N. Kurono et al. / Tetrahedron 56 (2000) 847–854
853
965 cmϪ1; 1H NMR (CDCl3) d 2.09 (1H, d, J2.6 Hz), 4.94
(2H, dd, J2.3, 6.3 Hz), 5.18 (1H, m), 5.37 (1H, m), 6.27 (1H,
dd, J6.3, 15.8 Hz), 6.65 (1H, d, J15.8 Hz), 7.31 (5H, m).
1125, 1024, 988, 913, 760, 702, 632 cmϪ1
;
1H NMR
(CDCl3) d 1.10 (3H, d, J9.9 Hz), 1.13 (3H, d, J
9.9 Hz), 2.11 (1H, d, J2.6 Hz), 2.20 (1H, d, J2.3 Hz),
2.28 (1H, d, J3.6 Hz), 2.55 (1H, d, J3.0 Hz), 2.83 (2H,
m, J5.3, 6.9, 9.9 Hz), 4.50 (1H, dd, J6.9 Hz), 4.73 (1H,
dd, J5.28 Hz), 7.33 (10H, m); 13C NMR (CDCl3): d 15.51,
17.33, 33.95, 35.01, 70.86, 71.29, 76.12, 77.36, 85.45,
85.79, 126.47, 126.60, 127.76, 128.03, 128.10, 128.30,
141.20, 141.26; EIMS m/z (relative intensity):160 (2),
79(50), 107(100), 79(47), 77(28), 51(9); HRMS Calcd for
C11H12O 160.0888. Found m/z 160.0898; Anal. Calcd for
C11H12O: C, 82.46; H, 7.55. Found: C, 82.26; H, 7.74.
2-Methyl-2-hepten-6-yn-4-ol (3d). IR (neat) 3298, 2118,
1678, 1631, 1584, 1442, 1377, 1270, 1217, 1168, 1112,
1
1035, 952, 836, 631 cmϪ1; H NMR (CDCl3) d 1.72 (3H,
d, J1.3 Hz), 1.75 (3H, d, J1.3 Hz), 1.85 (1H, s), 2.05
(1H, t, J2.6 Hz), 2.41 (2H, m, J2.6 Hz), 4.53 (1H, m,
J8.6 Hz), 5.26 (1H, m, J1.3, 8.6 Hz); 13C NMR (CDCl3)
d 18.28, 25.64, 27.60, 66.69, 70.33, 80.81, 125.84, 136.66.
2,2-Dimethyl-5-hexyn-3-ol (3e). IR (neat) 3446, 3306,
2118, 1482, 1426, 1399, 1366, 1291, 1243, 1208, 1178,
2,2-Dimethyl-1-phenyl-3-butyn-1-ol (5b). Bp 80–100ЊC/
0.4 mmHg; IR (neat) 3450, 3296, 2110, 1605, 1494, 1455,
1385, 1363, 1292, 1190, 1084,1046, 1010, 967, 921, 887,
825, 777, 701 cmϪ1; 1H NMR (CDCl3) d 1.11 (3H, s), 1.28
(3H, s), 2.26 (1H, s), 2.42 (1H, d, J4.0 Hz), 4.51 (1H, d,
J4.0 Hz), 7.34 (5H, m); 13C NMR (CDCl3): d 24.30,
26.33, 37.68, 70.77, 80.15, 89.27, 127.66, 127.69, 127.87,
139.78; EIMS m/z (relative intensity): 174 (3), 107(100),
79(50), 68(47), 51(9); HRMS Calcd for C12H14O
174.1044. Found m/z 174.1073; Anal. Calcd for C12H14O:
C, 82.72; H, 8.10. Found: C 82.66; H, 8.27.
1
1073, 1011, 908, 849, 769, 628 cmϪ1; H NMR (CDCl3) d
0.92 (9H, s), 2.06 (1H, t, J2.6 Hz,), 2.16 (1H, brs), 2.25
(1H, ddd, J2.6, 9.9, 16.4 Hz), 2.40 (1H, dt, J2.6, 3.45,
16.4 Hz), 3.45 (1H, dd, J2.6, 9.9 Hz); EIMS m/z (relative
intensity) 126 (1), 87 (56), 69 (26), 57 (55), 41 (100), 39
(35); HRMS Calcd for C8H14O. m/z 126.1045. Found m/z
126.1058.
2,2-Dimethyl-4,5-hexadien-3-ol (4e). IR (neat) 3446, 1959,
1
1482, 1426, 1291, 1178, 1073, 1011, 908, 849 cmϪ1; H
NMR (CDCl3) d 0.93 (9H, s), 2.16 (1H, brs), 3.83 (1H,
m), 4.86 (2H, dd, J2.6 Hz,), 5.28 (1H, q, J6.6 Hz).
4-Methyl-1-phenyl-2,3-pentadien-1-ol (6b). IR (neat) 3418,
1956, 1605, 1495, 1455, 1363, 1335, 1218, 1191, 1045,
1
2-Phenyl-4-pentyn-2-ol (3f). IR (neat) 3426, 3294, 2118,
1028 cmϪ1; H NMR (CDCl3) d(1.39 (3H, s), 1.43 (3H,
1603, 1495, 1447, 1425, 1376, 1274, 1183, 1102, 1070,
s), 2.42 (1H, s), 4.72 (1H, d, J6.6 Hz) 4.93 (1H, d,
1
1029, 948, 912, 854, 765, 700 cmϪ1; H NMR (CDCl3) d
J6.6 Hz), 7.33 (5H, m).
1.64 (3H, s), 2.05 (1H, t, J2.6 Hz), 2.39 (1H, s), 2.73 (2H,
m, J2.6 Hz), 7.37 (5H, m); 13C NMR (CDCl3) d 29.11,
34.50, 71.68, 73.14, 80.38, 124.64, 127.06, 128.18, 146.25;
EIMS m/z (relative intensity) 159 (0.6), 121 (100), 105 (13),
77 (15), 43 (83); HRMS Calcd for C11H11O (MϩϪ1). m/z
159.0809. Found m/z 159.0829; Anal. Calcd for C11H12O: C,
82.46; H, 7.55. Found: C, 82.25; H, 7.72.
1-Phenyl-2,2-pentamethylene-3-butyn-1-ol (5c). IR (neat)
3430, 2106, 1604, 1494, 1452, 1350, 1302, 1277, 1236,
1201, 1164, 1106, 1086, 1079, 1039, 1024, 908, 815,
1
706 cmϪ1; H NMR (CDCl3) d 1.16 (3H, m), 1.46 (1H,
m), 1.62 (5H, m), 2.03 (1H, m), 2.31 (1H, s), 2.47 (1H, d,
J2.6 Hz), 4.41 (1H, d, J4.6 Hz), 7.34 (5H, m); 13C NMR
(CDCl3) d 22.50, 22.66, 25.77, 32.83, 34.90, 43.70, 73.71,
80.76, 86.70, 127.58, 127.84, 140.04; EIMS m/z (relative
intensity) 214 (1), 107(29), 93(36), 79(100), 77(95).
51(24), 39(21); HRMS Calcd for C15H18O m/z 235.1361.
Found m/z 235.1363. Anal. Calcd for C15H18O: C, 84.07;
H, 8.47. Found: C, 84.11; H, 8.63.
2-Phenyl-3,4-pentadien-2-ol (4f). IR (neat) 3426, 1959,
1603, 1495, 1447, 1425, 1376, 1274, 1183, 1102, 1070,
1
1029, 948, 912, 854, 765, 700 cmϪ1; H NMR (CDCl3) d
1.66 (3H, s), 2.14 (1H, s), 4.96 (2H, dd, J6.6 Hz), 5.56
(1H, t, J6.6 Hz), 7.35 (5H, m).
1,1-Diphenyl-3-butyn-1-ol (3g). IR (neat) 3540, 3288,
1-Phenyl-4,4-pentamethylene-2,3-butadien-1-ol (6c). IR
2118, 1600, 1494, 1449, 1427, 1349, 1278, 1254, 1168,
(neat) 3344, 1967, 1604, 1493, 1448, 1344, 1280, 1262,
1054, 1033, 1014, 895, 860, 763, 699 cmϪ1
;
1H NMR
1240, 1018, 851 cmϪ1; H NMR (CDCl3) d 1.22 (6H, m),
1
(CDCl3) d 2.04 (1H, t, J2.6 Hz), 2.95 (1H, s), 3.16 (2H,
d, J2.6 Hz), 7.35 (10H, m); 13C NMR (CDCl3) d 33.37,
72.51, 77.20, 80.22, 126.07, 127.30, 128.19, 145.39; EIMS
m/z (relative intensity) 222 (1), 183 (100), 105 (74), 77 (39),
51 (8); HRMS Calcd for C16H14O. m/z 222.1045. Found m/z
222.1066; Anal. Calcd for C16H14O: C, 86.45; H, 6.35.
Found: C, 86.21; H, 6.51.
2.11 (4H, m), 2.18 (1H, s), 5.20 (1H, d, J5.6 Hz), 5.30
(1H, m, J2.0, 5.6 Hz), 7.34 (5H, m); EIMS m/z (relative
intensity) 214 (100), 213 (11), 196 (13), 132 (13), 131 (97),
128 (15), 109 (13), 108 (58), 107 (65), 105 (12), 103 (29), 93
(54), 91 (17), 80 (15), 79 (68), 77(46), 51 (11), 41 (12);
HRMS Calcd for C15H18O m/z 214.1358. Found m/z
214.1355.
1,1-Diphenyl-2,3-butadien-1-ol (4g). IR (neat) 3462, 1959,
1-Phenyl-3-pentyn-1-ol (5d). IR (neat) 3386, 1604, 1496,
1455, 1432,1400, 1333, 1202, 1083, 1049, 915, 873, 841,
756, 700 cmϪ1; 1H NMR (CDCl3) d 1.81 (3H, t, J2.6 Hz),
2.44 (1H, d, J3.3 Hz), 2.57 (2H, m), 4.81 (1H, m), 7.34
(5H, m); 13C NMR (CDCl3) d 3.52, 29.99, 72.60, 75.22,
78.67, 125.70, 127.75, 128.37, 142.80; EIMS m/z (relative
intensity) 159 (2), 107 (38), 77 (100), 51 (55), 39 (15);
HRMS Calcd for C11H11O (MϩϪ1). m/z 159.0810. Found
1600, 1494, 1448, 1349, 1279, 1254, 1168, 1054, 1033,
1
1014, 895, 852, 757, 700 cmϪ1; H NMR (CDCl3) d 2.62
(1H, s), 4.98 (2H, d, J6.6 Hz), 5.95 (1H, t, J6.6 Hz), 7.35
(10H, m).
2-Methyl-1-phenyl-3-butyn-1-ol (5a). Mp 90–91ЊC; IR
(neat) 3406, 3292, 2110, 1605, 1495, 1454, 1376, 1195,