IP Library Granted Patent US 10,287,293
Granted Patent B2
US 10,287,293 · App. 15/736,202 · Granted May 14, 2019

Bicyclic heterocyclic compounds as PDE2 inhibitors

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Quick Facts
Patent No.
US 10,287,293
App. No.
15/736,202
Granted
May 14, 2019
Kind
B2
Abstract

The present invention is directed to dihydropyrazolopyrimidinone compounds of formulas (I) and (II) which are useful as therapeutic agents for the treatment of central nervous system disorders associated with phosphodiesterase 2 (PDE2). The present invention also relates to the use of such compounds for treating neurological and psychiatric disorders, such as schizophrenia, psychosis, Parkinson's disease, Parkinson's disease dementia (PDD), or Huntington's disease, and those associated with striatal hypofunction or basal ganglia dysfunction.

Claims (72)

1. A compound of structural formulas I and II:

or a pharmaceutically acceptable salt thereof, wherein:

R 1 represents hydrogen, or C 1-6 alkyl, said alkyl optionally substituted with 1 to 3 groups of R b ,

R 2 represents OR, NR 2 , C 1-6 alkyl, (CH 2 ) 1-4 OR, C 1-4 haloalkyl, C(O)C 6-10 aryl, —(CH 2 ) n C 6-10 aryl, (CH 2 ) n C 3-10 heterocyclyl or (CH 2 ) n C 3-10 cycloalkyl wherein when R 2 is a heterocyclyl it is attached to the pyrazolopyrimidinone or imidazotriazinone ring through a carbon atom, and wherein said alkyl, aryl, heterocyclyl and cycloalkyl are optionally substituted with 1 to 3 groups of R a

R 3 and R 3a independently represent hydrogen, C 1-6 alkyl, or C 3-6 cycloalkyl, said alkyl, and cycloalkyl, optionally substituted with 1 to 3 groups of R a ,

or R 3 and R 3a can combine with the carbon atom to which they are attached to form a C 3-6 cycloalkyl, or C 4-10 heterocycloalkyl, said alkyl, cycloalkyl, and heterocycloalkyl optionally substituted with 1 to 3 groups of R a ,

R represents hydrogen, or C 1-6 alkyl,

R a is selected from the group consisting of hydrogen, halo, CN, SCF 3 , SF 5 , C 1-6 alkyl, (CH 2 ) n OR, (CH 2 ) n C 1-4 haloalkyl, O—C 1-4 haloalkyl, C 3-6 cycloalkyl, said alkyl and cycloalkyl optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo;

R b is selected from the group consisting of halo, CN, C 1-6 alkyl, (CH 2 ) n OR, (CH 2 ) n C 1-4 haloalkyl, O—C 1-4 haloalkyl, and

n represents 0, 1, 2, 3, or 4.

2. The compound according to claim 1 or a pharmaceutically acceptable salt thereof wherein R 1 is C 1-6 alkyl, said alkyl optionally substituted with 1 to 3 groups of R b .

3. The compound according to claim 2 or a pharmaceutically acceptable salt thereof wherein the optionally substituted C 1-6 alkyl of R 1 is selected from the group consisting of CH 3 , CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH 2 CHF 2 , CH(CH 2 OH)CH 3 .

4. The compound according to claim 1 or a pharmaceutically acceptable salt thereof wherein R 2 is optionally substituted C 1-6 alkyl.

5. The compound according to claim 4 or a pharmaceutically acceptable salt thereof wherein R 2 is selected from the group consisting OR, and NR 2 , (CH 2 ) n CH 3 , CH(CH 3 ) 2 , and C(CH 3 ) 3 .

6. The compound according to claim 1 or a pharmaceutically acceptable salt thereof wherein R 3 and R 3a independently represent hydrogen or optionally substituted C 1-6 alkyl.

7. The compound according to claim 6 or a pharmaceutically acceptable salt thereof wherein R 3 and R 3a independently represent methyl, ethyl, propyl, isopropyl, butyl, CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH 2 CHF 2 , or CH(CH 2 OH)CH 3 .

8. The compound according to claim 1 or a pharmaceutically acceptable salt thereof wherein R a is selected from OH, halo, (CH 2 ) n CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , (CH 2 ) n OCH 3 , OCH(CH 3 ) 2 , CH 2 F, CHF 2 , (CH 2 ) n CF 3 , CF 2 CH 3 , OCHF 2 , OCF 3 , CF 2 CF 3 , cyclobutyl, cyclopropyl said groups optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo.

9. The compound according to claim 1 represented by structural formula Ia:

or a pharmaceutically acceptable salt thereof.

10. The compound according to claim 9 or a pharmaceutically acceptable salt thereof wherein R 1 is optionally substituted C 1-6 alkyl selected from the group consisting of CH 3 , CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH(CH 2 OH)CH 3 , and R a is selected from OH, halo, (CH 2 ) n CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , (CH 2 ) n OCH 3 , OCH(CH 3 ) 2 , CH 2 F, CHF 2 , (CH 2 ) n CF 3 , CF 2 CH 3 , OCHF 2 , OCF 3 , CF 2 CF 3 , cyclobutyl, cyclopropyl said groups optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo.

11. The compound according to claim 9 or a pharmaceutically acceptable salt thereof wherein R 2 is selected from the group consisting OR, NR 2 , (CH 2 ) n CH 3 , CH(CH 3 ) 2 , and C(CH 3 ) 3 .

12. The compound according to claim 1 or a pharmaceutically acceptable salt thereof wherein R 3 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH 2 CHF 2 , and CH(CH 2 OH)CH 3 .

13. The compound according to 9 or a pharmaceutically acceptable salt thereof wherein R 1 is optionally substituted C 1-6 alkyl selected from the group consisting of CH 3 , CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH(CH 2 OH)CH 3 , R 2 and R 3 are methyl, and R a is selected from OH, halo, (CH 2 ) n CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , (CH 2 ) n OCH 3 , OCH(CH 3 ) 2 , CH 2 F, CHF 2 , (CH 2 ) n CF 3 , CF 2 CH 3 , OCHF 2 , OCF 3 , CF 2 CF 3 , cyclobutyl, cyclopropyl said groups optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo.

14. The compound of claim 1 of formula II represented by structural formula IIa:

or a pharmaceutically acceptable salt thereof.

15. The compound according to claim 14 or a pharmaceutically acceptable salt thereof wherein R 1 is optionally substituted C 1-6 alkyl selected from the group consisting of CH 3 , CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH(CH 2 OH)CH 3 , and R a is selected from OH, halo, (CH 2 ) n CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , (CH 2 ) n OCH 3 , OCH(CH 3 ) 2 , CH 2 F, CHF 2 , (CH 2 ) n CF 3 , CF 2 CH 3 , OCHF 2 , OCF 3 , CF 2 CF 3 , cyclobutyl, cyclopropyl said groups optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo.

16. The compound according to claim 14 or a pharmaceutically acceptable salt thereof wherein R 2 is selected from the group consisting OR, NR 2 , (CH 2 ) n CH 3 , CH(CH 3 ) 2 , and C(CH 3 ) 3 .

17. The compound according to claim 14 or a pharmaceutically acceptable salt thereof wherein R 3 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH 2 CHF 2 , and CH(CH 2 OH)CH 3 .

18. The compound according to claim 14 or a pharmaceutically acceptable salt thereof wherein R 1 is optionally substituted C 1-6 alkyl selected from the group consisting of CH 3 , CH 2 OH, CH 2 CH 2 OH, CH 2 CN, CH 2 CF 3 , CH 2 CH 2 F, CH 2 CH 2 CF 3 , CH(CH 2 OH)CH 3 , R 2 and R 3 are methyl, and R a is selected from OH, halo, (CH 2 ) n CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , (CH 2 ) n OCH 3 , OCH(CH 3 ) 2 , CH 2 F, CHF 2 , (CH 2 ) n CF 3 , CF 2 CH 3 , OCHF 2 , OCF 3 , CF 2 CF 3 , cyclobutyl, cyclopropyl said groups optionally substituted with 1 to 3 groups of C 1-6 alkyl or halo.

19. The compound according to claim 1 wherein R 3 and R 3a combine with the carbon atom to which they are attached to form a C 3-6 cycloalkyl, or C 4-10 heterocycloalkyl, said alkyl, cycloalkyl, and heterocycloalkyl optionally substituted with 1 to 3 groups of R a .

20. A compound which is selected from the group consisting of:

(R)-5-Methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(5)-5-Methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(R)-1-(2-Hydroxyethyl)-5-methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(S)-1-(2-Hydroxyethyl)-5-methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(R)-3-(1-(4-(tert-Butyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(S)-3-(1-(4-(tert-Butyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-3-(1-(3-Fluoro-4-(trifluoromethyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(S)-3-(1-(3-Fluoro-4-(trifluoromethyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-3-(1-(2-Fluoro-3-(trifluoromethyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(S)-3-(1-(2-Fluoro-3-(trifluoromethyl)phenyl)ethyl)-1-(2-hydroxyethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-5-Methyl-1-(2,2,2-trifluoroethyl)-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(S)-5-Methyl-1-(2,2,2-trifluoroethyl)-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one

(R)-1-(2-Fluoroethyl)-5-methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(S)-1-(2-Fluoroethyl)-5-methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one

(R)-3-(1-(4-(tert-Butyl)phenyl)ethyl)-1-(2-fluoroethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(S)-3-(1-(4-(tert-Butyl)phenyl)ethyl)-1-(2-fluoroethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-3-(1-(3-Fluoro-4-(trifluoromethyl)phenyl)ethyl)-1-(2-fluoroethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(S)-3-(1-(3-Fluoro-4-(trifluoromethyl)phenyl)ethyl)-1-(2-fluoroethyl)-5-methyl-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-5-Methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1-(3,3,3-trifluoropropyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one,

(S)-5-Methyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1-(3,3,3-trifluoropropyl)-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one

1-((R)-1-Hydroxypropan-2-yl)-5-methyl-3-((S)-1-(4-(trifluoromethyl)phenyl)ethyl)-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

1-((S)-1-Hydroxypropan-2-yl)-5-methyl-3-((R)-1-(4-(trifluoromethyl)phenyl)ethyl)-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

1,5-Dimethyl-3-(1-(4-(trifluoromethyl)phenyl)ethyl)-1,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one,

(R)-2,5-Dimethyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-2,5-Dimethyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one

(R)-5-(Hydroxymethyl)-2-methyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-5-(Hydroxymethyl)-2-methyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one

(R)-7-(1-(2-fluoro-4-(trifluoromethyl)phenyl)ethyl)-5-(hydroxymethyl)-2-methylimidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-7-(1-(2-fluoro-4-(trifluoromethyl)phenyl)ethyl)-5-(hydroxymethyl)-2-methylimidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(R)-5-(hydroxymethyl)-2-methyl-7-(1-(4-(trifluoromethoxy)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-5-(hydroxymethyl)-2-methyl-7-(1-(4-(trifluoromethoxy)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(R)-7-(1-(3-fluoro-4-(trifluoromethyl)phenyl)ethyl)-5-(hydroxymethyl)-2-methylimidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-7-(1-(3-fluoro-4-(trifluoromethyl)phenyl)ethyl)-5-(hydroxymethyl)-2-methylimidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(R)-5-(hydroxymethyl)-2-methyl-7-(1-(4-(1-methylcyclopropyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(S)-5-(hydroxymethyl)-2-methyl-7-(1-(4-(1-methylcyclopropyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

2-(2-Methyl-4-oxo-7-(1-(4-(trifluoromethyl)phenyl)ethyl)-3,4-dihydroimidazo[5,1-f][1,2,4]triazin-5-yl)acetonitrile,

(R)-5-(2-hydroxyethyl)-2-methyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one,

(5)-5-(2-hydroxyethyl)-2-methyl-7-(1-(4-(trifluoromethyl)phenyl)ethyl)imidazo[5,1-f][1,2,4]triazin-4(3H)-one

or a pharmaceutically acceptable salt thereof.

21. A pharmaceutical composition which comprises a pharmaceutically acceptable carrier and a compound of claim 1 or a pharmaceutically acceptable salt thereof.

22. A method of treating a disorder selected from psychotic disorders, delusional disorders and drug induced psychosis; anxiety disorders, movement disorders, mood disorders, Alzheimer's disease, schizophrenia, migraines, Parkinson's disease, Parkinson's disease dementia (PDD), Huntingtons's disease, and neurodegenerative disorders comprising administering a compound of claim 1 or a pharmaceutically acceptable salt thereof.

Assignments (4)
MERGER Recorded Aug 8, 2022
From: MERCK SHARP & DOHME CORP.
To: MERCK SHARP & DOHME LLC
Reel/Frame 061102/0145 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2017
From: STACHEL, SHAWN J.; SINZ, CHRISTOPHER J.; CHEN, YILI; DWYER, MICHAEL P.; PAONE, DANIEL V.; WILSON, JONATHAN E.
To: MERCK SHARP & DOHME CORP.
Reel/Frame 044404/0686 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2017
From: XU, SHIMIN
To: PHARMARON BEIJING CO. LTD.
Reel/Frame 044404/0817 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 15, 2017
From: PHARMARON BEIJING CO., LTD.
To: MERCK SHARP & DOHME CORP.
Reel/Frame 044404/0975 →