Isotope fractionation during synthesis of methamphetamine from propiophenone, NaNO2 and dimethyl carbonate

IF 2.6 3区 医学 Q2 CHEMISTRY, ANALYTICAL
Brendan M. Miller , James F. Carter , Sarah L. Cresswell , Wendy A. Loughlin , Peter N. Culshaw
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Abstract

Ephedrine remains a key precursor in the production of methamphetamine. A novel ephedrine-based route to methamphetamine involved the nitrosation of propiophenone to α-isonitrosopropiophenone, followed by catalytic hydrogenation to phenylpropanolamine (± − norephedrine). Cyclization-methylation of phenylpropanolamine to 3,4-dimethyl-5-phenyl-2-oxazolidinone using dimethyl carbonate, followed by basic hydrolysis or catalytic hydrogenolysis formed ephedrine or methamphetamine, respectively.
An investigation into the stable isotope fractionation during the synthesis of methamphetamine from propiophenone, NaNO2 and dimethyl carbonate was performed using isotope ratio mass spectrometry. A negative isotopic shift was observed for δ15N upon nitrosation of propiophenone to α-isonitrosopropiophenone, and a negative isotopic shift for δ2H during catalytic hydrogenation of α-isonitrosopropiophenone to phenylpropanolamine. Minimal change in δ13C was observed throughout the reaction until the methylation step with dimethyl carbonate, where a negative isotopic shift was observed.
The δ13C values for the methamphetamine presented in a similar range to methamphetamine reported in previous work where the norephedrine/norpseudoephedrine was prepared via different starting materials (benzaldehyde and nitroethane), confirming that similar δ13C values will result from fractionation during methylation with dimethyl carbonate regardless of the origin of the norephedrine/norpseudoephedrine. Chiral analysis confirmed methamphetamine to be racemic.

Abstract Image

丙烯酮、NaNO2和碳酸二甲酯合成甲基苯丙胺的同位素分馏
麻黄碱仍然是生产甲基苯丙胺的关键前体。以麻黄碱为基础的新型甲基苯丙胺生产工艺包括将苯丙酮亚硝化为 α-异亚硝基苯丙酮,然后催化加氢生成苯丙羟胺(± - 去甲麻黄碱)。使用碳酸二甲酯将苯丙羟胺环化-甲基化为 3,4-二甲基-5-苯基-2-恶唑烷酮,然后进行碱水解或催化氢化,分别生成麻黄碱或甲基苯丙胺。在将苯丙酮硝化成 α-异硝基苯丙酮的过程中,观察到 δ15N 发生了负同位素移动,在将α-异硝基苯丙酮催化氢化成苯丙羟胺的过程中,观察到 δ2H 发生了负同位素移动。在整个反应过程中,δ13C 的变化极小,直到与碳酸二甲酯发生甲基化反应时,才观察到负同位素位移。甲基苯丙胺的δ13C值与之前工作中报告的甲基苯丙胺的δ13C值范围相似,在之前的工作中,去甲麻黄碱/去甲伪麻黄碱是通过不同的起始原料(苯甲醛和硝基乙烷)制备的。手性分析证实甲基苯丙胺是外消旋的。
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来源期刊
Forensic Chemistry
Forensic Chemistry CHEMISTRY, ANALYTICAL-
CiteScore
5.70
自引率
14.80%
发文量
65
审稿时长
46 days
期刊介绍: Forensic Chemistry publishes high quality manuscripts focusing on the theory, research and application of any chemical science to forensic analysis. The scope of the journal includes fundamental advancements that result in a better understanding of the evidentiary significance derived from the physical and chemical analysis of materials. The scope of Forensic Chemistry will also include the application and or development of any molecular and atomic spectrochemical technique, electrochemical techniques, sensors, surface characterization techniques, mass spectrometry, nuclear magnetic resonance, chemometrics and statistics, and separation sciences (e.g. chromatography) that provide insight into the forensic analysis of materials. Evidential topics of interest to the journal include, but are not limited to, fingerprint analysis, drug analysis, ignitable liquid residue analysis, explosives detection and analysis, the characterization and comparison of trace evidence (glass, fibers, paints and polymers, tapes, soils and other materials), ink and paper analysis, gunshot residue analysis, synthetic pathways for drugs, toxicology and the analysis and chemistry associated with the components of fingermarks. The journal is particularly interested in receiving manuscripts that report advances in the forensic interpretation of chemical evidence. Technology Readiness Level: When submitting an article to Forensic Chemistry, all authors will be asked to self-assign a Technology Readiness Level (TRL) to their article. The purpose of the TRL system is to help readers understand the level of maturity of an idea or method, to help track the evolution of readiness of a given technique or method, and to help filter published articles by the expected ease of implementation in an operation setting within a crime lab.
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