The Addition of Methylmagnesium Iodide to Benzoyldurene

Abstract

In earlier studies embracing benzoylmesitylene (1), benzoylisodurene (1), benzoyldurene (2), the mesitoylnaphthalenes (3), and similar diaryl ketones, it has been demonstrated that addition of Grignard reagents occurs in spite of the excessive crowding about the carbonyl group. The addition may be 1,2, 1,4, or 1,6, depending on the nature of the ketone and of the Grignard reagent which is used. Recently Young and Roberts (4) made the surprising discovery that 1,2 addition occurs when benzyl and s-butenyl Grignard reagents are condensed with acetomesitylene. These and methylmagnesium iodide are the only Grignard reagents which have been found to combine with mesityl ketones in this manner.In most cases addition takes place in the 1,4 manner.There is evidence, however, that even 1,4 addition is limited to reagents having small alkyl or aryl groups. In fact, in two instances 1,6 addition has been observed; benzyl-and -butylmagnesium chloride react in this manner with benzoyldurene (2).

Synthesis and NMR data of some variously substituted diphenylmethanes and dibenzylbenzenes

“…In our hands, attempts to prepare the acetone from 3,4-dimethoxyphenylacetonitrile via the acetoacetonitrile (33) led chiefly to the recovery of unchanged dimethoxyphenylacetoacetonitrile. Ring closure of the acetone with nitromalondialdehyde (13), to give 3, was effected in aqueous base (4,6,(22)(23)(24). Etherification to give the methyl ether,…”

The Behavior of Conjugated Systems Containing Aromatic Double Bonds towards Organometallic Reagents.

“…In only one case has it been possible by extensive and exhaustive investigation of the reaction mixture to prove the occurrence of simultaneous 1,2-1,4-, and 1,6-addition of a Grignard reagent (24), Duryl phenyl ketone reacted with CODur XZ OCH3…”

REPLACEMENT OF METHOXYL GROUPS IN p-METHOXYARYL KETONES BY THE ACTION OF THE GRIGNARD REAGENT

“…When 2 g. of this gum was treated with 1.08 g. of bromine in 20 ml. of carbon tetrachloride for 4 hours, there was isolated 0.5 g. of a solid which was recrystallized from methanol. White crystals having the composition of a monobromo derivative were obtained; m.p.…”