亚稳态苯甲酸甲酯分子离子的脱羧作用。

Decarboxylation of metastable methyl benzoate molecular ions.

作者信息

Dechamps Noémie, Flammang Robert, Gerbaux Pascal, Nam Pham-Cam, Nguyen Minh-Tho

机构信息

Laboratory of Organic Chemistry, University of Mons-Hainaut, Avenue Maistriau 19, B-7000, Mons, Belgium.

Department of Chemistry, University of Leuven, Leuven, Belgium.

出版信息

J Am Soc Mass Spectrom. 2006 Jun;17(6):807-814. doi: 10.1016/j.jasms.2006.02.015. Epub 2006 Apr 17.

DOI:10.1016/j.jasms.2006.02.015

PMID:16603373

Abstract

By using a combination of mass spectrometric methodologies and density functional theory calculations [DFT/B3LYP/6-311 ++ G(d, p)], it is proposed that the decarboxylation of metastable methyl benzoate molecular ions occurs via distonic and ion-neutral complex (INC) intermediates. The same INC involving a complex between the benzyl radical and protonated carbon dioxide is also generated upon decarboxylation of metastable phenylacetic acid molecular ions. Internal proton transfer within the INC produces in fine a mixture of toluene and isotoluene radical cations.

摘要

通过结合质谱方法和密度泛函理论计算[DFT/B3LYP/6-311++G(d,p)]，提出亚稳态苯甲酸甲酯分子离子的脱羧反应通过双电荷离子和离子-中性复合物（INC）中间体进行。亚稳态苯乙酸分子离子脱羧时也会生成相同的涉及苄基自由基与质子化二氧化碳之间复合物的INC。INC内的质子内转移最终产生甲苯和异甲苯自由基阳离子的混合物。