Prostaglandin E.sub.1 analogues

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

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514573, 560121, 562503, A61K 31557, C07C40500

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active

055831583

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/JP93/01510 filed Oct. 20, 1993.


TECHNICAL FIELD

The present invention relates to novel prosta-glandin E.sub.1 analogues.


BACKGROUND ART

Since prostaglandin (hereinafter referred to as PG) shows various important physiological actions in a trace amount, natural PG analgogues and a vast number of derivatives thereof have been studied on synthesis and biological activities, with attempts to apply these compounds to pharmaceuticals. In particular, PGE.sub.1 has characteristic actions such as platelet aggregation inhibition, blood pressure lowering and the like and is already inpractical use as a drug for ameliorating peripheral circulatory disturbance. Therefore, a large number of PGE.sub.1 analogues have been investigated. Hitherto known PGE.sub.1 anologues, however, have a drawback of quick metobolism in living body and consequent short term effect. Further, hitherto proposed PGE.sub.1 analogues induce diarrhea as a side effect when administered orally and accordingly have a problem in that they cannot be administered orally in a sufficiently high amount to obtain the satisfactory effects.
Meanwhile, 13,14-didehydro-PGE.sub.1 methyl ester and 6-hydroxy-13,14-didehydro-PGE.sub.1 are known as 13,14-didehydro-PGE.sub.1 analogues obtained by converting the double bond between the 13- and 14-positions of PGE.sub.1 to a triple bond [Japanese Patent Application Kokai (Laid-Open) No. 100446/1977 and U.S. Pat. No. 4,131,738].
The main object of the present invention is to provide novel PGE.sub.1 analogues which have a higher efficacy, a more prolonged action and a lower side effect then hitherto known PGE.sub.1 analogues.


Disclosure of the Invention

The present inventors made a study and found out that PGE.sub.1 analogues having a triple bond between the 13- and 14-positions, a branch the 17-position and on oxygen or sulfur atom at the 3-position in pace of methylene have excellent and prolonged physiological activities and a low side effect. The finding has led to the completion of the present invention.
Thus, the present invention provides a prosta-glandin E.sub.1 analogue represented by formula ##STR4## wherein R.sup.1 represents a hydrogen atom or a C.sub.1 -C.sub.6 alkyl group; and X is a oxygen atom and R.sup.2 represents ##STR5## or X is a sulfur atom and R.sup.2 represents ##STR6## and a salt thereof.
In the present invention, "alkyl group" is a straight-chain or branched-chain saturated aliphatic hydrocarbon group. The C.sub.1 -C.sub.6 alkyl group includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sea-butyl, tert-butyl, n-pentyl, isopentyl and n-hexyl groups, etc. Of these, C.sub.1 -C.sub.4 alkyl groups are preferable.
In the formula (I), R.sup.1 is preferably a hydrogen atom or a C.sub.1 -C.sub.4 alkyl group (a methyl group, in particular).
The compound of formula (T) wherein R.sup.1 represents a hydrogen atom, can be present in the form of a free acid, or in the form of a salt. Examples of such salt include alkali metal salts such as sodium salt, potassium salt and the alkaline earth metal salts such as calcium salt, magnesium salt and the like; other metal salts such as aluminum salt and the like; ammonium salt; salts with organic amines such as trialkylamine (e.g. triethylamine), pyridine and the like. A pharmaceutically acceptable salt is particularly preferable.
The present compound of formula (I) can be produced, for example, by a process summarized in the following reaction scheme A. ##STR7##
In the above reaction scheme, R.sup.11 represents C.sub.1 -C.sub.6 alkyl group; R.sup.3 and R.sup.4 which may be the same or different, each represent a protective group for hydroxyl group; and X and R.sup.2 have the same definitions as given above.
The protective group for hydroxyl group can be a protective group which is removable by on ordinary reaction for protective group removal, such as hydrolysis, hydrocracking and the like and which is ordinarily used in prostaglandin chemistry. It includes, for example, tert-butyldimethylsilyl, trieth

REFERENCES:
patent: 4029681 (1977-06-01), Smith
patent: 4131737 (1978-12-01), Floyd, Jr. et al.
patent: 4131738 (1978-12-01), Smith
patent: 5449815 (1995-09-01), Sato
J. Org. Chem., vol. 53, p. 5590 (1988) (p. 6 lines 19-20).
Tetrahedron Lett., vol. 30, p. 7083 (1989) (p. 6 line 36) (p. 7) (line 1).
Nature, vol. 194, p. 927 (1962) (p. 11, lines 31-32).
English Abstract for Japanese 5117230, (1991).

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