4-(2-HYDROXYARYL)-1,2,3-SELENADIAZOLES AS PRECURSORS OF . . .
1647
refluxed for 5 h with protection from light until initial
compound IIa disappeared. An additional portion of
methyl iodide, 0.21 g (1.5 mmol), was added, and the
mixture was stirred for 15 min. The resulting suspen-
sion was filtered, and the light brown filtrate was
evaporated under reduced pressure. The tarry residue
was subjected to chromatography on a 3 20-cm
column charged with silica gel L 40/100 m, using
benzene as eluent. A fraction containing product X
was evaporated under reduced pressure. Yield 130 mg
(33%), light yellow oily substance; Rf 0.71 (benzene),
364 (19) M+, 231 (36) [M 2-O-C8H5O]+, 197 (10)
[M 2,4-(NO2)2C6H3Se]+, 133 (100) [M 2-NO-4-
NO2C6H3Se]+, 89 (14) [C7H6]+. Found, %: C 46.37,
46.18; H 2.45, 2.62. C14H8N2O5Se. Calculated, %:
C 46.15; H 2.20.
2-(2,4-Dinitrophenylseleno)-6-methylbenzofuran
(XIb) was synthesized as described above for com-
pound XIa from 0.239 g (1 mmol) of selenadiazole
IIb, 0.16 g (1.2 mmol) of K2CO3, and 0.202 g
(1 mmol) of 2,4-dinitrochlorobenzene. By column
chromatography we isolated 0.21 g (56%) of product
XIb as yellow crystals with mp 162 165 C (from
1
0.2 (heptane CCl4, 1:1). IR spectrum, , cm : 3060,
3000, 2926, 2830, 2150, 1589, 1562, 1485, 1440,
2-propanol), Rf 0.7 (CHCl3). 1H NMR spectrum
(CDCl3), , ppm: 2.53 s (CH3) 6.76 s (3-H), 7.18 d
(5-H), 7.33 s (7-H), 7.35 d (4-H), 7.56 d (6-H, C6H3),
8.15 d.d (5-H, C6H3), 9.16 d (3-H, C6H3). 13C NMR
spectrum (CDCl3), C, ppm: 21.8 (CH3), 111.4 (C3),
1
1250, 1180, 1160, 1110, 1043, 1020, 913, 743. H
NMR spectrum (CDCl3), , ppm: 2.38 s (SeCH3),
3.87 s (OCH3), 6.80 d (3-H), 6.88 t.d (5-H), 7.29 t.d
(4-H), 7.40 d (6-H). 13C NMR spectrum (CDCl3),
C, ppm: 9.93 (CH3Se), 55.7 (OCH3), 75.0 (C CSe),
94.3 (C CSe), 110.5 (C6), 120.3 (C3), 123.1 (C4),
129.5 (C5), 133.3 (C2), 157.0 (C1), 110.8 (C3), 111.5
(C7), 120.0 (C4), 122.8 (C5), 123.9 (C6), 128.8 (C9),
145.0 (C2), 157.0 (C8). Mass spectrum, m/z, (Irel, %):
226 (63.6) M+, 211 (6.3) [M CH3]+, 183 (6.3) [M
CH3 CO]+, 168 (14) [M 2CH3 CO]+, 131 (100)
[M CH3Se]+, 91 (24.7) [C7H7]+. Found, %: C 52.89,
53.02; H 4.63, 3.71. C10H10OSe. Calculated, %:
C 53.1; H 4.42.
111.9 (C7), 120.7 (C5, C6H3), 121 (C4), 121.4 (C5),
125.3 (C1, C6H3), 125.4 (C6), 127.3 (C9), 131.8 (C5,
C6H3), 137.2 (C6, C6H3), 140.3 (C2), 143.2 (C4,
C6H3), 147 (C2, C6H3), 158.6 (C8). Mass spectrum,
m/z, (Irel, %): 378 (10) M+, 231 (7) [M 2-O-6-CH3-
C8H4O]+, 211 (2) [M 2,4-(NO2)2C6H3Se]+, 147 (100)
[M 2-NO-4-NO2C6H3Se]+. Found, %: C 47.39,
47.61; H 2.23, 2.45. C15H10N2O5Se. Calculated, %:
C 47.62; H 2.64.
2-(2,4-Dinitrophenylseleno)-5-methylbenzofuran
(XIc) was synthesized as described above for com-
pound XIa from 0.5 g (2.08 mmol) of selenadiazole
IIc, 0.344 g (2.49 mmol) of K2CO3, and 0.42 g
(2.08 mmol) of 2,4-dinitrochlorobenzene. Yield 0.5 g
(63%), yellow crystals, mp 157 159 C (from 2-pro-
2-(2,4-Dinitrophenylseleno)benzofuran (XIa).
A suspension of 0.226 g (1 mmol) of selenadiazole
IIa, 10 ml of anhydrous acetonitrile, and 0.16 g
(1.2 mmol) of K2CO3 was refluxed for 10 30 min
under vigorous stirring, and 0.202 g (1 mmol) of
2,4-dinitrochlorobenzene in 5 ml of acetonitrile was
added to the dark cherry reaction mixture. The mixture
turned yellow green. It was refluxed for 5 h, cooled
to 20 C, poured into 25 ml of water, neutralized with
6% hydrochloric acid, and extracted with chloroform
(2 10 ml). The extract was dried over calcined
calcium chloride and evaporated under reduced pres-
sure. The residue was subjected to chromatography
on a 3 20-cm column charged with silica gel L
40/100 m (eluent heptane CHCl3, 1:1). Yield 0.15 g
(41%), yellow crystals with mp 166 167 C (from
1
panol), Rf 0.57 (CHCl3). H NMR spectrum (CDCl3),
, ppm: 2.49 s (CH3), 6.72 s (3-H), 7.35 d (6-H), 7.3 s
(4-H), 7.45 d (7-H), 7.62 d (6-H, C6H3), 8.15 d.d
(5-H, C6H3), 9.16 d (3-H, C6H3). 13C NMR spectrum
(CDCl3), C, ppm: 21.7 (CH3), 111.7 (C3), 120.9 (C7),
121.6 (C3, C6H3), 121.7 (C4), 127.7 (C5), 128.3 (C1,
C6H3), 128.4 (C6), 132.2 (C9), 133.82 (C5, C6H3),
141.5 (C6, C6H3), 143.5 (C2), 145.4 (C4, C6H3), 146.5
(C2, C6H3), 158.6 (C8). Mass spectrum, m/z, (Irel, %):
378 (15) M+, 231 (15) [M 2-O-5-CH3C8H4O]+, 211
(4) [M 2,4-(NO2)2C6H3Se]+, 147 (100) [M 2-NO-4-
NO2C6H3Se]+, 91 (10) [C7H7]+. Found, %: C 47.34,
47.53; H 2.47, 2.61. C15H10N2O5Se. Calculated, %:
C 47.62; H 2.64.
1
2-propanol), Rf 0.55 (heptane CHCl3, 1:1). H NMR
spectrum (CDCl3), , ppm: 6.87 s (3-H), 7.15 t.d
(5-H), 7.32 t.d (6-H), 7.43 d (7-H), 7.52 d (4-H),
7.72 d (6-H, dinitrophenyl), 8.17 d.d (5-H, dinitro-
phenyl), 9.17 d (3-H, dinitrophenyl). 13C NMR
1H NMR study of the decomposition of 4-(2-hy-
droxyphenyl)-1,2,3-selenadiazole (IIa). A solution
of compound IIa in DMSO-d6 was placed in an NMR
ampule, an equimolar amount of tetrabutylammonium
spectrum (CDCl3), C, ppm: 111.3 (C3), 112.2 (C7),
116.3 (C3, C6H3), 120.9 (C4), 122.3 (C5), 124.2 (C1,
C6H3), 124.7 (C6), 128.3 (C9), 132.2 (C5, C6H3),
1
141.6 (C6, C6H3), 145.2 (C2), 147.5 (C4, C6H3), 157.1
hydroxide was added, and H NMR spectra were re-
(C2, C6H3), 158.0 (C8). Mass spectrum, m/z (Irel, %):
corded on a Bruker AMX-400 instrument (400 MHz).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001