Gas‐phase F‐atom migration reaction of deprotonated N‐fluoroarenesulfonamides

Author:

Xia Yaoyu12,Zhang Yu‐Yang2,Zhang Qian1,Zhang Xiang3,Wang Hao‐Yang2ORCID

Affiliation:

1. School of Materials and Chemistry University of Shanghai for Science and Technology Shanghai People's Republic of China

2. Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai People's Republic of China

3. School of Food Science and Biotechnology Zhejiang Gongshang University Hangzhou People's Republic of China

Abstract

RationaleRecently N‐Fluoroarenesulfonamides (ArSO2NHF) were found to be promising precursors for the preparation of N‐fluorobenzenesulfonimide derivatives without applying F2. However, very few studies have discussed the mass spectrometric behaviors of ArSO2NHF with N–F structure.MethodsIn this article, we applied high‐resolution electrospray ionization tandem mass spectrometry (HR‐ESI‐MS/MS) to study the effect on the mass spectrometric behaviors of ArSO2NHF after the introduction of the F‐atom to the N‐atom of ArSO2NH2.ResultsHigh‐resolution electrospray ionization mass spectrometry (HR‐ESI‐MS) experiments showed that ArSO2NHF produced only good signals in negative ion mode, and the dominating product ion SO2F at m/z 83 was observed in all HR‐ESI‐MS/MS of ArSO2NF with different substituents in the Ar group. The formation of the product ion SO2F was proof of the gas‐phase F‐atom migration rearrangement from the N‐atom to the S‐atom in ESI‐MS/MS of ArSO2NF.ConclusionTo fully explain the gas‐phase reaction mechanism from ArSO2NF to SO2F, we studied the HR‐ESI‐MS/MS of deprotonated ArSO2NHF and also performed theoretical calculations. Both results confirmed that ArSO2NF first underwent Smiles rearrangement to yield intermediate I (INT1) ArNFSO2, and then the F‐atom of ArNFSO2 migrated from the N‐atom to the S‐atom to form intermediate II (INT2) ArNSO2F, which finally dissociated to SO2F at m/z 83 with loss of a neutral nitrene (ArN). All these results showed that the formation of the product ion SO2F from ArSO2NF was a common and intrinsic gas‐phase reactivity of ArSO2NF.

Funder

Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences

National Natural Science Foundation of China

Publisher

Wiley

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