CHAPITRE II : Synthèse en série Benzothiazole
IV. 2 3.1 Généralité sur les micro-ondes
V.6 Déméthylation (obtention du PIB)
Les déprotections des éthers de méthyle et de phényle requirent pour la plupart des conditions assez dures contre partie de leur grande stabilité dans diverses conditions réactionnelles.
La déméthylation des éthers peut se faire soit avec des acides de Brönsted (HBr, HI) ou de Lewis, les dérivés du bore sont particulièrement employés.
Généralement il s’agit de trihalogénoborane (le plus utilisé est le BBr3) libre ou
complexé, ou l’alkylhalogenoborane tel que le dimethylbromoborane. Les dérivés silylés sont également utilisés.185
Dans le cas de l’utilisation des acides fort acides (HBr, HI, BBr3), Le clivage nécessite
une protonation ou une coordination de l’oxygène, qui facilite la dealkylation par le nucléophile qui attaque le carbone de l’éther. Elle suit probablement le mécanisme ci-dessous (Schéma 81-II). R O Me H Br R O H R O Me Br ou R O B CH3Br H+ R O H CH3Br Br2B OR OR
Schéma 81-II : Déprotection éther
V.6.2 Résultats
En nous basant sur les travaux de(Mathis et al., 2003) 186, nous avons réalisé le clivage de l’éther avec BBr3 dans le dichloromothane à température ambiante (Schéma 82 –II).
N S NH H3CO BBr 3 DCM, t.a N S NH HO 1h, 67%
Schéma 82-II : Synthèse PIB par déméthylation
Le PIB est obtenu avec un rendement bon rendement (67 %). Cette stratégie s’avère une voie relativement efficace et flexible pour accéder à des dérives de ce type.
VI Conclusion
Les benzothiazoles constituent une famille de composés aux applications diverses. Le regain d’intérêt pour ces composés ces dernières années est dû surtout à la découverte il y a peu de leur aptitude à agir comme marqueur des plaques séniles qu’on rencontre chez les patients atteint de la Maladie d’Alzheimer permettant in fine d’accéder à un diagnostic précoce par Tomographie par Emission de Positons.
Un des marqueurs de cette famille, le PIB, est actuellement le plus utilisé en phase clinique pour le marquage in vivo des plaques amyloïdes, il a déjà fait l’objet d’essai sur plus de 2000 sujets187, 188. D’autres marqueurs sont aussi utilisés sont utilisés189.
Nous avons exploré des procédés simples et originaux, permettant d’accéder aux composés de cette famille suivant en nous appuyant principalement sur trois méthodes :
-Réaction directe sur champ micro-onde ou en solution avec un acide de Lewis -Réaction d’amino-réduction
-Réaction de Couplage de Suzuki entre des partenaires bromés et pour la première fois des dioxazaborocanes.
Ces méthodes de synthèses s’avèrent globalement efficaces et permettent une automatisation au moins partielle du procédé. Ceci pourra permettre d’agrandir de manière rapide et significative le tableau des analogues.
De plus, les voies de synthèses développées pourront permettre de synthétiser des ligands bifonctionnels avec d’autres familles de ligands comme les styrylbenzenes, les aminonaphtyls qui peuvent aussi se fixer sur d’autres sites des agrégats amyloïdes.
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