Solution
ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-1/12/a/ii/solution
Past exam of the chemistry course of the year 4 of the natural sciences course of the University of Cambridge 2022 Paper 1 12 a ii Solution by
Codex 0 2026-10-20
Treat this as standalone organophosphorus chemistry. The phosphorus(III) lone pair attacks the terminal nitrogen of the organic azide. Cyclization of the initial phosphazide and loss of nitrogen give an iminophosphorane:The ortho amide provides a neighboring acidic NH proton and a carbonyl oxygen donor. A proton relay to the imino nitrogen and intramolecular OP attack generate a five-membered, O-bound pentacoordinate phosphorus intermediate. Water can then attack phosphorus, with proton transfer to nitrogen, followed by P–N cleavage and opening of the neighboring-group contact.
The overall hydrolysis products areThe carbonyl group assists the hydrolysis and is regenerated; the product is an aniline and the ortho-carboxamide phosphine oxide, rather than an amide-linked ligation product. The favorable five-membered intramolecular interaction and proton delivery help hydrolyze a normally rather persistent aryl iminophosphorane. This explanation concerns only the printed chemical transformation.
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