Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Furoic Acid

Research Article pubs.acs.org/journal/ascecg

Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Furoic Acid: Transformation from C5 Platform to C6 Derivatives in Biomass Utilizations Sicheng Zhang,† Jihong Lan,† Zhuqi Chen, Guochuan Yin,* and Guangxing Li* School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Hongshan District, Wuhan 430074, P. R. China Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Wuhan 430074, P. R. China S Supporting Information *

ABSTRACT: 2,5-Furandicarboxylic acid (2,5-FDCA), a renewable alternative to p-phthalic acid, is the most promising subproduct from 5-hydroxymethylfurfural (HMF). However, HMF is currently synthesized from mono- and polysaccharides like glucose and fructose with limited volume, which apparently blocks the utilization of 2,5-FDCA to replace p-phthalic acid in the polymer industry. Here, we presented a novel route to 2,5-FDCA originating from C5based furfural which is industrially produced from bulky raw biomaterials, and is not competitive with food for humans. The starting chemical of this synthesis is furoic acid which is currently produced from furfural. Furoic acid can be feasibly transformed to 2,5-FDCA through consecutive bromination, esterification, carbonylation, and hydrolysis with 65% total yield in four steps and above 80% isolated yield in each step. In particular, the key step, palladium-catalyzed carbonylation of ethyl 5-bromo-furan-2-carboxylate, retains 90% isolated yield in the scale-up synthesis. The route introduced here has offered a promising opportunity to access HMF products from furfural derivatives with a large market; meanwhile it offers one of the key C1 resources, that is, CO, a promising utilization in industry. KEYWORDS: Pd-catalyzed carbonylation, 2,5-Furandicarboxylic acid, C5 to C6 platform transformation, Biomass, Noncompetitive with food

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INTRODUCTION

Up to now, the studies on polysaccharide utilization are majorly focused on C6-based carbohydrates, and less attention has been paid to the C5 carbohydrates like pentose which represent however a large amount of biomass resources, but are not competitive with food for humans.32 One exception is the commercial production of furfural from pentose. In consideration of the huge amount of its raw biomass resources, like corncobs, oat, wheat bran, sawdust, etc., the ongoing production of furfural is still very limited (less than 0.5 Mton/year) because of the narrow market volume of its subproducts. Therefore, exploring new products that have a large market for the furfural-based platform is extremely attractive. Recently hydrogenation of furfural to biofuel has been reported with great attention; we and others also explored the transformation of furfural to maleic acid and maleic anhydride through catalytic aerobic oxidations.33−43 Notably, Fu and co-workers explored the synthesis of 2,5-FDCA by disproportionation of furoic acid with furan as the coproduct,

With the rapid depletion of fossil resources, the exploitation of biomass to partly replace fossil feedstock as the source of carbon represents a promising alternative for the near future, and it apparently relies on the utilization of lignin, cellulose, and versatile polysaccharides, the most dominant biomaterials in nature.1−4 As cellulose and hemicellulose represent up to 70% of global biomass resources, their transformations to certain chemical platform molecules like 5-hydroxymethylfurfural (HMF) have attracted attention in recent years.5−12 These platform molecules can be employed to produce bulky chemicals which currently come from fossil resources.13−21 For example, 2,5-furandicarboxylic acid (2,5-FDCA) is one of the subproducts from HMF, which has been recognized as an alternative to p-phthalic acid, a monomer with a large market in the polymer industry.22 However, the challenge is that, because of the robust cellulose structures, its direct transformation to HMF for commercial synthesis is not successful in a large scale until now. Alternatively, HMF is commercially synthesized from mono- and polysaccharides like glucose and fructose, which are competitive with food for humans.23−31 © 2017 American Chemical Society

Received: July 17, 2017 Revised: August 7, 2017 Published: August 16, 2017 9360

DOI: 10.1021/acssuschemeng.7b02396 ACS Sustainable Chem. Eng. 2017, 5, 9360−9369

Research Article

ACS Sustainable Chemistry & Engineering

δ 7.07 (d, J = 3.5 Hz, 1H), 6.40 (d, J = 3.5 Hz, 1H), 4.31 (qd, J1 = 7.1 Hz, J2 = 2.7 Hz, 2H), 1.32 (td, J1 = 7.1, J2 = 2.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 157.64, 146.51, 127.30, 119.87, 113.89, 61.22, 14.28. In the concentrated H2SO4 recycling experiment, the residues after the above-mentioned extraction were diluted with 20 mL of recycled ethanol. A 1.51 g portion of 2 was added to this solution, and the reaction mixture was subjected to a second cycle of esterification following the same procedures described above. In these recycling experiments, petroleum ether can be collected through rotary evaporation and reused as the extractant, and the concentrated H2SO4 can be recycled at least three times without a significant decrease in yield of the product 3. Synthesis of Diethyl Furan-2,5-dicarboxylate (4) from Carbonylation of Ethyl 5-Bromo-furan-2-carboxylate (3) under Atmospheric CO. Pd(dppf)Cl2 (6.7 mg, 9 μmol), compound 3 (40.0 mg, 0.18 mmol), NaHCO3 (30.7 mg, 0.36 mmol), and EtOH (420.0 mg, 9 mmol) were successively added in dry DMF (1 mL). The reaction tube was evacuated and backfilled with CO (five times, balloon), and then heated up to 90 °C for 16 h under stirring. After the reaction, the reaction mixtures were cooled to room temperature and vented to discharge the excess CO. The product analysis was performed by GC using the internal standard method. Synthesis of Diethyl Furan-2,5-dicarboxylate (4) from Carbonylation of Ethyl 5-Bromo-furan-2-carboxylate (3) under Pressured CO. Pd(dppf)Cl2 (6.7 mg, 9 μmol), compound 3 (40.0 mg, 0.18 mmol), NaHCO3 (30.7 mg, 0.36 mmol), EtOH (420.0 mg, 9 mmol), and dry DMF (1 mL) were added to a reaction tube. Once sealed inside the stainless reactor, the system was purged with CO, pressurized to 10 bar and vented four times to clean the air residues. Then, the autoclave was pressurized to 10 bar with CO and stirred at 90 °C for 6 h. After the reaction, the reactor was allowed to cool to room temperature and was carefully depressurized to normal pressure. The product analysis was performed by GC using the internal standard method. After that, the mixture was diluted with 20 mL of water and then extracted with ethyl acetate (10 mL × 3). After removal of the organic phase, the residues were next treated by preparative thin-layer chromatography (PTLC) using a mixture of ethyl acetate and petroleum ether (PE) as the eluting solvent (EtOAc/ PE, v/v = 1:10) to afford the desired product as a colorless solid 4 (35.6 mg, 92%). 1H NMR (400 MHz, CDCl3): δ 7.21 (s, 1H), 4.40 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 158.09, 146.93, 118.24, 61.60, 14.25. Synthesis of Diethyl Furan-2,5-dicarboxylate (4) on a Gram Scale. Pd(dppf)Cl2 (334 mg, 0.46 mmol), compound 3 (2.0 g, 9.1 mmol), NaHCO3 (1.54 g, 18.3 mmol), EtOH (8.3 g, 180 mmol), and dry DMF (20 mL) were added to a reaction tube. Once the mixture was sealed inside the stainless reactor, the system was purged with CO, pressurized to 10 bar and vented four times to clean the air residues. Then, the autoclave was pressurized with CO, and then stirred at 90 °C for 6 h. After the reaction, the reactor was allowed to cool to room temperature and carefully depressurized to normal pressure. The product analysis was performed by GC using the internal standard method. After that, the mixture was diluted with 200 mL of water and extracted with ethyl acetate (100 mL × 3). After removal of the organic phase, the residues were next treated by silica-gel column chromatography by using a mixture of ethyl acetate and petroleum ether as the eluting solvent (EtOAc/PE, v/v = 1:10) to afford the desired product as a colorless solid 4 (1.74 g, 90%). Pd(dppf)Cl2 Catalyst Recycling Experiments. The reaction was conducted following the procedure under pressurized CO as described above. After the reaction, the reaction tube was taken out of the reactor, and the excess EtOH was removed by rotary evaporation. Next, the reaction mixtures were extracted with petroleum ether (20 mL × 4), and the upper organic phase was combined together. After removal of the organic phase by rotary evaporation, the residues were treated by PTLC using the eluting solvent described above to yield 91% (34.8 mg) of the desired product 4 as a colorless solid. In the second cycle, the remaining DMF solution containing catalyst after the above extraction was transferred from the separating funnel to the tube

achieving total carbon utilization.44 Here, we introduced the first example of catalytic carbonylation synthesis of 2,5-FDCA from furoic acid through consecutive bromination, esterification, carbonylation, and hydrolysis with 65% total yield in four steps (Scheme 1). Currently, the production of furoic acid is an Scheme 1. Synthetic Strategies for 2,5-Furandicarboxylic Acid from Furoic Acid

Reaction conditions i: Br2, CCl4/AcOH, 60 °C, and 24 h. Reaction conditions ii: H2SO4, EtOH, reflux, and 60 h. Reaction conditions iii: Pd(dppf)Cl2, NaHCO3, EtOH, CO (10 atm), DMF, 90 °C, and 6 h. Reaction conditions iv: H2SO4, MeOH/H2O, 160 °C, and 8 h. Isolated yield in each step. Total yield, 65%.

industrial process through the catalytic oxidation of furfural with O2 or air,45 which provides an easy access to the furfural platform. This process represents a novel route to the most promising HMF derivative from furfural, an industrially available, noncompetitive resource with food for humans; meanwhile, it provides the CO resource a promising utilization with a large market in industry.

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EXPERIMENTAL SECTION

Materials. All of the reagents are of analytic purity grade. DMF and ethanol were dehydrated via 4 Å MS (activated at 300 °C for 2 h in a muffle furnace) before use. Pd(OAc)2 was purchased from Strem Chemicals, Inc., and PPh3 was from Alfa Aesar. All other phosphine ligands, Pd(dppf)Cl2 (dppf, 1,1′-bis(diphenyphosphino)ferrocene), and Pd(PPh3)3Cl2 were purchased from Energy Chemical. Amines and inorganic bases were from Sinopharm Chemical Reagent Co., Ltd. 1 H and 13C NMR spectra were recorded on a Bruker AV-400 using TMS as an internal reference. Mass spectra were determined by a Bruker SolariX 7.0T spectrometer. Synthesis of 5-Bromofuran-2-carboxylic Acid (2) from Bromination of Furoic Acid (1). Furan-2-carboxylic acid (2.5 g, 22.3 mmol), CCl4 (20 mL), and glacial acetic acid (2 mL) were added into a 50 mL three-necked flask. A 2.4 mL (40 mmol) portion of bromine was subsequently added dropwise to the flask at room temperature in three portions per 6 h. The reaction mixture was warmed and stirred at 60 °C for 24 h. The solvent was then removed by rotary evaporation to yield a pale yellow solid. The crude product was washed by hot deionized water to give 3.46 g (86%) of 5bromofuroic acid (2) as an off-white solid. 1H NMR (400 MHz, DMSO-d6): δ 13.29 (s, 1H), 7.26 (d, J = 3.5 Hz, 1H), 6.81 (d, J = 3.5 Hz, 1H). 13C NMR (100 MHz, DMSO-d6): δ 158.71, 147.26, 127.19, 120.54, 114.83. Synthesis of Ethyl 5-Bromo-furan-2-carboxylate (3) from Esterification of 5-Bromofuran-2-carboxylic Acid (2). A 1.51 g (7.9 mmol) portion of compound 2 was dissolved in 20 mL of ethanol, to which 0.25 mL of concentrated H2SO4 (4.6 mmol) was next carefully added, and the reaction mixture was refluxed for 60 h. After being cooled to room temperature, ethanol was removed and collected by rotary evaporation. Next, the residues were extracted with petroleum ether (20 mL × 5). The combined organic layers were washed with NaHCO3 saturated solution, dried over Na2SO4, concentrated by rotary evaporation, and dried in a vacuum oven to afford a light yellow oil 3 (1.51 g, 87%). 1H NMR (400 MHz, CDCl3): 9361


Research Article

ACS Sustainable Chemistry & Engineering (approximately 0.5 mL of DMF loss during extraction), and the wall of the funnel was washed by 0.5 mL of additional DMF which was also transferred to the tube. Compound 3, NaHCO3, and EtOH were added to this solution, equivalent to the amounts in the first cycle. The reaction mixture was subjected to a second cycle following the same procedures described above, yielding 46% of 4 (17.6 mg) with complete conversion of 3. The reaction in the third cycle afforded 13% of 4 (5.0 mg) with 15% recovery of 3 (5.9 mg). After the DMF solution was treated by PTLC, 185 μmol (34.1 mg) of half-ester 6 was obtained, which cannot be extracted into petroleum ether. For determination of the yield of 6 in each cycle, an additional reaction was conducted with treatment by PTLC after the second cycle, affording 76 μmol (13.9 mg) of 6, indicating that 42% and 61% of 6 were obtained in the second and third cycle, respectively. Synthesis of 2,5-FDCA (5) from Hydrolysis of Diethyl Furan2,5-dicarboxylate (4). Compound 4 (1.06 g, 5 mmol) and H2SO4 (2.45 g, 25 mmol) were added into a mixed solvent of MeOH/H2O (v/v, 2 mL/20 mL) in a tube with a Teflon-sealed screw cap, and heated up to 160 °C until completion of the reaction as monitored by TLC analysis. After being cooled to room temperature and standing for several hours, the mixture was filtered and washed by icy distilled water. An off-white solid was obtained in 96% yield for the product 5 (0.75 g, 4.8 mmol) after being dried under vacuum. 1H NMR (400 MHz, DMSO-d6): δ 13.50 (s, 1H), 7.30 (s, 1H). 13C NMR (100 MHz, DMSO-d6): δ 159.37, 147.47, 118.88. In the H2SO4 aqueous solution recycling experiment, the abovementioned filtrate was concentrated to approximately 20 mL to which 2 mL of MeOH and 1.06 g of 4 were added. Then, the solution was subjected to a second cycle of hydrolysis following the same procedures described above. The petroleum ether can be recycled through rotary evaporation, and reused as the extractant; the H2SO4 aqueous solution can be recycled at least three times without a significant decrease in the yield of product 5.

source, and tri-n-butylamine (TNBA) was employed as a base; ethanol was employed as a nucleophile, and the results are summarized in Table 1. Using 5 mol % Pd(OAc)2 as the Table 1. Catalyst Scanning for the Carbonylation of Ethyl 5Bromo-furan-2-carboxylate entrya

Pd catalyst

conversion/%

yieldb/%

1 2 3 4 5 6 7 8 9 10 11 12 13 14

Pd(OAc)2/PPh3 (1:3) Pd(OAc)2 Pd(OAc)2/PBu3 (1:3) Pd(OAc)2/dppb (1:1) Pd(OAc)2/dppp (1:1) Pd(OAc)2/dppe (1:1) Pd(OAc)2/dppf (1:1) Pd(OAc)2/pyridine (1:3) Pd(OAc)2/2,2′-dipyridyl (1:1) Pd(OAc)2/1,10-phenanthroline (1:1) PdCl2/PPh3 (1:3) PdCl2/dppf (1:1) Pd(PPh3)2Cl2 Pd(dppf)Cl2

99.6 85.4 41.8 66.6 68.8 66.5 68.2 >99.9 65.7 6.5 99.6 81.9 >99.9 >99.9

48.2 15.3 2.9 12.7 11.3 6.5 12.8 20.6 16.3 3.4 43.2 47.2 52.7 55.4

a

Reaction conditions: 3 (0.18 mmol), Pd catalyst (5 mol %), tri-nbutylamine (3 equiv), EtOH (5 equiv), NMP (1 mL), CO balloon, 100 °C, and 12 h. dppb = 1,4-bis(diphenylphosphino)butane; dppp = 1,3-bis(diphenylphosphino)propane; dppe = 1,2-bis(diphenylphosphino)ethane; dppf = 1,1′-bis(diphenyphosphino)ferrocene. bYield based on GC analysis.

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catalyst with 10 mol % PPh3 as the ligand, it was found that ethyl 5-bromo-furan-2-carboxylate (3) could be feasibly carbonylated to diethyl furan-2,5-dicarboxylate (4), giving 48.2% yield with 99.6% conversion of ethyl 5-bromo-furan-2carboxylate (3) in 12 h at 100 °C (Table 1, entry 1), while, in the absence of PPh3, using Pd(OAc)2 alone as the catalyst showed very sluggish activity, providing only 15.3% yield, and a lot of palladium black was observed after the reaction (Table 1, entry 2). Using other phosphine ligands including P(t-Bu)3, dppb (1,4-bis(diphenylphosphino)butane), dppp (1,3-bis(diphenylphosphino)propane), dppe (1,2-bis(diphenylphosphino)ethane), and dppf instead of PPh3 led to a much lower activity of Pd(OAc)2 with a lower yield of diethyl furan-2,5-dicarboxylate (4). However, in the case of using PdCl2 as the catalyst, adding the dppf ligand demonstrated a slightly higher yield of diethyl furan-2,5-dicarboxylate (4) than using PPh3 (47.2% vs 43.2%; Table 1, entries 11 and 12). Remarkably, using a preprepared Pd(PPh3)2Cl2 complex as the catalyst offered a little higher yield of diethyl furan-2,5dicarboxylate (4) (52.7%) than adding free PPh3 as the ligand. In particular, 55.4% yield could be achieved with the preprepared Pd(dppf)Cl2 complex, whereas adding free dppf to Pd(OAc)2 demonstrated a very poor efficiency, giving only 12.8% yield with 68.2% conversion (Table 1, entries 7 and 12). These data clearly suggest that ligation of phosphine to palladium is essential for the efficient carbonylation reaction. In the complementary tests, nitrogen-containing ligands like pyridine, 2,2′-dipyridyl, and 1,10-phenanthroline are ineffective for diethyl furan-2,5-dicarboxylate (4) formation. As shown in Table 1, although ethyl 5-bromo-furan-2carboxylate (3) can be converted completely in certain cases, the preliminary tests for the selectivity of diethyl furan-2,5dicarboxylate (4) were generally poor, implicating the formation of other byproducts. Indeed, an isolated 21% yield

RESULTS AND DISCUSSION In the first step of transforming furfural-based furoic acid to 2,5FDCA (5) as shown in Scheme 1, some modifications for bromination have been made to the previous methods introduced by Li and Chen.46,47 In those reported procedures, they provided 70% and 78% of isolated yield for 5-bromo-furoic acid, respectively. In present studies, acetic acid was introduced to the reaction solution to help furoic acid dissolve in CCl4 at 60 °C. With stirring at room temperature, the dropwise addition of bromine in one portion was replaced by addition in three portions per 6 h. After the reaction, a pale yellow solid could be obtained by the removal of the solvent through rotary evaporation, in which the recycled CCl4 and acetic acid can be reused in the next turn. Then, the solid was washed by hot water, affording an off-white solid as 5-bromo-furoic acid (2) product with an improved yield of 86%. In the next step, ethyl 5-bromo-furan-2-carboxylate (3) can be feasibly synthesized through refluxing 5-bromo-furoic acid (2) in ethanol in the presence of concentrated H2SO4, which provided 87% yield of isolated product. In this process, both solvent and extractant are recyclable, and the concentrated H2SO4 can be reused three times with an esterification efficiency that is similar to that with fresh H2SO4 (Figure S1). Because carbonylation of 5-bromo-furan-2-carboxylate, the third step in Scheme 1, was not reported yet, it was investigated in detail in present studies. In the literature, palladium complexes were extensively reported as a catalyst in versatile carbonylation reactions with great achievements.48−60 Here, our efforts toward carbonylation of ethyl 5-bromo-furan-2carboxylate (3) were also focused on various palladium complexes. The reactions were first conducted in N-methyl-2pyrrolidone (NMP) solvent using a CO balloon as the CO 9362


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ACS Sustainable Chemistry & Engineering of ethyl 5-(dibutylcarbamoyl)furan-2-carboxylate as a byproduct was obtained in the case of using TNBA as the base with Pd(dppf)Cl2 as the catalyst. This can be attributed to a competitive attack of TNBA on the acyl-Pd intermediate, generated by the oxidative addition of ethyl 5-bromo-furan-2carboxylate (3) on the Pd catalyst, to form the amide byproduct.61−63 Other organic bases such as TMEDA (N,N,N′,N′-tetramethylethylenediamine), TEA (triethylamine), DNPA (dipropylamine), and DBU (1,8-diazabicycloundec-7ene) were also tested, which gave relatively low yields of diethyl furan-2,5-dicarboxylate (4) (Table 2, entries 2−5). To avoid

Table 3. Effect of Bases on the Product Formation of Carbonylation Reaction

yieldb/%

Table 2. Base Scanning for Catalytic Carbonylation of Ethyl 5-Bromo-furan-2-carboxylate entrya

baseb

conversion/%

yieldc/%

d

TNBA TMEDA TEA DNPA DBU Na2CO3 Na2CO3 K2CO3 Cs2CO3 NaOAc NaHCO3 NaHCO3 NaHCO3

98.8 92.3 91.0 96.6 96.2 86.4 >99.9 98.6 >99.9 >99.9 >99.9 >99.9 >99.9

55.4 13.6 41.3 9.6 32.4 43.8 50.9 22.5 2.1 48.1 57.5 57.3 42.8

1 2d 3d 4d 5d 6d 7 8 9 10 11 12e 13f

entrya

base

pKa

4

5

6

7

1c 2c 3c 4 5 6 7

TEA TNBA DNPA NaHCO3 Na2CO3 K2CO3 Cs2CO3

10.65 10.89 11.00

38 50 6 53 44 20 trace

NDd ND ND ND 8 24 62

11 13 10 5 6 7 9

10 21 67

a Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), base (3 equiv), EtOH (5 equiv), NMP (1 mL), CO balloon, 100 °C, and 16 h. b Isolated yield. c12 h. dND = not determined.

amide, while, for the secondary amine DNPA, the major product was the amide, giving 67% yield of amide and 10% yield of half ester with only 6% yield of diester, which can be attributed to its higher nucleophilicity than both tertiary amines and alcohol. On the other hand, the utilization of inorganic bases offered 2,5-FDCA (5) as a product. The total yield of the hydrolysis products 5 and 6 increased with the basicity of bases in the sequence of NaHCO3 < Na2CO3 < K2CO3 < Cs2CO3. Using NaHCO3 as a base, it provided 53% yield of diethyl furan-2,5dicarboxylate (4) with 5% yield of 5-(ethoxycarbonyl)furan-2carboxylic acid (6), and no 2,5-FDCA (5) was detected. With the basicity increasing, the yield of diethyl furan-2,5dicarboxylate (4) decreases, while the diacid formation increases sharply. In the case of Cs2CO3, there is no diethyl furan-2,5-dicarboxylate (4) detected, but 62% yield of 2,5FDCA (5) was achieved. It is worth mentioning that all of diester 4, diacid 5, and half-ester 6 products are expected carbonylation products as the alternative to p-phthalic acid. Next, using NaHCO3 as a base, a series of solvents were screened, and the results are summarized in Table 4 as well as their Snyder polarity indexes (SPIs).65,66 The carbonylation activity generally declined with the decreasing polarity of

a Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), base (3 equiv), EtOH (5 equiv), NMP (1 mL), CO balloon, 100 °C, and 16 h. b TMEDA = N,N,N′,N′-tetramethylethylenediamine; TNBA = tri-nbutylamine, TEA = triethylamine; DNPA = dipropylamine; DBU = 1,8-diazabicycloundec-7-ene. cYield based on GC analysis. d12 h. e2 equiv. f1 equiv.

the amide formation, some inorganic bases were next tested in place of organic amines. Among various inorganic bases, including NaHCO3, Na2CO3, K2CO3, and Cs2CO3, NaHCO3 demonstrated the best efficiency. For example, adding 2 equiv of NaHCO3 offered 57.5% yield of diethyl furan-2,5dicarboxylate (4), slightly higher than that by adding 3 equiv of TNBA. In particular, it is worth mentioning that, here, 57.5% yield of diethyl furan-2,5-dicarboxylate (4) was obtained by using a CO balloon as the CO source. In order to obtain further insights into the effect of the inorganic and organic bases on the product formation of present carbonylation reaction, we attempted to isolate all of the desired products with major byproducts, and the results are summarized in Table 3. The half-ester, 5-(ethoxycarbonyl)furan-2-carboxylic acid (6) was isolated as a byproduct in each case, which was plausibly generated by either nucleophilic attack of the water on the acyl-Pd intermediate or monohydrolysis of the generated diester product 4 during the reaction. However, the further hydrolysis product, 2,5-FDCA (5), was not detected by TLC analysis in the case of using organic bases. The pKa values of the three organic bases were very close to each other as shown in Table 3, and the basicity follows in the order of TEA < TNBA < DNPA.64 However, their influences on the reactivity are significantly different. For the tertiary amine, using TNBA demonstrated much higher activity than using TEA, giving a higher yield of all three isolated products including diester product 4, half-ester 6, and

Table 4. Solvent Scanning for the Carbonylation Reaction entrya

solvent

Snyder polarity index

conversion/%

yieldb/%

1 2 3 4 5 6 7 8 9

DMSO NMP DMAc DMF MeCN EtOH 1,4-dioxane anisole toluene

7.2 6.7 6.5 6.4 5.8 5.2 4.8 3.8 2.4

95.4 >99.9 >99.9 >99.9 52.1 19.2 56.7 34.8 10.3

28.2 57.3 56.6 59.8 26.5 8.7 18.6 13.3 6.2

a Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), NaHCO3 (2 equiv), EtOH (5 equiv), solvent (1 mL), CO balloon, 100 °C, and 16 h. bYield based on GC analysis.

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catalytic carbonylation of ethyl 5-bromo-furan-2-carboxylate (3) under this atmospheric CO condition. Remarkably, the yield of diethyl furan-2,5-dicarboxylate (4) could be further improved with a pressurized CO source, and an 88.8% yield of diethyl furan-2,5-dicarboxylate (4) could be achieved under 10 bar of CO in 16 h (Table 5, entry 9). More importantly, investigating the time course of the carbonylation reaction further revealed that a 98.8% yield of diethyl furan-2,5dicarboxylate (4) could be achieved in 6 h at 90 °C under 10 bar of CO. Then, it decreased at a longer reaction time, supporting the fact that the relatively low yield of diethyl furan2,5-dicarboxylate (4) at an extended reaction period can be attributed to its hydrolysis rather than competitive attack of water on the acyl-Pd intermediate (Figure 1). As evidence, in 6

solvents from DMSO to toluene as indicated by their decreased SPIs. Higher conversions can be achieved in solvents such as DMSO, NMP, DMAc, and DMF, whose Snyder polarity indexes are above 6.4. The obtained low yield (28.2%) of 4 with high conversion in DMSO is probably related to the unavoidable moisture in DMSO, because 55% half-ester was isolated after the reaction. The higher conversion in polar aprotic solvents could be attributed to their coordination ability toward the palladium center which may stabilize palladium(0), thus delaying the formation of palladium black.67 This is in line with the experimental fact that no palladium black formed in polar aprotic solvents, while palladium black could be obviously observed in nonpolar solvents. The poor efficiency of ethanol solvent, which also has an SPI value of 5.2, could be possibly related to its reactivity with the palladium catalyst through dehydrogenation, which can compete with the carbonylation reaction. However, the solvent effects are very complicated in organic synthesis; the direct, perfectly linear relationship was not observed between the reactivity and SPI of solvents in this system. Among all of the tested solvents, DMF demonstrated the best efficacy and was employed as the solvent for further studies. The reaction conditions for this carbonylation were further optimized in terms of the amount of ethanol as a nucleophile, reaction temperature, and CO pressure. As shown in Table 5, Table 5. Optimization of the Carbonylation Reaction entrya

EtOH (equiv)

temp/°C

CO pressure (bar)

conversion/%

yieldb/%

1 2 3 4 5 6 7 8 9

5 20 50 100 50 50 50 50 50

100 100 100 100 120 80 90 90 90

1 1 1 1 1 1 1 5 10

>99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9

59.8 61.3 63.2 57.3 46.1 66.0 71.5 77.1 88.8

Figure 1. Time course of the carbonylation reaction. Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), NaHCO3 (2 equiv), EtOH (50 equiv), DMF (1 mL), CO (10 bar), and 90 °C. The yield was based on GC analysis.

h of carbonylation time, it provided only a trace of a half-ester product, while 98.8% yield of diethyl furan-2,5-dicarboxylate (4) was obtained with the complete conversion of ethyl 5bromo-furan-2-carboxylate (3). In particular, after 12 h of reaction, a 7% yield of half-ester was obtained, which clearly confirms that the half-ester product originates from the monohydrolysis of diethyl furan-2,5-dicarboxylate (4). Figure 2A displays the influence of reaction temperature on carbonylation efficiency. In 6 h of reaction, with the reaction temperature elevated, the conversion of ethyl 5-bromo-furan-2carboxylate (3) and the formation of diethyl furan-2,5dicarboxylate (4) increased at the beginning, providing the highest yield (98.8%) at 90 °C. Then, the yield dropped to 93.1% at 100 °C with 4% yield of 5-(ethoxycarbonyl)furan-2carboxylic acid (6) generated. Next, the CO pressure was reexamined at 90 °C in detail within 6 h of reaction (Figure 2B). It was found that the CO pressure remarkably affected the carbonylation efficiency. Under atmospheric pressure of CO, 82.4% of ethyl 5-bromo-furan-2-carboxylate (3) could be converted in 6 h; however, the yield of diethyl furan-2,5dicarboxylate (4) was only 50.8%. Remarkably, the complete conversion of ethyl 5-bromo-furan-2-carboxylate (3) could be achieved at a slightly higher pressure of CO (2.5 bar), giving the yield of diethyl furan-2,5-dicarboxylate (4) up to 77.0%. The highest yield (98.8%) was obtained at 10 bar of CO with the complete conversion of ethyl 5-bromo-furan-2-carboxylate (3). Further increasing the CO pressure to 12.5 bar resulted in a lower yield of diethyl furan-2,5-dicarboxylate (4; 81.4%) with 13% yield of 5-(ethoxycarbonyl)furan-2-carboxylic acid (6).

a Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), NaHCO3 (2 equiv), EtOH, DMF (1 mL), CO, temp, and 16 h. bYield based on GC analysis.

with the CO balloon, the yield of diethyl furan-2,5dicarboxylate (4) increased gradually with the amount of increasing ethanol, and the maximum yield (63.2%) was achieved with 50 equiv of added ethanol (Table 5, entries 1−3). However, the addition of an extra 50 equiv of ethanol led to a decreased yield of diethyl furan-2,5-dicarboxylate (4) (57.3%; Table 5, entry 4), indicating that too much excess of ethanol was harmful to the reaction. This is consistent with the result from using ethanol as a solvent, which gave only 8.7% yield of diethyl furan-2,5-dicarboxylate (4) (Table 4, entry 6). The reaction temperature also showed an impact on the carbonylation reaction. The yield of diethyl furan-2,5-dicarboxylate (4) could reach 71.5% at 90 °C (Table 5, entry 7), and further elevating or lowering the temperature resulted in a lower yield of diethyl furan-2,5-dicarboxylate (4). Importantly, in addition to the 71.5% yield of diethyl furan-2,5-dicarboxylate (4) formation at 90 °C, 15% yield of 5-(ethoxycarbonyl)furan-2carboxylic acid (6) was also isolated as a byproduct. Taken together, a total yield of above 86% could be achieved for the 9364


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scale-up experiment proceeded smoothly without significant loss in the yield of diethyl furan-2,5-dicarboxylate (4), providing 95.8% of GC yield or 90% isolated yield. The catalyst recycling studies were also carried out to investigate the reusability of the Pd(dppf)Cl2 catalyst in this reaction. After achieving complete conversion, the reaction solution was extracted with petroleum ether. By this procedure, the product 4 could be easily separated from the DMF solution containing the catalyst. As shown in Table 6, the yield of 4 Table 6. Catalyst Recycling Tests for the Pd(II)-Catalyzed Carbonylation Reaction runa

time/h

1 2 3

6 14 36

recovery of 3/%

yield of 4b/%

yield of 6b/%

total yield (4 + 6)b/%

15

91 46 13

trace 42 61

91 88 74

a

Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), NaHCO3 (2 equiv), EtOH, DMF (1 mL), CO (10 atm), 90 °C, and time. bIsolated yield.

decreased dramatically to 46% with 42% of half-ester 6 formation after a prolonged reaction time in the second run, possibly because of the unavoidable moisture absorption, and catalyst deactivation and/or loss during the separation procedures. The 3rd run showed only 13% of 4 formation with 61% of 6, and 15% of the substrate was recovered after 36 h of reaction, indicating full deactivation of the catalyst. However, regarding that both product 4 and 6 are the carbonylation product, the first and second recycling experiments gave total yields of 88% and 74%, respectively, demonstrating the high efficiency of this homogeneous catalyst in the recycling experiment. A plausible mechanism for this carbonylation was proposed in Scheme 3 which follows the general carbonylation

Figure 2. Carbonylation of ethyl 5-bromo-furan-2-carboxylate (3) to diethyl furan-2, 5-dicarboxylate (4). Reaction conditions: 3 (0.18 mmol), Pd(dppf)Cl2 (5 mol %), NaHCO3 (2 equiv), DMF (1 mL), and 6 h. Yield based on GC analysis. (A) CO (10 bar), (B) 90 °C.

Scheme 3. Proposed Pd-Catalyzed Carbonylation Mechanism

However, a total yield of 94.4% for carbonylation products was still achieved, indicating that relatively low pressure of CO has been good enough for the carbonylation reaction here. In a complementary experiment using 2.5% loading of Pd(dppf)Cl2 catalyst, it afforded a 79.8% conversion with 69.6% yield of diethyl furan-2,5-dicarboxylate (4) in 6 h. Moreover, extending the reaction to 12 h could achieve complete conversion of ethyl 5-bromo-furan-2-carboxylate (3), and gave 80.1% yield of diethyl furan-2,5-dicarboxylate (4) with 10% yield of 5-(ethoxycarbonyl)furan-2-carboxylic acid (6), a total 90.1% yield of the carbonylation product, indicating the high efficiency of the Pd(dppf)Cl2 catalyst in this reaction. In addition, a 2 g (9.1 mmol) level experiment was conducted for this carbonylation reaction (Scheme 2). To our delight, the Scheme 2. Synthesis of Diethyl Furan-2,5-dicarboxylate (4) by Carbonylation of Ethyl 5-Bromo-furan-2-carboxylate (3) on a Gram Scale

mechanism in the literature.68−70 First, the process is initiated by the reduction of the Pd(II) catalyst to produce an active Pd(0) complex (I) which attacks ethyl 5-bromo-furan-2carboxylate (3) through oxidative addition to generate the aryl-Pd(II) intermediate (II). Next, the CO insertion of the aryl-Pd(II) intermediate (II) forms the acyl-Pd(II) intermediate (III). The desired product diethyl furan-2,5-dicarboxylate (4) was eliminated after nucleophilic attack of ethanol to the acyl palladium complex in the presence of NaHCO3, and the 9365


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loss in the separation procedures (Table 7). Taken together, the summarized process to 2,5-FDCA as shown in Scheme 1

regeneration of the Pd(0) complex completes the catalytic cycle. For the mechanistic aspects of this Pd-catalyzed carbonylation reaction, electrospray ionization mass spectrometry (ESI-MS) analysis was conducted directly using the reaction mixtures. On the basis of the characteristic isotope distribution of the Pd species,71,72 the identification of the reaction intermediates can be feasibly conducted through comparing the observed and calculated isotope distribution patterns of targeted Pd intermediates in ESI-MS spectra. Unfortunately, the acquisition of useful ESI-MS information to identify the Pd intermediates by conducting the carbonylation reaction for 3 h under the standard conditions with 10 bar of CO failed (Table 5, entry 9), possibly because of the low concentration of Pd catalyst in the reaction. Then, 20 mol % Pd(dppf)Cl2 was employed as a catalyst for carbonylation under atmospheric CO pressure, and the reaction was carried out for only 1 h before ESI-MS detection. Although the identifications of other intermediates like III and IV were not successful, one signal at m/z = 919.0, assigned to the potassium adduct of the intermediate II {[Pd(dppf)(3) + K]+}, was successfully identified. This mass information is in good agreement with the theoretical prediction of the isotopic peak distribution patterns (Figure 3a−c), providing valuable mechanistic information to support the proposed carbonylation mechanism as shown in Scheme 3.

Table 7. H2SO4 Aqueous Solution Recycling Tests in the Hydrolysis of 4 runa

time/h

yield of 5b/%

1 2 3 4

8 8 12 14

96 95 94 94

a Reaction conditions: 4 (1.06 g, 5 mmol), H2SO4 (2.45 g, 25 mmol), MeOH/H2O (v/v = 2 mL/20 mL), and 160 °C. bIsolated yield.

represents the first example for its synthesis through bromination−carbonylation of furfural which originates from bulky biomass, noncompetitive with food of humans. It is well-known that p-phthalic acid is one of the most important monomers in the polymer industry. It is currently produced from the oxidation of p-xylene in acetic acid using cobalt, manganese, and bromide ions, and the reaction needs to be conducted under high temperature (175−225 °C) with 1.5− 3.0 MPa of oxygen. Regarding the harsh conditions of pphthalic acid production with the rapid depletion of its raw fossil feedstock, looking for its sustainable alternatives with a greener process for its production from renewable biomass is greatly attractive.73 As 2,5-FDCA is a potential alternative to pphthalic acid in the polymer industry, its synthesis has attracted much attention in the community.74−77 If a practical catalyst could be explored for HMF synthesis from bulky cellulose in nature in the near future, the most attractive protocol should come from the selective oxidation of HMF to 2,5-FDCA.73−77 Because of the current challenge for HMF production from cellulose,23,24,78,79 an alternative route to 2,5-FDCA has also gained attention. Compared with the challenge from HMF production, furfural is currently produced from C5-based raw biomass which is also not competitive with the food of humans. Therefore, the transformation of furfural derivatives to 2,5FDCA can offer an alternative solution to current HMF challenges. Fu and co-workers explored the disproportionation of furoic acid to 2,5-FDCA and furan without carbon loss.44 Here, we explored a bromination−carbonylation method to 2,5-FDCA from furoic acid. Although it is currently a four-step process to 2,5-FDCA, it offers 2,5-FDCA as the sole product under ideal conditions, and this process has the opportunity to be optimized as a bromination−carbonylation, two-step process through catalyst design. Significantly, this process utilizes the CO resource to transform C5-based furoic acid to C6-based 2,5-FDCA, in which CO is another significantly sustainable resource which can be produced from catalytic gasification of bulky raw biomass.76,78 Regarding this issue, this process offers a new opportunity for sustainable furfural and CO utilization with a bright future.

Figure 3. ESI-MS spectra of (a) carbonylation with 20 mol % Pd(dppf)Cl2 under atmospheric pressure for 1 h. (b) Potassium adduct of the intermediate II [Pd(dppf)(3) + K]+ centered at m/z = 919.0, and (c) its theoretical isotopic peak distribution.

In the last step for the synthesis of 2,5-FDCA (5; Scheme 1), the hydrolysis of diethyl furan-2,5-dicarboxylate (4) was carried out in a mixed solvent of MeOH/H2O (v/v = 2 mL/20 mL) in the presence of 5 equiv of H2SO4 at 160 °C for 8 h. After the solution was cooled to room temperature, a white solid precipitate can be obtained after filtration and washed with water, giving 96% isolated yield. In the reusability tests of H2SO4 aqueous media, the filtrate was concentrated by rotary evaporation to approximately a 20 mL solution. The resulting concentrated H2SO4 aqueous media can be reused for three cycles without loss of the isolated yield of 5; however, the hydrolysis time needs to be extended, possibly because of acid

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CONCLUSION In the present work, a new synthesis route to 2,5-FDCA has been explored from C5-based furoic acid. Through consecutive bromination, esterification, carbonylation, and hydrolysis, furoic acid, a subproduct from renewable furfural, can be efficiently transformed to 2,5-FDCA, the most promising subproduct of HMF. Regarding (1) the large market of 2,5-FDCA as a sustainable alternative to p-phthalic acid in the polymer industry, (2) the limited production of HMF from C6 9366


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(9) Climent, M. J.; Corma, A.; Iborra, S. Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chem. 2014, 16, 516−547. (10) Guerbuez, E. I.; Wettstein, S. G.; Dumesic, J. A. Conversion of Hemicellulose to Furfural and Levulinic Acid using Biphasic Reactors with Alkylphenol Solvents. ChemSusChem 2012, 5, 383−387. (11) Zhu, S.; Xue, Y.; Guo, J.; Cen, Y.; Wang, J.; Fan, W. Integrated Conversion of Hemicellulose and Furfural into γ-Valerolactone over Au/ZrO2 Catalyst Combined with ZSM-5. ACS Catal. 2016, 6, 2035− 2042. (12) Li, C.; Zhang, Z.; Zhao, Z. K. Direct conversion of glucose and cellulose to 5-hydroxymethylfurfural in ionic liquid under microwave irradiation. Tetrahedron Lett. 2009, 50, 5403−5405. (13) Deuss, P. J.; Barta, K.; de Vries, J. G. Homogeneous catalysis for the conversion of biomass and biomass-derived platform chemicals. Catal. Sci. Technol. 2014, 4, 1174−1196. (14) Climent, M. J.; Corma, A.; Iborra, S. Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chem. 2014, 16, 516−547. (15) Serrano-Ruiz, J. C.; Luque, R.; Sepulveda-Escribano, A. Transformations of biomass-derived platform molecules: from high added-value chemicals to fuelsvia aqueous-phase processing. Chem. Soc. Rev. 2011, 40, 5266−5281. (16) Corma, A.; de la Torre, O.; Renz, M. High-Quality Diesel from Hexose- and Pentose-Derived Biomass Platform Molecules. ChemSusChem 2011, 4, 1574−1577. (17) Luque, R.; Clark, J. H.; Yoshida, K.; Gai, P. L. Efficient aqueous hydrogenation of biomass platform molecules using supported metal nanoparticles on Starbons. Chem. Commun. 2009, 5305−5307. (18) Jia, X.; Ma, J.; Wang, M.; Ma, H.; Chen, C.; Xu, J. Catalytic conversion of 5-hydroxymethylfurfural into 2,5-furandiamidine dihydrochloride. Green Chem. 2016, 18, 974−978. (19) Lan, J.; Lin, J.; Chen, Z.; Yin, G. Transformation of 5Hydroxymethylfurfural (HMF) to Maleic Anhydride by Aerobic Oxidation with Heteropolyacid Catalysts. ACS Catal. 2015, 5, 2035−2041. (20) Li, C.; Cai, H.; Zhang, B.; Li, W.; Pei, G.; Dai, T.; Wang, A.; Zhang, T. Tailored one-pot production of furan-based fuels from fructose in an ionic liquid biphasic solvent system. Chin. J. Catal. 2015, 36, 1638−1646. (21) Shen, Y.; Kang, Y.; Sun, J.; Wang, C.; Wang, B.; Xu, F.; Sun, R. Efficient production of 5-hydroxymethylfurfural from hexoses using solid acid SO42−/In2O3-ATP in a biphasic system. Chin. J. Catal. 2016, 37, 1362−1368. (22) Zhang, Z.; Deng, K. Recent Advances in the Catalytic Synthesis of 2,5-Furandicarboxylic Acid and Its Derivatives. ACS Catal. 2015, 5, 6529−6544. (23) Teong, S. P.; Yi, G.; Zhang, Y. Hydroxymethylfurfural production from bioresources: past, present and future. Green Chem. 2014, 16, 2015−2026. (24) Wang, T.; Nolte, M. W.; Shanks, B. H. Catalytic dehydration of C6 carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical. Green Chem. 2014, 16, 548−572. (25) Agirrezabal-Telleria, I.; Gandarias, I.; Arias, P. L. Heterogeneous acid-catalysts for the production of furan-derived compounds (furfural and hydroxymethylfurfural) from renewable carbohydrates: A review. Catal. Today 2014, 234, 42−58. (26) Xue, Z.; Cao, B.; Zhao, W.; Wang, J.; Yu, T.; Mu, T. Heterogeneous Nb-containing catalyst/N,N-dimethylacetamide−salt mixtures: novel and efficient catalytic systems for the dehydration of fructose. RSC Adv. 2016, 6, 64338−64343. (27) Jia, S.; Xu, Z.; Zhang, Z. C. Catalytic conversion of glucose in dimethylsulfoxide/water binary mix with chromium trichloride: Role of water on the product distribution. Chem. Eng. J. 2014, 254, 333− 339. (28) Yue, C.; Li, G.; Pidko, E. A.; Wiesfeld, J. J.; Rigutto, M.; Hensen, E. J. M. Dehydration of Glucose to 5-Hydroxymethylfurfural Using Nb-doped Tungstite. ChemSusChem 2016, 9, 2421−2429.

carbohydrates which are competitive with food for humans, and (3) the bulky, noncompetitive raw biomaterials for ongoing furfural production, but facing a limited market volume, here, the explored novel process to 2,5-FDCA through bromination− carbonylation from furoic acid has provided an opportunity for transforming a renewable C5-based furfural platform to C6 derivatives with a promising large market; meanwhile, it also offers the CO resource a promising utilization in industry.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b02396. H2SO4 recycling experimental tests; 1H NMR and 13C NMR spectral data for intermediates, product, and byproducts (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. (G.Y.) *E-mail: [email protected]. (G.L.) ORCID

Zhuqi Chen: 0000-0002-0503-9671 Guochuan Yin: 0000-0003-1003-8478 Author Contributions †

S.Z. and J.L. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The funds from the National Natural Science Foundation of China (21273086 and 21573082) are deeply appreciated. The product identifications by GC-MS and NMR were performed at the Analytical and Testing Center, Huazhong University of Science and Technology.

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REFERENCES

(1) Chandra, R.; Takeuchi, H.; Hasegawa, T. Methane production from lignocellulosic agricultural crop wastes: A review in context to second generation of biofuel production. Renewable Sustainable Energy Rev. 2012, 16, 1462−1476. (2) Dhepe, P. L.; Fukuoka, A. Cellulose conversion under heterogeneous catalysis. ChemSusChem 2008, 1, 969−975. (3) Sheldon, R. A. Green and sustainable manufacture of chemicals from biomass: state of the art. Green Chem. 2014, 16, 950−963. (4) Li, C.; Zhao, X.; Wang, A.; Huber, G. W.; Zhang, T. Catalytic transformation of lignin for the production of chemicals and fuels. Chem. Rev. 2015, 115, 11559−11624. (5) Wang, A.; Zhang, T. One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts. Acc. Chem. Res. 2013, 46, 1377−1386. (6) Shi, N.; Liu, Q.; Zhang, Q.; Wang, T.; Ma, L. High yield production of 5-hydroxymethylfurfural from cellulose by high concentration of sulfates in biphasic system. Green Chem. 2013, 15, 1967−1974. (7) Deng, T.; Liu, H. Promoting effect of SnOx on selective conversion of cellulose to polyols over bimetallic Pt−SnOx/Al2O3 catalysts. Green Chem. 2013, 15, 116−124. (8) Zheng, M.; Wang, A.; Ji, N.; Pang, J.; Wang, X.; Zhang, T. Transition Metal−Tungsten Bimetallic Catalysts for the Conversion of Cellulose into Ethylene Glycol. ChemSusChem 2010, 3, 63−66. 9367


Research Article

ACS Sustainable Chemistry & Engineering (29) Wang, J.; Xu, W.; Ren, J.; Liu, X.; Lu, G.; Wang, Y. Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid. Green Chem. 2011, 13, 2678−2681. (30) Hu, S.; Zhang, Z.; Song, J.; Zhou, Y.; Han, B. Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid. Green Chem. 2009, 11, 1746−1749. (31) Qi, X.; Watanabe, M.; Aida, T. M.; Smith, R. L., Jr. Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids. Green Chem. 2009, 11, 1327−1331. (32) Mariscal, R.; Maireles-Torres, P.; Ojeda, M.; Sadaba, I.; Lopez Granados, M. Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels. Energy Environ. Sci. 2016, 9, 1144−1189. (33) Lange, J.; van der Heide, E.; van Buijtenen, J.; Price, R. FurfuralA Promising Platform for Lignocellulosic Biofuels. ChemSusChem 2012, 5, 150−166. (34) Yan, K.; Chen, A. Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu−Fe catalyst. Fuel 2014, 115, 101−108. (35) Xu, W.; Xia, Q.; Zhang, Y.; Guo, Y.; Wang, Y.; Lu, G. Effective Production of Octane from Biomass Derivatives under Mild Conditions. ChemSusChem 2011, 4, 1758−1761. (36) Zhang, X.; Wang, T.; Ma, L.; Wu, C. Aqueous-phase catalytic process for production of pentane from furfural over nickel-based catalysts. Fuel 2010, 89, 2697−2702. (37) Shi, S.; Guo, H.; Yin, G. Synthesis of maleic acid from renewable resources: Catalytic oxidation of furfural in liquid media with dioxygen. Catal. Commun. 2011, 12, 731−733. (38) Guo, H.; Yin, G. Catalytic Aerobic Oxidation of Renewable Furfural with Phosphomolybdic Acid Catalyst: an Alternative Route to Maleic Acid. J. Phys. Chem. C 2011, 115, 17516−17522. (39) Lan, J.; Chen, Z.; Lin, J.; Yin, G. Catalytic aerobic oxidation of renewable furfural to maleic anhydride and furanone derivatives with their mechanistic studies. Green Chem. 2014, 16, 4351−4358. (40) Li, X.; Ho, B.; Zhang, Y. Selective aerobic oxidation of furfural to maleic anhydride with heterogeneous Mo−V−O catalysts. Green Chem. 2016, 18, 2976−2980. (41) Alonso-Fagundez, N.; Agirrezabal-Telleria, I.; Arias, P. L.; Fierro, J. L. G.; Mariscal, R.; Granados, M. L. Aqueous-phase catalytic oxidation of furfural with H2O2: high yield of maleic acid by using titanium silicalite-1. RSC Adv. 2014, 4, 54960−54972. (42) Alonso-Fagundez, N.; Granados, M. L.; Mariscal, R.; Ojeda, M. Selective Conversion of Furfural to Maleic Anhydride and Furan with VOx/Al2O3 Catalysts. ChemSusChem 2012, 5, 1984−1990. (43) Li, X.; Lan, X.; Wang, T. Selective oxidation of furfural in a biphasic system with homogeneous acid catalyst. Catal. Today 2016, 276, 97−104. (44) Pan, T.; Deng, J.; Xu, Q.; Zuo, Y.; Guo, Q.; Fu, Y. Catalytic Conversion of Furfural into a 2,5-Furandicarboxylic Acid-Based Polyester with Total Carbon Utilization. ChemSusChem 2013, 6, 47−50. (45) Csű rös, Z.; Soós, R.; Fogassy, E.; Szabó, G. T. Study on the catalytic oxidation with air of furane derivatives substituted in the α position. Period Polytech., Chem. Eng. 1974, 18, 249−261. (46) Zheng, F.; Ban, S.; Feng, X.; Zhao, C.; Lin, W.; Li, Q. Synthesis and In Vitro Protein Tyrosine Kinase Inhibitory Activity of Furan-2yl(phenyl)methanone Derivatives. Molecules 2011, 16, 4897−4911. (47) Fu, L.; Fu, W.; Cheng, P.; Xie, Z.; Fan, C.; Shi, M.; Ling, J.; Hou, J.; Zhan, X.; Chen, H. A diketopyrrolopyrrole molecule end-capped with a furan-2-carboxylate moiety: the planarity of molecular geometry and photovoltaic properties. J. Mater. Chem. A 2014, 2, 6589−6597. (48) Houlden, C. E.; Hutchby, M.; Bailey, C. D.; Ford, J. G.; Tyler, S. N. G.; Gagné, M. R.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. RoomTemperature Palladium-Catalyzed CH Activation: ortho-Carbonylation of Aniline Derivatives. Angew. Chem., Int. Ed. 2009, 48, 1830− 1833.

(49) Haffemayer, B.; Gulias, M.; Gaunt, M. J. Amine directed Pd(II)catalyzed C−H bond functionalization under ambient conditions. Chem. Sci. 2011, 2, 312−315. (50) López, B.; Rodriguez, A.; Santos, D.; Albert, J.; Ariza, X.; Garcia, J.; Granell, J. Preparation of benzolactams by Pd(II)-catalyzed carbonylation of N-unprotected arylethylamines. Chem. Commun. 2011, 47, 1054−1056. (51) Wrigglesworth, J. W.; Cox, B.; Lloyd-Jones, G. C.; BookerMilburn, K. I. New Heteroannulation Reactions of N-Alkoxybenzamides by Pd(II) Catalyzed C−H Activation. Org. Lett. 2011, 13, 5326−5329. (52) Zhang, H.; Shi, R.; Gan, P.; Liu, C.; Ding, A.; Wang, Q.; Lei, A. Palladium-Catalyzed Oxidative Double C-H Functionalization/Carbonylation for the Synthesis of Xanthones. Angew. Chem., Int. Ed. 2012, 51, 5204−5207. (53) Chen, M.; Ren, Z.; Wang, Y.; Guan, Z. Palladium-catalyzed oxidative carbonylation of the alkenyl C-H bonds of enamides: synthesis of 1,3-oxazin-6-ones. Angew. Chem., Int. Ed. 2013, 52, 14196−14199. (54) Schoenberg, A.; Bartoletti, I.; Heck, R. F. Palladium-catalyzed carboalkoxylation of aryl, benzyl, and vinylic halides. J. Org. Chem. 1974, 39, 3318−3326. (55) Mägerlein, W.; Indolese, A. F.; Beller, M. You have full text access to this contentA More Efficient Catalyst for the Carbonylation of Chloroarenes. Angew. Chem., Int. Ed. 2001, 40, 2856−2859. (56) Hu, J.; Zhang, Q.; Guan, Z.; Gu, Y.; Mo, W.; Li, T.; Li, G. Palladium-Catalyzed Carbonylation of Chloroacetates to Afford Malonates: Controlling the Selectivity of the Product in a Buffer. ChemCatChem 2012, 4, 1776−1782. (57) Crettaz, R.; Waser, J.; Bessard, Y. Synthetic Process Development and Scale Up of Palladium-Catalyzed Alkoxycarbonylation of Chloropyridines. Org. Process Res. Dev. 2001, 5, 572−574. (58) Blaser, H.-U.; Diggelmann, M.; Meier, H.; Naud, F.; Scheppach, E.; Schnyder, A.; Studer, M. No Stirring Necessary: Parallel Carbonylation of Aryl Halides with CO and Various Alcohols under Pressure. J. Org. Chem. 2003, 68, 3725−3728. (59) Quesnel, J. S.; Kayser, L. V.; Fabrikant, A.; Arndtsen, B. A. Acid Chloride Synthesis by the Palladium-Catalyzed Chlorocarbonylation of Aryl Bromides. Chem. - Eur. J. 2015, 21, 9550−9555. (60) Watson, D. A.; Fan, X.; Buchwald, S. L. Carbonylation of Aryl Chlorides with Oxygen Nucleophiles at Atmospheric Pressure. Preparation of Phenyl Esters as Acyl Transfer Agents and the Direct Preparation of Alkyl Esters and Carboxylic Acids. J. Org. Chem. 2008, 73, 7096−7101. (61) Mane, R. S.; Bhanage, B. M. Pd/C-Catalyzed Aminocarbonylation of Aryl Iodides via Oxidative C−N Bond Activation of Tertiary Amines to Tertiary Amides. J. Org. Chem. 2016, 81, 1223− 1228. (62) Fang, T.; Gao, X.; Tang, R.; Zhang, X.; Deng, C. A novel Pdcatalyzed N-dealkylative carbonylation of tertiary amines for the preparation of amides. Chem. Commun. 2014, 50, 14775−14777. (63) Najiba, D.; Carpentier, J. F.; Castanet, Y.; Biot, C.; Brocard, J.; Mortreux, A. Selective palladium-catalysed carbonylations of dichloroquinoline and simple dichloropyridines. Tetrahedron Lett. 1999, 40, 3719−3722. (64) Zeng, Y.; Chen, X.; Zhao, D.; Li, H.; Zhang, Y.; Xiao, X. Estimation of pKa values for carboxylic acids, alcohols, phenols and amines using changes in the relative Gibbs free energy. Fluid Phase Equilib. 2012, 313, 148−155. (65) Snyder, L. R. Classification of the solvent properties of common liquids. J. Chromatogr. A 1974, 92, 223−230. (66) Snyder, L. R. Classification of the solvent properties of common liquids. J. Chromatogr. Sci. 1978, 16, 223−234. (67) Jutand, A.; Négri, S. Rate and mechanism of the oxidative addition of vinyl triflates and halides to palladium (0) complexes in DMF. Organometallics 2003, 22, 4229−4237. (68) Albaneze-Walker, J.; Bazaral, C.; Leavey, T.; Dormer, P. G.; Murry, J. A. Improved Carbonylation of Heterocyclic Chlorides and 9368


Research Article

ACS Sustainable Chemistry & Engineering Electronically Challenging Aryl Bromides. Org. Lett. 2004, 6, 2097− 2100. (69) Barnard, C. F. J. Carbonylation of Aryl Halides: Extending the Scope of the Reaction. Org. Process Res. Dev. 2008, 12, 566−574. (70) Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Unparalleled Rates for the Activation of Aryl Chlorides and Bromides: Coupling with Amines and Boronic Acids in Minutes at Room Temperature. Angew. Chem., Int. Ed. 2002, 41, 4746−4748. (71) Carvalho, M. A.; Arruda, E. G. R.; Profirio, D. M.; Gomes, A. F.; Gozzo, F. C.; Formiga, A. L. B.; Corbi, P. P. Chemical and spectroscopic characterizations, ESI-QTOF mass spectrometric measurements and DFT studies of new complexes of palladium(II) with tryptamine and mefenamic acid. J. Mol. Struct. 2015, 1100, 6−13. (72) Zheng, Q.; Liu, Y.; Chen, Q.; Hu, M.; Helmy, R.; Sherer, E. C.; Welch, C. J.; Chen, H. Capture of Reactive Monophosphine Ligated Palladium(0) Intermediates by Mass Spectrometry. J. Am. Chem. Soc. 2015, 137, 14035−14038. (73) Fadzil, N. A. M.; Rahim, M. H. A.; Maniam, G. P. A brief review of para-xylene oxidation to terephthalic acid as a model of primary CH bond activation. Chin. J. Catal. 2014, 35, 1641−1652. (74) Zhang, J.; Li, J.; Tang, Y.; Lin, L.; Long, M. Advances in catalytic production of bio-based polyester monomer 2,5-furandicarboxylic acid derived from lignocellulosic biomass. Carbohydr. Polym. 2015, 130, 420−428. (75) van Putten, R. J.; van der Waal, J. C.; De Jong, E. D.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem. Rev. 2013, 113, 1499−1597. (76) Bozell, J. J.; Petersen, G. R. Technology development for the production of biobased products from biorefinery carbohydratesthe US Department of Energy’s “Top 10” revisited. Green Chem. 2010, 12, 539−554. (77) Lewkowski, J. Synthesis, chemistry and applications of 5hydroxymethylfurfural and its derivatives. ARKIVOC (Gainesville, FL, U. S.) 2001, 2001 (i), 17−54. (78) Zhou, C. H.; Xia, X.; Lin, C. X.; Tong, D.; Beltramini, J. Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chem. Soc. Rev. 2011, 40, 5588−5617. (79) Melero, J. A.; Iglesias, J.; Garcia, A. Biomass as renewable feedstock in standard refinery units. Feasibility, opportunities and challenges. Energy Environ. Sci. 2012, 5, 7393−7420.

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Catalytic Synthesis of 2,5-Furandicarboxylic Acid from Furoic Acid

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