2-(2-aryl-2-oxoethyl)-4H-benzo-1,4-thiazin-3-ones as products of the reaction of 2-aminothiophenol with β-aroylacrylic acids

Article abstract of DOI:10.1080/10426500490475166

Interaction of 2-aminothiophenol with β-aroylacrylic acids and their dibromo derivatives led to 2-(2-aryl-2-oxoethyl)-4H-benzo-1,4-thiazin-3-ones. The structure of synthesized compounds was confirmed by IR, ¹H, and ¹³C NMR spectra an

Full text of DOI:10.1080/10426500490475166

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2-(2-ARYL-2-OXOETHYL)-4H-BENZO-1,4-THIAZIN-3-
ONES AS PRODUCTS OF THE REACTION OF 2-
AMINOTHIOPHENOL WITH β-AROYLACRYLIC ACIDS
T. V. Beryozkina a , N. N. Kolos a , V. D. Orlov a , R. I. Zubatyuk b & O. V. Shishkin b
a Organic Chemistry Department, V. N. Karazin Kharkiv National University, Kharkiv, Ukraine
b Institute of Scintillation Materials, Kharkiv, Ukraine
Published online: 16 Aug 2010.
To cite this article: T. V. Beryozkina , N. N. Kolos , V. D. Orlov , R. I. Zubatyuk & O. V. Shishkin (2004): 2-(2-ARYL-2-
OXOETHYL)-4H-BENZO-1,4-THIAZIN-3-ONES AS PRODUCTS OF THE REACTION OF 2-AMINOTHIOPHENOL WITH β-AROYLACRYLIC
ACIDS, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:10, 2153-2162
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Phosphorus, Sulfur, and Silicon, 179:2153–2162, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490475166
2-(2-ARYL-2-OXOETHYL)-4H-BENZO-1,4-THIAZIN-3-
ONES AS PRODUCTS OF THE REACTION OF
2-AMINOTHIOPHENOL WITH β-AROYLACRYLIC
ACIDS
T. V. Beryozkina,a N. N. Kolos,a V. D. Orlov,a R. I. Zubatyuk,b
and O. V. Shishkinb
Organic Chemistry Department, V. N. Karazin Kharkiv
National University, Kharkiv, Ukraine;a Institute of
Scintillation Materials, Kharkiv, Ukraineb
(Received March 23, 2004; accepted April 6, 2004)
Interaction of 2-aminothiophenol with β-aroylacrylic acids and their
dibromo derivatives led to 2-(2-aryl-2-oxoethyl)-4H-benzo-1,4-thiazin-
3-ones. The structure of synthesized compounds was confirmed by IR,
1H, and 13C NMR spectra and X-ray analysis.
Keywords: 2-Aminothiophenol; β-aroylacrylic acids; Thiazinones;
NMR spectra
INTRODUCTION
The interaction of 2-aminothiophenol with α,β-unsaturated acids1,2
and α,β-unsaturated carbonyl compounds3,4 led to the formation
of 1,5-benzothiazepines. In similar studies several authors5−9 pro-
posed, on the basis of spectroscopic data and elemental analyses,
1,5-benzothiazepine structure for the products of the reaction of 2-
aminothiophenol with β-aroylacrylic acids. However, the formation of
1,4-benzothiazin-3-ones in this reaction has been reported earlier.10
We studied the reactions of β-aroylacrylic acids with substituted
o-phenylenediamines and with diamines of the pyrimidine series and
found that the products of the interaction are 3-phenacylquinoxalin-
2-one11 and pteridinone12 derivatives, correspondingly. The alter-
native direction of the heterocyclization with the formation of a
Address correspondence to V. D. Orlov, Organic Chemistry Department, V. N. Karazin
Kharkiv, National University, Svoboda sq. 4, UA-61077, Kharkiv, Ukraine. E-mail:
orlov@univer.kharkov.ua
2153

2154
T. V. Beryozkina et al.
seven-membered ring did not occur. In the present study we repro-
duced the conditions of the interaction of 2-aminothiophenol (1) with
β-aroylacrylic acids 2a–f, which have been reported earlier,5–9 and ad-
ditionally studied the structure of the reaction products.
RESULTS AND DISCUSSION
Refluxing of 2-aminothiophenol (1) with acids 2a–f in ethanol in the
presence of glacial acetic acid resulted in the formation of compounds
4a–f in the form of colorless crystals with good yields. Melting points of
compounds 4a–f as well as positions and intensity of signals in the 1H
NMR spectra of the product 4a (CDCl3) were similar to those reported
earlier.7,8
SCHEME 1
The structures of compounds 4a–f were confirmed by IR, 1H, and
13C NMR spectroscopic data, and X-ray and elemental analyses (see
Experimental section below). Thus, in the IR spectra sharp absorp-
tions were observed due to the stretching vibration of the carbonyl
groups in the region of 1668–1688 cm−1 and also the bands at 3182–
3206 cm−1. The latter we assign to the vibrations of the associated
NH–CO group, while others5−9 erroneously treated it as absorption
1
bands of OH group. The H NMR (DMSO-d6 + CCl4) spectra of com-
pounds 4a–f exhibited clear signals due to protons of the aromatic
ring at 6.92–7.99 ppm, a singlet due to proton of the NH group at
10.63–10.66 ppm (disappearing after exchange with deuterium), and

Thiazinones
2155
a group of signals due to protons of the CH2–CH unit with a typical
ABX structure: two doublets of doublets for the methylene group pro-
tons at δ = 3.10−3.72 ppm (J = 17.2−17.6 Hz, J = 6.4−7.0 Hz,
AB
AX
J
= 6.4−6.8 Hz) and doublet of doublets for the methine proton at
BX
δ = 4.05−4.07 ppm (J = 6.4−7.0 Hz, J = 6.4−6.8 Hz). Similar ABX
AX
BX
structure can be expected for the structure 3. The 13C NMR spectral
data agree with both structures 4 and 3. Thus, the spectroscopic data
and the results of elemental analysis cannot give an unambiguous
answer about the true structure of the compounds synthesized. Ulti-
mately, the structures of the products 4a–f were confirmed by X-ray
structural analysis for compound 4d, which is 2-[2-(4-bromophenyl)-2-
oxoethyl]-4H-benzo-1,4-thiazin-3-one (Tables I–III).
The heterocycle in the product 4d is found to exist in intermediate
conformation between twisted boat and chair type (Figure 1). Atoms
C(7) and C(8) deviate from the plane of the remaining ring atoms by
˚
˚
0.335(4) A and 1.024(4) A, respectively. The substituent at atom C(8) is
equatorially oriented (torsion angle O(2)–C(7)–C(8)–C(9)–172.9(2)◦). The
carbonyl group is slightly turned relative to the bromophenyl sub-
stituent (torsion angle O(2)–C(10)–C(11)–C(12) 11.5(4)◦) in consequence
of sterical difficulties (the short intramolecular contact C(9)–H(16)
13
˚
˚
2.36 A, sum of Van der Waals radii 2.87 A). In the crystalline state,
molecules 4d form centrosymmetrical dimers due to intermolecular hy-
. . .
. . .
˚
O distance 2.02 A,
drogen bonds N(1)–H(IN)
N H
O(1) (3-x, 2-y, 1-z) (H
◦
. . .
O angle 177 ). Their formation results in the lengthening of
the bond C(7)–O(1) up to 1.236(3) A in comparison with the mean value
1.210 A.
The conclusion that can be made from the above is that 2-
˚
14
˚
aminothiophenol (1) reacts with β-aroylacrylic acids 2a–f similar to
TABLE I Bond Lengths (d) in the Structure of Compound 4d
˚
˚
Bond
d(A)
Bond
d(A)
Br(1) C(14)
S(1) C(1)
S(1) C(8)
O(1) C(7)
O(2) C(10)
N(1) C(7)
N(1) C(6)
C(1) C(6)
C(1) C(2)
C(2) C(3)
C(3) C(4)
C(4) C(5)
1.896 (3)
1.758 (3)
1.822 (3)
1.236 (3)
1.204 (3)
1.354 (3)
1.414 (3)
1.378 (4)
1.387 (4)
1.376 (5)
1.372 (5)
1.392 (4)
C(5) C(6)
C(7) C(8)
C(8) C(9)
1.381 (4)
1.495 (4)
1.516 (4)
1.517 (4)
1.502 (4)
1.386 (4)
1.390 (4)
1.385 (4)
1.380 (5)
1.367 (4)
1.371 (4)
C(9) C(10)
C(10) C(11)
C(11) C(16)
C(11) C(12)
C(12) C(13)
C(13) C(14)
C(14) C(15)
C(15) C(16)

2156
T. V. Beryozkina et al.
TABLE II Bond Angles (ω) in the Structure of Compound 4d
Angle
ω (deg.)
Angle
ω (deg.)
C(1) S(1) C(8)
C(7) N(1) C(6)
C(6) C(1) C(2)
C(6) C(1) S(1)
C(2) C(1) S(1)
C(3) C(2) C(1)
C(4) C(3) C(2)
C(3) C(4) C(5)
C(6) C(5) C(4)
C(1) C(6) C(5)
C(1) C(6) N(1)
C(5) C(6) N(1)
O(1) C(7) N(1)
O(1) C(7) C(8)
N(1) C(7) C(8)
C(7) C(8) C(9)
97.2 (1)
126.1 (3)
119.1 (3)
119.8 (2)
121.1 (3)
120.8 (3)
120.4 (3)
119.1 (3)
120.5 (3)
120.2 (3)
121.2 (2)
118.6 (3)
120.6 (3)
122.9 (2)
116.4 (2)
112.8 (2)
C(7) C(8) S(1)
C(9) C(8) S(1)
107.8 (2)
108.5 (2)
113.3 (2)
120.7 (3)
122.3 (2)
116.9 (2)
118.8 (3)
123.1 (3)
118.1 (3)
120.4 (3)
118.9 (3)
121.4 (3)
118.7 (2)
120.0 (2)
119.5 (3)
121.0 (3)
C(8) C(9) C(10)
O(2) C(10) C(11)
O(2) C(10) C(9)
C(11) C(10) C(9)
C(16) C(11) C(12)
C(16) C(11) C(10)
C(12) C(11) C(10)
C(13) C(12) C(11)
C(14) C(13) C(12)
C(15) C(14) C(13)
C(15) C(14) Br(1)
C(13) C(14) Br(1)
C(14) C(15) C(16)
C(15) C(16) C(11)
TABLE III Coordinates (×104) and Equivalent Isotropic Thermal
Parameters for the Nonhydrogen Atmos in the Structure of Compound 4d
Atom
x
y
z
U(eq)
Br(1)
S(1)
O(1)
O(2)
N(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
3797 (1)
13144 (1)
13010 (3)
12887 (3)
15487 (3)
15517 (4)
16458 (5)
18287 (5)
19216 (5)
18277 (4)
16432 (4)
13889 (3)
13300 (4)
11376 (4)
11422 (4)
9543 (4)
6222 (1)
8425 (1)
9280 (2)
5769 (3)
9032 (3)
8399 (3)
8180 (4)
8232 (4)
8491 (4)
8718 (4)
8686 (3)
8698 (3)
7576 (3)
7442 (3)
6470 (3)
6410 (3)
5791 (4)
5710 (4)
6239 (4)
6797 (3)
6883 (3)
8727 (1)
2306 (1)
5194 (2)
5773 (2)
3646 (2)
1780 (2)
640 (3)
65 (1)
42 (1)
33 (1)
45 (1)
29 (1)
32 (1)
48 (1)
57 (1)
50 (1)
39 (1)
27 (1)
25 (1)
27 (1)
27 (1)
28 (1)
29 (1)
41 (1)
43 (1)
37 (1)
37 (1)
33 (1)
225 (3)
936 (3)
2080 (3)
2494 (2)
4249 (2)
3720 (2)
4382 (2)
5499 (2)
6261 (2)
7365 (3)
8103 (3)
7722 (3)
6627 (3)
5902 (3)
9488 (4)
7791 (4)
6162 (4)
6207 (4)
7887 (4)

Thiazinones
2157
FIGURE 1 Molecular structure of compound 4d.
o-phenylenediamine11 and forms, a thermodynamically more stable six-
membered ring.
It is necessary to note that compounds 4a–f were isolated with low
yields also in the reaction of 2-aminothiophenol (1) with 3-aroyl-2,3-
dibromopropionic acids 5a–f in boiling ethanol in the presence of tri-
ethylamine. We explain this unexpected result by the reduction of inter-
mediate α-bromoolefines into β-aroylacrylic acids with triethylamine.15
2-Aminothiophenol (1) can also play the role of the reductant. Thus, thi-
azinones 4a,c were obtained with 30% yields when triethylamine was
missing in the reaction mixture.
3ꢁ-Aryl-4H,2ꢁH[2,2ꢁ]di-(benzo-1,4-thiazinyl)-3-ones (6a,b) were iso-
lated as the by-products of that reaction. The formation of compounds
6a,b proceeds via the stage of nucleophylic substitution of bromine
atoms with consequent cyclization by the carbonyl and carboxyl groups.
1
The structures of products 6a,b were confirmed by the H NMR and
mass spectroscopic data. Thus, the 1H NMR spectrum of 6a (CD3)2CO
exhibited doublets due to CH protons on the positions 2 and 2ꢁ with
δ = 3.33 and 4.57 ppm (J = 11.0 Hz), a singlet due to the amino group
with δ = 10.78 ppm (disappearing after exchange with deuterium), and
multiplets due to the protons of the aromatic nuclei at 6.86–7.91 ppm.
In the mass spectrum of 6a the molecular ion signal was absent, but
the peaks of both benzothiazine fragments with m/z 224 (100%) and
164 (7%) were present.
EXPERIMENTAL
All melting points were taken on a Kofler melting point appara-
tus and are uncorrected. IR spectra were recorded on Impact-400

2158
T. V. Beryozkina et al.
spectrophotometer in KBr tablets. 1H and 13C NMR spectra were taken
on Varian Mercury 400 (400 MHz) spectrometer using DMSO-d6 + CCl4,
CDCl3 and (CD3)2O as solvents at 25◦C and tetramethyl silane (TMS) as
internal standard. Mass spectra were recorded on FINNIGAN MAT. IN-
COS 50 instrument at 70 eV. Microanalyses were carried out on LECO
CHNS-900 elemental analyzer.
General Procedure for the Preparation of the
2-(2-Aryl-2-oxoethyl)-4H-benzo-1,4-thiazin-3-ones (4a–f)
Method A
A solution of 1 (0.38 g, 3.00 mmol), corresponding acid 2a–f
(3.00 mmol), and glacial acetic acid (0.7 ml) in ethanol (15 ml) was
refluxed for 1 h. After cooling, the precipitate was filtered off and crys-
tallized from benzene twice. Duration of the reaction is 1.5 h for 4b and
15 min for 4c–f.
Method B
A solution of corresponding acid 5a–f (1.00 mmol) and triethy-
lamine (0.1 g, 1.00 mmol) in ethanol (6 ml) was refluxed for
10 min. 2-Aminobenzenethiole (0.13 g, 1 mmol) was then added
and the reaction mixture was refluxed for 10 min. After cool-
ing, the precipitate was filtered off and crystallized from benzene
twice.
2-(2-Oxoethyl-2-phenyl)-4H-benzo-1,4-thiazin-3-one (4a)
Yield: Method A, 0.68 g (80%), Method B, 0.09 g (30%); m.p. 163◦C
1
(173–175◦C,7 178◦C8). IR (KBr), ν (cm−1): 1688 (C O), 3185 (NH). H
NMR (CDCl3), δ (ppm): 3.22 (dd, 1H, CHA, J = 16.0 Hz, J = 8.0 Hz),
AB
AX
3.88 (dd, 1H, CHB, J = 17.4 Hz, J = 6.4 Hz), 4.33 (dd, 1H, CHX,
AB
AX
J
= 7.0 Hz, J = 6.4 Hz), 6.80–7.99 (m, 9H, Harom.), 8.70 (s, 1H, NH).
AX
BX
1H NMR (DMSO-d6 + CCl4), δ (ppm): 3.11 (dd, 1H, CHA, J = 17.4 Hz,
J
= 7.0 Hz), 3.70 (dd, 1H, CHB, J = 17.4 Hz, J =A6B.4 Hz), 4.05
AX
AB
BX
(dd, 1H, CHX, J = 7.0 Hz, J = 6.4 Hz), 6.92 (t, 1H, Harom.), 7.01
AX
BX
(d, 1H, Harom.), 7.14 (t, 1H, Harom.), 7.21 (d, 1H, Harom.), 7.46–7.60 (m,
3H, Harom.), 7.96 (d, 2H, Harom.), 10.63 (s, 1H, NH). Analysis: Calcd. For
C16H13NO2S (283.35): C, 67.82%; H, 4.62%; N, 4.94%. Found: C, 67.81%;
H, 4.60%; N, 4.94.

Thiazinones
2159
2-[2-(4-Methylphenyl)-2-oxoethyl]-4H-benzo-1,4-thiazin-
3-one (4b)
Yield: Method A, 0.63 g (71%), Method B, 0.08 g (26%); m.p. 203◦C
1
(205–206◦C,7 196◦C8). IR (KBr), ν (cm−1): 1678 (C O), 3206 (NH). H
NMR (DMSO-d6 + CCl4), δ (ppm): 2.42 (s, 3H, CH3), 3.10 (dd, 1H, CHA,
J
= 17.2 Hz, J = 6.8 Hz), 3.67 (dd, 1H, CHB, J = 17.2 Hz, J
=
AB
AX
AB
BX
6.6 Hz), 4.06 (dd, 1H, CHX, J = 6.8 Hz, J = 6.6 Hz), 6.94 (t, 1H,
AX
BX
Harom.), 7.03 (d, 1H, HAr), 7.15 (t, 1H, Harom.), 7.23 (d, 1H, Harom.), 7.29
(d, 2H, Harom.), 7.87 (d, 2H, Harom.), 10.64 (s, 1H, NH). Analysis: Calcd.
For C17H15NO2S (297.37): C, 68.66%; H, 5.08%; N, 4.71%. Found: C,
68.63%; H, 5.07%; N, 4.72.
2-[2-(4-Chlorophenyl)-2-oxoethyl]-4H-benzo-1,4-thiazin-
3-one (4c)
Yield: Method A, 0.71 g (75%), Method B, 0.10 g (32%); m.p. 193◦C
1
(188◦C,8 193–195◦C9). IR (KBr), ν (cm−1): 1673 (C O), 3190 (NH). H
NMR (DMSO-d6 + CCl4), δ (ppm): 3.12 (dd, 1H, CHA, J = 17.6 Hz,
J
= 6.4 Hz), 3.72 (dd, 1H, CHB, J = 17.6 Hz, J =A6B.8 Hz), 4.07
AX
AB
BX
(dd, 1H, CHX, J = 6.4 Hz, J = 6.8 Hz), 6.94 (t, 1H, Harom.), 7.03
AX
BX
(d, 1H, Harom.), 7.16 (t, 1H, Harom.), 7.23 (d, 1H, Harom.), 7.50 (d, 2H,
Harom.), 7.99 (d, 2H, Harom.), 10.66 (s, 1H, NH). 13C NMR (DMSO-
d6), δ (ppm): 37.2, 37.7, 117.8, 119.4, 123.6, 127.8, 128.1, 129.4, 130.6,
135.3, 137.5, 139.0, 166.5, 195.7. Analysis: Calcd. For C16H12ClNO2S
(317.79): C, 60.47%; H, 3.81%; N, 4.41%. Found: C, 60.44%; H, 3.80%;
N, 4.42.
2-[2-(4-Bromophenyl)-2-oxoethyl]-4H-benzo-1,4-thiazin-
3-one (4d)
Yield: Method A, 0.99 g (91%), Method B, 0.09 g (26%); m.p. 192◦C.
IR (KBr), ν (cm−1): 1673 (C O), 3190 (NH). 1H NMR (DMSO-d6
+
CCl4), δ (ppm): 3.09 (dd, 1H, CHA, J = 17.8 Hz, J = 7.0 Hz),
AB
AX
3.69 (dd, 1H, CHB, J = 17.8 Hz, J = 6.6 Hz), 4.04 (dd, 1H, CHX,
AB
BX
J
= 7.0 Hz, J = 6.6 Hz), 6.92 (t, 1H, Harom.), 7.01 (d, 1H, Harom.),
AX
BX
7.14 (t, 1H, Harom.), 7.21 (d, 1H, Harom.), 7.64 (d, 2H, Harom.), 7.90 (d,
2H, Harom.), 10.65 (s, 1H, NH). Analysis: Calcd. For C16H12BrNO2S
(362.24): C, 53.05%; H, 3.34%; N, 3.87%. Found: C, 53.05%; H, 3.33%;
N, 3.89.

2160
T. V. Beryozkina et al.
2-[2-(4-Fluorophenyl)-2-oxoethyl]-4H-benzo-1,4-thiazin-
3-one (4e)
Yield: Method A, 0.58 g (61%), Method B, 0.08 g (25%); m.p. 172◦C
1
(171–173◦C).7 IR (KBr), ν (cm−1): 1668 (C O), 3196 (NH). H NMR
(DMSO-d6 + CCl4), δ (ppm): 3.12 (dd, 1H, CHA, J = 17.6 Hz, J = 6.8
AB
AX
Hz), 3.71 (dd, 1H, CHB, J = 17.6 Hz, J = 6.8 Hz), 4.07 (dd, 1H, CHX,
AB
BX
J
= 6.8 Hz, J = 6.8 Hz), 6.94 (t, 1H, Harom.), 7.03 (d, 1H, Harom.), 7.15
AX
BX
(t, 1H, Harom.), 7.20–7.25 (m, 3H, Harom.), 8.05 (t, 2H, Harom.), 10.65 (s,
1H, NH). Analysis: Calcd. For C16H12FNO2S (317.79): C, 60.47%; H,
3.81%; N, 4.41%. Found: C, 60.44%; H, 3.80%; N, 4.42.
2-[2-(3,4-Difluorophenyl)-2-oxoethyl]-4H-benzo-1,4-
thiazin-3-one (4f)
Yield: Method A, 0.72 g (75%), Method B, 0.1 g (31%); m.p. 192◦C. IR
1
(KBr), ν (cm−1): 1683 (C O), 3190 (NH). H NMR (DMSO-d6 + CCl4),
δ (ppm): 3.12 (dd, 1H, CHA, J = 17.6 Hz, J = 6.4 Hz), 3.72 (dd, 1H,
AB
AX
CHB, J = 17.6 Hz, J = 6.8 Hz), 4.06 (dd, 1H, CHX, J = 6.4 Hz,
AB
BX
AX
J
= 6.8 Hz), 6.95 (t, 1H, Harom.), 7.03 (d, 1H, Harom.), 7.16 (t, 1H,
BX
Harom.), 7.23 (d, 1H, Harom.), 7.40–7.47 (k, 1H, Harom.), 7.88–7.97 (m,
2H, Harom.), 10.66 (s, 1H, NH). 13C NMR (DMSO-d6), δ (ppm): 37.2,
37.7, 117.8, 118.1, 118.3, 119.4, 123.6, 126.5, 127.8, 128.1, 134.2, 137.5,
166.5, 194.7. Analysis: Calcd. For C16H11F2NO2S (319.33): C, 60.18%;
H, 3.47%; N, 4.39%. Found: C, 60.20%; H, 3.48%; N, 4.36.
General Procedure for the Preparation of the
3ꢀ-Aryl-4H,2ꢀH[2,2ꢀ]di-(benzo-1,4-thiazinyl)-3-ones (6a,b)
A solution of corresponding acid 5a,c (1.00 mmol) and 1 (0.13 g,
1.00 mmol) in methanol (5 ml) was refluxed for 15 min. After cooling,
the precipitate was filtered off to give thiazinyl-3-ones 4a,c (30%). The
precipitate formed from mother liquor was filtered off and crystallized
from ethanol to give the products 6a,b.
3ꢀ-Phenyl-4H,2ꢀH[2,2ꢀ]di-(benzo-1,4-thiazinyl)-3-one (6a)
Yield: 0.039 g (10%); m.p. 232◦C. 1H NMR ((CD3)2CO), δ (ppm): 3.13
(d, 1H, CH, J = 11.2 Hz), 4.57 (d, 1H, CH, J = 11.2 Hz), 6.86 (d, 1H,
Harom.), 6.94–7.03 (m, 2H, Harom.), 7.13–7.58 (m, 10H, Harom.), 7.91 (d,
2H, Harom.), 10.78 (s, 1H, NH). MS, m/z (%): 226 (5), 225 (28), 224
(100), 165 (7), 121 (6), 77 (6), 58 (49). Analysis: Calcd. For C22H16N2OS2
(388.51): C, 68.01%; H, 4.15%; N, 7.21%. Found: C, 60.00%; H, 4.18%;
N, 7.24.

Thiazinones
2161
3ꢀ-(4-Chlorophenyl)-4H,2ꢀH[2,2ꢀ]di-(benzo-1,4-thiazinyl)-3-
one (6b)
1
Yield: 0.042 g (10%); m.p. 209◦C. H NMR (CDCl3), δ (ppm): 3.40
(d, 1H, CH, J = 11.0 Hz), 4.20 (d, 1H, CH, J = 11.0 Hz), 6.86 (d, 1H,
Harom.), 6.92–7.74 (m, 12H, Harom.), 8.40 (s, 1H, NH). Analysis: Calcd.
For C22H15ClN2OS2 (422.95): C, 62.47%; H, 3.57%; N, 6.62%. Found: C,
62.50%; H, 3.58%; N, 6.61.
X-Ray Structural Investigation
of Compound 4d
Crystals of the compound 4d (C16H12BrNO2S) are tr◦iclinic. At 20◦C
◦
˚
a = 7.762(3), b = 8.616(3), c = 12.357(4) A; α = 82.22(3) , β = 72.99(3) ,
γ = 68.96(2) , V = 737.2(4) A ; dcalc = 1.632 g/cm3; space group P1; Z = 2.
The unit cell parameters and intensities of 2479 independent reflections
(Rint = 0.039) were measured using a Siemens P3/PC automatic four-
circle diffractometer (λMoKα, graphite monochromator, θ/2θ scanning,
2θmax = 50◦).
◦
3
˚
The structure was solved by a direct method using the SHELXTL
PLUS16 computer package. The positions of hydrogen atoms were lo-
cated from the difference maps of electron density and refined using
“riding” model with fixed Uiso = 1.2Ueq of nonhydrogen atom bonded to
the given hydrogen atom. Refinement of F2 by the full-matrix, least-
squares analysis in the anisotropic approximation for nonhydrogen
atoms gave ωR2 = 0.111 for 2478 reflections (R1 = 0.045 for 1463 re-
flections with F > 4σ(F), S = 0.997). Adsorption correction was made
semiempirically using ψ-scan data (Tmax = 0.844, Tmin = 0.604). Bond
lengths, bond angles, and coordinates of nonhydrogen atoms are given
in Tables I–III.
REFERENCES
[1] W. H. Mills and J. B. Whitworth, J. Chem. Soc., 130, 2738 (1927).
[2] H. Duddeck, M. Kaiser, and A. Levai, Leibig’s Ann., 869 (1985).
[3] A. Levai and R. Bognar, Acta Chim. Acad. Sci. Hung., 88, 293 (1976).
[4] A. Levai and R. Bognar, Acta Chim. Acad. Sci. Hung., 92, 415 (1977).
[5] U. C. Pant, B. C. Gaur, and M. Chugn, Indian J. Chem., 26B, 947 (1987).
[6] U. C. Pant and M. Chugn, Indian J. Chem., 28B, 435 (1989).
[7] U. C. Pant and M. Chugn, Indian J. Chem., 28B, 437 (1989).
[8] M. Upreti, S. Pant, A. Dandia, and U. C. Pant, Phosphorus Sulfur Silicon, 113, 165
(1996).
[9] U. C. Pant, M. Upreti, S. Pant, A. Dandia, G. K. Patnaik, and A. K. Goel, Phosphorus
Sulfur Silicon, 126, 193 (1997).

2162
T. V. Beryozkina et al.
[10] F. K. Kirchner and E. J. Alexander, J. Am. Chem. Soc., 81, 1721 (1959).
[11] N. N. Kolos, A. A. Tishchenko, V. D. Orlov, T. V. Beryozkina, S. V. Shishkina, and
O. V. Shishkin, Khim. Geterotsikl. Soedin., 10, 1407 (2001). English translation in
Chem. Heterocycl. Comp., 10, 1407 (2001).
[12] N. Kolos, T. Beryozkina, and V. Orlov, Heterocycles, 60, 2115 (2003).
[13] Yu. V. Zefirov and P. M. Zorkii, Usp. Khim., 58, 713 (1989).
[14] H.-B. Burgi and J. D. Dunitz, Structure Correlation (Weinheim, VCH, 1994).
[15] G. S. Kajtmazova, N. P. Gambaryan, and E. M. Rokhlin, Usp. Khim., 58, 2011 (1989).
[16] G. M. Sheldrick, SHELXTL PLUS. PC Version. A system of computer programs
for the determination of crystal structure from X-ray diffraction data. Revision 5.1
(1998).