Neue Synthesen mit 1,3-ambident-nucleophilen Phosphor-Yliden, VII. Heterocyclische Triphenylphosphonium-chloride, Triphenylphosphonio-olate, acyclische Triphenylphosphonio-thiolate und ihre Wittig-Derivate
✍ Scribed by Capuano, Lilly ;Drescher, Stefan ;Huch, Volker
- Book ID
- 102365402
- Publisher
- John Wiley and Sons
- Year
- 1993
- Tongue
- English
- Weight
- 430 KB
- Volume
- 1993
- Category
- Article
- ISSN
- 0947-3440
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✦ Synopsis
Syntheses with 1,3‐Ambident‐Nucleophilic Phosphorus Ylides, VII. – Heterocyclic Triphenylphosphonium Chlorides, Triphenylphosphonio‐Olates, Acyclic Triphenylphosphonio‐Thiolates and Their Wittig Derivatives
Under mild conditions, benzoylmethylenetriphenylphosphorane (1b) reacts readily with oxalyl chloride to give the unstable 4‐(4,5‐dihydro‐4,5‐dioxo‐2‐phenyl‐3‐furyl)triphenylphosphonium chloride (3b). This undergoes rapid hydrolysis to afford the triphenylphosphonium chloride 4 of benzoylpyruvic acid. Thermolysis of 3b or 4 results in the formation of 2‐(triphenylphosphoranyliden)indan‐1,3‐dione (10), the structure of which was established by X‐ray diffraction analysis. – With phenylmalonyl chloride, the title compounds 1a, b, d react by formation of the triphenylphosphonio‐olates 7 of pyridine‐, pyran‐ and thiopyran‐dione, respectively. – The (thioaroylmethylene)triphenylphosphoranes 1e, f react with benzonitrile imine 12 to give the red hydrazonotriphenylphosphoniothiolates 16, the structures of which have been elucidated by an X‐ray diffraction analysis. Under rigorous conditions, compounds 16 undergo an intramolecular Wittig‐type reaction leading to pyrazoles 14.