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Formylation of tetrathiafulvalene; 4-formyltetrathiafulvalene

SyntheticPage 291
DOI: 10.1039/SP291
Submitted Jan 06, 2010, published Jun 29, 2008
Nikola Paul Chmel (n.chmel@warwick.ac.uk)
A contribution from Scott group, Warwick University


			Reaction Scheme: Formylation of tetrathiafulvalene

Chemicals Used

Diisopropylamine,
2.5 M solution of nBuLi in hexane,
tetrathiafulvalene (TTF) Page 290],
2M HCl,
THF (distilled over potassium, degassed),
diethyl ether (distilled over sodium/potassium alloy, degassed),

Procedure

A solution of LDA was prepared in situ. Diisopropylamine (1.54 ml, 0.011 mol) was dissolved in dry THF (5 ml) under argon, and cooled to -78°C. 2.5 M solution of nBuLi in hexane (4.4 ml, 0.011 mol) was added dropwise. The mixture was allowed to warm up to ambient temperature and was stirred for 2 hours. TTF (2.0 g, 0.01 mol) was dissolved in dry Et2O (120 ml) under argon and cooled to -78°C. The solution of LDA was added dropwise over a period of 5 min. and the mixture was stirred for 1.5 hours at -78°C. N-methyl-N-phenylformamide (2.4 ml, 0.02 mol) was added dropwise, stirring was continued for another 3 hours. The dry ice/acetone bath was replaced with dry ice/CH3CN (-40°C) and the mixture was allowed to warm up slowly overnight to ambient temperature. The mixture was diluted with water (60 ml) and acidified with 2M HCl (20 ml). The product was extracted with DCM (3×40 ml) and the collected DCM fractions dried over MgSO4. The product was purified by flash chromatography, unreacted TTF was washed off initially with toluene:hexane (1:1). Elution with DCM yielded product as deep red solid. Traces of N-methyl-N-phenylformamide were washed off with Et2O. Yield 1.62 g (70%).

Author's Comments

Used in subsequent reaction. Stored in vacuum dessicator.

Data

Anal calcd. for C6H4S4: C 36.19%, H 1.74%, S 55.20%. Found: C 36.42%, H 1.81%, S 55.14%. 1H NMR (400 MHz, CDCl3, 298 K) 6.34 (2×d, 2×1H, 3JHH=6Hz, 3JHH=6Hz, CH), 7.42 (s, 1H, CH), 9.47 (s, 1H, CHO) 13C NMR (100 MHz, CDCl3, 298 K) 105.49, 115.95, 118.69, 119.36, 139.82, 141.54, 179.63 MS (ESI+) m/z: 231.91

Lead Reference

Garin, J.; Orduna, J.; Uriel, S.; Moore, A. J.; Bryce, M. R.; Wegener, S.; Yufit, D. S.; Howard, J. A. K. Synthesis 1994, 489-493

Other References

Coles, S. R., University of Warwick, 2006

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Keywords: aldehydes, formylation, tetrathiafulvalenes

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