Vitamin D derivatives with acyloxy groups in the side chains, process for their production, and the use for the production of pharmaceutical agents

Vitamin D derivatives of general formula I,

• 6
• in which
• R1 and R2 each mean a hydrogen atom or together an exocyclic methylene group,
• R3 and R4, independently of one another, mean a hydrogen atom, a fluorine or chlorine atom, an alkyl group with 1 to 4 carbon atoms, together a methylene group or together with quaternary carbon atom 20 a 3- to 7-membered, saturated or unsaturated carbocyclic ring,
• A means a group —C(X)—R5, —C(X)—NH—R5, —C(X)—N(R5)2, —P(O)—(OR5)2, —SO2—OR5,
• X stands for an oxygen atom or a sulfur atom,
• R5 means a straight-chain or branched, saturated or unsaturated alkyl chain with 1 to 10 carbon atoms, which optionally can be substituted by 1-3 hydroxy groups, a group COOR12, a group CONR10R11, a group P(O)(OR10)2, P(O)(NR10R11)2, SO3R10, S(O)2NR10R11, an N(R10R11) group, whereby
• R10 and R11, independently of one another, mean hydrogen or a straight-chain or branched, saturated or unsaturated alkyl chain with 1 to 10 carbon atoms, but R10 and R11 cannot simultaneously mean hydrogen,
• an aromatic or heteroaromatic radical with 5-12 carbon atoms, which optionally can be substituted with nitro groups, with optionally 1-2 substituted C1-C6 alkyl groups, trihaloalkyl groups or alkoxy groups or halogen atoms, or an optionally substituted phenyl radical, benzyl radical or a 2-, 3- or 4-pyridyl radical,
• Y1 and Y2, independently of one another, each mean a hydrogen atom or a group —C(O)R6, whereby
• R6 stands for an aromatic or heteroaromatic radical with 5 to 12 C atoms, or for an aliphatic, straight-chain or branched, saturated or unsaturated C1-C12 alkyl radical, which optionally is interrupted by 1-2 oxygen atoms, 1-2 sulfur atoms and/or 1-2 NH groups and/or optionally is substituted by 1-2 hydroxy groups, 1-2 amino groups, 1-2 SH groups, 1-2 COOH groups and/or 1-2 phenyl groups,
• Z means a straight-chain or branched, saturated or unsaturated 1-oxoalkyl group with 2 to up to 12 carbon atoms, a 1-oxo-(C3-C7)-cycloalkyl group, a benzoyl group, a 2-pyridylcarbonyl group, or a group CN, COOR7, COSR7, CONHR7, CONR7R8, whereby
• R7 and R8, independently of one another, stand for a hydrogen atom or a saturated or unsaturated alkyl group with 1 to 8 C atoms,
• a cycloalkyl group with 3 to 8 carbon atoms,
• a saturated or unsaturated alkyl group with 1 to 12 C atoms, which can have hydroxy or amino groups that are optionally substituted by A at any positions 1-3, halogen atoms or carboxylic acid esters or -amide units, and optionally is linked by a carbonyl group, a hydroxymethylene group or an ethenyldiyl unit (—CH═CH—, E— or Z-geometry) with carbon atom 25,
• or a carbocyclic or heterocyclic optionally aromatic or heteroaromatic ring with 5- or 6-ring members, or a condensed ring system that consists of a 5- and a 6-membered ring or two 6-membered rings, which can be substituted by one or more halogen atoms, one or more hydroxy groups, one or more COOR6 groups, 1-3 C1-C5 perfluoroalkyl groups, one or more C1-C5 alkyl groups, which in turn can be substituted by one or more halogen atoms, C1-C6 alkoxy groups and/or COOR9 groups and/or can be interrupted by oxa, thia or aza functions, sulfoxy or sulfone groups, whereby
• R9 stands for a C1-C6 alkyl group, a benzyl group or a phenyl group, as well as all possible epimers or diastereomers and mixtures thereof.