Efficient Syntheses of Fluorous Primary Phosphines that Do Not Require PH₃

Abstract

Arbuzov reactions of the fluorous primary iodides R_fn(CH₂)_mI [R_fn = CF₃(CF₂)_n-1; n/m = 6/2, 8/2, 8/3, 10/2] and P(OEt)₃ (excess, 160 °C) give the fluorous phosphonates R_fn(CH₂)_mP(O)(OEt)₂ (56-59%), which are reduced with LiAlH₄ to the title compounds R_fn(CH₂)_mPH₂ (62-78%). Fluorophilicities (CF₃C₆F₁₁/toluene partition coefficients) increase with the length of the R_fn moiety, decrease with the length of the (CH₂)_m moiety, and decrease in the functional group sequence R_fn(CH₂)_mNH₂ > R_fn(CH₂)_mPH₂ > R_fn(CH₂)_mP(O)(OEt)₂.

Key words

phosphines - phosphonates - Arbuzov reaction - fluorous - partition coefficients

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28

Emnet, C.; Gladysz, J. A. manuscript in preparation.

30

The chromatographic purification of 1-4 is not necessary when they are used for the synthesis of 5-8. However, all P(OEt)₃ must be removed to avoid the formation of PH₃. Some of the byproduct EtP(O)(OEt)₂ can be carried along, as it gives the easily volatilized EtPH₂.