硝基化合物的质谱研究

A Study on the Mass Spectrometry of Nitro—Compounds

2,6—DNT、2,4,6—TNT、3,5—DNT、3,4,5—TNT、1,3,5—三硝基—1,3,5—三氮杂环已烷(RDX)、1,3,5,7—四硝基—1,3,5,7—四氮杂环辛烷(HMX)以及杂环硝胺偕二硝基化合物的裂解机理是用电子轰击方法研究的。在芳香硝基化合物中突出的反应机理是消去OH基的“邻位效应”和C—NO_2键裂分反应。RDX和HMX的裂解机理以典型的丢失结构单元CH_2NNO_2和基团NO_2、HNO_2、NO为特点。杂环硝胺偕二硝基化合物的裂解机理是以典型的丢失基团如NO_2、NO、HNO_2为特点。

Mass spectra of 2. 6-DNT, 2. 4. 6-TNT, 3. 5-DNT, 3.4.5-TNT, RDX, HMS and 1.1.2.2-Digemdinitro-4-nitro-Azacyclopantane, 1.1-Gemdinitro-3. 5-Dinitro-3. 5 Azacyclohexane, 1.1-Gemdinitro-3.6-dinitro-3.6-Azacycloheptane, 1.1.5.5-Digemdinitro-3.7-Dinitro-3. 7-Azacycioactane were recorded by the electron impact. The fragmentation pathways of these compounds were studied. In 2.4-DNT and 2. 4. 6-TNT with adjacent CH_3 and NO_2 groups, important fragmentation sequences are 'Ortho effect', the facile transfer of a methyl hydrogen to oxygen followed by loss of an OH group gives rise to the m/z210 ion. The similarity between the fragmentation pathways of RDX and HMX is apparent. In both compounds adduct ions are formed by addtion of NO, NO_2, nCH_2 NNO_2+H groups, producing [M+NO]^+, [M+NO_2]^+ and [M+nCH_2 NNO_2+H]^+ ions, n=1-5. Fragenet modes of Gemdinitro-azacyclonitroamino compounds are loss NO_2, NO and HNO_2 groups.