Thiol derivatives with metallopeptidase inhibitory activity

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Ester doai

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560 10, 560 16, 560147, 560 9, 562426, 562489, 562490, 562556, 562564, 514506, 514562, C07C32732, C07C32360, A61K 3855, C07K 506

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058666044

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BRIEF SUMMARY
This application has been filed under 35 USC 371 as a national stage application of PCT/EP96/00251, filed Jan. 23, 1996, published as WO96/22998 Aug. 1, 1996.
The present invention relates to thiol derivatives with metallopeptidase inhibitory activity and, more particularly, it relates to mercaptoacylamino derivatives useful in the treatment of cardiovascular diseases.
The pharmacologic interest towards the study of metallopeptidase inhibitory molecules derives from the role that said enzymes exert on the level of the cardiocirculatory system.
It is well-known, in fact, that compounds with angiotensin converting enzyme (ACE) inhibitory activity are mainly useful in the treatment of hypertension and of heart failure in that they inhibit the formation of angiotensin II, a substance which increases the blood pressure.
Compounds with endothelin converting enzyme (ECE) inhibitory activity are useful as anti-vasoconstrictors in that they inhibit the formation of endothelin, a 21 amino acid peptide with vasoconstrictor activity.
Instead, compounds with inhibitory activity of the neutral endopeptidase enzyme (NEP), also called enkephalinase, are useful as vasodilators in that the NEP enzyme is responsible for the inactivation, not only of endogenous enkephaline, but also of atrial natriuretic factor (ANF), a hormone secreted by heart which increases the vasodilation and, on the renal level, increases diuresis and natriuresis.
Therefore, even exerting their action on the cardiovascular system with different mechanisms of action, the compounds with metallopeptidase inhibitory activity are generally used, alone or in combination, in the treatment of hypertension, renal failure, congestive heart failure and ischemic cardiopathologies.
Among the metallopeptidase inhibitors having a mercaptoacylamino structure. first time by Roques et al. in Nature, Vol. 288, pages 286-288, (1980), and Captopril (The Merck Index, Xl ed., No. 1773, page 267) are considered the parent compounds for NEP-inhibitors and ACE-inhibitors, respectively.
Other molecules with a mercaptoacylamino structure endowed with metallopeptidase inhibitory activity are described in the literature.
The U.S. Pat. No. 4,401,677 (E. R. Squibb & Sons, Inc.) describes mercaptoalkanoyl amino acids endowed with enkephalinase inhibitory activity.
The European patent application No. 0 566 157 (Schering Corporation) describes mercaptoalkanoyl amino acids endowed with neutral metalloendopeptidase inhibitory activity.
The European patent application No. 0 419 327 (Societe Civile Bioproject) describes amino acid derivatives endowed with enkephalinase and ACE inhibitory activity.
The European patent application No. 0 449 523 (E.R. Squibb & Sons, Inc.) describes mercapto or acylthio trifluoromethylamides with NEP-inhibitory activity. S.A.--Institut National de la Sante et de la Recherche Medicale (INSERM)! describes .beta.,.beta.-disubstituted .alpha.-mercaptomethylpropionylamides endowed with a mixed ACE/NEP inhibitory activity.
Among the compounds described in the patent application No. WO 93/08162, the compound known with the abbreviation RB 105 mixed ACE/NEP inhibitor for the treatment of cardiovascular diseases 4072-4076, (1994)!. The European patent application No. 0 524 553 describes acylmercaptoalkanoyldipeptides endowed with neutral endopeptidase and peptidyldipeptidase A inhibitory activity.
Now we have found mercaptoacylamino derivatives which are endowed with a remarkable inhibitory activity on the angiotensin converting enzyme as well as on the neutral endopeptidase enzyme (mixed or dual ACE/NEP inhibitory activity) which makes them particularly useful in the cardiovascular therapy.
Therefore, object of the present invention are the compounds of formula ##STR2## wherein
R is a mercapto group or a R.sub.5 COS group convertible in the organism to mercapto group;
R.sub.1 is a hydrogen atom, a straight or branched C.sub.1 -C.sub.6 alkyl group, an aryl or an arylalkyl group having from 1 to 6 carbon atoms in the straight alkyl moiety wherein the aryl is a phenyl, a

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