title: Using tandem mass spectrometry to predict chemical transformations of 2-pyrimidinyloxy-N-arylbenzyl amine derivatives in solution.
abstract: Tandem mass spectrometry is used to predict the chemical transformations of 2-pyrimidinyloxy-N-arylbenzyl amine derivatives. Compound 1, N-2-2-4,6- dimethoxypyrimidin-2-yloxy benzylamino phenyl benzamide was selected as a model to present our idea. The CID reactions of protonated 1 include an intramolecular S(N)2 reaction and a cyclodehydration reaction. Under in-source CID conditions, deprotonated 1 undergoes a Smiles rearrangement reaction and then dissociates to the ion at m/z 349. Theoretical computations were invoked to shed light on the reaction mechanisms of 1 by the semiempirical PM3 method. These studies of gas-phase reactions show the reactivity of some potential reaction centers in this molecule, which inspired us to explore the solution phase analogous reactions of 1. Further experiments show that 1 has two analogous reactions in acidic solution: the acid-catalyzed cyclodehydration reaction and the acid-catalyzed Smiles rearrangement reaction. Moreover, 1 undergoes the base-catalyzed Smiles rearrangement under basic conditions. The present study demonstrates that mass spectrometry can play an important role in predicting the chemical solution phase transformations of 2-pyrimidinyloxy-N-arylbenzyl amine derivatives.
authors.affiliation: Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
authors.forename: Hao-Yang
authors.initials: HY
authors.lastname: Wang
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhang
authors.forename: Yin-Long
authors.initials: YL
authors.lastname: Guo
authors.forename: Qing-Hong
authors.initials: QH
authors.lastname: Tang
authors.forename: Long
authors.initials: L
authors.lastname: Lu
mesh_terms: D001596:Benzylamines / Q000032:analysis*; D018360:Crystallography, X-Ray; D004784:Environmental Monitoring; D007202:Indicators and Reagents; D008958:Models, Molecular; D010575:Pesticides / Q000032:analysis*; D012996:Solutions; D021241:Spectrometry, Mass, Electrospray Ionization; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
chemical_list: D001596:Benzylamines; D007202:Indicators and Reagents; D010575:Pesticides; D012996:Solutions