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United States Patent (19) 11 Patent Number: 5,041,635 Narisada Et Al

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United States Patent (19) 11 Patent Number: 5,041,635 Narisada Et Al United States Patent (19) 11 Patent Number: 5,041,635 Narisada et al. (45) Date of Patent: "Aug. 20, 1991 (54) 5(2)-7-(ENDO-3-BENZENESUL Jul. 17, 1986 (JP) Japan .............................. 61-1692.57 FONAMIDOBICYCLO(2.2.1]HEPT-EXO-2- 51) Int. Cl. ............................................ C07C311/20 YL)-5-HEPTENOIC ACID, SODIUM SALT 52 U.S. C. .................................................... 562/427 75) Inventors: Masayuki Narisada, Osaka; Mitsuaki 58) Field of Search ......................................... 562/427 Ohtani, Nara, both of Japan 73) Assignee: Shionogi & Co., Ltd., Osaka, Japan (56) References Cited U.S. PATENT DOCUMENTS *) Notice: The portion of the term of this patent subsequent to Aug. 29, 2006 has been 4,861,913 8/1989 Narisada et al. ...................... 549/23 disclaimed. OTHER PUBLICATIONS (21) Appl. No.: 541,491 Irwin, et al., J.A.C.S., pp. 8476-84.82 (1976), 98. 22 Filed: Jun. 20, 1990 Narisada et al., J. Med, Chem., 31(1988), pp. 1847-1854. Primary Examiner-Joseph P. Brust Related U.S. Application Data Attorney, Agent, or Firn-Wenderoth, Lind & Ponack 60 Continuation-in-part of Ser. No. 327,778, Mar. 23, 1989, which is a division of Ser. No. 927,823, Nov. 5, 57 ABSTRACT 1986, Pat. No. 4,861,913. There is provided 5(Z)-7-(endo-3-benzenesul (30) Foreign Application Priority Data fonamidobicyclo[2.2.1]hept-exo-2-yl)-5-heptenoic acid, Nov. 18, 1985 (JP) Japan ................................ 60-25915.4 sodium salt which is useful as an antithrombotic, anti Feb, l3, 1986 JP Japan .................................. 61-301.30 vasoconstricting and anti-bronchoconstricting agent. May 19, 1986 JP Japan ................................ 6-115599 Jun. 3, 1986 JP Japan ................................ 6-12901 1 Claim, No Drawings 5,041,635 1. 2 5(2)-7-(ENDO-3-BENZENESULFONAMIDOBICY. (Ia) CLO(2.2.1]HEPT-EXO-2-YL)-5-HEPTENOIC ACID, X-COOR SODIUM SALT s6 2 3 NHSO-R This is a continuation-in-part of Ser. No. 07/327,778 4. filed Mar. 23, 1989 which is a Rule 60 divisional of Ser. When R3 is hydrogen; Y is methylene; No. 06/927,823 filed Nov. 5, 1986, now U.S. Pat. No. m is 0; and n is 2. 4,861,913. (Ib) 10 X-COOR1 BACKGROUND OF THE INVENTION 1. Field of the Invention GO NHSO-R The present invention relates to new compounds used When R3 is hydrogen; Y is oxygen; as medicines for improving symptoms caused by throm m is 0; and n is 2. boxane. Moreover, this invention relates to compounds 15 as represented by the general formula (I) and their salts, X-COOR (Ic) which are used as antithrombotic, anti-vasconstricting, and anti-bronchoconstricting drugs. O NHSO-R When R3 is hydrogen; Y is vinylene; (CH2) X-COOR (I) m is 0; and n is 1. Y X-COOR (Id) Rs (CH2)n NHSO-R 25 NHSO-R wherein R1 is hydrogen or lower alkyl; R2 is alkyl, (CICH3 substituted or unsubstituted aryl, aralkyl or heterocycle; When R3 is methyl; Y is dimethylmethylene; R3 is hydrogen or methyl; X is alkylene or alkenylene m is 0; and n is 2. 30 which may be substituted by a fluorine atom or atoms (e) and may contain an oxygen, sulfur and/or phenylene in X-COOR the chain; Y is straight or branched alkylene or alkeny lene, oxygen, or sulfur; n indicates 0 or l; and n indi (CI NHSO-R cates 0, 1 or 2, or its salt. 35 When R3 is hydrogen; Y is ethylene; In detail, the compounds of this invention can be m is 0; and n is 2. represented by the following general formulae. X-COOR (If-a) X-COOR (IA) 2 4. 3 NHSO-R NHSO-R2 When R3 is hydrogen; Y is methylene; m is l; and n is 0. R When n is 0; and n is 2. CH3 (f-b) 45 CH X-COOR X-COOR (IB) V NHSO-R2 NHSO-R When R3 is hydrogen; Y is dimethylmethylene; R3 SO n is ; and n is 0. When n is 0; and n is . (Ig-a) O X-COOR X (IC) 55 O NHSO-R When R3 is hydrogen; Y is oxygen; R3 NHSO-R m is 1; and n is 0. When m is 1 and n is 0. (Ig-b) (ID) X-COOR V NHSO-R Rs CC.NHSO-R When R3 is hydrogen; Y is sulfur; When n is i and n is 1. n is 1; and n is 0. wherein R, R2, R3, X and Y each is as defined above. 65 X-COOR (Ih) In more detail, the compounds of this invention can be represented by the following general formulae (Ia) to (Ih). (I NHSO-R 5,041,635 3 4. -continued APA (Venton D. L. et al., J. Med. Chem., 22, 824 When R3 is hydrogen; Y is dimethylmethylene; (1979), PTA2 Lefer A. M. et al., Proc. Natl. Acad. Sci. m is l; and n is 1. U.S.A., 76,2566, (1979), BM-13177 Lefer A. M. et al.,. Drugs of Today, 21, 283 (1985), SQ-29548 Ogletree et wherein R R2 and X each is as defined above. al., J. Pharmacol. Exp. Ther., 34, 435, (1985)), and the When thrombin acts on platelets, cyclooxygenase is compounds as disclosed in patent application No. activated. By activation of cyclooxygenase, thrombox 259154/1985. ane A2 is produced enzymatically in platelets, vessel wall, and various other cells, from arachidonic acid SUMMARY through prostaglandins G2 and H2. This product has 10 Bicyclic sulfonamide derivatives represented by the various potent physiologic or pathogenic actions. In formula: particular, the potent platelet agglutination action and the action constricting the smooth muscle of bronchi and of coronary, cerebral and pulmonary arteries, etc. (CH), X-COOR are considered to be the factors which relate to the 15 onset and progress of such circulatory and respiratory diseases as angina pectoris, myocardial infarction, cere y bral infarction, and bronchial asthma. Moreover, it is R (CH2).m. NHSO-R said that the strong action occurs even at a concentra tion of 10-10-10-11M. Therefore, increasing attention 20 wherein R1 is a hydrogen or lower alkyl; R2 is an alkyl, has been paid to the development of thromboxane A2 substituted or unsubstituted aryl, aralkyl or heterocycle; antagonists or inhibitors as anti-thrombotics, anti-vaso R3 is a hydrogen or methyl; X is an alkylene or alkeny constrictives or anti-bronchoconstrictives. Inhibitors, lene which may be substituted by a fluorine atom or however, have some problems: in view of the fact that atoms and may contain a oxygen, sulfur and/or pheny they influence on prostaglandins which bear various 25 lene in the chain; Y is straight or branched alkylene or important roles as well as thromboxane A2, and uncon alkenylene, oxygen, or sulfur; m indicates 0 or l; and in trollable thromboxane-like harmful effects are caused indicates 0, 1 or 2, or their salts are provided in this by accumulated substrates such as prostaglandins H2. invention. Said compounds are used as antithrombotic, So, development of antagonists has especially been anti-vasoconstricting, and anti-bronchoconstricting sought. drugs. The inventors succeeded in the synthesis of the bicy clic sulfonamide derivatives represented by the general DESCRIPTION OF THE PREFERRED formula (I), and found that these new compounds have EMBODIMENTS potent activity as thromboxane A2 receptor antagonists, The following definitions are given for various terms and are chemically and biochemically stable. The pres 35 used throughout this specification. ent invention was based on these findings. The term "lower alkyl' means a straight or branched 2. Description of the Prior Art alkyl of C1-C5, for example, methyl, ethyl, n-propyl, The general course of atherosclerosis, which is re isopropyl, butyl, pentyl and so forth. The term "alkyl' garded as the main risk factor of myocardial infarction means a straight or branched alkyl of C1-C10, for exam and cerebral infarct, begins in the arterial intima with ple, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, mucoid accumulation and fibroblast formation, progres pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, and sively followed by degeneration, lipid and cholesterol so forth. The term "aryl' includes aromatic ring radi deposition, and destruction and atheromasia of the in cals such as phenyl, naphthyl or the like polycyclic tina tissue, with gradual formation of high-degree and aromatic hydrocarbon groups. The term "aralkyl' localized hypertrophy in the intima. The atherosclerosis 45 means the above-mentioned alkyl substituted by the has long been regarded to be caused by thrombuse above-mentioned aryl at an optional position. The term formation and fibrin deposition, but recent discoveries "heterocycle' means nitrogen-, oxygen- and/or sulfur of thromboxane A2 (TXA2) by Samuelsson et al. and containing 5- or 6-membered one, e.g., furyl, thienyl, prostacyclin (PGI2) by Vane et al. have revealed an oxazolyl, pyridyl, pyrimidyl, benzimidoyl and the like. interaction between platelets and vessel wall. Platelets 50 The substituents on the aryl, aralkyl or heterocycle are said to play an important role in the onset and include lower alkyl (e.g., methyl, ethyl), lower alkoxy progress of atherosclerosis. Therefore, it is now recog (e.g., methoxy), nitro, hydroxy, carboxy, cyano, amino, nized that the use of antithrombotic drugs, particularly lower alkylamino (e.g., methylamino), lower dialkyl drugs which inhibit platelet agglutination, are effective amino (e.g., dimethylamino) whose two alkyl groups for the treatment of atherosclerotic diseases. 55 may be different from each other, alkanoylamino (e.g., In addition to the conventional antithrombotic drugs acetamide), halogens (e.g., chloro, fluoro) and so forth. such as heparin and coumarin compounds, certain types The term "alkanoyl' means those of C1-C3 such as of prostaglandins are known to have a potent platelet formyl, acetyl, propionyl and so forth.
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