H. Yorimitsu et al.
Bull. Chem. Soc. Jpn., 74, No. 2 (2001) 233
H, 7.44%. Calcd for C16H27IO2: C, 50.80; H, 7.19%.
(m, 6H), 1.02−1.44 (m, 12H), 1.48−1.88 (m, 5H), 3.32−3.90 (m,
3.7H), 3.97−4.04 (m, 0.3H), 4.33 (dd, J = 9.3, 2.1 Hz, 0.3H), 4.79
(d, J = 2.1 Hz, 0.7H); 13C NMR (CDCl3): major isomer, δ 13.80,
13.90, 19.37, 22.52, 25.80, 28.95, 31.73, 31.98, 32.18, 36.97,
37.07, 59.59, 66.65, 97.00; minor isomer, δ 13.76, 13.90, 19.19,
22.52, 25.97, 31.80, 31.83, 31.94, 34.29, 36.42, 38.19, 65.28,
68.52, 102.01. Found: C, 73.37; H, 12.55%. Calcd for C14H28O2:
C, 73.63; H, 12.36%.
4-(2,2-Dimethylpropylidene)-2-ethoxy-1-oxaspiro[4.5]de-
cane (15c): IR (neat): 2926, 2856, 1447, 1362, 1322, 1210,
1189, 1146, 1120, 1095, 1056, 1021, 988, 889, 841 cm–1; 1H NMR
(CDCl3): δ 1.07 (s, 9H), 1.15−1.39 (m, 6H), 1.51−1.71 (m, 6H),
1.81−1.88 (m, 1H), 2.71−2.88 (m, 2H), 3.47 (dq, J = 9.9, 6.9 Hz,
1H), 3.80 (dq, J = 9.9, 7.2 Hz, 1H), 5.10 (t, J = 2.4 Hz, 1H), 5.16
(dd, J = 5.1, 1.5 Hz, 1H); 13C NMR (CDCl3): δ 15.00, 22.77,
22.93, 25.45, 30.37 (3C), 32.65, 36.62, 38.80, 38.85, 62.00, 85.22,
101.99, 130.47, 141.57. Found: C, 75.92; H, 11.45%. Calcd for
C16H28O2: C, 76.14; H, 11.18%.
2-Iodoethanal Ethyl 1-[2-(4-Methoxyphenyl)ethynyl]cyclo-
hexyl Acetal (14d): IR (neat): 2854, 2218, 1606, 1571, 1511,
1444, 1413, 1372, 1337, 1290, 1248, 1175–938 (broad), 905, 831
cm–1; 1H NMR (CDCl3): δ 1.19−1.34 (m, 5H), 1.56−1.80 (m, 6H),
1.90−2.14 (m, 2H), 3.24−3.37 (m, 2H), 3.60 (dq, J = 9.3, 7.2 Hz,
1H), 3.74−3.84 (m, 1H), 3.82 (s, 3H), 5.14 (dd, J = 3.9, 6.6 Hz,
1H), 6.88−6.88 (m, 2H), 7.36−7.42 (m, 2H); 13C NMR (CDCl3): δ
8.33, 14.97, 23.15 (2C), 25.14, 38.53, 38.93, 55.24, 62.15, 75.16,
87.46, 88.43, 97.96, 114.00 (2C), 114.68, 133.15 (2C), 159.84.
Found: C, 53.50; H, 5.93%. Calcd for C19H25IO3: C, 53.28; H,
5.88%.
2-Iodoethanal Butyl 2-Nonynyl Acetal (14a):
IR (neat):
2924, 2856, 1461, 1379, 1264, 1107, 1035, 1005 cm–1; H NMR
(CDCl3): δ 0.89 (t, J = 7.2 Hz, 3H), 0.93 (t, J = 7.5 Hz, 3H), 1.22−
1.64 (m, 12H), 2.22 (tt, J = 6.9, 2.1 Hz, 2H), 3.26 (d, J = 5.1 Hz,
2H), 3.48−3.56 (m, 1H), 3.61−3.69 (m, 1H), 4.25 (t, J = 2.1 Hz,
2H), 4.78 (t, J = 5.1 Hz, 1H); 13C NMR (CDCl3): δ 5.06, 13.67,
13.88, 18.59, 19.12, 22.39, 28.35, 28.40, 31.17, 31.54, 54.39,
66.67, 75.24, 87.51, 100.42. HRMS Found: m/z 239.2042, Calcd
for C15H27IO2 – I: 239.2011.
1
2-Butoxy-4-heptylidenetetrahydrofuran (15a):
(55/45
stereoisomers mixture) IR (neat): 2904, 2848, 1460, 1344, 1181,
1097, 1068, 1031, 997, 924 cm–1; 1H NMR (CDCl3): δ 0.88 (t, J =
6.9 Hz, 3H), 0.91 (t, J = 7.5 Hz, 3H), 1.20−1.42 (m, 10H), 1.50−
1.60 (m, 2H), 1.85−2.04 (m, 2H), 2.36−2.70 (m, 2H), 3.37−3.45
(m, 1H), 3.63−3.73 (m, 1H), 4.26−4.42 (m, 2H), 5.15 (d, J = 5.7
Hz, 0.45H), 5.22 (d, J = 5.1 Hz, 0.55H), 5.25−5.37 (m, 1H);
13C NMR (CDCl3): major isomer, δ 13.70, 13.93, 19.22, 22.50,
28.84, 29.18, 29.81, 34.64 (2C), 35.80, 66.96, 69.12, 103.86,
120.22, 136.05. minor isomer, δ 13.70, 13.93, 19.22, 22.50, 28.81,
29.22, 29.66, 31.64 (2C), 38.91, 66.83, 66.90, 103.27, 121.18,
135.89. HRMS Found: m/z 240.2066, Calcd for C15H28O2:
240.2089.
2-Iodoethanal Ethyl 1-(1-Hexynyl)cyclohexyl Acetal (14b):
IR (neat): 2922, 2854, 2230, 1446, 1412, 1372, 1338, 1297, 1176,
1116, 1043, 1002, 938, 905, 614 cm–1; 1H NMR (CDCl3): δ 0.93
(t, J = 7.2 Hz, 3H), 1.22 (t, J = 6.9 Hz, 3H), 1.37−1.74 (m, 12H),
1.78−1.86 (m, 1H), 1.91−2.00 (m, 1H), 2.26 (t, J = 6.9 Hz, 2H),
3.20−3.31 (m, 2H), 3.60 (dq, J = 9.3, 6.6 Hz, 1H), 3.74 (dq, J =
9.3, 6.9 Hz, 1H), 5.06 (dd, J = 6.6, 3.9 Hz, 1H); 13C NMR
(CDCl3): δ 8.34, 13.41, 14.86, 18.20, 21.82, 23.05 (2C), 25.10,
30.67, 38.55, 39.07, 61.34, 74.8, 80.64, 88.12, 97.67. Found: C,
51.03; H, 7.21%. Calcd for C16H27IO2: C, 50.80; H, 7.19%.
5-Ethoxy-2,2-pentamethylene-3-(pentylidene)tetrahydro-
furan (15b): (84/16 stereoisomers mixture) IR (neat): 2896,
2848, 1760, 1447, 1372, 1345, 1210, 1185, 1145, 1119, 1093,
1048, 977, 909, 841 cm–1; 1H NMR (CDCl3): δ 0.85−0.97 (m, 3H),
1.14−1.42 (m, 10H), 1.52−2.18 (m, 9H), 2.46−2.87 (m, 2H), 3.40−
3.52 (m, 1H), 3.74−3.86 (m, 1H), 5.04 (d, J = 5.1 Hz, 0.16H),
5.11−5.19 (m, 1.68H), 5.26 (t, J = 8.1 Hz, 0.16H); 13C NMR
(CDCl3): major isomer, δ 13.80, 14.94, 22.11, 22.56, 22.79, 25.39,
29.30, 31.52, 36.55, 38.59 (2C), 61.90, 83.84, 101.55, 119.84,
144.83. minor isomer, δ 13.80, 14.94, 22.25, 22.31, 22.72, 27.70,
32.35, 36.02, 36.43, 38.58, 41.65, 61.78, 83.06, 100.93, 121.54,
142.66. HRMS Found: m/z 252.2080, Calcd for C16H28O2:
252.2090.
4-[(4-Methoxyphenyl)methylene]-2-ethoxy-1-oxaspiro[4.5]-
decane (15d): (6/4 stereoisomers mixture) IR (neat): 2928,
1608, 1575, 1511, 1445, 1301, 1246, 1175, 1118, 1094, 1037, 982,
1
919, 867, 823, 764 cm–1; H NMR (CDCl3): δ 0.88−1.77 (m,
12.6H), 1.92 (d, J = 13.2 Hz, 0.4H), 2.66 (d, J = 16.2 Hz, 0.6H),
2.88−3.10 (m, 1.4H), 3.42−3.53 (m, 1H), 3.75−3.88 (m, 4H), 5.11
(d, J = 5.4 Hz, 0.6H), 5.26 (d, J = 5.1 Hz, 0.4H), 6.15 (t, J = 2.4 Hz,
0.4H), 6.47 (s, 0.6H), 6.81−6.88 (m, 2H), 7.13 (d, J = 8.1 Hz,
1.2H), 7.22 (d, J = 8.7 Hz, 0.8H); 13C NMR (CDCl3): major iso-
mer, δ 14.97, 22.18, 22.47, 25.09, 36.36, 37.12, 42.50, 55.01,
61.91, 83.59, 100.43, 113.12 (2C), 121.26, 130.01, 130.19 (2C),
146.35, 158.18. minor isomer, δ 14.94, 22.56, 22.84, 25.35, 38.30,
38.35, 38.65, 55.09, 62.08, 85.34, 101.87, 113.66 (2C), 119.50,
129.37 (2C), 130.64, 145.05, 158.15. Found: C, 75.20; H, 8.81%.
Calcd for C19H26O3: C, 75.46; H, 8.67%.
4-Deuteriophenyl Octyl Ether (2a-d, 88%D):
IR (neat):
3032, 2924, 2852, 1599, 1493, 1470, 1389, 1294, 1246, 1172,
1
1035, 840, 752, 690, 598 cm–1; H NMR (CDCl3): δ 0.89 (s, J =
6.6 Hz, 3H), 1.20−1.52 (m, 10H), 1.78 (quintet, J = 6.6 Hz, 2H),
3.95 (t, J = 6.6 Hz, 2H), 6.84−6.96 (m, 2.1H), 7.24−7.32 (m, 2H);
13C NMR (CDCl3): δ 13.96, 22.55, 25.98, 29.16, 29.22, 29.29,
31.74, 67.81, 114.52(2C), 120.2 (t, J = 24.8 Hz, 0.9C), 120.48 (s,
0.1C), 129.33 (1.8C), 129.44 (0.2C), 159.28. Found: C, 81.19;
H+D, 10.86%. Calcd for C14H21.1D0.9O: C, 81.14; H+D, 11.13%.
7-(1-Deuterio-1-methylethyl)-2,9-dioxabicyclo[4.3.0]nonane
(7g-d, > 99%D): (6/4 diastereomers mixture) IR (neat): 2928,
2864, 1467, 1402, 1254, 1226, 1148, 1093, 1073, 1043, 1018, 997,
1
952, 897, 871 cm–1; H NMR (CDCl3): δ 0.80 (s, 1.8H), 0.87 (s,
1.2H), 0.92 (s, 1.8H), 0.94 (s, 1.2H), 1.32−2.00 (m, 5.6H), 2.06−
2.17 (m, 0.4H), 3.43 (dt, J = 2.1, 11.1 Hz, 0.4H), 3.62−3.80 (m,
2.2H), 3.85−3.98 (m, 1H), 4.19 (t, J = 8.7 Hz, 0.4H) 4.99 (d, J =
3.3 Hz, 0.4H) 5.30 (d, J = 3.3 Hz, 0.6H); 13C NMR (CDCl3): major
isomer, δ 18.65, 20.69, 21.45, 23.12, 25.69 (t, J = 19.4 Hz), 35.57,
48.71, 60.60, 68.89, 102.03; minor isomer, δ 19.16, 20.57, 21.18,
23.34, 29.39 (t, J = 18.8 Hz), 41.18, 44.09, 64.20, 70.93, 102.42.
Found: C, 69.89; H, 9.99%. Calcd for C10H17DO2: C, 70.13; H,
10.00%.
2-Iodoethanal Ethyl 1-(3,3-Dimethyl-1-butynyl)cyclohexyl
Acetal (14c): IR (neat): 2920, 2856, 2224, 1445, 1411, 1363,
1338, 1301, 1261, 1205, 1177, 1099, 993, 939, 905, 889, 850
cm–1; 1H NMR (CDCl3): δ 1.23 (t, J = 7.2 Hz, 3H), 1.25 (s, 9H),
1.46−1.74 (m, 8H), 1.78−1.85 (m, 1H), 1.92−2.00 (m, 1H),
3.19−3.23 (m, 2H), 3.55 (dq, J = 9.3, 7.2 Hz, 1H), 3.77 (dq, J =
9.3, 7.2 Hz, 1H), 5.02 (dd, J = 3.3, 6.9 Hz, 1H); 13C NMR
(CDCl3): δ 8.27, 14.79, 23.02, 23.06, 25.03, 27.14, 30.83 (3C),
38.43, 39.02, 62.01, 74.38, 78.90, 96.62, 97.75. Found: C, 50.83;
3-(1-Deuterio-1-methylethyl)-2,3-dihydrobenzofuran (10c-d
,
87% D): IR (neat): 3044, 3028, 2866, 1610, 1595, 1482, 1463,
1454, 1387, 1368, 1325, 1222, 1163, 1099, 1017, 958, 812, 744,