Phosphonic acid: preparation and applications

Abstract

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

Designing of a Magnetodielectric System in Hybrid Organic–Inorganic Framework, a Perovskite Layered Phosphonate MnO3PC6H4‐m‐Br⋅H2O

“…The synthesis of the layered phosphonate Mn(H 2 O)PO 3 ‐C 6 H 4 ‐ m ‐Br requires in a first step the preparation of the 3‐bromophenylphosphonic acid. Aromatic phosphonic acids can be prepared by a series of methods but one of the most convenient consists in a phosphonation of bromoaryl derivatives according to the Tavs's method or a modified version of this catalytic assisted Arbuzov reaction . This procedure is usually very efficient for the preparation of mono or poly arylphosphonates .…”

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

“…In parallel to MOF research, another closely related family of supramolecular architectures known as hydrogen-bonded organic frameworks (HOFs) has attracted immense interest in recent years [26][27][28] . In HOFs, the linker connectivity is achieved via hydrogen-bonded networks rather than inorganic building units (IBUs) [29][30][31][32][33] . Hydrogen bonds provide simpler connectivity options compared to the complex molecular, one-, two-, and three-dimensional IBUs of MOFs [3]4 .…”

M(H2O)(PO3C10H6OH)·(H2O)0.5 (M = Co, Mn, Zn, Cu): a new series of layered metallophosphonate compounds obtained from 6-hydroxy-2-naphthylphosphonic acid

“…55 With the aim of producing compound (1) in larger quantities (more than 10 g in one batch), we adapted the Tavs's method, 56 which uses Ni(II) as the pre-catalyst and triethylphosphite as the reagent (nickel assisted Arbuzov reaction). 57 For this reaction, we used NiBr 2 (Scheme 1) and employed 6-bromo-2-naphthol as the substrate directly without protecting the phenol function. During the synthesis, we observed the formation, in small quantities, of a side product resulting from the alkylation of the phenol function with an ethyl group.…”

“…Then, the phosphonate (1) was transformed into the phosphonic acid 2 by using the McKenna method. 57 The phosphonic acid (2) O in distilled water and in the presence of one equivalent of urea. Urea was used herein to slowly increase the pH of the reaction media during the hydrothermal treatment to favor the reaction of the phosphonic acid function with the metal salts as previously reported.…”