7204 J . Org. Chem., Vol. 66, No. 21, 2001
Notes
ten e (13). Mp 147.6-150.0 °C (yellow prisms from ethanol); 1H
NMR (500 MHz, CDCl3) δ 2.17-2.24 (m, 1H), 2.34-2.40 (m, 1H),
3.14-3.20 (m, 2H), 3.40-3.45 (m, 1H), 3.50-3.54 (m, 1H), 6.73
(dd, 2H, J ) 1.4, 8.4 Hz), 6.92 (dd, 2H, J ) 1.4, 8.0 Hz), 6.96-
7.25 (m, 16H); 13C NMR (125 MHz, CDCl3) δ 27.3, 27.4, 30.1,
126.5, 126.8, 127.0, 127.16, 127.18, 127.3, 127.4, 127.6, 128.6,
130.7, 131.0, 131.1, 133.8, 136.5, 139.9, 140.2, 140.5, 142.1, 143.2,
143.4; IR (KBr) νmax 3051, 3018, 2929, 2894, 1597, 1541, 1488,
1442, 1285, 1077, 1030, 762, 745, 695 cm-1; MS m/z 556 (M+),
436, 356. Anal. Calcd for C31H26Se2: C, 66.91; H, 4.71. Found:
C, 66.84; H, 4.74.
cyclopropane derivatives as reactive intermediates with
extrusion of nitrogen. The benzylidene cyclopropanes
rearranged easily to afford butadienes via migration of
the selenenyl group on the cyclopropane rings. Diphenyl
diazomethane also reacted with the selenium-substituted
butadienes to form selenonium ylides, which provided
tetraphenyl-1-butene-3-yne.
Exp er im en ta l Section
1-P h en yl-2-(tr ip h en yl)vin yl-3,8-d iselen o-1-cycloocten e
(14). Mp 155.2-157.5 °C (pale yellow needles from ethanol); 1H
NMR (500 MHz, CDCl3) δ 2.10-2.35 (m, 4H), 2.80-2.88 (m, 2H),
3.11-3.15 (m, 1H), 3.91-3.97 (m, 1H), 6.70 (d, 2H, J ) 7.2 Hz),
6.84 (d, 2H, J ) 6.7 Hz), 6.94-7.01 (m, 5H), 7.06-7.12 (m, 6H),
7.17-7.20 (m, 5H); 13C NMR (125 MHz, CDCl3) δ 26.5, 30.1, 31.0,
31.1, 126.4, 126.5, 126.8, 127.1, 127.3, 127.36, 127.40, 127.44,
127.9, 130.9, 131.1, 131.2, 132.9, 139.8, 141.27, 141.29, 142.3,
143.0, 143.2, 143.3; IR (KBr) νmax 3048, 3018, 2915, 2839, 1597,
1489, 1441, 1266, 1076, 1030, 913, 762, 745, 700 cm-1; MS m/z
570 (M+), 436, 356. Anal. Calcd for C32H28Se2: C, 67.37; H, 4.95.
Found: C, 67.27; H, 4.98.
2,2-Dip h en yl-1,3-d iselen a n e (15). Mp 91.0-93.8 °C (pale
yellow solid); 1H NMR (500 MHz, CDCl3) δ 2.11 (quint, 2H, J )
5.8 Hz), 2.89 (t, 4H, J ) 5.8 Hz), 7.23 (t, 2H, J ) 7.6 Hz), 7.31
(t, 4H, J ) 7.6 Hz), 7.69 (d, 4H, J ) 7.6 Hz); 13C NMR (125 MHz,
CDCl3) δ 24.9, 25.1, 48.8, 127.2, 128.3, 130.0, 144.1; IR (KBr)
νmax 3058, 3027, 2916, 1491, 1443, 1408, 1243, 1035, 842, 750,
712, 699, 641 cm-1; MS m/z 366 (M+), 246, 165. Anal. Calcd for
Benzene was distilled from sodium metal before use. Column
chromatography was performed with Merck Kieselgel 60 (70-
230 mesh). All reactions were carried out under nitrogen in a
hood.
Gen er a l P r oced u r e for Rea ction of 1,3-Bis(a lk ylselen o)-
a llen es w ith Dip h en yl Dia zom eth a n e. A benzene solution
(10 mL) of 1,3-bis(alkylseleno)allene6,7 (0.3 mmol) and diphenyl
diazomethane10 (2 equiv) was refluxed for the desired period
under nitrogen. After removal of solvent in vacuo, the residue
was subjected to silica gel column chromatography. 1: 67%
conversion (13.5 h), 3 (46%), 4 (4%), 1011 (41%). 2: 52%
conversion (7 h), 3 (11%), 5 (7%), 66,12 (35%), 76,12 (9%), 813 (38%),
913 (32%), 10 (72%). 11: 58% conversion (6 h), 3 (37%), 10 (31%),
13 (55%), 15 (23%). 12: 63% conversion (6 h), 3 (32%), 10 (19%),
14 (43%), 16 (12%). dl-17: 62% conversion (6 h), 3 (26%), 10
(28%), meso-17 (19%), 18 (14%), 197 (4%). meso-17: 55% conver-
sion (6 h), 3 (36%), 10 (26%), dl-17 (18%), 18 (21%), 19 (4%).
Tetr a p h en yl-1-bu ten e-3-yn e (3). Mp 120.8-122.0 °C (yel-
1
low solid); H NMR (500 MHz, CDCl3) δ 7.01 (dd, 2H, J ) 1.8,
C
16H16Se2: C, 52.47; H, 4.40. Found: C, 52.30; H, 4.38.
7.5 Hz), 7.12-7.25 (m, 10H), 7.33-7.37 (m, 6H), 7.57 (dd, 2H, J
) 1.8, 6.7 Hz); 13C NMR (125 MHz, CDCl3) δ 92.4, 93.0, 121.5,
123.6, 127.0, 127.2, 127.6, 127.8, 127.87, 127.89, 127.93, 128.2,
130.0, 130.5, 131.1, 131.3, 139.6, 141.4, 142.8, 148.9; IR (KBr)
2,2-Dip h en yl-1,3-d iselen ep a n e (16). Mp 97.2-98.8 °C (pale
1
yellow solid); H NMR (500 MHz, CDCl3) δ 2.25-2.27 (m, 4H),
3.03-3.05 (m, 4H), 7.20 (t, 2H, J ) 7.6 Hz), 7.28 (t, 4H, J ) 7.6
Hz), 7.55 (d, 4H, J ) 7.6 Hz); 13C NMR (125 MHz, CDCl3) δ
27.1, 31.4, 58.8, 127.0, 128.1, 129.1, 146.0; IR (KBr) νmax 3052,
2899, 1590, 1487, 1440, 1404, 1215, 1032, 750, 712, 696, 639
cm-1; MS m/z 380 (M+), 246, 165. Anal. Calcd for C17H18Se2: C,
53.70; H, 4.77. Found: C, 53.57; H, 4.66.
ν
max 3078, 3020, 1594, 1489, 1441, 1027, 775, 754, 740, 697, 688,
606 cm-1; MS m/z 356 (M+), 279, 178. Anal. Calcd for C28H20
:
C, 94.34; H, 5.66. Found: C, 93.98; H, 5.78.
Dip h en ylm eth yl Meth yl Selen id e (4). Yellow liquid; 1H
NMR (500 MHz, CDCl3) δ 1.79 (s, 3H), 5.26 (s, 1H), 7.14 (tt,
2H, J ) 1.3, 7.6 Hz), 7.23 (t, 4H, J ) 7.6 Hz), 7.36 (dd, 4H, J )
1.3, 7.6 Hz); 13C NMR (125 MHz, CDCl3) δ 6.3, 48.6, 127.0, 128.5,
128.6, 141.5; IR (neat) νmax 3059, 3026, 2923, 1598, 1494, 1449,
1274, 1075, 1031, 748, 695 cm-1; MS m/z 262 (M+), 260, 245,
178; HRMS calcd for C14H1480Se 262.0215, found 262.0260.
Ben zyl Dip h en ylm eth yl Selen id e (5). Yellow liquid; 1H
NMR (500 MHz, CDCl3) δ 3.62 (s, 2H), 5.25 (s, 1H), 7.14 (d, 2H,
J ) 7.1 Hz), 7.18-7.31 (m, 9H), 7.41 (d, 4H, J ) 7.3 Hz); 13C
NMR (125 MHz, CDCl3) δ 29.5, 47.9, 126.6, 127.0, 128.4, 128.5,
128.8, 128.9, 138.9, 141.3; IR (neat) νmax 3060, 3027, 2923, 1598,
1494, 1449, 1076, 1030, 748, 696 cm-1; MS m/z 338 (M+), 336,
245, 167; HRMS calcd for C20H1880Se 338.0523, found 338.0573.
1-P h e n yl-2-(t r ip h e n yl)vin yl-3,7-d ise le n o-1-cycloh e p -
2,2-Dip h en yl-1,3-d iselen ola n e (18). Mp 59.0-61.0 °C (pale
orange solid); 1H NMR (500 MHz, CDCl3) δ 3.81 (s, 4H), 7.19 (t,
2H, J ) 7.6 Hz), 7.26 (t, 4H, J ) 7.6 Hz), 7.62 (d, 4H, J ) 7.6
Hz); 13C NMR (125 MHz, CDCl3) δ 38.3, 67.0, 126.8, 127.9, 128.8,
146.4; IR (KBr) νmax 3051, 3013, 2920, 1589, 1489, 1440, 1259,
1078, 1032, 750, 713, 698, 645 cm-1; MS m/z 352 (M+), 324, 246,
165. Anal. Calcd for C15H14Se2: C, 51.15; H, 4.01. Found: C,
50.95; H, 3.99.
Th er m a l Rea ction of Dip h en yl Dia zom eth a n e. A benzene
solution (3 mL) of diphenyl diazomethane (69 mg, 0.36 mmol)
was refluxed for 5 h under nitrogen. The reaction mixture was
subjected to silica gel column chromatography to give tetraphe-
nylethylene 10 in 22% yield.
Rea ction of Diben zyl Diselen id e (8) w ith Dip h en yl
Dia zom eth a n e. A benzene solution (2.5 mL) of dibenzyl dis-
elenide 8 (48 mg, 0.14 mmol) and diphenyl diazomethane (58
mg, 0.28 mmol) was refluxed for 2.5 h under nitrogen. After
removal of solvent in vacuo, the residue was subjected to gel-
permeation chromatography to give selenides 5 (26%) and 9
(23%) with 19% conversion of 8.
(8) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589.
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Ind.(London) 1962, 310. (b) Heinrich, F.; Lu¨ttke, W. Angew. Chem.,
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Int. Ed. Engl. 1973, 12, 332. (d) Creary, X. J . Am. Chem. Soc. 1980,
102, 1611. (e) Kaufmann, D.; de Meijere, A. Chem. Ber. 1984, 117, 1128.
(10) (a) Smith, L. I.; Howard, K. L. Organic Syntheses; Wiley: New
York, 1955; Collect. Vol. 3, 351. (b) Staudinger, H.; Anthes, E.;
Pfenninger, F. Chem. Ber. 1916, 49, 1928.
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463, 15.
(12) Isagawa, K.; Mizuno, K.; Majima, T. Tetrahedron Lett. 1999,
40, 9051.
Ack n ow led gm en t. This work was financially sup-
ported in part by a grant-in-aid for Scientific Research
from the Ministry of Education, Science, Sports, and
Culture, J apan.
(13) Painter, E. P.; Franke, K. W.; Gortner, R. A. J . Org. Chem. 1940,
5, 579.
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