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Evidence for the formation of isothiocyanate during sulphurisation of triphenyl phosphines using xanthane hydride

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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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
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,; Eckstein, F., Ed.;
Depositing User: Sara Taylor
Date Deposited: 04 Feb 2008 10:37
Last Modified: 28 Aug 2021 10:38

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