Page 15 of 25
The Journal of Organic Chemistry
N-Cyclohexyl-P-(3-fluorobenzyloxyl)-P-phenylphosphonic amide (3ia): White solid (131.4 mg, 76%),
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m.p.: 101 - 102 C. H NMR (400 MHz, CDCl3) δ = 7.83 (dd, J = 13.0, 7.3 Hz, 2H), 7.55 – 7.48 (m,
1H), 7.48 – 7.41 (m, 2H), 7.34 – 7.27 (m, 1H), 7.17 – 7.06 (m, 2H), 7.04 – 6.95 (m, 1H), 5.12 – 4.98 (m,
2H), 3.08 – 2.94 (m, 1H), 2.87 – 2.70 (m, 1H), 1.88 – 1.77 (m, 2H), 1.68 – 1.59 (m, 2H), 1.56 – 1.48 (m,
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1H), 1.27 – 1.04 (m, 5H) (ppm). 13C NMR (100 MHz, CDCl3) δ = 163.0 (JC-F = 246.3 Hz), 139.6 (JC-P
7.5 Hz), 132.0 (JC-P = 3.0 Hz), 131.6 (JC-P = 9.8 Hz), 131.3 (JC-P = 172.6 Hz), 130.2 (JC-P = 8.2 Hz),
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128.5 (JC-P = 14.3 Hz), 123.0 (JC-P = 3.0 Hz), 115.0 (JC-P = 21.1 Hz), 114.4 (JC-P = 22.1 Hz), 65.1 (JC-P
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5.0 Hz), 50.1, 36.0 (JC-P = 15.8 Hz), 25.4, 25.1 (ppm). F NMR (376 MHz, CDCl3) δ = -112.8 (ppm).
31P NMR (100 MHz, CDCl3) δ = 22.3 (ppm). MS (EI): m/z (%): 56.1 (11), 77.1 (11), 98.1 (22), 109.1
(83), 141.1 (13), 158.1 (13), 196.1 (20), 238.1 (100), 239.1 (17), 304.1 (60), 347.2 (19). IR (in KBr): ν =
3167, 2927, 2852, 1591, 1454, 1211, 1132, 1034, 922, 854, 787, 744, 688, 548, 511 (cm-1).
HRMS (ESI) (m/z) [M + H+]: Calcd. for C19H23FNO2P: 348.1529; Found. 348.1535.
P-(4-Chlorobenzyloxyl)-N-cyclohexyl-P-phenylphosphonic amide (3ja): White solid (163.3 mg, 90%),
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m.p.: 114 - 115 C. H NMR (400 MHz, CDCl3) δ = 7.80 (dd, J = 12.9, 7.7 Hz, 2H), 7.55 – 7.48 (m,
1H), 7.47 – 7.40 (m, 2H), 7.31 (bs, 4H), 5.08 – 4.96 (m, 2H), 3.05 – 2.92 (m, 1H), 2.76 – 2.63 (m, 1H),
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1.87 – 1.76 (m, 2H), 1.68 – 1.58 (m, 2H), 1.55 – 1.47 (m, 1H), 1.28 – 1.03 (m, 5H) (ppm). C NMR
(100 MHz, CDCl3) δ = 135.5 (JC-P = 7.2 Hz), 134.1, 132.0 (JC-P = 3.0 Hz), 131.6 (JC-P = 9.8 Hz), 131.3
(JC-P = 172.5 Hz), 129.2, 128.8, 128.6 (JC-P = 14.3 Hz), 65.2 (JC-P = 5.1 Hz), 50.1, 36.0 (JC-P = 15.3 Hz),
25.4, 25.1 (ppm). 31P NMR (100 MHz, CDCl3) δ = 22.4 (ppm). MS (EI): m/z (%): 91.1 (15), 98.1 (19),
125.0 (100), 127.0 (31), 141.1 (13), 238.1 (97), 239.1 (13), 320.1 (26), 363.2 (20). IR (in KBr): ν =
3184, 2924, 2850, 1444, 1211, 1134, 1047, 998, 857, 763, 559, 523 (cm-1). HRMS (ESI) (m/z) [M +
H+]: Calcd. for C19H24ClNO2P: 364.1233, Found. 364.1228.
P-(2-Bromobenzyloxyl)-N-cyclohexyl-P-phenylphosphonic amide (3ka): White solid (152.3 mg, 75%),
m.p.: 92 - 93 oC. 1H NMR (400 MHz, CDCl3) δ = 7.84 (dd, J = 12.9, 7.6 Hz, 2H), 7.56 – 7.47 (m, 3H),
7.46 – 7.39 (m, 2H), 7.30 (t, J = 7.5 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 5.22 – 5.13 (m, 1H), 5.13 – 5.05
(m, 1H), 3.08 – 2.94 (m, 1H), 2.92 – 2.82 (m, 1H), 1.87 – 1.76 (m, 2H), 1.67 – 1.57 (m, 2H), 1.54 – 1.45
(m, 1H), 1.25 – 1.01 (m, 5H) (ppm). 13C NMR (101 MHz, CDCl3) δ = 136.3 (JC-P = 8.2 Hz), 132.7,
131.9 (JC-P = 2.9 Hz), 131.5 (JC-P = 9.8 Hz), 131.4 (JC-P = 173.3 Hz), 129.5, 129.2, 128.5 (JC-P = 14.3
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Hz), 127.6, 122.6, 65.4 (JC-P = 4.6 Hz), 50.1, 36.0 (JC-P = 19.0 Hz), 25.4, 25.1 (ppm). P NMR (100
MHz, CDCl3) δ = 22.2 (ppm). MS (EI): m/z = 90.1 (16), 98.1 (13), 169.0 (54), 171.0 (53), 238.1 (51),
246.1 (14), 328.2 (100), 329.2 (21), 364.0 (22), 366.0 (21), 407.1 (2), 409.1 (2). IR (in KBr): ν = 3192,
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