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25) Melting points were taken on a Mel-Temp apparatus and are corrected; boiling points are uncorrected. All manipulations of phosphines were conducted in a nitrogen atmosphere in a glove bag. Proton nmr spectra were taken on a Varían A-60 or JEOL MH-100 spectrometer and are referenced to TMS. Proton-decoupled Fourier transform 13C spectra were obtained on a Bruker HFX-10 system at 22.62 MHz utilizing C6Fe In a 3-mm coaxial capillary as external heteronuclear lock; chemical shifts were measured from TMS and then referenced to CS2 using the relation ¿tms = 192.5 ppm. C-P coupling constants are ±1.2 Hz. Proton-decoupled 31P spectra (continuous wave mode) were obtained at 36.43 MHz In a 5-mm tube with C6Fe in a coaxial Insert as lock; offsets relative to prerun 85 % H3PO4 were used to determine values. Elemental analyses were obtained by M-H-W Laboratories, Garden City, Mich. Alkylphosphonous dichlorides used in the synthesis of 1 were commercial samples or were prepared by published methods. (26) G. Grüttner and M.

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A rapid synthetic procedure for the preparation of phospholanium perchlorates in high yield has been developed. The process involves the cleavage of tetrahydrofuran by lithium organophosphides, affording 4-hydroxybutylorganophosphines, which are then intramolecularly cyclized in an aqueous solution. The following phospholanium salts (very tediously prepared by other methods) have been obtained by this procedure: methylphenyl-, ethylphenyl-, n-propylphenyl-, n-butylphenyl-, and diphenylphospholanium perchlorate. Evidence is also presented to show that cleavage of THE by diethylphenylphosphine and lithium metal afforded not only the expected diethyl-4-hydroxybutylphosphine, but also ethyl-4-hydroxybutylphenylphosphine. Confirmation of this was obtained in the form of subsequent intramolecular cyclization of these phosphines to the corresponding diethylphospholanium perchlorate and ethylphenylphospholanium perchlorate. Extension of this synthetic procedure to tetrahydropyran also afforded the desired phosphorinanium perchlorate in good yield.