966 J . Org. Chem., Vol. 63, No. 4, 1998
Witt et al.
1,4-Diben zyliden e-2,3,5,6-tetr aph en ylcycloh exan e (16).
Mixture of isomers, separated with HPLC (silica gel/petroleum
ether). Yield: 49%. Mp: 194-198 °C. 1H NMR (CDCl3): δ
4.35, 4.50, 4.60, 4.66, 4.80, 4.95 (m, 4H, J ) 2 Hz), 5.95, 6.15,
6.30 (m, 2H, J ) 2 Hz), 6.66-7.35 (m, 30H). IR (KBr): 3080,
3050, 3020, 1590, 1460. MS (70 eV): m/e 384, 473, 565, 564
(100). Anal. Calcd for C44H36: C, 93.57; H, 6.43. Found: C,
93.35; H, 6.22.
1-Ben zyliden e-2,6-diph en ylcycloh exan e (17). Yield: 78%.
Bp: 250 °C/0.1 Torr (bath temperature). 1H NMR (CCl4): δ
1.6-2.7 (m, 6H), 3.6, 4.45 (2m, 2H), 5.95 (s, 1H), 7.0-7.7 (m,
15H). 13C NMR (CDCl3): δ 22.0, 30.6, 34.6, 40.8, 47.0, 125.7,
126.1, 126.3, 126.5, 127.6, 128.0, 128.2, 128.6, 128.8, 138.0,
142.3, 143.1, 147.7. IR (KBr): 3080, 3060, 3020, 2940, 2860,
1640. MS (70 eV): m/e 193, 233, 324 (100). Anal. Calcd for
143.48. IR (liquid): 3040, 3010, 2950, 2860, 1600, 1490, 1470,
1450, 1390, 1360, 1190, 1055, 1020, 920, 890, 880, 695. MS
(70 eV): m/e 133, 193, 194, 209, 222 (100), 278, 352. Anal.
Calcd for C24H32O2: C, 81.77; H, 9.15. Found: C, 81.49; H,
9.12.
1,3-Di-ter t-b u t oxy-1,3-d ip h en yl-2-m et h ylen ep r op a n e
(23b). Mixture of diastereoisomers, separated from 23a with
HPLC (petroleum ether/ether, 90/10). Yield: 73% together
1
with 23a . Bp: 138-145 °C/0.08 Torr (bath temperature). H
NMR (CDCl3): δ 0.98, 1.07 (2s, 18H), 4.53, 4.96, 5.17, 5.61
(4s, 4H), 7.17-7.31 (m, 10H). 13C NMR (CDCl3): δ 28.23,
28.52, 74.01, 74.21, 74.68, 74.75, 109.12, 113.95, 126.77,
126.94, 127.61, 127.70, 127.87, 127.96, 143.26, 143.41, 153.15,
153.69. IR (liquid): 3100, 3080, 3040, 2980, 2940, 2905, 2880,
1655, 1605, 1495, 1455, 1390, 1370, 1250, 1230, 1190, 1080,
1050, 1020, 910, 900, 765, 695. MS (70 eV): m/e 107, 221,
222 (100), 223, 239, 295, 352. Anal. Calcd for C24H32O2: C,
81.77; H, 9.15. Found: C, 81.37; H, 9.12.
C
25H24: C, 92.54; H, 7.46. Found: C, 92.11; H, 7.04.
1,3-Dip h en yl-2-ben zylid en e-5-ch lor op en ta n e (18).
A
complex product mixture that was not separated further was
obtained. Raw microanalyses and 1H and 13C NMR spectra
suggest that the main product is 18 with its hydrolysis
products. The 1H NMR and mass spectrometric data for 18
obtained from the mixture are as follows. Bp: 180-190 °C/
0.1 Torr (bath temperature). 1H NMR (CDCl3): δ 1.7-2.9 (m,
4H), 3.2-4.5 (m, 3H), 6.2, 6.5, 6.9 (m, 1H), 7.0-7.5 (m, 15H).
MS (70 eV): m/e 205, 206 (100), 207, 219, 310 (100), 311, 346.
1,2-Dip h en yl-3-ben zylid en ecyclop r op a n e (19). Yield:
76%. Mp: 108-110 °C (ether). 1H NMR (CCl4): δ 2.70, 2.90
(2dd, 2H, J ) 6, 3 Hz), 7.05-7.80 (m, 16H). 13C NMR
(CDCl3): δ 32.0, 34.4, 122.1, 126.1, 126.2, 126.4, 127.2, 127.3,
128.6, 130.9, 136.6, 139.8, 141.0. IR (KBr): 3080, 3060, 3030,
2980, 2920. MS (70 eV): m/e 191 (100), 282. Anal. Calcd for
1-ter t-Bu t oxy-1,3-d ip h en yla cet on e (24). Yield: 78%.
Mp: 38-40 °C. 1H NMR (CDCl3): δ 1.15 (s, 9H), 3.75 (2H, J
) 16 Hz), 5.00 (s, 1H), 6.90-7.55 (m, 10H). 13C NMR
(CDCl3): δ 27.89, 42.94, 75.45, 79.98, 125.90, 126.23, 127.52,
127.92, 128.16, 129.38, 134.12, 138.13, 207.28. IR (liquid):
3090, 3070, 3040, 2980, 2960, 1725, 1390, 1350. MS (70 eV):
m/e 107 (100), 163 (100), 181, 209, 282. Anal. Calcd for
C
19H22O: C, 80.79; H, 7.85. Found: C, 80.29; H, 7.76.
3,5-Dip h en yl-2-th ia p en ta n -4-on e (25). Yield: 91%. Mp:
64-65 °C. 1H NMR (CDCl3): δ 1.90 (s, 3H), 3.75 (2H, J )
12.5 Hz), 4.62 (s, 1H), 7.00-7.45 (m, 10H). 13C NMR (CDCl3):
δ 11.90, 44.54, 57.51, 124.63, 125.90, 126.23, 126.69, 127.57,
132.21, 133.82, 200.25. IR (KBr): 3090, 3060, 3030, 2960,
2915, 1710. MS (70 eV): m/e 121, 137 (100), 256. Anal. Calcd
for C16H19OS: C, 74.96; H, 6.29. Found: C, 74.67; H, 6.08.
2,4-Dip h en ylp en ta n -3-on e (26).24 Yield: 82%. Bp: 120-
130 °C/0.5 Torr. 1H NMR (CDCl3): δ 1.30 (d, 6H, J ) 7.0 Hz),
3.85 (q, 2H, J ) 7.0 Hz), 6.80-7.60 (m, 10H). 13C NMR
(CDCl3): δ 18.21, 51.39, 126.65, 127.88, 128.24, 140.00, 211.00.
IR (liquid): 3080, 3050, 2995, 2950, 2895, 1718. MS (70 eV):
m/e 105 (100), 133, 238. Anal. Calcd for C17H18O: C, 85.67;
H, 7.61. Found: C, 85.57; H, 7.56.
C
22H18: C, 93.57; H, 6.43. Found: C, 93.49; H, 6.74.
1,3-Bis(tr im eth ylsilyl)-2-ben zylid en ep r op a n e (20). Pu-
rification with HPLC (petroleum ether/dichloromethane, 95/
5). Yield: 94%. Bp: 140-143 °C/14 Torr. 1H NMR (CDCl3):
δ 0.0 (s, 9H), 0.1 (s, 9H), 1.6 (s, 2H), 1.8 (s, 2H), 6.1 (s, 1H),
7.2-7.6 (m, 5H). 13C NMR (CDCl3): δ -1.06, -0.58, 24.21,
31.09, 120.07, 124.83, 127.89, 128.41, 139.41, 139.82. IR
(liquid): 3090, 3060, 3020, 2960, 2900, 1630, 1600, 1490, 1405,
1245, 1145, 880, 830, 735, 690. MS (70 eV): m/e 173, 188, 204,
261, 276 (100). Anal. Calcd for C16H28Si2: C, 69.48; H, 10.20.
Found: C, 69.41; H, 10.16.
4-Ben zylid en e-2,6-d ith ia h ep ta n e (21a ). Yield: 85% to-
gether with 21b. Bp: 128-130 °C/0.08 Torr. Separated from
21b with HPLC (petroleum ether/ether, 97/3). 1H NMR
(CDCl3): δ 2.0, 2.1 (2s, 6H), 3.4 (s, 2H), 3.5 (s, 2H), 6.5 (s, 1H),
7.1-7.5 (m, 5H). 13C NMR (CDCl3): δ 14.50, 15.32, 32.03,
39.68, 126.71, 128.07, 128.53, 130.34, 133.53, 136.39. IR
(liquid): 3070, 3030, 2980, 2920, 1645, 1600, 1490, 1440, 1370,
740, 690. MS (70 eV): m/e 129 (100), 176, 224. Anal. Calcd
for C12H16S2: C, 64.23; H, 7.19. Found: C, 64.25; H, 7.23.
4-Meth ylen e-3-p h en yl-2,6-d ith ia h ep ta n e (21b). Sepa-
rated from 21a with HPLC (petroleum ether/ether, 97/3).
Yield: 85% together with 21a . Bp: 119-122 °C/0.08 Torr. 1H
NMR (CDCl3): δ 2.0 (s, 6H), 3.1 (dd, 2H, J ) 14 Hz), 4.7 (s,
1H), 5.2, 5.3 (2s, 2H), 7.2-7.6 (m, 5H). 13C NMR (CDCl3): δ
14.53, 15.44, 38.71, 53.63, 115.30, 127.05, 128.22, 139.57,
142.97. IR (liquid): 3080, 3050, 3020, 2970, 2910, 1630, 1590,
1485, 1445, 1415, 900, 730, 685. MS (70 eV): m/e 129 (100),
161, 176, 177, 244. Anal. Calcd for C12H16S2: C, 64.23; H,
7.19. Found: C, 64.05; H, 7.17.
2,6-Diph en ylcycloh exan on e (27)25 an d 1,3,6,8-Tetr aph e-
n ylocta n e-2,7-d ion e (28). Yield: 78%. Mp: 164 °C. 1H
NMR (CDCl3): δ 1.53, 1.76 (2m, 4H), 3.52 (dd, 4H, J ) 15.3
Hz), 3.56 (m, 2H), 6.98-7.31 (m, 20H). 13C NMR (CDCl3): δ
29.33, 48.66, 57.84, 126.86, 127.36, 128.44, 128.53, 128.97,
129.50, 134.09, 138.43, 207.02. IR (KBr): 3070, 3040, 2960,
2940, 2880, 1710, 1605, 1495, 1450, 1320, 1230, 1075, 1025,
760, 750, 720, 690. MS (70 eV): m/e 205, 206, 219, 231, 236,
249, 278, 309, 310 (100), 327, 446. Anal. Calcd for C32H30O2:
C, 86.06; H, 6.77. Found: C, 86.02; H, 6.86.
1,3,4,6-Tetr a p h en ylh exa n e-2,5-d ion e (29). Yield: 73%.
Mp: 191-192 °C. 1H NMR (CDCl3): δ 3.37 (dd, 4H, J ) 6.46
Hz), 4.67 (s, 2H), 7.25-6.67 (m, 20H). 13C NMR (CDCl3): δ
50.03, 59.14, 126.82, 127.55, 128.53, 128.76, 129.07, 129.49,
133.08, 135.93, 205.27. IR (liquid): 1710, 1600, 1490, 1450,
1410. MS (70 eV): m/e 91 (100), 327, 418. Anal. Calcd for
C
30H26O2: C, 86.09; H, 6.26. Found: C, 86.04; H, 6.14.
1-(Tr im et h ylsilyl)-2-(t r im et h ylsiloxy)-1,3-d ip h en yl-2-
p r op en e (30). Yield: 90%. Bp: 140-143 °C/1.8 Torr. 1H
NMR (THF-d8): δ 0.03, 0.11 (2s, 18H), 3.02 (s, 1H), 5.58 (s,
1H), 7.45-7.06 (m, 10H). 13C NMR (THF-d8): δ -1.15, 0.96,
47.94, 110.49, 126.17, 126.25, 128.72, 129.06, 129.80, 138.01,
140.85, 154.59. 29Si NMR (THF-d8): δ 0.00, 3.24, 17.25. IR
(liquid): 3060, 3025, 2955, 2900, 1635, 1245, 840. MS (70
eV): m/e 280 (100), 293, 354. Anal. Calcd for C21H30OSi2: C,
71.12; H, 8.53. Found: C, 70.94; H, 8.53.
2-Be n zylid e n e -1-p h e n yl-1,3-b is(t r im e t h ylsilyl)p r o-
p a n e (22). Yield: 92%. Bp: 143-148 °C/0.1 Torr. 1H NMR
(CDCl3): δ -0.1 (s, 9H), 0.0 (s, 9H), 1.8 (dd, 2H, J ) 13.6 Hz),
6.4 (s, 1H), 7.0-7.4 (m, 10H). IR (liquid): 3060, 3030, 2960,
2900, 1635, 1600, 1495, 1450, 1250, 835, 740, 695. MS (70
eV): m/e 135, 174, 249, 264 (100), 352. Anal. Calcd for C22H32
-
1,3-Dip h en yla llen e (31).26 Yield: 84%. Mp: 48 °C. 1H
NMR (CDCl3): δ 6.4 (s, 2H), 7.5-7.0 (m, 10H). 13C NMR
(CDCl3): δ 98.91, 127.71, 127.98, 129.40, 136.66, 208.37.
Si2: C, 74.92; H, 9.15. Found: C, 74.99; H, 9.12.
2-Ben zyliden e-1,3-di-ter t-bu toxy-1-ph en ylpr opan e (23a).
Separated from 23b with HPLC (petroleum ether/ether, 90/
10). Yield: 73% together with 23b. Bp: 142-150 °C/0.08 Torr
(bath temperature). 1H NMR (CDCl3): δ 1.1, 1.2 (2s, 18H),
3.8 (dd, 2H, J ) 10 Hz), 5.3 (s, 1H), 6.9 (s, 1H), 7.1-7.6 (m,
10H). 13C NMR (CDCl3): δ 27.56, 28.66, 72.93, 74.91, 126.58,
126.80, 127.64, 127.87, 127.90, 128.76, 128.90, 137.50, 141.94,
(24) Gelin, R.; Chautegrel, B. Bull. Soc. Chim. Fr. 1971, 2, 2527.
(25) Peyman, A.; Beckhaus, H.-D.; Ruechardt, C. Chem. Ber. 1988,
121, 1027.
(26) Walbrick, J . M.; Wilson, J . W.; J ones, W. M. J . Am. Chem. Soc.
1968, 90, 2895.