4
W. He et al. / Tetrahedron xxx (2016) 1e5
d
9.66 (br, 1H), 7.86e7.81 (m, 4H), 7.56e7.54 (m, 2H), 7.50e7.43 (m,
J¼10.3 Hz), 132.2(d, J¼2.9 Hz), 132.7(d, J¼102.1 Hz), 137.1(d,
J¼3.6 Hz), 160.5(d, J¼2.2 Hz).
6H), 7.22 (d, J¼8.4 Hz, 2H), 2.1 (s, 3H). 31P NMR (162 MHz, CDCl3):
d
42.6 (s, 1P). 13C NMR (100 MHz, CDCl3):
d
24.5, 118.1 (d, J¼5.8 Hz),
120.3, 128.8(d, J¼13.1 Hz), 131.5(d, J¼10.2 Hz), 132.2(d, J¼106.4 Hz),
4.2.12. S-(2,4-dimethoxyphenyl) diphenylphosphinothioate (3l).
132.6(d, J¼2.1 Hz), 136.4(d, J¼2.9 Hz), 140.4, 169.4.
Colorless oil (153 mg, 52%). IR (KBr): 2354, 1210, 1114, 742,
555 cmꢂ1. 1H NMR (400 MHz, CDCl3):
d 7.89e7.84 (m, 4H), 7.58(dd,
4.2.6. S-(4-cyanophenyl) diphenylphosphinothioate (3f). White
solid (202 mg, 60%). Mp:107e109 ꢀC. IR (KBr): 2232, 1215, 1102, 755,
J1¼8.8 Hz, J2¼1.6 Hz, 1H), 7.49e7.45 (m, 2H), 7.42e7.37 (m, 4H),
6.42(dd, J1¼8.8 Hz, J2¼2.8 Hz, 1H), 6.25 (d, J¼2.4 Hz, 1H), 3.72 (s,
551 cmꢂ1. 1H NMR (400 MHz, CDCl3):
d
7.88e7.83 (m, 4H), 7.63e7.61
(m, 2H), 7.58e7.54 (m, 2H), 7.51e7.46 (m, 6H). 31P NMR (162 MHz,
CDCl3):
41.8 (s,1P).13C NMR (100 MHz, CDCl3):
3H), 3.50 (s, 3H). 31P NMR (162 MHz, CDCl3): 41.3 (s, 1P). 13C NMR
d
(100 MHz, CDCl3):
d
55.40, 55.43, 99.1(d, J¼2.2 Hz), 104.2(d,
d
d
112.5 (d, J¼1.4 Hz),
J¼5.8 Hz), 105.4, 128.2(d, J¼13.2 Hz), 131.6(d, J¼10.9 Hz), 132.1(d,
J¼2.9 Hz), 133.2(d, J¼105.0 Hz), 139.0(d, J¼3.7 Hz), 160.7(d,
J¼2.9 Hz), 162.3(d, J¼1.4 Hz).MS (ESI, m/z): 371.1 (MþH)þ. HRMS
(ESI): calcd. For C20H19O3PS (MþH)þ: 371.0862, found: 371.0865.
118.1, 128.9(d, J¼6.9 Hz), 131.6(d, J¼10.2 Hz), 131.8(d, J¼107.9 Hz),
132.4(br),132.8(d, J¼2.9 Hz),133.8(d, J¼5.1 Hz),135.2(d, J¼4.4 Hz).MS
(ESI, m/z): 336.0 (MþH)þ. Anal. Calcd. For C19H14NOPS(%): C, 68.05; H,
4.21; N, 4.18. Found: C, 68.22; H, 4.14; N, 4.04.
4.2.13. S-(4-fluorophenyl) diphenylphosphinothioate (3m). White
solid (272 mg, 83%). Mp: 94e96 ꢀC. 1H NMR (400 MHz, CDCl3):
4.2.7. S-(2-methyl-5-nitrophenyl) diphenylphosphinothioate (3g).
Light yellow solid (182 mg, 50%). Mp: 91e94 ꢀC. IR (KBr):1508,1434,
d
7.85(dd, J1¼13.2 Hz, J2¼7.6 Hz, 4H), 7.52e7.48 (m, 2H), 7.45e7.43
1204, 1113, 758, 554 cmꢂ1. 1H NMR (400 MHz, CDCl3):
d
8.11 (s, 1H),
(m, 6H), 6.89 (t, J¼8.0 Hz, 2H). 31P NMR (162 MHz, CDCl3):
d 41.4 (d,
8.00 (d, J¼8.8 Hz, 1H), 7.86(dd, J1¼12.8 Hz, J2¼7.2 Hz, 4H), 7.58e7.54
J¼3.9 Hz, 1P). 19F NMR (376 MHz, CDCl3):
ꢂ111.6 (d, J¼5.6 Hz, 1F).
d
(m, 2H), 7.51e7.46 (m, 4H), 7.34 (d, J¼8.4 Hz, 1H), 2.57 (s, 3H). 31P
13C NMR (100 MHz, CDCl3):
d
116.3(dd, J1¼21.9 Hz, J2¼1.4 Hz),
NMR (162 MHz, CDCl3):
d
42.0 (s, 1P). 13C NMR (100 MHz, CDCl3):
121.2(t, J¼4.3 Hz), 128.6(d, J¼13.2 Hz), 131.6(d, J¼10.2 Hz), 132.3(d,
J¼106.4 Hz), 132.5(d, J¼3.0 Hz), 137.4(dd, J1¼8.8 Hz, J2¼3.7 Hz),
163.4(dd, J1¼248.7 Hz, J2¼2.2 Hz).
d
22.0, 123.9(d, J¼2.2 Hz), 127.8(d, J¼5.8 Hz), 128.8(d, J¼13.8 Hz),
131.2(d, J¼1.5 Hz), 131.4(d, J¼4.4 Hz), 131.5(d, J¼10.2 Hz), 131.9(d,
J¼105.8 Hz), 132.9(d, J¼3.0 Hz), 145.9(d, J¼1.5 Hz), 151.4(d,
J¼2.9 Hz).MS (ESI, m/z):370.0 (MþH)þ. Anal. Calcd. For
4.2.14. S-(4-chlorophenyl) diphenylphosphinothioate (3n). White
solid (293 mg, 84%). Mp: 104e105 ꢀC. 1H NMR (400 MHz, CDCl3):
C
19H16NO3PS(%): C, 61.78; H, 4.37; N, 3.79. Found: C, 62.04; H, 4.30;
N, 3.61.
d 7.87e7.81 (m, 4H), 7.55e7.51 (m, 2H), 7.48e7.43 (m, 4H),
7.39e7.37 (m, 2H), 7.17 (d, J¼8.4 Hz, 2H). 31P NMR (162 MHz, CDCl3):
4.2.8. S-(4-methylphenyl) diphenylphosphinothioate (3h). White
solid (235 mg, 94%). Mp: 106e107 ꢀC. 1H NMR (400 MHz, CDCl3):
d
41.4 (s, 1P). 13C NMR (100 MHz, CDCl3):
d
124.8(d, J¼5.1 Hz),
128.7(d, J¼13.1 Hz), 129.3(d, J¼1.4 Hz), 131.6(d, J¼10.2 Hz), 132.3(d,
J¼106.5 Hz), 132.5(d, J¼2.9 Hz), 135.5(d, J¼2.2 Hz), 136.5(d,
J¼3.6 Hz).
d
7.85(dd, J1¼13.2 Hz, J2¼7.2 Hz, 4H), 7.51e7.49 (m, 2H), 7.44e7.40
(m, 4H), 7.32(d. J¼6.8 Hz, 2H), 6.99(d, 7.6 Hz, 2H), 2.23 (s, 3H). 31P
NMR (162 MHz, CDCl3):
d
41.2 (s, 1P). 13C NMR (100 MHz, CDCl3):
d
21.2, 122.3(d, J¼5.1 Hz), 128.5(d, J¼13.1 Hz), 130.0(d, J¼1.4 Hz),
4.2.15. S-(4-bromophenyl) diphenylphosphinothioate (3o). White
solid (328 mg, 84%). Mp: 102e103 ꢀC. 1H NMR (400 MHz, CDCl3):
131.7(d, J¼10.2 Hz), 132.3(d, J¼2.9 Hz), 132.7(d, J¼105.8 Hz),
135.4(d, J¼3.6 Hz), 139.2(d, J¼2.9 Hz). MS (ESI, m/z): 324.9 (MþH)þ.
d
7.87e7.82 (m, 4H), 7.51e7.48 (m, 2H), 7.45e7.40 (m, 4H),
7.33e7.29 (m, 4H). 31P NMR (162 MHz, CDCl3): 41.3 (s, 1P). 13C
NMR (100 MHz, CDCl3):
d
4.2.9. S-(3,5-dimethylphenyl) diphenylphosphinothioate (3i). White
solid (280 mg, 83%). Mp: 112e113 ꢀC. IR (KBr):1439,1204,1102, 755,
d
123.8(d, J¼2.9 Hz), 125.5(d, J¼5.1 Hz),
128.7(d, J¼13.1 Hz), 131.6(d, J¼10.2 Hz), 132.2(d, J¼106.4 Hz),
132.3(d, J¼2.2 Hz), 132.6(d, J¼2.9 Hz), 136.8(d, J¼3.7 Hz).
566 cmꢂ1
.
1H NMR (400 MHz, CDCl3):
d
7.88e7.83 (m, 4H),
7.52e7.49 (m, 2H), 7.46e7.43 (m, 4H), 7.03 (s, 2H), 6.86 (s, 1H), 2.16
(s, 6H). 31P NMR (162 MHz, CDCl3): 41.1 (s,1P). 13C NMR (100 MHz,
CDCl3):
d
4.2.16. S-(2-bromophenyl) diphenylphosphinothioate (3p). White
solid (292 mg, 75%). Mp:76e78 ꢀC. 1H NMR (400 MHz, CDCl3):
d
21.1, 125.3(d, J¼5.1 Hz), 128.5(d, J¼13.1 Hz), 130.8(d,
J¼2.2 Hz), 131.7(d, J¼10.2 Hz), 132.2(d, J¼3.0 Hz), 132.8(d,
J¼105.7 Hz), 133.1(d, J¼4.4 Hz), 138.7(d, J¼2.2 Hz).MS (ESI, m/z):
339.1 (MþH)þ. Anal. Calcd. For C20H19OPS(%): C, 70.98; H, 5.66.
Found: C, 71.21; H, 5.62.
d 7.94e7.85 (m, 5H), 7.52e7.48 (m, 2H), 7.46e7.41 (m, 5H), 7.18(td,
J1¼8.0 Hz, J2¼1.2 Hz, 1H), 7.07e7.03 (m, 1H). 31P NMR (162 MHz,
CDCl3):
d d 127.9, 128.3(d,
42.2 (s, 1P). 13C NMR (100 MHz, CDCl3):
J¼5.1 Hz), 128.6(d, J¼13.2 Hz), 129.0(d, J¼4.4 Hz), 130.0, 131.7(d,
J¼10.2 Hz), 132.2(d, J¼107.2 Hz), 132.6(d, J¼2.9 Hz), 133.4, 136.5 (d,
J¼4.4 Hz).
4.2.10. S-(2,4,6-thimethylphenyl) diphenylphosphinothioate (3j).
White solid (124 mg, 41%). Mp: 95e96 ꢀC. IR (KBr): 1437, 1193, 1112,
723, 567 cmꢂ1
.
1H NMR (400 MHz, CDCl3):
d
7.79e7.74 (m, 4H),
7.54e7.50 (m, 2H), 7.44e7.39 (m, 4H), 6.84 (s, 2H), 2.24 (s, 6H), 2.23
(s, 3H). 31P NMR (162 MHz, CDCl3): 39.4 (s, 1P). 13C NMR (100 MHz,
CDCl3):
4.2.17. S-(3-bromophenyl) diphenylphosphinothioate (3q). White
solid (319 mg, 82%). Mp: 93e95 ꢀC. 1H NMR (400 MHz, CDCl3):
d
d
7.85(dd, J1¼13.2 Hz, J2¼7.2 Hz, 4H), 7.55e7.41 (m, 8H), 7.34 (d,
d
21.0, 22.4, 120.8(d, J¼6.6 Hz), 128.4(d, J¼13.1 Hz), 129.4(d,
J¼8.0 Hz, 1H), 7.03 (t, J¼7.6 Hz, 1H). 31P NMR (162 MHz, CDCl3):
J¼2.2 Hz), 131.4(d, J¼10.2 Hz), 132.2(d, J¼2.9 Hz), 133.5(d,
J¼105.0 Hz), 139.3(d, J¼2.9 Hz), 144.8(d, J¼3.6 Hz).MS (ESI, m/z):
353 (MþH)þ. HRMS (ESI): calcd. For C21H21OPS (MþH)þ: 353.1119,
found: 353.1123.
d
41.5 (s, 1P). 13C NMR (100 MHz, CDCl3):
d
122.5(d, J¼2.2 Hz),
128.4(d, J¼5.1 Hz), 128.7(d, J¼13.1 Hz), 130.3(d, J¼1.4 Hz), 131.6(d,
J¼10.2 Hz), 132.1(d, J¼106.5 Hz), 132.1(d, J¼2.1 Hz), 132.6(d,
J¼3.7 Hz), 133.9(d, J¼4.4 Hz), 137.6(d, J¼3.6 Hz).
4.2.11. S-(4-methoxyphenyl) diphenylphosphinothioate (3k). White
solid (230 mg, 68%). Mp: 131e134 ꢀC. 1H NMR (400 MHz, CDCl3):
4.2.18. S-naphthalen-1-yl diphenylphosphinothioate (3r). White
solid (323 mg, 90%). Mp: 106e107 ꢀC. 1H NMR (400 MHz, CDCl3):
d
7.87e7.81 (m, 4H), 7.53e7.49 (m, 2H), 7.46e7.41 (m, 4H),7.34e7.32
d
8.41 (d, J¼8.4 Hz, 1H), 7.85e7.80 (m, 5H), 7.71 (t, J¼7.6 Hz, 2H),
7.47e7.38 (m, 4H), 7.34e7.25 (m, 5H). 31P NMR (162 MHz, CDCl3):
41.4 (s, 1P). 13C NMR (100 MHz, CDCl3):
123.7(d, J¼5.9 Hz),
125.6(d, J¼2.2 Hz), 126.0, 126.2, 126.8, 128.3, 128.5(d, J¼13.1 Hz),
(m, 2H), 6.73 (d, J¼9.2 Hz, 2H), 3.73 (s, 3H). 31P NMR (162 MHz,
CDCl3):
d
41.2 (s, 1P). 13C NMR (100 MHz, CDCl3):
d
55.3, 114.8(d,
d
d
J¼1.4 Hz), 116.1(d, J¼5.1 Hz), 128.5(d, J¼13.2 Hz), 131.7(d,