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Double acylation of a titanaselenide by triphosgene; 4,5-ethylenedithio-1,3-diselenol-2-one

SyntheticPage 420
DOI: 10.1039/SP420
Submitted May 28, 2010, published Jun 01, 2010
Nikola Paul Chmel (
A contribution from Scott group, Warwick University

			Reaction Scheme: Double acylation of a titanaselenide by <SPAN class=csm-chemical-name id=csm1288163056557 title=triphosgene>triphosgene</SPAN>

Chemicals Used

Bis(η5-cyclopentadienyl)(5,6-dihydro-1,4-dithiine-2,3-diselenolato-κ2Se,Se')titanium(IV) synthesis

bis(trichloromethyl)carbonate (triphosgene)

THF (refluxed over potassium, degassed)


Bis(η5-cyclopentadienyl)(5,6-dihydro-1,4-dithiine-2,3-diselenolato-κ2Se,Se')titanium(IV) (3.0 g, 6.66 mmol) and bis(trichloromethyl) carbonate (1.98 g, 6.66 mmol) were dissolved in dry THF (200 ml) under nitrogen. The mixture was heated to reflux for 1 h. Cooled mixture was quenched with methanol (10 ml) and stirred for further 15 min. The solids were removed by filtration and the filtrate was evaporated dry under reduced pressure. The residue was purified on silica using DCM:hexane (1:1) as eluent. Orange/yellow fraction collected. The solvents were removed under reduced pressure and the residue was re-dissolved in acetonitrile (100 ml) and heated to reflux with activated carbon for 0.5 h. The hot solution was filtered and the filtrate was concentrated to approximately half volume. The solution was left at -30°C overnight for crystallisation. Pale yellow solid was collected by filtration and washed with small amount of cold acetone. Yield 0.33 g (16%).

Author's Comments

This is an intermediate in the synthesis of BEDT-TSF (BETS).

This procedure has been published in outline by Kato et al. and Courcet et al., to our knowledge however this is the first detailed synthetic procedure for this reaction. We would like to thank prof. Hiroki Akutsu for help with this procedure.


1H NMR (400 MHz, 298K, CDCl3) δH 3.44 (s, 4H, CH2)

13C NMR (125 MHz, 298K, CDCl3) δC 185.49 (C=O), 116.92 (C=C), 33.12 (CH2)

Lead Reference

R. Kato, H. Kobayashi and A. Kobayashi, Synth. Met., 1991, 42, 2093-2096.

Other References

T. Courcet, I. Malfant, K. Pokhodnia and P. Cassoux, New J. Chem., 1998, 22, 585-589.

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Get structure file (.cdx, .sk2, .mol)

Keywords: BEDT-TSeF, BEDT-TSF, BETS, bisethylenedithiotetraselenafulvalene, heterocyclic compounds, organometallics

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