Gas Chromatographic and Mass Spectral Analysis of Amphetamine Products Synthesized from 1-Phenyl-2-NitropropeneJack DeRuiter, C. Randall Clark and F. Taylor Noggle
Journal of Chromatographic Science, Vol. 32, 511-519 (1994)
The conversion of 1-phenyl-2-nitropropene to amphetamine is investigated under a variety of reaction conditions using gas chromatography-mass spectrometry (GC-MS). This versatile intermediate is prepared by treating benzaldehyde with butylamine and nitroethane. GC—MS analysis revealed that amphetamine is produced as the major product upon catalytic reduction of 1-phenyl-2-nitropropene. However, a number of partial reduction products are also present in the mixture. Reduction of the nitropropene with a 5-molar excess of lithium aluminum hydride yields 1-phenyl-2-propanoxime as the major component. A variety of other partial reduction products and products of competing reactions are also present in this product mixture, as well as amphetamine. When this reduction is carried out with a large excess of lithium aluminum hydride, amphetamine is formed as the major product. 1-Phenyl-2-nitropropene is also converted to the ketone, 1-phenyl-2-propanone, by partial reduction and hydrolysis. Amination of this ketone under Leuckart and reductive amination conditions provide amphetamine as the principle product. GC—MS analysis reveals that these samples also contain several by-products characteristic of these routes of synthesis.
____ ___ __ _Methods for the Differentiation of Methamphetamine from Regioisomeric PhenethylaminesF. Taylor Noggle, C. Randall Clark, Kamal H. Bouhadir and Jack DeRuiter
Journal of Chromatographic Science, Vol. 29, 31-36 (1991)
The analytical profiles are described for five amines, methamphetamine, and four isomeric phenethylamines of MW = 149. These five amines all contain an unsubstituted benzyl moiety, thus the regioisomerism is within the carbon-carbon bond located
- to the amine moiety. Therefore these phenethylamines are regioisomeric within the imine fragment (m/z = 58), which is the base peak in the electron impact (EI) mass spectrum of methamphetamine. The ultraviolet absorption spectra for these compounds show the characteristic phenethylamine absorption bands in the (250-260 nm) range. These amines are best differentiated by chromatographic separation and are well resolved by liquid chromatographic techniques. The five regioisomeric amines are separated using an isocratic reversed-phase system consisting of a C18
stationary phase and a mobile phase of pH 3 phosphate buffer and methanol. The elution order under these conditions appears to parallel the length of the carbon chain attached to the aromatic ring.
____ ___ __ _-Benzyl-N-Methylphenethylamine (BNMPA), an Impurity of Illicit Methamphetamine Synthesis: III. Detection of BNMPA and Metabolites in Urine of Methamphetamine UsersKarla A. Moore, Abd Ismaiel and Alphonse Poklis
Journal of Analytical Toxicology, Vol. 20, 89-92 (1996)
Eighty urine specimens collected from drug rehabilitation programs, which had been screened by immunoassay and confirmed positive by gas chromatography–mass spectrometry (GC–MS) for methamphetamine, were further analyzed for a-benzyl-N-methylphenethylamine (BNMPA) and its urinary metabolites, N-demethyl-BNMPA, diphenyl-2-propanone (DP2P), diphenyl-2-propanol, p-OH-N-demethyl-BNMPA, and p-OH-BNMPA. BNMPA is an impurity of illicit methamphetamine synthesis. Analysis of BNMPA and its metabolites was performed by quantitative GC–MS following
-glucuronidase hydrolysis, liquid–liquid extraction, and derivatization with heptafluorobutyric anhydride. Two urine specimens contained detectable amounts of BNMPA and/or its metabolites. One contained trace amounts (greater than the limit of detection but less than the limit of quantitation) of N-demethyl-BNMPA and DP2P, as well as 0.04 mg/L p-OH-N-demethyl-BNMPA. The other contained trace amounts of BNMPA, p-OH-BNMPA, and p-OH-N-demethyl-BNMPA, as well as 0.03 mg/L N-demethyl-BNMPA. Prior to analyzing these urine specimens, pure reference material of p-OH-BNMPA was made available, and analysis confirmed our previous tentative identification of p-OH-BNMPA as a major metabolite of BNMPA. Detection of BNMPA or its metabolites in biological samples may serve as a marker of illicit methamphetamine administration.
____ ___ __ _Identification of -Phenylethylamine in judicial SamplesE. Meyer, J. F. Van Bocxlaer, W. E. Lambert, L. Thienpont and A. P. De Leenheer
Journal of Analytical Toxicology, Vol. 20, 116-120 (1996)
-Phenylethylamine was recently identified in samples from several judicial cases using chromatographic (high-performance liquid chromatography–diode-array detection, gas chromatography–mass spectrometry, and gas chromatography–Fourier transform infrared detection) and spectrometric (nuclear magnetic resonance) techniques. In the first case, 1 kg of a white powder was found in a basement laboratory. It contained caffeine and more than 15%
-phenylethylamine. In the second case, two white powders were seized from a female. One powder consisted of pure amphetamine, and the other was a mixture of caffeine, amphetamine, and
-phenylethylamine. Four months later, a couple, who were known drug users, were found dead in their apartment. Urine samples of both victims contained large amounts of amphetamine together with
-phenylethylamine. Recently, 0.13 kg of a white powder and 0.30 kg of an orange powder were seized during a law enforcement operation. Both powders were mixtures of caffeine, amphetamine, and
-phenylethylamine. The data presented demonstrate the recent and unrelated repetitive occurrence of
-phenylethylamine in the circuit of illicit drugs.
____ ___ __ _Analysis of Impurities in Illicit MethamphetamineK. Tanaka, T. Ohmori And T. Inoue
Forensic Science International 56, 157-165 (1992)
Impurity profiles of methamphetamine samples seized in Japan have been investigated. The samples are extracted with small amounts of hexane under alkaline conditions and the extracts are analyzed by gas chromatography (GC). Several impurity peaks are found in each chromatogram and the comparison of impurity profiles permits the establishment of common or different origins of methamphetamine seizures. The presence of ephedrine, which is a starting material for illegal methamphetamine preparations, is confirmed in all samples. In addition, methamphetamine dimer is newly found as an impurity and its structure is elucidated by the comparison of its retention time on GC and its mass spectrum with that of the authentic compound synthesized by condensation of cis-1,2-dimethyl-3-phenyl aziridine and (+)-methamphetamine.
____ ___ __ _Gas Chromatographic and Mass Spectral Analysis of Methamphetamine Synthesized From AllylbenzeneF. Taylor Noggle, C. Randall Clark and Jack DeRuiter
Journal of Chromatographic Science, Vol 33, 153-161 (1995)
The synthesis of methamphetamine from allylbenzene is investigated using gas chromatography–mass spectrometry. Treatment of allylbenzene with HBr yields 1-phenyl-2-bromopropane as a major product. Smaller amounts of 1-phenyl-3-bromopropane, as well as 2,3-, 1,2-, and 1,3-dibromopropane, are also formed during the course of this reaction; both diastereomeric forms of 1,2-dibromopropane are detected in the product mixture. Amination of the crude bromination product with methylamine yields primarily methamphetamine and other amines characteristic of this synthetic method, including the methamphetamine isomer, N-methyl-1-phenyl-1-propanamine.