Secondary phosphites reactions

The reactions of dimethyl phenylphosphonite with acid chlorides, a-halogeno-ketones, and iV-(bromomethyl)phthalimide have been used to prepare acyl phos-phinates, /3-keto-alkylphosphinates, and phthalimidomethylphosphinates as intermediates in the synthesis of a-diazophosphinic esters.39 a-Amino-phosphonates have also been prepared by the addition of secondary phosphites to nitriles40 and to isocyanides.41... 

An interesting series of reactions were carried out starting from bis (cyclopentadienyl)nickel and secondary phosphite esters (Scheme 24).1713 Finally, the mixed-ligand complex [Pt (MeO)2PO 2diphos] can act by itself as a ligand towards nickel perchlorate giving the mixed metal oligomer (225).1714... 

Miscellaneous Reactions.—-Mixed alkylalkoxydiphosphines (103) have been prepared from secondary phosphites and chlorophosphines under basic conditions the alternative reaction between secondary phosphine and chloro-phosphite gave much lower yields. Surprisingly, oxidation of (103) with... 

Mixtures of cis- and /ra/w-enaminephosphonates were obtained from the reaction of secondary phosphites with ynamines, the stereochemistry being inferred from n.m.r. data in each case. 

Secondary phosphites and thiophosphites react with silylketens to give vinylphosphonates (58), presumably through rearrangement of (59). The reactions of keten dimers with tervalent phosphorus compounds are much more complicated and have been the subject of extensive study by Bentrude... 

As shown in Table 5.35, blends of immiscible polyesters may be compatibilized through copolymer formation mediated by addition of a phosphite condensing agent. Block copolymer results when the phosphite-activated end-group of one PEST reacts with a nucleophilic end-group of another PEST. The reaction takes place at the phase interface. A secondary phosphite is a byproduct. The relative proportions of copolymer vs. simple chain-extended PEST may depend upon the relative solubihty of condensing agent in each of the immiscible polymer phases. 

The reaction of A -methyl benzaldehyde imine with dichloroethoxyphosphine gives (27) with 2-chloro-l,3,2-dioxaphospholan the product is (28). Acid-catalysed additions of secondary phosphites to glyoxal give the mono- (29) or di-phosphonates (30) which are useful synthons and complexing agents." Basic alumina is an alternative to KF or CsF as catalyst for the preparation of 1-hydroxyalkanephosphonates from carbonyl compounds and secondary phosphites in the absence of solvent. 

An interesting approach to the synthesis of alkylphosphonates from A-tosylhydrazones has been presented (Scheme 4.63) [95]. The overall reaction was essentially a coupling reaction between the A-tosylhydrazones and a secondary phosphite. The catalyst system for this chemistry consisted of copper iodide along with a mineral base. For the hydra-zones derived from ketones, the most effective base was potassium carbonate however, for analogous reactions involving hydrazones derived from aldehydes, the most effective... 

The hydrophosphonylation of imines bearing a variety of organic fragments has been reported under a range of conditions. Even crowded substrates are typically responsive to the addition reaction. As an example of this, an anthracene bearing imine has been successfully functionalized using secondary phosphites (Scheme 4.87) [160]. Simply refluxing the reaction mixture for 14h afforded moderate yields of the a-aminophosphonates. 

A redox neutral process for the preparation of a-aminophosphonates has been reported (Scheme 4.96) [88]. One of the attractive aspects of this chemistry was that it was successful under metal-free conditions and only used a weak acid (benzoic acid) as the catalyst. This is formally a three-component reaction that couples a pyrrolidine, secondary phosphite, and an aromatic aldehyde to generate the a-aminophosphonates. One of the challenges with this type of reaction was the formation of different regioisomers. This arises due to a... 

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