Hanusek, Jifi, Russell, Mark A., Laws, Andrew P. and Page, Michael I. (2007) Evidence for the formation of isothiocyanate during sulphurisation of triphenyl phosphines using xanthane hydride. Tetrahedron Letters, 48 (3). pp. 417-419. ISSN 0040-4039
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Abstract
Contrary to a previous report, the sulfurisation of triphenylphosphines and trialkyl phosphites by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products but unstable thiocarbamoyl isothiocyanate which has been trapped with nucleophiles.
Item Type: | Article |
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Additional Information: | UoA 18 (Chemistry) |
Subjects: | Q Science > Q Science (General) Q Science > QD Chemistry |
Schools: | School of Applied Sciences School of Applied Sciences > Biomolecular Sciences Research Centre |
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References: | 1. (a) Eckstein, F.; Gish, G. Trends Biochem. Sci. 1989, 14, 97–100; Zon G.; (b) Stec, W. J. In Oligonucleotides and Analogues: A Practical ApproaIRL Press: Oxford, 1991; pp 87–108; (c) Iversen, P. Anti- Cancer Drug Des. 1991, 6, 539–568; (d) Zamecnik, P. C. In Prospects for Antisense Nucleic Acid Therapy for Cancer and AIDS; Wickstrom, E., Ed.; Wiley Liss.: New York, 1991; pp 1–6; (e) Agrawal, S. Trends Biotechnol. 1992, 10, 152; (f) Mirabelli, C. K.; Crooke, S. T. In Antisense Research and Applications; Crooke, S. T., Lebleu, B., Eds.; CRC: Ann Arbor, 1993; pp 7–35, and references cited therein. 2. (a) Crooke, S. T.; Bennett, C. F. Ann. Rev. Pharmacol. Toxicol. 1996, 36, 107–129; (b) Braasch, D. A.; Corey, D. R. Biochemistry 2002, 41, 4503–4510. 3. Tang, J.-Y.; Han, Z.; Tang, J. X.; Zhang, Z. Org. Proc. Res. Dev. 2000, 4, 194–198. 4. Goerdeler, J.; Lu¨dke, H. Chem. Ber. 1970, 103, 3393–3406. 5. Spurlock, L. A.; Newallis, P. E. J. Org. Chem. 1968, 33, 2073–2076. 6. 3-Amino-1,2,4-dithiazole-5-thione (1) (1 g, 6.7 mmol) was dissolved in 400 ml of acetonitrile under a nitrogen atmosphere at 30 C and a solution containing 1.75 g (6.7 mmol) of triphenylphosphine in 100 ml of acetonitrile was added in one portion. The reaction mixture was stirred for 5 min and then 0.92 g (6.7 mmol) of 4-nitroaniline in 20 ml acetonitrile was added. After 15 h, the acetonitrile was removed and the solid residue was quickly extracted with 3 · 40 ml of 3% aqueous potassium hydroxide solution. After filtration, the insoluble material which was practically pure triphenylphosphine sulfide (1.85 g, 94%) was recovered. The filtrate was immediately neutralised by concentrated HCl (pH = 3). Precipitated 1- (4-nitrophenyl)dithiobiuret was filtered off and dried. Yield 1.65 g (97%). Mp 168–170 C, 1H NMR (DMSOd6, 500 MHz) d 7.97 (AA0XX0, J 9.05, 2H, Ar–2H), 8.25 (AA0XX0, J 9.1, 2H, Ar–2H), 9.1 and 9.42 (2 · br s, 2H, NH2), 11.01 (br s, 1H, NH), 13.22 (br s, 1H, NH). 13C NMR (DMSO-d6, 125 MHz) d 123.3, 124.6, 143.7, 144.3, 177.3, 179.2. m/z (ESI) 255.0016 (M, C8H7N4O2S2 requires 255.0005). The same procedure was carried with trimethyl phosphite instead of triphenylphosphine. Yield of 1-(4-nitrophenyl)- dithiobiuret was 1.35 g (80%). 7. Davies, W. C.; Lewis, W. P. G. J. Chem. Soc. 1934, 1599– 1604. 8. Bartlett, P. D.; Meguerian, G. J. Am. Chem. Soc. 1956, 78, 3710–3715. 9. Hall, C. D.; Tweedy, B. R.; Kayhanian, R.; Lloyd, J. R. J. Chem. Soc., Perkin Trans. 2 1992, 775–779. 10. Henderson, W. A., Jr.; Streuli, C. A. J. Am. Chem. Soc. 1960, 82, 5791–5794. 11. Perrin, D. D.; Dempsey, B.; Serjeant, E. P. In pKa Prediction for Organic Acids and Bases; Chapman and Hall: London, 1981.ch; Eckstein, F., Ed.; |
Depositing User: | Sara Taylor |
Date Deposited: | 04 Feb 2008 10:37 |
Last Modified: | 28 Aug 2021 10:38 |
URI: | http://eprints.hud.ac.uk/id/eprint/506 |
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Evidence for formation of isothiocyanate during sulphurisaton of triphenyl phosphines using xanthane hydride. (deposited 01 Feb 2008 16:40)
- Evidence for the formation of isothiocyanate during sulphurisation of triphenyl phosphines using xanthane hydride. (deposited 04 Feb 2008 10:37) [Currently Displayed]
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