Symmetrical Bis-Phosphorus Compounds and Macrocycles with two 1,3,2-Benzodiazaphosphorinone Units – Oxidation and X-Ray Structure Analysis of Selected Compounds

✍ Scribed by Zhaofu Fei; Yingzi Lu; Matthias Freytag; Peter G. Jones; Reinhard Schmutzler

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: German
• Weight: 149 KB
• Volume: 626
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(200004)626:4<969::aid-zaac969>3.0.co;2-w

✦ Synopsis

The hydrolysis of 1,2-bis(5,6-benzo-1-methyl-2chloro-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 compounds 3 and 4. Reaction of 1 and 2 with bis(trimethylsiloxy)ethane formed the symmetrical macrocycles 5 and 6, which could readily be oxidized by (H 2 N) 2 C(:O) ´H2 O 2 or elemental sulfur, leading to the formation of the phosphoryl compounds 7 and 10, and the thiophosphoryl derivatives 9 and 11, respectively. The influence of the ring size on the reaction rate of the oxidation was investigated. For the sulfurization of 6, the stepwise addition of sulfur to phosphorus was proved by NMR spectroscopy. All compounds exist as single conformers in common organic solvents such as toluene, diethyl ether, dichloromethane or chloroform. For compounds 7 (dichloromethane solvate) and 9, single crystal X-ray structure analyses were conducted; both diastereomeric molecules were shown to display RR/SS configuration. In both structures one short non-classical hydrogen bond was observed.