NEW MATERIAL:The compound of formula I [R is CH3, CH2SCN, CH2SC(=S) OR' (R' is lower alkyl), etc.; X is SCN, N3, SCH2CH2X' (X is OH, acyloxy, N3 halogen or SCN), lower alkynyl or lower alkynyloxy; dotted line represents the presence or absence of double bond].

EXAMPLE: 6α-Thiocyanatoandrost-4-ene-3,17-dione.

USE: An agent for suppressing proliferation of estrogen-dependent tumor.

PREPARATION: The compound of formula I can be produced e.g. by reacting an epoxy derivative of formula II (Y is O or ketal group) (e.g. 5α,6α- epoxyandrostane-3,17-dione) with a compound such as sodium thiocyanate and subjecting the reaction product to dehydration reaction.