当前位置: X-MOL 学术Phys. Chem. Chem. Phys. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Infrared spectra and structures of protonated amantadine isomers: detection of ammonium and open-cage iminium ions
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-06-13 , DOI: 10.1039/d2cp01947g
Martin Andreas Robert George 1 , Otto Dopfer 1
Affiliation  

The protonated form of amantadine (1-C10H15NH2, Ama), the amino derivative of adamantane (C10H16, Ada), is a wide-spread antiviral and anti-Parkinsonian drug and plays a key role in many pharmaceutical processes. Recent studies reveal that the adamantyl cage (C10H15) of Ama can open upon ionization leading to distonic bicyclic iminium isomers, in addition to the canonical nascent Ama+ isomer. Herein, we study protonation of Ama using infrared photodissociation spectroscopy (IRPD) of Ar-tagged ions and density functional theory calculations to characterize cage and open-cage isomers of AmaH+ and the influence of the electron-donating NH2 group on the cage-opening reaction potential. In addition to the canonical ammonium isomer (AmaH+(I)) with an intact adamantyl cage, we identify at least one slightly less stable protonated bicyclic iminium ion (AmaH+(II)). While the ammonium ion is generated by protonation of the basic NH2 group, AmaH+(II) is formally formed by H addition to a distonic bicyclic iminium ion produced upon ionization of Ama and subsequent cage opening.

中文翻译:

质子化金刚烷胺异构体的红外光谱和结构:铵离子和开笼亚胺离子的检测

金刚烷胺 (1-C 10 H 15 NH 2 , Ama)的质子化形式是金刚烷 (C 10 H 16 , Ada) 的氨基衍生物,是一种广泛使用的抗病毒和抗帕金森病药物,在许多疾病中起关键作用制药工艺。最近的研究表明,除了典型的新生 Ama +异构体之外,Ama 的金刚烷基笼 (C 10 H 15 ) 可以在电离时打开,从而产生二张双环亚胺异构体。在此,我们使用 Ar 标记离子的红外光解离光谱 (IRPD) 和密度泛函理论计算来研究 Ama 的质子化,以表征 AmaH +的笼式和开笼式异构体以及给电子NH 2基团对开笼反应电位的影响。除了具有完整金刚烷基笼的典型铵异构体 (AmaH + ( I )) 之外,我们还确定了至少一种稍微不太稳定的质子化双环亚胺离子 (AmaH + ( II ))。虽然铵离子是通过碱性 NH 2基团的质子化产生的,但 AmaH + ( II ) 是通过将 H 添加到在 Ama 电离和随后的笼子打开时产生的二张双环亚胺离子上形成的。
更新日期:2022-06-13
down
wechat
bug