, 2.52 g (20 mmol), was added to a so-
lution of 6.47 g (10 mmol) of compound IIIa in 40 ml
of anhydrous chloroform. The mixture was heated for
2,2′-(3,3′-Diphenyl-1,1′,2,2′-tetrahydro-6,6′-bi-
quinoxaline-2,2′-diylidene)bis(1-phenylethanone)
Scheme 1.
O
Ar
NH2
NH2
O
N
Ar
H
N
H2N
H2N
Ar
+
Ar
–2H2O
N
H
Ar
N
O
Ar
O
Ia, Ib
II
IIIa, IIIb
Ar = Ph (a), 4-MeC6H4 (b).
466

SYNTHESIS OF NEW HETEROCYCLIC ENAMINES AND THEIR CYCLIZATION
467
Scheme 2.
Ar
Ar
O
O
Ar
O
N
Ar
N
H
O
N
N
2(COCl)2
–4HCl
O
O
N
N
O
H
N
N
Ar
O
Ar
Ar
Ar
IIIa, IIIb
IVa, IVb
Ar = Ph (a), 4-MeC6H4 (b).
100 min under reflux, evaporated to a volume of
20 ml, diluted with anhydrous hexane, and cooled, and
the precipitate was filtered off. Yield 6.03 g (80%),
yellow crystals, decomposition point 289–291°C (from
chloroform–hexane, 2:3). IR spectrum, ν, cm–1: 1830
of reactions was monitored, by TLC on Silufol UV-254
plates using hexane–ethyl acetate (5:1) as eluent.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-00448).
1
(C2=O), 1719 (C3=O). H NMR spectrum: δ 7.13–
8.25 ppm, m (26H, Harom). Found, %: C 76.36; H 3.46;
N 7.77. C48H26N4O6. Calculated, %: C 76.39; H 3.47;
N 7.42.
REFERENCES
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line-2,2′-diyl]bis[5-(4-methylphenyl)-2,3-dihydro-
furan-2,3-dione] (IVb) was synthesized in a similar
way. Yield 6.48 g (80%), yellow crystals, decomposi-
tion point 319–320°C (from chloroform–hexane, 2:3).
IR spectrum, ν, cm–1: 1830 (C2=O), 1715 (C3=O).
1H NMR spectrum, δ, ppm: 2.34 s (6H, Me), 2.46 s
(6H, Me), 7.19–8.30 m (22H, Harom). Found, %:
C 77.00; H 4.26; N 6.94. C52H34N4O6. Calculated, %:
C 77.03; H 4.23; N 6.91.
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The IR spectra were recorded from samples dis-
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The H NMR spectra were measured on a Varian
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1
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a Leco CHNS-932 automatic analyzer. The purity of
the isolated compounds was checked, and the progress
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011