Application of High-field NMR Spectroscopy for Differentiating Cathinones for Forensic Identification

Colonial Academic Alliance Undergraduate Research Journal Volume 5 Article 1 2015 Application of High-field NMR Spectroscopy for Differentiating Cathinones for Forensic Identification Jessica N. Krummel Towson University, Lauren N. Russell Towson University, Danniebelle N. Haase Towson University, Susan M. Schelble Metropolitan State University of Denver, Ethan Tsai Metropolitan State University of Denver, See next page for additional authors Follow this and additional works at: https://scholarworks.wm.edu/caaurj Recommended Citation Krummel, Jessica N.; Russell, Lauren N.; Haase, Danniebelle N.; Schelble, Susan M.; Tsai, Ethan; and Elkins, Kelly M. (2015) "Application of High-field NMR Spectroscopy for Differentiating Cathinones for Forensic Identification," Colonial Academic Alliance Undergraduate Research Journal: Vol. 5 , Article 1. Available at: https://scholarworks.wm.edu/caaurj/vol5/iss1/1 This Article is brought to you for free and open access by the Journals at W&M ScholarWorks. It has been accepted for inclusion in Colonial Academic Alliance Undergraduate Research Journal by an authorized editor of W&M ScholarWorks. For more information, please contact . Application of High-field NMR Spectroscopy for Differentiating Cathinones for Forensic Identification Cover Page Note The authors gratefully acknowledge the National Science Foundation (TUES DUE 1245666 and MRI DUE 0923051) for the support of this research and 300 MHz Bruker Avance NMR and 400SS MHz JEOL NMR instruments that made this study possible. The authors acknowledge Tim Brunker for his technical assistance and advice. Authors Jessica N. Krummel, Lauren N. Russell, Danniebelle N. Haase, Susan M. Schelble, Ethan Tsai, and Kelly M. Elkins This article is available in Colonial Academic Alliance Undergraduate Research Journal: https://scholarworks.wm.edu/caaurj/vol5/iss1/1 Krummel et al.: High-field NMR of Cathinones for Forensic Identification Introduction Synthetic cathinone family compounds are the major naturally--occurring psychostimulant and hallucinogenic designer drugs that are used illegally in the U.S. and several other countries for their cocaine, methylenedioxymethamphetamine (MDMA), and amphetamine-like like effects (http://www.deadiversion.usdoj.gov/fed_regs/rules/2014/fr0307_2.htm http://www.deadiversion.usdoj.gov/fed_regs/rules/2014/fr0307_2.htm) [1-2]. Cathinone (Figure 1) is a natural product found in the leaves of the Catha edulis plant, also known as khat khat, chewed by Middle Eastern and African populations in Yemen and Somalia [3-5] 5]. Cathinone has no accepted medical use and has been determined to be highly addictive by the Drug ug Enforcement Agency (DEA) in the U.S.; it is a member of the United States (U.S.) Controlled Substances Act (CSA) Schedule I. The cathinone in khat converts to cathine (d-norpseudoephedrine) norpseudoephedrine) upon aging and drying [6]. Both cathinone and cathine exhibit structural similarities to amphetamine but the cathine is less potent [6]. Members of the cathinone family may be used for therapeutic purposes (e.g,, Bupropion (Wellbutrin ®), not controlled; Diethylpropion (Tenuate®), CSA Category IV; Pyrovalerone (Centroton® (Centroton®), CSA Category V) but within the last decade synthetic cathinones have been used for recreational purposes as a “legal high” with varying biochemical effects [1-3, 7-8]. Figure 1 Cathinone (also known as benzoylethanamine or β-ketoamphetamine) ketoamphetamine) A growing number of novel recreational drug substances abused by young people in the U.S.,, Europe and Australia are designer cathinones [3]. Synthetic pathways for producing drugs have been available in the literature since 1912 (e.g., MDMA) but synthetic drugs only started appearing in seized drugs in the U.S. in 1979 with China White in California [2]. Synthetic cathinones have been presented in the literature for almost a hundre hundred years. Methcathinone, the first synthetic cathinone, was synthesized in 1928 [2]. Designer cathinones are crystalline white or yellow solids, depending upon the purity. Due to their simple structures, designer cathinones are simple to synthesize synthesize; this partly rtly explains their Published by W&M ScholarWorks, 2015 1 Colonial Academic Alliance Undergraduate Research Journal, Vol. 5 [2015], Art. 1 growing popularity as per unit costs are relatively low. At the present time, most of the designer cathinones are reported to originate in China or India [1]. Most forensic laboratories began to encounter designer cathinones in casework in 2009 with a significant increase by 2011-2012 (National Drug Intelligence Center, Product Number 2011-S0787-004) [2, 9-11]. In 2009, poison control centers received no calls reporting bath salt overdose but 303 calls were fielded in 2010, and 5625 calls were received in 2011 [3]. As long as the particular compounds are not controlled, designer cathinones may be sold in “head shops,” “smart shops,” gas stations, convenience stores, or the Internet [1-2, 11]. To avoid federal and state legislative restrictions, designer cathinones are sold as “bath salts,” “fertilizer,” “plant food,” and “research chemicals” and labeled “not for human consumption” or ‘‘not tested for hazards or toxicity” [1-2, 11]. As the ingredient list on purchased products gives the user no indication of the presence of psychoactive compounds, there is the potential for serious harm and toxicity - and no or little safety information is provided [1]. Users take the drugs—bought and sold in the form of powders, capsules and tablets—most commonly by insufflation (snorting), intravenous or intramuscular injection, ingestion as pills or with other liquids, but also rectally, in the eye (“eye-balling”), and subcutaneously [1-2]. Around 2010 the most prevalent were mephedrone (4methylmethcathinone) and MDPV (3,4-methylenedioxypyrovalerone) [1]. Due to their increased prevalence and no accepted medical use in the U.S., in March 2014, one of the synthetic cathinones in this study, pentylone, among others, was one of the 10 synthetic cathinones temporarily placed in Schedule I of the U.S. CSA - but more than 30 designer cathinones have been observed in Europe [1] and more are observed each year worldwide. Dealers increase their product and profits by extending the quantity of “drug” by adding other cheap, white, nearly indistinguishable powders called cutting agents or adulterants. The cutting agents may impart little (e.g., caffeine, lidocaine) to no (e.g., sugar) drug-like effects. The designer cathinones often contain various concentrations (<2–96%) of adulterants including benzocaine, lidocaine, caffeine, benzocaine, piperazines and paracetamol, among others [1-2]. In many cases, drug paraphernalia shows evidence of more than one drug and more than one cathinone. For example, 4-methylethcathinone (4-MEC) is a designer drug that is structurally similar to mephedrone [10]. The purity was observed at 5 (...truncated)