Synthesis and Characterization of the Very Bulky Phenols Ar*OH and Ar′OH (Ar* = C6H3-2,6-Trip2, Trip = C6H2-2,4,6-iPr3; Ar′ = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) and Their Lithium and Sodium Derivatives (LiOAr′)2 and (NaOAr*)2

✍ Scribed by Corneliu Stanciu; Marilyn M. Olmstead; Andrew D. Phillips; Matthias Stender; Philip P. Power

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 155 KB
• Volume: 2003
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200300306

✦ Synopsis

Abstract

The very bulky phenols Ar*OH (1) and Ar′OH (2), where Ar* = C~6~H~3~‐2,6‐Trip~2~ (Trip = C~6~H~2~‐2,4,6‐__i__Pr~3~) and Ar′ = C~6~H~3~‐2,6‐Dipp~2~ (Dipp = C~6~H~3~‐2,6‐__i__Pr~2~), as well as their lithium and sodium derivatives (LiOAr*)~2~ (3), (LiOAr′)~2~ (4) and (NaOAr*)~2~ (5) have been synthesized and characterized. The terphenols 1 and 2 were obtained by the reaction of the aryllithium reagents with nitrobenzene and were isolated in ca. 70% yield. The lithium or sodium salts 3−5 were isolated by the reaction of 1 or 2 with __n__BuLi or sodium metal. All compounds were characterized spectroscopically, and by X‐ray crystallography in the case of 1, 2, 4 and 5. The large terphenyl substituents prevent hydrogen‐bonded association of the phenols 1 and 2. Instead, the O−H hydrogens interact with the π‐electron cloud on one of the flanking Trip or Dipp rings. The dimeric structures of 4 and 5 are relatively rare examples of structurally characterized alkali metal phenoxides that are unsolvated by internal electron pair donors or classical Lewis bases such as ethers or amines. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)