- 5-Hydroxymethyl-2-vinylfuran: A biomass-based solvent-free adhesive
-
5-Hydroxymethylfurfural (HMF) is an important platform chemical derived from biomass. Tremendous efforts have been made to transform HMF into valuable chemicals for applications in biofuels, materials science, and pharmaceuticals. Here we report the conversion of HMF into 5-hydroxymethyl-2-vinylfuran (HMVF), a versatile adhesive. HMVF can bond to a variety of substrates, e.g. metal, glass, plastics and rubber, under heating or acid treatment at room temperature. Mechanistic studies show that the vinyl group undergoes free radical polymerization and the hydroxyl group dehydrates to form an ether linkage to crosslink HMVF under either heating or acid treatment. The bonding strength (τ) of HMVF cured by heating (h-HMVF) is close to that of Krazy Glue (Loctite 401, cyanoacrylate) and higher than that of white glue (Pattex No. 710, PVA) and Pattex PKME15C epoxy glue. The outstanding adhesive performance of HMVF is attributed both to the interaction of hydroxyl groups with substrates and crosslinking by etherification between hydroxyl groups. Similar to Krazy Glue, HMVF is also used in its monomer form, which eliminates the use of solvents. Cells show good adhesion on crosslinked HMVF, which makes HMVF a potential bio-adhesive.
- Han, Miaomiao,Liu, Xiao,Zhang, Xiaosa,Pang, Yuanyuan,Xu, Peng,Guo, Jianwei,Liu, Yadong,Zhang, Shuangyan,Ji, Shengxiang
-
-
Read Online
- An efficient catalyst for the conversion of fructose into methyl levulinate
-
The catalytic alcoholysis of fructose in methanol to methyl levulinate was performed by using phosphotungstic acid iron catalysts. The catalysts were characterized by powder X-ray diffraction, infrared spectroscopy, and X-ray fluorescence spectroscopy. The results showed that the exchanging of H + with Fe3+ ions could modify the acidity of H 3PW12O40 and introduce some Lewis acidity into the molecules. The highest yield of methyl levulinate was obtained over the Fe-HPW-1 catalyst. This catalyst showed 100 % fructose conversion with 73.7 % yield of methyl levulinate at 130 °C, 2 MPa for 2 h, and it could be reused at least five times without obvious loss of activity. The results suggest that the combination of Bronsted acidity with some Lewis acidity could effectively promote the conversion of fructose in methanol to methyl levulinate.
- Liu, Yan,Liu, Chun-Ling,Wu, Hai-Zhen,Dong, Wen-Sheng
-
-
Read Online
- Facile and high-yield synthesis of methyl levulinate from cellulose
-
Efficient production of chemicals from cellulose provides sustainable routes for the utilization of natural renewable resources to meet the requirements of human society. Herein, we reported a highly efficient and simple metal salt catalyst, Al2(SO4)3, for cellulose conversion to methyl levulinate (ML) under microwave conditions. A highest ML yield of 70.6% was obtained at 180 °C within a very short time of 40 min. The introduction of water could reduce humin/coke formation and solvent consumption, and could also switch the reaction pathway via the more reactive intermediate glucose. Kinetic and mechanistic studies of the subreactions showed that both cellulose hydrolysis and alcoholysis pathways were involved in the cellulose conversion to ML, with the former as the main route in the presence of water. The Lewis acid species [Al(OH)x(H2O)y]n+ and the Br?nsted acid species H+, generated by in situ hydrolysis of Al2(SO4)3, were responsible for the reaction conversions. The reaction with microwave heating showed accelerated reaction rates of 25 times the reaction with conventional oil heating, and even more times for the rates of glucose and methyl glucoside (MG) dehydration, resulting in higher reaction selectivity toward ML production. The catalyst was also successfully recycled and applied to the conversion of cellulose to other alkyl levulinates, as well as the conversion of raw biomass to ML with high yields. The homogeneous nature of Al2(SO4)3, together with its high efficiency and excellent recyclability, make it a potential catalyst for the large-scale production of ML in industry.
- Huang, Yao-Bing,Yang, Tao,Lin, Yu-Ting,Zhu, Ying-Zhi,Li, Li-Cheng,Pan, Hui
-
-
Read Online
- Preparation of potential biofuel 5-ethoxymethylfurfural and other 5-alkoxymethylfurfurals in the presence of oil shale ash
-
5-Ethoxymethylfurfural (EMF) can be prepared from the corresponding halomethylfurfural and absolute ethanol in good yield. The use of significantly more affordable 96% ethanol results in formation of levulinic acid or its ester in considerable amount (up to 16%), which is difficult to separate from the desired EMF. In the present study we report that the addition of oil shale ash prevents the hydrolysis of the furan ring and enables the use of 96% ethanol with great success. The developed procedure is applicable to a wide range of aqueous alcohols, is operationally simple and utilizes an inexpensive basic ash, which is deposited in millions of tons per year. Notably, the basicity of the ash is decreased during the process, making its deposits less hazardous to the environment.
- Viil, Indrek,Bredihhin, Aleksei,Maeeorg, Uno,Vares, Lauri
-
-
Read Online
- Synergistic Production of Methyl Lactate from Carbohydrates Using an Ionic Liquid Functionalized Sn-Containing Catalyst
-
Considerable progress has been made recently in the catalytic conversion of renewable biomass resources to methyl lactate (MLA). However, conceiving eco-friendly and effective catalytic systems for the production of MLA from biomass carbohydrates remains a key challenge. Herein, we report a multifunctional catalyst Sn(salen)/IL, consisting of a Sn(salen) complex and an imidazolium-based ionic liquid (IL), which acts via an intramolecular synergistic effect to convert carbohydrates to MLA in methanol. The versatile properties of the resultant catalyst were revealed to be responsible for the conversion of fructose to MLA and the efficient suppression of undesired side reactions. This catalyst displayed outstanding catalytic activity, high selectivity, and excellent recyclability, giving an MLA yield of up to 68.9 % at 160 °C after 2 h. The results of this study will contribute to new approaches for designing synergistic catalysts for producing liquid fuels and chemicals from biomass resources.
- Wang, Fenfen,Wen, Yi,Fang, Yanxiong,Ji, Hongbing
-
-
Read Online
- Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents
-
Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.
- Zhu, Hong,Cao, Quan,Li, Chunhu,Mua, Xindong
-
-
Read Online
- Efficient synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over sulfonated organic polymer catalyst
-
Herein, we investigated catalytic potential of a functionalized porous organic polymer bearing sulfonic acid groups (PDVTA-SO3H) to the etherification of 5-hydroxymethylfurfural (HMF) to 5-ethoxymethylfurfural (EMF) under solvent-free conditions. The PDVTA-SO3H material was synthesized via post-synthetic sulfonation of the porous co-polymer poly-divinylbenzene-co-triallylamine by chlorosulfonic acid. The physicochemical properties of the PDVTA-SO3H were characterized by FT-IR, SEM, TG-DTG, and N2 adsorption isotherm techniques. PDVTA-SO3H had high specific surface area (591 m2 g-1) and high density of -SO3H group (2.1 mmol g-1). The reaction conditions were optimized via Box-Behnken response surface methodology. Under the optimized conditions, the PDVTA-SO3H catalyst exhibited efficient catalytic activity with 99.8% HMF conversion and 87.5% EMF yield within 30 min at 110 °C. The used PDVTA-SO3H catalyst was readily recovered by filtration and remained active in recycle runs.
- Xiang, Yanping,Wen, Sha,Tian, Yi,Zhao, Kangyu,Guo, Dongwen,Cheng, Feng,Xu, Qiong,Liu, Xianxiang,Yin, Dulin
-
-
Read Online
- Etherification of 5-hydroxymethylfurfural using a heteropolyacid supported on a silica matrix
-
In this work, Preyssler-type heteropolyacids and their silica-included counterparts were employed in the etherification reaction of HMF and n-BuOH. Materials were synthesized with a Preyssler acid load of 12.5percent w/w using the sol-gel technique, which improved surface areas and modulated their acid strength. Prepared materials were used as heterogeneous solid acid catalysts in the selective etherification of 5-hydroxymethylfurfural (HMF) to 5-butoxymethylfurfural (5BMF). The high catalytic performance of the bulk Preyssler acids is related to their high acid strength, while selectivity related to the decrease in acidity by the inclusion effects. Different reaction parameters were optimized, with PWMo(12.5percent)&at;SiO2 exhibited the highest catalytic activity with 89percent of HMF conversion and 73percent of 5BMF selectivity. The catalyst is reusable up to five cycles without noticeable decrease in selectivity.
- Casella, Mónica,Lick, Daniela I.,Luque, Rafael,Martínez, José J.,Portilla-Zu?iga, Omar M.,Romanelli, Gustavo P.,Sathicq, ángel G.
-
-
- Etherification of biomass-derived furanyl alcohols with aliphatic alcohols over silica-supported nickel phosphide catalysts: Effect of surplus P species on the acidity
-
The acidity of nickel phosphide (Ni2P) catalysts plays a crucial role in producing a desired hydrodeoxygenation molecule from biomass-derived substrates; yet, it has never been explored in acid-catalyzed reactions. Herein, we demonstrated the activity of silica-supported Ni2P catalyst prepared with the nominal P/Ni ratio of 2 (Ni2P/SiO2-2P) in the etherification of furanyl alcohols (particularly, 5-(hydroxymethyl)furfural) with aliphatic alcohols including ethanol. By comparing the characteristics of Ni/SiO2, PxOy/SiO2, and Ni2P/SiO2-xP (x = 0.5 and 1), Ni2P/SiO2-2P was revealed to contain the Br?nsted and Lewis acid sites of which both contributed to the etherification reaction. Notably, the Br?nsted acidity was associated with the surplus P species added to produce the Ni2P phase. Consequently, supported Ni2P catalysts can work in acid-catalyzed reactions if an adequate ratio of Br?nsted to Lewis acid sites is provided by the amount of the surplus P species determined by adjusting the P/Ni ratio.
- Kim, Jinsung,Shin, Mi,Suh, Young-Woong
-
-
- Importance of the synergistic effects between cobalt sulfate and tetrahydrofuran for selective production of 5-hydroxymethylfurfural from carbohydrates
-
In this study, an effective catalytic system (CoSO4·7H2O/THF) for selective conversion of fructose to 5-hydroxymethylfurfural (HMF; yield: 88%) was developed. The synergistic effects among Co2+, SO42-, crystal water and tetrahydrofuran (THF) were crucial for achieving selective dehydration of fructose to HMF. Co2+ worked as a Lewis acid for catalyzing mainly dehydration of fructose to HMF but not the further decomposition of HMF to levulinic acid. THF could help to retain HMF while CoSO4 could coordinate with HMF, enhancing the thermal stability of HMF in THF. The crystal water in cobalt sulfate could help to coordinate with fructose, which facilitated the conversion of fructose via dehydration reactions. The CoSO4·7H2O/THF catalytic system could also catalyze the conversion of inulin and cellulose into HMF. The main advantages of the CoSO4·7H2O/THF catalytic system are the low cost, the easy recycling of the CoSO4·7H2O catalyst and the easy separation of HMF from volatile THF.
- Dong, Dehua,Hu, Xun,Li, Qingyin,Li, Xueli,Shao, Yuewen,Sun, Kai,Wang, Yi,Ye, Zhengmao,Zhang, Lijun,Zhang, Shu
-
p. 2293 - 2302
(2020/04/20)
-
- Structure-based design and synthesis of novel furan-diketopiperazine-type derivatives as potent microtubule inhibitors for treating cancer
-
Plinabulin, a synthetic analog of the marine natural product “diketopiperazine phenylahistin,” displayed depolymerization effects on microtubules and targeted the colchicine site, which has been moved into phase III clinical trials for the treatment of non-small cell lung cancer (NSCLC) and the prevention of chemotherapy-induced neutropenia (CIN). To develop more potent anti-microtubule and cytotoxic derivatives, the co-crystal complexes of plinabulin derivatives were summarized and analyzed. We performed further modifications of the tert-butyl moiety or C-ring of imidazole-type derivatives to build a library of molecules through the introduction of different groups for novel skeletons. Our structure–activity relationship study indicated that compounds 17o (IC50 = 14.0 nM, NCI-H460) and 17p (IC50 = 2.9 nM, NCI-H460) with furan groups exhibited potent cytotoxic activities at the nanomolar level against various human cancer cell lines. In particular, the 5-methyl or methoxymethyl substituent of furan group could replace the alkyl group of imidazole at the 5-position to maintain cytotoxic activity, contradicting previous reports that the tert-butyl moiety at the 5-position of imidazole was essential for the activity of such compounds. Immunofluorescence assay indicated that compounds 17o and 17p could efficiently inhibit microtubule polymerization. Overall, the novel furan-diketopiperazine-type derivatives could be considered as a potential scaffold for the development of anti-cancer drugs.
- Ding, Zhongpeng,Li, Feifei,Li, Feng,Li, Wenbao,Liu, Yuqian,Wang, Shixiao,Zhao, Jianchun,Zhong, Changjiang
-
-
- PROCESS FOR THE CONVERSION OF A SOLID LIGNOCELLULOSIC MATERIAL
-
A process, which process includes the following steps: a) converting a solid material containing hemicellulose, cellulose and lignin, by: (i) hydrolyzing, at a temperature equal to or less than 40 °C, preferably equal to or less than 30 °C, at least part of the hemicellulose of the solid material with a first aqueous hydrochloric acid solution, which first aqueous hydrochloric acid solution has a hydrochloric acid concentration in the range from equal to or more than 15.0 wt. % to less than 40.0 wt. %, based on the weight amount of water and hydrochloric acid in such first aqueous hydrochloric acid solution, yielding a remaining solid material and a hydrochloric acid- containing, aqueous, first hydrolysate product solution; (ii) hydrolyzing, at a temperature equal to or less than 40 °C, preferably equal to or less than 30 °C, at least part of the cellulose of the remaining solid material with a second aqueous hydrochloric acid solution, which second aqueous hydrochloric acid solution has a hydrochloric acid concentration in the range from equal to or more than 40.0 wt. % to equal to or less than 51.0 wt. %, based on the weight amount of water and hydrochloric acid in such second aqueous hydrochloric acid solution, yielding a residue and a hydrochloric acid- containing, aqueous, second hydrolysate product solution. (b) forwarding to step (c) a, hydrochloric acid-containing, aqueous intermediate product solution comprising: - a part of or the whole of the hydrochloric acid-containing, aqueous first hydrolysate product solution of step (a); and/or - a part of or the whole of the, hydrochloric acid-containing, aqueous second hydrolysate product solution of step (a); and (c) heating at least part of the hydrochloric acid-containing, aqueous intermediate product solution to a temperature equal to or more than 60 °C, yielding a product solution containing 5-(chloromethyl)furfural, and extracting the 5-(chloromethyl)furfural from such product solution into an extraction solvent.
- -
-
Paragraph 0192-0193
(2019/08/26)
-
- Phosphotungstic acid heterogenized by assembly with pyridines for efficient catalytic conversion of fructose to methyl levulinate
-
Solid acid-catalyzed sugar degradation has been considered to be an efficient approach to synthesize alkyl levulinates (which can be used as fuel additives and surfactants). However, those catalytic processes typically involve harsh reaction conditions and high cost for catalyst preparation. We prepared a series of phosphotungstic acid organic hybrids by a simple solvothermal method, and used them as heterogeneous catalysts for the selective degradation of fructose to methyl levulinate (ML) in methanol with high efficiency under mild reaction conditions. The catalysts were characterized systematically, and the effects of different substituents in pyridine, reaction temperature/time, catalyst dose, and fructose concentration studied. The 3-FPYPW hybrid prepared from 3-fluoropyridine and phosphotungstic acid exhibited superior catalytic activity for the synthesis of ML (82.5%) from fructose (97.8%). A possible reaction pathway was proposed. In addition, the catalyst could be separated from the reaction mixture readily, and reused without remarkable loss of reactivity.
- Fang, Chengjiang,Li, Yan,Zhao, Wenfeng,Wu, Weibo,Li, Hu,He, Chao,Yang, Song
-
p. 16585 - 16592
(2018/05/23)
-
- PRODRUG AND PROTECTED FORMS OF 5-HYDROXYMETHYLFURFURANAL (5-HMF) AND ITS DERIVATIVES
-
Prodrugs and derivatives of 5-hydoxymethyl-2-furfural (5-HMF) with protected or modified aldehyde and/or alcohol moieties are provided. The prodrugs or derivatives exhibit increased bioavailability, e.g. due to having extended half-lives in circulation. The drugs are therefore administered i) at lower doses and/or ii) less frequently than 5-HMF, while still maintaining the beneficial therapeutic effects of 5-HMF.
- -
-
Page/Page column 35
(2018/02/27)
-
- A bifunctional cerium phosphate catalyst for chemoselective acetalization
-
Acid-base solid catalysts synthesized with structurally controlled uniform active sites can lead to unique catalysis. In this study, a CePO4 catalyst was synthesized using a hydrothermal method and found to exhibit high catalytic performance for the chemoselective acetalization of 5-hydroxymethylfurfural with alcohols, in sharp contrast to other homogeneous and heterogeneous acid and/or base catalysts. In the presence of CePO4, various combinations of carbonyl compounds and alcohols are efficiently converted into the corresponding acetal derivatives in good to excellent yields. Mechanistic studies show that CePO4 most likely acts as a bifunctional catalyst through the interaction of uniform Lewis acid and weak base sites with 5-hydroxymethylfurfural and alcohol molecules, respectively, which results in high catalytic performance.
- Kanai, Shunsuke,Nagahara, Ippei,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
-
p. 3146 - 3153
(2017/04/04)
-
- Design, Synthesis, and Biological Evaluation of Ester and Ether Derivatives of Antisickling Agent 5-HMF for the Treatment of Sickle Cell Disease
-
Candidate drugs to counter intracellular polymerization of deoxygenated sickle hemoglobin (Hb S) continue to represent a promising approach to mitigating the primary cause of the pathophysiology associated with sickle cell disease (SCD). One such compound is the naturally occurring antisickling agent, 5-hydroxymethyl-2-furfural (5-HMF), which has been studied in the clinic for the treatment of SCD. As part of our efforts to develop novel efficacious drugs with improved pharmacologic properties, we structurally modified 5-HMF into 12 ether and ester derivatives. The choice of 5-HMF as a pharmacophore was influenced by a combination of its demonstrated attractive hemoglobin modifying and antisickling properties, well-known safety profiles, and its reported nontoxic major metabolites. The derivatives were investigated for their time- and/or dose-dependent effects on important antisickling parameters, such as modification of hemoglobin, corresponding changes in oxygen affinity, and inhibition of red blood cell sickling. The novel test compounds bound and modified Hb and concomitantly increased the protein affinity for oxygen. Five of the derivatives exhibited 1.5- to 4.0-fold higher antisickling effects than 5-HMF. The binding mode of the compounds with Hb was confirmed by X-ray crystallography and, in part, helps explain their observed biochemical properties. Our findings, in addition to the potential therapeutic application, provide valuable insights and potential guidance for further modifications of these (and similar) compounds to enhance their pharmacologic properties.
- Xu, Guoyan G.,Pagare, Piyusha P.,Ghatge, Mohini S.,Safo, Ronni P.,Gazi, Aheema,Chen, Qiukan,David, Tanya,Alabbas, Alhumaidi B.,Musayev, Faik N.,Venitz, Jürgen,Zhang, Yan,Safo, Martin K.,Abdulmalik, Osheiza
-
p. 3499 - 3511
(2017/10/11)
-
- A fructose-based biomass catalytic conversion systems furan derivatives
-
A method for preparing furan derivatives by catalytic conversion of fructose-based biomass is characterized by: taking biomass such as fructose, cane sugar, inulin and the like as raw materials, taking low-boiling-point alcohols comprising aliphatic alcohols or alicyclic alcohols all with six or less than six carbon atoms as a solvent, and under the effect of a catalyst, performing reactions comprising hydrolysis, dehydration, etherfication and the like for coupling so as to obtain furan derivatives such as 5-alkoxymethyl furfural, levulinate esters, 5-hydroxymethylfurfural and the like. The method has the advantages of high raw material utilization rate, high in-situ coupling efficiency in the dehydration and etherfication reactions, and easily separated and purified system.
- -
-
Paragraph 0017
(2017/02/09)
-
- Production of methyl levulinate from cellulose: Selectivity and mechanism study
-
The alcoholysis of cellulose into methyl levulinate (ML) in methanol media was investigated in the presence of several kinds of acid catalyst. One of the synthesized solid niobium-based phosphate catalysts was found to be highly efficient for the generation of ML, reaching an ML yield as high as 56%, higher than the LA yield (52%) in aqueous solution with the same reaction conditions as those used in our previous study (Green Chem., 2014, 16, 3846-3853). More interestingly, in water, very strong Lewis acid promoted the formation of LA; but in methanol, Br?nsted acid enhanced the formation of ML. In-depth investigation showed that the mechanism and type of intermediates of cellulose alcoholysis in methanol were different from those in water and a high Br?nsted/Lewis acid ratio (known as B/L acid ratio) of solid catalysts is needed to prevent the generation of by-products, namely, methyl lactate and 1,1,2-trimethoxyethane. This new-proposed reaction mechanism affected by the B/L acid ratio was very helpful for the design of efficient catalysts.
- Ding, Daqian,Xi, Jinxu,Wang, Jianjian,Liu, Xiaohui,Lu, Guanzhong,Wang, Yanqin
-
p. 4037 - 4044
(2015/07/15)
-
- One-pot catalytic conversion of carbohydrate biomass to lactic acid using an ErCl3 catalyst
-
Cellulose was hydrothermally converted into lactic acid in the presence of an ErCl3 catalyst. Lactic acid yields as high as 91.1% were obtained when reacting 0.1 g cellulose, 0.05 g catalyst and 30 mL water at 240 °C under 2 MPa N2 for 30 min. Other carbohydrate biomass materials could also be converted into lactic acid effectively under the same reaction conditions. Materials tested included monosaccharides, disaccharides, polysaccharides, and raw biomass such as corn stalks, wheat stems and rice straw. The ErCl3 catalyst could be reused at least five times without any obvious loss of activity.
- Lei, Xing,Wang, Fen-Fen,Liu, Chun-Ling,Yang, Rong-Zhen,Dong, Wen-Sheng
-
-
- METHOD OF PREPARING FURFURAL COMPOUNDS
-
Provided is a two-step method of producing a compound of chemical formula 1 in the presence of an alcohol solvent and a Group 3B metal catalyst or a salt thereof, comprising a first step comprising alkylation or isomerization of an aldohexose-containing substrate to obtain an intermediate, and a second step comprising dehydration of the intermediate to produce a compound of chemical formula 1. Preferably, additional solvent and/or catalyst are not added in the second step.
- -
-
Paragraph 0039; 0040; 0061
(2014/05/20)
-
- METHOD OF PRODUCING 5-HYDROXYMETHYLFURFURAL FROM CARBOHYDRATES
-
Disclosed herein is a process for preparing 5-hydroxymethylfurfural comprising the step of contacting a carbohydrate and a Br?nsted acid in an alcoholic solvent comprising an alcohol selected from the group consisting of secondary alcohols, tertiary alcohols, aryl alcohols and combinations thereof under conditions to dehydrate the carbohydrate thereby forming a reaction product containing 5-hydroxymethylfurfural.
- -
-
Page/Page column 35; 36; 37
(2013/04/10)
-
- Conversion of fructose into 5-hydroxymethylfurfural and alkyl levulinates catalyzed by sulfonic acid-functionalized carbon materials
-
A series of sulfonic acid-functionalized carbon materials (C-SO 3H), including poly(p-styrenesulfonic acid)-grafted carbon nanotubes (CNT-PSSA), poly(p-styrenesulfonic acid)-grafted carbon nanofibers (CNF-PSSA), benzenesulfonic acid-grafted CMK-5 (CMK-5-BSA), and benzenesulfonic acid-grafted carbon nanotubes (CNT-BSA), have been studied for fructose dehydration to 5-hydroxymethylfurfural (HMF) and fructose alcoholysis to alkyl levulinate. A study for optimizing the reaction conditions such as the catalyst loading, the reaction time, and the temperature has been performed. Under the optimal conditions, high HMF and ethyl levulinate yields of up to 89% and 86%, respectively, are obtained. The catalytic activities of C-SO3H for the conversions of fructose into both HMF and ethyl levulinate follow the order of their acid strength. The relationship between the catalytic activity and acid density of C-SO3H shows a linear correspondence in the fructose dehydration to HMF. The facile separation, ease of recovery, and high thermal stability make the developed C-SO3H efficient and environment-friendly catalytic materials for transforming biomass carbohydrate into fine chemicals.
- Liu, Ruliang,Chen, Jinzhu,Huang, Xing,Chen, Limin,Ma, Longlong,Li, Xinjun
-
supporting information
p. 2895 - 2903
(2013/10/08)
-
- PROCESS FOR THE CONVERSION OF A CARBOHYDRATE-CONTAINING FEEDSTOCK
-
A carbohydrate-containing feedstock is converted in a process, which process comprises contacting the feedstock in a first step with an alcohol in the presence of a first acid catalyst at a temperature below 100 °C to yield an intermediate product, and contacting at least part of the intermediate product in a second step with an alcohol in the presence of a second acid catalyst at a temperature of at least 100 °C. Products of such conversion may include hydroxymethylfurfural, hydroxymethylfurfural ethers, levulinic acid, esters thereof and furfural.
- -
-
Page/Page column 11
(2012/07/14)
-
- A direct synthesis of 5-alkoxymethylfurfural ethers from fructose via sulfonic acid-functionalized ionic liquids
-
5-Alkoxymethylfurfural ethers are synthesized directly from fructose using ionic liquids (imidazolium propanesulfonic acids) and alcohols in a novel biphasic system. The Royal Society of Chemistry.
- Kraus, George A.,Guney, Tezcan
-
p. 1593 - 1596
(2013/02/22)
-
- The production of 5-hydroxymethylfurfural from fructose in isopropyl alcohol: A green and efficient system
-
Solving problems: An isopropyl alcohol-mediated reaction system for the production of 5-hydroxymethylfurfural (HMF) from fructose reaches a yield of up to 87 %. The solvent can be easily recycled by evaporation, giving the HMF product. The system avoids the use of large amounts of organic solvent, has a minimal environmental impact, and offers a new route to large-scale economically viable processes.
- Lai, Linke,Zhang, Yugen
-
experimental part
p. 1745 - 1748
(2012/03/27)
-
- MIXTURE OF FURFURAL AND 5-(ALKOXYMETHYL)FURFURAL DERIVATIVES FROM SUGARS AND ALCOHOLS
-
Accordingly, the current invention provides a method for the manufacture of a mixture of a furfural and a 5-(alkoxymethyl)furfural derivative by reacting a C5 and C6 sugar- containing starting material with an alcohol in the presence of an acid catalyst, followed by the hydrogenation and/or etherification of the mixture of furfural and 5-(alkoxymethyl)furfural to convert the aldehyde function of both 5-(alkoxymethyl)furfural and furfural into an alkoxymethyl function or methyl function.
- -
-
Page/Page column 9
(2009/04/25)
-
- HYDROXYMETHYLFURFURAL ETHERS FROM SUGARS OR HMF AND MIXED ALCOHOLS
-
Accordingly, the current invention provides a method for the manufacture of a mixture of 5-hydroxymethylfurfural ethers by reacting a hexose-containing starting material or HMF with mixed alcohols in the presence of an acid catalyst.
- -
-
Page/Page column 9
(2009/04/25)
-
- Total syntheses of natural furan derivatives rehmanones A, B, and C
-
The synthesis of naturally occurring furan derivatives rehmanones A, B, and C is described. Diverse alternative synthetic strategies were developed for the preparation of these natural products. Conjugate addition of a furan to captodative alkene 1-acetylvinyl 4-nitrobenzoate was carried out under Lewis acid catalysis to give the corresponding adduct, which was transformed into rehmanones B and C in three and two steps, respectively. They were also prepared by condensation of acetone with the key furan-2-carbaldehyde intermediates, which could be readily obtained from D-fructose. The bis-furan rehmanone A was not only obtained in a one-step procedure by a double condensation of acetone with 5-(methoxymethyl)furan-2-carbaldehyde, but by condensing the latter with rehmanone B in high overall yields. Georg Thieme Verlag Stuttgart.
- Quiroz-Florentino, Hector,Aguilar, Raul,Santoyo, Blanca M.,Diaz, Francisco,Tamariz, Joaquin
-
p. 1023 - 1028
(2008/12/22)
-
- FURAN DERIVATIVES FOR PREVENTING AND CURING OSTEOPOROSIS AND PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME
-
The present invention relates to furan derivatives and pharmaceutical compositions containing them to prevent and cure osteoporosis. The furan derivatives of the present invention have effect on bone proliferation with the side effect reduced, so that they can be used for bone disease.
- -
-
Page/Page column 5-6
(2008/12/08)
-
- FURAN DERIVATIVES FOR PREVENTING AND CURING OSTEOPOROSIS AND PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME
-
The present invention relates to furan derivatives and pharmaceutical compositions containing them to prevent and cure osteoporosis. The furan derivatives of the present invention have effect on bone proliferation with the side effect reduced, so that they can be used for bone disease.
- -
-
Page 8; 21-22
(2008/06/13)
-
- Selective dehydration of glucose to hydroxymethylfurfural and a one-pot synthesis of a 4-acetylbutyrolactone from glucose and trioxane in solutions of aluminium salts
-
Saturated water solutions of Al2(SO4)3 and AlCl3 were applied as solvent/matrices for dehydration of Glc to hydroxymethylfurfural (HMF). Addition of oxygen ligands: methanol, ethanol, THF, furan, dibutyl ether, ethyl orthoformate and trioxane influenced the yield and selectivity, the best being observed with ethanol. When Glc and trioxane were present together in reacting solution, formation of a 4-acetylbutyrolactone was observed. Copyright (C) 1999 Elsevier Science Ltd.
- Tyrlik, Stanislaw K.,Szerszen, Dorota,Olejnik, Marian,Danikiewicz, Witold
-
p. 268 - 272
(2007/10/03)
-
- Chemistry of glucal halohydrins(II): An unusual protecting group effect in the competitive formation of formyl furanosides and methyl glycosides
-
A remarkable protecting group influence was observed in the base-induced reaction of protected halohydrins derived from D-glycals. Tri-O-methyl and tri-O-benzyl halohydrins react with cesium carbonate in methanol at room temperature to give methyl glycosides as the major product and unsaturated formyl furanosides as the minor product. Whereas, the tri-O-tert-butyldimethylsilyl (t-BuMe2Si)-protected halohydrins reacted with cesium carbonate in methanol at room temperature to give a mixture of epimeric formyl furanosides, and at reflux to give an unsaturated formyl furanoside, as the only products. The tri-O-methyl and tri-O-benzyl halohydrins react slowly at elevated temperature to give predominantly furans. In comparison, the tri-O-t-BuMe2Si halohydrins reacted completely after five minutes to give a mixture of epimeric formyl furanosides. The tri-O-t-BuMe2Si iodohydrins were oxidized to the corresponding iodolactones, which also underwent a based-induced ring contraction in methanol to give the furanose 1-methylcarboxylate esters.
- Kozlowski, John S.,Marzabadi, Cecilia H.,Rath, Nigam P.,Spilling, Christopher D.
-
p. 301 - 313
(2007/10/03)
-
- Photo-oxygenation des derives de l'hydroxymethyl-5 furfural-2
-
Photosensitized oxygenations in alcoholic solution of the furfural compounds 1,6-9 and the furanic compounds 10-17 yield the hydroxybutenolides 2a, 1, 20, 21, 22, the alkoxybutenolides 5, 19, 23, 24 and the unsaturated compounds 25 and 26.With rose bengal fixed on the polysaccharide resin Sephadex A 25 as sensitizer, the quantum yields of singlet oxygen formation in methanol or ethanol are higher (19 to 116percent) than those obtained with the commercial resin Sensitox.Kinetic results for these photo-oxygenations show the electronic influence of the substitution on C2 or C5.Depending on these substituants, several reaction pathways can be envisaged in order to explain the formation of the products.
- Cottier, Louis,Descotes, Gerard,Nigay, Henri,Parron, Jean-Claude,Gregoire, Veronique
-
p. 844 - 850
(2007/10/02)
-