Reaction of 5-arylfuran-2(3H)-ones with amines

Article abstract of DOI:10.1134/S1070428009120112

5-(4-Chlorophenyl)- and 5-phenylfuran-2(3H)-ones reacted with guanidine carbonate at the methylene group in the unsaturated lactone molecule, leading to the formation of 4-(2-aryl-5-oxo-2,5-dihydrofuran-2-yl)-5-aryltetrahydrofuran-2-ones, while 5-(4-methy

Full text of DOI:10.1134/S1070428009120112

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 12, pp. 1818–1823. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © L.M. Potikha, A.A. Lysakovskii, V.A. Kovtunenko, A.V. Turov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 12, pp. 1822–1827.
Reaction of 5-Arylfuran-2(3H)-ones with Amines
L. M. Potikha, A. A. Lysakovskii, V. A. Kovtunenko, and A. V. Turov
Taras Shevchenko Kiev National University, ul. Vladimirskaya 64, Kiev, 01033 Ukraine
e-mail: potikha_l@mail.ru
Received March 24, 2009
Abstract—5-(4-Chlorophenyl)- and 5-phenylfuran-2(3H)-ones reacted with guanidine carbonate at the
methylene group in the unsaturated lactone molecule, leading to the formation of 4-(2-aryl-5-oxo-2,5-dihydro-
furan-2-yl)-5-aryltetrahydrofuran-2-ones, while 5-(4-methylphenyl)furan-2(3H)-one under analogous condi-
tions gave rise to N,N′-bis[4-(4-methylphenyl)-4-oxobutanoyl]guanidine. The reactions of 5-arylfuran-2(3H)-
ones with thioacetamide afforded 4-aryl-N-{1-[5-aryl-2-oxo-2,3-dihydrofuran-3-ylidene]ethyl}-4-oxobutan-
amides. The corresponding N-(4-aryl-4-oxobutanoyl)thioureas were obtained by heating 5-arylfuran-2(3H)-
ones with thiourea.
DOI: 10.1134/S1070428009120112
Various nitrogen-containing heterocyclic systems
are often synthesized following an approach based on
the reaction of equimolar amounts of difunctional elec-
trophiles with amines. 5-Arylfuran-2(3H)-ones I are
synthetic equivalents of 1,4-bielectrophiles. Although
studies on the properties of these compounds have
been initiated long ago by Biedermann [1] and Fittig
[2] in the end of the XIXth century, known reactions of
5-arylfuran-2(3H)-ones I with amines are strongly
limited; examples of their reactions with hydrazine
derivatives and primary and secondary alkyl- and aryl-
amines have been reported; in some cases, these reac-
tions led to the formation of pyrrole [3–5] and pyrida-
zine derivatives [6]. We now report on the reactions of
5-arylfuran-2(3H)-ones Ia–Ic with 1,3-binucleophiles,
namely guanidine, thiourea, and thioacetamide, which
were expected to produce nitrogen- and sulfur-and-
nitrogen-containing heterocycles.
oxobutanoic acid derivatives [7]. In the IR spectrum
of the product we observed νNH bands at 3350 and
3289 cm–1. In keeping with the mass-spectral data, the
product was diacyl-substituted guanidine (m/z 408
[M + 1]+). The above spectral data are consistent with
three isomeric structures: N,N′-bis[4-(4-methylphenyl)-
4-oxobutanoyl]guanidine (IIc), N,N-bis[4-(4-methyl-
phenyl)-4-oxobutanoyl]guanidine (III), and N,N″-bis-
[4-(4-methylphenyl)-4-oxobutanoyl]guanidine (IV)
1
(Scheme 1). Taking into account that the H NMR
spectrum of the product contained only one set of
signals from 4-aryl-4-oxobutanoyl fragment (i.e., the
product has a symmetric structure) and that its IR spec-
trum lacked strong absorption bands at 1700 cm–1 and
above (which could be assigned to imido group [8]), it
was identified as isomer IIc.
The reactions of 5-arylfuran-2(3H)-ones Ia and Ib
with guanidine carbonate under analogous conditions
(120–130°C) followed a different path. According to
the data of elemental analysis and mass spectrometry,
the products were previously unknown bis-lactones.
They displayed in the IR spectra absorption bands due
to stretching vibrations of carbonyl groups in the
region 1757–1773 cm–1, while no strong absorption
bands were present in the region 1665–1685 cm–1 typ-
ical of the Ar–C=O fragment in compounds resulting
from opening of the lactone ring [7]; these findings
indicated conservation of the cyclic lactone structure
It is known that heating of 5-arylfuran-2(3H)-ones I
with amines results in opening of the lactone ring and
formation of the corresponding 4-aryl-4-oxobutanoic
acid amides [2, 3, 5]. 5-(4-Methylphenyl)furan-2(3H)-
one (Ic) reacted with guanidine carbonate according to
a similar scheme: fusion of a mixture of the reactants
at 120–130°C gave a 4-(4-methylphenyl)-4-oxobutan-
amide derivative. The product structure followed from
1
its H NMR spectrum which contained signals from
methylene protons as two triplets at δ 2.70 and
3.22 ppm (3J = 6.5 Hz) and NH proton signal at
δ 9.33 ppm, br.s. This pattern is typical of 4-aryl-4-
1
[9]. The H NMR spectra of the isolated compounds,
apart from signals belonging to protons in two non-
1818

REACTION OF 5-ARYLFURAN-2(3H)-ONES WITH AMINES
1819
Scheme 1.
NH
O
NH
O
+
·H2CO3
Ar
Ar
Ar
O
Ar = 4-MeC6H4
H2N
NH2
N
H
N
O
H
O
O
Ic
IIc
HN
N
O
NH2
O
NH2
O
Ar
Ar
N
N
O
H
O
O
Ar
O
O
Ar
III
IV
HN=C(NH2)2 ·H2CO3
–H+
Ar
O
Ar
O
Ar
O
Ar = Ph, 4-ClC6H4
O
O
O
Ia, Ib
V
VI
Ar
V
O
O
O
Ar
O
VIIa, VIIb
Ar = Ph (a), 4-ClC6H4 (b), 4-MeC6H4 (c).
equivalent phenyl groups, characteristically contained
signals from olefinic protons as two doublets with
a coupling constant J of 6 Hz and signals from ali-
phatic protons as an ABMX spin system. The spectral
pattern suggests that the product molecule consists of
two fragments of initial compound I linked to each
other and partially reduced.
NOESY spectra. Figure 1 illustrates assignment of
signals and structurally significant correlations (shown
with arrows) in the HMBC (A) and NOESY spectra
(B). Thus the 1H signal at δ 3.52 ppm displayed numer-
ous NOEs with protons in both furan rings and ortho-
protons in the corresponding phenyl substituents. The
same proton showed correlations in the HMBC spec-
trum with four quaternary carbon atoms (carbonyl car-
bon atom, δC 175.5 ppm, C5, and carbon atoms in the
two benzene rings), with the sp3-hybridized carbon
atom resonating at δC 91.2 ppm, and with sp3-carbon
atoms in the CH and CH2 groups. These findings reli-
ably indicated the presence of a 4-substituted 2-oxo-5-
phenyltetrahydrofuran fragment in molecule VIIa. The
presence of another structural fragment, 5-substituted
5-phenyl-2-oxo-2,5-dihydrofuran moiety, follows
from the cross peaks between protons resonating at
δ 6.40 and 8.18 ppm and carbonyl carbon atom
(δC 172.0 ppm) and between the proton resonating at
δ 8.18 ppm and quaternary carbon atoms (δC 91.2 and
137.6 ppm). Some specific features of the steric con-
figuration of molecule VIIa were established on the
basis of the NOESY data. The 4-H proton displayed
coupling with ortho protons in the phenyl substituent
on C5. This means that the substituents on C4 and C5
Examples of dimerization of furan-2(3H)-one de-
rivatives on heating in acetic anhydride [10, 11], under
irradiation [12], and in reactions with bases [13, 14]
have been reported. We presumed that the reactions of
lactones Ia and Ib with guanidine are examples of
dimerization by the action of bases. According to the
mechanism proposed in [13] for the dimerization of
α-angelicalactone, β,γ-unsaturated lactone I on heating
with a base (in our case, guanidine) is converted into
α,β-unsaturated lactone V; proton abstraction from the
sp3-carbon atom in V gives anion VI which adds at the
double bond of V with formation of the corresponding
dimeric products, 5-aryl-4-(2-aryl-5-oxo-2,5-dihydro-
furan-2-yl)tetrahydrofuran-2-ones VIIa and VIIb
(Scheme 1).
To elucidate the structure of compounds VII, we
examined the 13C NMR spectrum of VIIa, as well as
its two-dimensional COSY, HMQC, HMBC, and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009

POTIKHA et al.
1820
O
7.43
7.34
126.1
137.6
O
7.23
1'
7.34
2'''
172.0
H
O
H
O
Ph
6.40
6.40
3'
7.43 6.89
5.26
3'
121.3
91.2
H
5.26
2''
159.6
139.9
81.6
4
49.4
29.5
Ph
O
5'
8.18
3.25
126.4
3.52
8.18
O
2
3
O1
O
O
2.24
O
6.89
2.24
175.5
6.89
7.23
2.88
2.88
O
O
A
B
C
Fig. 1. Structurally significant correlations in the HMBC (A) and NOESY spectra (B) and the most populated conformation (C) of
4-(5-oxo-2-phenyl-2,5-dihydrofuran-2-yl)-5-phenyltetrahydrofuran-2-one (VIIa).
are oriented trans. The 4-H atom also appears spatially
close to the 3′-H proton and ortho protons in the ben-
zene ring attached to C2′, and the latter protons exhibit
NOE due to coupling with 5-H, so that the most popu-
lated conformation of molecule VIIa may be illustrat-
ed by structure C (Fig. 1).
The reactions of 5-arylfuran-2(3H)-ones Ia and Ib
with thioacetamide were accompanied by opening of
the lactone ring, but the products had a more compli-
cated structure than simple 4-aryl-4-oxobutanoic acid
amides. According to the spectral data, the products
were formed from two molecules of the lactone and
1
one thoacetamide molecule. Their H NMR spectra
Lactones Ia–Ic reacted with thiourea at a higher
temperature (140–150°C) than in the reaction with
guanidine, and the products were the corresponding
N-(4-aryl-4-oxobutanoyl)thioureas VIIIa–VIIIc
(Scheme 2). Rotation about formally single bonds in
the H2N–CS–NH–CO– fragment is likely to be re-
stricted due to formation of intramolecular hydrogen
bond. As a result, protons in the NH2 group become
nonequivalent, and they appear in the 1H NMR spectra
as differently broadened signals at δ 9.20 and 9.58 ppm.
The NH stretching vibration frequency in the IR spec-
tra of VIIIa–VIIIc (νNH 3300 cm–1 and lower) also
indicates hydrogen bonding with participation of the
amino groups.
contained signals from two nonequivalent phenyl
rings, four methylene protons in 4-oxobutanoic acid
fragment, and methyl protons (δ 2.63 ppm), as well as
a singlet at δ 7.02 ppm from an olefinic proton. In the
IR spectra of these compounds we observed three
strong absorption bands in the region corresponding
to carbonyl stretching vibrations, at 1731, 1709, and
1687 cm–1. It was shown previously [15–18] that
5-arylfuran-2(3H)-ones readily react with carbonyl
compounds to form condensation products at the
α-methylene group. Taking into account the above
stated, as well as the absence of sulfur in the product
molecules (according to their elemental analyses), the
Scheme 2.
O
S
S
Ar
+
N
NH2
Ar
O
O
H
H2N
NH2
O
Ia–Ic
VIIIa–VIIIc
Me
O
O
S
Ar
or
4-MeC6H4
+
N
OH
Ar
O
Ar
O
H
Me
NH2
O
O
O
Ia–Ic
O
IXa, IXb
X
Ar = Ph (a), 4-ClC6H4 (b), 4-MeC6H4 (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009

REACTION OF 5-ARYLFURAN-2(3H)-ONES WITH AMINES
1821
NOE
2.62
2.84
32.0
2'
7.01
19.0CH3
O
2'''
151.6
136.9
128.5
7.99
101.4
4
33.5
3.36
1
7.51
N
106.7
3''
129.3
148.3
11.0
O
O
124.5
169.1
1''
O
NOE
7.41
7.64
Fig. 2. Structurally significant correlations in the HMBC and NOESY spectra of 4-oxo-N-[1-(2-oxo-5-phenyl-2,3-dihydrofuran-
3-ylidene)ethyl]-4-phenylbutanamide (IXa).
protons in the C2H2 methylene group fairly acidic, so
products obtained from lactones Ia and Ib and thio-
that the reaction with guanidine (which is a strong
base) occurs as base-catalyzed dimerization. In the
reaction with thioacetamide, the initial reaction step is
condensation at the methylene group. If a donor sub-
stituent (methyl group) is present, the main reaction
pathway is nucleophilic attack on the carbonyl carbon
atom, which is followed by cleavage of the lactone
ring with formation of 4-(4-methylphenyl)-4-oxobut-
anoic acid derivative.
acetamide were assigned the structure of 4-aryl-N-[1-
(5-aryl-2-oxo-2,3-dihydrofuran-3-ylidene)ethyl]-4-oxo-
butanamides IXa and IXb, respectively (Scheme 2).
The structure of compound IXa was confirmed by
two-dimensional NMR spectra (COSY, HMQC,
HMBC; Fig. 2). The HMBC spectrum of IXa showed
correlations of the olefinic 4″-H proton (δ 7.01 ppm)
with three carbon atoms in the lactone ring (δC 169.1,
148.3, 106.7 ppm) and quaternary carbon atom in the
phenyl substituent (δC 129.3 ppm), indicating the pres-
ence of a 5-aryl-2oxo-2,3-dihydrofuran fragment in
molecule IXa. Correlations were also observed be-
tween protons in the methyl group and amino group
(δ 11.0 ppm), on the one hand, and quaternary carbon
atom in the lactone ring (δC 106.7 ppm), which is con-
sistent with the formation of condensation product at
the methylene group of Ia. The steric configuration of
molecule IXa was reliably determined on the basis of
the NOESY spectrum which revealed coupling be-
tween the methyl protons and 4″-H. The existence of
such coupling suggests Z configuration of the 1-amino-
ethylidene fragment.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Perkin–
Elmer Spectrum BX instrument. The 1H and 13C NMR
spectra were measured from solutions in DMSO-d6 on
a Varian Mercury 400 spectrometer at 400 MHz for 1H
and 100 MHz for 13C using tetramethylsilane as inter-
nal reference. The melting points were determined on
a Boetius melting point apparatus and are uncorrected.
The purity of the isolated compounds was checked by
TLC on Silufol UV-254 plates using chloroform as
eluent and by HPLC–MS on an Agilent 1100 Series
instrument coupled with an Agilent LC/MSD SL mass-
selective detector (samples were introduced in a tri-
fluoroacetic acid matrix). Initial 5-arylfuran-2(3H)-
ones Ia–Ic were synthesized according to the proce-
dure reported in [19].
In the reaction of 5-(4-methylphenyl)furan-2(3H)-
one (Ic) with thioacetamide we isolated 4-(4-methyl-
phenyl)-4-oxobutanoic acid (X) which was identified
by comparison of its physical constants and spectral
parameters with those reported in [19]. Presumably,
initially formed 4-oxobutanoic acid derivative under-
went hydrolysis during the isolation process (the
product was purified by recrystallization from aqueous
ethanol).
N,N′-Bis[4-(4-methylphenyl)-4-oxobutanoyl]-
guanidine (IIc). A mixture of 0.33 g (1.87 mmol) of
lactone Ic and 0.23 g (1.87 mmol) of guanidine car-
bonate was fused at 120–130°C over a period of 2 h.
After cooling, the solid product was recrystallized
from acetic acid. Yield 0.19 g (52%), mp 216–217°C
(from AcOH). IR spectrum, ν, cm–1: 3350 (NH), 3289
(NH), 1687 (C=O), 1667 (C=O), 1642 (C=N), 1516,
Our results led us to draw some conclusions con-
cerning the effect of substituent in the benzene ring of
5-arylfuran-2(3H)-ones on their reactivity. The pres-
ence of an electrophilic group (such as 4-chlorophenyl
or unsubstituted phenyl) on C5 in the furan ring makes
1
1329, 1158, 788, 638. H NMR spectrum, δ, ppm:
2.41 s (6H, CH3), 2.70 t (4H, 3-H, J = 6.5 Hz), 3.22 t
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009

POTIKHA et al.
1822
(4H, 2-H, J = 6.5 Hz), 7.29 d (4H, m-H, J = 8.0 Hz),
7.86 d (4H, o-H, J = 8.0 Hz), 9.33 br.s (3H, NH). Mass
spectrum, m/z (Irel, %): 408 (100) [M + 1]+, 410 (20).
Found, %: C 67.50; H 6.07; N 10.33. C23H25N3O4. Cal-
culated, %: C 67.80; H 6.18; N 10.31.
(from DMF). IR spectrum, ν, cm–1: 3300 (NH), 3171
(NH), 3042, 1703, 1678 br.s (C=O), 1611, 1597, 1530,
1407, 1147, 973, 755, 691, 638. 1H NMR spectrum, δ,
ppm: 2.75 t (2H, 3-H, J = 6.0 Hz), 3.27 t (2H, 2-H, J =
6.0 Hz), 7.49 t (2H, m-H, J = 8.0 Hz), 7.60 t (1H, p-H,
J = 8.0 Hz), 7.96 d (2H, o-H, J = 8.0 Hz), 9.21 s and
9.57 s (1H each, CSNH2, 11.16 s (1H, CONH). Found,
%: C 55.84; H 5.09; N 11.86; S 13.61. C11H12N2O2S.
Calculated, %: C 55.91; H 5.12; N 11.86; S 13.57.
4-(5-Oxo-2-phenyl-2,5-dihydrofuran-2-yl)-5-
phenyltetrahydrofuran-2-one (VIIa). A mixture of
0.3 g (1.87 mmol) of lactone Ia and 0.23 g (1.87 mmol)
of guanidine carbonate was fused at 120–130°C over
a period of 2 h. After cooling, the solid product was
recrystallized from acetic acid. Yield 0.21 g (71%),
mp 179–180°C (decomp.; from AcOH). IR spectrum,
ν, cm–1: 3087, 1771 (C=O), 1757 (C=O), 1449, 1211
(C–O), 1172, 1119, 1015, 962, 914, 819, 761, 699.
N-(Aminocarbonothioyl)-4-(4-chlorophenyl)-4-
oxobutanamide (VIIIb). Yield 0.28 g (51%), mp 252–
254°C (from DMF). IR spectrum, ν, cm–1: 3300 (NH),
3160 (NH2), 1681 br.s (C=O), 1611, 1589, 1533, 1401,
1
1150, 1085, 985, 663. H NMR spectrum, δ, ppm:
2
1H NMR spectrum, δ, ppm: 2.24 d.d (1H, 3-H, J =
2.75 t (2H, 3-H, J = 6.0 Hz), 3.25 t (2H, 2-H, J =
6.0 Hz), 7.49 d (2H, m-H, J = 8.0 Hz), 7.96 d (1H,
o-H, J = 8.0 Hz), 9.17 s and 9.58 s (1H each, CSNH2),
11.10 s (1H, CONH). Found, %: C 48.73; H 4.05;
Cl 13.12; N 10.34; S 11.89. C11H11ClN2O2S. Calculat-
ed, %: C 48.80; H 4.10; Cl 13.09; N 10.35; S 11.84.
3
2
3
18.0, J = 5.2 Hz), 2.88 d.d (1H, 3-H, J = 18.0, J =
10.0 Hz), 3.52 m (1H, 4-H), 5.26 d (1H, 5-H, J =
4.8 Hz), 6.40 d (1H, 4′-H, J = 5.6 Hz), 6.89 m (2H,
o-H), 7.23 m (3H, m-H, p-H), 7.34 m (3H, m′-H, p′-H),
7.43 d (2H, o′-H, J = 7.5 Hz), 8.18 d (1H, 3′-H, J =
5.6 Hz). 13C NMR spectrum, δC, ppm: 29.5 (C3), 49.4
(C4), 81.6 (C5), 91.2 (C2′), 121.3 (C4′), 126.0 (Co′),
126.4 (Co), 128.9 (Cp), 129.1 (Cm), 129.2 (Cp′), 129.6
(Cm′), 137.6 (Ci′), 139.9 (Ci), 159.6 (C3′), 172.0 (C5′),
175.5 (C2). Mass spectrum: m/z 321 (Irel 100%)
[M + 1]+. Found, %: C 74.86; H 4.89. C20H16O4. Cal-
culated, %: C 74.99; H 5.03.
N-(Aminocarbonothioyl)-4-(4-methylphenyl)-4-
oxobutanamide (VIIIc). Yield 0.3 g (60%), mp 223–
225°C (from DMF). IR spectrum, ν, cm–1: 3300 (NH),
3148 (NH2), 1676 br.s (C=O), 1606, 1536, 1404, 1152,
1
646, 610. H NMR spectrum, δ, ppm: 2.41 s (3H,
CH3), 2.74 t (2H, 3-H, J = 6.0 Hz), 3.23 t (2H, 2-H, J =
6.0 Hz), 7.29 d (2H, m-H, J = 8.0 Hz), 7.85 d (1H,
o-H, J = 8.0 Hz), 9.18 s and 9.58 s (1H each, CSNH2),
11.14 s (1H, CONH). Found, %: C 57.50; H 5.59;
N 11.21; S 12.86. C12H14N2O2S. Calculated, %:
C 57.58; H 5.64; N 11.19; S 12.81.
5-(4-Chlorophenyl)-4-[2-(4-chlorophenyl)-5-oxo-
2,5-dihydrofuran-2-yl]tetrahydrofuran-2-one
(VIIb) was synthesized in a similar way from 0.37 g
(1.87 mmol) of lactone Ib. Yield 0.25 g (68%),
mp 178–180°C (decomp.; from AcOH). IR spectrum,
ν, cm–1: 3081, 1773 br.s (C=O), 1757, 1491, 1200
(C–O), 1175, 1094, 1013, 828. 1H NMR spectrum, δ,
4-Oxo-N-[1-(2-oxo-5-phenyl-2,3-dihydrofuran-3-
ylidene)ethyl]-4-phenylbutanamide (IXa). A mixture
of 0.3 g (1.87 mmol) of lactone Ia and 0.14 g
(1.87 mmol) of thioacetamide was fused at 120–130°C
over a period of 4 h. After cooling, the solid product
was recrystallized from nitromethane. Yield 0.16 g
(48%), mp 183–185°C (from MeNO2). IR spectrum, ν,
cm–1: 3266 (NH), 2913, 1731 (C=O), 1709 (C=O),
1687 (C=O), 1631, 1594, 1343, 1228, 1141, 1119, 750,
2
3
ppm: 2.28 d.d (1H, 3-H, J = 18.0, J = 7.2 Hz),
2
3
2.75 d.d (1H, 3-H, J = 18.0, J 9.2 Hz), 3.57 m (1H,
4-H), 5.23 d (1H, 5-H, J = 6.0 Hz), 6.30 d (1H, 4′-H,
J = 5.6 Hz), 6.98 d (2H, o-H, J = 8.0 Hz), 7.23 d (2H,
m-H, J = 8.0 Hz), 7.30 d (2H, m′-H, J = 8.0 Hz), 7.43 d
(2H, o′-H, J = 8.0 Hz), 8.14 d (1H, 3′-H, J = 5.6 Hz).
Found, %: C 61.54; H 3.50; Cl 18.24. C20H14Cl2O4.
Calculated, %: C 61.72; H 3.63; Cl 18.22.
1
688. H NMR spectrum, δ, ppm: 2.62 s (3H, CH3),
2.84 t (2H, 3-H, J = 6.0 Hz), 3.36 t (2H, 2-H, J =
6.0 Hz), 7.01 s (1H, p-H), 7.32 t (1H, p′-H, J =
8.0 Hz), 7.41 t (2H, m′-H, J = 8.0 Hz), 7.51 t (2H,
m′-H, J = 7.5 Hz), 7.61 t (1H, 4′-H, J = 7.5 Hz), 7.64 d
(2H, o′-H, J = 8.0 Hz), 7.99 d (2H, o-H, J = 7.5 Hz),
11.01 s (1H, NH). 13C NMR spectrum, δC, ppm: 19.0
(CH3), 32.0 (C3), 33.5 (C2), 101.4 (C4′), 106.7 (C3′),
124.5 (Co′), 128.5 (Co), 129.1 (Cm, Cm′), 129.2 (Cp′),
129.3 (Ci′), 133.6 (Cp), 136.9 (Ci), 148.3 (C5′), 151.6
N-(4-Aryl-4-oxobutanoyl)thioureas VIIIa–VIIIc
(general procedure). A mixture of 2.0 mmol of lactone
Ia–Ic and 0.15 g (2.0 mmol) of thiourea was fused at
140–150°C over a period of 5 h. After cooling, the
solid product was recrystallized from dimethyl-
formamide.
N-(Aminocarbonothioyl)-4-oxo-4-phenylbutan-
amide (VIIIa). Yield 0.26 g (56%), mp 187–188°C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009

REACTION OF 5-ARYLFURAN-2(3H)-ONES WITH AMINES
1823
(=CCH3), 169.1 (C2''), 171.4 (C1), 198.1 (C4). Found,
%: C 73.02; H 5.28; N 3.90. C22H19NO4. Calculated,
%: C 73.12; H 5.30; N 3.88.
6. Hashem, A.I., Shaban, M.E., and El-Kafravy, A.F.,
Indian J. Chem., Sect. B, 1982, vol. 21, p. 763.
7. Hithings, G.L., Thomas, M.D., and Vernon, J.M.,
J. Chem. Soc., Perkin Trans. 1, 1992, p. 895.
4-(4-Chlorophenyl)-N-{1-[5-(4-chlorophenyl)-2-
oxo-2,3-dihydrofuran-3-ylidene]ethyl}-4-oxobutan-
amide (IXb) was synthesized in a similar way from
0.37 g (1.87 mmol) of lactone Ib. Yield 0.17 g (43%),
mp 208–209°C (from MeNO2). IR spectrum, ν, cm–1:
3260 (NH), 2924, 1731 (C=O), 1709 (C=O), 1681
(C=O), 1631, 1603, 1348, 1231, 1124, 1091, 1010,
8. Pentin, Yu.A. and Vilkov, L.V., Fizicheskie metody issle-
dovaniya v khimii (Physical Methods of Investigation in
Chemistry), Moscow: Mir, 2003, p. 251.
9. Knochel, P. and Rao, C.J., Tetrahedron, 1993, vol. 49,
p. 29.
10. Fang, C.S. and Bergmann, W., J. Org. Chem., 1951,
vol. 16, p. 1231.
1
831, 780. H NMR spectrum, δ, ppm: 2.61 s (3H,
11. Begley, M.J., Crombie, L., Griffiths, G.L., Jones, R.C.F.,
and Rahmani, M., J. Chem. Soc., Chem. Commun.,
1981, p. 823.
12. Martinez-Utrilla, R. and Miranda, M.A., Tetrahedron,
1981, vol. 37, p. 2111.
13. Syhora, K., Collect. Czech. Chem. Commun. 1961,
CH3), 2.84 t (2H, 3-H, J = 6.0 Hz), 3.34 t (2H, 2-H, J =
6.0 Hz), 7.10 s (1H, 4′-H), 7.42 d (2H, m′-H, J =
8.5 Hz), 7.53 d (2H, m-H, J 8.0 Hz), 7.65 d (2H, o′-H,
J = 8.5 Hz), 7.99 d (2H, o-H, J = 8.0 Hz), 10.98 s (1H,
NH). Found, %: C 61.35; H 3.92; Cl 16.50; N 3.27.
C22H17Cl2NO4. Calculated, %: C 61.41; H 3.98;
Cl 16.48; N 3.26.
vol. 26, p. 2058.
14. Filler, R. and Piasek, E.J., J. Org. Chem., 1963, vol. 28,
p. 3400.
4-(4-Methylphenyl)-4-oxobutanoic acid (X) was
isolated in the reaction of 0.33 g (1.87 mmol) of lac-
tone Ic with thioacetamide according to the procedure
described above for the synthesis of compound IXa.
Yield 0.16 g (45%), mp 125–126°C; published data
[20]: mp 127°C.
15. Miller, G.A., Heindel, N.D., and Minatelli, J.A.,
J. Heterocycl. Chem., 1981, vol. 18, p. 1253.
16. Egorova, A.Yu., Reshetov, P.V., Morozova, N.A., and
Sedavkina, V.A., Khim. Geterotsikl. Soedin., 1997,
p. 1043.
17. Barrett, C.B., Beer, R.J.S., Dodd, G.M., and Robert-
son, A., J. Chem. Soc., 1957, p. 4810.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009