The synthesis and study of a crown ether functionalized with both phosphine and phenol groups

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Crabill, Todd W.
Storhoff, Bruce N.
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Thesis (M.S.)
Department of Chemistry
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This study has resulted in a crown ether functionalized with both phosphine and phenol groups, 5-diphenylphosphino-1,3-xylyl-18-crown-5. The target molecule was obtained from a six step synthesis. 4-Bromophenol was treated in sequence with formaldehyde, dimethylsulfate, and phosphorus tribromide producing 4-bromo-2,6-bis(bromomethyl)anisole. The main intermediate, 5-diphenylphosphino-1,3-xylyl-18-crown-5, was obtained by treating 4-bromo-2,6-bis(bromomethyl)anisole in sequence with tetraethylene glycol, lithium iodide, and methyldiphenyl phosphonite. The lithium iodide cleaved the anisole-to-methyl group bond, and the methyldiphenyl phosphonite provided the phosphine group for the crown ether following a lithium bromine exchange reaction. The 31P NMR of the phosphine crown ether showed a single signal at 6 -5.9, showing consistency of a single product. The IH NMR of the phosphine crown ether in deuterated chloroform showed signals at 6 3.55-3.7 (crown CH2), 6 4.6 (benzylic CH2), 6 7.1 (d, J = 7.o Hz, crown aromatic CH2), and 6 7.2-7.4 (noncrown aromatic CH2).