TY  - JOUR
PY  - 2009//
TI  - Chemical aromatization of 19-hydroxyandrosta-1,4-diene-3,17-dione with acid or alkaline: elimination of the 19-hydroxymethyl group as formaldehyde
JO  - Steroids
A1  - Numazawa, Mitsuteru
A1  - Yamashita, Kouwa
A1  - Kimura, Nao
A1  - Takahashi, Madoka
SP  - 208
EP  - 211
VL  - 74
IS  - 2
N2  - In order to determine whether or not a 19-hydroxymethyl group of 19-hydroxyandrosta-1,4-diene-3,17-dione (2, 19-hydroxy ADD), an intermediate of aromatase-catalyzed estrone formation from ADD, a suicide substrate of aromatase, is eliminated as formaldehyde, we examine chemical nature of removal of the 19-hydroxymethyl group. 19-acetate 3 and 19-tert-butyldimethylsiloxy compound 4 are known to convert rapidly to estrone with treatment of NaOH or n-Bu4NF. Since compound 2 was unstable and unobtainable under these conditions, compounds 3 and 4 as equivalents to compound 2 were used in this study. The acetate 3 with 5 mol/l HCl in acetone and 10% KOH in MeOH along with the silyl ether 4 with 5 mol/l HCl in acetone and 1 mol/l n-Bu4NF in THF gave formaldehyde and estrone in which a ratio of the aldehyde to estrone was near 1. This result indicates that the 19-hydroxymethyl groups of compound 3 and 4 are eliminated as formaldehyde along with estrone derived from the steroid skeleton under the acid or base treatment. The findings suggest that a single hydroxylation at the 19 carbon of ADD (1) would be, chemically, all that was required for estrone formation.<p /> <p>Language: en</p>
LA  - en
SN  - 0039-128X
UR  - http://dx.doi.org/10.1016/j.steroids.2008.10.011
ID  - ref1
ER  -