2006
A. C. Razus et al.
(4.45), 323 (4.47), 368 (4.37), 388 (4.37), 405 sh (4.32),
643 (2.59) nm; MS (ESI): m/z = 393 ([M?1]?, 80Se).
5H, Ph), 7.44 (t, 3J = 9.8 Hz, 1H, 5-H), 7.54 (t,
3J = 9.8 Hz, 1H, 7-H), 7.77 (t, 3J = 9.8 Hz, 1H, 6-H),
8.48 (s, 1H, 2-H), 8.71 (dd, 3J = 9.8 Hz, 4J = 0.6 Hz, 1H,
4-H), 9.62 (dd, 3J = 10.0 Hz, 4J = 0.5 Hz, 1H, 8-H) ppm;
13C NMR (100 MHz, CDCl3): d = 51.2, 112.7, 116.9,
125.9, 128.0, 129.0, 129.1, 133.8, 138.0, 139.0, 140.0,
142.2, 145.7, 147.8, 165.3 ppm; UV–Vis (methanol,
c = 3 9 10-5 mol dm-3): kmax (log e) = 233 (4.49), 260
(4.36), 287 (4.52), 298 (4.48), 361 (3.76), 368 (3.80), 533
(2.66) nm; MS (ESI): m/z = 343 ([M?1]?, 80Se).
3-(Phenylselanyl)azulen-1-yl benzoate (8c, C23H16O2Se)
1
Green crystals; yield: 286 mg (71 %); m.p.: 103 °C; H
NMR (400 MHz, CDCl3): d = 7.10–7.20 (m, 5H, PhSe),
3
3
7.22 (t, J = 9.7 Hz, 1H, 7-H), 7.25 (t, J = 9.8 Hz, 1H,
5-H), 7.57 (t, 3J = 7.7 Hz, 2H, PhCO2,m), 7.68 (t,
3J = 7.7 Hz, 1H, PhCO2,p), 7.68 (t, 3J = 9.8 Hz, 1H,
6-H), 8.18 (s, 1H, 2-H), 8.33 (dd, 3J = 8.0 Hz,
4J = 1.5 Hz, 2H, PhCO2,o), 8.38 (d, 3J = 9.7 Hz, 1H,
3
8-H), 8.69 (d, J = 9.6 Hz, 1H, 4-H) ppm; 13C NMR (100
3-(Phenylselanyl)azulene-1-carbaldehyde
(8f, C17H12OSe)
Red-brownish crystals; yield: 258 mg (83 %); m.p.:
MHZ, CDCl3): d = 109.1, 123.6, 124.2, 125.8, 128.7,
129.0, 129.1, 129.2, 129.5, 130.2, 132.6, 133.7, 134.5,
135.1, 137.5, 137.9, 138.7, 139.6, 164.7 ppm; UV–Vis
(methanol, c = 3 9 10-5 mol dm-3): kmax (log e) = 235
(4.60), 281 (4.62), 292 (4.51), 361 (3.77), 598 (2.65) nm;
MS (ESI): m/z = 405 ([M?1]?, 80Se).
1
110 °C; H NMR (400 MHz, CDCl3): d = 7.11–7.20 (m,
5H, Ph), 7.64 (t, 3J = 9.8 Hz, 1H, 5-H), 7.72 (t,
3J = 9.8 Hz, 1H, 7-H), 7.94 (t, 3J = 9.8 Hz, 1H, 6-H),
3
8.46 (s, 1H, 2-H), 8.85 (d, J = 9.9 Hz, 1H, 4-H), 9.69 (d,
Phenyl[3-(phenylselanyl)azulen-1-yl]sulfane
(8d, C22H16SSe)
3J = 9.8 Hz, 1H, 8-H), 10.35 (s, 1H, CHO) ppm; 13C NMR
(100 MHz, CDCl3): d = 114.5, 125.9, 126.2, 129.2, 129.4,
129.5, 130.9, 133.2, 138.1, 139.9, 140.8, 141.5, 147.0,
149.7, 186.4 ppm; UV–Vis (methanol, c = 3 9 10-5
mol dm-3): kmax (log e) = 235 (4.40), 275 (4.35), 294
(4.38), 305 (4.35), 368 sh (3.74), 376 (3.77), 384 sh (3.74),
504 (2.81) nm; MS (ESI): m/z = 313 ([M?1]?, 80Se).
Blue crystals; yield: 293 mg (75 %); m.p.: 116 °C; 1H
3
NMR (400 MHz, CDCl3): d = 7.01 (bd, J = 8.5 Hz, 2H,
Ph), 7.07 (bt, J = 7.2 Hz, 1H, Ph), 7.10–7.19 (m, 7-H,
3
3
3
Ph), 7.41 (t, J = 9.8 Hz, 1H, 5-H), 7.43 (t, J = 9.7 Hz,
1H, 7-H), 7.78 (t, 3J = 9.8 Hz, 1H, 6-H), 8.23 (s, 1H, 2-H),
8.75(bd, 3J = 9.8 Hz, 2H, 4-H, 8-H) ppm; 13C NMR
(100 MHz, CDCl3): d = 112.6, 116.0, 125.2, 125.9, 126.0,
126.1, 126.4, 128.8, 129.1, 134.2, 136.2, 138.1, 139.6,
139.7, 143.2, 143.7, 150.6 ppm; UV–Vis (methanol,
c = 3 9 10-5 mol dm-3): kmax (log e) = 236 (4.54), 253
(4.47), 282 (4.52), 294 (4.42), 363 (3.76), 571 (2.60) nm;
MS (ESI): m/z = 393 ([M?1]?, 80Se).
1-[3-(Phenylselanyl)azulen-1-yl]ethanone
(8g, C18H14OSe)
Red-violet crystals; yield: 257 mg (79 %); m.p.: 101 °C;
1H NMR (400 MHz, CDCl3): d = 2.71 (s, 3H, Me), 7.12
(s, 5H, Ph), 7.59 (t, 3J = 9.7 Hz, 1H, 5-H), 7.71 (t,
3J = 9.7 Hz, 1H, 7-H), 7.90 (t, 3J = 9.8 Hz, 1H, 6-H),
3
8.50 (s, 1H, 2-H), 8.83 (d, J = 9.8 Hz, 1H, 4-H), 9.96 (d,
Synthesis of azulen-1-yl(phenyl)selanes substituted
with electron-withdrawing groups using
3J = 9.9 Hz, 1H, 8-H) ppm; 13C NMR (100 MHz, CDCl3):
d = 29.2, 112.5, 125.1, 126.0, 128.7, 128.9, 129.2, 130.7,
133.8, 139.4, 139.8, 140.5, 141.5, 146.2, 148.4, 195.2 ppm;
UV–Vis (methanol, c = 3 9 10-5 mol dm-3): kmax (log
e) = 236 (4.42), 272 (4.38), 292 (4.38), 303 (4.35), 370 sh
(3.73), 385 (3.75), 531 (2.69) nm; MS (ESI): m/z = 327
([M?1]?, 80Se).
phenylseleninyl chloride (8e–8h)—general procedure
To a stirred solution of compound 6 with electron acceptor
substituents (1 mmol) in 2 cm3 dry DCM protected from
atmosphere by an oil trap at room temperature was slowly
added 192 mg PhSeCl (1 mmol) during 3–5 min as a
solution in 2 cm3 dry DCM. The reaction was stirred for
2 hours and is worked up as above. The column separation
was made on silica gel with n-pentane-DCM (with DCM
gradient). After the first colored fraction which contained
an undefined product (probably diphenyldiselenide), the
second fraction was formed from the desired product and
the third, contained the unreacted starting material.
2,2,2-Trifluoro-1-[3-(phenylselanyl)azulen-1-yl]ethanone
(8h, C18H11F3OSe)
Red crystals; yield: 303 mg (80 %); m.p.: 94 °C; 1H NMR
(400 MHz, CDCl3): d = 7.14–7.18 (m, 5H, Ph), 7.78 (t,
3
3J = 10.6 Hz, 1H, 5-H), 7.88 (t, J = 10.6 Hz, 1H, 7-H),
8.04 (t, 3J = 9.8 Hz, 1H, 6-H), 8.60 (q, CFJ = 2.3 Hz, 1H,
3
4
2-H), 8.90 (dd, J = 9.9 Hz, J = 1.0 Hz, 1H, 4-H), 9.95
3
4
(dd, J = 9.9 Hz, J = 1.0 Hz, 1H, 8-H) ppm; 13C NMR
(100 MHz, CDCl3): d = 115.3, 117.3, 126.4, 129.3, 131.2,
132.7, 132.8, 139.8, 140.2, 141.6, 145.1, 148.0, 148.5,
175.7 ppm; UV–Vis (methanol, c = 3 9 10-5 mol dm-3):
kmax (log e) = 233 (4.46), 279 (4.42), 291 (4.40), 299
Methyl 3-(phenylselanyl)azulene-1-carboxylate
(8e, C18H14O2Se)
Red crystals; yield: 280 mg (82 %); m.p.: 78 °C; 1H NMR
(400 MHz, CDCl3): d = 3.88 (s, 3H, Me), 6.91-7.04 (m,
123