2
998
E. Shi, C. Pei
PAPER
Diphenyl Phosphorocyanidate (2h)
Yield: 83%; bp 128–130 °C/0.4 mm.
References
(
1) (a) Luz, Z.; Silver, B. L. J. Am. Chem. Soc. 1961, 83, 4518.
b) Luz, Z.; Silver, B. L. J. Am. Chem. Soc. 1962, 84, 1095.
–
1
IR (film): 1322.0 (P=O), 2210.9 cm (C≡N).
(
1
H NMR (CDCl , 500 Hz): d = 7.17–7.41 (m, 5 H).
3
(c) Bailey, W. J.; Fox, R. B. J. Org. Chem. 1963, 28, 531.
(d) Bailey, W. J.; Fox, R. B. J. Org. Chem. 1964, 29, 1013.
1
3
C NMR (CDCl , 125 Hz): d = 111.36, 113.21, 119.91, 120.11,
3
(
1
e) Reuben, J.; Samuel, D.; Silver, B. L. J. Am. Chem. Soc.
963, 85, 3093. (f) Samuel, D. Pure Appl. Chem. 1964, 9,
449.
1
25.90, 126.95, 129.76, 130.27.
3
1
P NMR (CDCl , 125Hz): d = –29.20.
3
(
(
2) (a) Williams, R. H.; Hamilton, L. A. J. Am. Chem. Soc. 1952,
74, 5418. (b) Steinberg, G. M. J. Org. Chem. 1950, 15, 637.
EI-MS: m/z (%) = 259 (M, 75), 166 (5), 140 (100), 119 (25), 94
90), 77 (45), 65 (22), 51 (21).
(
(
c) Gajda, T.; Zwierzak, A. Synthesis 1976, 243.
3) (a) Petrov, K. A.; Bliznyuk, N. K.; Mansurov, I. Y. Zh.
Obshch. Khim. 1961, 31, 176; Chem. Abstr. 1961, 55,
Diphenyl Phosphor(isothiocyanidate) (2i)
Yield: 77%; bp 144–146 °C/0.2 mm.
22097. (b) Grayson, M.; Farley, C. E.; Streuli, C. E.
Tetrahedron 1967, 23, 1065.
(4) (a) Pudovik, A. N.; Arbuzov, B. A. Dokl. Akad. Nauk SSSR
1950, 73, 327; Chem. Abstr. 1951, 45, 2853. (b) Miller, R.
C.; Bradley, J. S.; Hamilton, L. A. J. Am. Chem. Soc. 1956,
–
IR (film): 1300.7 (P=O), 1986.9 cm (N=C=S).
1
1
H NMR (CDCl , 500 Hz): d = 7.07–7.42 (m, 5 H).
3
1
3
C NMR (CDCl , 125 Hz): d = 120.13, 120.23, 124.76, 126.32,
3
1
29.51, 130.10.
78, 5299.
3
1
P NMR (CDCl , 125 Hz): d = –27.71.
3
(5) (a) Miller, R. C.; Miller, C. D.; Rogers, W.; Hamilton, L. A.
J. Am. Chem. Soc. 1957, 79, 424. (b) Rauhaut, M. M.;
Hechenbliekner, I.; Currier, H. A.; Wystrack, V. P. J. Am.
Chem. Soc. 1958, 80, 6690.
EI-MS: m/z (%) = 292 (M + 1, 7), 291 (M, 78), 258 (5), 215 (18),
70 (8), 140 (12), 94 (38), 77 (100).
1
(
6) (a) Atherton, F. R.; Openshaw, H. T.; Todd, A. R. J. Chem.
Soc. 1945, 660. (b) Atherton, F. R.; Todd, A. R. J. Chem.
Soc. 1947, 674. (c) For example: Xiao, Q.; Sun, J.; Sun, Q.;
Ju, Y.; Zhao, Y. F.; Cui, Y. X. Synthesis 2003, 107.
Ethyl Phenylphosphonazidate (2j) from Ph(EtO)P(O)H
To a solution of Ph(EtO)P(O)H (3.40 g, 20 mmol), CCl (30 mmol),
and NaN (1.95 g, 30 mmol) in MeCN (50 mL) maintained at r.t.,
3
4
was added Et N (2 mmol) dropwise and slowly. The mixture was
3
(
(
7) Encyclopedia of Reagents for Organic Synthesis, Vol. 1-8;
Paquette, L. A., Ed.; Wiley: New York, 1995.
8) (a) Wu, Y.; Yan, T.; Gao, Z.; Pan, H.; Guo, W. Huaxue Shiji
then stirred for 30 min. After filtration, the filtrate was concentrated
in vacuo and then distilled to give Ph(EtO)P(O)N3.
Yield: 71%; bp 106–108 °C/0.25 mm.
1
992, 14, 377; Chem. Abstr. 1993, 119, 49457. (b) Shioiri,
T.; Yamada, S. Org. Synth. 1984, 62, 187.
(9) (a) Shi, E.; Pei, C. Phosphorus, Sulfur Silicon Relat. Elem.
003, 178, 1093; and references cited therein. (b) Shi, E.;
Pei, C. Synth. Commun. 2004, 34, 1285.
(10) (a) Łopusiski, A.; Łuczak, L.; Michalski, J. Tetrahedron
–
IR (film): 1254.4 (P=O), 2154.3 cm (N3).
1
1
H NMR (CDCl , 500 Hz): d = 1.41 (d, J = 7.0 Hz, 3 H), 2.05 (t,
3
2
J = 9.0 Hz, 2 H), 7.50–7.87 (m, 5 H).
1
3
C NMR (CDCl , 125 Hz): d = 16.10, 63.01, 128.30, 128.61,
3
1
31.24, 133.26.
1982, 38, 679. (b) Pudovik, A. N.; Romanov, G. V.;
3
1
P NMR (CDCl , 125 Hz): d = 19.29.
3
Stepanova, T. Y. Zh. Obshch. Khim. 1979, 49, 1425; Chem.
Abstr. 1979, 91, 123808. (c) Kenner, G. W.; Khorana, H. G.;
Stedman, R. J. J. Chem. Soc. 1953, 673.
EI-MS: m/z (%) = 211 (M, 6), 169 (27), 141 (100), 91 (7), 77 (44),
5 (7), 51 (18), 47 (14).
6
(
11) (a) Kong, A.; Engel, R. Bull. Chem. Soc. Jpn. 1985, 58,
3
671. (b) Georgiev, E. M.; Kaneti, J.; Troev, K.; Roundhill,
Atherton–Todd Reactions of Ph PHO
2
D. M. J. Am. Chem. Soc. 1993, 115, 10964.
12) Tong, T. S.; Tai, C. S. Hua Hsuch Pao 1965, 31, 199; Chem.
Abstr. 1965, 63, 16380.
13) Reichardt, C. Solvent Effects in Organic Chemistry (Chin.
Transl.) 1970, 336.
14) Nifantiev, E. E.; Blagowestenskij, A. M.; Sokorenko, A. M.;
Skljarskij, L. S. Zh. Obshch. Khim. 1974, 44, 108; Chem.
Abstr. 1974, 80, 96089.
To a solution of Ph PHO (404 mg, 2 mmol) and HNu (Nu = Oi-Bu,
2
(
(
(
SPr; 2 mmol) in CCl (5 mL) was added Et N (0.2 mmol). After stir-
3
4
ring the mixture for 10 min, samples were taken without further iso-
31
lation for P NMR or GC-MS analysis.
Diphenylphosphonic Acid
1
3
P NMR (CDCl , 125 Hz): d = 31.50.
3
(
(
15) (a) Crofts, P. C.; Downie, I. M.; Williamson, K. J. Chem.
Soc. 1964, 1240. (b) Yuan, C. Y.; Yuan, Q. Huaxue Xuebao
Isobutyl Diphenylphosphonate
EI-MS: m/z (%) = 274 (M, 6), 219 (100), 201 (45), 141 (22), 132
1
980, 38, 339; Chem. Abstr. 1981, 94, 47415.
16) (a) Derkach, G. I.; Liptuga, N. I. Zh. Obshch. Khim. 1968,
8, 1779; Chem. Abstr. 1969, 70, 4231. (b) Gilyarov, V. A.;
(
38), 77 (57), 51 (21).
3
S-Propyl Diphenylphosphinothioate
EI-MS: m/z (%) = 276 (M, 15), 234 (30), 202 (90), 201 (100), 183
Kabachnik, M. I. Zh. Obshch. Khim. 1972, 42, 2148; Chem.
Abstr. 1973, 78, 57669. (c) Felcht, U.; Regitz, M. Liebigs
Ann. Chem. 1977, 1309.
(8), 155 (12), 125 (11), 77 (17).
(
17) (a) Harger, M. J. P.; Westlake, S. Tetrahedron 1982, 38,
1511. (b) Harger, M. J. P.; Stephen, M. A. J. Chem. Soc.,
Acknowledgment
Perkin Trans. 1 1981, 736. (c) Tomaschewski, G.; Otto, A.
Arch. Pharm. (Weinheim, Ger.) 1968, 301, 520.
(18) (a) McCombie, H.; Saunders, B. C.; Stacey, G. J. J. Chem.
Soc. 1945, 380. (b) Hewitt, D. G. Aust. J. Chem. 1979, 32,
We sincerely thank Dr. J. Xiao for his helpful advice and encoura-
gement.
463. (c) Hunt, B. B.; Saunders, B. C. J. Chem. Soc. 1957,
2413.
Synthesis 2004, No. 18, 2995–2998 © Thieme Stuttgart · New York