Durch Addition von Nitrosylchlorid (II) an Schiffsche Basen (I) entstehen die α‐Chloralkylnitroso‐alkylamine (III), von denen die Chlormethylverbindungen (IIIa) isoliert werden können.
Aus den Diindiketonen (I) und (IV) unter der Einwirkung von Tris‐[triphenylphosphin]‐RhCl entstehende instabile Komplexe lassen sich mit Acetylenen zu den Naphthochinonen (II) (IR‐Banden, 1H‐NMR‐Spektren) und (V) (IR‐Banden, 1H‐NMR‐Spektren), mit m‐Chlor‐perbenzoesäure, S, rotem Se oder Nitrosobenzol (alle Reaktionen in siedendem Benzol) zu den Benzochinonen (VI) (IR‐Banden, 1H‐NMR‐Spektren) umsetzen.
Based on gas‐chromatographic measurements coupled with MS the anodic oxidation of the labeled acetic acid (I) at graphite eIectrodes is shown to proceed via the open‐chain intermediate (II).
Aus dem Bis‐acetylenketon (I) erhält man bei der Umsetzung mit m‐Chlorperbenzoesäure, Schwefel, Selen oder Nitrosobenzol in Gegenwart von Tris‐triphenylphosphin‐rhodium(I)‐chlorid als Katalysator die isokondensierten heterocyclischen Benzochinone (IIa)‐(IId).
Carbonylation O 0305Palladium-Catalyzed Carbonylation of 4-Substituted 2-Iodoaniline Derivatives: Carbonylative Cyclization and Aminocarbonylation. -Iodoanilines (I) and various primary or secondary amines, including amino acid esters, undergo an aminocarbonylation reaction with double CO insertion at the iodo-substituted position to give 2-ketocarboxamides. In the absence of nucleophiles like amines or alcohols, anilines (I) undergo two types of 'dimeric' intramolecular aminocarbonylation reactions, depending on the substituents, to give benzoxazine derivatives (IX) or diazocine derivatives (X). -(ACS, P.; MUELLER, E.; RANGITS, G.; LORAND, T.; KOLLAR*, L.; Tetrahedron 62 (2006) 51, 12051-12056; Dep. Inorg. Chem., Janus Pannonius Univ., H-7624 Pecs, Hung.; Eng.) -Klein 13-041
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