An improved process for the preparation of 4-(n,...

C - Chemistry – Metallurgy – 07 – C

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C07C 217/00 (2006.01) C07C 213/00 (2006.01) C07D 295/088 (2006.01) C07C 217/40 (2006.01)

Patent

CA 2487957

The invention disclosed in this application relates to an improved process for the preparation of compounds of formula (I): R1R2NCH2CH2CH2CH(OR3)2; wherein, R1 = R2 = C1-C16 alkyl; C3-C7 cycloalkyl; R1 = C1-C16 alkyl; R2 = C3-C7 cycloalkyl; NR1R2 = pyrrolidino, piperidino, morpholino, thiomorpholino, R1 = C1-C6 alkyl; R2 = ArCH2; Ar =4-R4-C6H4-, R4 = MeO, EtO, Me, Et, NMe2, NEt2, SMe, SEt, etc; R3=C1-C6 alkyl; C3-C7 cycloalkyl which comprises: (i) Reacting 3-(N, N-disubstitutedamino)propyl halide of formula (XXI): R1R2NCH2CH2CH2X; wherein, R1, R2 = as defined above, X = C1 or Br, with magnesium in the presence of a solvent to get the Grrgnard reagent 3-(N, N-disubstitutedamino)- propylmagnesium halide; (ii) Reacting the resulting 3-(N, N- disubstitutedamino) propylmagnesium halide (Grignard reagent) with the trisubstituted orthoformate of formula (XVII): HC(OR5)(OR3)2; wherein, R3 and R5 is same or different and represent C1 to C6 alkyl, C3 to C7 cycloalkyl OR R3 is as defined above and R5 represents phenyl radical; (iii) Filtering off the resultant reaction mixture and distilling the filtrate to isolate the compound of the formula (I). These substituted butyraldehyde derivatives of the formula (I) are very important building blocks for the synthesis of various tryptamine derivatives. In particular 4-(N, N- dimethylamino)butyraldehyde dimethyl or diethyl acetals are crucial intermediates for the synthesis of commercially available anti-migraine drugs, like sumatriptan, zolmitriptan, and rizatriptan.

L'invention concerne un procédé amélioré pour l'élaboration de composés représentés par la formule (I) R?1¿R?2¿NCH¿2?CH¿2?CH¿2?CH(OR?3¿)¿2?. Dans cette formule, R?1¿ = R?2¿ = alkyle C¿1?-C¿16?; cycloalkyle C¿3?-C¿7?; R?1 ¿= alkyle C¿1?-C¿16?; R?2¿ = cycloalkyle C¿3?-C¿7?; NR?1¿R?2¿ = pyrrolidino, pipéridino, morpholino, thiomorpholino, R?1¿ = alkyle C¿1?-C¿6?; R?2¿ = ArCH¿2?; Ar =4-R?4¿-C¿6?H¿4?-, R?4 ¿= MeO, EtO, Me, Et, NMe¿2?, NEt¿2?, SMe, SEt, etc; R?3¿= alkyle C¿1?-C¿6?; cycloalkyle C¿3?-C¿7?. Le procédé comprend les étapes suivantes: (i) réaction d'halogénure de 3-(N, N-aminodisubstitué)propyle de formule (XXI) R?1¿R?2¿NCH¿2?CH¿2?CH¿2? (R?1¿, R?2¿ tels que définis ci-dessus, X = C1 ou Br) et de magnésium en présence de solvant pour obtenir le réactif de Grignard halogénure de 3-(N, N-aminodisubstitué)propylmagnésium, (ii) réaction de cet halogénure de 3-(N, N-aminodisubstitué)propylmagnésium (réactif de Grignard) et d'orthoformate trisubstitué de formule (XVII) HC(OR?5¿)(OR?3¿)2 ( R?3¿ et R?5¿ identiques ou différents et représentant alkyle C¿1?-C¿6?, cycloalkyle C¿3?-C¿7?; OR R?3¿ tel que défini ci-dessus, et R?5¿ représentant un radical phényle), (iii) filtrage du mélange de réaction résultant et distillation du filtrat pour isoler le composé de formule (I). Les dérivés de butyraldéhyde substitués en question, représentés par la formule (I) sont des éléments constitutifs très importants pour la synthèse de différents dérivés de tryptamine. En particulier, les acétals de diméthyle ou de diéthyle de 4-(N, N-diméthylamino)butyraldéhyde sont des intermédiaires essentiels pour la synthèse de médicaments anti-migraine disponibles dans le commerce, comme le sumatriptane, le zolmitriptane, et le rizatriptane.

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