Novel skeletal rearrangement of 3Β-acetoxy-5α-pregna-14,16-dien-20-one to 3Β-acetoxy-17-acetyl-5α-etiojerva-12,14,16-triene

Conclusions Reaction of 3-acetoxy-5-pregna-14,16-dien-20-one with 2-acetylcyclopent-4-en-1,3-dione under conditions of thermal diene synthesis causes a previously unreported skeletal rearrangement of the steroidal 1,3-diene to 3-acetoxy-17-acetyl-5-etiojerva-12,14,16-triene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1396–1398, June, 1988.     

Structure of 3-acetoxy-16β,17β-cyclopropano-17α-pregn-5-en-3β-ol-20-one in the crystal and in solution

Conclusions The structure of 3-acetoxy-160,17-cyclopropano-17-pregn-5-en-3-ol-20-one was studied. The conformations of its 17-side chain, which differ somewhat from each other, correspond on the whole to the trans-coplanar arrangement of the 20-keto group and the cyclopropane ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 333–338, February, 1985.     

Condensation of Δ5-pregnen-3β-ol-20-one acetate with acylic dienes

Russian Chemical Bulletin -     

Ozonation of 3β-acetoxy-5α-chloro-cholestane in solution. X-ray study of 3β-acetoxy-5α-chloro-14-cholestene-ozonide.

A selected saturated steroid derivative has been subjected to ozonation in solution. As the main reaction product 14,15-ozonide has been isolated in crystalline form whose structure has been unambiguously confirmed by the X-ray difraction method.     

Crystal structure of 3 -acetoxy-17 -iodo- 5 -androstenes

The crystal structure of 3β-acetoxy-17α-iodo-Δ⁵-androstene (C₂₁H₃₁O₂I) has been determined from three-dimensional X-ray data and refined to a final reliability index of R = 5.1% for the 2352 observed reflexions. Crystals grown from methylene chloride/methanol are orthorhombic, space group P2₁2₁2₁, with cell constants a = 6.430, b = 10.563, c = 29.369 Å.     

Electrochemical reduction of 16α,17α-epoxypregn-5-en-3β-ol-20-one

Conclusions A method was developed for the quantitative production of 3,16-diacetoxypregnenolone by the electrochemical reduction of 16,17-epoxypregnenolone in aqueous ethanol in the presence of tetramethylammonium bromide and catalytic amounts of hydrobromic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1901–1903, August, 1984.     

Transformed steroids. Communication 154. Production of A 17-spirooxetan-20-one under conditions of 21-hydroxylation of 16α-acetamidopregn-5-ene-3β,17α-diol-20-one with iodosobenzene diacetate

Conclusions The possibility of the one-step synthesis of 17-spirooxetan-20-ones from 17-acetyl-17-hydroxy steroids with the aid of iodosobenzene diacetate in a methanol solution of alkali was demonstrated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1659–1663, July, 1986.     

Mass spectrometry of steroid glucuronide conjugates. I. Electron impact fragmentation of 5alpha-/5beta-androstan-3alpha-ol-17-one glucuronides, 5alpha-estran-3alpha-ol-17-one glucuronide and deuterium-labelled analogues

Owing to the developments of analytical instruments and interfaces (e.g. coupling high-performance liquid chromatography to mass spectrometry), there has been increased interest in new reference materials, for example in doping analysis with steroid glucuronide conjugates. The synthesized reference material has to pass several characterization steps including the use of gas chromatography/mass spectrometry (GC/MS) for its structure confirmation. In the present study, the fragmentation and mass spectrometric behaviour of several steroid glucuronide conjugates of endogenous and anabolic steroids after derivatization to pertrimethylsilylated products and to methyl ester pertrimethylsilylated products were investigated using GC/MS ion trap and GC/MS quadrupole instruments. The mass spectra of the derivatives of androsterone glucuronide, d5-androsterone glucuronide, epiandrosterone glucuronide, etiocholanolone glucuronide, 11beta-hydroxy etiocholanolone glucuronide, 19-norandrosterone glucuronide, d4-19-norandrosterone glucuronide and 1alpha-methyl-5alpha-androstan-3alpha-ol-17-one glucuronide are presented and the origin of typical fragment ions of the glycosidic and steroidal moieties is proposed, based on different derivatization techniques including derivatization with d18-bistrimethylsilylacetamide, methyl ester and trimethylsilyl ester derivatization and selected reaction monitoring. Typical fragmentation patterns which are related to the steroid structure are discussed.     

Synthesis of (20R)-3β-acetoxy-δ5-bisnorcholenal

Conclusions We have prepared oxirane (IV) by reaction of pregnenolone acetate (II) with fimdyldofium in yields of up to 90%; treatment with BF₃ etherate quantitatively isomerized it to (20R)-3-acetoxy-⁵-bisnorcholenal (III).Translated from Izvestiya Akademii, Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2581–2584, November, 1976.