Substituted peptidylamine calcium channel blockers

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

Patent

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Details

530334, 530343, A61K 3805, C07K 1600

Patent

active

061178411

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

The present invention relates to compounds that act to block calcium channels; methods of using the compounds to treat stroke, cerebral ischemia, pain, head trauma or epilepsy; and to pharmaceutical compositions that contain the compounds of the present invention.


BACKGROUND OF THE INVENTION

The entry of excessive amounts of calcium ions into neurons following an ischemic episode or other neuronal trauma has been well documented. Uncontrolled high concentrations of calcium in neurons initiates a cascade of biochemical events that disrupts normal cellular processes. Among these events are the activation of proteases and lipases, breakdown of neuronal membranes and the formation of free radicals, which may ultimately lead to cell death. Several types of calcium channels have been discovered and called the L, N, P, Q, R, and T types. Each type possesses distinct structural features, functional properties and cellular/subcellular distributions. Type selective calcium channel blockers have been identified. For example, SNX-111 has been shown to be a selective N-type calcium channel blocker and has demonstrated activity in a number of models of ischemia and pain (Bowersox S. S., et al., Drug News and Perspective, 1994:7:261-268 and references cited therein). The compounds of the present invention are calcium channel blockers that can block N-type calcium channels and can be used to treat stroke, pain, cerebral ischemia, head trauma, and epilepsy.


SUMMARY OF THE INVENTION

The present invention provides compounds having the Formula I ##STR2## wherein * denotes a first chiral center when R.sup.3 and R.sup.4 are different; C.sub.3 -C.sub.7 cycloalkyl, C.sub.3 -C.sub.6 heterocycloalkyl, C.sub.3 -C.sub.7 substituted C.sub.2 -C.sub.8 alkenyl, ##STR3## C.sub.2 -C.sub.8 substituted alkenyl, --CH.sub.2 --COC.sub.1 -C.sub.6 alkyl, --CH.sub.2 --COH, -substituted C.sub.3 -C.sub.7 heterocycle, or R.sup.1 and R.sup.2 may be taken together to form a 5- to 7-membered ring which may contain heteroatoms, provided that R.sup.1 and R.sup.2 are not both hydrogen; -C.sub.8 alkyl; --N(R.sup.3)(CH.sub.2).sub.n --, --(CH.sub.2).sub.n N(R.sup.3)--, --C.tbd.C--; -C.sub.7 cycloalkyl, substituted C.sub.3 -C.sub.7 cycloalkyl, or C.sub.1 -C.sub.8 alkyl; ##STR4## --NH(CH.sub.2).sub.n -heterocycloalkyl, --OC.sub.1 -C.sub.6 alkyl, ##STR5## --NH(CH.sub.2).sub.n heterocycle, --NH(CH.sub.2).sub.n substituted heterocycle; definitions of R.sup.3 and R.sup.5 above, R.sup.3 and R.sup.5 can together with the nitrogen atom form a ring having from 3 to 7 atoms; and prodrugs thereof.
In a preferred embodiment of the compound of Formula I, R.sup.1 is methyl.
In another preferred embodiment of the compounds of Formula I, R.sup.3, R.sup.5, and R.sup.6 are hydrogen.
In another preferred embodiment of the compounds of Formula I, ##STR6## or --O-tert-butyl.
In another preferred embodiment of the compounds of Formula I, ##STR7##
In another preferred embodiment of the compounds of Formula I, Z is phenyl.
In another preferred embodiment of the compounds of Formula I, R.sup.1 is methyl, R.sup.3, R.sup.5, and R.sup.6 are hydrogen, R.sup.4 is isobutyl, ##STR8## Y is --OCH.sub.2 --, and Z is phenyl.
In another preferred embodiment of the compounds of Formula I, R.sup.3 is hydrogen and R.sup.2 is C.sub.1 -C.sub.8 alkyl, substituted cyclohexyl, cyclohexyl, cyclohexenyl, --CH.sub.2 -phenyl, --CH.sub.2 -substituted phenyl, --CH.sub.2 -cyclohexyl, ##STR9## R.sup.2 and R.sup.3 taken together along with the nitrogen atom form a ring having the structure ##STR10##
In another preferred embodiment of the compounds of Formula I, R.sup.3 is isobutyl, and R.sup.4 is hydrogen.
In another preferred embodiment of the compounds of Formula I, R.sup.5 and R.sup.6 are hydrogen.
In another preferred embodiment of the compounds of Formula I, R.sup.2 is C.sub.1 -C.sub.8 alkyl, cyclohexyl, substituted cyclohexyl, --CH.sub.2 -phenyl, or --CH.sub.2 -substituted phenyl.
In another preferred embodiment of the compounds of Formula I, ##STR11## --O-tert-butyl, ##STR12##

REFERENCES:
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H.L.Slates et al.; "Degradation of alpha-methyl-3,4-dihydroxyphenylalanine", J.Org.Che. 29(6), 1424-9(1964);also cited as CA61:1933e, Jun. 1964.
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DeSarro, G.B., et al., "Anticonvulsant effects of some calcium entry blockers in DBA/2 mice," Br. J. Pharmacol., 1988, 93:247-256.
Valentino, K., et al., "A selective N-type calcium channel antagonist protects against neuronal loss after global cerebral ischemia," Proc. Natl. Acad. Sci. USA, Aug. 1993, vol. 90, pp. 7894-7897.
Chaplan, S.R., et al., "Role of Voltage-Dependent Calcium Channel Subtypes in Experimental Tactile Allodynia," The Journal of Pharmacology and Experimental Therapeutics, 1994, vol. 269, No. 3, 1117-1123.
Buchan, A.M., et al., "A Selective N-Type Ca2+-Channel Blocker Prevents CA1 Injury 24 h Following Severe Forebrain Ischemia and Reduces Infarction Following Focal Ischemia," Journal of Cerebral Blood Flow and Metabolism, 1994, 14:903-910.
Kwapiszewski, W. and Bialasiewicz, W., "Synthesis of .alpha.-Perhydroheterocyclicalkyl Acids," Acta Poloniae Pharmaceutica--Drug Research, 1994, vol. 51, No. 3, pp 227-229.
Malmberg, A.B. and Yaksh, T.L., "Voltage-Sensitive Calcium channels in Spinal Nociceptive Processing: Blockade of N- and P-type Channels Inhibits Formalin-induced Nociception," The Journal of Neuroscience, Aug. 1994, 14(B)L4882-4890.
IBID, "Effect of continuous intrathecal infusion of .omega.-conopeptides, N-type calcium-channel blockers, on behavior and antinociception in the formalin and hot-plate tests in rats," Pain, 1995, 60:83-90.
Takizawa, S., et al., "A Selective N-Type Calcium Channel Antagonist Reduces Extracellular Glutamate Release and Infarct Volume in Focal Cerebral Ischemia," Journal of Cerebral Blood Flow and Metabolism, 1995, 15:611-618.
Yenari, M.A., et al., "Time-course and treatment response with SNX-111, an N-type calcium channel blocker, in a rodent model of focal cerebral ischemia using diffusion-weighted MRI," Brain Research, 1996, 739:36-45.
Pringle, A.K., et al., "Selective N-Type Calcium Channel Antagonist Omega Conotoxin MVIIA Is Neuroprotective Against Hypoxic Neurodegeneration in Organotypic Hippocampal-Slice Cultures," Stroke, Nov. 1996, vol. 27, No. 11, 2124-2130.
Bowersox, S.S., et al., "Selective N-type Neuronal voltage-Sensitive Calcium Channel Blocker, SNX-111, Produces Spinal Antinociception in Rat Models of Acute, Persistent and Neuropathic Pain," The Journal of Pharmacology and Experimental Therapeutics, 1996, vol. 279, No. 3, 1243-1249.
Jackson, H.C. and Scheideler, M.A., "Behavioural and anticonvulsant effects of CA2+ channel toxins in DBA/2 mice," Psychopharmacology, 1996, 126:85-90.
Diaz, A. and Dickenson, A. H., "Blockade of spinal N- and P-type, but not L-type, calcium channels inhibits the excitability of rat dorsal horn neurones produced by subcutaneous formalin inflammation," Pain, 1997, 69:93-100.

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