Nitrophenyl phosphates, reaction + amines

Bunton CA, Diaz S, HeUyer JM, Ihara Y, lonescu LG. Micellar effects on the reactions of 2,4-dinitrophenyl phosphate and ethyl p-nitrophenyl phosphate with amines. J Org Chem. 1975 40 2313-2317. 

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. 

The reactivity of zinc complexes supported by a variety of tridentate amine donor ligands (Fig. 44) with diphenyl 4-nitrophenyl phosphate in 20% (v/v) acetonitrile-water, and with 2,4-dinitrophenyl diethyl phosphate in 1 % (v/v) in methanol-water, has been investigated. 5 For the former reaction, the second-order rate constant for the hydrolysis of 2,4-dinitrophenyl diethyl phosphate correlates linearly with the —AH value for the formation of the [(ligand)Zn(OH2)]2 + complex from free chelate ligand and aqueous zinc ion. This indicates that in this series of complexes, faster hydrolysis of 2,4-dinitrophenyl diethyl phosphate corresponds to weaker chelate... 

Full details on the phosphorylation of water and alcohols by 4-nitrophenyl dihydrogen phosphate and the NfC H ) - and N(CH3) -salts of its mono- and dianion have been published 146>. Phosphoryl group transfer from the monoanion and dianion is thought to proceed via the monomeric POf ion. Addition of the sterically unhindered amine quinuclidine to an acetonitrile solution containing the phosphate monoanion and tert-butanol produces t-butyl phosphate at a faster rate than does the addition of the more hindered diisopropylethylamine. This nucleophilic catalysis of the phosphorylation reaction is also explained by the intermediacy of the POf ion. 

To date, four main types of catalytic activity have been reported in detail for thermal polyamino acids. These are (with the most studied substrates in parentheses) hydrolyses (p-nitrophenyl acetate, p-nitro-phenyl phosphate, ATP), decarboxylations (OAA, glucuronic acid, pyruvic acid), and aminations (a-ketoglutaric acid, OAA, pyruvic acid, phenylpyruvic acid). The fourth type is a deamination reaction yielding a-ketoglutaric acid (51). For some of the actions of the thermal polymers the products are identified quantitatively, and the kinds of amino acid side chain necessary for activity in the polymer elucidated. In others, products have yet to be fully identified. The activities of thermal polyamino acids are manifest on substrates which range from chemically labile to relatively stable. 

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