Synthesis and Characterization of β-Phosphaenones. An Investigation on the Conjugativ Properties of the P=C Bond

Autor: Manfred Regitz, Wolfgang Eisfeld, Anthony L. Spek, Nora Veldman, Huub Kooijman, Friedrich Bickelhaupt, Marcel van der Sluis
Přispěvatelé: Organic Chemistry
Jazyk: angličtina
Rok vydání: 1995
Předmět:
Zdroj: Chemische Berichte, 128, 465-476. John Wiley and Sons Ltd
van der Sluis, M, Bickelhaupt, F, Veldman, N, Kooijman, H, Spek, A L, Eisfeld, W & Regitz, M 1995, ' Synthesis and Characterization of β-Phosphaenones. An Investigation on the Conjugativ Properties of the P=C Bond. ', Chemische Berichte, vol. 128, pp. 465-476 . https://doi.org/10.1002/cber.19951280506
ISSN: 0009-2940
DOI: 10.1002/cber.19951280506
Popis: Thermally and air-stable β-phosphaenones were synthesized by functionalization of Mes*PCCl2 (1; Mes* = supermesityl = 2,4,6-tri-tert-butylphenyl). At low temperature, 1 was lithiated by halogen-metal exchange with n-butyllithium to give the phosphanylidene carbenoid (Z)-Mes*PC(Cl)Li [(Z)-2] which reacted with acid chlorides to furnish the C-carbonyl-substituted phosphaalkenes (Z)-Mes*PC(Cl)R (3: P = COtBu; 4: R = COPh; 5: R = COOEt). The reaction of (Z)-2 with carbon dioxide furnished the carboxylate 6, which was converted by treatment with pivaloyl chloride or trimethylsilyl chloride into the phosphaalkenes 7 and 8 functionalized at the carbon atom by an anhydride or a trimethylsilyl ester function, respectively. Acidification of 6 or hydrolysis of 8 with water in chloroform solution afforded the novel carboxylic acid (Z)-Mes*PC(Cl)COOH (9). Spectroscopic investigations (NMR, UV, IR) of 3–9 and the X-ray structures of 3 and 4 are presented. Based on these properties and on theoretical calculations, the occurrence of conjugation in the β-phosphaenone system is discussed and compared with the well-known conjugation in normal enones.
Databáze: OpenAIRE
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