POLYAZAPHOSPHORUS MACROCYCLES - SYNTHETIC APPROACHES TO SYMMETRIC OR DISSYMMETRIC 18-MEMBERED, 20-MEMBERED, 22-MEMBERED, AND 30-MEMBERED RINGS

High-yield synthetic routes to symmetric, functionalized or unfunctionalized, 18-, 20-, 22-, or 30-membered rings containing P-N-N linkages, i.e., 5c,c′, 5d,d′, 6b, 7a,c, 8b, and 9a,b, via [1 + 1], [2 + 2], or [3 + 3] condensation reactions involving phosphodihydrazides 1a-c and 1,2, 1,3, or 1,4 dialdehydes are reported. The mechanism of formation of these compounds has been elucidated by 31P NMR studies. The structure of one of these compounds, 5a, has been resolved by X-ray crystallography. Crystal data at room temperature are a = 16.94 (3) Å, b = 6.16 (4) Å, c = 28.41 (2) Å, β = 93.6 (1)°, Z = 2 for monoclinic system, space group C2/c, R = 0.046 for 190 parameters refined with 2400 reflections with I > 3σ (I). New phosphorus multifunctionalized 1,11 dialdehydes 13a,b are prepared and used as starting materials for the synthesis of the dissymmetric 18-membered ring 14. © 1990, American Chemical Society. All rights reserved.