ChemInform Abstract: SYNTHESIS OF CHIRAL AND NON‐CHIRAL PHOSPHITES CONTAINING THE HEXAFLUOROISOPROPOXY GROUP

Dakternieks, Dainis; Roeschenthaler, G.-V.; Schmutzler, R.

doi:10.1002/chin.197831276

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1981

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“…C6H&' [OCH(CF:,)2]2 was prepared by reacting a well stirred suspension of NaOCH(CF& (11 g, 58 mmol) with a solution of CGHSPC12 (8.9 g, 50 mmol) in dry benzene (75 ml), as previously described [7]. After filtration and removal of the solvent, CGHSP[OCH(CF:<)2]2 was distilled under reduced pressure and treated with excess hexafluoroacetone according to the procedure used for similar compounds [ 8 ] .…”

Section: Methodsmentioning

confidence: 99%

The hydrolysis of phosphoranes in aqueous dioxane

Queen¹,

Lemire²,

Janzen³

1981

Int J of Chemical Kinetics

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The entropy of activation for the hydrolysis of pentaphenoxyphosphorane in 25% aqueous dioxane is -188 J/mol deg. T h e enthalpy of activation is 22.5 kJ/mol, which is small for the relatively slow reaction. This suggests that the reaction is a multistep process having a preliminary equilibrium with a negative heat of reaction. This conclusion is supported by the results obtained for the hydrolysis of C6H~'OC(CF:~)2C(CFs)20IOCH(CF:1)2]2. A kinetic isotope effect k~* / k~* o of 3.46 was found for the latter reaction. Orders in water were ohtained, and a mechanism of hydrolysis is proposed.

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Section: Methodsmentioning

confidence: 99%