Tert-Butylmagnesium chloride, reaction with

High yields (76-81%) of alcohols are also obtained by adding solutions of acyl chlorides in anhydrous dioxane or diethyl carbitol to a suspension of sodium borohydride in dioxane and brief heating of the mixtures on the steam bath [751], by stirring solutions of acyl chlorides in ether for 2-4 hours at room temperature with aluminum oxide (activity I) impregnated with a 50% aqueous solution of sodium borohydride (Alox) (yields 80-90%) [1014], by refluxing acyl chlorides with ether solutions of sodium trimethoxyborohydride [99], or by treatment of acyl chlorides in dichloromethane solutions with tetrabutylammonium borohydride at —78° [771]. A 94% yield of neopentyl alcohol was achieved by the reaction of trimethylacetyl chloride with tert-butylmagnesium chloride [324]. 

MAD and MAT have played a crucial role in the stereoselective synthesis of hitherto inaccessible equatorial carbinols from cyclohexanones and primary allyl Grignard reagents or methyllithium [44). In the reaction of cyclohexanone derivatives with tert-butylmagnesium chloride, reduction takes precedence over alkylation in the presence of MAD (Scheme 6.37) [45). 

The rate of the reaction decreases with increasing number of substituents in the acetylenic halide, and it is higher with acetylenic bromides than with the corresponding chlorides. Methyl magnesium iodide gives equal amounts of 1,1- and 1,3--substitution products, whereas tert.-butylmagnesium bromide does not react. However, for some tert.-butyl substituted allenes there exists an attractive com-... 

The formation of dihydropyridazines by the reaction of tert-butyl Grignard with trisubstituted pyridazines has attracted particular attention. 3,4,6-Trichloropyridazine reacts with tm-butylmagnesium chloride, giving a... 

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