4-Chloro-2-(chloromethyl)pyridine → 2-(Azidomethyl)-4-chloropyridine

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Reaction Steps

The starting material may be obtained as follows. Reaction of 2-chloromethyl-4-chloropyridine with excess tetramethylquinoline azide in CH2Cl2 at ambient temperature for 24 hours gave 2-azidomethyl-4-chloropyridine. n.m.r. in CDCl3 : 4.5(s, 2H); 7.3(m, 2H); 8.5(d, 1H). Reduction of this compound in MeOH in the presence of 2 equivalents of acetic anhydride with Raney nickel at ambient temperature for 30 minutes gave, after purification by silica gel chromatography, 2-acetylaminomethyl-4-chloropyridine, n.m.r. in CDCl3 : 2.1(s, 3H); 4.56(d, 2H); 7.3(m, 2H); 8.48(d, 2H). Reaction of the compound with excess dimethyl sulphate for 30 minutes at 40° gave 2-acetylaminomethyl-4-chloro-1-methylpyridinium methyl sulphate, n.m.r. in solvent F: 2.0(s, 3H); 3.44(s, 3H); 4.3(s, 3H); 4.7(s, 2H); 8.2(m, 2H); 9.04(d, 1H).

Provenance & Evidence