A. K. Gupta et al. / Tetrahedron Letters 49 (2008) 2232–2235
2235
6. (a) Gerstenberger, M. R. C.; Haas, A. Angew Chem., Int. Ed. Engl.
1981, 20, 647; (b) Farooq, O. New J. Chem. 2000, 24, 81; (c) Farooq,
O. J. Chem. Soc., Perkin Trans. 1 1998, 839; (d) Saville, B. J. Chem.
Soc. 1961, 4624; (e) Wozniak, L. A.; Chworos, A.; Pyzowski, J.; Stec,
W. J. J. Org. Chem. 1998, 63, 8109; (f) Chworos, A.; Wozniak, L. A.
Tetrahedron Lett. 1999, 40, 9337.
7. (a) Schmutzler, R. Chem. Ber. 1965, 98, 552; (b) Roesky, H. W. Inorg.
Nucl. Chem. Lett. 1969, 5, 891; (c) Heuer, L.; Sell, M.; Schmutzler, R.;
Schomberg, D. Polyhedron 1987, 6, 1295; (d) Heuer, L.; Jones, P. G.;
Schmutzler, R. New J. Chem. 1990, 14, 891.
8. (a) Michalski, J.; Lopusinski, A. Angew. Chem., Int. Ed. Engl. 1982,
21, 294; (b) Dabkowski, W.; Cramer, F.; Michalski, J. Tetrahedron
Lett. 1987, 28, 3561.
9. Konieczko, W. T.; Lopusinski, A.; Michalski, J. Phosphorus, Sulfur,
Silicon Relat. Elem. 1989, 42, 103.
heterogeneous reaction mixture was filtered and the filtrate
was distilled to give the desired products.
We also carried out the reaction on large scale; di-
isopropylphosphite (166 g, 1.0 mol), TCA (289 g, 2.0 mol)
and KF (64 g, 1.1 mol) gave the product diisopropyl fluo-
rophosphate in 92% yield.
In summary, we have described an efficient, convenient
and one-pot synthesis of dialkyl fluorophosphates from
dialkylphosphites at room temperature. Moreover, the pro-
cedure offers several advantages including excellent yield,
operational simplicity, cleaner reaction and 100%
conversion.
10. (a) Bugerenko, E. F.; Chernyshev, E. A.; Popv, E. M. Bull. Acad. Sci.
USSR 1996, 1334; (b) Nesterov, L. V.; Kvepysheva, N. E.; Sabirova,
R. A.; Romanova, G. N. J. Gen. Chem. USSR 1971, 41, 2449; (c)
Dabkowski, W.; Michalski, J. J. Chem. Soc., Chem. Commun. 1987,
755.
11. (a) Dabkowski, W.; Cramer, F.; Michalski, J. Tetrahedron Lett. 1987,
28, 3561; (b) Dabkowski, W.; Cramer, F.; Michalski, J. J. Chem. Soc.,
Perkin Trans. 1 1992, 1447; (c) Konieczko, W. T.; Lopusinski, A.;
Michalski, J. Phosphorus, Sulfur, Silicon Relat. Elem. 1989, 42, 103.
12. Dabkowski, W.; Michalski, J.; Skrzypczynski, Z. Phosphorus, Sulfur,
Silicon Relat. Elem. 1986, 26, 321.
Acknowledgements
We thank Dr. R. Vijayaraghavan, Director, DRDE,
Gwalior for his keen interest and encouragement. The
authors also thank to Mr. Avik Mazumder for NMR
analysis.
References and notes
13. Sierakowski, T.; Kiddle, J. J. Tetrahedron Lett. 2005, 46, 2215.
14. Laszlo, P. Organic Reactions: Simplicity and Logic; Wiley: New York,
1995.
1. (a) Saunders, B. C. Some Aspects of the Chemistry and Toxic Action of
Organic Compounds Containing Phosphorus and Fluorine; Cambridge
University Press: Cambridge, 1957; (b) Majoral, J. P. New Aspects in
Phosphorus Chemistry I & II; Berlin Heidelberg, 2000; (c) Wilson, B.
W.; Walkar, C. R. Proc. Natl. Acad. Sci. U.S.A. 1974, 71, 3194; (d)
Metzler, D. E. In Biochemistry; Academic Press: New York, 1950;
Vol. 371; p 1013; (e) Bartlett, P. A.; Lamdem, L. A. Bioorg. Chem.
1986, 14, 356.
2. (a) Eto, M. Organophosphorus Pesticides: Organic and Biological
Chemistry; CRC press: USA, 1974; (b) Engel, R. Chem. Rev. 1977, 77,
349; (c) Kosolapoff, G. M. In Organic Phosphorus Compounds; Wiley
Interscience: New York, 1950; Vol. 6, 319-510.
3. (a) Camps, F.; Coll, J.; Fabrias, G.; Guerrero, A. Tetrahedron 1984,
40, 2871; (b) De Frank, J. J. Applications of Enzyme Biotechnology.
In Kelly, J. W., Baldwin, T. O., Eds.; Plenum: New York, 1991; pp
165–180.
4. (a) Sikder, A. K.; Ghosh, A. K.; Jaiswal, D. K. J. Pharm. Sci. 1993,
82, 258; (b) Marjit, D. N.; Sharma, U. S. Ind. J. Chem. 1989, 28A, 958;
(c) Sikder, A. K.; Pandey, K. S.; Jaiswal, D. K.; Dube, S. N.; Kumar,
D.; Hussain, K.; Bhattacharya, R.; Das Gupta, S. J. Pharm.
Pharmacol. 1992, 44, 1038.
15. (a) Green Chemistry: Frontiers in Benign Chemical Synthesis And
Process; Williamson, P. T., Anantas, T. C., Eds.; Oxford University
Press: Oxford, 1998; (b) Zhang, T. Y. Chem. Rev. 2006, 106, 2583.
16. (a) Jang, D. U.; Park, D. J.; Kim, J. Tetrahedron Lett. 1999, 40, 5323;
(b) Vago, I.; Greiner, I. Tetrahedron Lett. 2002, 43, 6039.
17. (a) Shakya, P. D.; Dubey, D. K.; Pardasani, D.; Palit, M.; Gupta, A.
K. J. Chem. Res. 2005, 821–823; (b) Acharya, J.; Shakya, P. D.;
Pardasani, D.; Palit, M.; Dubey, D. K.; Gupta, A. K. J. Chem. Res.
2005, 3, 194; (c) Shakya, P. D.; Dubey, D. K.; Pardasani, D.; Palit,
M.; Gupta, A. K. Catal. Commun. 2005, 6, 669; (d) Gupta, A. K.;
Palit, M.; Pardasani, D.; Shakya, P. D.; Shrivastava, R. K.; Dubey,
D. K. Eur. J. Mass Spectrom. 2005, 10, 309.
18. Typical experimental procedure: Diisopropylphosphite (16.6 g,
0.10 mol) was slowly added to a stirred suspension of TCA (28.9 g,
0.05 mol) and KF (6.38, 0.11 mol) at room temperature. The resulting
mixture was stirred and refluxed for the time mentioned in Table 1,
with monitoring by GC and 31P NMR. After the completion of the
reaction, the reaction mixture was cooled to room temperature and
filtered to remove the KCl. The solid precipitate was washed with
2 Â 10 mL of ether. The filtrate and washings were combined. The
solvent was removed by distillation and the product was obtained by
distillation under vacuum. Bp 83–84/20 mmHg; Yield; 16.95 g (92%).
5. (a) Eyer, P. Toxicol. Rev. 2003, 22, 165; (b) Kim, T. H.; Oh, K. A.;
Park, N. J.; Park, N. S.; Kim, Y. J.; Yum, E. K.; Jung, Y. S. J. Appl.
Biomed. 2006, 4, 67; (c) Koelle, G. J. Pharmacol. Exp. Ther. 1946, 88,
232.