p-methoxyamphetamine Latest Revision: May 16, 2013 1. SYNONYMS CFR: p-methoxyamphetamine (PMA) CAS #: Base: 23239-32-9 Hydrochloride: 3706-26-1 Other Names: Phenethylamine, p-methoxy-alpha-methyl-, (+/-)- Benzeneethanamine,4-methoxy-alpha-methyl-, (+/-) (+/-)-p- Methoxyamphetamine 4-Methoxyamphetamine (+/-)-p-methoxy-.alpha.-methyl-phenethylamine PMA 1-(4-Methoxyphenyl)-2-propanamine 2. CHEMICAL AND PHYSICAL DATA 2.1. CHEMICAL DATA Form Chemical Formula Molecular Weight Base C 10 H 15 NO 165.2 Hydrochloride C 10 H 15 NO HCl 201.7 2.2. SOLUBILITY Form A C E H M W Base * S * * VS VSS Hydrochloride I SS I I VS S A = acetone, C = chloroform, E = ether, H = hexane, M = methanol and W = water, VS = very soluble, FS = freely soluble, S = soluble, PS = sparingly soluble, SS = slightly soluble, VSS = very slightly soluble and I = insoluble *No literature available
3. SCREENING TECHNIQUES 3.1. COLOR TESTS REAGENT Mandelin s Froehde s Meckes COLOR PRODUCED Green Green Light Olive Green 3.2. GAS CHROMATOGRAPHY Method: PMA-GCMSQ-1 Samples are to be dissolved in an appropriate solvent such as methanol or base extracted previous to injection Instrument: Column: Carrier gas: Gas Chromatograph/Mass Spectrometer HP-5MS 15.0 m x 0.25 mm x 0.25 µm film Helium at 1.0 ml/min Temperatures: Injector: 260 C Transfer Line: 280 C Oven program: 1) 140 C initial temperature for 0.5 min 2) Ramp to 310 C at 38 C/min 3) Hold final temperature for 0.7 min Injection Parameters: Split Ratio=25:1, 1 µl injected COMPOUND RRT COMPOUND RRT dimethyl sulfone 0.46 caffeine 2.05 amphetamine 0.64 lidocaine 2.15 methamphetamine 0.71 chlorpheniramine 2.40 PMA 1.00 procaine 2.44 pseudo/ephedrine 1.05 cocaine 2.78 PMMA 1.11 triprolidine 2.88
MDA 1.26 O-6 monoacetylmorphine 3.34 MDMA 1.47 heroin 3.51 acetaminophen 1.70 3.3. GAS CHROMATOGRAPHY Method: PMA-GCMSQ-2 Samples are to be dissolved in an appropriate solvent such as methanol or base extracted before injection. Instrument: Column: Carrier gas: Gas Chromatograph/Iontrap ZB-5 30.0 m x 0.25 mm dia. x 0.25µm film Helium at 1.0 ml/min Temperatures: Injector: 250 C Transfer Line: 280 C Oven program: 1) 100 C initial temperature for 1.0 min 2) Ramp to 310 C at 30 C/min 3) Hold final temperature for 3.5 min Injection Parameters: Split Ratio=20:1, 1 µl injected COMPOUND RRT COMPOUND RRT dimethyl sulfone 0.50 caffeine 1.41 amphetamine 0.52 lidocaine 1.44 methamphetamine 0.79 chlorpheniramine 1.54 pseudo/ephedrine 0.97 procaine 1.55 PMA 1.00 cocaine 1.68 PMMA 1.05 triprolidine 1.71 MDA 1.09 O-6 monoacetylmorphine 1.92 MDMA 1.14 heroin 2.01 acetaminophen 1.27
3.4. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY Method PMA-LCQ1 The samples are to be dissolved in an appropriate solvent such as 0.1 N HCl or water. Instrument: Column: Detector: Flow: High performance liquid chromatograph equipped with diode array C18, 5 µm, 150 mm x 4.6 mm UV, 210 nm, 10 BW 1.0 ml/min Injection Volume: 3 µl Buffer: Mobile Phase: Typical Retention Time: 4000 ml distilled water, 30 ml phosphoric acid, 10 g sodium hydroxide and 8.0 ml hexylamine at ph 2.5 Buffer: acetonitrile 93:7 for12 min PMA: 5.677min COMPOUND RRT (min) pseudoephedrine 0.58 amphetamine 0.76 MDA 0.85 methamphetamine 0.90 MDMA/PMA 1.00 PMMA 1.20 MDEA 1.32 caffeine 1.79 ketamine 1.93 **MDMA and PMA coelute. 4. SEPARATION TECHNIQUES PMA can be separated from matrixes by solvent extraction using the solubility.
5. QUANTITATIVE PROCEDURES 5.1. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY Method PMA-LCQ1 Standard Solution Preparation: Accurately weigh and prepare a standard solution of PMA hydrochloride at approximately 0.50 mg/ml using 0.1 N HCl. Sample Preparation: Accurately weigh an amount of sample into a volumetric flask and dilute with 0.1 N HCl. If necessary dilute the sample so the final concentration approximates the standard concentration or falls within the linear range. Filter sample with a 0.45-micron filter. Instrument: Column: Detector: Flow: High performance liquid chromatograph equipped with diode array C18, 5 µm, 150 mm x 4.6 mm UV, 210 nm, 10 BW 1.0 ml/min Injection Volume: 3 µl Buffer: Mobile Phase: Typical Retention Time: Linear Range: 4000 ml distilled water, 30 ml phosphoric acid, 10 g sodium hydroxide and 8.0 ml hexylamine at ph 2.5 Buffer: acetonitrile 93:7 for 12min PMA: 5.677min 0.0612-1.224 mg/ml Repeatability: RSD less than 3% Correlation Coefficient: 0.99999 Accuracy: Error less than 5% COMPOUND RRT pseudoephedrine 0.58 amphetamine 0.76
MDA 0.85 methamphetamine 0.90 MDMA/PMA 1.00 PMMA 1.20 MDEA 1.32 caffeine 1.79 ketamine 1.93 **Please note MDMA and PMA coelute. This method is not valid for mixtures of MDMA and PMA. 6. QUALITATIVE DATA See spectra on the following pages for FT-IR, Mass Spectrometry, Nuclear Magnetic Resonance, UV, and Vapor Phase IR. 7. REFERENCES Blachut, Dariusz, Wojtasiewicz, Krystyna, Czarnocki, Zbigniew, Identification and Synthesis of Some Contaminants Present in 4-Methoxyamphetamine (PMA) Prepared by the Leukart Method, Forensic Science International, 127, 2002. Clarke, E.G.C., Isolation and Identification of Drugs, 2nd Edition, The Pharmaceutical Press, 1986. Coates, J., and Reffner, J., "Visualization of Micro-ATR Infrared Spectroscopy," Spectroscopy, Vol. 14, #4, April 1999. Coumbaros, John C., Kirkbride, K. Paul, and Klass, Gunter, Application of Solid-Phase Micrextraction to the Profiling of an Illicit Drug: Manufacturing Impurities in Illicit 4-Methoxyamphetamine, Technical Note (DEA). Del Cason, Terry, The Identification of 4-Methoxyamphetamine (PMA) and 4-Methoxymethamphetamine (PMMA), Microgram, Volume 23, No. 8, August 2000. Kirkbride, K. Paul, Ward, A. David, Jenkins, Natalie F., Klass, Gunter, and Coumbaros, John C., Synthesis of 4-Methyl-5-Arylpyrimidines and 4-Arylpyrimidines: Route Specific Markers for the Leukardt Preparation of Amphetamine, 4-Methoxyamphetamine, and 4-Methoxymethamphetamine, Forensic Science International, 115, 2001. Kochana, J., Wilamowski, J., and Parczewski, A., Profiling of Impurities in p-methoxymethamphetamine (PMMA) by means of SPE/TLC method, Examination of the Influence of Experimental Conditions According to 2 4 factorial, Forensic Science International, 134, 2003.
Kochana, J., Wilamowski, J., Parczewski, M., Surma, M., Synthesis of Standards of the Most Important Markers of Leuckart p-methoxymethamphetamine (PMMA), Examination of the Influence of Experimental Conditions and a Drug Diluent on SPE/TLC Profiling, Forensic Science International, 134, 2003. Waumans, Dieter, Bruneel, Noel, Hermans, Bas, and Tytgat, Jan, A Rapid and Simple GC/MS Screening Method for 4-Methoxyphenol in Illicit Prepared 4-Methoxyamphetamine (PMA), Technical Note (DEA). 8. ADDITIONAL RESOURCES Forendex Wikipedia
Relative Abundance Abundance MS (EI, Quadrupole): p-methoxyamphetamine 3200000 3000000 2800000 2600000 2400000 2200000 2000000 1800000 1600000 1400000 1200000 1000000 800000 600000 44 Scan 185 (1.347 min): PMA.D 122 400000 200000 0 m/ z--> 78 91 51 65 107 134 58 85 101 115 128 150 165 40 50 60 70 80 90 100 110 120 130 140 150 160 170 PMA #292 RT: 4.63 AV: 1 NL: 1.13E7 T: + c Full ms [ 40.00-550.00] 100 95 90 85 80 75 70 65 MS (EI, ion trap): p-methoxyamphetamine 122 60 55 50 45 44 40 35 121 30 25 20 15 10 5 0 77 78 91 40 60 80 100 120 140 160 m/z 107 51 79 65 89 92 106 118 50 52 63 80 134 132 148 66 76 94 151 163 123
1512.61 1248.09 1035.50 2962.38 806.88 2930.15 %Transmittance 1116.46 1177.26 1611.87 1442.81 1463.95 2833.30 2786.92 560.55 2913.03 2804.71 1509.71 1254.96 2707.62 1032.64 807.46 2605.63 1180.24 2502.94 2520.38 1614.80 1461.51 1300.98 1387.86 %Transmittance 1110.36 848.02 2059.23 1081.65 561.14 753.22 FTIR: p-methoxyamphetamine Hydrochloride KBr 4 scans, 4.000 cm -1 resolution 55 50 45 40 35 30 25 20 15 10 5 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1) 100 98 FTIR: p-methoxyamphetamine base, KBr smear 4 scans, 4.000 cm -1 resolution 96 94 92 90 88 86 84 82 80 78 76 74 72 70 68 4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers (cm-1)
117.1 115 FTIR (Diamond ATR): p-methoxyamphetamine HCl 4 scans, 4.000 cm -1 resolution 4-Methoxyamphetamine HCl 110 105 637.47 100 2518.80 2059.25 95 2604.76 90 2706.50 1000.76 %T 85 80 1613.84 1387.45 1301.37 1082.49 1111.07 848.44 757.62 75 1461.67 70 65 1180.26 60 1506.31 55 1032.18 1252.73 807.86 49.7 2901.63 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600.0 cm-1 80.5 FTIR (Diamond ATR): p-methoxyamphetamine base 4 scans, 4.000 cm -1 resolution 78 76 74 72 70 68 2928.74 66 1611.33 1442.28 %T 64 62 1177.09 807.61 60 58 1034.59 56 54 52 1509.54 49.4 1245.89 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600.0 cm-1
3.60 3.58 7.27 7.25 6.99 2.90 2.88 7.01 1.31 1.29 3.83 IR (VAPOR PHASE): p-methoxyamphetamine Na 2 CO 3 extracted CH 2 Cl 2 NMR (Proton): p-methoxyamphetamine 26.7 mg/ml in D 2 O with TSP and 5.019 mg Maleic Acid 400 MHz No. (ppm) 1 1.29 2 1.31 3 2.88 4 2.90 5 3.58 6 3.60 7 3.83 8 6.99 9 7.01 10 7.25 11 7.27 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm)
58.34 52.16 160.98 131.58 42.15 20.39 117.37 133.61 NMR (Carbon): p-methoxyamphetamine 26.7 mg/ml in D 2 O with TSP and 5.019 mg Maleic Acid 400 MHz No. (ppm) 1 20.39 2 42.15 3 52.16 4 58.34 5 117.37 6 131.58 7 133.61 8 160.98 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) mau DAD1, 5.349 (1285 mau, - ) of 042-0102.D UV: p-methoxyamphetamine HCl in 0.1 N HCl 1200 1000 800 600 400 200 0 200 250 300 350 400 450 500 550 nm