Δ5, 7-Steroids. XII.1, 2 Steroidal Cyclic Ketals. I. Cyclic Ketals of Δ4, 7-3-Ketosteroids

Antonucci, Rose; Bernstein, Seymour; Littell, Ruddy; Sax, Karl; Williams, James H.

doi:10.1021/jo50010a010

Cited by 47 publications

(15 citation statements)

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“…In order to unambiguously confirm the structure of 3α-ureido-androst-4-en-17-one, reference material was synthesised according to published methods 31 32. In brief, dehydroepiandrosterone (DHEA) was converted into its 17-ethylene ketal by means of ethylene glycol under acidic conditions, followed by oxidation of the 3-hydroxy function to yield androst-4-ene-3-one-17-ethylene ketal.…”

Section: Methodsmentioning

confidence: 99%

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

et al. 2012

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The administration of musk extract, that is, ingredients obtained by extraction of the liquid secreted from the preputial gland or resulting grains of the male musk deer (eg, Moschus moschiferus), has been recommended in Traditional Chinese Medicine (TCM) applications and was listed in the Japanese pharmacopoeia for various indications requiring cardiovascular stimulation, anti-inflammatory medication or androgenic hormone therapy. Numerous steroidal components including cholesterol, 5α-androstane-3,17-dione, 5β-androstane-3,17-dione, androsterone, etiocholanolone, epiandrosterone, 3β-hydroxy-androst-5-en-17-one, androst-4-ene-3,17-dione and the corresponding urea adduct 3α-ureido-androst-4-en-17-one were characterised as natural ingredients of musk over several decades, implicating an issue concerning doping controls if used for the treatment of elite athletes. In the present study, the impact of musk extract administration on sports drug testing results of five females competing in an international sporting event is reported. In the course of routine doping controls, adverse analytical findings concerning the athletes' steroid profile, corroborated by isotope-ratio mass spectrometry (IRMS) data, were obtained. The athletes' medical advisors admitted the prescription of TCM-based musk pod preparations and provided musk pod samples for comparison purposes to clarify the antidoping rule violation. Steroid profiles, IRMS results, literature data and a musk sample obtained from a living musk deer of a local zoo conclusively demonstrated the use of musk pod extracts in all cases which, however, represented a doping offence as prohibited anabolic-androgenic steroids were administered.

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Section: Methodsmentioning

confidence: 99%

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

et al. 2012

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“…4, is consistent with a composite of both the delocalized D 5,7 -diene moiety of 3-oxo-7dC with l max at 263, 272, 282 and 294 nm (as for 7dC and 7d25C) and a spectrum, consisting of prominent shoulders, contributed by the more-extensively-delocalized D 3,5,7 -triene moiety of its apparently spontaneously enolized and co-migrating (or co-equilibrating) ''3-enol'' isomer, i.e. cholesta-3,5,7-triene-3-ol, with l max 303, 315 and 330 nm (Antonucci et al, 1952a) (Fig. 2A).…”

Section: Oppenhauer Oxidation Of 7dcmentioning

confidence: 97%

“…However, the 3-oxo moiety can be protected as a ketal (Antonucci et al, 1952a) with a photosensitive, ketoneblocking (PSKB) agent (Bochet, 2002;Blanc and Bochet, 2003). The resulting lipophilic 3-oxo-7dC precursor ketals are non-toxic, enter tissues easily and rapidly release 3-oxo-7dC upon irradiation with relatively innocuous long-wave UV-light (365 nm) in just a few minutes.…”

Section: Introductionmentioning

confidence: 99%

Studies on the black box: Incorporation of 3-oxo-7-dehydrocholesterol into ecdysteroids by Drosophila melanogaster and Manduca sexta

Warren

O’Connor

Gilbert

2009

Insect Biochemistry and Molecular Biology

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“…In previous papers of this series (3) it was shown that aqueous acetic acid rather than dilute sulfuric acid may be used in the hydrolysis of steroid ethylene ketals. Application of this hydrolytic procedure to the di-ethylene ketal of cortisone (VIII) led to a very interesting result.…”

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confidence: 99%

STEROIDAL CYCLIC KETALS. III.^{1, 2} HYDROCORTISONE AND RELATED CORTICOIDS

Antonucci¹,

Bernstein²,

Heller³

et al. 1953

J. Org. Chem.

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The purpose of this paper is to describe the preparation of hydrocortisone3 (XIV), 11-epi-hydrocortisone (XV), and Reichstein's Substance E diacetate (V) from cortisone4 (VII), or its acetate (111), by an essentially new and facile method which entails the protection of carbonyl groups as ethylene k e t a l~.~ In this connection, Wendler, Huang-Minlon, and Tishler (1) have selectively protected the C-3, and -20 carbonyl groups of cortisone (VII) by semicarbazone formation. Moreover, these investigators demonstrated that cortisone acetate (111) formed only a 3-mono-semicarbazone. This revealed that the C-21 acetate group hindered the condensation reaction a t the neighboring (2-20 position. This steric effect has been noted previously by Mancera (2). Lithium borohydride reduction of cortisone-3,20-di-semicarbazone, followed by acetylation, and hydrolysis of the semicarbazone groupings (exchange reaction with pyruvic acid) afforded hydrocortisone acetate (XVI).Reichstein's Substance S acetate (I) (Flowsheet I) on treatment with excess ethylene glycol (benzene, p-toluenesulfonic acid) afforded a mono-ethylene ketal to which the structure I1 has been assigned. The product exhibited no selective absorption in the ultraviolet region of the spectrum. The coincident rearrangement of the double bond from the C-4 to the -5 position during the formation of ethylene ketals of A4-3-ketosteroids has been discussed previously (3). It is to be noted that here also the C-21 acetate group hindered the condensation of the C-20 carbonyl group with ethylene glycol. Similarly, only a 3-mono-ethylene ketal (IV) was obtained from cortisone acetate (111) (64% yield). However, and Rosenkranz, Pataki, and Djerassi (7b). (This last publication appeared after completion of our work.) 70An lla-hydroxyl group (in contrast to the 118-isomer) is capable of acetylation, as shown by Long and Gallagher, J .

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Δ^{5, 7}-Steroids. XII.^{1, 2} Steroidal Cyclic Ketals. I. Cyclic Ketals of Δ^{4, 7}-3-Ketosteroids

Cited by 47 publications

References 2 publications

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

Studies on the black box: Incorporation of 3-oxo-7-dehydrocholesterol into ecdysteroids by Drosophila melanogaster and Manduca sexta

STEROIDAL CYCLIC KETALS. III.^{1, 2} HYDROCORTISONE AND RELATED CORTICOIDS

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Δ5, 7-Steroids. XII.1, 2 Steroidal Cyclic Ketals. I. Cyclic Ketals of Δ4, 7-3-Ketosteroids

Cited by 47 publications

References 2 publications

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

Traditional Chinese medicine and sports drug testing: identification of natural steroid administration in doping control urine samples resulting from musk (pod) extracts

Studies on the black box: Incorporation of 3-oxo-7-dehydrocholesterol into ecdysteroids by Drosophila melanogaster and Manduca sexta

STEROIDAL CYCLIC KETALS. III.1, 2 HYDROCORTISONE AND RELATED CORTICOIDS

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Δ^{5, 7}-Steroids. XII.^{1, 2} Steroidal Cyclic Ketals. I. Cyclic Ketals of Δ^{4, 7}-3-Ketosteroids

STEROIDAL CYCLIC KETALS. III.^{1, 2} HYDROCORTISONE AND RELATED CORTICOIDS