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US4690936A Expired / Lapsed US ⏱️ 0.0 years remaining

Anti-hypertensive agents

Assignee: University of Miami
•
Filing: 1980-05-02
•
Granted: 1987-09-01
•
Expires: 2000-05-02
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Abstract

Abstract Novel inhibitors of angiotensin converting enzyme having the general formula R--A--S--Z are disclosed as potent inhibitors of angiotensin converting enzyme and are useful anti-hypertensive agents.

Inventors

  • 👤 James W. Ryan
  • 👤 Alfred Chung

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 11:22
CPC Classifications
C; C07; C07D; C07D403/00; C07D403/02; C07D403/12; C07C; C07C327/00; C07D207/00; C07D207/02; C07D207/04; C07D207/10; C07D207/16; C07D207/18; C07D207/22; C07D207/46; C07D207/50; C07D211/00; C07D211/04; C07D211/06; C07D211/36; C07D211/60; C07D211/62; C07D211/68; C07D211/72; C07D211/74; C07D211/76; C07D211/80; C07D211/84; C07D211/86; C07D277/00; C07D277/02; C07D277/04; C07D277/06; C07D417/00; C07D417/02; C07D417/12; C07K; C07K5/00; C07K5/04; C07K5/06; C07K5/06086; C07K5/06139; C07K5/06173; C07K5/08; C07K5/0821; A; A61; A61K; A61K38/00

Claims Analysis

Total Claims: 55
Claim 1
Independent Claim 860 words
A new compound having the general formula R--A--S--Z wherein, R is hydrogen, formyl, acetyl, propanoyl, butanoyl, phenylacetyl, phenylpropanoyl, benzoyl, cyclopentanecarbonyl, tert-butyloxycarbonyl, cyclopentanecarbonyl-L-lysyl, pyro-L-glutamyl-L-lysyl, L-arginyl, L-lysyl or pyro-L-glutamyl; A is a divalent moiety derived from phenylglycine, β-benzyl aspartic acid, γ-benzyl glutamic acid, S-benzyl cysteine, O-benzyl aspartic acid, O-benzyl tyrosine, O-benzyl threonine, β-phenyl serine, thyronine, β-2-thienylserine, β-2-thienylalanine, α-methyl histidine, α-methyl tyrosine, α-methyl phenylalanine, α-methyl tryptophan, substituted tyrosine wherein the substituent is halo, nitro, methoxy or hydroxy, or substituted phenylaline wherein the substituent is selected from nitro, amino and methoxy or substituted tryptophan wherein the substituent is selected from methyl and methoxy, the α-amino group of which moiety is in amide linkage with R when R is acyl, and forms a primary amino group with R when R is H, and the carboxyl group of which moiety is in thioester linkage with S; S is a sulfur atom joined in thioester linkage to A; and Z is selected from the following: ##STR69## wherein, (i) R 1 and R 1 ' are each hydrogen or halogen, and R 2 and R 3 are each hydrogen, lower alkyl or trifluoromethyl provided that only one of R 2 and R 3 may be trifluoromethyl and further provided that at least one of R 1 , R 1 ', R 2 and R 3 must be halogen or trifluoromethyl (ii) R 23 is hydrogen or lower alkyl and (iii) m is 0 or 1; ##STR70## wherein (i) R 4 and R 5 are each hydrogen, lower alkyl or phenyl-lower alkylene (ii) N is 1, 2 or 3 (iii) R 6 is hydrogen or hydroxy or when n is 2, R 6 may also be halogen and (iv) m and R 23 are as stated in II. above; ##STR71## wherein (i) R 7 is hydrogen, lower alkanoyl or amino (imino)methyl; (ii) p is 0 or an integer of from 1 to 4; (iii) R 25 is hydrogen but when m is 1, p is 0, R 4 is hydrogen and R 7 is selected from hydrogen, lower alkyl and hydroxy lower alkylene; and R 9 is selected from hydrogen, lower alkyl, phenyl, phenyl-lower alkylene, hydroxy-lower alkylene, hydroxy-phenyl-lower alkylene, mercapto-lower alkylene, lower alkyl-thio-lower alkylene, imidazolyl-lower alkylene, indolyl-lower alkylene, carbamoyl-lower alkylene and carboxy-lower alkylene, but R 8 and R 9 may together constitute a (CH 2 ) v bridge wherein v is 3 or 4, thus forming a 5 or 6-membered ring with the N and C to which R 8 and R 9 are respectively attached and in such instance whcn v is 3 one hydrogen of (CH 2 ) v may be replaced by OH or halogen and when v is 4, one such hydrogen may be replaced by OH; (v) m and R 23 are each as defined in II. above; and (vi) R 4 is as defined in III. above, provided further, however, that m and p may not both be 0; ##STR72## wherein (i) R 10 is hydrogen or lower alkyl; (ii) R 11 is hydrogen, lower alkyl or lower alkanoyl (iii) X is 0 or S; (iv) m and R 23 are as stated in II. above, and (v) R 8 , R 9 and p are as stated in IV. above; ##STR73## wherein (i) R 12 is selected from carboxy, lower alkoxycarbonyl, carbamoyl, N-substituted carbamoyl and cyano; (ii) m and R 23 are as stated in II. above; and (iii) R 8 , R 9 and p are as stated in IV. above. ##STR74## wherein (i) R 13 is hydrogen, lower alkyl or phenyl-lower alkylene; (ii) R 14 is selected from hydrogen, lower alkyl, phenyl-lower alkylene, hydroxy-lower alkylene, amino-lower alkylene, guanidino-lower alkylene, imidazolyl-lower alkylene, indolyl-lower alkylene, mercapto-lower alkylene, lower alkyl-thio-lower alkylene, carbamoyl-lower alkylene and carboxy-lower alkylene; (iii) R 4 and R 5 are each as stated in III. above; and (iv) q is 0, 1 or 2; ##STR75## wherein (i) R 15 and R 16 are each hydrogen, lower alkyl, phenyl or phenyl-lower alkylene; (ii) r is 0, 1 or 2; (iii) s is 1, 2 or 3; (iv) R 17 is hydrogen, hydroxy or lower alkyl and when s is 2, R 17 may also be halogen; (v) R 24 is hydroxy, amino or lower alkoxy; ##STR76## wherein (i) R 18 is hydrogen or lower alkyl; (ii) R 19 and R 20 are each lower alkyl and may together constitute a (CH 2 ) w bridge wherein w is 4, to form a ring of 5-carbons with the carbon to which they are each attached; (iii) R 21 is hydrogen or lower alkyl and may constitute with R 19 a (CH 2 ) x bridge wherein x is 3, to form a five-membered ring with the N and C to which they are respectively attached; ##STR77## wherein (i) R 22 is hydrogen or lower alkyl; (ii) t is 0 or 1; and (iii) R 26 is selected from ##STR78## wherein u is 0 or 1 and R 23 is as defined for formula II., above; ##STR79## wherein (i) z is 2 or 3; (ii) R 10 is as stated in V. above; and (iii) R 23 is as stated in II. above.
Claim 2
Dependent Claim 860 words
A new compound having the general formula R--A--S--Z wherein, R is hydrogen, formyl, acetyl, propanoyl, butanoyl, phenylacetyl, phenylpropanoyl, benzoyl, cyclopentanecarbonyl, tert-butyloxycarbonyl, cyclopentanecarbonyl-L-lysyl, pyro-L-glutamyl-L-lysyl, L-arginyl, L-lysyl or pyro-L-glutamyl; A is a divalent moiety derived from phenylglycine, β-benzyl aspartic acid, γ-benzyl glutamic acid, S-benzyl cysteine, O-benzyl aspartic acid, O-benzyl tyrosine, O-benzyl threonine, β-phenyl serine, thyronine, β-2-thienylserine, β-2-thienylalanine, α-methyl histidine, α-methyl tyrosine, α-methyl phenylalanine, α-methyl tryptophan, substituted tyrosine wherein the substituent is halo, nitro, methoxy or hydroxy, or substituted phenylaline wherein the substituent is selected from nitro, amino and methoxy or substituted tryptophan wherein the substituent is selected from methyl and methoxy, the α-amino group of which moiety is in amide linkage with R when R is acyl, and forms a primary amino group with R when R is H, and the carboxyl group of which moiety is in thioester linkage with S; S is a sulfur atom joined in thioester linkage to A; and Z is selected from the following: ##STR69## wherein, (i) R 1 and R 1 ' are each hydrogen or halogen, and R 2 and R 3 are each hydrogen, lower alkyl or trifluoromethyl provided that only one of R 2 and R 3 may be trifluoromethyl and further provided that at least one of R 1 , R 1 ', R 2 and R 3 must be halogen or trifluoromethyl (ii) R 23 is hydrogen or lower alkyl and (iii) m is 0 or 1; ##STR70## wherein (i) R 4 and R 5 are each hydrogen, lower alkyl or phenyl-lower alkylene (ii) N is 1, 2 or 3 (iii) R 6 is hydrogen or hydroxy or when n is 2, R 6 may also be halogen and (iv) m and R 23 are as stated in II. above; ##STR71## wherein (i) R 7 is hydrogen, lower alkanoyl or amino (imino)methyl; (ii) p is 0 or an integer of from 1 to 4; (iii) R 25 is hydrogen but when m is 1, p is 0, R 4 is hydrogen and R 7 is selected from hydrogen, lower alkyl and hydroxy lower alkylene; and R 9 is selected from hydrogen, lower alkyl, phenyl, phenyl-lower alkylene, hydroxy-lower alkylene, hydroxy-phenyl-lower alkylene, mercapto-lower alkylene, lower alkyl-thio-lower alkylene, imidazolyl-lower alkylene, indolyl-lower alkylene, carbamoyl-lower alkylene and carboxy-lower alkylene, but R 8 and R 9 may together constitute a (CH 2 ) v bridge wherein v is 3 or 4, thus forming a 5 or 6-membered ring with the N and C to which R 8 and R 9 are respectively attached and in such instance whcn v is 3 one hydrogen of (CH 2 ) v may be replaced by OH or halogen and when v is 4, one such hydrogen may be replaced by OH; (v) m and R 23 are each as defined in II. above; and (vi) R 4 is as defined in III. above, provided further, however, that m and p may not both be 0; ##STR72## wherein (i) R 10 is hydrogen or lower alkyl; (ii) R 11 is hydrogen, lower alkyl or lower alkanoyl (iii) X is 0 or S; (iv) m and R 23 are as stated in II. above, and (v) R 8 , R 9 and p are as stated in IV. above; ##STR73## wherein (i) R 12 is selected from carboxy, lower alkoxycarbonyl, carbamoyl, N-substituted carbamoyl and cyano; (ii) m and R 23 are as stated in II. above; and (iii) R 8 , R 9 and p are as stated in IV. above. ##STR74## wherein (i) R 13 is hydrogen, lower alkyl or phenyl-lower alkylene; (ii) R 14 is selected from hydrogen, lower alkyl, phenyl-lower alkylene, hydroxy-lower alkylene, amino-lower alkylene, guanidino-lower alkylene, imidazolyl-lower alkylene, indolyl-lower alkylene, mercapto-lower alkylene, lower alkyl-thio-lower alkylene, carbamoyl-lower alkylene and carboxy-lower alkylene; (iii) R 4 and R 5 are each as stated in III. above; and (iv) q is 0, 1 or 2; ##STR75## wherein (i) R 15 and R 16 are each hydrogen, lower alkyl, phenyl or phenyl-lower alkylene; (ii) r is 0, 1 or 2; (iii) s is 1, 2 or 3; (iv) R 17 is hydrogen, hydroxy or lower alkyl and when s is 2, R 17 may also be halogen; (v) R 24 is hydroxy, amino or lower alkoxy; ##STR76## wherein (i) R 18 is hydrogen or lower alkyl; (ii) R 19 and R 20 are each lower alkyl and may together constitute a (CH 2 ) w bridge wherein w is 4, to form a ring of 5-carbons with the carbon to which they are each attached; (iii) R 21 is hydrogen or lower alkyl and may constitute with R 19 a (CH 2 ) x bridge wherein x is 3, to form a five-membered ring with the N and C to which they are respectively attached; ##STR77## wherein (i) R 22 is hydrogen or lower alkyl; (ii) t is 0 or 1; and (iii) R 26 is selected from ##STR78## wherein u is 0 or 1 and R 23 is as defined for formula II., above; ##STR79## wherein (i) z is 2 or 3; (ii) R 10 is as stated in V. above; and (iii) R 23 is as stated in II. above.
Claim 3
Dependent Claim 16 words
The compound of claim 1 wherein R is hydrogen, acetyl, benzoyl, cyclopentanecarbonyl, tert-butyloxycarbonyl, cyclopentanecarbonyl-L-lysyl or pyro-L-glutamyl.
Claim 4
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula II.
Claim 5
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula III.
Claim 6
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula IV.
Claim 7
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula V.
Claim 8
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula VI.
Claim 9
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula VII.
Claim 10
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula VIII.
Claim 11
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula IX.
Claim 12
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula X.
Claim 13
Dependent Claim 12 words
The compound of claim 1 wherein Z is defined by formula XI.
Claim 14
Dependent Claim 9 words
The compound of claim 4 wherein n is 2.
Claim 15
Dependent Claim 53 words
The compound of claim 5, 6 or 7 wherein R 8 and R 9 together form a --CH 2 CH 2 CH 2 -- bridge which completes a ring of 5 atoms with the nitrogen and carbon to which they are attached, one carbon optionally bearing a hydroxy group or a halogen group.
Claim 16
Dependent Claim 9 words
The compound of claim 9 wherein s is 2.
Claim 17
Dependent Claim 39 words
The compound of claim 10 wherein R 19 and R 21 together form a --CH 2 CH 2 CH 2 -- bridge which completes a ring of 5 atoms with the nitrogen and carbon to which they are attached.
Claim 18
Dependent Claim 10 words
The compound of claim 11 wherein R 26 is ##STR80##
Claim 19
Dependent Claim 9 words
The compound of claim 12 wherein z is 2.
Claim 20
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 1.
Claim 21
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 2.
Claim 22
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 3.
Claim 23
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 4.
Claim 24
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 5.
Claim 25
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 6.
Claim 26
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 7.
Claim 27
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 8.
Claim 28
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 9.
Claim 29
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 10.
Claim 30
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 11.
Claim 31
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 12.
Claim 32
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 13.
Claim 33
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 14.
Claim 34
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 15.
Claim 35
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 16.
Claim 36
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 17.
Claim 37
Dependent Claim 28 words
A method for inhibiting angiotensin converting enzyme in vivo which comprises administering to a mammal in need thereof a therapeutically effective dose of the compound of claim 18.
Claim 38
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 1.
Claim 39
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 2.
Claim 40
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 3.
Claim 41
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 4.
Claim 42
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 5.
Claim 43
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 6.
Claim 44
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 7.
Claim 45
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 8.
Claim 46
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 9.
Claim 47
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 10.
Claim 48
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 11.
Claim 49
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 12.
Claim 50
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 13.
Claim 51
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 14.
Claim 52
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 15.
Claim 53
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 16.
Claim 54
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 17.
Claim 55
Dependent Claim 29 words
A method for reducing in vivo the blood pressure of a mammal in the hypertensive state which comprises administering a therapeutically effective dose of the compound of claim 18.

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3.5 Years (Year 4) 1990-08-31 1991-03-02 1991-09-01 $2000.00 Window Closed / Lapsed
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