Phosphorus Compounds

Abstract

Phosphorus compounds exhibit an enormous variety of chemical and physical properties as a result of the wide range in the oxidative states and coordination numbers for the phosphorus atom. The intermediate electronegativity of phosphorus also plays a role. Phosphorus oxides, halides, sulfides, hydrides (phosphines), nitrogen compounds, and metal phosphides, as well as organophosphorus compounds, are reviewed. Emphasis is placed on the commercially important phosphorus trichloride, phosphorus pentachloride, phosphorus pentasulfide, phosphorus (V) oxide, and phosphine. Structure and nomenclature of phosphorus compounds and their organic derivatives are presented. Properties of the PO, PS, PH, PC, and PX (X = halogen) bonds are given. The manufacture of the commercial phosphorus compounds is outlined. Phosphorus compounds are found in or used as intermediates for the manufacture of oil additives, heat‐transfer and hydraulic fluids, water‐treatment chemicals, catalysts, herbicides, flame retardants, pesticides, pharmaceuticals, semiconductors, and surfactants. Intermediates in the preparation of organophosphorus derivatives are reviewed.

Recent Developments in the Addition of Phosphinylidene‐Containing Compounds to Unactivated Unsaturated Hydrocarbons: Phosphorus–Carbon Bond Formation by Hydrophosphinylation and Related Processes

“…[iv] Hypophosphorous acid is an industrial commodity and is sold as aqueous solutions. [v] It is prepared from elemental white phosphorus (P 4 ) through reaction with an inorganic base, followed by acidification (Scheme 2). HPA and its salts are therefore readily available, and their preparation is much more environmentally benign than that of phosphorus trichloride (P 4 + Cl 2 + heat) which is the precursor of many organophosphorus reagents currently used in P-C bond forming reactions, even if the chlorine atoms are typically not part of the final products (Scheme 2).…”

A Direct Catalytic Synthesis of Sodium Diarylphosphinates and Their Corresponding Acids from Sodium Phosphinate

“…Organophosphinic acids R 2 P(O)OH (R = hydrocarbyl group) and their esters and salts are relevant compounds in many fields: from flame retardants to solar cells and from ligands for catalysis to pharmaceutical applications and metal extraction. [1,2] They are interesting intermediates in the synthesis of other Pderivatives such as phosphines through reduction and/or functionalization. [3] Current processes for the industrial production of organophosphinic acids and derivatives involve the use of phosphorus trichloride (PCl 3 ) as starting material.…”

“…troless plating. [2] They are registered under REACH as non-hazardous compounds. [6] In synthesis, sodium phosphinate has been applied as a reducing agent [7] and for the hydrophosphination of alkenes and terminal alkynes.…”

ChemInform Abstract: Green, Palladium‐Catalyzed Synthesis of Benzylic H‐Phosphinates from Hypophosphorous Acid and Benzylic Alcohols.

“…Phosphorus trichloride is the main building block in the "organophosphorus economy"; [1] however, the chlorine atoms are not typically retained in the final products. Phosphorus-carbon bond-forming reactions are the object of intense studies because of the fact that organophosphorus compounds have a major impact in everyday life, from phosphane ligands in catalysis, to phosphonates and phosphinates as extractants, flame retardants, and biologically active molecules.…”

“…There are a few examples of benzylic acetate couplings, [5] which include in situ activation, [5a] but none that proceed through the benzylic alcohol directly. [6] Recently, we described the synthesis of allylic-H-phosphinates from H 3 PO 2 and allylic acetates [7] or alcohols [8] [Equation (1)]. Realizing that this type of reaction should constitute a general pattern of reactivity, similar to that of benzylic acetates, we investigated benzylic alcohols in place of allylic alcohols in order to achieve the "green", catalytic synthesis of benzylic-Hphosphinates without the need for any prior activation.…”