芳氧基烷醇类化合物的硅烷衍生物质谱碎裂中的重排反应  

Electron ionization induced skeleton rearrangements for the aryl alkanol silane derivatives

作　　者：常静 梁芝梅 何育峰 陈丽 王毅 CHANG Jing;LIANG Zhi-mei;HE Yu-feng;CHEN Li;WANG Yi(Xi’an Manareco New Materials Co.,Ltd,xi’an 710077,China)

机构地区：[1]西安瑞联新材料股份有限公司,陕西西安710077

出　　处：《化学研究与应用》2020年第10期1764-1771,共8页Chemical Research and Application

摘　　要：首先,利用气相色谱质谱联用仪(GCMS)在电子电离源(EI)下对苯氧乙醇及其同系物的三甲基硅烷(TMS)衍生物进行分析,结果表明这一类化合物均可产生显著的骨架重排产物离子m/z 166或其次级碎裂产物离子m/z 151。然后,对其它类型的芳氧烷醇、芳氧烷酸等的三甲基硅烷衍生物的质谱分析结果同样有此重排产物离子产生,对这一类化合物的二甲基叔丁基硅烷(TBDMS)衍生物、二甲基五氟苯基硅烷(DMPFS)衍生物的质谱分析也均得到了相应的重排产物离子。最后,推测重排产物离子可能的质谱裂解途径为芳氧基氧原子上的非键n电子被电离成为活性反应中心后,在游离基中心的诱导下,硅烷基作为迁移基团迁移到氧原子上形成新的O-Si键,得到重排产物离子m/z[89+Ar],该离子通过α断裂得到次级重排产物离子m/z[74+Ar]。The trimethylsilyl derivatives of phenoxyethanol and its homologues were analyzed by gas chromatography mass spectrometer under the electron ionization source,and it was found that all the compounds could produce significant skeleton rearrangement product ion m/z 166 or secondary fragmentation product ion m/z 151,analysis of other aryl alkyl alcohol and acids showed that such rearrangement products ions also produced.when used different types of silane derivatives,the corresponding rearrangement product ion were also obtained.It was speculated that the mass fragmentation pathway was that the nonbonding n electrons on the aryloxy oxygen atom were ionized to become the active reaction center under the induction of the free radical center,trimethylsilyl groups migrated to the oxygen atoms to from new O-Si bond,and the rearrangement product of ion m/z[89+Ar]was obtained,which then produced the cecondary rearrangement product ion m/z[74+Ar]byα-clearage.

关 键 词：骨架重排 硅烷衍生物 苯氧烷醇 气质联用 

分 类 号：O657.31[理学—分析化学]