BRPI0615631A2 - compound, pharmaceutical composition, and use of a pharmaceutical composition - Google Patents
compound, pharmaceutical composition, and use of a pharmaceutical composition Download PDFInfo
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- BRPI0615631A2 BRPI0615631A2 BRPI0615631-2A BRPI0615631A BRPI0615631A2 BR PI0615631 A2 BRPI0615631 A2 BR PI0615631A2 BR PI0615631 A BRPI0615631 A BR PI0615631A BR PI0615631 A2 BRPI0615631 A2 BR PI0615631A2
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- disorder
- alkyl
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- disorders
- amino
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/50—Three nitrogen atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
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- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
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Abstract
COMPOSTO, COMIPOSIçãO FARMACêUTICA, E, USO DE UMA COMPOSIçãO FARMACêUTICA A presente invenção refere-se aos derivados de pirimidina de fórmula geral 1ou seus sais e seu uso como abridores dos canais de íon potássio de família KNCQ, particularmente no tratamento de epilepsia.COMPOUND, PHARMACEUTICAL COMPOSITION, AND, USE OF A PHARMACEUTICAL COMPOSITION The present invention relates to the pyrimidine derivatives of the general formula 1 or their salts and their use as openers of the KNCQ family potassium ion channels, particularly in the treatment of epilepsy.
Description
"COMPOSTO, COMPOSIÇÃO FARMACÊUTICA, E, USO DE UMACOMPOSIÇÃO FARMACÊUTICA""COMPOUND, PHARMACEUTICAL COMPOSITION, AND, USE OF A PHARMACEUTICALPOSAL"
CAMPO DA INVENÇÃOFIELD OF INVENTION
A presente invenção refere-se aos compostos, que sãoabridores de canais de íon potássio de família KCNQ. Os compostos são úteisno tratamento de distúrbios e de doenças sendo responsivas à abertura decanais de íon potássio de família KCNQ, uma tal doença é epilepsia.The present invention relates to compounds which are KCNQ family potassium ion channel openers. The compounds are useful in the treatment of disorders and diseases being responsive to KCNQ family potassium ion channel opening, one such disease is epilepsy.
FUNDAMENTOS DA INVENÇÃOBACKGROUND OF THE INVENTION
Canais de íons são proteínas celulares que regulam o fluxo deíons, incluindo potássio, cálcio, cloreto e sódio para dentro e para fora dascélulas. Tais canais estão presentes em todas as células de animais e dehumanos e afetam uma variedade de processos incluindo transmissãoneuronal, contração muscular e secreção celular.Ion channels are cellular proteins that regulate the flow of ions, including potassium, calcium, chloride and sodium into and out of cells. Such channels are present in all animal and human cells and affect a variety of processes including neuronal transmission, muscle contraction and cell secretion.
Humanos possuem mais de 70 genes codificadores de subtiposde canal de potássio (Jentsch, Nature Reviews Neuroscience 2000, 1, 21-30)com uma diversidade grande com relação a ambas estrutura e função. Canaisde potássio neuronais, que são encontrados no cérebro, são primariamenteresponsáveis pela manutenção de um potencial de membrana em repousonegativo, bem como pelo controle de repolarização de membrana após umpotencial de ação.Humans have over 70 potassium channel subtype coding genes (Jentsch, Nature Reviews Neuroscience 2000, 1, 21-30) with a wide diversity with respect to both structure and function. Neuronal potassium channels, which are found in the brain, are primarily responsible for maintaining a membrane potential in negative home as well as controlling membrane repolarization after an action potential.
Um subconjunto de genes de canal de potássio é a famíliaKCNQ. Tem sido mostrado que mutações em quatro de cinco dos genesKCNQ são responsáveis por doenças incluindo arritmias cardíacas, surdez eepilepsia (Jentsch, Nature Reviews Neuroscience 2000, 1, 21-30).A subset of potassium channel genes is the KCNQ family. Mutations in four of five of the KCNQ genes have been shown to be responsible for diseases including cardiac arrhythmias, deafness and epilepsy (Jentsch, Nature Reviews Neuroscience 2000, 1, 21-30).
É considerado que o gene KCNQ4 codifica o correlatomolecular de um canal de potássio encontrado em células pilosas externas decóclea e em células pilosas de Tipo I do aparelho vestibular, nas quaismutações podem acarretar uma forma de surdez hereditária.It is considered that the KCNQ4 gene encodes the molecular correlate of a potassium channel found in decochlear external hair cells and vestibular Type I hair cells, in which mutations may lead to a form of hereditary deafness.
KCNQl (KvLQTl) é co-montado com o produto do geneKCNEl (proteína de canal de potássio K(+) mínima) no coração para formaruma corrente de K(+) semelhante a retificador retardado cardíaco. Mutaçõesneste canal podem causar uma forma de síndrome de QT longo de tipo 1(LQT1), bem como estão associadas com uma forma de surdez (Robbins,Pharmacol. Ther. 2001, 90, H9).KCNQ1 (KvLQTl) is co-assembled with the gene product KCNEl (minimal K (+) potassium channel protein) in the heart to form a K (+) current similar to a delayed cardiac rectifier. Mutations in this channel can cause a form of type 1 long QT syndrome (LQT1) as well as being associated with a form of deafness (Robbins, Pharmacol. Ther. 2001, 90, H9).
Os genes KCNQ2 e KCNQ3 foram descobertos em 1988 eparecem estar mutados em uma forma hereditária de epilepsia conhecidacomo convulsões neonatais familiares benignas (Rogawski, Trends inNeurosciences 2000, 23, 393-398). As proteínas codificadas pelos genesKCNQ2 e KCNQ3 estão localizadas nos neurônios piramidais do hipocampoe do córtex de humano, regiões do cérebro associadas com geração epropagação de convulsão. (Cooper et ai. Proeeedings National Aeademy ofScience USA 2000, 97, 4914-4919).The KCNQ2 and KCNQ3 genes were discovered in 1988 and appear to be mutated in a hereditary form of known epilepsy as benign familial neonatal seizures (Rogawski, Trends in Neurosciences 2000, 23, 393-398). The proteins encoded by the KCNQ2 and KCNQ3 genes are located in the hippocampal pyramidal neurons of the human cortex, brain regions associated with seizure generation and propagation. (Cooper et al. Proeeedings National Aeademy of Science USA 2000, 97, 4914-4919).
KCNQ2 e KCNQ3 são duas subunidades de canal de potássioque formam "correntes-M" quando expressadas in vitro. A corrente-M é umacorrente de potássio não-inativadora verificada em muitos tipos de célulaneuronal. Em cada tipo de célula ela é dominante no controle deexcitabilidade de membrana pelo fato de ser a única corrente mantida na faixade iniciação de potencial de ação (Marrion, Annual Review Physiology 1997,59, 483-5-04). Modulação da corrente-M tem efeitos dramáticos sobreexcitabilidade neuronal, por exemplo ativação de corrente reduzirá aexcitabilidade. Abridores destes canais KCNQ, ou ativadores da corrente-M,reduzirão a atividade neuronal excessiva e assim podem ser usados notratamento de convulsões e de outras doenças e distúrbios caracterizados poratividade neuronal excessiva, tal como hipersensibilidade neuronal incluindodistúrbios convulsivos, epilepsia e dor neuropática.KCNQ2 and KCNQ3 are two potassium channel subunits that form "M-currents" when expressed in vitro. M-current is a non-inactivating potassium current found in many types of celluluronal cells. In each cell type, it is dominant in controlling membrane excitation because it is the only current maintained at the initiation of action potential (Marrion, Annual Review Physiology 1997,59, 483-5-04). M-current modulation has dramatic effects on neuronal excitation, for example current activation will reduce excitation. Openers of these KCNQ channels, or M-current activators, will reduce excessive neuronal activity and thus may be used to treat seizures and other diseases and disorders characterized by excessive neuronal activity, such as neuronal hypersensitivity including seizure disorders, epilepsy and neuropathic pain.
Retigabina (D-23129; etil-éster de ácido N-(2-amino-4-(4-fluoro-benzil-amino)-fenil)-carbâmico) e seus análogos são descritos emEP554543. Retigabina é um composto anti-convulsivo com um amploespectro e propriedades anticonvulsivas potentes, tanto in vitro quanto invivo. É ativa após administração oral e intraperitoneal em ratos ecamundongos em uma variedade de testes anticonvulsivos incluindo:convulsões eletricamente induzidas; convulsões induzidas quimicamente porpentileno-tetrazol, picrotoxina e N-metil-D-aspartato (NMDA) e em ummodelo animal genético, o camundongo DBA/2 (Rostock et al. EpilepsyResearch 1996, 23, 211-223). Em adição, retigabina é ativa no modelo deignição de amídala de convulsões parciais complexas, adicionalmenteindicando que este composto possui potencial para terapia anticonvulsiva. Emtestes clínicos, tem sido recentemente mostrado que retigabina é eficaz naredução da incidência de convulsões em pacientes epilépticos (Bialer et al.Epilepsy Research 2002, 51, 31-71).Retigabine (D-23129; N- (2-Amino-4- (4-fluoro-benzyl-amino) -phenyl) -carbamic acid ethyl ester) and analogues thereof are described in EP554543. Retigabine is an anticonvulsant compound with a broad spectrum and potent anticonvulsant properties, both in vitro and in vitro. It is active following oral and intraperitoneal administration in mice and rats in a variety of anticonvulsant tests including: electrically induced seizures; chemically induced seizures by pententylene tetrazole, picrotoxin and N-methyl-D-aspartate (NMDA) and in a genetic animal model, the DBA / 2 mouse (Rostock et al. Epilepsy Research 1996, 23, 211-223). In addition, retigabine is active in the amygdeal deignition model of complex partial seizures, further indicating that this compound has potential for anticonvulsive therapy. In clinical trials, retigabine has recently been shown to be effective in reducing the incidence of seizures in epileptic patients (Bialer et al. Epilepsy Research 2002, 51, 31-71).
Tem sido mostrado que retigabina ativa uma corrente K(+) emcélulas neuronais e a farmacologia desta corrente induzida exibe concordânciacom a farmacologia publicada do canal-M, que recentemente foicorrelacionado com heteromultímero de canal KCNQ2/3 K(+). Isto sugereque a ativação de canais KCNQ2/3 pode ser responsável por alguma atividadeanticonvulsiva deste agente (Wickenden et al. Molecular Pharmacology2000, 58, 591-600) e que outros agentes funcionando pelo mesmo mecanismopodem ter usos similares.Retigabine has been shown to activate a K (+) current in neuronal cells and the pharmacology of this induced current exhibits agreement with the published M-channel pharmacology, which has recently been correlated with KCNQ2 / 3 K (+) channel heteromultimer. This suggests that KCNQ2 / 3 channel activation may be responsible for some anticonvulsant activity of this agent (Wickenden et al. Molecular Pharmacology2000, 58, 591-600) and that other agents functioning by the same mechanism may have similar uses.
Também tem sido relatado que canais KCNQ 2 e 3 são supra-regulados em modelos de dor neuropática (Wickenden et al. Society forNeuroscience Abstracts 2002,454.7), e tem sido concluído por hipótese quesão ativos tanto em dor neuropática quanto em epilepsia (Schroder et al.Neuropharmacology 2001, 40, 888-898).KCNQ channels 2 and 3 have also been reported to be up-regulated in neuropathic pain models (Wickenden et al. Society forNeuroscience Abstracts 2002,454.7), and have been hypothesized to be active in both neuropathic pain and epilepsy (Schroder et al. al. Neuropharmacology 2001, 40, 888-898).
Também tem sido mostrado que retigabina é benéfica emmodelos animais de dor neuropática (Blackburn-Munro e Jensen, EuropeanJournal of Pharmacology 2003, 460, 109-116), e assim é sugerido que osabridores de canais KCNQ serão usados no tratamento de distúrbios de dorneuropática.Retigabine has also been shown to be beneficial in animal models of neuropathic pain (Blackburn-Munro and Jensen, European Journal of Pharmacology 2003, 460, 109-116), and thus it is suggested that KCNQ channel openers will be used in the treatment of dorneuropathic disorders.
A localização de mRNA de canal KCNQ é relatada no cérebroe em outras áreas do sistema nervoso central associadas com dor (Goldstein etal. Society for Neuroscienee Abstracts 2003, 53.8).Localization of KCNQ channel mRNA is reported in the brain and in other areas of the central nervous system associated with pain (Goldstein et al. Society for Neuroscienee Abstracts 2003, 53.8).
Em adição a um papel em dor neuropática, a expressão demRNA para KCNQ 2-5 nos gânglios de raiz dorsal e trigeminal e no núcleocaudado trigeminal implica que os abridores destes canais também podemafetar o processamento sensorial de dor de enxaqueca (Goldstein et ai. Soeietyfor Neuroscience Abstraets 2003, 53.8).In addition to a role in neuropathic pain, the demRNA expression for KCNQ 2-5 in the dorsal and trigeminal root ganglia and trigeminal nucleus implies that the openers of these channels can also affect sensory processing of migraine pain (Goldstein et al. Soeietyfor Neuroscience Abstraets 2003, 53.8).
Relatórios recentes demonstram que mRNA para KCNQ 3 e 5,em adição àquele para KCNQ2, são expressados em astrócitos e células gliais.Assim os canais KCNQ 2, 3 e 5 podem ajudar a modular a atividade sinápticano CNS e contribuem para os efeitos neuroprotetores de abridores de canalKCNQ (Voda et al., Soeiety for Neuroscienee Abstraets 2003, 53.9).Recent reports demonstrate that mRNA for KCNQ 3 and 5, in addition to that for KCNQ2, are expressed in astrocytes and glial cells. Thus KCNQ channels 2, 3 and 5 can help modulate CNS synaptic activity and contribute to the neuroprotective effects of openers. of channel KCNQ (Voda et al., Soeiety for Neuroscience and Abstracts 2003, 53.9).
Retigabina e outros moduladores de KCNQ assim podemexibir proteção contra os aspectos neurodegenerativos de epilepsia, porquetem sido mostrado que retigabina previne neurodegeneração límbica e aexpressão de marcadores de apoptose após estado epiléptico induzido porácido caínico no rato (Ebert et al. Epilepsia 2002,43 Suppl 5, 86-95). Istopode ter relevância para prevenir a progressão de epilepsia em pacientes, i.e.ser antiepileptogênico. Também tem sido mostrado que retigabina retarda aprogressão de ignição hipocampal no rato, um outro modelo dedesenvolvimento de epilepsia (Tober et al. European Journal ofPharmaeology 1996, 303, 163-169).Retigabine and other KCNQ modulators may thus exhibit protection against neurodegenerative aspects of epilepsy, because retigabine has been shown to prevent limbic neurodegeneration and apoptosis marker expression following rat-induced kapic acid-induced epileptic status (Ebert et al. Epilepsy 2002,43 Suppl 5 86-95). This may have relevance in preventing the progression of epilepsy in patients, i.e. being antiepileptogenic. Retigabine has also been shown to retard the progression of hippocampal ignition in the rat, another developmental model of epilepsy (Tober et al. European Journal of Pharmaeology 1996, 303, 163-169).
Assim é sugerido que estas propriedades de retigabina e deoutros moduladores de KCNQ podem prevenir dano neuronal induzido porativação neuronal excessiva, e tais compostos podem ser usados notratamento de doenças neurodegenerativas, e serem modificadoras de doença(ou antiepileptogênicas) em pacientes com epilepsia.Dado que compostos anticonvulsivos tais comobenzodiazepinas e clormetiazol são clinicamente usados no tratamento desíndrome de abstinência de etanol e que outros compostos anticonvulsivose.g. gabapentina são muito efetivos em modelos animais desta síndrome(Watson et al. Neuropharmacology 1997, 36, 1369-1375), outros compostosanticonvulsivos tais como abridores de KCNQ e é assim esperado que sãoefetivos nesta condição.Thus it is suggested that these properties of retigabine and other KCNQ modulators may prevent neuronal damage induced by excessive neuronal activation, and such compounds may be used to treat neurodegenerative diseases, and be disease modifying (or antiepileptogenic) in patients with epilepsy. Anticonvulsants such as benzodiazepines and chlormetiazole are clinically used in the treatment of ethanol withdrawal syndrome and that other anticonvulsivose compounds.g. gabapentin are very effective in animal models of this syndrome (Watson et al. Neuropharmacology 1997, 36, 1369-1375), other anticonvulsant compounds such as KCNQ openers and are thus expected to be effective in this condition.
mRNA para subunidades KCNQ 2 e 3 são encontrados emregiões do cérebro associadas com ansiedade e comportamentos emocionaistais como distúrbio bipolar e.g. hipocampo e amídala (Saganich et al. Journalof Neuroscience 2001, 21, 4609-4624), e retigabina é relatadamente ativa emalguns modelos animais de comportamento semelhante à ansiedade (Hartz etal. Journal of Psychopharmacology 2003, 17 suppl. 3, A28,B16), e outroscompostos anticonvulsivos clinicamente usados no tratamento de distúrbiobipolar. Assim, abridores de KCNQ podem ser úteis para o tratamento deansiedade e de distúrbio bipolar.mRNA for KCNQ 2 and 3 subunits are found in brain regions associated with anxiety and emotional behaviors such as bipolar disorder and hippocampus and amygdala (Saganich et al. Journalof Neuroscience 2001, 21, 4609-4624), and retigabine is reportedly active in some animal models. anxiety-like behavior (Hartz et al. Journal of Psychopharmacology 2003, 17 suppl. 3, A28, B16), and other anticonvulsant compounds clinically used to treat bipolar disorder. Thus, KCNQ openers may be useful for the treatment of anxiety and bipolar disorder.
WO 200196540 descreve o uso de moduladores de corrente-Mformada pela expressão de genes KCNQ2 e KCNQ3 para insônia, enquantoque WO 2001092526 descreve que moduladores de KCNQ5 podem serutilizados para o tratamento de distúrbios de sono.WO 200196540 describes the use of M-stream modulators by expressing KCNQ2 and KCNQ3 genes for insomnia, whereas WO 2001092526 describes that KCNQ5 modulators may be used for the treatment of sleep disorders.
WO01/022953 descreve o uso de retigabina para profilaxia etratamento de dor neuropática tais como alodínia, dor hiperalgésica, dorfantasma, dor neuropática relacionada com neuropatia diabética e dorneuropática relacionada com enxaqueca.WO01 / 022953 describes the use of retigabine for prophylaxis and treatment of neuropathic pain such as allodynia, hyperalgesic pain, phantom pain, diabetic neuropathy-related neuropathic pain and migraine-related dorneuropathic pain.
WO02/049628 descreve o uso de retigabina para o tratamentode distúrbios de ansiedade tais como ansiedade, distúrbio de ansiedadegeneralizada, ansiedade de pânico, distúrbio obsessivo compulsivo, fobiasocial, ansiedade de desempenho, distúrbio de estresse pós-traumático, reaçãode estresse agudo, distúrbios de ajuste, distúrbios hipocondríacos, distúrbio deansiedade de separação, agorafobia e fobias específicas.WO02 / 049628 describes the use of retigabine for the treatment of anxiety disorders such as anxiety, generalized anxiety disorder, panic anxiety, obsessive compulsive disorder, phobiasocial, performance anxiety, posttraumatic stress disorder, acute stress reaction, adjustment disorders , hypochondriac disorders, separation anxiety disorder, agoraphobia and specific phobias.
W097/15300 descreve o uso de retigabina para o tratamentode distúrbios neurodegenerativos tais como mal de Alzheimer; Coréia deHuntington; esclerose tal como esclerose múltipla e esclerose lateralamiotrófica; doença de Creutzfeld-Jakob; doença de Parkinson; encefalopatiasinduzidas por AIDS ou infecção por vírus da rubéola, vírus do herpes, borréliae patógenos conhecidos; neurodegeneração induzida por trauma; estados dehiperexcitação neuronal tais como em abstinência ou intoxicaçãomedicamentosa; e doenças neurodegenerativas do sistema nervoso periféricotais como polineuropatias e polineuritides.WO97 / 15300 describes the use of retigabine for the treatment of neurodegenerative disorders such as Alzheimer's disease; Huntington's Korea; sclerosis such as multiple sclerosis and amyotrophic lateral sclerosis; Creutzfeld-Jakob disease; Parkinson's disease; encephalopathies induced by AIDS or rubella virus infection, herpes virus, borrelia and known pathogens; trauma-induced neurodegeneration; neuronal hyperexcitation states such as abstinence or drug intoxication; and neurodegenerative diseases of the peripheral nervous system such as polyneuropathies and polyneuritides.
Também é verificado que abridores de canal de KCNQ sãoefetivos no tratamento de derrame cerebral, portanto pode ser esperado queabridores de KCNQ seletivos são efetivos no tratamento de derrame cerebral(Schroder et al., Pflugers Arch., 2003; 446(5): 607-16; Cooper e Jan5 ArchNeurol., 2003, 60(4):496-5-00; Jensen5 CNSDrugRev., 2002, 8(4):353-60).KCNQ channel openers are also found to be effective in treating stroke, so it can be expected that selective KCNQ openers are effective in treating stroke (Schroder et al., Pflugers Arch., 2003; 446 (5): 607- 16; Cooper and Jan 5 ArchNeurol., 2003, 60 (4): 496-5-00; Jensen5 CNSDrugRev., 2002, 8 (4): 353-60).
Tem sido mostrado que canais KCNQ são expressados emcircuitos dopaminérgicos e colinérgicos no cérebro que estão associados como sistema de recompensa cerebral, particularmente a área tegmental ventral(Cooper et al., J. Neurosei., 2001, 21, 9529-9540). Portanto, é esperado queabridores de canal KCNQ são efetivos em distúrbios de hiperexcitabilidadeque envolvem o sistema de recompensa cerebral tais como abuso de cocaína,abstinência de nicotina e abstinência de etanol.KCNQ channels have been shown to be expressed in dopaminergic and cholinergic circuits in the brain that are associated with the brain reward system, particularly the ventral tegmental area (Cooper et al., J. Neurosei., 2001, 21, 9529-9540). Therefore, KCNQ channel openers are expected to be effective in hyperexcitability disorders involving the brain reward system such as cocaine abuse, nicotine withdrawal and ethanol withdrawal.
Canais de potássio compreendidos das subunidades KCNQ4são expressados no ouvido interno (Kubisch et al., Cell, 1999 Feb5;96(3):437-46) e portanto é esperado que abertura destes canais trata tinido.Potassium channels comprised of the KCNQ4 subunits are expressed in the inner ear (Kubisch et al., Cell, 1999 Feb5; 96 (3): 437-46) and therefore opening of these channels is expected to treat tinnitus.
Como conseqüência, há um grande desejo de compostos novosque são abridores potentes de família KCNQ de canais de potássio.As a consequence, there is a great desire for new compounds that are potent KCNQ family potassium channel openers.
Também são desejados compostos novos com propriedadesmelhoradas em relação aos compostos conhecidos, que são abridores decanais de potássio de família KCNQ, tal como retigabina. melhoria de um oumais dos seguintes parâmetros é desejada:Novel compounds with improved properties over known compounds, which are KCNQ family potassium decanters such as retigabine, are also desired. Improvement of one or more of the following parameters is desired:
meia-vida, depuração, seletividade, interações com outrasmedicações, biodisponibilidade, potência, formulabilidade, estabilidadequímica, estabilidade metabólica, permeabilidade de membrana, solubilidadee índice terapêutico. A melhoria de tais parâmetros pode acarretar melhoriastais como:half-life, clearance, selectivity, interactions with other medications, bioavailability, potency, formulability, chemical stability, metabolic stability, membrane permeability, solubility and therapeutic index. Improvement of such parameters may lead to improvements such as:
um regime de dosagem melhorado pela redução donúmero de doses requeridas por dia,an improved dosing regimen by reducing the number of doses required per day,
· facilidade de administração a pacientes sob medicaçõesmúltiplas,· Ease of administration to patients on multiple medications,
• efeitos colaterais reduzidos,• reduced side effects,
• índice terapêuticos aumentado,• increased therapeutic index,
• tolerabilidade melhorada ou• improved tolerability or
· consentimento melhorado.· Improved consent.
SUMÁRIO DA INVENÇÃOSUMMARY OF THE INVENTION
Um objetivo da invenção é a provisão de compostos que sãoabridores potentes dos canais de potássio de família KCNQ.An object of the invention is the provision of compounds that are potent openers of the KCNQ family potassium channels.
Os compostos da invenção são derivados de pirimidinasubstituídos de fórmula I abaixo ou seus saisThe compounds of the invention are derivatives of the substituted pyrimidines of formula I below or salts thereof.
<formula>formula see original document page 8</formula><formula> formula see original document page 8 </formula>
na qual R1 , R2 , R3, R4, R5 e q são como definidos abaixo.wherein R1, R2, R3, R4, R5 and q are as defined below.
A invenção proporciona um composto de fórmula I para usocomo um medicamento.The invention provides a compound of formula I for use as a medicament.
A invenção proporciona uma composição farmacêuticacompreendendo um composto de fórmula I e um diluente ou veículofarmaceuticamente aceitável.The invention provides a pharmaceutical composition comprising a compound of formula I and a pharmaceutically acceptable diluent or carrier.
A invenção proporciona o uso de um composto de fórmula Ipara a preparação de um medicamento para o tratamento de distúrbiosconvulsivos, distúrbios de ansiedade, dor neuropática e distúrbios de dor deenxaqueca, outros distúrbios de dor, tal como dor de câncer, distúrbiosneurodegenerativos, derrame cerebral, abuso de cocaína, abstinência denicotina, abstinência de etanol ou distúrbios de audição, tal como tinido.The invention provides the use of a compound of formula I for the preparation of a medicament for the treatment of convulsive disorders, anxiety disorders, neuropathic pain and migraine pain disorders, other pain disorders such as cancer pain, neurodegenerative disorders, stroke, cocaine abuse, denicotin withdrawal, ethanol withdrawal or hearing disorders such as tinnitus.
A invenção adicionalmente se refere ao uso de um compostode fórmula I em um método de tratamento de distúrbios convulsivos,distúrbios de ansiedade, dor neuropática e distúrbios de dor de enxaqueca,outros distúrbios de dor, tal como dor de câncer, distúrbiosneurodegenerativos, derrame cerebral, abuso de cocaína, abstinência denicotina, abstinência de etanol ou distúrbios de audição, tal como tinido.The invention further relates to the use of a compound of formula I in a method of treating seizure disorders, anxiety disorders, neuropathic pain and migraine pain disorders, other pain disorders such as cancer pain, neurodegenerative disorders, stroke, cocaine abuse, denicotin withdrawal, ethanol withdrawal or hearing disorders such as tinnitus.
DEFINIÇÃO DE SUBSTITUINTESDEFINITION OF SUBSTITUENTS
O termo "heteroátomo" refere-se a um átomo de nitrogênio, deoxigênio ou de enxofre.The term "heteroatom" refers to a nitrogen, deoxygen or sulfur atom.
"Halogênio" significa fluoro, cloro, bromo ou iodo. "Halo"significa halogênio."Halogen" means fluoro, chloro, bromo or iodo. "Halo" means halogen.
"Ciano" designa O=N que é ligado no restante da molécula viao átomo de carbono."Cyano" means O = N which is attached to the remainder of the molecule via the carbon atom.
"Amino" designa NH2, que é ligado no restante da moléculavia o átomo de nitrogênio."Amino" means NH2, which is attached in the remainder of the molecule to the nitrogen atom.
A expressão "C1-6-alqu(en/in)ila" significa C1-6-alquila, C2-6-alquenila ou C2-6-alquinila.The term "C 1-6 alkyl (en / in) yl" means C 1-6 alkyl, C 2-6 alkenyl or C 2-6 alkynyl.
O termo "C1-6-alquila" refere-se a um grupo alquila não-ramificado ou ramificado possuindo de um a seis átomos de carbono,incluindo mas não limitado a metila, etila, prop-l-ila, prop-2-ila, 2-metil-prop-l-ila, 2-metil-prop-2-ila, 2,2-dimetil-prop-l-ila, but-l-ila, but-2-ila, 3-metil-but-l-ila, 3-metil-but-2-ila, pent-l-ila, pent-2-ila, pent-3-ila, hex-l-ila,hex-2-ila e hex-3-ila.The term "C 1-6 alkyl" refers to an unbranched or branched alkyl group having from one to six carbon atoms, including but not limited to methyl, ethyl, prop-1-yl, prop-2-yl 2-methyl-prop-1-yl, 2-methyl-prop-2-yl, 2,2-dimethyl-prop-1-yl, but-1-yl, but-2-yl, 3-methyl-but -1-yl, 3-methyl-but-2-yl, pent-1-yl, pent-2-yl, pent-3-yl, hex-1-yl, hex-2-yl and hex-3-yl .
O termo "C2-6-alquenila" refere-se a um grupo alquenilaramificado ou não-ramificado possuindo dois a seis átomos de carbono e umaligação dupla, incluindo mas não limitado a etenila, propenila e butenila.The term "C 2-6 alkenyl" refers to an alkenylamified or unbranched group having two to six carbon atoms and a double bond, including but not limited to ethenyl, propenyl and butenyl.
O termo "C2.6-alquinila" refere-se a um grupo alquinilaramificado ou não-ramificado possuindo dois a seis átomos de carbono e umaligação tripla, incluindo mas não limitado a etinila, propinila e butinila.The term "C 2-6 alkynyl" refers to an alkynylamified or unbranched group having two to six carbon atoms and a triple bond, including but not limited to ethinyl, propynyl and butynyl.
A expressão "CM0-alqu(en/in)ila" significa Ci.10-alquila, C2-I0-alquenila ou C2.i0-alquinila.The term "CM0-alkyl (en / yn) yl" means C1-10-alkyl, C2-10-alkenyl or C2-10-alkynyl.
O termo "Ci_i0-alquila" refere-se a um grupo alquila não-ramificado ou ramificado possuindo de um a dez átomos de carbono,incluindo mas não limitado a metila, etila, prop-l-ila, prop-2-ila, 2-metil-prop-l-ila, 2-metil-prop-2-ila, 2,2-dimetil-prop-l-ila, but-l-ila, but-2-ila, 3-metil-but-l-ila, 3-metil-but-2-ila, pent-l-ila, pent-2-ila, pent-3-ila, hex-l-ila,hex-2-ila, hex-3-ila, 2-metil-4,4-dimetil-pent-l-ila e hept-l-ila.The term "C1-10 alkyl" refers to an unbranched or branched alkyl group having from one to ten carbon atoms, including but not limited to methyl, ethyl, prop-1-yl, prop-2-yl, 2 -methyl-prop-1-yl, 2-methyl-prop-2-yl, 2,2-dimethyl-prop-1-yl, but-1-yl, but-2-yl, 3-methyl-but-1 -yl, 3-methyl-but-2-yl, pent-1-yl, pent-2-yl, pent-3-yl, hex-1-yl, hex-2-yl, hex-3-yl, 2 -methyl-4,4-dimethyl-pent-1-yl and hept-1-yl.
O termo "C2.i0-alquenila" refere-se a um grupo alquenilaramificado ou não-ramificado possuindo de dois a dez átomos de carbono euma ligação dupla, incluindo mas não limitado a etenila, propenila e butenila.The term "C20-10 alkenyl" refers to an alkenylamified or unbranched group having from two to ten carbon atoms and a double bond, including but not limited to ethenyl, propenyl and butenyl.
O termo "C2_i0-alquinila" refere-se a um grupo alquinilaramificado ou não-ramificado possuindo de dois a dez átomos de carbono euma ligação tripla, incluindo mas não limitado a etinila, propinila e butinila.The term "C 2-10 alkynyl" refers to an alkynylamified or unbranched group having from two to ten carbon atoms and a triple bond, including but not limited to ethinyl, propynyl and butynyl.
A expressão "C3.8-ciclo-alqu(en)ila" significa C3.8-ciclo-alquilaou C3.8-ciclo-alquenila.The term "C3.8-cycloalkyl (en) yl" means C3.8-cycloalkyl or C3.8-cycloalkenyl.
O termo "C3.8-ciclo-alquila" designa um carbociclomonocíclico ou bicíclico possuindo três a oito átomos de carbono, incluindomas não limitado a ciclo-propila, ciclo-pentila, ciclo-hexila, biciclo-heptila talcomo 2-biciclo-[2.2.1]heptila.The term "C 3-8 cycloalkyl" means a carbocyclomonomonocyclic or bicyclic having three to eight carbon atoms, including but not limited to cyclopropyl, cyclopentyl, cyclohexyl, bicycloheptyl such as 2-bicyclo [2.2 .1] heptyl.
O termo "C3.8-ciclo-alquenila" designa um carbociclomonocíclico ou bicíclico possuindo três a oito átomos de carbono e umaligação dupla, incluindo mas não limitado a ciclo-pentenila e ciclo-hexenila.The term "C 3-8 cycloalkenyl" means a carbocyclomonomonocyclic or bicyclic having three to eight carbon atoms and a double bond, including but not limited to cyclopentenyl and cyclohexenyl.
O termo "lialo-C1-6-alqu(en/in)ila" designa C1-6-alqu(en/in)ilaestando substituída com halogênio, incluindo mas não limitado atrifluorometila.The term "C 1-6 alkyl (en / in) yl)" means C 1-6 alkyl (en / in) yl being halogen substituted, including but not limited to atrifluoromethyl.
O termo "halo-C1-6-alqu(en/in)iloxila" designa C1-6-alqu(en/in)iloxila estando substituída com halogênio, incluindo mas nãolimitado a trifluorometiloxilaThe term "halo-C1-6-alkyl (en / in) yloxy" means C1-6-alkyl (en / in) yloxy being substituted with halogen, including but not limited to trifluoromethyloxyl
Similarmente, "halo-C3-8-ciclo-alqu(en)ila" designa C3-8-ciclo-alqu(en)ila estando substituída com halogênio, incluindo mas não limitada acloro-ciclo-propano e clorociclo-hexano.Similarly, "C 3-8 halo-cycloalkyl" means C 3-8 cycloalkyl being substituted with halogen, including but not limited to chloro-cyclopropane and chlorocyclohexane.
Similarmente, "halo-C3-8-ciclo-alqu(en)iloxila" designa C3-8-ciclo-alqu(en)iloxila estando substituída com halogênio, incluindo mas nãolimitada a cloro-ciclo-propiloxila e cloro-ciclo-hexiloxila.Similarly, "C 3-8 -cycloalkyl (en) yloxy" means C 3-8 -cycloalkyl (en) yloxy being substituted with halogen, including but not limited to chloro-cyclopropyloxy and chloro-cyclohexyloxy.
Similarmente, "halo-C3.8-ciclo-alqu(en)il-C1-6-alqu(en/in)iloxila" designa halo-C3.8-ciclo-alqu(en)ila estando ligada norestante da molécula via C1-6-alqu(en/in)iloxila.Similarly, "halo-C 3-8 -cyclo-alkyl (en) yl-C 1-6-alkyl (en / in) yloxy" means halo-C 3-8 -cycloalkyl (en) yl being linked to the north-east of the molecule via C1 Alkyl (en / in) yloxy.
O termo "C1-6-alqu(en/in)iloxila" designa Ci.6-alqu(en/in)ilaestando ligada no restante da molécula via um átomo de oxigênio.The term "C 1-6 alkyl (en / in) yloxy" means C 1-6 alkyl (en / in) yl being attached to the remainder of the molecule via an oxygen atom.
Similarmente, "C3-8-ciclo-alqu(en)iloxila" designa C3-8-ciclo-alqu(en)ila estando ligada no restante da molécula via um átomo de oxigênio.Similarly, "C3-8-cycloalkyl (en) yloxy" means C3-8-cycloalkyl (en) yl being attached to the remainder of the molecule via an oxygen atom.
O termo "arila" designa sistemas aromáticos monocíclicos oubicíclicos sendo selecionados do grupo consistindo de fenila, naftila, tiofeno,furano, benzotiofeno e benzofurano.The term "aryl" refers to monocyclic or bicyclic aromatic systems being selected from the group consisting of phenyl, naphthyl, thiophene, furan, benzothiophene and benzofuran.
O termo "aril-Ci.6-alqu(en/in)ila opcionalmente substituída"designa aril-C1-6-alqu(en/in)ila na qual o grupo arila está opcionalmentesubstituído, tal como com 1, 2 ou 3 substituintes independentementeselecionados do grupo consistindo de halogênio, ciano, C1-6-alqu(en/in)ila,C3-8-ciclo-alqu(en)ila, C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila, halo-C1-6-alqu(en/in)ila, halo-C3.8-ciclo-alqu(en)ila, halo-C3.8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila, C1-6-alqu(en/in)iloxila, C3.8-ciclo-alqu(en)iloxila e C3.8-ciclo-alqu(en)il-C1-6-alqu(en/in)iloxila.The term "optionally substituted aryl-C1-6 alkyl (en / in) yl" means aryl-C1-6 alkyl (en / in) yl in which the aryl group is optionally substituted, such as with 1, 2 or 3 substituents. independently selected from the group consisting of halogen, cyano, C1-6-alkyl (en / in) yl, C3-8-cycloalkyl (en) yl, C3-8-cycloalkyl (en) yl-C1-6-alkyl (en / in) yl, halo-C 1-6 -alkyl (en / in) yl, halo-C 3-8 -cycloalkyl (en) yl, halo-C 3-8-cycloalkyl (en) yl -6-alkyl (en / in) yl, C 1-6-alkyl (en / in) yloxy, C 3-8-cycloalkyl and C 3-8 -cyclo-C 1-6 alkyl alkyl (en / in) yloxyl.
Similarmente, "arila opcionalmente substituída "designa arilana qual a arila está opcionalmente substituída, tal como com 1, 2 ou 3substituintes independentemente selecionados do grupo consistindo dehalogênio, ciano, C1-6-alqu(en/in)ila, C3-8-ciclo-alqu(en)ila, C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila, halo-C1-6-alqu(en/in)ila, halo-C3-8-ciclo-alqu(en)ila, halo-C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila, C1-6-alqu(en/in)iloxila, C3-8-ciclo-alqu(en)iloxila e C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)iloxila.Similarly, "optionally substituted aryl" means arylane which aryl is optionally substituted on, such as with 1, 2 or 3 substituents independently selected from the group consisting of halogen, cyano, C1-6-alkyl (en / in) yl, C3-8-cyclo -C 1-8 alkyl, C 3-8 -cyclo (C 1-6) alkyl-C 1-6 alkyl (en / in) yl, halo C 1-6 alkyl (en / in) yl, C 3-8 halo -cyclo-alkyl (en) yl, halo C 3-8 -cyclo-alkyl (en) yl C 1-6 alkyl (en / in) yl, C 1-6 alkyl (en / in) yloxy, C 3-8 -cyclo-alkyl (en) yloxy and C 3-8-cycloalkyl (en) yl-C 1-6 alkyl (en / in) yloxy.
Nas expressões "C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila","aril-C1-6-alqu(en/in)ila" e "C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)iloxila", ostermos "C1-6-alqu(en/in)ila", "C3-8-ciclo-alqu(en)ila", "arila" e "C1-6-alqu(en/in)iloxila" são como definidos acima.In the terms "C3-8-cycloalkyl (en) yl-C1-6-alkyl (en / in) yla", "aryl-C1-6-alkyl (en / in) yla" and "C3-8-cycle" -C1-6-alkyl (en / in) yloxy "," C1-6-alkyl (en / in) yl "," C3-8-cycloalkyl "," aryl "and" C1-6-alkyl (en / in) yloxy "are as defined above.
DESCRIÇÃO DA INVENÇÃODESCRIPTION OF THE INVENTION
A presente invenção refere-se aos derivados de pirimidinasubstituídos que são abridores potentes de canais de potássio KCNQ.The present invention relates to substituted pyrimidine derivatives which are potent KCNQ potassium channel openers.
A presente invenção refere-se a um composto representadopela fórmula geral I ou seus sais:The present invention relates to a compound represented by general formula I or salts thereof:
<formula>formula see original document page 12</formula><formula> formula see original document page 12 </formula>
na qual:in which:
q é 0 ou 1;q is 0 or 1;
R1 e R2 são independentemente selecionados do grupoconsistindo de hidrogênio e aril-Ci.6-alqu(en/in)ila opcionalmente substituída,desde que R1eR2 não sejam ambos hidrogênio, ou R1 e R2 juntos com onitrogênio no qual estão ligados formam um anel de 5 a 7 membrosopcionalmente contendo outro heteroátomo;R 1 and R 2 are independently selected from the group consisting of hydrogen and optionally substituted aryl-C 1-6 alkyl (en / in) yl, provided that R 1 and R 2 are not both hydrogen, or R 1 and R 2 together with onitrogen to which they are attached form a ring. 5 to 7 members optionally containing another heteroatom;
R3 e R4 são independentemente selecionados de hidrogênio,halogênio, ciano, amino, Ci.6-alqu(en/in)ila, C3.8-ciclo-alqu(en)ila, halo-Ci_6-alqu(en/in)ila, halo-C3.8-ciclo-alqu(en)ila, Ci.6-alqu(en/in)iloxila, C3.8-ciclo-alqu(en)iloxila, C3.8-ciclo-alqu(en)il-Ci_6-alqu(en/in)iloxila, halo-Ci_6-alqu(en/in)iloxila, halo-C3.8-ciclo-alqu(en)iloxila e halo-C3_8-ciclo-alqu(en)il-C1-6-alqu(en/in)iloxila, desde que R3 e R4 não sejam ambos hidrogênio;R3 and R4 are independently selected from hydrogen, halogen, cyano, amino, C1-6 alkyl (en / in) yl, C3.8-cycloalkyl (en) yl, halo-C1-6 alkyl (en / in) yl , halo-C 3-8 -cycloalkyl (en) yl, C 1-6 -alkyl (en / in) yloxy, C 3-8-cycloalkyl (en) yloxy, C 3-8-cycloalkyl (en) yl -C 1-6 alkyl (en / in) yloxy, halo-C 1-6 alkyl (en / in) yloxy, halo C 3-8 -cycloalkyl (en) yloxy and halo C 3-8-cycloalkyl (en) yl Alkyl (en / in) yloxy, provided that R 3 and R 4 are not both hydrogen;
R5 é selecionado do grupo consistindo de C1-10-alqu(en/in)ila,C3-8-ciclo-alqu(en)il-Ci_6-alqu(en/in)ila, aril-Ci.6-alqu(en/in)ila opcionalmentesubstituída e arila opcionalmente substituída;R5 is selected from the group consisting of C1-10-alkyl (en / in) yl, C3-8-cyclo-alkyl (en) yl-C1-6-alkyl (en / in) yl, aryl-C1-6-alkyl (en) (in) optionally substituted yl and optionally substituted aryl;
Em uma modalidade do composto de fórmula I, q é 0.In one embodiment of the compound of formula I, q is 0.
Em outra modalidade do composto de fórmula I, q é 1.In another embodiment of the compound of formula I, q is 1.
Em uma outra modalidade do composto de fórmula I R1 e R2são independentemente selecionados de hidrogênio e aril-Ci_6-alqu(en/in)ilaopcionalmente substituída, desde que R1 e R2 não sejam ambos hidrogênio.In another embodiment of the compound of formula I R 1 and R 2 are independently selected from hydrogen and optionally substituted aryl-C 1-6 alkyl (en / in), provided that R 1 and R 2 are not both hydrogen.
Em uma outra modalidade do composto de fórmula I R1 e R2juntos com o nitrogênio no qual estão ligados formam um anel de 5 a 7membros opcionalmente contendo um outro heteroátomo; em outramodalidade o citado outro heteroátomo é oxigênio; em outra modalidade ocitado anel é um anel de 6 membros; em outra modalidade o citado anel é umanel de morfolina.In another embodiment of the compound of formula I R 1 and R 2 together with the nitrogen to which they are attached form a 5 to 7 membered ring optionally containing another heteroatom; in another mode the aforementioned other heteroatom is oxygen; in another embodiment said ring is a 6 membered ring; in another embodiment said ring is a morpholine ring.
Em uma outra modalidade do composto de fórmula I R3 e R4são independentemente selecionados de amino e C1-6-alqu(en/in)ila,preferivelmente metila.In another embodiment of the compound of formula I R 3 and R 4 are independently selected from amino and C 1-6 alkyl (en / in) yl, preferably methyl.
Em uma outra modalidade do composto de fórmula I R5 éselecionado do grupo consistindo de CM0-alqu(en/in)ila, C3-8-ciclo-alqu(en)il-C1-6-alqu(en/in)ila, aril-C1-6-alqu(en/in)ila opcionalmente substituída e arilaopcionalmente substituída.In another embodiment of the compound of formula I R5 is selected from the group consisting of CM0-alkyl (en / in) yl, C3-8-cycloalkyl (en) yl-C1-6-alkyl (en / in) yl, aryl Optionally substituted and optionally substituted aryl (en / in) alkyl.
Uma outra modalidade refere-se a um composto de fórmula Icomo a base livre ou um sal do mesmo, o citado composto é selecionado doscompostos do seguinte esquema:Another embodiment relates to a compound of formula I as the free base or a salt thereof, said compound is selected from the compounds of the following scheme:
Exemplo no. NomeExample no. Name
Ia N-[4-Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirimidin-5- il]-2-ciclo-pentil-acetamidaIb N-[4-Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirimidiri-5- il]-3, 3-dimetil-butiramidaIc N-[4-Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirimidin-5- il]-2-(4-fluoro-fenil)-acetamidaId [4-Amino-6-metil-2-(44rifluorometil-benzil-amino)-pirimidin-5-il]- amida de ácido hexanóicoIe N-[4-Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirimidin-5- il] -2-(3 -cloro-fenil)-acetamida2a 2-Ciclo-pentil-N-(4,6-dimetil-2-morfolin-4 il-pirimidin-5-il)- acetamida2b N-(4,6-Dimetil-2-morfolin-4 il-pirimidin-5-il)-3,3-dimetil-butiramida2c N-(4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il)-2-(4fluoro-fenil)- acetamida2d 2-(3,4-Dif!uoro-fenil)-N-(4,6-dimetil-2-morfolin-4-il-pirimidin-5-il)- acetamida2e N-(4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il)-2-(3 fluoro-fenil)- acetamida2f (4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il)-amida de ácido hexanóico1a N- [4-Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -2-cyclopentyl-acetamide N- [4-Amino-6-methyl-2 - (4-trifluoromethyl-benzyl-amino) -pyrimidiri-5-yl] -3,3-dimethyl-butyramide N- [4-Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-2-one N-[4-Amino-6-methyl-2- (44-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -amide-5-yl] -2- (4-fluoro-phenyl) -acetamide N- [4 -Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -2- (3-chloro-phenyl) -acetamide2a 2-Cyclopentyl-N- (4,6- dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -acetamide2b N- (4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -3,3-dimethyl-butyramide2c N- ( 4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -2- (4-fluorophenyl) acetamide2d 2- (3,4-Difluoro-phenyl) -N- (4,6 -dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) acetamide2- N- (4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -2- (3-fluoro-phenyl ) - hexanoic acid acetamide2f (4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -amide
Cada um destes compostos é considerado uma modalidadeespecífica e podem ser submetidos às reivindicações individuais.Each of these compounds is considered a specific embodiment and may be subject to individual claims.
A presente invenção também compreende sais dospresentes compostos, tipicamente sais farmaceuticamente aceitáveis. Osais da invenção incluem sais de adição de ácido, sais de metal, sais deamônio e de amônio alquilado.The present invention also comprises salts of the present compounds, typically pharmaceutically acceptable salts. Salts of the invention include acid addition salts, metal salts, deamonium and alkylated ammonium salts.
Os sais da invenção são preferivelmente sais de adição deácido. Os sais de adição de ácido da invenção são preferivelmente saisfarmaceuticamente aceitáveis dos compostos da invenção formados comácidos não-tóxicos. Sais de adição de ácido incluem sais de ácidosinorgânicos bem como de ácidos orgânicos. Exemplos de ácidosinorgânicos adequados incluem ácidos clorídrico, bromídrico, iodídrico,fosfórico, sulfurico, sulfâmico, nítrico e semelhantes. Exemplos de ácidosorgânicos apropriados incluem ácidos fórmico, acético, tricloroacético,trifluoroacético, propiônico, benzóico, cinâmico, cítrico, fumárico,glicólico, itacônico, lático, metano-sulfônico, maleico, málico, malônico,mandélico, oxálico, pícrico, pirúvico, salicílico, succínico, metano-sulfônico, etano-sulfônico, tartárico, ascórbico, pamóico, bis-metileno-salicílico, etano-dissulfônico, glicônico, citracônico, aspártico, esteárico,palmítico, EDTA, glicólico, p-amino-benzóico, glutâmico, benzeno-sulfônico, p-tolueno-sulfônico, ácido teofílina-acético, bem como as 8-halo-teofilinas, por exemplo 8-bromo-teofilina e semelhantes. Outrosexemplos de sais de adição de ácido inorgânico ou orgânicofarmaceuticamente aceitável incluem os sais farmaceuticamente aceitáveislistados em J. Pharm. Sei. 1977, 66, 2, que é aqui incorporado comoreferência.The salts of the invention are preferably acid addition salts. The acid addition salts of the invention are preferably pharmaceutically acceptable salts of the compounds of the invention formed as non-toxic acids. Acid addition salts include salts of inorganic acids as well as organic acids. Examples of suitable inorganic acids include hydrochloric, hydrobromic, hydroiodic, phosphoric, sulfuric, sulfamic, nitric and the like. Examples of suitable organic acids include formic, acetic, trichloroacetic, trifluoroacetic, propionic, benzoic, cinnamic, citric, fumaric, glycolic, itaconic, lactic, methanesulfonic, maleic, malonic, mandelic, oxalic, picric, pyruvic, salicylic acids, succinic, methanesulfonic, ethanesulfonic, tartaric, ascorbic, pamoic, bismethylene salicylic, ethanesulfonic, glyconic, citraconic, aspartic, stearic, palmitic, EDTA, glycolic, p-amino-benzoic, glutamic, benzene- sulfonic acid, p-toluenesulfonic acid, theophylline acetic acid, as well as 8-halo theophyllines, for example 8-bromo-theophylline and the like. Other examples of pharmaceutically acceptable inorganic or organic acid addition salts include the pharmaceutically acceptable salts listed in J. Pharm. Know. 1977, 66, 2, which is incorporated herein by reference.
Também intencionados como sais de adição de ácido são oshidratos, que os presentes compostos são capazes de formar.Also intended as acid addition salts are the hydrates, which the present compounds are capable of forming.
Exemplos de sais de metal incluem sais de lítio, de sódio,de potássio, de magnésio e semelhantes.Examples of metal salts include lithium, sodium, potassium, magnesium salts and the like.
Exemplos de sais de amônio e de amônio alquilado incluemsais de amônio, sais de metil-, dimetil-, trimetil-, etil-, hidróxi-etil, dietil-,n-butil-, sec-butil-, terc-butil-, tetrametil-amônio e semelhantes.Examples of ammonium and alkylated ammonium salts include ammonium salts, methyl-, dimethyl-, trimethyl-, ethyl-, hydroxy-ethyl, diethyl-, n-butyl-, sec-butyl-, tert-butyl-, tetramethyl salts -ammonium and the like.
Em adição, os compostos desta invenção podem existir emformas não solvatadas bem como solvatadas com solventesfarmaceuticamente aceitáveis tais como água, etanol e semelhantes. Emgeral, as formas solvatadas são consideradas equivalentes às formas nãosolvatadas para propósitos desta invenção.In addition, the compounds of this invention may exist in unsolvated as well as solvated forms with pharmaceutically acceptable solvents such as water, ethanol and the like. In general, solvated forms are considered equivalent to non-solvated forms for purposes of this invention.
Os compostos da presente invenção podem possuir um oumais centros assimétricos e é intencionado que quaisquer isômeros ópticos(i.e. enantiômeros ou diastereômeros), como isômeros ópticos separados,puros ou parcialmente purificados e quaisquer misturas dos mesmosincluindo misturas racêmicas, i.e. uma mistura de estereoisômeros, estãoincluídos dentro do escopo da invenção.The compounds of the present invention may have one or more asymmetric centers and it is intended that any optical isomers (ie enantiomers or diastereomers) as separate, pure or partially purified optical isomers and any mixtures thereof including racemic mixtures, ie a mixture of stereoisomers, are included within. scope of the invention.
Formas racêmicas podem ser resolvidas em antípodasópticos por métodos conhecidos, por exemplo, por separação de seus saisdiastereoméricos com um ácido opticamente ativo, e liberação docomposto aminado opticamente ativo por tratamento com uma base. Outrométodo para resolver racematos em antípodas ópticos baseia-se emcromatografia sobre uma matriz opticamente ativa. Compostos racêmicosda presente invenção também podem ser resolvidos em seus antípodasópticos, por exemplo por cristalização fracionada. Os compostos dapresente invenção também podem ser resolvidos por formação dederivados diastereoméricos. Métodos adicionais para a resolução deisômeros ópticos, conhecidos por aquelas pessoas experientes na arte,podem ser utilizados. Tais métodos incluem aqueles discutidos por J.Jaques, A. Collet e S. Wilen no livro-texto Enantiomers, Racemates, andResolutions, John Wiley e Sons, New York (1981). Compostosopticamente ativos também podem ser preparados a partir de materiaisiniciais opticamente ativos ou por síntese estereosseletiva.Racemic forms may be resolved into antipodasoptics by known methods, for example by separating their diastereomeric salts with an optically active acid, and optically active amino compound release by treatment with a base. Another method for resolving racemates in optical antipodes is based on chromatography on an optically active matrix. Racemic compounds of the present invention may also be resolved into their antipodasoptics, for example by fractional crystallization. The compounds of the present invention may also be resolved by formation of diastereomeric derivatives. Additional methods for resolving optical isomers, known to those skilled in the art, may be used. Such methods include those discussed by J.Jaques, A. Collet and S. Wilen in the textbook Enantiomers, Racemates, andResolutions, John Wiley and Sons, New York (1981). Optically active compounds may also be prepared from optically active starting materials or by stereoselective synthesis.
Ainda mais, quando uma ligação dupla ou um sistema deanel total ou parcialmente saturado estiver presente na molécula isômerosgeométricos poderão ser formados. É intencionado que quaisquerisômeros geométricos, como isômeros geométricos separados, puros ouparcialmente purificados ou misturas dos mesmos sejam incluídos dentrodo escopo da invenção. Igualmente, moléculas possuindo uma ligaçãocom rotação restringida podem formar isômeros geométricos. Estestambém são intencionados para estarem incluídos dentro do escopo dapresente invenção.Further, when a double bond or a fully or partially saturated deanel system is present in the isometric isomers molecule may be formed. Any geometric isomers, such as separate, pure or partially purified geometric isomers or mixtures thereof, are intended to be included within the scope of the invention. Also, molecules having a restricted rotation bond may form geometric isomers. These are also intended to be included within the scope of the present invention.
Em adição, alguns dos compostos da presente invençãopodem existir em formas tautoméricas diferentes e é intencionado quequaisquer formas tautoméricas que os compostos são capazes de formarestejam incluídas dentro do escopo da presente invenção.In addition, some of the compounds of the present invention may exist in different tautomeric forms and it is intended that any tautomeric forms that the compounds are capable of forming are within the scope of the present invention.
A invenção também inclui pró-drogas dos presentescompostos, que sob administração sofrem conversão química porprocessos metabólicos antes de se tornarem substânciasfarmacologicamente ativas. Em geral, tais pró-drogas serão derivadosfuncionais de compostos de fórmula geral I, que são prontamenteconversíveis in vivo no composto de fórmula I requerido. Procedimentosconvencionais para a seleção e a preparação de derivados de pró-drogaadequados são descritos, por exemplo, em Design of Prodrugs, ed. H.Bundgaard, Elsevier, 1985.The invention also includes prodrugs of the present compounds, which upon administration undergo chemical conversion by metabolic processes before becoming pharmacologically active substances. In general, such prodrugs will be functional derivatives of compounds of formula I, which are readily convertible in vivo to the required compound of formula I. Conventional procedures for selecting and preparing suitable prodrug derivatives are described, for example, in Design of Prodrugs, ed. H. Bundgaard, Elsevier, 1985.
A invenção também inclui metabólitos ativos dos presentescompostos.The invention also includes active metabolites of the present compounds.
Os compostos de acordo com a invenção possuem afinidadepelo subtipo de receptor de KCNQ2 com uma EC50 menor do que 15.000 nMtal como menor do que 10.000 nM conforme medida pelo teste de "Efluxorelativo através de canal KCNQ2" que é descrito abaixo.Uma modalidaderefere-se a tais compostos de fórmula I possuindo afinidade pelo subtipo dereceptor de KCNQ2 com uma EC50 menor do que 2.000 nM tal como menordo que 1.500 nM conforme medida pelo teste de "Efluxo relativo através decanal KCNQ2" que é descrito abaixo. Para adicionalmente ilustrar sem limitara invenção uma modalidade refere-se a tais compostos possuindo afinidadepelo subtipo de receptor de KCNQ2 com uma EC50 menor do que 200 nM talcomo menor do que 150 nM conforme medida pelo teste de "Efluxo relativoatravés de canal KCNQ2" que é descrito abaixo.The compounds according to the invention have affinity for the KCNQ2 receptor subtype with an EC50 of less than 15,000 nMtal as less than 10,000 nM as measured by the "KCNQ2 channel efflective" test which is described below. such compounds of formula I having affinity for the KCNQ2 receptor subtype having an EC50 of less than 2,000 nM as less than 1,500 nM as measured by the "KCNQ2 decanal relative efflux" test which is described below. To further illustrate without limiting the invention one embodiment relates to such compounds having affinity for the KCNQ2 receptor subtype with an EC50 of less than 200 nM as less than 150 nM as measured by the "Relative Flow Through KCNQ2 Channel" test which is described. below, down, beneath, underneath, downwards, downhill.
Uma modalidade refere-se a tais compostos de fórmula Ipossuindo uma ED50 menor do que 15 mg/kg no teste de "Eletrochoquemáximo" que é descrito abaixo. Para adicionalmente ilustrar sem limitar ainvenção uma modalidade refere-se a tais compostos possuindo uma ED50menor do que 5 mg/kg no teste de "Eletrochoque máximo" que é descritoabaixo.One embodiment relates to such compounds of formula having an ED50 of less than 15 mg / kg in the "Electroshock" test which is described below. To further illustrate without limiting the invention one embodiment relates to such compounds having an ED50 of less than 5 mg / kg in the "Maximum Electroshock" test which is described below.
Uma modalidade refere-se a tais compostos de fórmula Ipossuindo uma ED50 menor do que 5 mg/kg no "Teste de limiar de convulsãoelétrica" e "Teste de limiar de convulsão química" que é descrito abaixo.One embodiment relates to such compounds of formula having an ED50 of less than 5 mg / kg in the "Electrical Seizure Threshold Test" and "Chemical Seizure Threshold Test" which is described below.
Uma modalidade refere-se a tais compostos de fórmula Ipossuindo efeitos colaterais poucos ou clinicamente insignificantes. Algunsdos compostos de acordo com a invenção são portanto testados em modelosde ações sedativas, hipotérmicas e atáxicas indesejadas.One embodiment relates to such compounds of formula having few or clinically insignificant side effects. Some of the compounds according to the invention are therefore tested on unwanted sedative, hypothermic and ataxic action models.
Uma modalidade refere-se a tais compostos de fórmula Ipossuindo um índice terapêutico grande entre eficácia anticonvulsiva e efeitoscolaterais tais como enfraquecimento de atividade locomotora ou efeitosatáxicos conforme medidos pelo desempenho sobre um bastão rotativo. Taiscompostos serão esperadamente bem tolerados em pacientes permitindo quedoses altas sejam usadas tornando o tratamento mais eficaz em pacientes quede outro modo teriam efeitos colaterais com outras medicações.One embodiment relates to such compounds of formula having a large therapeutic index between anticonvulsant efficacy and side effects such as impairment of locomotor activity or ataxic effects as measured by performance on a rotating stick. Such compounds will be expected to be well tolerated in patients allowing high dosages to be used making treatment more effective in patients who would otherwise have side effects with other medications.
Como já mencionado, os compostos de acordo com a invençãopossuem efeito sobre os canais de potássio de família KCNQ, em particular asubunidade KCNQ2, e são portanto considerados úteis para aumentar o fluxoiônico em um canal de potássio dependente de voltagem em um mamífero talcomo um humano. Os compostos da invenção são aplicáveis no tratamento deum distúrbio ou de uma doença sendo responsivo a um fluxo iônicoaumentado em um canal de potássio tal como os canais de íon potássio defamília KCNQ. Tal distúrbio ou doença é preferivelmente um distúrbio ouuma doença do sistema nervoso central.As already mentioned, the compounds according to the invention have an effect on KCNQ family potassium channels, in particular the KCNQ2 subunit, and are therefore considered useful for increasing ionic flux in a voltage-dependent potassium channel in a mammal such as a human. The compounds of the invention are applicable in the treatment of a disorder or disease being responsive to an increased ionic flux in a potassium channel such as the KCNQ family potassium ion channels. Such disorder or disorder is preferably a disorder or disorder of the central nervous system.
Em um aspecto, os compostos da invenção podem seradministrados como o único composto terapeuticamente efetivo.In one aspect, the compounds of the invention may be administered as the only therapeutically effective compound.
Em outro aspecto os compostos da invenção podem seradministrados como uma parte de uma terapia de combinação, i.e. oscompostos da invenção podem ser administrados em combinação com outroscompostos terapeuticamente efetivos possuindo e.g. propriedadesanticonvulsivas. Os efeitos de tais outros compostos possuindo propriedadesanticonvulsivas podem incluir mas não são limitados às atividades sobre:In another aspect the compounds of the invention may be administered as a part of a combination therapy, i.e. the compounds of the invention may be administered in combination with other therapeutically effective compounds having e.g. anticonvulsive properties. The effects of such other compounds having anticonvulsant properties may include but are not limited to activities on:
• canais de íons tais como canais de sódio, de potássio, oude cálcio;• ion channels such as sodium, potassium or calcium channels;
• os sistemas de aminoácido excitatório e.g. bloqueio oumodulação de receptores de NMDA;Excitatory amino acid systems e.g. blocking or modulating NMDA receptors;
• os sistemas neurotransmissores inibitórios e.g. de liberaçãode GABA, ou bloqueio de captação de GABA ou• inhibitory neurotransmitter systems e.g. GABA release, or GABA uptake block or
• efeitos de estabilização de membrana.• membrane stabilization effects.
Medicações anticonvulsivas correntes incluem, mas não sãolimitadas a, tiagabina, carbamazepina, valproato de sódio, lamotrigina,gabapentina, pregabalina, etosuximida, levetiracetam, fenitoína, topiramato,zonisamida bem como membros da classe de benzodiazepina e barbiturato.Current anticonvulsant medications include, but are not limited to, tiagabine, carbamazepine, sodium valproate, lamotrigine, gabapentin, pregabalin, etosuximide, levetiracetam, phenytoin, topiramate, zonisamide as well as members of the benzodiazepine and barbiturate class.
Um aspecto da invenção proporciona um composto de fórmulaI ou um seu sal para uso como um medicamento.One aspect of the invention provides a compound of formula I or a salt thereof for use as a medicament.
Em uma modalidade, a invenção refere-se ao uso de umcomposto de fórmula I ou de um seu sal em um método de tratamento.In one embodiment, the invention relates to the use of a compound of formula I or a salt thereof in a treatment method.
Uma modalidade da invenção proporciona uma composiçãofarmacêutica compreendendo um composto de fórmula I ou um seu sal e umou mais diluentes ou veículos farmaceuticamente aceitáveis. A composiçãopode compreender qualquer uma das modalidades de fórmula I como descritoacima.One embodiment of the invention provides a pharmaceutical composition comprising a compound of formula I or a salt thereof and one or more pharmaceutically acceptable diluents or carriers. The composition may comprise any of the embodiments of formula I as described above.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para aumentar o fluxo iônico em umcanal de potássio de um mamífero tal como um humano.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof to increase the ionic flux in a potassium channel of a mammal such as a human.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para o tratamento de um distúrbio ou deuma doença sendo responsivo a um fluxo iônico aumentado em um canal depotássio, tal distúrbio ou doença é preferivelmente um distúrbio ou umadoença do sistema nervoso central.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the treatment of a disorder or disease being responsive to an increased ion flux in a depotassium channel, such disorder or disease is preferably a disorder or disease. of the central nervous system.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de uma doença ou de um distúrbio no qual umabridor de canal de potássio KCNQ tal como um abridor de canal de potássioKCNQ2 é benéfico. Tipicamente, tal distúrbio ou doença é selecionado dogrupo consistindo de distúrbios convulsivos, distúrbios de ansiedade, dorneuropática e distúrbios de dor de enxaqueca, outros distúrbios de dor, talcomo dor de câncer, distúrbios neurodegenerativos, derrame cerebral, abusode cocaína, abstinência de nicotina, abstinência de etanol ou distúrbios deaudição, tal como tinido.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of a disease or disorder in which a KCNQ potassium channel opener such as a potassium channel opener is used. potassiumKCNQ2 is beneficial. Typically, such disorder or disease is selected from the group consisting of seizure disorders, anxiety disorders, dorneuropathic and migraine pain disorders, other pain disorders, such as cancer pain, neurodegenerative disorders, stroke, cocaine abuse, nicotine withdrawal, withdrawal ethanol or hearing disorders such as tinnitus.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de distúrbios convulsivos.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of seizure disorders.
Tipicamente, os distúrbios convulsivos a serem tratados sãoselecionados do grupo consistindo de convulsões agudas, convulsões, estadoepiléptico e epilepsia tais como síndromes epilépticas e convulsõesepilépticas.Typically, seizure disorders to be treated are selected from the group consisting of acute seizures, seizures, epileptic status and epilepsy such as epileptic syndromes and epileptic seizures.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de distúrbios de ansiedade.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of anxiety disorders.
Tipicamente, os distúrbios de ansiedade a serem tratados sãoselecionados do grupo consistindo de ansiedade e distúrbios e doençasrelacionados com ataque de pânico, agorafobia, distúrbio de pânico comagorafobia, distúrbio de pânico sem agorafobia, agorafobia sem história dedistúrbio de pânico, fobia específica, fobia social e outras fobias específicas,distúrbio obsessivo compulsivo, distúrbio de estresse pós-traumático,distúrbios de estresse agudo, distúrbio de ansiedade generalizada, distúrbio deansiedade devido à condição médica geral, distúrbio de ansiedade induzidapor substância, distúrbio de ansiedade de separação, distúrbios de ajuste,ansiedade de desempenho, distúrbios hipocondríacos, distúrbio de ansiedadedevido à condição médica geral e distúrbio de ansiedade induzida porsubstância e distúrbio de ansiedade não diferentemente especificado.Typically, anxiety disorders to be treated are selected from the group consisting of anxiety and panic attack-related disorders and diseases, agoraphobia, panic disorder, agoraphobia, panic disorder without agoraphobia, history of panic disorder, specific phobia, and social phobia. other specific phobias, obsessive compulsive disorder, posttraumatic stress disorder, acute stress disorder, generalized anxiety disorder, anxiety disorder due to general medical condition, substance-induced anxiety disorder, separation anxiety disorder, adjustment disorder, anxiety performance, hypochondriac disorders, anxiety disorder due to general medical condition, and substance-induced anxiety disorder, and anxiety disorder not differently specified.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de dor neuropática e distúrbios de dor deenxaqueca.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of neuropathic pain and migraine pain disorders.
Tipicamente, a dor neuropática e distúrbios de dor deenxaqueca a serem tratados são selecionados do grupo consistindo dealodínia, dor hiperalgésica, dor fantasma, dor neuropática relacionada comneuropatia diabética, dor neuropática relacionada à neuralgia trigeminal e dorneuropática relacionada com enxaqueca.Typically, neuropathic pain and migraine pain disorders to be treated are selected from the group consisting of dealodynia, hyperalgesic pain, phantom pain, diabetic neuropathic-related neuropathic pain, trigeminal neuralgia-related neuropathic pain and migraine-related dorneuropathic pain.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de distúrbios neurodegenerativos.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of neurodegenerative disorders.
Tipicamente os distúrbios neurodegenerativos a serem tratadossão selecionados do grupo consistindo de mal de Alzheimer, Coréia deHuntington, esclerose múltipla, esclerose lateral amiotrófica, doença deCreutzfeld-Jakob, doença de Parkinson, encefalopatias induzidas por AIDS ouinfecção por vírus da rubéola, vírus do herpes, borrélia e patógenosconhecidos, neurodegeneração induzida por traumas, estados dehiperexcitação neuronal tais como em abstinência ou intoxicaçãomedicamentosa e doenças neurodegenerativas do sistema nervoso periféricotais como polineuropatias e polineuritides.Typically the neurodegenerative disorders to be treated are selected from the group consisting of Alzheimer's disease, Huntington's chorea, multiple sclerosis, amyotrophic lateral sclerosis, Creutzfeld-Jakob disease, Parkinson's disease, AIDS-induced encephalopathy, rubella virus infection, herpes virus and known pathogens, trauma-induced neurodegeneration, states of neuronal hyperexcitation such as in abstinence or drug intoxication, and peripheral nervous system neurodegenerative diseases such as polyneuropathies and polyneuritides.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de distúrbios bipolares ou distúrbio dehiperatividade com déficit de atenção.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of bipolar disorder or attention deficit hyperactivity disorder.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de distúrbios de sono; tal como insônia.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of sleep disorders; such as insomnia.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de fibromialgia, um distúrbio motor oudistúrbio de movimento, espasmos, mioquímia ou incontinência urinária.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of fibromyalgia, a motor disorder or movement disorder, spasms, myopia or urinary incontinence.
Uma outra modalidade da invenção refere-se ao uso de umcomposto de fórmula I ou um seu sal para a preparação de uma composiçãofarmacêutica para o tratamento de derrame cerebral, abuso de cocaína,abstinência de nicotina, abstinência de etanol ou distúrbios de audição, talcomo tinido.Another embodiment of the invention relates to the use of a compound of formula I or a salt thereof for the preparation of a pharmaceutical composition for the treatment of stroke, cocaine abuse, nicotine withdrawal, ethanol withdrawal or hearing impairment such as tinnitus. .
O termo "tratamento" como aqui usado em conexão com umadoença ou um distúrbio também inclui prevenção, inibição e melhoria deacordo com as circunstâncias.The term "treatment" as used herein in connection with a disease or disorder also includes prevention, inhibition and amelioration according to the circumstances.
A invenção proporciona compostos mostrando efeito em umou mais dos seguintes testes:The invention provides compounds showing effect in one or more of the following tests:
• "Efluxo relativo através de canal KCNQ2"Que é uma medição da potência do composto como um canalalvo.• "Relative flow through channel KCNQ2" Which is a measure of compound power as a target channel.
• "Eletrochoque máximo"• "Maximum Electroshock"
Que é uma medição de convulsões induzidas por estimulaçãode CNS não-específicas por meios elétricosWhich is a measurement of non-specific CNS stimulation induced seizures
• "Convulsões induzidas por pilocarpina"• "Pilocarpine-induced seizures"
Convulsões induzidas por pilocarpina são muitas vezes difíceisde tratar com muitas das medicações anticonvulsivas existentes e assimrefletem um modelo de "convulsões resistentes à droga" .Pilocarpine-induced seizures are often difficult to treat with many of the existing anticonvulsant medications and thus reflect a "drug-resistant seizures" model.
"Testes de limiar de convulsão elétrica" e "Testes delimiar de convulsão química" Estes modelos medem o limiar no qualconvulsões são iniciadas, assim sendo modelos que detectam se os compostospoderiam retardar a iniciação de convulsão."Electrical Seizure Threshold Tests" and "Chemical Seizure Boundary Tests" These models measure the threshold at which seizures are initiated, and thus models that detect whether the compounds could delay seizure initiation.
"Ignição de amídala""Amygdala Ignition"
Que é usada como uma medição de progressão da doença,porque em animais normais as convulsões neste modelo são mais severas àmedida que o animal recebe outras estimulações.Which is used as a measure of disease progression, because in normal animals the convulsions in this model are more severe as the animal receives other stimulations.
COMPOSIÇÕES FARMACÊUTICASPHARMACEUTICAL COMPOSITIONS
A presente invenção também se refere a uma composiçãofarmacêutica. Os compostos da invenção podem ser administrados sozinhosou em combinação com diluentes ou veículos farmaceuticamente aceitáveis,em doses quer únicas quer múltiplas. As composições farmacêuticas deacordo com a invenção podem ser formuladas com diluentes ou veículosfarmaceuticamente aceitáveis bem como com quaisquer outros excipientes eadjuvantes conhecidos de acordo com técnicas convencionais tais comoaquelas descritas em Remington: The Science and Practice of Pharmaey, 19ΛEdition, Gennaro, Ed., Mack Publishing Co., Easton, PA, 1995.The present invention also relates to a pharmaceutical composition. The compounds of the invention may be administered alone or in combination with pharmaceutically acceptable diluents or carriers in either single or multiple doses. Pharmaceutical compositions according to the invention may be formulated with pharmaceutically acceptable diluents or carriers as well as any other known adjuvant excipients according to conventional techniques such as those described in Remington: The Science and Practice of Pharmaey, 19th Edition, Gennaro, Ed., Mack Publishing Co., Easton, PA, 1995.
As composições farmacêuticas podem ser especificamenteformuladas para administração por qualquer rota adequada tal como rota oral,retal, nasal, pulmonar, tópica (incluindo bucal e sublingual), transdermal,intracisternal, intraperitoneal, vaginal e parenteral (incluindo subcutânea,intramuscular, intratecal, intravenosa e intradermal), a rota oral sendopreferida. Será reconhecido que a rota preferida dependerá da condição gerale da idade do indivíduo a ser tratado, da natureza da condição a ser tratada edo ingrediente ativo escolhido.Pharmaceutical compositions may be specifically formulated for administration by any suitable route such as oral, rectal, nasal, pulmonary, topical (including buccal and sublingual), transdermal, intracisternal, intraperitoneal, vaginal and parenteral routes (including subcutaneous, intramuscular, intrathecal, intravenous and intradermal), the oral route is preferred. It will be appreciated that the preferred route will depend upon the general condition and age of the subject to be treated, the nature of the condition to be treated and the active ingredient chosen.
As composições farmacêuticas formadas pela combinação docomposto da invenção e os veículos farmaceuticamente aceitáveis são entãoprontamente administradas em uma variedade de formas de dosagemadequadas para as rotas de administração descritas. As formulações podemser convenientemente apresentadas em forma de dosagem unitária pormétodos conhecidos na arte de farmácia.The pharmaceutical compositions formed by the compound of the invention and the pharmaceutically acceptable carriers are then administered in a variety of dosage forms suitable for the administration routes described. The formulations may conveniently be presented in unit dosage form by methods known in the art of pharmacy.
Os compostos desta invenção são geralmente utilizados comoa substância livre ou como um seu sal farmaceuticamente aceitável. Umexemplo é um sal de adição de ácido de um composto possuindo a utilidadede uma base livre. Quando um composto da invenção contiver uma base livretais sais são preparados em uma maneira convencional pelo tratamento deuma solução ou suspensão de uma base livre da invenção com um equivalentequímico de um ácido farmaceuticamente aceitável. Exemplos representativossão mencionados acima.The compounds of this invention are generally used as the free substance or as a pharmaceutically acceptable salt thereof. An example is an acid addition salt of a compound having the utility of a free base. Where a compound of the invention contains a base booklets salts are prepared in a conventional manner by treating a solution or suspension of a free base of the invention with a chemical equivalent of a pharmaceutically acceptable acid. Representative examples are mentioned above.
As composições farmacêuticas para administração oral podemser sólidas ou líquidas. Formas de dosagem sólidas para administração oralincluem e.g. cápsulas, tabletes, drágeas, pílulas, pastilhas losângicas, pós etablete e.g. adicionado em uma cápsula de gelatina dura na forma de pó ou depelota ou e.g. na forma de uma pastilha losângica ou comprimido. Ondeapropriado, composições farmacêuticas para administração oral podem serpreparadas com revestimentos tais como revestimento entéricos ou podem serformuladas de modo a proporcionar liberação controlada do ingrediente ativotal como liberação prolongada ou retardada de acordo com métodos bemconhecidos na arte. Formas de dosagem líquidas para administração oralincluem e.g. soluções, emulsões, suspensões, xaropes e elixires.Pharmaceutical compositions for oral administration may be solid or liquid. Solid dosage forms for oral administration include e.g. capsules, tablets, pills, pills, lozenge pellets, etablete powders e.g. added in a hard gelatin capsule in powder or depot form or e.g. in the form of a lozenge tablet or tablet. Accordingly, pharmaceutical compositions for oral administration may be prepared with coatings such as enteric coatings or may be formulated to provide controlled release of the activotal ingredient as prolonged or delayed release according to methods well known in the art. Liquid dosage forms for oral administration include e.g. solutions, emulsions, suspensions, syrups and elixirs.
Formulações da presente invenção adequadas paraadministração oral podem ser apresentadas como unidades discretas tais comocápsulas ou tabletes, cada uma contendo uma quantidade predeterminada deingrediente ativo, e que pode incluir um ou mais excipientes apropriados.Ainda mais, as formulações oralmente disponíveis podem estar na forma deum pó ou de grânulos, uma solução ou suspensão em um líquido aquoso ounão aquoso, ou em uma emulsão de óleo-em-água ou de água-em-óleo.Formulations of the present invention suitable for oral administration may be presented as discrete units such as capsules or tablets, each containing a predetermined amount of active ingredient, and which may include one or more appropriate excipients. Further, orally available formulations may be in the form of a powder. or granules, a solution or suspension in an aqueous or non-aqueous liquid, or in an oil-in-water or water-in-oil emulsion.
Veículos farmacêuticos adequados incluem cargas ou diluentessólidos inertes, solução aquosa estéril e vários solventes orgânicos. Exemplosde veículos sólidos são lactose, terra alba, sacarose, ciclo-dextrina, talco,gelatina, ágar, pectina, acácia, estearato de magnésio, ácido esteárico, alquil-ésteres inferiores de celulose, amido de milho, amido de batata, gomas esemelhantes. Exemplos de veículos líquidos são xarope, óleo de amendoim,azeite de oliva, fosfolipídeos, ácidos graxos, aminas de ácido graxo,polioxietileno e água.Suitable pharmaceutical carriers include inert fillers or diluents, sterile aqueous solution and various organic solvents. Examples of solid carriers are lactose, terra alba, sucrose, cyclodextrin, talc, gelatin, agar, pectin, acacia, magnesium stearate, stearic acid, lower alkyl esters of cellulose, corn starch, potato starch, similar gums. Examples of liquid carriers are syrup, peanut oil, olive oil, phospholipids, fatty acids, fatty acid amines, polyoxyethylene and water.
O veículo ou diluente pode incluir qualquer material deliberação prolongada conhecido na arte, tal como monoestearato de glicerilaou diestearato de glicerila, sozinho ou misturado com uma cera.The carrier or diluent may include any prolonged deliberation material known in the art, such as glyceryl monostearate or glyceryl distearate, alone or mixed with a wax.
Quaisquer adjuvantes ou aditivos normalmente usados paratais propósitos tais como colorantes, aromatizantes, conservantes etc. podemser utilizados desde que sejam compatíveis com os ingredientes ativos.Any adjuvants or additives commonly used for purposes such as colorings, flavorings, preservatives etc. may be used provided they are compatible with the active ingredients.
A quantidade de veículo sólido pode variar mas normalmenteserá de cerca de 25 mg a cerca de 1 g. Se um veículo líquido for usado, apreparação poderá estar na forma de um xarope, uma emulsão, cápsula degelatina mole ou líquido estéril injetável tal como uma solução ou suspensãolíquida aquosa ou não aquosa.The amount of solid carrier may vary but will usually be from about 25 mg to about 1 g. If a liquid carrier is used, the preparation may be in the form of a syrup, emulsion, soft degelatin capsule or sterile injectable liquid such as an aqueous or non-aqueous liquid solution or suspension.
Tabletes podem ser preparados por misturação do ingredienteativo com adjuvantes ou diluentes ordinários e subseqüente compressão damistura em uma máquina de preparação de tabletes convencional.Tablets may be prepared by mixing the active ingredient with ordinary adjuvants or diluents and subsequent mixing compression in a conventional tabletting machine.
Composições farmacêuticas para administração parenteralincluem emulsões, suspensões, dispersões estéreis aquosas injetáveis ou nãoaquosas injetáveis bem como pós estéreis a serem reconstituídos em dispersões ousoluções estéreis injetáveis antes do uso. Formulações injetáveis de deposiçãotambém são contempladas como estando dentro do escopo da presente invenção.Pharmaceutical compositions for parenteral administration include injectable or non-aqueous injectable aqueous sterile emulsions, suspensions, dispersions as well as sterile powders to be reconstituted into sterile injectable dispersions or solutions prior to use. Injectable deposition formulations are also contemplated as being within the scope of the present invention.
Para administração parenteral, soluções do composto dainvenção em soluções aquosas estéreis, propileno-glicol aquoso, vitamina Eaquosa, óleo de amendoim ou de gergelim podem ser empregadas. Taissoluções aquosas devem ser adequadamente tamponadas se necessário e odiluente líquido primeiro tornado isotônico com suficiente agente salino ouglicose. As soluções aquosas são particularmente adequadas paraadministração intravenosa, intramuscular, subcutânea e intraperitoneal. Osmeios aquosos estéreis empregados são todos prontamente disponíveis portécnicas padrão conhecidas por aquelas pessoas experientes na arte.For parenteral administration, solutions of the inventive compound in sterile aqueous solutions, aqueous propylene glycol, aqueous vitamin E, peanut or sesame oil may be employed. Aqueous solutions should be adequately buffered if necessary and the odorous liquid first made isotonic with sufficient saline or glucose agent. Aqueous solutions are particularly suitable for intravenous, intramuscular, subcutaneous and intraperitoneal administration. Sterile aqueous media employed are all readily available standard techniques known to those skilled in the art.
Soluções para injeções podem ser preparadas pela dissoluçãodo ingrediente ativo e de possíveis aditivos em uma parte do solvente parainjeção, preferivelmente água estéril, ajustando a solução para o volumedesejado, esterilizando a solução e enchendo ampolas ou frascos com ela.Qualquer aditivo adequado convencionalmente usado na arte pode seradicionado, tais como agentes de tonicidade, conservantes, antioxidantes, etc.Solutions for injections may be prepared by dissolving the active ingredient and possible additives in a portion of the solvent for injection, preferably sterile water, adjusting the solution to the desired volume, sterilizing the solution and filling ampoules or vials with it. Any suitable additive conventionally used in the art can be added such as tonicity agents, preservatives, antioxidants, etc.
Outras formas de administração adequadas incluemsupositórios, borrifos, ungüentos, cremes, geles, inalantes, remendos dermais,implantes etc.Other suitable forms of administration include suppositories, sprays, ointments, creams, gels, inhalants, dermal patches, implants, etc.
Uma dosagem oral típica está dentro da faixa de cerca de0,001 mg/kg de peso corporal por dia a cerca de 100 mg/kg de peso corporalpor dia, preferivelmente de cerca de 0,01 mg/kg de peso corporal por dia acerca de 50 mg/kg de peso corporal por dia, e com maior preferência de cercade 0,05 mg/kg de peso corporal por dia a cerca de 10 mg/kg de peso corporalpor dia administrado em uma ou mais dosagens tais como 1 a 3 dosagens. Adosagem exata dependerá da freqüência e do modo de administração, do sexo,da idade, do peso e da condição geral do indivíduo tratado, da natureza e daseveridade da condição tratada e de quaisquer doenças concomitantes a seremtratadas e de outros fatores evidentes para aquelas pessoas experientes na arte.A typical oral dosage is within the range of about 0.001 mg / kg bodyweight per day to about 100 mg / kg bodyweight per day, preferably about 0.01 mg / kg bodyweight per day. 50 mg / kg body weight per day, and most preferably about 0.05 mg / kg body weight per day to about 10 mg / kg body weight per day administered at one or more strengths such as 1 to 3 strengths . Exact dosing will depend on the frequency and mode of administration, gender, age, weight and general condition of the individual being treated, the nature and severity of the condition being treated and any concomitant diseases to be treated, and other factors evident to those experienced. in art.
As formulações podem ser convenientemente apresentadas naforma de dosagem unitária por métodos conhecidos por aquelas pessoasexperientes na arte. Uma forma de dosagem unitária típica para administraçãooral uma ou mais vezes por dia tal como 1 a 3 vezes por dia pode conter de0,01 mg a cerca de 1.000 mg, preferivelmente de cerca de 0,05 mg a cerca de500 mg, e com maior preferência de cerca de 0,5 mg a cerca de 200 mg.The formulations may conveniently be presented in unit dosage form by methods known to those skilled in the art. A typical unit dosage form for oral administration once or more times a day such as 1 to 3 times a day may contain from 0.01 mg to about 1,000 mg, preferably from about 0.05 mg to about 500 mg, and more frequently. preferably from about 0.5 mg to about 200 mg.
Para rotas parenterais tal como administração intravenosa,intratecal, intramuscular e semelhante, doses tipicamente são da ordem decerca de metade da dose empregada para administração oral.For parenteral routes such as intravenous, intrathecal, intramuscular administration and the like, doses typically are in the order of about half the dose employed for oral administration.
Exemplos típicos de receitas para a formulação da invençãosão as seguintes:Typical examples of recipes for formulating the invention are as follows:
1) Tabletes contendo 5,0 mg de um composto da invençãocalculado como a base livre1) Tablets containing 5.0 mg of a compound of the invention calculated as free base
base:base:
<table>table see original document page 27</column></row><table><table> table see original document page 27 </column> </row> <table>
2) Tabletes contendo 0,5 mg de um composto da invenção2) Tablets containing 0.5 mg of a compound of the invention.
<table>table see original document page 27</column></row><table>4) Solução para injeção contendo por mililitro:<table> table see original document page 27 </column> </row> <table> 4) Solution for injection containing per milliliter:
Composto da invenção 0,5 mgCompound of the invention 0.5 mg
Sorbitol 5,1 mgSorbitol 5.1 mg
Ácido acético 0,05 mgAcetic Acid 0.05 mg
Sacarina sódica 0,5 mgSodium saccharin 0.5 mg
Água ad ImLWater ad ImL
A expressão um composto da invenção significa qualquer umadas modalidades de fórmula I como aqui descrita.The term a compound of the invention means any of the embodiments of formula I as described herein.
Em um outro aspecto a presente invenção refere-se a ummétodo de preparar um composto da invenção como descrito a seguir.In another aspect the present invention relates to a method of preparing a compound of the invention as described below.
MÉTODOS DE PREPARAÇÃO DE COMPOSTOS DA INVENÇÃOMETHODS FOR PREPARING COMPOUNDS OF THE INVENTION
Os compostos da invenção fórmula geral I, na qual R1, R2, R3,R4, R5, e q são como definidos acima podem ser preparados pelos métodoscomo apresentados nos esquemas e como descritos abaixo.The compounds of the invention formula I, wherein R 1, R 2, R 3, R 4, R 5, and q are as defined above may be prepared by the methods as set forth in the schemes and as described below.
Nos compostos de fórmulas gerais I - XX, R1, R2, R3, R4, R5 eq são como definidos sob a fórmula I.In the compounds of formulas I-XX, R1, R2, R3, R4, R5 and q are as defined under formula I.
Para os compostos que podem existir como equilíbrio entredois ou mais tautômeros, apenas um tautômero é representado nos esquemas,embora possa não ser o tautômero mais estável. Tais compostos incluem, masnão são limitado a hidróxi-pirimidinas de fórmula geral IX, Χ, XVII, XVIIIbem conhecidos pelos químicos experientes na arte.For compounds which may exist as equilibrium between or more tautomers, only one tautomer is represented in the schemes, although it may not be the most stable tautomer. Such compounds include, but are not limited to, hydroxy pyrimidines of formula IX, Χ, XVII, XVIII well known to those skilled in the art.
Compostos de fórmulas gerais II, III, VII, VIII, IX, Χ, XI,XIV, XVI, XVII, XIX e XX são quer obtidos de fornecedores comerciais,quer preparados por métodos padrão conhecidos pelos químicos experientesna arte.Compounds of general formulas II, III, VII, VIII, IX, Χ, XI, XIV, XVI, XVII, XIX and XX are either obtained from commercial suppliers or prepared by standard methods known to those skilled in the art.
Compostos de fórmula geral IV (Esquema 1) podem serobtidos pela reação de compostos de fórmula geral II com aminas de fórmulageral III com ou sem a adição de bases, tais como trialquil-aminas, carbonatode potássio ou de sódio, em um solvente adequado, tal como acetonitrila,Ν,Ν-dimetil-formamida ou etanol, em uma temperatura adequada, tais comotemperatura ambiente, temperatura de refluxo ou em temperatura mais altasob irradiação de microondas em um vaso vedado.Compounds of formula IV (Scheme 1) may be obtained by reacting compounds of formula II with amines of formula III with or without the addition of bases such as trialkyl amines, potassium carbonate or sodium in a suitable solvent such as such as acetonitrile, Ν, Ν-dimethylformamide or ethanol, at a suitable temperature, such as room temperature, reflux temperature or higher temperature under microwave irradiation in a sealed vessel.
Compostos de fórmula geral V podem ser preparados a partirde compostos de fórmula geral IV, pela redução do grupo nitro a um grupoamino, com agentes redutores adequados tais como pó de zinco ou de ferro napresença de ácido tal como ácido acético ou ácido clorídrico aquoso, ou porgás hidrogênio ou formiato de amônio na presença de um catalisador dehidrogenação adequado tal como paládio sobre carbono ativado em solventesadequados tais como metanol, etanol, acetato de etila ou tetra-hidro-furano,em temperaturas adequadas ou sob irradiação ultra-sônica. Alternativamente,cloreto de estanho (II) ou ditionito de sódio podem ser usados como agentesredutores sob condições bem conhecidas pelos químicos experientes na arte.Compounds of formula V may be prepared from compounds of formula IV by reducing the nitro group to an amino group with suitable reducing agents such as zinc or iron powder in the presence of acid such as acetic acid or aqueous hydrochloric acid, or hydrogen gas or ammonium formate in the presence of a suitable hydrogenation catalyst such as palladium on activated carbon in suitable solvents such as methanol, ethanol, ethyl acetate or tetrahydrofuran at appropriate temperatures or under ultrasonic irradiation. Alternatively, tin (II) chloride or sodium dithionite may be used as reducing agents under conditions well known to chemists skilled in the art.
Compostos da invenção de fórmula geral I podem serpreparados pela reação de compostos de fórmula geral V com reagenteseletrofílicos adequados, tais como, mas não limitados a, fluoretos de ácidocarboxílico, cloretos de ácido carboxílico, brometos de ácido carboxílico,iodetos de ácido carboxílico, anidridos de ácido carboxílico, ésteres ativados,cloro-formiatos, e com ou sem a adição de bases, tais como piridina, trialquil-aminas, carbonato de potássio, óxido de magnésio ou alcoolatos de lítio, desódio, ou de potássio, em um solvente adequado, tal como acetato de etila,dioxano, tetra-hidro-furano, acetonitrila ou dietil-éter, em temperaturasadequadas, tais como temperatura ambiente, temperatura de refluxo ou emtemperatura mais alta em um vaso vedado sob irradiação de microondas.Compounds of the invention of formula I may be prepared by reacting compounds of formula V with suitable electrophilic reagents such as, but not limited to, carboxylic acid fluorides, carboxylic acid chlorides, carboxylic acid bromides, carboxylic acid iodides, carboxylic acid, activated esters, chloro-formates, and with or without the addition of bases such as pyridine, trialkyl amines, potassium carbonate, magnesium oxide or lithium, sodium or potassium alcoholates in a suitable solvent, such as ethyl acetate, dioxane, tetrahydrofuran, acetonitrile or diethyl ether, at suitable temperatures, such as room temperature, reflux temperature or higher temperature in a sealed vessel under microwave irradiation.
Ésteres ativados e anidridos carboxílicos podem ser preparados a partir deácidos carboxílicos adequadamente substituídos sob condições conhecidaspelos químicos experientes na arte, por exemplo como descrito por F.Albericio e L.A. Carpino, "Coupling reagents and activation" em Methods inenzymology: Solid-phase peptide synthesis, pp. 104-126, Academic Press,New York, 1997. Haletos de ácido carboxílicos podem ser preparados a partirácidos carboxílicos adequadamente substituídos pela ativação com reagentestais como, mas não limitados a, cloreto de tionila, cloreto de oxalila,tribrometo de fósforo ou triiodeto de fósforo sob condições bem conhecidaspelos químicos experientes na arte.Activated esters and carboxylic anhydrides may be prepared from suitably substituted carboxylic acids under conditions known to chemists skilled in the art, for example as described by F.Albericio and LA Carpino, "Coupling reagents and activation" in Methods inenzymology: Solid-phase peptide synthesis, pp. 104-126, Academic Press, New York, 1997. Carboxylic acid halides may be prepared from carboxylic acids suitably substituted by activation with reagents such as, but not limited to, thionyl chloride, oxalyl chloride, phosphorus tribromide or phosphorus triiodide. under conditions well known by chemists skilled in the art.
Esquema IScheme I
<formula>formula see original document page 30</formula><formula> formula see original document page 30 </formula>
Compostos de fórmula geral II podem se preparados comomostrado em Esquema 2. Compostos de fórmula geral IX são preparados pelacondensação de uréia com 1,3-dicarbonil-compostos VII ou seus equivalentestais como carbonil-compostos insaturados VIII em um solvente adequado talcomo Ν,Ν-dimetil-formamida, N-metil-pirrolidinona ou etanol, com ou sem aadição de catalisador tal como ácidos clorídrico, sulfurico, metano-sulfônico,ou polifosfórico ou ácidos de Lewis em uma temperatura adequada, tais comotemperatura ambiente, temperatura de refluxo ou em temperatura mais altasob irradiação de microondas em um vaso vedado. Compostos de fórmulageral X podem ser preparados a partir de compostos de fórmula geral IX, porreações de nitração conhecidas pelos químicos experientes na arte, tais comoreação com ácido nítrico concentrado, nitrito de sódio ou nitrato de sódio, emum solvente adequado, tal como ácido acético glacial, anidrido acético, ácidotrifluoroacético, ácido sulfurico concentrado ou suas misturas, emtemperaturas apropriadas, por exemplo como descrito por P.B.D. de Ia Mare eJ.H. Ridd, "Preparative methods of nitration" em Aromatic substitutions, pp.48-5-6, Butterworths Scientific Publications, London, 1959. Compostos defórmula geral X podem ser convertidos em compostos de fórmula geral II pormétodos conhecidos pelos químicos experientes na arte tal como reação decloração ou bromação com óxi-cloreto de fósforo ou óxi-brometo de fósforo.Compostos de fórmula geral II, na qual X é flúor ou iodeto, podem serpreparados a partir de compostos de fórmula geral II, na qual X é cloreto oubrometo, por reação de substituição de halogênio com reagentes apropriadostais como ácido iodídrico, fluorídrico, iodeto de sódio, fluoreto de potássiosob condições conhecidas pelos químicos experientes na arte.Esquema IICompounds of formula II may be prepared as shown in Scheme 2. Compounds of formula IX are prepared by the urea condensation with 1,3-dicarbonyl compounds VII or their equivalent as carbonyl unsaturated compounds VIII in a suitable solvent such as Ν, Ν- dimethylformamide, N-methylpyrrolidinone or ethanol, with or without the addition of catalyst such as hydrochloric, sulfuric, methanesulfonic acids, or polyphosphoric or Lewis acids at a suitable temperature, such as room temperature, reflux temperature or temperature highest under microwave irradiation in a sealed vessel. Compounds of formula X may be prepared from compounds of formula IX by nitration reactions known to chemists skilled in the art such as concentrated nitric acid, sodium nitrite or sodium nitrate in a suitable solvent such as glacial acetic acid , acetic anhydride, trifluoroacetic acid, concentrated sulfuric acid or mixtures thereof, at appropriate temperatures, for example as described by PBD by Ia Mare eJ.H. Ridd, "Preparative methods of nitration" in Aromatic substitutions, pp.48-5-6, Butterworths Scientific Publications, London, 1959. Compounds of formula X may be converted to compounds of formula II by methods known to chemists skilled in the art such as dechlorination or bromination reaction with phosphorus oxide chloride or phosphorus oxide bromide. Compounds of formula II, in which X is fluorine or iodide, may be prepared from compounds of formula II, in which X is chloride or bromide, by halogen substitution reaction with suitable reagents such as hydroiodic acid, hydrofluoric acid, sodium iodide, potassium fluoride under conditions known to chemists skilled in the art.
<formula>formula see original document page 31</formula><formula> formula see original document page 31 </formula>
Compostos de fórmulas gerais XII e XV (Esquema 3) podemser preparados a partir de guanidinas apropriadamente substituídas de fórmulageral XI por reação de condensação com 1,3-dicarbonil-compostos ou seuscarbonil-compostos insaturados equivalentes de fórmulas gerais VII, VIII(onde LG é um grupo de saída adequado tal como alcoxila ou dialquil-amino)ou XIV sob condições como descritas sob o Esquema 2 para preparação doscompostos de fórmula geral IX. Compostos de fórmula geral XII podem serconvertidos em compostos de fórmula geral XV por copulação diazo bemconhecida pelos químicos experientes na arte. Alternativamente, compostosde fórmula geral XV podem ser nitrados como descrito sob o Esquema 2 paraa preparação de compostos de fórmula geral X. Compostos de fórmula geralV podem ser preparados a partir de compostos de fórmulas gerais XIII ou XV,pela redução de grupo nitro ou de grupo diazo, respectivamente, em um grupoamino, sob condições descritas acima para a preparação de compostos defórmula geral V sob Esquema 1.Esquema 3Compounds of formula XII and XV (Scheme 3) may be prepared from appropriately substituted guanidines of formula XI by condensation reaction with 1,3-dicarbonyl compounds or their equivalent unsaturated carbonyl compounds of formulas VII, VIII (where LG is a suitable leaving group such as alkoxy or dialkylamino) or XIV under conditions as described under Scheme 2 for preparation of the compounds of formula IX. Compounds of formula XII may be converted to compounds of formula XV by diazo copulation well known to chemists skilled in the art. Alternatively, compounds of formula XV may be nitrated as described under Scheme 2 for the preparation of compounds of formula X. Compounds of formula V may be prepared from compounds of formula XIII or XV by reduction of nitro group or group. diazo, respectively, in an amino group under conditions described above for the preparation of compounds of general formula V under Scheme 1.
<formula>formula see original document page 32</formula><formula> formula see original document page 32 </formula>
Em particular, condensação de guanidinas substituídas defórmula geral XI com cetoésteres ou cetoácidos de fórmula geral XVI(Esquema 4) sob condições descritas acima sob Esquema 3 podem levar àformação de compostos de fórmula geral XVII, que podem ser nitrados sobcondições descritas acima sob para proporcionar compostos de fórmula geralXVIII. O grupo hidroxila em XVIII pode ser convertido em compostos defórmula geral XX (XIII onde R4 é halogênio) por reação de halogenação sobcondições descritas acima sob para a preparação de compostos com a fórmulageral II. Alternativamente, compostos de fórmula geral XX (XIII onde R4 éhalogênio) podem ser preparados a partir de compostos de fórmula geral XIX(XIII onde R4 é amino) por reação de diazotação seguida por substituiçãonucleofílica na presença de ânio halogênio sob condições bem conhecidaspelos químicos experientes na arte. Compostos de fórmula geral XIII, na qualR4 é Cι_6-alqu(en/in)ila, C3.8-ciclo-alqu(en)ila, C3_8-ciclo-alqu(en)il-Ci.6-alqu(en/in)ila, halo-Ci.6-alqu(en/in)ila, halo-C3.8-ciclo-alqu(en)ila ou Iialo-C3.8-ciclo-alqu(en)il-Ci_6-alqu(en/in)ila, podem ser preparados a partir decompostos de fórmula geral XX (XIII onde R4 é halogênio) por meio dereações de copulação cruzada conhecidas pelos químicos experientes na arte,tal como copulação de Negishi (Ε. I. Negishi, A.O. King e N. Okukado, J.Org Chem., 1977, 42, 1821), copulação de Sonogashira (K. Sonogashira, Y.Tohda e N. Hagihara, Tet.Lett., 1975, 16, 4467), ou outras reações decopulação cruzada catalisada por metal de transição (W. Dohle, D.M. Lindsaye P. Knochel, Org.Lett., 2001, 3, 2871).In particular, condensation of substituted guanidines of formula XI with ketoesters or keto acids of formula XVI (Scheme 4) under conditions described above under Scheme 3 may lead to the formation of compounds of formula XVII, which may be nitrated under conditions described above to provide compounds. of formula XVIII. The hydroxyl group in XVIII can be converted to compounds of general formula XX (XIII where R4 is halogen) by halogenation reaction under the conditions described above for the preparation of compounds of formula II. Alternatively, compounds of formula XX (XIII where R4 is halogen) may be prepared from compounds of formula XIX (XIII where R4 is amino) by diazotation reaction followed by nucleophilic substitution in the presence of halogen ion under conditions well known by chemists experienced in the art. art. Compounds of formula XIII, wherein R4 is C1-6-alkyl (en / in) yl, C3.8-cycloalkyl (en) yl, C3-8-cycloalkyl (en) yl-C1-6 alkyl (en / in) ) yl, halo-C1-6 alkyl (en / in) yl, halo-C3.8-cycloalkyl (en) yl or Iialo-C3.8-cycloalkyl (en) yl-C1-6 alkyl (en) (in) ila, can be prepared from decompositions of general formula XX (XIII where R4 is halogen) by cross-coupling reactions known to chemists skilled in the art, such as Negishi copulation (Ε. I. Negishi, AO King and N. Okukado, J. Org Chem., 1977, 42, 1821), Sonogashira copulation (K. Sonogashira, Y.Tohda and N. Hagihara, Tet.Lett., 1975, 16, 4467), or other cross-coupling reactions. transition metal catalyzed (W. Dohle, MD Lindsaye P. Knochel, Org.Lett., 2001, 3, 2871).
Adicionalmente, compostos de fórmula geral XIII, na qual R4é ciano, podem ser preparados a partir de compostos de fórmula geral XX(XIII onde R4 é halogênio) por meio de reações de cianação catalisadas porníquel conhecidas pelos químicos experientes na arte por exemplo comodescrito porL. Cassar, J. Organomet.Chem., 1973, 54, C57-058.Additionally, compounds of formula XIII, wherein R 4 is cyano, may be prepared from compounds of formula XX (XIII where R 4 is halogen) by means of pornographic catalyzed cyanation reactions known to chemists skilled in the art for example as described by L. Cassar, J. Organomet.Chem., 1973, 54, C57-058.
Ademais, compostos de fórmula geral XIII, na qual R4 é Cw-alqu(en/in)iloxila, C3.8-ciclo-alqu(en)iloxila ou C3.8-ciclo-alqu(en)il-Ci.6-alqu(en/in)iloxila, podem ser preparados a partir de compostos de fórmulageral XX (XIII onde R4 é halogênio) pela reação com os alcoolatos de lítio, desódio, ou de potássio apropriados ou álcoois na presença de base tal comohidróxido de lítio, de sódio, ou de potássio, hidreto de lítio, de sódio, ou depotássio, e com ou sem a adição de um catalisador tal como sulfato de cobre,em um solvente adequado tal como dioxano, em temperaturas adequadas, taiscomo temperatura ambiente ou temperatura de refluxo.In addition, compounds of formula XIII, wherein R4 is Cw-alkyl (en / in) yloxy, C3.8-cycloalkyl (en) yloxy or C3.8-cycloalkyl (en) yl-C1-6. alkyl (en / in) yloxyl may be prepared from compounds of formula XX (XIII where R4 is halogen) by reaction with appropriate lithium, disodium, or potassium alcoholates or alcohols in the presence of base such as lithium hydroxide, sodium, or potassium, lithium hydride, sodium, or depotassium, and with or without the addition of a catalyst such as copper sulphate, in a suitable solvent such as dioxane, at appropriate temperatures, such as room temperature or reflux.
Esquema 4Scheme 4
<formula>formula see original document page 33</formula><formula> formula see original document page 33 </formula>
Alquinos preparados pelas reações de Sonogashira podem serreduzidos a alquenos ou alcanos por redução com gás hidrogênio ou formiatode amônio na presença de um catalisador de hidrogenação adequado tal comopaládio sobre carbono ativado ou platina sobre carbono ativado em solventesadequados tais como metanol, etanol ou tetra-hidro-furano, em temperaturasadequadas por exemplo como descrito por S. Siegel, "Heterogeneous catalytichydrogenation of C=C and alkynes" em Comprehensive Organic Synthesis, v.8, pp. 417-442, Pergamon Press, 1991.Alkines prepared by the Sonogashira reactions may be reduced to alkenes or alkanes by reduction with hydrogen gas or ammonium formiat in the presence of a suitable hydrogenation catalyst such as activated carbon palladium or activated carbon platinum in suitable solvents such as methanol, ethanol or tetrahydro- furan, at suitable temperatures for example as described by S. Siegel, "Heterogeneous catalytichydrogenation of C = C and alkynes" in Comprehensive Organic Synthesis, v.8, pp. 25-30. 417-442, Pergamon Press, 1991.
Preparação de compostos da invençãoPreparation of compounds of the invention
ExemplosExamples
Dados de LC-MS analíticos foram obtidos em um instrumentoPE Sciex API 150EX equipado com fotoionização em pressão atmosférica eum sistema Shimadzu LC-8A/SLC-10A LC. Coluna: coluna WatersSymmetry Cl8 de 30 mm X 4,6 mm com tamanho de partícula de 3,5 μηι;Sistema de solventes: A = água/ácido trifluoroacético (100:0,05) e B =água/acetonitrila/ácido trifluoroacético (5:95:0,03); Método: Eluição emgradiente linear com 90% A a 100% B em 4 minutos e com uma vazão defluxo de 2 mL/minuto. Os tempos de retenção (tR) são expressados emminutos.Analytical LC-MS data were obtained on a Sciex API 150EX PE instrument equipped with atmospheric pressure photoionization and a Shimadzu LC-8A / SLC-10A LC system. Column: WatersSymmetry Cl8 30 mm X 4.6 mm column with 3.5 μηι particle size; Solvent system: A = water / trifluoroacetic acid (100: 0.05) and B = water / acetonitrile / trifluoroacetic acid ( 5: 95: 0.03); Method: Gradient elution with 90% A to 100% B in 4 minutes and with a flow rate of 2 mL / minute. Retention times (tR) are expressed in minutes.
Espectros de 1H NMR foram registrados a 500,13 MHz em uminstrumento Bruker Avance DRX500.1H NMR spectra were recorded at 500.13 MHz on a Bruker Avance DRX500 instrument.
Dimetil-sulfóxido deuterado (99,8%D) foi usado comosolvente. Tetrametil-silano foi usado como padrão de referência interno.Valores de deslocamento químico são expressados em valores de ppmrelativos ao tetrametil-silano. As seguintes abreviações são usadas paramultiplicidade de sinais de NMR: s = singleto, d = dubleto, t = tripleto, q =quarteto, qui = quinteto, h = hepteto, dd = dubleto duplo, ddd = dubleto duploduplo, dt = tripleto duplo, dq = quarteto duplo, tt = tripleto de tripletos, m =multipleto e br = singleto largo.Deuterated dimethyl sulfoxide (99.8% D) was used as a solvent. Tetramethyl silane was used as the internal reference standard. Chemical displacement values are expressed in ppm values relative to tetramethyl silane. The following abbreviations are used for NMR signal multiplicity: s = singlet, d = doublet, t = triplet, q = quartet, chi = quintet, h = heptet, dd = double doublet, ddd = double doublet, dt = double triplet, dq = double quartet, tt = triplet of triplets, m = multiplet and br = broad singlet.
Experimentos em microondas foram realizados em reatores oufrascos de processo vedados usando um Emrys Synthesizer ou EmrysOptimizer EXP da Personal Chemistry ou da Milestone MicrosynthInstrument of Milestone. Quando a reação foi aquecida em um instrumento demicroondas, ela foi esfriada para 25°C antes da etapa de processo seguinte.Preparação de intermediáriosMicrowave experiments were performed on sealed reactors or process flasks using an Emrys Synthesizer or EmrysOptimizer EXP from Personal Chemistry or Milestone Microsynthesis Instrument of Milestone. When the reaction was heated in a microwave oven, it was cooled to 25 ° C prior to the next process step.
<formula>formula see original document page 35</formula><formula> formula see original document page 35 </formula>
6-Metil-5-nitro-N*2 *- (4-trifluorometil-benzil) -pirimidina-2,4-diamina6-Methyl-5-nitro-N * 2 * - (4-trifluoromethyl-benzyl) -pyrimidine-2,4-diamine
Uma mistura de 2-cloro-6-metil-5-nitro-pirimidin-4-il-amina(300 mg, 1,591 mmol), 4-trifluorometil-benzil-amina (369 mg, 2,107 mmol)em acetonitrila (3 ml) e trietil-amina (0,5 ml) foi jateada com argônio, vedadano frasco de processo Emrys e aquecida a 120°C por 2 min sob irradiação demicroondas. A suspensão obtida foi extinta com bicarbonato de sódio aquoso10% (2 ml) e voláteis orgânicos foram evaporados sob pressão reduzida.Metanol (5 ml) e água (100 ml) foram adicionados no resíduo. O produto foiseparado por filtração, lavado com água e seco em vácuo para dar 490 mg desólido amarelo. Rendimento de 94%. LC-MS (m/z) 328,1 (MH+); tR = 2,58.1H NMR (500 MHz, DMSO-Cl6): ca. 3:1 mistura de dois rotâmeros, 2,54 (s,3H), 4,57 (d, 1,5H), 4,63 (d, 0,5H), 7,52 (t, 2H), 7,68 (d, 2H), 7,81 (s, 0,5H,NH2), 8,0 (s, 1,5H, NH2), 8,17 (t, 0,25H, NH), 8,48 (t, 0,75H, NH).A mixture of 2-chloro-6-methyl-5-nitro-pyrimidin-4-yl-amine (300 mg, 1.591 mmol), 4-trifluoromethyl-benzyl-amine (369 mg, 2.107 mmol) in acetonitrile (3 mL) and triethylamine (0.5 ml) was blasted with argon, sealed in the Emrys process flask and heated at 120 ° C for 2 min under demi-microwave irradiation. The suspension obtained was quenched with 10% aqueous sodium bicarbonate (2 mL) and organic volatiles were evaporated under reduced pressure. Methanol (5 mL) and water (100 mL) were added to the residue. The product was filtered off, washed with water and dried in vacuo to give 490 mg yellow solid. Yield 94%. LC-MS (m / z) 328.1 (MH +); t R = 2.58.1H NMR (500 MHz, DMSO-Cl6): ca. 3: 1 mixture of two rotamers, 2.54 (s, 3H), 4.57 (d, 1.5H), 4.63 (d, 0.5H), 7.52 (t, 2H), 7, 68 (d, 2H), 7.81 (s, 0.5H, NH 2), 8.0 (s, 1.5H, NH 2), 8.17 (t, 0.25H, NH), 8.48 ( t, 0.75H, NH).
<formula>formula see original document page 35</formula><formula> formula see original document page 35 </formula>
6-Metil-N*2 *-(4-trifluorometil-benzil)-pirimidina-2,4, 5-triamina.6-Methyl-N * 2 * - (4-trifluoromethyl-benzyl) -pyrimidine-2,4,5-triamine.
Em uma solução vigorosamente agitada de 6-metil-5-nitro-N*2*-(4-trifluorometil-benzil)-pirimidina-2,4-diamina (450 mg, 1,376 mmol)em tetra-hidro-furano (20 ml) e ácido acético (5 ml) em banho de água fria,pó de zinco (tamanho de partícula <10 micrômetros, 5 g) foi adicionado emporções em 2 min. Banho de água foi removido e mais pó de zinco (2 g) foiadicionado. A suspensão foi agitada na temperatura ambiente por 60 min eextinta com bicarbonato de sódio aquoso 10% para pH>8. A suspensão obtidafoi extraída com acetato de etila (10 vezes). A solução orgânica combinadafoi filtrada via camada de gel de sílica (10 g) e eluída com 20% em acetato deetila para dar 430 mg de óleo amarelo pálido após evaporação. O produtosolidificou após secagem em vácuo. Rendimento de 100%. Foi usado na etapaseguinte sem purificação adicional. LC-MS (m/z) 298,1 (MH+); tR = 1,68. 1HNMR (500 MHz, DMSO-d6): 2,02 (s, 3H), 3,1-3,8 (br, NH2+ H2O), 4,43 (d,2H), 5,88 (br, 2H), 6,26 (t, 1H, NH), 7,48 (d, 2H), 7,62 (d, 2H).In a vigorously stirred solution of 6-methyl-5-nitro-N * 2 * - (4-trifluoromethyl-benzyl) -pyrimidine-2,4-diamine (450 mg, 1.376 mmol) in tetrahydrofuran (20 mL ) and acetic acid (5 ml) in cold water bath, zinc dust (particle size <10 micrometers, 5 g) was added portionwise within 2 min. Water bath was removed and more zinc dust (2 g) was added. The suspension was stirred at room temperature for 60 min and quenched with 10% aqueous sodium bicarbonate to pH> 8. The suspension obtained was extracted with ethyl acetate (10 times). The combined organic solution was filtered via silica gel layer (10 g) and eluted with 20% in ethyl acetate to give 430 mg of pale yellow oil after evaporation. The product solidified after vacuum drying. Yield 100%. It was used in the next step without further purification. LC-MS (m / z) 298.1 (MH +); t R = 1.68. 1H NMR (500 MHz, DMSO-d6): 2.02 (s, 3H), 3.1-3.8 (br, NH 2 + H 2 O), 4.43 (d, 2H), 5.88 (br, 2H) 6.26 (t, 1H, NH), 7.48 (d, 2H), 7.62 (d, 2H).
Cloreto de 3,4-difluoro-fenil-acetila.3,4-Difluoro-phenyl acetyl chloride.
Acido 3-cloro-fenil-acético (19,7 g) em cloreto de tionila (100ml) foi aquecido sob refluxo por 3 h. Voláteis foram removidos em vácuo e oresíduo oleoso obtido foi usado na etapa seguinte sem purificação adicional.3-Chloro-phenyl acetic acid (19.7 g) in thionyl chloride (100ml) was heated under reflux for 3 h. Volatiles were removed in vacuo and the obtained oily residue was used in the next step without further purification.
1H NMR (500 MHz, CDCl3): 4,12 (s, 2H), 7,16 (d, 1H), 7,27-7,34 (m, 3H).1H NMR (500 MHz, CDCl3): 4.12 (s, 2H), 7.16 (d, 1H), 7.27-7.34 (m, 3H).
Os seguintes cloretos de ácido foram preparados analogamentea partir dos ácidos correspondentes:The following acid chlorides were prepared analogously from the corresponding acids:
Cloreto de 3-cloro-fenil-acetila.3-Chloro-phenyl acetyl chloride.
1H NMR (500 MHz, CDCl3): 4,10 (s, 2H), 7,0 (m, 1H), 7,11(ddd, 1H), 7,17 (dt, 1H).1H NMR (500 MHz, CDCl3): 4.10 (s, 2H), 7.0 (m, 1H), 7.11 (ddd, 1H), 7.17 (dt, 1H).
Cloreto de 3-fluoro-fenil-acetila.3-Fluoro-phenyl acetyl chloride.
O composto título foi usado na etapa seguinte semcaracterização.The title compound was used in the next step without characterization.
<formula>formula see original document page 36</formula>4-(4,6-Dimetil-pirimidin-2-ü)-morfolina.<formula> formula see original document page 36 </formula> 4- (4,6-Dimethyl-pyrimidin-2-ü) -morpholine.
Em uma suspensão de bromidrato de morfolino-formamidina(2,0 g, 9,52 mmol) em etanol (6 ml) terc-butóxido de potássio (1,068 g, 9,52mmol) então acetil-acetona (2 ml, 20 mmol) foram adicionados. A misturareacional foi rapidamente vaporizada com argônio, vedada em frasco deprocesso Emrys e aquecida sob irradiação de microondas a 140°C por 5 min.Após esfriamento ela foi extinta com acetato de etila (50 ml), filtrada viacamada de SiO2 (5 g) e eluída com acetato de etila. Voláteis foram removidosem vácuo a 70°C para dar 1,65 g de óleo marrom pálido que solidificoudurante a noite. Rendimento de 90%. LC-MS (m/z) 193,9 (MH+); tR = 0,71.1H NMR (500 MHz, DMSOd6): 2,23 (s, 6H), 3,62 (m, 4H), 3,67 (m, 4H),6,44 (s, 1H).In a suspension of morpholine-formamidine hydrobromide (2.0 g, 9.52 mmol) in ethanol (6 mL) potassium tert-butoxide (1.068 g, 9.52 mmol) then acetyl acetone (2 mL, 20 mmol) have been added. The reaction mixture was rapidly sprayed with argon, sealed in an Emrys pressure-vial and heated under microwave irradiation at 140 ° C for 5 min. After cooling it was quenched with ethyl acetate (50 ml), filtered via SiO2 (5 g) and filtered. eluted with ethyl acetate. Volatiles were removed under vacuum at 70 ° C to give 1.65 g of pale brown oil which solidified overnight. Yield 90%. LC-MS (m / z) 193.9 (MH +); t R = 0.71.1H NMR (500 MHz, DMSOd6): 2.23 (s, 6H), 3.62 (m, 4H), 3.67 (m, 4H), 6.44 (s, 1H).
Método A. Em uma solução agitada de 4-(4,6-Dimetil-pirimidin-2-il)-morfolina (8,94 g, 46,3 mmol) em ácido acético glacial (50ml) ácido nítrico fiimegante (5,75 ml, 3 eq.) foi adicionado em gotas. Amistura reacional foi aquecida a 70°C por 15 min então mais ácido nítrico(3,8 ml, 2 eq.) foi adicionado. Após 15 min adicionais a 70°C ela foi esfriadae derramada em porções pequenas dentro de uma mistura de gelo e solução de hidróxido de sódio (44g) em água (200 ml). O produto foi separado porfiltração para dar 0,637 g de sólido amarelo. Rendimento de 6%. LC-MS(m/z) 239,0 (MH+); tR = 2,76.Method A. In a stirred solution of 4- (4,6-Dimethyl-pyrimidin-2-yl) -morpholine (8.94 g, 46.3 mmol) in glacial acetic acid (50ml) fiery nitric acid (5.75 ml, 3 eq.) was added dropwise. Reaction mixture was heated at 70 ° C for 15 min then more nitric acid (3.8 ml, 2 eq.) Was added. After an additional 15 min at 70 ° C it was cooled and poured into small portions into a mixture of ice and sodium hydroxide solution (44g) in water (200ml). The product was filtered off to give 0.637 g of yellow solid. Yield 6%. LC-MS (m / z) 239.0 (MH +); t R = 2.76.
Método B. Em uma solução agitada quente (65°C) de 4-(4,6-dimetil-pirimidin-2-il)-morfolina (4 g, 20,7 mmol) em ácido trifluoroacético(100 ml) nitrato de sódio (3,52 g, 41,4 mmol) foi adicionado. Após 3 h mais4-(4,6-Dimetil-5-nitro pirimidin-2-il)-morfolinanitrato de sódio foi adicionado (1,8 g, 20,7 mmol) e a mistura reacional foimantida a 65°C durante a noite. Ela foi cuidadosamente derramada emporções em bicarbonato de sódio aquoso 10% (600 ml) e o produto foiseparado por filtração. Rendimento de 1,637 g, 33%. LC-MS (m/z) 238,9Method B. In a hot (65 ° C) stirred solution of 4- (4,6-dimethyl-pyrimidin-2-yl) -morpholine (4 g, 20.7 mmol) in trifluoroacetic acid (100 mL) sodium nitrate (3.52 g, 41.4 mmol) was added. After 3 h more sodium 4- (4,6-Dimethyl-5-nitro-pyrimidin-2-yl) -morpholininitrate was added (1.8 g, 20.7 mmol) and the reaction mixture was kept at 65 ° C overnight. . It was carefully poured into portions of 10% aqueous sodium bicarbonate (600 ml) and the product was filtered off. Yield 1.637 g, 33%. LC-MS (m / z) 238.9
(MH+); tR = 2,70. 1H NMR (500 MHz, DMSOd6): 2,44 (s, 6H), 3,65 (m, 4H),3,83 (m, 4H).(MH +); t R = 2.70. 1H NMR (500 MHz, DMSOd6): 2.44 (s, 6H), 3.65 (m, 4H), 3.83 (m, 4H).
<formula>formula see original document page 38</formula><formula> formula see original document page 38 </formula>
4,6-Dimetil-2-morfolin-4 il-pirimidin-5-il-amina.4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl-amine.
A suspensão de 4-(4,6-dimetil-5-nitro-pirimidin-2-il)-morfolina (2,2 g, 9,23 mmol), 5% paládio sobre carbono (50% úmido, 1,09g), formiato de amônio (8,76 g) foi vedada em frasco de processo Emrys eaquecida a 150°C sob irradiação de microondas por 2 min. A misturareacional foi filtrada e evaporada. O resíduo foi tratado com acetato de etila efiltrado para dar 1,62 g de produto cristalino laranja após evaporação emvácuo. Rendimento de 84%. LC-MS (m/z) 208,9 (MH+); tR = 0,44. 1H NMR(500 MHz, DMSOd6): 2,2 (s, 6H), 3,44 (m, 4H), 3,62 (m, 4H), 4,19 (br, 211,facilmente formados por métodos conhecidos pela pessoa experiente na arte.NH2).The suspension of 4- (4,6-dimethyl-5-nitro-pyrimidin-2-yl) -morpholine (2.2 g, 9.23 mmol), 5% palladium on carbon (50% wet, 1.09g) , ammonium formate (8.76 g) was sealed in an Emrys process flask and heated to 150 ° C under microwave irradiation for 2 min. The reaction mixture was filtered and evaporated. The residue was treated with filtered ethyl acetate to give 1.62 g of orange crystalline product after vacuum evaporation. Yield 84%. LC-MS (m / z) 208.9 (MH +); t R = 0.44. 1H NMR (500 MHz, DMSOd6): 2.2 (s, 6H), 3.44 (m, 4H), 3.62 (m, 4H), 4.19 (br, 211) readily formed by methods known in the art. experienced person in the art.NH2).
Compostos da invençãoCompounds of the invention
Sais de adição de ácido dos compostos da invenção podem serAcid addition salts of the compounds of the invention may be
Exemplo 1Example 1
Ia N-[4 Amino-6-metil-2-(4-trÍfluorometil-benzil-amino)-pirimidin-5-il]-2-ciclo-pentil-acetamida.<formula>formula see original document page 39</formula>1a N- [4-Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -2-cyclopentyl-acetamide. <formula> formula see original document page 39 </ formula >
Em uma solução agitada fria (banho de gelo/água) de 6-metil-In a cold stirred (ice / water bath) solution of 6-methyl
N*2*-(4-trifluorometil-benzil)-pirimidina-2,4,5-triamina (119 mg, 0,401mmol) em acetonitrila (3 ml), cloreto de ciclo-pentil-acetila (59 mg, 0,402mmol) foi adicionado em gotas em 2 min. Banho frio foi removido e agitaçãocontinuou por 20 min. A suspensão obtida foi extinta com água (85 ml) ebicarbonato de sódio aquoso 10% (0,5 ml). Voláteis orgânicos foramremovidos sob pressão reduzida, acetato de etila (0,5 ml) foi adicionado e amistura foi extinta com heptano (20 ml). A suspensão bifásica obtida foifiltrada. O produto foi lavado com água e heptano, seco em vácuo para dar 40mg de sólido amarelo pálido. Rendimento de 25%. LC-MS (m/z) 408,3(MH+); tR = 2,11. 1H NMR (500 MHz, DMSOd6): 1,17 (m, 2H), 1,50 (m,2H), 1,59 (m, 2H), 1,74 (m, 2H), 1,93 (s, 3H), 2,2 (m, 1H), 2,25 (d, 2H), 4,5(d, 2H), 5,96 (br, 211, NH2), 6,96 (br, IH5 NH), 7,5 (d, 2H), 7,64 (d, 2H), 8,57(s, 1H, NHCO).N * 2 * - (4-trifluoromethyl-benzyl) -pyrimidine-2,4,5-triamine (119 mg, 0.401 mmol) in acetonitrile (3 mL), cyclopentyl acetyl chloride (59 mg, 0.402 mmol) was added dropwise in 2 min. Cold bath was removed and stirring continued for 20 min. The suspension obtained was quenched with water (85 ml) and 10% aqueous sodium bicarbonate (0.5 ml). Organic volatiles were removed under reduced pressure, ethyl acetate (0.5 mL) was added and the mixture was quenched with heptane (20 mL). The obtained biphasic suspension was filtered. The product was washed with water and heptane, dried in vacuo to give 40mg of pale yellow solid. Yield 25%. LC-MS (m / z) 408.3 (MH +); t R = 2.11. 1H NMR (500 MHz, DMSOd6): 1.17 (m, 2H), 1.50 (m, 2H), 1.59 (m, 2H), 1.74 (m, 2H), 1.93 (s , 3H), 2.2 (m, 1H), 2.25 (d, 2H), 4.5 (d, 2H), 5.96 (br, 211, NH 2), 6.96 (br, IH5 NH ), 7.5 (d, 2H), 7.64 (d, 2H), 8.57 (s, 1H, NHCO).
Ib N-[4 Amino-6-metil-2-(4-trifluorometil-benzil-amÍno)-pirimidin-5-il]-3,3-dimetil-butiramida.Ib N- [4-Amino-6-methyl-2- (4-trifluoromethyl-benzylamino) -pyrimidin-5-yl] -3,3-dimethyl-butyramide.
<formula>formula see original document page 39</formula><formula> formula see original document page 39 </formula>
N*2*-(4-trifluorometil-benzil)-pirimidina-2,4,5-triamina (341 mg, 1,15mmol) em acetonitrila (7,5 ml), cloreto de terc-butil-acetila (0,16 ml, 1,15mmol) foi adicionado em gotas em 2 min. Banho frio foi removido e agitaçãoN * 2 * - (4-trifluoromethyl-benzyl) -pyrimidine-2,4,5-triamine (341 mg, 1.15 mmol) in acetonitrile (7.5 mL), tert-butyl acetyl chloride (0.16 ml, 1.15mmol) was added dropwise within 2 min. Cold bath was removed and shaking
Em uma solução agitada fria (banho de gelo/água) de 6-metil-continuou por 45 min. A mistura reacional obtida foi derramada em colunaSCX (10 g, forma H+), lavada com acetonitrila (20 ml), metanol (100 ml), e oproduto foi eluído com NH3 4 M em metanol (60 ml). Os voláteis foramremovidos em vácuo e o produto bruto foi purificado por cromatografia devaporização instantânea sobre gel de sílica (20 g) com gradiente de heptano-acetato de etila para dar 153 mg de sólido. Rendimento de 33,7%. LC-MS(m/z) 395,9 (MH+); tR = 2,00. 1H NMR (500 MHz, DMSO-Cl6): 1,02 (s, 9H),1,96 (s, 3H), 2,15 (s, 2H), 4,5 (d, 2H), 5,9 (br, 2H, NH2), 6,97 (br, 1H, NH),7,5 (d, 2H), 7,65 (d, 2H), 8,57 (s, 1H, NHCO).In a cold stirred (ice / water bath) solution of 6-methyl continued for 45 min. The obtained reaction mixture was poured onto SCX column (10 g, H + form), washed with acetonitrile (20 mL), methanol (100 mL), and the product was eluted with 4 M NH3 in methanol (60 mL). The volatiles were removed in vacuo and the crude product was purified by flash chromatography on silica gel (20 g) with heptane-ethyl acetate gradient to give 153 mg of solid. Yield 33.7%. LC-MS (m / z) 395.9 (MH +); tR = 2.00. 1H NMR (500 MHz, DMSO-Cl6): 1.02 (s, 9H), 1.96 (s, 3H), 2.15 (s, 2H), 4.5 (d, 2H), 5.9 (br, 2H, NH 2), 6.97 (br, 1H, NH), 7.5 (d, 2H), 7.65 (d, 2H), 8.57 (s, 1H, NHCO).
Os seguintes compostos foram preparados analogamenteusando os cloretos de ácido correspondentes:The following compounds were prepared analogously using the corresponding acid chlorides:
1c N-[4 Amino-6-metil-2-(4-trifiuorometil-benzil-amino)-pirimidin-5-il]-2-(4-fluoro-fenil)-acetamida.1c N- [4 Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -2- (4-fluoro-phenyl) -acetamide.
<formula>formula see original document page 40</formula><formula> formula see original document page 40 </formula>
Rendimento de 12%. LC-MS (m/z) 434,3 (MH+); tR = 2,07. 1HNMR (500 MHz, DMSO-d6): 1,81 (s, 3H), 3,57 (d, 2H), 4,49 (d, 2H), 6,08(br, 2H, NH2), 6,96 (br, 1H, NH), 7,13 (t, 2H), 7,36 (dd, 2H), 7,49 (d, 2H),7,64 (d, 2H), 8,83 (s, 1H, NHCO).Yield 12%. LC-MS (m / z) 434.3 (MH +); t R = 2.07. 1 H NMR (500 MHz, DMSO-d 6): 1.81 (s, 3H), 3.57 (d, 2H), 4.49 (d, 2H), 6.08 (br, 2H, NH 2), 6, 96 (br, 1H, NH), 7.13 (t, 2H), 7.36 (dd, 2H), 7.49 (d, 2H), 7.64 (d, 2H), 8.83 (s 1H, NHCO).
1d [4-Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirÍmidin-5-il]-amÍda de ácido hexanóico.Rendimento de 39,7 mg, 50%. LC-MS (m/z) 396,1 (MH+); tR= 2,08. 1H NMR (500 MHz, DMSO-d6): 0,87 (t, 3H), 1,28 (m, 4H), 1,56 (qui,2H), 1,91 (s, 3H), 2,24 (t, 2H), 4,49 (d, 2H), 5,98 (br, 2H, NH2), 6,95 (br, 1H,NH), 7,5 (d, 2H), 7,65 (d, 2H), 8,55 (s, 1H, NHCO).Hexanoic acid 1d [4-Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyridin-5-yl] -amide. Yield 39.7 mg, 50%. LC-MS (m / z) 396.1 (MH +); t R = 2.08. 1H NMR (500 MHz, DMSO-d6): 0.87 (t, 3H), 1.28 (m, 4H), 1.56 (thi, 2H), 1.91 (s, 3H), 2.24 (t, 2H), 4.49 (d, 2H), 5.98 (br, 2H, NH 2), 6.95 (br, 1H, NH), 7.5 (d, 2H), 7.65 ( d, 2H), 8.55 (s, 1H, NHCO).
1e N-[4 Amino-6-metil-2-(4-trifluorometil-benzil-amino)-pirimidin-5-il]-2-(3-cloro-fenil)-acetamida.1e N- [4-Amino-6-methyl-2- (4-trifluoromethyl-benzyl-amino) -pyrimidin-5-yl] -2- (3-chloro-phenyl) -acetamide.
<formula>formula see original document page 41</formula><formula> formula see original document page 41 </formula>
Rendimento de 45,4 mg, 50%. LC-MS (m/z) 450,1 (AlHf); tR= 2,17. 1H NMR (500 MHz, DMSO-Cl6): 1,82 (s, 3H), 3,61 (s, 2H), 4,49 (d,2H), 6,12 (br, 2H, NH2), 6,97 (br, 1H, NH), 7,3 (m, 2H), 7,35 (t, 1H), 7,41 (s,1H), 7,49 (d, 2H), 7,64 (d, 2H), 8,87 (s, 1H, NHCO).Yield 45.4 mg, 50%. LC-MS (m / z) 450.1 (AlHf); t R = 2.17. 1H NMR (500 MHz, DMSO-Cl6): 1.82 (s, 3H), 3.61 (s, 2H), 4.49 (d, 2H), 6.12 (br, 2H, NH 2), 6 , 97 (br, 1H, NH), 7.3 (m, 2H), 7.35 (t, 1H), 7.41 (s, 1H), 7.49 (d, 2H), 7.64 ( d, 2H), 8.87 (s, 1H, NHCO).
Exemplo 2Example 2
<formula>formula see original document page 41</formula><formula> formula see original document page 41 </formula>
2a 2-Ciclo-pentil-N-(4,6-dimetil-2-morfolin-4 il-pirimidin-5-il)-acetamida.2a 2-Cyclopentyl-N- (4,6-dimethyl-2-morpholin-4-yl-pyrimidin-5-yl) -acetamide.
Em uma solução agitada fria (banho de gelo/água) de 4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il-amina (2,04 g, 9,79 mmol) emacetonitrila (40 ml) cloreto de ciclo-pentil-acetila (1,65 ml, 11,75 mmol) foiadicionado. O banho de gelo foi removido e a mistura reacional foi agitada natemperatura ambiente por 30 min. Ela foi derramada em hidrogeno-carbonatode sódio aq. sat. (100 ml) e água e filtrada. O sólido obtido foi recristalizadoem acetonitrila para dar 1,877 g de sólido incolor. Rendimento de 60%. LC-MS (m/z) 318,9 (MHt); tR = 1,80. 1H NMR (500 MHz, DMSOd6): 1,21 (m,2H), 1,52 (m, 2H), 1,61 (m, 2H), 1,76 (m, 2H), 2,15 (s, 6H), 2,25 (m, 1H),2,28 (d, 2H), 3,63 (m, 4H), 3,65 (m, 4H).In a cold stirred (ice / water bath) solution of 4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl-amine (2.04 g, 9.79 mmol) emacetonitrile (40 ml) cyclopentyl acetyl chloride (1.65 ml, 11.75 mmol) was added. The ice bath was removed and the reaction mixture was stirred at room temperature for 30 min. It was poured into aq. Sodium hydrogen carbonate. sat. (100 ml) and water and filtered. The obtained solid was recrystallized from acetonitrile to give 1.877 g of colorless solid. Yield 60%. LC-MS (m / z) 318.9 (MHt); t R = 1.80. 1H NMR (500 MHz, DMSOd6): 1.21 (m, 2H), 1.52 (m, 2H), 1.61 (m, 2H), 1.76 (m, 2H), 2.15 (s , 6H), 2.25 (m, 1H), 2.28 (d, 2H), 3.63 (m, 4H), 3.65 (m, 4H).
2b N-(4,6-Dimetil-2-morfolin-4 ü-pirimidin-5-U-S, 3-dimetil-butiramida.2b N- (4,6-Dimethyl-2-morpholin-4'-pyrimidin-5-U-S-3-dimethylbutyramide.
<formula>formula see original document page 42</formula><formula> formula see original document page 42 </formula>
Em uma solução de 4,6-dimetil-2-morfolin-4-ilpirimidin-5-il-amina (2,1 g, 10,4 mmol) em acetonitrila (30 ml) e trietil-amina (2,9 ml, 20,8mmol) cloreto de terc-butil-cetila (2,9 ml, 20,8 mmol) foi adicionado emgotas. Após 90 min a mistura reacional foi extinta com água e extraída comacetato de etila duas vezes. A fase orgânica foi lavada com hidrogeno-carbonato de sódio aq. sat. (100 ml), seca sobre sulfato de magnésio epurificada por cromatografia de vaporização instantânea sobre SiO2 (20 g,gradiente de heptano-acetato de etila). O produto bruto obtido foirecristalizado em tolueno quente para dar 946 mg de sólido incolor.In a solution of 4,6-dimethyl-2-morpholin-4-ylpyrimidin-5-yl-amine (2.1 g, 10.4 mmol) in acetonitrile (30 mL) and triethylamine (2.9 mL, 20.8mmol) tert-Butyl ketyl chloride (2.9 ml, 20.8 mmol) was added in stock. After 90 min the reaction mixture was quenched with water and extracted with ethyl comacetate twice. The organic phase was washed with aq. Sodium hydrogen carbonate. sat. NaHCO 3 (100 ml), dried over magnesium sulfate and purified by flash chromatography on SiO 2 (20 g, heptane-ethyl acetate gradient). The obtained crude product was recrystallized from hot toluene to give 946 mg of colorless solid.
Rendimento de 30%. LC-MS (m/z) 307,9 (MH+); tR = 1,69. 1H NMR (500MHz, DMSOd6): 1,04 (s, 9H), 2,16 (s, 6H), 2,19 (s, 2H), 3,64 (m, 8H), 9,13(s, 1H).Yield 30%. LC-MS (m / z) 307.9 (MH +); t R = 1.69. 1H NMR (500MHz, DMSOd6): 1.04 (s, 9H), 2.16 (s, 6H), 2.19 (s, 2H), 3.64 (m, 8H), 9.13 (s, 1H).
O seguinte composto foi preparado analogamente a partir decloreto de ácido correspondente:The following compound was prepared analogously from the corresponding acid chloride.
2c N-(4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il-2-(4 jluoro-fenil) -acetam ida2c N- (4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl-2- (4-fluoro-phenyl) -acetamide
<formula>formula see original document page 42</formula>O composto título foi recristalizado em acetato de etila quenteapós purificação por cromatografia de vaporização instantânea. Rendimentode 1,193 g, 37%. LC-MS (m/z) 345,1 (MH+); tR = 1,81. 1H NMR (500 MHz,DMSOd6): 2,09 (s, 6H), 3,6-3,66 (m de recobrimento, 10H), 7,16 (t, 2H),7,38 (dd, 2H), 9,42 (s, 1H).<formula> formula see original document page 42 </formula> The title compound was recrystallized from hot ethyl acetate after purification by flash chromatography. Yield 1.193 g, 37%. LC-MS (m / z) 345.1 (MH +); t R = 1.81. 1H NMR (500 MHz, DMSOd6): 2.09 (s, 6H), 3.6-3.66 (m, 10H), 7.16 (t, 2H), 7.38 (dd, 2H) 9.42 (s, 1H).
2d 2-(3,4-Difluoro-fenil)-N-(4,6-dimetü-2-morfolin-4-U-pirim idin-5- il) -acetam ida.2d 2- (3,4-Difluoro-phenyl) -N- (4,6-dimethyl-2-morpholin-4-U-pyrimidin-5-yl) -acetamide.
<formula>formula see original document page 43</formula><formula> formula see original document page 43 </formula>
Em uma solução agitada fria (banho de gelo/água) de 4,6-dimetil-2-morfolin-4-il-pirimidin-5-il-amina (52,4 mg, 0,25 mmol) emacetonitrila (1 ml) cloreto de 3,4-difluoro-fenil-cetila (0,065 ml, 0,3 mmol) foiadicionado. A mistura reacional foi mantida a 60°C por 1 min e permitidaesfriar. Ela foi derramada em coluna SCX (lOg, forma H+), lavada comacetonitrila e metanol e eluída com NH3 4 M em metanol. Após evaporação oproduto bruto foi precipitado de solução concentrada em acetato de etila comheptano e filtrado dar 34 mg de sólido incolor. Rendimento de 37%. LC-MS(m/z) 363,3 (MH+); tR = 1,96. 1H NMR (500 MHz, DMSOd6): 2,09 (s, 6H),3,63 (m, 10H), 7,19 (m, 1H), 7,38 (m, 1H), 7,41 (m, 1H), 9,43 (s, 1H).In a cold stirred (ice / water bath) solution of 4,6-dimethyl-2-morpholin-4-yl-pyrimidin-5-yl-amine (52.4 mg, 0.25 mmol) emacetonitrile (1 ml) 3,4-Difluoro-phenyl ketyl chloride (0.065 ml, 0.3 mmol) was added. The reaction mixture was kept at 60 ° C for 1 min and allowed to cool. It was poured onto SCX column (10g, H + form), washed with comacetonitrile and methanol and eluted with 4 M NH3 in methanol. After evaporation the crude product was precipitated from concentrated solution in ethyl acetate with heptane and filtered to give 34 mg of colorless solid. Yield 37%. LC-MS (m / z) 363.3 (MH +); t R = 1.96. 1H NMR (500 MHz, DMSOd6): 2.09 (s, 6H), 3.63 (m, 10H), 7.19 (m, 1H), 7.38 (m, 1H), 7.41 (m , 1H), 9.43 (s, 1H).
Os seguintes compostos foram preparados analogamenteusando cloretos de ácido apropriados:The following compounds were prepared analogously using appropriate acid chlorides:
2e N-(4,6-Dimetil-2-morfolin-4-il-pirimidin-5-il-2-(3 fluoro-fenil)-acetamida.2e N- (4,6-Dimethyl-2-morpholin-4-yl-pyrimidin-5-yl-2- (3-fluoro-phenyl) -acetamide.
<formula>formula see original document page 43</formula>O composto título foi purificado por cromatografia devaporização instantânea sobre SiO2 (20 g, gradiente de heptano-acetato deetila). Rendimento de 27 mg, 31%. LC-MS (m/z) 345,0 (MIT); tR = 1,83. 1HNMR (500 MHz, DMSOd6): 2,09 (s, 6H), 3,62 (m, 4H), 3,64 (m, 4H), 3,66(s, 2H), 7,08 (dt, 1H), 7,18 (dd de recobrimento, 1H), 7,19 (d derecobrimento, 1H), 7,38 (dt, 1H), 9,45 (s, 1H).<formula> formula see original document page 43 </formula> The title compound was purified by flash chromatography on SiO 2 (20 g, heptane-ethyl acetate gradient). Yield 27 mg, 31%. LC-MS (m / z) 345.0 (MIT); t R = 1.83. 1H NMR (500 MHz, DMSOd6): 2.09 (s, 6H), 3.62 (m, 4H), 3.64 (m, 4H), 3.66 (s, 2H), 7.08 (dt, 1H), 7.18 (dc, 1H), 7.19 (dc, 1H), 7.38 (dt, 1H), 9.45 (s, 1H).
2f (4,6-Dimetil-2-morfolin-4Al-pirimidin-5-il-amida de ácidohexanóicoHexanoic Acid 2f (4,6-Dimethyl-2-morpholin-4Al-pyrimidin-5-yl-amide)
<formula>formula see original document page 44</formula><formula> formula see original document page 44 </formula>
O composto título foi purificado por cromatografia devaporização instantânea sobre SiO2 (20 g, gradiente de heptano-acetato deetila). Rendimento de 49 mg, 64%. LC-MS (m/z) 307,2 (MHf); tR = 1,84. 1HNMR (500 MHz, DMSO-d6): 0,88 (t, 3H), 1,31 (m, 4H), 1,60 (qui, 2H), 2,14(s, 6H), 2,28 (t, 2H), 3,63 (m, 4H), 3,65 (m, 4H), 9,16 (s, 1H).The title compound was purified by flash chromatography on SiO 2 (20 g, heptane-ethyl acetate gradient). Yield 49 mg, 64%. LC-MS (m / z) 307.2 (MH +); t R = 1.84. 1H NMR (500 MHz, DMSO-d6): 0.88 (t, 3H), 1.31 (m, 4H), 1.60 (Thi, 2H), 2.14 (s, 6H), 2.28 ( t, 2H), 3.63 (m, 4H), 3.65 (m, 4H), 9.16 (s, 1H).
Tabela 1. Reagentes usados para a preparação de compostos.Table 1. Reagents used for compound preparation.
<formula>formula see original document page 44</formula><formula> formula see original document page 44 </formula>
Testes in vitro e in vivoOs compostos da invenção têm sido testados e mostrado efeitoem um ou mais dos modelos abaixo:In vitro and in vivo tests The compounds of the invention have been tested and shown to be effective in one or more of the following models:
Efluxo relativo através de canal KCNQ2Relative flow through channel KCNQ2
Isto exemplifica um protocolo de triagem de KCNQ2 paraavaliar os compostos da presente invenção. O ensaio mede o efluxo relativoatravés de canal KCNQ2, e foi realizado de acordo com um método descritopor Tang et al. (Tang, W. et al, J. Biomol. Screen. 2001, 6, 325-331) paracanais de potássio hERG com as modificações descritas abaixo.This exemplifies a KCNQ2 screening protocol for evaluating the compounds of the present invention. The assay measures relative efflux through the KCNQ2 channel, and was performed according to a method described by Tang et al. (Tang, W. et al., J. Biomol. Screen. 2001, 6, 325-331) hERG potassium parachannels with the modifications described below.
Um número adequado de células CHO estavelmenteexpressando canais KCNQ2 desbloqueados por voltagem foram plaqueadosem uma densidade suficiente para dar uma camada mono-confluente no diado experimento. As células foram semeadas no dia antes do experimento ecarregadas com 1 μα/ml [°°Rb] durante a noite. No dia do experimento ascélulas foram lavadas com um tampão contendo HBSS. As células foram pré-incubadas com droga por 30 minutos e o efluxo de 86Rb+ foi estimulado poruma concentração submáxima de KCl 15 mM KCl na presença continuada dedroga por 30 minutos adicionais. Após um período de incubação adequado, osobrenadante foi removido e contado em um contador de cintilação líquida(Tricarb). As células foram lisadas com NaOH 2 mM e a quantidade de 86Rb+foi contada. O efluxo relativo foi calculado((CPMSUper/(CPMSUper+CPMceii))cmpd/ (CPMsuper/(CPMsuper+ CPMcell))15mMKCI)*100-100.An adequate number of CHO cells stably expressing voltage-unlocked KCNQ2 channels were plated at a density sufficient to give a mono-confluent layer in the day of the experiment. Cells were seeded the day before the experiment and loaded with 1 μα / ml [°° Rb] overnight. On the day of the experiment, cells were washed with a buffer containing HBSS. Cells were preincubated with drug for 30 minutes and 86 Rb + efflux was stimulated by a submaximal concentration of 15 mM KCl in the continued presence of drug for an additional 30 minutes. After a suitable incubation period, the supernatant was removed and counted in a liquid scintillation counter (Tricarb). The cells were lysed with 2 mM NaOH and the amount of 86 Rb + was counted. Relative efflux was calculated ((CPMSUper / (CPMSUper + CPMceii)) cmpd / (CPMsuper / (CPMsuper + CPMcell)) 15mMKCI) * 100-100.
Os compostos da invenção possuem uma EC50 menor do que20.000 nM, na maioria dos casos menor do que 2.000 nM e em muitos casosmenor do que 200 nM. Conseqüentemente, os compostos da invenção sãoconsiderados úteis no tratamento de doenças associadas com os canais depotássio de família KCNQ.The compounds of the invention have an EC 50 of less than 20,000 nM, in most cases less than 2,000 nM and in many cases less than 200 nM. Accordingly, the compounds of the invention are considered useful in the treatment of diseases associated with the KCNQ family depotassium channels.
Registros eletrofisiológicos de patch-clampPatch Clamp Electrophysiological Records
Correntes de KCNQ2 ativadas por voltagem foram registradasde células CHO de mamífero pelo uso de técnicas de registro de patch-clampconvencionais na configuração de patch-clamp de célula inteira (Hamill O. P.et ai. Pflügers Arch 1981; 391: 85-100). As células CHO com expressãoestável de canais de KCNQ2 ativados por voltagem foram crescidas sobcondições de cultura de célula normais em incubadoras de CO2 e usadas pararegistros eletrofisiológicos 1-7 dias após aplicação em placa. Os canais depotássio KCNQ2 foram ativados por degraus de voltagem de até + 80 mV emincrementos de 5-20 mV (ou com um protocolo de rampa) de um potencial demanutenção de membrana entre -100 mV e - 40 mV (Tatulian L et al JVoltage-activated KCNQ2 streams have been recorded from mammalian CHO cells by use of conventional patch-clamp recording techniques in the whole-cell patch-clamp configuration (Hamill O. P. et al. Pflügers Arch 1981; 391: 85-100). CHO cells with stable expression of voltage-activated KCNQ2 channels were grown under normal cell culture conditions in CO2 incubators and used for electrophysiological records 1-7 days after plating. The KCNQ2 potassium channels were activated by voltage steps up to + 80 mV in 5-20 mV increments (or with a ramp protocol) of a potential membrane maintenance between -100 mV and -40 mV (Tatulian L et al J
Neuroscience 2001; 21 (15): 5535-5-545). Os efeitos eletrofisiológicosinduzidos pelos compostos foram avaliados sobre vários parâmetros dacorrente de KCNQ2 ativada por voltagem. Especialmente foram estudadosefeitos sobre o limite de ativação para a corrente e sobre a corrente induzidamáxima.Neuroscience 2001; 21 (15): 5535-5-545). The electrophysiological effects induced by the compounds were evaluated on several voltage-activated KCNQ2 current parameters. In particular, effects on the activation threshold for current and maximum induced current have been studied.
Alguns dos compostos da invenção têm sido testados nesteteste. E esperado que um deslocamento para a esquerda do limite de ativaçãoou um aumento na corrente de potássio induzida máxima diminua a atividadeem redes neuronais e assim tornar os compostos úteis em doenças comatividade neuronal aumentada - como epilepsia.Some of the compounds of the invention have been tested in this test. It is expected that a left shift of the activation threshold or an increase in maximum induced potassium current will decrease activity in neuronal networks and thus make the compounds useful in diseases with increased neuronal activity - such as epilepsy.
Eletrochoque máximoMaximum electroshock
O teste foi conduzido em grupos de camundongos machosusando eletrodos corneais e administrando uma corrente de onda quadrada de26 mA por 0,4 segundo com o objetivo de induzir uma convulsãocaracterizada por uma extensão tônica de membro posterior (Wlaz et al.Epilepsy Research 1998, 30, 219-229).The test was conducted on groups of male mice using corneal electrodes and administering a 26 mA square wave current for 0.4 seconds to induce a seizure characterized by a posterior limb tonic extension (Wlaz et al. Epilepsy Research 1998, 30, 219-229).
Convulsões induzidas por pilocarpinaPilocarpine-induced seizures
Convulsões induzidas por pilocarpina são induzidas porinjeção intraperitoneal injeção de pilocarpina 250mg/kg em grupos decamundongos machos observando a atividade de convulsão resultando emperda de postura dentro de um período de 30 minutos (Starr et al.Pharmacology Biochemistry andBehavior 1993, 45, 321-325).Pilocarpine-induced seizures are induced by intraperitoneal injection pilocarpine injection 250mg / kg in male mouse groups observing seizure activity resulting in posture loss within a 30-minute period (Starr et al. Pharmacology Biochemistry and Behavior 1993, 45, 321-325) .
Teste de limiar de convulsão elétricaElectrical seizure threshold test
Uma modificação do método de up-and-down (Kimball et al.Radiation Research 1957, H2) foi usada para determinar o limiar médio parainduzir extensão tônica de membro posterior em resposta ao eletrochoquecorneal em grupos de camundongos machos. O primeiro camundongo de cadagrupo recebeu um eletrochoque a 14 mA, (0,4 s, 50 Hz) e foi observado paraatividade de convulsão. Se uma convulsão foi observada a corrente foireduzida em 1 mA para o camundongo seguinte, contudo, se nenhumaconvulsão foi observada então a corrente foi aumentada em 1 mA. Esteprocedimento foi repetido para todos os 15 camundongos no grupo detratamento.A modification of the up-and-down method (Kimball et al.Radiation Research 1957, H2) was used to determine the mean threshold to induce posterior limb tonic extension in response to electroshock in groups of male mice. The first cadagroup mouse received a 14 mA electroshock (0.4 s, 50 Hz) and was observed for seizure activity. If a seizure was observed the current was reduced by 1 mA for the next mouse, however, if no convulsion was observed then the current was increased by 1 mA. This procedure was repeated for all 15 mice in the treatment group.
Teste de limiar de convulsão químicaChemical Seizure Threshold Test
A dose limite de pentileno-tetrazol requerida para induzir umaconvulsão clônica foi medida por infusão temporizada de pentileno-tetrazol(5mg / mL a 0,5 mL/minuto) para dentro da veia de cauda lateral de grupos decamundongos machos (Nutt et al. J Pharmacy and Pharmaeology 1986, 38,697-698).The threshold dose of pentylene tetrazole required to induce clonic convulsion was measured by timed infusion of pentylene tetrazole (5 mg / mL at 0.5 mL / min) into the lateral tail vein of male mouse groups (Nutt et al. J Pharmacy and Pharmaeology 1986, 38,697-698).
Ignição de amídalaTonsil ignition
Ratos sofreram cirurgia para implantação de eletrodostripolares na amídala dorsolateral. Após a cirurgia os animais forampermitidos se recuperarem antes de os grupos de ratos receberem quer dosesvariadas de composto de teste quer o veículo da droga. Os animais foramestimulados com seu limite de pós-descarga inicial de + 25 μΑ diariamentepor 3-5-semanas e em cada ocasião severidade de convulsão, duração deconvulsão, e duração de pós-descarga elétrica foram anotadas. (Racine,Electroencephalography and ClinicalNeurophysiology 1972, 32, 281-294).Rats underwent surgery for implantation of electrodostripolar electrodes in the dorsolateral tonsil. After surgery the animals were allowed to recover before the rat groups received either varying doses of test compound or the drug vehicle. Animals were stimulated with their initial post-discharge limit of + 25 μΑ daily for 3-5 weeks and on each occasion seizure severity, seizure duration, and electrical post-discharge duration were noted. (Racine, Electroencephalography and Clinical Neurophysiology 1972, 32, 281-294).
Efeitos colateraisEfeitos colaterais de sistema nervoso central foram medidospela medição do tempo que os camundongos permaneceriam sobreaparelhagem rotarod (Capacio et al. Drug and Chemical Toxicology 1992,15, 177-201); ou pela medição de sua capacidade locomotora pela contagemdo número de feixes infravermelhos cruzados em uma gaiola de teste (Watsonet al. Neuropharmacology 1997, 36, 1369-1375). Ações hipotérmicas docomposto sobre a temperatura central corporal dos animais foram medidasquer por sonda retal quer por transmissores de radiotelemetria implantadoscapazes de medir temperatura (Keeney et al. Physiology and Behaviour 2001,74, 177-184).Side effects Central nervous system side effects were measured by measuring the time the mice would remain on rotarod mating (Capacio et al. Drug and Chemical Toxicology 1992,15, 177-201); or by measuring its locomotor capacity by counting the number of infrared beams crossed in a test cage (Watsonet al. Neuropharmacology 1997, 36, 1369-1375). Hypothermic actions on the body core temperature of the animals were measured either by rectal probe or by implanted radiotelemetry transmitters capable of measuring temperature (Keeney et al. Physiology and Behavior 2001,74, 177-184).
FarmacocinéticaPharmacokinetics
As propriedades farmacocinéticas dos compostos foramdeterminadas via dosagem i.v. e p.o. em ratos Sprague Dawley, e, depois,coletando amostras de sangue durante 20 horas. Concentrações plásmicasforam determinadas com LC/MS/MS.Pharmacokinetic properties of the compounds were determined via i.v. and p.o. Sprague Dawley rats, and then collecting blood samples for 20 hours. Plasma concentrations were determined with LC / MS / MS.
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| US7786146B2 (en) * | 2007-08-13 | 2010-08-31 | Valeant Pharmaceuticals International | Derivatives of 5-amino-4,6-disubstituted indole and 5-amino-4,6-disubstituted indoline as potassium channel modulators |
| WO2010097379A1 (en) * | 2009-02-24 | 2010-09-02 | Neurosearch A/S | Substituted pyrimidin derivatives and their medical use |
| JP5763758B2 (en) * | 2010-07-08 | 2015-08-12 | ファイザー・インク | Piperidinyl pyrimidineamide as a Kv7 potassium channel opener |
| US8552200B2 (en) * | 2010-10-20 | 2013-10-08 | Gruenenthal Gmbh | Substituted 6-amino-nicotinamides as KCNQ2/3 modulators |
| CN103508943B (en) * | 2012-06-29 | 2017-06-09 | 江苏先声药业有限公司 | As the compound of potassium channel modulating agents |
| CN103508960B (en) * | 2012-06-29 | 2017-12-12 | 江苏先声药业有限公司 | Benzheterocyclic derivatives |
| JP6217866B2 (en) * | 2014-10-24 | 2017-10-25 | 小野薬品工業株式会社 | KCNQ2-5 channel activator |
| CN119490430A (en) | 2019-08-02 | 2025-02-21 | H.隆德贝克有限公司 | Alcohol derivatives as Kv7 potassium channel openers for use in epilepsy or epileptic seizures |
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| AU2003202115A1 (en) * | 2002-02-12 | 2003-09-04 | Pfizer Inc. | Non-peptide compounds affecting the action of gonadotropin-releasing hormone (gnrh) |
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