Acid catalyzed rearrangements of aryl 3-(2-nitroaryl)oxiran-2-yl ketones

Article abstract of DOI:10.1007/s11172-020-2791-x

Studies of chemical behavior of aryl 3-(2-nitrophenyl)oxiran-3-yl ketones in acidic medium revealed the possible occurrence of two competitive rearrangements leading to 2-(2-oxo-2-arylacetamido)benzoic acids and 3-hydroxyquinolin-4(1H)-ones.

Full text of DOI:10.1007/s11172-020-2791-x

Russian Chemical Bulletin, International Edition, Vol. 69, No. 3, pp. 510—516, March, 2020
510
Acid catalyzed rearrangements of aryl 3-(2-nitroaryl)oxiran-2-yl ketones*
V. A. Mamedov, V. L. Mamedova, A. T. Gubaidullin, D. B. Krivolapov, G. Z. Khikmatova,
E. M. Mahrous, D. E. Korshin, and O. G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry,
Federal Research Center "Kazan Scientific Center of the Russian Academy of Sciences,"
8 ul. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 27 5532. E-mail: mamedov@iopc.ru
Studies of chemical behavior of aryl 3-(2-nitrophenyl)oxiran-3-yl ketones in acidic medium
revealed the possible occurrence of two competitive rearrangements leading to 2-(2-oxo-2-
arylacetamido)benzoic acids and 3-hydroxyquinolin-4(1H)-ones.
Key words: oxiranes, aryl 3-(2-nitroaryl)oxiran-3-yl ketones, rearrangements, anthranilic
acid derivatives, 2-(2-oxo-2-arylacetamido)benzoic acids, 3-hydroxyquinolin-4-ones.
Scheme 1
Oxirane derivatives are of great importance for organic
synthesis.1—8 Despite the large number of publications
devoted to the chemistry of oxirane derivatives, the pub-
lications describing their unexpected transformations still
appear.9—14
Earlier,11,12 we have performed detailed studies on the
chemical behavior of 3-aryl-2,3-epoxypropionic acid
anilides in acidic medium. It has been found11 that sulfu-
ric acid-mediated tandem transformation7 of these anilides
via the Meinwald-type rearrangement with a 1,2-aryl shift
and subsequent intramolecular Friedel—Crafts cyclization
provided a quinolinone scaffold. However, if the aryl
substituent at the oxirane ring has the ortho-positioned
nitro group, the dramatically different result has been
obtained. The brief reflux of the starting material quanti-
tatively afforded N1-(2-carboxyphenyl)-N2-(aryl)oxal-
amides that can be considered as the derivatives of both
oxalic and anthranilic acids.12 This unique atom economic
transformation involved the Meinwald rearrangement with
the hydrogen shift, intramolecular redox reaction, the
C—C bond cleavage, and the C—N bond formation.7,12
Under the experimental conditions, some aryl 3-(2-nitro-
aryl)oxiran-2-yl ketones 1 underwent similar transforma-
tions to give the corresponding anthranilic acid derivatives.
However, compounds 1 gave the products in the yields
lower than those achieved from 3-(2-nitrophenyl)-2,3-
epoxypropionic acid anilides.
1
a
b
c
d
e
f
R
H
H
H
H
Ar
Ph
4-MeC6H4
4-MeOC6H4
4-ClC6H4
Naphthalen-1-yl
4-MeOC6H4
4-ClC6H4
H
5-Cl
4-NO2
g
Reagents and conditions: MeONa, MeOH, 15 C, 15 min.
With the aim to increase the yields of the anthranilic de-
rivatives, we lowered the reaction temperature, and the
reaction mixtures were heated to dissolve compounds 1
but not refluxed. Compounds 1a—c in the amounts of
1.5 mmol dissolve in a mixture of AcOH (4 mL) and H2SO4
(0.2 mL) at water bath temperatures of 28, 40, and 65 C,
respectively; while, the reaction mixture temperatures
reach 45, 50, and 73 C. This is indicative of the exother-
mic reactions and the reactions were completed under
stirring within 10 min. To dissolve compounds 1d—g
under similar conditions, the external heating temperature
of 85 C is needed, and in the case of compounds 1e,g
longer stirring time (30 min) is required to complete the
reaction. From the reaction mixtures obtained using com-
pounds 1d—g as the starting materials, anthranilic acid
derivatives 2d—g (Scheme 2) were isolated in the yields
of 78, 72, 84, and 77%, respectively. The 1H NMR spec-
In the present work, we studied in detail the chemical
behavior of various aryl 3-(2-nitroaryl)oxiran-2-yl ketones
1 that were synthesized by the Darzens condensation15
(Scheme 1) in acetic acid in the presence of sulfuric acid.
* Based on the materials of the International Markovnikov
Congress on Organic Chemistry (June 21—28, 2019, Moscow—
Kazan, Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0510—0516, March, 2020.
1066-5285/20/6903-0510 © 2020 Springer Science+Business Media LLC

Acid rearrangements of oxiranyl ketones
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
511
Scheme 2
ca. 1 : 1 were isolated from the reaction mixture obtained
after refluxing compound 1a in AcOH in the absence of
H2SO4. A single crystal X-ray detraction analysis of the
second product allowed us to unambiguously determine
the structure of this product as 3a (see Scheme 2, Fig. 1).
According to X-ray diffraction analysis data, compound
3a crystallizes with two independent molecules in the
asymmetric unit of the orthorhombic unit cell; the inde-
pendent molecules form H-bonded stable dimers (see
Fig. 1). Bond lengths and geometry of the two molecules
are almost the same. The only noticeable difference be-
tween two independent molecules is the dihedral angle
between the planes of the phenyl ring and the bicyclic
scaffold that is equal to 62.3(9) for one molecule and
40.2(9) for another. It is important that this difference in
the geometry of the two molecules is not the result of the
dynamic processes. The low-temperature measurements
of the crystal of this compound (3a_LT) and molecular
geometry analysis indicate that the difference between two
molecules is retained even at –173 C as it can be seen
from Fig. 2 demonstrating the nominal overlap of two
independent molecules. At –173 C, the abovementioned
dihedral angles are equal to 61.1(1) and 40.7(1). It is
notable that at both temperatures the differences between
two independent molecules are almost the same. The
presence of the strong electron withdrawing and electron
donating groups predetermines the overall supramolecu-
lar crystal structure of compound 3a. The main supramo-
lecular synthons in crystal of 3a are classical H-bonded
dimers (see Fig. 1) that are connected via the N—H...O-
Reagents and conditions: AcOH, H2SO4, 45—90 C, stirring,
10—30 min.
tra of the crude products isolated by an aqueous workup
of the reaction mixtures obtained by heating compounds
1a—c in AcOH—H2SO4 (thick dark-brown oils in the
case of 1a,b and brownish solid in the case of 1c) show the
signals for the second product at  11.70, 11.80, and 11.78
along with the NH proton signals of products 2a—c at
 12.38, 12.35, and 12.34 (the integral intensity ratios of
these signals are 1 : 1, 1 : 0.6, 1 : 0.5, respectively) (Table 1).
From the reaction mixtures obtained by heating com-
pounds 1b,c in AcOH—H2SO4, pure products 2b,c were
isolated in the yields of 60 and 62%, respectively. In the
case of compound 1a, we succeeded to isolate both prod-
ucts by column chromatography (elution with CHCl3).
The attempts to reveal the effects of the concentrations of
the starting compound and H2SO4 in the reaction mixtures
1a—AcOH—H2SO4 (1a (0.45 g, 1.5 mmol) in the mixtures
AcOH—H2SO4 with ratios of 2 : 0.1, 8 : 0.4, 4 : 0.1, 4 : 0.8,
v/v) on the reaction course failed to give obvious informa-
tion. It should be noted that both products in a ratio of
N(1A)
O(4A)
O(3A)
O(3B)
Table 1. Studies of chemical behavior of compound 1 (1.5 mmol)
in a mixture of AcOH and H2SO4 (4 and 0.2 mL, respectively)
O(4B)
Com-
pound
Tsolv/Ca
Δt/C
b/min Ratioc of
2 : 3
bath
flask
N(1B)
1a
1b
1с
1d
1e
1f
28
40
65
85
85
85
85
45
50
73
87
85
91
85
17
10
18
12
10
16
10
10
10
10
10
30
10
30
1 : 1
1 : 0.6
1 : 0.5
1 : 0
1 : 0
Fig. 1. Crystal geometry of two independent molecules in the
crystal of compound 3a. Nonhydrogen atoms are drawn as dis-
placement ellipsoids at the 50% probability level, hydrogen atoms
are drawn as spheres with arbitrary radii. The O—H…O hydrogen
bonds in the dimer are shown by the dotted lines; the parameters
of the H-bonds are as follows: d(O(3A)…O(4B)) = 2.87(2) Å,
d(O(3B)…O(4A)) = 2.72(2) Å.
1 : 0
1g
1 : 0
aa
Tsolv is temperature of dissolution of compound 1 (coincides
with the reaction temperature).
b  is the reaction time.
c 1H NMR data.

Mamedov et al.
512
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
hydrogen bonds between the NH hydrogen atoms of the
neighboring symmetrical H-bonded dimers into 2D supra-
molecular layer (Fig. 3). The final crystal packing of
molecules 3a is formed by parallel stacking of these 2D
H-bonded layers along the 0c crystallographic axis. Accord-
ing to the earlier revealed regularity,16,17 the H-bonded
molecular layers are in the plane defined by the two small-
est unit cell parameters (Fig. 4). In the crystal of 3a, the
voids potentially available for the solvate molecules were
not found. The calculated packing factor is relatively high
been equal to 68.3% and regularly increases to 69.6% with
a decrease in experimental temperature to –173 C.
Earlier,16 we prepared compound having structure 3a
with identical physicochemical properties by acid hydro-
Fig. 2. Nominal overlap of two independent molecules 3a in the
crystal according to a low temperature experiment.
N(1B)
O(4A)
O(4B)
N(1A)
O(4B)
Fig. 3. Fragment of the system of classical H-bonds in the crystal of compound 3a (only hydrogen atoms participating in the H-bonding
are shown); parameters of the N…O interactions are as follows: d(N(1A)…O(4B´)) [1/2 + x, 3/2 – y, z] = 2.85(2) Å,d(O(4A)…N(1B))
[1/2 + x, 1/2 – y, z] = 2.99(2) Å.
b
c
a
Fig. 4. View of the crystal packing of molecules 3a along the 0a crystallographic axis.

Acid rearrangements of oxiranyl ketones
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
513
Scheme 3
lysis of 4-bromo-3-hydroxy-2-phenylquinoline.18—28 It
is of note that only few methods for synthesizing 3-hydr-
oxyquinolin-4-ones have been described. Among them,
the synthesis of 6-chloro-1,3-dihydroxy-2-phenylquino-
lin-4-one (4) by treatment of [3-(2-nitroaryl)oxiran-2-
yl](phenyl)methanone (1a) with ethereal hydrogen chloride
is notable.27,28 In our hands, this procedure gave the same
results. Physicochemical properties of compound 4 are
given in Experimental. The mechanism of the transforma-
tion of compound 1a to product 4 is shown in Scheme 3.
Changing the reaction conditions, namely, heating the
suspension of 1a in an AcOH—H2SO4 mixture instead of
Scheme 4
Scheme 5
i. Meinwald rearrangement. ii, iii. Baeyer—Drewson type indigo synthesis.

Mamedov et al.
514
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
flask charged with compound 1 (1.5 mmol) and equipped with
a thermometer and a refluxing condenser was placed into a water
bath equipped with a thermometer. When a mixture of AcOH
(4 mL) and H2SO4 (0.2 mL) was added to compound 1. The
mixture was slowly heated under stirring and temperatures of
both the bath and the mixture corresponding to the complete
dissolution of compound 1 were detected. Stirring at this tem-
perature was continued for 10 min in the case of compounds
1a—d,f and for 30 min in the case of compounds 1e,g. The reac-
tion mixtures were poured into water (75 mL). In the case of
compounds 1a,b, heavy dark-brown oils were precipitated, which
were washed by decantation with water (3×25 mL), and air dried.
1H NMR spectra of these oils show the signals of compounds
2a,b and 3a,b in the ratios of 1 : 1 and 1 : 0.6, respectively. Column
chromatography (silica gel 40 A, elution with CHCl3) afforded
pure compounds 2a,b and 3a. In the case of compounds 1c—g,
the precipitates formed were collected by filtration, washed with
water (2×15 mL), and dried. 1H NMR spectra of the crude
products obtained from compounds 1d,e—g revealed the signals
of compounds 2d,e—g. These compounds were purified by wash-
ings with diethyl ether (2×8 mL). In the case of the crude prod-
a solution of 1a in diethyl ether saturated with HCl, we
obtained 1,6-unsubstituted 3-hydroxy-2-phenylquinolin-
4-one (3a) along with anthranilic acid derivative 2a.
Quinolin-4-one 3a is resulted from the loss of two oxygen
atoms by the molecule of [3-(2-nitrophenyl)oxiran-2-yl]-
(phenyl)methanone (1a). Taking into account this fact, we
assume that compound 3a is formed as shown in Scheme 4.
Mechanism of formation of anthranilic acid derivative 2
is adapted from our earlier work12 (Scheme 5).
In summary, in the present work the chemical behav-
ior of aryl 3-(2-nitroaryl)oxiran-2-yl ketones in acetic acid
in the presence of sulfuric acid was studied and the pos-
sibility of the formation of the two types of compounds
hardly available by other methods, viz., 2-(2-oxy-2-aryl-
acetamido)benzoic acids and 2-arylquinolin-4-one in the
case of [3-(2-nitrophenyl)oxiran-2-yl](phenyl)methan-
one, was revealed.
Experimental
1
uct obtained from compound 1c, H NMR spectrum exhibited
signals of compounds 2c and 3c in a 1 : 0.6 ratio. Compound 2c
was isolated pure by column chromatography (silica gel 40 A,
elution with CHCl3).
Melting points were measured with a Stuart SMP-10 appa-
ratus. IR spectra were recorded on a Bruker Vector-22 spectrom-
eter in KBr pellets. 1H NMR spectra were run on Bruker
Avance-400 (1e—g, 2a,b,d,e), Bruker Avance-50 (2f), and Bruker
Avance-600 (2c,g, 3a, 4) spectrometers in DMSO-d6.
Aryl 3-(2-nitrophenyl)oxiran-2-yl ketones 1a—g were syn-
thesized under the Darzens condensation conditions as earlier
described15 using 0.01 mmol of the starting compounds. Physico-
chemical properties of compounds 1a—d are in agreement with
those published earlier.12,15
Naphthalen-1-yl-[3-(2-nitrophenyl)oxiran-2-yl]methanone
(1e). Yield 0.46 g (95%), m.p. 130—131 C. Found (%): C, 71.62;
H, 3.91; N, 4.22. C19H13NO4. Calculated (%): C, 71.47; H, 4.10;
N, 4.39. IR, /cm–1: 1684, 1521, 1343. 1H NMR, : 4.57, 4.63
(both d, 1 H each, Hox, J = 1.9 Hz)*; naphthyl + C6H4: 7.58—7.72
(m, 5 H), 7.84 (dd, 1 H, J = 7.4 Hz, J = 7.4 Hz), 8.03 (d, 1 H,
J = 7.4 Hz), 8.17 (d, 1 H, J = 7.5 Hz), 8.21 (dd, 2 H, J = 7.2 Hz,
J = 7.5 Hz), 8.56 (d, 1 H, J = 8.5).
2-(2-Oxo-2-phenylacetamido)benzoic acid (2a). Yield 0.14 g
(35%), m.p. 184—185 C. Found (%): C, 66.83; H, 4.23; N, 5.32.
C15H11NO4. Calculated (%): C, 66.91; H, 4.12; N, 5.20. IR,
1
/cm–1: 1699, 1670, 1583, 1519, 1258. H NMR, : 7.29, 7.74
(both dd, 1 H each, H(4), H(5), NC6H4, J = 7.5 Hz, J = 7.7 Hz);
7.59 (dd, 2 H, H(3), H(5), C6H4, J = 7.8 Hz, J = 7.8 Hz); 7.70
(dd, 1 H, H(4), C6H4, J = 7.8 Hz, J = 7.8 Hz); 8.06, 8.63 (both d,
1 H each, H(3), H(6), NC6H4, J = 7.6 Hz, J = 7.8 Hz); 8.21 (d,
2 H, H(2), H(6), C6H4, J = 7.9 Hz); 12.38 (s, 1 H, NH).
3-Hydroxy-2-phenylquinolin-4(1H)-one (3a). Yield 0.14 g
(40%), m.p. 269—270 C (cf. Ref. 18: 270—271 C). Found (%):
C, 75.81; H, 4.45; N, 5.79. C15H11NO2. Calculated (%): C, 75.94;
H, 4.67; N, 5.90. IR, /cm–1: 3241, 1632, 1549, 1487, 1402,
1368, 1267. 1H NMR, : 7.28, 7.58 both dd, 1 H each, H(6),
H(7), Hquin, J = 7.2 Hz, J = 7.8 and J = 7.2 Hz, J = 6.8 Hz)**;
7.45—7.75 (m, 5 H, Ph); 7.78, 8.17 (both d, 1 H each, H(5),
H(8), Hquin, J = 6.7 Hz and J = 7.9 Hz); 11.70 (br.s, 1 H, NH).
2-[2-Oxo-2-(p-tolyl)acetamido]benzoic acid (2b). Yield 0.25 g
(60%), m.p. 200—201 C (cf. Ref. 12: 199—201 C). Found (%):
C, 67.73; H, 4.51; N, 4.76. C16H13NO4. Calculated (%): C, 67.84;
H, 4.63; N, 4.94. IR, /cm–1: 1699, 1678, 1668, 1584, 1524,
[3-(5-Chloro-2-nitrophenyl) oxiran-2-yl](4-methoxyphenyl)-
methanone (1f). Yield 2.87 g (96%), m.p. 153—154 C. Found (%):
C, 57.64; H, 3.41; Cl, 10.78; N, 4.09. C16H12ClNO5. Calculat-
ed (%): C, 57.58; H, 3.63; Cl, 10.62; N, 4.20. IR, /cm–1: 1678,
1
1599, 1512, 1340, 1242, 839. H NMR, : 3.85 (s, 3 H, OMe);
4.55, 4.73 (both br.s, 1 H each, Hox); 7.06, 8.06 (both d, 2 H each,
C6H4, J = 8.7 Hz); 7.57 (s, 1 H, H(6), C6H3); 7.72, 8.22 (both d,
1 H each, H(3), H(4), C6H3, J = 8.4 Hz).
1
1266, 754. H NMR, : 2.41 (s, 3 H, Me); 7.27, 7.68 (both dd,
1 H each, H(4), H(5), NC6H4, J = 7.6 Hz, J = 7.6 Hz); 7.39,
8.14 (both d, 2 H each, C6H4, J = 7.7 Hz); 8.05, 8.64 (both d,
1 H each, H(3), H(6), NC6H4, J = 7.6 Hz); 12.35 (s, 1 H, NH).
2-[2-(4-Methoxyphenyl)-2-oxoacetamido]benzoic acid (2c).
Yield 0.28 g (62%), m.p. 211—212 C (cf. Ref. 12: 178—181 C).
Found (%): C, 64.13; H, 4.42; N, 4.53. C16H13NO5. Calculat-
ed (%): C, 64.21; H, 4.38; N, 4.68. IR, /cm–1: 1701, 1675,
1601, 158, 1528, 1263, 753. 1H NMR, : 3.87 (s, 3 H, OMe);
7.10, 8.26 (both d, 2 H each, C6H4, J = 8.9 Hz); 7.27, 7.68
(both dd, 1 H each, H(4), H(5), NC6H4, J = 7.2 Hz, J = 7.1 Hz);
8.05, 8.62 (both d, 1 H each, H(3), H(6), NC6H4, J = 7.2 Hz);
12.34 (s, 1 H, NH).
(4-Chlorophenyl)[3-(2,4-dinitrophenyl)oxiran-2-yl]methan-
one (1g). Yield 13.38 g (97%), m.p. 154—155 C. Found (%):
C, 51.73; H, 3.01; Cl, 10.12; N, 15.62. C15H9ClN2O6. Calculat-
ed (%): C, 51.66; H, 2.61; Cl, 10.17; N, 15.55. IR, /cm–1: 1683,
1531, 1348. 1H NMR, : 4.70, 4.82 (both d, 1 H each, Hox
,
J = 4.0 Hz); 7.64, 8.11 (both d, 2 H each, C6H4, J = 8.5 Hz); 7.88
(d, 1 H, H(6), C6H3, J = 8.6 Hz); 8.65 (dd, 1 H, H(5), C6H3,
J = 8.6 Hz, J = 2.3 Hz); 8.85 (d, 1 H, H(3), C6H3, J = 2.3 Hz).
Studies of the chemical behavior of aryl 3-(2-nitroaryl)oxiran-
2-yl ketones 1a—g in acidic medium. Experiment 1. A two-neck
* Hox stands for the oxirane ring protons.
** Hquin stands for the quinoxaline ring protons.

Acid rearrangements of oxiranyl ketones
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
515
2-[2-(4-Chlorophenyl)-2-oxoacetamido]benzoic acid (2d).
Yield 0.35 g (78%), m.p. 199—200 C. Found (%): C, 59.63;
H, 3.50; Cl, 11,37; N, 4.55. C15H10ClNO4. Calculated (%):
C, 59.32; H, 3.32; Cl, 11,67; N, 4.61. IR, /cm–1: 1698, 1682,
1671, 1584, 1542, 1263. 1H NMR, : 7.29, 7.70 (both dd, 1 H each,
H(4), H(5), NC6H4, J = 7.6 Hz, J = 7.6 Hz); 7.66, 8.25 (both d,
2 H each, C6H4, J = 8.4 Hz); 8.07, 8.65 (both d, 1 H each, H(3),
H(6), NC6H4, J = 7.7 Hz); 12.44 (s, 1 H, NH).
2-[2-(Naphthalen-1-yl)-2-oxoacetamido]benzoic acid (2e).
Yield 0.34 g (72%), m.p. 213—215 C. Found (%): C, 71.53;
H, 4.22; N, 4.43. C19H13NO4. Calculated (%): C, 71.47; H, 4.10;
N, 4.39. IR, /cm–1: 1682, 1586, 1509, 1233. 1H NMR, : 7.30
(dd, 1 H, H(4), NC6H4, J = 7.6 Hz, J = 7.8 Hz); 7.59—7.75
(m, 4 H), 8.09 (dd, 2 H, J = 7.6 Hz, J = 7.8 Hz), 8.26 (dd, 2 H,
J = 6.2 Hz, J = 6.4 Hz), 8.48 (d, 1 H, J = 8.3 Hz) — naphthyl +
+ H(3), H(5), NC6H4; 8.67 (d, 1 H, H(6), NC6H4, J = 8.3 Hz);
12.55 (s, 1 H, NH).
2-[2-(4-Chlorophenyl)-2-oxoacetamido]-4-nitrobenzoic acid
(2g). Yield 0.40 g (77%), m.p. 283—284 C. Found (%): C, 51.52;
H, 2.47; Cl, 10.24; N, 8.432. C15H9ClN2O6. Calculated (%):
C, 51.67; H, 2.60; Cl, 10.17; N, 8.03. IR, /cm–1: 1703, 1675,
1529, 1512,1255, 993. 1H NMR, : 7.67, 8.28 (both d, 2 H each,
C6H4, J = 8.0 Hz); 8.05, 8.29 (both d, 1 H each, H(5), H(6),
C6H3, J = 7.8 Hz); 9.46 (s, 1 H, H(3), C6H3); 12.59 (s, 1 H, NH).
Experiment 2. Through a solution of compound 1a (0.40 g,
1.5 mmol) in diethyl ether (250 mL) cooled to 0—5 C, dry
gaseous HCl was slowly bubbled for 3 h. The precipitate formed
after removal of ~1/3 of the solvent under the reduced pressure
was collected by filtration and dried to afford 0.31 g (73%) of 4,
m.p. 263—264 C (cf. Ref. 28: 270 C; cf. Ref. 29: 264 C).
Found (%): C, 62.59; H, 3.22; Cl, 12.48, N, 4.63. C15H10ClNO3.
Calculated (%): C, 62.62; H, 3.50; Cl, 12.32; N, 4.87. IR, /cm–1
:
3434, 3073, 2689, 1582, 1386, 1371, 688. 1H NMR, : 7.46—7.52
(m, 5 H, Ph); 7.75 (dd, 1 H, H(7), J = 9.2 Hz, J = 2.1 Hz); 7.93
(d, 1 H, H(8), J = 9.2 Hz); 8.21 (d, 1 H, H(5), J = 2.0 Hz).
Single crystal X-ray diffraction analysis of compound 3a was
performed with a Bruker Kappa Apex II CCD automated system
((Mo-K) = 0.71073 Å, graphite monochromator, φ and 
scan modes) at 23 C (3a) and –173 C (3a_LT). The data were
collected, processed, and the unit cell parameters were refined
using APEX2 software.30 Semiempirical absorption corrections
were applied using SADABS program.31. The structure was solved
by the direct method and refined by the full-matrix least-squares
5-Chloro-2-[2-(4-methoxyphenyl)-2-oxoacetamido]benzoic
acid (2f). Yield 0.42 g (84%), m.p. 245—246 C. Found (%):
C, 57.48; H, 3.41; Cl, 10.22; N, 4.44. C16H12ClNO5. Calculat-
ed (%): C, 57.60; H, 3.63; Cl, 10.63; N, 4.20. IR, /cm–1: 1702,
1
1681, 1598, 1577, 1510, 1250, 1158. H NMR, : 3.87 (s, 3 H,
OMe); 7.09, 8.24 (both d, 2 H each, C6H4, J = 8.9 Hz); 7.72
(dd, 1 H, H(4), C6H3, J = 8.9 Hz, J = 2.4 Hz); 7.96 (d, 1 H,
H(6), C6H3, J = 2.4 Hz); 8.61 (d, 1 H, H(3), C6H3, J = 8.8 Hz);
12.27 (s, 1 H, NH).
Table 2. Crystallographic parameters and X-ray data collection and structure refinement statistics for
compounds 3a_LT and 3a
Parameter
3a_LT
3a
Molecular formula
C
15H11NO2
C15H11NO2
Prismatic
237.25
Crystal habit
Prismatic
237.25
M/g mol–1
T/K
100(2)
296(2)
Crystal system
Orthorhombic
Pna21
0.322×0.423×0.595
8
Orthorhombic
Pna21
0.272×0.183×0.121
8
Space group
Crystal size/mm3
Z
Unit cell parameters
a/Å
9.8536(10)
12.9367(12)
18.0722(16)
2303.7(4)
992
9.889(8)
13.027(10)
18.189(14)
2343(3)
992
1.345
0.090
b/Å
c/Å
V/Ǻ3
F(000)
dcalc/g cm–3
1.368
0.092
/mm–1
/deg
1.94    28.38
32657
1.92    27.24
17651
Number of measured reflections
Number of independent reflections
Rint
5651
0.0679
4286
331
4952
0.1541
1089
325
Number of reflections with I > 2(I)
Number of refinement parameters
for all reflections with I > 2(I)
R1
0.0526
0.1391
1.025
0.0992
0.1758
0.889
wR2
GOOF on F2
Residual electron
density (max/min)/e Ǻ–3
0.265/–0.238
0.374/–0.354

Mamedov et al.
516
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 3, March, 2020
method first in isotropic and then in anisotropic approximations
(for all non-hydrogen atoms) with SHELXL program.32 The
positions of hydrogen atoms were calculated based on stereo-
chemical considerations and refined using the corresponding
riding models. All calculations were performed with WinGX
program.33 The intermolecular interactions were analyzed and
the molecular structures and crystal packing diagrams were drawn
using PLATON34 and Mercury35 software. Crystallographic data
found at 23 C (3a) and –173 C (3a_LT) and the parameters of
X-ray diffraction experiment are given in Table 2.
The atomic coordinates and structural parameters of com-
pound 3a at 23 C (3a) and –173 C (3a_LT) were deposited
with the Cambridge Crystallographic Data Centre (CCDC
1958154, 1958155) and are available free of charge at www.ccdc.
cam.ac.uk/data_request/cif.
14. Y. Xia, J. Zhao, Polymer, 2018, 143, 343.
15. V. A. Mamedov, V. L. Mamedova, V. V. Syakaev, D. E.
Korshin, G. Z. Khikmatova, E. V. Mironova, O. B. Bazanova,
I. Kh. Rizvanov, Tetrahedron, 2017, 73, 5082.
16. A. T. Gubaidullin, A. I. Samigullina, Z. A. Bredikhina, A. A.
Bredikhin, CrystEngComm, 2014, 16, 6716.
17. A. I. Samigullina, A. T. Gubaidullin, L. V. Mustakimova,
V. A. Mamedov, Russ. Chem. Bull., 2014, 63, 1444.
18. V. A. Mamedov, V. L. Mamedova, G. Z. Khikmatova, E. M.
Mahrous, D. E. Korshin, V. V. Syakaev, R. R. Fayzullin, E. V.
Mironova, Sh. K. Latypov, O. G. Sinyashin, Russ. Chem.
Bull., 2019, 68, 1020.
19. J. T. Hodgkinson, W. R. J. D. Galloway, Sh. Saraf, I. R.
Baxendale, S. V. Ley, M. Ladlow, M. Welch, D. R. Spring,
Org. Biomol. Chem., 2011, 9, 57.
20. F. Gao, K. F. Johnson, J. B. Schlenoff, J. Chem. Soc., Perkin
Trans. 2, 1996, 269.
21. D. A. Yushchenko, M. D. Bilokin, O. V. Pyvovarenko,
G. Duportail, Y. Mely, V. G. Pivovarenko, Tetrahedron Lett.,
2006, 47, 905.
22. P. Hradil, J. Jirman, Coll. Czech. Chem. Commun., 1995,
60, 1357.
23. P. Hradil, J. Hlavac, K. Lemr, J. Heterocycl. Chem., 1999,
36, 141.
24. P. Hradil, L. Kvapil, J. Hlavac, T. Weidlich, A. Lycka,
K. Lemr, J. Heterocycl. Chem., 2000, 37, 831.
25. P. Hradil, M. Grepl, J. Hlavac, A. Lycka, Heterocycles, 2007,
71, 2, 269.
26. M. M. Heravi, H. A. Oskooie, L. Bahrami, M. Ghassemzadeh,
Ind. J. Chem., 2006, 45B, 779.
27. T. W. M. Spence, G. Tennant, J. Chem. Soc. D, 1970, 1100.
28. T. W. M. Spence, G. Tennant, J. Chem. Soc., 1971, 3712.
29. I. P. Sword, J. Chem. Soc. (C), 1971, 820.
The authors are grateful for the staff of the Assigned
Spectral and Analytical Center for Study of the Structure,
Properties and Composition of Substances and Materials
of the Federal Research Center "Kazan Scientific Center
of the Russian Academy of Sciences" for the physico-
chemical studies.
This work was financially supported in part by the
Russian Science Foundation (Project No. 18-13-00315).
References
1. R. E. Parker, N. S. Isaacs, Chem. Rev., 1959, 59, 737.
2. A. S. Rao, S. K. Paknikar, J. G. Kirtane, Tetrahedron, 1983,
14, 2323.
3. J. G. Smith, Synthesis, 1984, 8, 629.
30. APEX2 (Version 2.1), SAINTPlus. Data Reduction and
Correction Program (Version 7.31A), Bruker Advanced X-ray
Solutions/BrukerAXS, Inc., Madison, Wisconsin, USA, 2006.
31. G. M. Sheldrick, SADABS, Program for Empirical X-Ray
Absorption Correction, Bruker-Nonius, 1990—2004.
32. G. M. Sheldrick, SHELXL-97, Program for Cristal Structure
Refinement, University of Göttingen, Göttingen, Germany,
1997.
33. L. J. Farrugia, J. Appl. Crystallorg., 1999, 32, 837.
34. A. L. Spek, Acta Crystallogr., Sect. A: Found. Crystallogr.,
1990, 46, part s1, 34.
35. I. J. Bruno, J. C. Cole, P. R. Edgington, M. K. Kessler, C. F.
Macrae, P. McCabe, J. Pearson, R. Taylor, Acta Crystallogr.,
Sect. B: Struct. Sci., 2002, 58, 389.
4. M. Sasaki, K. Takeda, Synlett, 2012, 23, 2153.
5. C.-Y. Huang, A. G. Doyle, Chem. Rev., 2014, 114, 8153.
6. S. Faiz, A. F. Zahoor, Mol. Diversity, 2016, 20, 969.
7. V. L. Mamedova, G. Z. Khikmatova, Chem. Heterocycl.
Compd., 2017, 53, 976.
8. M. Fallah-Mehrjardi, A. R. Kiasat, K. Niknam, J. Iran. Chem.
Soc., 2018, 15, 2033.
9. J. C. Badenock, Prog. Heterocycl. Chem., 2018, 30, 43.
10. S. Ahmad, A. F. Zahoor, S. A. R. Naqvi, Mol. Diversity, 2018,
22, 191.
11. V. A. Mamedov, V. L. Mamedova, S. F. Kadyrova, G. Z.
Khikmatova, A. T. Gubaidullin, I. Kh. Rizvanov, Sh. K.
Latypov, Tetrahedron, 2015, 71, 2670.
12. V. A. Mamedov, V. L. Mamedova, G. Z. Khikmatova, E. V.
Mironova, D. V. Krivolapov, O. B. Bazanova, D. V. Chachov,
S. A. Katsyuba, I. Kh. Rizvanov, Sh. K. Latypov, RSC Adv.,
2016, 6, 27885.
13. D.-H. Lan, N. Fan, Y. Wang, X. Gao, P. Zhang, L. Chen,
C.-T. Au, Sh.-F. Yin, Chin. J. Catal., 2016, 37, 826.
Received October 15, 2019;
accepted December 8, 2019