Neutral Heroin Impurities from Tetrahydrobenzylisoquinoline Alkaloids

Abstract

Laudanosine, reticuline, codamine, and laudanine are members of the tetrahydrobenzylisoquinoline family of natural products. These alkaloids are present in the opium poppy, Papaver somniferum, and are subsequently found as impurities in clandestinely processed morphine. Morphine is then synthesized to heroin using hot acetic anhydride. During the course of this study, it was determined that these four tetrahydrobenzylisoquinolines undergo degradation to a series of 18 neutral impurities when subjected to hot acetic anhydride. Based on the degradation pathway, these new impurities were categorized into two sets of impurities called the C1-acetates compounds and the stilbene compounds. Synthesis, isolation, and structural elucidation information is provided for the tetrahydrobenzylisoquinoline alkaloids, and the new neutral impurities have been studied. Several hundred authentic heroin samples were analyzed using an established heroin signature program method. This methodology features the detection of trace neutral impurities present in heroin samples. It was determined that all 18 new impurities were detected in various quantities in four different types of heroin samples. Analytical results featuring these new impurities are reported for South American-, Southwest Asian-, Mexican-, and Southeast Asian-type heroin samples. These new impurities, coupled with other established forensic markers, enhance the ability to classify illicit heroin samples.

Nationwide increase in hospitalizations for heroin-related soft tissue infections: Associations with structural market conditions

“…Part of the STRIDE data is collected for use in the Heroin Signature Program that collects heroin samples for the purpose of identifying source region (Toske et al, 2006). We used this series to construct a variable identifying the percentage of heroin samples in each MSA for each year that originates from Colombia or Mexico.…”

Fragmentation pathways of heroin‐related alkaloids revealed by ion trap and quadrupole time‐of‐flight tandem mass spectrometry

“…A number of chromatographic and electrophoretic methods for the analysis of heroin‐related alkaloids and their metabolites in various matrices have been reported 2. Gas chromatography (GC)3–5 and GC/mass spectrometry (GC/MS)6–8 have been used for the determination of some components of interest in street heroin samples and biological fluids. However, GC‐based methods are problematic for analytes such as morphine, 6‐MAM and narcotine which are either thermally degradable or nonvolatile and thus exhibit poor chromatographic performance.…”

UHPLC–MS/MS quantitation of porphyroxine in opium and application of porphyroxine‐acetylated products as signature markers for heroin

“…Illicit heroin production involves the extraction of morphine from opium followed by its acetylation to heroin; thus, a number of alkaloids from opium and/or their derivative products are likely to be present in the final heroin. More than 80 alkaloids have been identified in opium poppy plants; numerous publications have cited the identification and characterization of opium alkaloid‐related impurities found in street heroin . The presence, absence, and/or the relative abundance of the alkaloids (including the primary alkaloids such as morphine, codeine, thebaine, noscapine, and papaverine) varies in opium of different varieties of Papaver somniferum , commonly known as the opium poppy .…”