Synthesis and Reactivity of Allenes
J . Org. Chem., Vol. 66, No. 5, 2001 1793
× 104), 264 (ꢀ 2.38 × 104), 304 (sh, ꢀ 1.23 × 104) nm; MS m/z
404 (M+, 17%), 349 (21%), 270 (100%), 190 (80%). Anal. Calcd
for C19H18Se2: C, 56.45; H, 4.49. Found: C, 56.71; H, 4.50.
(100%), 269 (7%), 189 (36%). Anal. Calcd for C19H18Se2: C,
56.45; H, 4.49. Found: C, 56.44; H, 4.49.
2,7,9,10-Tet r a p h en yl-3,6-d iselen ob icyclo[6.2.0]d eca -
(Z,Z,Z)-1,7,9-tr ien e (18). Mp 196.0-197.0 °C (yellow solid);
1H NMR (500 MHz, CDCl3) δ 3.37 (s, 4H), 6.54 (d, 4H, J ) 7.6
Hz), 6.82 (t, 4H, J ) 7.6 Hz), 6.93-6.99 (m, 6H), 7.05 (t, 2H,
J ) 7.6 Hz), 7.26 (d, 4H, J ) 7.3 Hz); 13C NMR (125 MHz,
CDCl3) δ 30.7, 115.3, 126.9, 127.1, 127.3, 127.6, 127.9, 130.6,
131.8, 140.8, 145.3, 152.9; IR (KBr) νmax 3058, 2909, 1598,
1479, 1440, 1409, 1227, 1074, 1028, 882, 768, 756, 696, 677
cm-1; MS m/z 566 (M+, 26%), 540 (42%), 460 (100%), 380 (31%),
1,3,10,12-Tetr a p h en yl-4,9,13,18-tetr a selen ocycloocta -
d eca -1,2,10,11-tetr a en e (5c). As a dl/ meso mixture (≈ 1/1):
mp 144.9-172.0 °C (colorless solid); 1H NMR (500 MHz,
CDCl3) δ 1.84-1.92 (m, 8H), 2.72-2.86 (m, 8H), 7.23-7.35 (m,
12H), 7.50-7.54 (m, 8H); 13C NMR (125 MHz, CDCl3) δ 26.6,
26.8, 30.0, 30.2, 103.0, 103.8, 127.1, 127.2, 128.08, 128.14,
128.6 (duplicate), 135.0 (duplicate), 196.3, 196.9; IR (KBr) νmax
3051, 3022, 2925, 1901, 1593, 1489, 1443, 1172, 1076, 1027,
865, 761, 691, 640 cm-1; MS m/z 540 (M+-8(CH2)-2Se, 1%), 460
(3%), 380 (35%), 190 (100%). Anal. Calcd for C38H36Se4: C,
56.45; H, 4.49. Found: C, 55.94; H, 4.47. One stereoisomer of
302 (31%); HRMS calcd for
568.0203.
C
32H2480Se2 568.0208, found
2,5,7,8-Te t r a p h e n yl-3,4-d ise le n ob icyclo[4.2.0]oct a -
1
(Z,Z,Z)-1,5,7-tr ien e (19). Mp 196.0-196.5 °C (red needles
5c: mp 170.2-171.9 °C (colorless solid); H NMR (500 MHz,
1
from chloroform-hexane); H NMR (500 MHz, CDCl3) δ 6.94
CDCl3) δ 1.83-1.93 (m, 8H), 2.72-2.87 (m, 8H), 7.26 (t, 4H, J
) 7.9 Hz), 7.33 (t, 8H, J ) 7.9 Hz), 7.53 (d, 8H, J ) 7.9 Hz);
13C NMR (125 MHz, CDCl3) δ 26.8, 30.2, 103.0, 127.3, 128.1,
128.6, 135.1, 197.0; IR (KBr) νmax 3055, 3027, 2940, 1909, 1593,
1490, 1444, 1173, 1075, 1027, 865, 761, 690, 640 cm-1; MS m/z
596 (M+- 4(CH2) - 2Se, 0.3%), 460 (5%), 380 (32%), 302 (3%),
190 (100%).
(d, 4H, J ) 7.7 Hz), 7.01 (t, 4H, J ) 7.7 Hz), 7.11-7.14 (m,
6H), 7.22 (t, 2H, J ) 7.7 Hz), 7.29 (d, 4H, J ) 7.5 Hz); 13C
NMR (125 MHz, CDCl3) δ 105.8, 127.6, 127.9, 128.0, 128.3,
128.6, 130.2, 131.6, 135.6, 136.8, 145.8; IR (KBr) νmax 3046,
1486, 1439, 1066, 1027, 767, 758, 694, 538 cm-1; MS m/z 538
(M+, 100%), 460 (30%), 380 (23%), 302 (63%). Anal. Calcd for
C
30H20Se2: C, 66.92; H, 3.74. Found: C, 66.87; H, 3.85.
Gen er a l P r oced u r e for th e Th er m a l Rea ction of Se-
len iu m -Su bstitu ted Allen es. A p-xylene solution (20 mL)
of selenium-substituted allene (1.0 mmol) was refluxed for a
desired period under nitrogen. After removal of solvent in
vacuo, the residue was subjected to silica gel column chroma-
tography (benzene/hexane). 1: 79% conversion (3 d), 66,12
(34%), 76,12 (7%), 8 (21%), 9 (9%). 2: 90% conversion (1.5 h), 6
(36%), 7 (8%), 1013 (57%), 1113 (25%). 3: 40% conversion (1.5
h), 6 (28%), 7 (7%). 4c: 34% conversion (55 h), 16 (59%). dl-
5a : 96% conversion (8 h), 6 (3%), 7 (1%), 18 (41%), 19 (11%),
20 (6%), meso-5a (10%). meso-5a : 84% conversion (8 h), 6 (5%),
7 (3%), 18 (36%), 19 (4%), 20 (7%), dl-5a (7%).
1,3-Dip h en yl-4,7,8,11-t et r a selen ocyclou n d eca -1,2-d i-
en e (20). Mp 112.3-114.2 °C (yellow solid); 1H NMR (500
MHz, CDCl3) δ 3.07-3.12 (m, 2H), 3.24-3.37 (m, 4H), 3.53-
3.58 (m, 2H), 7.27 (t, 2H, J ) 7.0 Hz), 7.35 (t, 4H, J ) 7.0 Hz),
7.53 (d, 4H, J ) 7.0 Hz); 13C NMR (125 MHz, CDCl3) δ 27.8,
31.9, 102.3, 127.8, 128.3, 128.7, 134.6, 198.1; IR (KBr) νmax
3055, 3019, 2916, 1904, 1594, 1489, 1444, 1408, 1231, 1158,
1075, 1029, 858, 755, 693 cm-1; MS m/z 562 (M+, 7%), 378 (8%),
80
350 (23%), 270 (87%), 189 (100%); HRMS calcd for C19H18
Se4 565.8069, found 565.8106.
-
Gen er a l P r oced u r e for th e P h otoch em ica l Rea ction
of Selen iu m -Su bstitu ted Allen es. A benzene solution (100
mL) of selenium-substituted allene (0.4 mmol) was irradiated
with a 450 W medium-pressure mercury lamp through a Pyrex
filter under argon for a desired period. After removal of solvent
in vacuo, the residue was subjected to gel-permeation chro-
matography (chloroform) or silica gel column chromatography
(benzene/hexane). 1: 82% conversion (1 h), 6 (20%), 7 (20%),
23 (10%). 2: 79% conversion (1 h), 6 (22%), 7 (16%), 10 (57%).
4b: 95% conversion (1 h), 6 (29%), 7 (23%), 25 (8%). 4c: 69%
conversion (1 h), 6 (8%), 7 (7%), 26 (51%). dl-5a : 86%
conversion (100 min), 6 (19%), 7 (16%), 20 (11%), meso-5a (8%).
meso-5a : 96% conversion (90 min), 6 (18%), 7 (17%), 20 (15%),
dl-5a (9%).
(Z,Z)-3,4-Bis{r-(m eth ylselen o)ben zylid en e}-1,2-d ip h e-
n ylcyclobu ten e (8). Mp 153.6-155.0 °C (yellow needles from
1
chloroform-methanol); H NMR (500 MHz, CDCl3) δ 1.70 (s,
6H), 6.64 (dd, 4H, J ) 1.2, 7.9 Hz), 6.81 (t, 4H, J ) 7.9 Hz),
6.90-6.96 (m, 8H), 7.10 (dd, 4H, J ) 1.2, 7.7 Hz); 13C NMR
(125 MHz, CDCl3) δ 8.9, 114.8, 126.66, 126.72, 127.1, 127.2,
127.8, 130.3, 131.9, 138.4, 142.2, 151.6; IR (KBr) νmax 3050,
2920, 1600, 1480, 1440, 1410, 1260, 1070, 1025, 910, 770, 700
cm-1; MS m/z 568 (M+, 26%), 475 (100%), 460 (33%), 380 (97%).
Anal. Calcd for C32H26Se2: C, 67.61; H, 4.61. Found: C, 67.38;
H, 4.71.
(E,Z)-3,4-Bis{r-(m eth ylselen o)ben zylid en e}-1,2-d ip h e-
n ylcyclobu t en e (9). Mp 112.1-113.8 °C (yellow solid); 1H
NMR (500 MHz, CDCl3) δ 1.26 (s, 3H), 1.53 (s, 3H), 6.59 (dd,
2H, J ) 1.1, 7.9 Hz), 6.80 (t, 2H, J ) 7.9 Hz), 6.87-6.97 (m,
6H), 7.27-7.34 (m, 4H), 7.41-7.45 (m, 4H), 7.54 (dd, 2H, J )
1.2, 8.3 Hz); 13C NMR (125 MHz, CDCl3) δ 7.4, 7.8, 116.9,
117.8, 126.6, 126.7, 127.1, 127.2, 127.4, 127.6, 127.7, 127.8,
128.6, 129.1, 130.3, 131.1, 131.9, 133.1, 138.3, 139.7, 140.3,
141.3, 152.5, 152.9; IR (KBr) νmax 3076, 3017, 2999, 1595, 1489,
1442, 1305, 1160, 1070, 1028, 923, 772, 755, 727, 699, 685
cm-1; MS m/z 568 (M+, 4%), 475 (100%), 460 (25%), 380 (85%).
Anal. Calcd for C32H26Se2: C, 67.61; H, 4.61. Found: C, 67.58;
H, 4.64.
cis-1,3-Dip h e n yl-4,9-d ise le n ob icyclo[4.3.0]n on a -2-
en e (16). Mp 92.5-93.5 °C (pale yellow plates from benzene-
hexane); 1H NMR (500 MHz, CDCl3) δ 2.46-2.57 (m, 3H), 2.73
(dd, 1H, J ) 4.2, 12.1 Hz), 2.93 (dd, 1H, J ) 2.2, 12.1 Hz),
3.23-3.28 (m, 1H), 3.38-3.44 (m, 1H), 6.58 (s, 1H), 7.21 (tt,
1H, J ) 1.5, 7.6 Hz), 7.28-7.32 (m, 3H), 7.36 (t, 2H, J ) 7.3
Hz), 7.54 (d, 2H, J ) 7.3 Hz), 7.70 (dd, 2H, J ) 1.5, 7.6 Hz);
13C NMR (125 MHz, CDCl3) δ 19.9, 23.4, 36.7, 49.8, 60.9, 125.1,
126.7, 126.9, 128.0, 128.3, 128.5, 128.7, 129.1, 140.8, 144.8;
IR (KBr) νmax 3050, 2949, 1595, 1487, 1442, 1279, 964, 758,
747, 733, 704, 693 cm-1; MS m/z 404 (M+, 11%), 351 (6%), 297
3,3-Bis(m eth ylselen o)-1,3-d ip h en ylp r op yn e (23). Mp
98.5-101.0 °C (pale yellow solid); 1H NMR (500 MHz, CDCl3)
δ 2.26 (s, 6H), 7.26 (t, 1H, J ) 7.4 Hz), 7.33-7.56 (m, 7H),
7.89 (d, 2H, J ) 7.4 Hz); 13C NMR (125 MHz, CDCl3) δ 9.7,
34.0, 88.5, 89.8, 122.7, 127.2, 127.8, 128.3, 128.4, 128.5, 131.8,
141.4; IR (KBr) νmax 3050, 3011, 2913, 1594, 1489, 1445, 1269,
1031, 910, 758, 699, 691, 520 cm-1; UV (cyclohexane) λmax 250
(ꢀ 4.41 × 103), 302 (sh, ꢀ 7.20 × 102) nm; MS m/z 378 (M+,
5%), 285 (100%), 270 (44%), 189 (50%); HRMS calcd for
C
17H1680Se2 379.9582, found 379.9626.
2-P h en eth yn yl-2-p h en yl-1,3-d iselen a n e (25). Pale yel-
1
low liquid; H NMR (500 MHz, CDCl3) δ 2.10-2.22 (m, 1H),
2.29-2.36 (m, 1H), 3.07-3.12 (m, 2H), 3.73 (dt, 2H, J ) 2.2,
13.3 Hz), 7.30-7.42 (m, 6H), 7.56-7.58 (m, 2H), 7.98 (dd, 2H,
J ) 1.2, 8.2 Hz); 13C NMR (125 MHz, CDCl3) δ 25.3, 26.4, 26.7,
89.2, 91.4, 122.9, 127.1, 128.4, 128.45, 128.47, 128.7, 131.7,
140.6; IR (neat) νmax 3056, 2915, 1596, 1489, 1446, 1242, 1030,
859, 756, 691 cm-1; UV (cyclohexane) λmax 224 (ꢀ 2.13 × 104),
251 (ꢀ 2.32 × 104) nm; MS m/z 390 (M+, 2%), 270 (21%), 190
(100%); HRMS calcd for C18H1680Se2 391.9582, found 391.9566.
2-P h en eth yn yl-2-ph en yl-1,3-diselen epa n e (26). Pale yel-
1
low liquid; H NMR (500 MHz, CDCl3) δ 2.35-2.50 (m, 4H),
3.18-3.28 (m, 2H), 3.35-3.45 (m, 2H), 7.28 (t, 1H, J ) 7.4
Hz), 7.34-7.38 (m, 5H), 7.54-7.57 (m, 2H), 7.98 (dd, 2H, J )
1.1, 8.4 Hz); 13C NMR (125 MHz, CDCl3) δ 27.0, 31.3, 35.4,
90.1, 91.4, 122.9, 126.8, 128.1, 128.3, 128.5 (duplicate), 131.7,
141.4; IR (neat) νmax 3055, 2919, 2847, 1596, 1489, 1443, 1261,
1030, 757, 694 cm-1; MS m/z 404 (M+, 4%), 351 (15%), 270
(12) Isagawa, K.; Mizuno, K.; Majima, T. Tetrahedron Lett. 1999,
40, 9051.
(13) Painter, E. P.; Franke, K. W.; Gortner, R. A. J . Org. Chem. 1940,
5, 579.