5306-85-4Relevant articles and documents
Intramolecular cyclisation of isosorbide by dimethylcarbonate chemistry
Tundo, Pietro,Aricò, Fabio,Gauthier, Guillaume,Baldacci, Agostino
, p. 652 - 655 (2011)
In this work the synthesis of a tricyclic isosorbide derivative in moderate yield directly from the dicarboxymethyl isosorbide in a continuous-flow apparatus is reported. The tricyclic structure has been isolated as pure and fully characterized. This product confirms the potentiality of dimethylcarbonate (DMC) as dehydrating agent also for complicated structure and opens up further investigation and application of DMC chemistry on renewable starting materials.
Dimethyl isosorbideviaorganocatalystN-methyl pyrrolidine: scaling up, purification and concurrent reaction pathways
Annatelli, Mattia,Aricò, Fabio,Dalla Torre, Davide,Musolino, Manuele
, p. 3411 - 3421 (2021/06/06)
Dimethyl isosorbide (DMI) is a well-known bio-based green replacement for conventional dipolar solvents such as dimethyl sulfoxide and dimethylformamide. The synthesis of DMI mainly relies on the etherification of the bio-based platform chemical isosorbide in the presence of basic or acid catalysts and by employing different alkylating agents. Among them, dimethyl carbonate (DMC) is considered one of the most promising for its good biodegradability and low toxicity. In this work, we report on a comprehensive investigation on high yielding methylation of isosorbideviaDMC chemistry promoted by nitrogen organocatalystN-methyl pyrrolidine (NMPy). Reaction conditions were optimized and then efficiently applied for the methylation of isosorbide epimers, isoidide and isomannide, and for some preliminary scale-up tests (up to 10 grams of isosorbide). The purification of DMI from the reaction mixture was achieved by both column chromatography and distillation at reduced pressure. NMPy demonstrated to be an excellent catalyst also for the one-pot conversion ofd-sorbitol into DMI. Furthermore, for the first time, all seven methyl and methoxycarbonyl intermediates observed in the etherification of isosorbide were synthetised, isolated and fully characterised. This has provided an insight on the concurrent reaction pathways leading to DMI and on the role played by NMPy in the methylation of isosorbide. Finally, the reaction mechanisms for the methylation, methoxycarbonylation and decarboxylation promoted by NMPy partaking in the conversion of isosorbide into DMIviaDMC chemistry have been proposed.
Methylation of Polyols with Trimethylphosphate in the Presence of a Lewis or Br?nsted Acid Catalyst
Duclos, Marie-Christine,Herbinski, Aurélien,Mora, Anne-Sophie,Métay, Estelle,Lemaire, Marc
, p. 547 - 551 (2018/01/16)
The alkylation of alcohols and polyols has been investigated with alkylphosphates in the presence of a Lewis or Br?nsted acid catalyst. The permethylation of polyols was developed under solvent-free conditions at 100 °C with either iron triflate or Aquivion PW98, affording the isolated products in yields between 52 and 95 %. The methodology was also adjusted to carry out peralkylation with longer alkyl chains.