N-pyrazole A2A adenosine receptor agonists

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Carbohydrate doai

Reexamination Certificate

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C536S027300, C536S027600, C536S027610, C536S027620, C536S027630

Reexamination Certificate

active

06403567

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of Invention
This invention includes N-pyrazole substituted 2-adenosine compositions that are useful as A
2A
receptor agonists. The compositions of this invention are vasodialating agents that are useful as heart imaging aids that aid in the identification of mammals, and especially humans who are suffering from coronary disorders such poor coronary perfusion which is indicative of coronary artery disease (CAD). The compositions of this invention can also be used as therapeutics for coronary artery disease as well as any other disorders mediated by the A
2A
receptor.
2. Description of the Art
Pharmacological stress is frequently induced with adenosine or dipyridamole in patients with suspected CAD before imaging with T1 scintigraphy or echocardiography. Both drugs effect dilation of the coronary resistance vessels by activation of cell surface A
2
receptors. Although pharmacological stress was originally introduced as a mean of provoking coronary dilation in patients unable to exercise, several studies have shown that the prognostic value of
201
T1 or echocardiographic imaging in patients subjected to pharmacological stress with adenosine or dipyridamole was equivalent to patients subjected to traditional exercise stress tests. However, there is a high incidence of drug-related adverse side effects during pharmacological stress imaging with these drugs such as headache and nausea, that could be improved with new therapeutic agents.
Adenosine A
2B
and A3 receptors are involved in a mast cell degranulation and, therefore, asthmatics are not give the non-specific adenosine agonists to induce a pharmacological stress test. Additionally, adenosine stimulation of the A
1
receptor in the atrium and A-V mode will diminish the S-H interval which can induce AV block (N. C. Gupto et al.;
J. Am Coll. Cardiol
; (1992) 19: 248-257). Also, stimulation of the adenosine A
1
receptor by adenosine may be responsible for the nausea since the A
1
receptor is found in the intestinal tract (J. Nicholls et al.;
Eur. J. Pharm.
(1997) 338(2) 143-150).
Animal data suggests that specific adenosine A
2A
subtype receptors on coronary resistance vessels mediate the coronary dilatory responses to adenosine, whereas subtype A
2B
receptor stimulation relaxes peripheral vessels (note: the latter lowers systemic blood pressure). As a result there is a need for pharmaceutical compositions that are A
2A
receptor agonists that have no pharmacological effect as a result of stimulating the A
1
receptor in vivo. Furthermore, there is a need for A
2A
receptor agonists that have a short half-life, and that are well tolerated by patients undergoing pharmacological coronary stress evaluations.
SUMMARY OF THE INVENTION
In one aspect, this invention includes 2-adenosine N-pyrazole compositions that are useful A
2A
receptor agonists.
In another aspect, this invention includes pharmaceutical compositions including 2-adenosine N-pyrazole that are well tolerated with few side effects.
Still another aspect of this invention are N-pyrazole compositions that can be easily used in conjunction with radioactive imaging agents to facilitate coronary imaging.
In one embodiment, this invention includes 2-adenosine N-pyrazole compositions having the following formula:
In another embodiment, this invention includes methods for using compositions of this invention to stimulate coronary vasodilatation in mammals, and especially in humans, for stressing the heart induced steal situation for purposes of imaging the heart.
In still another embodiment, this invention is a pharmaceutical composition of matter comprising one or more compositions of this invention and one or more pharmaceutical excipients.
DESCRIPTION OF THE CURRENT EMBODIMENT
This invention includes a new class of 2-adenosine N-pyrazoles having the formula:
wherein R
1
=CH
2
OH, —CONR
5
R
6
;
R
3
is independently selected from the group consisting of C
1-15
alkyl, halo, NO
2
, CF
3
, CN, OR
20
, SR
20
, N(R
20
)
2
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, SO
2
NR
20
COR
22
, SO
2
NR
20
CO
2
R
22
, SO
2
NR
20
CON(R
20
)
2
, N(R
20
)
2
NR
20
COR
22
, NR
20
CO
2
R
22
, NR
20
CON(R
20
)
2
, NR
20
C(NR
20
)NHR
23
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, CONR
20
SO
2
R
22
, NR
20
SO
2
R
22
, SO
2
NR
20
CO
2
R
22
, OCONR
20
SO
2
R
22
, OC(O)R
20
, C(O)OCH
2
OC(O)R
20
, and OCON(R
20
)
2
,—CONR
7
R
8
, C
2-15
alkenyl, C
2-15
alkynyl, heterocyclyl, aryl, and heteroaryl, wherein the alkyl, alkenyl, alkynyl, aryl, heterocyclyl and heteroaryl substituents are optionally substituted with from 1 to 3 substituents independently selected from the group consisting of halo, alkyl, NO
2
, heterocyclyl, aryl, heteroaryl, CF
3
, CN, OR
20
, SR
20
, N(R
20
)
2
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, SO
2
NR
20
COR
22
, SO
2
NR
20
CO
2
R
22
, SO
2
NR
20
CON(R
20
)
2
, N(R
20
)
2
, NR
20
COR
22
, NR
20
CO
2
R
22
, NR
20
CON(R
20
)
2
, NR
20
C(NR
20
)NHR
23
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, CONR
20
SO
2
R
22
, NR
20
SO
2
R
22
, SO
2
NR
20
CO
2
R
22
, OCONR
20
SO
2
R
22
, OC(O)R
20
, C(O)OCH
2
OC(O)R
20
, and OCON(R
20
)
2
and wherein the optional substituted heteroaryl, aryl, and heterocyclyl substituents are optionally substituted with halo, NO
2
, alkyl, CF
3
, amino, mono- or di-alkylamino, alkyl or aryl or heteroaryl amide, NCOR
22
, NR
20
SO
2
R
22
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, NR
20
CON(R
20
)
2
, OC(O)R
20
, OC(O)N(R
20
)
2
, SR
20
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, CN, or OR
20
;
R
5
and R
6
are each individually selected from H, and C
1
-C
15
alkyl that is optionally substituted with from 1 to 2 substituents independently selected from the group of halo, NO
2
, heterocyclyl, aryl, heteroaryl, CF
3
, CN, OR
20
, SR
20
, N(R
20
)
2
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, SO
2
NR
20
COR
22
, SO
2
NR
20
CO
2
R
22
, SO
2
NR
20
CON(R
20
)
2
, N(R
20
)
2
, NR
20
COR
22
, NR
20
CO
2
R
22
, NR
20
CON(R
20
)
2
, NR
20
C(NR
20
)NHR
23
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, CONR
20
SO
2
R
22
, NR
20
SO
2
R
22
, SO
2
NR
20
CO
2
R
22
, OCONR
20
SO
2
R
22
, OC(O)R
20
, C(O)OCH
2
OC(O)R
20
, and OCON(R
20
)
2
wherein each optional substituted heteroaryl, aryl, and heterocyclyl substituent is optionally substituted with halo, NO
2
, alkyl, CF
3
, amino, monoalkylamino, dialkylamino, alkylamide, arylamide, heteroarylamide, NCOR
22
, NR
20
SO
2
R
22
, COR
20
, CO
2
R
20
, CON(R
20)
2
, NR
20
CON(R
20
)
2
, OC(O)R
20
, OC(O)N(R
20
)
2
, SR
20
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, CN, and OR
20
;
R
7
is selected from the group consisting of hydrogen, C
1-15
alkyl, C
2-15
alkenyl, C
2-15
alkynyl, heterocyclyl, aryl and heteroaryl, wherein the alkyl, alkenyl, alkynyl, aryl, heterocyclyl and heteroaryl substituents are optionally substituted with from 1 to 3 substituents independently selected from the group of halo, NO
2
, heterocyclyl, aryl, heteroaryl, CF
3
, CN, OR
20
, SR
20
, N(R
20
)
2
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, SO
2
NR
20
COR
22
, SO
2
NR
20
CO
2
R
22
, SO
2
NR
20
CON(R
20
)
2
, N(R
20
)
2
, NR
20
COR
22
, NR
20
CO
2
R
22
, NR
20
CON(R
20
)
2
, NR
20
C(NR
20
)NHR
23
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, CONR
20
SO
2
R
22
, NR
20
SO
2
R
22
, SO
2
NR
20
CO
2
R
22
, OCONR
20
SO
2
R
22
, OC(O)R
20
, C(O)OCH
2
OC(O)R
20
and OCON(R
20
)
2
and wherein each optional substituted heteroaryl, aryl and heterocyclyl substituent is optionally substituted with halo, NO
2
, alkyl, CF
3
, amino, mono- or di-alkylamino, alkyl or aryl or heteroaryl amide, NCOR
22
, NR
20
SO
2
R
22
, COR
20
, CO
2
R
20
, CON(R
20
)
2
, NR
20
CON(R
20
)
2
, OC(O)R
20
, OC(O)N(R
20
)
2
, SR
20
, S(O)R
22
, SO
2
R
22
, SO
2
N(R
20
)
2
, CN, and OR
20
;
R
8
is selected from the group consisting of hydrogen, C
1-15
alkyl, C
2-15
alkenyl, C
2-15
alkynyl, heterocyclyl, aryl, and heteroaryl, wherein the alkyl, alkenyl, alkynyl, aryl, heterocyclyl, and heteroaryl substituents are optionally substituted with from 1 to 3 substituents independently selected from the group consisting of halo, NO
2
, heterocyclyl, aryl, heteroaryl, CF

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