512 Bull. Chem. Soc. Jpn. Vol. 81, No. 4 (2008)
Hydrothiolation of Electron-Rich Alkynes
2967, 2926, 2855, 1458, 1362, 1252, 1203, 722 cmꢁ1
;
1H NMR
1.20–1.36 (m, 6H), 1.40–1.48 (m, 2H), 2.33 (s, 3H), 2.39–2.46 (m,
2H), 6.65–6.71 (m, 1H), 7.00 (dd, J ¼ 2:0, 7.5 Hz, 2H), 7.07 (d,
J ¼ 7:5 Hz, 2H), 7.37–7.43 (m, 4H), 7.45–7.51 (m, 2H), 7.84–
7.90 (m, 4H); 13C NMR (CDCl3) ꢀ 14.06, 21.03, 22.53, 28.81,
28.85 (d, J ¼ 8:0 Hz), 31.53, 32.12 (d, J ¼ 4:0 Hz), 121.45 (d,
J ¼ 7:1 Hz), 121.47 (d, J ¼ 7:6 Hz), 128.25 (d, J ¼ 13:4 Hz),
129.56, 131.08, 131.65 (d, J ¼ 2:9 Hz), 131.79 (d, J ¼ 11:0 Hz),
133.78 (d, J ¼ 83:6 Hz), 136.40, 156.27 (d, J ¼ 6:6 Hz); 31P NMR
(CDCl3) ꢀ 63.68. Anal. Found: C, 67.09; H, 6.43%. Calcd for
C27H31PS3: C, 67.18; H, 6.47%.
(CDCl3) ꢀ 0.88 (t, J ¼ 7:0 Hz, 3H), 1.22 (s, 9H), 1.23–1.33 (m,
16H), 1.34–1.44 (m, 2H), 1.70 (tt, J ¼ 7:0, 7.5 Hz, 2H), 2.64 (t,
J ¼ 7:5 Hz, 2H); 13C NMR (CDCl3) ꢀ 14.09, 22.67, 28.22, 28.69,
29.01, 29.14, 29.33, 29.46, 29.58, 29.62, 29.65, 31.00, 31.90,
35.49, 67.05, 102.08. Anal. Found: C, 76.54; H, 12.26%. Calcd
for C18H34S: C, 76.52; H, 12.13%.
Dodecyl Ethynyl Sulfide (12j): IR (neat) 3309, 2925, 2854,
1
2044, 1466, 1061, 722, 666, 530 cmꢁ1; H NMR (CDCl3) ꢀ 0.88
(t, J ¼ 7:0 Hz, 3H), 1.20–1.35 (m, 16H), 1.36–1.44 (m, 2H), 1.74
(tt, J ¼ 7:0, 7.5 Hz, 2H), 2.73 (t, J ¼ 7:5 Hz, 2H), 2.74 (s, 1H);
13C NMR (CDCl3) ꢀ 14.10, 22.68, 28.22, 29.07, 29.14, 29.33,
29.46, 29.56, 29.62, 29.63, 31.91, 35.11, 74.76, 81.69. Anal.
Found: C, 74.21; H, 11.74%. Calcd for C14H26S: C, 74.26; H,
11.57%.
(E)-1-Dodecylsulfanyl-2-p-methoxyphenylethenyl Diphenyl-
dithiophosphinate (13e): IR (neat) 2925, 2853, 1605, 1506,
;
1437, 1252, 1177, 1097, 1034, 722 cmꢁ1 1H NMR (CDCl3) ꢀ
0.90 (t, J ¼ 7:0 Hz, 3H), 1.14–1.36 (m, 18H), 1.40–1.48 (m, 2H),
2.72 (t, J ¼ 7:5 Hz, 2H), 3.80 (s, 3H), 6.85 (d, J ¼ 9:0 Hz, 2H),
7.08 (d, J ¼ 3:5 Hz, 1H), 7.44–7.54 (m, 8H), 8.00–8.06 (m, 4H);
13C NMR (CDCl3) ꢀ 14.06, 22.61, 28.61, 29.06, 29.27, 29.32,
29.38, 29.48, 29.55, 29.57, 31.83, 34.32, 55.15, 113.30, 121.79
(d, J ¼ 8:1 Hz), 128.35 (d, J ¼ 13:4 Hz), 128.60 (d, J ¼ 2:9 Hz),
131.28 (d, J ¼ 1:4 Hz), 131.80 (d, J ¼ 11:0 Hz), 131.80 (d, J ¼
3:3 Hz), 133.86 (d, J ¼ 82:6 Hz), 146.08 (d, J ¼ 7:6 Hz), 159.37;
31P NMR (CDCl3) ꢀ 63.40. Anal. Found: C, 67.81; H, 7.44%.
Calcd for C33H43OPS3: C, 68.00; H, 7.44%.
(E)-1-Dodecylsulfanyl-2-o-methoxyphenylethenyl Diphenyl-
dithiophosphinate (13f): IR (neat) 3056, 2924, 2853, 1597,
1481, 1464, 1436, 1247, 1097, 748, 720, 690, 654 cmꢁ1; 1H NMR
(CDCl3) ꢀ 0.90 (t, J ¼ 7:0 Hz, 3H), 1.14–1.32 (m, 18H), 1.36–
1.44 (m, 2H), 2.67 (t, J ¼ 7:5 Hz, 2H), 3.76 (s, 3H), 6.82 (d,
J ¼ 7:5 Hz, 1H), 6.91 (dd, J ¼ 7:5, 7.5 Hz, 1H), 7.22–7.27 (m,
1H), 7.35 (d, J ¼ 4:0 Hz, 1H), 7.44–7.54 (m, 6H), 7.60 (d, J ¼
7:5 Hz, 1H), 8.01–8.08 (m, 4H); 13C NMR (CDCl3) ꢀ 14.07,
22.63, 28.63, 29.09, 29.12, 29.29, 29.40, 29.51, 29.57, 29.59,
31.85, 34.19, 55.37, 110.16, 119.71, 124.77 (d, J ¼ 8:1 Hz),
124.84 (d, J ¼ 2:4 Hz), 128.35 (d, J ¼ 13:4 Hz), 129.63, 130.66
(d, J ¼ 1:9 Hz), 131.76 (d, J ¼ 2:9 Hz), 131.86 (d, J ¼ 11:0 Hz),
133.94 (d, J ¼ 83:0 Hz), 141.30 (d, J ¼ 7:6 Hz), 156.90 (d, J ¼
0:9 Hz); 31P NMR (CDCl3) ꢀ 63.16. Anal. Found: C, 68.03; H,
7.31%. Calcd for C33H43OPS3: C, 68.00; H, 7.44%.
(E)-1-Dodecylsulfanyl-2-p-(trifluoromethyl)phenylethenyl
Diphenyldithiophosphinate (13g): IR (neat) 2926, 2854, 1437,
1324, 1167, 1126, 1068, 908, 722 cmꢁ1; 1H NMR (CDCl3) ꢀ 0.91
(t, J ¼ 7:5 Hz, 3H), 1.16–1.36 (m, 18H), 1.42–1.50 (m, 2H), 2.75
(t, J ¼ 7:5 Hz, 2H), 7.14 (d, J ¼ 3:0 Hz, 1H), 7.44–7.62 (m, 10H),
8.00–8.08 (m, 4H); 13C NMR (CDCl3) ꢀ 14.04, 22.60, 28.54,
29.02, 29.26, 29.36 (ꢃ2), 29.46, 29.54, 29.55, 31.82, 34.48,
123.96 (q, J ¼ 270:5 Hz), 124.83 (q, J ¼ 3:8 Hz), 128.44 (d,
J ¼ 4:8 Hz), 128.49 (d, J ¼ 8:1 Hz), 129.39 (d, J ¼ 32:5 Hz),
129.65 (d, J ¼ 1:4 Hz), 131.77 (d, J ¼ 10:9 Hz), 132.00 (d,
J ¼ 2:9 Hz), 133.62 (d, J ¼ 83:5 Hz), 139.15 (d, J ¼ 1:0 Hz),
143.17 (d, J ¼ 7:6 Hz); 31P NMR (CDCl3) ꢀ 63.87. Anal. Found:
C, 63.71; H, 6.47%. Calcd for C33H40F3PS3: C, 63.84; H, 6.49%.
(E)-2-Cyclohexyl-1-(dodecylsulfanyl)ethenyl Diphenyldi-
(E)-1-Dodecylsulfanyl-2-phenylethenyl Diphenyldithiophos-
phinate (13a): IR (neat) 3056, 2925, 2853, 1437, 1097, 925,
749, 721, 690, 655 cmꢁ1
;
1H NMR (CDCl3) ꢀ 0.90 (t, J ¼ 7:0
Hz, 3H), 1.14–1.34 (m, 18H), 1.38–1.46 (m, 2H), 2.71 (t, J ¼
8:0 Hz, 2H), 7.12 (d, J ¼ 3:5 Hz, 1H), 7.23–7.27 (m, 1H), 7.29–
7.34 (m, 2H), 7.45–7.56 (m, 8H), 8.00–8.07 (m, 4H); 13C NMR
(CDCl3) ꢀ 14.10, 22.65, 28.63, 29.09, 29.31, 29.36, 29.41, 29.51,
29.59, 29.60, 31.88, 34.40, 125.02 (d, J ¼ 8:1 Hz), 127.94,
128.07, 128.44 (d, J ¼ 13:4 Hz), 129.61 (d, J ¼ 1:5 Hz), 131.85
(d, J ¼ 10:9 Hz), 131.91 (d, J ¼ 3:4 Hz), 133.81 (d, J ¼ 83:0
Hz), 135.84 (d, J ¼ 2:9 Hz), 145.73 (d, J ¼ 7:6 Hz); 31P NMR
(CDCl3) ꢀ 63.45. Anal. Found: C, 69.64; H, 7.50%. Calcd for
C32H41PS3: C, 69.52; H, 7.47%.
(E)-2-Phenyl-1-p-tolylsulfanylethenyl Diphenyldithiophos-
phinate (13b):
IR (nujol) 2924, 2855, 1458, 1437, 1377,
1H NMR (CDCl3) ꢀ 2.31
1095, 928, 898, 813, 718, 652 cmꢁ1
;
(s, 3H), 7.02 (d, J ¼ 8:0 Hz, 2H), 7.07 (d, J ¼ 8:0 Hz, 2H),
7.22–7.34 (m, 3H), 7.36–7.42 (m, 4H), 7.46–7.52 (m, 3H), 7.57
(d, J ¼ 7:5 Hz, 2H), 7.80–7.94 (m, 4H); 13C NMR (CDCl3) ꢀ
21.11, 123.39 (d, J ¼ 8:1 Hz), 128.07, 128.35 (d, J ¼ 13:4 Hz),
128.71, 129.60 (d, J ¼ 1:4 Hz), 129.65, 130.43, 130.55, 131.80
(d, J ¼ 3:3 Hz), 131.87 (d, J ¼ 10:9 Hz), 133.67 (d, J ¼ 83:0
Hz), 135.53 (d, J ¼ 2:4 Hz), 137.06, 149.55 (d, J ¼ 7:1 Hz);
31P NMR (CDCl3) ꢀ 64.81. Anal. Found: C, 68.03; H, 5.03%.
Calcd for C27H23PS3: C, 68.32; H, 4.88%. mp 87.5–88.0 ꢂC. The
crystal data have been deposited at CCDC, Cambridge, UK and
given the reference number CCDC 670503. Copies of the data
conts/retrieving.html (or from the Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge, CB2 1EZ, UK; Fax:
+44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk).
(E)-1-Dodecylsulfanyl-1-octenyl Diphenyldithiophosphinate
IR (neat) 3056, 2924, 2854, 1457, 1437, 1097, 852,
1H NMR (CDCl3) ꢀ 0.88 (t, J ¼ 7:0
(13c):
748, 721, 690, 656 cmꢁ1
;
Hz, 6H), 1.18–1.45 (m, 28H), 2.25–2.33 (m, 2H), 2.60 (t,
J ¼ 7:5 Hz, 2H), 6.30 (dt, J ¼ 3:5, 7.5 Hz, 1H), 7.42–7.53 (m,
6H), 7.95–8.20 (m, 4H); 13C NMR (CDCl3) ꢀ 14.08 (ꢃ2),
22.55, 22.65, 28.60, 28.77 (d, J ¼ 2:4 Hz), 28.83, 29.17, 29.32,
29.49, 29.56 (ꢃ2), 29.61, 29.62, 31.61, 31.72 (d, J ¼ 1:9 Hz),
31.88, 33.41, 122.64 (d, J ¼ 7:6 Hz), 128.33 (d, J ¼ 13:4 Hz),
131.80 (d, J ¼ 11:0 Hz), 134.05 (d, J ¼ 83:1 Hz), 148.04 (d,
J ¼ 7:1 Hz), 152.70 (d, J ¼ 7:8 Hz); 31P NMR (CDCl3) ꢀ 62.34.
Anal. Found: C, 68.73; H, 8.72%. Calcd for C32H49PS3: C,
68.52; H, 8.80%.
thiophosphinate (13h):
IR (neat) 3056, 2925, 2852, 1956,
1899, 1810, 1437, 1097, 721, 690, 656 cmꢁ1; 1H NMR (CDCl3) ꢀ
0.89 (t, J ¼ 7:5 Hz, 3H), 1.00–1.34 (m, 23H), 1.36–1.46 (m, 2H),
1.56–1.70 (m, 5H), 2.56–2.66 (m, 3H), 6.17 (dd, J ¼ 3:5, 10.0 Hz,
1H), 7.41–7.52 (m, 6H), 7.95–8.02 (m, 4H); 13C NMR (CDCl3) ꢀ
14.05, 22.60, 25.37, 25.76, 28.53, 29.13, 29.26, 29.43, 29.45,
29.51, 29.54, 29.57, 31.83, 32.14 (d, J ¼ 2:4 Hz), 33.27, 40.70 (d,
J ¼ 0:9 Hz), 120.86 (d, J ¼ 7:6 Hz), 128.26 (d, J ¼ 13:4 Hz),
131.65 (d, J ¼ 2:9 Hz), 131.76 (d, J ¼ 11:0 Hz), 134.02 (d, J ¼
83:0 Hz), 157.86 (d, J ¼ 7:1 Hz); 31P NMR (CDCl3) ꢀ 62.13.
(E)-1-p-Tolylsulfanyl-1-octenyl Diphenyldithiophosphinate
(13d): IR (neat) 2954, 2925, 2855, 2370, 1491, 1437, 1097,
1
805, 721 655 cmꢁ1; H NMR (CDCl3) ꢀ 0.89 (t, J ¼ 7:0 Hz, 3H),