204244-83-7

Upstream product

• 79037-28-8 [1α,2α-2H2]androst-4-ene-3,17-dione 
• 897-06-3 Androsta-1,4-diene-3,17-dione 
• 4273-45-4 [1α,2,2,4,6,6,16,16-2H8]androst-4-ene-3,17-dione 

Downstream Products

• 638163-38-9 [1α,16,16,17α-2H4]androst-4-en-6β,17β-diol-3-one 
• 638163-36-7 [1α,16,16,17α-2H4]androst-4-en-17β-ol-3-one 

Relevant academic research and scientific papers

Syntheses of stable isotope-labeled 6β-hydroxycortisol, 6β-hydroxycortisone, and 6β-hydroxytestosterone

A method is described for the preparation of two types of multi-labeled 6β-hydroxycortisol containing either five deuterium atoms at C-19 methyl and C-1 methylene or four 13C atoms at C-1, C-2, C-4, and C-19 in addition to the five deuterium atoms for use as analytical internal standards for gas chromatography-mass spectrometry (GC-MS). BMD derivatives of [1,1,19,19,19-2H5]cortisone and [1,2,4,19- 13C4,1,1,19,19,19-2H5]cortisone (cortisone-2H5-BMD and cortisone-13C 4,2H5-BMD) were first synthesized via indan synthon method starting from optical active 11-oxoindanylpropionic acid and labeled isopropenyl anion ([1,1,3,3,3-2H5]- or [1,3- 13C2,1,1,3,3,3-2H5]isopropenyl anion). The labeled isopropenyl anion was prepared from commercially available [1,1,1,3,3,3-2H6]- or [1,3-13C 2,1,1,1,3,3,3-2H6]acetone. Ultraviolet (UV) irradiated autoxidation at C-6 position of 3-ethyl-3,5-dienol ether derivatives of the labeled cortisone-BMDs gave 6β-hydroxy-[1,1,19,19,19- 2H5]cortisone-BMD and 6β-hydroxy-[1,2,4,19- 13C4,1,1,19,19,19-2H5]cortisone-BMD, respectively, as a mixture of 6β- and 6α-epimers in a ratio of 4:1. Separation of 6β- and 6α-epimers by thin-layer chromatography (TLC) and subsequent hydrolysis of the BMD group at C-17 gave pure labeled 6β-hydroxycortisone. After protecting the keto group at C-3 of the labeled 6β-hydroxycortisone-BMD as semicarbazone, reduction of 11-keto group with NaBH4 and subsequent removal of the C-3 and C-17 protecting groups gave 6β-hydroxy-[1,1,19,19,19-2H5]cortisol (6β-hydroxycortisol-2H5) and 6β -hydroxy-[1,2,4,19-13C4,1,1,19,19,19-2H 5]cortisol (6β-hydroxycortisol-13C4, 2H5), respectively, as a mixture of 6β- and 6α-epimers (6β:6α=4.4:1). The isotopic compositions of 6β-hydroxycortisol-2H5 and 6β -hydroxycortisol-13C4,2H5 were 90.9 and 92.1 at.%, respectively. Furthermore, 6β-hydroxy-[1α ,16,16,17α-2H4]testosterone was synthesized by the UV irradiated autoxidation at C-6 position of 3-ethyl-3,5-dienol ether derivative of deuterium-labeled testosterone ([1α,16,16,17α- 2H4]testosterone) obtained by using catalytic deuteration and hydrogen-deuterium exchange reactions.