Synthesis of New Dicoordinated Phosphorus Compounds with a P(III)=N Bond

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

“…Primary and secondary o -phenylenediamines react with hexamethylphosphorus triamide to afford tetramers (Scheme ). ,,

110

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“…571 Primary and secondary o-phenylenediamines react with hexamethylphosphorus triamide to afford tetramers (Scheme 110). 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).…”

Anellated Heterophospholes and Phospholides and Analogies with Related Non-Phosphorus Systems

“…N -Monoalkyl- o -phenylenediamines when refluxed with P(NMe 2 ) 3 form oligomers 20 of 1,3,2-benzodiazaphospholes. The monomer benzodiazaphospholes 21 (X = NR) are less stable than the similarly synthesized pyrido- or thiazolo-anellated triazaphospholes 18 or 19 but exist in equilibrium with the oligomers 20 at elevated temperatures and could be trapped by the Lewis acid BF 3 as stable adduct 22 (X = NR) (Scheme ) . The N-phenyl derivative also preferably forms the oligomeric product .…”

“…o -Aminophenol and -thiophenol behave analogously affording oligomers which on treatment with BF 3 (X = S) or AlCl 3 (X = O) give stable adducts 22 (X = S) or 23 of the monomers. 23 on reacting with a base generates free benzoxazaphosphole that oligomerizes again after some time 59b. Formation of anellated 1,3,2-diazaphospholes has also been claimed from the condensation of diaminopyrimidine and -pyridine with triphenyl phosphite although physical properties indicate their oligomeric nature …”

“…A 1,2-addition product was obtained with diethylamine. The reaction with ethylene glycol leads to a spirocyclic σ 5 P product 150 through 1,2-addition followed by the 1,1-addition of the other hydroxy group (Scheme ) 59c. A cyclohexane-anellated 1,2,3-diazaphosphole is reported to undergo 1,2-addition with MeOH, but as the product is unstable it loses phosphorus to form a hydrazone …”