STEREOCHEMICAL PROPERTIES OF THE 1-CHLORO-1- PHENYL-2,5-DIMETHYL-2-PHOSPHOLENIUM ION AND DERIVED OXIDE AND PHOSPHINE |
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Authors: | Louis D. Quin Ronald C. Stocks |
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Affiliation: | Gross Chemical Laboratory , Duke University , Durham , North Carolina , 27706 , U.S.A. |
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Abstract: | Abstract The cycloaddition of phenylphosphonous dichloride and trans, trans-2,4-hexadiene, or the addition of chlorine to trans-1-phenyl-cis-2,5-dimethyl-3-phospholene, gave 1-chloro-1-phenyl-2,5-dimethyl-2-phospholenium chloride. This compound shows no evidence in its 31P and 1H nmr spectra for the existence of cis, trans isomers, yet on hydrolysis or dehalogenation with magnesium the resulting oxide and phosphine, respectively, are seen to be isomer mixtures. This phenomenon is explained by a rapid equilibration of the cis, trans form of the I-chloro ion through a pentacovalent species. Structures of the oxides and phosphines were assigned by 1H and 13C nmr relations. The 1-phenyl-cis-2,5-dimethyl-3-phospholenium ion and related compounds were also characterized. |
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