in testosterone at the C19 position has been removed, and the C17β position is where esters are attached to nandrolone. Nandrolone, also known as 19-nortestosterone (19-NT) or as estrenolone, as well as estra-4-en-17β-ol-3-one or 19-norandrost-4-en-17β-ol-3-one, is a
naturally occurring estrane (19-norandrostane)
steroid and a
derivative of
testosterone (androst-4-en-17β-ol-3-one). It can be detected during
pregnancy in women. Nandrolone esters have an
ester such as
decanoate or
phenylpropionate attached at the C17β position. This family is subdivided into two groups: the
estranes and the
gonanes. Updated: alternative: The elaboration of a method for the reduction of aromatic rings to the corresponding dihydrobenzenes under controlled conditions by A. J. Birch opened a convenient route to compounds related to the putative
19-norprogesterone. This reaction, now known as the
Birch reduction, is typified by the treatment of the monomethyl ether of
estradiol (
1) with a solution of lithium metal in liquid ammonia in the presence of alcohol as a proton source. Initial reaction constituents of 1,4-dimetalation of the most electron deficient positions of the aromatic ring–in the case of an estrogen, the 1 and 4-positions. Rxn of the intermediate with the proton source leads to a dihydrobenzene; a special virtue of this sequence in steroids is the fact that the double bond at 2 is in effect becomes an enol ether moiety. Treatment of this product, 1,4-Dihydroestradiol 3-methyl ether [1091-93-6] (
2), with weak acid, e.g.
oxalic acid, leads to the hydrolysis of the enol ether, producing β,γ-unconjugated ketone
Prenortestosterone [1089-78-7] (
3). Hydrolysis under more strenuous conditions (
mineral acids) results in migration/conjugation of the olefin to yield nandrolone (
4). The
Prenortestosterone [1089-78-7] is also of interest to us because it has use in the synthesis of
Dienolone. Birch reduction of
estrone methyl ether will work. Back-oxidation of the 17beta-hydroxy group will give
Bolandione (cmp 14). Reduction of the 3-keto group in nandrolone (
lithium aluminium hydride was given in patent) will give
bolandiol.
Esters • Treatment of
4 with decanoic anhydride and
pyridine affords
nandrolone decanoate. • Acylation of
4 with phenylpropionyl chloride yields
nandrolone phenpropionate.
Detection in body fluids Nandrolone use is directly detectable in hair or indirectly detectable in urine by testing for the presence of
19-norandrosterone, a
metabolite. The
International Olympic Committee has set a limit of 2.0 μg/L of 19-norandrosterone in urine as the upper limit, beyond which an
athlete is suspected of
doping. In the largest nandrolone study performed on 621 athletes at the
1998 Nagano Olympic Games, no athlete tested over 0.4 μg/L. 19-Norandrosterone was identified as a trace contaminant in commercial preparations of
androstenedione, which until 2004 was available without a prescription as a dietary supplement in the U.S. A number of nandrolone cases in
athletics occurred in 1999, which included high-profile athletes such as
Merlene Ottey,
Dieter Baumann, and
Linford Christie. However, the following year the detection method for nandrolone at the time was proved to be faulty.
Mark Richardson, a British Olympic relay runner who tested positive for the substance, gave a significant amount of urine samples in a controlled environment and delivered a positive test for the drug, demonstrating that false positives could occur, which led to an overhaul of his competitive ban. Heavy consumption of the essential amino acid
lysine (as indicated in the treatment of cold sores) has allegedly shown false positives in some and was cited by American
shotputter
C. J. Hunter as the reason for his positive test, though in 2004 he admitted to a federal
grand jury that he had injected nandrolone. A possible cause of incorrect urine test results is the presence of metabolites from other anabolic steroids, though modern
urinalysis can usually determine the exact anabolic steroid used by analyzing the ratio of the two remaining nandrolone metabolites. As a result of the numerous overturned verdicts, the testing procedure was reviewed by
UK Sport. In October 2007, three-time Olympic gold medalist for track and field
Marion Jones admitted to use of the drug, and was sentenced to six months in jail for lying to a federal grand jury in 2000.
Mass spectrometry is also used to detect small amounts of nandrolone in urine samples. ==History==