5306-85-4Relevant academic research and scientific papers
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.
Method for purifying diether of anhydrosugar alcohol with high purity
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Paragraph 0036-0037; 0041-0049; 0059-0065; 0071-0089, (2021/04/20)
The present invention relates to a method for purifying anhydrosugar alcohol diethers and, more specifically, to a method, which purifies crude anhydrosugar alcohol diethers through a thin film distillation process under distillation temperature and degree of vacuum conditions of a specific range, and thus can obtain highly pure (for example, a purity of 98% or more) anhydrosugar alcohol diethers in a high yield (for example, a yield of 80% or more).
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.
Method for preparing diether of anhydrosugar alcohol with improved yield
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Paragraph 0037-0040; 0045-0059, (2020/11/03)
The present invention relates to a method for manufacturing diether of anhydrosugar alcohol. More specifically, the present invention relates to a method which, in manufacturing diether of anhydrosugar alcohol by conducting a reaction of anhydrosugar alcohol with an alkylating reagent (for example, dimethyl sulfate or methyl chloride) conducts a reaction of monoether of anhydrosugar alcohol with an alkylating reagent together with anhydrosugar alcohol, thereby being able to improve the yield compared to the case where anhydride alcohol is reacted with the alkylating reagent alone, and being able to reduce process waste and process cost by utilizing distillation by-products generated during a diether purification of anhydrosugar alcohol, as a supply source of the monoether of anhydrosugar alcohol.
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.
One-Pot Preparation of Dimethyl Isosorbide from d-Sorbitol via Dimethyl Carbonate Chemistry
Aricò,Aldoshin,Tundo
, p. 53 - 57 (2017/01/17)
Direct synthesis of dimethyl isosorbide (DMI) from d-sorbitol via dimethyl carbonate (DMC) chemistry is herein first reported. High yield of DMI was achieved using the nitrogen superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90 to 200 °C. In this procedure, DMC features its full capacity acting in the different steps of the process as carboxymethylating, leaving-group (cyclization), and methylating agent; DMC is also employed as the reaction media.
A method of synthesizing 1,4:3,6-dianhydro-hexitol methyl ether
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Paragraph 0029; 0030; 0031; 0032; 0033; 0034, (2016/12/01)
A method of synthesizing 1,4:3,6-dianhydro-hexitol methyl ether is disclosed. 1,4:3,6-dianhydro-hexitol is adopted as an initial raw material, a methyl ether compound is adopted as a methylation agent, and the 1,4:3,6-dianhydro-hexitol methyl ether is generated through etherification with existence of an acidic catalyst. The 1,4:3,6-dianhydro-hexitol methyl ether is selected from monomethyl ether and dimethyl ether of isosorbide, isomannite and isoidide, preferentially the monomethyl ether and the dimethyl ether of the isosorbide, and the total yield of isosorbide methyl ether is 80% or above. The environmental friendly acidic catalyst is adopted, and therefore the catalyzing efficiency is high, generation of a large amount of halide salt side products in traditional etherification methods is avoided, and a corrosion problem caused by strong alkalis is avoided. A novel and efficient synthesis route of the 1,4:3,6-dianhydro-hexitol methyl ether is provided and environmental friendly catalyzed etherification is achieved.
Method for preparing dialkyloxydianhyrohexitol by etherification of dianhydrohexitol using a light alcohol, in the presence of an acidic catalyst
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Page/Page column 10-11, (2016/05/19)
A method for preparing a dialkyloxydianhyrohexitol (dimethylisosorbide) composition by etherification of dianhydrohexitol (isosorbide). The aim is to achieve a “clean” method that avoids the use of a methylation agent such as dimethyl sulfate or methyl chloride, which generates stoechiometric quantities of salts, or expensive dialkyl-carbonates, wherein only one of the two methyl groups participates in the preparation of mixed isosorbide ethers. The method involves using at least one O-alkylation agent and a catalyst including an acid or an acid salt, preferably a catalyst having Lewis or Br?nsted acid properties. A device for carrying out the method wherein the device includes a vaporization oven and a reaction oven is also described.
METHOD FOR PREPARING DIALKYLOXYDIANHYROHEXITOL BY ETHERIFICATION OF DIANHYDROHEXITOL USING A LIGHT ALCOHOL, IN THE PRESENCE OF AN ACIDIC CATALYST
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Paragraph 0125-0138, (2015/07/27)
A method for preparing a dialkyloxydianhyrohexitol (dimethylisosorbide) composition by etherification of dianhydrohexitol (isosorbide). The aim is to achieve a “clean” method that avoids the use of a methylation agent such as dimethyl sulfate or methyl chloride, which generates stoechiometric quantities of salts, or expensive dialkyl-carbonates, wherein only one of the two methyl groups participates in the preparation of mixed isosorbide ethers. The method involves using at least one O-alkylation agent and a catalyst including an acid or an acid salt, preferably a catalyst having Lewis or Br?nsted acid properties. A device for carrying out the method wherein the device includes a vaporization oven and a reaction oven is also described.
Catalytic etherification of hydroxyl compounds to methyl ethers with 1,2-dimethoxyethane
Che, Penghua,Lu, Fang,Si, Xiaoqin,Xu, Jie
, p. 24139 - 24143 (2015/03/18)
1,2-Dimethoxyethane is explored for the first time as etherification agent for the acid-catalyzed synthesis of methyl ethers from biomass-derived hydroxyl compounds. H3PW12O40 catalyst can provide the formation of isosorbi
