Photochemical decomposition of the diazoketone (I) gives rise to the formation of the well known keto Carbene ‐ oxirene equilibrium (II)‐(IV) from which not only the product of the Wolff rearrangement, the ketene (XII) can be derived [as its EtOH addition product, the ester (XIII)] but also the intramolecular addition product (VIII) [isolated in the rearranged form (IX) (space group P21/c with Z=4)] and the insertion products (X) [which exists as the enol (XI) as expected] and (V), which is in equilibrium with its enol (VI).
Die Diolester (I) setzen sich mit AsF3 zu den Arsadiolanen (II) um, reagieren analog mit AsCl3 und PCl3, bilden mit Trimethylsilylchlorid (III) stabile Monosubstitutionsprodukte, wie z.B. (IV) [die erst nach vollständigem Verbrauch eines Mols (III) weiter zu Disubstitutionsprodukten, wie (V), reagieren] und bilden mit den Säurechloriden (VI) über Monosubstitutionsprodukte, wie (VII), Diester, wie (VIII).
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