4378 J . Org. Chem., Vol. 61, No. 13, 1996
Mordini et al.
methoxybenzyl)oxy]-1-octen-3-ol (5) and 22 mg of (Z)-1-(4-
methoxyphenyl)-2-nonene-1,4-diol (6).
(52%), 1-[(4-methylbenzyl)oxy]-1-octen-3-ol (16a ) (21%, Z/E 84:
16), and 2-(4-methylphenyl)-3-(1-hydroxyhexyl)oxetane (15a )
(27%) was obtained, which after purification by column chro-
matography (petroleum ether/ethyl acetate, 3:1) gave 9 mg of
15a and 7 mg of 16a .
2-(4-Meth ylp h en yl)-3-(1-h yd r oxyh exyl)oxeta n e (15a ):
1H-NMR (CDCl3)δ 7.2-7.1 (4H, m), 5.48 (1H, d, J ) 6.2), 4.71
(2H, d, J ) 7.4), 4.0-3.8 (1H, m), 2.91 (1H, m), 2.36 (3H, s),
1.59 (1H, bs), 1.6-1.0 (8H, m), 0.88 (3H, t, J ) 4.4); 13C-NMR
(CDCl3)δ 139.49, 137.83, 129.23, 125.64, 84.80, 72.35, 70.02,
49.74, 34.96, 31.69, 25.00, 22.54, 21.19, 13.97; MS m/ z 167
(9), 149 (100), 121 (36), 119 (14), 105 (12), 97 (15), 94 (11), 93
(13), 91 (13), 85 (22), 84 (24), 83 (19), 71 (27), 70 (13), 69 (28),
57 (49), 55 (39). Anal. Calcd for C16H24O2: C, 77.38; H, 9.14.
Found: C, 77.10; H, 10.00.
(Z)-1-(4-Meth oxyp h en yl)-2-n on en e-1,4-d iol (6): 1H-NMR
(CDCl3)δ 7.4-7.2 (2H, m), 7.0-6.8 (2H, m), 5.76 (1H, ddd, J
) 7.2, 5.6, 0.8), 5.56 (1H, ddd, J ) 7.2, 5.6, 0.8), 5.52 (1H, d,
J ) 5.6), 4.6-4.5 (1H, m), 3.80 (3H, s), 2.8-2.2 (2H, m), 1.4-
1.2 (6H, m), 0.86 (3H, t, J ) 4.6); 13C-NMR (CDCl3)δ 159.14,
135.30, 134.30, 133.94, 127.39, 114.04, 69.59, 67.76, 55.29,
31.19, 31.67, 25.01, 22.56, 13.98; MS m/ z 264 (0.05, M+), 247
(6), 246 (28), 189 (100), 175 (48), 163 (18), 150 (34), 147 (35),
137 (16), 135 (76), 121 (34), 115 (21), 109 (21), 107 (15), 103
(15), 94 (25), 91 (35), 84 (18), 81 (38), 78 (17), 77 (61), 55 (24),
43 (37).
Isom er iza t ion of (E)-1-(Ben zyloxy)-2,3-ep oxyoct a n e
(7). The general procedure was used, obtaining 81 mg (70%)
of a crude product which was then purified by column
chromatography (petroleum ether/ether, 1:2), giving 38 mg
(33%) 2-phenyl-3-(1-hydroxyhexyl)oxetane (8): 1H-NMR (CD-
Cl3)δ 7.5-7.2 (5H, m), 5.52 (1H, d, J ) 6.6), 4.72 (2H, d, J )
7.6), 4.0-3.9 (1H, m), 2.91 (1H, m), 1.63 (1H, d, J ) 5.4), 1.5-
1.2 (8H, m), 0.87 (3H, t, J ) 6.2); 13C-NMR (CDCl3)δ 142.44,
128.55, 127.99, 125.51, 84.77, 72.21, 70.10, 49.58, 34.93, 31.67,
24.99, 22.54, 13.98; MS m/ z 163 (7), 133 (12), 115 (12), 108
(13), 107 (92), 105 (48), 103 (13), 99 (17), 91 (20), 86 (19), 85
(24), 84 (42), 79 (75), 77 (59), 72 (80), 67 (12), 57 (100), 55 (58),
51 (23), 43 (71).
(Z)-1-[(4-Meth ylben zyl)oxy]-1-octen -3-ol [(Z)-16a ]: 1H-
NMR (CDCl3)δ 7.2-7.0 (4H, m), 6.08 (1H, d, J ) 5.6), 4.77
(2H, s), 4.53 (1H, m), 4.6-4.4 (1H, m), 2.35 (3H, s), 1.7-1.1
(9H, m), 0.88 (3H, t, J ) 6.2); 13C-NMR (CDCl3)δ 145.86,
137.91, 134.00, 129.23, 127.59, 110.91, 74.06, 66.45, 37.33,
31.80, 30.94, 25.08, 22.65, 21.18, 14.06; MS m/ z 167 (5), 149
(39), 121 (12), 105 (100), 85 (13), 84 (18), 69 (14), 57 (20), 55
(20).
(E)-1-[(4-Meth ylben zyl)oxy]-1-octen -3-ol [(E)-16a ]: 1H-
NMR (CDCl3)δ 7.2-7.0 (4H, m), 6.55 (1H, d, J ) 12.4), 4.92
(1H, dd, J ) 12.4, 8.0), 4.71 (2H, s), 4.2-4.0 (1H, m), 2.35 (1H,
s), 1.7-1.1 (9H, m), 0.88 (3H, J ) 6.2). Anal. Calcd for
C16H24O2: C, 77.38; H, 9.74. Found: C, 77.56; H, 9.71.
Isom er iza tion of (E)-1-[(4-ter t-Bu tylben zyl)oxy]-2,3-
ep oxyocta n e (14b). (a ) Rea ction w ith 1 equ iv of LIDA-
KOR. The general procedure was used, obtaining 96 mg (66%)
of a 63:37 mixture of the two isomeric 1-[(4-tert-butylbenzyl)-
oxy]-1-octen-3-ol (16b) (Z:E ) 48:52) and 2-(4-tert-butylphenyl)-
3-(2-hydroxyhexyl)oxetane (15b). After a further purification
by column chromatography (eluent petroleum ether/ethyl
acetate, 3:1), 16b (32 mg) and 15b (30 mg) were obtained.
2-(4-ter t-Bu tylph en yl)-3-(2-h ydr oxyh exyl)oxetan e (15b):
1H-NMR (CDCl3)δ 7.4-7.2 (4H, m), 5.49 (1H, d, J ) 6.2), 4.70
(2H, app d, J ) 7.8), 4.0-3.9 (1H, m), 2.94 (1H, m), 1.63 (1H,
d, J ) 5.2), 1.5-1.2 (8H, m), 1.33 (9H, s), 0.87 (3H, t, J ) 6.0);
13C-NMR (CDCl3)δ 151.06, 139.40, 125.48, 125.40, 84.70, 72.32,
70.01, 49.41, 34.96, 34.58, 31.69, 31.32, 25.01, 22.54, 13.96;
MS m/ z 290 (0.1, M+), 163 (100), 147 (79), 115 (11), 91 (26),
86 (11), 84 (18), 57 (58), 55 (17). Anal. Calcd for C19H30O2: C,
78.57; H, 10.41. Found: C, 78.33; H, 10.58.
(2S,3R,1′S)-2-P h en yl-3-(1′-h ydr oxyh exyl)oxetan e 8: [R]20
-31.0 (c 0.98, CHCl3).
D
Isom er iza tion of (E)-1-[(4-F lu or oben zyl)oxy]-2,3-ep -
oxyocta n e (10). The general procedure was used obtaining
79 mg (63%) of a 56:44 mixture of the two isomeric 1-[(4-
fluorobenzyl)oxy]-1-octen-3-ol (12) (Z:E ) 30:70) and 2-(4-
fluorophenyl)-3-(2-hydroxyhexyl)oxetane (11). After a further
purification by column chromatography (petroleum ether/ethyl
acetate, 3:2), 12 (42 mg) and 11 (32 mg) were obtained.
2-(4-Flu or oph en yl)-3-(2-h ydr oxyh exyl)oxetan e (11): 1H-
NMR (CDCl3)δ 7.5-7.3 (2H, m), 7.1-7.0 (2H, m), 5.50 (1H, d,
J ) 6.6), 4.70 (2H, app d, J ) 7.6), 4.0-3.9 (1H, m), 2.89 (1H,
m), 1.57 (1H, d, J ) 5.4), 1.5-1.2 (8H, m), 0.87 (3H, t, J )
6.6); 13C-NMR (CDCl3)δ 162.50 (d, J ) 246.7), 138.28 (d, J )
3.0), 127.38 (d, J ) 7.5), 115.45 (d, J ) 21.9), 84.16, 72.08,
69.94, 49.81, 34.96, 31.69, 24.96, 22.53, 13.96; MS m/ z 251
(0.1, M+ - 1), 125 (100), 123 (17), 97 (12), 86 (13), 84 (25), 72
(19), 57 (41), 55 (12), 43 (15). Anal. Calcd for C15H21O2F: C,
71.40; H, 8.39. Found: C, 71.11; H, 8.63.
(E)-1-[(4-F lu or oben zyl)oxy]-1-octen -3-ol [(E)-12]: 1H-
NMR (CDCl3)δ 7.4-7.2 (2H, m), 7.1-7.0 (2H, m), 6.55 (1H, d,
J ) 12.8), 4.93 (1H, dd, J ) 12.8, 8.6), 4.72 (2H, s), 4.1-4.0
(1H, m), 1.6-1.2 (9H, m), 0.89 (3H, t, J ) 6.8); MS m/ z 251
(0.2, M+ - 1), 110 (18), 109 (100), 83 (14), 43 (14), 41 (12).
Anal. Calcd for C15H21O2F: C, 71.40; H, 8.39. Found: C, 71.36;
H, 8.37.
(E)-1-[(4-ter t-Bu tylben zyl)oxy]-1-octen -3-ol [(E)-16b]:
1H-NMR (CDCl3)δ 7.4-7.2 (4H, m), 6.57 (1H, d, J ) 12.4), 4.93
(1H, dd, J ) 12.4, 8.4), 4.72 (2H, s), 4.1-4.0 (1H, m), 1.6-1.2
(9H, m), 1.32 (9H, s), 0.88 (3H, t, J ) 6.2); 13C-NMR (CDCl3)δ
151.12, 145.99, 133.59, 127.53, 125.46, 107.88, 73.98, 71.07,
37.93, 34.56, 31.69, 31.29, 25.34, 22.64, 14.04; MS m/ z 149
(10), 148 (19), 147 (100), 132 (25), 131 (13), 119 (13), 117 (39),
115 (15), 105 (12), 91 (25), 57 (11), 55 (11). Anal. Calcd for
C19H30O2: C, 78.57; H, 10.41. Found: C, 78.77; H, 10.32.
(Z)-1-[(4-ter t-Bu tylben zyl)oxy]-1-octen -3-ol [(Z)-16b]:
1H-NMR (CDCl3)δ 7.4-7.2 (4H, m), 6.10 (1H, d, J ) 5.8), 4.78
(2H, s), 4.7-4.5 (2H, m), 1.6-1.2 (9H, m), 1.32 (9H, s), 0.88
(3H, t, J ) 6.2); 13C-NMR (CDCl3)δ 148.59, 145.99, 134.03,
127.28, 125.46, 110.79, 73.98, 66.45, 37.33, 34.56, 31.78, 31.29,
25.08, 22.64, 14.04.
(Z)-1-[(4-F lu or oben zyl)oxy]-1-octen -3-ol [(Z)-12]: 1H-
NMR (CDCl3)δ 7.4-7.2 (2H, m), 7.1-7.0 (2H, m), 6.07 (2H, d,
J ) 5.4), 4.77 (2H, s), 4.6-4.5 (2H, m), 1.6-1.2 (9H, m), 0.9-
0.8 (3H, m).
Isom er iza tion of (E)-1-[(4-Meth ylben zyl)oxy]-2,3-ep -
oxyocta n e (14a ). A solution of butyllithium in hexane (0.55
mmol), diisopropylamine (56 mg, 0.55 mmol), and potassium
tert-butoxide (62 mg, 0.55 mmol) was mixed together in
pentane (3 mL). After 15 min, 14a (124 mg, 0.50 mmol) was
added and the mixture stirred for 15 h at 25 °C before it was
treated with ether (3 mL) and H2O (2 mL). The aqueous phase
was then extracted with ether (2 × 3 mL) and the organic
solution dried. After evaporation of the solvent 44 mg of a
mixture of (E)-1-[(4-methylbenzyl)oxy]-2,3-epoxyoctane (14a )
Ack n ow led gm en t. Financial support provided by
the Consiglio Nazionale delle Ricerche is gratefully
acknowledged.
J O960226D