Magnesium halogen derivatives

Several years ago, Castro, Villieras and coworkers described the preparation of the magnesium enolate derived from an alkyl a,a-dihaloacetate by halogen-metal exchange between isopropyhnagnesium chloride and alkyl trihaloacetate. THF is required as solvent (equation 7) °. 

Reaction XLIII. (c) Condensation of a-Halogen Fatty Acid Esters with Aldehydes and Ketones by means of Zinc or Magnesium (Reformatsky-Grignard). (C., (1901), I., 1196 II., 30 (1902), I., 856.)—This is an extension of the Grignard and zinc alkyl reactions which enables a-halogen esters to be condensed with carbonyl compounds as if they were simple alkyl halogen compounds. The zinc or magnesium alkyl derivative is neither prepared beforehand nor isolated in the reaction, but there is little doubt that some such compound is transitorily formed. Zinc is the metal... 

Grignard s Synthesis.—Magnesium reacts with halogen derivatives of the aromatic hydrocarbons as well as with those derived from the paraffins. The compounds so formed are decomposed by water, and hydrocarbons are formed. By the application of this method a halogen compound can be converted into the corresponding hydrocarbon —... 

These compounds are obtained by action of halogenated organic derivatives on lead alloys (magnesium or alkaline metal alloys). 

Antimony trioxide and chlorinated paraffinic derivatives are common materials used as fire retardants, as are intumescent zinc (or calcium) borate, aluminium hydroxide and magnesium hydroxide. These inorganic materials, used as bulk fillers, act to reduce the fire hazard. Halogenated materials release chlorine, which then combines with the antimony trioxide to form the trichloride, which is a flame suppressant. 

Remarkably, halogen-magnesium exchange can also be extended to aryl and heteroaryl bromides [24, 25], Thus, the functionalized aryl bromides 28 and 29 (Scheme 2.7) were converted, at 0 °C and at —30 °C, respectively, into the corresponding Grignard reagents. After treatment with CuCN, the copper derivative 30 and 31 were obtained. Subsequent treatment with typical electrophiles such as benzoyl bromide or allyl bromide furnished the products 32 and 33, in 70 and 80% yields. 

An intramolecular 1,5-C,H insertion reaction was reported from substituted bromo-iodoalkane and halogen-magnesium exchange reaction (equation 24) °. Indeed, treatment of bromoiodoalkane (86) with i-PrMgCl in ether at —78°C to —20°C resulted in the formation of magnesium carbenoid 87. The 1,5-C,H insertion of 87 took place to afford a cyclopentane derivative (88) however, the yield was not satisfactory. 

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