Thiophene-2-carboxylic acid derivatives

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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5483151, A61K 31415, C07D40912

Patent

active

053526929

DESCRIPTION:

BRIEF SUMMARY
The invention relates to novel therapeutically valuable derivatives of thiophene-2-carboxylic acid and to a process for the preparation thereof.
EP-A1-0 109 381 discloses a compound of formula (I') ##STR2## in which R in position 3 or 4 is hydrogen, methyl, chlorine or bromine and R.sup.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, having a potent inhibitory effect on thromboxane synthethase without a significant inhibition of the effect of the enzymes prostacycline synthetase or cyclooxygenase from microsomes of thrombocytes.
However, when orally administered, the compound of formula (I'), in which R.sup.1 is H, has only a low resorption.
Now it has been found that the 1-alkoxycarbonyloxyethyl esters of the compound of formula (I') have an improved resorption, when orally administered, since after passage through the intestinal tract they are present in the blood in form of the free carboxylic acid. Therefore, they are suitable prodrugs of the compound of formula (I').
Thereby, the compounds of the invention having the formula (I) given below have, when orally administered, a strong inhibitory effect on the thromboxane synthetase without a significant inhibition of the effect of the enzymes prostacycline synthetase or cyclooxygenase from microsomes of thrombocytes, i.e. these compounds inhibit the conversion of prostaglandin-H.sub.2 into thromboxane B.sub.2 via thromboxane A2, being an unstable intermediate product, from which it is known that it induces the irreversible aggregation of platelets and contracts smooth muscles, especially those of the blood vessels. This fact shows that the compounds of formula (I) inhibit the biosynthesis of thromboxane A.sub.2 and thus are suitable for the treatment of diseases caused by thromboxane A.sub.2 such as inflammatory disease, hypertension, thrombus, apoplexy, asthma, angina pectoris, ischemic heart disease, ischemic attacks, migraine and vascular complications of diabetes.
Thus, subject matter of the present invention are novel compounds of the general formula (I) ##STR3## in which R in position 3 or 4 is hydrogen, methyl, chlorine or bromine and R.sup.2 is C.sub.1 -C.sub.10 -alkyl, C.sub.3 -C.sub.7 -cycloalkyl or benzyl, and the pharmaceutically acceptable addition salts thereof with weak organic acids.
The resorption of the compounds of the invention, when orally administered, is at least three times the degree of the resorption of the compounds of EP-A1-0 109 381, when orally administered.
A further subject matter of the present invention is a process for preparing the novel compounds of formula (I), in which R and R.sup.2 are as defined above, comprising the reaction of a salt of a compound of formula (I") ##STR4## in which R is as defined above, with a compound of the general formula (II) ##STR5## in which X is a leaving group suitable for nucleophilic replacement, such as e.g. halogen, preferably chlorine or bromine, and R.sup.2 is as defined above, and the conversion of the obtained compound of formula (I) into an addition salt with a weak organic acid.
The reaction is carried out usually by addition of at least one equivalent of a strong base, such as e.g. an alkali hydride or alkali carbonate, to a solution of the starting compound in an anhydrous inert organic aprotic solvent, such as e.g. hexamethylphosphoric acid triamide, dimethylformamide or dimethylsulfoxide, and addition of the compound of formula (II), preferably in equivalent amounts or in a slight excess in the same solvent.
The reaction is carried out at a temperature in the range of room temperature to about 100.degree. C. Generally it is preferred to heat the reaction mixture, e.g. to 80.degree. C., so as to accelerate the reaction. Under these conditions the reaction is completed usually within 2.5 hours.
The reaction mixture is worked up in conventional manner, for instance by solvent extraction.
The compounds of formula (I) of the invention having a basic imidazole group can be converted into their pharmaceutically acceptable salts with weak organic acids in usual manner. Examples of suitabl

REFERENCES:
patent: 3795681 (1974-03-01), Ruschig et al.
Chemical Abstracts, vol. 103, 1985, 103:134809z.
Chemical Abstracts, vol. 104. 1986, 104: 14751y.
Chemical Abstracts, vol. 113, 1990, 113: 97353e.

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