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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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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
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,
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–
8. Bartlett, P. D.; Meguerian, G. J. Am. Chem. Soc. 1956, 78,
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: 20 Oct 2008 09:50

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