1574
J. Liu et al.
PAPER
TEMPO (156.5 mg, 1.0 mmol), and NaCl (58.3 mg, 1.0 mmol) in
toluene (10 mL) afforded 2p (1.5166 g, 87%) as a solid; mp 52–
53 °C (c-hexane).
13C NMR (75.4 MHz, CDCl3): δ = 176.84, 164.14, 131.77, 130.22,
113.58, 95.86, 79.52, 55.41, 31.66, 29.00, 28.88, 28.84, 27.73,
22.51, 19.06, 13.96.
IR (neat): 2199, 1668, 1595, 1574, 1538, 1491, 1462, 1434, 1362,
1296, 1278, 1246, 1184, 1159, 1110, 1041, 1018, 979 cm–1.
1H NMR (300 MHz, CDCl3): δ = 7.49 (dd, J = 7.7, 1.7 Hz, 1 H,
ArH), 7.44–7.37 (m, 1 H, ArH), 6.96–6.86 (m, 2 H, ArH), 3.88 (s,
3 H, OCH3), 2.45 (s, 3 H, CH3).
13C NMR (75.4 MHz, CDCl3): δ = 184.60, 161.31, 134.86, 132.41,
120.45, 110.71, 108.91, 92.27, 87.52, 55.69, 32.62.
MS (EI): m/z (%) = 272 (M+, 5.74), 135 (100).
HRMS: m/z calcd for C18H24O2 (M+): 272.1776; found: 272.1775.
1-(3-Methoxyphenyl)undec-2-yn-1-one (2t)
Method A: The reaction of 1-(3-methoxyphenyl)undec-2-yn-1-ol
(2.7443 g, 10 mmol), Fe(NO3)39H2O (202.2 mg, 0.5 mmol),
TEMPO (46.9 mg, 0.3 mmol), and NaCl (29.1 mg, 0.5 mmol) in tol-
uene (10 mL) afforded 2t (2.7050 g, 99%) as an oil.
MS (EI): m/z (%) = 174 (M+, 69.00), 159 (100).
IR (neat): 2925, 2855, 2221, 1645, 1583, 1485, 1463, 1431, 1322,
1271, 1222, 1182, 1104, 1042, 994 cm–1.
Anal. Calcd for C11H10O2: C, 75.84; H, 5.79. Found: C, 75.82; H,
5.80.
1H NMR (300 MHz, CDCl3): δ = 7.75 (dt, J = 7.5, 1.2 Hz, 1 H,
ArH), 7.62 (dd, J = 2.7, 1.5 Hz, 1 H, ArH), 7.37 (t, J = 7.8 Hz, 1 H,
ArH), 7.13 (ddd, J = 8.1, 2.7, 0.9 Hz, 1 H, ArH), 3.85 (s, 3 H,
OCH3), 2.48 (t, J = 7.2 Hz, 2 H, COCH2), 1.70–1.60 (m, 2 H), 1.52–
1.39 (m, 2 H), 1.39–1.20 (m, 8 H), 0.87 (t, J = 6.8 Hz, 3 H, CH3).
13C NMR (75.4 MHz, CDCl3): δ = 177.95, 159.65, 138.27, 129.44,
122.73, 120.65, 112.81, 96.75, 79.69, 55.38, 31.73, 29.07, 28.96,
28.93, 27.76, 22.58, 19.17, 14.03.
1-(4-Chlorophenyl)undec-2-yn-1-one (2q)
Method A: The reaction of 1-(4-chlorophenyl)undec-2-yn-1-ol
(2.7879 g, 10 mmol), Fe(NO3)39H2O (201.8 mg, 0.5 mmol),
TEMPO (47.1 mg, 0.3 mmol), and NaCl (29.0 mg, 0.5 mmol) in tol-
uene (10 mL) afforded 2q (2.7184 g, 98%) as an oil.
IR (neat): 2926, 2856, 2237, 2200, 1647, 1587, 1464, 1400, 1261,
1170, 1090, 1013 cm–1.
1H NMR (300 MHz, CDCl3): δ = 8.06 (dt, J = 9.0, 2.1 Hz, 2 H,
ArH), 7.44 (dt, J = 8.4, 1.8 Hz, 2 H, ArH), 2.49 (t, J = 7.2 Hz, 2 H,
C≡CCH2), 1.72–1.60 (m, 2 H), 1.52–1.20 (m, 10 H), 0.88 (t, J = 6.6
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): δ = 176.85, 140.39, 135.30, 130.81,
128.80, 97.48, 79.36, 31.74, 29.07, 28.95, 28.94, 27.72, 22.59,
19.18, 14.04.
MS (EI): m/z (%) = 278 [M+(37Cl), 0.37], 276 [M+(35Cl), 1.27], 139
(100).
HRMS: m/z calcd for C17H2135ClO (M+): 276.1281; found:
276.1282.
MS (EI): m/z (%) = 272 (M+, 11.87), 135 (100).
HRMS: m/z calcd for C18H24O2 (M+): 272.1776; found: 272.1775.
1-(2-Methoxyphenyl)undec-2-yn-1-one (2u)
Method A: The reaction of 1-(2-methoxyphenyl)undec-2-yn-1-ol
(2.7440 g, 10 mmol), Fe(NO3)39H2O (202.3 mg, 0.5 mmol),
TEMPO (46.9 mg, 0.3 mmol), and NaCl (28.9 mg, 0.5 mmol) in tol-
uene (10 mL) afforded 2u (2.6250 g, 96%) as an oil.
IR (neat): 2927, 2856, 2212, 1648, 1625, 1596, 1576, 1486, 1464,
1435, 1299, 1237, 1180, 1164, 1132, 1092, 1048, 1023, 908 cm–1.
1H NMR (300 MHz, CDCl3): δ = 8.01 (dd, J = 7.8, 1.8 Hz, 1 H,
ArH), 7.53–7.45 (m, 1 H, ArH), 7.04–6.93 (m, 2 H, ArH), 3.90 (s,
3 H, OCH3), 2.43 (t, J = 7.1 Hz, 2 H, COCH2), 1.67–1.56 (m, 2 H),
1.49-1.19 (m, 10 H), 0.86 (t, J = 6.9 Hz, 3 H, CH3).
13C NMR (75.4 MHz, CDCl3): δ = 177.13, 159.55, 134.60, 132.91,
126.71, 120.03, 112.00, 95.32, 81.66, 55.74, 31.70, 29.04, 28.94,
28.84, 27.75, 22.54, 19.17, 14.00.
1-(4-(Trifluoromethyl)phenyl)undec-2-yn-1-one (2r)
Method A: The reaction of 1-(trifluoromethyl)undec-2-yn-1-ol
(3.1237 g, 10 mmol), Fe(NO3)39H2O (202.3 mg, 0.5 mmol),
TEMPO (47.2 mg, 0.3 mmol), and NaCl (29.4 mg, 0.5 mmol) in tol-
uene (10 mL) afforded 2r (3.0551 g, 98%) as an oil.
IR (neat): 2928, 2857, 2237, 2201, 1652, 1583, 1509, 1465, 1411,
1323, 1262, 1172, 1131, 1107, 1065, 1016 cm–1.
1H NMR (300 MHz, CDCl3): δ = 8.23 (d, J = 8.7 Hz, 2 H, ArH),
7.74 (d, J = 8.4 Hz, 2 H, ArH), 2.52 (t, J = 7.1 Hz, 2 H, C≡CCH2),
1.75–1.59 (m, 2 H), 1.53–1.22 (m, 10 H), 0.88 (t, J = 6.8 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): δ = 176.91, 139.40 (d, J = 1.3 Hz),
134.91 (q, J = 32.6 Hz), 129.72, 125.49 (q, J = 3.8 Hz), 123.52 (q,
J = 272.9 Hz), 98.38, 79.38, 31.73, 29.06, 28.94, 27.68, 22.57,
19.17, 13.97.
19F NMR (282 MHz, CDCl3): δ = –63.14.
MS (EI): m/z (%) = 310 (M+, 0.88), 145 (100).
HRMS: m/z calcd for C18H21F3O (M+): 310.1545; found: 310.1539.
MS (EI): m/z (%) = 272 (M+, 5.59), 135 (100).
HRMS: m/z calcd for C18H24O2 (M+): 272.1776; found: 272.1778.
Hexadec-7-yn-6-one (2v)
Method A: The reaction of hexadec-7-yn-6-one (2.3838 g, 10
mmol), Fe(NO3)39H2O (202.3 mg, 0.5 mmol), TEMPO (46.8 mg,
0.3 mmol), and NaCl (29.2 mg, 0.5 mmol) in toluene (10 mL) af-
forded 2v31 (2.3067 g, 98%) as an oil.
IR (neat): 2957, 2932, 2860, 2213, 1675, 1466, 1235 cm–1.
1H NMR (300 MHz, CDCl3): δ = 2.51 (t, J = 7.4 Hz, 2 H, C≡CCH2),
2.35 (t, J = 7.1 Hz, 2 H, COCH2), 1.71–1.52 (m, 4 H), 1.45–1.20 (m,
14 H), 0.93–0.82 (m, 6 H).
13C NMR (75.4 MHz, CDCl3): δ = 188.62, 94.28, 80.87, 45.48,
31.76, 31.11, 29.07, 28.95, 28.82, 27.68, 23.82, 22.60, 22.35, 18.90,
14.04, 13.84.
1-(4-Methoxyphenyl)undec-2-yn-1-one (2s)
Method A: The reaction of 1-(4-methoxyphenyl)undec-2-yn-1-ol
(2.7443 g, 10 mmol), Fe(NO3)39H2O (202.2 mg, 0.5 mmol),
TEMPO (47.0 mg, 0.3 mmol), and NaCl (29.4 mg, 0.5 mmol) in tol-
uene (10 mL) afforded 2s (2.5087 g, 92%) as an oil.
MS (EI): m/z (%) = 236 (M+, 0.55), 221 (M+ – CH3, 0.95), 165 (M+
– C5H11, 42.49), 43 (100).
Anal. Calcd for C16H28O: C, 81.29; H, 11.94. Found: C, 81.61; H,
11.94.
IR (neat): 2927, 2855, 2237, 2198, 1638, 1596, 1574, 1509, 1463,
1421, 1316, 1253, 1165, 1114, 1029, 911 cm–1.
1H NMR (300 MHz, CDCl3): δ = 8.10 (d, J = 8.7 Hz, 2 H, ArH),
6.94 (d, J = 8.7 Hz, 2 H, ArH), 3.88 (s, 3 H, OCH3), 2.48 (t, J = 7.1
Hz, 2 H, C≡CCH2), 1.73–1.60 (m, 2 H), 1.53–1.20 (m, 10 H), 0.88
(t, J = 6.2 Hz, 3 H).
Undec-2-ynal (2w)
Method A: The reaction of undec-2-yn-1-ol (1.6825 g, 10 mmol),
Fe(NO3)39H2O (202.1 mg, 0.5 mmol), TEMPO (46.9 mg, 0.3
mmol), and NaCl (29.3 mg, 0.5 mmol) in toluene (10 mL) afforded
2w32 (1.6157 g, 97%) as an oil.
Synthesis 2012, 44, 1569–1576
© Georg Thieme Verlag Stuttgart · New York