PAPER
Formation of S-Aryl, Se-Aryl, and Te-Aryl Phosphorochalcogenoates
1085
13C NMR (100 MHz, CDCl3): d = 135.5 (d, JC-P = 4.7 Hz, 2 C),
129.4 (d, JC-P = 1.9 Hz, 2 C), 128.7 (d, JC-P = 2.3 Hz, 1 C), 123.9 (d,
JC-P = 8.3 Hz, 1 C), 67.9 (d, JC-P = 6.4 Hz, 2 C), 31.3 (s, 2 C), 30.0
(d, JC-P = 7.2 Hz, 2 C), 25.1 (s, 2 C), 22.5 (s, 2 C), 13.9 (s, 2 C).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C11H17O3PTe: 359.0056;
found: 359.0059.
O-Isopropyl O-(2¢,3¢-O,O-Isopropylideneuridinyl) S-Phenyl
Phosphorothioate (10)
31P NMR (162 MHz, CDCl3): d = 19.69 [s (isotopes 76, 78, 80, 82)
Colorless oil. Many 1H and 13C NMR signals were split due to the
presence of (phosphate) diastereoisomers in the sample.
and d (isotope 77), 1JP-Se = 479.8 Hz].
MS (ESI): m/z = 407 [M + H]+, 429 [M + Na]+.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C18H31O3PSe: 407.1255;
IR (film): 3183, 3062, 2985, 2938, 2821, 1694, 1632, 1582, 1455,
1418, 1380, 1261, 1158, 1069, 989, 860, 750 cm–1.
found: 407.1262.
1H NMR (400 MHz, CDCl3): d = 9.02 (br s, 1 H, NH), 7.60–7.55
(m, 2 H, Harom), 7.37–7.28 (m, 4 H, H6, 3 Harom), 5.86 and 5.81 (2 d,
J = 1.8, 2.6 Hz, 1 H, H1¢), 5.65–5.60 (m, 1 H, H5), 4.88–4.80 (m, 1
H, CHMe2), 4.75–4.66 (m, 2 H, H2¢, H3¢), 4.40–4.25 (m, 3 H, H4¢,
H5¢), 1.57 and 1.56 [2 s, 3 H, =C(CH3)2], 1.37–1.26 (m, 9 H, CH3).
13C NMR (100 MHz, CDCl3): d = 162.95 (C4), 149.97, 149.94 (C2),
141.23, 141.18 (C6), 134.66, 134.61, 134.47, 134.41 (CHarom),
129.46, 129.43, 129.41 (CHarom), 129.31, 129.28, 129.22, 129.20
(CHarom), 126.06, 126.02, 125.99, 125.95 (Carom), 114.67, 114.62
(=CMe2), 102.70, 102.68 (C5), 93.11, 92.72 (C1¢), 84.91, 84.82,
84.68, 84.60 (C4¢), 84.42, 84.28 (C2¢), 80.41, 80.38 (C3¢), 74.35,
74.31, 74.29, 74.24 (CHMe2), 66.74, 66.68 (C5¢), 27.11, 27.09
[=C(CH3)2], 25.24 [=C(CH3)2], 23.94, 23.91, 23.88 [CH(CH3)2],
23.51, 23.45 [CH(CH3)2].
O,O-Dihexyl Se-4-Tolyl Phosphoroselenoate (4h)
Pale yellow oil.
IR (film): 3021, 2956, 2929, 2859, 1489, 1467, 1380, 1253, 1117,
1039, 991, 854, 803, 722 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.53–7.50 (m, 2 H), 7.11 (d,
J = 8.1 Hz, 2 H), 4.16–4.02 (m, 4 H), 2.33 (d, J = 1.5 Hz, 3 H),
1.67–1.60 (m, 4 H), 1.34–1.22 (m, 12 H), 0.88 (t, J = 6.9 Hz, 6 H).
13C NMR (100 MHz, CDCl3): d = 138.9 (d, JC-P = 2.8 Hz, 1 C),
135.5 (d, JC-P = 4.5 Hz, 2 C), 130.2 (d, JC-P = 2.1 Hz, 2 C), 120.0 (d,
JC-P = 8.4 Hz, 1 C), 67.8 (d, JC-P = 6.4 Hz, 2 C), 31.3 (s, 2 C), 30.0
(d, JC-P = 7.2 Hz, 2 C), 25.1 (s, 2 C), 22.5 (s, 2 C), 21.1 (s, 1 C), 13.9
(s, 2 C).
31P NMR (162 MHz, CDCl3): d = 22.83, 22.75.
MS (ESI): m/z = 499 [M + H]+, 521 [M + Na]+.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C21H27N2O8PS:
31P NMR (162 MHz, CDCl3): d = 20.01 [s (isotopes 76, 78, 80, 82)
and d (isotope 77), 1JP-Se = 486.4 Hz].
MS (ESI): m/z = 421 [M + H]+, 443 [M + Na]+.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C19H33O3PSe: 421.1412;
499.1304; found: 499.1310.
found: 421.1419.
O-Isopropyl O-(2¢,3¢-O,O-Isopropylideneuridinyl) Se-Phenyl
Phosphorothioate (11)
Se-4-Chlorophenyl O,O-Dihexyl Phosphoroselenoate (4i)
Pale yellow oil.
Pale yellow oil. Many 1H and 13C NMR signals were split due to the
presence of (phosphate) diastereoisomers in the sample.
IR (film): 3063, 2956, 2930, 2859, 1474, 1388, 1254, 1090, 1038,
1010, 991, 815, 788, 729 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.59–7.55 (m, 2 H), 7.29–7.26 (m,
2 H), 4.17–4.03 (m, 4 H), 1.68–1.61 (m, 4 H), 1.35–1.22 (m, 12 H),
0.88 (t, J = 6.8 Hz, 6 H).
13C NMR (100 MHz, CDCl3): d = 136.7 (d, JC-P = 4.8 Hz, 2 C),
135.2 (d, JC-P = 2.8 Hz, 1 C), 129.6 (d, JC-P = 1.7 Hz, 2 C), 122.0 (d,
JC-P = 8.3 Hz, 1 C), 68.0 (d, JC-P = 6.6 Hz, 2 C), 31.2 (s, 2 C), 30.0
(d, JC-P = 7.2 Hz, 2 C), 25.1 (s, 2 C), 22.5 (s, 2 C), 13.9 (s, 2 C).
IR (film): 3185, 3060, 2984, 2937, 2821, 1694, 1632, 1578, 1455,
1419, 1380, 1158, 1069, 983, 860, 812, 741 cm–1.
1H NMR (400 MHz, CDCl3): d = 9.18 (br s, 1 H, NH), 7.65–7.62
(m, 2 H, Harom), 7.36–7.27 (m, 4 H, H6, 3 Harom), 5.87 and 5.80 (2d,
J = 2.0, 2.5 Hz, 1 H, H1¢), 5.65 and 5.58 (2 dd, J = 8.1, 1.7, 8.1, 1.8
Hz, 1 H, H5), 4.90–4.81 (m, 1 H, CHMe2), 4.77–4.63 (m, 2 H, H2¢,
H3¢), 4.39–4.24 (m, 3 H, H4¢, H5¢), 1.57 and 1.56 [2 s, 3 H,
=C(CH3)2], 1.37–1.28 (m, 9 H, CH3).
13C NMR (100 MHz, CDCl3): d = 163.08, 163.05 (C4), 150.02,
149.99 (C2), 141.29, 141.14 (C6), 135.67, 135.63, 135.36, 135.31
(CHarom), 129.60, 129.58 (CHarom), 129.11, 129.09, 128.98, 128.96
(CHarom), 123.50, 123.42, 123.33, 123.25 (Carom), 114.62, 114.56
(=CMe2), 102.68, 102.63 (C5), 93.21, 92.64 (C1¢), 84.91, 84.82,
84.60, 84.52 (C4¢), 84.47, 84.31 (C2¢), 80.47, 80.42 (C3¢), 74.12,
74.08, 74.06, 74.02 (CHMe2), 66.49, 66.45, 66.39 (C5¢), 27.11,
27.08 [=C(CH3)2], 25.25 [=C(CH3)2], 23.95, 23.92, 23.89
[C(CH3)2], 23.51, 23.49, 23.44 [C(CH3)2].
31P NMR (162 MHz, CDCl3): d = 18.95 [s (isotopes 76, 78, 80, 82)
and d (isotope 77), 1JP-Se = 473.0 Hz].
MS (ESI): m/z = 441 [M + H]+, 463 [M + Na]+.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C18H30ClO3PSe:
441.0913; found: 441.0920.
O,O-Diethyl Te-4-Tolyl Phosphorotelluroate (5d)
Pale yellow oil.
31P NMR (162 MHz, CDCl3): d = 17.63, 17.46 [s (isotopes 76, 78,
IR (film): 2981, 2926, 2867, 1486, 1442, 1391, 1240, 1160, 1011,
962, 799, 758 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.72 (dd, J = 8.0, 1.6 Hz, 2 H),
7.07 (d, J = 2.0 Hz, 2 H), 4.20–4.08 (m, 4 H), 2.34 (d, J = 0.9 Hz, 3
H), 1.32 (t, J = 7.1 Hz, 6 H).
80, 82) and d (isotope 77), 1JP-Se = 493.5, 496.9 Hz].
MS (ESI): m/z = 547 [M + H]+, 569 [M + Na]+.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C21H27N2O8PSe:
547.0750; found: 547.0755.
13C NMR (100 MHz, CDCl3): d = 140.1 (d, JC-P = 3.9 Hz, 2 C),
139.1 (d, JC-P = 2.7 Hz, 1 C), 130.6 (d, JC-P = 2.0 Hz, 2 C), 104.7 (d,
JC-P = 8.0 Hz, 1 C), 63.4 (d, JC-P = 5.3 Hz, 2 C), 21.3 (s, 1 C), 15.7
(d, JC-P = 7.4 Hz, 2 C).
Acknowledgment
The authors would like to acknowledge financial support from
Major Program of National Natural Science Foundation of China
(20732004, J0630429) and Projects of International Cooperation of
the Ministry of Science and Technology of the People’s Republic of
China (2006DFA43030).
31P NMR (162 MHz, CDCl3): d = –0.49 [s (isotopes 122, 124, 126,
128, 130) and d (isotope 125), 1JP-Te = 1356.7 Hz].
MS (ESI): m/z = 359 [M + H]+, 381 [M + Na]+.
Synthesis 2009, No. 7, 1081–1086 © Thieme Stuttgart · New York