Generation and Reaction of Monocarbonyliodonium Ylides
J. Am. Chem. Soc., Vol. 119, No. 48, 1997 11603
2H), 4.27 (d, J ) 4.9 Hz, 1H), 3.86 (d, J ) 4.9 Hz, 1H), 2.22 (dt, J )
17.0, 7.3 Hz, 1H), 2.15 (dt, J ) 17.0, 7.3 Hz, 1H), 1.55-0.90 (m,
12H), 0.87 (t, J ) 6.7 Hz, 3H); MS m/z (relative intensity) 340 (13),
338 (12, M+), 178 (27), 169 (52), 89 (100), 71 (85); HRMS calcd for
C17H23O2Br (M+) 338.0881, found 338.0890.
3H); MS m/z (relative intensity) 212 (16, M+), 183 (39), 141 (58), 71
(82), 57 (100); HRMS calcd for C13H24O2 (M+) 212.1776, found
212.1777.
(E)-10,11-Epoxyeicosan-9-one ((E)-12j): white powder; mp 40-
40.5 °C (recrystallized from methanol); IR (KBr) 2921, 2851, 1716,
1467, 1404, 1379, 882, 855, 726 cm-1; 1H NMR (CDCl3) δ 3.21 (d, J
) 2.0 Hz, 1H), 3.03 (dt, J ) 2.0, 5.3 Hz, 1H), 2.42 (dt, J ) 17.3, 7.3
Hz, 1H), 2.28 (dt, J ) 17.3, 7.3 Hz, 1H), 1.70-1.15 (m, 28H), 1.00-
0.79 (6H); MS m/z (relative intensity) 310 (25, M+), 183 (42), 141
(100), 71 (63), 57 (81), 43 (66); HRMS calcd for C20H38O2 (M+)
310.2872, found 310.2865. Anal. Calcd for C20H38O2: C, 77.36; H,
12.33. Found: C, 77.17; H, 12.34.
(E)-1-(4-Chlorophenyl)-1,2-epoxyundecan-3-one ((E)-12f): color-
less leaflets; mp 64-65 °C (recrystallized from methanol); IR (KBr)
2922, 2850, 1708, 1496, 1471, 1438, 1096, 838 cm-1; 1H NMR (CDCl3)
δ 7.35 (br d, J ) 8.5 Hz, 2H), 7.22 (br d, J ) 8.5 Hz, 2H), 3.95 (d, J
) 1.7 Hz, 1H), 3.47 (d, J ) 1.7 Hz, 1H), 2.54 (dt, J ) 17.6, 7.6 Hz,
1H), 2.44 (dt, J ) 17.6, 7.6 Hz, 1H), 1.73-1.50 (m, 2H), 1.44-1.15
(m, 10H), 0.88 (t, J ) 6.3 Hz, 3H); MS m/z (relative intensity) 296
(12), 294 (41, M+), 209 (9), 154 (75), 138 (66), 125 (67), 89 (100), 81
(77); HRMS calcd for C17H23O2Cl (M+) 294.1387, found 294.1390.
Anal. Calcd for C17H23O2Cl‚1/3H2O: C, 67.88; H, 7.93. Found: C,
67.65; H, 7.64.
(Z)-10,11-Epoxyeicosan-9-one ((Z)-12j): colorless leaflets; mp 33-
34 °C (recrystallized from methanol-dichloromethane); IR (CHCl3)
2920, 2850, 1715, 1460, 1375 cm-1; 1H NMR (CDCl3) δ 3.58 (d, J )
4.9 Hz, 1H), 3.20 (q, J ) 4.9 Hz, 1H), 2.52 (t, J ) 7.3 Hz, 2H), 1.70-
1.15 (m, 28H), 0.95-0.80 (6H); MS m/z (relative intensity) 310 (76,
M+), 183 (42), 141 (91), 95 (28), 71 (70), 57 (100), 43 (98); HRMS
calcd for C20H38O2 (M+) 310.2872, found 310.2882. Anal. Calcd for
C20H38O2‚1/4H2O: C, 76.25; H, 12.31. Found: C, 76.63; H, 12.21.
(E)-4,5-Epoxy-2-methyltetradecan-6-one ((E)-12k): pale yellow
(Z)-1-(4-Chlorophenyl)-1,2-epoxyundecan-3-one ((Z)-12f): color-
1
less oil; IR (CHCl3) 2915, 2845, 1715, 1490, 1090 cm-1; H NMR
(CDCl3) δ 7.31 (br s, 4H), 4.29 (d, J ) 4.9 Hz, 1H), 3.86 (d, J ) 4.9
Hz, 1H), 2.22 (dt, J ) 17.2, 7.6 Hz, 1H), 2.15 (dt, J ) 17.2, 7.6 Hz,
1H), 1.51-0.90 (m, 12H), 0.86 (t, J ) 6.7 Hz, 3H); MS m/z (relative
intensity) 296 (8), 294 (21, M+), 209 (6), 161 (20), 125 (100), 89 (91),
71 (92); HRMS calcd for C17H23O2Cl (M+) 294.1387, found 294.1400.
1
oil; IR (CHCl3) 2950, 2925, 2845, 1705, 1460, 1365, 985 cm-1; H
NMR (CDCl3) δ 3.19 (d, J ) 2.0 Hz, 1H), 3.05 (dt, J ) 2.0, 5.9 Hz,
1H), 2.43 (dt, J ) 17.3, 7.5 Hz, 1H), 2.29 (dt, J ) 17.3, 7.5 Hz, 1H),
1.85 (nonet, J ) 6.6 Hz, 1H), 1.67-1.44 (m, 4H), 1.35-1.17 (m, 10H),
0.99 (d, J ) 6.8 Hz, 3H), 0.98 (d, J ) 6.8 Hz, 3H), 0.88 (t, J ) 6.8
Hz, 3H); MS m/z (relative intensity) 240 (11, M+), 183 (46), 141 (75),
71 (80), 57 (100); HRMS calcd for C15H28O2 (M+) 240.2089, found
240.2112.
(E)-1,2-Epoxy-1-(4-fluorophenyl)undecan-3-one ((E)-12g): color-
less leaflets; mp 51-52 °C (recrystallized from methanol); IR (KBr)
2957, 2922, 2850, 1709, 1610, 1518, 1466, 1248, 839 cm-1; 1H NMR
(CDCl3) δ 7.26 (br dd, J ) 8.5 Hz, JHF ) 5.4 Hz, 2H), 7.06 (br t, J )
8.5 Hz, JHF ) 8.5 Hz, 2H), 3.96 (d, J ) 1.7 Hz, 1H), 3.48 (d, J ) 1.7
Hz, 1H), 2.55 (dt, J ) 17.3, 7.1 Hz, 1H), 2.43 (dt, J ) 17.3, 7.1 Hz,
1H), 1.76-1.51 (m, 2H), 1.46-1.19 (m, 10H), 0.88 (t, J ) 6.2 Hz,
3H); MS m/z (relative intensity) 278 (18, M+), 180 (10), 138 (93), 109
(100), 71 (88), 57 (80); HRMS calcd for C17H23O2F (M+) 278.1682,
found 278.1679. Anal. Calcd for C17H23O2F: C, 73.35; H, 8.33.
Found: C, 73.24; H, 8.35.
(Z)-4,5-Epoxy-2-methyltetradecan-6-one ((Z)-12k): colorless oil;
1
IR (CHCl3) 2920, 2850, 1710, 1460, 1370 cm-1; H NMR (CDCl3) δ
3.57 (d, J ) 4.6 Hz, 1H), 3.24 (dt, J ) 4.6, 5.3 Hz, 1H), 2.52 (t, J )
7.3 Hz, 2H), 1.91-1.53 (m, 3H), 1.49-1.18 (m, 12H), 0.99 (d, J )
6.6 Hz, 3H), 0.94 (d, J ) 6.6 Hz, 3H), 0.88 (t, J ) 6.6 Hz, 3H); MS
m/z (relative intensity) 240 (50, M+), 183 (84), 141 (93), 99 (46), 85
(41), 71 (87), 57 (100); HRMS calcd for C15H28O2 (M+) 240.2089,
found 240.2097.
(Z)-1,2-Epoxy-1-(4-fluorophenyl)undecan-3-one ((Z)-12g): color-
1
less oil; IR (CHCl3) 2920, 2845, 1710, 1605, 1505 cm-1; H NMR
(CDCl3) δ 7.35 (br dd, J ) 8.6 Hz, JHF ) 5.6 Hz, 2H), 7.02 (br t, J )
8.6 Hz, JHF ) 8.6 Hz, 2H), 4.29 (d, J ) 4.7 Hz, 1H), 3.84 (d, J ) 4.7
Hz, 1H), 2.23-2.12 (m, 2H), 1.47-0.89 (m, 12H), 0.86 (t, J ) 6.7
Hz, 3H); MS m/z (relative intensity) 278 (16, M+), 180 (12), 138 (17),
122 (48), 109 (100), 71 (45), 57 (53); HRMS calcd for C17H23O2F (M+)
278.1682, found 278.1661.
(E)-3,4-Epoxy-2-methyltridecan-5-one ((E)-12l): colorless oil; IR
1
(CHCl3) 2930, 2850, 1705, 1465, 1375, 890 cm-1; H NMR (CDCl3)
δ 3.26 (d, J ) 1.7 Hz, 1H), 2.85 (dd, J ) 1.7, 6.6 Hz, 1H), 2.43 (dt,
J ) 16.6, 7.6 Hz, 1H), 2.28 (dt, J ) 16.6, 7.6 Hz, 1H), 1.78-1.51 (m,
2H), 1.43-1.10 (m, 11H), 1.05 (d, J ) 6.8 Hz, 3H), 0.99 (d, J ) 6.8
Hz, 3H), 0.88 (t, J ) 6.8 Hz, 3H); MS m/z (relative intensity) 226 (5,
M+), 183 (68), 141 (68), 71 (80), 57 (100); HRMS calcd for C14H26O2
(M+) 226.1933, found 226.1945.
(E)-1,2-Epoxy-1-(4-nitrophenyl)undecan-3-one ((E)-12h): color-
less needles; mp 37-38 °C (recrystallized from dichloromethane-
hexane); IR (KBr) 2923, 2853, 1722, 1604, 1526, 1469, 1437, 1350,
1108, 853, 752 cm-1; 1H NMR (CDCl3) δ 8.24 (br d, J ) 8.8 Hz, 2H),
7.46 (br d, J ) 8.8 Hz, 2H), 4.09 (d, J ) 1.7 Hz, 1H), 3.50 (d, J ) 1.7
Hz, 1H), 2.72 (dt, J ) 17.6, 7.3 Hz, 1H), 2.46 (dt, J ) 17.6, 7.3 Hz,
1H), 1.78-1.52 (m, 2H), 1.41-1.18 (m, 10H), 0.88 (t, J ) 6.8 Hz,
3H); MS m/z (relative intensity) 305 (48, M+), 165 (18), 141 (100), 71
(77), 57 (95), 43 (66); HRMS calcd for C17H23O4N (M+) 305.1627,
found 305.1637. Anal. Calcd for C17H23O4N: C, 66.86; H, 7.59; N,
4.59. Found: C, 66.66; H, 7.49; N, 4.52.
(Z)-3,4-Epoxy-2-methyltridecan-5-one ((Z)-12l): pale yellow oil;
1
IR (CHCl3) 2920, 2840, 1700, 1455 cm-1; H NMR (CDCl3) δ 3.60
(d, J ) 4.9 Hz, 1H), 2.89 (dd, J ) 4.9, 9.3 Hz, 1H), 2.53 (t, J ) 7.3
Hz, 2H), 1.71-1.51 (m, 2H), 1.48-1.20 (m, 11H), 1.13 (d, J ) 6.6
Hz, 3H), 0.88 (d, J ) 6.6 Hz, 3H), 0.88 (t, J ) 6.8 Hz, 3H); MS m/z
(relative intensity) 226 (16, M+), 225 (14), 183 (52), 141 (37), 85 (100),
71 (67), 57 (92); HRMS calcd for C14H26O2 (M+) 226.1933, found
226.1917.
(E,E)-4,5-Epoxy-2-tetradecen-6-one ((E,E)-12m): colorless oil; IR
(CHCl3) 2920, 2845, 1710, 1450, 1360 cm-1; 1H NMR (CDCl3) δ 6.03
(dq, J ) 15.4, 6.6 Hz, 1H), 5.19 (ddq, J ) 15.4, 8.1, 1.7 Hz, 1H), 3.42
(dd, J ) 1.9, 8.1 Hz, 1H), 3.37 (d, J ) 1.9 Hz, 1H), 2.45 (dt, J ) 17.3,
7.3 Hz, 1H), 2.32 (dt, J ) 17.3, 7.3 Hz, 1H), 1.78 (dd, J ) 6.6, 1.7
Hz, 3H), 1.70-1.52 (m, 2H), 1.41-1.18 (m, 10H), 0.88 (t, J ) 6.8
Hz, 3H); MS m/z (relative intensity) 224 (15, M+), 172 (20), 146 (84),
99 (38), 84 (100), 71 (84), 57 (99); HRMS calcd for C14H24O2 (M+)
224.1776, found 224.1762.
(Z)-1,2-Epoxy-1-(4-nitrophenyl)undecan-3-one ((Z)-12h): colorless
1
oil; IR (CHCl3) 2920, 2845, 1720, 1600, 1520, 1350, 850 cm-1; H
NMR (CDCl3) δ 8.21 (br d, J ) 8.6 Hz, 2H), 7.57 (br d, J ) 8.6 Hz,
2H), 4.42 (d, J ) 4.9 Hz, 1H), 3.99 (d, J ) 4.9 Hz, 1H), 2.24 (t, J )
7.2 Hz, 2H), 1.40-0.90 (m, 12H), 0.85 (t, J ) 6.7 Hz, 3H); MS m/z
(relative intensity) 305 (100, M+), 165 (19), 149 (27), 97 (36), 57 (65),
43 (67); HRMS calcd for C17H23O4N (M+) 305.1627, found 305.1618.
(E)-3,4-Epoxytridecan-5-one ((E)-12i): colorless oil; IR (CHCl3)
2915, 2845, 1700, 1455, 1375, 870 cm-1; 1H NMR (CDCl3) δ 3.23 (d,
J ) 2.0 Hz, 1H), 3.04 (dt, J ) 2.0, 5.4 Hz, 1H), 2.43 (dt, J ) 17.3, 7.3
Hz, 1H), 2.28 (dt, J ) 17.3, 7.3 Hz, 1H), 1.78-1.46 (m, 4H), 1.38-
1.16 (m, 10H), 1.02 (t, J ) 7.3 Hz, 3H), 0.88 (t, J ) 6.8 Hz, 3H); MS
m/z (relative intensity) 212 (14, M+), 183 (44), 141 (100), 71 (77), 57
(98); HRMS calcd for C13H24O2 (M+) 212.1776, found 212.1790.
(Z,E)-4,5-Epoxy-2-tetradecen-6-one ((Z,E)-12m): colorless oil; IR
1
(CHCl3) 2920, 2840, 1715 cm-1; H NMR (CDCl3) δ 6.06 (dq, J )
15.4, 6.6 Hz, 1H), 5.22 (ddq, J ) 15.4, 8.6, 1.5 Hz, 1H), 3.75 (d, J )
4.9 Hz, 1H), 3.63 (dd, J ) 4.9, 8.6 Hz, 1H), 2.51 (t, J ) 7.3 Hz, 2H),
1.74 (dd, J ) 6.6, 1.5 Hz, 3H), 1.70-1.18 (m, 12H), 0.88 (t, J ) 6.8
Hz, 3H); MS m/z (relative intensity) 224 (6, M+), 183 (2), 172 (3),
141 (14), 84 (85), 49 (100); HRMS calcd for C14H24O2 (M+) 224.1776,
found 224.1791.
(Z)-3,4-Epoxytridecan-5-one ((Z)-12i): pale yellow oil; IR (CHCl3)
1
2920, 2840, 1715, 1455 cm-1; H NMR (CDCl3) δ 3.60 (d, J ) 4.9
Hz, 1H), 3.17 (dt, J ) 4.9, 6.1 Hz, 1H), 2.52 (t, J ) 7.3 Hz, 2H),
1.71-1.15 (m, 14H), 1.02 (t, J ) 7.3 Hz, 3H), 0.88 (t, J ) 6.8 Hz,
(E)-4,4-Dimethyl-1,2-epoxy-1-(4-methylphenyl)pentan-3-one
((E)-12n): colorless needles; mp 56-59 °C (recrystallized from