Sodium 2,6-dimethylphenoxide

Methylthio-l, 2-dithiolium cations attack sodium phenoxide in the 2-position13,20 and sodium 2,6-dimethylphenoxide in the 4-position.31... 

A reaction in which perchloryl fluoride functions as an ambident electrophile, somewhat analogous to Neeman s oxofluorination, was discovered by Kende and MacGregor on passing FCIOj into a suspension of sodium 2,6-dimethylphenoxide in pentane or toluene at 0°. Workup and chromatography gave 2,6-dimethylphenol, 2,6-dimethylbenzoquinone, 2,2, 6,6 -tetramethyl-4,4 -diphenoquinone and, in about 20% yield, a new compound characterized as the dimer (3) of 6-fluoro-2,6-dimethyl-... 

Correlation of phenolate reaction sites with electrophiles is as valid as in the other ambident systems. Thus, only the methyl ethers are produced from the reaction of sodium 2,6-dimethylphenoxide with methyl brosylate (181) or sodium 2-naphthoxide with dimethyl sulfate (182). Analysis of aroyl-ation of 2-naphthoxides in hexane (183) indicates that (0 softer Li enolate gives higher C/O ratios than the Na enolate, and (//) more C-acylation occurs with the aroyl chloride of softer nature. 

Alkylation at Phosphorus. Phosphines and phosphites undergo easy quaternization. Thus methylation of tris(2,6-dimethyl-phenoxy)phosphine with MeOTf, followed by treatment of the product with sodium 2,6-dimethylphenoxide, gave methyltetrakis (2,6-dimethylphenoxy)phosphane. Methoxyphosphonium tri-flates are relatively stable intermediates in Arbuzov reactions Phosphine oxides and sulfides are alkylated. S-Methylation of chiral phosphine sulfides, followed by treatment with hexam-ethylphosphorous triamide, has been advocated as a general synthesis of optically active phosphines. ... 

A. Lithium 2,6-dimethylphenoxide. In a 300-ml. flask, equipped with a magnetic stirrer and a reflux condenser and flushed with nitrogen, are placed 150 ml. of toluene (freshly distilled from sodium), 1.40 g. (0.202 mole) of lithium metal (Note 1) and 25.0 g. (0.205 mole) of resublimed 2,6-dimethylphenol. The mixture... 

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