Organolithium displacement of aryl anions from tertiary phosphine derivatives of diphenyl ether

Article abstract of DOI:10.1080/10426509608545211

Methyllithium displaces a phenyl anion from 10-phenyl-10H-phenoxaphosphine to produce a 70:30 mixture of 10-methyl-10H-phenoxaphosphine and starting phosphine. Butyllithium gives 50% conversion to 10-butyl-10H-phenoxaphosphine. These reactions could take place either by a one-step nucleophilic displacement or by ring cleavage followed by recyclization. To show the feasibility of the two-step process, non-heterocyclic lithiated tertiary phosphines were generated and shown to cyclize to phenoxaphosphines. For example, reaction of 2-phenoxyphenyldiphenylphospnine with phenyllithium produced 10-phenyl-10H-phenoxaphosphine (by lithiation ortho to oxygen followed by cyclization) along with triphenylphosphine (by direct displacement of 2-lithiodiphenyl ether). Other compounds prepared in this work: 2,2′-bis(diphenylphosphino)-diphenyl ether, bis(2-phenoxyphenyl)phenylphospnine, tris(2-phenoxyphenyl)phosphine, 4-carboxy-10-phenyl-10H-phenoxaphosphine, and the oxides and sulfides of the phosphines.

Full text of DOI:10.1080/10426509608545211

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Phosphorus, Sulfur, and Silicon and
the Related Elements
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Organolithium Displacement
of Aryl Anions from Tertiary
Phosphine Derivatives of Diphenyl
Ether
Jack B. Levy , Richard C. Walton , Ron E. Olsen &
Courtland Symmes Jr
a University of North Carolina at Wilmington , Wilmington,
N.C., USA
b University of North Carolina at Wilmington , Wilmington,
N.C., USA
c University of North Carolina at Wilmington , Wilmington,
N.C., USA
d University of North Carolina at Wilmington , Wilmington,
N.C., USA
Published online: 06 Aug 2008.
To cite this article: Jack B. Levy , Richard C. Walton , Ron E. Olsen & Courtland Symmes
Jr (1996) Organolithium Displacement of Aryl Anions from Tertiary Phosphine Derivatives of
Diphenyl Ether, Phosphorus, Sulfur, and Silicon and the Related Elements, 109:1-4, 545-548,
DOI: 10.1080/10426509608545211
To link to this article: http://dx.doi.org/10.1080/10426509608545211
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