IP Library Granted Patent US 7,084,151
Granted Patent B2
US 7,084,151 · App. 10/684,227 · Granted Aug 1, 2006

5-(1',1'-cycloalkyl/alkenyl)methylidene 1,2-dihydro-

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Quick Facts
Patent No.
US 7,084,151
App. No.
10/684,227
Granted
Aug 1, 2006
Kind
B2
Abstract

The present invention is directed to compounds, pharmaceutical compositions, and methods for modulating processes mediated by Progesterone Receptor. Also provided are methods of making such compounds and pharmaceutical compositions.

Claims (100)

1. A compound of the formula:

wherein:

R 1 is selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 heteroalkyl, COR 5 , CO 2 R 5 , SO 2 R 5 , and CONR 5 R 6 ;

R 2 and R 3 each independently is selected from the group of hydrogen, C 1 –C 6 alkyl, and C 1 –C 6 haloalkyl; or

R 2 and R 3 taken together form a cycloalkyl ring of from three to twelve carbons;

R 4 is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, and C 1 –C 4 heteroalkyl;

R 5 and R 6 each is independently selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 heteroalkyl, and C 1 –C 4 haloalkyl;

R 7 through R 9 each independently is selected from the group of hydrogen, F, Cl, Br, I, NO 2 , CN, OR 5 , NR 5 R 6 , SR 5 , COR 5 , CO 2 R 5 , CONR 5 R 6 , C 1 –C 8 alkyl, C 1 –C 8 heteroalkyl, C 1 –C 8 haloalkyl, C 2 –C 8 alkenyl, C 2 –C 8 alkynyl;

R 10 through R 15 each independently is selected from the group of hydrogen, F, Cl, Br, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, and C 1 –C 4 heteroalkyl; or

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 ; or

R 10 and R 14 taken together form a bond, when Z is CR 14 R 15 ;

Y and Z each independently is selected from the group of O, S, NR 6 and CR 14 R 15 ; and

n is 0, 1, 2, or 3;

or a pharmaceutically acceptable salt thereof.

2. A compound of the formula:

wherein:

R 1 is selected from the group of hydrogen, C 1 –C 4 alkyl, COR 5 , CO 2 R 5 , and SO 2 R 5 ;

R 2 and R 3 each independently is selected from the group of C 1 –C 4 alkyl;

R 4 is selected from the group of hydrogen, F, Cl, Br, C 1 –C 4 alkyl, and C 1 –C4 haloalkyl;

R 5 and R 6 each is independently selected from the group of hydrogen, and C 1 –C 4 alkyl;

R 7 through R 9 each independently is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , C 1 –C 8 alkyl, C 1 –C 8 heteroalkyl, and C 1 –C 8 haloalkyl;

R 10 through R 15 each independently is selected from the group of hydrogen, F, Cl, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl; or

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 ; or

R 10 and R 14 taken together form a bond, when Z is CR 14 R 15 ;

Y and Z each independently is selected from the group of S, and CR 14 R 15 ; and

n is 0, 1, or 2;

or a pharmaceutically acceptable salt thereof.

3. A compound according to claim 2 , wherein

R 1 is hydrogen;

R 2 and R 3 is CH 3 ;

R 4 is selected from the group of F, Cl, Br, CH 3 , and CF 3 ;

R 7 is hydrogen or F;

R 8 is selected from the group of H, CH 3 , OH, and OCH 3 ;

R 9 is selected from the group of hydrogen, F, Cl, Br, CN, OCH 3 , CH 3 , and CF 3 ;

R 10 , R 11 , R 13 , R 15 each independently is selected from the group of hydrogen, F, Cl, CH 3 , and CF 3 ; and

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 .

4. compound according to claim 1 , wherein said compound is selected from the group of:

9-Fluoro-5-(1,3-dithia-2-cyclohexylidene)-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]quinoline (compound 10);

8-methoxy-5-(1,3-dithia-2-cyclohexylidene)-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]quinoline (compound 13);

7,9-difluoro-5-(1,3-dithia-2-cyclohexylidene)-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]quinoline (compound 15);

7-fluoro-5-(1,3-dithia-2-cyclohexylidene)-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]quinoline (compound 17);

7-fluoro-5-cyclohexylidene-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]quinoline (compound 19);

7,9-difluoro-5-cyclohexylidene-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]-quinoline (compound 20);

7-fluoro-5-(1,3-dithio-2-cyclohexylidene)-1,2-dihydro-2,2-dimethyl-5H-chromeno[3,4-f]quinoline (compound 21); and

7-fluoro-5-(2-cyclohexenylidene)-1,2-dihydro-2,2,4-trimethyl-5H-chromeno[3,4-f]-quinoline (compound 23).

5. A compound of the formula:

wherein:

R 2 and R 3 each independently is selected from the group of C 1 –C 4 alkyl, and C 1 –C 4 haloalkyl;

R 4 is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, and C 1 –C 4 heteroalkyl;

R 5 is selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 heteroalkyl, and C 1 –C 4 haloalkyl;

R 7 and R 9 each independently is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , NR 5 R 6 , SR 5 , COR 5 , C 1 –C 4 alkyl, C 1 –C 4 heteroalkyl, C 1 –C 4 haloalkyl, C 2 –C 4 alkenyl;

n is 0, 1, 2, or 3;

or a pharmaceutically acceptable salt thereof.

6. A compound of the formula:

wherein:

R 2 and R 3 are CH 3 ;

R 4 is selected from the group of F, Cl, Br, CH 3 , and CF 3 ;

R 5 is selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 heteroalkyl, and C 1 –C 4 haloalkyl;

R 7 is hydrogen or F;

R 9 selected from the group of hydrogen, F, Cl, Br, CN, OCH 3 , CH 3 , and CF 3 ;

n is 0, 1, 2 or 3;

or a pharmaceutically acceptable salt thereof.

7. A pharmaceutical composition comprising a pharmaceutically acceptable carrier and a compound of formula:

wherein:

R 1 is selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, C 1 –C 4 heteroalkyl, COR 5 , CO 2 R 5 , SO 2 R 5 , and CONR 5 R 6 ;

R 2 and R 3 each independently is selected from the group of hydrogen, C 1 –C 6 alkyl, and C 1 –C 6 haloalkyl; or

R 2 and R 3 taken together form a cycloalkyl ring of from three to twelve carbons;

R 4 is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, and C 1 –C 4 heteroalkyl;

R 5 and R 6 each is independently selected from the group of hydrogen, C 1 –C 4 alkyl, C 1 –C 4 heteroalkyl, and C 1 –C 4 haloalkyl;

R 7 through R 9 each independently is selected from the group of hydrogen, F, Cl, Br, I, NO 2 , CN, OR 5 , NR 5 R 6 , SR 5 , COR 5 , CO 2 R 5 , CONR 5 R 6 , C 1 –C 8 alkyl, C 1 –C 8 heteroalkyl, C 1 –C 8 haloalkyl, C 2 –C 8 alkenyl, C 2 –C 8 alkynyl;

R 10 through R 15 each independently is selected from the group of hydrogen, F, Cl, Br, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl, and C 1 –C 4 heteroalkyl; or

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 ; or

R 10 and R 14 taken together form a bond, when Z is CR 14 R 15 ;

Y and Z each independently is selected from the group of O, S, NR 6 and CR 14 R 15 ;

n is 0, 1, 2, or 3;

or a pharmaceutically acceptable salt thereof.

8. A pharmaceutical composition comprising a pharmaceutically acceptable carrier and a compound of formula:

wherein:

R 1 is selected from the group of hydrogen, C 1 –C 4 alkyl, COR 5 , CO 2 R 5 , and SO 2 R 5 ;

R 2 and R 3 each independently is selected from the group of C 1 –C 4 alkyl;

R 4 is selected from the group of hydrogen, F, Cl, Br, C 1 –C 4 alkyl, and C 1 –C 4 haloalkyl;

R 5 and R 6 each is independently selected from the group of hydrogen, and C 1 –C 4 alkyl;

R 7 through R 9 each independently is selected from the group of hydrogen, F, Cl, Br, CN, OR 5 , C 1 –C 8 alkyl, C 1 –C 8 heteroalkyl, and C 1 –C 8 haloalkyl;

R 10 through R 15 each independently is selected from the group of hydrogen, F, Cl, OR 5 , C 1 –C 4 alkyl, C 1 –C 4 haloalkyl; or

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 ; or

R 10 and R 14 taken together form a bond, when Z is CR 14 R 15 ;

Y and Z independently is selected from the group of S, and CR 14 R 15 ; and

n is 0, 1, or 2;

or a pharmaceutically acceptable salt thereof.

9. A pharmaceutical composition according to claim 8 , wherein

R 1 is hydrogen;

R 2 and R 3 is CH 3 ;

R 4 is selected from the group of F, Cl, Br, CH 3 , and CF 3 ;

R 7 is hydrogen or F;

R 8 is selected from the group of H, CH 3 , OH, and OCH 3 ;

R 9 selected from the group of hydrogen, F, Cl, Br, CN, OCH 3 , CH 3 , and CF 3 ;

R 10 , R 11 , R 13 , R 15 each independently is selected from the group of hydrogen, F, Cl, CH 3 , and CF 3 ; and

R 12 and R 14 taken together form a bond, when Y is CR 14 R 15 .

10. A compound according to claim 1 , wherein R 2 and R 3 each independently is selected from the group of hydrogen, C 1 –C 6 alkyl, and C 1 –C 6 haloalkyl.

11. A pharmaceutical composition according to claim 7 , wherein R 2 and R 3 each independently is selected from the group of hydrogen, C 1 –C 6 alkyl, and C 1 –C 6 haloalkyl.

Assignments (2)
SECURITY INTEREST Recorded Oct 18, 2023
From: CYDEX PHARMACEUTICALS, INC.; LIGAND PHARMACEUTICALS INCORPORATED; METABASIS THERAPEUTICS, INC.; PFENEX INC.
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 065271/0025 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 12, 2004
From: ZHI, LIN; VAN OEVEREN, CORNELIS ARJAN
To: LIGAND PHARMACEUTICALS INCORPORATED
Reel/Frame 015977/0220 →