Synthesis and structure of N-Aryl(phenoxy, benzylidene)acetyl-1,4- benzoquinone monoimines

Article abstract of DOI:10.1134/S1070428012100089

New N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines were synthesized by reaction of aminophenols with arylacetyl, phenoxyacetyl, and cinnamoyl chlorides in dimethylformamide-acetic acid (1 : 3) in the presence of anhydrous sodium acetate. Structural parameters of the products and their probable biological activity were determined. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012100089

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 10, pp. 1309–1319. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, V.M. Vasil’eva, O.V. Shishkin, G.V. Palamarchuk, V.N. Baumer, 2012, published in Zhurnal
Organicheskoi Khimii, 2012, Vol. 48, No. 10, pp. 1313–1323.
Synthesis and Structure of N-Aryl(phenoxy, benzylidene)acetyl-
1,4-benzoquinone Monoimines
A. P. Avdeenkoa, S. A. Konovalovaa, V. M. Vasil’evaa, O. V. Shishkinb, c,
G. V. Palamarchukb, and V. N. Baumerb
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine
c Karazin Kharkov Natsional University, Kharkov, Ukraine
Received April 9, 2012
Abstract—New N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines were synthesized by reac-
tion of aminophenols with arylacetyl, phenoxyacetyl, and cinnamoyl chlorides in dimethylformamide–acetic
acid (1:3) in the presence of anhydrous sodium acetate. Structural parameters of the products and their
probable biological activity were determined.
DOI: 10.1134/S1070428012100089
N-Acyl-1,4-benzoquinone monoimines synthesized
previously [1–6] are biologically active compounds.
Among these, the most interesting is N-acetyl-1,4-
benzoquinone monoimine which is a hepatotoxic me-
tabolite of N-(4-hydroxyphenyl)acetamide (acetamino-
phen, paracetamol) [7] widely used in medical prac-
tice. Introduction of alkyl substituents into the quinoid
ring of N-acetyl-1,4-benzoquinone monoimine essen-
tially affects its biological activity and toxicity [3, 8].
N-(4-Hydroxyphenyl) carboxamides can be syn-
thesized by acylation of 4-aminophenols with acid
chlorides in the presence of triethylamine, sodium
acetate, or sodium carbonate [13, 14] in pyridine,
diethyl ether, or dimethylformamide–acetic acid. Our
experiments showed that the best results (i.e., the
highest yield and purity of the products) were obtained
when reactions of aminophenols Ia–Ig with acyl chlo-
rides II–V were performed in a mixture of DMF with
AcOH at a ratio of 1:3 in the presence of anhydrous
sodium acetate. We thus isolated the corresponding
N-(4-hydroxyphenyl)-2-aryl(phenoxy)acetamides
VIa–VIg, VIIa–VIIg, and VIIIa–VIIIg and
(2E)-N-(4-hydroxyphenyl)-3-phenylprop-2-enamides
IXa–IXg (Scheme 1). The procedure was also advan-
tageous due to relatively low cost of the solvents used.
The present work was aimed at extending the series
of N-acyl-1,4-benzoquinone monoimines by synthesiz-
ing new N-(4-hydroxyphenyl)-2-aryl(phenoxy)acet-
amides, (2E)-N-(4-hydroxyphenyl)-3-phenylprop-2-
enamides, and the corresponding N-aryl(phenoxy,
benzylidene)acetyl-1,4-benzoquinone monoimines
having various alkyl groups in the quinoid ring. We
also intended to determine their structural parameters
and estimate probable biological activity.
N-(4-Hydroxyphenyl)-2-aryl(phenoxy)acetamides
and (2E)-N-(4-hydroxyphenyl)-3-phenylprop-2-
enamides may be regarded as structural analogs of
acetaminophen in which one or two hydrogen atoms in
the MeCO group are replaced by an Ar, PhCH=, or
PhO fragment. The target compounds were synthesized
on the basis of arylacetic, cinnamic, and phenoxyacetic
acids whose derivatives are widely used as herbicides,
pesticides, fungicides [9], and medicines [10–12].
The IR spectra of compounds VI–IX contained ab-
sorption bands at 3380–3430, 3200–3350, and 1580–
1665 cm–1, typical of stretching vibrations of OH, NH,
and C=O groups, respectively. Quinone imines X–XIII
displayed in the IR spectra carbonyl absorption bands
at 1680–1730 (amide) and 1620–1650 cm–1 (quinone)
and C=N absorption band at 1570–1610 cm–1. In the
1H NMR spectra of amides VI–IX, the OH and NH
protons resonated as singlets at δ 9.26–9.92 (OH) and
7.81–9.20 ppm (NH). Protons in the CH2 and OCH2
groups gave singlets at δ 3.55–3.59 and 4.60–4.62 ppm,
1309

AVDEENKO et al.
1310
Scheme 1.
OH
OH
O
R1
R4
R2
R3
R1
R4
R2
R1
R4
R2
R3
O
[O]
+
X
Cl
R3
NH2
NHC(O)X
NC(O)X
Ia–Ig
II–V
VIa–VIg, VIIa–VIIg
VIIIa–VIIIg, IXa–IXg
Xa–Xg, XIa–XIg
XIIa–XIIg, XIIIa–XIIIg
II, VI, X, X = PhCH2; III, VII, XI, X = 4-MeC6H4CH2; IV, VIII, XII, X = PhOCH2; V, IX, XIII, X = PhCH=CH; R1 = R2 = R3 =
R4 = H (a); R2 = R3 = R4 = H, R1 = Me (b); R1 = R4 = Me, R2 = R3 = H (c); R1 = R3 = Me, R2 = R4 = H (d); R1 = R2 = H, R3 = R4 =
Me (e); R1 = i-Pr, R2 = R4 = H, R3 = Me (f); R1 = R2 = Me, R3 = R4 = H (g).
respectively, and the CH=CH fragment appeared as
two doublets at δ 6.88–7.53 ppm.
IR spectroscopy. Their IR spectra contained absorption
bands at 1680–1730, 1620–1650, and 1570–1610 cm–1
typical of amide carbonyl, quinone carbonyl, and C=N
bond respectively, whereas no absorption was ob-
served in the region 3380–3430 cm–1 (NH, OH).
N-Substituted 1,4-benzoquinone monoimines are
generally synthesized by oxidation of the correspond-
ing aminophenols [1–7, 13, 15, 16] with lead tetraace-
tate in acetic acid, silver oxide in chloroform, and
sodium dichromate in acetic acid. Oxidant should be
selected with account taken of the redox potential and
stability of targeted quinone imine. We found that the
most appropriate oxidant for the preparation of com-
pounds Xc–Xg, XIc–XIg, XIIc–XIIg, and XIIIc–
XIIIg is lead tetraacetate and that quinone imines Xa,
Xb, XIa, XIb, XIIa, XIIb, XIIIa, and XIIIb are better
to obtain using silver(I) oxide in chloroform.
N-Aryl(phenoxy, benzylidene)-3,5-dimethyl-
acetyl-1,4-benzoquinone monoimines Xe–XIIIe
characteristically displayed in the 1H NMR spectra one
singlet from protons in the quinoid ring (δ 6.38–
6.45 ppm) and one singlet from the methyl protons at
δ 2.02–2.16 ppm. Signals from protons in the quinoid
ring and methyl groups in the spectra of isomeric
2,6-dimethyl derivatives Xg–XIIIg also appeared as
singlets at δ 6.47–6.84 and 1.94–2.06 ppm, respec-
tively. These data indicate fast (on the NMR time
scale) Z,E-isomerization about the C=N bond; i.e., the
energy barrier to that isomerization is low [17]. Analo-
gous pattern was observed previously in the spectra of
N-acetyl-2,6(3,5)-dialkyl analogs [3]. The barrier to
Z,E-isomerization in N-benzoyl-2,6-di-tert-butyl-1,4-
benzoquinone monoimine was experimentally estimat-
ed at 43.3 kJ/mol [17].
The formation of compounds Xa, Xb, XIa, XIb,
XIIa, XIIb, XIIIa, and XIIIb was proved by TLC and
C15
C6
O1
C1
C2
O1A
C15A
C5
C6A
C1A
C16
C5A
1
C16A
In the H NMR spectra of XIa, XIb, and XIe dou-
C3
C2A
C4
blets from aromatic protons (2′-H/6′-H and 3′-H/5-H)
in the p-tolyl fragment were located very closely to
each other, while the four aromatic protons in the
spectra of XIc, XId, XIf, and XIg resonated as one
broadened singlet, indicating magnetic equivalence of
these protons.
C4A
C3A
N1
N1A
O2A
C7
O2
C7A
C8A
C8
C9
C10
The structure of quinone imines Xg, XIIg, and
XIIIg was unambiguously proved by X-ray analysis;
for comparison, the X-ray diffraction data were also
obtained for N-acetyl and N-benzoyl derivatives XIVg
and XV which were synthesized previously (Figs. 1–5;
Table 1). Replacement of hydrogen atom in the acetyl
group of XIVg by benzyl or phenoxy group in going to
Xg or XIIg did not result in appreciable variation of
geometric parameters. The examined molecules are
C14
C9A
C10A
C11
C12
C11A
C12A
C14A
C13
C13A
Fig. 1. Structure of the molecule of N-(3,5-dimethyl-4-oxo-
cyclohexa-2,5-dien-1-ylidene)phenylacetamide (Xg) accord-
ing to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

SYNTHESIS AND STRUCTURE OF N-ARYL(PHENOXY, BENZYLIDENE)ACETYL-...
1311
C9
characterized by almost orthogonal orientation of the
substituent on the nitrogen atom with respect to the
quinoid ring and some twist of the double C=N bond
(cf. torsion angles C3–C4=N–C7; Table 1). An excep-
tion is N-acetyl derivative in which the double C=N
bond is not twisted, presumably due to the lack of
steric hindrances.
O2
C2
C3
O1
C1
O3
C12
C7
C11
C4
C13
C14
C8
N1
C5
C6
C10
C16
C15
The C–N=C bond angles in Xg, XIIg, XIVg, and
XV differ insignificantly, and the C=N and C–N bond
lengths therein are also similar (Table 1). Considerable
differences are observed only for quinone imine XIIIg
which is characterized by the largest C–N=C bond
angle, longest N–C7 and C=N bonds, and largest
dihedral angle formed by the C7=O group and quinoid
ring plane (C1–C6). According to quantum-chemical
Fig. 2. Structure of the molecule of N-(3,5-dimethyl-4-oxo-
cyclohexa-2,5-dien-1-ylidene)phenoxyacetamide (XIIg) ac-
cording to the X-ray diffraction data.
C10
C2
O2
C7
C13
O1
C11
C12
C3
C4
C1
C14
C15
calculations (Table 2), strong πC=C(Ph)→π*
and
CH=CH
C8
πCH=CH→π* conjugative interactions (71.14 and
C=O
C17
N1
C16
78.42 kJ/mol, respectively) in molecule XIIIg consid-
erably increase the energy of the π-bonding orbital of
the C=O group and reduce the energy of its π-anti-
bonding orbital, as compared to XIVg. On the other
hand, the energies of both π-bonding and π-antibond-
ing orbitals of the C=N bond increase (Table 2). As
a result, πC=N→π* and nN→π* interactions in
C6
C5
C9
Fig. 3. Structure of the molecule of N-(3,5-dimethyl-4-oxo-
cyclohexa-2,5-dien-1-ylidene)-3-phenylprop-2-enamide
(XIIIg) according to the X-ray diffraction data.
C=O
C=O
O2
N1
C3
C1
XIIIg become much stronger, which leads to the above
structural peculiarities.
C9
C4
C5
C2
C7
C6
Strong πC=C(Ph)→π*
conjugative interaction
C=O
O1
C8
(76.45 kJ/mol) is also typical of N-benzoyl derivative
XV (Table 2) which was synthesized by us previously
[18]; as well as compounds Xg and XIIg–XIVg,
quinone imine XV may be classed with N-acyl-1,4-
C10A
C6A
C8A
C10
C1A
O1A
C5A
benzoquinone monoimines. The πC=C(Ph)→π* inter-
C=O
C7A
O2A
action in XV favors (cf. XIIIg) coplanar arrangement
of the phenyl fragment and C=O group (Fig. 5;
Table 1); the dihedral angle between the C7=O group
and the C8–C13 ring plane is as small as 6.59°. Insignif-
icant differences in the geometric parameters of the
quinoid ring and C4=N–C=O fragment in XV and
XIVg (Table 1) suggest their structural similarity and
hence similar reactivities.
C9A
C4A
C3A
C2A
N1A
Fig. 4. Structure of the molecule of N-(3,5-dimethyl-4-oxo-
cyclohexa-2,5-dien-1-ylidene)acetamide (XIVg) according
to the X-ray diffraction data.
C15
O2
C10
C11
C9
C2
C8
Amides VI–IX are structural analogs of acetamino-
phen which is widely used in medical practice; there-
fore, these compounds were expected to exhibit bio-
logical activity. For example, theoretical and experi-
mental studies revealed high antimicrobial activity of
compound IXa [19]. Probable biological activity of
newly synthesized N-(4-hydroxyphenyl)-2-phenyl-
(phenoxy)acetamides VIa–VIe, VIg, VIIIa–VIIIe,
and VIIIg and (2E)-N-(4-hydroxyphenyl)-3-phenyl-
prop-2-enamides IXa–IXe and IXg, as well as of
C3
C4
C7
C1
O1
N1
C12
C13
C5
C6
C14
Fig. 5. Structure of the molecule of N-(3,5-dimethyl-4-oxo-
cyclohexa-2,5-dien-1-ylidene)benzamide (XV) according to
the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

AVDEENKO et al.
1312
Table 1. X-Ray diffraction data for quinone imines Xg, XIIg–XIVg, and XV
Me
2
O
3
X
1
7
6
4
O
N
Me
5
Xg
molecule A molecule B
XIVg
Parameter
XIIg
XIIIg
XV
molecule A molecule B
∠C7NC4, deg
d(C4=N), Å
d(C7–N), Å
123.4(1)
1.287(2)
1.405(2)
122.7(1)
1.293(2)
1.406(2)
122.2(1)
1.289(2)
1.399(2)
119.7(1)
1.313(1)
1.455(2)
122.3(2)
1.284(3)
1.412(3)
123.5(2)
1.284(3)
1.405(5)
123.0(1)
1.286(2)
1.398(2)
Dihedral angle between
the C7=O bond and
C1–C6 plane, deg
58.51
60.65
63.67
66.41
58.87
54.06
61.19
d(C7···C3), Å
2.887
2.615
2.865
2.588
3.2(2)
2.841
2.547
2.717
2.390
2.858
2.576
0.4(2)
2.882
2.608
1.1(2)
2.865
2.562
d(C7···H3), Å
Torsion angle C3C4NC7, deg
–2.8(2)
–6.7(1)
–4.5(2)
–4.9(2)
Table 2. Calculated energies of orbitals and orbital interactions in quinone imines Xg, XIIg–XIVg, and XV
Me
2
O
3
X
1
7
6
4
O
N
Me
5
Energy, kJ/mol
Orbital (interaction)
Xg
XIIg
XIIIg
XIVg
XV
π(C4=N)
π*(C4=N)
π(C7=O)
π*(C7=O)
n(N)
–923.07
00–7.30
–1292.110
–231.15
–970.67
–032.40
–036.45
–934.44
0–24.84
–905.11
00–9.92
–1094.650
–099.45
–959.91
–100.49
–046.52
–919.61
00–4.65
–1219.570
–173.89
–970.99
–040.88
–041.76
–914.41
00–1.08
–1110.590
–093.42
–966.05
–092.80
–048.86
–1200.060
–123.50
–986.11
–062.66
–033.06
π* →π*
C=N
C=O
nN→π*
C=O
N-(4-hydroxyphenyl)acetamides XIVa–XIVe and
XIVg described previously, was estimated using PASS
(Prediction of Activity Spectra for Substances) pro-
gram [20]. It was found that in most cases enhance-
ment of “useful” activity (antipyretic and analgesic) in
the examined series of compounds is accompanied by
increase in their hepatotoxicity, which is a considerable
drawback. However, compounds VIa–VIe and VIg
were predicted to possess enhanced antibacterial and
antirheumatic activity, whereas amides IXa–IXe and
IXg were expected to exhibit cytoprotective, anti-
cancer, and antihelminthic properties with simultane-
ous appreciable reduction of hepato- and neurotoxicity.
EXPERIMENTAL
Quantum-chemical calculations were performed
using GAUSSIAN 03 software package [21]. The
molecular structures were calculated in terms of the
density functional theory using B3LYP functional
[22–27] and 6-31+G(d) standard basis set [28, 29].
Conjugative and hyperconjugative interactions were
analyzed in terms of the NBO (natural bond orbital)
theory [30] using NBO 5.0 program [31]. The X-ray
diffraction data were used as initial parameters for
structure optimization. The optimized geometric pa-
rameters of quinone imines Xg, XIIg–XIVg, and XV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

SYNTHESIS AND STRUCTURE OF N-ARYL(PHENOXY, BENZYLIDENE)ACETYL-...
Table 3. Principal crystallographic parameters of compounds Xg, XIIg–XIVg, and XV
1313
Parameter
Xg
XIIg
XIIIg
XIVg
XV
a, Å
08.555(1)
12.868(1)
13.409(1)
110.969(8)
091.165(7)
099.715(8)
1353.4(2)
Triclinic
P-1
13.983(1)0
14.540(1)0
06.9145(6)
90.0(0)00
91.870(7)
90.0(0)00
1405.0(2)
Monoclinic
P21/c
14.324(1)0
14.613(1)0
06.9496(2)
90.0(0)00
92.688(3)
90.0(0)00
1452.98(8)
Monoclinic
P21/c
09.817(2)
14.615(3)
13.759(4)
90.0(0)
106.52(3)
90.0(00
1892.5(9)
Monoclinic
P21/n
08.326(1)
08.326(1)
15.763(2)
090.0
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
090.0
120.0
946.4(1)
Tetragonal
P32
Crystal system
Space group
Z
4
4
4
8
3
F(000)
536
568
560
752
378
d
calc, g/cm3
1.243
1.273
1.213
1.244
1.259
μ(MoKα), mm–1
0.082
0.088
0.080
0.087
0.084
2θmax, deg
60
60
90
52
50
Total number of reflections
19595
13833
4401
17187
3183
Number of independent
reflections
06114
0.045
3871
4008
0.031
2646
03636
0.119
1400
1951
0,011
1856
Rint
0.052
Number of reflections
with F > 4σ(F)
Number of refined parameters
wR2
347
0.181
0.065
1.000
862189
241
0.124
0.054
1.011
862187
102
241
0.098
0.055
0.834
862188
215
0.073
0.031
1.022
864058
0.077
R1 [F > 4σ(F)]
Goodness of fit S
Entry no. in CCDC
862190
were very consistent with the experimental X-ray dif-
fraction data.
(C17H15NO2, M 265.30) was examined by the X-ray
powder diffraction method on a Siemens D500 dif-
fractometer (CuKα irradiation, graphite monochro-
mator on the reflected beam) using Bragg–Brentano
geometry (θ–2θ scan). The complete X-ray powder
diffraction patterns were measured in the range 2 <
2θ < 90° through a step of 0.02° (measurement time
60 s). The instrument was calibrated against LaB6
which was analyzed under analogous conditions. The
diffraction patterns were processed using POWDERX
[33], ITO [34], and DICVOL programs [35], and the
structure was solved using FOX program [36] and
refined according to Rietveld using FULLPROF pro-
gram [37]. The positions of hydrogen atoms were set
on the basis of geometry considerations and were
refined according to the riding model. The principal
crystallographic parameters of compounds Xg, XIIg–
XIVg, and XV are given in Table 3. The final coor-
dinates of atoms, geometric parameters of molecules,
The X-ray diffraction data for compounds Xg
(C16H15NO2, M 253.29), XIIg (C16H15NO3, M 269.29),
XIVg (C10H11NO2, M 177.20), and XV (C15H13NO2,
M 239.26) were acquired at 293 K on an Xcalibur 3
automatic four-circle diffractometer (MoKα irradiation,
graphite monochromator, CCD detector, ω-scanning).
The structures were solved by the direct method using
SHELXTL software package [32] and were refined in
anisotropic approximation for non-hydrogen atoms.
Hydrogen atoms were localized by difference synthesis
of electron density, and their positions were refined
according to the riding model with Uiso = nUeq for non-
hydrogen atom linked to the given hydrogen atom (n =
1.5 for methyl groups and n = 1.2 for other hydrogen
atoms); the refinement was performed with fixed
thermal vibration parameters (Xg, XIVg) or in iso-
tropic approximation (XIIg, XV). Compound XIIIg
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

AVDEENKO et al.
1314
and crystallographic data were deposited to the Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44 1223 336033;
e-mail: deposit@ccdc.cam.ac.uk).
(1H, OH). Found, %: N 5.36, 5.55. C16H17NO2. Cal-
culated, %: N 5.49.
N-(4-Hydroxy-2,5-dimethylphenyl)-2-phenyl-
acetamide (VId). Yield 36%, mp 214–215°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.99 s
(3H, 2-Me), 2.03 s (3H, 5-Me), 3.58 s (2H, CH2),
6.57 s (1H, 6-H), 9.60 s (1H, 3-H), 7.23–7.34 m (5H,
Ph), 9.07 br.s (1H, NH), 9.25 s (1H, OH). Found, %:
N 5.36, 5.55. C16H17NO2. Calculated, %: N 5.49.
The IR spectra of VI–IX, Xc–Xg, XIc–XIg, XIIc–
XIIg, and XIIIc–XIIIg were recorded in KBr on
a UR-20 spectrometer, and the spectra of Xa, Xb, XIa,
XIb, XIIa, XIIb, XIIIa, and XIIIb were measured
from solutions in CHCl3 on a Bruker Vertex-70 instru-
1
ment. The H and 13C NMR spectra were run on
N-(4-Hydroxy-3,5-dimethylphenyl)-2-phenyl-
acetamide (VIe). Yield 40%, mp 186–187°C (from
a Varian VXR-300 spectrometer at 300 and 75.4 MHz,
respectively, using tetramethylsilane as internal refer-
ence. The purity of amides VI–IX and quinone imines
X–XIII was checked by TLC on Silufol UV-254
plates; compounds VI–IX were applied from solutions
in acetone, and ethanol–chloroform (1 : 10) and
hexane–ethyl acetate (1 :2) were used as eluents;
quinone imines X–XIII were applied from chloroform,
and benzene–hexane (10:1) was used as eluent; spots
were detected under UV light.
1
i-PrOH). H NMR spectrum (DMSO-d6), δ, ppm:
1.97 s (6H, 3-Me, 5-Me), 3.58 s (2H, CH2), 6.43 s (2H,
2-H, 6-H), 7.21–7.37 m (5H, Ph), 9.13 br.s (1H, NH),
9.15 br.s (1H, OH). Found, %: N 5.40, 5.54.
C16H17NO2. Calculated, %: N 5.49.
N-(4-Hydroxy-2,6-dimethylphenyl)-2-phenyl-
acetamide (VIg). Yield 44%, mp 185–186°C (from
1
i-PrOH). H NMR spectrum (DMSO-d6), δ, ppm:
2.12 s (6H, 2-Me, 6-Me), 3.55 s (2H, CH2), 7.13 s (2H,
3-H, 5-H), 7.21–7.32 m (5H, Ph), 7.97 s (1H, NH),
9.77 br.s (1H, OH). Found, %: N 5.37, 5.54.
C16H17NO2. Calculated, %: N 5.49.
Acid chlorides II–V were synthesized according to
the procedure described in [38]. Phenoxyacetic acid
was prepared from phenol and ethyl chloroacetate,
followed by hydrolysis of the resulting ester with
aqueous alkali and acidification as described in [39].
N-(4-Hydroxyphenyl)-2-(4-methylphenyl)acet-
amide (VIIa). Yield 30%, mp 214–215°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.27 s
(3H, CH3C6H4), 3.51 s (2H, CH2), 6.68 d (2H, 2-H,
6-H, J = 8.7 Hz), 7.11 d (2H, 2′-H, 6′-H, J = 8.7 Hz),
7.20 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.36 d (2H, 3-H,
5-H, J = 8.7 Hz), 9.19 s (1H, NH), 9.87 s (1H, OH).
Found, %: N 5.78, 5.85. C15H15NO2. Calculated, %:
N 5.81.
N-(4-Hydroxyphenyl)-2-aryl(phenoxy)acet-
amides VIa–VIg, VIIa–VIIg, and VIIIa–VIIIg and
(2E)-N-(4-hydroxyphenyl)-3-phenylprop-2-en-
amides IXa–IXg (general procedure). Acid chloride
II–V, 2.2 mmol, was added dropwise under stirring to
a solution of 2.2 mmol of amide Ia–Ig and 2.2 mmol
of anhydrous sodium acetate in 25 ml of DMF–AcOH
(1:3), and the mixture was stirred for 2–3 h at room
temperature. The mixture was then poured into an ice–
water mixture and left to stand until complete crystal-
lization, and the precipitate was filtered off and recrys-
tallized from acetic acid or isopropyl alcohol.
N-(4-Hydroxy-3-methylphenyl)-2-(4-methyl-
phenyl)acetamide (VIIb). Yield 68%, mp 180–182°C
(from AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.07 s (3H, 2-Me), 2.27 s (3H, CH3C6H4), 3.50 s (2H,
CH2), 6.67 d (1H, 6-H, J = 8.1 Hz), 7.11 d (2H, 2′-H,
6′-H, J = 8.7 Hz), 7.16–7.19 d.d (1H, 5-H, J = 2.4,
8.1 Hz), 7.20 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.25 d
(1H, 3-H, J = 2.4 Hz), 9.06 s (1H, NH), 9.79 s (1H,
OH). Found, %: N 5.45, 5.50. C16H17NO2. Calculated,
%: N 5.49.
N-(4-Hydroxyphenyl)-2-phenylacetamide (VIa).
1
Yield 39%, mp 176–177°C (from AcOH). H NMR
spectrum (DMSO-d6), δ, ppm: 3.58 s (2H, CH2), 6.68 d
(2H, 2-H, 6-H, J = 8.7 Hz), 7.23–7.33 m (5H, Ph),
7.38 d (2H, 3-H, 5-H, J = 8.7 Hz), 9.19 s (1H, NH),
9.92 s (1H, OH). Found, %: N 6.05, 6.23. C14H13NO2.
Calculated, %: N 6.16.
N-(4-Hydroxy-2,3-dimethylphenyl)-2-(4-methyl-
phenyl)acetamide (VIIc). Yield 48%, mp 229–230°C
(from AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
1.95 s (3H, 2-Me), 2.03 s (3H, 3-Me), 2.27 s (3H,
CH3C6H4), 3.52 s (2H, CH2), 6.59 d (1H, 6-H, J =
8.4 Hz), 6.81 d (1H, 5-H, J = 8.4 Hz), 7.14 d (2H,
2′-H, 6′-H, J = 7.8 Hz), 7.22 d (2H, 3-H, 5′-H, J =
N-(4-Hydroxy-2,3-dimethylphenyl)-2-phenyl-
acetamide (VIc). Yield 37%, mp 192–193°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.95 s
(3H, 2-Me), 2.04 s (3H, 3-Me), 3.58 s (2H, CH2),
6.59 d (1H, 6-H, J = 8.4 Hz), 6.81 d (1H, 5-H, J =
8.4 Hz), 7.23–7.34 m (5H, Ph), 9.11 s (1H, NH), 9.35 s
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SYNTHESIS AND STRUCTURE OF N-ARYL(PHENOXY, BENZYLIDENE)ACETYL-...
1315
7.8 Hz), 9.18 br.s (1H, NH), 9.34 s (1H, OH). Found,
%: N 5.18, 5.25. C17H19NO2. Calculated, %: N 5.20.
8.92 br.s (1H, NH), 9.56 br.s (1H, OH). Found, %:
N 5.45, 5.50. C15H15NO3. Calculated, %: N 5.44.
N-(4-Hydroxy-2,5-dimethylphenyl)-2-(4-methyl-
phenyl)acetamide (VIId). Yield 72%, mp 245–246°C
(from AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
1.99 s (3H, 2-Me), 2.03 s (3H, 5-Me), 2.27 s (3H,
CH3C6H4), 3.52 s (2H, CH2), 6.58 s (1H, 6-H), 6.89 s
(1H, 3-H), 7.12 d (2H, 2′-H, 6′-H, J = 7.8 Hz), 7.22 d
(2H, 3′-H, 5′-H, J = 7.8 Hz), 9.09 s (1H, NH), 9.24 s
(1H, OH). Found, %: N 5.15, 5.25. C17H19NO2. Cal-
culated, %: N 5.20.
N-(4-Hydroxy-2,3-dimethylphenyl)-2-phenoxy-
acetamide (VIIIc). Yield 75%, mp 172–173°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.97 s
(3H, 2-Me), 2.05 s (3H, 3-Me), 4.65 s (2H, OCH2),
6.62 d (1H, 6-H, J = 8.1 Hz), 6.84 d (1H, 5-H, J =
8.1 Hz), 6.95–7.35 m (5H, Ph), 9.14 br.s (1H, NH),
9.34 br.s (1H, OH). Found, %: N 5.15, 5.20.
C16H17NO3. Calculated, %: N 5.16.
N-(4-Hydroxy-2,5-dimethylphenyl)-2-phenoxy-
acetamide (VIIId). Yield 47%, mp 176–177°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.00 s
(3H, 2-Me), 2.05 s (3H, 5-Me), 4.65 s (2H, OCH2),
6.60 s (1H, 6-H), 6.95 s (1H, 3-H), 6.98–7.35 m (5H,
Ph), 9.17 br.s (1H, NH), 9.28 s (1H, OH). Found, %:
N 5.15, 5.20. C16H17NO3. Calculated, %: N 5.16.
N-(4-Hydroxy-3,5-dimethylphenyl)-2-(4-methyl-
phenyl)acetamide (VIIe). Yield 75%, mp 195–196°C
1
(from i-PrOH). H NMR spectrum (DMSO-d6), δ,
ppm: 1.96 s (6H, 3-Me, 5-Me), 2.28 s (3H, CH3C6H4),
3.53 s (2H, CH2), 6.42 s (2H, 2-H, 6-H), 7.11 d (2H,
2′-H, 6′-H, J = 7.8 Hz), 7.25 d (2H, 3′-H, 5′-H, J =
7.8 Hz), 9.09 br.s (2H, NH, OH). Found, %: N 5.25,
5.15. C17H19NO2. Calculated, %: N 5.20.
N-(4-Hydroxy-3,5-dimethylphenyl)-2-phenoxy-
acetamide (VIIIe). Yield 68%, mp 180–181°C (from
1
i-PrOH). H NMR spectrum (DMSO-d6), δ, ppm:
N-[4-Hydroxy-2-methyl-5-(propan-2-yl)phenyl]-
2-(4-methylphenyl)acetamide (VIIf). Yield 70%,
2.00 s (6H, 3-Me, 5-Me), 4.67 s (2H, OCH2), 6.46 s
(2H, 2-H, 6-H), 6.95–7.35 m (5H, Ph), 9.19 s (1H,
NH), 9.23 s (1H, OH). Found, %: N 5.10, 5.20.
C16H17NO3. Calculated, %: N 5.16.
1
mp 179–180°C (from AcOH). H NMR spectrum
(DMSO-d6), δ, ppm: 1.12 d [6H, CH(CH3)2, J =
6.9 Hz], 1.99 s (3H, 3-Me), 2.28 s (3H, CH3C6H4),
3.09–3.18 m [1H, CH(CH3)2], 3.52 s (2H, CH2), 6.61 s
(1H, 2-H), 6.97 s (1H, 5-H), 7.11 d (2H, 2′-H, 6′-H,
J = 7.8 Hz), 7.25 d (2H, 3′-H, 5′-H, J = 7.8 Hz), 9.17 s
(1H, NH), 9.33 s (1H, OH). Found, %: N 4.65, 4.70.
C19H23NO2. Calculated, %: N 4.71.
N-[4-Hydroxy-2-methyl-5-(propan-2-yl)phenyl]-
2-phenoxyacetamide (VIIIf). Yield 85%, mp 165–
1
166°C (from i-PrOH). H NMR spectrum (DMSO-d6),
δ, ppm: 1.12 d [6H, CH(CH3)2, J = 6.9 Hz], 1.99 s
(3H, 3-Me), 3.09–3.18 m [1H, CH(CH3)2], 4.65 s
(2H, OCH2), 6.61 s (1H, 2-H), 6.97 s (1H, 5-H), 6.98–
7.35 m (5H, Ph), 9.17 s (1H, NH), 9.33 s (1H, OH).
Found, %: N 4.50, 4.70. C18H21NO3. Calculated, %:
N 4.68.
N-(4-Hydroxy-2,6-dimethylphenyl)-2-(4-methyl-
phenyl)acetamide (VIIg). Yield 60%, mp 214–215°C
(from AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.11 s (6H, 2-Me, 6-Me), 2.27 s (3H, CH3C6H4), 3.49 s
(2H, CH2), 7.10 d (2H, 2′-H, 6′-H, J = 7.8 Hz), 7.12 s
(2H, 2-H, 6-H), 7.20 d (2H, 3′-H, 5′-H, J = 7.8 Hz),
7.99 s (1H, NH), 9.74 br.s (1H, OH). Found, %:
N 5.24, 5.18. C17H19NO2. Calculated, %: N 5.20.
N-(4-Hydroxy-2,6-dimethylphenyl)-2-phenoxy-
acetamide (VIIIg). Yield 60%, mp 214–215°C (from
1
i-PrOH). H NMR spectrum (DMSO-d6), δ, ppm:
2.14 s (6H, 2-Me, 6-Me), 4.62 s (2H, OCH2), 6.94–
7.34 m (5H, Ph), 7.18 s (2H, 3-H, 5-H), 8.07 s (1H,
NH), 9.69 s (1H, OH). Found, %: N 5.24, 5.18.
C16H17NO3. Calculated, %: N 5.16.
N-(4-Hydroxyphenyl)-2-phenoxyacetamide
(VIIIa). Yield 65%, mp 170–171°C (from AcOH).
1H NMR spectrum (DMSO-d6), δ, ppm: 4.71 s (2H,
OCH2), 6.99–7.71 m (5H, Ph), 7.15 d (2H, 2-H, 6-H,
J = 9 Hz), 7.69 d (2H, 3-H, 5-H, J = 9 Hz). Found, %:
N 5.78, 5.85. C14H13NO3. Calculated, %: N 5.76.
(2E)-N-(4-Hydroxyphenyl)-3-phenylprop-2-en-
amide (IXa). Yield 55%, mp 215–216°C (from
1
AcOH). H NMR spectrum (DMSO-d6), δ, ppm:
6.75 d (2H, 2-H, 6-H, J2,6 = 8.4 Hz), 6.83 d (1H,
CH=CH, J = 15.9 Hz), 7.39–7.63 m (5H, Ph), 7.43 d
(2H, 3-H, 5-H, J3,5 = 8.7 Hz), 7.55 d (1H, CH=CH, J =
15.3 Hz), 9.26 br.s (1H, NH), 9.99 br.s (1H, OH).
Found, %: N 5.70, 5.90. C15H13NO2. Calculated, %:
N 5.85.
N-(4-Hydroxy-3-methylphenyl)-2-phenoxyacet-
amide (VIIIb). Yield 70%, mp 160–162°C (from
AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.11 s
(3H, 2-Me), 4.61 s (2H, OCH2), 6.71 d (1H, 6-H, J =
6.3 Hz), 7.22–7.24 d.d (1H, 5-H, J = 6.3, 0.6 Hz),
7.30 d (1H, 3-H, J = 0.6 Hz), 6.96–7.34 m (5H, Ph),
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AVDEENKO et al.
1316
(2E)-N-(4-Hydroxy-3-methylphenyl)-3-phenyl-
Ph), 7.53 d (1H, CH=CH, J = 15.6 Hz), 8.07 br.s
(1H, NH), 9.86 br.s (1H, OH). Found, %: N 5.12, 5.30.
C17H17NO2. Calculated, %: N 5.24.
prop-2-enamide (IXb). Yield 62%, mp 189–190°C
(from AcOH). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.12 s (3H, 2-Me), 6.73 d (1H, 6-H), 6.80 d (1H,
CH=CH, J = 15.9 Hz), 7.33–7.36 d.d (1H, 5-H), 7.39 d
(1H, 3-H, J = 1.5 Hz), 7.40–7.62 m (5H, Ph), 7.53 d
(1H, CH=CH, J = 15.6 Hz), 9.14 s (1H, NH), 9.91 s
(1H, OH). Found, %: N 5.50, 5.55. C16H15NO2. Cal-
culated, %: N 5.53.
N-Aryl(phenoxy, benzylidene)acetyl-1,4-benzo-
quinone monoimines Xa–Xg, XIa–XIg, XIIa–XIIg,
and XIIIa–XIIIg (general procedures). a. Silver(I)
oxide, 2.1 mmol, was added to 2 mmol of amide VIa,
VIb, VIIa, VIIb, VIIIa, VIIIb, IXa, or IXb in 20 ml
of anhydrous chloroform, the mixture was stirred for
2–3 h, and the precipitate of silver was filtered off. We
failed to isolate crystalline quinone imines Xa, Xb,
XIa, XIb, XIIa, XIIb, XIIIa, and XIIIb; they were
obtained only in chloroform solution, and their forma-
tion was proved by TLC and IR spectroscopy.
(2E)-N-(4-Hydroxy-2,3-dimethylphenyl)-3-
phenylprop-2-enamide (IXc). Yield 66%, mp 211–
1
212°C (from AcOH). H NMR spectrum (DMSO-d6),
δ, ppm: 2.06 s (3H, 2-Me), 2.08 s (3H, 3-Me), 6.65 d
(1H, 6-H, J5,6 = 8.7 Hz), 6.98 d (1H, 5-H, J5,6
=
8.7 Hz), 6.89 d and 7.52 d (1H each, CH=CH, J =
15.9 Hz), 7.40–7.62 m (5H, Ph), 9.15 s (1H, NH),
9.38 s (1H, OH). Found, %: N 5.12, 5.29. C17H17NO2.
Calculated, %: N 5.24.
b. A suspension of 3.7 mmol of amide VIc–VIg,
VIIc–VIIg, VIIIc–VIIIg, or IXc–IXg in 4–5 ml of
glacial acetic acid was cooled in a bath, 4.1 mmol of
lead tetraacetate was added, and the mixture was
stirred for 10 min until a yellow crystalline material
was formed. A few drops of ethylene glycol was
added, the mixture was stirred for 5 min, and the
precipitate was filtered off.
(2E)-N-(4-Hydroxy-2,5-dimethylphenyl)-3-
phenylprop-2-enamide (IXd). Yield 66%, mp 286–
1
287°C (from AcOH). H NMR spectrum (DMSO-d6),
δ, ppm: 2.09 s (3H, 2-Me), 2.11 s (3H, 5-Me), 6.65 s
(1H, 6-H), 7.13 s (1H, 3-H), 6.92 d (1H, CH=CH, J =
15.9 Hz), 7.40–7.63 m (5H, Ph), 7.54 d (1H, CH=CH,
J = 15.9 Hz), 9.15 s (1H, NH), 9.33 s (1H, OH).
Found, %: N 5.12, 5.29. C17H17NO2. Calculated, %:
N 5.24.
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)phenylacetamide (Xc). Yield 40%, mp 114–
115°C (from n-hexane). 1H NMR spectrum (CDCl3), δ,
ppm: 1.82 s (3H, 3-Me), 2.10 s (3H, 2-Me), 3.84 s (2H,
CH2), 6.22 s (1H, 5-H), 6.46 s (1H, 6-H), 7.25–7.50 m
(5H, Ph). Found, %: N 5.50, 5.55. C16H15NO2. Calcu-
lated, %: N 5.53.
(2E)-N-(4-Hydroxy-3,5-dimethylphenyl)-3-
phenylprop-2-enamide (IXe). Yield 84%, mp 246–
1
248°C (from i-PrOH). H NMR spectrum (DMSO-d6),
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)phenylacetamide (Xd). Yield 90%, mp 94–
δ, ppm: 2.16 s (6H, 3-Me, 5-Me), 6.45 s (2H, 2-H,
6-H), 6.67 d (1H, CH=CH, J = 15.9 Hz), 7.41–7.63 m
(5H, Ph), 7.56 d (1H, CH=CH, J = 15.9 Hz), 9.24 s
(1H, NH), 9.32 s (1H, OH). Found, %: N 5.14, 5.31.
C17H17NO2. Calculated, %: N 5.24.
1
95°C (from benzene–n-hexane, 2:1). H NMR spec-
trum (CDCl3), δ, ppm: 1.82 d (3H, 5-Me, J = 1.5 Hz),
2.10 d (3H, 2-Me, J = 1.5 Hz), 3.84 s (2H, CH2),
6.21 q (1H, 3-H, J = 1.5 Hz), 6.46 q (1H, 6-H, J =
1.2 Hz ), 7.24–7.36 m (5H, Ph). Found, %: N 5.34,
5.55. C16H15NO2. Calculated, %: N 5.53.
(2E)-N-[4-Hydroxy-2-methyl-5-(propan-2-yl)-
phenyl]-3-phenylprop-2-enamide (IXf). Yield 95%,
1
mp 210–211°C (from AcOH). H NMR spectrum
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)phenylacetamide (Xe). Yield 83%, mp 88–
(DMSO-d6), δ, ppm: 1.15 d [6H, CH(CH3)2, J =
6.0 Hz], 2.09 s (3H, 3-Me), 3.11–3.19 m [1H,
CH(CH3)2], 6.64 s (1H, 2-H), 6.89 d (1H, CH=CH,
J = 15.0 Hz), 7.14 s (1H, 5-H), 7.42–7.63 m (5H, Ph),
7.53 d (1H, CH=CH, J = 15.0 Hz), 9.19 s (1H, NH),
9.37 s (1H, OH). Found, %: N 4.60, 4.75. C19H21NO2.
Calculated, %: N 4.74.
1
89°C (from benzene–n-hexane, 2:1). H NMR spec-
trum (CDCl3), δ, ppm: 2.03 s (6H, 2-Me, 6-Me), 3.89 s
(2H, CH2), 6.38 s (2H, 3-H, 5-H), 7.27–7.36 m (5H,
Ph). Found, %: N 5.42, 5.29. C16H15NO2. Calculated,
%: N 5.53.
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)phenylacetamide (Xg). Yield 87%, mp 59–
(2E)-N-(4-Hydroxy-2,6-dimethylphenyl)-3-
phenylprop-2-enamide (IXg). Yield 58%, mp 205–
1
60°C (from n-hexane). H NMR spectrum (CDCl3),
1
δ, ppm: 1.94 s (6H, 3-Me, 5-Me), 3.82 s (2H, CH2),
6.49 s (2H, 2-H, 6-H), 7.24–7.34 m (5H, Ph). Found,
%: N 5.42, 5.61. C16H15NO2. Calculated, %: N 5.53.
206°C (from AcOH). H NMR spectrum (DMSO-d6),
δ, ppm: 2.17 s (6H, 2-Me, 6-Me), 6.81 d (1H, CH=CH,
J = 15.6 Hz), 7.27 s (2H, 3-H, 5-H), 7.37–7.62 m (5H,
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N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)-4-methylphenylacetamide (XIc). Yield 50%,
mp 96–97°C (from n-hexane). H NMR spectrum
OCH2), 6.50 d (1H, 5-H, J = 9.9 Hz), 6.79 d (1H, 6-H,
J = 9.9 Hz), 6.88–7.32 m (5H, Ph). Found, %: N 5.10,
5.20. C16H15NO3. Calculated, %: N 5.20.
1
(CDCl3), δ, ppm: 2.02 d (3H, 3-Me), 2.11 d (3H,
2-Me), 2.32 s (3H, CH3C6H4), 3.80 s (2H, CH2), 6.32 d
(1H, 5-H, J = 9.9 Hz), 6.42 s (1H, 6-H, J = 9.9 Hz),
7.12 br.s (4H, CH3C6H4). Found, %: N 5.36, 5.18.
C17H17NO2. Calculated, %: N 5.24.
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)phenoxyacetamide (XIId). Yield 77%, mp 97–
98°C (from benzene–n-hexane, 2:1). H NMR spec-
trum (CDCl3), δ, ppm: 1.96 d (3H, 5-Me, J = 1.2 Hz),
2.06 d (3H, 2-Me, J = 0.9 Hz), 4.85 s (2H, OCH2),
6.51 d (1H, 6-H, J = 0.9 Hz), 6.61 d (1H, 3-H, J =
1.2 Hz), 6.89–7.32 m (5H, Ph). Found, %: N 5.10,
5.33. C16H15NO2. Calculated, %: N 5.20.
1
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)-4-methylphenylacetamide (XId). Yield
40%, mp 115–116°C (from benzene–n-hexane, 2:1).
1H NMR spectrum (CDCl3), δ, ppm: 1.81 d (3H, 5-Me,
J = 1.2 Hz), 2.10 d (3H, 2-Me, J = 1.2 Hz), 2.32 s (3H,
CH3C6H4), 3.80 s (2H, CH2), 6.19 q (1H, 3-H, J =
1.5 Hz), 6.46 q (1H, 6-H, J = 1.2 Hz), 7.13 s (4H,
CH3C6H4). Found, %: N 5.20, 5.30. C17H17NO2. Cal-
culated, %: N 5.24.
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)phenoxyacetamide (XIIe). Yield 70%, mp 95–
1
96°C (from benzene–n-hexane, 2:1). H NMR spec-
trum (CDCl3), δ, ppm: 2.02 s (6H, 2-Me, 6-Me), 4.88 s
(2H, OCH2), 6.42 s (2H, 3-H, 5-H), 6.86–7.32 m (5H,
Ph). Found, %: N 5.30, 5.25. C16H15NO3. Calculated,
%: N 5.20.
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)-4-methylphenylacetamide (XIe). Yield 65%,
1
N-[2-Methyl-4-oxo-5-(propan-2-yl)cyclohexa-
2,5-dien-1-ylidene]phenoxyacetamide (XIIf). Yield
mp 95–96°C (from benzene–n-hexane, 2:1). H NMR
spectrum (CDCl3), δ, ppm: 2.03 s (6H, 2-Me, 6-Me),
2,33 s (3H, CH3C6H4), 3.85 s (2H, CH2), 6.38 br.s (2H,
3-H, 5-H), 7.12 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.16 d
(2H, 3′-H, 5′-H, J = 8.7 Hz). Found, %: N 5.20, 5.29.
C17H17NO2. Calculated, %: N 5.24.
1
45%, mp 65–66°C (from n-hexane). H NMR spec-
trum (CDCl3), δ, ppm: 0.87 d [6H, CH(CH3)2, J =
6.9 Hz], 2.12 s (3H, 2-Me), 2.81–2.91 m [1H,
CH(CH3)2], 4.85 s (2H, OCH2), 5.97 br.s (1H, 6-H),
6.44 d (1H, 3-H, J = 1.2 Hz), 6.89–7.32 m (5H, Ph).
Found, %: N 4.50, 4.70. C18H19NO3. Calculated, %:
N 4.71.
N-[2-Methyl-4-oxo-5-(propan-2-yl)cyclohexa-
2,5-dien-1-ylidene]-4-methylphenylacetamide (XIf).
Yield 50%, mp 75–76°C (from benzene–n-hexane,
1
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)phenoxyacetamide (XIIg). Yield 60%, mp 52–
2:1). H NMR spectrum (CDCl3), δ, ppm: 0.86 d [6H,
CH(CH3)2, J = 6.9 Hz], 2.11 s (3H, 2-Me), 2.30 s (3H,
CH3C6H4), 2.79–2.89 m [1H, CH(CH3)2], 3.81 s (2H,
CH2), 5.97 br.s (1H, 6-H), 6.44 d (1H, 3-H, J =
1.2 Hz), 7.12 br.s (4H, CH3C6H4). Found, %: N 4.65,
4.70. C19H21NO2. Calculated, %: N 4.71.
1
53°C (from n-hexane). H NMR spectrum (CDCl3), δ,
ppm: 2.02 s (6H, 3-Me, 5-Me), 4.82 s (2H, OCH2),
6.72 s (2H, 2-H, 6-H), 6.90–7.32 m (5H, Ph). Found,
%: N 5.10, 5.33. C16H15NO3. Calculated, %: N 5.20.
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-3-phenylprop-2-enamide (XIIIc). Yield 65%,
mp 89–90°C (from n-hexane). H NMR spectrum
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)-4-methylphenylacetamide (XIg). Yield
80%, mp 77–78°C (from n-hexane). H NMR spec-
1
1
(CDCl3), δ, ppm: 2.09 s (3H, 3-Me), 2.24 s (3H,
2-Me), 6.51 d (1H, 5-H, J = 10.2 Hz), 6.67 d (1H,
CH=CH, J = 16.2 Hz), 6.87 d (1H, 6-H, J = 10.2 Hz),
7.35–7.58 m (5H, Ph), 7.53 d (1H, CH=CH, J =
16.2 Hz). Found, %: N 5.20, 5.25. C17H15NO2. Calcu-
lated, %: N 5.28.
trum (CDCl3), δ, ppm: 1.94 s (6H, 3-Me, 5-Me), 2.32 s
(3H, CH3C6H4), 3.78 s (2H, CH2), 6.47 br.s (2H, 2-H,
6-H), 7.13 br.s (4H, CH3C6H4). 13C NMR spectrum
(CDCl3), δC, ppm: 16.06 (3-Me, 5-Me), 21.03
(CH3C6H4), 44.89 (CH2), 129.28 (C3, C5), 129.44 (C2′,
C6'), 129.64 (C3′, C5′), 131.37 (C1′), 137.23 (C4′),
143.25 (C2, C6), 154.29 (C1), 185.43 (C4), 186.91
(C=O). Found, %: N 5.15, 5.25. C17H17NO2. Calculat-
ed, %: N 5.24.
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-3-phenylprop-2-enamide (XIIId). Yield 65%,
mp 125–126°C (from benzene–n-hexane, 2:1).
1H NMR spectrum (CDCl3), δ, ppm: 1.97 d (3H, 5-Me,
J = 1.5 Hz), 2.24 d (3H, 2-Me, J = 1.2 Hz), 6.57 q (1H,
3-H, J = 1.2 Hz), 6.66 d (1H, CH=CH, J = 15.6 Hz),
6.71 q (1H, 6-H, J = 1.5 Hz), 7.41–7.58 m (5H, Ph),
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)phenoxyacetamide (XIIc). Yield 55%, mp 73–
1
74°C (from n-hexane). H NMR spectrum (CDCl3), δ,
ppm: 2.05 s (3H, 3-Me), 2.07 s (3H, 2-Me), 4.83 s (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012

AVDEENKO et al.
1318
Rev., 2005, vol. 37, p. 581; Rosen, G.M., Rauck-
man, E.J., Ellington, S.P., Dahlin, D.C., Christie, J.L.,
and Nelson, S.D., Mol. Pharmacol., 1984, vol. 25,
p. 151.
7.55 d (1H, CH=CH, J = 15.6 Hz). Found, %: N 5.20,
5.35. C17H15NO2. Calculated, %: N 5.28.
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-3-phenylprop-2-enamide (XIIIe). Yield 78%,
mp 115–116°C (from benzene–n-hexane, 2 : 1).
1H NMR spectrum (CDCl3), δ, ppm: 2.16 s (6H, 2-Me,
6-Me), 6.45 s (2H, 3-H, 5-H), 6.67 d and 7.56 d
(1H each, CH=CH, J = 15.9 Hz), 7.41–7.59 m (5H,
Ph). Found, %: N 5.21, 5.34. C17H15NO2. Calculated,
%: N 5.28.
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N-[2-Methyl-4-oxo-5-(propan-2-yl)cyclohexa-
2,5-dien-1-ylidene]-3-phenylprop-2-enamide
(XIIIf). Yield 58%, mp 86–87°C (from n-hexane).
1H NMR spectrum (CDCl3), δ, ppm: 1.06 d [6H,
CH(CH3)2, J = 6.9 Hz], 2.23 d (3H, 2-Me, J = 1.5 Hz),
2.97–3.06 m [1H, CH(CH3)2], 6.56 q (1H, 3-H, J =
1.5 Hz), 6.60 d (1H, 6-H, J = 1.2 Hz), 6.69 d and
7.55 d (1H each, CH=CH, J = 16.2 Hz), 7.426–7.58 m
(5H, Ph). Found, %: N 4.50, 4.70. C19H19NO2. Calcu-
lated, %: N 4.77.
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-3-phenylprop-2-enamide (XIIIg). Yield 65%,
1
mp 115–116°C (n-hexane). H NMR spectrum
(CDCl3), δ, ppm: 2.06 s (6H, 3-Me, 6-Me), 6.67 d (1H,
CH=CH, J = 16.2 Hz), 6.84 br.s (2H, 2-H, 6-H), 7.41–
7.57 m (5H, Ph), 7.55 d (1H, CH=CH, J = 16.2 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 17.09 (3-Me,
5-Me), 122.16 (COCH=), 129.54 (C3′, C5′), 129.83
(C2′, C6′), 131.80 (C1′), 134.83 (C4′), 138.80 (C3, C5),
144.45 (C2, C6), 147.00 (=CHPh), 157.39 (C1), 181.05
(C4), 187.95 (C=O). Found, %: N 5.20, 5.25.
C17H15NO2. Calculated, %: N 5.28.
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