Reactions of N'-[2-Oxo-5-R-furan-3(2H)-ylidene]acylhydrazides with Primary and Secondary Alcohols

Article abstract of DOI:10.1134/S1070363220050096

Abstract: Reactions of primary and secondary alcohols with N'-[2-oxo-5-R-furan-3(2H)-ylidene]acylhydrazides resulted in the furan ring decylization toform 2-[2-(arylcarbonyl)hydrazinylidene]-4-alkyl esters of R-4-oxobutanoicacids.

Full text of DOI:10.1134/S1070363220050096

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 5, pp. 815–821. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 5, pp. 715–722.
Reactions of N'-[2-Oxo-5-R-furan-3(2H)-ylidene]acylhydrazides
with Primary and Secondary Alcohols
I. A. Kizimovaa,*, N. M. Igidova, M. A. Kiseleva, D. V. Ivanovb, and A. I. Syutkinaa
a Perm State Pharmaceutical Academy of the Ministry of Health of the Russian Federation, Perm, 614990 Russia
b Perm State National Research University, Perm, 614068 Russia
*e-mail: icekingakiratotsuka@gmail.com
Received December 13, 2019; revised December 13, 2019; accepted December 22, 2019
Abstract—Reactions of primary and secondary alcohols with N'-[2-oxo-5-R-furan-3(2H)-ylidene]acylhydrazides
resulted in the furan ring decylization to form 2-[2-(arylcarbonyl)hydrazinylidene]-4-alkyl esters of R-4-oxobutanoic
acids.
Keywords: N'-[2-oxo-5-R-furan-3(2H)-ylidene]acylhydrazides, alkyl esters of 2-[2-(arylcarbonyl)hydrazinylidene]-
4-R-4-oxobutanoic acids, primary and secondary alcohols
DOI: 10.1134/S1070363220050096
3-Hydrazinylidene(imino)-3H-furan-2-ones
containing several reaction sites are widely used as
polyfunctional synthons in the preparation of acyclic
and heterocyclic compounds [1–5]. Reactions of N'-[2-
oxofuran-3(2H)-ylidene]acylhydrazides [6, 7] have been
studied only with primary aromatic and heterocyclic
amines [8, 9]. To continue the study of the reactivity of N'-
[2-oxofuran-3(2H)-ylidene]aroylhydrazides 1a–1i, herein
we investigated their reaction with OH nucleophiles.
(2–69%), as well as cyclic form C (6–92%), except for
compounds 2e, 2j, 2q, and 2t. These compounds exist
in DMSO-d6 solution as a mixture of hydrazone form
A and cyclic form B. The spectrum of hydrazone form
A contains the proton signal of the methylene group at
4.07–4.65 ppm and the proton signal of the NH group at
11.07–11.45 ppm. The proton signal of the methylene
group of hydrazone C is located at 3.86‒4.42 ppm;
the proton signal of the amino group is recorded at
12.77–13.05 ppm. In the NMR spectrum of cyclic form
C, two asymmetric doublet signals of the protons of the
methylene group are observed at 2.91–3.32 and 3.31–
3.46 ppm, and the signal of the proton of the semi-acetal
hydroxyl group is in the form of a singlet in the range of
5.73–7.33 ppm or in the field of aromatic protons.
Decyclization of the furan ring in compounds 1a–1i
upontheactionofprimaryandsecondaryalcoholsproceeds
only in the presence of catalytic amounts of triethylamine
and leads to the formation of the corresponding alkyl 2-
[2-(arylcarbonyl)hydrazinylidene]-4-R-4-oxobutanoates
2a–2aꞌ, existing in solutions as a mixture of tautomeric
forms (Scheme 1).
The mass peak of the molecular ion [M]+, m/z
395(9.0), and peaks of fragment ions confirming the
proposed structure are present in the mass spectrum of
compound 2l.
The obtained compounds 2a–2aꞌ are colorless or
yellow crystalline substances, soluble in dimethyl
sulfoxide, dimethylformamide, poorly soluble in
isopropyl alcohol, insoluble in water and hexane.
In summary, the decyclization reaction of N'-[2-oxo-
5-R-furan-3(2H)-ylidene]acylhydrazides under the action
of nucleophilic reagents opens up wide possibilities in the
synthesis of new derivatives of acylpyruvic acids with
potential biological activity.
The IR spectra of the synthesized compounds show
absorption bands of stretching vibrations of N‒H bonds
in (3380–3145 cm–1), an ester carbonyl group (1745–
1666 cm–1), and C=N bond (1642–1574 cm–1).
EXPERIMENTAL
1
The data of H NMR spectra of the obtained
compounds indicate their existence in DMSO-d6 solution
in the form of two hydrazone forms A (6–86%) and B
IR spectra were recorded on an FSM-1201 instrument
from mineral oil. NMR spectra were recorded on a Bruker
815

816
KIZIMOVA et al.
Scheme 1.
Methyl 4-oxo-4-phenyl-2-[2-(phenylcarbonyl)-
hydrazinylidene]butanoate (2b). Yield 0.94 g
(58%), colorless crystals, mp 140‒141°C (propan-2-ol).
IR spectrum, ν, cm–1: 3335, 3269, 1721, 1687, 1637, 1590.
1Н NMR spectrum, δ, ppm: form A (13%), 3.76 s (3Н,
МеО), 4.65 s (2Н, СН2), 7.63 m (10Н, НAr), 11.40 br. s
(1Н, NH); form B (74%), 3.32 d (1H, C4H2, J = 20.0 Hz),
3.38 d (1H, C4H2, J = 20.0 Hz), 3.80 s (3Н, МеО),
7.28 br. s (1Н, OH), 7.63 m (10Н, НAr); form C (13%),
3.79 s (3Н, МеО), 4.42 s (2Н, СН2), 7.63 m (10Н, НAr),
13.01 s (1Н, NH). Found, %: C 66.67; H 4.94; N 8.64.
C18H16N2O4. Calculated, %: C 66.65; H 4.96; N 8.61.
Avance III instrument from DMSO-d6 solutions operating
at 400 (1H) and 100 MHz (13C). Purity of the obtained
compounds and the reaction progress were monitored
by TLC on Sorbfil PTC P-A-UV-254 plates, eluting
with diethyl ether–benzene–acetone system (10 : 9 : 1)
and detecting with iodine vapor. Elemental analysis was
performed on a Leco CHNS-932 instrument. Melting
(decomposition) temperatures were determined on an
SMP40 instrument. The obtained elemental analysis data
correspond to the calculated ones.
Alkyl 2-[(2-arylcarbonyl)hydrazinylidene]-4-oxo-
4-R-butanoates 2a‒2aꞌ. To a suspension of 0.01 mol of
the corresponding 3-hydrazinylidenefuran-2(3H)-one
were added 20 mL of primary or secondary alcohol and
0.001 mol of triethylamine (catalyst). The mixture was
heated for 10–30 min at 64–83°С. After cooling to 0°C,
the precipitate was filtered off and recrystallized from
propan-2-ol.
Methyl 4-(4-methoxyphenyl)-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]butanoate (2c). Yield 0.96 g
(54%), yellow crystals, mp 143‒145°C (propan-2-ol).
IR spectrum, ν, cm–1: 3231, 3145, 1721, 1658, 1603. 1Н
NMR spectrum, δ, ppm: form A (59%), 3.76 s (3Н, МеО),
4.59 s (2Н, СН2), 7.55 m (9Н, НAr), 11.25 s (1Н, NH);
form B (36%), 3.28 d (1H, C4H2, J = 20.0 Hz), 3.40 d
(1H, C4H2, J = 20.0 Hz), 3.88 s (3Н, МеО), 7.55 m (10Н,
НAr + OH); form C (5%), 3.79 s (3Н, МеО), 4.35 s (2Н,
СН2), 7.55 m (9Н, НAr), 12.98 br. s (1Н, NH). Found, %:
C 64.40; H 5.12; N 7.91. C19H18N2O5. Calculated, %: C
64.42; H 5.15; N 7.93.
Methyl 5,5-dimethyl-4-oxo-2-[2-(phenylcarbonyl)-
hydrazinylidene]hexanoate (2a). Yield 0.78 g (51%),
yellow crystals, mp 153‒154°C (propan-2-ol). IR
1
spectrum, ν, cm–1: 3310, 1745, 1705, 1672, 1600. Н
NMR spectrum, δ, ppm: formA (71%), 1.17 s (9H, t-Bu),
3.71 s (3Н, МеO), 4.11 s (2Н, СН2), 7.67 m (5Н, НAr),
11.07 s (NH); form B (11%), 1.05 s (9H, t-Bu), 2.97 d
(1H, C4H2, J = 20.0 Hz), 3.45 d (1H, C4H2, J = 20.0 Hz),
3.73 s (3Н, МеО), 6.33 br. s (1Н NMR spectrum, ОH),
7.67 m (5Н, НAr); form C (18%), 1.15 s (9H, t-Bu), 3.78 s
(3Н, МеO), 3.86 s (2Н, СН2), 7.67 m (5Н, НAr), 12.77 br. s
(1Н NMR spectrum, NH). Found, %: C 63.14; H 6.62;
N 9.20. C16H20N2O4. Calculated, %: C 63.16; H 6.60;
N 9.22.
Methyl 4-(4-bromophenyl)-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]butanoate (2d). Yield
1.25 g (62%), colorless crystals, mp 148‒150°C
(propan-2-ol). IR spectrum, ν, cm–1: 3310, 1718, 1638,
1586. 1Н NMR spectrum, δ, ppm: form A (15%), 3.74 s
(3Н, МеО), 4.59 s (2Н, СН2), 7.60 m (9Н, НAr),
11.25 s (1Н NMR spectrum, NH); form B (83%),
3.31 d (1H, C4H2, J = 20.0 Hz), 3.37 d (1H, C4H2, J =
20.0 Hz), 3.78 s (3Н, МеО), 7.26 s (1Н, ОН), 7.60 m
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REACTIONS OF N'-[2-OXO-5-R-FURAN-3(2H)-YLIDENE]ACYLHYDRAZIDES
817
(9Н, НAr); form C (2%), 3.77 s (3Н, МеО), 4.34 s (2Н,
СН2), 7.60 m (9Н, НAr), 12.86 br. s (1Н, NH). Found,
%: C 53.62; H 3.75; N 6.95. C18H15BrN2O4. Calculated,
%: C 53.64; H 3.73; N 6.97.
spectrum, δ, ppm: form A (13%), 1.24 m (3Н, Ме), 4.23 m
(2Н, СН2), 4.58 s (2Н, СН2), 7.63 m (9Н, НAr), 11.30 s
(1Н, NH); form B (85%), 1.24 m (3Н, Ме), 3.31 d (1H,
C4H2, J = 20.0 Hz), 3.36 d (1H, C4H2, J = 20.0 Hz), 4.23 m
(2Н, СН2), 7.33 s (OH), 7.63 m (9Н, НAr); form C (2%),
1.14 t (3Н, Ме, J = 20.0 Hz), 4.23 m (2Н, СН2), 4.35 s
(2Н, СН2), 7.63 m (9Н, НAr), 12.94 br. s (1Н, NH). Found,
%: C 54.69; H 4.11; N 6.71. C19H17BrN2O4. Calculated,
%: C 54.66; H 4.14; N 6.73.
Ethyl 5,5-dimethyl-4-oxo-2-[2-(phenylcarbonyl)-
hydrazinylidene]hexanoate (2e). Yield 0.81 g (52%),
colorless crystals, mp 130‒131°C (propan-2-ol). 1Н NMR
spectrum, δ, ppm: form A (88%), 1.18 s (9H, t-Bu), 1.24 t
(3Н, Ме, J = 7.0 Hz), 4.13 s (2Н, СН2), 4.18 q (2Н, СН2,
J = 7.0 Hz), 7.63 m (5Н, НAr), 11.27 s (1Н, NH); form
B (12%), 1.06 s (9H, t-Bu), 1.20 t (3Н, Ме, J = 7.0 Hz),
2.95 d (1H, C4H2, J = 20.0 Hz), 3.46 d (1H, C4H2, J =
20.0 Hz), 4.20 q (2Н, СН2, J = 7.0 Hz), 7.67 m (6Н,
НAr + ОН). 13С NMR spectrum, δС, ppm: 13.89, 25.52,
25.93, 35.85, 43.93, 60.94, 61.15, 103.05, 127.70,
128.08, 128.80, 130.82, 131.79, 141.96, 133.16, 163.79,
209.88. Found, %: C 64.13; H 6.97; N 8.80. C17H22N2O4.
Calculated, %: C 64.15; H 6.94; N 8.83.
Isopropyl 5,5-dimethyl-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]hexanoate (2i). Yield 1.01 g
(61%), colorless crystals, mp 95‒96°C (propan-2-ol). 1Н
NMR spectrum, δ, ppm: form A (25%), 1.28 m (15Н,
t-Bu, 2Ме), 4.12 s (2Н, СН2), 5.09 m (1Н NMR spectrum,
СН), 7.70 m (5Н, НAr), 11.08 s (1Н, NH); form B (6%),
1.10 s (9Н, t-Bu), 1.21 m (6Н, 2Ме), 2.98 d (1H, C4H2,
J = 20.0 Hz), 3.45 d (1H, C4H2, J = 20.0 Hz), 4.23 m (2Н,
СН2), 5.09 m (1Н, СН), 5.76 br. s (OH), 7.70 m (5Н,
НAr); form C (69%), 1.21 m (15Н, t-Bu, 2Ме), 3.89 s (2Н,
СН2), 5.09 m (1Н, СН), 7.70 m (5Н, НAr), 12.96 br. s (1Н,
NH). Found, %: C 65.04; H 7.28; N 8.43. C18H24N2O4.
Calculated, %: C 65.06; H 7.25; N 8.46.
Ethyl 4-oxo-4-phenyl-2-[2-(phenylcarbonyl)hyd-
razinylidene]butanoate (2f). Yield 0.93 g (55%), yellow
crystals, mp 98‒100°C (propan-2-ol). IR spectrum, ν,
1
cm–1: 3358, 1709, 1638, 1588. Н NMR spectrum, δ,
ppm: form A (17%), 3.77 t (3Н, Ме, J = 7.1 Hz), 4.60 s
(2Н, СН2), 7.62 m (10Н, НAr), 11.30 s (1Н, NH); form
B (48%), 3.28 d (1H, C4H2, J = 20.0 Hz), 3.36 d (1H,
C4H2, J = 20.0 Hz), 7.17 s (OH), 7.62 m (10Н, НAr); form
C (35%), 1.14 t (3Н, Ме, J = 7.1 Hz), 4.36 s (2Н, СН2),
7.62 m (10Н, НAr), 12.95 br. s (1Н, NH). Found, %: C
67.45; H 5.36; N 8.28. C19H18N2O4. Calculated, %: C
67.47; H 5.33; N 8.29.
Isopropyl 4-oxo-4-phenyl-2-[2-(phenylcarbonyl)-
hydrazinylidene]butanoate (2j). Yield 1.06 g (60%),
1
yellow crystals, mp 95‒96°C (propan-2-ol). Н NMR
spectrum, δ, ppm: form A (17%), 1.21 d (6Н, 2Ме, J =
6.3 Hz), 4.59 s (2Н, СН2), 4.99 m (1Н, СН), 7.63 m
(10Н, НAr), 11.29 s (1Н, NH); form B (51%), 1.25 t (6Н,
2Ме, J = 5.9 Hz), 3.27 d (1H, C4H2, J = 20.0 Hz), 3.35 d
(1H, C4H2, J = 20.0 Hz), 5.06 t. d (1Н, СН, J = 6.2,
4.1 Hz), 7.16 br. s (OH), 7.63 m (10Н, НAr); form C
(32%), 1.14 d (6Н, 2Ме, J = 6.3 Hz), 4.33 s (2Н, СН2),
5.06 t. d (1Н, СН, J = 6.2 Hz), 7.63 m (10Н, НAr),
13.01 s (1Н, NH). Found, %: C 68.14; H 5.75; N 7.98.
C20H20N2O4. Calculated, %: C 68.16; H 5.73; N 7.96.
Ethyl 4-(4-methylphenyl)-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]butanoate (2g). Yield 0.99 g
(56%), yellow crystals, mp 119‒120°C (propan-2-ol). IR
spectrum, ν, cm–1: 3236, 3145, 1715, 1683, 1662, 1605.
1Н NMR spectrum, δ, ppm: form A (36%), 1.23 m (3Н,
Ме), 2.29 s (3Н, Ме), 4.23 m (2Н, СН2), 4.57 s (2Н, СН2),
7.57 m (9Н, НAr), 11.30 s (1Н, NH); form B (54%), 1.23
m (3Н, Ме), 2.40 s (3Н, Ме), 3.26 d (1H, C4H2, J = 20.0
Hz), 3.34 d (1H, C4H2, J = 20.0 Hz), 4.23 m (2Н, СН2),
7.07 br. s (OH), 7.57 m (9Н, НAr); form C (10%), 1.14
t (3Н, Ме, J = 20.0 Hz), 2.34 s (3Н, Ме), 4.23 m (2Н,
СН2), 4.32 s (2Н, СН2), 7.57 m (9Н, НAr), 12.95 br. s (1Н,
NH). Found, %: C 68.17; H 5.72; N 7.95. C20H20N2O4.
Calculated, %: C 68.19; H 5.70; N 7.92.
Isopropyl 4-(4-bromophenyl)-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]butanoate (2k). Yield 1.38 g
(64%), yellow crystals, mp 116‒117°C (propan-2-ol). 1Н
NMR spectrum, δ, ppm: form A (23%), 1.21 d (6Н, 2Ме,
J = 6.3 Hz), 4.56 s (2Н, СН2), 4.99 m (1Н, СН), 7.62 m
(9Н, НAr), 11.19 s (1Н, NH); form B (71%),1.25 m (6Н,
2Ме), 3.29d(1H, C4H2,J=20.0Hz), 3.34d(1H, C4H2,J=
20.0 Hz), 5.05 m (1Н, СН), 7.31 br. s (OH), 7.62 m
(9Н, НAr); form C (6%), 1.14 d (6Н, 2Ме, J =
6.3 Hz), 4.32 s (2Н, СН2), 5.05 m (1Н, СН), 7.62 m
(9Н, НAr), 12.96 br. s (1Н, NH). Found, %: C 55.70; H
4.44; N 6.50. C20H19BrN2O4. Calculated, %: C 55.73; H
4.42; N 6.53.
Ethyl 4-(4-bromophenyl)-4-oxo-2-[2-(phenyl-
carbonyl)hydrazinylidene]butanoate (2h). Yield 1.38 g
(66%), yellow crystals, mp 106‒107°C (propan-2-ol).
IR spectrum, ν, cm–1: 3358, 1710, 1637, 1588. 1Н NMR
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KIZIMOVA et al.
Methyl (Z)-5,5-dimethyl-4-oxo-2-{2-[2-(phenyl-
131.42, 133.42, 133.56, 136.58, 139.60, 141.94, 142.53,
142.63, 143.84, 144.02, 145.12, 161.51, 164.73, 167.38,
193.69. Found, %: C 69.92; H 5.40; N 9.78. C25H23N3O4.
Calculated, %: C 69.94; H 5.43; N 9.76.
amino)phenylcarbonyl]hydrazinylidene}hexanoate
(2l). Yield 1.60 g (81%), yellow crystals, mp 152‒154°C
(propan-2-ol). IR spectrum, ν, cm–1: 3380, 3202, 1722,
1640, 1584. 1Н NMR spectrum, δ, ppm: form A (86%),
1.15 s (9H, t-Bu), 3.73 s (3Н, МеO), 4.08 s (2Н, СН2),
7.24 m (9Н, НAr), 8.50 br. s (1Н, NH), 11.32 s (1Н, NH);
form B (14%), 2.91 d (1H, C4H2, J = 20.0 Hz), 3.43 d (1H,
C4H2, J = 20.0 Hz), 3.72 s (3Н, МеО), 6.46 br. s (1Н, ОH),
7.24 m (10Н, НAr + NH). 13С NMR spectrum, δС, ppm:
25.41, 25.87, 35.92, 43.96, 52.13, 116.72, 117.7, 118.95,
119.07, 121.47, 129.07, 130.26, 132.33, 141.96, 143.73,
146.25, 161.22, 164.39, 209.79. Mass spectrum, m/z
(Irel, %): 395 (9.0) [M]+, 336 (4.0) [M ‒ COOCH3]+, 196
(100.0) [2-(PhNH)С6Н4CO]+, 168 (7.0) [M ‒ COOCH3 ‒
PhNHPh]+. Found, %: C 66.82; H 6.37; N 10.63.
C22H25N3O4. Calculated, %: C 66.84; H 6.34; N 10.65.
Methyl (Z)-4-(4-methoxyphenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2o). Yield 1.11 g (50%), yellow crystals, mp
100‒102°C (propan-2-ol). IR spectrum, ν, cm–1: 3356,
1
1725, 1684, 1673, 1645, 1595. Н NMR spectrum, δ,
ppm: form A (58%), 3.79 s (3Н, МеO), 3.87 s (3Н, МеO),
4.54 s (2Н, СН2), 7.24 m (13Н, НAr), 8.57 br. s (1Н, NH),
11.45 s (1Н, NH); form B (37%), 3.28 d (1H, C4H2, J =
20.0 Hz), 3.34 d (1H, C4H2, J = 20.0 Hz), 3.75 s (3Н,
МеО), 3.85 s (3Н, МеО), 7.24 m (15Н, НAr + NH + ОН);
form C (5%), 3.72 s (3Н, МеО), 3.79 s (3Н, МеО), 4.30 s
(2Н, СН2), 7.24 m (14Н, НAr + NH), 12.99 br. s (1Н,
NH). 13С NMR spectrum, δС, ppm: 37.22, 50.67, 52.29,
55.08, 55.61, 94.25, 113.27, 113.94, 116.58, 117.86,
118.30, 118.97, 119.05, 119.53, 120.91, 121.59, 123.74,
126.10, 128.96, 129.14, 129.26, 130.29, 130.62, 132.42,
141.94, 142.65, 143.85, 145.13, 158.57, 161.53, 163.53,
163.47, 164.74, 167.46, 192.58. Found, %: C 67.41; H
5.20; N 9.43. C25H23N3O5. Calculated, %: C 67.43; H
5.22; N 9.46.
Methyl (Z)-4-oxo-4-phenyl-2-{2-[2-(phenylamino)-
phenylcarbonyl]hydrazinylidene}butanoate (2m).
Yield 1.04 g (50%), yellow crystals, mp 100‒102°C
(propan-2-ol). IR spectrum, ν, cm–1: 3341, 1720, 1646,
1594. 1Н NMR spectrum, δ, ppm: form A (24%), 3.76 s
(3Н, МеO), 4.60 s (2Н, СН2), 7.31 m (14Н, НAr), 8.56 br. s
(1Н, NH), 11.46 s (1Н, NH); form B (76%), 3.29 d (1H,
C4H2, J = 20.0 Hz), 3.36 d (1H, C4H2, J = 20.0 Hz),
Methyl (Z)-4-oxo-2-{2-[2-(phenylamino)phenyl-
carbonyl]hydrazinylidene}-4-(4-ethoxyphenyl)-
butanoate (2p). Yield 1.63 g (71%), yellow crystals,
mp 130‒132°C (propan-2-ol). IR spectrum, ν, cm–1:
3354 br, 3205, 1722, 1667, 1598. 1Н NMR spectrum, δ,
ppm: form A (39%), 1.32 t (3Н, Ме, J = 7.0 Hz), 3.79 s
(3Н, МеO), 4.02 q (2H, OCH2CH3, J = 7.0 Hz), 4.54 s
(2Н, СН2), 7.27 m (13Н, НAr), 8.57 s (1Н, NH), 11.45 s
(1Н, NH); form B (57%), 1.37 t (3Н, Ме, J = 7.0 Hz),
3.28 d (1H, C4H2, J = 20.0 Hz), 3.33 d (1H, C4H2, J =
20.0 Hz), 3.75 s (3Н, МеО), 4.16 q (2H, OCH2CH3, J =
7.0 Hz), 7.24 m (15Н, НAr + NH + ОН); form C (4%),
1.32 t (3Н, Ме, J = 7.0 Hz), 3.72 s (3Н, МеО), 4.29 s
(2Н, СН2), 7.24 m (14Н, НAr + NH), 13.02 br. s (1Н,
NH). 13С NMR spectrum, δС, ppm: 14.41, 14.62, 37.19,
50.79, 52.28, 63.00, 63.63, 94.28, 113.74, 114.33, 116.57,
117.86, 118.29, 118.96, 119.05, 119.53, 120.91, 121.59,
123.66, 126.08, 128.80, 129.14, 129.26, 130.29, 130.62,
131.41, 132.42, 134.42, 140.99, 141.94, 142.50, 142.64,
143.85, 145.04, 157.82, 161.45, 162.76, 164.75, 167.37,
192.54. Found, %: C 67.96; H 5.48; N 9.14. C26H25N3O5.
Calculated, %: C 67.98; H 5.46; N 9.17.
3.79 s (3Н, МеО), 7.31 m (16Н, НAr + NH + ОН). 13
С
NMR spectrum, δС, ppm: 50.92, 52.34, 94.26, 117.89,
118.31, 119.04, 119.55, 120.94, 121.57, 124.75, 127.39,
127.94, 128.72, 129.15, 129.20, 130.59, 131.46, 132.42,
133.54, 135.98, 141.94, 142.52, 142.85, 143.84, 145.18,
161.48, 164.73, 167.38, 194.11. Found, %: C 69.39; H
5.14; N 10.14. C24H21N3O4. Calculated, %: C 69.36; H
5.16; N 10.17.
Methyl (Z)-4-methylphenyl-4-oxo-2-{2-[2-(phenyl-
amino)phenylcarbonyl]hydrazinylidene}butanoate
(2n). Yield 1.37 g (64%), yellow crystals, mp 135‒136°C
(propan-2-ol). IR spectrum, ν, cm–1: 3351, 1719, 1678,
1642, 1594. 1Н NMR spectrum, δ, ppm: form A (19%),
2.41 s (3Н, Ме), 3.78 s (3Н, МеO), 4.56 s (2Н, СН2),
7.24 m (13Н, НAr), 8.56 s (1H, NH), 11.45 s (1Н, NH);
form B (48%), 2.38 s (3Н, Ме), 3.26 d (1H, C4H2, J =
20.0 Hz), 3.34 d (1H, C4H2, J = 20.0 Hz), 3.78 s (3Н,
МеО), 7.24 m (15Н, НAr + NH + ОН); form C (3%),
2.30 s (3Н, Ме), 3.72 s (3Н, МеО), 4.32 s (2Н, СН2),
7.24 m (14Н, НAr + NH). 13С NMR spectrum, δС, ppm:
20.58, 21.16, 37.46, 50.88, 52.31, 94.3, 116.56, 117.83,
118.33, 118.95, 119.05, 119.52, 120.94, 121.58, 123.65,
124.7, 128.36, 128.49, 129.14, 129.26, 130.3, 130.57,
Methyl (Z)-4-(3,4-dimethoxyphenyl)-4-oxo-2-{2-
[2-(phenylamino)phenylcarbonyl]hydrazinylidene}-
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REACTIONS OF N'-[2-OXO-5-R-FURAN-3(2H)-YLIDENE]ACYLHYDRAZIDES
819
butanoate (2q). Yield 1.31 g (55%), yellow crystals, mp
103‒105°C (propan-2-ol). IR spectrum, ν, cm–1: 3279,
1714, 1668, 1589. Н NMR spectrum, δ, ppm: form A
138.50, 141.87, 142.35, 142.68, 143.76, 145.15, 161.39,
164.63, 167.29, 192.69. Found, %: C 66.51; H 4.65; N
9.69. C24H20FN3O4. Calculated, %: C 66.54; H 4.63; N
9.67.
1
(48%), 3.75 s (3Н, МеО), 3.75 s (3Н, МеО), 4.56 s (2Н,
СН2), 7.26 m (12Н, НAr), 8.57 s (1Н, NH), 11.14 s (1Н,
NH); form A (52%), 3.27 d (1Н, СН2, J = 20.0 Hz),
3.36 d (1Н, СН2, J = 20.0 Hz), 3.75 s (3Н, МеО), 3.75 s
(3Н, МеО), 7.24 m (14Н, НAr + NH + ОН). 13С NMR
spectrum, δС, ppm: 37.19, 52.3, 55.47, 55.58, 55.65,
55.86, 94.19, 109.06, 110.62, 111.02, 111.35, 116.59,
117.18, 117.58, 118.45, 118.99, 119.02, 119.37, 121.02,
121.59, 123.23, 123.57, 128.89, 129.15, 129.25, 130.26,
130.54, 131.36, 132.4, 141.93, 142.49, 143.8, 145.22,
148.64, 153.52, 164.7, 167.4, 192.64. Found, %: C 67.96;
H 5.48; N 9.14. C26H25N3O5. Calculated, %: C 67.98; H
5.46; N 9.17.
Methyl (Z)-4-(4-chlorophenyl)-4-oxo-2-(2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2t). Yield 1.40 g (62%), yellow crystals, mp
1
132‒134
°C (propan-2-ol). Н NMR spectrum, δ, ppm:
form A (24%), 3.79 s (3Н, МеО), 4.58 s (2Н, СН2), 7.36 m
(13Н, НAr), 8.54 br. s (1Н, NH), 11.44 s (1Н, NH); form
B (76%), 3.13 d (1H, C4H2, J = 20.0 Hz), 3.35 d (1H,
C4H2, J = 20.0 Hz), 3.75 s (3Н, МеО), 7.36 m (14Н,
НAr + OH), 8.92 br. s (1Н, NH). 13С NMR spectrum, δС,
ppm: 50.70, 52.35, 93.66, 118.19, 119.03, 119.36, 119.71,
120.83, 123.95, 126.88, 127.84, 128.85, 129.12, 130.10,
130.49, 131.46, 132.09, 141.48, 142.40, 142.81, 145.26,
161.42, 167.29. Found, %: C 64.07; H 4.48; N 9.34.
C24H20ClN3O4. Calculated, %: C 64.05; H 4.46; N 9.37.
Methyl (Z)-4-(4-bromophenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylylidene}-
butanoate (2r). Yield 1.24 g (50%), yellow crystals, mp
133‒135°C (propan-2-ol). IR spectrum, ν, cm–1: 3257,
Ethyl (Z)-5,5-dimethyl-4-oxo-2-{2-[2-(phenyl-
amino)phenylcarbonyl]hydrazinylidene}hexanoate
(2u). Yield 1.76 g (86%), yellow crystals, mp 129‒130°C
(propan-2-ol). IR spectrum, ν, cm–1: 3378, 1709, 1639,
1589. 1Н NMR spectrum, δ, ppm: form A (85%), 1.15 s
(9Н, t-Bu), 1.23 m (3Н, CH2CH3), 4.07 s (2Н, СН2), 4.18 q
(2Н, CH2CH3, J = 7.1 Hz), 7.25 m (13Н, НAr), 8.48 br. s
(1Н, NH), 11.31 s (1Н, NH); form B (15%), 1.03 s (9H,
t-Bu), 1.23 m (3Н, CH2CH3), 2.91 d (1H, C4H2, J =
20.0 Hz), 3.43 d (1H, C4H2, J = 20.0 Hz), 4.18 q (2Н,
CH2CH3, J = 7.1 Hz), 6.45 br. s (1Н, OH), 7.25 m (10Н,
НAr + NH). 13С NMR spectrum, δС, ppm: 13.97, 25.54,
25.97, 35.98, 43.99, 61.01, 116.78, 119.00, 119.16,
121.50, 129.04, 129.24, 130.36, 132.34, 142.07, 143.75,
163.85, 209.85. Found, %: C 67.46; H 6.65; N 10.26.
C23H27N3O4. Calculated, %: C 67.48; H 6.63; N 10.29.
1
1707, 1656, 1574. Н NMR spectrum, δ, ppm: form
A (12%), 3.76 s (3Н, МеО), 4.58 s (2Н, СН2), 7.26 m
(13Н, НAr), 8.55 br. s (1Н, NH), 11.45 s (1Н, NH); form
B (86%), 3.26 d (1H, C4H2, J = 20.0 Hz), 3.35 d (1H,
C4H2, J = 20.0 Hz), 3.79 s (3Н, МеО), 7.26 m (14Н, НAr +
ОН); form C (2%), 3.73 s (3Н, МеО), 4.35 s (2Н, СН2),
7.26 m (14Н, НAr + NH), 13.02 br. s (1Н, NH). 13С NMR
spectrum, δС, ppm: 50.67, 52.35, 61.30, 93.71, 118.21,
118.39, 119.05, 119.70, 120.67, 120.84, 123.92, 127.23,
129.13, 129.25, 130.20, 130.50, 130.78, 131.47, 131.82,
141.94, 142.43, 142.81, 145.27, 161.42,167.30, 193.34.
Found, %: C 58.31; H 4.08; N 8.50. C24H20BrN3O4.
Calculated, %: C 58.33; H 4.06; N 8.52.
Methyl (Z)-4-(4-fluorophenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2s). Yield 1.10 g (51%), yellow crystals, mp
123‒125°C (propan-2-ol). IR spectrum, ν, cm–1: 3345 br,
Ethyl (Z)-4-oxo-4-phenyl-2-{2-[2-(phenylamino)-
phenylcarbonyl]hydrazinylidene}butanoate (2v).
Yield 1.83 g (87%), yellow crystals, mp 142‒144°C
(propan-2-ol). IR spectrum, ν, cm–1: 3380, 3276, 1714,
1
3169 br, 1717, 1692, 1640, 1595. Н NMR spectrum,
1
δ, ppm: form A (68%), 3.75 s (3Н, МеO), 4.58 s (2Н,
СН2), 7.36 m (12Н, НAr), 8.56 br. s (1Н, NH), 11.44 s
(1Н, NH); form B (24%), 3.21 d (1H, C4H2, J = 20.0 Hz),
3.37 d (1H, C4H2, J = 20.0 Hz), 3.79 s (3Н, МеО), 7.36 m
(14Н, НAr + NH + ОН); form C (8%), 3.82 s (3Н, МеO),
4.32 s (2Н, СН2), 7.36 m (13Н, НAr + NH). 13С NMR
spectrum, δС, ppm: 37.50, 50.71, 52.27, 93.73, 114.40,
114.62, 115.58, 115.80, 116.56, 118.14, 118.95, 119.59,
120.80, 121.51, 123.82, 126.92, 127.00, 129.07, 129.19,
130.24, 130.46, 131.14, 131.23, 131.38, 132.38, 132.67,
1684, 1640, 1595. Н NMR spectrum, ppm: form
A (25%), 1.23 t (3Н, CH2CH3, J = 7.1 Hz), 4.23 t
(2Н, CH2CH3, J = 7.1 Hz), 4.56 s (2Н, СН2), 7.27 m
(14Н, НAr), 8.56 br. s (1Н, NH), 11.44 s (1Н, NH);
form B (49%), 1.25 t (3Н, CH2CH3, J =7.1 Hz), 3.26 d
(1H, C4H2, J = 20.0 Hz), 3.33 d (1H, C4H2, J = 20.0 Hz),
4.23 m (2Н, CH2CH3), 7.27 m (15Н, НAr + ОН), 9.01 br. s
(1Н, NH); form C (6%), 1.12 t (3Н, CH2CH3, J = 7.1 Hz),
4.23 m (2Н, CH2CH3), 4.30 s (2Н, СН2), 7.27 m (15Н,
НAr + NH), 13.05 br. s (1Н, NH). 13С NMR spectrum,
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820
KIZIMOVA et al.
δС, ppm: 13.52, 13.98, 20.58, 21.15, 37.44, 43.74, 50.93,
61.11, 61.28, 61.72, 94.28, 116.53, 117.31, 117.63,
118.45, 118.94, 119.04, 119.42, 119.53, 119.66, 120.99,
121.58, 121.98, 123.55, 124.69, 128.23, 128.35, 128.49,
128.82, 129.14, 129.25, 129.29, 129.33, 130.31, 130.62,
131.43, 132.37, 133.53, 133.60, 136.53, 139.69, 141.95,
142.57, 142.62, 144.00, 144.14, 161.01, 161.40, 164.18,
167.39, 193.76, 196.31. Found, %: C 69.92; H 5.40; N
9.78. C25H23N3O4. Calculated, %: C 69.94; H 5.43; N 9.76.
mp 112‒114°C (propan-2-ol). IR spectrum, ν, cm–1:
3329 br, 3257, 1705, 1666, 1589. H NMR spectrum,
1
δ, ppm: form A (6%), 1.23 t (3Н, CH2CH3, J =
7.1 Hz), 4.26 m (2Н, CH2CH3), 4.57 s (2Н, СН2),
7.28 m (13Н, НAr), 8.53 br. s (1Н, NH), 11.40 s (1Н,
NH); form B (92%), 1.26 t (3Н, CH2CH3, J = 7.1 Hz),
3.17 d (1H, C4H2, J = 20.0 Hz), 3.35 d (1H, C4H2, J =
20.0 Hz), 4.26 m (2Н, CH2CH3), 7.28 m (15Н, НAr + NH +
ОН); form C (2%), 1.12 t (3Н, CH2CH3, J = 7.1 Hz),
4.26 m (2Н, CH2CH3), 4.34 s (2Н, СН2), 7.28 m (15Н,
НAr + NH), 13.03 br. s (1Н, NH). 13С NMR spectrum, δС,
ppm:13.98, 50.76, 61.30, 93.63, 118.03, 118.32, 120.90,
123.85, 126.69, 127.84, 129.13, 130.53, 131.47, 132.06,
141.50, 142.49, 142.75, 145.54, 160.92, 167.30, 193.21.
Found, %: C 64.73; H 4.78; N 9.06. C25H22ClN3O4.
Calculated, %: C 64.71; H 4.76; N 9.03.
Ethyl (Z)-4-oxo-4-methylphenyl-2-{2-[2-(phenyl-
amino)phenylcarbonyl]hydrazinylidene}butanoate
(2w). Yield 1.86 g (84%), yellow crystals, mp 155‒157°C
(propan-2-ol). IR spectrum, ν, cm–1: 3351, 1712, 1685,
1577. 1Н NMR spectrum, δ, ppm: form A (23%), 1.23 t
(3Н, CH2CH3, J = 7.1 Hz), 2.30 s (3Н, Ме), 4.26 m (2Н,
CH2CH3), 7.25 m (13Н, НAr), 8.56 br. s (1Н, NH), 11.44 s
(1Н, NH); form B (73%), 1.26 t (3Н, CH2CH3, J = 7.1 Hz),
2.41 s (3Н, Ме), 3.26 d (1H, C4H2, J = 20.0 Hz), 3.33 d
(1H, C4H2, J = 20.0 Hz), 7.25 m (15Н, НAr + NH + ОН);
form C (4%), 1.12 t (3Н, CH2CH3, J = 7.1 Hz), 2.38 s
(3Н, Ме), 4.30 s (2Н, СН2), 7.25 m (14Н, НAr + NH),
13.04 br. s (1Н, NH). 13С NMR spectrum, δС, ppm:
13.98, 20.58, 21.15, 37.45, 50.93, 61.12, 61.26, 94.28,
116.54, 117.63, 118.45, 119.04, 121.00, 123.55, 124.69,
128.35, 128.49, 129.14, 129.25, 129.34, 131.43, 133.60,
136.53, 139.69, 141.95, 142.57, 142.62, 144.00, 145.40,
161.01, 164.18, 167.39, 193.77. Found, %: C 70.41; H
5.68; N 9.47. C26H25N3O4. Calculated, %: C 70.43; H
5.65; N 9.49.
Isopropyl 5,5-dimethyl-4-oxo-2-{2-[2-(phenyl-
amino)phenylcarbonyl]hydrazinylidene}hexanoate
(2z). Yield 1.14 g (54%), yellow crystals, mp 105‒107°C
(propan-2-ol). 1Н NMR spectrum, δ, ppm: form A (60%),
1.07 s (9Н, t-Bu), 1.25 d (6Н, 2Ме, J = 6.3 Hz), 4.07 s
(2Н, СН2), 5.02 m (1Н, СН), 7.24 m (5Н, НAr), 8.40 br. s
(1H, NH), 11.15 s (1H, NH); form B (8%), 1.18 t (6Н,
Ме, J = 3.7 Hz), 2.95 d (1H, C4H2, J = 20.0 Hz), 3.41 d
(1H, C4H2, J = 20.0 Hz), 5.09 m (1Н, СН), 5.73 br. s
(OH), 7.24 m (6Н, НAr + NH); form C (32%), 1.18 t (6Н,
Ме, J = 3.3 Hz), 3.84 s (2Н, СН2), 5.09 m (1Н, СН),
7.24 m (5Н, НAr), 8.91 br. s (1H, NH), 12.98 br. s (1H,
NH). Found, %: C 68.06; H 6.90; N 9.92. C24H29N3O4.
Calculated, %: C 68.04; H 6.93; N 9.95.
Ethyl (Z)-4-(4-methoxyphenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2x). Yield 1.15 g (50%), yellow crystals, mp
140‒142°C (propan-2-ol). IR spectrum, ν, cm–1: 3352,
3164, 1706, 1681, 1595. 1Н NMR spectrum, δ, ppm: form
A (86%), 1.23 m (3Н, CH2CH3), 3.87 s (3Н, МеО), 4.22 m
(2Н, СН2СН3), 4.53 s (2Н, СН2), 7.25 m (13Н, НAr),
8.53 br. s (1Н, NH), 11.43 s (1Н, NH); form C (14%),
1.23 m (3Н, CH2CH3), 3.75 s (3Н, МеО), 4.22 m (2Н,
СН2СН3), 4.26 s (2Н, СН2), 7.25 m (14Н, НAr + NH).
13С NMR spectrum, δС, ppm: 13.91, 37.13, 55.01, 55.53,
61.05, 113.20, 113.87, 116.50, 118.34, 118.90, 118.96,
121.50, 126.02, 128.91, 129.07, 129.19, 130.21, 130.54,
131.35, 132.32, 134.53, 141.88, 143.74, 163.40, 164.13,
192.60. Found, %: C 67.96; H 5.48; N 9.14. C26H25N3O5.
Calculated, %: C 67.94; H 5.45; N 9.16.
Isopropyl 4-(4-methylphenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2aꞌ). Yield 1.19 g (52%), yellow crystals,
1
mp 123‒125°C (propan-2-ol). Н NMR spectrum, δ,
ppm: form A (40%), 1.24 d (6Н, Ме, J = 6.3 Hz), 2.43 s
(3Н, Ме), 4.52 s (2Н, СН2), 5.08 m (1Н, СН), 7.26 m
(9Н, НAr), 8.47 br. s (1H, NH), 11.27 s (1H, NH); form
B (48%), 1.29 m (6Н, Ме), 2.32 s (3Н, Ме), 3.26 d (1H,
C4H2, J = 20.0 Hz), 3.36 d (1H, C4H2, J = 20.0 Hz),
5.02 m (1Н, СН), 7.26 m (11Н, НAr + NH + ОН); form
C (32%), 1.17 d (6Н, 2Ме, J = 6.3 Hz), 2.43 s (3Н, Ме),
26 s (2Н, СН2), 5.08 m (1Н, СН), 7.26 m (9Н, НAr),
8.91 br. s (1H, NH), 12.97 s (1H, NH). Found, %: C
70.88; H 5.95; N 9.18. C27H27N3O4. Calculated, %: C
70.85; H 5.97; N 9.16.
Ethyl (Z)-4-(4-chlorophenyl)-4-oxo-2-{2-[2-
(phenylamino)phenylcarbonyl]hydrazinylidene}-
butanoate (2y). Yield 1.72 g (74%), yellow crystals,
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821
5. Zalesov, V.V. and Rubtsov, A.E., Chem. Heterocycl.
Compd., 2004, vol. 40, no. 2, p. 133.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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