Helvetica Chimica Acta Vol. 87 (2004)
1653
oil. IR (film): 3009s, 2932vs, 2864vs, 1709vs, 1468vs, 1445vs, 1414s, 1361s, 1258s, 1204s, 1133m, 1016m, 967m,
927m, 919m, 733vs, 720vs. 1H-NMR (600 MHz, CDCl3): 5.50 5.44 (m, HÀC(2')); 5.19 (tq, J 11.2, 4J(1,Me)
1.5, HÀC(1')); 3.06 (mc, HÀC(3)); 2.83 (ddd, 2J 15.8, J 11.8, 3.0, HaÀC(12)); 2.35 (d, J(2a,3) 4.4,
HaÀC(2)); 2.34 (s, HbÀC(2)); 2.25 (ddd, 2J 15.8, J 5.3, 3.5, HbÀC(12)); 2.00, 1.42 (2mc, CH2(11)); 1.69
(dd, 3J(Me,2') 6.7, 4J(Me,1') 1.5, Me); 1.41 1.21 (m, 14 H). 13C-NMR (150 MHz, CDCl3): 211.6 (s, C(1));
134.4 (d, C(1')); 124.0 (d, C(2')); 48.8 (t, C(2)); 39.3 (t, C(12)); 31.7 (d, C(3)); 30.3 (t); 25.8( t); 24.2 (t); 24.0 (t);
.
23.9 (t); 23.2 (t); 22.6 (t); 22.2 (t, C(11)); 13.4 (q, Me). EI-MS: 222 (8, M ), 193 (10), 179 (10), 151 (7), 137 (8),
123 (12), 109 (18), 95 (50), 81 (52), 67 (69), 55 (100). Alternatively, a 1:1 mixture ( E)/(Z)-21 (96% yield) was
prepared accordingly from a 1:1 mixture of (E)/(Z)-1-bromopropene.
(E/Z)-3-(Prop-1-enyl)cyclotridecanone (23). GP 2, with 1.56 g (8.03 mmol) of 14 and a 1 :1 mixture of
(E/Z)-1-bromopropene. The crude product was purified by CC (hexane/AcOEt 40 :1) to give a 1:1 mixture of
(E)/(Z)-23 (1.88 g, 99%). Colorless solid. M.p. 278. IR (film): 3008s, 2932vs, 2861vs, 1710vs, 1461vs, 1445vs,
1407s, 1360s, 1206s, 1166m, 1125m, 1079m, 1067m, 1033m, 966m, 731s, 712s. 1H-NMR (300 MHz, CDCl3): 5.49
5.39 (m, HÀC(2')); 5.19 (td, J 10.7, 1.4, HÀC(1')); 2.91 (mc, HÀC(3) of (Z)-isomer); 2.52 2.20 (m, HÀC(3)
of (E)-isomer, CH2(2,13)); 1.78 1.68 ( m, HaÀC(12)); 1.67 (dd, J 6.8, 1.7, Me); 1.45 1.12 (m, 17 H).
13C-NMR (75 MHz, CDCl3): 211.3, 211.2 (2s, C(1)); 134.8, 134.4 (2d, C(1')); 124.1, 123.5 (2d, C(2')); 48.8, 48.7
(2t, C(2)); 42.04, 41.96 (2t, C(13)); 38.3, 31.9 (2d, C(3)); 33.0 (t); 32.4 (t); 26.4 (t); 26.2 (t); 25.9 (t); 25.5 (t); 25.4
.
(t); 25.3 (t); 24.4 (t); 24.0 (t); 23.9 (t); 23.6 (t); 22.3 (t); 17.7, 13.0 (2q, Me). EI-MS of (Z)-23: 236 (38, M ), 207
(40, [M À CHO] ), 193 (52, [M À CHO À CH2] ), 137 (48), 123 (51), 109 (52), 95 (52), 81 (100), 67 (55), 55
.
(53). EI-MS of (E)-23: 236 (26, M ), 207 (32, [M À CHO] ), 193 (52, [M À CHO À CH2] ), 179 (11, [M À
CHO À 2CH2] ), 165 (6), 137 (35), 123 (45), 109 (44), 95 (48), 81 (100), 67 (48), 55 (51).
3-(Isopropenyl)cyclododecanone (24). GP 2, with 2.25 g (12.48mmol) of 6. The crude product was purified
by CC (hexane/AcOEt 40 :1) to give 24 (2.58g, 93%). Colorless oil. IR (film): 3074 w, 2933vs, 2866vs, 1709vs,
1
1645s, 1469vs, 1445s, 1374s, 1256m, 1205m, 1131m, 889vs. H-NMR (300 MHz, CDCl3): 4.78, 4.74 (2quint., J
1.4, CH2(2')); 2.81 2.71 (m, HÀC(3) and HaÀC(12)); 2.56 (dd, 2J 13.6, 3J 11.9, HaÀC(2)); 2.36 (dd, 2J
13.6, 3J 3.0, HbÀC(2)); 2.31 (ddd, 2J 16.2, J 5.8, 2.2, HbÀC(12)); 1.97 (mc, HaÀC(11)); 1.63 (t, J 0.7, Me);
1.51 1.20 (m, 15 H). 13C-NMR (75 MHz, CDCl3): 211.4 (s, C(1)); 147.1 (s, C(1')); 110.6 (t, C(2')); 47.0 (t, C(2));
40.5 (d, C(3)); 39.3 (t, C(12)); 27.1 (t); 25.2 (t); 24.0 (t); 23.9 (t); 23.7 (t); 22.5 (t); 22.4 (t); 22.0 (t); 19.7 (q, Me).
.
EI-MS: 222 (15, M ), 207 (29), 179 (30), 151 (28), 137 (35), 123 (42), 109 (39), 95 (50), 81 (100), 67 (45), 55
(41).
3-(Isopropenyl)cyclotridecanone (25). GP 2, with 1.20 g (6.18mmol) of 14. The crude product was purified
by CC (hexane/AcOEt 40 :1) to give 25 (1.37 g, 94%). Colorless solid. M.p. 34 368. IR (film): 3074w, 2932vs,
2860vs, 1710vs, 1645s, 1461s, 1445s, 1408m, 1375m, 1245m, 8 8 s9. 1H-NMR (300 MHz, CDCl3): 4.75 (s, CH2(2'));
2.62 2.39 (m, HÀC(3), HaÀC(2), CH2(13)); 2.35 (dd, 2J 12.9, J(2b,3) 1.9, HbÀC(2)); 1.75 1.56
(m, CH2(12)); 1.68( s, Me); 1.41 1.29 (m, 16 H). 13C-NMR (75 MHz, CDCl3): 211.2 (s, C(1)); 147.7 (s, C(1'));
110.4 (t, C(2')); 47.8( t, C(2)); 42.2 (d, C(3)); 42.0 (t, C(13)); 30.1 (t); 26.2 (t); 25.7 (t); 25.4 (t); 25.3 (t); 24.4 (t);
.
24.0 (t); 23.8( t); 22.4 (t); 19.6 (q, Me). EI-MS: 236 (56, M ), 221 (49), 207 (10), 193 (88), 179 (51), 165 (65),
151 (76), 137 (71), 123 (78), 109 (85), 95 (100), 81 (96), 67 (99), 55 (92).
(E)-3-(1-Methylprop-1-enyl)cyclododecanone ((E)-26). GP 2, with 2.96 g (16.42 mmol) of 6 and a 1:1
mixture of (E/Z)-2-bromobutene. The crude product was purified by CC (hexane/AcOEt 40 :1) to give (E)-26
(3.37 g, 87%). (The presence of < 10% of the (Z)-isomer was detected by GC- as well as 13C-NMR analyses).
Colorless oil. IR (film): 2932vs, 2860vs, 1709vs, 1667m, 1469vs, 1445vs, 1377vs, 1261s, 1205s, 1132s, 1024m, 952s,
814s, 711s. 1H-NMR (300 MHz, CDCl3): 5.34 5.27 (m, HÀC(2')); 3.26 3.17 (m, HÀC(3)); 3.07 2.96
(m, HaÀC(12)); 2.45 2.04 (m, 4 H); 1.68( dd, J 6.8, 1.4, MeÀC(2')); 1.57 (t, J 1.5, MeÀC(1')); 1.40 1.16
(m, 15 H). 13C-NMR (75 MHz, CDCl3): 211.7, 211.5 (2s, C(1)); 137.2, 137.0 (2s, C(1')); 120.4, 119.3 (2d, C(2'));
48.5, 48.1 (2t, C(2)); 42.4, 33.6 (2d, C(3)); 38.5, 37.6 (2t, C(12)); 27.0 (t); 26.2 (t); 25.6 (t); 24.0 (t); 23.8( t); 23.5
(t); 23.2 (t); 23.1 (t); 22.9 (t); 22.4 (t); 22.3 (t); 21.8( t); 21.6 (t); 18.6, 13.9, 13.1, 12.6 (4q, Me). EI-MS of (E)-26:
.
.
236 (8, M ), 123 (18), 109 (33), 95 (44), 81 (57), 67 (68), 55 (100). EI-MS of ( Z)-26: 236 (22, M ), 207 (40),
179 (19), 151 (13), 137 (16), 123 (45), 109 (68), 95 (84), 81 (89), 67 (90), 55 (100).
(E)-3-(1-Methylprop-1-enyl)cyclotridecanone ((E)-27). GP 2, with 1.09 g (5.61 mmol) of 14 and a 1:1
mixture of (E/Z)-2-bromobutene. The crude product was purified by CC (hexane/AcOEt 40 :1) to give (E)-27
(1.25 g, 89%). (The presence of < 10% of the (Z)-isomer was detected by GC as well as 13C-NMR analyses).
Colorless oil. IR (film): 2930vs, 2860vs, 1709vs, 1460s, 1445s, 1407m, 1375m, 1250s, 1185s, 1124m, 1066m, 8 44s.
1H-NMR (300 MHz, CDCl3): 5.28( qd, 3J(2',Me) 6.8, J(2',3) 1.4, HÀC(2')); 3.12 3.06 (m, HÀC(3)); 2.59
2.44 (m, HaÀC(2), CH2(13)); 2.17 (dd, 2J 12.8, J(2b,3) 2.9, HbÀC(2)); 1.79 1.67 (m, HaÀC(12)); 1.65
(dd, J 6.8, 1.5, MeÀC(2')); 1.57 (t, J 1.4, MeÀC(1')); 1.40 1.28( m, 17 H). 13C-NMR (75 MHz, CDCl3):