47072-02-6

Upstream product

• 13367-81-2 10-methylacridinium cation 
• 79798-57-5 C₁₇H₁₅⁽²⁾HN₂O 
• 17260-79-6 1-benzyl-3-carbamoyl-1,4-dihydroquinoline 
• 125076-52-0 1-Benzyl-4-hydroxy-1,4-dihydro-quinoline-3-carboxylic acid amide 
• 42206-02-0 N-methyl-9-phenylacridinium cation 
• 66665-62-1 9-(4-amino-phenyl)-10-methyl-acridinium 
• 362055-71-8 9-(3,5-dichloro-phenyl)-10-methyl-acridinium 
• 123091-98-5 9-(4-methoxy-phenyl)-10-methyl-acridinium 
• 6631-16-9 9?phenylxanthen?9?ylium perchlorate 

Downstream Products

• 13367-81-2 10-methylacridinium cation 
• 17260-79-6 1-benzyl-3-carbamoyl-1,4-dihydroquinoline 
• 125076-52-0 1-Benzyl-4-hydroxy-1,4-dihydro-quinoline-3-carboxylic acid amide 

Relevant academic research and scientific papers

A classical but new kinetic equation for hydride transfer reactions

A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions. The Royal Society of Chemistry.

Thermodynamic diagnosis of the properties and mechanism of dihydropyridine-type compounds as hydride source in acetonitrile with molecule id card

A series of 45 dihydropyridine-type organic compounds as hydride source were designed and synthesized. The thermodynamic driving forces (defined as enthalpy changes or redox potentials in this work) of the dihydropyridines to release hydride anions, hydrogen atoms (hydrogen for short), and electrons in acetonitrile,the thermodynamic driving forces of the radical cations of the dihydropyridines to release protons and hydrogens in acetonitrile, and the thermodynamic driving forces of the neutral pyridine-type radicals of the dihydropyridines to release electron in acetonitrile were determined by using titration calorimetry and electrochemical methods. The rates and activation parameters of hydride transfer from the dihydropyridines to acridinium perclorate, a well-known hydride acceptor, were determined by using UV-vis absorption spectroscopy technique. The relationship between the thermodynamic driving forces and kinetic rate of the hydride transfer was examined. Thermodynamic characteristic graph (TCG) of the dihydropyridines as an efficient Molecule ID Card was introduced. The TCG can be used to quantitatively diagnose or predict the characteristic chemical properties of the dihydropyridines and their various reaction intermediates. The mechanism of hydride transfer from the dihydropyridines to acridinium perclorate was diagnosed and elucidated by using the determined thermodynamic parameters and the activation parameters..

The tightness contribution to the Bronsted α for hydride transfer between NAD+ analogues

It has been shown that the rate of symmetrical hydride transfer reaction varies with the hydride affinity of the (identical) donor and acceptor. In that case, Marcus theory of atom and group transfer predicts that the Bronsted α depends on the location of the substituent, whether it is in the donor or the acceptor, and the tightness of the critical configuration, as well as the resemblance of the critical configuration to reactants or products. This prediction has now been confirmed for hydride transfer reactions between heterocyclic, nitrogen-containing cations, which can be regarded as analogues of the enzyme cofactor, nicotinamide adenine dinucleotide (NAD+). A series of reactions with substituents in the donor gives Bronsted α of 0.67 ± 0.03 and a tightness parameter, τ of 0.64 ± 0.06. With substituents in the acceptor α = 0.32 ± 0.03 and τ = 0.68 ± 0.08. The reactions are all spontaneous, with equilibrium constants between 0.4 and 3 x 104, and the two sets span about the same range of equilibrium constants. The two τ values are essentially identical with an average value of 0.66 ± 0.05. These results can be semiquantitatively mimicked by rate constants calculated for a linear, triatomic model of the reaction. Variational transition state theory and a physically motivated but empirically calibrated potential function were used. The computed rate constants generate an α value of 0.56 if the hydride affinity of the acceptor is varied and an α of 0.44 if the hydride affinity of the donor is varied. The calculated kinetic isotope effects are similar to the measured values. A previous error in the Born charging term of the potential function has been corrected. Marcus theory can be successfully fitted to both the experimental and computed rate constants, and appears to be the most compact way to express and compare them. The success of the linear triatomic model in qualitatively reproducing these results encourages the continued use of this easily conceptualized model to think about group, ion, and atom transfer reactions.

Thermodynamic control in ion radical cleavages through out-of-cage diffusion of products. Dynamics of C-C fragmentation in cation radicals of tert-butylated NADH analogues and other ion radicals

According to the nature of the alkyl group, cation radicals of NADH analogues alkylated para to the nitrogen atom (AHR), generated by direct or indirect electrochemical means, may undergo C-C fragmentation or deprotonation. The former reaction is dominant

The Marcus theory of reactions of quinolinium ions with BH4- and OH-1

The reactions of quinolinium ions with alkaline solutions of BH4- in a 4:1 mixture of 2-propanol and water were studied. Four 1-benzyl-3-cyanoquinolium ions and two 3-(aminocarbonyl)-1-benzylquinolinium ions were used. The quinolinium ions first reversibly add a nucleophile (mostly to the 4-position) and then are more slowly reduced to the 1,2- and 1,4-dihydroquinolines. The equilibrium constant for the addition of OH- or OR-, the rate constant for the addition, the rate constant for solvolysis of the adduct, and the rate constant for reaction of BH4- with the quinolinium ion were determined in each case. The quinolinium ion concentration was kept low enough so that only one of the hydridic hydrogens of BH4- was transferred to a quinolinium ion. Adduct formation and reduction by BH4- both have rates in the range 105-107 M-1 s-1, and the Br?nsted α values are similar. Both sets of rate constants can, roughly, be fitted by the Marcus theory of atom and group transfer if the intrinsic barrier is assumed to arise exclusively from the reorganization of the quinolinium ion. Since the presumptive critical complex for H- transfer between BH3 units, B2H7-, is a known, stable ion, it is reasonable that the reorganization of BH4- does not contribute significantly to the intrinsic barrier for its reactions. The Marcus theory, and related ideas, such as the Leffler-Hammond principle, apparently can be usefully applied to reactions quite different from the original model, but the exact values of the derived parameters quite possibly do not have their apparent physical significance.

Energetic Comparison between Photoinduced Electron-Transfer Reactions from NADH Model Compounds to Organic and Inorganic Oxidants and Hydride-Transfer Reactions from NADH Model Compounds to p-Benzoquinone Derivatives

Kinetics studies on photoinduced electron-transfer reactions from dihydropyridine compounds (PyH2) as being NADH model compounds to organic and inorganic oxidants and hydride-transfer reactions from PyH2 to p-benzoquinone derivatives (Q) in the absence and presence of Mg2+ ion are reported by determining over 150 rate constants.These results, combined with the values of Gibbs energy change of the photoinduced electron-transfer reactions as well as those of each step of the hydride-transfer reactions as being the e--H+-e- sequence, which are determined independently, revealed that the rate constants of the photoinduced electron-transfer reactions obey the Rehm-Weller-Gibbs energy relationship and that the activation barrier of the hydride-transfer reactions from PyH2 to Q is dependent solely on the Gibbs energy changes of the initial electron transfer from PyH2 to Q and the following proton transfer from PyH2.+ to Q.- and thus independent of the Gibbs energy change of the final electron transfer from PyH. to QH..The retarding effect of Mg2+ ion observed on the photoinduced electron transfer and hydride-transfer reactions of PyH2 is ascribed to the positive shifts of the redox potentials of the ground and excited states of PyH2 due to the complex formation with Mg2+ ion.

Regioselectivity and Kinetics of Hydride Transfer in Substituted 1-Benzyl-3-quinolinecarboxamide Redox Reactions

A systematic study on the factors that affect the regioselectivity and rate of hydride transfer in systems involving 1-benzyl-4-methyl-3-quinolinecarboxamides as donors or acceptors is reported.The study reports two major findings: (1) Hydride transfers from borohydride or 1-propyl-1,4-dihydronicotinamide to 1-benzyl-4-methyl-3-quinolinecarboxamide cation display distinct regioselective patterns-borohydride results in hydride transfer to the 2-position of the acceptor and dihydronicotinamide results in hydride transfer to the 4-position of the acceptor. (2) Substitution of the 4-hydrogen by a methyl group on either the oxidant or reductant quinoline lowers the rate constants for hydride transfer by a factor of over 2000.When methyl replaces hydrogen in both the oxidant and reductant, the rate constant for hydride transfer is lowered by a factor of over 5 000 000.These observations are interpreted in terms of a two-step mechanism: (1) formation of a ?-complex between the oxidant and reductant stabilized by charge-transfer interactions and (2) rate-determining hydride transfer within the complex.

Reaction of NADH models with methylene blue

The NADH models, (1R)-1,4-dihydronicotinamide and (1R)-1,4-dihydroquinoline-3-carboxamide (1-4, R=X-benzyl or octyl), are readily oxidized by methylene blue (MB), yielding the corresponding pyridium ions and leuco-methylene blue (MBH).Under aerobic reaction conditions, molecular oxygen, present in the reaction solution, rapidly reoxidizes MBH to MB, thereby allowing the study of the oxidation of the NADH models under pseudo-first-order reaction conditions.In order to elucidate the mechanism of the oxidation of the NADH models by MB, the influence of the MB concentration, solvent and temperature has been studied as well as the effect of substituent variation in the benzyl group in a series of 1-(X-benzyl)-1,4-dihydronicotinamides (1a-f).For one of the model compounds, 1-benzyl-1,4-dihydronicotinamide (1a, BNAH), the primary and the secondary isotope effect and the temperature dependence of the kinetic isotope effect have been determined.It is concluded that oxidation of the NADH models by MB most likely proceeds by a rate-determining hydride transfer process via a linear, symmetrical transition-state structure.

Hydride Transfer and Oxyanion Addition Equilibria of NAD+ Analogues

Equilibrium constants, K, have been determined for the reduction of 10-methylacridinium ion by 15 N-heterocyclic hydride donors: acridine, quinoline, pyridine, and phenanthridine derivatives.The solvent was a mixture of 2-propanol and water in the ratio 4 : 1 by volume.Reduction potentials have been estimated for the corresponding cations in aqueous solution by assuming that the K's would be the same and accepting -361 mV as the reduction potential of the 3-(aminocarbonyl)-1-benzylpyridinium ion.These reduction potentials span 430 mV.Values of pKR have also been determined for six of the cations in the same solvent.For derivatives of the same ring system, -ΔlogK is approximately equal to ΔpKR, but a 4 log unit discrepancy appears when phenanthridine derivatives are compared with the 9-methylacridinium ion.

Ferricyanide Oxidation of Dihydropyridines and Analogues

The reaction of the N1-substituted dihydronicotinamides (1-6), N-benzyl-3-carbomyl-1,4-dihydropyridine (7), and tritiated N-methylacridan (8) with Fe(CN)63- is first order in 3-> and .The oxidations of 1