Trimethylstannylation of mono- and dichloroarenes by the SRN1 mechanism in liquid ammonia†

The photostimulated reaction of methyl 2,5-dichloro benzoate (1) or methyl 3,6-dichloro-2-methoxy benzoate (7) with −SnMe3 ions give good yields of the disubstitution products by the SRN1 mechanism in liquid ammonia. Conversely, in dark conditions, substrate 1 reacts with −SnMe3 ions to afford the mono-substitution products by the SRN1 mechanism. On the other hand, substrate 7 reacts with −SnMe3 ions in dark conditions to give mono-reduced product probably by a halogen metal exchange reaction. In addition, the photostimulated reaction of 2-chloro-N4-ethyl-N6-isopropyl-1,3,5-triazin-4,6-diamine (Atrazine, 11) with −SnMe3 ions affords the reduced and substitution products in liquid ammonia-DMSO as co-solvent. Copyright © 2006 John Wiley & Sons, Ltd.