Chemistry of iminofurans: XII.1Synthesis of 2-(arylimino)furan-3(2H)-ones and their reaction with amines

Article abstract of DOI:10.1134/S1070428016060154

2-(Arylimino)-5-(het)arylfuran-3(2H)-ones were synthesized by reaction of 5-(het)arylfuran-2,3-diones with N-(triphenyl-λ⁵-phosphanylidene)anilines, and their aminolysis afforded N-aryl-4-amino-4-(het)aryl-2-oxobut-3-enamides.

Full text of DOI:10.1134/S1070428016060154

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 6, pp. 848–856. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © E.R. Nasibullina, A.N. Vasyanin, S.N. Shurov, A.E. Rubtsov, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52,
No. 6, pp. 862–870.
Chemistry of Iminofurans: XII.1 Synthesis of 2-(Arylimino)furan-
3(2H)-ones and Their Reaction with Amines
E. R. Nasibullina, A. N. Vasyanin, S. N. Shurov, and A. E. Rubtsov*
Perm State National Research University, ul. Bukireva 15, Perm, 614990 Russia
*e-mail: rubtsov@psu.ru
Received February 29, 2016
Abstract—2-(Arylimino)-5-(het)arylfuran-3(2H)-ones were synthesized by reaction of 5-(het)arylfuran-2,3-
diones with N-(triphenyl-λ5-phosphanylidene)anilines, and their aminolysis afforded N-aryl-4-amino-4-
(het)aryl-2-oxobut-3-enamides.
DOI: 10.1134/S1070428016060154
The first data on furan derivatives containing oxo
and imino groups in positions 3 and 2, respectively,
were reported more than hundred years ago; specifi-
cally, the synthesis of 1-benzofuran-3(2H)-one
2-oxime was described [2]. After a century, the
diversity of information on the synthesis and chemical
transformations of iminofuran derivatives has been
considerably extended. It is known that replacement of
the lactone carbonyl oxygen atom by less electronega-
tive nitrogen atom in going from 5-arylfuran-2,3-di-
ones to N-substituted 2-iminofuran-3(2H)-ones reduces
the electrophilicity of C2, so that the reactivity of the
latter essentially changes, and their preparative poten-
tial extends. However, there are only a few publica-
tions concerned with 2-iminofuran-3(2H)-ones [3].
nucleophilic attack by varying substituents on the
heterocycle and imino nitrogen atom. Recyclizations
of iminofuranones and cycloadditions to the C=N bond
therein also provide wide possibilities from the syn-
thetic viewpoint. We were interested in extending the
series of substituents on the imino nitrogen atom and
studying chemical properties of 5-aryl-2-iminofuran-
3(2H)-ones. The most convenient method for the
synthesis of 5-aryl-2-(aryl-imino)furan-3(2H)-ones is
based on the Staudinger imination of the lactone car-
bonyl of 5-arylfuran-2,3-diones [4–7].
5-(Het)arylfuran-2,3-diones 1a–1e reacted with
N-(triphenyl-λ5-phosphanylidene)anilines 2a–2f to
give 2-(arylimino)-5-(het)arylfuran-3(2H)-ones 3a–3t
and triphenylphosphine oxide (Scheme 1). Compounds
3a–3t were isolated as yellow crystalline substances.
Their IR spectra characteristically showed absorption
bands due to C3=O and C2=N groups in the region
The structure of 2-iminofuran-3(2H)-ones deter-
mines their rich synthetic potential. The presence of
several electron-deficient centers in their molecules
provides the possibility of controlling the direction of
1
1697–1721 cm–1. The H NMR spectra of 3a–3t
Scheme 1.
O
O
+
Ph3P=NR2
Ph3P–NR2
R1
O
R1
NR2
–Ph3P=O
O
O
1a–1e
2a–2f
3a–3t
1, R1 = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c), naphthalen-1-yl (d), thiophen-2-yl (e); 2, R2 = Ph (a), 3-NCC6H4 (b), 3-O2NC6H4 (c),
3-F3CC6H4 (d), 4-EtOC(O)C6H4 (e), 4-AcC6H4 (f); 3, R1 = Ph, R2 = Ph (a), 3-NCC6H4 (b), 3-O2NC6H4 (c), 3-F3CC6H4 (d),
4-EtOC(O)C6H4 (e), 4-AcC6H4 (f); R1 = 4-MeC6H4, R2 = Ph (g), 3-NCC6H4 (h), 3-O2NC6H4 (i), 3-F3CC6H4 (j), 4-EtOC(O)C6H4 (k);
R1 = 4-ClC6H4, R2 = Ph (l), 3-O2NC6H4 (m), 3-F3CC6H4 (n), 4-EtOC(O)C6H4 (o), 4-AcC6H4 (p); R1 = naphthalen-1-yl, R2 =
3-O2NC6H4 (q); R1 = thiophen-2-yl, R2 = 3-O2NC6H4 (r), 3-F3CC6H4 (s), 4-EtOC(O)C6H4 (t).
1
For communication XI, see [1].
848

CHEMISTRY OF IMINOFURANS: XII.
849
Scheme 2.
O
O
R1
R2
N
+
R3R4NH
H
R1
3c, 3k, 3m, 3o, 3t
NR2
N
O
R3
R4
5a–5k
O
4a–4f
4, R3 = H, R4 = Et (a), PhCH2 (b), Cy (c), 1-Ad (d); R3 = R4 = Et (e); R3R4N = morpholin-4-yl (f); 5, R3 = H, R4 = Et, R2 =
3-O2NC6H4, R1 = Ph (a), 4-ClC6H4 (b); R1 = thiophen-2-yl, R2 = 4-EtOC(O)C6H4 (c); R1 = 4-ClC6H4, R2 = 4-EtOC(O)C6H4, R3 = H,
R4 = PhCH2 (d); R3 = H, R4 = Cy: R1 = 4-ClC6H4, R2 = 3-O2NC6H4 (e); R1 = 4-MeC6H4, R2 = 4-EtOC(O)C6H4 (f); R1 = thiophen-
2-yl, R2 = 4-EtOC(O)C6H4, R3 = H, R4 = 1-Ad (g); R3 = R4 = Et, R1 = 4-ClC6H4, R2 = 3-O2NC6H4 (h); R1 = 4-MeC6H4, R2 =
4-EtOC(O)C6H4 (i); R3R4N = morpholin-4-yl, R1 = 4-ClC6H4, R2 = 3-O2NC6H4 (j); R1 = 4-MeC6H4, R2 = 4-EtOC(O)C6H4 (k).
contained a singlet at δ 6.33–6.56 ppm due to 4-H and
aromatic proton signals centered at δ 7.6 ppm. Presum-
ably, compounds 3 are formed through a four-center
transition state. We found that phosphine imides 2 con-
taining electron-withdrawing groups in the aromatic
ring reacted with furandiones 1 more readily and with
higher yields, which may be rationalized by additional
stabilization of the negative charge on the nitrogen
atom.
out to change in the reverse order. Therefore, the
charge-controlled reaction should involve nucleophilic
attack on C2, and the orbital-controlled reaction, on C5.
We failed to calculate geometric and electronic
characteristics of I(C5)-1; optimization of its geometric
parameters led to increase of the C5···N distance, i.e.,
ethylamine molecule moved apart from the imino-
furanone molecule. Insofar as the calculations were
performed for the gas phase, intermediate I(C5)-1
should be regarded as unstable. Probably, under real
experimental conditions, effective solvation stabilizes
that intermediate. Therefore, the formation of I(C5)-1
in the reaction under study was postulated. Subsequent
transformations of I(C5)-1 may follow two pathways
involving proton transfer from the nitrogen atom to O1
or C4 with formation of intermediate I(C5)-2 or I(C5)-3
(Etot = –1161.4771 Ha), respectively. Geometry optimi-
zation of I(C5)-2 showed that proton transfer to O1
(formation of O1–H bond) is accompanied by internal
rotation about the C2–C3 bond, leading to structure
I(C5)-2A (Etot = –1116.4892 Ha) with an imidic acid
fragment. Intermediate I(C5)-2A is stabilized by two
intramolecular hydrogen bonds N–H ···N=C1 and
C1O–H···O=C2, as follows from the corresponding
calculated interatomic distances (1.803 and 1.753 Å,
respectively). The transformation of I(C5)-2A into
more stable amide I(C5)-4 (Etot = –1161.5143 Ha) is
also accompanied by internal rotation about the C1–C2
bond so that intramolecular hydrogen bond
N–H···O=C1 (1.740 Å) is formed. The formation of
amide 5a requires internal rotation about the C2–C3
bond in I(C5)-4. This rotation was analyzed by the
reaction coordinate method where the reaction coor-
dinate was the dihedral angle Θ (OC2C3C4). The maxi-
mum on the Etot—Θ curve corresponds to transition
state TS(C5)-1. Optimization of its structure by
SADPOINT procedure gave Etot = –1161.4866 Ha for
Θ = 92.0°. Further decrease of Θ led to amide 5a
(Etot = –1161.5233 Ha). The calculated N–H···O=C2
The reactions of 2-(arylimino)-5-(het)arylfuran-
3(2H)-ones 3c, 3k, 3m, 3o, and 3t with primary and
secondary aliphatic amines 4a–4f afforded N-aryl-
4-amino-4-(het)aryl-2-oxobut-3-enamides 5a–5k
(Scheme 2). Amides 5a–5k are yellow crystalline
substances. They showed in the IR spectra absorption
bands at 3346–3255 (NH), 1697–1676 (C=O, amide),
1
and 1607–1588 cm–1 (C2=O). In the H NMR spectra
of 5a–5k, the NH proton resonated as a singlet at
δ 9.44–10.95 ppm, signals from aromatic protons were
observed at about δ 7.5–7.6 ppm, and the vinylic 3-H
proton signal appeared as a singlet at δ 5.92–6.60 ppm.
Compounds 5 are likely to be formed via initial
nucleophilic attack by the amino nitrogen atom on C5
of the furan ring to produce zwitterionic intermediate
I(C5)-1 which is stabilized by proton transfer from
the ammonium nitrogen atom to either O1 or C4, lead-
ing to intermediates I(C5)-2 and I(C5)-3, respectively.
Possible further transformation pathways are shown in
Scheme 3. This scheme was verified by quantum
chemical calculations of the total energies Etot (in
hartree units, Ha) and electronic and geometric pa-
rameters of possible intermediates at the B3LYP/
6-311G(d) level of theory. Initial iminofuranone 3c
molecule (Etot = –1026.2546 Ha) possesses three elec-
trophilic centers, C2, C3, and C5, with total Mulliken
charges of +0.3445, +0.2542, and +0.2360 a.u.,
respectively. However, the contributions of 2pz atomic
orbitals constituting the LUMO of molecule 3c turned
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 6 2016

NASIBULLINA et al.
850
Scheme 3.
O
O
O
H
N
Ph
Et
Ar
N
N
Et
Et
H
N
N
O
N
O
Ph
Ph
HO
Ar
Ar
I(C5)-3
I(C5)-5
I(C5)-6
5a
≠
Oδ–
O
O
H
H
δ+
N
H
EtNH2
N
Ph
Et
Ar
Ph
N
N
Ar
O
O
Ph
N
O
H
Ar
Et
3c
I(C5)-1
TS(C5)-1
O
O
O
H
O
H
N
H
N
Ph
Ph
Et
Ar
N
Ph
N
N
N
O
HO
H
H
Ar
Et
Ar
Et
I(C5)-2
I(C5)-2A
I(C5)-4
Ar = 3-O2NC6H4.
distance (1.866 Å) in 5a confirms the presence of in-
tramolecular hydrogen bond, which does not contradict
the spectral data.
The attack by amine on C3 (Scheme 4) could lead to
diiminofuran 6 through intermediates I(C3)-1 and
I(C3)-2. Geometry optimization of I(C3)-1 failed for
the reasons mentioned above. Intermediate I(C3)-2
(Etot = –1161.4552 Ha) has a higher energy than
I(C5)-2a and I(C5)-3, and its formation seems to be
less probable. A hypothetic supermolecule consisting
An alternative path for the formation of amide 5a
includes intermediates I(C5)-5 and I(C5)-6. Interme-
diate I(C5)-5 (Etot = –1161.4602 Ha) appears as a result
of proton transfer from the nitrogen atom to O1 of the
heterocycle. The subsequent proton transfer to the
nitrogen atom of the C1=N fragment in I(C5)-5 gives
of 6 (Etot = –1085.0099 Ha) and water (Etot
=
–76.4348 Ha) is also less stable than amide 5a. Pre-
sumably, this is the reason why nucleophilic attack is
not directed at C3 of 3c and compound 6 is not formed.
more stable α-oxo amide structure I(C5)-6 (Etot
=
–1161.4989 Ha), and migration of one proton from the
methylene group to the imino nitrogen atom yields
final product 5a.
The attack on C2 (Scheme 5) could give rise to
amidine 7a or 7b. Zwitterionic intermediate I(C2)-1
Scheme 4.
Et
H
H
Et
Oδ–
δ+N
NH
N
OH
N
Et
Ph
3c
+ 4a
–H2O
Ph
Ph
N
Ar
N
O
O
O
Ar
Ar
I(C3)-1
I(C3)-2
6
Ar = 3-O2NC6H4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 6 2016

CHEMISTRY OF IMINOFURANS: XII.
851
Scheme 5.
O
O
H
H
H
N
δ+N
Et
Nδ–
Ar
I(C2)-1
3c
+ 4a
Et
Ph
Ph
O
O
NH
Ar
I(C2)-2
H
Et
O
O
Ar
N
N
N
Ph
Ar
N
H
Et
O
O
H
Ph
H
I(C2)-3
7b
H
O
Ar
Et
Ar
N
N
Ph
Et
N
N
H
O
O
H
Ph
O
H
I(C2)-4
7a
Ar = 3-O2NC6H4.
could be converted into I(C2)-2 via proton migration
from the ethylammonium fragment to the imino
nitrogen atom. The calculated total energy of I(C2)-2 is
Etot = –1161.4814 Ha. Its stabilization may be achieved
by proton transfer to O1 either from the NHC2H5
nitrogen atom or from the NHAr group with formation
of intermediate I(C2)-3 or I(C2)-4, respectively. The
total energies of I(C2)-3 and I(C2)-4 are –1161.4884
and –1161.4909 Ha, respectively. Internal rotation
about the C2–C3 bond could produce more stable struc-
tures 7a and 7b with intramolecular hydrogen bond
C4–OH···O=C2. Amidine 7a (Etot = –1161.4978 Ha) is
more stable than 7b (Etot = –1161.4909 Ha).
EXPERIMENTAL
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
The 1H and 13C NMR spectra were measured on Varian
Mercury Plus-300 (300 MHz), Bruker Avance III (400
and 100 MHz, respectively), and Bruker 500 instru-
ments (500.13 MHz); the chemical shifts were deter-
mined relative to tetramethylsilane as internal standard
or solvent signals. The mass spectra (electron impact,
70 eV) were recorded on a Kratos MS-30 mass spec-
trometer (ion source temperature 200°C). The elemen-
tal analyses were obtained on a Leco CHNS-932
analyzer. The purity of compounds was checked, and
the progress of reactions was monitored, by TLC on
Sorbfil PTSKh P-A-UF-254 plates with diethyl ether–
benzene–acetone (10:9:1) as eluent; spots were de-
tected under UV light or by treatment with iodine
vapor. Quantum chemical calculations of reaction
intermediates with full optimization of all parameters
were performed on a supercomputer (Tesla Center for
Parallel and Distributed Computations, Perm State
National Research University) using Firefly [8].
As follows from the calculated total energies of key
intermediates I(C5)-2, I(C3)-2, and I(C2)-2, the former
should be regarded as the most stable. Intermeditate I
(C5)-4 is also more stable than I(C2)-4. Furthermore,
real product 5a is more stable than hypothetical struc-
ture 7a. Thus, the reaction following the path
3c + EtNH2 → I(C5)-1 → I(C5)-2A
→ I(C5)-4 → 5a
seems to be energetically more favorable. Other imino-
furanones should react with amines according to
an analogous scheme.
Commercially available triphenylphosphine, tri-
ethylamine (Vekton), 4-methylacetophenone, 4-chloro-
acetophenone, 2-acetylthiophene (Sigma–Aldrich),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 6 2016

NASIBULLINA et al.
852
acetophenone, 4-aminoacetophenone, diethyl oxalate,
and morpholine (Reakhim) were used. Chloroform,
methanol, benzene, toluene, dioxane, and acetonitrile
of chemically pure grade were subjected to additional
purification [9] prior to use; rectified ethanol was of
de luxe grade. Compounds 1a–1e were synthesized
according to the procedure reported in [10] from the
corresponding (het)aroylpyruvic acids which were
prepared as described in [11, 12]. Compounds 1a–1c
and 1e were reported previously [10, 13]. Phosphine
imides 2a–2f were synthesized according to [14] from
the corresponding substituted anilines. Compounds 2a
[14], 2b, 2e [15], 2c [16], and 2f [17] were reported
previously.
N 9.52. C16H10N2O4. Calculated, %: C 65.30; H 3.40;
N 9.52.
5-Phenyl-2-{[(3-(trifluoromethyl)phenyl]imino}-
furan-3(2H)-one (3d). Yield 0.49 g (32%), yellow
crystals, mp 141–143°C (from MeCN). IR spectrum, ν,
1
cm–1: 1711 (C=O, C=N), 1600 (C=C). H NMR spec-
trum (CDCl3), δ, ppm: 6.41 s (1H, 4-H), 7.27–8.02 m
(9H, Harom). Found, %: C 64.36; H 3.18; N 4.41.
C17H10F3NO2. Calculated, %: C 64.35; H 3.15; N 4.42.
Ethyl 4-[3-oxo-5-phenylfuran-2(3H)-ylidene-
amino]benzoate (3e). Yield 0.48 g (31%), yellow
crystals, mp 120–122°C (from MeCN). IR spectrum, ν,
cm–1: 1724 (C=O, ester), 1710 (C=O, C=N), 1600
(C=C). 1H NMR spectrum, δ, ppm: 1.40 t (3H, Me, J =
7.1 Hz), 4.38 q (2H, OCH2, J = 7.1 Hz), 6.39 s (1H,
4-H) 7.25–8.14 m (9H, Harom). Found, %: C 71.02;
H 4.71; N 4.36. C19H15NO4. Calculated, %: C 71.03;
H 4.67; N 4.36.
5-(Naphthalen-1-yl)furan-2,3-dione (1d). Yield
80%, red–brown crystals, decomposition point 160–
162°C (from benzene). IR spectrum, ν, cm–1: 1814
1
(C2=O), 1708 (C3=O). H NMR spectrum (DMSO-d6),
δ, ppm: 6.23 s (1H, 4-H), 7.25–7.87 m (7H, Harom).
Found, %: C 75.00; H 3.60. C14H8O3. Calculated, %:
C 75.00; H 3.57.
2-[(4-Acetylphenyl)imino]-5-phenylfuran-3(2H)-
one (3f). Yield 0.83 g (57%), yellow crystals, mp 155–
157°C (from MeCN). IR spectrum, ν, cm–1: 1710
1
2-(Arylimino)-5-(het)arylfuran-3(2H)-ones 3a–3t
(general procedure). Phosphine imide 2a–2f, 5 mmol,
was added to a solution of 5 mmol of 5-arylfuran-2,3-
dione 1a–1e in 10 mL of anhydrous toluene, and the
mixture was stirred until it became homogeneous.
After 24 h, the precipitate was filtered off and recrys-
tallized from acetonitrile.
(C=O, C=N), 1677 (C=O, Ac), 1597 (C=C). H NMR
spectrum (CDCl3), δ, ppm: 2.64 s (3H, Me), 6.42 s
(1H, 4-H), 7.30–8.07 m (9H, Harom). Found, %:
C 74.22; H 4.50; N 4.81. C18H13NO3. Calculated, %:
C 74.23; H 4.47; N 4.81.
5-(4-Methylphenyl)-2-(phenylimino)furan-
3(2H)-one (3g). Yield 0.6 g (46%), yellow crystals,
mp 176–177°C (from MeCN). IR spectrum, ν, cm–1:
5-Phenyl-2-(phenylimino)furan-3(2H)-one (3a).
Yield 0.94 g (76%), yellow crystals, mp 155–156°C
(from MeCN). IR spectrum, ν, cm–1: 1703 (C=O,
1
1700 (C=O, C=N), 1605 (C=C). H NMR spectrum
(CDCl3), δ, ppm: 2.45 s (3H, Me), 6.33 s (1H, 4-H),
7.31–7.40 m (4H, Harom), 7.45 m (1H, Harom, J =
7.6 Hz), 7.59 m (2H, Harom, J = 8.1 Hz), 7.75 m (2H,
1
C=N), 1603 (C=C). H NMR spectrum (CDCl3), δ,
ppm: 6.38 s (1H, 4-H), 7.25–7.87 m (10H, Harom).
Found, %: C 71.10; H 4.45; N 5.62. C16H11NO2. Cal-
culated, %: C 71.11; H 4.42; N 5.62.
Harom, J = 8.1 Hz). Found, %: C 77.55; H 4.98; N 5.32.
C17H13NO2. Calculated, %: C 77.57; H 4.94; N 5.32.
3-[3-Oxo-5-phenylfuran-2(3H)-ylideneamino]-
benzonitrile (3b). Yield 0.55 g (70%), yellow crystals,
mp 178–179°C (from MeCN). IR spectrum, ν, cm–1:
2229 (CN), 1711 (C=O), 1702 (C=N), 1605 (C=C).
1H NMR spectrum (CDCl3), δ, ppm: 6.45 s (1H, 4-H),
7.57–7.86 m (9H, Harom). Found, %: C 74.45; H 3.67;
N 10.21. C17H10N2O2. Calculated, %: C 74.45; H 3.65;
N 10.22.
3-[5-(4-Methylphenyl)-3-oxofuran-2(3H)-ylidene-
amino]benzonitrile (3h). Yield 0.60 g (78%), yellow
crystals, mp 189–191°C (from MeCN). IR spectrum, ν,
cm–1: 2224 (CN), 1715 (C=O), 1698 (C=N), 1603
1
(C=C). H NMR spectrum (CDCl3), δ, ppm: 2.48 s
(3H, Me), 6.39 s (1H, 4-H), 7.37–7.80 m (8H, Harom).
Found, %: C 74.99; H 4.20; N 9.72. C18H12N2O2. Cal-
culated, %: C 75.00; H 4.17; N 9.72.
2-[(3-Nitrophenyl)imino]-5-phenylfuran-3(2H)-
one (3c). Yield 0.94 g (71%), yellow crystals, mp 174–
176°C (from MeCN). IR spectrum, ν, cm–1: 1716
5-(4-Methylphenyl)-2-[(3-nitrophenyl)imino]-
furan-3(2H)-one (3i). Yield 1.18 g (77%), yellow
crystals, mp 190–192°C (from MeCN). IR spectrum, ν,
cm–1: 1716 (C=O, C=N), 1598 (C=C). H NMR spec-
1
1
(C=O, C=N), 1598 (C=C). H NMR spectrum
(CDCl3), δ, ppm: 2.46 s (3H, Me), 6.39 s (1H, 4-H),
trum (CDCl3), δ, ppm: 2.46 s (3H, Me), 6.39 s (1H,
7.25–8.19 m (9H, Harom). Found, %: C 65.31; H 3.43;
4-H), 7.25–8.19 m (8H, Harom). Found, %: C 66.23;
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CHEMISTRY OF IMINOFURANS: XII.
853
H 3.92; N 9.09. C17H12N2O4. Calculated, %: C 66.23;
H 3.90; N 9.09.
7.62 d (2H, Harom, J = 8.4 Hz), 8.13 d (2H, Harom, J =
8.4 Hz). Found, %: C 64.14; H 3.97; N 3.94.
C19H14ClNO4. Calculated, %: C 64.22; H 3.94; N 3.94.
5-(4-Methylphenyl)-2-[(3-trifluoromethyl-
phenyl)imino]furan-3(2H)-one (3j). Yield 0.57 g
(36%), yellow crystals, mp 139–140°C (from MeCN).
IR spectrum, ν, cm–1: 1717 (C=O, C=N), 1606 (C=C).
1H NMR spectrum (CDCl3), δ, ppm: 2.4 s (3H, Me),
6.36 s (1H, 4-H), 7.24–7.84 m (8H, Harom). Found, %:
C 65.26; H 3.65; N 4.23. C18H12F3NO2. Calculated, %:
C 65.25; H 3.63; N 4.23.
2-[(4-Acetylphenyl)imino]-5-(4-chlorophenyl)-
furan-3(2H)-one (3p). Yield 0.59 g (36%), yellow
crystals, mp 185–187°C (from MeCN). IR spectrum, ν,
cm–1: 1697 (C=O, C=N), 1672 (MeC=O), 1598 (C=C).
Found, %: C 66.37; H 3.71; N 4.30. C18H12ClNO3.
Calculated, %: C 66.46; H 3.69; N 4.31.
5-(Naphthalen-1-yl)-2-[(3-nitrophenyl)imino]-
furan-3(2H)-one (3q). Yield 1.13 g (66%), yellow
crystals, mp 160–161°C (from MeCN). IR spectrum, ν,
Ethyl 4-[5-(4-methylphenyl)-3-oxofuran-2(3H)-
ylideneamino]benzoate (3k). Yield 0.64 g (38%),
yellow fibers, mp 112–114°C (from MeCN). IR spec-
trum, ν, cm–1: 1717 (C=O, ester), 1703 (C=O, C=N),
1603 (C=C). 1H NMR spectrum (CDCl3), δ, ppm: 1.39 t
(3H, Me, J = 6.9 Hz), 2.45 s (3H, Me), 4.38 q (2H,
CH2, J = 6.9 Hz), 6.35 s (1H, 4-H), 7.25–8.14 m (8H,
1
cm–1: 1713 (C=O, C=N), 1592 (C=C). H NMR spec-
trum (CDCl3), δ, ppm: 6.53 s (1H, 4-H), 7.24–8.48 m
(11H, Harom). Found, %: C 74.28; H 3.84; N 6.66.
C26H16N2O4. Calculated, %: C 74.29; H 3.81; N 6.67.
2-[(3-Nitrophenyl)imino]-5-(thiophen-2-yl)furan-
3(2H)-one (3r). Yield 0.83 g (55%), yellow crystals,
mp 202–203°C (from MeCN). IR spectrum, ν, cm–1:
Harom). Found, %: C 71.63; H 5.11; N 4.18. C20H17NO4.
Calculated, %: C 71.64; H 5.07; N 4.18.
1
1715 (C=O, C=N), 1598 (C=C). H NMR spectrum
5-(4-Chlorophenyl)-2-(phenylimino)furan-3(2H)-
one (3l). Yield 0.95 g (60%), yellow crystals, mp 224–
226°C (from MeCN). IR spectrum, ν, cm–1: 1721
(CDCl3), δ, ppm: 6.26 s (1H, 4-H), 7.25–8.50 m (7H,
H
arom, C4H3S). Found, %: C 56.00; H 2.69; N 9.33;
S 10.68. C14H8N2O4S. Calculated, %: C 56.00; H 2.67;
N 9.33; S 10.67.
1
(C=O, C=N), 1606 (C=C). H NMR spectrum
(CDCl3), δ, ppm: 6.38 s (1H, 4-H), 7.27–7.98 m (9H,
5-(Thiophen-2-yl)-2-[(3-trifluoromethylphenyl)-
imino]furan-3(2H)-one (3c). Yield 0.75 g (53%),
yellow crystals, mp 162–164°C (from MeCN). IR
spectrum, ν, cm–1: 1708 (C=O, C=N), 1583 (C=C).
1H NMR spectrum (CDCl3), δ, ppm: 6.24 s (1H, 4-H),
7.25–7.86 m (7H, Harom, C4H3S). Found, %: C 55.73;
H 2.49; N 4.33; S 9.92. C15H8F3NO2S. Calculated, %:
C 55.73; H 2.48; N 4.33; S 9.91.
H
arom). Found, %: C 67.74; H 3.55; N 4.94.
C16H10ClNO2. Calculated, %: C 67.84; H 3.53; N 4.95.
5-(4-Chlorophenyl)-2-[(3-nitrophenyl)imino]-
furan-3(2H)-one (3m). Yield 0.77 g (47%), yellow
crystals, decomposition point 224–226°C (from
MeCN). IR spectrum, ν, cm–1: 1716 (C=O, C=N), 1599
1
(C=C). H NMR spectrum (CDCl3), δ, ppm: 6.42 s
(1H, 4-H), 7.25–8.21 m (8H, Harom). Found, %:
C 58.46; H 2.76; N 8.52. C16H9ClN2O4. Calculated, %:
C 58.53; H 2.74; N 8.54.
Ethyl 4-[3-oxo-5-(thiophen-2-yl)furan-2(3H)-
ylideneamino]benzoate (3t). Yield 0.98 g (61%),
yellow crystals, mp 139–141°C (from MeCN). IR
spectrum, ν, cm–1: 1707 (C=O, ester), 1707 (C=O,
5-(4-Chlorophenyl)-2-[(3-trifluoromethyl-
phenyl)imino]furan-3(2H)-one (3n). Yield 0.54 g
(31%), yellow crystals, mp 155.5–157°C (from
MeCN). IR spectrum, ν, cm–1: 1703 (C=O, C=N), 1598
1
C=N), 1597 (C=C). H NMR spectrum (CDCl3), δ,
ppm: 1.41 t (3H, Me, J = 7.0 Hz), 4.39 q (2H, CH2,
J = 7.0 Hz), 6.23 s (1H, 4-H), 7.26–8.13 m (7H,
1
(C=C). H NMR spectrum (CDCl3), δ, ppm: 6.39 s
H
arom, C4H3S). Found, %: C 62.37; H 4.00; N 4.28;
(1H, 4-H), 7.24–8.81 m (8H, Harom). Found, %:
C 58.06; H 2.58; N 3.98. C17H9ClF3NO2. Calculated,
%: C 58.11; H 2.56; N 3.99.
S 9.79. C17H13NO4S. Calculated, %: C 62.38; H 3.98;
N 4.28; S 9.79.
N-Aryl-4-(ethylamino)-4-(het)aryl-2-oxobut-
3-enamides 5a–5c (general procedure). A solution of
0.41 g (5 mmol) of ethylamine (4a) hydrochloride in
5 mL of 5% aqueous alkali was added to a solution of
5 mmol of iminofuranone 3c, 3m, or 3t in 10 mL of
toluene, and the mixture was stirred for 3 h. The
precipitate was filtered off and recrystallized from
acetonitrile.
Ethyl 4-[5-(4-chlorophenyl)-3-oxofuran-2(3H)-
ylideneamino]benzoate (3o). Yield 1.3 g (93%),
yellow crystals, mp 180–182°C (from MeCN). IR
spectrum, ν, cm–1: 1711 (C=O, ester, C3=O, C=N),
1
1604 (C=C). H NMR spectrum (CDCl3), δ, ppm:
1.40 t (3H, Me, J = 7.0 Hz), 4.38 q (2H, CH2, J =
7.0 Hz), 6.39 s (1H, 4-H), 7.47–7.54 m (4H, Harom),
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NASIBULLINA et al.
854
4-(Ethylamino)-N-(3-nitrophenyl)-2-oxo-4-phe-
N,4-Diaryl-4-(cyclohexylamino)-2-oxobut-3-en-
amides 5e and 5f (genral procedure). Cyclohexyl-
amine (4c), 0.6 mL (5 mmol), was added to a solution
of 5 mmol of compound 3k or 3m in 10 mL of toluene,
and the mixture was stirred for 3 h at 60°C. The mix-
ture was evaporated by half under reduced pressure,
and the precipitate was filtered off.
nylbut-3-enamide (5a). Yield 1.02 g (89%), yellow
crystals, mp 167–169°C (from MeCN). IR spectrum, ν,
cm–1: 3317 (N–H), 1685 (C=O, amide), 1602 (C2=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.24 t (3H,
Me, J = 7.1 Hz), 3.36 q (2H, CH2, J = 7.1 Hz), 6.22 s
(1H, 3-H), 7.40–8.04 m (8H, Harom), 8.60 s (1H, Harom),
9.70 s (1H, NH), 11.31 br.s (1H, NH). Found, %:
C 63.71; H 5.05; N 12.38. C18H17N3O4. Calculated, %:
C 63.72; H 5.01; N 12.39.
4-(4-Chlorophenyl)-4-(cyclohexylamino)-N-(3-ni-
trophenyl)-2-oxobut-3-enamide (5e). Yield 1.73 g
(81%), yellow crystals, mp 187–189°C (from toluene).
IR spectrum, ν, cm–1: 3308 (N–H), 1678 (C=O,
4-(4-Chlorophenyl)-4-(ethylamino)-N-(3-nitro-
phenyl)-2-oxobut-3-enamide (5b). Yield 1.38 g
(74%), yellow crystals, mp 142–143°C (from MeCN).
IR spectrum, ν, cm–1: 3309 (N–H), 1682 (C=O,
1
amide), 1588 (C2=O). H NMR spectrum (DMSO-d6),
δ, ppm: 1.24–2.52 m (10H, CH2, Cy), 3.43 m (1H,
NHCH), 5.92 s (1H, 3-H), 7.35–7.65 m (5H, Harom),
7.96 m (1H, Harom, J = 8.1 Hz), 8.24 m (1H, Harom, J =
7.5 Hz), 8.89 s (1H, Harom), 10.95 s (1H, NH), 11.54 d
(1H, NH, J = 8.7 Hz). 13C NMR spectrum (DMSO-d6),
δC, ppm: 23.2, 24.6, 33.0, 39.0, 39.2, 39.6, 39.8, 39.9,
40.0, 52.31, 91.50, 114.20, 118.43, 126.19, 129.0,
129.2, 130.0, 135.0, 139.4, 147.9, 162.6, 167.0, 178.4.
Mass spectrum, m/z (Irel, %): 427 (29) [M]+, 286 (42),
264 (98), 262 (100), 180 (51), 139 (22), 55 (17).
Found, %: C 61.76; H 5.18; N 9.82. C22H22ClN3O4.
Calculated, %: C 61.83; H 4.65; N 9.84. M 427.89.
1
amide), 1598 (C2=O). H NMR spectrum (DMSO-d6),
δ, ppm: 1.25 t (3H, Me, J = 7.2 Hz), 3.35 q (2H, CH2,
J = 7.2 Hz), 6.17 s (1H, 3-H), 7.34–8.05 m (7H, Harom),
8.57 s (1H, Harom), 9.62 s (1H, NH), 11.25 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 373 (29) [M]+, 286
(28), 210 (49), 208 (100), 138 (51), 102 (26), 92 (27),
72 (42), 43 (28). Found, %: C 57.84; H 4.31; N 11.24.
C18H16ClN3O4. Calculated, %: C 57.90; H 4.29;
N 11.26. M 373.80.
Ethyl 4-{[4-(ethylamino)-2-oxo-4-(thiophen-2-
yl)but-3-enoyl]amino}benzoate (5c). Yield 1.54 g
(83%), yellow crystals, mp 117–119°C (from MeCN).
IR spectrum, ν, cm–1: 3254 (N–H), 1705 (C=O, ester),
Ethyl 4-{[4-(cyclohexylamino)-4-(4-methylphe-
nyl)-2-oxobut-3-enoyl]amino}benzoate (5f). Yield
1.34 g (63%), light yellow crystals, mp 148–149°C
(from toluene). IR spectrum, ν, cm–1: 3284 (N–H),
1725 (C=O, ester), 1676 (C=O, amide), 1604 (C2=O).
1H NMR spectrum (CDCl3), δ, ppm: 1.23–2.34 m
(10H, CH2, Cy), 1.37 t (3H, Me, J = 7.0 Hz), 2.40 s
(3H, Me), 3.50 m (1H, NHCH), 4.35 q (2H, CH2, J =
7.0 Hz), 6.17 s (1H, 3-H), 7.17–7.30 m (4H, Harom),
7.68 m (2H, Harom, J = 7.8 Hz), 8.03 m (2H, Harom, J =
7.8 Hz), 9.62 s (1H, NH), 11.50 d (1H, NH, J =
8.7 Hz). Mass spectrum, m/z (Irel, %): 434 (33) [M]+,
286 (55), 243 (100), 160 (47), 135 (32), 120 (24), 55
(24), 43 (43). Found, %: C 71.87; H 6.96; N 6.45.
C26H30N2O4. Calculated, %: C 71.89; H 6.28; N 6.91.
M 434.54.
1
1687 (C=O, amide), 1605 (C2=O). H NMR spectrum
(DMSO-d6), δ, ppm: 1.24 m (6H, Me), 3.63 q (2H,
CH2, J = 6.8 Hz), 4.27 q (2H, CH2, J = 6.9 Hz), 6.19 s
(1H, 3-H), 7.27–8.02 m (7H, Harom), 10.69 s (1H, NH),
11.47 t (1H, NH, J = 6.2 Hz). Found, %: C 61.27;
H 5.41; N 7.52; S 8.61. C19H20N2O4S. Calculated, %:
C 61.29; H 5.38; N 7.53; S 8.60.
Ethyl 4-{[4-(benzylamino)-4-(4-chlorophenyl)-2-
oxobut-3-enoyl]amino}benzoate (5d). Benzylamine,
0.55 mL (5 mmol), was added to a solution of 1.77 g
(5 mmol) of iminofuranone 3o in 10 mL of toluene,
and the mixture was stirred for 1 h at 30°C. The mix-
ture was evaporated by half under reduced pressure,
and the precipitate was filtered off. Yield 1.36 g (59%),
light yellow crystals, mp 140–142°C (from toluene).
IR spectrum, ν, cm–1: 3291 (N–H), 1714 (C=O, ester),
Ethyl 4-{[4-(1-adamantylamino)-2-oxo-4-(thio-
phen-2-yl)but-3-enoyl]amino}benzoate (5g). Ada-
mantan-1-amine (4d), 0.76 g (5 mmol), was added to
a solution of 1.64 g (5 mmol) of iminofuranone 3t in
10 mL of toluene, and the mixture was refluxed for
1 h. The precipitate was filtered off. Yield 1.53 g
(64%), yellow crystals, mp 172–173°C (from toluene).
IR spectrum, ν, cm–1: 3299 (N–H), 1702 (C=O, ester),
1
1691 (C=O, amide), 1606 (C2=O). H NMR spectrum
(CDCl3), δ, ppm: 1.37 t (3H, Me, J = 7.0 Hz), 3.37 s
(2H, CH2), 4.36 q (2H, CH2, J = 7.0 Hz), 5.93 s (1H, 3-
H), 7.23–8.13 m (8H, Harom), 9.44 s (1H, NH), 10.97 t
(1H, NH, J = 6.2 Hz). Found, %: C 67.46; H 5.01;
N 6.05. C26H23ClN2O4. Calculated, %: C 67.53;
H 4.98; N 6.06.
1
1687 (C=O, amide), 1605 (C2=O). H NMR spectrum
(CDCl3), δ, ppm: 1.53–2.05 m (15H, Ad), 1.37 t (3H,
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CHEMISTRY OF IMINOFURANS: XII.
855
Me, J = 7.0 Hz), 4.36 (2H, CH2, J = 7.0 Hz), 6.21 s
(1H, 3-H), 7.06 m (1H, Th, J = 5.1 Hz), 7.23 m (1H,
Th, J = 5.1 Hz), 7.46 m (1H, Th, J = 5.1 Hz), 7.4 m
(2H, Harom, J = 8.4 Hz), 8.02 m (2H, Harom, J = 8.4 Hz),
9.57 s (1H, NH), 11.54 s (1H, NH). Mass spectrum,
m/z (Irel, %): 478 (15) [M]+, 286 (100), 135 (70), 93
(14), 44 (14). Found, %: C 67.76; H 6.32; N 5.85;
S 6.70. C27H30N2O4S. Calculated, %: C 67.78; H 6.28;
N 5.86; S 6.69. M 478.62.
precipitate was filtered off and recrystallized from
acetonitrile.
4-(4-Chlorophenyl)-4-(morpholin-4-yl)-N-(3-ni-
trophenyl)-2-oxobut-3-enamide (5j). Yield 1.76 g
(85%), yellow crystals, mp 166–168°C (from MeCN).
IR spectrum, ν, cm–1: 3306 (N–H), 1688 (C=O,
1
amide), 1606 (C2=O). H NMR spectrum (DMSO-d6),
δ, ppm: 2.07–3.80 (8H, morpholine), 6.60 s (1H, 3-H),
7.44–8.21 m (7H, Harom), 8.87 s (1H, Harom), 10.70 s
(1H, NH). Mass spectrum, m/z (Irel, %): 415 (2) [M]+,
346 (12), 286 (44), 252 (42), 250 (100), 181 (64), 135
(13), 111 (15), 43 (49). Found, %: C 57.77; H 4.36;
N 10.10. C20H18ClN3O5. Calculated, %: C 57.76;
H 4.33; N 10.11. M 415.84.
N,4-Diaryl-4-(diethylamino)-2-oxobut-3-en-
amides 5h and 5i (general procedure). Diethylamine
(4e), 0.51 mL (5 mmol), was added to a solution of
5 mmol of compound 3m or 3k in 10 mL of toluene,
and the mixture was stirred for 2–4 h at 60°C. The
mixture was evaporated, the residue was treated with
hexane, and the precipitate was filtered off.
Ethyl 4-{[4-(4-methylphenyl)-4-(morpholin-
4-yl)-2-oxobut-3-enoyl]amino}benzoate (5k). Yield
1.84 g (87%), light yellow crystals, mp 146–148°C
(from MeCN). IR spectrum, ν, cm–1: 3285 (N–H),
1709 (C=O, ester), 1691 (C=O, amide), 1607 (C2=O).
1H NMR spectrum (CDCl3), δ, ppm: 1.36 t (3H, Me,
J = 7.1 Hz), 2.42 s (3H, Me), 3.19–3.86 m (8H, mor-
pholine), 4.33 q (2H, CH2, J = 7.1 Hz), 6.55 s (1H,
3-H), 7.11 m (2H, Harom, J = 7.5 Hz), 7.30 m (2H,
Harom, J = 7.5 Hz), 7.63 m (2H, Harom, J = 9.0 Hz),
7.99 m (2H, Harom, J = 9.0 Hz), 9.46 s (1H, NH). Mass
spectrum, m/z (Irel, %): 422 (8) [M]+, 286 (61), 230
(100), 145 (18), 119 (23), 43 (18). Found, %: C 68.23;
H 6.20; N 6.63. C24H26N2O5. Calculated, %: C 68.25;
H 6.16; N 6.63. M 422.49.
4-(4-Chlorophenyl)-4-(diethylamino)-N-(3-nitro-
phenyl)-2-oxobut-3-enamide (5h). Yield 1.56 g
(78%), yellow crystals, mp 148–149°C (from toluene).
IR spectrum, ν, cm–1: 3346 (N–H), 1689 (C=O,
1
amide), 1619 (C2=O). H NMR spectrum (CDCl3), δ,
ppm: 1.06 t (3H, Me, J = 6.8 Hz), 1.40 t (3H, Me, J =
6.9 Hz), 3.13 q (2H, CH2, J = 6.8 Hz), 3.63 q (2H,
CH2, J = 6.8 Hz), 6.47 s (1H, 3-H), 7.13–8.65 m (8H,
Harom), 9.54 s (1H, NH). Mass spectrum, m/z (Irel, %):
401 (14) [M]+, 346 (15), 286 (26), 237 (38), 236 (100),
181 (58), 139 (44), 72 (18), 56 (20), 43 (41). Found,
%: C 59.78; H 5.02; N 10.46. C20H20ClN3O4. Calculat-
ed, %: C 59.85; H 4.99; N 10.47.
Ethyl 4-{[4-(diethylamino)-4-(4-methylphenyl)-
2-oxobut-3-enoyl]amino}benzoate (5i). Yield 1.71 g
(84%), light yellow crystals, mp 141–143°C (from
toluene). IR spectrum, ν, cm–1: 3292 (N–H), 1701
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