Author Topic: N-Methyl Hallucinogenic Amphetamine Analysis  (Read 5538 times)

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Rhodium

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N-Methyl Hallucinogenic Amphetamine Analysis
« on: March 11, 2004, 12:02:00 AM »
Identification of the N-Methylated Analogs of the Hallucinogenic Amphetamines
K. Bailey, A.W. By,

Journal of the Association of Official Analytical Chemists, 56(1), 62-69 (1975)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/n-methyl-amphetamines.pdf)

Abstract
The drugs 2-, 3-, and 4-methoxy-N-methylamphetamine, 3-methoxy-4,5-methylenedioxy-N-methylamphetamine and 3,4-methylenedioxy-N-methylamphetamine are identified by spectroscopic techniques. The ultraviolet and mass spectra of isomers are similar, but proton magnetic resonance and infrared spectra are distinctly different, and reference spectra and data are provided. Gas-liquid and thin layer chromatographic systems for the analysis are discussed.


Islamybad

  • Guest
Did you see these? dimethoxyamphetamines ...
« Reply #1 on: March 14, 2004, 02:06:00 AM »
Did you see these?

dimethoxyamphetamines
Journal of the AOAC Vol. 57 pages 70-78 (1974)

brominated dimethoxyamphetamines
Journal of the AOAC Vol. 59 pages 1162-1169 (1976)

methoxy and methylamphetamines
Journal of the AOAC Vol. 57 pages 1134-1143 (1974)

MDA, 3,4-MDphenylnitropropene, MDP2P, etc.
Journal of the AOAC Vol. 61 pages 951-967 (1978)

Islamybad

  • Guest
Here's the IR spectrum of myristicin from two...
« Reply #2 on: March 14, 2004, 02:53:00 AM »
Here's the IR spectrum of myristicin from two sources:

http://www.geocities.com/milkmandan2003/myristicinIR.html


Rhodium

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Analysis of MDMA & Related Analogs
« Reply #3 on: April 23, 2004, 02:55:00 PM »
Gas Chromatographic-Mass Spectrometric and Liquid Chromatographic Analysis of Designer Butanamines Related to MDMA
C. Randall Clark, Jack DeRuiter, Allen Valaer, F. Taylor Noggle

Journal of Chromatographic Science, Vol. 33, 328-337 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/designer.mdma.butanamines.pdf)

Abstract
A series of N-substituted, 1-(3,4-methylenedioxyphenyl)-2-butanamines (MDP-2-B) is prepared from piperonal via the 2-butanone intermediate. The analytical properties of these compounds are compared with the structurally similar 3,4-methylenedioxyamphetamine (MDA) derivatives, a popular series of drugs of abuse. The ultraviolet absorption properties of these compounds are determined by the methylenedioxyphenyl ring, which shows major absorption bands in the 285- and 235-nm range. The primary amine (MDP-2-B) and the N-substituted derivatives of MDP-2-B are separated by reversed-phase liquid chromatography under acidic mobile-phase conditions. The compounds are not completely resolved by gas chromatography on an HP-1 phase, and the separation is complicated by extensive thermal degradation of the N-hydroxy derivative (MDP-2-OHB). The mass spectra for these compounds provide specific structural information for the identification of these compounds. The amines undergo -cleavage reactions to produce ions at [M-135]+ from the loss of the 3,4-methylenedioxybenzyl radical and [M-29]+ from loss of the other -group, the ethyl radical.
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Liquid Chromatographic and Mass Spectral Analysis of 1-(3,4-Methylenedioxyphenyl)-3-butanamines, Homologues of 3,4-Methylenedioxyamphetamines
F. Taylor Noggle, Jr., C. Randall Clark and Jack DeRuiter

Journal of Chromatographic Science, Vol. 27, 240-243 (1989)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/noggle.mdp-3-butanamines.pdf)

Abstract
The 1-(3,4-methylenedioxyphenyl)-3-butanamines (HMDAs) are prepared via reductive amination of the corresponding ketone with a series of low molecular weight alkylamines. These amines are homologues of the N-substituted 3,4-methylenedioxyamphetamines (MDAs). Compounds of the HMDA series have UV absorption properties similar to the MDAs because both series contain the same 3,4-methylenedioxyphenyl chromophore. The HMDAs are separated via reversed-phase liquid chromatographic methods using a C,0 stationary phase and an acidic aqueous acetonitrile mobile phase. The mass spectra of these potential designer drugs are very similar to the spectra of the MDA homologues having the same N-substituent.
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Chromatographic and Spectroscopic Methods of Identification for the Side-Chain Regioisomers of 3,4-Methylenedioxyphenethylamines Related to MDEA, MDMMA, and MBDB
Laura Aalberg, Jack DeRuiter, F. Taylor Noggle, Erkki Sippola, and C. Randall Clark

Journal of Chromatographic Science, Vol. 41, 227-233 (2003)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdea-mdmma-mbdb.regioisomers.pdf)

Abstract
Three regioisomeric 3,4-methylenedioxyphenethylamines having the same molecular weight and major mass spectral fragments of equivalent mass have been reported as components of clandestine drug samples in recent years. These drugs of abuse are 3,4-methylenedioxy-N-ethylamphetamine, 3,4-methylenedioxy-N, N-dimethylamphetamine, and N-methyl-1 -(3,4-methylenedioxyphenyl)-2-butanamine. These three compounds are a subset of a total of ten regioisomeric 3,4-methylenedioxyphenethylamines of molecular weight 207, yielding regioisomeric fragment ions of equivalent mass (m/z 72 and 135/136) in the electron impact mass spectrum. The specific identification of one of these compounds in a forensic drug sample depends upon the analyst's ability to eliminate the other regioisomers as possible interfering or coeluting substances. This paper reports the synthesis, mass spectral characterization, and chromatographic analysis of these ten unique regioisomers. The ten regioisomeric methylenedioxyphenethylamines are synthesized from commercially available precursor chemicals. The electron impact mass spectra of these regioisomers show some variation in the relative intensity of the major ions with only one or two minor ions that might be considered side-chain specific fragments. Thus, the ultimate identification of any one of these amines with the elimination of the other nine regioisomeric substances depends heavily upon chromatographic methods. Chromatographic separation of these ten uniquely regioisomeric amines is studied using gas chromatographic temperature program optimization.
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Liquid Chromatographic and Mass Spectral Analysis of 1-(3,4-Methylenedioxyphenyl)-1-propanamines: Regioisomers of the 3,4-Methylenedioxyamphetamines
Jack DeRuiter, C. Randall Clark and F. Taylor Noggle, Jr.

Journal of Chromatographic Science, Vol. 28,  129-132 (1990)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mda.alpha-analogs.pdf)

Abstract
The title 1-(3,4-methylenedioxyphenyl)-1-propanamines represent positional isomers of the N-substituted 3,4-methylenedioxyamphetamines, clandestinely produced drugs frequently encountered by forensic laboratories. These propanamines are prepared by reductive amination of 3,4-methylenedioxypropiophenone with a series of N-alkylamines. Analytical methods are developed to distinguish these compounds from the MDA series. The ultraviolet spectra of the propanamines are very similar to those of the MDAs with absorption maxima at 284 and 236 nm. The propanamines are separated under reversed-phase liquid chromatographic conditions by using a C18 stationary phase and a mobile phase of acidic (pH 3) acetonitrile containing methanol and triethylamine. The relative retention properties of these compounds parallel those observed in the MDA series. The electron impact mass spectra of the propanamines are determined by GC-MS, and the fragmentation pattern clearly distinguishes these compounds from those of the MDA series having the same molecular weight.
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Liquid Chromatographic and Mass Spectral Analysis of 1-(3,4-Methylenedioxyphenyl)-3-Propanamines: Regioisomers of MDMA
F. Taylor Noggle, Jr., C. Randall Clark, Kamal H. Bouhadir and Jack DeRuiter

Journal of Chromatographic Science, Vol. 29, 78-82 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdma.3-propanamines.pdf)

Abstract
The 1-(3,4-methylenedioxyphenyl)-3-propanamines are prepared from 1-(3,4-methylenedioxyphenyl)propanoic acid via amide formation followed by hydride reduction. The 3-propanamines are regioisomeric with the 1-(3,4-methylenedioxyphenyl)-2-propanamines MDA and MDMA, a series of popular drugs of abuse. The N-substituted 3-propanamines were separated via reversed-phase liquid chromatography (LC) using an acidic mobile phase (pH 3). Similar reversed-phase conditions were used to separate the N-methyl derivatives of the regioisomeric 1-, 2-, and 3-propanamines. The electron impact (EI) mass spectra for the 3-propanamines show the characteristic amine base peak and can be used to differentiate these compounds from the regioisomeric 2-propanamines.
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Methods for the Analysis of 1-(3,4-Methylenedioxyphenyl)-2-Butanamine and N-Methyl-1-(3,4-Methylenedioxyphenyl)-2-Propanamine (MDMA)
F. Taylor Noggle, Jr., C. Randall Clark, Shridhar Andurkar, and Jack DeRuiter

Journal of Chromatographic Science, Vol 29, 103-106 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdma-bdb.analysis.pdf)

Abstract
The infrared and mass spectra of N-methyl-1-(3,4-methylenedioxyphenyl)-2-propanamine (MDMA) and 1-(3,4-methylenedioxyphenyl)-2-butanamine are quite similar. These two compounds differ only in the position of substitution of a single methyl group. MDMA is a controlled street drug known as Ecstasy, while the isomeric butanamine is a member of a new class of potential psychotherapeutic agents called entactogens. These two compounds produce similar mass spectral fragmentation patterns including a common base peak at m/z 58. Reversed-phase liquid chromatographic (RPLC) methods consisting of a C18 stationary phase and an aqueous acidic mobile phase were used to separate these two compounds. Thus, LC methods can be used to differentiate MDMA from the isomeric butanamine for forensic analysis.
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Liquid Chromatographic and Mass Spectral Analysis of N-Substituted Analogues of 3,4-Methylenedioxyamphetamine
F. Taylor Noggle, Jr., C. Randall Clark, Alan K. Valaer, and Jack DeRuiter

Journal of Chromatographic Science, Vol. 26, 410-415 (1988)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/n-alkyl-mda.analysis.pdf)

Abstract
The C1 to C3 N-alkyl, N,N-dimethyl, and N-hydroxy analogues of 3,4-methylenedioxyamphetamine (MDA) are identified by high performance liquid chromatographic (HPLC) and spectrometric techniques. The compounds are separated using reversed-phase procedures on C18 stationary phase with an acidic (pH 3) aqueous methanol mobile phase. The mass spectra of the compounds are distinctive and reference spectra are provided. The N-hydroxy derivative is unstable at high temperatures and decomposes to MDA and the oxime of 3,4-methylenedioxyphenyl-2-propanone.


Rhodium

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Analysis of 'Bromosafrole Route' Preparations
« Reply #4 on: April 23, 2004, 02:59:00 PM »
Note that no yields are given, and that the chromatograms of their 'products' are highly impure. These papers are not to be taken as descriptions of a working procedure.

Gas Chromatographic and Mass Spectrometric Analysis of Samples from a Clandestine Laboratory Involved in the Synthesis of Ecstacy from Sassafras Oil
F.T. Noggle, Jr., C. Randall Clark and Jack DeRuiter

Journal of Chromatographic Science, Vol. 29, 168-173 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/noggle.sassy2mdma-1.pdf)

Abstract
The various samples from a clandestine drug laboratory reported to be involved in the synthesis of 3,4-methylenedioxymethamphetamine (MDMA, Ecstacy, or XTC) are analyzed by gas chromatography–mass spectrometry (GC–MS). Safrole, the starting material for the synthesis, is obtained from the roots of the sassafras plant. GC–MS of the sassafras oil reveals the presence of safrole (4-allyl-1,2-methylenedioxybenzene) as the major component, as well as smaller quantities of camphor, eugenol, a dimethoxyallyl- and trimethoxyallylbenzene. A second sample obtained from the clandestine laboratory is from the treatment of the sassafras oil with HBr. Although this sample contains many brominated and several nonbrominated components, the major constituent is the synthetic precursor for MDMA, 1-(3,4-methylenedioxyphenyl)-2-bromopropane, along with quantities of the regioisomeric 3-bromopropane. The samples from the clandestine laboratory do not reveal the presence of any MDMA. However, upon treatment with methylamine, the brominated sassafras oil gives MDMA as the major amine product.
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Gas Chromatographic and Mass Spectrometric Analysis of N-Methyl-1-Aryl-2-Propanamines Synthesized from the Substituted Allylbenzenes Present in Sassafras Oil
F.T. Noggle, Jr., C. Randall Clark and Jack DeRuiter

Journal of Chromatographic Science, Vol 29, 267-271 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/noggle.sassy2mdma-2.pdf)

Abstract
One method used for the synthesis of the illicit drug N-methyl-1-(3,4-methylenedioxyphenyl)-2-propanamine (methylenedioxymethamphetamine, MDMA) involves the treatment of safrole with HBr to form the intermediate 2-bromosafrole, followed by bromide displacement with methylamine. The starting material required for this synthesis, safrole, may be obtained from sassafras oil which is isolated from the roots of the sassafras plant. In addition to safrole, sassafras oil contains other allylbenzenes such as eugenol and 4-allyl-1,2-dimethoxybenzene. Gas chromatography–mass spectrometric (GC–MS) studies show that these allylbenzenes may also be brominated and undergo amine displacement to yield the corresponding N-methyl-1-aryl-2-propanamines. These studies also show that the regioisomeric 3-bromosafrole intermediate and 3-propanamine are not formed during this synthesis. Furthermore, the isomeric allylbenzenes isosaf role and isoeugenol that are generated in these reactions do not form stable bromo products and therefore no N-methyl-1-aryl-1-propanamine products are produced during the course of the bromination and amine displacement reactions.
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Analysis of 1-(3-Methoxy-4,5-Methylenedioxyphenyl)-2-Propanamine (MMDA) Derivatives Synthesized from Nutmeg Oil and 3-Methoxy-4,5-Methylenedioxybenzaldehyde
C. Randall Clark, F. Taylor Noggle and Jack DeRuiter

Journal of Chromatographic Science, Vol. 34, 34-42 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mmda.nutmeg.pdf)

Abstract
Myristicin, a natural product found in nutmeg oil and nutmeg extract, contains the carbon skeleton for a series of drugs of abuse related to the 3,4-methylenedioxyamphetamines (MDAs). Myristicin, 1-(3-methoxy-4,5-methylenedioxyphenyl)-2-propene, was identified as the major component of commercially available nutmeg oil and in the organic extract of nutmeg powder. The starting materials, intermediates, and products in the synthesis of the drug of abuse N-methyl-1-(3-methoxy-4,5-methylenedioxyphenyl)-2-propanamine (MMDMA) from myristicin were characterized by gas chromatographic-mass spectrometric analysis. MMDMA and several primary amine derivatives including 1-(3-methoxy-4,5-methylenedioxyphenyl)-2-ethanamine, -propanamine, and -butanamine were also prepared from the commercially available aldehyde, 3-methoxy-4,5-methylenedioxybenzaldehyde. Each of these amine derivatives has a distinct mass spectrum characterized by amine-dominated fragmentation. All four amines in this study were resolved by reversed-phase liquid chromatography using an acidic aqueous mobile phase. Relative retention in this system was determined by differences in the hydrophobic surface area of the four amines.


Rhodium

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Analysis of 2C-B/2C-H/DOB/2,5-DMA Isomers
« Reply #5 on: April 23, 2004, 03:00:00 PM »
LC and GC-MS Analysis of 4-Bromo-2,5-Dimethoxyphenethylamine (Nexus) and 2-Propanamine and 2-Butanamine Analogues
Jack DeRuiter, C. Randall Clark and F. Taylor Noggle

Journal of Chromatographic Science, Vol. 33, 583-590 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/2c-b.dob.4c-b.analysis.pdf)

Abstract
The street drug Nexus (4-bromo-2,5-dimethoxyphenethylamine) has appeared in clandestine samples in recent years. This hallucinogenic phenethylamine is prepared from the commercially available aldehyde, 2,5-dimethoxybenzaldehyde, and other readily available precursor chemicals and reagents. Nexus and some designer analogues are separated by liquid chromatography using a C18 stationary phase and an acidic (pH 3) mobile phase. Nexus, a brominated phenethylamine, shows enhanced reversed-phase retention relative to the unbrominated precursor phenethylamine. The mass spectra of these amines show fragment ions consistent with amine-dominated reactions common to phenethylamines and substituted phenethylamines. The gas chromatographic—mass spectrometric analysis of mixtures of the amines and the synthetic precursor nitroethenes show on-column reaction products that complicate the analytical results. These reaction products are identified as the imines that result from condensation of the amine with the substituted benzaldehyde, which is generated from the 2-nitroethene.
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Gas Chromatographic-Mass Spectrometric and High-Performance Liquid Chromatographic Analyses of the Bromination Products of the Regioisomeric Dimethoxyphenethylamines: Differentiation of Nexus from Five Positional Isomers
Jack DeRuiter, C. Randall Clark and F. Taylor Noggle

Journal of Chromatographic Science, Vol. 36, 23-28 (1998)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/2c-b.regioisomers.pdf)

Abstract
The brominated products from all six positional isomers of dimethoxyphenethylamine are prepared, and their analytical properties are evaluated. The major bromination product from 3,5-dimethoxyphenethylamine is the 2,6-dibromo isomer; all other regioisomers of dimethoxyphenethylamine yield a monobromo species as the major product. The mass spectra divide these compounds into two distinct groups: one group showing a strong m/z 180 ion via loss of bromine from the molecular ion (M-Br)+ and a second group showing no significant m/z 180 ion. The three compounds that do not show the m/z 180 ion in their electron-impact mass spectra are brominated 2,4-; 2,5-; and 2,6-dimethoxyphenethylamine. These compounds are well-resolved by reversed-phase liquid chromatographic methods using a Hypersil Elite C18 stationary phase and a mobile phase of phosphate buffer (pH 3) and methanol-acetonitrile.
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Liquid Chromatographic and Mass Spectral Methods of Identification for Regioisomeric Dimethoxyamphetamines and Brominated Dimethoxyamphetamines
Jack DeRuiter, Pamela Holston, C. Randall Clark and F. Taylor Noggle

Journal of Chromatographic Science, Vol. 36, 73-79 (1998)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/dma-dob.regioisomers.pdf)

Abstract
The six regioisomeric dimethoxyamphetamines are prepared from the commercially available dimethoxybenzaldehydes. The dimethoxyamphetamines show very similar mass spectra, and chromatographic methods must be used to differentiate the positional isomers. Bromination of the six isomeric dimethoxyamphetamines yields a monobromination product as the major component in all cases except for 3,5-dimethoxyamphetamine, which yields the 2,6-dibrominated species as the major product. Mass spectrometric analysis readily divides the regioisomeric bromodimethoxyamphetamines into two groups of three compounds each. Only those isomers having a bromine substituent "ortho-" to the alkylamine side-chain show a major fragment at m/z 194 from loss of bromine from the molecular ion. The major drug of abuse 4-bromo-2,5-dimethoxyamphetamine (DOB) is one of three compounds that do not yield the m/z 194 ion. Though the mass spectra for the three "non-m/z 194" isomers show some subtle differences, these compounds are best differentiated by a reversed-phase liquid chromatographic system.


Rhodium

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Analysis of Meth Impurities/Analogs
« Reply #6 on: April 23, 2004, 03:02:00 PM »
Gas Chromatographic and Mass Spectral Analysis of Amphetamine Products Synthesized from 1-Phenyl-2-Nitropropene
Jack DeRuiter, C. Randall Clark and F. Taylor Noggle

Journal of Chromatographic Science, Vol. 32, 511-519 (1994)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/amphetamine.phenylnitropropene.pdf)

Abstract
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.
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Methods for the Differentiation of Methamphetamine from Regioisomeric Phenethylamines
F. Taylor Noggle, C. Randall Clark, Kamal H. Bouhadir and Jack DeRuiter

Journal of Chromatographic Science, Vol. 29, 31-36 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/meth-pea.differentiation.pdf)

Abstract
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.
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-Benzyl-N-Methylphenethylamine (BNMPA), an Impurity of Illicit Methamphetamine Synthesis: III. Detection of BNMPA and Metabolites in Urine of Methamphetamine Users
Karla A. Moore, Abd Ismaiel and Alphonse Poklis

Journal of Analytical Toxicology, Vol. 20, 89-92 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/bnmpa-3.detection.pdf)

Abstract
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.
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Identification of -Phenylethylamine in judicial Samples
E. Meyer, J. F. Van Bocxlaer, W. E. Lambert, L. Thienpont and A. P. De Leenheer

Journal of Analytical Toxicology, Vol. 20, 116-120 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/alpha-pea.identification.pdf)

Abstract
-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.
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Analysis of Impurities in Illicit Methamphetamine
K. Tanaka, T. Ohmori And T. Inoue

Forensic Science International 56, 157-165 (1992)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/meth.impurities.japan.pdf)

Summary
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.
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Gas Chromatographic and Mass Spectral Analysis of Methamphetamine Synthesized From Allylbenzene
F. Taylor Noggle, C. Randall Clark and Jack DeRuiter

Journal of Chromatographic Science, Vol 33, 153-161 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/meth.allylbenzene.pdf)

Abstract
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.


Rhodium

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Dimethoxyamphetamines Bromination Products
« Reply #7 on: April 28, 2004, 10:37:00 PM »
Investigation and Identification of the Bromination Products of Dimethoxyamphetamines
Keith Bailey, Denise R. Gagné, and Richard K. Pike

Journal of the AOAC, Vol. 59, No. 5, pp. 1162-1169 (1976)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/jaoac.dob-analogs.pdf)

Abstract
The qualitative analysis of the aromatic bromination products of the 6 isomeric dimethoxyamphetamines and their hydrochloride or hydrobromide salts is described. Their ultraviolet, mass, and proton magnetic resonance spectra are not sufficiently different for distinction but infrared spectra allow a positive identification to be made and reference spectra are provided for the bromination products of 2,4-, 2,5-, 2,6-, 4,5-, and 3,5-dimethoxyamphetamines. The application of gas-liquid and thin layer chromatography for the analysis of these products is discussed. The bromination of 2,3-dimethoxyamphetamine consistently gave mixtures which could not be separated satisfactorily; spectra are included for completeness of the comparison of products.


Rhodium

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Methyl/Methoxy-amphetamines & Leuckart Meth
« Reply #8 on: May 03, 2004, 08:55:00 PM »
Identification of 2-, 3-, and 4-Methoxyamphetamines and 2-, 3-, and 4-Methylamphetamines
Keith Bailey Harry D. Beckstead, Donald Legault, and Denise Verner

Journal of the AOAC 57(5), 1134-1143  (1974)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/metyl.methoxy.amph.pdf)

Abstract
The identity of samples of 2-, 3-, and 4-Methoxyamphetamines and 2-, 3-, and 4-Methylamphetamines is conclusively established by comparison of their spectra. Ultraviolet, proton magnetic resonance, and mass spectra distinguish and identify the two series and infrared spectra differentiate isomers; reference spectra and data are provided. Thin layer and gas-liquid chromatographic systems suitable for distinguishing these compounds are described.
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Identification of Impurities in Illicit Methamphetamine Samples
Robert P. Barron, Alice V. Kruegel, James. M. Moore and Theodore C. Kram

Journal of the AOAC 57(5), 1147-1158  (1974)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/jaoac.meth.impurities.pdf)

Abstract
Three impurities have been identified in illicit methamphetamine samples. One of these, N-formyl-methamphetamine, is an intermediate in the synthesis of methamphetamine by the Leuckart reaction. The remaining two, N,?,?-trimethyldiphenethylamine and ?-benzyl-N-methylphenethylamine are by-products of methamphetamine synthesis. Ultraviolet, infrared, nuclear magnetic resonance, and gas chromatographic-mass spectral techniques were used to identify these compounds. The data obtained are discussed and synthetic pathways are postulated to explain the presence of each compound in samples of methamphetamine.


Rhodium

  • Guest
MeO-Methamphetamines + 2,3-MDA/3,4-MDA
« Reply #9 on: May 07, 2004, 02:19:00 AM »
The Identification of Methoxy-N-Methylamphetamines
Charles C. Clark

Journal of Forensic Sciences 29(4), 1056-1071 (1984)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/methoxy-n-methyl-amphetamines.pdf)

Abstract
Thirteen mono, di, and trimethoxy-N-methylamphetamines have been synthesized and characterized. Gas-liquid chromatographic data and ultraviolet, infrared, proton magnetic resonance and mass spectra are presented. The specificity of each technique for the identification of methoxy-N-methylamphetamines is discussed.
____ ___ __ _

Differentiation of 2,3-Methylenedioxyamphetamine from 3,4-Methylenedioxyamphetamine
William H. Soine, Robert E. Shark and Delbert T. Agee

Journal of Forensic Sciences 28(2), 386-390 (1983)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/23-mda.34-mda.differentiation.pdf)

Abstract
The 2,3- and 3,4-methylenedioxyamphetamine isomers can be distinguished using the sulfuric acid color test, gas chromatography, infrared spectroscopy, mass spectrometry, and 13C nuclear magnetic resonance.


PolytheneSam

  • Guest
Can you get Journal of Agricultural and Food...
« Reply #10 on: May 07, 2004, 02:44:00 AM »
Can you get Journal of Agricultural and Food Chemistry Vol. 22, No. 4, 1974 pages 658-664?  It has IR spectra and NMR, mass spec and UV data for apiole, dill apiole and myristicin in it.


Rhodium

  • Guest
Dill oil reference
« Reply #11 on: May 07, 2004, 03:41:00 AM »
Insecticidal and synergistic components isolated from dill plants
E. Paul Lichtenstein, Tony T. Liang, Ken R. Schulz, Heinrich K. Schnoes, and Guy T. Carter
Journal of Agricultural and Food Chemistry 22(4), 658-664 (1964)




All JAOAC articles you requested in

Post 494929

(Islamybad: "Did you see these? dimethoxyamphetamines ...", Serious Chemistry)
has been retrieved, three of them has been posted above, and the last one in

Post 487726

(Rhodium: "MDA - Precursors, Intermediates, and Impurities", Methods Discourse)



Rhodium

  • Guest
Identification of Amphetamines & Related Amines
« Reply #12 on: May 20, 2004, 06:53:00 PM »
Identification of Amphetamines and Related Sympathomimetic Amines
R. J. Warren, P. P. Begosh, And J. E. Zarembo

J. Ass. Off. Anal. Chem. 54(5), 1179-1191 (1971)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/amphetamine.identification.pdf)

Abstract
The IR, UV, and NMR spectral data as well as the pKa' values of a series of 18 phenylpropyl amines are presented and discussed. The series includes the amphetamines and many of the commercially available phenylpropyl amines being used in the field of medicine as sympathomimetic agents. These data provide a basis for rapid identification of samples from biological, forensic, and medical research.


Rhodium

  • Guest
Dimethoxyamphetamines: Analytical data
« Reply #13 on: May 24, 2004, 07:00:00 PM »
Spectroscopic and Chromatographic Identification of Dimethoxyamphetamines
Keith Bailey, Donald Legault, and Denise Verner

Journal of the AOAC, Vol. 57, No. 1, 70-78 (1974)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/jaoac.dma.identification.pdf)

Abstract
The qualitative analysis of the 6 isomeric dimethoxyamphetamines and their hydrochloride salts is described. Their ultraviolet spectra are insufficiently different for distinction, but mass, proton magnetic resonance, and infrared spectra allow a positive identification to be made, and reference spectra are provided. The application of gas-liquid and thin layer chromatographic systems for the analysis is discussed.
____ ___ __ _

The Mass Spectra of Dimethoxyamphetamine Hydrochlorides
K. Bailey

Anal. Chim. Acta 60, 287-292 (1972)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/dma-hcl.mass-spectra.pdf)

Summary
The six dimethoxyamphetamine hydrochlorides give weak but distinguishable mass spectra useful for analytical purposes. The principal fragmentation pathways are discussed in terms of the changing aromatic substitution pattern.
____ ___ __ _

Some chromatographic and electrophoretic data for amphetamine-like drugs
G. P. Cartoni, M. Lederer and F. Polidori

J. Chromatogr. 71, 370-375 (1972)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/amph.chromatographic.data.pdf)

Summary
Several amphetamine-like drugs has been differentiated using thin-layer chromatography on a range of supports, with several different solvent systems and two-dimensional development. Electrophoretic data is also supplied, as is TLC data on the dansyl derivatives of the substances. The following drugs were included in this study: Amphetamine, Methamphetamine, Dimethamphetamine, Ethylamphetamine, Methoxyphenamine, Phentermine, Methylphenidate, Phenmetrazine, Mephentermine, Prolintane, Ephedrine, Pseudoephedrine, Phencamphamine, Tranylcypromine and Diethylpropion.


Rhodium

  • Guest
Forensic Chemistry Notes
« Reply #14 on: May 31, 2004, 06:47:00 PM »
Isolation and Characterisation of Simple Psychotropic Substances as 2C-I and 2C-T-2, Hard to Get Standard Compounds: How to Save a Million!
Mogens Johannsen
Forensic Science International 136 (Suppl. 1), p 97-98 (2003)

The use of simple psychotropic compounds as standards in the analysis of forensic samples demands a reliable source for providing the necessary references. Even though there is a wide spread use of these reference substances the commercialisation has been hampered by several factors. First of all the time, paperwork and money, which have to be spend on written applications for import and export certificates. These are usually time limited, issued on a case-to-case basis and relatively costly. Secondly, more companies only offers the desired compounds in small 1 ml ampoules containing e.g. 1 mg of the active compounds at prizes exceeding 50 EUR a piece. Thirdly, companies as e.g. Sigma-Aldrich import many controlled substances from the USA. Due to the stringent rules of exportation from the USA and the decision that controlled substances may not be re-exported within Europe they can not be distributed via the usual routes i.e. through Germany for Scandinavian deliveries, but has to be send directly from the USA to the recipient country. This does not improve on the practicability and time of delivery, which can exceed several months if possible at all, if the compounds have to be imported from e.g. the USA. However, even for pan-European deliveries one usually has to be armed with patience. Finally, novel designer drugs will usually not be commercially available for a long period of time. All these facts contrast the often-enormous amounts of police seizures that contains the wanted compounds and at no cost, for the forensic laboratory, what so ever. The sole problem is to be able to isolate or synthesise, purify and of course thoroughly characterise the compounds in order to meet the requirements of a chemical reference substance.

A simple and general extraction methodology has been used to isolate and purify MDMA (pKa 8.5), methamphetamine (pKa 9.9), 2C-I (pKa ~9) and 2C-T-2 (pKa ~9) in amounts ranging from 1-15000 mg from different seizures. The procedure, which is quite straight forward, involves a liquid-liquid extraction of a neutralised aqueous phase containing the street sample with ether. Adjustment of pH with HCl delivers the insoluble hydrochloride salt of the active alkaloid, which can be re-crystallised from IPA and ether to give the desired compound. The procedure is tolerant to many of the usual additives and adulterants present in street samples such as caffeine (pKa 3.6), phenazone (pKa 1.5), salicylic acid (pKa 3.0) and salicylic acid amide (pKa 8.2). These impurities can either be removed by careful adjustment of pH during the acidification of the mother liquor or by re-crystallisation of the crude hydrochloride salts. It can, however be noted that most of the alkaloidic impurities are less basic than the psychotropic compound itself making the selective protonation of the designer drug relatively easy. The obtained compounds all give satisfactorily chemical analysis (i.e. GC-MS, 1H and 13C NMR, HPLC, IR and micro elemental analysis) and therefore meet the requirements for reference substances. Moreover, it can be mentioned that quantification of e.g. the purified MDMA hydrochloride gave a concentration of exactly 100%. In the case of 2C-I and 2C-T-2 no reference compounds or spectra were available and since standard 1H and 13C NMR does not give conclusive evidence to establish the position of the substituents on the aromatic ring, a series of 2D-NOESY NMR experiments were conducted. Based on these results it was possible to verify the structure of these relatively new designer drugs.
____ ___ __ _

The Synthetic Route Specific Impurities in 3,4-Methylenedioxyphenylpropanone and 3,4-Methylenedioxymethamphetamine Prepared from Isosafrole and Piperonal
Malgorzata Swist, Dariusz Zuba, Roman Stanaszek, Jaroslaw Wilamowski, and Andrzej Parczewski
Forensic Science International 136 (Suppl. 1), p 102-103 (2003)

Profiling of drugs appears a useful method in criminal investigation aimed at searching for illicit drug production and distribution. It is based on physical and chemical characterisation of seized samples of drugs. Profiling serves as a tool to relate different street drug seizures to a common source, to determine the origin of drug manufactured from natural sources or synthetic routes for synthetic drugs and to identify addictives or impurities found in illicit drugs which may cause public health risks because of their inherent chemical or biological hazards. Concerning 3,4-methylenedioxymethamphetamine (MDMA), the main synthesis routes used for its production has been already well known, though only a few articles deal with profiling of MDMA seizures. One of the most popular synthesis method of MDMA is the low pressure reductive amination of 3,4-methylenedioxyphenyl-2-propanone (MDP2P or PMK) which can be prepared by two different routes, i.e. by oxidising isosafrole in an acid medium or from piperonal via 1-(3,4-methylenedioxyphenyl)-2-nitro-1-propene. The main aim of our study was to establish which impurities found in the prepared PMK are also present in the final product (MDMA) as well as to establish which of the impurities found in PMK are parent compounds for other impurities found in MDMA final product. PMK was obtained by oxidising isosafrole and from piperonal. Each synthesis was repeated three times in order to establish variety in composition of impurities between different batches of PMK. Fourier transform infrared spectroscopy (FTIR) was used for identification of the final products. Thin layer chromatography (TLC) and gas chromatography coupled to mass spectrometry (GC-MS) were applied to identify precursors, intermediates, and by-products. The impurity profile of 1-(3,4-methylenedioxyphenyl)- 2-nitro-1-propene, which is an intermediate in the 'nitropropene route', and the profiles of PMK prepared by different routes, were obtained, and ’route specific’ impurities were found. The impurities in commercially available precursors, isosafrole and piperonal, were also analysed by means of TLC and GC-MS. MDMA was prepared by low pressure reductive amination from PMK. Each synthesis route was repeated in triplicate in order to establish variety in composition of impurities between different batches of MDMA. MDMA hydrochloride was obtained from both - crude and distilled MDMA in its basic form.

Impurities of MDMA were extracted as follow: 200 mg of the final product of MDMA hydrochloride synthesis was dissolved in 2 ml of buffer (extraction was performed in two different buffers: phosphate buffer of pH 7 and carbonate buffer of pH 10), the suspension was vigorously shaken for 25 min at 1800 rpm, then a volume of 200 µl of n-heptane, containing 35 mg/l diphenylamine as an internal standard, was added and again vigorously shaken for 30 min. The organic phase was subjected to TLC and GC-MS analysis. TLC impurity profiles of both PMK and MDMA were obtained on Merck aluminium plates (Kieselgel 60 F-254) and spots were visualised with UV and/or ninhydrine. The mobile phase was a mixture of chloroform: methanol (9:1, v/v). GC-MS analysis was carried out on Hewlett-Packard 6890 series gas chromatograph coupled to 5984B mass spectrometer. Chromatographic separation was achieved on HP5-MS fused silica capillary column (30 m x 0.25 mm x 0.25 µm) and helium 6.0 was used as a carrier gas (1.0 ml/min). The injection (2 µl) was made splitless by the autosampler. The following temperature program was applied: 50°C maintained for 1 min, then ramped at 10°C/min up to 150°C, maintained 5.5 min, and again increased to 280°C at 10°C /min ramp, and then maintained for the final 10 min. Mass spectrometer was operated in positive electron ionisation mode (EI). A full-scan mass spectra 40-500 amu were obtained. The repeatability of the procedure was tested by triplicate extractions of MDMA impurities and triplicate injections of each extract. The analysis of the distilled reaction mixture after PMK synthesis from isosafrole showed the presence of different oxygenated products of isosafrole, including acetonide, carbanate and diformate.

The results of the study show that the extraction of impurities from MDMA at pH 10 was significantly more efficient compared to pH 7. Therefore the impurity profiles (pH 10) were richer and chromatographic peak areas were bigger. Extraction at pH 7 revealed only one possible 'MDMA route specific' marker, 3,4-methylenedioxy-N-methylbenzylamine, whilst extraction at pH 10 enabled also to detect other markers, e.g. N,N-dimethyl-[1,2-(methylenedioxy)-4-(2-aminopropyl)]benzene and N-ethyl,N-methyl-[1,2-(methylenedioxy)-4-(2-aminopropyl)]benzene. The proposed analytical procedures enable identification of the precursors (isosafrole, safrole, piperonal), intermediates (e.g. 1-(3,4-methylenedioxyphenyl)-2-nitro-1-propene) and some reaction by-products (N,N-dimethyl-[1,2-(methylenedioxy)-4-(2-aminopropyl)]benzene and N-ethyl,N-methyl-[1,2-(methylenedioxy)-4-(2-aminopropyl)]benzene), and determination the 'route specific' impurities.


Rhodium

  • Guest
A. M. A. Verweij: MDMA & Meth Impurities
« Reply #15 on: June 05, 2004, 04:42:00 AM »
Hydrastinin: An Impurity in 3,4-(Methylenedioxy)methamphetamine
Anthonie M. A. Verweij

Arch. Krim. 188(1-2), 54-57 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdma.hydrastinin.pdf)
____ ___ __ _

Impurities in illicit amphetamine 6.
Identification of phenyl-2-propanol, amphetamine and N,N-dimethylamphetamine in methamphetamine

A. M. v. d. Ark, A. B. E. Theeuwen and A. M. A. Verweij

Arch. Krim. 162, 171-175 (1978)

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/amph.impurities-6.html)

Summary
By means of GC-MS analysis three impurities, amphetamine, N,N-dimethylamphetamine and phenyl-2-propanol could be found in methylamphetamine synthesized by a high pressure reductive amination of methylamine and benzylmethylketone.


methyl_ethyl

  • Guest
Analysis of illicit amphetamine seizures by CZE
« Reply #16 on: June 06, 2004, 06:23:00 PM »
Analysis of illicit amphetamine seizures by capillary zone
electrophoresis

Veronique Piette, Frans Parmentier
Journal of Chromatography A, 979 (2002) 345–352




Abstract:

Capillary zone electrophoresis was applied for the determination of amphetamine and related substances in seized drugs. A
buffer made of 0.1 M phosphoric acid adjusted to pH 3.0 with triethanolamine was selected. With this background
electrolyte, triethanolamine is adsorbed to the capillary wall and the electroosmotic flow is reversed. This gives rise to peaks
with good symmetry, high efficiency and reproducible migration times. The separation of the different analytes was
performed in a fused-silica capillary thermostatted at 25 8C and the applied voltage was 25 kV. Under these experimental
conditions, amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine
(MDMA), 3,4-methylenedioxyethamphetamine, N-methyl-1-(1,3-benzodioxol-5-yl)-2-butamine and ephedrine were resolved
within 8 min and without interference from adulterants usually found in illicit powders. Their identification by the migration
time was confirmed by their UV spectra recorded with a diode array UV detector (190–350 nm). The selected method was
then applied to identify these substances in illicit tablets known as ‘‘Ecstasy’’ and the MDMA determined in these samples
according to a laboratory validation procedure.


Rhodium

  • Guest
3,4-MD-(alpha-pyrrolidino)propiophenon
« Reply #17 on: June 11, 2004, 10:09:00 AM »
N-Ethyl-2-(3,4-methylenedioxyphenyl)-propan-1-amin eine neue Designerdroge mit der Struktur eines beta-isomeren MDE
P. Rösner, L. Zechlin, Th. Junge

Toxichem + Krimtech 70(2), 82-86 (2003)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/n-ethyl-2-%5B3.4-methylendioxyphenyl%5D-1-propanamin.beta-mde.pdf)
____ ___ __ _

[New, previously unavailable on the illegal drug market amphetamine derivatives with a partial propiophenone structure]
Fritschi G, Klein B, Rösner P

Arch Kriminol. 200(1-2), 8-16 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/34-md-2-pyr-propiophenone.pdf)

Abstract
Two new clandestine synthesized derivatives of amphetamine were seized in the FRG. They show a propiophenone-structure. A well known representative of this class of compounds is 2-Diethylaminopropiohenone. The compounds are not submissed under the German law. NMR, IR- and MS-datas of these compounds and additionally synthesized derivatives are reported.


Rhodium

  • Guest
Clandestinely Prepared Amphetamine/Cocaine
« Reply #18 on: July 15, 2004, 08:51:00 PM »
Contamination of Clandestinely Prepared Drugs with Synthetic By-products
William H. Soine

NIDA Monograph #95, pp. 44-50 (1989)

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/amphetamine-cocaine.impurities.html)


Rhodium

  • Guest
Impurity profiling of methamphetamine
« Reply #19 on: July 29, 2004, 02:11:00 AM »
Impurity profiling of methamphetamine hydrochloride drugs seized in the Philippines
Fabian M. Dayrit and Morphy C. Dumlao

Forensic Science International 144(1), 29-36 (2004)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/meth.hcl.impurities.philippines.pdf)

Abstract
Methamphetamine hydrochloride is one of the most widely used illicit drugs in the Philippines. In this study, we describe the application of cluster analysis of trace impurities in the profiling of the seized methamphetamine drug samples.
Thirty milligrams of a homogenized drug sample were dissolved in 1 mL of pH 10.5 buffer solution and extracted with ethyl acetate containing three internal standards. The trace impurities were identified using gas chromatography–mass spectrometry (GC–MS) and quantified by gas chromatography with a flame ionization detector (GC–FID).
Following previously reported methodologies, 30 impurity peaks were selected from the GC–FID chromatograms. The peak areas and retention times were referenced to the internal standards. The peak areas of the selected peaks were then grouped for cluster analysis. In order to check for consistency of clustering, two further cluster analyses were performed using 40 and 50 impurity peaks. Changes in clustering were observed in going from 30 to 40 impurity peaks, while analyses using 40 and 50 impurity peaks gave similar results. Thus, for the seized drug samples used in this study, cluster analysis using at least 40 impurity peaks showed better consistency of clustering as compared to analysis using 30 peaks only.
Ten of the impurity peaks were identified, of which four were identified for the first time in methamphetamine drug samples. These are p-bromotoluene, N-benzyl amphetamine, N-ethyl amphetamine, and N-ethyl methamphetamine. The presence of phenyl-2-propanone (P2P), N,N-dimethyl amphetamine, and N-formyl amphetamine is indicative that these casework samples were synthesized using the Leuckart method.
____ ___ __ _

Profiling of impurities in illicit methamphetamine by HPLC and capillary electrochromatography
Ira S. Lurie, Christopher G. Bailey, Deon S. Anex, M. Jason Bethea, Timothy D. McKibben, John F. Casale

Journal of Chromatography A, 870, 53–68 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/meth.impurity.profiling.pdf)

Abstract
High performance liquid chromatography (HPLC) with photodiode array (PDA) UV and fluorescence (FL) detection, and capillary electrochromatography (CEC) with laser-induced fluorescence (LIF) detection were investigated for the analysis of acidic extracts derived from illicit methamphetamine. These compounds include major impurities from the hydriodic acid/red phosphorous reduction method, i.e., 1,3-dimethyl-2-phenylnaphthalene and 1-benzyl-3-methylnaphthalene, and other trace-level, structurally related impurities. For certain of these solutes, HPLC with conventional FL detection gave at least a 603 increase in sensitivity over UV detection. In addition, other highly fluorescent impurities were detected in methamphetamine produced via four other synthetic routes. The use of a rapid scanning FL detector (with acquisition of ‘‘on the fly’’ excitation or emission) provided structural information and gave ‘‘optimum’’ excitation and emission detection wavelengths. CEC with LIF detection using UV laser excitation provided greatly improved chromatography over HPLC, with good detection limits in the low ng/ml range. Both methodologies provide good run-to-run repeatability, and have the capability to distinguish between samples.


methyl_ethyl

  • Guest
Stereochemical Analysis of MDMA/Metabolites(human)
« Reply #20 on: August 23, 2004, 03:28:00 AM »
Stereochemical analysis of 3,4-methylenedioxymethamphetamine and its main metabolites in human samples including the catechol-type metabolite (3,4-dihydroxymethamphetamine).
Pizarro N, Farre M, Pujadas M, Peiro AM, Roset PN, Joglar J, De La Torre R.
Drug Metab Dispos. 2004 Sep;32(9):1001-7.

Medline (PMID=15319342)





Abstract:

3,4-Methylenedioxymethamphetamine (MDMA; "ecstasy") is a designer drug commonly misused in large segments of young populations. MDMA is usually formulated in tablets of its racemate (1:1 mixture of its enantiomers) in doses ranging from 50 to 200 mg. MDMA has an enantioselective metabolism, the (S)-enantiomer being metabolized faster than the (R)-enantiomer. Different pharmacologic properties have been attributed to each enantiomer. The carbon responsible for MDMA chirality is preserved along its metabolic disposition. An analytical method has been developed to determine MDMA enantiomers and those from its major metabolites, 3,4-methylenedioxyamphetamine (MDA), 3,4-dihydroxymeth-amphetamine (HHMA), and 4-hydroxy-3-methoxymethamphet-amine (HMMA). It has been applied to the analysis of plasma and urine samples from healthy recreational users of MDMA who participated voluntarily in a clinical trial and received 100 mg (R,S)-MDMA. HCl orally. (R)/(S) ratios both in plasma (0-48 h) and urine (0-72 h) for MDMA and MDA were >1 and <1, respectively. Ratios corresponding to HHMA and HMMA, close to unity, deviate from theoretical expectations and are most likely explained by the ability of MDMA to autoinhibit its own metabolism. The short elimination half-life of (S)-MDMA (4.8 h) is consistent with the subjective effects and psychomotor performance reported in subjects exposed to MDMA, whereas the much longer half-life of the (R)-enantiomer (14.8 h) correlates with mood and cognitive effects experienced on the next days after MDMA use.

regards,

methyl_ethyl


Rhodium

  • Guest
Chromatopgraphy of DOM/DOET & other drugs
« Reply #21 on: October 01, 2004, 12:58:00 AM »
Chromatographic Methods for the Identification of the New Hallucinogen, 4-Methyl-2,5-dimethoxy-?-methylphenethylamine, and Related Drugs
K. Genest and D. W. Hughes

The Analyst, Vol. 93, No 1109 485-489 (1968)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/dom.chromatography.pdf)

Summary
Thin-layer and gas-chromatographic methods are described for the detection of  4-methyl-2,5-dimethoxy-?-methylphenethylamine in the sub-microgram range. Chromatographic criteria of identity for this new hallucinogen and for the related amines, amphetamine, methamphetamine, mescaline, and the hallucinogens, dimethyltryptamine and bufotenine are also reported.
____ ___ __ _

Crystal and Molecular Structure of the Psychotropic Drug 2-(4-Ethyl-2,5-dimethoxyphenyl)-1-methylethylamine (4-Ethyl-2,5-dimethoxyamphetamine)
Olga Kennard, Carmel Giacovazzo, Alan S. Horn, Romano Mongiorgi and Lodovico Riva di Sanseverino

J. Chem. Soc. Perkin Trans. 2, 1160-1163 (1974)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/doet.crystal.structure.pdf)

Summary
The molecular conformation of the title compound was determined by X-ray diffraction analysis. The crystals are triclinic. a = 7.43(4). b = 16.73(4). c = 5.25(6) Å. ? = 93° 30'. ? = 87° 30'. ? = 96° 18', P1, Z = 2. The structure was solved by direct methods. The molecular conformation resembles that of 2,4,5-trimethoxyamphetamine and differs from other substituted phenethylamines including dopamine hydrochloride and norepinephrine hydrochloride. This is the first determination of a free base in this class of compounds.
____ ___ __ _

Forensic Aspects of High-Pressure Liquid Chromatography
B. B. Wheals

Journal of Chromatography, 122, 85–105 (1976)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/hplc.forensic.aspects.djvu)

Summary
This paper reviews the applications of high-pressure liquid chromatography (HPLC) to forensic problems, and discusses some of the developments that have taken place in the use of the technique in the Metropolitan Police Laboratory. Preparation of octadecyltrichlorosilane-modified silica is described and some of the chromatographic characteristics of this material are investigated. Applications of HPLC to the analysis of cannabis, opium alkaloids, amphetamine-related materials, LSD and polynuclear hydrocarbons are described.
____ ___ __ _

The separation of a wide range of drugs of abuse by high-pressure liquid chromatography
I. Jane

Journal of Chromatography, 111, 227-233 (1975)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/hplc.drugs-of-abuse.separation.pdf)


Rhodium

  • Guest
Impurity profiling of seized MDMA tablets
« Reply #22 on: October 04, 2004, 07:07:00 AM »
Impurity profiling of seized MDMA tablets by capillary gas chromatography
Fabien Palhol, Sophie Boyer, Norbert Naulet, Martine Chabrillat

Anal. Bioanal. Chem. 374(2), 274-281 (2002)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/mdma.tablets.impurity.profiling.pdf)

Abstract
Impurity profiles of 3,4-methylenedioxymethylamphetamine (MDMA) tablets seized in France have been examined. The samples were extracted with methylene chloride under basic conditions and then analyzed by capillary gas chromatography. Almost 30 compounds were identified as precursors, intermediates and by-products. Palmitic and stearic acid were also found as tableting materials. The comparison of the different profiles obtained by the reported procedure provided very useful information about the synthetic processes used by clandestine laboratories and enabled a classification into several groups of profiles. According to these results, the reductive amination route appears to be the most common synthetic pathway in Western Europe. Furthermore, 3,4-methylenedioxyphenyl-2-propanone seems to be the most used precursor in clandestine laboratories.


Fig. 5 Structure of impurities found in MDMA tablets.


Lenin

  • Guest
4-bromotoluene
« Reply #23 on: October 04, 2004, 02:54:00 PM »
Thanks for the various forensic related articles Rhodium!

Comrade Lenin has been reading some of them and has a question concerning the following article: Fabian M. Dayrit and Morphy C. Dumlao; Impurity profiling of methamphetamine hydrochloride drugs seized in the Philippines (

https://www.thevespiary.org/rhodium/Rhodium/pdf/forensic/meth.hcl.impurities.philippines.pdf

)

The abstract reads: Ten of the impurity peaks were identified, of which four were identified for the first time in methamphetamine drug samples. These are p-bromotoluene, N-benzyl amphetamine, N-ethyl amphetamine, and N-ethyl methamphetamine. The presence of phenyl-2-propanone (P2P), N,N-dimethyl amphetamine, and N-formyl amphetamine is indicative that these casework samples were synthesized using the Leuckart method.

Is there anyone who can follow their hypothesis for the formation of p-bromotoluene? The route they suggest makes Lenin raise his eyebrows...

Lilienthal

  • Guest
Compound 18 looks very interesting, ...
« Reply #24 on: October 04, 2004, 03:51:00 PM »
Compound 18 looks very interesting, unfortunately they don't comment on it.

Chimitant

  • Guest
Compound 22?
« Reply #25 on: October 05, 2004, 03:17:00 AM »
Seems they investigated MDNA tablets contaminated with amphetamine and cocaine. Phtalates seem strange to me in a MDMA tablet, may be from plastic bags they have been stored in ?  What about compound 22? Is that used as a cutting agent?


pashov

  • Guest
Hmm.. How does number 7 in "Impurity...
« Reply #26 on: October 05, 2004, 10:16:00 PM »
Hmm.. How does number 7 in "Impurity profiling of seized MDMA tablets by capillary gas chromatography" happen?

moo

  • Guest
Probably by reductive amination of piperonal...
« Reply #27 on: October 05, 2004, 10:31:00 PM »
Probably by reductive amination of piperonal (no. 5) with methylamine.


methyl_ethyl

  • Guest
Capillary Electrophoresis Analysis
« Reply #28 on: October 07, 2004, 04:29:00 AM »
Capillary Electrophoresis Analysis of a Wide Variety
of Seized Drugs

Ira S. Lurie Patrick A. Hays Kimberly Parker
Electrophoresis 2004, 25, 1580–1591
DOI:

10.1002/elps.200405894




Capillary electrophoresis methodology is presented for the routine analysis of a wide variety of seized drugs using the same capillary with dynamic coatings and multiple run buffers. The types of exhibits analyzed using diode array UV detection include phenethylamines, cocaine, oxycodone, heroin, lysergic acid diethylamide (LSD), opium, hallucinogenic mushrooms, and G-Hydroxybutyrate G-butryolactone (GHB-GBL} Both qualitative and quantitative analyses are achieved using run buffers that contain additives that provide for secondary equilibrium and/or dynamic coating of the capillary. Dynamic coating of the capillary surface is accomplished by rapid flushes of 0.1 N sodium hydroxide, water, buffer containing polycation coating reagent, and a buffer containing a polyanionic coating reagent (with or without cyclodextrin(s)) or a micelle coating reagent. Dynamic coating with a polyanionic coating reagent is used for the analysis of moderately basic seized drugs and adulterants. The use of cyclodextrin in the run buffer not only allows for chiral analysis but also greatly enhances separation selectivity for achiral solutes. A capillary dynamically coated with a micelle allows for the analysis of neutral, acidic, and weakly basic drugs (GHB, GBL and neutral, acidic, and weakly basic adulterants). Dynamic coating, which gives rise to a relatively high and robust electroosmotic flow at pH, 7, allows for rapid, precise and reproducible separations. For a wide variety of drugs, excellent linearity and migration time precision and good peak area precision (external and internal standard) is obtained. Quantitative results for synthetic mixtures are in good agreement with actual values. Screening for adulterants is greatly enhanced by the use of automated library searches.

regards,

methyl_ethyl


Rhodium

  • Guest
(Meth)Amphetamine Impurity Analysis
« Reply #29 on: October 13, 2004, 04:42:00 AM »
Analyses of impurities in methamphetamine by inductively coupled plasma mass spectrometry and ion chromatography
Shin-Ichi Suzuki, Hitoshi Tsuchihashi. Kunio Nakajima, Akira Matsushita, Takeo Nagao

J. Chrom. 437, 322-327 (1988)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/meth.impurity.analysis.icp-ms.pdf)
____ ___ __ _

Use of Bonded-Phase Silica Sorbents for Rapid Sampling of Impurities in Illicit Amphetamine for High-Performance Liquid Chromatographic Analyses
Marit Lambrechts and Knut E. Rasmussen

J. Chrom. 331, 339-348 (1985)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/amph.impurity.sampling.pdf)

Summary
A simple and rapid method has been developed for the extraction of impurities from illicit amphetamine samples using bonded-phase silica sorbents. The drug is dissolved in phosphate buffer (pH 7) and added to a C8 Bond Elut™ extraction column. The column is washed with water, and the impurities are then eluted with acetonitrile. The eluate is directly injected into the liquid chromatograph. This sample preparation technique has been compared with the traditional liquid–liquid extraction method. High-performance liquid chromatographic analysis of the impurities is carried out on a reversed-phase C18 column with an acetonitrile–water gradient as mobile phase. Peaks are monitored by UV detection at 220 and 254 nm. A series of seized amphetamine samples has been analysed, and the procedure gives detailed impurity patterns suitable for the comparison of samples. Compounds are identified by absorbance ratios (A220/A254).


Natrix

  • Guest
DOB
« Reply #30 on: October 19, 2004, 01:46:00 PM »
Identificazione della 4-bromo-2,5-dimetossiamfetamina (DOB) in compresse clandestine sequestrate in Italia
FURNARI, OTTAVIANO, ROSATI

Ann. Ist. Super. Sanità, vol. 37, n. 2 (2001), pp. 297-300

(http://www.iss.it/publ/anna/2001/2/372297.pdf)

Summary
(Identification of the 4-bromo-2,5-dimetoxyamphetamine (DOB) encountered in illicit tablets seized in Italy)
Some of the molecules belonging to the amphetamines group (4-bromo-2,5-dimethoxyamphetamine, DOB) or to the phenethylamines (4-bromo-2,5-dimethoxy-phenethylamine, 2C-B or Nexus) have closely related structures that make their identification quite difficult. The unambiguous identification is crucial in forensic responses. This paper describes the analytical approach used to achieve the identification of the main ingredient contained in tablets seized in the illicit market of Rome (Italy) and submitted to our laboratory by the Court of Law of Rome. The procedure entails the basic extraction of the main ingredient from the tablets with tert-butyl methyl ether followed by qualitative gas chromatographic mass-spectrometric (GC-MS) analysis using both electron impact detection (EI) and chemical ionization (CI). The examination of the mass spectra obtained from the native molecule and from its pentafluoropropionyl-derivative allows the structural identification of the side chain and the substitutions on the aromatic ring. This analytical approach can thus be useful to distinguish between amphetamine-like and phenetylamine-like compounds using instruments and techniques commonly available in the forensic toxicology laboratories.

methyl_ethyl

  • Guest
MDxx detection in urine by fluor. HPLC detection
« Reply #31 on: October 19, 2004, 08:15:00 PM »
I swore I posted this previously however it is not coming up in the search engine.

Determination of MDMA, MDEA and MDA in urine by high
performance liquid chromatography with fluorescence detection

Jos Luiz da Costa, Alice Aparecida da Matta Chasin
Journal of Chromatography B, 811 (2004) 41–45
DOI:

10.1016/j.chromb.2004.03.076




Abstract:
This paper describes the development and validation of analytical methodology for the determination of the use of MDMA, MDEA and
MDA in urine. After a simple liquid extraction, the analyses were carried out on a high performance liquid chromatography (HPLC) in an
octadecyl column, with fluorescence detection. The mobile phase using a sodium dodecyl sulfate ion-pairing reagent allows good separation
and efficiency. The method showed good linearity and precision. Recovery was between 85 and 102% and detection limits were 10, 15 and
20 ng/ml for MDA, MDMA and MDEA, respectively. No interfering substances were detected with fluorescence detection.



Question for all y'all chromatographic professionals.

I notice that the y axis in the chromatograms in the above pdf. is measured in %f.  I have found this is the norm when dealing with hp 1049 detectors usually running chemstation software.  I am not a fan of chemstation software, nor do I favor Agilent/HP Liquid Chromatographs.  I have found that Waters LC's running Empower/Milennium and using a Waters 474 fluorescence detector measure mV along the Y axis, which makes sense to me.  I was wondering if anyone actually knows what %f is.  I would assume that it could not simply be % of total fluorescence (because it does not add up that way).  My problem lies in transferring a method from an Agilent platform running chemstation to a Waters platform running Empower Software.  Perhaps the actual difference lies in how the detectors actually measure the fluorescence.  If this is the case I doubt there would be an accurate means of comparing the two detectors/Platforms.

Any thoughts/comments on the topic would be greatly appreciated.

much_love

methyl_ethyl