ChemInform Abstract: N,N′‐DIPHOSPHORYLATED 1,3,2‐DIAZAPHOSPHOLANES

Abstract

o‐Phenylendiamin (I) wird mit Phosphortrichlorid oder dem Triamidophosphit (IV) zu Benzodiazaphospholanen (II) bzw. (V) cyclisiert.

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…When a diamide is made to react with a 2-or 3-fold molar amount of a phosphamide, di-542 and triphosphorus 551 -containing heterocycles are produced, for example, see Scheme 103.…”

“…532,572,573 Depending on the reaction conditions and the ratio of the reactants, unsubstituted o-phenylenediamine is converted upon phosphorylation by phosphorus diand triamides into either ordinary phosphoruscontaining rings or the products of their additional phosphorylation at nitrogen. 551,574,575 It can be seen that N,N-tetraethyl phenylphosphonous diamide can react according to a standard scheme 576 or according to an abnormal route, which includes disproportionation (Scheme 111). 577 Note that systems related to the resulting phosphorane regarding the coordination of phosphorus are being thoroughly studied now.…”

Synthesis, Characterization, and Solution Properties of Skeletally Stabilized Triphosphazanes

“…The introduction of a bridging group, e.g., an o -phenylene ring, between adjacent nitrogen atoms in a phosphazane chain has allowed the synthesis of acyclic and cyclic oligomers of the general form 1 . − As part of our effort to find efficient routes to these new molecules, especially the cyclooligomers (e.g., n = 2, 3), we wished to obtain two- and three-phosphorus synthons which in subsequent reactions might (i) form known rings in improved yields and also (ii) lead to new ring systems. Of particular interest for this are difunctional triphosphazanes ( 2 , X = halogen) which can be envisaged to react at both exo −P(R)X units.…”

Synthesis and Coordination of a Cleft-Stabilized Triphosphazane Hydride: C6H4N2[P(S)(NEt2)2]2PH

“…Skeletally stabilized triphosphazanes ( 1 ) − react with a variety of reagents regioselectively at P(2) in the molecular “cleft” created between the bulky −P(E)(NEt 2 ) 2 groups.Reactivity studies show the cleft to be large enough to accommodate alkoxy and alkylamino groups (X) in size up to i -PrO− and Et 2 N−, respectively; 1a, modeling studies establish the average cleft width to be 6.0 ∓ 0.5 Å in disulfide 1 (E = S, X = NEt 2 ). This cleft can protect the P−X functionality within it, allowing for stabilization of bonds that might not be isolable in a less protected environment.…”