A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia.
Molecules. 2022 Oct 14;27(20):6910. doi: 10.3390/molecules27206910.
Allyl halides with triflamide under oxidative conditions form halogen-substituted amidines. Allyl cyanide reacts with triflamide in acetonitrile or THF solutions in the presence of NBS to give the products of bromotriflamidation with a solvent interception, whereas in CHCl two regioisomers of the bromotriflamidation product without a solvent interception were obtained. The formed products undergo base-induced dehydrobromination to give linear isomers with the new C=C bond conjugated either with the nitrile group or the amidine moiety or alkoxy group. Under the same conditions, the reaction of allyl alcohol with triflamide gives rise to amidine, which was prepared earlier by the reaction of diallyl formal with triflamide. Unlike their iodo-substituted analogs, bromo-substituted amidines successfully transform into imidazolidines under the action of potassium carbonate.
烯丙基卤化物与三氟甲酰胺在氧化条件下形成卤代脒。烯丙基氰化物在 NBS 的存在下，在乙腈或四氢呋喃溶液中与三氟甲酰胺反应，得到具有溶剂捕获的溴代三氟甲酰胺化产物，而在 CHCl 中，得到没有溶剂捕获的溴代三氟甲酰胺化产物的两个区域异构体。形成的产物经历碱诱导脱溴化氢，得到具有新的 C=C 键的线性异构体，该新的 C=C 键与腈基或脒部分或烷氧基共轭。在相同条件下，烯丙醇与三氟甲酰胺反应生成脒，脒是由二烯丙基甲醛与三氟甲酰胺反应早先制备的。与它们的碘代类似物不同，溴代脒在碳酸钾的作用下成功转化为咪唑烷。
