The Journal of Organic Chemistry
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959, 841, 561 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for
C15H23BrN2OS 358.0714, found 358.0703.
2854, 1645, 1592, 1489, 1215, 1163, 920, 749, 690 cmꢀ1; HRMS (TOF
MS EIþ) m/z calcd for C16H23BrO 310.0932, found 310.0934.
(Z)-(1-Bromooct-1-en-2-yl)(p-tolyl)sulfane (3p): light yellow
oil (146 mg, 93%); 1H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 7.6 Hz,
2H), 7.11 (d, J = 7.6 Hz, 2H), 6.19 (s, 1H), 2.32 (s, 3H), 2.07 (t, J = 7.6
Hz, 2H), 1.37ꢀ1.33 (m, 2H), 1.20ꢀ1.10 (m, 6H), 0.81 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 143.0, 138.2, 133.7, 129.8, 128.1,
102.4, 35.9, 31.4, 28.3, 28.1, 22.4, 21.2, 14.0; IR (neat) 2966, 2923, 1576,
1491, 1455, 1401, 1234, 1068, 891, 808, 728 cmꢀ1; HRMS (TOF MS
EIþ) m/z calcd for C15H21BrS 312.0547, found 312.0543.
(Z)-(2-Bromo-1-cyclohexylvinyl)(p-tolyl)sulfane (3q): light
yellow oil (145 mg, 93%); 1H NMR (400 MHz, CDCl3) δ 7.26 (d, J =
8.4 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.41 (s, 1H), 2.34 (s, 3H), 2.02 (t,
J = 11.8 Hz, 1H), 1.88 (d, J = 12.8 Hz, 2H), 1.70 (d, J = 11.2 Hz, 2H),
1.60 (m, 1H), 1.27ꢀ1.18 (m, 2H), 1.14ꢀ1.01 (m, 3H); 13C NMR (100
MHz, CDCl3) δ 147.2, 137.3, 131.7, 129.8, 129.5, 106.6, 44.9, 32.8, 26.4,
26.0, 21.1; IR (neat) 2979, 2923, 1565, 1489, 1447, 1402, 1247, 1053,
892, 805, 647 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for C15H19BrS
310.0391, found 310.0388.
(Z)-(1-Bromo-3-methylbut-1-en-2-yl)(p-tolyl)sulfane (3r):
light yellow oil (112 mg, 83%); 1H NMR (400 MHz, CDCl3) δ
7.31ꢀ7.28 (m, 2H), 7.14 (d, J = 7.6 Hz, 2H), 6.43 (d, J = 0.8 Hz,
1H), 2.46ꢀ2.39 (m, 1H), 2.36 (s, 3H), 1.11 (s, 3H), 1.09 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 148.6, 137.7, 132.3, 130.1, 129.6, 106.0,
35.0, 22.3, 21.4; IR (neat) 2964, 2925, 1573, 1490, 1459, 1232, 1108,
997, 806, 758 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for C12H15BrS
270.0078, found 270.0077.
(Z)-2-(1-Bromodec-1-en-2-ylthio)pyrimidin-4(1H)-one (3h):
white solid (104 mg, 60%); mp 81ꢀ82 °C; 1H NMR (400 MHz,
CDCl3) δ 12.45 (br, 1H), 7.88 (d, J = 6.4 Hz, 1H), 6.89 (s, 1H), 6.29 (d,
J = 6.8 Hz, 1H), 2.55 (t, J = 7.6 Hz, 2H), 1.58ꢀ1.54 (m, 2H), 1.32ꢀ1.27
(br, 10H), 0.88 (t, J = 6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
164.8, 159.4, 155.3, 135.9, 116.5, 111.7, 38.1, 31.7, 29.2, 29.1, 28.8, 28.0,
22.6, 14.0; IR (KBr) 3447, 3085, 3038, 2926, 2854, 1685, 1626, 1567,
1537, 1450, 1272, 1777, 1073, 982, 917, 847 cmꢀ1; HRMS (TOF MS
EIþ) m/z calcd for C14H21BrN2OS: 344.0558, found 344.0550.
(Z)-2-(1-Bromodec-1-en-2-ylthio)pyridine (3i): light yellow
oil (149 mg, 91%); 1H NMR (400 MHz, CDCl3) δ 8.45 (d, J = 4.8 Hz,
1H), 7.54 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 7.6 Hz, 1H), 7.07ꢀ7.04 (m,
1H), 6.61 (s, 1H), 2.40 (t, J = 7.4 Hz, 2H), 1.49ꢀ1.44 (m, 2H),
1.26ꢀ1.18 (m, 10H), 0.84 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 156.8, 150.0, 139.9, 136.7, 123.8, 120.7, 110.7, 37.4, 31.7, 29.1,
29.0, 28.7, 28.1, 22.6, 14.0; IR (neat) 2978, 2921, 1573, 1450, 1412,
1249, 1052, 893, 758, 722 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for
C15H22BrNS 327.0656, found 327.0666.
(Z)-2-(1-Bromodec-1-en-2-ylthio)aniline (3k): light yellow oil
(147 mg, 86%); 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.6 Hz, 1H),
7.19 (t, J = 7.8 Hz, 1H), 6.72 (d, J = 7.6 Hz, 1H), 6.70 (t, J = 7.2 Hz, 1H),
6.21 (s, 1H), 4.20 (s, 2H), 1.98 (t, J = 7.6 Hz, 2H), 1.41ꢀ1.12 (m, 12H),
0.88 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 149.2, 142.7,
137.2, 131.0, 118.3, 115.0, 113.1, 101.2, 35.2, 31.8, 29.1, 28.7, 28.1, 22.6,
14.1; IR (neat) 3472, 3372, 2923, 1731, 1608, 1479, 1448, 1246, 1072,
746 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for C16H24BrNS 341.0813,
found 341.0818.
(Z)-(1-Bromo-4-methylpent-1-en-2-yl)(p-tolyl)sulfane (3s):
light yellow oil (135 mg, 95%); 1H NMR (400 MHz, CDCl3) δ 7.34 (d,
J = 7.6 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 6.21 (s, 1H), 2.36 (s, 3H), 1.97
(d, J = 6.8 Hz, 2H), 1.80ꢀ1.74 (m, 1H), 0.77 (s, 3H), 0.75 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 142.0, 138.2, 133.7, 129.7, 128.1, 103.1, 45.0,
26.4, 21.8, 21.2; IR (neat) 2985, 2922, 1576, 1491, 1459, 1385, 1254,
1212, 1068, 892, 808, 745 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for
C13H17BrS 284.0234, found 284.0245.
(Z)-(1-Bromodec-1-en-2-yl)(phenyl)sulfane (3l): light yellow
oil (152 mg, 93%); 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.2 Hz,
2H), 7.33ꢀ7.29 (m, 3H), 6.31 (s, 1H), 2.14 (t, J = 7.6 Hz, 2H),
1.44ꢀ1.39 (m, 2H), 1.28ꢀ1.15 (m, 10H), 0.88 (t, J = 7.0 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 142.7, 133.3, 132.3, 129.2, 128.2, 104.3,
36.4, 32.0, 29.4, 29.3, 28.9, 28.4, 22.9, 14.3; IR (neat) 2966, 2924, 2853,
1581, 1473, 1438, 1211, 1023, 741, 691, 652 cmꢀ1; HRMS (TOF MS
EIþ) m/z calcd for C16H23BrS 326.0704, found 326.0705.
(2-p-Tolylsulfanylethynyl)benzene (3t):24 white solid (86 mg,
77%); 1H NMR (400 MHz, CDCl3) δ 7.52ꢀ7.50 (m, 2H), 7.40 (d, J =
8.4 Hz, 2H), 7.37ꢀ7.33 (m, 3H), 7.18 (d, J = 8.0 Hz, 2H), 2.35 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 136.9, 131.9, 130.3, 129.5, 128.8, 128.6,
126.9, 123.3, 97.5, 76.4, 21.3.
(Z)-(1-Bromodec-1-en-2-yl)(p-tolyl)sulfane (3m): light yel-
low oil (160 mg, 94%); 1H NMR (400 MHz, CDCl3) δ 7.34 (d, J = 8.0
Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.23 (s, 1H), 2.36 (s, 3H), 2.10 (t, J =
7.4 Hz, 2H), 1.42ꢀ1.37 (m, 2H), 1.29ꢀ1.13 (m, 10H), 0.89 (t, J = 7.0
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 143.0, 138.2, 133.7, 129.8,
128.2, 102.4, 35.9, 31.8, 29.1, 29.0, 28.6, 28.2, 22.6, 21.2, 14.1; IR (neat)
2923, 2853, 1578, 1490, 1459, 1245, 1073, 1019, 808, 725 cmꢀ1; HRMS
(TOF MS EIþ) m/z calcd for C17H25BrS 340.0860, found 340.0859.
(Z)-Benzyl(1-bromodec-1-en-2-yl)sulfane (3n) and benzyl-
(dec-1-ynyl)sulfane (3w): obtained as a mixture, which could not be
separated by column chromatography. 3n (79 mg, 46%): 1H NMR (400
MHz, CDCl3) δ 7.37ꢀ7.32 (m, 5H), 6.17 (s, 1H), 4.01 (s, 2H), 2.27 (t, J =
8.0 Hz, 2H), 1.56ꢀ1.46 (m, 2H), 1.28 (br, 10H), 0.91 (t, J = 6.8 Hz, 3H).
3w (23 mg, 17%): 1H NMR (400 MHz, CDCl3) δ 7.30ꢀ7.24 (m, 5H),
3.89 (s, 1H), 2.27 (t, J = 8.0 Hz, 2H), 1.56ꢀ1.46 (m, 2H), 1.28 (br, 10H),
0.91 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 142.0, 137.2,
137.0, 128.9, 128.8, 128.5, 128.4, 127.5, 127.2, 103.3, 96.0, 67.9, 40.2, 36.6,
35.6, 31.8, 31.7, 29.2, 29.1, 29.0, 28.9, 28.8, 28.7, 28.2, 22.6, 20.1, 14.0; IR
(neat) 2924, 2853, 1576, 1494, 1455, 1236, 1070, 762, 698 cmꢀ1; HRMS
(TOF MS EIþ): 3n m/z calcd for C17H25BrS 340.0860, found 340.0872;
3w m/z calcd for C17H24S 260.1599, found 260.1595.
1-((Z)-1-Bromodec-1-en-2-yl)-2-((Z)-1-bromodec-1-en-2-ylthio)-
1H-benzimidazole (3u): light yellow oil (242 mg, 83%); 1H NMR (400
MHz, CDCl3) δ 7.80ꢀ7.77 (m, 1H), 7.31ꢀ7.27 (m, 1H), 7.19ꢀ7.16
(m, 1H), 6.64 (s, 1H), 6.52 (s, 1H), 2.67ꢀ2.56 (m, 2H), 2.49ꢀ2.41 (m,
2H), 1.54ꢀ1.51 (m, 2H), 1.46ꢀ1.38 (m, 2H), 1.33ꢀ1.20 (m, 20H),
0.88ꢀ0.83 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 144.8, 143.4,
140.3, 138.9, 134.9, 123.4, 122.7, 119.6, 110.3, 108.5, 107.5, 36.9, 36.4,
31.74, 31.71, 29.2, 29.12, 29.10, 29.08, 29.03, 28.7, 28.1, 26.8, 22.6, 14.0;
IR (neat) 2923, 2853, 1585, 1428, 1365, 1263, 798, 739 cmꢀ1; HRMS
(TOF MS EIþ) m/z calcd for C27H40Br2N2S 582.1279, found 582.1273.
(Z)-2-(1-Bromooct-1-en-2-ylthio)-1H-benzimidazole (3v):
1
white solid (144 mg, 85%); mp 123ꢀ125 °C; H NMR (400 MHz,
CDCl3) δ 10.48 (br, 1H), 7.66ꢀ7.62 (m, 2H), 7.28ꢀ7.25 (m, 2H), 6.33
(s, 1H), 2.35 (t, J = 7.6 Hz, 2H), 1.48ꢀ1.41 (m, 2H), 1.18ꢀ1.04 (m,
6H), 0.77 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 145.3,
139.8, 139.7, 123.2, 115.3, 107.1, 37.3, 31.6, 28.6, 28.3, 22.7, 14.2; IR
(KBr) 3447, 3072, 2954, 2926, 2606, 1584, 1407, 1351, 1267, 1230, 975,
834, 745 cmꢀ1; HRMS (TOF MS EIþ) m/z calcd for C15H19BrN2S
338.0452, found 338.0456.
(Z)-(1-Bromodec-1-en-2-yloxy)benzene (3o): light yellow oil
(39 mg, 25%); 1H NMR (400 MHz, CDCl3) δ 7.33 (t, J = 8.2 Hz, 2H),
7.07 (t, J = 7.2 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 5.76 (s, 1H), 2.24 (t, J =
7.4 Hz, 2H), 1.50ꢀ1.45 (m, 2H), 1.30ꢀ1.26 (m, 10H), 0.89 (t, J = 6.8
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 155.4, 155.0, 129.5, 122.6,
116.8, 91.3, 32.1, 31.8, 29.2, 29.1, 28.8, 26.3, 22.6, 14.0; IR (neat) 2925,
Representative Procedure for Amination of 1,1-Dibromo-
1-alkenes:
Synthesis of (Z)-1-(1-Bromodec-1-en-2-yl)-1H-benzimidazole
(5a) To a stirred solution of benzoimidazole (59 mg, 0.5 mmol) and
TBAF 3H2O (788 mg, 2.5 mmol) in DMF (1.0 mL) was added
3
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dx.doi.org/10.1021/jo2000176 |J. Org. Chem. 2011, 76, 2448–2458