IP Library Granted Patent US 8,877,757
Granted Patent B2
US 8,877,757 · App. 13/222,072 · Granted Nov 4, 2014

Pyrazine derivatives and use as PI3K inhibitors

Inventors: Pascale Gaillard (Collonges sous Salève, FR); Anna Quattropani (Geneva, CH); Vincent Pomel (Groisy, FR); Thomas Rueckle (Geneva, CH); Jasna Klicic (Biberach, DE); Dennis Church (Commugny, CH)
Assignee: Merck Serono SA
C07D241/44C07D403/12C07D405/12C07D471/04C07D407/12C07D409/12C07D401/12C07D417/12C07D413/12
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Quick Facts
Patent No.
US 8,877,757
App. No.
13/222,072
Granted
Nov 4, 2014
Kind
B2
Abstract

The present invention is related to pyrazine derivatives of Formula (I) in particular for the treatment and/or prophylaxis of autoimmune disorders and/or inflammatory diseases, cardiovascular diseases, neurodegenerative diseases, bacterial or viral infections, kidney diseases, platelet aggregation, cancer, transplantation, graft rejection or lung injuries.

Claims (62)

1. A compound according to Formula (I),

wherein:

A is nitrogen and B, D and E are carbon; or A, B and E are carbon and D is nitrogen;

R l is H, halogen, nitro, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 2 is H, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 3 is H, halo, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted alkoxy, optionally substituted aryl or optionally substituted heteroaryl;

R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl C 1 -C 6 -alkyl, optionally substituted heteroaryl C 1 -C 6 -alkyl, optionally substituted C 3 -C 8 cycloalkyl optionally substituted C 1 -C 6 -alkyl, optionally substituted heterocycloalkyl C 1 -C 6 -alkyl, optionally substituted aryl C 2 -C 6 -alkenyl or optionally substituted heteroaryl C 2 -C 6 -alkenyl;

n is an integer selected from 0, 1, 2, 3 and 4;

an optionally substituted group is substituted with from 1 to 5 substituent's selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, cycloalkyl, heterocycloalkyl, C 1 -C 6 -alkyl aryl, C 1 -C 6 -alkyl heteroaryl, C 1 -C 6 -alkyl cycloalkyl, C 1 -Co-alkyl heterocycloalkyl, amino, ammonium, acyl, acyloxy, acylamino, aminocarbonyl, alkoxycarbonyl, ureido, aryl, carbamate, heteroaryl, sulfinyl, sulfonyl, alkoxy, sulfanyl, halogen, carboxy, trihalomethyl, cyano, hydroxy, mercapto and nitro;

with the first proviso that when R 4 is thiophenyl, it is not selected from the group consisting of: unsubstituted thiophenyl, unsubstituted chloro-5-thiophenyl and unsubstituted bromo-5thiophenyl; with the second proviso that when R 4 is a phenyl, it is a mono-substituted phenyl that is not selected from the group consisting of: p-bromo phenyl; p-methoxy phenyl; p- ethoxy phenyl; o-, m- or p-chloro phenyl; m- or p-methyl phenyl; o- or p-fluoro phenyl; o-CF3- phenyl; p- or m-nitro phenyl; p-NHAc-phenyl and p-amino phenyl; or it is a multi-substituted phenyl, that is not an unsubstituted bi-substituted phenyl selected from the group consisting of:

m-, p-dimethyl phenyl; m-, m-dimethyl phenyl; o-, p-dimethyl phenyl; o-, m-dimethyl phenyl; o-methyl p-fluoro phenyl; m-, m-dichloro phenyl; o-, m-dichloro phenyl; p-chloro m-nitro phenyl and o-ethoxy m-bromo phenyl;

with the final proviso that wherein R 4 is a 1,4 benzodioxin it is a substituted benzodioxin;

or an optically active form or a pharmaceutically acceptable salt thereof.

2. The compound according to claim 1 , wherein R 1 is H or halogen.

3. The compound according to claim 1 , wherein R 2 is methyl or substituted methyl.

4. The compound according to claim 1 , wherein R 3 is H, alkoxy or substituted alkoxy.

5. The compound according to claim 1 , wherein R 3 is halo, optionally substituted aryl or optionally substituted heteroaryl.

6. The compound according to claim 1 , wherein R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl C 1 -C 6 -alkyl or optionally substituted heteroaryl C 1 -C 6 -alkyl.

7. The compound according to claim 1 , wherein R 4 is optionally substituted aryl or optionally substituted heteroaryl.

8. The compound according to claim 1 , wherein R 1 is H or halogen; R 2 is substituted methyl; and R 3 is H or substituted alkoxy.

9. The compound according to claim 1 , wherein R 1 is H or halogen; R 2 is methyl; R 3 is H or alkoxy.

10. The compound according to claim 1 ,

wherein:

A, B and E are carbon and D is nitrogen;

R 1 is H, halogen, nitro, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 2 is H, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 3 is H, halo, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted alkoxy, optionally substituted aryl or optionally substituted heteroaryl;

R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl C 1 -C 6 -alkyl, optionally substituted heteroaryl C 1 -C 6 -alkyl, optionally substituted C 3 -C 8 cycloalkyl optionally substituted C 1 -C 6 -alkyl, optionally substituted heterocycloalkyl C 1 -C 6 -alkyl, optionally substituted aryl C 2 -C 6 -alkenyl or optionally substituted heteroaryl C 2 -C 6 -alkenyl;

n is an integer selected from 0, 1, 2, 3 and 4;

an optionally substituted group is substituted with from 1 to 5 substituents selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, cycloalkyl, heterocycloalkyl, C 1 -C 6 -alkyl aryl, C 1 -C 6 -alkyl heteroaryl, C 1 -C 6 -alkyl cycloalkyl, C 1 -C 6 -alkyl heterocycloalkyl, amino, ammonium, acyl, acyloxy, acylamino, aminocarbonyl, alkoxycarbonyl, ureido, aryl, carbamate, heteroaryl, sulfinyl, sulfonyl, alkoxy, sulfanyl, halogen, carboxy, trihalomethyl, cyano, hydroxy, mercapto and nitro;

with the first proviso that when R 4 is thiophenyl, it is not selected from the group consisting of: unsubstituted thiophenyl, unsubstituted chloro-5-thiophenyl and unsubstituted bromo-5-thiophenyl; with the second proviso that when R 4 is a phenyl, it is a mono-substituted phenyl that is not selected from the group consisting of: p-bromo phenyl; p-methoxy phenyl; p- ethoxy phenyl; o-, m- or p-chloro phenyl; m- or p-methyl phenyl; o- or p-fluoro phenyl; o-CF3- phenyl; p- or m-nitro phenyl; p-NHAc-phenyl and p-amino phenyl; or it is a multi-substituted phenyl, that is not an unsubstituted bi-substituted phenyl selected from the group consisting of: m-, p-dimethyl phenyl; m-, m-dimethyl phenyl; o-, p-dimethyl phenyl; o-, m-dimethyl phenyl; o-methyl p-fluoro phenyl; m-, m-dichloro phenyl; o-, m-dichloro phenyl; p-chloro m-nitro phenyl and o-ethoxy m-bromo phenyl;

with the final proviso that wherein R 4 is a 1,4 benzodioxin it is a substituted benzodioxin;

or an optically active form or a pharmaceutically acceptable salt thereof.

11. The compound according to claim 10 , wherein R 1 is H or halogen.

12. The compound according to claim 10 , wherein R 2 is methyl or substituted methyl.

13. The compound according to claim 10 , wherein R 3 is H, alkoxy or substituted alkoxy.

14. The compound according to claim 10 , wherein R 3 is halo, optionally substituted aryl or optionally substituted heteroaryl.

15. The compound according to claim 10 , wherein R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl C 1 -C 6 -alkyl or optionally substituted heteroaryl C 1 -C 6 -alkyl.

16. The compound according to claim 10 , wherein R 4 is optionally substituted aryl or optionally substituted heteroaryl.

17. The compound according to claim 10 , wherein R 1 is H or halogen; R 2 is substituted methyl; and R 3 is H or substituted alkoxy.

18. The compound according to claim 10 , wherein R 1 is H or halogen; R 2 is methyl; R 3 is H or alkoxy.

19. The compound according to claim 1 , wherein:

A is nitrogen and B, D and E are carbon;

R 1 is H, halogen, nitro, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 2 is H, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl or optionally substituted C 2 -C 6 -alkynyl;

R 3 is H, halo, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted alkoxy, optionally substituted aryl or optionally substituted heteroaryl;

R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl C 1 -C 6 -alkyl, optionally substituted heteroaryl C 1 -C 6 -alkyl, optionally substituted C 3 -C 8 cycloalkyl optionally substituted C 1 -C 6 -alkyl, optionally substituted heterocycloalkyl C 1 -C 6 -alkyl, optionally substituted aryl C 2 -C 6 -alkenyl or optionally substituted heteroaryl C 2 -C 6 -alkenyl;

n is an integer selected from 0, 1, 2, 3 and 4;

an optionally substituted group is substituted with from 1 to 5 substituents selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, cycloalkyl, heterocycloalkyl, C 1 -C 6 -alkyl aryl, C 1 -C 6 -alkyl heteroaryl, C 1 -C 6 -alkyl cycloalkyl, C 1 -C 6 -alkyl heterocycloalkyl, amino, ammonium, acyl, acyloxy, acylamino, aminocarbonyl, alkoxycarbonyl, ureido, aryl, carbamate, heteroaryl, sulfinyl, sulfonyl, alkoxy, sulfanyl, halogen, carboxy, trihalomethyl, cyano, hydroxy, mercapto and nitro;

with the first proviso that when R 4 is thiophenyl, it is not selected from the group consisting of: unsubstituted thiophenyl, unsubstituted chloro-5-thiophenyl and unsubstituted bromo-5-thiophenyl; with the second proviso that when R 4 is a phenyl, it is a mono-substituted phenyl that is not selected from the group consisting of: p-bromo phenyl; p-methoxy phenyl; p- ethoxy phenyl; o-, m- or p-chloro phenyl; m- or p-methyl phenyl; o- or p-fluoro phenyl; o-CF3- phenyl; p- or m-nitro phenyl; p-NHAc-phenyl and p-amino phenyl; or it is a multi-substituted phenyl, that is not an unsubstituted bi-substituted phenyl selected from the group consisting of:

m-, p-dimethyl phenyl; m-, m-dimethyl phenyl; o-, p-dimethyl phenyl; o-, m-dimethyl phenyl; o-methyl p-fluoro phenyl; m-, m-dichloro phenyl; o-, m-dichloro phenyl; p-chloro m-nitro phenyl and o-ethoxy m-bromo phenyl;

with the final proviso that wherein R 4 is a 1,4 benzodioxin it is a substituted benzodioxin;

or an optically active form or a pharmaceutically acceptable salt thereof.

20. The compound according to claim 19 , wherein R 1 is H or halogen.

21. The compound according to claim 19 , wherein R 2 is methyl or substituted methyl.

22. The compound according to claim 19 , wherein R 3 is H, alkoxy or substituted alkoxy.

23. The compound according to claim 19 , wherein R 3 is halo, optionally substituted aryl or optionally substituted heteroaryl.

24. The compound according to claim 19 , wherein R 4 is optionally substituted C 1 -C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkynyl, optionally substituted aryl C 1 -C 6 -alkyl or optionally substituted heteroaryl C 1 -C 6 -alkyl.

25. The compound according to claim 19 , wherein R 4 is optionally substituted aryl or optionally substituted heteroaryl.

26. The compound according to claim 19 , wherein R 1 is H or halogen; R 2 is substituted methyl; and R 3 is H or substituted alkoxy.

27. The compound according to claim 19 , wherein R 1 is H or halogen; R 2 is methyl; R 3 is H or alkoxy.

28. A pharmaceutical composition comprising a pharmaceutically acceptable carrier, diluent or excipient and the compound according to claim 1 .

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 1, 2011
From: GAILLARD, PASCALE; QUATTROPANI, ANNA; POMEL, VINCENT; RUECKLE, THOMAS; KLICIC, JASNA; CHURCH, DENNIS
To: LABORATOIRES SERONO S.A.
Reel/Frame 027003/0242 →
CHANGE OF NAME Recorded Oct 1, 2011
From: LABORATOIRES SERONO SA
To: MERCK SERONO SA
Reel/Frame 027003/0380 →
Priority Claims (1)
EP 05107838 · Aug 26, 2005 · regional
Continuity (3)
Division 12064284
Provisional Application 60711873 · Aug 26, 2005
Related Publication 20110312960A1 · Dec 22, 2011