Symmetrical bis-phosphorus compounds and macrocycles with two 1,3,2-benzodiazaphosphorinone units - Oxidation and X-ray structure analysis of selected compounds

The hydrolysis of 1,2-bis(5,6-benzo-1-methyl-2-chloro-1.3,2-diazaphosphorin -4-on-3-yl)ethane (1) and its 1,3-propane derivative (2) with excess water led, without decomposition, to the formation of the bis-phosphoryl compound s 3 and 4. Reaction of 1 and 2 with bis(trimethylsiloxy)ethane formed the s ymmetrical macrocycles 5 and 6, which could readily be oxidized by (H2N)(2) C(:O) . H2O2 or elemental sulfur, leading to the formation of the phosphory l compounds 7 and 10, and the thiophosphoryl derivatives 9 and 11, respecti vely. The influence of the ring size on the reaction rate of the oxidation was investigated. For the sulfurization of 6, the stepwise addition of sulf ur to phosphorus was proved by NMR spectroscopy. All compounds exist as sin gle conformers in common organic solvents such as toluene, diethyl ether, d ichloromethane or chloroform. For compounds 7 (dichloromethane solvate) and 9, single crystal X-ray structure analyses were conducted; both diastereom eric molecules were shown to display RR/SS configuration. In both structure s one short non-classical hydrogen bond was observed.