5735-86-4

Upstream product

• 70-47-3 L-asparagine 
• 3130-87-8 ASPARAGINE 
• 7732-18-5 water 
• 344930-64-9 (2-oxo-4-phenylthioazetidin-1-yl)methyl benzoate 
• 344930-63-8 (2-oxo-4-phenylsulfonylazetidin-1-yl)methyl benzoate 
• 344930-67-2 (3,3-diethyl-2-oxo-4-phenylsulfonylazetidin-1-yl)methyl benzoate 
• 16871-54-8 hexachloroplatinate(II) 

Downstream Products

• 76205-19-1 1-(para-chlorophenyl)-3-hydroxypyrazole 

Relevant academic research and scientific papers

Kinetics and mechanistic approach to the oxidative behavior of biological anticancer platinum(IV) complex toward L-asparagine in acid medium and the effect of copper(II) catalyst

The catalytic effect of copper(II) ions toward the oxidation of L-asparagine (Asn) by an anticancer platinum(IV) complex in the form of hexachloroplatinate(IV) (HCP) has been investigated in aqueous acid medium at the constant ionic strength and temperature. The progress of both uncatalyzed and copper(II)-catalyzed oxidation reactions has been monitored spectrophotometrically. The stoichiometry in both cases is [Asn]/[HCP] = 1:1. The kinetics of both redox reactions is first order with respect to [oxidant] and less than the unit order in [acid]. The order with respect to [Asn]T decreases from unity in the uncatalyzed path to less than unity in the catalyzed one. The catalyzed path is first order in [CuII]T. Increasing ionic strength and dielectric constant decreases the oxidation rates. The final oxidation products of L-asparagine are identified as the corresponding aldehyde (α-formyl acetamide), ammonium ion, and carbon dioxide. Tentative mechanisms of both reactions have been suggested. The appropriate rate laws are deduced. The activation parameters of the uncatalyzed reaction have been evaluated and discussed.

Oxidative deamination and decarboxylation of L-asparagine by the aqueous alkaline diperiodatonickelate(IV) complex

The kinetics of the oxidation of L-asparagine, (L-asp) by diperiodatonickelate(IV), (DPN) in aqueous alkaline medium at a constant ionic strength of 0.5 mol·dm-3, was studied spectrophotometrically. The reaction is first order in [DPN] and of fractional order in both [L-asp] and [alkali]. Addition of the products has no significant effect on the reaction rate. However, increasing the ionic strength or decreasing the dielectric constant of the medium increases the reaction rate. The oxidation process in alkaline medium is shown to proceed via two paths, one involving the interaction of L-asparagine with diperiodatonickelate(IV) ion in a slow step to yield the products, and the other path involving the interaction of alkali with the diperiodatonickelate(IV) ion to give nickel(II). Some reaction constants involved in the mechanism were determined, and calculated and observed rate constants are in excellent agreement. The activation parameters were computed for the slow step of the mechanism.

Kinetics and Mechanistic Approach to the Oxidative Behavior of Biological Anticancer Platinum(IV) Complex toward -Asparagine in Acid Medium and the Effect of Copper(II) Catalyst

The catalytic effect of copper(II) ions toward the oxidation of -asparagine (Asn) by an anticancer platinum(IV) complex in the form of hexachloroplatinate(IV) (HCP) has been investigated in aqueous acid medium at the constant ionic strength and temperature. The progress of both uncatalyzed and copper(II)-catalyzed oxidation reactions has been monitored spectrophotometrically. The stoichiometry in both cases is [Asn]/[HCP] = 1:1. The kinetics of both redox reactions is first order with respect to [oxidant] and less than the unit order in [acid]. The order with respect to [Asn]T decreases from unity in the uncatalyzed path to less than unity in the catalyzed one. The catalyzed path is first order in [CuII]T. Increasing ionic strength and dielectric constant decreases the oxidation rates. The final oxidation products of -asparagine are identified as the corresponding aldehyde (α-formyl acetamide), ammonium ion, and carbon dioxide. Tentative mechanisms of both reactions have been suggested. The appropriate rate laws are deduced. The activation parameters of the uncatalyzed reaction have been evaluated and discussed.

Transition metal-catalyzed oxidation of l-asparagine by platinum(IV) in acid medium: a kinetic and mechanistic study

Abstract Kinetic investigations of Pt(IV) oxidation of l-asparagine catalyzed by transition metals with different valencies, namely Ag(I), Pd(II), Cr(III) and Zr(IV), were studied spectrophotometrically in sulfuric acid medium at constant ionic strength and temperature. The reaction was first order in [Pt(IV)], while the orders with respect to the concentrations of Asn, sulfuric acid and transition metal were less than unity over the concentration range studied. The rate constants decreased with increasing ionic strength and dielectric constant, while increasing temperature enhanced the rate. The order of catalytic efficiency was: Ag(I) > Cr(III) > Pd(II) > Zr(IV). A mechanism involving the formation of a complex between the catalyst and substrate is proposed. Oxidation by Pt(IV) is suggested to take place by an inner-sphere mechanism in which Pt(IV) is reduced to Pt(II) on the catalyst-bound substrate in a one-step two-electron transfer process. The oxidation products of Asn were identified as α-formyl acetamide, ammonium ion and carbon dioxide. The rate law associated with the reaction mechanism was deduced. Activation parameters of the reactions were evaluated and discussed.

Kinetics and Mechanism of Hydrolysis of N-Acyloxymethyl Derivatives of Azetidin-2-one

The pH-independent, acid-catalyzed and base-catalyzed hydrolyses of N-acyloxymethylazetidin-2-ones all occur at the ester function. The pH-independent hydrolysis involves rate-limiting alkyl C-O fission and formation of an exocyclic β-lactam iminum ion. This iminium ion is then trapped by water at the exocyclic iminium carbon atom, rather than at the β-lactam carbonyl carbon atom, to form the corresponding N-hydroxymethylazetidin-2-ones. Calculations carried out at the B3LYP/6-31+G(d) level of theory also support that nucleophilic attack by water takes place at the exocyclic carbon rather than at the β-lactam carbonyl carbon of the iminium ion. The mechanism for the acid-catalyzed pathway involves a preequilibrium protonation, probably at the β-lactam nitrogen, followed by rate-limiting alkyl C-O fission with formation of an exocyclic iminum ion. The base-catalyzed hydrolysis involves rate-limiting hydroxide attack at the ester carbonyl carbon. These results imply formation of a β-lactam system containing a positively charged amide nitrogen atom that hydrolyzes via a pathway that preserves the β-lactam structure in the product and provide further evidence that cleavage of the β-lactam C-N bond is not as facile as is commonly imagined.

Oxidative deamination and decarboxylation of L-isomers of amino acids by potassium permanganate in moderately concentrated sulphuric acid medium

The oxidation reactions of L-isomers of amino acids, viz. asparatic acid, glutamic acid, asparagine and glutamine have been carried out in moderately concentrated sulphuric acid medium. The reactions are found to be two-stage processess. In both the stages the reactions follow first order behaviour with respect to each of substrate and permanganate. The reactions are acid-catalysed and the rate is related to the activity of water and also to the acidity function. Primary salt-effect is nil, but at higher concentration of neutral salts the logarithm of the rate constant is linearly related to ionic strength. Specific ionic effects have also been investigated. Activation parameters have been reported. Mechanism pertinent with the observation has been suggested.

Kinetics and Mechanism of the Ruthenium, Osmium and Neodymium Catalysed thallic Oxidation of 2,4-Diamino-4-Oxobutanoic Acid in Perchloric Acid Medium

The titled reaction abides second order relationship being unity in oxidant and substrate.Reaction rate is a direct function of catalyst and reverse in case with +>.Retardation in rate on the addition of reaction products and neutral electrolytes was observed.Catalytic activity is of the order Ru(III) > Os(VIII) > Nd(III).Reaction is preceded by initial complexation between catalyst and amino acid.A free radical mechanism involving single e transfer in two steps is operative.The values of different kinetic and activation parameters alongwith theoretical values of rate constants have been evaluated.

Amide derivatives of VLB, leurosidine, leurocristine and related dimeric alkaloids

Amide derivatives of VLB, leurosidine, leurocristine and related dimeric alkaloids are useful as anti viral and anti-neoplastic agents or as intermediates in the preparation of such agents.