Phosphorous acid derivatives

Lecithins are fatty acid esters of glycero-phosphoric acid derivatives. Commercially glycerophosphoric acid is used to prepare the medicinal glycerophosphate salts, c.g. the calcium salt. 

Esters of phosphorous acid derived from aUphatic alcohols and unhindered phenols, eg, tris(nonylphenyl)phosphate (24), hydrolyze readily and special care must be taken to minimize decomposition by exposure to water or high humidity. The phosphorous acid formed by hydrolysis is corrosive to processing equipment, particularly at high temperatures. 

Monoester salts of phosphoric acid derived from fatty alcohol ethylene oxide adduct or alkylphenol ethylene oxide adduct useful as surfactants are prepared by addition of R(OCH2CH2) OH, alkali fluoride and (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to + 10°C and hydrolysis of the Cl-containing intermediates with a base. The monoester phosphates showed comparable or better washing and foaming efficiency than commercial products [12]. 

Deoxy-sugars. Part XVI. A Study of the Stabilities of Some Phosphoric Acid Derivatives of D-Galactose and 2-Deoxy-D-Gaiactose, A. B. Foster, W. G. Overend, and M. Stacey, /. Chem. Soc., (1951) 987-991. 

B. Solvolysis of Phosphoric Acid Derivatives.—Interest continues in neighbouring-group participation in the solvolysis of phosphate esters. As a potential model compound for investigating the mechanism of ribo-nuclease action, the phenyl hydrogen phosphate ester of c/j-3,4-tetrahydro-furandiol (24) has been the subject of a detailed study. Above (and probably also below) pH 4 hydrolysis gives solely the cyclic phosphate (25)... 

Phosphonolipids (glycerophosphonolipids) found mainly in protozoans and marine invertebrates are lipids with phosphoric acid derivatives esterified to the glycerol backbone. 

J. P. Guthrie, Hydration and Dehydration of Phosphoric Acid Derivatives Free Energies of Formation of the Pentacoordinate Intermediates for Phosphate Ester Hydrolysis and of Monomeric Metaphosphate, J. Am. Chem. Soc. 1977, 99, 3391. 

Carboxylic acids can also be activated by the formation of mixed anhydrides with various phosphoric acid derivatives. Diphenyl phosphoryl azide, for example, is an effective reagent for conversion of amines to amides.140 The proposed mechanism involves formation of the acyl azide as a reactive intermediate. 

Catalysts for Transacylation Reactions of Carboxylic and Phosphoric Acid Derivatives... 

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Catalysis in Transacylation Reactions. The principal objective of the study was to evaluate 4 as an effective organic soluble lipophilic catalyst for transacylation reactions of carboxylic and phosphoric acid derivatives in aqueous and two-phase aqueous-organic solvent media. Indeed 4 catalyzes the conversion of benzoyl chloride to benzoic anhydride in well-stirred suspensions of CH2CI2 and 1.0 M aqueous NaHCC>3 (Equations 1-3). The results are summarized in Table 1 where yields of isolated acid, anhydride and recovered acid chloride are reported. The reaction is believed to involve formation of the poly(benzoyloxypyridinium) ion intermediate (5) in the organic phase (Equation 1) and 5 then quickly reacts with bicarbonate ion and/or hydroxide ion at the interphase to form benzoate ion (Equation 2 and 3). Apparently most of the benzoate ion is trapped by additional 5 in the organic layer or at the interphase to produce benzoic anhydride (Equation 4), an example of normal phase-... 

Reaction of Polychloronitrosoethanes with Phosphorous Acid Derivatives." Seriya... 

Synthesis of glycosyl phosphates by reaction of hemiacetals with activated phosphoric acid derivatives... 

Most reactions of sulfuric and phosphoric acid derivatives can be rationalized by considering that the S=0 and P=0 functionalities are equivalent to the carbonyl group, and that polarization in these groups allows similar nucleophilic reactions to occur. Initial nucleophilic addition will then be followed by loss of an appropriate leaving group and regeneration of the S=0 or P=0. 

Fig. 3 Phosphoric acids derived from BINOL and Hj-BINOL...

The last few years have witnessed major advances in the use of small organic molecules as organic acid catalysts in asymmetric catalysis [1], Selected examples of such organic acid catalysts include urea and thiourea [2], TADDOL [3], BINOL [4], and phosphoric acid derived from BINOL [5] (Figure 2.1). 

Most notably, the Antilla laboratory has employed VANOL and VAPOL phosphoric acid derivatives in several novel asymmetric transformations. In addition, TADDOL and phosphordiamide phosphoric acid derivatives have been applied in several Mannich-type reactions. 

Prior to Yamamoto s entry into this field, the scope of chiral phosphoric acid catalysis was strictly limited to electrophiUc activation of imine substrates. By designing a catalyst with higher acidity it was suspected that activation of less Lewis basic substrates might be possible. To this end, Yamamoto reported incorporation of the strongly electron accepting N-triflyl group [57] into a phosphoric acid derivative to yield the highly acidic N-triflyl phosphoramide 13 (Scheme 5.32)... 

Since A,A -disubstituted hydrazines are readily available from a variety of sources (see Volume I, Chapter 14), their dehydrogenation constitutes a widely applicable route to both aliphatic and aromatic azo compounds. Such oxidative procedures are of particular value in the aliphatic series because so many of the procedures applicable to aromatic compounds, such as the coupling with diazonium salts, have no counterpart. The oxidation reactions permit the formation not only of azoalkanes, but also of a host of azo compounds containing other functional groups, e.g., a-carbonyl azo compounds [83], a-nitrile azo compounds [84], azo derivatives of phosphoric acid [85], phenyl-phosphoric acid derivatives [86],... 

Those reactions of carboxylic acid and phosphoric acid derivatives which are susceptible to metal ion catalysis in nonenzymatic systems are almost without exception catalyzed by enzymes containing metal ions. This circumstantial evidence indicates strongly that the metal ions in the enzymatic reactions are concerned with the catalytic action, and not simply binding. 

Carbon-13 shifts of representative phosphines [364], phosphonium salts [365], phospho-nium ylides [365, 366], diphosphines [367], phosphonates [368], phosphorous and phosphoric acid derivatives [369] are summarized in Table 4.49. I3C shift data of some group V organoelement compounds are compared in Table 4.50. It turns out that a sp3 carbon nuclei of phosphines and arsines are shielded (0-25 ppm) relative to those of amines (30-60 ppm), as expected from the heavy atom effect, sp2 carbons of CC double bonds behave correspondingly, as shown for the triphenyl derivatives in Table 4.50, with... 

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