Objective To study the identification method for 4'-F-4-methylaminorex （4'-F-4-MAR） in samples without reference substance. Methods Gas chromatography-mass spectrometry （GC-MS）, ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry （UPLC-QTOF-MS）, nuclear magnetic resonance （NMR） and Fourier transform infrared （FTIR） were comprehensively used for the structure identification of 4'-F-4-MAR in samples. Results Under the positive electrospray ionization （ESI+） mode, quasi-molecular ion in the first order mass spectrometry of the unknown compound was 195.092 6 and its molecular formula was inferred to be C10H11FN2O. The fragment ions in the mass spectrometry of the unknown compound were compared with the related fragment ions of 4,4'-dimethylaminorex （4,4'-DMAR） in literature. It was found that the main fragment ions of the unknown compound were all 4 bigger than the corresponding fragment ions of 4,4'-DMAR. Therefore, the unknown compound was inferred to be a 4,4'-DMAR analogue with a methyl substituted by a fluorine in the benzene ring. The equivalent protons at δ=7.30 and δ=7.06 in 1H-nuclear magnetic resonance （1H-NMR） spectra and the characteristic spin-spin coupling constants （1JC-F=245.2 Hz, 2JC-F=21.3 Hz, 3JC-F=8.1 Hz） for 13C-19F interactions in carbon spectra, further proved that the fluorine substituted methyl at the para-position of the benzene ring. Finally, the unknown compound was determined as 4'-F-4-MAR. Conclusion A method that comprehensively used the identification materials 4'-F-4-MAR in GC-MS, UPLC-QTOF-MS, NMR and FTIR is established and the fragmentation mechanism of fragmentation ions of 4'-F-4-MAR created under the two modes -- electron impact （EI） and electrospray ionization under collision induced dissociation （ESI-CID） is deduced. The information will assist forensic science laboratories in identifying this compound or other substances with similar structure in their case work.
题目: 阿米雷司类似物4’-F-4-MAR的结构解析与表征.
摘要: 目的 研究在没有对照品情况下鉴定检材中4’-F-4-甲基阿米雷司（4’-F-4-methylaminorex，4’-F-4-MAR）的方法。 方法 综合利用气相色谱-质谱法（gas chromatography-mass spectrometry，GC-MS）、超高效液相色谱-串联四极杆飞行时间质谱（ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry，UPLC-QTOF-MS）、核磁共振（nuclear magnetic resonance，NMR）和傅里叶变换红外光谱仪（Fourier transform infrared spectrometer，FTIR）实现对检材中4’-F-4-MAR的结构鉴定。 结果 在电喷雾正离子化（positive electrospray ionization，ESI+）模式下，未知化合物的一级质谱图中准分子离子为195.092 6，推测其分子式为C10H11FN2O。将未知化合物质谱图中的碎片离子与文献中4，4’-二甲基阿米雷司（4，4’-Dimethylaminorex，4，4’-DMAR）的相关碎片离子比较，发现未知化合物的主要碎片离子比4，4’-DMAR的对应碎片离子均大于4，由此推断出未知化合物为4，4’-DMAR的结构类似物，具体为苯环中的甲基被氟原子取代。根据核磁共振氢谱中δ=7.30和δ=7.06位置的等效质子，以及碳谱中13C-19F相互作用的特征自旋-自旋耦合常数（1JC-F=245.2 Hz，2JC-F=21.3 Hz，3JC-F=8.1 Hz），进一步证明了氟取代基的位置在苯环的对位。最终确定未知化合物为4’-F-4-MAR。 结论 建立了综合利用GC-MS、UPLC-QTOF-MS、NMR和FTIR鉴定检材中4’-F-4-MAR的方法，对4’-F-4-MAR在电子轰击和电喷雾离子化-碰撞诱导解离两种模式下生成的碎片离子进行了碎裂机理的推导。这些信息将有助于法庭科学实验室在案件中鉴定该物质或其他具有类似结构的化合物。.
关键词: 法医毒理学；新精神活性物质；气相色谱-质谱法；谱学，傅里叶变换红外；核磁共振；阿米雷司；4’-F-4-甲基阿米雷司.
Keywords: forensic toxicology; new psychoactive substance; gas chromatography-mass spectrometry; spectroscopy, Fourier transform infrared; nuclear magnetic resonance; aminorex; 4’-F-4-methylaminorex （4’-F-4-MAR）.
Copyright© by the Editorial Department of Journal of Forensic Medicine.