Benzene-condensed heterocyclic derivatives and their uses

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

Reexamination Certificate

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C514S419000, C548S491000, C548S503000, C548S509000, C548S510000

Reexamination Certificate

active

06323235

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a novel benzene-condensed heterocyclic derivative and to an antagonist against thromboxane A
2
(hereinafter referred to as “TXA
2
”) receptor, comprising the compound as an active ingredient.
BACKGROUND ART
TXA
2
discovered by Samuelsson et al. in 1975 has a strong platelet aggregation activity as well as vascular smooth muscle-contracting activity and bronchial smooth muscle-contracting activity (Proc. Natl. Acad. Sci. U.S.A., 72, 2994 (1975)). On the other hand, plastaglandin I
2
(PGI
2
) is known as a compound having activities opposite to the above-mentioned activities, that is, as a compound having a strong platelet aggregation inhibiting activity and vasodilation activity (Nature, 263, 663(1976)). Since these two compounds are synthesized from arachidonic acid in the body and since their activities are strong, it is said that the balance between TXA
2
and PGI
2
is important for keeping the homeostasis of circulatory system. Therefore, if this balance is inclined to the side of TXA
2
, activation of platelets and subsequent thrombus formation and vasoconstriction are caused, which is thought to be a cause of circulatory disorders including ischemic heart diseases such as angina pectoris and myocardial infarction, cerebrovascular diseases, renal disorders and the like. Further, since TXA
2
has a strong bronchial smooth muscle-contracting activity, it is thought that TXA
2
also has a relationship to bronchial asthma. Thus, inhibition of activities of TXA
2
is thought to be effective for therapies of circulatory disorders including ischemic heart diseases such as angina pectoris and myocardial infarction, cerebrovascular diseases and renal disorders, as well as bronchial asthma. So far, as the drugs to inhibit the activities of TXA
2
, a TXA
2
receptor antagonist (Circulation, 81, Suppl. I, I-69(1990); Medicinal Research Reviews, 11, 503(1991)), and an inhibitor of TXA
2
synthetase have been reported.
However, no drugs which sufficiently inhibit the activities of TXA
2
have been obtained yet.
DISCLOSURE OF THE INVENTION
Accordingly, an object of the present invention is to provide an excellent TXA
2
receptor antagonist.
The present inventors searched a TXA
2
receptor antagonist having a novel structure to discover benzene-condensed heterocyclic derivatives having strong TXA
2
receptor antagonist activities, thereby completing the present invention.
That is, the present invention provides a benzene-condensed heterocyclic derivative of the formula (I):
(wherein R
1
is —X—(CH
2
)
n
COOR (wherein X is —O—, —S— or —CH
2
—, R
3
is hydrogen, C
1
-C
5
lower alkyl, or an atom or group which gives a pharmaceutically acceptable salt, and n is an integer of 1 to 3);
R
2
is
i) —CR
4
═CR
5
—O—,
ii) —CR
5
═CR
4
—O—, or
iii) —NR
4
-CR
5
R
6
—CHR
7
— (wherein R
4
is —(CH
2
)
m
—Y—R
8
(wherein m is an integer of 1 to 4,
Y is
1) —O—,
2) —CH
2
—,
3) —S(O)
p
— (p is an integer of 0 to 2),
4) —CO—,
5) —CH(OH)—,
6) —NR
9
SO
2
—, (wherein R
9
is
a) hydrogen,
b) C
1
-C
5
alkyl,
c) phenyl (which may be substituted),
d) C
1
-C
5
alkyl substituted with phenyl (which may be substituted)
7) —NR
9
CO— (wherein R
9
represents the same meanings as described above)
8) —CONR
9
— (wherein R
9
represents the same meanings as described above)
9) —NR
9
— (wherein R
9
represents the same meanings as described above)
10) —O—N═CR
9
— (wherein R
9
represents the same meanings as described above), or
11) the group represented by the formula (II):
R
8
is
1) phenyl, thienyl, furyl, naphthyl or C
3
-C
8
cycloalkyl,
2) substituted phenyl, substituted thienyl, substituted furyl or substituted naphthyl,
3) C
1
-C
5
alkyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
4) C
2
-C
5
alkenyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
5) C
3
-C
5
alkynyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
6) C
2
-C
8
alkoxyalkyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
7) C
1
-C
5
hydroxyalkyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
8) C
2
-C
8
alkylthioalkyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy;
9) C
1
-C
5
aminoalkyl which is substituted with one or two substituents selected from the group consisting of phenyl (which may be substituted), thienyl (which may be substituted), furyl (which may be substituted), naphthyl (which may be substituted), C
3
-C
8
cycloalkyl and phenoxy; or
10) —CH
2
—C(O)—R
10
(wherein R
10
is phenyl (which may be substituted) or C
1
-C
5
alkyl substituted with one or two phenyl groups (which may be substituted);
R
5
is
1) hydrogen,
2) C
1
-C
5
alkyl,
3) C
1
-C
5
hydroxyalkyl or acetoxyalkyl,
4) C
1
-C
5
alkyl substituted with one or two phenyl groups (which may be substituted), or
5) C
2
-C
8
alkoxyalkyl substituted with one or two phenyl groups (which may be substituted);
R
6
and R
7
represent hydrogen or R
6
and R
7
are covalently bonded to represent a double bond)).
The present invention also provides an antagonist against TXA
2
receptor, comprising the above-described compound of the present invention as an active ingredient.
The compounds of the present invention have strong TXA
2
receptor antagonist activities and PGI
2
receptor agonist activities, so that they are effective for therapy and prevention of diseases related to TXA
2
.
BEST MODE FOR CARRYING OUT THE INVENTION
As mentioned above, the compound of the present invention is represented by the above-described formula (I).
Although the meanings of R
1
and R
2
in formula (I) are described above, the meanings will now be described in more detail. It should be noted that, in the present specification, the term “lower” in phrases such as “lower alkyl” means that the number of carbon atoms is 1 to 5, unless otherwise specified.
In cases where R
3
is a pharmaceutically acceptable cation, examples of the cation include metal cations, ammonium, amine cations and quaternary ammonium cations. Especially preferred metal cations are those derived from alkaline metals such as lithium, sodium and potassium, and those derived from alkaline earth metals such as magnesium and calcium. Needless to say, cations of, for example, aluminum, zinc and iron are also included in the present invention.
The pharmaceutically acceptable amine cations are those derived from primary, secondary or tertiary amines. Examples of the suitable amines include methylamine, dimethylamine, triethylamine, ethylamine, dibutylamine, triisopropylamine, N-methylhexylamine, decylamine, dodecylamine, allylamine, crotylamine, cyclopentylamine, dicyclohexylamine, benzylamine, dibenzylamine, &agr;-phenylethylamine, &bgr;-phenylethylamine, ethylenediamine, diethylenetriamine, and similar aliphatic, alicyclic and heterocyclic amines having up to 18 carbon atoms such as 1-methylpi

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