The Journal of Organic Chemistry
Article
7.81 (d, J = 8.0, 2H), 7.21 (d, J = 8.0, 2H), 4.35 (s, 2H), 2.36 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 190.90, 144.99, 131.32, 129.50,
128.99, 31.01, 21.72; IR (neat) 2957, 1702, 1602, 1184, 802, 694;
HRMS (ESI) m/z calcd for C9H9BrO 212.9910 (M + H+), found
212.9921.
13C NMR (100 MHz, CDCl3) δ 201.47, 44.42, 38.69, 34.05, 31.52,
20.95; IR (neat) 3004, 2932, 1726, 1428, 1024, 732; HRMS (ESI) m/z
calcd for C6H10BrClO 212.9677 (M + H+), found 212.9678.
Data for 1,6-dibromohexan-2-one (2m): colorless solid (73.52
1
mg, 95% yield); mp 54−55 °C; H NMR (400 MHz, CDCl3) δ 3.89
Data for 2-bromo-1-(4-(tert-butyl)phenyl)ethanone (2c):21
(s, 2H), 3.41 (t, J = 6.4, 2H), 2.71 (t, J = 7.2, 2H), 1.91−1.84 (m, 2H),
1.81−1.74 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 201.60, 38.62,
34.11, 33.11, 31.67, 22.20; IR (neat) 3002, 2928, 1726, 1428, 1026,
744; HRMS (ESI) m/z calcd for C6H10Br2O 256.9171 (M + H+),
found 256.9174.
1
colorless solid (65.06 mg, 85% yield); mp 51−52 °C; H NMR (400
MHz, CDCl3) δ 7.93 (d, J = 8.8, 2H), 7.50 (d, J = 8.8, 2H), 4.44 (s,
2H), 1.34 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 190.87, 157.83,
131.23, 128.86, 125.78, 35.18, 30.98, 30.95; IR (neat) 2964, 1700,
1584, 1182, 802, 696; HRMS (ESI) m/z calcd for C12H15BrO
255.0379 (M + H+), found 255.0385.
Data for 6-bromo-5-oxohexyl methanesulfonate (2n): color-
less oil (71.29 mg, 87% yield); 1H NMR (400 MHz, CDCl3) δ 4.17 (t,
J = 5.8, 2H), 3.84 (s, 2H), 2.95 (s, 3H), 2.67 (t, J = 6.4, 2H), 1.76−
1.71 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 201.34, 69.47, 38.63,
37.25, 34.16, 28.15, 19.58; IR (neat) 3746, 2943, 1732, 1346, 1176,
800; HRMS (ESI) m/z calcd for C7H13BrO4S 272.9791 (M + H+),
found 272.9797.
Data for 6-bromo-5-oxohexyl 4-methylbenzenesulfonate
(2o): colorless oil (92.20 mg, 88% yield); 1H NMR (400 MHz,
CDCl3) δ 7.77 (d, J = 8.4, 2H), 7.35 (d, J = 8.4, 2H), 4.01 (t, J = 5.8,
2H), 3.85 (s, 2H), 2.63 (t, J = 6.6, 2H), 2.44 (s, 3H), 1.66−1.64 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 201.31, 144.83, 132.69, 129.83,
127.77, 69.93, 38.57, 34.13, 27.81, 21.57, 19.58; IR (neat) 2932, 1744,
1600, 1358, 1104, 766; HRMS (ESI) m/z calcd for C13H17BrO4S
349.0104 (M + H+), found 349.0106.
Data for 6-bromo-5-oxohexyl acetate (2p): colorless oil (68.99
mg, 97% yield); 1H NMR (400 MHz, CDCl3) δ 4.00 (t, J = 6.4, 2H),
3.83 (s, 2H), 2.64 (t, J = 6.6, 2H), 1.98 (s, 3H), 1.63−1.58 (m, 4H);
13C NMR (100 MHz, CDCl3) δ 201.60, 171.06, 63.80, 39.01, 34.10,
27.72, 20.88, 20.11; IR (neat) 2941, 1764, 1596, 1336, 1056, 736;
HRMS (ESI) m/z calcd for C8H13BrO3 237.0121 (M + H+), found
237.0128.
Data for 2-bromo-1-(4-methoxyphenyl)ethanone (2d):22
colorless solid (58.41 mg, 85% yield); mp 73−74 °C; 1H NMR
(400 MHz, CDCl3) δ 7.96 (d, J = 8.4, 2H), 6.95 (d, J = 8.4, 2H), 4.40
(s, 2H), 3.88 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 189.90, 164.05,
131.29, 126.76, 113.99, 55.52, 30.77; IR (neat) 2902, 1701, 1592,
1184, 802, 596; HRMS (ESI) m/z calcd for C9H9BrO2 228.9859 (M +
H+), found 228.9863.
Data for 2-bromo-1-(m-tolyl)ethanone (2e): colorless solid
(59.45 mg, 93% yield); mp 47−48 °C; 1H NMR (400 MHz, CDCl3) δ
7.72 (d, J = 8.0, 2H), 7.34−7.30 (m, 2H), 4.38 (s, 2H), 2.35 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 191.43, 138.74, 134.73, 133.94,
129.32, 128.68,126.09, 31.08, 21.30; IR (neat) 2954, 1700, 1601, 1186,
802, 694; HRMS (ESI) m/z calcd for C9H9BrO 212.9910 (M + H+),
found 212.9917.
Data for 2-bromo-1-(4-fluorophenyl)ethanone (2f):23 color-
less solid (60.55 mg, 93% yield); mp 49−50 °C; 1H NMR (400 MHz,
CDCl3) δ 8.03 (dd, J = 8.8, 5.6, 2H), 7.18 (t, J = 8.8, 2H), 4.43 (s,
2H); 13C NMR (100 MHz, CDCl3) δ 189.80, 166.08 (d, JC−F = 254),
131.69 (d, JC−F = 9.6 Hz), 130.24, (d, JC−F = 3.0 Hz), 116.06 (d, JC−F
=
22), 30.51; IR (neat) 2982, 1700, 1601, 1184, 988, 695; HRMS (ESI)
m/z calcd for C8H6BrFO 216.9659 (M + H+), found 216.9664.
Data for 2-bromo-1-(4-bromophenyl)ethanone (2g):22 color-
Data for 6-(benzyloxy)-1-bromohexan-2-one (2q): colorless
1
oil (72.72 mg, 85% yield); H NMR (400 MHz, CDCl3) δ 7.37−7.27
1
less solid (62.23 mg, 91% yield); mp 108−109 °C; H NMR (400
(m, 5H), 4.42 (s, 2H), 3.79 (s, 2H), 3.41 (t, J = 6.6, 2H), 2.61 (t, J =
7.2, 2H), 1.68−1.64 (m, 2H), 1.58−1.55 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 201.90, 138.37, 128.33, 127.61, 127.53, 72.88, 69.77,
39.40, 34.25, 28.88, 20.67; IR (neat) 2922, 1776, 1614, 1228, 1026,
742; HRMS (ESI) m/z calcd for C13H17BrO2 285.0485 (M + H+),
found 285.0493.
MHz, CDCl3) δ 7.85 (d, J = 8.8, 2H), 7.64 (d, J = 8.8, 2H), 4.41 (s,
2H); 13C NMR (100 MHz, CDCl3) δ 190.37, 132.50, 132.16, 130.37,
129.27, 30.44; IR (neat) 2944, 1699, 1582, 1184, 802, 700; HRMS
(ESI) m/z calcd for C8H6Br2O 276.8858 (M + H+), found 276.8866.
Data for 2-bromo-1-(3-bromophenyl)ethanone (2h): color-
less solid (63.60 mg, 93% yield); mp 51−52 °C; 1H NMR (400 MHz,
CDCl3) δ 8.03 (s, 1H), 7.82 (d, J = 8.0, 1H), 7.65 (d, J = 5.0, 1H),
7.30 (t, J = 8.0, 1H), 4.34 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
189.95, 136.74, 135.55, 131.81, 130.36, 127.41,123.11, 30.44; IR
(neat) 2944, 1699, 1582, 1184, 802, 700; HRMS (ESI) m/z calcd for
C8H6Br2O 276.8858 (M + H+), found 276.8864.
Data for 6-bromo-5-oxohexyl benzoate (2r): colorless oil
1
(85.26 mg, 95% yield); H NMR (400 MHz, CDCl3) δ 8.02 (d, J =
7.2, 2H), 7.54 (t, J = 7.6, 1H), 7.42 (t, J = 7.6, 2H), 4.32 (t, J = 6.0,
2H), 3.88 (s, 2H), 2.74 (t, J = 6.4, 2H), 1.80−1.77 (m, 4H); 13C NMR
(100 MHz, CDCl3) δ 201.57, 166.48, 132.87, 130.15, 129.45, 128.29,
64.28, 39.06, 34.10, 27.91, 20.24; IR (neat) 2944, 1740, 1594, 1356,
1122, 780; HRMS (ESI) m/z calcd for C13H15BrO3 299.0278 (M +
H+), found 299.0283.
Data for 1-bromo-6-((tert-butyldiphenylsilyl)oxy)hexan-2-
one (2s): colorless oil (113.13 mg, 87% yield); 1H NMR (400
MHz, CDCl3) δ 7.59 (dd, J = 8.0, 1.6, 4H), 7.32−7.29 (m, 6H), 3.75
(s, 2H), 3.59 (t, J = 6.4, 2H), 2.54 (t, J = 7.2, 2H),1.69−1.61 (m, 2H),
1.53−1.47 (m, 2H), 0.97 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
201.93, 135.51, 133.80, 129.56, 127.60, 63.25, 39.40, 34.20, 31.61,
26.83, 20.25, 19.15; IR (neat) 3070, 2919, 1732, 1444, 1066, 766;
HRMS (ESI) m/z calcd for C22H29BrO2Si 433.1193 (M + H+), found
433.1198.
Data for 1-bromo-4-phenylbutan-2-one (2i):24 colorless solid
(66.09 mg, 97% yield); mp 38−39 °C; 1H NMR (400 MHz, CDCl3) δ
7.23−7.19 (m, J = 7.2, 2H), 7.13−7.10 (m, 3H), 3.76 (s, 2H), 2.90−
2.86 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 201.17, 140.21, 128.51,
128.23, 126.27, 41.33, 34.37, 29.75; IR (neat) 2942, 1726, 1466, 1062,
782; HRMS (ESI) m/z calcd for C10H11BrO 227.0066 (M + H+),
found 227.0072.
Data for 2-bromo-1-(thiophene-3-yl)ethanone (2j): colorless
1
solid (57.83 mg, 94% yield); mp 62−63 °C; H NMR (400 MHz,
CDCl3) δ 8.18 (dd, J = 2.8, 0.8, 1H), 7.58 (dd, J = 4.8, 0.8, 1H), 7.36
(dd, J = 4.8, 2.8, 1H), 4.34 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
185.53, 138.74, 133.76, 127.27, 126.87, 31.55; IR (neat) 2958, 1702,
1584, 1186, 804, 696; HRMS (ESI) m/z calcd for C6H5BrOS
204.9317 (M + H+), found 204.9322.
Data for N-(6-bromo-5-oxohexyl)benzamide (2t): colorless oil
1
(84.09 mg, 94% yield); H NMR (400 MHz, CDCl3) δ 7.72 (dd, J =
7.2, 2H), 7.41 (t, J = 7.2, 1H), 7.33 (t, J = 7.4, 2H), 6.68 (br s, 1H),
3.82 (s, 2H), 3.35 (q, J = 6.4, 2H), 2.63 (t, J = 6.4, 2H), 1.63−1.54 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 202.04, 167.61, 134.44, 131.27,
128.40, 126.82, 39.31, 39.06, 34.23, 28.67, 20.66; IR (neat) 2970,
1772, 1474, 1383, 1081, 762; HRMS (ESI) m/z calcd for
C13H16BrNO2 298.0437 (M + H+), found 298.0441.
Data for 1-bromododecan-2-one (2k):25 colorless solid (74.23
1
mg, 94% yield); mp 40−41 °C; H NMR (400 MHz, CDCl3) δ 3.88
(s, 2H), 2.64 (t, J = 7.2, 2H), 1.61−1.58 (m, 2H), 1.33−1.22 (m,
14H), 0.88 (t, J = 7.2, 3H); 13C NMR (100 MHz, CDCl3) δ 202.24,
39.80, 34.36, 31.83, 29.49, 29.39, 29.26, 28.97, 23.80, 22.63, 14.08; IR
(neat) 3706, 2919, 1708, 1466, 1045, 788; HRMS (ESI) m/z calcd for
C12H23BrO 263.1005 (M + H+), found 263.1009.
Data for 2-(6-bromo-5-oxohexyl)isoindoline-1,3-dione
(2u):26 colorless solid (94.33 mg, 97% yield); mp 112−113 °C; H
1
Data for 1-bromo-6-chlorohexan-2-one (2l): colorless oil
(61.49 mg, 96% yield); 1H NMR (400 MHz, CDCl3) δ 3.87 (s,
2H), 3.53 (t, J = 6.4, 2H), 2.69 (t, J = 6.8, 2H), 1.78−1.75 (m, 4H);
NMR (400 MHz, CDCl3) δ 7.84 (dd, J = 5.2, 2.8, 2H), 7.72 (dd, J =
5.2, 2.8, 2H), 3.89 (s, 2H), 3.71 (t, J = 6.8, 2H), 2.75 (t, J = 6.8,
2H),1.73−1.67 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 201.51,
9193
dx.doi.org/10.1021/jo401437w | J. Org. Chem. 2013, 78, 9190−9195