Synthesis, properties and solid state structure of 5-diphenylphosphino-2-hydroxy-1,3-xylyl-18-crown-5

✍ Scribed by Rex A. Corbin; Todd W. Crabill; Bruce N. Storhoff; John C. Huffman

• Publisher: Journal of Heterocyclic Chemistry
• Year: 2006
• Tongue: English
• Weight: 173 KB
• Volume: 43
• Category: Article
• ISSN: 0022-152X
• DOI: 10.1002/jhet.5570430427

✦ Synopsis

Abstract

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5‐Diphenylphosphino‐2‐hydroxy‐1,3‐xylyl‐18‐crown‐5 has been synthesized from 5‐bromo‐2‐hydroxy‐18‐crown‐5 by reacting it in sequence at low temperature with n‐butyl lithium and methyl diphenylphosphonite. The phosphorous donor properties of this phenol phosphine (OH derivative) and the corresponding phenoxide (O^−^ derivative) have been studied in the presence and absence of alkali metal ions by determining the frequencies of the A~1~ ν(CO) bands of Ni(CO)~3~L complexes. For the OH and O^−^ derivatives, the latter generated by addition of CsOH to the former, the ν(CO) bands are observed at 2067.6 and 2063.4 cm^−1^, respectively, providing the trend predicted by Hammett parameters for OH and O^−^ substituents. Addition of Na^+^ or K^+^ to the OH derivative has little effect on this stretching frequency, but the former ion shifts the O^−^ derivative band to 2067.7 cm^−1^ A solid state structure has been obtained of the OH derivative, and two independent molecules were found in the unit cell. Both have a single water molecule hydrogen bonded to two across‐ring oxygen atoms and the phenol hydrogen. The crown ether ring has the usual gauche and anti arrangements for the C‐C and CO bonds.