Proton-induced reactions of [2.2]-paracyclophane in the gas phase. A study by FT-ICR-spectrometry and DFT calculation

Abstract

The reactions of the [2-2]-paracyclophane 1 and the [2-2]-metaparacyclopane 2 in the gas phase after protonation by CI(CH) or CI(I-CH) were studied by FT-ICR mass spectrometry. The ions CH produced in the external ion source of the FT-ICR instrument were transferred into the ICR cell containing the neutral reactant, and the reactions were analyzed measuring the efficiency of the transfer of a proton to a series of bases with known proton affinity and gas phase basicity as well as the efficiency of the ion-molecule reaction with ethyl vinyl ether. Both reaction types show that the ions CH produced by chemical ionization (CI) consist of two sets of isomeric ions A and B which exhibit distinctly different behavior on deprotonation and of the reaction with ethyl methyl ether. Isomer(s) A (about 65% of the ion population) react efficiently with this vinyl ether by an addition/elimination process typical of primary and secondary benzylic carbenium ions, while isomer B (about 35% of the ion population) undergoes only an ineffective deprotonation by the vinyl ether. By bracketing deprotonation, it is shown that A is actually composed of two isomers A and A with slightly different proton affinity and gas phase basicity. These two ions have been identified using CA-mass spectrometry as protonated 3-phenethylstyrene (A) and protonated 4-phenethylstyrene (A). The CA-mass spectrum of the isomer B indicated that these ions CH correspond to protonated 1-(ethyl phenyl)-1-phenyl-ethene. This agrees with the rather strong basicity of the conjugated base of ions B, which results in a slow deprotonation. A protonated 1-(ethyl phenyl)-1-phenyl-ethene can arise from a protonated 2-phenethylstyrene by H- and subsequent phenyl shifts, but requires the preceding rearrangement of the protonated [2.2]-paracyclophane into the protonated isomer "[2.2]-orthocyclophane" - the 1,5-dibenzocyclooctadiene. The possibility of such a deep-sited rearrangement was studied by the computation of the relevant reaction routes applying DFT-methods at the level B3LYP/6-311+g(3d,2p)//B3LYP/3-21g) to analyze the reaction mechanisms.

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

“…But the odd one out of the simple [2.2]cyclophane series appears to be [2.2]metaparacyclophane (3). Compared to the other two isomers, there has been scant research [18][19][20][21][22][23] conducted on this framework. A search for the word `[2.2]metacyclophane*` in SciFinder gives 315 hits (192 hits on Web of Science) while a search for word ` [2.2]metaparacyclophane*ò nly has 69 hits on Scifinder (and 35 for Web of Science; searches were conducted 29th September 2020).…”