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20th August 2013 @ 15:23

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Reaction information

*#Reaction file
*Reaction file type CDX

Following a procedure reported by Swepston, a 50 mL Schlenk flask containing 1,4-cyclohexanedimethanol (1/1 cis-/trans-; 2.88 g, 20.0 mmol) was evacuated and refilled with argon. Pyridine (20 mL) was added, and the mixture was stirred at r.t. for 10 minutes. After cooling to 0 °C, p-toluenesulfonylchloride (8.39 g, 44.0 mmol, 2.20 eq.) was added, under argon. Stirring at low temperature for further 10 minutes yielded a thick suspension that was then kept in the fridge (1 °C) for 65 hours (over the weekend).  After warming to r.t. the mixture was diluted with water (50 mL) and its pH (slightly acidic) was neutralized with diluted NaOH. The resulting suspension was vacuum filtered; the solid was dissolved in MeOH (50 mL), precipitated with H2O and filtered again.  Washing the solid with MeOH (2 x 20 mL) and evaporation of the filtrate yielded respectively 6.14 g (trans-enriched) and 2.43 g (cis-enriched) of crude product, with a reaction yield > 95%. Higher purity was achieved by crystallization in the case of the trans-isomer. The cis-enriched fraction was refluxed in MeOH (2 h; slightly saturated), then let cooling slowly to r.t. under stirring (kept in the oil bath). The solution was filtered to remove the trans-containing solid and concentrated. Iteration of the procedure yielded a reasonably pure cis-isomer (purification yield 93%; white solid, purity ~ 90%, 187 mg, 0.41 mmol, yield 2 %). Both isomers were used in the next step without further purification.

*Yield (%) 2 %
*Type of Yield Isolated pure product

PhD Thesis - 16Sep2010_final p25.pdf
PhD Thesis - 16Sep2010_final p132-134.pdf

Swepston, P. N.; Lin, S.-T.; Hawkins, A.; Humphrey, S.; Siegel, S.; Cordes, A. W. J. Org. Chem. 1981, 46, 3754-3756

Further information Compound 44: cis-O,O’-Cyclohexane-1,4-diylbis(methylene)toluensulfonate

For multistep reactions (or their steps):

Overall reaction? False
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step Reaction 46: Displacement of tosyl-group using a thioacetate: cis-S,S’-cyclohexane-1,4-diylbis(methylene)diethanetioate
Attached Files
PhD Thesis - 16Sep2010_final p25.pdf
PhD Thesis - 16Sep2010_final p132-134.pdf