4792-78-3Relevant articles and documents
Benzo-Fused 1,4-Heterocycles via Dialkyl Carbonate Chemistry
Musolino, Manuele,Aricò, Fabi
supporting information, p. 1770 - 1778 (2019/04/05)
A novel halogen-free synthesis of benzo-fused six-membered 1,4-heterocycles through the chemistry of dialkyl carbonates is reported. Commercially available catechol, 2-aminophenol, and 2-aminothiophenol were reacted first with ethylene carbonate in an autoclave to give O -hydroxyethyl, N -hydroxyethyl, and S -hydroxyethyl derivatives respectively, through a B Al 2 mechanism. Then 2-(2-hydroxyethoxy)phenol and 2-(2-hydroxyethylamino)phenol were cyclized in excellent yields by reaction with dimethyl carbonate (DMC) and DABCO as a bicyclic organic base to give the corresponding benzodioxine and benzoxazine derivative, respectively. Moreover, 2-(2-aminophenylthio)ethanol afforded the benzothiazine derivative in good yield by reaction with DMC with an excess of a strong base such as NaH. The investigation on the cyclization reaction has highlighted that several equilibria are involved leading to the formation of carbonate and carbamate intermediates through B Ac 2 mechanisms. Depending on the reaction conditions employed, these intermediates may undergo either kinetic-controlled ring closure by a B Al 2 mechanism or by-product formation.
Harnessing C?H Activation of Benzhydroxamates as a Macrocyclization Strategy: Synthesis of Structurally Diverse Macrocyclic Isoquinolones
Krieger, Jean-Philippe,Ricci, Gino,Lesuisse, Dominique,Meyer, Christophe,Cossy, Janine
supporting information, p. 13469 - 13473 (2016/09/13)
Macrocycles are arising considerable interest in medicinal chemistry. With the goal of harnessing C?H activation reactions for the development of efficient macrocyclization processes, the ruthenium(II)-catalyzed cyclization of O-methyl benzhydroxamates possessing an ω-acetylenic chain was investigated to access new structurally diverse macrocyclic isoquinolones. A slow addition of the substrate and the presence of Cu(OAc)2?H2O as an additive were crucial for the success of the macrocyclization that features an excellent functional-group compatibility, as illustrated by the successful synthesis of a library of 21 macrocyclic isoquinolones of different ring sizes and substitution patterns. These results contribute to significantly highlight the synthetic interest of C?H activation-mediated processes for the synthesis of new macrocyles incorporating heterocyclic scaffolds of potential interest in medicinal chemistry.
NOVEL PROCESS FOR THE SYNTHESIS OF PHENOXYETHYL DERIVATIVES
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Page/Page column 22, (2011/09/19)
The present invention provides an improved process for the synthesis of 2-[2- (2,2,2-trifluoroethoxy)phenoxy]ethanol intermediate, its derivatives and/or its pharmaceutically acceptable salts, useful in the synthesis of α-1 adrenoceptor blockers such as silodosin.
