Phosphorus aryl phosphites

Attack on Halogen. Predictably, the 3-bromo-3-cyano-imides (56) and (57) form quasiphosphonium salts (58) with aryl phosphites, phosphonites, and phosphinites.47 In the case of (56) these salts cyclize to the oxazaphosphorane (59), which is in equilibrium with the iminophosphorane (60), depending on the phosphorus ester used. 

Tetracarbonyl cations [Cr(CO)4(L2)]+, where L2 represents arylphosphines, alkyl, or aryl phosphites, or a bidentate ligand with phosphorus or arsenic donor atoms, have been produced by both chemical and electrochemical means. However, oifly one of these complexes, namely, tra i -[Cr(CO)4(PPh3)2]+, is stable enough to be isolated as the perchlorate salt. Exposure to light and moisture produces tra i -Cr(CO)4(PPh3)2 via disproportionation. Just as easily isolated, but somewhat less sensitive, are the [Cr(CO)3(PR3)3]+ cations. " Oxidation with a silver ion or NO+ converts the /uc-(R3 = Me2Ph, (OMe)3) and mer-(R3 = (OMe)3, (OMe)2Ph, (OPh)3) complexes into Cr products with mer structures. Light and heat promote the formation of reduced wer-Cr(CO)3 (PR3)3. These tetra(carbonyl) and tri(carbonyl) cations have been the subject of ESR spectroscopy and theoretical study. 

It was discovered early in the development of aromatic polyesters that addition of alkyl phosphite esters or alkyl-aryl phosphite esters to the melt resulted in significant improvements to the process stability of the polymers [1]. Since then, process/thermal stabilisers based on derivatives of phosphorus-based acids have remained the main additives used commercially for this purpose. 

A specialty alkyl-aryl phosphite with a very high phosphorus content. It is an effective secondary stabilizer for a variety of polymers where regulatory approval for food contact Is not required. 

Tris(fluorosulfuroyl)fluoromethane (329) reacted with bis(diethylamido)benzyl phosphite to yield an intermediate (330) which extruded a molecule of SO2 to give as final product the bis(fluorosulfonyl) compound (331). The kinetics and mechanism of the reaction of fluorinated tricoordinate phosphorus compounds (332) and aryl 2,2,2-trifluoroethyl sulfenates (333) have been reviewed. ... 

The nature of alkyl halide and the environment of the phosphorus atom make a substantial contribution to the direction of the reaction. Thus, cyclic phosphites [108], like trialkyl phosphites [110], react with preservation of the coordination of the P(III) phosphorus atom (126-132 ppm). If the alkoxyl group is substituted by amide, alkyl, or aryl, the nucleophilicity of the phosphorus atom in the corresponding amidophosphite (phosphonite) increases in comparison with the trialkyl phosphite. This probably promotes attack by 1 -haloalkyl-2-pyrrolidone at the phosphorus atom and not the oxygen, and this was confirmed experimentally. As a result of the investigated reactions amidophosphonates or ethyl phenyl phosphinates llOa-c were isolated compounds with P(III) were not detected in these cases. 

Obrycki. R.. and Griffin. C.E.. Phosphonic acids esters. Part 19. Syntheses of substimted phenyl- and arylphosphonates by the photoinitiated arylation of trialkyl phosphites, J. Org. Chem., 33, 632, 1968. Engel. R.. Synthesis of Carbon-Phosphorus Bonds, CRC Press, Boca Raton, 1988, p. 137. 

In these reactions, hydrolysis of diphenyl and triaryl phosphites to monoaryl phosphites and phenol was coupled by dehydration between carboxylic acids and amines or alcohols to the corresponding amides and esters. Therefore, the reaction can be generalized as a hydrolysis-dehydration reaction (Scheme 2). The concept of the hydrolysis-dehydration reaction using phosphites has been drown to be applicable also to reactions with other phosphorus compounds such as phosphinites, phos-phonites and phosphorates s Aryl esters of these phosphorus compounds are effective as condensing agents in the production of carboxylic amides and esters (from carboxylic acids and amines or alcohols, respectively) whereas alkyl esters are ineffective (Eqs. (1-3)) ... 

Many examples of orthometallation of aryl phosphines and phosphites are known. The phosphines produce four-membered rings when phosphorus is attached directly to the ring being metallated ... 

Organophosphorus compounds (OPs) are utilized on a large scale as flame retarding agents and plasticizers in a variety of products, such as plastic materials, rubbers, varnishes, lubricants, hydraulic fluids, and other industrial applications. This family of chemicals consists of alkylated and arylated phosphate or phosphonate esters and related compounds such as phosphites, phosphines, and related dimeric forms as well as ionic forms (Figure 31.2). " The low volatility of phosphoric acid and derivatives makes it the preferred choice of the phosphorus based FRs. These FRs are most effective in polymers that char readily. Also halogenated phosphate esters, such as tris(l-chloroisopropyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP), are widely used. These combine the properties of both the halogen and the phosphorus compounds. 

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