Building the "Phosphoindigo" Backbone by Oxidative Coupling of Phosphindolin-3-ones with Selenium Dioxide

Oxidative coupling of racemic 1‐ethoxy‐1‐oxophosphindolin‐3‐one (1) and its 5‐CF3‐derivative 6 with SeO2 furnishes 1,1′‐diphosphaindigo derivatives 5 and 7 as bis‐phosphinic esters, i. e. as PV‐compounds. Like indigo and thioindigo, 5 and 7 exist in the E‐configuration; the crude products of 5 and 7...

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Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2008-07, Vol.634 (8), p.1321-1325
Main Authors: Vollbrecht, Sebastian, Dobreva, Guergana, Cartis, Ioana, du Mont, Wolf-W., Jeske, Jörg, Ruthe, Frank, Jones, Peter G., Ernst, Ludger, Grahn, Walter, Papke, Ulrich, Marzini, Michael, Mayer, Hermann A.
Format: Article
Language:English
Subjects:
Indigo dyes
Oxidative coupling
Phosphindole
Phosphinic acids
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Summary:Oxidative coupling of racemic 1‐ethoxy‐1‐oxophosphindolin‐3‐one (1) and its 5‐CF3‐derivative 6 with SeO2 furnishes 1,1′‐diphosphaindigo derivatives 5 and 7 as bis‐phosphinic esters, i. e. as PV‐compounds. Like indigo and thioindigo, 5 and 7 exist in the E‐configuration; the crude products of 5 and 7 are mixtures of isomers that are trans‐ and cis‐configurated with respect to the relative orientation of the ester groups oat phosphorus. The structure of the centrosymmetric E‐P(R)P′(S) isomer [(E)‐trans‐isomer] of 5 was determined by X‐ray crystallography. Ester cleavage of 5, followed by addition of triethylamine to bis‐phosphinic acid 9 (the 1,1,1′,1′‐tetroxide of “phosphoindigo”), furnishes the related bis‐triethylammonium salt 10 as a crystalline hydrate that exhibits an extended hydrogen bonding network.
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.200800054