Quinuclidine esters process and intermediate for their preparati

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

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546137, A61K 31435, C07D45362

Patent

active

055434193

DESCRIPTION:

BRIEF SUMMARY
This application is the national phase of PCT/EP92/02067 filed on Sep. 3, 1992.


BACKGROUND OF THE INVENTION

This invention relates to 3-quinuclidinyl esters specifically to certain 3-quinuclidinyl 3-hydroxymethyl 2-phenyl or thienyl alkanoates which are lung-selective antimuscarinic bronchodilators. Thus these compounds are particularly useful in the treatment of chronic obstructive airways disease (COAD) and asthma.
COAD is a term encompassing conditions which exhibit, to differing extents, several major progressively developing clinicopathological features, namely inflammatory swelling of airway walls, hypertrophy of submucosal glands, and hyperplasia of epithelial secretory cells leading to hypersecretion of viscous muscous which cannot be cleared effectively, progressive increase in irreversible bronchospasm and decrease in lung function, with respiratory impairment, increasing morbidity and, finally, death.
Thus COAD, and also asthma, are diseases of reduced lung function in which antimuscarinic bronchodilators are known to improve airway patency. However, existing agents are non-selective for smooth muscle muscarinic sites in lung and this reduces their effectiveness as bronchodilators and leads to unwanted side effects. Sub-types of muscarinic receptor are now known to exist in the airways (see P. J. Barnes, P. Minette and J. Maclagan, TIPS, 1988, 9, 412.); M1 receptors are present on sympathetic nerves and parasympathetic ganglia; M2 receptors on pulmonary cholinergic nerves (pre-junctional inhibitory receptors) and M3 receptors are located on smooth muscle (post-junctional receptors). The compounds of the present invention generally have bronchospasmolytic effects at doses which do not significantly affect other tissues such as brain, heart, gastro-intestinal tract, eye and salivary gland. Furthermore they generally show selectivity for the lung post-junctional M.sub.3 receptors as opposed to the pulmonary. pre-junctional M.sub.2 receptors and cardiac M.sub.2 receptors. Therapeutic action at some other smooth muscle sites may be envisaged. For example, the compounds are also likely to be useful in treating urinary incontinence.


SUMMARY OF THE INVENTION

The present invention provides a compound of formula (I): ##STR2## or a pharmaceutically acceptable salt thereof, wherein X is either (a) a phenyl group optionally substituted by 1 or 2 substituents each independently selected from halo, CF.sub.3, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy and hydroxy or (b) a thienyl group; ##STR3## where A and B are independently 0, 1 or 2, or (b) a group of formula (Yb) ##STR4## where D and E are independently 0 or 1, F is 0, 1, 2 or 3 and D+E+F=1, 2 or 3, R.sub.1 and R.sub.2 are joined together to form, with the carbon atom to which they are attached, a 3- to 6- membered carbocyclic ring, and or benzyl group optionally substituted by up to 3 substituents each independently selected from halo, CF.sub.3, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy and hydroxy.
"Halo" means F, Cl, Br or I. C.sub.3 and C.sub.4 alkyl and alkoxy groups may be straight or branched chain.
X is preferably an unsubstituted phenyl group. When Y is of formula (Ya) R.sub.1 and R.sub.2 are preferably H or, when A=1 and B=0, R.sub.1 and R.sub.2 are preferably independently H, methyl or ethyl. R.sub.3 is preferably a methyl group.
The compounds of formula (I) have two asymmetric centres, at the positions identified as 2 and 3' in formula (I) above. When R.sub.1 and R.sub.2 are different the compounds have a third asymmetric centre at the carbon atom to which R.sub.1, and R.sub.2 are attached, and when Z=1 there is a fourth asymmetric centre at the sulphur atom. All diastereoisomers whether separated or not are within the scope of the invention. The preferred compounds are however the 3R-quinuclidinyl esters. Also the preferred stereochemistry at the 2- position is S when the hydrocarbon moiety of Y adjacent the 2-position has at least two carbon atoms. Thus the preferred compounds are (2S,3'R) 3-quinuclidinyl esters and can be re

REFERENCES:
patent: 4843074 (1989-06-01), Rzeszotavski
Katekar G. F., Thomson R. M. (1972) Aust. J. Chem. 25, 647-53.
Patel S. K., Paterson I. (1983) Tetrahedron Lett. 24(12) 1315-1318.
Hassner A., Naidorf-Meir S. (1989) J. Org. Chem. 54, 4954-4957.

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