Methylmagnesium halides, reaction with

N-Methylisobutylamine, 44, 77 Methyl isocyanide, 41, 15 N-Methylisopropylamine, 44, 77 Methylmagnesium halides, reaction with... 

Reaction of methylmagnesium halide with the 6-ketones (26), (27) and (28) yields the 6a-methyl-6/ -hydroxy compounds. 

Grignard reaction, of methylmagnesium halides with 2,6-dimethylpyrone, 44, 102 (... 

Tetramethylbiphosphine disulfide has been prepared by reaction of methylmagnesium halides with thiophosphoryl chloride. ... 

On the whole, reactions of thioketones with vinyl-, allyl-, propargyl-, benzyl-, and, sometimes, methylmagnesium halides proceed by carbophilic addition [1-3] (though subsequent rearrangements to the thiophilic product may occur [2]) ... 

Cross coii ing of Grignard reagents with 1-alkenyl halides, in marked contrast to alkyl halides, occurs readily with the reduced iron catalyst, as described above. The iron-catalyzed reaction of Grignard reagents with 1-alkenyl halides can, however, be differentiated from the reaction with alkyl halides. Thus, a mixture of propenyl bromide and ethyl bromide on reaction with methylmagnesium bromide afforded butene-2 but no cross-over products such as pentene-2 or propylene. The latter certainly would have resulted if a propenyliron species per se were involved in the catalytic process. Cross coupling under tEese circumstances clearly merits further study. 

Methylmagnesium halide reacts stereospecifically with a 19-aldehyde (269) to give the (I )-19-methyl-19-ol (270), whereas lithium aluminium hydride reduced the 19-methyl-19-oxo-compound (271) to give the 19(S)-alcohol 212) Both reactions indicate a preferred conformation for the 19-carbonyl compound, with the carbonyl oxygen atom close to C-5. 

Dimethylphenylphosphine is a ligand commonly used to prepare a large range of transition metal-organophosphorus complexes. This basic phosphine is easy to handle and presents a small cone angle.1,2 It is usually prepared in 40-50% yield by reaction of a solution of methylmagnesium halide with phenylphosphonous dichloride followed by hydrolysis with an excess of saturated aqueous ammonium chloride solution.3 4 In the present preparation the yield has been greatly increased (to 85%). 

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