Analysis of Impurities in Illicit Heroin by Mass Spectrometry

Klein, Michael D.

doi:10.1007/978-1-4613-4151-2_30

Cited by 7 publications

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References 6 publications

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“…It is not uncommon for the acidic and neutral components extracted from a South-West Asian crudely refined heroin base sample to yield a 250+ component high-resolution GC chromatogram. Only a relative few of these compounds have been fully characterized [34,[36][37][38][39]. The most significant chemistry underlying the generation of a majority of these 250+ compounds is found in the works of Polonovski and Polonovski and of Mariella and the associated papers [40][41][42][43][44][45][46].…”

Section: Methods For the Determination Of Trace Componentsmentioning

confidence: 99%

United Nations Publications

African Studies Companion Online

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Methods for impurity profiling of heroin and cocaine 1982 to coordinate research on the physical and chemical characteristics of heroin for the purpose of tracing origin and movement in the illicit traffic [2]. In 1992, a consultative meeting on chemical characterization and impurity profiling of drug seizures was held in Vienna; that meeting expanded coverage beyond heroin to include cocaine and synthetic drugs and, in particular, amphetamine [3]. At its thirty-ninth session, in 1996, the Commission on Narcotic Drugs recognized the need for a cohesive international strategy in the field of drug characterization and impurity profiling. In so doing the Commission requested the Executive Director of the United Nations International Drug Control Programme (now called UNODC) to develop standard protocols and methods for the profiling/ signature analysis of key narcotic drugs and psychotropic substances [4]. The objectives of the Office in this area are to develop guidelines for characterization and impurity profiling of key narcotic drugs and psychotropic substances and to make the guidelines available to national forensic laboratories with the aim of providing them with a scientific tool to support law enforcement work for both evidential and strategic intelligence purposes. At the same time, the UNODC reference services, which include the provision of training, reference samples, material and scientific literature, were expanded to include specific aspects of drug characterization and impurity profiling as well. In this context and in view of the focus of the General Assembly at its twentieth special session on, inter alia, the need for enhanced measures to counter illicit manufacture of and trafficking in drugs, it was considered timely to review profiling methods for heroin and cocaine, along with the broader concepts of drug characterization and impurity profiling of both plant-based and synthetic drugs. To this end, the Laboratory and Scientific Section of UNODC convened a Consultative Meeting on Recommended Methods for the Impurity Profiling of Heroin and Cocaine, in cooperation with the

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Section: Methods For the Determination Of Trace Componentsmentioning

confidence: 99%

United Nations Publications

African Studies Companion Online

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ThePolonovski Reaction

Grierson¹

1990

Organic Reactions

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In connection with their interest in the isolation and medicinal properties of the “gen alkaloids” ( N ‐oxides), Max and Michel Polonovski reported in 1927 their discovery that the treatment of a tertiary amine N ‐oxide with acetic anhydride or acetyl chloride results in a rearrangement in which one of the alkyl groups attached to nitrogen is cleaved, and the N ‐acetyl derivative of the corresponding secondary amine and aldehyde are obtained. As the original work by the Polonovskis was mainly carried out on bicyclic tropane N ‐oxide derivatives, the products of the reaction were the demethylated amides and formaldehyde. The reaction was thus looked upon as a means of effecting N ‐demethylation of tertiary amines. As such it was, and still remains, a viable alternative to the use of cyanogen bromide, alkyl chloroformates, azocarboxylic esters, or nitrous acid for this purpose. These methods often require more drastic conditions and/or promote unwanted side reactions. The central feature of the Polonovski reaction is the transformation of an N ‐oxide to an iminium ion intermediate. Depending on the structure of the substrate and the acid anhydride or other activating reagent employed, iminium ion formation can occur through loss of an α hydrogen, or through fragmentation of a Cαcarbon bond. Again, depending on conditions, the reaction will either stop at this stage and iminium ions become the Polonovski products, or proceed to give enamines or tertiary amides and/or secondary amines and aldehydes. The often close relationship between structure and reaction conditions, which determine both product types and reaction regiochemistry, is discussed. In its initial stages the Polonovski reaction resembles other reactions in which a tertiary amine is oxidized through interaction of the pair of electrons on nitrogen with an agent X followed by elimination of the elements of HX. Reagents like lead tetraacetate, N ‐bromosuccinimide and in particular mercuric acetate have been employed for this purpose. However, the Polonovski reaction can offer certain advantages in selectivity and experimental ease. In principle, any reagent capable of activating the N ‐oxide oxygen could promote the Polonovski reaction. However, three major types of activating agents, acid anhydrides and chlorides (including chloroformate esters), iron salts and complexes, and sulfur dioxide, are usually employed. Perhaps the most important contribution to the use of the Polonovski reaction in modern organic synthesis was the discovery in the 1960s that on replacing acetic anhydride by trifluoroacetic anhydride the reaction could be stopped at the iminium ion stage. Considering the rich chemistry of iminium ions, many applications of this modified, or Polonovski–Potier, reaction have appeared in the literature, the most spectacular of which was the first successful approach to the synthesis of the indole antitumor agents of the vinblastine group. In this chapter the discussion is limited to examples of the Polonovski reaction in which the abovementioned activating reagents are employed. The coverage is restricted to tertiary amine oxides in which at least one of the substituents on nitrogen is an alkyl group. Both acyclic and cyclic amine oxides such as piperidine N ‐oxide fall into this category, whereas heteroaromatic N ‐oxides do not. With the exception of one special case, nitrones are also omitted from the discussion. The literature coverage includes articles appearing before the end of August 1988.

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Efficient N-Demethylation of Opiate Alkaloids Using a Modified Nonclassical Polonovski Reaction

et al. 2003

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A modified Polonovski reaction has been employed to N-demethylate several opiate alkaloids in moderate to high yield. This method provides an alternative to traditional N-demethylation procedures which utilize toxic reagents such as cyanogen bromide or expensive reagents such as vinyl chloroformate. The current synthesis involves N-oxide formation, isolation of the corresponding N-oxide hydrochloride, and an FeSO(4).7H(2)O mediated Polonovski reaction to afford the desired secondary amine.

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Analysis of Impurities in Illicit Heroin by Mass Spectrometry

Cited by 7 publications

References 6 publications

United Nations Publications

United Nations Publications

ThePolonovski Reaction

Efficient N-Demethylation of Opiate Alkaloids Using a Modified Nonclassical Polonovski Reaction

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