Geminal acylnitrostyrenes in the reaction with ortho-aminothiophenol

Article abstract of DOI:10.1134/S1070363211060156

The synthesis of previously unknown 2,3- and 2,5-dihydro-1,5- benzothiazepines sontaining nitro group was performed by the easy sondensation of geminal acylnitrostyrenes with the o-aminothiophenol. The structure of the obtained sompounds was studied by physicochemical methods. By X-ray diffraction analysis the geometry and structural parameters of 4-methyl-3-nitro-2-phenyl-2, 3-dihydro-1,5-benzothiazepine were determined. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070363211060156

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 6, pp. 1163–1170. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.M. Berestovitskaya, R.I. Baichurin, N.I. Aboskalova, K.A. Lysenko, I.V. Anan’ev, 2011, published in Zhurnal Obshchei Khimii,
2011, Vol. 81, No. 6, pp. 970–977.
Geminal Acylnitrostyrenes in the Reaction
with ortho-Aminothiophenol
V. M. Berestovitskayaa, R. I. Baichurina, N. I. Aboskalovaa, K. A. Lysenkob, and I. V. Anan’evb
a Herzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
b Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
Received December 28, 2009
Abstract—The synthesis of previously unknown 2,3- and 2,5-dihydro-1,5-benzothiazepines sontaining nitro
group was performed by the easy sondensation of geminal acylnitrostyrenes with the o-aminothiophenol. The
structure of the obtained sompounds was studied by physicochemical methods. By X-ray diffraction analysis
the geometry and structural parameters of 4-methyl-3-nitro-2-phenyl-2,3-dihydro-1,5-benzothiazepine were
determined.
DOI: 10.1134/S1070363211060156
α,β-Conjugated enketones are known to possess
high reactivity. They are convenient precursors for the
synthesis of a wide range of various carbocyclic and
heterocyclic compounds. Of particular interest are the
reactions where the enketones act as bielectrophiles,
interacting with binucleophilic reagents to form five-,
six- and seven-membered cyclic structures [1–4].
VII–IX, from the gem-benzoylnitrostyrenes IV–VI
linear S-adducts X–XII were obtained in 80–98% yield.
Apparently, the reaction of o-aminothiophenol with
gem-acylnitrostyrenes I–VI leads initially to the
formation of an adduct at the multiple C=C bond
(AdN), which is isolated in the case of a compound
with the benzoyl group X–XII, but the S-adduct
obtained from the gem-acetylnitrostyrene I–III im-
mediately suffers heterocyclizaton. This difference
may be due to the difference in activity of carbonyl
groups in the benzoyl and acetyl functions of the
addition products. Probably the attack of amino group
on the bezoyl carbonyl group in the adducts X–XII is
difficult compared to the acetyl analogs due to steric
and electronic factors [12–14].
The introduction of another acceptor, the nitro
group, to the enketone molecule in the gem-position to
the carbonyl function increases electrophilicity of the
unsaturated compound and significantly expands the
range of its synthetic performance. Previously, based
on the preparatively available gem-acylnitroethenes,
carbocyclic and heterocyclic structures were obtained
with potentially useful properties, namely, gem-acyl-
nitrocyclohexenes, pyrimidines, 1,2,3-triazoles, pyra-
zoles, dihydrofurans, and others [5–11].
Note that the enketones without nitro group react
with o-aminothiophenol to form the seven-membered
benzothiazepine ring under fairly rigid conditions (at
boiling in methanol for several hours in the presence of
acid [15] or basic [16] catalyst, or at boiling without a
catalyst, but in a high-boiling solvent such as toluene
[17]) and, depending on conditions, either linear S-
adducts, or substituted 2,3-dihydrobenzothiazepines
are isolated [18–20]. Recently information appeared on
the reaction of activated geminal enketones like aryl-
idenacetylacetones and arylidenacetoacetic esters with
o-aminothiophenol and its derivatives in methanol at room
temperature, but the reaction proceeded over at least
Aiming to study further the chemical behavior of
nitroenketones we investigated a reaction of gem-
acetyl- and gem-benzoylnitrostyrenes I–VI with o-
aminothiophenol. These reactions proceed successfully
at equimolar ratio of reagents under very mild
conditions: At 18–20ºC in methanol, in the absence of
a catalyst, in 10–20 min, to form new compounds VII–
XII, respectively, immediately precipitating from the
reaction solution as crystalline substances. However,
while the gem-acetylnitrostyrenes I–III afford 2-aryl-
4-methyl-3-nitro-2,3-dihydro-1,5-benzothiazepines
1163

1164
Ar
BERESTOVITSKAYA et al.
HA
Ar
S
NO2
NO2
HB
Ar
HA
NO2
S
X = CH3
1
2
CH3
HB
3
X
H2O
4
5
O
O
N
CH3
NH2
I_VI
+
VII_IX
CH3OH
18_20оС,
HS
H2N
10_20 min
HA
HB
HB
Ar
S
NO2
C6H5
Ar
HA
NO2
S
CH3OH, Δ, HCl
X = C6H5
H2O
O
N
C6H5
NH2
X_XII
NO2
Ar = 4-(H3C)2NC6H4
H2C
C(O)C6H5
X = C6H5
N
S
N(CH3)2
H
Ar
XV
S
2
CH3OH, Δ, HCl
1
3
NO2
C6H5
4
5
N
H
XIII, XIV
X = CH3: Ar = C6H5 (I), 4-H3COC6H4 (II), 4-(H3C)2NC6H4 (III); X = C6H5: Ar = C6H5 (IV), 4-H3COC6H4 (V),
4-(H3C)2NC6H4 (VI); Ar = C6H5 (VII, X, XIII), 4-H3COC6H4 (VIII, XI, XIV), 4-(H3C)2NC6H4 (IX, XII).
1 h. The S-adducts isolated were converted into the
cyclic dihydro-1,5-benzothiazepine structures [21, 22].
aminothiophenol by boiling the reagents in a methanol
solutions for 1–3 h in the presence of hydrochloric
acid.
In order to obtain nitrobenzothiazepine structures
with phenyl substituent at the C4 atom, the obtained
linear S-adducts X and XI were heated in alcohol
solution in the presence of an acidic agent (methanol,
10 drops of concentrated hydrochloric acid, 1–3 h of
reflux). As a result, we isolated 2-aryl-3-nitro-4-
phenyl-2,5-dihydro-1,5-benzothiazepines XIII and
XIV, respectively, which can be regarded as the
products of isomerization of initially formed 2,3-
dihydro-1,5-benzothiazepines. This prototropic trans-
formation is likely to be caused by the ability of the
phenyl substituent, in contrast to the methyl group, to
participate in conjugation with nitroenamine fragment.
We were able to obtain the same compounds XIII and
XIV in a one-pot reaction directly from the cor-
responding gem-benzoylnitrostyrenes IV and V and o-
Synthesized cyclic structures VII–IX, XIII, XIV
and linear S-adducts X, XI are fairly stable, colorless
or yellowish crystalline substances, with sharp melting
points. Only the S-adduct XII derived from the gem-
benzoylnitrostyrene containing dimethylamino group
in the para-position of benzene ring is unstable, and
gradually spontaneously undergoes an intramolecular
transformation, which, however, does not lead to
benzothiazepine. In this case, the process is accom-
panied by the release of benzoylnitromethane and the
formation of a highly conjugated aromatic system of 2-
(4-N,N-dimethylaminophenyl)benzothiazole (XV). In
favor of assignment of this structure to compound XV
speaks the close value of the melting point and spectral
characteristics of the synthesized substance with the
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GEMINAL ACYLNITROSTYRENES IN THE REACTION WITH ortho-AMINOTHIOPHENOL
1165
Table 1. Yields, melting points, and the data of IR and 1H NMR spectra of dihydro-1,5-benzothiazepines VII–IX, XIII, XIV
and S-adducts X–XII
IR spectraа (СНCl3), ν, cm–1
1H NMR spectra (СDCl3), δ, ppm (J, Hz)
Comp. Yield,
mp,
°С
СН3
(OCH3)
[NCH3]
no.
VII
VIII
IX
%
81
98
98
NO2
C=O (C=N)
NH2
NH2 (NH+) НА (H)
НВ
Ar
(NOO−) [C=C, C=N+]
(NH+)
136–137 1560, 1360
132–134 1560, 1360
144–146 1560, 1360
(1645)
(1645)
(1645)
–
–
–
5.52 d
5.27 d
2.44 s 7.17–7.58 m
–
–
Δδ 0.25
3JAB 11.90
5.45 d 5.25 d
2.43 s 6.79 d, 7.11 d, 7.20 t,
(3.76 s) 7.29 d, 7.52 t, 7.57 d
Δδ 0.20
3JAB 11.90
5.46 d
5.23 d
2.43 s 6.57 d, 7.03 d, 7.18 t,
[2.91 s] 7.28 d, 7.50 t, 7.58 d
–
Δδ 0.23
3JAB 11.90
98
80
124–126 1560, 1355
104–106 1560, 1355
1695
1695
3480, 3375
3480, 3375
6.74 d
5.17 d
–
6.43 t, 6.61 d, 6.74 d,
4.08 s
X
Δδ 1.57
7.06 t, 7.22 m, 7.59 t,
7.72 t, 8.18 d
3JАВ 11.29
6.67 d
5.13 d
(3.77 s) 6.44 t, 6.61 d, 6.77 d.d, 4.11 s
XI
Δδ 1.54
7.07 t, 7.14 d, 7.58 t,
7.71 t, 8.16 d
3JАВ 11.29
XIIb
80
102–104 1560, 1360
1695
3480, 3375
6.68 d
5.10 d
[2.92 s] 6.37–7.14 m, 6.57 m,
7.08 m, 7.38–8.17 m
4.10 s
4.18 s
Δδ 1.58
3JAB 11.29
6.66 d
5.04 d
[2.81 s]
Δδ 1.62
3JAB 11.29
57 (32c) 161–163 (1125–1295)
40 (51c) 147–149 (1180–1290)
[1630]
[1610]
3330
3390
(6.30 s)
(6.24 s)
–
–
–
6.82–7.60 m
(6.48 s)
(6.45 s)
XIII
XIV
(3.68 s) 6.60–7.60 m
a
IR spectrum of sompound XIII was taken from KBr pellets. b Compound XII was isolated as a mixture of diastereomers in a ratio a:b =
c
2.5:1, in the 1H NMR spectrum the signals of the HA and HB protons of the “a” isomer are shifted downfield compared to “b.” In
parentheses are given the yields of compounds XIII and XIV obtained by one-pot technique.
corresponding parameters of the sample described
previously in the literature and obtained by another
method [23].
X–XII contain strong absorption bands of stretching
vibrations of nonconjugated nitro group (1560, 1355–
1360 cm–1). In the IR spectra of compounds with linear
structure X–XII there are the absorption bands of the
carbonyl function (1695 cm–1) and of the primary
amino group (3480 cm–1, 3375 cm–1). The stretching
vibrations of C=N bond give rise to the absorption
band at 1645 cm–1 in the spectra of 2,3-dihydro-1,5-
benzothiazepine systems VII–IX.
The composition and structure of the first
synthesized compounds were confirmed by elemental
analysis, IR, UV, 1H NMR and 13C NMR spectroscopy
(Tables 1 and 2). Thus, the IR spectra of 3-nitro-2,3-
dihydro-1,5-benzothiazepines VII–IX and S-adducts
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1166
BERESTOVITSKAYA et al.
Table 2. The data of 13C NMR spectra of compounds VII–XI (CDCl3, δ, ppm)
Comp.
no.
С=О
(С=N)
OCH3
[N(CH3)2]
CНА
СНВ
СН3 (Ar)
90.98
58.70
(162.76)
(162.68)
(162.74)
186.31
21.99 (120.50, 124.56, 126.39, 126.60, 129.02, 129.23,131.04,
135.28, 139.89,150.09)
22.05 (114.49, 120.59, 121.68, 124.54, 126.54, 127.69, 130.93,
132.11, 135.24, 150.00, 159.90)
22.09 (112.41, 121.00, 124.44, 126.29, 126.41, 127.29, 130.67,
135.30, 150. 00, 150.04, 150.70)
(112.85, 115.26, 118.33, 128.20, 128.76, 129.17, 129.35, 129.73,
131.64, 135.22, 149.94)
–
VII
VIII
IX
91.30
91.46
89.34
89.66
58.43
59.01
51.09
50.71
55.38
[40.41]
–
X
186.25
(113.04, 114.00, 115.22, 118.31, 128.07, 129.14, 129.33, 129.48,
129.58, 129.67, 131.58, 134.82, 135.16, 138.23, 149.96, 159.59)
55.36
XI
The IR spectra of 3-nitro-2,5-dihydro-1,5-
benzothiazepines XIII and XIV of the nitroenamine
structure differ substantially from the IR spectra of 3-
nitro-2,3-dihydro-1,5-benzothiazepines VII–IX. They
do not contain the characteristic bands of a covalent
nitro group, while there are strong absorption bands at
1125–1295 cm–1 of ionized nitro group and a set of
multiple bands of C=C and C=N+ bonds at 1610–
1630 cm–1. Such spectral pattern indicates a high
polarization of the molecules due to the involvement of
the nitro and amino groups and of their significant
contribution into the bipolar structure of the ground
state. The data of electronic spectroscopy do not
contradict these findings. Thus, in the electronic
spectra of 2,5-dihydro-1,5-benzothiazepines XIII and
XIV dissolved in ethanol there are long-wavelength
absorption band at 395 nm (ε 8700) and 394 nm
(ε 6800) typical of nitroenamines [24].
doubling of methine proton signals occurs in the spec-
trum, indicating the appearance of a second diastereo-
mer [HA, δ = 6.73, HB, δ = 5.12 ppm, Δδ = 1.61 ppm,
3J(HAHB) = 11.29 Hz]. Likewise behaves compound
XI dissolved in CDCl3, which originally was diastereo-
merically uniform. In contrast to compounds X and XI.
1
the S-adduct XII is formed, according to H NMR
spectra, at once as a mixture of diastereomers in a ratio
of a:b = 2.5:1.
1
In the H NMR spectra of 2,3-dihydro-1,5-benzo-
thiazepines VII–IX, taken from the solutions in
chloroform-d1, same as in the spectra of linear S-
adducts, there are two doublet signal of HA and HB
protons at 5.45–5.52 and 5.23–5.27 ppm respectively
(Δδ 0.20–0.25 ppm) with a spin-spin coupling constant
3J(HAHB) = 11.90 Hz; to the protons of methyl groups
(C4–CH3) correspond singlets at 2.43–2.44 ppm. In
contrast to 2,3-dihydro-1,5-benzothiazepines VII–IX,
1
in the H NMR spectra of 2,5-dihydro-1,5-benzothia-
H
H
Ar
Ar
S
S
zepines XIII and XIV the signals of methine protons
of the heterocycle appear at 6.30 and 6.24 ppm, and
the signals at 6.48 and 6.45 ppm belong to the protons
of NH groups in the two compounds, respectively (in
the case of compounds VII–IX they are absent).
NO2
C6H5
NOO
C6H5
N
H
N
H
XIII, XIV
In the 13C–{1H} NMR spectra of linear S-adducts X
1
The H NMR spectra of linear S-adducts X and XI
taken immediately after dissolving in chloroform-d,
indicate that these substances are individual diastereo-
and XI the signal of the carbonyl carbon atom appears
13
at 186 ppm, whereas in the C–{1H} NMR spectra of
1
2,3-dihydro-1,5-benzothiazepines VII–IX the most
downfield signal occurs at ~163 ppm and can be attri-
buted to the carbon of C=N group. The signals of carbon
atoms of CHA and CHB fragments appear at 90.98–
91.46 and 58.43–59.01 ppm, respectively (compounds
VII and VIII) and at 89.34–89.66 and 50.71–51.09 ppm,
respectively in the case of compounds X and XI.
mers. For example, in the H NMR spectrum of
compound X there are two distinct doublets of methine
protons of HA and HB at 6.74 and 5.17 ppm,
respectively (Δδ = 1.57 ppm) with a spin-spin coupling
3
constant J(HAHB) = 11.29 Hz; the protons of NH2
groups give rise to a singlet at 8.4 ppm. However, after
keeping the solution of compound X for two days, the
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GEMINAL ACYLNITROSTYRENES IN THE REACTION WITH ortho-AMINOTHIOPHENOL
1167
The final conclusion on the structure of newly
synthesized 2,3-dihydro-1,5-benzothiazepines VII–IX
containing nitro group was done on the basis of X-ray
diffraction data of compound VII as a representative of
this series (Fig. 1, Table 3). The X-ray diffraction
study showed that in the molecule of compound VII
the seven-membered heterocycle has a distorted boat
conformation, with the deviation from the plane of the
atoms C3, C6 and C7 by 0.599(5), 1.214(7) and
1.226(7) Å, respectively. This conformation, in turn,
leads to a lack of conjugation of the C4–N5 double
bond with the aromatic ring, which is confirmed by the
values of bond lengths [C4–N5 1.2742(16) Å, N5–C6
1.4136(15) Å], and torsion angle C4N5C6C7 52.64(16)º.
The seven-membered rings with similar geometry (up
to similarity in bond lengths and bond angles) have
been described previously in [25–27]. The location of
the substituents at the C2–C3 corresponds to staggered
conformation: the hydrogen atoms are almost anti-
periplanar to each other (torsion angle H2AC2C3H3A is
167º) .
Fig. 1. General view of 4-methyl-3-nitro-2-phenyl-2,3-di-
hydro-1,5-benzothiazepine VII molecule in the representa-
tion of atomic thermal vibration ellipsoids (p = 50%).
In the crystal, the molecules are packed along b
axis (Fig. 2) due to sufficiently strong CH···O inter-
action between C2–H2A group and the oxygen atom of
the nitro group (2.36 Å), as well as due to a short
contact between the electron pair of the sulfur atom
and the π-density of benzothiazepine ring (the shortest
S···C contact is 3.48 Å).
thesized compounds can be recommended for further
study as potential biologically active substances.
Currently, in medical practice pharmaceuticals are
widely used that contain the benzothiazepine hetero-
cycle in the molecules of active substances. These are,
for example, dilthiazem, showing anthianginal,
antihypertensive and anthiarrhythmic action, quethia-
pine, belonging to neuroleptics, etc. [28, 29]. High
medical significance of these drugs implies the need
for comprehensive studies aimed at developing new
methods of synthesis of the thiazepine structures, as
well as expanding the range of their derivatives.
Summing up, it should be noted that the reaction of
gem-acylnitroethenes with o-aminothiophenol should
be regarded as a convenient preparative method for the
synthesis of new 2,3- and 2,5-dihydro-1,5-benzo-
thiazepine structures containing nitro group. The syn-
Table 3. Selected geometric parameters [bond lengths (d, Å) and bond angles (ω, deg)] of compound VII
Bond
d
Bond angle
ω
Bond angle
ω
S1–C7
S1–C2
O1–N2
O2–N2
C2–C12
C2–C3
N2–C3
C3–C4
C4–N5
N5–C6
C6–C7
1.7692(12)
1.8391(12)
1.2276(14)
1.2176(14)
1.5102(15)
1.5262(16)
1.5141(15)
1.5331(15)
1.2742(16)
1.4136(15)
1.4080(16)
C7S1C2
C12C2C3
C12C2S1
C3C2S1
O2N2O1
O2N2C3
O1N2C3
N2C3C2
N2C3C4
C2C3C4
N5C4C18
102.21(5)
114.26(9)
112.57(8)
108.40(8)
124.53(11)
119.36(10)
116.06(10)
110.21(9)
108.47(9)
113.72(9)
120.32(10)
N5C4C3
C18C4C3
C4N5C6
C11C6C7
C11C6N5
C7C6N5
C8C7C6
C8C7S1
C6C7S1
C9C8C7
C8C9C10
121.31(10)
118.37(10)
119.69(10)
119.64(11)
118.66(10)
121.58(11)
119.43(11)
119.66(9)
120.83(9)
120.49(11)
119.93(11)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1168
BERESTOVITSKAYA et al.
bond lengths and angles, and anisotropic displacement
parameters are deposited in the Cambridge structural
data base, no. 805415.
Synthesis of the initial gem-acylnitrostyrenes I–VI
was carried out using the methods described in [11,
31]. o-Aminothiophenol was obtained by the proce-
dure in [32].
4-Methyl-3-nitro-2-phenyl-2,3-dihydro-1,5-benzo-
thiazepine (VII). To 0.38 g of 3-nitro-4-phenyl-3-
butene-2-one I was added 0.25 g of o-aminothiophenol
dissolved in 10 ml of methanol. After 10 min 0.39 g of
colorless crystals of compound VII was filtered off.
From the mother liquor additionally 0.09 g of
substance VII was isolated. The total yield of com-
pound VII 0.48 g (81%), mp 136–137ºC (from petro-
leum ether). Found, %: C 64.61, H 4.91, N 9.15.
C16H14N2O2S. Calculated, %: C 64.41, H 4.73, N 9.39.
Fig. 2. Fragment of crystal packing of compound VII,
illustrating the C–H···O bonding and S···π interaction.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on a
Jeol JNM-ECX400A spectrometer with operating
frequencies 100.53 (13C) and 399.78 (1H) MHz from
the samples in chloroform-d1 using the residual signal
of undeuterated solvent as an internal reference. The
IR spectra were obtained on a Shimadzu IR Prestige-
21 Fourier spectrometer (from solutions in chloroform,
c 0.1–0.001 M, and pellets with KBr). The electron
absorption spectra were recorded on a SHIMADZU
UV-2401 PC spectrophotometer, ethanol was used as
the solvent. The elemental analysis was performed on
the analyzer EuroVector (EA 3022 CHN Dual).
4-Methyl-2-(4-methoxyphenyl)-3-nitro-2,3-dihyd-
ro-1,5-benzothiazepine (VIII). To 0.44 g of 4-(4-
methoxyphenyl)-3-nitro-3-buten-2-one II was added
0.25 g of o-aminothiophenol dissolved in 10 ml of
methanol. After 10 min 0.60 g of pale yellow crystals
of substance VIII was filtered off. From the mother
liquor additionally 0.04 g of substance VIII was
isolated. The total yield of compound VIII 0.64 g
(98%), mp 132–134ºC (from ethanol). Found, %: N
8.80. C17H16N2O3S. Calculated, %: N 8.53.
X-ray diffraction analysis of compound VII.
Crystals of VII for X-ray analysis were grown from a
solution in diethyl ether, C16H14N2O2S (M = 298.35), at
100 K monoclinic, space group P21/c; a = 14.2490(12) Å,
b = 5.5159(5) Å, c = 18.3825(15) Å, β = 96.9715(17)°,
V = 1434.1(2) Å3, Z = 4 (Z' = 1), dcalc = 1.382 g cm–3,
μ(MoKα) = 1.70 cm–1, F(000) = 624. The intensities of
10859 reflections were measured on a Bruker Smart
Apex II CCD diffractometer [μ(MoKα) = 0.71072 Å,
ω-scanning, 2θ < 58°], 3809 independent reflections
(Rint = 0.0305) were used in further refinement. The
structure was solved by the direct method and refined
by the full-matrix least-squares method in the aniso-
tropic approximation on F2hkl. The positions of the
hydrogen atoms were calculated from the geometric
considerations and refined with fixed thermal
parameters Uiso equal to 1.2Ciso in the isotropic appro-
ximation. The final value of the factors of uncertainty:
R1 = 0.0345 [calculated from Fhkl for 3313 reflections
with I > 2σ(I)], wR2 = 0.0998 (calculated on F2hkl for all
3809 independent reflections), GOF = 1.005. The
calculations were performed using the program
package SHELXTL 5.10 [30]. Atomic coordinates,
2-(4-N,N-Dimethylaminophenyl)-4-methyl-3-
nitro-2,3-dihydro-1,5-benzothiazepine (IX). To 0.47
g of (4-N,N-dimethylaminophenyl)-3-nitro-3-buten-2-
one III was added 0.25 g of o-aminothiophenol dis-
solved in 10 ml of methanol. After 15 minutes 0.65 g
of pale orange crystals of substance IX was filtered
off. From the mother liquor 0.02 g of compound IX
was additionally isolated. The total yield of compound
IX 0.67 g (98%), mp 144–146ºC (from ethanol).
Found, %: N 12.01. C18H19N3O2S. Calculated, %: N
12.31.
3-(2-Aminophenylsulfanyl)-1,3-diphenyl-2-nitro-
propan-1-one (X). To 0.51 g of 1,3-diphenyl-2-nitro-
2-propen-1-one IV was added 0.25 g of o-amino-
thiophenol dissolved in 10 ml of methanol. After
10 min 0.69 g of light yellow crystals of substance X
was filtered off. From the mother liquor an additional
0.05 g portion of compound X was isolated. The total
yield of substance X 0.74 g (98%), individual
diastereomer, mp 124–126ºC (from ethanol). Found,
%: C 67.07, H 4.86, N 7.15. C21H18N2O3S. Calculated,
%: C 66.65, H 4.79, N 7.40.
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GEMINAL ACYLNITROSTYRENES IN THE REACTION WITH ortho-AMINOTHIOPHENOL
1169
3-(2-Aminophenylsulfanyl)-3-(4-methoxyphenyl)-
2-nitro-1-phenylpropan-1-one (XI). To 0.57 g of 3-
(4-methoxyphenyl)-2-nitro-1-phenyl-2-propen-1-one
V was added 0.25 g of o-aminothiophenol dissolved in
10 ml of methanol. After 20 min 0.61 g of light yellow
crystals of substance XI was filtered off. From the
mother liquor an additional 0.04 g portion of substance
XI was isolated. The total yield of compound XI
0.65 g (80%), individual diastereomer, mp 104–106ºC
(from ethanol). Found, %: C 64.96, H 5.04, N 6.66.
C22H20N2O4S. Calculated, %: C 64.69, H 4.94, N 6.86.
for 50 min and then poured into a Petri dish. After
evaporation of the solvent the residue was treated with
ethanol. 0.11 g (40%) of yellow fine-grained material
XIV was obtained, mp 147–149ºC (from ethanol).
Found, %: C 67.44, H 4.74, N 6.92. C21H18N2O3S.
Calculated, %: C 67.67, H 4.65, N 7.17.
b. To a mixture of 0.57 g of 3-(4-methoxyphenyl)-
2-nitro-1-phenyl-2-propen-1-one V, 0.25 g of o-amino-
thiophenol, and 10 ml of methanol was added 10 drops
of concentrated hydrochloric acid, and the reaction
solution was refluxed for 50 min and then poured into
a Petri dish. The residue after solvent evaporation was
treated with ethanol. 0.40 g (51%) of yellow fine-
grained material XIV was isolated, mp 147–149ºC
(from ethanol). The mixed sample with the substance
synthesized by the method a showed no melting point
depression.
2-(4-N,N-dimethylaminophenyl)benzothiazole
(XV). Solid 3-(2-aminophenylsulfanyl)-3-(4-N,N-di-
methylaminophenyl)-2-nitro-1-phenylpropan-1-one
XII when stored for ~2 weeks at room temperature,
slowly became a semi-solid mass with colorless
needles of nitroacetophenone, mp 98–100ºC, mixing
the sample with an authentic sample showed no
melting point depression. After treating the mass with
acetone pale orange crystals of substance XV were
isolated, mp 176–178ºC (from ethanol), published
data: mp 174–175ºC [23]. Found, %: C 70.49, H 5.64,
N 10.71. C15H14N2S. Calculated, %: C 70.83, H 5.55,
N 11.01.
3-(2-Aminophenylsulfanyl)-3-(4-N,N-dimethyl-
aminophenyl)-2-nitro-1-phenylpropan-1-one (XII).
To 0.59 g of 3-(4-N,N-dimethylaminophenyl)-2-nitro-
1-phenyl-2-propen-1-one VI was added 0.25 g of o-
aminothiophenol dissolved in 10 ml of methanol. After
10 min 0.63 g of light orange crystals of substance XII
was filtered off. From the mother liquor an additional
0.04 g portion of compound XII was isolated. The
total yield of substance XII 0.67 g (80%), a mixture of
diastereomers at a ratio of a:b = 2.5:1, mp 102–104ºC
(from ethanol).
2,4-Diphenyl-3-nitro-2,5-dihydro-1,5-benzothia-
zepine (XIII). a. To a suspension of 0.13 g of 3-(2-
aminophenylsulfanyl)-1,3-diphenyl-2-nitropropan-1-
one X in 5 ml of methanol was added 10 drops of
concentrated hydrochloric acid, the reaction solution
was heated for 3 h and then poured into a Petri dish.
After evaporation of the solvent, the residue was
treated with ethanol. 0.07 g (57%) of yellow fine-
grained compound XIII was obtained, mp 161–163ºC
(from ethanol). Found, %: N 7.42. C21H18N2O2S. Cal-
culated, %: N 7.77.
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