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Synlett 2006(6): 954-956  
DOI: 10.1055/s-2006-939056
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Symmetrical and Unsymmetrical Functionalized Arylphosphines from Chlorophosphines and Organozinc Reagents

Erwan Le Gall*, Karima Ben Aïssi, Isabelle Lachaise, Michel Troupel
Laboratoire d’Electrochimie, Catalyse et Synthèse Organique, LECSO, CNRS-Université Paris, 12 Val de Marne, UMR 7582, 2-8 rue Henri Dunant, 94320 Thiais, France
Fax: +33(1)49781148; e-Mail: legall@glvt-cnrs.fr;
Further Information

Publication History

Received 17 January 2006
Publication Date:
14 March 2006 (online)

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Abstract

A stepwise procedure allowing the formation of symmetrical arylphosphines is described. It relies on the use of preformed functionalized aromatic organozinc reagents to perform arylations of chlorophosphines. Some preliminary results concerning the synthesis of unsymmetrical diarylphenylphosphines through sequential coupling of organozinc species with dichlorophenylphosphine are also reported.

Key words

phosphorus - arylation - organometallic reagents - chlorophosphines - functionalized arylphosphines

    References and Notes

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7

In a typical procedure, about 10-12 mmol of the organozinc reagent were prepared from 15 mmol of an aryl bromide according to the method described in ref. 6. To the filtered solution containing the organozinc reagent was added chlorodiphenylphosphine (10 mmol) at r.t. Stirring was continued for additional 2 h at r.t. The reaction was quenched using a 5% HCl solution and the resulting mixture was extracted with CH2Cl2. After evaporation to dryness, the chromatographic purification of the crude oil over silica gel using a pentane-Et2O mixture as an eluent afforded the analytically pure phosphine derivative.

8

The protection of phosphines could be verified using 31P NMR (80 MHz, CDCl3). Indeed, the δ value shifts from ca. -12 ppm (R3P) to ca. 13 ppm (R3PBH3).

10

In order to add exactly the required amount of the organozinc compound, a titration was realized as follows: aliquots of the solution were exposed to iodine and analyzed using GC. The amount of aryl iodide so obtained was compared to the amount of the starting aryl bromide using dodecane as internal standard.

11

Coupling products were characterized using 1H NMR (200 MHz, CDCl3), 13C NMR (50 MHz, CDCl3) when required, 31P NMR (80 MHz, CDCl3), mass spectroscopy and, when useful, 19F NMR (188 MHz, CDCl3) and FT-IR spectroscopy.
Some Data for Selected Compounds.
Diphenyl[3-(trifluoromethyl)phenyl]phosphine (1d): 1H NMR: δ = 7.80-7.10 (m, 14 H) ppm. 31P NMR: δ = -9.99 ppm. 19F NMR: δ = -62.38 ppm. MS: m/z (rel. intensity) = 330 (100) [M], 251 (19) [M - 79], 203 (18) [M - 127], 183 (48) [M - 147], 108 (22) [M - 222].
Phenylbis[3-(trifluoromethyl)phenyl]phosphine (2c): 1H NMR: δ = 7.84-7.23 (m, 13 H) ppm. 31P NMR: δ = -9.97 ppm. 19F NMR: δ = -62.71 ppm. MS: m/z (rel. intensity) = 399 (24) [M + 1], 398 (100) [M], 397 (21) 9M - 1], 251 (40) [M - 147], 203 (44) [M - 195], 183 (22) [M - 215].
Tris(3-methylphenyl)phosphine (3g): 1H NMR: δ = 7.15-6.94 (m, 12 H), 2.19 (s, 9 H) ppm. 31P NMR: δ = -10.22 ppm. MS: m/z (rel. intensity) = 304 (100) [M], 303 (37) [M - 1], 211 (36) [M - 93], 197 (20) [M - 107]. (4-Methoxyphenyl)(phenyl)(o-tolyl)phosphine oxide (4c): 1H NMR: δ = 7.83-6.92 (m, 13 H), 3.81 (s, 3 H), 2.43 (s, 3 H) ppm. 31P NMR: δ = 29.08 ppm. MS: m/z (rel. intensity) = 322 (40) [M], 321 (100) [M - 1], 213 (21) [M - 109].