Nitrophenyl phosphoramides

Kinetic studies of the acid hydrolysis of two A-aryl phosphoramidates XC6H4NHPO3H were reported, that of the A-(3-chloro-2-methylphenyl) compound at pH 0.00-7.46 and that of the A-(4-methyl-2-nitrophenyl) compound in 0.10-7.0M HCl. Kinetic studies in 30% dioxane-water at 338 K of the acid hydrolysis of bis[A-(4-methyl-2-nitrophenyl)] phosphoramidate at pH 0.00-7.46 were reported. ... 

The phosphoramidic chloride (11) has been employed to phosphorylate phenols and alcohols, including carbohydrates.16 Other activity in phosphorylation chemistry has been mostly concentrated in two main areas. In the first of these, Japanese workers have continued their studies on the use of 2-substituted-4-nitrophenyl-phosphoric acids. The 7V-protonated form of the 2-dimethylamino-compound (12 R = Me) is a better phosphorylating agent than the corresponding 2-diethylamino-compound. The reaction of (12) with hydroxy-amines results in selective O-phos-... 

O. O-Dimethyl S-methylcarbamoylmethyl phosphorodithioate, 2009 Dimethyl 4-nitrophenyl thionophosphate, 2979 Dimethyl phosphoramidate, 0952... 

The X-ray structure of [Zn2(8-H)F is shown in Pig. 2. The p for the doubly coordinated pendant alcohol is below 4, in accord with corresponding measurements made on water molecules coordinated to a pair of Zn(II) ions in a cyclic octaamine (<7) 22), or in a cyclic tetraamine with four pendant amines (<5.3) 23). On reaction with 4-nitrophenyl phosphate, 4-nitrophenol is released and a complexed phosphoramide is produced, [Zn2(9)] +, resulting from attack of a secondary amine at phosphorus. 

Ethyl 4-nitrophenyl phosphate coordinated to the pentaam-minecobalt(III) moiety liberates nitrophenolate in basic solution 10 -fold faster than the free phosphodiester. The reaction proceeds by attack of coordinated amido ion to give a four-membered N,0 chelate phosphoramidate ethyl ester (1) shown in Eq. (2). Interestingly, the four-membered chelate does not display the enhanced reactivity of the five-membered-ring cyclic ethylene phosphates but decays with cobalt-ligand... 

The phosphodiester complexes (ethyl 4-nitrophenyl phosphate )pentaam-mineiridium(III) and bis(4-nitrophenyl phosphate )pentaammineiridium(III) have also been prepared and their reactivities under basic conditions studied. Both complexes react predominantly via intramolecular attack of a deprotonated coordinated ammonia to liberate 4-nitrophenolate ion. The four-membered phosphoramidate chelate ring thus formed rapidly ring-opens, probably via P—O and P—N rupture, to yield N—bonded phosphoramidate monoester and O—bonded phosphate ester complexes. The rate constant... 

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