83077-38-7

Upstream product

• 13367-81-2 10-methylacridinium cation 
• 79798-57-5 C₁₇H₁₅⁽²⁾HN₂O 
• 948-43-6 N-methylacridinium iodide 

Relevant academic research and scientific papers

Diazaphosphinanes as hydride, hydrogen atom, proton or electron donors under transition-metal-free conditions: Thermodynamics, kinetics, and synthetic applications

Exploration of new hydrogen donors is in large demand in hydrogenation chemistry. Herein, we developed a new 1,3,2-diazaphosphinane 1a, which can serve as a hydride, hydrogen atom or proton donor without transition-metal mediation. The thermodynamics and kinetics of these three pathways of 1a, together with those of its analog 1b, were investigated in acetonitrile. It is noteworthy that, the reduction potentials (Ered) of the phosphenium cations 1a-[P]+ and 1b-[P]+ are extremely low, being-1.94 and-2.39 V (vs. Fc+/0), respectively, enabling corresponding phosphinyl radicals to function as neutral super-electron-donors. Kinetic studies revealed an extraordinarily large kinetic isotope effect KIE(1a) of 31.3 for the hydrogen atom transfer from 1a to the 2,4,6-tri-(tert-butyl)-phenoxyl radical, implying a tunneling effect. Furthermore, successful applications of these diverse P-H bond energetic parameters in organic syntheses were exemplified, shedding light on more exploitations of these versatile and powerful diazaphosphinane reagents in organic chemistry.

Intramolecular kinetic isotope effect in hydride transfer from dihydroacridine to a quinolinium ion. Rejection of a proposed two-step mechanism with a kinetically significant intermediate

The intramolecular kinetic isotope effect (KIE) for hydride transfer from 10-methyl-9,10-dihydroacridine to 1-benzyl-3-cyanoquinolinium ion has been found to be 5-6 by both 1H NMR and mass spectrometry. This KIE is consistent with other hydride transfers. It is inconsistent with the high intermolecular KIEs derived by fitting to a two-step mechanism with a kinetically significant intermediate complex, and it is inconsistent with the strong temperature dependence of those KIEs. We therefore reject the two-step mechanism for this reaction, and we suggest that other cases proposed to follow this mechanism are in error.

REDUCTION OF N-METHYLACRIDINUM ION BY 3-AMINOCARBONYL-N-BENZYL-1,4-DIHYDROQUINOLINE: SUPPORTING EVIDENCE FOR THE MULTI-STEP MECHANISM OF THE NADH MODEL REDUCTION

The reduction of N-methylacridinium ion by 3-aminocarbonyl-N-benzyl-1,4-dihydroquinoline showed the isotope effect discrepancy.The result supports the multi-step hydrogen transfer mechanism.