Please use this identifier to cite or link to this item: http://dx.doi.org/10.18419/opus-1279
Authors: Becker, Gerd
Becker, Winfried
Knebl, Robert
Schmidt, Helmut
Hildenbrand, Ute
Westerhausen, Matthias
Title: Alkylidynephosphines : syntheses and reactivity
Issue Date: 1987
metadata.ubs.publikation.typ: Zeitschriftenartikel
metadata.ubs.publikation.source: Phosphorus and sulfur and the related elements 30 (1987), S. 349-352. URL http://dx.doi.org./10.1080/03086648708080592
URI: http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-58065
http://elib.uni-stuttgart.de/handle/11682/1296
http://dx.doi.org/10.18419/opus-1279
Abstract: In the past, different methods have been utilized for the preparation of alkylidynephosphines. Whereas, however, small amounts of thermally instable derivatives might be obtained from reactions in the gas phase, the synthesis of phosphines which are stable under an inert atmosphere, as for instance those with a tert-butyl or a 1-adamantyl substituent at the carbon atom of the PEC group, is best started with tris (trimethylsilyl) phosphine itself or with the more reactive lithium bis (trimethylsilyl) phosphide.2 tetrahydrofuran complex. Treatment of either compound with acyl halides results in the formation of acylbis (trimethylsilyl) phosphines which, at room temperature, rearrange to the corresponding trimethylsilyl [1-(trimethylsiloxy) alkylidene] isomers. As traces of hydrogen halide accelerate the conversion of tris (trimethylsilyl) phosphine to the triacyl derivatives, the use of the lithium phosphide is strongly recommended in all cases where impure acyl halides are used. In the presence of small amounts of solid sodium hydroxide suspended in an etherial solvent, the thus prepared trimethyl[1-(trimethylsiloxy)-alkylidene]phosphines eliminate hexamethyldisiloxane to yield the required alkylidyne compounds. Running the decomposition without a solvent at a higher temperature, Regitz and coworkers were able to improve this method further.
Appears in Collections:03 Fakultät Chemie

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