III Chloride-tris tetrahydrofuran

C4H80 CrCl Ohromium(III) chloride-tris(tetrahydrofuran), 8 150... 

Some salts could not be dehydrated in THF. Iron(III) chloride for example, polymerizes THF and must be prepared using neat trimethylchlorosilane. Cobalt(II) chloride dihydrate gave a similar result requiring neat trimethylchlorosilane. In both cases, nearly quantitative yields of the anhydrous salt were obtained. Hydrated zinc chloride, which we prepared by adding 10 wt % water to the anhydrous chloride because well-defined hydrates are not commercially available, was very efficiently dehydrated in neat trimethylchlorosilane to give a 96% yield of zinc chloride. In contrast, the THF/trimethylchlorosilane mixture afforded a comparatively modest 71% yield of the tetrahydrofuranate. Chromium(III) chloride hexahydrate, on the other hand, could not be completely dehydrated in neat trimethylchlorosilane and required THF for an efficient reaction giving 89% yield of chromium(III) chloride tris(tetrahydrofuran). Our results are summarized in Table I. 

Cl303ScC,2H24, Scandium(III), trichloro-tris(tetrahydrofuran)-, 21 139 Cl303TiCi2H24, Titanium(III), trichloro-tris(tetrahydrofuran)-, 21 137 CI3O3VC12H24, Vanadium(III), trichlorotris-(tetrahydrofuran)-, 21 138 CLPr, Praseodynium chloride, 22 39 CIsSbCuHio, Antimony(V), trichlorodi-phenyl-, 23 194... 

Anhydrous samarium(III) chloride [Rare Earth Products, Johnson Matthey] (2.40 g, 9.40 mmol) is placed in a 200-mL Schlenk tube containing a magnetic stirring bar. Tetrahydrofuran (THF) (100 mL) is introduced via a cannula at 20 °C. The mixture is stirred at 20 °C for 2 h. Solid (2,6-di-tert-butylphenoxo)-lithium-diethyl etherate (8.13g, 28.4 mmol) is added to this slurry at 20 °C. A reflux condenser is then fitted to the Schlenk tube, and the reaction mixture is heated under reflux for 8 h. After h, the solid dissolves to yield a clear yellow-green solution. The solvent is removed at 25 °C and 10 torr, leaving a yellow-green solid, which is scraped from the sides of the Schlenk tube with a spatula and transferred to a sublimation tube. Sublimation at 255-260°C and 10 torr affords yellow crystals of tris(2,6-di-tert-butyl-phenoxo)samarium. Yield 4.46 g (62%). ... 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

Fig. 1 Reaction scheme for the synthesis of the 2 -0-allyluridine building block Reagents i, l,3-dichlorO l,l,3,3-tetraisopropyldisiloxane in pyridine ii, chlorotri-methylsilane, and triethylamine in 1,2-dichloroethane, iii, 2-mesitylenesulfonyl chloride, triethylamine, and 4-dimethyIaminopyndine in dichloromethane iv, 2,6-dichlorophenol, l,4-diazabicyclo[2 2.2]octane and triethylamine v, p-toluene sulfonic acid monohydrate in THF/dichloromethane, vi, allyl ethyl carbonate, l,4-bis(diphenylphosphino)butane and tris(dibenzylideneacetone)dipalladium(0) in tetrahydrofuran, vii, tetrabutylammonium fluoride in tetrahydrofuran viii, 2-nitro-benzaldoxime and 1,1,3,3-tetramethylguanidine in acetonitrile, ix, 4,4 -dimethoxytrityl chloride and triethylamine in pyridine x, 2-cyanoethoxy M -diisopropyl-aminochlorophosphine and //,iV-diisopropylethyiamine in 1,2-dichloroethane.

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