Polyphosphonic acids

Polyphosphonic acids are conveniently esterified by treatment with orthoformate esters with distillation of the lower-boiling alcohol. This procedure worked well for the acid (74), which readily dimerizes, and was also used to establish the structure of the dimer (75). ... 

Low molecular compounds Glucose, Sucrose, ATP, CH3CH2S03Na, Ct-Amino Acid, Polyphosphonic Acid, etc. 

Some alternative syntheses use malic acid, urea, and PPA (61 SCI 1923) or maleic/fumaric acid, urea, and polyphosphonic acid (PPA) (71S154). The reaction of formylacetate with thiourea is convenient for the synthesis of 2-thiouracil (08JA547 10JA19). Another main synthesis involves the... 

Reports of examples of arylphosphonates include those of water-soluble phosphinic-polyphosphonic acids, e.g. 132, and the phosphonate 133 which when coupled to alcohols, to give e.g. 134, act as linkers to proteins in experiments intended to generate antibodies to catalyse cationic cyclisation reactions.Novel water-soluble phosphonate-substituted phthalocyanines have been prepared.The phosphonate esters 135 are insoluble in water but can be hydrolysed by hydrochloric acid to give the water-soluble phosphonic acids 136. Aromatic phosphonate-phosphines 137, and their air-stable complexes, have been obtained from the reaction of 4-halogeno-substituted phenylphosphonates with lithium diphenylphosphide. ... 

In the past, polyvalent anions such as polyphosphonic acids could not be analyzed by ion chromatography, because their retention times increase drastically with increasing charge number. Strong adsorptive forces, caused by the organic skeleton of these com-... 

Generally, these compounds form complexes with alkaline-earth metals that are less stable than the corresponding complexes of the polyphosphonic acids. WeiB and Hagele [96] investigated the chromatographic behavior of a variety of aliphatic and olefinic polyphosphonic and polyphosphinic acids, respectively, with 1 to 4 phosphorus atoms [87,88], that are applied in medicine and in pharmaceutical chemistry. 

Fig. 3-102. Separation of an aromatic polyphosphinic and polyphosphonic acid of equal carbon backbone. — Chromatographic conditions see Fig. 3-96 solute concentrations 200 ppm each of 7 and 6.

In addition to structural isomers, stereoisomeric and, recently, rotational isomeric polyphosphonic and polyphosphinic acids can be separated. Most intriguing in this connection is the chromatogram in Fig. 3-103 of the sterically-crowded polyphosphonic acid 10,... 

Recently, another method for the separation and determination of polyphosphonic acids via anion exchange chromatography was described by Vaeth et al. [84], The objective of this work was to develop a phosphorus-specific detection, because the reaction... 

Fig. 3-104. Separation of polyphosphonic acids upon application of phosphorus-specific detection. - Separator column IonPac AS7 eluent 0.17 mol/L KC1 + 0.0032 mol/L EDTA, pH 5.1 flow rate 0.5 mL/min detection photometry at 410 nm after hydrolysis and derivatization with vana-date/molybdate injection 50 pL, l-hydroxyethane-l,l-diphosphonic acid (HEDP), aminotris-(methylenephosphonic acid) (ATMP), ethylenediamine-tetramethylenephosphonic acid (EDTP), l,l-diphosphonopropane-2,3-dicarboxylic acid (DPD), and 2-phosphonobutane-l,2,4-tricarboxylic add (PBTC) (taken from [84]).

Polyphosphonic acids can be separated on a special latex-based anion exchanger. They are photometrically determined after complexation with ferric nitrate [27] (see Section 3.3.5.2). This method enables a qualitative analysis of inorganic and organic phosphates that are contained in conditioners. Fig. 8-27 illustrates this with the chromatogram of a commercial product. Clearly, it is a multicomponent mixture with two main components and several minor components. 

After 48 hrs at 120 °C a polymer with Mn =4,180 was formed in 35 % yield. At room temperature after 69 days the corresponding polyphosphonic acid diester with Mn = 7,560 was formed in 48% yield. 

This is an area in which the syntheses of functionalized acids (as their esters) has predominated (Chapter 3, Sections VI and VII). Nevertheless, the procedure is not without its uses in non-functionalized systems, and it has also received attention as a means for the synthesis of polyphosphonic acids (as their esters). 

Addition of hydrogenphosphonates to the 1,4-quinonemethides 383 to give the 4-hydroxyphenyl polyphosphonic acids as their esters 384 is well established , and that of hydrogenphosphonates to / -benzoquinone itself is reported to give the 2,5-dihydrox-yphenyl-l,4-bisphosphonic acid derivative. ... 

Combinations of boric oxide with polyacrylic and polyphosphonic acid exhibit quick setting and hardening based on the formation of hydrogen-bonded complexes. 

Calcium Sequestering Powers of Polyphosphonic Acids at pH = 10 Compound... 

The degree of difficulty involved in the ion chromatographic separation and determination of polyphosphonic acids made this task virtually impossible many years ago. The primary reason is that polyphosponic acids are multivalent at alkaline pH and, thus exhibit a very high affinity toward the stationary phase of anion exchangers. 

In addition to aminopolyphosphonic acids, polyphosphonic acids without amino function may also be analyzed by ion chromatography. Such compounds also serve as complexing agents for alkaline-earth metals and several auxiliary group elements. As for the monophosphonic acids, 2-phosphonobutane-l,2,4-tricarboxylic acid (PBTC) is of very high industrial importance. In diphosphonic... 

Figure 3.195 Separation of aliphatic and aromatic polyphosphonic acids. Separator column lonPac AS7 eluent 40mmol/L HNO3 other chromatographic conditions see Figure 3.192 injection volume 50 pL peaks lOOmg/L each of 1, 5, 8, 9, and 6.

Figure 3.199 Polyphosphonic acid analysis utilizing phosphorus-specific detection. Separator column lonPac AS7 eluent 0.17 mol/L KCI -h 3.2 mmol/L EDTA, pH 5.1 flow rate ...

---