H. Below, W.-D. Pfeiffer, K. Geisler, A. S. Saghyan, C. Fischer, and P. Langer
Vol 000
ꢀ
1
1
(
3
(
s), 1609 (m), 2934 (m), 2962 (m)cm
.
H NMR (CDCl3
(Ar), 149.18 (5-C, Hetar), 150.85 (4-C, Hetar), 156.78 (2-C,
77
00 MHz): δ = 3.82 (s, 3H, MeO), 6.94–7.88 (m, 4H, ArH), 8.03
Hetar). SeNMR (38.18 MHz, CDCl , 60% Me Se in CDCl :
3 2 3
2
2
13
s, 1H, JSeH = 49 Hz, 5-H), 9.90 (s, 1H, JSeH = 59Hz, 2-H).
NMR (CDCl , 75MHz): δ = 55.29 (MeO), 114.11 (C-5), 116.46
CH, Ar), 127.97 (CH, Ar), 128.08 (Ar), 156.68 (C-4), 158.17 (C-2),
C
δ = 806.24. MS (70 eV): m/z = 285 (60) [M+], 257 (13), 204
(15), 178 (100), 170 (21), 105 (55), 77 (42). Anal. Calcd. for
C H11NSe (284.22): C, 63.39; H, 3.90; N, 4.93. Found: C,
15
3
(
1
77
59.47 (C to O). Se NMR (CDCl , 60% Me Se in CDCl ):
63.21; H, 3.94; N, 4.93.
3
2
3
+
δ = 806.24. MS (EI, 70 eV): m/z = 239 (M , 88), 212 (59), 210 (31),
09 (22), 132 (49), 130 (100), 91 (16), 89 (19), 77 (6), 64 (15), 28
12). Anal.: Calcd. for C10 NOSe (238.15): C, 50.44; H, 3.81;
N, 5.88. Found: C, 50.68; H, 4.04; N, 5.67.
-(4-Nitrophenyl)-1,3-selenazole (3e).
carried out following the procedure as given for the synthesis of
a (method B). Starting with a MeOH solution (100 mL) of 2e
1,3-Selenazole (5).
To a MeOH solution (10 mL) of
2
(
bromoacetaldehyde (14.8 mmol) was added pyridine (0.82 mL).
Subsequently, a MeOH solution (10 mL) of selenoformamide 1
was added portionwise with stirring at 35 °C. The progress of
the reaction was monitored by HPLC. After stirring for 12 h at
H
9
4
The reaction was
2
35 °C, the mixture was poured into H O, and an aqueous
3
(
solution of NaOH (10 M) was added until the solution was
adjusted to pH = 4. The solution was extracted with ether
(4 × 50 mL), and the combined organic layers were extracted
with HCl (3.5%, 50 mL). To the aqueous layer was added an
aqueous solution of NaOH (10 M) until the solution was
adjusted to pH = 4; subsequently, the solution was extracted
again with ether. This procedure was repeated until pyridine
was not detectable anymore by HPLC. The combined organic
layers were dried (Na SO ) and filtered, and the solvent was
+
2.44 g, 10.0 mmol), 5 g of Amberlite IR-120 (Na form, Merck)
and selenoformamide, 3e was isolated as beige needles (0.716 g,
2
(
1
(
8%), mp 158–161 °C (MeOH/H O). IR (KBr): eν = 820 (s), 870
2
s), 897 (m), 1030 (w), 1110 (m), 1180 (m), 1295 (m), 1348 (s),
ꢀ
1
1
445 (m), 1520 (s), 1608 (s), 3110 (w) cm
.
H NMR
DMSO-d , 200 MHz): δ = 8.25–8.26 (m, 4H, ArH), 9.05
6
2
2
(
s, 1H, J = 47 Hz, 5-H), 10.21 (s, 1H, J = 47.1 Hz, 2-H).
SeH
SeH
1
3
C NMR (DMSO-d , 50 MHz): δ = 123.67 (C-5), 125.34
6
2
4
(
1
CH, Ar), 127.15 (CH, Ar), 140.89 (Ar), 146.39 Ar), 153.39 (C-4),
53.39 (C-2). MS (EI, 70 eV): m/z =254 (M , 100), 227 (24), 224
removed by distillation in vacuo to give a brownish oil (0.050 g,
3%), bp. = 110 °C (determined by gas chromatography). All
attempts to remove a rest of solvent resulted in decomposition
+
(16), 208 (8), 197 (16), 181 (24), 169 (12), 128 (4), 117 (4), 101
(
11), 89 (62), 75 (18), 63 (12), 51 (10). Anal.: Calcd. for
(product/solvent = 2:1). A small amount of an unknown
C H N O Se (253.12): C, 42.71; H, 2.39; N, 11.07. Found: C,
impurity could not be removed. IR (KBr): eν = 728 (m), 789 (s),
3
(w), 3074 cm . H NMR (300 MHz, CDCl ): δ = 8.01 (d,
3
9
6 2 2
4
2.64; H, 2.12; N, 11.21.
-Phenyl-l,3-selenazole (3f). Yield: 0.395g (19%): colorless
needles (petroleum ether), mp 66–67°C. IR (KBr): 815 (s), 890 (s),
31 (m), 1021 (m). 1030 (m), 1080 (w), 1181 (s), 1235 (w), 1291
844 (w), 1020 (m), 1396 (s), 1438 (m), 1489 (s), 1651(m), 2926
–
1
1
4
2
J
= 3.7 Hz, J = 50.23, 1H, 5-H), 8.06 (q, J = 65.9 Hz,
SeH SeH
4,5
2
13
9
1H, 4-H), 9.92 (d, J2,5 = 0.8 Hz, JSeH = 60.29, 1H, 2-H).
NMR (75 MHz, CDCl ,): δ = 124.61 (C-5), 143.90 (C-4),
159.28 (C-2). Se NMR (CDCl , 60% Me Se in CDCl ):
C
ꢀ
1 1
(
(
(
m), 1305 (m), (m), 1445 (m), 1495 (s), 3111 (m) cm . H NMR
200 MHz, CDCI ): δ = 7.34–7.79 (m, 25H, ArH), 8.19
s, JseH = 47.1 Hz, 1H, 5-H, Hetar), 9.93 (s, JSeH = 47.1 Hz, 1H,
3
77
3
3
2
3
2
δ = 728.9. MS (EI, 70 eV): m/z (%) = 128/129 (18/15), 130/132
13
+
2
-H, Hetar). CNMR (50 MHz, CDCI ): δ = 118.44 (5-C,
(48/100), 134 (15) [M ], 108 (9), 106 (50), 104 (24), 103 (8),
3
Hetar), 126.71 (CH, Ar), 127.99 (CH, Ar), 128.24 (CH, Ar).
102 (9), 82 (3), 80 (18), 78 (7), 77 (3), 76 (3), 51 (2). HR-
+
1
35.03 (Ar), 156.90 (4-C, Hetar), 158.38 (2-C, Hetar). MS
FTICR-MS: Calcd. for C
3
H
4
NSe ([M + H] ): 133.95089; found:
(
(
70 eV): m/z = 209 (77) [M+], 207 (39) 182 (73), 141 (3), 129
3), 117 (4), 102 (100), 77 (22), 64 (15), 51 (19), 28 (4). Anal.
133.95017 (dm = 5.4 ppm).
Calcd. for C H NSe (208.10): C, 51.90; H, 3.39; N, 6.73;
9
7
Found: C, 51.75; H, 3.73; N, 6.75.
-Tolyl-l,3-selenazole (3g). Yield: 0.40 g (18%); colorless
needles (petroleum ether), mp 66–68.5 °C. IR (KBr): 810 (s),
91 (s), 1010 (w), 1024 (w). 1110 (w), 1171 (111), 1125
m), 1230 (w), 1280 (w), 1300 (m) 1315 (m), 1445 (s), 1495
Acknowledgments. We are grateful to Prof. Dr. Axel Kramer
Institut für Hygiene und Umweltmedizin, Universität Greifswald)
for his generous support of this work.
4
(
8
(
(
(
ꢀ
1
1
s), 2930 (w), 3030 (w), 3070 (w), 3109 (m) cm
. HNMR
REFERENCES AND NOTES
1] (a) Larsen, R.. 1,3-Selenazoles, in Comprehensive Heterocycl.
200 MHz, CDCl ): δ = 2.35 (s, 3H, Me), 7.20–7.87 (m, 4H,
3
2
ArH), 8.12 (s,
JSeH = 48 Hz, 1H, 2-H, Hetar). CNMR (50 MHz, CDCI3):
JSeH = 44 Hz, 1H, 5-H, Hetar), 9.90 (s,
[
2
13
Chemystry II; Shinkai, I.; Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V.,
Eds.; Elsevier Science: Oxford, 1996; Vol. 3, pp. 493–510; (b) Pfeiffer, W.
D. 1,3-Selenazoles, in Science of Synthesis; Schaumann, E., Ed.; Thieme
Verlag: Stuttgart, New York, 2002, Vol. 11, pp. 941–989; (c) Lalezari,
I.; Shafiee, M. 1,3-Selenazoles, in Comprehensive Heterocycl. Chemystry;
Katritzky, A. R.; Rees, C. W.; Potts, K. T., Eds.; Elsevier Science: Oxford,
1984; Vol. 6, pp 333–363.; (d) Wirth, T. Organoselenium Chemistry, in
Modern Developments in Organic Synthesis; Springer: Berlin, 2000;
(e) Koketsu, M.; Ishihara, H. Curr Org Chem 2003, 7, 175.
δ = 21.22 Me). 115.57 (5-C, Hetar), 126.58 (CH, Ar), 129.44
(
(
CH, Ar), 132.32 (Ar). 137.81 (Ar), 156.92(4-C, Hetar), 158.23
2-C, Hetar). MS (70 eV): m/z = 223 (84) [M ], 196 (57), 194
+
(
31), 193 (21), 116(48), 114 (100), 91 (16), 89 (18), 77 (6), 64
(
16), 28 (11). Anal. Calcd. for C H NSe (222.15): C, 54.05; H,
10 9
4
.08; N, 6.30. Found: C, 54.27; H, 3.77; N, 6.13.
,5-Diphenyl-l,3-selenazole (3h). Yield: 0,568 g (77%);
beige needles (petroleum ether), mp 73–74 °C. IR (KBr): 875
4
[2] Hofmann, G. Liebigs Ann Chem 1889, 250, 294.
[
3] (a) Koketsu, M.; Nada, F.; Ishihara, H., Synthesis 2002, 195;
b) Kaminski, R.; Glass, R. S.; Skowronska, A. Synthesis 2001, 1308;
(c) Ishihara, H.; Koketsu, M.; Fukuta, Y.; Nada, F. J Am Chem Soc
001, 123, 8408; (d) Koketsu, M.; Fukuta, Y.; Ishihara, H. Tetrahedron
(
m), 945 (w), 1030 (w), 1080 (w), 1170 (w), 1190 (w), 1270
(
(
(
w), 1330 (w), 1445 (s), 1495 (m), 1502 (111), 1605 (m), 3080
ꢀ
m) cm 1. 1HNMR (200 MHz, CDCI ): d = 7.30–7.56 (m, 10H,
3
2
2
13
ArH), 9.86 (s,
JSeH = 57.26 Hz, 1H, 2-H, Hetar). CNMR
Lett 2001, 42, 6333; (e) Zhang, P.-F.; Chen, Z.-C. Synthesis 2000, 9,
1219; (f) Lai, L.-L.; Reid, D. H. Synthesis 1993, 870; (g) Ogawa, A.;
Miyaka, J.; Karasaki, Y.; Murai, S.; Sonoda, N. J. Org Chem 1985, 50, 384;
(
50 MHz, CDCI3): δ = 127.59 (Ar), 128.0 (Ar), 128.34 (Ar),
1
28.66 (Ar), 129.35 (Ar), 129.84 (Ar), 133.96 (Ar), 135.25
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet