Bednarski, Patrick J. and Ehrensperger, Edmund and Schönenberger, Helmut and Burgemeister, Thomas (1991) Aqueous chemistry of mixed-amine cis- and transplatin analogues. Intramolecular preference for a kinetic six-membered ring over a thermodynamic five-membered ring ortho-platination product. Inorganic chemistry 30 (15), pp. 3015-3025.
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A series of mixed-amine cis- and trans-platin analogs, contg. benzylamine and 2-phenylethylamine functionalities, were synthesized and the aq. soln. chem. investigated. The cis- and trans-Pt(NH3)LCl2 (I; L = (1,2-bis(4-methoxyphenyl)ethylamine (MREA), 2-(4-methoxyphenyl)-1-phenylethylamine (MPPEA), bis(4-methoxyphenyl)methylamine (MPMA)) were synthesized in >98% isomeric purity. With the aim of investigating the pharmacoactivation of this class of compds., a reversed-phase HPLC assay was developed for detg. the rates of Pt-Cl hydrolysis of the cis-configured isomers. The precolumn addn. of KBr to the reaction solns. trapped the aquachloro- and diaquaplatinum hydrolysis products as their bromo adducts. The sepns. of dichloro-, bromochloro-, and dibromoplatinum complexes allowed the quantification of their time-dependent concns., and the hydrolysis rate consts. for cis-I could be detd. Following Pt-Cl hydrolysis, an intramol. ortho-platination occurred with I. Proton NMR studies showed that, for the trans-I (L = MPEA, MPPEA), the kinetically favored, 6-membered ring cycloplatinated products were formed specifically over the thermodn., 5-membered ring ones. For cis-I (L = MPEA), the kinetic product was formed selectively. The 6-membered cycloplatinated ring could be converted into the 5-membered, thermodn. favored one by heating in dil. KCl. The implications of these novel findings are discussed from both mechanistic chem. and pharmacol. points of view.
|Additional information (public):||CAN 115:84115 78-7 Inorganic Chemicals and Reactions 135192-25-5; 135192-26-6; 135192-27-7; 135192-28-8; 135192-29-9; 135192-31-3; 135192-32-4; 135225-03-5; 135269-32-8; 135269-33-9; 135270-97-2 Role: RCT (Reactant), RACT (Reactant or reagent) (HPLC of); 135192-30-2P Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from 6-numbered chelate); 93922-81-7 Role: PRP (Properties) (kinetics of hydrolysis of); 135192-19-7P; 135192-20-0P; 135192-21-1P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and kinetics of hydrolysis and orthoplatination of); 135192-22-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and thermal rearrangement of); 135192-23-3P; 135192-24-4P; 135269-29-3P; 135269-30-6P; 135269-31-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 13820-91-2; 15663-27-1 Role: RCT (Reactant), RACT (Reactant or reagent) (reactions of, with phenylalkylamines)|
|Institutions:||Chemistry and Pharmacy > Institute of Pharmacy > Retired Professors > Prof. Schönenberger|
|Keywords:||Kinetics of metalation (cycloplatination, of ammine phenylalkylamine complexes) Hydrolysis Kinetics of hydrolysis (of platinum ammine phenylalkylamine complexes) Metalation (cycloplatination, of ammine phenylalkylamine complexes) Chromatography (high-performance, of platinum amine phenylalkylamine complexes) orthoplatination ammine methoxyphenylalkylamine isomer complex platinum isomer complex methoxyphenylalkylamine kinetics hydrolysis platinum isomer complex|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Yes|
|Deposited On:||12 Nov 2010 07:14|
|Last Modified:||12 Nov 2010 07:14|