Morphine 6-monoacetyl

Dioctyl sulfo-succinate codeine, morphine, monoacetyl-mor-phine, heroin stabilization dipping solution, 20% in ethanol [94]... 

Fig. 1 Concentrations reported for opiods and cannabinoids in surface water of different European countries. MOR morphine Nor-MOR nor-morphine 6ACM 6-monoacetyl morphine HER heroin MET methadone EDDP 2-ethylidene-l,5-dimethyl-3,3 diphenylpyrrolidine THC A9-tetrahydro-cannabinol THC-COOH 11-nor 9-carboxy-THC N/A Values not availabe, not measured...

Moghaddam, A., Borgen, T., Stacy, J., Kausmally.L., Simonsen, B., Marvik, O. J., et al. (2003) Identification of scFv antibody fragments that specifically recognise the heroin metabolite 6-monoacetyl-morphine but not morphine. /. Immunol. Meth. 280, 139-155. 

J. M. Moore and M. Klein, Identification of 03-monoacetyl-morphine in illicit heroin by using gas chromatography-electron-capture detection and mass spectrometry, J. Chromatogr., 154 16... 

Lerner and Mills (JjO reported the presence of 0 -monoacetyl-morphine as a common constituent in heroin and suggested that the ratio of heroin to monoacetylmorphine would not change during adulteration. Others have dealt primarily with the identification of the adulterants present, either other drug substances or sugars (6,7). Grooms (j3) and Miller (9) have attempted to include the analysis of adulterants with the presence of monoacetylmorphine. In each of these cases, the resolution of the various components was insufficient to provide good quantitative data. 

Note Abbreviations are as follows COC, cocaine BE, benzoylecgonine 6-AM, monoacetyl-morphine MOR, morphine. 

Another interesting aspect of this study was the comparison of MEKC and HPLC. While in MEKC the drugs represented in Figure 8.1 migrated in the order morphine (1), phenobarbital (2), 6-monoacetylmoprhine (6-MAM) (3), 3-monoacetyl morphine (3-MAM) (4), methaqualone (5), heroin (6), acetylcodeine (7), papaverine (8), and noscapine (9), in reversed-phase HPLC the elution pattern was substantially different and not correlated with MEKC... 

Mule SJ, Casella GA. Rendering the poppy-seed defense defenseless Identification of 6-monoacetyl-morphine in urine by gas chromatography/mass spectroscopy. Clin Chem 1988 34 1427-30. 

Sample No. Morphine 6-0-Monoacetyl-Morphine Codeine Acetyl -Codeine Heroin hydrochloride... 

Vongerichten reported the isolation, as a by-product in the preparation of 3 4-diacetoxyphenanthrene by heating diacetyl-morphine with silver acetate and acetic anhydride at 180° C., of a /3-morphi-methine that could be methylated to /3-codeimethine methiodide [88], Repetition of this work revealed the product to be a monoacetylated /3-morphimethine that can be methylated and hydrolysed to /3-codeimethine, and reduced to [lxxi, R = Ac] [51]. 

Codein is the methyl ether of morphin, or its superior homo-logue, and resembles that alkaloid in some of its reactions thus under similar circumstances both form apomorphin, and morphin may be converted into codein by the action of methyl iodid in the presence of KHO. Codein, however, only contains one OH group and forms a monoacetylic derivative with acetyl chlorid,. while morphin produces a diacetylic. 

When the urine extract is derivatized with acetic anhydride, morphine is converted into the two monoacetyl derivatives and diacetylmorphine, and codeine and DHC are converted into the analogous 6-acetyl esters (Table 8-9). The metabolites of noscapine and papaverine, like those of morphine, can be determined with adequate sensitivity only after derivatization. 

Heroin production Morphine free base is refluxed in acetic anhydride for 5h. The mixture is allowed to cool and is neutralized with sodium carbonate causing the precipitation of crude diacetyl-morphine free base, the illicit drug in heroin samples. Monoacetylation of morphine and acetylation of any codeine present also occurs. The crude product is purified by dissolving in acidified water containing charcoal and the free base precipitated by the addition of sodium carbonate. If the hydrochloride salt is required the free base is dissolved in acetone and the product precipitated by the addition of hydrochloride acid. 

Samples thought to contain heroin require derivatization to help resolve some of the components though diamorphine itself chromatographs well without derivatization. Introduction into the GC system causes acetylation of morphine and monoacetyl morphine thus inflating the concentration of diamorphine above the actual value if GC is used as the quantifying technique. Heroin samples are generally profiled using a GC/MS system. 

W. Hanisch and L.V. Meyer, Determination of the heroin metabolite 6-monoacetyl-morphine in urine by high-performance liquid chromatography with electrochemical detection, J. Anal. Toxicol, 1993, 17, 48-50. 

---