ChemInform Abstract: 1‐3 ISOMERIZATION IN A SERIES OF PHOSPHORYLATED INDOLES

Abstract

Das 1‐Indolyl‐phosphorigsäurediamid (II) hydrolysiert durch eine äquivalente Menge Wasser unter gleichzeitiger Isomerisierung zum 3‐Indolylphosphonit (I) und durch Alkoholezu "den O,O‐Dialkyl‐3‐indolylphosphoniten (III).

N → C3 migration of dichlorophosphino group in the phosphorylation of N‐unsubstituted indole with phosphorus trichloride

“…However, when using amidophosphorous esters as phosphorylating agents, initially formed N-phosphorylated derivatives rearrange intramolecularly to C 3 -substituted products [5] under the catalytic action of amine hydrochlorides present in the reaction mixture. A similar N → C 3 sigmatropic rearrangement of phosphorylated indoles occurs in the hydrolysis and alcoholysis of N-indolylamidophosphite with respective equimolar amounts of water or alcohol [6]. As previously found by us [7], the phosphorylation of unsubstituted pyrrole with phosphorus trichloride in polar solvents leads to a successive N → C 2 → C 3 migration of the dichlorophosphino group in the pyrrole nucleus.…”