The invention comprises 19-nor-androstane compounds with a saturated or unsaturated bond between C-atoms 4 and 5, which are not oxygenated in 3-position, having in 17-position either a hydrogen atom and a free or functionally converted hydroxyl group or a lower aliphatic hydrocarbon radical and a free or functionally converted hydroxyl group, or a free or functionally converted oxo group and which may in addition have a lower alkyl group in 1-position and/or a free or functionally converted hydroxyl or oxo group in 16-position, particularly compounds of the formula <FORM:0811961/IV (b)/1> in which X represents hydrogen or a lower aliphatic hydrocarbon radical and R represents an hydroxyl group having 1-10 carbon atoms or X and R together represent a free or functionally converted oxo group, the corresponding saturated compounds and a process for the preparation of new biologically active 19-nor-steroid compounds, characterized in that a steroid compound with an aromatic ring A which in 3-position has an etherified hydroxyl group, in 17-position either a free or functionally converted hydroxyl group and a lower aliphatic hydrocarbon radical or a free or functionally converted hydroxyl group and a hydrogen atom, and which may in addition in the steroid nucleus contain one or more double bonds, free or functionally converted hydroxyl groups and oxo groups, lower alkyl groups and halogen atoms, is allowed to react with an alkali metal in a lower aliphatic primary amine, as a result of which a D 4-19-nor-androstine compound is formed which is not oxygenated in 3-position, after which, if desired, the double bond or bonds present is/are reduced and/or one or more of the free or functionally converted secondary hydroxyl groups present are oxidized, or hydrolysed and oxidized to an oxo group. As alkali metal there may be used lithium, sodium or potassium and as lower aliphatic primary amine are mentioned methylamine, ethylamine, n-propylamine and isopropylamine. Initially the starting substances are dissolved in an organic solvent, e.g. dimethyl ether, methyl ethyl ether, diethyl ether, dioxane or tetrahydrofurane, to which solution is added the alkali metal in primary amine. Specified starting substances are the 3-ethers of 17a -methyl oestradiol, 17a -ethyl oestradiol, 17a -methyl oestradiol - 17 - propionate, 17b - butyl oestradiol - 17 - phenylpropionate, 17b - ethyl oestradiol - 17 - phenylpropionate, 17a - capryloestradiol - 17 - capronate, 17a - ethyl oestradiol - 17-isocapronate, 17a - methyl oestradiol - 17-cycohexylbutyrate, 1 - methyl - oestradiol, 1-methyl oestradiol - 17 - acetate, 1 - methyl oestradiol - 17 - phenylpropionate, oestrol oestriol 16,17-diacetate, oestriol-16-propionate-17 - acetate, D 1,3,5(10) - 3 - hydroxy - 20 - oxopregnatriene and D 1,3,5(10) - 3,20 - dihydroxypregnatriene. The D 4-19-nor androstene compounds are isolated by distribution of the crude reaction product between aqueous methanol and petroleum ether. Examples describe the production of D 4-17a -methyl-17b -hydroxy-19-nor - androstene, 17a - methyl - 17b - hydroxy-19 - nor - androstane, D 4 - 17a - ethyl - 17b - hydroxy - 19 - nor - androstene, 17a - ethyl - 17b -hydroxy - 19 - nor - androstane D 4 - 17b - hydroxy - 19 - norandrostene, the benzoate and acetate thereof and the corresponding androstanes, D 4 - 17 - oxo - 19 - nor - androstene, 17-oxo - 19 - nor - androstane, D 4 - 16a ,17b - dihydroxy - 19 - nor - androstene, 16a ,17b - dihydroxy - 19 - nor - androstane, D 4 - 1 - methyl-17 - hydroxy - 19 - nor - androstene, 1 - methyl-17 - oxo - 19 - nor - androstene, 1 - methyl - 17-hydroxy - 19 - nor androstane and 1 - methyl-17-oxo-19-nor-androstane.ALSO:19-Nor-androstane compounds with a saturated or unsaturated bond between the C-atoms 4 and 5, which are not oxygenated in 3-position, having in 17-position either a hydrogen atom and a free or functionally converted hydroxy group or a lower aliphatic hydrocarbon radical and a free or functionally converted oxo group and which may in addition have a lower alkyl group in 1-position and/or a free or functionally converted hydroxyl or oxo group in 16-position are employed as an injection preparation by solution in a suitable solvent or for oral administration in the form of tablets, pills or coated tablets. For oral use a filling substance such as lactose, a disintegrating agent such as starch, a lubricant such as talc and magnesium stearate, taste correcting agents and dyes may be present. Steroid compounds of the above structure are D 4 - 17a - methyl - 17b - hydroxy - 19 - nor - androstene, 17a - ethyl - 17b - hydroxy - 19 - nor - androstene and 1 - methyl - 17 - hydroxy - 19-nor-androstene.