Magnesium,chloro hydroxymethylation

Chloro-2-[3-(bromomethyl)-5-methyl-4H-l,2,4-triazol-4-yl]-benzophenone A solution of 5-chloro-2-[3-(hydroxymethyl)-5-methyl-4H-l,2,4-triazol-4-yl]-benzophenone (328 mg, 0.001 mol) in dry, hydrocarbon-stabilized chloroform (5 ml) was cooled in an ice-bath and treated with phosphorus tribromide (0.1 ml). The colorless solution was kept in the ice-bath for 55 minutes, at ambient temperature (22-24°C), for 5 hours. The resulting yellow solution was poured into a mixture of ice and dilute sodium bicarbonate. This mixture was extracted with chloroform. The extract was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was crystallized from methylene chloride-ethyl acetate to give 0.285 g of melting point 200-240°C (decomposition) and 0.030 g of melting point 200-220°C (decomposition) of 5-chloro-2-[3-(bromomethyl)-5-methyl-4H-l,2,4-triazol-4-yl]benzophenone. The analytical sample had a melting point of 200-240°C. 

Other aldehydes and related compounds have been reacted either alone or catalyzed with sulfuric acid, zinc chloride, magnesium chloride, ammonium chloride, or diammonium phosphate (94). Compounds such as l,3-bis(hydroxymethyl)-2-imidazolidone, glycol acetate, acrolein, chloroacetaldehyde, heptaldehyde, o- and p-chloro-benzaldehydes, furfural, p-hydroxybenzaldehyde, and m-nitrobenz-aldehyde all achieve the ASE by a bulking mechanism and not by low-level cross-linking. At weight gains of 15-25%, the highest ASE reported is 40%. 

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