P.-Y. Renard, C. Mioskowski et al.
FULL PAPER
7.5 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d 174.1, 112.2 (SCN), 53.5;
(d, 3J(P,C) 14 Hz, 2C), 118.7, 62.7 (d, 2J(P,C) 7.5 Hz), 28.8, 26.6, 16.4 (d,
4J(P,C) 7.5 Hz), 15.9; 31P NMR (121.5 MHz, CDCl3): d 44.20; IR (neat):
nÄ 2984, 2926, 2247 (CN), 1439, 1227, 1119, 1021, 956 cmÀ1; MS (I.C./NH3):
48.4, 41.2, 31.6, 26.9, 21.3, 9.4; IR (neat): nÄ 2979, 2154 (SCN), 1742, 1639
(C O), 1461, 1422, 1158, 1071 cmÀ1; MS (I.C./NH3): m/z (%): 201 [MH]
(40), 218 [MNH4] (100).
m/z (%): 287 [MNH4] ; elemental analysis calcd (%) for C11H17O3PS: C
50.76, H 6.58; found C 50.65, H 6.71.
[(Cyclohexylamino)thioxomethyl]-phenylphosphinic O-ethyl ester (5): A
mixture of thiocyanato cyclohexane 3b (141 mg, 1 mmol), diisopropyl-
ethylamine (174 mL, 1 mmol), and ethyl phenylphosphinate 4a (151 mL,
1 mmol) in dry DMF (10 mL) was heated under reflux for 4 h. After the
mixture had cooled, DMF and amine were evaporated under vacuum, and
the crude reaction mixture was chromatographed (CH2Cl2/acetone 9:1) to
yield thioamide 5 (243 mg, 78%) as a pale yellow powder. M.p. 109
109.58C; 1H NMR (300.15 MHz, CDCl3): d 9.45 (brt, 1H; NH), 7.98
(m, 2H), 7.57 (m, 1H), 7.45 (m, 2H), 4.39 (m, 1H), 4.15 (m, 2H), 2.10 (m,
1H), 1.98 (m, 1H), 1.80 1.60 (m, 4H), 1.38 (t, 3J(H,H) 7.5 Hz, 3H), 1.35
(m, 2H), 1.23 (m, 2H); 13C NMR (75.4 MHz, CDCl3): d 193.8 (d,
Diphenylphosphinothioic S-cyclohexyl ester (6b): Pale orange crystals;
m.p. 81 828C; 1H NMR (300.15 MHz, CDCl3): d 7.90 7.80 (m, 4H),
7.52 7.35 (m, 6H), 3.27 (q of t, 1H, 2J(H,P) 3J(Hax,Hax) 10.5 Hz,
3J(Hax,Heq) 3.5 Hz), 1.96 1.81 (m, 2H), 1.69 1.57 (m, 2H), 1.55 1.40
(m, 3H), 1.33 1.15 (m, 3H); 13C NMR (75.4 MHz, CDCl3): d 134.2 (d,
1J(P,C) 105 Hz, 2C), 132.2 (2C), 131.45 (d, 2J(P,C) 9.5 Hz, 4C), 128.6 (d,
3J(P,C) 12 Hz, 4C), 44.5, 35.6 (d, 3J(P,C) 5 Hz, 2C), 25.8 (2C), 25.35; 31
P
NMR (121.5 MHz, CDCl3): d 42.49; IR (KBr): nÄ 3057, 2931, 2853, 1438,
1196, 1114, 996, 751, 726, 698, 570 cmÀ1; MS (ESI-TOF): m/z (%): 316 [M]
(100), 338 [MNa] (30); elemental analysis calcd (%) for C18H21OPS:
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1J(P,C) 119 Hz), 133.2, 133.1 (d, J(P,C) 12 Hz, 2C) 128.3 (d, J(P,C)
12 Hz, 2C), 127.55 (d, 1J(P,C) 144 Hz), 62.7 (d, 2J(P,C) 5 Hz), 54.2 (d,
3J(P,C) 5 Hz), 31.1, 31.0, 25.4, 24.9 (2C), 16.4 (d, 4J(P,C) 5 Hz); 31P
NMR (121.5 MHz, CDCl3): d 19.59; MS (I.C./NH3): m/z (%): 312
C 68.33, H 6.69; found C 68.33; H 6.66.
Diphenylphosphinothioic S-benzyl ester (6c): Colorless crystals; m.p. 87
888C; 1H NMR (300.15 MHz, CDCl3): d 7.92 7.83 (m, 4H), 7.54 7.39
(m, 6H), 7.22 7.15 (m, 5H), 4.03 (d, 3J(P,H) 9 Hz, 2H); 13C NMR
(75.4 MHz, CDCl3): d 136.8, 133.1 (d, 1J(P,C) 107 Hz, 2C), 132.4 (2C),
131.6 (d, 2J(P,C) 9 Hz, 2C), 129.0 (d, 3J(P,C) 14 Hz, 2C), 128.8 (4C),
127.5, 33.3; 31P NMR (121.5 MHz, CDCl3): d 43.40; IR (KBr): nÄ 3058,
[MH] (80), 329 [MNH4] (100).
General procedure for phosphonothioate formation: Phosphazene P4-tBu
(1.0 m in n-hexanes, 0.025 mL, as supplied by Fluka) was added to a
mixture of phosphinate (2.5 mmol, as supplied by Aldrich) and alkyl
thiocyanate (2.5 mmol, prepared as previously described) in toluene
(10 mL).
1437, 1192, 1114, 996 cmÀ1; MS (I.C./NH3): m/z (%): 325 [MH] (70), 342
[MNH4] (100); elemental analysis calcd (%) for C19H17OPS: C, 70.35, H,
5.28; found C, 70.52; H, 5.31.
Diphenylphosphinothioic S-(3-hydroxypropyl) ester (6d): Pale yellow oil;
1H NMR (300.15 MHz, CDCl3): d 7.92 7.81 (m, 4H), 7.61 7.43 (m, 6H),
Caution: In order to remove produced hydrogen cyanide, a gentle nitrogen
flow to a bubbling bottle containing 1.0m aqueous sodium hydroxide
solution has to be used, and the pH of the solution was regularly checked
and maintained (>12). Once TLC or GC/MC indicated the complete
consumption of the starting products, the solvents were evaporated, and the
crude reaction mixture was directly chromatographed on silica gel (CH2Cl2/
acetone 8:2).
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3.79 (t, J(H,H) 6.0 Hz, 2H) 2.93 (dt, J(P,H) 13 Hz, J(H,H) 6.0 Hz,
2H), 1.83 (quint., J(H,H) 6.0 Hz, 2H); 13C NMR (75.4 MHz, CDCl3): d
132.9 (d, 1J(P,C) 108 Hz, 2C), 132.6 (2C), 131.6 (d, 2J(P,C) 6 Hz, 2C),
128.8 (d, 3J(P,C) 14 Hz, 2C), 58.4, 33.1, 25.8; 31P NMR (121.5 MHz,
CDCl3): d 46.92; IR (neat): nÄ 3383 (broad), 3058, 2932, 2871, 1436, 1183,
1114, 1065 cmÀ1
[MNH4] (30).
;
MS (I.C./NH3): m/z (%): 293 [MH] (100), 310
Phenylphosphonothioic acid S-cyclohexyl ester O-ethyl ester (4b): Color-
1
less oil; H NMR (300.15 MHz, CDCl3): d 7.90 7.80 (m, 2H), 7.61 7.55
(m, 1H), 7.52 7.45 (m, 2H), 4.21 (m, 2H), 3.15 (q of t, 3J(P,H)
3J(Hax,Hax) 11 Hz, 3J(Hax,Heq) 4 Hz, 1H), 1.90 (m, 1H), 1.80 (m, 1H),
1.70 1.55 (m, 2H), 1.50 1.10 (m, 5H), 1.30 (t, 3J(H,H) 7.0 Hz, 3H);
Diphenylphosphinothioic acid S-(3-cyanopropyl) ester (6e): Pale yellow
1
oil; H NMR (300.15 MHz, CDCl3): d 7.92 7.80 (m, 4H), 7.59 7.42 (m,
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6H), 2.87 (dt, J(P,H) 14.5 Hz, J(H,H) 7.0 Hz, 2H), 2.46 (t, J(H,H)
7.0 Hz, 2H), 2.01 (quint., J(H,H) 7.0 Hz, 2H); 13C NMR (75.4 MHz,
CDCl3): d 134.7 (d, 1J(P,C) 110 Hz, 2C), 132.7 (2C), 131.5 (d, 2J(P,C)
1
13C NMR (75.4 MHz, CDCl3): d 132.4 (d, J(P,C) 105 Hz), 132.4, 131.1
(d, 2J(P,C) 10 Hz, 2C), 128.5 (d, 3J(P,C) 11 Hz, 2C), 62.1 (d, 2J(P,C)
7 Hz), 45.1, 35.5 (d, J(P,C) 5 Hz), 35.34 (d, 3J(P,C) 5 Hz), 25.9 (2C,
4J(P,C) 5 Hz), 25.34, 16.4 (d, 4J(P,C) 7.5 Hz) ; 31P NMR (121.5 MHz,
CDCl3): d 44.70; IR (neat): nÄ 2982, 2931, 2854, 1441, 1231, 1118, 1024,
7 Hz, 2C), 128.9 (d, 3J(P,C) 12 Hz, 2C), 118.8 (CN), 28.1, 26.6, 15.95; 31
P
NMR (121.5 MHz, CDCl3): d 44.00; IR (neat): nÄ 3058, 2929, 2247 (CN),
1589, 1481, 1436, 1196, 1115, 1097 cmÀ1; MS (I.C./NH3): m/z (%): 302
952 cmÀ1; MS (ESI-TOF): m/z (%): 285 [MH] ; elemental analysis calcd
[MH] (40), 319 [MNH4] (100).
(%) for C14H21O2PS: C 59.13, H 7.44; found C 58.85; H 7.24.
Thiophosphoric S-cyclohexyl ester O,O'-diethyl ester (7b): Pale orange oil;
1H NMR (300.15 MHz, CDCl3): d 4.12 (m, 4H); 3.21 (q of t, 3J(P,H)
3J(Hax,Hax) 11.5 Hz; 3J(Hax,Heq) 3.5 Hz, 1H), 2.05 (m, 2H), 1.75 (m,
2H), 1.55 1.20 (m, 6H), 1.32 (t, 3J(H,H) 7.0 Hz, 3H); 13C NMR
(75.4 MHz, CDCl3): d 63.45 (d, 2J(P,C) 5 Hz, 2C), 45.6 (d, 2J(P,C)
5 Hz), 35.35, 35.3, 25.9 (2C), 25.3, (d, 3J(P,C) 6 Hz, 2C); 31P NMR
(121.5 MHz, CDCl3): d 28.23; IR (neat): nÄ 2984, 2933, 2856, 1448, 1251,
Phenylphosphonothioic S-benzyl ester O-ethyl ester (4c): Colorless oil;
1H NMR (300.15 MHz, CDCl3): d 7.90 7.80 (m, 2H), 7.61 7.55 (m, 1H),
7.52 7.45 (m, 2H), 7.22 (m, 5H), 4.35 4.09 (m, 2H), 4.05 3.90 (m, 2H),
3
1.30 (t, J(H,H) 7.0 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d 137.1 (d,
3J(P,C) 5 Hz), 132.4, 132.65 (d, 1J(P,C) 105 Hz), 131.05 (d, 2J(P,C)
10 Hz, 2C), 128.75 (2C), 128.45 (2C), 128.4 (d, 3J(P,C) 11 Hz, 2C),
127.3, 62.1 (d, 2J(P,C) 7 Hz), 34.4, 16.2 (d, 4J(P,C) 5 Hz); 31P NMR
(121.5 MHz, CDCl3): d 44.20; IR (neat): nÄ 3061, 3030, 2982, 2929, 1602,
1590, 1495, 1454, 1438, 1391, 1227, 1119, 1022, 954 cmÀ1; MS (I.C./NH3): m/z
1019, 968 cmÀ1; MS (ESI-TOF): m/z (%): 252 [MH] , 274 [MNa]
(100).
Thiophosphoric acid S-benzyl ester O,O'-diethyl ester (7c): Colorless oil;
1H NMR (300.15 MHz, CDCl3): d 7.35 7.25 (m, 5H), 4.09 (m, 4H), 3.99
(d, 3J(P,H) 14.5 Hz, 2H), 1.42 (t, 3J(H,H) 7 Hz, 6H); 13C NMR
(75.4 MHz, CDCl3): d 138.5 (d, 3J(P,C) 5 Hz), 129.9 (2C), 129.7 (2C),
(%): 310 [MH] .
Phenylphosphonothioic O-ethyl ester S-(3-hydroxypropyl) ester (4d):
Colorless oil; 1H NMR (300.15 MHz, CDCl3), d 7.95 7.80 (m, 2H),
7.61 7.45 (m, 3H), 4.26 (m, 2H), 3.86 3.79 (m, 1H), 3.72 3.65 (m, 1H),
3.48 (broad s, OH), 3.08 2.87 (m, 2H), 1.92 1.72 (m, 2H), 1.40 (t,
3J(H,H) 7.0 Hz, 3 H) ; 13C NMR (75.4 MHz, CDCl3): d 132.7, 132.4 (d,
1J(P,C) 120 Hz), 131.15 (d, 2J(P,C) 12.5 Hz, 2C), 128.7 (d, 3J(P,C)
15 Hz, 2C), 62.7 (d, 2J(P,C) 7.5 Hz), 58.9, 33.4, 26.5, 16.4 (d, 4J(P,C)
8.5 Hz); 31P NMR (121.5 MHz, CDCl3): d 47.11; IR (neat): nÄ 3466
(broad), 2930, 1439, 1214, 1119, 1021, 956 cmÀ1; MS (I.C./NH3): m/z (%):
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128.6, 64.5 (d, J(P,C) 7 Hz, 2C), 36.0, 16.95 (d, J(P,C) 6 Hz, 2C); 31P
NMR (121.5 MHz, CDCl3): d 27.22; IR (neat): nÄ 2981, 2929, 2601, 2495,
2052, 1496, 1476, 1454, 1393, 1256, 1014, 972 cmÀ1; MS (I.C./NH3): m/z (%):
261 [MH] , 278 [MNH4] (100).
Thiophosphoric acid O,O'-diethyl ester S-(3-hydroxypropyl) ester (7d):
Yellow oil, rapidly turning brown upon standing at room temperature;
1H NMR (300.15 MHz, CDCl3): d 4.19 (m, 4H), 3.77 (t, 3J(H,H) 6.5 Hz,
2H), 3.02 (td, 3J(P,H) 17 Hz, 3J(H,H) 6.5 Hz, 2H), 1.90 (quint.
3J(H,H) 6.5 Hz, 2H), 1.33 (t, 3J(H,H) 7.0 Hz, 3H); 13C NMR
(75.4 MHz, CDCl3): d 64.0 (2C), 59.3, 33.5, 27.2 (d, 2J(P,C) 5.0 Hz),
16.1 (d, 3J(P,C) 7.5 Hz, 2C); 31P NMR (121.5 MHz, CDCl3): d 27.35; MS
261 [MH] (85), 278 [MNH4] (100).
Phenylphosphonothioic acid S-(3-cyanopropyl) ester O-ethyl ester (4e):
Pale yellow oil; 1H NMR (300.15 MHz, CDCl3): d 7.92 7.80 (m, 2H),
7.63 7.45 (m, 3H), 4.26 (m, 2H), 2.99 2.79 (m, 2H), 2.43 (td, 3J(H,H)
7.0 Hz, 5J(P,H) 3.0 Hz, 2H), 1.98 (quint. d, 3J(H,H) 7.0 Hz, 4J(P,H)
(I.C./NH3): m/z (%): 229 [MH] (70), 246 [MNH4] (100).
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3.0 Hz, 2H) 1.41 (t, J(H,H) 7.0 Hz, 3H); 13C NMR (75.4 MHz, CDCl3):
Thiophosphoric S-(3-cyanopropyl) ester O,O'-diethyl ester (7e): Pale
orange oil; 1H NMR (300.15 MHz, CDCl3): d 4.32 4.05 (m, 4H), 2.93
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d 132.9, 132.5 (d, J(P,C) 115 Hz), 131.2 (d, J(P,C) 10 Hz, 2C), 128.8
2914
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0813-2914 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 13