Reactivity of fused 1,3-benzothiaphospholes: Formation of pentacoordinated derivatives

✍ Scribed by Graziano Baccolini; Giorgio Orsolan; Elisabetta Mezzina; Paolo Sgarabotto; Corrado Rizzoli

• Book ID: 102846583
• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 518 KB
• Volume: 5
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520050108

✦ Synopsis

Fused I ,3-benzothiaphospholes 2 (cis-2,6,1 O-trimethyl-[1 ,3]benzothiaphospholo [2,3-bl[l, 3lbenzothiaphosphole) reacts with H 2 0 2 and S8, giving the corresponding oxide and sulfide, respectively. The reactions of 2 with &ethyl azodicarboxylate (DEAD)/ catechol or DEAD/cl-aminophenol, o-azidophenol, and tetrachloro-o-benzoquinone (TOB) give the first examples of spiro pentacoordinated phosphorus derivatives of this heterocyclic system. The X-ray structural analysis of spiro compound 3 showed a trigonal bipyramidal configuration at phosphorus in which the three rings assume axial-equatorial positions.

INTROD UCTIOh,

Recently, we devised [l] the facile and highly stereoselective synthesis of cis-2,10-dimethyl[ 1,2,3]benzothiadiphospholo [2, 3-b][lI 2, 3lbenzothiadiphosphole 1, a new fused heterocyclic system containing an unusual P-P(S2) unit, by treating p- ''To whom correspondence should be addressed.