Michael Neugebauer

Western Australian Sandalwood Oil—New Constituents of Santalum spicatum (R. Br.) A. DC. (Santalaceae)

Abstract Commercial Australian sandalwood oil produced from Santalum spicatum (R. Br.) A. DC. roots was analyzed using GC and GC/MS. Seventy constituents were identified: four monoterpenes, 64 sesquiterpenes and two others. Four compounds (Z)-β-curcumen-12-ol, (Z)-12-hydroxysesquicineole,6,10-epoxybisabol-2-en-12-olandnor-helifolen-12-al were found to our knowledge for die first time in nature and were characterized using 1H-, 13C-N M R, GC/FTIR and GC/MS analyses.

Stereoselective metabolic study of famprofazone

Famprofazone (1) metabolites were studied in human urine after medication by 50 mg oral dose. The human urine was collected over 48 h from six volunteers at time intervals of 6, 12, 24 and 48 h. The amount of famprofazone metabolites were recovered from the urine samples by application of Extrelut extraction method. The resultant extracts were derivatized using N-methyl-N-trimethylsilytrifluoroacetamide (MSTFA) for trimethylsilylation followed by N-methyl-bis-trifluoroacetamide (MBTFA) for trifluoroacetylation. Methamphetamine (2) and 3-hydroxymethyl-propyphenazone (3), excreted in human urine, were identified as famprofazone metabolites by gas chromatography-mass spectrometry (GC-MS). The quantitative results revealed that the average amounts of 2 and 3, excreted in human urine were equal to 2.6 and 4 mg, respectively, through 48 h. However, 3 was analysed after enzymatic hydrolysis of the urine samples using beta-glucuronidase/arylsulphatase. The excreted methamphetamine enantiomers could be separated by application of indirect GC-technique using S-(-)-N-trifluoroacetylprolyl chloride (TPC) as a chiral derivatizing agent. The average amount of (-)-methamphetamine isomer excreted in the urine was found to be three fold those of the (+)-isomer.

Some new urinary metabolites of famprofazone and morazone in man.

The human urinary metabolism of two pyrazolone derivatives, morazone and famprofazone, has been investigated. After administration of morazone, the metabolites p-hydroxymorazone and phenazone-4-carboxylic acid were excreted in addition to the known metabolite, phenmetrazine, and unchanged morazone. Metabolism of famprofazone led to the formation of methamphetamine; the pyrazolone moiety was excreted as 3-hydroxymethyl-propyphenazone.

Bisepoxylignan glycosides from Stauntonia hexaphylla

Abstract Three bisepoxylignan glycosides were isolated from Stauntonia hexaphylla . One is a new compound, (+)-1-hydroxysyringaresinol-1-β- d -glucoside named staunoside C, whilst the other two, (+)-fraxiresinol-1-β- d -glucoside and (+)-1-hydroxypinoresinol-1-β- d -glucoside, are reported in this genus for the first time. Structures were established on the basis of spectroscopic analysis and chemical evidence, and their 1 H NMR signals were assigned in detail by means of 2D-NMR techniques.

Santalum spicatum (R. Br.) A. DC. (Santalaceae)—nor-Helifolenal and Acorenol Isomers: Isolation and Biogenetic Considerations

Abstract Six stereoisomers of nor-helifolen-12-al and four isomers of acoren-11-ol (α-acorenol, epi-α-acorenol, β-acorenol, epi-β-acorenol) were identified for the first time in Australian sandalwood oil.

Investigation of the Essential Oils from Aristolochia triangularis

ABSTRACT The volatile oils from roots, stems and leaves of Aristolochia triangularis Chamisso were analyzed by GC and GC/MS. Twenty components were identified including the previously reported (−)-α-copaene and β-elemene. The oils consist mainly of sesquiterpenes and a small amount of monoterpenes. Caryophyllene and other sesquiterpenes hydrocarbons predominate in the oil from leaves, whereas the stems and roots contain β-bisabolene, trans-nerolidol and unidentified sesquiterpene alcohols as major components. The characteristic pungent earthy aroma of these oils could make them of potential interest to the fragrance industry.

Study on the metabolism of racemic prolintane and its optically pure enantiomers.

1. Asian and European volunteers were given racemic prolintane, and the metabolites in the 24 h urine were identified and quantified by g.l.c. mass spectroscopy using synthetic reference compounds. 2. R-(+)- and S-(-)-prolintane were synthesized from optically active phenylalanine. The metabolism of the enantiomers differs mainly in the quantitative amounts of metabolites.

Extraction, quantitative gas chromatographic determination and gas chromatographic/mass spectrometric detection of ecgonine for identification of cocaine and its metabolites in urine

ZusammenfassungEs wurden quantitative Untersuchungen zur Extraktion von Urin durchgeführt, dem Cocain, Benzoylecgonin, Ecgoninmethylester und Ecgonin zugesetzt wurden. Die Summe dieser Verbindungen kann über eine vorgeschaltete Hydrolyse zu Ecgonin indirekt bestimmt werden. Nach Hydrolyse wird Ecgonin an einem Kationenaustauscher isoliert und der Extrakt an einem Anionenaustauscher gereinigt. Die quantitative Bestimmung erfolgt gaschromatographisch nach Silylierung mit MSTFA. Dabei beträgt die Wiederfindungsrate 77% bei Konzentrationen von 150 μg Ecgonin/ml Urin. Der qualitative Nachweis von Ecgonin durch GC/MS ist bis zu einer Nachweisgrenze von 20 ng/ml möglich. Damit eignet sich die Methode zum Nachweis einer Cocain-Einnahme im Urin.SummaryQuantitative extraction studies from urine were carried out by addition of cocaine, benzoylecgonine, ecgonine methyl ester and ecgonine to urine samples. After hydrolysis to ecgonine the compounds were analyzed together. Ecgonine was isolated by a cation-exchange resin and purified by an anion-exchange resin. The quantitative determination was performed by GC after silylation with MSTFA. The recovery was 77% at a concentration of 150 μg ecgonine/ml urine. A qualitative determination of ecgonine by GC/MS was possible up to the detection limit of 20 ng/ ml. The method can be applied for the detection of cocaine abuse.

Spaltung von 2-Phenylpropan-1-ol-und 2-Phenylpropan-2-ol-Glucuronid, zweier Metaboliten des Isopropylbenzol (Cumol)

SummaryThe behaviour of 2-phenyl-1-propanol (I) and 2-phenyl-2-propanol (II) and their glucuronides with HCl has been investigated. While I shows a high acidic constancy, II undergoes a partial conversion into 2-phenylpropane (III) which itself yields numerous products. The glucosidic bond of glucuronide I is quantitatively split by 10.0% HCl, whereby an aglucone yield of nearly 100% is obtained. The second glucuronide behaves otherwise: the recovery of II is very low (only 40% to 45%) with HCl concentrations of 1.0%–20.0%, although with 1.0% HCl 100% of the glucuronide is hydrolysed.ZusammenfassungEs wird über das Verhalten von 2-Phenylpropan-1-ol (I) und 2-Phenylpropan-2-ol (II) (beide sind Metaboliten von Cumol) und ihrer Glucuronide gegenüber HCl berichtet. Während I eine hohe Säurebeständigkeit aufweist, erfährt II eine Umwandlung in 2-Phenylpropen (III), aus dem durch Folgereaktionen zahlreiche Produkte entstehen. Die glykosidische Bindung des I-Glucuronides wird mit 10,0% HCl quantitativ gespalten, wobei eine Aglykonausbeute von nahezu 100% erzielt wird. Anders verhält sich das II-Glucuronid: die Wiederfindungsraten an II liegen mit nur 40 bis 45% im gesamten HCl-Konzentrationsbereich (1,0% bis 20,0%) sehr niedrig, obwohl schon mit 1,0% HCl eine Hydrolyserate des Glucuronides von 100% erreicht wird.

Untersuchungen über die Spaltung von synthetischem Pentazocin-Glucuronid mit Salzsäure

SummaryIt has been reported before that pentazocine (I) and pentazocine-glucuronide (II) form an artifact (III) by the addition of water to the double bond in the presence of HCl. This reaction leads to different results concerning the investigation of the rate of hydrolysis of II and the recovery of I. The glucuronide was quantitatively hydrolized by 20% HCl, but yielded only 15% of I (about 64% was detected as III). With 5% HCl the rate of hydrolysis only amounted to 40%–43%, whereas I yielded 31% (only 9% was recovered as III). The best III yield was obtained with a HCl concentration of 17.5%.ZusammenfassungBei der Behandlung von Pentazocin (I) und Pentazocinglucuronid (II) mit Salzsäure wird bekanntlich durch Anlagerung von Wasser an die Doppelbindung ein Artefakt (III) gebildet. Dies führt zu sehr unterschiedlichen Ergebnissen hinsichtlich der Hydrolyserate von II und der Wiederfindung von I. Mit 20% HCl wurde die Glucuronidbindung quantitativ gespalten, aber die Ausbeute an I lag bei nur 15% (ca. 64% der berechneten Menge wurden als III wiedergefunden); mit 5% HCl betrug die Hydrolyserate nur 40–43%, die Pentazocinausbeute jedoch 31% (nur 9% wurden als III wiedergefunden). Die höchste Ausbeute an III wurde mit HCl-Konzentrationen von 17,5% (30 min im siedenden Wasserbad) erzielt.