August 2003
969
1.85 (4H, t, Jϭ6.4 Hz), 2.48 (4H, t, Jϭ6.4 Hz), 3.99 (4H, s), 7.23—7.33
(10H, m). MS m/z (%) 318 (Mϩ, 97), 232 (50), 217 (100), 202 (53). Calcd
for C22H22O2: M, 318.1618. Found: m/z 318.1616. Anal. Calcd for C22H22O2:
C, 82.99; H, 6.96. Found: C, 82.85; H, 6.92.
1-(2-Phenylthiovinylidene)-4,4-ethylenedioxycyclohexane (13g) Yel-
low oil; IR (neat) 2952, 2881, 1953 (allene), 1583, 1439, 1118, 1088, 1032,
903, 742 cmϪ1; 1H-NMR d 1.60—1.64 (2H, m), 1.68—1.73 (2H, m), 2.28—
2.32 (4H, m), 3.94 (4H, s), 5.83 (1H, m), 7.21—7.41 (5H, m). MS m/z (%)
274 (Mϩ, 27), 165 (36), 99 (100), 86 (50). Calcd for C16H18O2S: M,
274.1028. Found: m/z 274.1021.
mixture through a canula and the temperature of the reaction
mixture was slowly allowed to warm to room temperature to
give the allene. The value of the specific rotation of the pro-
duced allene 19c was found to be zero and the HPLC showed
that the allene was totally racemic. From these results, this
allene synthesis is quite likely to take place through the mag-
nesium alkylidene carbenoid 23 which has no chiral informa-
tion from the optical active 18b.
1-(2-Methoxycarbonyl-2-methylvinylidene)-4,4-ethylenedioxycyclo-
hexane (13h) Colorless oil; IR (neat) 2958, 1965 (allene), 1712, 1696,
Experimental
1
All melting points are uncorrected. H-NMR spectra were measured in a 1435, 1269, 1119, 1031, 939 cmϪ1
;
1H-NMR d 1.76—1.81 (4H, m), 1.85
CDCl3 solution with JEOL JNM-LA 400 and 500 spectrometer. Electron- (3H, s), 2.33—2.38 (4H, m), 3.71 (3H, s), 3.98 (4H, s). MS m/z (%) 238
impact mass spectra (MS) were obtained at 70 eV by direct insertion. Silical (Mϩ, 42), 179 (17), 99 (45), 86 (100). Calcd for C13H18O4: M, 238.1203.
gel 60 (MERCK) containing 0.5% fluorescence reagent 254 and quartz col- Found: m/z 238.1187.
umn were used for column chromatography and the products having UV ab-
(2-Phenylvinylidene)cyclopentadecane (17a) Colorless oil; IR (neat)
sorption were detected by UV irradiation. In experiments requiring a dry 2929, 2857, 1946 (allene), 1598, 1460, 1216, 909, 760 cmϪ1
;
1H-NMR d
reagent and solvent, diisopropylamine was distilled from CaH2 and THF was 1.37—1.40 (20H, m), 1.50—1.55 (4H, m), 2.12 (4H, dt, Jϭ6.8, 2.4 Hz),
distilled from diphenylketyl. DMPU, HMPA and TMEDA were dried over 6.08 (1H, m), 7.11—7.19 (1H, m), 7.24—7.31 (4H, m). MS m/z (%) 310
CaSO4 and distilled before use. Methanol and liquid N2 were used for the (Mϩ, 24), 155 (24), 144 (81), 129 (100), 91 (31). Calcd for C23H34: M,
cooling bath at Ϫ100 °C.
310.2659. Found: m/z 310.2659.
1-(2-Phenylvinylidene)-4,4-ethylenedioxycyclohexane (13a) To a so-
[2-(1-Naphthyl)vinylidene]cyclopentadecane (17b) Colorless oil; IR
1
lution of 7 (100 mg, 0.31 mmol) in 2.5 ml of dry THF in a flame-dried flask (neat) 3057, 2928, 2856, 1944 (allene), 1460, 771 cmϪ1; H-NMR d 1.37—
at Ϫ78 °C under argon atmosphere was added t-BuMgCl (0.155 mmol) 1.43 (20H, m), 1.54—1.60 (4H, m), 2.14—2.22 (4H, m), 6.80 (1H, m), 7.42
dropwise with stirring. After 10 min, EtMgCl (0.93 mmol) was added drop- (1H, t, Jϭ7.7 Hz), 7.42—7.51 (2H, m), 7.57 (1H, d, Jϭ7.2 Hz), 7.69 (1H, d,
wise to the reaction mixture at Ϫ78 °C to give the magnesium alkylidene Jϭ8.3 Hz), 7.83 (1H, d, Jϭ7.6 Hz), 8.26 (1H, d, Jϭ8.2 Hz). MS m/z (%) 360
carbenoid 9. Benzyl phenyl sulfone (crystals, 216 mg, 0.93 mmol) was (Mϩ, 95), 191 (50), 179 (100), 178 (99), 165 (44). Calcd for C27H36: M,
added to a solution of n-BuLi (1.12 mmol) in 3 ml of dry THF in another
360.2814. Found: m/z 360.2806.
flame-dried flask at 0 °C under argon atmosphere to give yellow clear solu-
(2,2-Diphenylvinylidene)cyclopentadecane (17c) Colorless crystals;
tion, and this solution was cooled to Ϫ78 °C. This solution was added to the mp 48—49 °C (hexane). IR (KBr) 3058, 2928, 2856, 1942 (allene), 1598,
solution of the carbenoid 9 through a canula. The temperature of the reaction 1491, 1455, 767, 695 cmϪ1
;
1H-NMR d 1.25—1.35 (20H, m), 1.53—1.56
mixture was gradually allowed to warm to room temperature for 2 h. The re- (4H, m), 2.18 (4H, t, Jϭ7.0 Hz), 7.21—7.47 (10H, m). MS m/z (%) 386
action was quenched with sat. aq. NH4Cl and the whole was extracted with (Mϩ, 60), 246 (10), 217 (30), 205 (100). Calcd for C29H38: M, 386.2972.
CHCl3 and the extract was dried over MgSO4. After removal of the solvent, Found: m/z 386.2980. Anal. Calcd for C29H38: C, 90.09; H, 9.91. Found: C,
the product was purified by silica gel column chromatography to give 13a 89.76; H, 10.02.
(49 mg, 65%) as colorless crystals; mp 73—74 °C (AcOEt–hexane). IR
(2-Methyl-2-phenylvinylidene)cyclopentadecane (17d) Colorless oil;
1
(KBr) 2944, 2878, 1954 (allene), 1230, 1117, 1068, 1033, 904, 698, IR (neat) 2929, 2856, 1946 (allene), 1492, 1459, 1444, 758, 692 cmϪ1; H-
1
668 cmϪ1; H-NMR d 1.81—1.85 (4H, m), 2.34—2.47 (4H, m), 3.99 (4H,
NMR d 1.36—1.54 (24H, m), 2.04—2.16 (4H, m), 2.08 (3H, s), 7.16 (1H, t,
s), 6.03 (1H, m), 7.15—7.31 (5H, m). MS m/z (%) 242 (Mϩ, 100), 213 (8), Jϭ7.5 Hz), 7.30 (2H, t, Jϭ7.5 Hz), 7.40 (2H, d, Jϭ7.5 Hz). MS m/z (%) 324
197 (10), 170 (20), 156 (33), 141 (65), 128 (83). Calcd for C16H18O2: M,
(Mϩ, 49), 309 (7), 156 (38), 143 (100). Calcd for C24H36: M, 324.2815.
242.1305. Found: m/z 242.1313. Anal. Calcd for C16H18O2: C, 79.31; H, Found: m/z 324.2817.
7.49. Found: C, 79.34; H, 7.42.
(2-Ethenylvinylidene)cyclopentadecane (17e) Colorless oil; IR (neat)
1-{2-[2-(4-Methoxyphenyl)ethyl]vinylidene}-4,4-ethylenedioxycyclo- 2928, 2857, 1944 (allene), 1614, 1459, 987, 893 cmϪ1; H-NMR d 1.33—
hexane (13b) Colorless oil; IR (neat) 2949, 1966 (allene), 1612, 1513,
1.48 (24H, m), 1.99—2.07 (4H, m), 4.91 (1H, d, Jϭ10.1 Hz), 5.13 (1H, d,
1246, 1118, 1078, 1034, 901 cmϪ1; H-NMR d 1.70 (4H, octet, Jϭ5.6 Hz), Jϭ17.1 Hz), 5.77 (1H, d, Jϭ10.4 Hz), 6.17 (1H, ddd, Jϭ17.1, 10.4,
2.20 (4H, dt, Jϭ6.4, 1.9 Hz), 2.26 (2H, q, Jϭ6.9 Hz ), 2.65 (2H, t, Jϭ7.6 Hz),
10.1 Hz). MS m/z (%) 260 (Mϩ, 11), 105 (22), 94 (100). Calcd for C19H32:
1
1
3.78 (3H, s), 3.95 (4H, s), 5.03 (1H, m), 6.82 (2H, d, Jϭ8.6 Hz ), 7.10 (2H, M, 260.2502. Found: m/z 260.2503.
d, Jϭ8.6 Hz). MS m/z (%) 300 (Mϩ, 19), 238 (11), 121 (100). Calcd for
C19H24O3: M, 300.1724. Found: m/z 300.1713.
[2-(1-Heptynyl)vinylidene]cyclopentadecane (17f) Yellow oil; IR
(neat) 2857, 2232 (acetylene), 1942 (allene), 1461, 727 cmϪ1 1H-NMR d
;
1-[2-(1-Naphthyl)vinylidene]-4,4-ethylenedioxycyclohexane (13c) 0.90 (3H, t, Jϭ7.0 Hz), 1.32—1.55 (30H, m), 2.02 (4H, dt, Jϭ10.7, 2.5 Hz),
Colorless crystals; mp 78—79 °C (AcOEt–hexane). IR (KBr) 2954, 1949 2.28 (2H, dt, Jϭ7.1, 2.1 Hz), 5.29 (1H, m). MS m/z (%) 328 (Mϩ, 7), 224
(allene), 1437, 1231, 1083, 1031, 899, 797 cmϪ1 1H-NMR d 1.86 (4H, t, (36), 72 (77), 55 (99), 41 (100). Calcd for C24H40: M, 328.3130. Found: m/z
;
Jϭ6.0 Hz), 2.42—2.51 (4H, m), 3.99 (4H, s ), 6.71 (1H, m), 7.40—7.51
(4H, m), 7.71 (1H, d, Jϭ8.3 Hz), 7.84 (1H, d, Jϭ7.8 Hz), 8.25 (1H, d,
328.3132.
1,3-Diphenyl-1,2-butadiene (19a) Colorless oil; IR (neat) 3027, 1936
1H-NMR d 2.23 (3H, d,
Jϭ8.1 Hz). MS m/z (%) 292 (Mϩ, 100), 247 (40), 230 (78), 191 (62), 178 (allene), 1597, 1493, 1449, 762, 693 cmϪ1
;
(99). Calcd for C20H20O2: M, 292.1462, Found: m/z 292.1452. Anal. Calcd Jϭ2.9 Hz), 6.47 (1H, q, Jϭ2.9 Hz), 7.10—7.47 (10H, m). MS m/z (%) 206
for C20H20O2: C, 82.16; H, 6.89. Found: C, 82.21; H, 6.91.
(Mϩ, 100), 191 (99), 179 (94), 123 (69), 105 (82), 77 (79). Calcd for C16H14:
1-(2-Ethenylvinylidene)-4,4-ethylenedioxycyclohexane (13d) Yellow M, 206.1094. Found: m/z 206.1095.
oil; IR (neat) 2954, 1951 (allene), 1614, 1442, 1236, 1107, 1071, 1032,
1-(1-Naphthyl)-3-phenyl-1,2-propadiene (19b) Yellow oil; IR (neat)
897 cmϪ1 1H-NMR d 1.75 (4H, t, Jϭ6.5 Hz), 2.31 (4H, m), 3.97 (4H, s),
3059, 2922, 1935 (allene), 1493, 774, 693 cmϪ1 1H-NMR d 2.28 (3H, d,
;
;
4.94 (1H, dq, Jϭ10.1, 1.6 Hz), 5.14 (1H, dq, Jϭ17.1, 1.6 Hz), 5.72 (1H, d, Jϭ2.6 Hz), 7.17 (1H, d, Jϭ2.6 Hz), 7.21—7.88 (11H, m), 8.29 (1H, d,
Jϭ8.3 Hz), 6.17 (1H, ddd, Jϭ17.1, 10.1, 8.3 Hz). MS m/z (%) 192 (Mϩ, 9), Jϭ7.9 Hz). MS m/z (%) 256 (Mϩ, 61), 241 (100), 239 (44), 179 (25). Calcd
101 (38), 99 (100), 86 (63). Calcd for C12H16O2: M, 192.1149. Found: m/z for C20H16: M, 256.1251. Found: m/z 256.1253.
192.1159.
1-[2-(1-Heptynyl)vinylidene]-4,4-ethylenedioxycyclohexane (13e)
Yellow oil; IR (neat) 2954, 2218 (acetylene), 1955 (allene), 1442, 1241, (3H, t, Jϭ7.4 Hz), 1.34—1.41 (2H, m), 1.46—1.56 (2H, m), 1.86 (3H, d,
Jϭ2.8 Hz), 2.08—2.18 (2H, m), 6.73 (1H, m), 7.40—7.53 (4H, m), 7.69
1-(1-Naphthyl)-3-methyl-1,2-heptadiene (19c) Colorless oil; IR (neat)
2956, 2929, 1950 (allene), 1591, 1510, 1465, 771 cmϪ1 1H-NMR d 0.89
;
1115, 1067, 1032, 942 cmϪ1; 1H-NMR d 0.90 (3H, t, Jϭ7.1 Hz), 1.27—1.38
(4H, m), 1.50—1.55 (2H, m), 1.69—1.81 (4H, m), 2.27—2.36 (6H, m), 3.97 (1H, d, Jϭ8.3 Hz), 7.83 (1H, d, Jϭ8.0 Hz), 8.25 (1H, d, Jϭ8.3 Hz). MS m/z
(4H, s), 5.27 (1H, m). MS m/z (%) 260 (Mϩ, 3), 153 (9), 101 (90), 99 (100). (%) 236 (Mϩ, 38), 193 (60), 179 (100). Calcd for C18H20: M, 236.1563.
Calcd for C17H24O2: M, 260.1777. Found: m/z 260.1766.
Found: m/z 236.1558.
1-(2,2-Diphenylvinylidene)-4,4-ethylenedioxycyclohexane (13f) Col-
1-Chloro-2-(2,3-methylenedioxyphenyl)-1-(p-tolylsulfinyl)-1-ethene
orless crystals; mp 106—107 °C (AcOEt–hexane). IR (KBr) 2924, 1950 (al- (20a) A solution of 2 (944 mg, 5 mmol) in dry THF (13 ml) was added
1
lene), 1597, 1488, 1441, 1261, 1120, 1031, 900, 775, 697 cmϪ1; H-NMR d dropwise to a solution of LDA (5.2 mmol) in 13 ml of THF at Ϫ78 °C. The