Synthesis 2005(6): 1012-1018  
DOI: 10.1055/s-2005-861815
PAPER
© Georg Thieme Verlag Stuttgart · New York

Efficient Syntheses of Fluorous Primary Phosphines that Do Not Require PH3

Charlotte Emnet, J. A. Gladysz*
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany
Fax: +49(9131)8526865; e-Mail: gladysz@organik.uni-erlangen.de;
Further Information

Publication History

Received 12 November 2004
Publication Date:
14 February 2005 (eFirst)

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Abstract

Arbuzov reactions of the fluorous primary iodides Rfn(CH2)mI [Rfn = 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 Rfn(CH2)mP(O)(OEt)2 (56-59%), which are reduced with LiAlH4 to the title compounds Rfn(CH2)mPH2 (62-78%). Fluorophilicities (CF3C6F11/toluene partition coefficients) increase with the length of the Rfn moiety, decrease with the length of the (CH2)m moiety, and decrease in the functional group sequence Rfn(CH2)mNH2 > Rfn(CH2)mPH2 > Rfn(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.