NEW METHOD OF SYNTHESIS OF 5-ACYL-1,3-THIAZINES
313
+
bending vibrations of hydrogen-bonded NH and OH
groups, as well as alkyl C H bands.
Mass spectrum, m/z (I , %): 201 (67) [M] , 141 (31)
rel
+
+
[M COS] , 124 (22), 113 (64) [M COS CO] ,
+
1
5
02 (11), 85 (14), 69 (80), 57 (100) [CH CH CO] ,
3 2
5
-Acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-
+
6 (33) [M COS CO CH CH CO] , 44 (42).
3
2
dione (Ia). a. Acetic anhydride, 45 ml, was added to
a solution of 21 g of malonic acid in 100 ml of acetic
acid. After 15-min stirring at 20 25 C, potassium
thioacynate, 19 g, was added in one portion. The
mixture was stirred for 1 h, allowed to stand at 20 C
for 48 h, and then diluted with 300 ml of water. The
precipitate that formed was filtered off, washed with
water (2.100 ml), and dried in air to obtain 25 g
Found, %: C 41.77; H 3.55; N 6.97; S 15.91.
C H NO S. Calculated, %: C 41.79; H 3.51; N 6.96;
7
7
4
S 15.93.
5-Butyryl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-
dione (Ic) was prepared similarly to thiazine Ia by
procedure a from malonic acid and butyric anhydride
in butyric acid at the same reagent molar ratio. Yield
20%, mp 128 129 C (benzene hexane), R 0.51. H
1
(46%) of thiazine Ia, mp 198 200 C (from benzene)
f
(
published data: mp 184 C [4]), R 0.44. IR spectrum,
NMR spectrum (CDCl ), , ppm: 1.02 t (3H, CH ),
f
3
3
1
1
.71 m (2H, CH ), 3.04 t (2H, CH ), 8.97 br.s (1H,
,
cm : 3500 br (OH), 3150, 3050 (NH), 2850 2950
2 2
1
3
2
(6)
NH), 17.95 br.s (1H, OH). C NMR spectrum
(CH), 1710 (H CC=O), 1660, 1655 (C =O). UV
3
1
(DMSO-d6), , ppm: 13.5 (CH ), 17.9 (CH ), 40.2
C
3
2
spectrum (alcohol or dioxane),
NMR spectrum (CDCl ), , ppm: 2.69 s (3H, CH ),
, nm: 260. H
max
5
2
4
6
(
CH ), 100.5 (C ), 163.2, 173.6, 179.8 (C , C , C ),
2
3
3
1
3
201.4 (H C C=O). Mass spectrum, m/z (I , %): 215
7 3 rel
8
.43 br.s (1H, NH), 17.67 s (1H, OH). C NMR
+
+
(
74) [M] , 155 (14) [M COS] , 138 (57), 127 (60)
spectrum (DMSO-d ), , ppm: 26.8 (CH ), 101.2
6
C
3
+
5
2
4
6
[M COS CO], 99 (24) [M COS CO CO] , 97
14), 84 (38), 71 (81) [CH CH CH CO] , 70 (28), 69
(
(
[
C ), 163.2, 173.4, 180.3 (C , C , C ), 198.4
H CC=O). Mass spectrum, m/z (I , %): 187 (28)
M] , 127 (28) [M COS] , 99 (30) [M COS
+
(
3 2 2
3
rel
+
+
(69), 55 (45), 43 (100) [HNCO]. Found, %: C 44.68;
H 4.19; N 6.49; S 14.93. C H NO S. Calculated, %:
+
+
8
9
4
CO] , 84 (22) [M COS CH CO] , 69 (25) [M
3
+
+
C 44.65; H 4.21; N 6.51; S 14.90.
COS(CH )CO NH] , 43 (100) [CH CO] . Found,
3
3
%
: C 38.3; H 2.72; N 7.51; S 17.11. C H NO S.
The mass spectra were obtained on an MX-1321
6
5
4
1
13
Calculated, %: C 38.5; H 2.69; N 7.48; S 17.13.
instrument, ionizing energy 70 eV. The H and
C
NMR spectra were measured on a Bruker AM-500
spectrometer (500 and 125 MHz, respectively). The
IR spectra were taken on a Specord IR-75 instrument.
Reaction progress and purity of products were con-
trolled by TLC on Sorbfil plates (eluent toluene di-
oxane ethanol, 2:2:1).
b. A mixture of 1.05 g of dithiocarbamide and
2
2
.2 g of malonic acid in 3 ml of PCl was heated from
3
h at 70 C. Volatile components were removed in a
vacuum ( 20 mm), the residue was treated with water,
and the precipitate was filtered off and recrystallized
from water to obtain 0.35 g (19%) of compound Ia,
mp 198 200 C, R 0.44. The NMR, IR, and UV spec-
tra are identical to those of the sample obtained by
procedure a.
ACKNOWLEDGMENTS
f
The work was financially supported by the Prog-
ram for Support of Basic Research in Natural and
Exact Sciences of the Ministry of Education of the
Russian Federation (project no. E02-5.0-384 2003
2004).
c. A mixture of 5 mmol of thiazine II and 15 ml of
acetic anhydride was heated for 35 40 min at 90
9
5 C and then poured while hot onto ice and ground,
The precipitate was filtered off, washed with water,
REFERENCES
and dried. Yield 22%, mp 198 200 C, R 0.44. The
f
NMR, IR, and UV spectra are identical to those of the
1. Mironova, G.A. Kuklin, V.N., Kirilova, E.N., and
samples obtained by procedures a and b.
Ivin, B.A., Khim. Geterotsikl. Soedin., 1986, no. 1, p. 3.
2
3
4
. Quiniou, H. and Guilloton, O., Adv. Heterocycl. Chem.,
990, vol. 50, p. 85.
4
-Hydroxy-5-propionyl-2H-1,3-thiazine-2,6(3H)-
1
dione (Ib) was prepared similarly to thiazine Ia by
procedure a from malonic acid and propionic an-
hydride in propionic acid at the same reagent molar
ratio. Yield 30%, mp 139 140 C (benzene hexane),
R 0.47. H NMR spectrum (CDCl ), , ppm: 1.22 t
3H, CH ), 3.09 3.14 q (2H, CH ), 8.56 br.s (1H,
NH), 18.08 s (1H, OH). C NMR spectrum (DMSO-
d6),
63.3, 173.2, 179.5 (C , C , C ), 202.3 (H C C=O).
. Ryabukhin, Yu.I., Korzhavina, O.B., and Suzdalev, K.F.,
Adv. Heterocycl. Chem., 1996, vol. 66, p. 131.
. Ziegler, E. and Steiner, E., Monatsch. Chem., 1964,
vol. 95, p. 495.
1
f
3
(
5. Strelova O.Yu., Cand. Sci. (Chem.) Dissertation, St.
3
2
1
3
Petersburg, 1998.
5
, ppm: 8.6 (CH ), 32.3 (CH ), 100.4 (C ),
6. Kuklin, V.N., Doctoral (Chem.) Dissertation, St.
C
3
2
2
4
6
1
Petersburg, 1996.
5
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 2 2004