Acids bis-phosphoric

Fast red salt Dissolve 5 mg of naphthol AS BI phosphoric acid sodium salt m 1 drop of DMF in a glass tube. Dissolve 5 mg of Fast red TR salt in 10 mL of veronal acetate buffer, pH 9 2 Mix the two solutions together and filter... 

A stock solution (10 mg/ml) of naphthol AS-MX, or naphthol AS phosphate, or naphthol AS-BI phosphoric acid sodium salt (Sigma) in DMF is prepared and diluted 50 times with 100 mM Tris-HCl buffer, pH 8.2. The solution is stable at 4°C for several weeks (in their original work. Mason and Sammons used naphthol AS phosphate and a buffer of pH 9.0). The substrate solution is prepared by dissolving Fast Blue BBN or Fast Red TR (1 mg/ml) in the naphthol stock solution. 

SCHEME 6.13. TADDOL and chiral bis-phosphoric acid catalyzed Diels-Alder reactions of acrolin-derivatives with amidodienes. 

Recently, chiral bis-phosphoric acid 77 bearing a new chiral scaffold with triple axial chirality assisted by intramolecular hydrogen-bonding between two phosphoric acid moieties was designed as a new chiral Bronsted acid catalyst by the Terada group [33], Application of this catalyst in the Diels-Alder reaction between substituted acroleins 66 and amido-dienes 76 produced the corresponding cycloadducts 78 with excellent enantioselectivities (Scheme 38.22). In comparison with the mono-phosphoric acid, bis-phosphoric acid 77 showed obviously higher catalytic activity and selectivity. 

The gels precipitated as described above are not useful in ion-exchange systems because their fine size impedes fluid flow and allows particulate entrainment. Controlled larger-sized particles of zirconium phosphate are obtained by first producing the desired particle size zirconium hydrous oxide by sol—gel techniques or by controlled precipitation of zirconium basic sulfate. These active, very slightly soluble compounds are then slurried in phosphoric acid to produce zirconium bis (monohydrogen phosphate) and subsequently sodium zirconium hydrogen phosphate pentahydrate with the desired hydrauhc characteristics (213,214). 

Ferrocene (46.4 g., 0.250 mole) (Note 1) is added to a well-stirred solution of 43.2 g. (0.422 mole) of bis(dimethylamino)-methane (Note 2) and 43.2 g. of phosphoric acid in 400 ml. of acetic acid in a 2-1. three-necked round-bottomed flask equipped with a condenser, a nitrogen inlet, and a mechanical stirrer (Note 3). The resulting suspension is heated on a steam bath under a slow stream of nitrogen (Note 4) for 5 hours (Note 5). The reaction mixture, a dark-amber solution, is allowed to cool to room temperature and is diluted with 550 ml. of water. The unreacted ferrocene is removed by extracting the solution with three 325-ml. jiortions of ether. The aqueous solution is then looled in ice water and made alkaline by the addition of 245 g. 

Saccharin and the three diphenols, pyrocatechol, resorcinol and hydroquinone, react only weakly or not at all. The same is true of picric acid. On the other hand, cyclohexanesulfamic acid and bis-(2-ethylhexyl)-phosphoric acid are readily detected [1]. 

N,N -Bis( -chloroethyl)phosphoric acid amide dichloride T riethylamine 1,3-Propanolamine... 

A solution of 75 g (Mo mol) of 1,3-propanolamine and 202 g of triethylamine in 100 cc of absolute dioxane Is added dropwise at 25°C to 30°C while stirring well to a solution of 25.9 g (Vio mol) of N,N-bis-( -chloroethyl)-phosphorlc acid amide dichlorlde in 100 cc of absolute dioxane. After the reaction is complete, the product is separated from the precipitated triethylamine hydrochloride and the filtrate Is concentrated by evaporation In waterjet vacuum at 35°C. The residue Is dissolved in a large amount of ether and mixed to saturation with water. The N,N-bis-( -chloroethyl)-N,0-propylene phosphoric acid diamide crystallizes out of the ethereal solution, after it has stood for some time in a refrigerator, in the form of colorless water-soluble crystals. MP 48 C to 49°C. Yield 65% to 70% of the theoretical. 

A solution of bis-triethylamine phosphate was prepared by slowly adding 2.36 ml of B5% phosphoric acid to 20 ml of acetonitrile containing 9.9 ml of triethylamine at 20°C. This solution was added to a stirred solution of 4.70 g of 9a-fluoro-11(3,170,21 -trihydroxy-160-methyl-1,4-pregnadiene-3,20-dione 21 -methanesulfonate and 20 ml of acetonitrile. The mixture was heated under reflux for four hours and then evaporated under reduced pressure to a volume of 12 ml. This mixture was a concentrated solution of 9a-fluoro-11(3,170,21 -tri-hydroxy-160-methyl-1,4-pregnadiene-3,20-dione 21 -phosphate triethylamine salt with some inorganic phosphate. 

N,N-bis-(2phosphoric acid amide dichloride N-(2-ChloroethyI)-N-(3-hydroxypropyl)-amine hydrochloride Triethylamine... 

N,N -Bis(/3phosphoric acid amide dichloride Cyclophosphamide Defosfamide T rofosfamide... 

The first reported method for the direct phosphonomethylation of amino acids used phosphorous acid and formaldehyde (7). Typically, aqueous solutions of the amino acid, phosphorous acid, and concentrated (coned) hydrochloric acid were heated to reflux with excess aqueous formaldehyde or paraformaldehyde. The reaction proceeded equally well with either primary or secondary amines. However, with primary amines such as glycine, the yield of glyphosate was usually quite low, even at reduced temperature, and 1 1 1 stoichiometry. The resulting glyphosate acid (GLYH3) reacted faster than glycine, so the bis-phosphonomethyl adduct 2 always predominated. With excess phosphorous acid and formaldehyde, good isolated yields of this 2 1 adduct 2 have been obtained (8). 

Under microwave irradiation and applying MCM-41-immobilized nano-iron oxide higher activity is observed [148]. In this case also, primary aliphatic alcohols could be oxidized. The TON for the selective oxidation of 1-octanol to 1-octanal reached to 46 with 99% selectivity. Hou and coworkers reported in 2006 an iron coordination polymer [Fe(fcz)2Cl2]-2CH30H with fez = l-(2,4-difluorophenyl)-l,l-bis[(l//-l,2,4-triazol-l-yl)methyl]ethanol which catalyzed the oxidation of benzyl alcohol to benzaldehyde with hydrogen peroxide as oxidant in 87% yield and up to 100% selectivity [149]. An alternative approach is based on the use of heteropoly acids, whereby the incorporation of vanadium and iron into a molybdo-phosphoric acid catalyst led to high yields for the oxidation of various alcohols (up to 94%) with molecular oxygen [150]. 

A. Synthetic Methods.—There have been no strikingly new approaches to the general problem of phosphorylation, but several ingenious methods of preparing suitable active esters under mild conditions have been reported. Typical of these is the reactive intermediate (1) formed from reaction of a mono- or di-ester of phosphoric acid with (2), itself produced by reaction of triphenylphosphine with bis(2-pyridyl) disulphide (preferably in the presence of mercuric ion as scavenger for the 2-mercaptopyridine liberated). 

Hydrolysis products With an excess of water by weight, QL form 2-diisopropylaminoethanol, ethanol, and methyl phosphorous acid. With traces of water or other proton donors QL will produce diethylmethyl phosphonite and 0,0 -bis-(2-diisopropylaminoethyl) methylphosphonite. Diethylmethyl phosphonite has a boiling point of 120°C and a vapor pressure of 11 mmHg at 20°C and is highly flammable. 

The heats of ionisation and neutralisation of amino and hydroxylic bis and tris phosphonic acids have been investigated.253 Calorimetry in combination with u.v. and n.m.r. spectroscopy uas used to study the adducts of fluoroalkyl carboxylic acids with diethyl phosphonate.254 The heats of formation of the t-butoxytriphenylphosphoranyl radical uas consistent with the phosphonium structure (92).255 There has been a thermal analysis of the adducts of phosphonic and phosphoric acids with... 

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