Selective thioketalization process, process for preparing...

C - Chemistry – Metallurgy – 07 – J

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C07J 31/00 (2006.01) C07C 319/14 (2006.01)

Patent

CA 2074430

K604 ABSTRACT A selective thioketalization process for the preparation of a thioketal from a dione where one, but not the other, keto group of the dione is .alpha.,.beta.-unsaturated, and where selective thioketali- zation occurs at the keto group of the dione which is not .alpha.,.beta.-unsaturated, comprising the step of contacting the dione with a thiol, in the presence of a protic acid catalyst which is a complex of a Lewis acid and a protic source, wherein the temp- erature of the reaction medium is maintained below about 25°C during the reaction. Preferably, further, (i) the acid catalyst is employed in excess and/or (ii) the thiol is employed in excess. The inventive process may be employed, for example, in the preparation of a 3-keto,17-thioketalandros- tene from the corresponding 3,17-diketoandrostene. A process for the preparation of thioenolethers from thioketals, especially 3-keto,17-thioenoletherandrostenes from 3-keto,17-thioketalandrostenes, wherein the thioketal is contacted with a protic acid catalyst. A process for the preparation of thioketals, especially mixed thioketals such as mixed 3-keto,17- thioketalandrostenes, from thioenolethers, comprising the step of contacting a thioenolether with a thiol in the presence of a protic acid catalyst.

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