7241-35-2Relevant academic research and scientific papers
New insights into themetabolism ofmethyltestosterone and metandienone: Detection of novel a-ring reducedmetabolites
Botrè, Francesco,Bureik, Matthias,Iannone, Michele,Keiler, Annekathrin Martina,Liu, Lingyu,Loke, Steffen,Parr, Maria Kristina,Scheffler, Heike,Schl?rer, Nils,Wenzel, Maxi,de la Torre, Xavier
, (2021)
Metandienone and methyltestosterone are orally active anabolic-androgenic steroids with a 17α-methyl structure that are prohibited in sports but are frequently detected in anti-doping analysis. Following the previously reported detection of long-term metabolites with a 17ξ-hydroxymethyl- 17ξ-methyl-18-nor-5ξ-androst-13-en-3ξ-ol structure in the chlorinated metandienone analog dehydrochloromethyltestosterone (“oral turinabol”), in this study we investigated the formation of similar metabolites of metandienone and 17α-methyltestosterone with a rearranged D-ring and a fully reduced A-ring. Using a semi-targeted approach including the synthesis of reference compounds, two diastereomeric substances, viz. 17α-hydroxymethyl-17β-methyl-18-nor-5β-androst-13-en-3α-ol and its 5α-analog, were identified following an administration of methyltestosterone. In post-administration urines of metandienone, only the 5β-metabolite was detected. Additionally, 3α,5β-tetrahydro-epi-methyltestosterone was identified in the urines of both administrations besides the classical metabolites included in the screening procedures. Besides their applicability for antidoping analysis, the results provide new insights into the metabolism of 17α-methyl steroids with respect to the order of reductions in the A-ring, the participation of different enzymes, and alterations to the D-ring.
Preparation method of androstane-17alpha-methyl-17beta-hydroxy-3-ketone
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, (2019/05/04)
The invention provides a preparation method of androstane-17alpha-methyl-17beta-hydroxy-3-ketone. According to the method, methyltestosterone as a raw material is subjected to ketalation, catalytic hydrogenation and a hydrolysis reaction to obtain the androstane-17alpha-methyl-17beta-hydroxy-3-ketone. The method has the advantages that the process is simple and clear, the production cost is low, the purity of the product is high, and the method is suitable for industrial production.
A [...] intermediate androst - 17 α - methyl - 17 β - hydroxy -3 - ketone (by machine translation)
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, (2019/05/04)
The present invention provides a [...] intermediate androst - 17 α - methyl - 17 β - hydroxy - 3 - ketone synthesis method, the method is to 4 - androstenedione (abbreviated as 4 AD) as raw materials, through the 3 position alkone pyridynyl alkylene ether, 17 [...] addition; then in Grignard addition after acid hydrolysis is not carried out in advance 5 at the catalytic hydrogenation reaction of the olefinic bond, then do the 3 bit ether with the 17 bit dual-hydrolysis preparation to obtain compound androst - 17 α - methyl - 17 β - hydroxy - 3 - one, HPLC purity 99.0% or more. The method of the invention route is brief, the production process is easy to control, environmental friendly, low production cost, is suitable for industrial scale production. (by machine translation)
Preparation method of mestanolone
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Paragraph 0013; 0017; 0021, (2017/11/18)
The invention relates to a preparation method of mestanolone. The preparation method comprises the following steps of adopting 4AD as a raw material, carrying out acid catalyzed reaction on the 4AD and triethyl orthoformate in an organic solvent such as lower alcohol to obtain etherate; carrying out grignard addition reaction on the etherate and a methyl-grignard-reagent in an organic solvent to obtain grignard which is 3-ethyoxyl-17a methyl-androstane-3,5-diene-17-alcohol; then catalyzing through palladium-charcoal, carrying out double-bond hydrogenation on a grignard 5 bit to obtain hydride which is 3-ethyoxyl-androstane-3 alkene-17-ketone, finally carrying out acid-catalyzed hydrolysis on the hydride in the organic solvent such as lower alcohol to obtain a mestanolone crude product, and then carrying out decoloration refining through ethyl alcohol and activated carbon to obtain the mestanolone. The HPLC content is 99.5 percent or more, the melting point is 192.5 to 194.0 DEG C, and the synthesis weight total yield is 76 to 83 percent. The preparation method provided by the invention is cheap and easily available in raw materials, simple and convenient in process operation, good in product purity, high in yield, high in solvent recovery rate, reduced in production cost by 25 to 30 percent, and favorable for industrial production.
Characterization of desoxymethyltestosterone main urinary metabolite produced from cultures of human fresh hepatocytes
Gauthier, Julie,Poirier, Donald,Ayotte, Christiane
experimental part, p. 635 - 643 (2012/06/01)
Desoxymethyltestosterone (DMT; 17β-hydroxy-17α-methyl-5α- androst-2-ene) is a designer steroid present in hormonal supplements distributed illegally as such or in combination with other steroids, for self-administration. It figures on the list of substances prohibited in sports and its detection in athlete's urine samples is based upon the presence of the parent compound or the main urinary metabolite, which has not been characterized yet. Following its isolation from cultures of human fresh hepatocytes and S9 fractions of liver homogenates, we were able to identify this metabolite as being 17α-methyl-2β,3α,17β-trihydroxy-5α-androstane. Other minor metabolites were also characterized. The production, isolation, NMR, mass spectral analyses and chemical synthesis are presented.
Efficient oxidizing methods for the synthesis of oxandrolone intermediates
Ginotra, Sandeep K.,Chhikara, Bhupender S.,Singh, Manish,Chandra, Ramesh,Tandon, Vibha
, p. 989 - 991 (2007/10/03)
Mild, efficient and eco-friendly oxidation of 17α-methylandrostan- 3β-17β-diol (1) has been studied with three different reagents viz. pentavalent iodine reagent 2-iodoxy benzoic acid (IBX) in DMSO at 65°C, sodium hypochlorite and H2O2/Na2WO4 under phase transfer conditions to give 17β-hydroxy-17α- methylandrostan-3-one (mestanolone 2), a drug intermediate as oxidized product. The H2O2/Na2WO4/PTC gave mestanolone in high yield and purity whereas sodium hypochlorite/PTC system yielded some chlorinated material along with the mestanolone. However, 1 with 2.5 equivalent of IBX gave 17β-hydroxy-17α-methyl- Δ1-androsten-3- one (3) under the similar reaction conditions in good yield and single step reaction.
IBX in an ionic liquid: Eco-friendly oxidation of 17α- methylandrostan-3β,17β-diol, an intermediate in the synthesis of anabolic oxandrolone
Chhikara, Bhupender S.,Chandra, Ramesh,Tandon, Vibha
, p. 7585 - 7588 (2007/10/03)
An easily available hypervalent iodine(V) reagent, 2-iodoxybenzoic acid (IBX) immobilized in the ionic liquid [bmim][Br] was found to be an efficient and eco-friendly protocol for the oxidation of 17α-methylandrostan- 3β,17β-diol (1). At ambient temperature oxidation of 1 with IBX gave mestanolone (2) in good yield and with an increased stoichiometric amount of IBX, oxidation adjacent to the carbonyl functionality (α,β- unsaturation) occurred to give dehydrogenated 17β-hydroxy-17α-methyl- Δ1-androsten-3-one (3) as the major product in a one-pot reaction. The product is easily obtained by extraction with diethyl ether and evaporation of the solvent.
A convenient synthesis of oxandrolone through a regioselective Candida antarctica lipase-catalyzed transformation
Ferraboschi, Patrizia,Colombo, Diego,Prestileo, Paolo
, p. 2781 - 2785 (2007/10/03)
The use of a regioselective CAL-catalyzed transformation of a suitable intermediate allowed a convenient synthesis of oxandrolone, an anabolic hormone actually employed to improve the quality of life for patients with HIV-infections.
17-Epimerization of 17α-methyl anabolic steroids in humans: metabolism and synthesis of 17α-hydroxy-17β-methyl steroids
Schaenzer, Willi,Opfermann, Georg,Donike, Manfred
, p. 537 - 550 (2007/10/02)
The 17-epimers of the anabolic steroids bolasterone (I), 4-chlorodehydromethyltestosterone (II), fluoxymesterone (III), furazabol (IV), methanedienone (V), mestanolone (VI), methyltestosterone (VII), methandriol (VIII), oxandrolone (IX), oxymesterone (X), oxymetholone (XI), stanozolol (XII), and the human metabolites 7α,17α-dimethyl-5β-androstane-3α,17β-diol (XIII) (metabolite of I), 6β-hydroxymetandienone (XIV) (metabolite of V), 17α-methyl-5β-androst-1-ene-3α,17β-diol (XV) (metabolite of V), 3'-hydroxystanozolol (XVI) (metabolite of XII), as well as the reference substances 17β-hydroxy-17α-methyl-5β-androstan-3-one (XVII), 17β-hydroxy-17α-methyl-5β-androst-1-en-3-one (XVIII) (also a metabolite of V), the four isomers 17α-methyl-5α-androstane-3α,17β-diol (XIX) (also a metabolite of VI, VII, and XI), 17α-methyl-5α-androstane-3β,17β-diol (XX), 17α-methyl-5β-androstane-3α,17β-diol (XXI) (also a metabolite of V, VII, and VIII), 17α-methyl-5β-androstane-3β,17β-diol (XXII), and 17β-hydroxy-7α,17α-dimethyl-5β-androstan-3-one (XXIII) were synthesized via a 17β-sulfate that spontaneously hydrolyzed in water to several dehydration products, and to the 17α-hydroxy-17β-methyl epimer.The 17β-sulfate was prepared by reaction of the 17β-hydroxy-17α-methyl steroid with sulfur trioxide pyridine complex.The 17β-methyl epimers are eluted in gas chromatography as trimethylsilyl derivatives from a capillary SE-54 or OV-1 column 70-170 methylen units before the corresponding 17α-methyl epimer.The electron impact mass spectra of the underivatized and trimethylsilylated epimers are in most cases identical and only for I, II, and V was a differentiation between the 17-epimers possible. 1H nuclear magnetic resonance (NMR) spectra show for the 17β-methyl epimer a chemical shift for the C-18 protons (singlet) of about 0.175 ppm (in deuterochloroform) to a lower field. 13C NMR spectra display differences for the 17-epimeric steroids in shielding effects for carbons 12-18 and 20.Excretion studies with I-XII with identification and quantification of 17-epimeric metabolites indicate that the extent of 17-epimerization depends on the A-ring structure and shows a great variation for the different 17α-methyl anabolic steroids.Keywords: anabolic steroids; 17-epimerization; nuclear magnetic resonance; Kovats indices; mass spectrometry; metabolism; gas chromatography
Studies on anabolic steroids. 9. Tertiary sulfates of anabolic 17α-methyl steroids: synthesis and rearrangement
Bi, Honggang,Masse, Robert,Just, George
, p. 306 - 312 (2007/10/02)
A simple and convenient method has been developed to prepare sulfates of anabolic 17β-hydroxy-17α-methyl steroids.The sulfates of methandienone, 17α-methyltestosterone, mestanolone, oxandrolone, and stanozolol were prepared.Different A-ring functions were not affected under the sulfation condition.The buffered hydrolyses of these sulfates provided the 17-epimers of the original steroids and 17,17-dimethyl-18-nor-13(14)-ene steroids, presumably via the 17-carbocations. Keywords: steroids, tertiary sulfates; 17α-methyl steroids; 17β-methyl steroids; 17,17-dimethyl-18-norandrost-13(14)-enes; NMR
