Chemistry of iminofuran: VIII. Recyclization of 5-aryl-3-arylimino-3H- furan-2-ones effected by cyanoacetic acid derivatives

Article abstract of DOI:10.1134/S1070428013020115

The recyclization of 5-aryl-3-arylimino-3H-furan-2-ones under the action of esters, nitriles, and amides of cycnoacetic acids resulted in the corresponding esters, nitriles, and amides of (5E)-2-amino-1-aryl-4-oxo-5-(2-oxoethylidene)- 1H-4,5-dihydropyrrol

Full text of DOI:10.1134/S1070428013020115

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 2, pp. 243−252. © Pleiades Publishing, Ltd., 2013.
Original English Text © S.S. Kharitonova, N.M. Igidov, A.V. Zakhmatov, A.E. Rubtsov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 2,
pp. 252−261.
Chemistry of Iminofuran: VIII.*
Recyclization of 5-Aryl-3-arylimino-3H-furan-2-ones
Effected by Cyanoacetic Acid Derivatives
S. S. Kharitonovaa, N. M. Igidovb, A. V. Zakhmatovb, and A. E. Rubtsova
aPerm State University, Perm, 614990 Russia
e-mail: rubtsov@psu.ru
bPerm State Pharmaceutical Academy, Perm, Russia
Received May 29, 2012
Abstract—The recyclization of 5-aryl-3-arylimino-3H-furan-2-ones under the action of esters, nitriles, and amides
of cycnoacetic acids resulted in the corresponding esters, nitriles, and amides of (5E)-2-amino-1-aryl-4-oxo-5-(2-
oxoethylidene)-1H-4,5-dihydropyrrole-3-carboxylic acids.
DOI: 10.1134/S1070428013020115
The structure of 3-imino-3H-furan-2-one underlies
their rich synthetic opportunities. The presence of several
electron-deficient sites in the molecule of furan-2-ones
makes it possible to change the direction of the nucleo-
phile’s attack by varying the substituents in the hetero-
cycle and the imino function thus altering the structure
of the final reaction products. By now a wide range of
OH-, SH-, NH-nucleophiles has been tested in the reac-
tions with 3-imino-3H-furan-2-ones [2–7]. Wide synthetic
opportunities are contained in the recyclization reactions
of 3-imino-3H-furan-2-ones which are available and
convenient objects for building up versatile acyclic and
heterocyclic structures. The transformations of 3-imino-
3H-furan-2-ones in the reactions with CH-nucleophiles
were not yet investigated. According to published data
the cyanoacetic acid derivatives as the example of the
CH-nucleophile were examined in reactions with diverse
four- [8, 9], five- [10–15], and six-membered [16, 17]
oxoheterocycles leading as a rule to the formation of recy-
clization products belonging to new heterocyclic systems.
We formerly demonstrated by two examples the synthetic
opportunities of 3-(4-bromophenylimino)-5-phenyl-3H-
furan-2-one in the reactions with malonodinitrile and
ethyl cyanoacetate resulting in the ester and the nitrile
of (5E)-2-amino-1-(4-bromo-phenyl)-4-oxo-5-(2-oxo-2-
phenylethylidene)-1H-4,5-dihydropyrrole-3-carboxylic
acid [18].
In order to test the opportunities of this method and to
increase the diversity of the substituted (5E)-2-amino-1-
aryl-4-oxo-5-(2-oxoethylidene)-1H-4,5-dihydropyrrole-
3-carboxylic acids we primarily synthesized by the known
methods from 4-aryl-2-hydroxy-4-oxobut-2-enoic acids
Ia–Ig and arylamines IIa–IIl 4-aryl-2-arylamino-4-
oxobut-2-enoic acids IIIa–IIIz2, that treated with acetic
anhydride underwent cyclization forming the corre-
sponding 5-aryl-3-arylimino-3H-furan-2-ones IVa– IVz2
(Scheme 1) [1, 19].
5-Aryl-3-arylimino-3H-furan-2-ones IVa, IVh,
IVl, IVm, IVo, IVr reacted with malonodinitrile in the
presence of triethylamine in dioxane to form nitriles
of 2-amino-5-(2-aryl-2-oxoethylidene)-4-oxo-1H-4,5-
dihydropyrrole-3-carboxylic acids Va–Vg (Scheme 2).
Aminopyrroles Va–Vf are colorless crystalline sub-
stances. Their IR spectra contain absorption bands of NH
group in the region 3418–3082 cm–1, of nitrile group at
2212–2207 cm–1, and of carbonyl groups in the region
1691–1639 cm–1. In the 1H NMR spectra the following
signals were observed: a singlet of the proton of the
NH group in the region 9.13–8.16 ppm, a multiplet of
the aromatic protons at 7.60 ppm, and a singlet of vinyl
proton at 5.74–5.57 ppm.
5-Aryl-3-arylimino-3H-furan-2-ones IVf, IVh reacted
with cyanoacetamide in the presence of triethylamine in
dioxane giving 2-amino-5-(2-aryl-2-oxoethylidene)-4-
––––––––––––––––
*For Communicacion VII, see [1].
243

KHARITONOVA et al.
244
Scheme 1.
Ar2
H
N Ar2
O
H
O
O
O
N
Ac2O
Ar2NH2
OH
+
OH
Ar1
Ar1
_H2O
Ar1
2AcOH
O
Iа_Ig
IIа_IIl
IVа_IVz2
O
O
IIIа_IIIz1
I, Ar1 = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-ClC6H4 (d), 4-FC6H4 (e), 2,4-Me2C6H3 (f), 1-naphthyl (g); II, Ar2 =
Ph(a), 4-FC6H4 (b), 2-ClC6H4 (c), 3-ClC6H4 (d), 4-ClC6H4 (e), 4-BrC6H4 (f), 2-IC6H4 (g), 3-NO2C6H4 (h) 4-NO2C6H4 (i),
3-CF3C6H4 (j), 2-Me-5-NO2C6H3 (k), 4-EtOOCC6H4 (l). III, IV,Ar1 = Ph,Ar2 = Ph (a), 4-FC6H4 (b), 2-ClC6H4 (c), 3-ClC6H4
(d), 4-ClC6H4 (e), 4-BrC6H4 (f), 2-IC6H4 (g), 4-NO2C6H4 (h), 3-CF3C6H4 (i), 2-Me-5-NO2C6H3 (j); Ar1 = 4-MeC6H4, Ar2 =
4-FC6H4 (k), 2-ClC6H4 (l), 3-ClC6H4 (m), 4-ClC6H4 (n), 4-BrC6H4 (o), 4-EtOOCC6H4 (p), 4-MeC6H4 (q), 3-NO2C6H4 (r),
4-NO2C6H4 (s), 2-Me-5-NO2C6H3 (t);Ar1 = 4-MeOC6H4,Ar2 = 4-EtOOCC6H4 (u), 2-Me-5-NO2C6H3 (v); Ar1 = 4-EtOC6H4,
2-Me-5-NO2C6H3 (w); Ar1 = 4-ClC6H4, Ar2 = 4-ClC6H4 (x), 2-Me-5-NO2C6H3 (y); Ar1 = 4-FC6H4, Ar2 = 2-Me-5-NO2C6H3
(z); Ar1 = 2,4-Me2C6H3, Ar2 = 2-Me-5-NO2C6H3 (z1); Ar1 = 1-naphthyl, Ar2 = 2-Me-5-NO2C6H3 (z2).
oxo-1H-4,5-dihydropyrrole-3-carboxamides VIa, VIb
(Scheme 3).
IVz2 reacted with ethyl cyanoacetate in the presence of
triethylamine in dioxane to form ethyl 2-amino-5-(2-
aryl-2-oxoethylidene)-4-oxo-1H-4,5-dihydropyrrole-3-
carboxylates VIIa–VIIz1 (Scheme 4).
Aminopyrroles VIa, VIb are colorless crystalline
substances. Their IR spectra contain absorption bands of
NH group in the region 3466–3306 cm–1 and of carbonyl
Aminopyrroles VIIa–VIIz1 are colorless crystalline
substances. Their IR spectra contain absorption bands of
NH group (3439–3302 cm–1), of ester group (1713–1686
cm–1) and of carbonyl groups (1649–1603 cm–1). In the
1H NMR spectra the following signals were observed:
singlets of the proton of the NH group (8.34–7.65 ppm),
multiplets of the aromatic protons (7.60 ppm), singlet
of vinyl proton (5.72–5.42 ppm), quartet of methylene
1
groups in the region 1669–1616 cm–1. In the H NMR
spectra the following signals were observed: singlets of
the proton of the NH group in the region 8.68–8.17 ppm,
multiplets of the aromatic protons at 7.60 ppm, singlets of
the amide group protons at 7.15–6.88 ppm and of vinyl
protons at 5.83–5.71 ppm.
5-Aryl-3-arylimino-3H-furan-2-ones IVa–IVq, IVs–
Scheme 2.
Scheme 4.
N Ar2
CN
CN
N Ar2
NC
H2N
O
EtOOC
H2N
O
O
,
Et3N
,
Et3N
O
CN
Ar1
COOEt
Ar1
Ar1
O
Ar1
IVа_IVr, IVt_IVz2
O
O
N
Ar2
O
N
Ar2
IVа, IVh, IVl, IVm, IVn, IVs
Vа_Vf
VIIа_VIIz1
V, Ar1 = Ph, Ar2 = Ph (a), 4-NO2C6H4 (b); Ar1 =
4-MeC6H4, Ar2 = 2-ClC6H4 (c), 3-ClC6H4 (d), 4-BrC6H4
(e), 3-NO2C6H4 (f).
VII, Ar1 = Ph, Ar2 = Ph (a), 4-FC6H4 (b), 2-ClC6H4 (c),
3-ClC6H4 (d), 4-ClC6H4 (e), 4-BrC6H4 (f), 2-IC6H4 (g),
4-NO2C6H4 (h), 3-CF3C6H4 (i), 2-Me-5-NO2C6H3 (j);Ar1
= 4-MeC6H4,Ar2 = 4-FC6H4 (k), 2-ClC6H4 (l), 3-ClC6H4
(m), 4-ClC6H4 (n), 4-BrC6H4 (o), 4-EtOOCC6H4 (p),
4-MeC6H4 (q), 3-NO2C6H4 (r), 2-Me-5-NO2C6H3 (s);
Ar1 = 4-MeOC6H4, Ar2 = 4-EtOOCC6H4 (t), 2-Me-5-
NO2C6H3 (u); Ar1 =4-EtOC6H4, 2-Me-5-NO2C6H3 (v);
Ar1 = 4-ClC6H4, Ar2 = 4-ClC6H4 (w), 2-Me-5-NO2C6H3
(x);Ar1 = 4-FC6H4,Ar2 = 2-Me-5-NO2C6H3 (y);Ar1=2,4-
Me2C6H3, Ar2 = 2-Me-5-NO2C6H3 (z);Ar1 = 1-naphthyl,
Ar2 = 2-Me-5-NO2C6H3 (z1).
Scheme 3.
N Ar2
O
H2NOC
H2N
O
CN
CONH2
O
Et N
,
3
Ar1
Ar1
O
N
Ar2
IVf, IVh
VIа, VIb
VI, Ar1 = Ph, Ar2 = 4-BrC6H4 (a), 4-NO2C6H4 (b).
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CHEMISTRY OF IMINOFURAN: VIII.
245
1H NMR spectra were registered on spectrometers Varian
Mercury Plus-300 (300.05 MHz) and Tesla BS-567A(100
MHz), internal reference HMDS. Elemental analysis was
carried out on an analyzer Leco CHNS-932. The monitor-
ing of the reaction progress and checking the compounds
purity was performed by TLC on Silufol UV-254 plates,
eluent ethyl ether–benzene–acetone, 10 : 9 : 1, spots vi-
sualized in iodine vapor. Mass spectrum was registered
on an instrument MKh-1310, emission current 1000 mA,
ionizing electrons energy 70eV, vaporizer temperature
120°C, ion source temperature 200°C.
(4.13–4.07 ppm) and triplet of methyl (1.20–1.14 ppm)
protons of the ethyl carboxylate.
The formation of compounds V–VII (Scheme 5)
proceeds evidently through the primary nucleophilic at-
tack of the carbanion formed from the cyanoacetic acid
derivative under the action of triethylamine [20] on the C2
atom of the furan ring givng intermediate A [15]. Further
the charges in the molecule undergo a redistribution with
the cleavage of the O1–C2 bond and the formation of in-
termediate B with a negative charge on the O atom and
a delocalized double bond conjugated with the aromatic
ring. The negative charge is apparently delocalized along
all conjugation system O–C–C–C–N.
4-Aryl-2-arylamino-4-oxobut-2-enoic acids IIIa–
IIIz2 were obtained by procedure [21] from 0.01 mol of
4-aryl-2-hydroxy-4-oxobut-2-enoi acids Ia–Ig and 0.01
mol of substituted anilines IIa–IIl. Compounds IIIa, IIIe,
IIIn, IIIh) [19] and IIIf, IIIg, IIIi, IIIj, IIIp, IIIt, IIIu,
IIIv) [21] were described previously.
The atom N possessing excess electron density due
to the presence of an excessive negative charge in the
conjugation system attacks the electro-deficient C atom
of the nitrile group with the formation of intermediate
C. In the next stage apparently a proton goes from the
triethylammonium to intermediate C giving intermediate
D suffering subsequently an imino-eHimine tautomeric
transformation into compounds V–VII due to the forma-
tion of a more stable conjugated system.
4-Oxo-4-phenyl-2-(4-fluorophenylamino)but-2-
enoic acid (IIIb). Yield 1.92 g (67%), yellow crystals,
t.decomp. 189–190°C (acetonitrile). IR spectrum, ν,
1
cm–1: 3256 (NH), 1730 (COOH). H NMR spectrum
(DMSO-d6), δ, ppm: 6.46 s (1H, CH), 7.60 m (9H, Ar),
11.96 s (1H, NH). Found, %: C 67.39; H 4.25; N 4.91.
C16H12FNO3. Calculated, %: C 67.36; H 4.24; N 4.93.
EXPERIMENTAL
4-Oxo-4-phenyl-2-(2-chlorophenylamino)but-
2-enoic acid (IIIc). Yield 2.35 g (78%), yellow crys-
tals, t.decomp. 161–162°C (ethanol). IR spectrum, ν,
IR spectra were recorded on spectrophotometers
FSM-1201 and Specord M-80 from mulls in mineral oil,
Scheme 5.
N Ar2
N Ar2
O
N Ar2
O
RCH2C N + Et3N
d+
O
Ar1
Ar1
N
C
Ar1
O
O
C N
CH
R
C N
O
CH
R
Et3N + H
HC
IV
R
A
N Ar2
O
N Ar2
O
HC
O
Ar1
R
O
Ar1
Ar1
O
N
C N
C N
O
C N
CH
CH
Ar2
R
R
B
R
O
O
O
O
Ar1
R
N
Ar1
R
Et3N + H
Et3N
Ar1
H2N
N
Ar2
NH
C
O
N
C
O
N
Ar2
Ar2
V_VII
C
D
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KHARITONOVA et al.
246
cm–1: 3230 (NH), 1590 sh (COOH, C4=O, C=C, C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 6.63 s (1H, CH),
7.60 m (9H, Ar), 12.17 s (1H, NH). Found, %: C 63.65;
H 4.03; Cl 11.72; N 4.63. C16H12ClNO3. Calculated, %:
C 63.68; H 4.02; Cl 11.78; N 4.62.
4-oxobut-2-enoic acid (IIIr). Yield 2.48 g (76%),
t.decomp. 181–182°C (ethanol). IR spectrum, ν, cm–1:
3217 (NH), 1686, 1678, 1608 (C4=O, C=C, C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.38 s (3H, Me),
6.61 s (1H, CH), 7.6 m (8H,Ar), 11.65 s (1H, NH). Found,
%: C 62.55; H 4.30; N 8.61. C17H14N2O5. Calculated, %:
C 62.57; H 4.32; N 8.59.
4-Oxo-4-phenyl-2-(3-chlorophenylamino)but-2-
enoic acid (IIId). Yield 2.77 g (92%), yellow crystals,
t.decomp. 174–175°C (acetonitrile). IR spectrum, ν, cm-
1: 3225 (NH), 1603, 1557 (C4=O, C=C, C=N). 1H NMR
spectrum (DMSO-d6), δ, ppm: 6.50 s (1H, CH), 7.50 m
(9H, Ar), 11.75 s (1H, NH). Found, %: C 63.68; H 4.02;
Cl 11.78; N 4.62. C16H12ClNO3. Calculated, %: C 63.69;
H 4.01; Cl 11.75; N 4.64.
4-(4-Methylphenyl)-2-(4-nitrophenylamino)-
4-oxobut-2-enoic acid (IIIs). Yield 2.81 g (86%),
t.decomp. 144–145°C (ethanol). IR spectrum, ν, cm–1:
3219 (NH), 1755 (COOH), 1651, 1589 (C4=O, C=C,
C=N). 1H NMR spectrum, δ, ppm: 2.44 s (3H, Me), 6.79 s
(1H, CH), 7.60 m (8H, Ar), 11.58 s (1H, NH). Found, %:
C 62.59; H 4.30; N 8.55. C17H14N2O5. Calculated, %:
C 62.57; H 4.32; N 8.59.
4-(4-Methylphenyl)-4-oxo-2-(4-fluorophenylami-
no)but-2-enoic acid (IIIk). Yield 2 g (69%), yellow
crystals, t.decomp. 158–159°C (ethanol). IR spectrum,
ν, cm–1: 3199 (NH), 1655, 1607 (C4=O, C=C, C=N).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.37 s (3H, Me),
6.38 s (1H, CH), 7.60 m (8H,Ar), 11.9 s (1H, NH). Found,
%: C 68.22; H 4.71; N 4.68. C17H14FNO3.Calculated, %:
C 68.20; H 4.70; N 5.00.
2-(2-Methyl-5-nitrophenylamino)-4-(4-methoxy-
phenyl)-4-oxobut-2-enoic acid (IIIv). Yield 2.71 g
(76%), t.decomp. 168–169°C (dioxane). IR spectrum, ν,
cm–1: 3210 br. (NH), 1728 (COOH) 1630, 1604, 1580
(C4=O, C=C, C=N). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.46 s (3H, Me), 3.82 s (3H, MeO), 6.52 s (1H, CH),
7.50 m (7H, Ar), 11.84 s (1H, NH). Found, %: C 60.59;
H 4.48; N 7.91. C18H16N2O6. Calculated, %: C 60.67;
H 4.53; N 7.86.
4-(4-Methylphenyl)-4-oxo-2-(2-chlorophenylami-
no)but-2-enoic acid (IIIl). Yield 2.7 g (85%), yellow
crystals, t.decomp. 161–162°C (aceto-nitrile). IR spec-
trum, ν, cm–1: 3230 (NH), 1605 sh (COOH, C4=O, C=C,
2-(2-Methyl-5-nitrophenylamino)-4-oxo-4-(4-
ethoxyphenyl)but-2-enoic acid (IIIw). Yield 2.99 g
(81%), t.decomp. 175–176°C (dioxane). IR spectrum, ν,
cm–1: 3244 (NH), 1708, 1648, 1582 (COO, C4=O, C=C,
C=N). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.38 t (3H,
Me), 2.45 s (3H, Me), 4.08 q (2H, CH2), 6.57 s (1H, CH),
7.55 m (7H, Ar), 11.83 s (1H, NH). Found, %: C 61.58;
H 4.84; N 7.59. C19H18N2O6. Calculated, %: C 61.62;
H 4.90; N 7.56.
1
C=N). H NMR spectrum (DMSO-d6), δ, ppm: 2.38 s
(3H, Me), 6.58 s (1H, CH), 7.40 m (8H, Ar), 12.09 s
(1H, NH). Found, %: C 64.65; H 4.48; Cl 11.20; N 4.43.
C17H14ClNO3. Calculated, %: C 64.68; H 4.49; Cl 11.22;
N 4.42.
4-(4-Methylphenyl)-4-oxo-2-(3-chlorophenylami-
no)but-2-enoic acid (IIIm). Yield 2.7 g (85%), t.decomp.
160–161°C (acetonitrile). IR spectrum, ν, cm–1: 3202
1
(NH), 1597, 1554, 1522 (C4=O, C=C, C=N). H NMR
4-Oxo-4-(4-chlorophenyl)-2-(4-chlorophenyl-
amino)-but-2-enoic acid (IIIx). Yield 2.92 g (87%),
t.decomp. 198–199°C (ethanol). IR spectrum, ν, cm–1:
spectrum (DMSO-d6), δ, ppm: 2.37 s (3H, Me), 6.48 s
(1H, CH), 7.40 m (8H, Ar), 11.73 s (1H, NH). Found,
%: C 64.67; H 4.47; Cl 11.23; N 4.44. C17H14ClNO3.
Calculated, %: C 64.67; H 4.47; Cl 11.23; N 4.44.
1
3228 (NH), 1647, 1598 (C4=O, C=C, C=N). H NMR
spectrum (DMSO-d6), δ, ppm: 6.71 s (1H, CH), 7.5 m
(8H, Ar), 11.45 s (1H, NH). Found, %: C 57.08; H 3.27;
Cl 21.13; N 4.21. C16H11Cl2NO3. Calculated, %: C 57.17;
H 3.30; Cl 21.09; N 4.17.
4-(4-Methylphenyl)-2-(4-methylphenylamino)-
4-oxobut-2-enoic acid (IIIq). Yield 2.30 g (78%),
t.decomp. 154–155°C (benzene). IR spectrum, ν, cm–1:
3229 (NH), 1734 (COOH), 1640, 1600, 1577 (C4=O,
2-(2-Methyl-5-nitrophenylamino)-4-oxo-4-(4-
chlorophenyl)but-2-enoic acid (IIIy). Yield 2.02 g
(56%), t.decomp. 174–175°C (dioxane). IR spectrum, ν,
cm–1: 3212 (NH), 1670, 1652, 1578 (COOH, C4=O, C=C,
C=N). 1H NMR spectrum, δ, ppm: 2.34 s (3H, Me), 6.49 s
(1H, CH), 7.60 m (7H, Ar), 11.87 s (1H, NH). Found, %:
C 56.64; H 3.57; Cl 9.87; N 7.69. C17H13ClN2O5. Calcu-
1
C=C, C=N). H NMR spectrum (DMSO-d6), δ, ppm:
2.29 s (3H, Me), 2.43 c (3H, Me), 6.48 c (1H, CH),
7.30 m (8H, Ar), 12.09 c (1H, NH). Found, %: C 73.23;
H 5.79; N 4.74. C18H17NO3. Calculated, %: C 73.20;
H 5.80; N 4.74.
4-(4-Methylphenyl)-2-(3-nitrophenylamino)-
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CHEMISTRY OF IMINOFURAN: VIII.
247
1
(C=Olactone). H NMR spectrum (DMSO-d6), δ, ppm:
7.06 s (1H, CH), 7.60 m (9H, Ar). Found, %: C 67.79;
H 3.57; Cl 12.47; N 4.96. C16H10ClNO2. Calculated, %:
C 67.74; H 3.55; Cl 12.50; N 4.94.
lated, %: C 56.60; H 3.63; Cl 9.83; N 7.76.
2-(2-Methyl-5-nitrophenylamino)-4-oxo-4-(4-
fluorophenyl)but-2-enoic acid (IIIz). Yield 2.17 g
(63%), t.decomp. 169–170°C (dioxane). IR spectrum, ν,
cm–1: 3150 br. (NH), 1744 (COOH), 1625, 1608, 1592
(C4=O, C=C, C=N). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.47 c (3H, Me), 6.60 s (1H, CH), 7.50 m (7H, Ar),
11.84 c (1H, NH). Found, %: C 59.38; H 3.76; N 8.10.
C17H13FN2O5. Calculated, %: C 59.31; H 3.81; N 8.14.
5-(4-Methylphenyl)-3-(4-fluorophenylimino)-3H-
furan-2-one (IVk). Yield 2.1 g (77%), orange crystals,
t.decomp. 179–180°C (toluene). IR spectrum, ν, cm–1:
1
1801 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
ppm: 2.39 s (3H, Me), 7.08 s (1H, CH), 7.60 m (8H,
Ar). Found, %: C 72.57; H 4.32; N 4.97. C17H12FNO2.
Calculated, %: C 72.59; H 4.30; N 4.98.
4-(2,4-Dimethylphenyl)-2-(2-methyl-5-
nitrophenylamino)-4-oxobut-2-enoic acid (IIIz1).
Yield 2.66 g (75%), t.decomp. 171–172°C (dioxane). IR
spectrum, ν, cm–1: 3150 br. (NH), 1734 (COOH), 1686,
5-(4-Methylphenyl)-3-(2-chlorophenylimino)-3H-
furan-2-one (IVl). Yield 2.14 g (72%), orange crystals,
t.decomp. 157–158°C (toluene). IR spectrum, ν, cm–1:
1
1668, 1616 (C4=O, C=C, C=N). H NMR spectrum, δ,
1
1801 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
ppm: 2.31 s (3H, Me), 2.42 s (3H, Me), 2.46 s (3H, Me),
6.18 s (1H, CH), 7.5 m (6H,Ar), 11.61 s (1H, NH). Found,
%: C 64.44; H 5.09; N 7.88. C19H18N2O5. Calculated, %:
C64.40; H 5.12; N 7.90.
ppm: 2.36 s (3H, Me), 7.05 s (1H, CH), 7.50 m (8H, Ar).
Found, %: C 68.57; H 4.07; Cl 11.95; N 4.68. C17H12Cl-
NO2. Calculated, %: C 68.58; H 4.06; Cl 11.91; N 4.70.
5-(4-Methylphenyl)-3-(3-chlorophenylimino)-3H-
furan-2-one (IVm). Yield 2.32 g (78%), orange crystals,
t.decomp. 154–156°C (toluene). IR spectrum, ν, cm–1:
2-(2-Methyl-5-nitrophenylamino)-1-naphthyl-
4-oxobut-2-enoic acid (IIIz2). Yield 2.44 g (65%),
t.decomp. 179–180°C (dioxane). IR spectrum, ν, cm–1:
3215 br. (NH), 1732 (COOH), 1612 уш (C4=O, C=C,
C=N). 1H NMR spectrum, δ, ppm: 2.52 s (3H, Me), 6.28 s
(1H, CH), 7.90 m (10H, Ar), 11.82 c (1H, NH). Found,
%: C 67.08; H 4.32; N 7.48. C21H16N2O5. Calculated, %:
C 67.02; H 4.28; N 7.44.
1
1801 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
ppm: 2.39 s (3H, Me), 6.99 s (1H, CH), 7.50 m (8H, Ar).
Found, %: C 68.56; H 4.03; Cl 11.95; N 4.68. C17H12Cl-
NO2. Calculated, %: C 68.58; H 4.06; Cl 11.91; N 4.70.
5-(4-Methylphenyl)-3-(4-methylphenylimino)-3H-
furan-2-one (IVq). Yield 2.02 g (73%), orange crystals,
t.decomp. 165–167°C (toluene). IR spectrum, ν, cm–1:
5-Aryl-3-arylimino-3H-furan-2-ones IVb–IVz2
were prepared by procedure [1] from 0.01 mol of 4-aryl-
2-hydroxy-4-oxobut-2-enoic acids IIIa– IIIz2 and acetic
anhydride. Compounds IVg, IVi, IVj, IVo, IVp, IVt,
IVu) [1], (IIIn) [19] were described before.
1
1796 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
ppm: 2.26 s (3H, Me), 2.39 s (3H, Me), 7.04 s (1H, CH),
7.40 m (8H, Ar). Found, %: C 77.98; H 5.46; N 5.03.
C18H15NO2. Calculated, %: C 77.96; H 5.45; N 5.05.
5-Phenyl-3-(4-fluorophenylimino)-3H-furan-2-one
(IVb). Yield 2.11 g (79%), orange crystals, t.decomp.
169–171°C (toluene). IR spectrum, ν, cm–1: 1801
5-(4-Methylphenyl)-3-(3-nitrophenylimino)-3H-
furan-2-one (IVr). Yield 2.2 g (73%), orange crystals,
t.decomp. 198–199°C (toluene). IR spectrum, ν, cm–1:
1811 (C=Olactone). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.39 s (3H, Me), 7.03 s (1H, CH), 7.60 m (8H,Ar). Found,
%: C 66.20; H 3.95; N 9.06. C17H12N2O4.Calculated, %:
C 66.23; H 3.92; N 9.09.
1
(C=Olactone). H NMR spectrum (DMSO-d6), δ, ppm:
7.14 s (1H, CH), 7.60 m (9H, Ar). Found, %: C 71.87;
H 3.74; N 5.26. C16H10FNO2. Calculated, %: C 71.91;
H 3.77; N 5.24.
5-Phenyl-3-(2-chlorophenylimino)-3H-furan-2-one
(IVc). Yield 1.96 g (69%), orange crystals, t.decomp.
103–105°C (toluene). IR spectrum, ν, cm–1: 1809
5-(4-Methylphenyl)-3-(4-nitrophenylimino)-3H-
furan-2-one (IVs). Yield 2.62 s (85%), orange crystals,
t.decomp. 178–179°C (toluene). IR spectrum, ν, cm–1:
1
(C=Olactone). H NMR spectrum (DMSO-d6), δ, ppm:
1
1801 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
7.07 s (1H, CH), 7.60 m (9H, Ar). Found, %: C 67.76;
H 3.53; Cl 12.51; N 4.93. C16H10ClNO2. Calculated, %:
C 67.74; H 3.55; Cl 12.50; N 4.94.
ppm: 2.36 s (3H, Me), 7.06 s (1H, CH), 7.60 m (8H,
Ar). Found, %: C 66.22; H 3.91; N 9.08. C17H12N2O4.
Calculated, %: C 66.23; H 3.92; N 9.09.
5-Phenyl-3-(3-chlorophenylimino)-3H-furan-2-one
(IVd). Yield 2.12 g (75%), orange crystals, t.decomp.
133–134°C (toluene). IR spectrum, ν, cm–1: 1803
3-(2-Methyl-5-nitrophenylimino)-5-(4-
methoxyphenyl)-3H-furan-2-one (IVv). Yield 1.76 g
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KHARITONOVA et al.
248
(52%), orange crystals, t.decomp. 154–156°C (toluene).
IR spectrum, ν, cm–1: 1808 (C=Olactone). 1H NMR spec-
trum (CDCl3), δ, ppm: 2.35 s (3H, Me), 3.85 s (3H, MeO),
6.20 s (1H, CH), 7.50 m (7H, Ar). Found, %: C 63.78;
H 4.22; N 8.24. C18H14N2O5. Calculated, %: C 63.90;
H 4.17; N 8.28.
δ, ppm: 2.35 s (3H, Me), 6.72 s (1H, CH), 7.80 m (10H,
Ar). Found, %: C 70.42; H 3.91; N 7.85. C21H14N2O4.
Calculated, %: C 70.39; H 3.94; N 7.82.
(5E)-2-Amino-1-aryl-5-(2-arylethylidene-2-oxo)-
4-oxo-1H-4,5-dihydropyrrole-3-carbonitriles Va–Vf.
A solution of 0.01 mol of an appropriate furanone IV
and 0.66 g (0.01 mol)of malonodinitrile in 30 ml of an-
hydrous dioxane was heated at 70°C, 1 g (0.01 mol) of
triethylamine was added, and the mixture was cooled. The
separated precipitate was filtered off and recrystallized
from acetonitrile.
3-(2-Methyl-5-nitrophenylimino)-5-(4-ethoxy-
phenyl)-3H-furan-2-one (IVw). Yield 1.72 g (49%),
orange crystals, t.decomp. 164–165°C (toluene). IR
spectrum, ν, cm–1: 1816 (C=Olactone). 1H NMR spectrum
(CDCl3), δ, ppm: 1.36 t (3H, Me), 2.28 s (3H, Me), 4.08 q
(2H, Me), 6.73 s (1H, CH), 7.50 m (7H, Ar). Found, %:
C 64.73; H 4.59; N 7.91. C19H16N2O5. Calculated, %:
C 64.77; H 4.58; N 7.97.
(5E)-2-Amino-4-oxo-5-(2-oxo-2-phenyl-ethylid-
ene)-1-phenyl-1H-4,5-dihydropyrrole-3-carbonitrile
(Va). Yield 1.98 g (65%), colorless crystals, mp 240–
241°C (acetonitrile). IR spectrum, ν, cm–1: 3356, 3266
5-(4-Chlorophenyl)-3-(4-chlorophenylimino)-3H-
furan-2-one (IVx). Yield 2.14 g (78%), orange crystals,
t.decomp. 234–235°C (toluene). IR spectrum, ν, cm–1:
1
(NH), 2207 (C≡N), 1660 (C=O). H NMR spectrum
(DMSO-d6), δ, ppm: 5.51 s (1H, CH), 7.60 m (9H, Ar),
8.53 br.s (2H, NH). Found, %: C 63.33; H 3.36; N 15.55.
C19H13N3O2. Calculated, %: C 72.37; H 4.16; N 13.33.
1
1803 (C=Olactone). H NMR spectrum (DMSO-d6), δ,
ppm: 6.97 s (1H, CH), 7.30 m (8H, Ar). Found, %: C
60.44; H 2.86; Cl 22.27; N 4.43. C16H9Cl2NO2. Calcu-
lated, %: C 60.40; H 2.85; Cl 22.29; N 4.40.
(5E)-2-Amino-1-(4-nitrophenyl)-4-oxo-5-(2-oxo-
2-phenylethylidene)-1H-4,5-dihydropyrrole-3-carbo-
nitrile (Vb). Yield 2.29 g (75%), colorless crystals, mp
241–242°C (acetonitrile). IR spectrum, ν, cm–1: 3367,
3-(2-Methyl-5-nitrophenylimino)-5-(4-chloro-
phenyl)-3H-furan-2-one (IVy). Yield 1.44 g (42%),
orange crystals, t.decomp. 220–221°C (toluene). IR
spectrum, ν, cm–1: 1820 (C=Olactone). 1H NMR spectrum
(CDCl3), δ, ppm: 2.36 s (3H, Me), 6.34 s (1H, CH),
7.70 m (7H, Ar). Found, %: C 59.61; H 3.26; Cl 10.29;
N 8.13. C17H11ClN2O4. Calculated, %: C 59.58; H 3.23;
Cl 10.34; N 8.17.
1
3268 (NH), 2207 (C≡N), 1686, 1658 (C=O). H NMR
spectrum (DMSO-d6), δ, ppm: 5.74 s (1H, CH), 7.60 m
(9H, Ar), 8.32 s (1H, NH) 9.13 C (1H, NH). Found, %:
C 63.30; H 3.39; N 15.54. C19H12N4O4. Calculated, %:
C 63.33; H 3.36; N 15.55.
(5E)-2-Amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-4-oxo-1-(2-chlorophenyl)-1H-4,5-
dihydropyrrole-3-carbonitrile (Vc). Yield 3.16 g
(87%), colorless crystals, mp 226–227°C (ethanol). IR
spectrum, ν, cm–1: 3379, 3164 (NH), 2207 (C≡N), 1657
3-(2-Methyl-5-nitrophenylimino)-5-(4-fluorop-
henyl)-3H-furan-2-one (IVz). Yield 1.56 g (48%),
orange crystals, t.decomp. 194–195°C (toluene). IR
spectrum, ν, cm–1: 1816 (C=Olactone). 1H NMR spectrum
(CDCl3), δ, ppm: 2.30 s (3H, Me), 6.50 s (1H, CH),
7.50 m (7H, Ar). Found, %: C 62.62; H 3.36; N 8.53.
C17H11FN2O4. Calculated, %: C 62.58; H 3.39; N 8.58.
1
(C=O). H NMR spectrum (DMSO-d6), δ, ppm: 2.34 s
(3H, Me), 5.62 s (1H, CH), 7.60 m (8H, Ar), 8.21 s (1H,
NH) 8.92 s (1H, NH). Found, %: C 66.01; H 3.87; Cl
9.59; N 11.56. C20H14ClN3O2. Calculated, %: C 66.03;
H 3.88; Cl 9.57; N 11.55.
5-(2,4-Dimethylphenyl)-3-(2-methyl-5-
nitrophenylimino)-3H-furan-2-one (IVz1). Yield 2.49 g
(74%), orange crystals, t.decomp. 171–172°C (toluene).
IR spectrum, ν, cm–1: 1808 (C=Olactone). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 2.35 s (3H, Me), 2.37 s (3H,
Me), 2.44 s (3H, Me), 6.15 s (1H, CH), 7.50 m (6H, Ar).
Found, %: C 67.81; H 4.76; N 8.35. C19H16N2O4. Calcu-
lated, %: C 67.85; H 4.79; N 8.32.
(5E)-2-Amino-5-[2-(4-methylphenyl)-2-oxo-
ethylidene]-4-oxo-1-(3-chlorophenyl)-1H-4,5-dihy-
dropyrrole-3-carbonitrile (Vd). Yield 2.98 g (83%),
colorless crystals, mp 210–211°C (ethanol). IR spectrum,
ν, cm–1: 3452, 3278 (NH), 2202 (C≡N), 1691, 1639
1
(C=O). H NMR spectrum (DMSO-d6), δ, ppm: 2.36 s
3-(2-Methyl-5-nitrophenylimino)-5-(2-naphthyl)-
3H-furan-2-one (IV z2). Yield 1.15 g (32%), orange
crystals, t.decomp. 161–162°C (toluene). IR spectrum, ν,
cm–1: 1808 (C=Olactone). 1H NMR spectrum (DMSO-d6),
(3H, Me), 5.58 s (1H, CH), 7.60 m (8H, Ar), 8.22 s (1H,
NH) 9.04 s (1H, NH). Found, %: C 66.01; H 3.87; Cl 9.59;
N 11.56. C20H14ClN3O2.Calculated, %: C 66.03; H 3.88;
Cl 9.57; N 11.55.
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CHEMISTRY OF IMINOFURAN: VIII.
249
(5E)-2-Amino-1-(4-bromophenyl)-5-[2-(4-
methylphenyl)-2-oxoethylidene]-4-oxo-1H-4,5-dihy-
dropyrrole-3-carbonitrile (Ve). Yield 3.6 g (89%) color-
less crystals, mp 278–279°C (dioxane). IR spectrum, ν,
cm–1: 3380, 3260 (NH), 2208 (C≡N), 16866, 1659 (C=O,
VIIz1. A solution of 0.01 mol of an appropriate furanone
IV and 1.13 g (0.01 mol) of ethyl cyanoacetate in 30 ml of
anhydrous dioxane was heated at 70°C, 1 g (0.01 mol) of
triethylamine was added, and the mixture was cooled. The
separated precipitate was filtered off and recrystallized.
1
C=C). H NMR spectrum (DMSO-d6), δ, ppm: 2.35 s
Ethyl (5E)-2-amino-1-phenyl-4-oxo-5-(2-oxo-2-
phenylethylidene)-1H-4,5-dihydropyrrole-3-carbox-
ylate (VIIa). Yield 2.64 g (73%), colorless crystals, mp
246–248°C (dioxane). IR spectrum, ν, cm–1: 3423, 3225
(NH), 1714 (COOEt), 1646, 1601 (C=C, C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.13 t (3H, CMe), 4.03 q
(2H, CH2), 5.57 s (1H, CH), 7.65 m (10H,Ar), 8.12 s (1H,
NH), 8.35 s (1H, NH). Found, %: C 69.61; H 5.01; N 7.70.
C21H18N2O4. Calculated, %: C 69.60; H 5.01; N 7.73.
(3H, Me), 5.58 s (1H, CH), 7.60 m (8H, Ar), 8.17 s (1H,
NH), 9.03 s (1H, NH). Found, %: C 58.83; H 3.42; Br
19.54; N 10.31. C20H14BrN3O2. Calculated, %: C 58.84;
H 3.46; Br 19.57; N 10.29.
(5E)-2-Amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-1-(3-nitrophenyl)-4-oxo-1H-4,5-dihy-
dropyrrole-3-carbonitrile (Vf). Yield 2.73 g (74%) col-
orless crystals, mp 207–208°C (ethanol). IR spectrum, ν,
cm–1: 3418, 3082 (NH), 2212 (C≡N), 1666, 1639 (C=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.36 s (3H,
Me), 5.69 s (1H, CH), 7.70 m (8H, Ar), 8.25 s (1H, NH),
9.08 s (1H, NH). Found, %: C 64.15; H 3.79; N 14.96.
C20H14N4O4. Calculated, %: C 64.17; H 3.77; N 14.97.
Ethyl (5E)-2-amino-4-oxo-5-(2-oxo-2-phenyl-
ethylidene)-1-(4-fluorophenyl)-1H-4,5-dihydropyr-
role-3-carboxylate (VIIb). Yield 2.39 g (86%), colorless
crystals, mp 251–252°C (acetonitrile). IR spectrum, ν,
cm–1: 3433, 3234 (NH), 1711 (COOEt), 1643, 1603
1
(C=O). H NMR spectrum (DMSO-d6), δ, ppm: 1.14 t
(5E)-2-Amino-1-aryl-4-oxo-5-(2-oxo-2-
phenylethylidene)-1H-4,5-dihydropyrrole-3-carbox-
amides VIa, VIb.Asolution of 0.01 mol of an appropriate
furanone IV and 0.8 g (0.01 mol) of cyanoacetamide
in 30 ml of anhydrous dioxane was heated at 70°C, 1 g
(0.01 mol) of triethylamine was added, and the mixture
was cooled. The separated precipitate was filtered off and
recrystallized from acetonitrile.
(3H, CMe), 4.17 q (2H, CH2), 5.49 s (1H, CH), 7.65 m
(9H, Ar), 8.17 s (1H, NH), 8.30 s (1H, NH). Found, %:
C 66.34; H 4.52; N 7.38. C21H17FN2O4. Calculated, %:
C 66.31; H 4.50; N 7.36.
Ethyl (5E)-2-amino-4-oxo-5-(2-oxo-2-phenyl-
ethylidene)-1-(2-chlorophenyl)-1H-4,5-dihydropyr-
role-3-carboxylate (VIIc). Yield 3.09 g (78%), colorless
crystals, mp 239–240°C (dioxane). IR spectrum, ν, cm–1:
3380, 3109 (NH), 1712 (COOEt), 1658 (C=C, C=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.15 t (3H, CMe),
4.09 q (2H, CH2), 5.61 s (1H, CH), 7.65 m (9H,Ar), 8.02 s
(1H, NH), 8.19 s (1H, NH). Found, %: C 63.53; H 4.30;
Cl 8.97; N 7.09. C21H17ClN2O4. Calculated, %: C 63.56;
H 4.32; Cl 8.93; N 7.06.
(5E)-2-Amino-1-(4-bromophenyl)-4-oxo-5-(2-oxo-
2-phenylethylidene)-1H-4,5-dihydro-pyrrole-3-car-
boxamide (VIa). Yield 3.74 g (91%), colorless crystals,
mp 235–236°C. IR spectrum, ν, cm–1: 3402, 3306 (NH),
1
1674, 1655 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 5.71 s (1H, CH), 6.88 s (1H, CONH2), 7.13 s (1H,
CONH2), 7.60 m (9H, Ar), 8.35 s (1H, NH) 8.55 s (1H,
NH). Found, %: C 55.35; H 3.43; Br 19.39; N 10.18.
C19H14BrN3O3.Calculated, %: C 55.36; H 3.42; Br 19.38;
N 10.19.
Ethyl (5E)-2-amino-4-oxo-5-(2-oxo-2-phenyl-
ethylidene)-1-(3-chlorophenyl)-1H-4,5-dihydropyr-
role-3-carboxylate (VIId). Yield 2.33 g (59%), colorless
crystals, mp 220–221°C (toluene). IR spectrum, ν, cm–1:
3377, 2955 (NH), 1664 (COOEt), 1595 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.17 t (3H, CMe), 4.11 q
(2H, CH2), 5.56 s (1H, CH), 7.65 m (9H, Ar), 7.68 s
(1H, NH), 8.19 s (1H, NH). Found, %: C 63.54; H 4.35;
Cl 6.95; N 7.08. C21H17ClN2O4. Calculated, %: C 63.56;
H 4.32; Cl 8.93; N 7.06.
(5E)-2-Amino-1-(4-nitrophenyl)-4-oxo-5-(2-oxo-
2-phenylethylidene)-1H-4,5-dihydropyrrole-3-car-
boxamide (VIb). Yield 3.25 g (86%), colorless crystals,
mp 242–243°C. IR spectrum, ν, cm–1: 3466, 2954 (NH),
1
1686, 1658 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 5.83 s (1H, CH), 6.92 s (1H, CONH2), 7.15 s (1H,
CONH2), 7.60 m (9H, Ar), 8.43 s (1H, NH, 8.68 s (1H,
NH). Found, %: C 60.31; H 3.74; N 14.80. C19H14N4O5.
Calculated, %: C 60.32; H 3.73; N 14.81.
Ethyl (5E)-2-amino-4-oxo-5-(2-oxo-2-phenyl-
ethylidene)-1-(4-chlorophenyl)-1H-4,5-dihydropyr-
role-3-carboxylate (VIIe). Yield 2.61 g (66%), colorless
crystals, mp 264–265°C (acetonitrile). IR spectrum, ν,
Ethyl (5E)-2-amino-1-aryl-5-(2-aryl-2-oxoethylid-
ene)-1H-4,5-dihydropyrrole-3-carboxylates VIIa–
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KHARITONOVA et al.
250
cm–1: 3440, 3260 (NH), 1716 (COOEt), 1645, 1612
(C=O, C=C). H NMR spectrum (DMSO-d6), δ, ppm:
1.09 t (3H, CMe), 3.48 q (2H, CH2), 5.42 s (1H, CH),
7.50 m (9H,Ar), 8.02 br.s (2H, NH2). Found, %: C 63.53;
H 4.34; Cl 8.97; N 7.08. C21H17ClN2O4. Calculated, %:
C 63.56; H 4.32; Cl 8.93; N 7.06.
8.25 s (1H, NH), 8.42 s (1H, NH). Mass spectrum, m/z
(Irel, %): 430 (22) [M]+, 385 (9) [M – EtO]+, 357 (9.2)
[M – EtOCO]+, 290 (15.0) [M – EtOCO – CF3]+, 253
(3.0) [M – EtOCO –PhCO]+, 212 (29.0), [M – EtOCO –
CF3C6H4]+, 145 (11.0) [CF3C6H4]+, 105 (100) [PhCO]+,
77 (58) [Ph]+, 68 (19) [CF3]+. Found, %: C 61.43; H 3.96;
N 6.55. C22H17F3N2O4. Calculated, %: C 61.40; H 3.98;
N 6.51. M 430.38.
1
Ethyl (5E)-2-amino-1-(4-bromophenyl)-4-oxo-5-
(2-oxo-2-phenylethylidene)-1H-4,5-dihydropyrrole-
3-carboxylate (VIIf). Yield 3.79 g (86%), colorless
crystals, mp 264–266°C (acetonitrile). IR spectrum, ν,
cm–1: 3441, 3281 (NH), 1711 (COOEt), 1665, 1645
(C=O). 1H, NMR spectrum (DMSO-d6), δ, ppm: 1.14 t
(3H, CMe), 4.07 q (2H, CH2), 5.55 s (1H, CH), 7.60 m
(9H, Ar), 8.15 s (1H, NH), 8.30 s (1H, NH). 13C NMR
spectrum, δ, ppm: 14.52 (CH3), 58.36 (CH2), 85.88 (C3),
108.53 (=CH), 123.32 (C), 128.44 (CH), 128.50 (CH),
131.36 (CH), 132.05 (C), 132.98 (CH), 133.48 (CH),
137.23 (C), 141.79 (C2), 164.48 (C5), 166.08 (CO) 174.68
(C4), 193.62 (CO). Found, %: C 57.12; H 3.85; Br 18.15;
N 6.32. C21H17BrN2O4. Calculated, %: C 57.16; H 3.88;
Br 18.11; N 6.35.
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-4-
oxo-5-(2-oxo-2-phenylethylidene)-1H-4,5-dihydropyr-
role-3-carboxylate (VIIj). Yield 3.20 g (76%), colorless
crystals, mp 222–223°C (2-propanol). IR spectrum, ν,
cm–1: 3304 (NH), 1697 (COOEt), 1648, 1600 (C=O,
1
C=C). H NMR spectrum (DMSO-d6), δ, ppm: 1.10 t
(3H, CMe), 2.24 s (3H, Me), 3.99 q (2H, CH2), 5.40 s
(1H, CH), 7.80 m (8H, Ar), 8.24 s (1H, NH), 8.32 s (1H,
NH). Found, %: C 62.73; H 4.56; N 9.94. C22H19N3O6.
Calculated, %: C 62.70; H 4.54; N 9.97.
Ethyl 5E)-2-amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-4-oxo-1-(4-fluorophenyl)-1H-4,5-
dihydropyrrole-3-carboxylate (VIIk). Yield 3.07 g
(78%), colorless crystals, mp 233–234°C (2-propanol).
IR spectrum, ν, cm–1: 3439, 3317 (NH), 1713 (COOEt),
Ethyl (5E)-2-amino-1-(2-iodophenyl)-4-oxo-5-(2-
oxo-2-phenylethylidene)-1H-4,5-dihydro-pyrrole-3-
carboxylate (VIIg). Yield 4.25 g (86%), colorless crys-
tals, mp 212–213°C (acetonitrile). IR spectrum, ν, cm–1:
3298 (NH), 1682 (COOEt), 1655, 1606 (C=O). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.14 t (3H, CMe), 4.07 q
(2H, CH2), 5.55 s (1H, CH), 7.60 m (9H, Ar), 8.15 s (1H,
NH), 8.30 s (1H, NH). Found, %: C 51.68; H 3.54; N 5.72.
C21H17IN2O4. Calculated, %: C 51.66; H 3.51; N 5.74.
1
1631, 1606 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.14 t (3H, CMe), 2.36 s (3H, Me), 4.08 q (2H,
CH2), 5.42 s (1H, CH), 7.65 m (8H,Ar), 8.15 s (1H, NH),
8.27 s (1H, NH). Found, %: C 67.02; H 4.84; N 7.12.
C22H19FN2O4. Calculated, %: C 67.00; H 4.86; N 7.10.
Ethyl (5E)-2-amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-4-oxo-1-(2-chlorophenyl)-1H-4,5-
dihydropyrrole-3-carboxylate (VIIl). Yield 3.06 g
(75%), colorless crystals, mp 226–227°C (ethanol). IR
spectrum, ν, cm–1: 3376, 3114 (NH), 1674, 1662, 1602
Ethyl (5E)-2-amino-1-(4-nitrophenyl)-4-oxo-5-
(2-oxo-2-phenylethylidene)-1H-4,5-dihydropyrrole-
3-carboxylate (VIIh). Yield 3.46 g (85%), colorless
crystals, mp 295–296°C (ethanol). IR spectrum, ν, cm–1:
3439, 3237 (NH), 1709 (COOEt), 1637, 1605 (C=O,
1
(COOEt, C=C, C=O). H NMR spectrum (DMSO-d6),
δ, ppm: 1.51 t (3H, CMe), 2.36 s (3H, Me), 4.07 q (2H,
CH2), 5.51 s (1H, CH), 7.60 m (8H, Ar), 8.12 s (1H, NH)
8.31 s (1H, NH). Found, %: C 64.30; H 4.65; Cl 8.67;
N 6.79. C22H19ClN2O4. Calculated, %: C 64.31; H 4.66;
Cl 8.63; N 6.82.
1
C=C). H NMR spectrum (DMSO-d6), δ, ppm: 1.20 t
(3H, CMe), 4.13 q (2H, CH2), 5.72 s (1H, CH), 7.65 m
(9H, Ar), 8.13 s (1H, NH), 8.29 s (1H, NH). Found, %:
C 61.92; H 4.21; N 10.33. C21H17N3O6. Calculated, %:
C 61.91; H 4.21; N 10.31.
Ethyl (5E)-2-amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-4-oxo-1-(3-chlorophenyl)-1H-4,5-
dihydropyrrole-3-carboxylate (VIIm). Yield 3.24 g
(79%), colorless crystals, mp 228–229°C (ethanol). IR
spectrum, ν, cm–1: 3302 (NH), 1686 (COOEt), 1649,
Ethyl (5E)-2-amino-4-oxo-5-(2-oxo-2-phenyl-
ethylidene)-1-(3-tpifluoromethylphenyl)-1H-4,5-
dihydropyrrole-3-carboxylate (VIIi). Yield 2.97 g
(69%), colorless crystals, mp 256–257°C (2-propanol).
IR spectrum, ν, cm–1: 3422, 3242 (NH), 1717 (COOEt),
1
1637 (C=O). H NMR spectrum (DMSO-d6), δ, ppm:
1
1667, 1642, 1612 (C=O, C=C). H NMR spectrum
1.51 t (3H, CMe), 2.36 s (3H, Me), 4.07 q (2H, CH2),
5.51 s (1H, CH), 7.60 m (8H,Ar), 8.17 s (1H, NH), 8.34 s
(1H, NH). Found, %: C 64.29; H 4.63; Cl 8.66; N 6.80.
(DMSO-d6), δ, ppm: 1.15 t (3H, CMe), 2.36 s (3H, Me),
4.08 q (2H, CH2), 5.52 c (1H, CH), 7.70 m (9H, Ar),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 2 2013

CHEMISTRY OF IMINOFURAN: VIII.
251
C22H19ClN2O4. Calculated, %: C 64.31; H 4.66; Cl 8.63;
N 6.82.
CH2), 5.36 s (1H, CH), 7.80 m (8H,Ar), 8.25 s (1H, NH),
8.32 s (1H, NH). Found, %: C 62.72; H 4.66; N 9.95.
C22H19N3O6. Calculated, %: C 62.70; H 4.54; N 9.97.
Ethyl (5E)-2-amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-4-oxo-1-(4-chlorophenyl)-1H-4,5-dihy-
dropyrrole-3-carboxylate (VIIn). Yield 2.58 g (63%),
colorless crystals, mp 263–264°C (ethanol). IR spectrum,
ν, cm–1: 3445, 3293 (NH), 1725 (COOEt), 1658, 1642,
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-
5-[2-(4-methylphenyl)-2-oxoethylidene]-4-oxo-1H-
4,5-dihydropyrrole-3-carboxulate (VIIs). Yield 2.09
g (48%), colorless crystals, mp 251–252°C (ethanol). IR
spectrum, ν, cm–1: 3303, 3168 (NH), 1672, 1646, 1608
1
1618 (C=O, C=C). H NMR spectrum (DMSO-d6), δ,
1
(COOEt, C=O, C=C). H NMR spectrum (DMSO-d6),
ppm: 1.14 t (3H, CMe), 2.36 s (3H, Me), 4.07 q (2H,
CH2), 5.51 s (1H, CH), 7.60 m (8H,Ar), 8.16 s (1H, NH),
8.32 s (1H, NH). Found, %: C 64.33; H 4.64; Cl 8.66;
N 6.80. C22H19ClN2O4. Calculated, %: C 64.31; H 4.66;
Cl 8.63; N 6.82.
δ, ppm: 1.09 t (3H, CMe), 2.25 s (3H, Me), 2.28 s (3H,
Me), 3.92 q (2H, CH2), 5.34 s (1H, CH), 7.80 m (7H,Ar),
8.24 s (1H, NH), 8.34 s (1H, NH). Found, %: C 63.40;
H 4.89; Cl 8.63; N 9.62. C23H21N3O6. Calculated, %:
C 63.44; H 4.86; N 9.65.
Ethyl 5E)-2-amino-1-(4-bromophenyl)-5-[2-
(4-methylphenyl)-2-oxoethylidene]-4-oxo-1H-4,5-
dihydropyrrole-3-carboxylate (VIIo). Yield 3.54 g
(78%), colorless crystals, mp 275–276°C (acetonitrile).
IR spectrum, ν, cm–1: 3302 (NH), 1686 (COOEt), 1649,
Ethyl (5E)-2-amino-5-[2-(4-methoxyphenyl)-2-
oxoethylidene]-4-oxo-1-(4-ethoxycarbonylphenyl)-
1H-4,5-dihydropyrrole-3-carboxylate (VIIt). Yield
3.07 g (75%), colorless crystals, mp 194–196°C (ethanol).
IR spectrum, ν, cm–1: 3352, 3229 (NH), 1720, 1674
(COOEt), 1647, 1601 (C=O). 1H NMR spectrum (DMSO-
d6), δ, ppm: 1.51 t (3H, CMe), 2.36 s (3H, Me), 4.07 q
(2H, CH2), 5.51 s (1H, CH), 7.60 m (8H, Ar), 8.16 s (1H,
NH), 8.32 s (1H, NH). Found, %: C 64.62; H 5.24; N 6.02.
C25H24N2O7. Calculated, %: C 64.65; H 5.21; N 6.03.
1
1637 (C=C, C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.14 t (3H, CMe), 2.36 s (3H, Me), 4.07 q (2H,
CH2), 5.51 s (1H, CH), 7.60 m (8H, Ar), 8.16 C (1H,
NH), 8.32 s (1H, NH). Found, %: C 58.02; H 4.24; Br
17.53; N 6.12. C22H19CrN2O4. Calculated, %: C 58.04;
H 4.21; Br 17.55; N 6.15.
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-
5-[2-(4-methoxyphenyl)-2-oxoethylidene]-4-oxo-1H-
4,5-dihydropyrrole-3-carboxylate (VIIu). Yield 2.07
g (46%), colorless crystals, mp 255–256°C (ethanol). IR
spectrum, ν, cm–1: 3312, 3184 (NH), 1676, 1650, 1602
Ethyl (5E)-2-amino-5-[2-(4-methyl-phenyl)-2-
oxoethylidene]-4-oxo-1-(4-ethoxycarbonylphenyl)-
1H-4,5-dihydropyrrole-3-carboxylate (VIIp). Yield
3.85 g (86%), colorless crystals, mp 178–180°C (ethanol).
IR spectrum, ν, cm–1: 3308 (NH), 1714, 1682 (COOEt),
1604 (C=O). Found, %: C 66.92; H 5.36; N 6.22. C25H-
24N2O6. Calculated, %: C 66.95; H 5.39; N 6.25.
1
(COOEt, C=O, C=C). H NMR spectrum (DMSO-d6),
δ, ppm: 1.16 t (3H, CMe), 2.28 s (3H, Me), 3.77 s (3H,
OMe), 4.0 q (2H, CH2), 5.38 s (1H, CH), 7.80 m (7H,Ar),
8.26 s (1H, NH), 8.35 s (1H, NH). Found, %: C 61.22;
H 4.66; N 9.34. C23H21N3O7. Calculated, %: C 61.19;
H 4.69; N 9.31.
Ethyl (5E)-2-amino-1-(4-methylphenyl)-5-[2-(4-
methylphenyl)-2-oxoethylidene]-4-oxo-1H-4,5-dihy-
dropyrrole-3-carboxylate (VIIq). Yield 3.04 g (78%),
colorless crystals, mp 222–223°C (ethanol). IR spectrum,
ν, cm–1: 3322, 3145 (NH), 1696 (COOEt), 1662, 1615
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-
4-oxo-5-[2-oxo-2-(4-ethoxyphenylethylidene)]-1H-
4,5-dihydropyrrole-3-carboxylate (VIIv). Yield 3.39 g
(73%), colorless crystals, mp 222–223°C (ethanol). IR
spectrum, ν, cm–1: 3292, 3244 (NH), 1678, 1648, 1606
1
(C=O, C=C). H NMR spectrum (DMSO-d6), δ, ppm:
1.08 t (3H, CMe), 2.28 s (3H, Me), 2.32 s (3H, Me),
4.52 q (2H, CH2), 5.29 s (1H, CH), 7.60 m (8H, Ar),
7.92 br.s (2H, NH). Found, %: C 70.72; H 5.66; N 7.22.
C23H22N2O4. Calculated, %: C 70.75; H 5.67; N 7.18.
1
(COOEt, C=C, C=O). H NMR spectrum (DMSO-d6),
δ, ppm: 1.16 t (3H, CMe), 1.33 t (3H, Me), 4.12 m (4H,
2CH2), 5.38 s (1H, CH), 7.60 m (7H, Ar), 8.29 s (1H,
NH), 8.38 s (1H, NH). Found, %: C 61.96; H 4.94; N 9.01.
C24H23N3O7. Calculated, %: C 61.93; H 4.98; N 9.03.
Ethyl (5E)-2-amino-5-[2-(4-methylphenyl)-2-
oxoethylidene]-1-(3-nitrophenyl)-4-oxo-1H-4,5-
dihydropyrrole-3-carboxylate (VIIr). Yield 3.07 g
(82%), colorless crystals, mp 256–257°C (ethanol). IR
spectrum, ν, cm–1: 3309, 3172 (NH), 1673, 1648, 1608
Ethyl (5E)-2-amino-1-(4-chlorophenyl)-4-oxo-5-
[2-oxo-2-(4-chlorophenylethylidene)]-1H-4,5-dihy-
dropyrrole-3-carboxylate (VIIw). Yield 2.46 g (57%),
colorless crystals, mp 266–267°C (ethanol). IR spectrum,
1
(COOEt, C=O, C=C). H NMR spectrum (DMSO-d6),
δ, ppm: 1.08 t (3H, CMe), 2.26 s (3H, Me), 3.94 q (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 2 2013

KHARITONOVA et al.
252
ν, cm–1: 3301, 3186 (NH), 1676 1652, 1593 (COOEt,
C=C, C=O). H NMR spectrum (DMSO-d6), δ, ppm:
ACKNOWLEDGMENTS
1
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant no.
11-03-00882) and of Ministry of Education of Perm Ter-
ritiry (project MIG).
1.16 t (3H, CMe), 4.05 q (2H, CH2), 5.41 s (1H, CH),
7.50 m (8H,Ar), 8.31 s (1H, NH), 8.39 s (1H, NH). Found,
%: C 58.55; H 3.76; Cl 16.41; N 6.47. C21H16Cl2N2O4.
Calculated, %: C 58.49; H 3.73; Cl 16.44; N 6.50.
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-4-
oxo-5-[2-oxo-2-(4-chlorophenylethylidene)]-1H-4,5-
dihydropyrrole-3-carboxylate (VIIx). Yield 2.32 g
(51%), colorless crystals, mp 265–266°C (ethanol). IR
spectrum, ν, cm–1: 3296, 3172 (NH), 1670 (COOEt),
REFERENCES
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vol. 202, no. 9, p. 654.
1
1650, 1596 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.16 t (3H, CMe), 2.29 s (3H, Me), 4.0 q (2H,
CH2), 5.43 s (1H, CH), 7.80 m (7H,Ar), 8.34 s (1H, NH),
8.40 s (1H, NH). Found, %: C 57.95; H 3.96; Cl 7.73;
N 9.26. C22H18ClN3O6. Calculated, %: C 57.97; H 3.98;
Cl 7.77; N 9.22.
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)
4-oxo-5-[2-oxo-2-(4-fluorophenylethylidene)]-1H-
4,5-dihydropyrrole-3-carboxylate (VIIy). Yield 2.50 g
(57%), colorless crystals, mp 258–259°C (ethanol). IR
spectrum, ν, cm–1: 3308, 3184 (NH), 1672 (COOEt),
1
1648, 1596 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.16 t (3H, CMe), 2.29 s (3H, Me), 4.0 q (2H,
CH2), 5.43 s (1H, CH), 7.70 m (8H,Ar), 8.31 s (1H, NH),
8.40 s (1H, NH). Found, %: C 60.18; H 4.09; N 9.51.
C22H18FN3O6. Calculated, %: C 60.14; H 4.13; N 9.56.
Ethyl (5E)-2-amino-5-[2-(2,4-dimethylphenyl)-2-
oxoethylidene]-1-(2-methyl-5-nitrophenyl)-4-oxo-1H-
4,5-dihydropyrrole-3-carboxylate (VIIz). Yield 3.06 g
(68%), colorless qpandCtaл-лы, mp 242–243°C (etha-
nol). IR spectrum, ν, cm–1: 3296 (NH), 1676 (COOEt),
1
1650, 1612 (C=O). H NMR spectrum (DMSO-d6), δ,
ppm: 1.16 t (3H, CMe), 2.26 s (3H, Me), 2.26 s (3H, Me),
2.26 s (3H, Me), 4.0 q (2H, CH2), 5.43 s (1H, CH), 7.80 m
(8H, Ar), 8.32 s (1H, NH), 8.40 s (1H, NH). Found, %:
C 64.12; H 5.19; N 9.39. C24H23N3O6. Calculated, %:
C 64.13; H 5.16; N 9.35.
Ethyl (5E)-2-amino-1-(2-methyl-5-nitrophenyl)-
5-[2-(1-naphthyl)-2-oxoethylidene]-4-oxo-1H-4,5-
dihydropyrrole-3-carboxylate (VIIz1). Yield 2.21 g
(47%), colorless crystals, mp 249–250°C (ethanol). IR
spectrum, ν, cm–1: 3288, 3216 (NH), 1676, 1646, 1612
16. Junek, H. and Sterk, H., Monatsch. Chem., 1967, vol. 98,
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21. Igidov, N.M., Rubtsov, A.E., Tyuneva, A.V., Zalesov, V.V.,
Borodin, A.Yu., and Bukanova, E.V., Russ. J. Org. Chem.,
2009, vol. 45, p. 698.
1
(COOEt, C=C, C=O). H NMR spectrum (DMSO-d6),
δ, ppm: 1.10 t (3H, CMe), 2.31 s (3H, Me), 4.02 q (2H,
CH2), 5.71 s (1H, CH), 7.90 m (10H, Ar), 8.73 s (1H,
NH), 8.80 s (1H, NH). Found, %: C 66.22; H 4.44; N 8.94.
C26H21N3O6. Calculated, %: C 66.24; H 4.49; N 8.91.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 2 2013