GB1476300A - Substituted ferrocene compounds and processes for their production - Google Patents

Abstract

1476300 Ferrocene derivatives FISONS Ltd 12 Nov 1974 [21 Nov 1973 17 July 1974] 54002/73 and 31609/74 Heading C2J The invention comprises compounds of the general formula in which R is alkyl, Cl, Br, a thiophene ring, a ring, a furan ring, phenyl or alkyl. or halophenyl, one of X and Y is -CO-, -CHOH-, or -CH 2 - and the other is an exocyclic C-C bond and A is a C 5 -C 7 unsubstituted cyclic hydrocarbyl group which may be unsaturated at the C atom connected to X and, when saturated and when X is -CO-, may be substituted by -OH on the C atom to which Y is attached, X and Y being attached to adjacent C atoms on the A group. The compounds are prepared by the following processes: (a) when X is a direct bond, A is a cycloalkene group and Y is -CO- either by (1) reacting ferrocene with (usually in the presence of a Lewis acid such as AlCl 3 ) where n is 4, 5 or 6 and R<SP>1</SP> is -CN, -COOH or an acid halide or anhydride thereof and, when R<SP>1</SP> is -CN, hydrolysing the product, or (11) cyclizing and dehydrating under acidic conditions a ferrocene substituted by the group -CO(CH 2 ) n COR; (b) when X is -CO- and A is a saturated cyclic hydrocarbyl group substituted by an -OH group at the C atom to which Y (direct bond) is attached by cyclizing a ferrocene substituted by -CO(CH 2 ) n COR under basic conditions (e.g. ring NaH in dioxan or NaOH in ethanol); (c) when one of X and Y is -CHOH- or -CH 2 - by selective reduction of a compound of the invention obtained by process (a), (b) or (f), usually by using Pd on charcoal at 20-80‹ C. or by use of or a Clemmensen reduction; (d) when one of X and Y is -CO- by selective oxidation of a -CHOH- containing product of process (c), e.g. using CrO 3 .dipyridine complex; (e) when R is phenyl or halo- or alkylphenyl by reacting a ferrocene substituted by the group where R<SP>1</SP> and n are as defined under (a) (i) above with benzene or a halo- or alkylbenzene usually under Friedel-Crafts conditions; and (f) when X is -CO- and A is unsaturated by dehydrating a compound obtained by process (b) using similar conditions to that process but preferably lower reaction temperatures. The compounds have pharmacological properties and may be formulated into pharmaceutical compositions which may also include Vitamins B12 and C, folic acid, aspirin, an anthelmintic or an oral contraceptive.