Efficient Synthesis of 5-(Hydroxymethyl)furfural Esters from Polymeric Carbohydrates Using 5-(Chloromethyl)furfural as a Reactive Intermediate

Abstract

This work reports an efficient, gram-scale synthesis of 5-(hydroxymethyl)furfural (HMF) esters using biomassderived 5-(chloromethyl)furfural (CMF) as a reactive intermediate. The HMF-esters have potential applications as chemical intermediates, fuel additives, and bioactive compounds. Initially, CMF was prepared in good yields directly from polymeric carbohydrates (starch, inulin, and cellulose) and cellulosic materials (cotton and filter paper) using a biphasic batch reaction system, consisting of aqueous hydrochloric acid and 1,2-dichloroethane. The use of ZnCl 2 as an additive allowed the reaction to proceed under milder conditions while significantly improving the isolated yield of CMF. The effects of reaction temperature, reaction time, extracting solvent, and ZnCl 2 loading on CMF yield were investigated. Microcrystalline cellulose was converted into CMF with a 72% isolated yield under optimized reaction conditions (80 °C, 2 h). After that, CMF was transformed into various novel esters of HMF in excellent isolated yields (>85%) by reacting with a slight excess amount of the triethylammonium salt of various alkyl/aryl carboxylic acids under solvent-free conditions.

Preparation of 5-(Acyloxymethyl)furfurals from Carbohydrates Using Zinc Chloride/Acetic Acid Catalyst System and Their Synthetic Value Addition

“…In a two-step strategy, AcMF has been produced in good yield by the nucleophilic substitution of CMF using suitable bases . In a recent report, CMF was reacted with the triethylammonium salt of various alkyl and aryl carboxylic acids to synthesize various AMFs in good scalability and yield . HMF can be esterified with AcOH in the presence of a suitable acid catalyst, forming AcMF .…”

“… 15 In a recent report, CMF was reacted with the triethylammonium salt of various alkyl and aryl carboxylic acids to synthesize various AMFs in good scalability and yield. 16 HMF can be esterified with AcOH in the presence of a suitable acid catalyst, forming AcMF. 17 Fructose was transesterified into 1,6-diacetylfructose by vinyl acetate using lipase catalyst, which was then dehydrated and partially deacetylated into AcMF using a cation-exchange resin.…”

Surface Nanoarchitectonics of Boron Nitride Nanosheets for Highly Efficient and Sustainableipso-Hydroxylation of Arylboronic Acids

“…Phenols constitute an important class of biologically active compounds owing to their antibacterial, antihyperglycemic, antitumor, antiviral, antitumor, antimutagenicity, pro-oxidant, and cardioprotective properties. , Phenols and their derivatives are commonly used in industries and companies for the synthesis of fine chemicals, pharmaceuticals, and agrochemicals. , Phenolic motifs are also present in various natural products, such as terpenoids, macrolides, quinines, alkaloids, and aryl steroids. , Due to their prevalent importance, dedicated efforts have been put forward to ease the synthesis of phenols. To date, different approaches have been utilized for the synthesis of phenolic compounds like nucleophilic substitution of aryl halides by hydroxyl group, C–H aryl ring oxidation and hydrolysis of diazonium salts, hydroxylation of aryl halides using hydroxide salts, hydroxylation of aryl halides, and so on. − However, the use of toxic solvents, homogeneous catalysts, harsh reaction conditions, and expensive metal-based catalysts, tedious reaction workups, and longer reaction time made these processes undesirable for large scale applications. , …”

“…7−9 However, the use of toxic solvents, homogeneous catalysts, harsh reaction conditions, and expensive metal-based catalysts, tedious reaction workups, and longer reaction time made these processes undesirable for large scale applications. 10,11 In this regard ipso-hydroxylation of arylboronic acids has gained widespread attention due to ease of availability, low cost, nontoxicity, and high stability of arylboronic acids which can be converted into the desired moieties even in the presence of other functional groups. 12,13 Various catalysts and reagents have been studied for the ipso-hydroxylation of arylboronic acids to corresponding phenols in past years.…”

Renewable synthesis of novel acrylates from biomass‐derived 5‐substituted‐2‐furaldehydes by Morita‐Baylis‐Hillman reaction

“…As evident from Scheme 1, this work has given more importance to exploring the reactivity of renewable furfurals toward MBH reaction with change in substitution at the 5‐position and reports several novel acrylates. The 5‐substituted‐2‐furaldehydes reported in this work were prepared using 5‐(chloromethyl)furfural (CMF) as the reactive intermediate using procedures reported earlier [17–19] . Acrylic acid can be synthesized renewably from various components of biomass following chemical‐catalytic pathways.…”