Tosylate salts, anhydrous

Methods for preparing anhydrous tosylate salts are also described. Analytical and infrared data for the anhydrous tosylate salts are presented in Tables I and n. The IR spectra of the hydrated salts are essentially identical to those of the anhydrous salts, except extra bands due to water are present near 3150-3500 and 1650-1700 cm . ... 

TABLE I. Analytical Data for the Anhydrous Tosylate Salts "... 

Anhydrous tosylate salts can be prepared by heating the corresponding hydrated salts under vacuum to 160°C for 1 h. Yields are nearly quantitative. Infrared data for these compounds are shown in Table El. 

TABLE ni. Infrared Data for the Anhydrous Tosylate Salts"... 

The anhydrous tosylate salts are soluble in methanol and water, but are insoluble in acetonitrile and diethylether. 

A solution of cholestane-5a,6a-diol 6-tosylate (115a, 0.15 g) in dimethylformamide (20 ml) containing calcium carbonate (0.2 g) is heated for 8 hr on a steam bath. The reaction mixture is then cooled, filtered and diluted with water. The mixture is extracted with ether and the ether extracts are washed with water and saturated salt solution, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give the A-homo-B-norketone (116a, 85 mg) mp 123-125° [a]j> 21° (CHCI3). 

The synthesis of 2C-T-17 R required starting with the S isomer of secondary butanol. The S 2-butanol in petroleum ether gave the lithium salt with butyllithium which was treated with tosyl chloride (freshly crystallized from naphtha, hexane washed, used in toluene solution) and the solvent was removed. The addition of 2,5-dimethoxythiophenol, anhydrous potassium carbonate, and DMF produced S 2,5-dimethoxyphenyl s-butyl sulfide. The conversion to R 2,5-dimethoxy-4-(s-butyl-thio)benzaldehyde (which melted at 78-79 °C compared to 86-87 °C for the racemic counterpart) and its conversion in turn to the nitro-styrene, S -2,5-dimethoxy-4-(s)-butylthio-B-nitrostyrene which melted at 70-71 °C compared to 68-69 °C for the racemic counterpart, followed the specific recipes above. The preparation of the intermediates to 2C-T-17 S follows the above precisely, but starting with R 2-butanol instead. And it is at these nitrostyrene stages that this project stands at the moment. 

The iodonium triflate (460 mg, 1 mmol) was added to a stirred slurry of anhydrous sodium p-toluene sulphinate (180 mg, 1.01 mmol) in dichloromethane (15 ml) at 20°C under nitrogen. After 15 min water (10 ml) was added and the phases were separated the aqueous layer was extracted with additional dichloromethane (2 x 5 ml), and the combined organic extracts were dried. The filtered solution was treated with hexanes (30 ml) and concentrated. The solid residue was purified by radial chromatography (silica gel, 200-400 mesh, dichloromethane-hexanes) to afford 3-tosyl-bicyclo[3.2.0]-3-heptene-2-one (197 mg, 75%), m.p. 164-165°C. The method is general for the preparation of sulphones with a cyclopentenone moiety other alkenyl iodonium salts gave alkynyl sulphones with sulphinates (Section 9.4.4). 

Silver tosylate [16836-95-6] M 279.1. The anhydrous salt is obtained by recrystallisation from H2O. Store it in the dark. [Claesson Wallin Chem Ber 12 1851 1879, Beilstein 11 H 97,99.]... 

Under an inert atmosphere, prepare a suspension of sodium hydride (0.96 g, 20 mmol [50 per cent in mineral oil]) in dry THF (50 mL) in a 250 mL twonecked round-bottomed flask fitted with a reflux condenser and pressure equalized addition funnel. Stir for 30 min under an inert atmosphere. Slowly add a solution of 8-hydroxyquinoline (2.90 g, 20 mmol) in dry THF (50 mL) to this through the addition funnel. Make up a solution of triethylene glycol ditosylate, 2, (4.60 g, 10 mmol) in dry THF (50 mL), ensuring that no solids remain (filter if necessary) or the addition funnel may become blocked. Once the effervescence subsides following the formation of the sodium 8-hydroxyquinolinate salt, add the ditosylate solution and reflux for 24 h. After 24 h, allow the solution to cool to room temperature, filter off the precipitated sodium tosylate and remove the THF by rotary evaporation. Dissolve the residue in dichloromethane (30 mL) and wash with distilled water (3 x 30 mL). Dry the organic phase over anhydrous sodium sulphate, filter and remove dichloromethane by rotary evaporation to give the crude product, l,9-bis(8-quinolinyloxy)-3,6-dioxanonane (4) as a pale brown oil. Further purification may be afforded by column chromatography (silica, elute with acetone/dichloromethane). 

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