Swist M, Wilamowski J, Zuba D, Kochana J, Parczewski A
Department of Analytical Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow 30-060, Poland.
Forensic Sci Int. 2005 May 10;149(2-3):181-92. doi: 10.1016/j.forsciint.2004.06.016.
In our study 1-(3,4-methylenedioxyphenyl)-2-propanone (MDP-2-P or PMK) was prepared by two different routes, i.e. by oxidizing isosafrole in an acid medium and by 1-(3,4-methylenedioxyphenyl)-2-nitropropene reduction. The final product-MDP-2-P was subjected to GC/MS analysis. The intermediates and reaction by-products were identified and the 'route specific' impurities were established. The following impurities are the markers of the greatest importance: 1-(3,4-methylenedioxyphenyl)-1-propanone (compound 10, Table 2), 1-methoxy-1-(3,4-methylenedioxyphenyl)-2-propanone (compound 11, Table 2) and 2,2,4-trimethyl-5-(3,4-methylenedioxyphenyl)-[1,3]dioxolane (compound 13, Table 2) (the 'oxidising isosafrole route') and N-cyclohexylacetamide (compound 3, Table 1), 3-methyl-6,7-methylenedioxyisoquinoline-1,4-dione (compound 15, Table 1) (the 'MDP-2-nitropropene reduction route'). Subsequently, MDMA was prepared by reductive amination of MDP-2-P using NaBH4 as reducing agent (so-called 'cool method'). Impurities were extracted with n-heptane under alkaline conditions. The impurity profiles were obtained by means of GC/MS, some reaction by-products were identified by means of the EI mass spectra including low energy EI mass spectra and 'route specific' impurities were established. 4-Methyl-5-(3,4-methylenedioxyphenyl)-[1,3]dioxolan-2-one (compound 22, Table 2), N-methyl-2-methoxy-1-methyl-2-(3,4-methylenedioxyphenyl)-ethaneamine (compound 18, Table 2), 3-methyl-6,7-methylenedioxyisoquinoline-1,4-dione (compound 15, Table 1) and N-cyclohexyloacetamide (compound 3, Table 1) were found to be the synthesis markers of greatest importance.
在我们的研究中，1-（3,4-亚甲二氧基苯基）-2-丙酮（MDP-2-P或PMK）通过两种不同途径制备，即通过在酸性介质中氧化异黄樟素以及通过1-（3,4-亚甲二氧基苯基）-2-硝基丙烯还原。对最终产物MDP-2-P进行气相色谱/质谱分析。鉴定了中间体和反应副产物，并确定了“特定途径”杂质。以下杂质是最重要的标志物：1-（3,4-亚甲二氧基苯基）-1-丙酮（化合物10，表2）、1-甲氧基-1-（3,4-亚甲二氧基苯基）-2-丙酮（化合物11，表2）和2,2,4-三甲基-5-（3,4-亚甲二氧基苯基）-[1,3]二氧戊环（化合物13，表2）（“氧化异黄樟素途径”）以及N-环己基乙酰胺（化合物3，表1）、3-甲基-6,7-亚甲二氧基异喹啉-1,4-二酮（化合物15，表1）（“MDP-2-硝基丙烯还原途径”）。随后，以硼氢化钠作为还原剂，通过MDP-2-P的还原胺化反应制备摇头丸（所谓的“冷法”）。在碱性条件下用正庚烷萃取杂质。通过气相色谱/质谱获得杂质谱，通过电子轰击质谱（包括低能量电子轰击质谱）鉴定了一些反应副产物，并确定了“特定途径”杂质。发现4-甲基-5-（3,4-亚甲二氧基苯基）-[1,3]二氧戊环-2-酮（化合物22，表2）、N-甲基-2-甲氧基-1-甲基-2-（3,4-亚甲二氧基苯基）-乙胺（化合物18，表2）、3-甲基-6,7-亚甲二氧基异喹啉-1,4-二酮（化合物15，表1）和N-环己基乙酰胺（化合物3，表1）是最重要的合成标志物。
