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首页> 外文期刊>Journal of mass spectrometry: JMS >The ESI CAD fragmentations of protonated 2,4,6-tris(benzylamino)- and tris(benzyloxy)-1,3,5-triazines involve benzyl-benzyl interactions: A DFT study
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The ESI CAD fragmentations of protonated 2,4,6-tris(benzylamino)- and tris(benzyloxy)-1,3,5-triazines involve benzyl-benzyl interactions: A DFT study

机译：DSI研究：质子化的2,4,6-三（苄氨基）-和三（苄氧基）-1,3,5-三嗪的ESI CAD片段涉及苄基-苄基相互作用

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The electrospray ionization collisionally activated dissociation (CAD) mass spectra of protonated 2,4,6-tris(benzylamino)-1,3,5-triazine (1) and 2,4,6-tris(benzyloxy)-1,3,5-triazine (6) show abundant product ion of m/z 181 (C _(14)H _(13) ~+). The likely structure for C _(14)H _(13) ~+ is α-[2-methylphenyl]benzyl cation, indicating that one of the benzyl groups must migrate to another prior to dissociation of the protonated molecule. The collision energy is high for the 'N' analog (1) but low for the 'O' analog (6) indicating that the fragmentation processes of 1 requires high energy. The other major fragmentations are [M + H-toluene] ~+ and [M + H-benzene] ~+ for compounds 1 and 6, respectively. The protonated 2,4,6-tris(4-methylbenzylamino)-1,3,5-triazine (4) exhibits competitive eliminations of p-xylene and 3,6-dimethylenecyclohexa-1,4- diene. Moreover, protonated 2,4,6-tris(1-phenylethylamino)-1,3,5-triazine (5) dissociates via three successive losses of styrene. Density functional theory (DFT) calculations indicate that an ioneutral complex (INC) between benzyl cation and the rest of the molecule is unstable, but the protonated molecules of 1 and 6 rearrange to an intermediate by the migration of a benzyl group to the ring 'N'. Subsequent shift of a second benzyl group generates an INC for the protonated molecule of 1 and its product ions can be explained from this intermediate. The shift of a second benzyl group to the ring carbon of the first benzyl group followed by an H-shift from ring carbon to 'O' generates the key intermediate for the formation of the ion of m/z 181 from the protonated molecule of 6. The proposed mechanisms are supported by high resolution mass spectrometry data, deuterium-labeling and CAD experiments combined with DFT calculations.
机译：质子化的2,4,6-三（苄氨基）-1,3,5-三嗪（1）和2,4,6-三（苄氧基）-1,3的电喷雾电离碰撞激活解离（CAD）质谱5-三嗪（6）显示出m / z 181（C _（14）H _（13）〜+）的丰富产物离子。 C _（14）H _（13）〜+的可能结构是α-[2-甲基苯基]苄基阳离子，表明其中一个苄基必须在质子化分子解离之前迁移至另一个。 “ N”模拟物（1）的碰撞能量较高，而“ O”模拟物（6）的碰撞能量较低，表明1的碎裂过程需要高能量。其他主要片段分别是化合物1和6的[M + H-甲苯]〜+和[M + H-苯]〜+。质子化的2,4,6-三（4-甲基苄氨基）-1,3,5-三嗪（4）表现出对二甲苯和3,6-二亚甲基环己-1,4-二烯的竞争性消除。此外，质子化的2,4,6-三（1-苯基乙基氨基）-1,3,5-三嗪（5）通过连续三个苯乙烯损失而解离。密度泛函理论（DFT）计算表明，苄基阳离子与分子其余部分之间的离子/中性络合物（INC）不稳定，但是1和6的质子化分子通过苄基向C的迁移而重排为中间体。敲“ N”。随后第二个苄基的移位产生质子化分子1的INC，其产物离子可由该中间体解释。第二个苄基向第一个苄基的环碳转移，然后从环碳向“ O” H转移，产生了从6的质子化分子形成m / z 181离子的关键中间体高分辨率质谱数据，氘标记和CAD实验结合DFT计算为所提出的机制提供了支持。

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